The Isocyanide Complexes cis-[MCl2(CNC6H4-4-X)2] (M = Pd, Pt; X = Cl, Br) as Tectons in Crystal Engineering Involving Halogen Bonds
Round 1
Reviewer 1 Report
The manuscript provides an interesting perspective on the influence of halogen bonds on the supramolecular structures of dihalogen diisocyanide planar group 10 organometallic compounds. The manuscript is relevant, presents a well-organized structure, properly discussed, and it can be a trustworthy reference for other researchers in the field of Crystal Engineering using organometallic compounds. Experimental evidence is well supported by appropriate theoretical calculations. Therefore, I recommend it to be published with minor corrections, mainly concerning English issues.
However, I would like the authors to address some particular questions:
1 – According to figure S4 C-H…X-C interactions support HaBs in the formation of 1D-chain motifs. However, a table with geometrical parameters of these hydrogen bonds (such as tables 1, 3 and 4) is not included in the text. Not only the table should be included, but also in figure 2 both interactions should be represented, since the text where they are mentioned (lines 130 to 132) leads to this figure.
2 - While for all other theoretical methods the authors include in the main text some pertinent results that support their structural experimental results, when they mention Hirshfeld Surface Analysis they do not present any results from this type of calculation. The Hirshfeld surfaces figure included in the Supplementary Material (Figure S5) shows the location of some red spots indicating shorter contacts reported in the main text, but it is not a complete list.
3 - In line 180 the authors compare de M…X distances with the sum of Alvarez radii and include a proper reference, referring to the data in Table 3. However, in table 3 captions (line 185) they mention Rowland radii. Please check this situation.
Therefore, it is my suggestion that the authors should also include a table reporting the contribution (in percentage) of all four types of interactions (HaBs, C-H…X-C, M…X, C…C) to the Hirshfeld surface area of the various supramolecular contacts in all three compounds. Some of these results (or at least a reference to this table if they decide to include it as supplementary material) should be included in the main text. As it is, the relevance of the Hirshfeld Analysis is not totally evident.
Minor revisions suggested on the main text:
Line 11/13: “The crystal packing is provided by C–X···X’–C halogen bonds, C-H···X-C hydrogen bonds and pairs of X···M semicoordination and C···C contacts between the C atoms from an areneisocyanide ligands.”
Line 14 – “all three types”
Line 23 – “such as the catalytic activity”
Line 25 – Remove the hyphen after luminescence-, sensing-, biological-
Line 30 – Remove trans- in trans-palladium and trans-platinum since you repeat trans- in line 31
Line 34 – “metal ligated bonded”
Line 41 – “(XS = Cl, Br, I), the organometallic compounds”
Line 46 – Remove coma “in this work, we performed”
Line 48 – “cis-[PtCl2(CNC6H4-4-Br)2] (3), all exhibiting well-defined cis-geometries”
Line 65 – “with the ShelXT”
Line 66 – “with the ShelXL”
Line 83 – “were performed in using Gaussian-09 [59]”
Line 84 – “relativistic calculations requested requesting relativistic core Hamiltonian”
Line 86 – “performed in applying Multiwfn 3.8”
Line 87 – “were created in utilizing Chemcraft”
Line 91 – “leads either to unsolvated”
Line 93/94 – “Compounds All 1–3 crystallize”
Line 98 – “The metal–carbon distance distances”
Line 105 – “revealed and visualized intrinsic”
Line 113 – “HaBs (a); Cl···Pd”: replace ; by ,
Line 115 – “reported given in Fig. S2X and S3X (the Supporting Information)
Line 120 – “and those around X’ are close”
Line 124 – “These data indicate that this these short contact contacts is due to are HaB,”
Line 126 – “In these structures, the complex”: remove the coma ,
Line 130/131 – “interactions and the following supporting C–H···X–C hydrogen bonds was were further investigated by theoretical calculations”
Line 135 – “[78] allow allows to find the”
Line 144 – “clusters of all types..”: remove one dot .
Line 158 – “ to the electrophilic partner”
Line 159 – “ nearer to the nucleophilic partner”
Line 173 – “tend to 90°, due to the tetragonal”: place a coma ,
Line 177 – “In the crystal structure of 1–3, The the halogen atoms X are located”
Line 181 – “the existence of semicoordination should be confirmed by theoretical calculations”
Line 186 – “semicoordination was indeed”
Line 201 – Replace “comp lex” by complex
Line 220 – Should you use “XB donor and acceptor” or “HaB donor and acceptor”?
Line 230 – “C–Cl•••Cl’–C HaBs (a); Cl•••Pd semicoordination”: replace ; by ,
Comments for author File: 
Comments.pdf
Author Response
The manuscript provides an interesting perspective on the influence of halogen bonds on the supramolecular structures of dihalogen diisocyanide planar group 10 organometallic compounds. The manuscript is relevant, presents a well-organized structure, properly discussed, and it can be a trustworthy reference for other researchers in the field of Crystal Engineering using organometallic compounds. Experimental evidence is well supported by appropriate theoretical calculations. Therefore, I recommend it to be published with minor corrections, mainly concerning English issues.
Authors’ reply: We are grateful to the reviewer for such a positive assessment of our submission. With respect to the language corrections, manuscript was carefully checked with the help of a native English speaker.
- According to figure S4 C-H…X-C interactions support HaBs in the formation of 1D-chain motifs. However, a table with geometrical parameters of these hydrogen bonds (such as tables 1, 3 and 4) is not included in the text. Not only the table should be included, but also in figure 2 both interactions should be represented, since the text where they are mentioned (lines 130 to 132) leads to this figure.
Authors’ reply: We considered the C–H···X–C hydrogen bonds in section 3.3 and included the parameters these contacts in Table 2. Additionally, we represented the C–H···X–C interactions in Figure 2 and Figures S2, S3 (Supplemenaty Information).
- While for all other theoretical methods the authors include in the main text some pertinent results that support their structural experimental results, when they mention Hirshfeld Surface Analysis they do not present any results from this type of calculation. The Hirshfeld surfaces figure included in the Supplementary Material (Figure S5) shows the location of some red spots indicating shorter contacts reported in the main text, but it is not a complete?
Authors’ reply: We includes a Table S4 and Firgure S7 reporting the contribution (in percentage) of short interactions to the Hirshfeld surface area of the various supramolecular contacts in all three complexes. We also reported about C–H···Cl–M (section S2.1) and C–H···X–C (section 3.3) hydrogen bonds which red spots on the Hirshfeld surfaces indicating.
- In line 180 the authors compare de M…X distances with the sum of Alvarez radii and include a proper reference, referring to the data in Table 3. However, in table 3 captions (line 185) they mention Rowland radii. Please check this situation.
Authors’ reply: We corrected this typo and mentioned Alvarez radii and proper reference in Table 4.
- Line 11/13: “The crystal packing is provided by C–X···X’–C halogen bonds, C-H···X-C hydrogen bonds and pairs of X···M semicoordination and C···C contacts between the C atoms from an areneisocyanide ligands.”
Authors’ reply: We agree and corrected this sentence in the abstract part.
- Line 14 – “all three types”
Authors’ reply: We corrected this typo in the abstract part.
- Line 23 – “such as the catalytic activity”
Authors’ reply: This typo was corrected.
- Line 25 – Remove the hyphen after luminescence-, sensing-, biological-
Authors’ reply: We agree and corrected this typo in the intoduction.
- Line 30 – Remove trans- in trans-palladium and trans-platinum since you repeat trans- in line 31
Authors’ reply: We agree and revised the sentence.
- Line 34 – “metal ligated bonded”
Authors’ reply: We fully agree and rewrote the collocation.
- Line 41 – “(XS = Cl, Br, I), the organometallic compounds”
Authors’ reply: This typo was corrected.
- Line 46 – Remove coma “in this work, we performed”
Authors’ reply: We corrected this typo.
- Line 48 – “cis-[PtCl2(CNC6H4-4-Br)2] (3), all exhibiting well-defined cis-geometries”
Authors’ reply: We revised the sentence.
- Line 65 – “with the ShelXT”
Authors’ reply: This typo was corrected in section 2.2.
- Line 66 – “with the ShelXL”
Authors’ reply: We corrected this typo.
- Line 83 – “were performed in using Gaussian-09 [59]”
Authors’ reply: We fully agree and rewrote the collocation.
- Line 84 – “relativistic calculations requested requesting relativistic core Hamiltonian”
Authors’ reply: We agree and corrected this typo.
- Line 86 – “performed in applying Multiwfn 3.8”
Authors’ reply: We revised the sentence.
- Line 87 – “were created in utilizing Chemcraft”
Authors’ reply: We also revised the sentence.
- Line 91 – “leads either to unsolvated”
Authors’ reply: This typo was corrected.
- Line 93/94 – “Compounds All 1–3 crystallize”
Authors’ reply: This typo was corrected.
- Line 98 – “The metal–carbon distance distances”
Authors’ reply: We agree and corrected this typo.
- Line 105 – “revealed and visualized intrinsic”
Authors’ reply: We agree and corrected this typo.
- Line 113 – “HaBs (a); Cl···Pd”: replace ; by ,
Authors’ reply: This typo was corrected.
- Line 115 – “reported given in Fig. S2X and S3X (the Supporting Information)
Authors’ reply: We fully agree and corrected this typo.
- Line 120 – “and those around X’ are close”
Authors’ reply: We fully agree and rewrote the collocation.
- Line 124 – “These data indicate that this these short contact contacts is due to are HaB,”
Authors’ reply: These typos were corrected.
- Line 126 – “In these structures, the complex”: remove the coma ,
Authors’ reply: This typo was corrected.
- Line 130/131 – “interactions and the following supporting C–H···X–C hydrogen bonds was were further investigated by theoretical calculations”
Authors’ reply: We agree and revised the sentense.
- Line 135 – “[78] allow allows to find the”
Authors’ reply: This typo was corrected.
- Line 144 – “clusters of all types..”: remove one dot .
Authors’ reply: We corrected this typo.
- Line 158 – “ to the electrophilic partner”
Authors’ reply: This typo was corrected.
- Line 159 – “ nearer to the nucleophilic partner”
Authors’ reply: We agree and corrected this typo.
- Line 173 – “tend to 90°, due to the tetragonal”: place a coma ,
Authors’ reply: We corrected this typo.
- Line 177 – “In the crystal structure of 1–3, The the halogen atoms X are located”
Authors’ reply: This typo was corrected.
- Line 181 – “the existence of semicoordination should be confirmed by theoretical calculations”
Authors’ reply: We agree and revised the sentense.
- Line 186 – “semicoordination was indeed”
Authors’ reply: We agree and rewrote the collocation.
- Line 201 – Replace “comp lex” by complex
Authors’ reply: This typo was corrected.
- Line 220 – Should you use “XB donor and acceptor” or “HaB donor and acceptor”?
Authors’ reply: We agree and corrected all ‘XB’ abbreviations to ‘HaB’.
- Line 230 – “C–Cl•••Cl’–C HaBs (a); Cl•••Pd semicoordination”: replace ; by ,
Authors’ reply: This typo was corrected.
Reviewer 2 Report
This manuscript details several crystal structures and probes the sources of the intermolecular attractions via DFT calculations. The crystal geometries are suggestive of halogen bonds between pairs of halogen atoms, as well as M--X semi-coordinate bonds. AIM analyses provide bond paths along these putative bonds, although the critical point parameters are all quite small. Relative displacement of the positions of the MEP and density minima along these bond paths are also suggestive of some sort of interaction. Altogether, the computed data are supportive of the authors' contention of noncovalent bonds of the sort they conjecture, and the work can be promoted for acceptance. It would be useful to a reader, though, if the authors would emphasize the weakness of these bonds, emanating not only from the calculated data, but also as the interatomic distances are roughly equivalent to vdW radius sums.
Author Response
Authors’ reply: We are grateful to the reviewer for such a positive assessment of our submission. We added the following phrase to the text “It should be noted that the interatomic C–X···X’–C distances are roughly equivalent to the sum of Bondi vdW radii and the critical point parameters are small therefore, these C–X···X’–C interactions can be classified as weak HaBs.”
Reviewer 3 Report
The reported structures are new and the structures are interesting. Before acceptance, the authors encouraged to modify the manuscript according to the following comments:
1.The abstract part must be rewritten. Please explain the abbreviation ELF, ED. Also, state the important findings.
2.The English of the text must be improved.
3.The Coordination sphere of Pt and Pd is not clear. Please provide more clear data about this. For example in Figure 6, what are the atom symbols? modify the figures and add the atom names.
4.As stated in the abstract, please add the DFT calculations and also Bandgap of complexes based on HOMO LUMO diagram.
Author Response
The reported structures are new and the structures are interesting. Before acceptance, the authors encouraged to modify the manuscript according to the following comments:
Authors’ reply: We are grateful to the reviewer for such a positive assessment of our submission.
- The abstract part must be rewritten. Please explain the abbreviation ELF, ED. Also, state the important findings.
Authors’ reply: We fully agree and rewrote the abstract part with introduction a new data.
- The English of the text must be improved.
Authors’ reply: We fully agree and revised the all text to the best of our ability. With respect to the language corrections, manuscript was carefully checked with the help of a native English speaker.
- The Coordination sphere of Pt and Pd is not clear. Please provide more clear data about this. For example in Figure 6, what are the atom symbols? modify the figures and add the atom names.
Authors’ reply: We modified the Figures 6, 7 with atom symbols to make the coordination sphere of metals clear.
- As stated in the abstract, please add the DFT calculations and also Bandgap of complexes based on HOMO LUMO diagram.
Authors’ reply: The results of DFT calculations can be found in the end of each paragraph about noncovalent interactions under consideration (Table 2 and Figures 2-9). Views of HOMOs and LUMOs and their energies were added in Figure S8.
Round 2
Reviewer 3 Report
The authors modified the text sufficiently and I can recommend it for publication.
