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Article

Stabilization of Tetrachloride with Mn (II) and Co (II)Complexes and 4-Tert-Butylpyridinium Organic Cation: Elaboration of the Structure and Hirshfeld Surface, Optical, Spectroscopic and Thermal Analyses

by
Abdullah A. Alotaibi
1,
Chaima Ayari
2,
Elham Bajuavfir
3,
Ashfaq Ahmad
3,
Fatima Al-Nahdi
3,
Abdullah M. Alswieleh
3,
Khalid M. Alotaibi
3,
Jin-Xiao Mi
4,
Cherif Ben Nasr
2 and
Mohamed Habib Mrad
1,2,*
1
Department of Chemistry, College of Sciences and Humanities, Shaqra University, Shaqraa 11911, Saudi Arabia
2
Materials Chemistry Laboratory, Faculty of Sciences of Bizerte, University of Carthage, Tunis 7021, Tunisia
3
Department of Chemistry, College of Science, King Saud University, Riyadh 11451, Saudi Arabia
4
Department of Materials Science and Engineering, College of Materials, Xiamen University, Xiamen 361000, China
*
Author to whom correspondence should be addressed.
Crystals 2022, 12(2), 140; https://doi.org/10.3390/cryst12020140
Submission received: 12 December 2021 / Revised: 6 January 2022 / Accepted: 11 January 2022 / Published: 19 January 2022
Browse Figures
Versions Notes

Abstract

:
[C9H14N]2[MnCl4] (I) and [C9H14N]2[CoCl4] (II) are isostructural compounds produced via gradual evaporation at room temperature. Both compounds consolidate in the tetragonal space group I 4 ¯ 2d (No. 122), as shown by single-crystal X-ray diffraction observations. A slightly deformed tetrahedral geometry is formed by four chloride atoms around each cation MII (M = Mn or Co). The [C9H14N]+ groups and the isolated [MCl4]2− units are connected via C–H…Cl and N–H…Cl H-bonds to form sheets parallel to the (10 1 ¯ ), (011), (0 1 ¯ 1) and (101) planes. The morphology and the chemical composition of compounds (I) and (II)were determined here using SEM and EDX. The functional groups contained in both compounds were determined using FT-IR spectroscopy. The study of the optical characteristics showed that the two compounds exhibited semiconductor behavior. The thermal analysis (TGA-DTA) was used to determine their thermal stability.

Graphical Abstract

1. Introduction

Among the organic ligands, pyridine is often utilized during synthesis due to the presence of an aromatic nitrogen atom with an unbound electron pair that is ideally positioned to operate in synthetic fragments. Indeed, this atom and its derivatives have been manipulated with several transition metals to produce new materials with different structures and properties [1,2,3]. Transition metal complexes represent a very important area in the field of chemistry due to their coordination properties. The cobalt (II) and manganese (II) halides are the dominant entities in metal halides due to their coordination forms, structural variety, and application in chemical and material sciences [4,5,6,7,8,9,10]. Mn (II) halides have multiple advantages, including the ease of their preparation, their high light intensity, increased thermal stability, low toxicity, and affordable cost. As has been reported, Mn (II) halides generate green to dark red fluorescence due to the crystal field and different ligands [11,12]. Cobalt–organic hybrid material complexes are very interesting materials in inorganic chemistry, with their features including adjustable band gaps, electric mobility, thermal stability and magnetic properties, while their structural varieties make very good catalysts [13,14]. In addition, for compounds based on Co and Mn (belonging to the fourth row of the periodic table),the tetrahedral and square plan geometries are generally more common [15,16,17,18]. Furthermore, the N-H… X-M and C-H… X-M H-bonds with assisted charge have a great influence on the geometry of the halo-metallate anions and on the relative stability of the different crystalline phases [19,20,21,22,23,24,25,26,27,28,29,30,31]. These latter phases have a variety of uses, such as in magnetic and thermochromic compounds [32,33,34].
NLO is widely used in optoelectronic sectors; in particular, saturable absorbers, switches and harmonic generators are all made with this material. The investigation of new materials possessing rather important NLO properties remains justified by the potential applications, along with investigations of the fundamental understanding of photo physics, which can be deduced from the correlations in the chemical structure and nonlinear signals [35,36,37,38]. Within this context, our goal was to synthesize two new compounds based on 4-tert-butylpyridine that can be applied in material sciences in the future due to their properties. Additionally, these compounds, which crystallize in the I 4 ¯ 2d space group, may be suitable for nonlinear optical applications.
The following article discusses the chemical preparation, crystallographic description, spectroscopic properties and thermal behavior of two novel isostructural complexes bis(4-tert-butylpyridinium)tetrachloromanganate [C9H14N]2[MnCl4] (I) and bis(4-tert-butylpyridinium)tetrachlorocobaltate [C9H14N]2[CoCl4] (II).

2. Experimental

2.1. Chemical Preparation

MnCl2· 3 2 H2O(for compound (I)) and CoCl2·5H2O(for compound (II)) were each dissolved alone in 10 mL of dilute hydrochloric acid (1M), then each mixture was added to a solution containing the amine 4-tert-butylpyridine (C9H13N) (0.27 g, 2 mmol) diluted in 10 mL of ethanol with a molar ratio of 1:2 under magnetic stirring for 4 h.
After two weeks of gradual evaporation at ambient temperature, block-shaped colorless crystals appropriate for XRD (X-ray diffraction) investigation were produced for compound (I), while block-shaped blue crystals were produced for (II).
The atomic percentage of the formula [C9H14N]2[MnCl4] was determined by the CHN-elemental analysis: C: 46.08 wt%/45.92 wt%; N:5.97 wt%/5.86 wt%; H:6.02 wt%/5.84 wt%; Cl:30.22 wt%/29.98 wt%(Theoretical/Experimental). On the other hand, the CHN-elemental analysis for the formula [C9H14N]2[CoCl4] gave the following results: C:45.70 wt%/45.18 wt%; N:5.92 wt%/5.80 wt%; H:5.97 wt%/5.83 wt% Cl:29.97 wt%/29.68 wt% (Theo/Exp).
The chemical reaction schemes were as follows:
For (I): 2 C9H13N + 2 HCl + MnCl2→[C9H14N]2[MnCl4]
For (II): 2 C9H13N + 2 HCl + CoCl2 →[C9H14N]2[CoCl4]

2.2. Characterization

2.2.1. SEM Observation and EDX Analysis

To determine the morphology of the crystals and the mass titer (%) of the elements present in complexes (I) and (II), we utilized an SEM (JOEL–IT 300, Tokyo, Japan). For the surface element analysis, the SEM was fitted with an energy-dispersive X-ray spectroscopy module (EDX, Oxford, UK).

2.2.2. Single-Crystal X-ray Structural Investigation

For the single-crystal XRD (X-ray diffraction) investigation, an Atlas X-ray diffractometer (Agilent Technologies Inc., Santa Clara, CA, USA) was employed. The data were collected using a diffraction system with graphite-monochromated MoKα radiation. We solved the structures using SHELXT and optimized them using full-matrix least-squares on F2 while employing SHELXL-2014/7 [39]. Mercury software [40] was used to create their molecular structures and Diamond 2.0 version [41] was used to generate all projections. Here, C5, C6 and C7 (compound (I)) and C4, C5, C6 and C7 (compound (II)) were disordered with an occupancy factor equal to 0.5. Table 1 shows the results of the experiment.

2.2.3. IR spectroscopy, UV Spectroscopy and Thermal Analysis (TGA-DTA)

A Nicolet Impact 410 FT-IR spectrophotometer (SpectraLab Scientific Inc., Markham, ON, Canada) was used to record the FT-IR spectra of both compounds (I) and (II). Using a Perkin Elmer Lambda 35 UV-Vis spectrophotometer (Waltham, MA, USA), the UV absorption spectra of the two materials were recorded. Finally, the TGA-DTA thermograms were generated in the temperature range 300–700 K under an inert atmosphere (nitrogen) using a PYRIS 1 TGA instrument (Perkin Elmer, Waltham, MA, USA).

3. Results and Discussion

3.1. SEM/EDX Observation

The compound’s surface morphology was investigated using an SEM examination. The photograph in Figure 1a shows that compound (I) exhibits a somewhat special morphology (is not porous). The figure presents a white spot surrounded by uneven structures. The dispersive spectrum analysis indicated the existence of atoms C, N, Cl and Mn in addition to hydrogen in the sample. An assembly of the different-sized nanoparticles is represented as the morphology of compound (II) in Figure 1b, while the EDX spectrum of the produced chemical shows the presence of carbon, cobalt, chlorine, and nitrogen.
It has been shown by SEM examination that the crystals of both compounds are not hygroscopic in nature and are homogeneous in structure. They also seem to be suitable for X-ray diffraction studies. In addition, the EDX spectra show that the most significant intensities for both compounds surface are C, Co, Mn, Cl, and N atoms.

3.2. Description of the Structure

The two isostructural compounds bis(4-tert-butylpyridinium) tetrachloromanganate (II) [C9H14N]2[MnCl4] (I) and bis(4-tert-butylpyridinium)tetrachlorocobltate (II) [C9H14N]2[CoCl4] (II) crystallize in the tetragonal space group I 4 ¯ 2d. All the crystallographic data are reported in Table 1. As seen in Figure 2, the molecular structure is constituted by one-quarter of [MCl4]2− anions (M = Mn for (I) and M = Co(II)) and is constituted by a 4-tert-butylpyridinium cation to ensure charge balance. Hence, the asymmetric unit contains half of the 4-tert-butylpyridinium, where the N-H group lays the two-fold axis, whereas the inorganic anion is deduced by a rotoinversion axis, which is a combination of an inversion center and a rotation axis. The Mn1 and Co1 ions have site symmetry C4 in Wyckoff position 4a, while the Cl1 and Cl2 ions have site symmetry C1 in Wyckoff position 16e.
Figure 3 illustrates the atomic arrangement projected along the a-axis of compounds (I) and (II). Their structures can be described by alternative layers, where each layer is formed by [C9H14N]+ groups and [MCl4]2− units. Figure 4 shows that the organic cations of both compounds occupy special sites in the crystal lattice. The center of the ring (C5N) part in [C9H14N]+ groups, whose ring planes run parallel to the (101) or (−101) planes, occupies the ( 1 4 ,   1 4 ,   1 8 ) positions (Wyckoff position 8d). The base plane of the butyl part in the [C9H14N]+ groups is perpendicular to the above-mentioned ring plane, and also to the b-axis. The geometry of the butyl part contains a three-fold rotation axis which is not consistent with the two-fold rotation axis along the b-axis in space group I 4 ¯ 2d, leading to the disordered distribution of C4, C5, C6 and C7 in the both compounds.
The cohesion of the three-dimensional network is ensured by hydrogen bonds of N-H…Cl and C-H…Cl (Table 2) and electrostatic interactions at low energy. The centroid of two neighboring rings is separated by 4.843 Å. This value is greater than 3.8 Å, which excludes the presence of π-π stacking.

3.2.1. Geometry of the [MCl4]2−Anions

A view of the inorganic portion in perspective (Figure 4a,b) shows that the isolated [MCl4]2− occurs in the (0, 0, 0), (0, ½, ¼), (½, 0, ¾)and (½, ½, ½) positions. If we look at compound (I), we can see that the [MnCl4]2-tetrahedron is defined by manganese and four chloride atoms (Cl1, Cl1i, Cl1ii and Cl1iii). The four Mn-Cl distances have the same value equal to 2.3665 (7) Å. However, the Cl-Mn-Cl angles vary from 106.73 (2)° to 115.10 (4)° (Table 3). According to comparable compounds, these values are consistent [42,43,44]. The analysis of the geometry can be carried out using the τ4 metric developed by Yang [45] for tetra-coordinated complexes. The τ4 value is calculated as follows (in the case of a perfect square planer geometry τ4 = 0, while τ4 = 1 for a tetrahedral geometry):
τ 4 = 360 − ( α   +   β ) 141  
Thus, for the [MnCl4]2− tetrahedron, which is near perfect, the same holds for the isostructural compound (II) (distances are equal to 2.2798 (17) Å—the Cl-Co-Cl angles range from 107.20 (6)° to 114.12 (12)° (Table 3) [46]).

3.2.2. Geometry of the Organic Cation

Regarding the structure of compound (I), the C-C distances in the 4-tert-butylpyridinium are in the range of 1.23 (2) Å–1.90 (2) Å and the C-N distance is equal to 1.331 (5) Å. However, the C-C-C, C-N-C and C-C-N angle values vary between 48.2 (10) and 149.3 (10), while in compound (II), the C-C distances vary from 1.351 (13) to 1.540 (13) Å and the C-N distance is equal to 1.324 (11) Å. The C-C-C, C-N-C and C-C-N angle values are between 105 (2)° and 126.4 (9)°. These values are compatible with those of bis(2-amino-6-methylpyridinium)tetrachlorozincate (II) [47]. The interatomic distances (Å) and angles (°) of [C9H14N]+ groups in the two compounds are summarized in Table 4.
Comparing the crystallographic features of [C9H14N]2[MCl4] (M = Mn or Co) (A) with those of [C7H11N2]2[MnCl4] (B) [48], the key variations between them are the space group (I 4 ¯ 2d for (A) and P-1 for (B) with Z = 4 for (A) and Z = 2 for (B)). An isolated [MnCl4]2− anion and 4-(dimethylamino)pyridinium (C7H11N2)+ cation form the basis of the structure of (B), which is coupled by a network of N–H…Cl, C–H…Cl H-bonds. These changes inevitably have an impact on the atomic arrangement and the method in which the structure is stabilized. Both compounds (A) and (B) are stabilized by many hydrogen bonds and the electrostatic interaction that increases the stability and the union of the three-dimensional network.

3.3. Hirshfeld Surface (HS) Investigation

To investigate the HS surface and types of intermolecular interactions and their contributions of synthesized compounds (I) and (II), we used CrystalExplorer version 3.1[49]. Chemical interactions can be demonstrated visually by examining how neighboring atoms of two complexes (I) and (II) interact with each other on the dnorm surface, curved, surface and shape index surface. Figure 5 shows the absence of flat areas with a blue border on the curved surface, while the absence of neighboring blue and red triangles on the shape index surface indicates the absence of π-π interactions for both compounds. The dark red circles on the dnorm map characterize the interactions between the chlorine atom and the hydrogen atom (Figure 6a,b). Therefore, the H-bonds C-H…Cl and N-H…Cl are thought to be responsible for the red zones. Table S1 reports the enrichment ratios EXY for a pair of elements (X, Y). Figure 7 shows the entire fingerprint plots for both compounds. The big blue zone in the center of the 2D fingerprint, which accounts for 51% of the interactions for both materials, is attributed to the H…H contacts (Figure 7a,g), with an enrichment rate larger than unity EHH = 1.22(I) and EHH = 1.19 for (II) due to the high abundance of the hydrogen of the Hirshfeld surface SH = 65.3% for (I) and SH = 64.55% for (II). The H…Cl/Cl…H contacts rank (di + de~ 2.6 Å)is the second rate with a contribution equal to 15.7% for compound [C9H14N]2[MnCl4] and 15.8% for compound [C9H14N]2[CoCl4] due to the presence of H-bonds(strong hydrogen bonds interactions) in the crystal structures of both complexes, with molecular surfaces of SH = 65.3% and SCl = 12.6% for (I) and SH = 64.55% and SCl = 12.55% for (II) and enrichment ratios of EHCl = 0.95 for (I) and EHCl = 0.97 (II), as identified by two pointed winglets in the fingerprint maps(Figure 7b,h). For compound (I), the contribution of 9.1% is reserved for the Mn...Cl/Cl...Mn contacts with de + di~ 2.4 Å and appears as a straight line in the middle of the plot, as shown in Figure 7c. The C…C contacts rank fourth, with a contribution of 7.1%, as shown in Figure 7d, which confirmed the absence of π-π interactions between two neighboring aromatic rings, as revealed by the X-ray diffraction analysis. The other intermolecular contacts present in (I) are Mn…H/H…Mn (5.9%; Figure 7e) and C…H/H…C (5.2%; Figure 7f), which are marked by low enrichment ratios of EMnH = 0.60 (I) and ECH = 0.35 (II), showing their weak roles in the crystal stability of both compounds. For compound (II), the C...C contacts (SC = 12.9%) and Co...Cl/Co...Cl contacts (Figure 7i,j) are classified in the third rank, with a contribution of 8.9% of the total area for each of them. The other intermolecular contacts present in (II) are C…H/H…C (4.9%; Figure 7k) and Co…H/H…Co (4.6%; Figure 7l) [50].

3.4. FT–IR Spectroscopy

Figure 8a,b shows a comparison of the IR absorption spectra of compound (I) and (II). As can be observed, the two spectra are similar, and the different vibrational modes of these compounds may be compared to those of other compounds containing the same organic cation [51,52,53,54,55].
The elongation vibrations of NH+ groups and the asymmetric elongation vibrations of the CH to bonds of the aromatic ring are responsible for the first four peaks observed at 3179, 3133, 3064 and 2968 cm−1 in (a), and at 3198, 3133, 3057, and 2967 cm−1 in (b). The bands at 1636, 1590 and 1495 cm−1 in (a), and at 1639, 1594, and 1501 cm−1 in (b) are allocated to v(C=C) and v(C=N) stretching modes present in the organic motif. The deformation vibrations of the methyl groups –CH3 are demonstrated by a peak located at 1381 cm−1 (Figure 8a) and at 1368 cm−1 (Figure 8b). The three successive peaks lying between 1279 and 1200 cm−1 in (a) and between 1285 and 1196 cm−1 in (b) corresponds to the C-H scissoring vibrations of the pyridine ring. However, the v(C–N) and v(C–C) are seen through bands located in 1200–1000 cm−1 regions in both spectra. In (a) and (b), the set of peaks that their wavenumbers vary from 1000 to 500 cm−1 are assigned to out-of-plane bending modes of C–N, C–C, and C–H [56,57].

3.5. Optical Behavior

Compounds (I) and (II) were examined for their UV–Vis absorption spectra at ambient temperature by changing the wavelength from 200 to 700 nm (Figure 9a). The two observed bands at about 234 nm and 300 nm are assigned to π → π* transitions of the aromatic pyridine ring. The four bands located at 338, 421, 436 and 549 nm are ascribed to the electronic transitions of the tetrahedral-coordinated Mn2+ ions in such a way that the electron pass from the fundamental state which is 6A1 (S) to the excited states, which are 4 T1 (P), 4 E (D), 4 T2 (D), [4 A1 (G), 4 E (G)], 4 T2 (G) and 4 T1 (G), respectively [58]. According to its absorption spectrum, [C9H14N]2[CoCl4] exhibits low and high-intensity absorption bands in the ultraviolet domain, followed by high- and low-intensity absorption bands with long wavelengths in the visible domain. At 229, 265, 345 and 394 nm, there are indeed four absorption bands owing to the transitions within the organic part (Figure 9b). In actuality, the first two bands correspond to the π-π* transitions due to the presence of a heteroatom in the pyridine ring, whereas the remaining two bands belong to the n-π* transitions. It can be seen that most of the organic cations do not give rise to bands in the visible domain [59,60,61,62]. The LMCT phenomenon (ligand-to-metal charge transfer) between the chloride atom Cl and metal atom Co can be observed in two bands located at 423 and 469 nm [63,64,65,66,67,68,69]. The bands located at 542, 558 and 576 nm are intended for d-d electronic transitions, showing that the geometry of the cobalt atom contain stetrahedral [CoCl4]2−(4 A2 (F)→4 T2 (F), 4 A2 (F)→4 T1 (F) and 4 A2 (F)→4 T1 (P), which are generally attributed to compounds based on cobalt Co (II) [70,71,72].
The Eg (gap energy) is defined as the energy difference between the lowest empty conduction bands and the highest band filled with electrons (the valence band), which reflects the properties of the materials from the point of view of electrical conductivity. Figure 9 shows the change in(αhv)2 versus hv, where the band gap energy Eg is determined using the method of extrapolation of the linear part [73]. Complex (I) has two values of Eg, with the first value being equal to 1.54 eV and the second one being equal to 1.77 eV. For complex (II), the value of the gap energy is equal to 2.06 eV. These values show that the synthesized compounds can be considered as semiconductor materials.

3.6. Thermal Phenomena

The TGA–DTA result for compound (I) is shown in Figure 10a (where TGA is the therogravimetric analysis and DTA is the differential thermal analysis). On the DTA curve, a sequence of endothermic peaks can be seen, as well as a mass loss on the TGA curve. According to the TGA curve, compound [C9H14N]2[MnCl4] does not show any loss of mass before 450 K. However, the two endothermic peaks on the DTA curve at 365 K and 403 K with ΔH = 186.115 J·g−1 and ΔH = 18.294 J·g−1, respectively, can be attributed to the two-phase transition. The same is true for (II), where Figure 10b shows an endothermic peak at 401 K in the DTA curve that can be attributed to a phase transition phenomenon, without mass loss in the corresponding TGA curve. After 450 K, the DTA thermogram of compound (I) presents several endothermic peaks at 486 (ΔH = 485.991 J·g−1), 542 K (ΔH = 628.36 J·g−1), 567 K (ΔH = 72.144 J·g−1), 587 K (ΔH = 162.983 J·g−1) and 607 K (ΔH = 208.252 J·g−1), which are ascribed to the organic component that degrades first, followed by the inorganic matrix decomposing. The decomposition produces an unpleasant odor, which is most likely caused by chlorine gas escaping from the resulting black substance. Indeed, the presence of carbon and manganese oxide is revealed by this black viscous residue. The FTIR spectra recorded at 600 K are represented in Figure 11 and confirm the total degradation of the organic part. On the other hand, compound (II) remains stable up to a temperature of 458 K. Above this temperature, we notice four endothermic peaks in the DTA curve and two mass losses in the TGA curve. The two peaks detected at 461 K and 485 K (ΔH = 187.821 J·g−1, ΔH = 400.904 J·g−1, respectively) correspond to the elimination of one organic cation with two chlorine atoms, with a theoretical loss of 32.83% and experimental loss of 31.35%. The other two peaks at 548 K (ΔH = 104.97 J·g−1) and 575 K (ΔH = 215.929 J·g−1) are assigned to the departure of the second organic cation, with two chlorine atoms and a cobalt atom (Calc/Exp: 42.17%/42.97%).

4. Conclusions

Physicochemical techniques were used to describe two new Mn(II) and Co(II) isostructural complexes, [C9H14N]2[MnCl4] (I) and [C9H14N]2[CoCl4] (II), which were produced as single crystals at room temperature. In the arrangement of compounds (I) and (II), the cations [C9H14N]+ and the anions form layers in four different planes. The cohesion between the organic and inorganic entities is ensured by various H-bonds, giving rise to a 3D network. The study of the results of the SEM and EDX techniques proved the purity of compounds (I) and (II). The vibrational modes were studied using infrared spectroscopy. The optical properties of both complexes were investigated by UV-Vis spectroscopy. Tauc’s method for compound (I) gave two values 1.54 and 1.77 eV, while for (II) gave a single value equal to 1.99 eV. These values show that (I) and (II) are semiconductor materials. The TGA and DTA technique revealed that compound (I) is stable up to a temperature of 450 K, compound (II) is stable up to 458 K and their decomposition occurs in two stages.
The isostructurality of these materials will offer new possibilities for crystal engineering and for many other domains. These compounds, which crystallize in the I 4 ¯ 2d space group, may be suitable for nonlinear optical applications.

Supplementary Materials

The following supporting information can be downloaded at: https://www.mdpi.com/article/10.3390/cryst12020140/s1, Table S1. Molecular surface values and enrichment ratios of (I) and (II).

Author Contributions

Conceptualization, M.H.M. and C.B.N.; methodology, A.M.A. and F.A.-N.; software, E.B.; validation, A.A.; formal analysis, J.-X.M.; investigation, M.H.M.; resources, K.M.A.; data curation, A.A.A.; writing—original draft preparation, C.A.; writing—review and editing, A.A.A.; visualization, C.B.N.; supervision, M.H.M.; project administration, K.M.A.; funding acquisition, K.M.A. All authors have read and agreed to the published version of the manuscript.

Funding

This research was funded by King Saud University’s grant number RG-1441-303 and The APC was funded by King Saud University’s.

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

Not applicable.

Acknowledgments

The authors want to express their gratitude to King Saud University’s Deanship of Scientific Research for financing this study via research group No. RG-1441-303.

Conflicts of Interest

The authors declare no conflict of interest.

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Crystals 12 00140 g001 550
Figure 1. (a) EDX (left)and SEM (right)of images of compound (I). (b)EDX (left) and SEM (right) of images of compound (II).
Figure 1. (a) EDX (left)and SEM (right)of images of compound (I). (b)EDX (left) and SEM (right) of images of compound (II).
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Crystals 12 00140 g002 550
Figure 2. Molecular structures showing 50% probability ellipsoids of [C9H14N]2[MnCl4] (a) and [C9H14N]2[CoCl4] (b). The hydrogen atoms are removed for clarity in the figure.
Figure 2. Molecular structures showing 50% probability ellipsoids of [C9H14N]2[MnCl4] (a) and [C9H14N]2[CoCl4] (b). The hydrogen atoms are removed for clarity in the figure.
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Crystals 12 00140 g003 550
Figure 3. Projection along the a-axes of compounds (I) and (II); the only difference is in the orientation of the organic cations (the tert-butyl groups have been omitted for clarity).
Figure 3. Projection along the a-axes of compounds (I) and (II); the only difference is in the orientation of the organic cations (the tert-butyl groups have been omitted for clarity).
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Crystals 12 00140 g004 550
Figure 4. The various locations of organic cations and inorganic anions in the lattices for both compounds: (a) compound (I); (b) compound (II).
Figure 4. The various locations of organic cations and inorganic anions in the lattices for both compounds: (a) compound (I); (b) compound (II).
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Crystals 12 00140 g005 550
Figure 5. HS cartography showing dnorm (a), shape index (b), and curved ness surface (c) profiles for compounds (I) and (II).
Figure 5. HS cartography showing dnorm (a), shape index (b), and curved ness surface (c) profiles for compounds (I) and (II).
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Crystals 12 00140 g006 550
Figure 6. H-bonds present in compound [C9H14N]2[MnCl4] (a) and in compound [C9H14N]2[CoCl4] (b).
Figure 6. H-bonds present in compound [C9H14N]2[MnCl4] (a) and in compound [C9H14N]2[CoCl4] (b).
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Crystals 12 00140 g007 550
Figure 7. The 2D fingerprint maps of compounds (I) and (II): (a) H…H contacts for compound(I); (b) H…Cl/H…Cl contacts of compound (I); (c) Mn…Cl/Cl…Mn contacts of compound (I); (d) C…C contacts of compound (I); (e) Mn…H/H…Mn contacts of compound (I); (f) C…H/H…C contacts of compound (I); (g) H…H contacts of compound(II); (h) H…Cl/H…Cl contacts of compound (II); (i) C…C contacts of compound (II); (j) Co…Cl/Cl…Co contacts of compound(II); (k) C…H/H…C contacts of compound (II); (l) Co…Cl/Cl…Co contacts of compound (II).
Figure 7. The 2D fingerprint maps of compounds (I) and (II): (a) H…H contacts for compound(I); (b) H…Cl/H…Cl contacts of compound (I); (c) Mn…Cl/Cl…Mn contacts of compound (I); (d) C…C contacts of compound (I); (e) Mn…H/H…Mn contacts of compound (I); (f) C…H/H…C contacts of compound (I); (g) H…H contacts of compound(II); (h) H…Cl/H…Cl contacts of compound (II); (i) C…C contacts of compound (II); (j) Co…Cl/Cl…Co contacts of compound(II); (k) C…H/H…C contacts of compound (II); (l) Co…Cl/Cl…Co contacts of compound (II).
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Crystals 12 00140 g008 550
Figure 8. The experimental IR absorption spectra of compounds (I) (a) and (II) (b).
Figure 8. The experimental IR absorption spectra of compounds (I) (a) and (II) (b).
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Crystals 12 00140 g009 550
Figure 9. (a,b)UV–Vis spectrum associated with the Taucplot ((αhv)2 versus hv) for compound (I); (c,d) UV–Vis spectrum associated with the Taucplot ((αhv)2 versus hv) for compound (II).
Figure 9. (a,b)UV–Vis spectrum associated with the Taucplot ((αhv)2 versus hv) for compound (I); (c,d) UV–Vis spectrum associated with the Taucplot ((αhv)2 versus hv) for compound (II).
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Crystals 12 00140 g010 550
Figure 10. (a) TG and DTA curves of [C9H14N]2[MnCl4]. (b) TG and DTA curves of [C9H14N]2[CoCl4].
Figure 10. (a) TG and DTA curves of [C9H14N]2[MnCl4]. (b) TG and DTA curves of [C9H14N]2[CoCl4].
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Crystals 12 00140 g011 550
Figure 11. The FT–IR absorption spectra of compound (I) at 470 K and 600 K.
Figure 11. The FT–IR absorption spectra of compound (I) at 470 K and 600 K.
Crystals 12 00140 g011
Table
Table 1. Experimental details.
Table 1. Experimental details.
Crystal DataCompound (I)Compound (II)
Chemical formula C18H28N2 MnCl4C18H28N2 CoCl4
Mr(g·mol–1)469.16473.15
Crystal system, space groupTetragonal, I 4 ¯ 2dTetragonal, I 4 ¯ 2d
Temperature (K)293293
a (Å)15.6644 (11)15.4429 (4)
c (Å)9.6754 (17)9.7925 (5)
V(Å3)2374.1 (5)2335.35 (17)
Z44
Radiation typeMoKαMoKα
µ (mm−1)1.011.20
Crystal size (mm)
Form, Color		0.35 × 0.25 × 0.16
Block, Colorless		0.20 × 0.15 × 0.10
Block, Blue
Data collection
DiffractometerAtlasAtlas
Absorption correctionCCD plate scansCCD plate scans
θmin, θmax (°)2.5, 28.32.2, 28.3
No. of measured, independent and 2221, 1259, 11791726, 846, 800
observed [I > 2σ(1)] reflections
Rint0.020.033
(sinθ/λ)max(Å−1)0.6660.572
Refinement
R[F2 > 2σ(F2)], wR(F2), S0.035, 0.098, 1.090.072, 0.199, 1.08
No. of reflections1259864
No. of parameters7277
Δρmin,Δρmax(e.Å3)−0.37, 0.22−0.67, 0.70
CCDC No.21013872101388
Table
Table 2. H-bonds of compounds (I) and (II) (Å, °).
Table 2. H-bonds of compounds (I) and (II) (Å, °).
D—H···AD—H (Å)H···A(Å)D···A(Å)D―H···A(°)
Compound (I)
C1―H1···Cl10.932.713.622 (4)166
C2―H2···Cl1i0.932.873.772 (4)165
C2―H2···Cl1ii0.932.963.440 (5)114
N1―H1A···Cl1iii0.862.613.252 (4)133
N1―H1A···Cl1ii0.862.613.252 (4)133
Compound (II)
N1―H1N···Cl1v0.862.613.248 (10)132
N1―H1N···Cl1vi0.862.613.248 (10)132
C1―H1···Cl1vii0.932.823.735 (11)167
C1―H1···Cl1vi0.932.953.429 (13)114
C2―H2···Cl10.932.703.613 (11)167
Symmetry codes of compound (I): (i) x, −y+1/2, −z+1/4; (ii) y, x+1/2, z+1/4; (iii) –y+1/2, x+1/2,−z+1/2. Symmetry codes of compound (II): (v) y−1/2, −x+5/2, −z+5/2; (vi) y−1/2, x, z−1/4; (vii) −x+5/2, y, −z+11/4.
Table
Table 3. The principal interatomic distances (Å) and angles (°) of [MnCl4]2− and [CoCl4]2−.
Table 3. The principal interatomic distances (Å) and angles (°) of [MnCl4]2− and [CoCl4]2−.
Distances (Å)Angles (°)
[MnCl4]2− of Compound (I) with τ4 = 0.920
Cl1―Mn1―Cl1i106.73 (2)
Mn1―Cl12.3664 (7)Cl1―Mn1―Cl1ii115.10 (4)
Mn1―Cl1i2.3665 (7)Cl1i―Mn1―Cl1ii106.73 (2)
Mn1―Cl1ii2.3665 (7)Cl1―Mn1―Cl1iii106.73 (2)
Mn1―Cl1iii2.3665 (7)Cl1i―Mn1―Cl1iii115.10 (4)
Cl1ii―Mn1―Cl1iii106.73 (2)
[CoCl4]2− of Compound (II) with τ4 = 0.934
Cl1―Co1―Cl1ii107.20 (6)
Co1―Cl12.2798 (17)Cl1―Co1―Cl1iii107.20 (6)
Co1―Cl1ii2.2798 (17)Cl1ii―Co1―Cl1iii114.12 (12)
Co1―Cl1iii2.2798 (17)Cl1―Co1―Cl1iv114.12 (12)
Co1―Cl1iv2.2798 (18)Cl1ii―Co1―Cl1iv107.20 (6)
Cl1iii―Co1―Cl1iv107.20 (6)
Codes for symmetry (compound (I)): (i) –y, x, –z; (ii) –x, –y, –z; (iii) y, –x, –z. Codes for symmetry (compound (II)): (ii) y, –x +3, –z+3; (iii) –y+3, x, –z+3; (iv) –x+3, –y+3, z.
Table
Table 4. The main interatomic distances (Å) and angles (°) of the organic group of (I) and of (II).
Table 4. The main interatomic distances (Å) and angles (°) of the organic group of (I) and of (II).
Distances (Å)Angles (°)
[C9H14N]+ in (I)
N1―C2iv1.331 (5)N1—C2—C1120.0 (4)
N1―C21.331 (5)C2—N1—C2iv122.2 (5)
C1—C21.371 (7)C2—C1—C3120.6 (4)
C1—C31.400 (5)C1—C3—C1iv116.7 (5)
C3—C1iv1.400 (5)C1—C3—C4121.7 (3)
C3—C41.523 (8)C1iv—C3—C4121. 7 (3)
[C9H14N]+ in (II)
N1—C1i1.324 (11)C1i—N1—C1122.0 (11)
N1—C11.324 (11)N1—C1—C2120.3 (8)
C1—C21.351 (13)C1—C2—C3120.4 (8)
C2—C31.398 (10)C2—C3—C2i116. 6 (10)
C3—C2i1.398 (10)C2—C3—C4117. 0 (9)
C3—C41.530 (17)C2i—C3—C4126. 4 (9)
Symmetry codes of compound (I): (iv) x, −y+1/2, −z+1/4. Symmetry codes of compound (II): (i) x, −y+5/2, −z+9/4.
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Alotaibi, A.A.; Ayari, C.; Bajuavfir, E.; Ahmad, A.; Al-Nahdi, F.; Alswieleh, A.M.; Alotaibi, K.M.; Mi, J.-X.; Nasr, C.B.; Mrad, M.H. Stabilization of Tetrachloride with Mn (II) and Co (II)Complexes and 4-Tert-Butylpyridinium Organic Cation: Elaboration of the Structure and Hirshfeld Surface, Optical, Spectroscopic and Thermal Analyses. Crystals 2022, 12, 140. https://doi.org/10.3390/cryst12020140

AMA Style

Alotaibi AA, Ayari C, Bajuavfir E, Ahmad A, Al-Nahdi F, Alswieleh AM, Alotaibi KM, Mi J-X, Nasr CB, Mrad MH. Stabilization of Tetrachloride with Mn (II) and Co (II)Complexes and 4-Tert-Butylpyridinium Organic Cation: Elaboration of the Structure and Hirshfeld Surface, Optical, Spectroscopic and Thermal Analyses. Crystals. 2022; 12(2):140. https://doi.org/10.3390/cryst12020140

Chicago/Turabian Style

Alotaibi, Abdullah A., Chaima Ayari, Elham Bajuavfir, Ashfaq Ahmad, Fatima Al-Nahdi, Abdullah M. Alswieleh, Khalid M. Alotaibi, Jin-Xiao Mi, Cherif Ben Nasr, and Mohamed Habib Mrad. 2022. "Stabilization of Tetrachloride with Mn (II) and Co (II)Complexes and 4-Tert-Butylpyridinium Organic Cation: Elaboration of the Structure and Hirshfeld Surface, Optical, Spectroscopic and Thermal Analyses" Crystals 12, no. 2: 140. https://doi.org/10.3390/cryst12020140

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