Synthesis and Crystal Structure of A Pyrithione Derivative: Bis{2-[(1-oxidopyridin-2-yl)sulfanyl]-4,5-dihydro-1H-imidazol-3-ium} tetrachlorocuprate(2-)
Round 1
Reviewer 1 Report
The authors reported the synthesis and structure analysis of a imidazolium salts in this manuscript. The work seems to have been conducted to a high standard and will appeal to a wide range of organic chemists, as such I would recommend acceptance of the manuscript after addressing a few minor issues.
P5. L146: Change “Yai, L.“ to “Yao, L.“
P5. L153: Change “Kukolish, S.G.” to “Kukolich, S.G.”
P5. L155: Change “J. Am. Chem. Soc., 1950,” to “J. Am. Chem. Soc., 1950,”
P5. L171: Change “Ma, Z.Y.” to “Ma, Z.Z.” and “Yang, Q.H.” to “Yang, Z.H.”
Author Response
Response to Reviewer 1 Comments
Point 1:
The authors reported the synthesis and structure analysis of a imidazolium salts in this manuscript. The work seems to have been conducted to a high standard and will appeal to a wide range of organic chemists, as such I would recommend acceptance of the manuscript after addressing a few minor issues.
P5. L146: Change “Yai, L.“ to “Yao, L.“
P5. L153: Change “Kukolish, S.G.” to “Kukolich, S.G.”
P5. L155: Change “J. Am. Chem. Soc., 1950,” to “J. Am. Chem. Soc., 1950,”
P5. L171: Change “Ma, Z.Y.” to “Ma, Z.Z.” and “Yang, Q.H.” to “Yang, Z.H.”
Response 1:
All names on page 5 have been changed and the text has been bolded.
Author Response File: 
Author Response.docx
Reviewer 2 Report
The paper by Balewski et al. reports the synthesis, characterization, and X-ray structural analysis of a new tetrachlorocuprate/pyrithione derivative salt.
The manuscript is clear and the experimental part results adequate; therefore, I recommend it for publication in Molbank with minor changes.
1- Some errors and inaccuracies can be found along the text. For example:
Line 32, page 1: ‘ It was also demonstrated’ (moreover, it was demonstrated)
Lines 34-35, page 1: 'Recently, copper pyrithione is considered for use in supplanting zinc pyrithione in view of the fact low-toxicity standpoint' (Copper pyrithione has been recently considered in supplanting zinc pyrithione in view of its low-toxicity.)
Line 39, page 1: ‘regarded to be’ (regarded as)
Line 40, page 1: ‘effect’ (effects)
2 – The N12-H12 bond distance = 0.721 Ǻ is definitely too short
Author Response
Response to Reviewer 2 Comments
Point 1:
The paper by Balewski et al. reports the synthesis, characterization, and X-ray structural analysis of a new tetrachlorocuprate/pyrithione derivative salt. The manuscript is clear and the experimental part results adequate; therefore, I recommend it for publication in Molbank with minor changes. Some errors and inaccuracies can be found along the text. For example:
Line 32, page 1: ‘ It was also demonstrated’ (moreover, it was demonstrated)
Lines 34-35, page 1: 'Recently, copper pyrithione is considered for use in supplanting zinc pyrithione in view of the fact low-toxicity standpoint' (Copper pyrithione has been recently considered in supplanting zinc pyrithione in view of its low-toxicity.)
Line 39, page 1: ‘regarded to be’ (regarded as)
Line 40, page 1: ‘effect’ (effects)
Response 1:
All sentences have been changed according to the Reviewer's comments.
Point 2:
The N12-H12 bond distance = 0.721 Ǻ is definitely too short.
Response 2:
Both N-H distances have been standardized to 0.88 Å, the value used by the SHELXL program at 130 K. All H atoms have been refined as riding on their carriers. Corrected cif file has been deposited with CCDC.
Author Response File: Author Response.docx
Reviewer 3 Report
Two issues are obvious, and will have been tackled by the other reviewers.
1. A CuCl4- anion located on a 2-fold axis is a rare example, and I would have expected a comparison with other CuCl4- salts.
2. The chain-type hydrogen bonding scheme of this compound should have been mentioned and shown in both parts of figure 1.
Author Response
Response to Reviewer 3 Comments
Point 1:
Two issues are obvious, and will have been tackled by the other reviewers. A CuCl4- anion located on a 2-fold axis is a rare example, and I would have expected a comparison with other CuCl4- salts. The chain-type hydrogen bonding scheme of this compound should have been mentioned and shown in both parts of figure 1.
Response 1:
Information about hydrogen-bonded chains is added to the Fig. 1 caption.
Author Response File: Author Response.docx
Reviewer 4 Report
Report on the manuscript entitled « Synthesis and Crystal Structure of A Pyrithione 2 Derivative: 3 Bis{2-[(1-oxidopyridin-2-yl)sulfanyl]-4,5-dihydro-1H-i4 midazol-3-ium} tetrachlorocuprate(2-)”
The authors present the synthesis and the structural characterization by single crystal X-ray diffraction of the title compound that may be related to potential bio-active compounds.
The paper is ready for publication; only minor points are listed below.
l. 34-35: “Recently, copper pyrithione is considered for use in supplanting 34 zinc pyrithione in view of the fact low-toxicity standpoint” is unclear; please clarify the end of this sentence.
l. 72-74: “The conformation adopted by the cation results in a 73 large deviation from 120° of the endocyclic bond angles at the pyridine C2 atom [N1-C2-S7 74 111.01(11)° and C3-C2-S7 129.23(11)°] and in short intramolecular contact H3···C8 of 2.51 Å.” => would the author propose an analysis to explain this large deviation from 120°? May it be possible to have some proof that it is due to repulsive H3…C8 contact. May it be related to a possible O1…S7 attraction? One possibility may be to perform quantum chemistry calculation to explore this in details.
Other contacts may be interesting to be mentioned; for example there is a chalcogen bond between the cation and the anion with S7…Cl2 (sigma hole of S7 toward electron rich region of Cl2).
Author Response
Response to Reviewer 4 Comments
Point 1:
The authors present the synthesis and the structural characterization by single crystal X-ray diffraction of the title compound that may be related to potential bio-active compounds.
The paper is ready for publication; only minor points are listed below.
l. 34-35: “Recently, copper pyrithione is considered for use in supplanting 34 zinc pyrithione in view of the fact low-toxicity standpoint” is unclear; please clarify the end of this sentence.
Response 1:
The sentence has been clarified and changed as follows:
“Copper pyrithione has been recently considered in supplanting zinc pyrithione in view of its low-toxicity [12].”
Point 2:
l. 72-74: “The conformation adopted by the cation results in a 73 large deviation from 120° of the endocyclic bond angles at the pyridine C2 atom [N1-C2-S7 74 111.01(11)° and C3-C2-S7 129.23(11)°] and in short intramolecular contact H3···C8 of 2.51 Å.” => would the author propose an analysis to explain this large deviation from 120°? May it be possible to have some proof that it is due to repulsive H3…C8 contact. May it be related to a possible O1…S7 attraction? One possibility may be to perform quantum chemistry calculation to explore this in details. Other contacts may be interesting to be mentioned; for example there is a chalcogen bond between the cation and the anion with S7…Cl2 (sigma hole of S7 toward electron rich region of Cl2).
Response 2:
Repulsive interactions between H3 and C8 have been indicated as a plausible reason of observed angular deviations.
Information about a short S7-Cl2 contact has been added in the text.
Author Response File: Author Response.docx
