Structure and vibrational spectroscopy of lithium and potassium methanesulfonates

In this work, we have determined the structures of lithium methanesulfonate, Li(CH3SO3), and potassium methanesulfonate, K(CH3SO3), and analysed their vibrational spectra. The lithium salt crystallizes in the monoclinic space group C2/m with two formula units in the primitive cell. The potassium salt is more complex, crystallizing in I4/m with 12 formula units in the primitive cell. The lithium ion is fourfold coordinated in a distorted tetrahedron, while the potassium salt exhibits three types of coordination: six-, seven- and ninefold. Vibrational spectroscopy of the compounds (including the 6Li and 7Li isotopomers) confirms that the correlation previously found, that in the infrared spectra there is a clear distinction between coordinated and not coordinated forms of the methanesulfonate ion, is also valid here. The lithium salt shows a clear splitting of the asymmetric S–O stretch mode, indicating a bonding interaction, while there is no splitting in the spectrum of the potassium salt, consistent with a purely ionic material.


Are the interpretations and conclusions justified by the results? Yes
Is the language acceptable? Yes

Do you have any ethical concerns with this paper? No
Have you any concerns about statistical analyses in this paper? No

Recommendation? Reject
Comments to the Author(s) Parker et al. report in this manuscript the study on the crystal structures of the lithium and potassium methanesulfonates. Both compounds have been characterised through the inelastic neutron scattering, Raman and infrared spectroscopies. In addition, DFT calculations have been performed. These studies are of high quality, but some doubts arise from this work. The introduction is extremely short, the syntheses of the studied compounds have not been reported in detail (what about the yield of the synthetic procedure and the analysis of the purity and homogeneity of the samples?), and some parts of the crystallographic data have been communicated previously in conference abstracts and in a Thesis (in the case of the Li compound). In my opinion, in its present form, the manuscript is neither suitable nor scientifically sound. For these reasons, I do not recommend its publication in the journal RSOS (maybe this work could be more suitable for Polyhedron or RSC Adv.) Decision letter (RSOS-200413.R0) 15-Apr-2020 Dear Dr Parker: Manuscript ID: RSOS-200413 Title: "Structure and vibrational spectroscopy of lithium and potassium methanesulfonates" Thank you for submitting the above manuscript to Royal Society Open Science. Your paper was sent to reviewers and their comments are included at the bottom of this letter.
In view of the concerns raised by the reviewers, the manuscript has been rejected in its current form. However, a new manuscript may be submitted which takes into consideration these comments.
Please note that resubmitting your manuscript does not guarantee eventual acceptance, and that your resubmission will be subject to peer review before a decision is made.
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We look forward to receiving your resubmission. Reviewers' Comments to Author: Reviewer: 1 Comments to the Author(s) This is a really nice paper, communicating important vibrational analysis data on methanesulfonate. While I find the paper a bit too short (Introduction and Methods), the data and analysis are very good. I would recommend acceptance with minor corrections.

Reviewer: 2
Comments to the Author(s) The authors successfully collected vibrational spectra of Li and K methanesulfonates and observed satisfactory agreement between calculated and observed spectra. Upon this, they demonstrated a fourfold structure for Li salt and multi-fold structure for K salt. But I think the authors should introduce the motivation of this work more clearly and how it is related to the previous investigations.

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Do you have any ethical concerns with this paper? No

Recommendation? Accept as is
Comments to the Author(s) I think the authors make significant efforts to address the issues and the current manuscript is in better shape to be published on RSOS.

Recommendation? Accept with minor revision (please list in comments)
Comments to the Author(s) I appreciate the efforts that the authors have made in response to my questions and concerns. The revision clarifies almost all the points I raised and helps me (and hopefully readers) to understand this manuscript. I think the authors may still take into account the following point: Please, regarding the yield reported in the revised manuscript, give a more accurate value ("...>90%" is not valid for me).

Decision letter (RSOS-200776.R0)
We hope you are keeping well at this difficult and unusual time. We continue to value your support of the journal in these challenging circumstances. If Royal Society Open Science can assist you at all, please don't hesitate to let us know at the email address below.
Dear Dr Parker: Title: Structure and vibrational spectroscopy of lithium and potassium methanesulfonates Manuscript ID: RSOS-200776 Thank you for submitting the above manuscript to Royal Society Open Science. On behalf of the Editors and the Royal Society of Chemistry, I am pleased to inform you that your manuscript will be accepted for publication in Royal Society Open Science subject to minor revision in accordance with the referee suggestions. Please find the reviewers' comments at the end of this email.
The reviewers and handling editors have recommended publication, but also suggest some minor revisions to your manuscript. Therefore, I invite you to respond to the comments and revise your manuscript.
Because the schedule for publication is very tight, it is a condition of publication that you submit the revised version of your manuscript before 07-Jun-2020. Please note that the revision deadline will expire at 00.00am on this date. If you do not think you will be able to meet this date please let me know immediately.
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Once again, thank you for submitting your manuscript to Royal Society Open Science. The chemistry content of Royal Society Open Science is published in collaboration with the Royal Society of Chemistry. I look forward to receiving your revision. If you have any questions at all, please do not hesitate to get in touch. ************************************* RSC Associate Editor Comments to the Author: (There are no comments.) ************************************** Reviewer comments to Author: Reviewer: 3 Comments to the Author(s) I appreciate the efforts that the authors have made in response to my questions and concerns. The revision clarifies almost all the points I raised and helps me (and hopefully readers) to understand this manuscript. I think the authors may still take into account the following point: Please, regarding the yield reported in the revised manuscript, give a more accurate value ("...>90%" is not valid for me).

Reviewer: 2
Comments to the Author(s) I think the authors make significant efforts to address the issues and the current manuscript is in better shape to be published on RSOS.

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Title: Structure and vibrational spectroscopy of lithium and potassium methanesulfonates Manuscript ID: RSOS-200776.R1 It is a pleasure to accept your manuscript in its current form for publication in Royal Society Open Science. The chemistry content of Royal Society Open Science is published in collaboration with the Royal Society of Chemistry.
The comments of the reviewer(s) who reviewed your manuscript are included at the end of this email.
Thank you for your fine contribution. On behalf of the Editors of Royal Society Open Science and the Royal Society of Chemistry, I look forward to your continued contributions to the Journal. Thank you for the reviewers comments, I see that we have the full gamut from "accept as is" to "minor revision" to "reject"! On the following pages, I give detailed responses to the points raised by the reviewers. I hope that with these changes the manuscript is now acceptable for publication in Royal Society Open Science.

Yours sincerely
Prof Stewart F. Parker I have to say that I do not understand this comment. The K salt was purchased from Aldrich and has a stated purity of 98%. This was used for the single crystal X-ray structure determination and there was no evidence for impurities or a second phase, thus we did not see the need to prepare the K salt ourselves. We note that the infrared spectra of all the methanesulfonates, including that of the K salt, are shown and discussed in what was Figure 9 (now Figure 8).
Reviewer: 3 Comments to the Author(s) Parker et al. report in this manuscript the study on the crystal structures of the lithium and potassium methanesulfonates. Both compounds have been characterised through the inelastic neutron scattering, Raman and infrared spectroscopies. In addition, DFT calculations have been performed. These studies are of high quality, but some doubts arise from this work.
The introduction is extremely short, As noted above, we have expanded on the motivation for the paper and its relationship to previous work in the Introduction.
the syntheses of the studied compounds have not been reported in detail (what about the yield of the synthetic procedure and the analysis of the purity and homogeneity of the samples?), As requested, we have provided more details on the synthesis and characterisation of the Li salts.
and some parts of the crystallographic data have been communicated previously in conference abstracts and in a Thesis (in the case of the Li compound).
This is correct, but crucially the structures have not been reported by us, they have been determined completely from new. Also, as we state in the paper, the structures are not available from any recognised crystallographic database. As part of the submission process, the structures were deposited with the Cambridge Structural Database (CCDC 1989314 for K(CH3SO3) and CCDC 1989315 for Li(CH3SO3)), thus are now generally available. This is new information.
In my opinion, in its present form, the manuscript is neither suitable nor scientifically sound.
Unsurprisingly, we completely disagree with this conclusion. We note that, to a degree, the referee has contradicted themselves: in their opening paragraph they state "These studies are of high quality", this cannot be "nor scientifically sound".
For these reasons, I do not recommend its publication in the journal RSOS.
We hope that with the improvements to the manuscript prompted by the reviewers, it will now be considered acceptable for publication in Royal Society Open Science. Thank you for the reviewers comments, I am very pleased that both have now recommended publication in Royal Society Open Science. The only change to the manuscript is in "section 2.1. Materials" as Reviewer 3 requested that a more accurate value for the yield of the lithium salts was provided as ("...>90%" is not valid for me). I have rechecked my notes and amended the value to 96%.

Yours sincerely
Prof Stewart F. Parker