{"doi":"10.1002/hc.520020608","title":"The structure of tetramethyl μ‐monothiopyrophosphate","abstract":"<jats:title>Abstract</jats:title><jats:p>The compound tetramethyl μ‐monothiopyrophosphate (C<jats:sub>4</jats:sub>H<jats:sub>12</jats:sub>O<jats:sub>6</jats:sub>P<jats:sub>2</jats:sub>S) crystallizes in the monoclinic space group C 2/c, with (at ‐130°C) <jats:italic>a</jats:italic> = 10.322 Å, <jats:italic>b</jats:italic> = 8.229 Å, <jats:italic>c</jats:italic> = 12.062 Å, β = 98.44°, and <jats:italic>D</jats:italic><jats:sub>calc</jats:sub> = 1.639 g/mL<jats:sup>3</jats:sup> and <jats:italic>Z</jats:italic> = 4. The crystal structure has been determined by single crystal X‐ray diffraction to give a final <jats:italic>R</jats:italic> value of 0.0329 for 614 independent observed reflections [<jats:italic>F</jats:italic><jats:sub>˚</jats:sub> &gt; 2.5σ(<jats:italic>F</jats:italic><jats:sub>˚</jats:sub>)]. The sulfur atom resides on a crystallographic two‐fold axis. The PSP bond angle is 105.4° and the PS bond lengths are 2.093 Å. The bond angles around phosphorus range from 99.1° to 118.2°. The terminal PO bond is 1.465 Å, and the methoxyl PO bond is about 1.556 Å. The H<jats:sub>3</jats:sub>COP bond angle is about 119.5°. Many structural features are interpreted in terms of π‐bonding to phosphorus. Comparisons with the structures of pyrophosphate and related compounds indicate that the combined effects of increased acuteness of the PSP bond and the increased length of the P—S bonds lead to an increase of about 0.4 Å in the separation of phosphorus atoms in the sulfur‐bridging compound. These facts, together with the weakness of the PS bond, must be taken into account in the interpretation of kinetic data for enzymatic reactions of phosphorothiolates as substrates in place of phosphates.</jats:p>","journal":"Heteroatom Chemistry","year":1991,"id":596193,"datarank":0.10397207708399181,"base_score":0.6931471805599453,"endowment":0.6931471805599453,"self_citation_contribution":0.10397207708399181,"citation_network_contribution":0.0,"self_endowment_contribution":0.10397207708399181,"citer_contribution":0.0,"corpus_percentile":null,"corpus_rank":null,"citation_count":1,"citer_count":0,"citers_with_citation_signal":0,"citers_with_endowment":0,"datacite_reuse_total":0,"is_dataset":false,"is_dataset_confidence":null,"is_data_producer":false,"deposit_databanks":null,"is_oa":false,"file_count":0,"downloads":0,"has_version_chain":false,"published_date":null,"fair_score":null,"fair_percentile":null,"algorithm_id":"datarank_citation_only_1hop_v6","ranking_scope":"data_only","authors":[{"id":1526796,"name":"Matthew Benning","orcid":null,"position":1,"is_corresponding":false},{"id":1526797,"name":"Perry A. Frey","orcid":null,"position":2,"is_corresponding":false},{"id":1526795,"name":"Christopher J. Halkides","orcid":null,"position":0,"is_corresponding":false}],"reference_count":0,"raw_metadata":{"has_enrichment":true,"resolved":true,"title":"The structure of tetramethyl μ‐monothiopyrophosphate","abstract":"<jats:title>Abstract</jats:title><jats:p>The compound tetramethyl μ‐monothiopyrophosphate (C<jats:sub>4</jats:sub>H<jats:sub>12</jats:sub>O<jats:sub>6</jats:sub>P<jats:sub>2</jats:sub>S) crystallizes in the monoclinic space group C 2/c, with (at ‐130°C) <jats:italic>a</jats:italic> = 10.322 Å, <jats:italic>b</jats:italic> = 8.229 Å, <jats:italic>c</jats:italic> = 12.062 Å, β = 98.44°, and <jats:italic>D</jats:italic><jats:sub>calc</jats:sub> = 1.639 g/mL<jats:sup>3</jats:sup> and <jats:italic>Z</jats:italic> = 4. The crystal structure has been determined by single crystal X‐ray diffraction to give a final <jats:italic>R</jats:italic> value of 0.0329 for 614 independent observed reflections [<jats:italic>F</jats:italic><jats:sub>˚</jats:sub> &gt; 2.5σ(<jats:italic>F</jats:italic><jats:sub>˚</jats:sub>)]. The sulfur atom resides on a crystallographic two‐fold axis. The PSP bond angle is 105.4° and the PS bond lengths are 2.093 Å. The bond angles around phosphorus range from 99.1° to 118.2°. The terminal PO bond is 1.465 Å, and the methoxyl PO bond is about 1.556 Å. The H<jats:sub>3</jats:sub>COP bond angle is about 119.5°. Many structural features are interpreted in terms of π‐bonding to phosphorus. Comparisons with the structures of pyrophosphate and related compounds indicate that the combined effects of increased acuteness of the PSP bond and the increased length of the P—S bonds lead to an increase of about 0.4 Å in the separation of phosphorus atoms in the sulfur‐bridging compound. These facts, together with the weakness of the PS bond, must be taken into account in the interpretation of kinetic data for enzymatic reactions of phosphorothiolates as substrates in place of phosphates.</jats:p>","is_dataset_classified":null,"base_score":0.0,"endowment":0.0,"datacite_reuse_total":0,"file_count":0,"downloads":0,"views":0,"has_version_chain":false,"is_dataset":false,"is_oa":false,"pmid":"23304386","pmcid":null,"openalex_id":"https://openalex.org/W2102401648","authors":[],"funders":[],"total_grants":0,"fwci":0.0,"citation_percentile":0.24181555,"influential_citations":0,"citation_trend":[],"oa_status":"closed","license":"http://onlinelibrary.wiley.com/termsAndConditions#vor","oa_locations":[{"url":"https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Fhc.520020608","host_type":"publisher"},{"url":"https://onlinelibrary.wiley.com/doi/pdf/10.1002/hc.520020608","host_type":"publisher"},{"url":"https://doi.org/10.1002/hc.520020608","host_type":"journal"}],"fields_of_study":["Organophosphorus compounds synthesis","Metal complexes synthesis and properties","HIV/AIDS drug development and treatment"],"mesh_terms":[],"keywords":["Chemistry","Monoclinic crystal system","Bond length","Crystallography","Molecular geometry","Crystal structure","Single bond","Bond order","Pyrophosphate","Phosphorus","Sulfur","Stereochemistry","Molecule","Group (periodic table)","Organic chemistry","Enzyme"],"sdg_mappings":[{"sdg_number":0,"sdg_label":"Clean water and sanitation"}],"linked_datasets":[],"clinical_trials":[],"software_tools":[],"database_accessions":[],"source":"live","citation_network_status":"fetched"},"created_at":"2026-07-28T05:18:12.344318Z","pmid":null,"pmcid":null,"fwci":null,"citation_percentile":null,"influential_citations":0,"oa_status":null,"license":null,"views":0,"total_file_size_bytes":0,"version_count":0,"fair_f":null,"fair_a":null,"fair_i":null,"fair_r":null,"fair_zscore":null,"fair_rationale":null,"fair_model":null,"fair_agent_version":null,"fair_fulltext_source":null,"fair_has_llm":null,"fair_computed_at":null,"clinical_trials":[],"software_tools":[],"db_accessions":[],"linked_datasets":[],"topics":[]}