b3cd39ab808f4aba9b6592e78eb236b5 crystals_a2021v11n2p191.pdf 5549a6ec288b3625dc243e72956f25b16e06c702 crystals_a2021v11n2p191.pdf d1ca1a9ff10b918d79183d7442b4e81978dbfa7ec371d4c7c3cb844695443e68 crystals_a2021v11n2p191.pdf Title: Cocrystals Based on 4,4’-bipyridine: Influence of Crystal Packing on Melting Point Subject: The reactions of piperonylic acid (HPip) and cinnamic acid (HCinn) with 4,4’-bipyridine (4,4’-bipy) have been assayed using the same synthetic methodology, yielding two binary cocrystals with different acid:4,4’-bipy molar ratios, (HPip)(4,4’-bipy) (1) and (HCinn)2(4,4’-bipy) (2). The melting point (m.p.) of these cocrystals have been measured and a remarkable difference (T 78 C) between them was observed. Moreover, the two cocrystals have been characterized by powder X-ray diffraction (PXRD), elemental analysis (EA), FTIR-ATR, 1H NMR spectroscopies, and single-crystal X-ray diffraction. The study of their structural packings via Hirshfeld surface analysis and energy frameworks revealed the important contribution of the and C-H interactions to the formation of different structural packing motifs, this being the main reason for the difference of m.p. between them. Moreover, it has been observed that 1 and 2 presented the same packing motifs as the crystal structure of their corresponding carboxylic acids, but 1 and 2 showed lower m.p. than those of the carboxylic acids, which could be related to the lower strength of the acid-pyridine heterosynthons respect to the acid-acid homosynthons in the crystal structures. Keywords: cocrystals; 4,4’-bipyridine; piperonylic acid; cinnamic acid; acid-pyridine heterosynthon; X-ray crystal structures; melting point; Hirshfeld surface analysis; energy frameworks Author: Daniel Ejarque, Teresa Calvet, Mercè Font-Bardia and Josefina Pons Creator: LaTeX with hyperref Producer: pdfTeX-1.40.21 CreationDate: Tue Feb 16 11:01:26 2021 CET ModDate: Tue Feb 16 11:06:49 2021 CET Custom Metadata: no Metadata Stream: no Tagged: no UserProperties: no Suspects: no Form: none JavaScript: no Pages: 16 Encrypted: no Page size: 595.276 x 841.89 pts (A4) Page rot: 0 File size: 3453509 bytes Optimized: no PDF version: 1.7 name type encoding emb sub uni object ID ------------------------------------ ----------------- ---------------- --- --- --- --------- MWHIBA+VnURWPalladioL Type 1 Custom yes yes no 10 0 DDIUXT+EURM10 Type 1 Builtin yes yes no 15 0 MVYNAL+URWPalladioL-Ital Type 1 Custom yes yes no 19 0 LUHOBN+URWPalladioL-Bold Type 1 Custom yes yes no 24 0 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yes yes no 246 0 LMJGPP+PalatinoLinotype,Bold TrueType WinAnsi yes yes no 260 0 LMJHAA+PalatinoLinotype CID TrueType Identity-H yes yes yes 263 0 LMJHAB+PalatinoLinotype TrueType WinAnsi yes yes no 269 0 LMJHBD+PalatinoLinotype,Italic TrueType WinAnsi yes yes no 272 0 Jhove (Rel. 1.28.0, 2023-05-18) Date: 2024-10-02 03:54:59 CEST RepresentationInformation: crystals_a2021v11n2p191.pdf ReportingModule: PDF-hul, Rel. 1.12.4 (2023-03-16) LastModified: 2023-03-31 11:50:29 CEST Size: 3453509 Format: PDF Version: 1.7 Status: Well-Formed and valid SignatureMatches: PDF-hul MIMEtype: application/pdf PDFMetadata: Objects: 481 FreeObjects: 1 IncrementalUpdates: 0 DocumentCatalog: PageLayout: SinglePage PageMode: UseNone Outlines: Item: Title: Introduction Destination: section.1 Item: Title: Experimental Section Destination: section.2 Children: Item: Title: Materials and General Methods Destination: subsection.2.1 Item: Title: Synthesis of Cocrystals 1 and 2 Destination: subsection.2.2 Item: Title: X-ray Crystallographic Data Destination: subsection.2.3 Item: Title: Computational Details of Hirshfeld Surface Analysis, Energy Frameworks, and Lattice Energy Destination: subsection.2.4 Item: Title: Results and Discussion Destination: section.3 Children: Item: Title: Synthesis and Characterization of Cocrystals 1 and 2 Destination: subsection.3.1 Item: Title: Crystal and Extended Structure of (HPip)(4,4’-bipy) (1) Destination: subsection.3.2 Item: Title: Crystal and Extended Structure of (HCinn)2(4,4’-bipy) (2) Destination: subsection.3.3 Item: Title: Hirshfeld Surface Analysis and Energy Frameworks Calculations of 1 and 2 Destination: subsection.3.4 Item: Title: Relationship of Melting Point Values with Packing Effects of Cocrystals 1 and 2 Destination: subsection.3.5 Item: Title: Conclusions Destination: section.4 Item: Title: References Destination: section.4 Info: Title: Cocrystals Based on 4,4’-bipyridine: Influence of Crystal Packing on Melting Point Author: Daniel Ejarque, Teresa Calvet, Mercè Font-Bardia and Josefina Pons Subject: The reactions of piperonylic acid (HPip) and cinnamic acid (HCinn) with 4,4’-bipyridine (4,4’-bipy) have been assayed using the same synthetic methodology, yielding two binary cocrystals with different acid:4,4’-bipy molar ratios, (HPip)(4,4’-bipy) (1) and (HCinn)2(4,4’-bipy) (2). The melting point (m.p.) of these cocrystals have been measured and a remarkable difference (T 78 C) between them was observed. Moreover, the two cocrystals have been characterized by powder X-ray diffraction (PXRD), elemental analysis (EA), FTIR-ATR, 1H NMR spectroscopies, and single-crystal X-ray diffraction. The study of their structural packings via Hirshfeld surface analysis and energy frameworks revealed the important contribution of the and C-H interactions to the formation of different structural packing motifs, this being the main reason for the difference of m.p. between them. Moreover, it has been observed that 1 and 2 presented the same packing motifs as the crystal structure of their corresponding carboxylic acids, but 1 and 2 showed lower m.p. than those of the carboxylic acids, which could be related to the lower strength of the acid-pyridine heterosynthons respect to the acid-acid homosynthons in the crystal structures. Keywords: cocrystals; 4,4’-bipyridine; piperonylic acid; cinnamic acid; acid-pyridine heterosynthon; X-ray crystal structures; melting point; Hirshfeld surface analysis; energy frameworks Creator: LaTeX with hyperref Producer: pdfTeX-1.40.21 CreationDate: Tue Feb 16 11:01:26 CET 2021 ModDate: Tue Feb 16 11:06:49 CET 2021 ID: 0x40c9114f4fd0ad58f3f1d9a5a23c5d5c, 0x40c9114f4fd0ad58f3f1d9a5a23c5d5c Filters: FilterPipeline: FlateDecode Fonts: Type1: Font: BaseFont: HVSBKL+PazoMath FontSubset: true FirstChar: 68 LastChar: 229 FontDescriptor: FontName: HVSBKL+PazoMath Flags: Symbolic FontBBox: -40, -283, 878, 946 FontFile: true Font: BaseFont: WNMGGZ+CMSY10 FontSubset: true FirstChar: 0 LastChar: 106 FontDescriptor: FontName: WNMGGZ+CMSY10 Flags: Symbolic FontBBox: -29, -960, 1116, 775 FontFile: true Font: BaseFont: JZKDWD+CMR10 FontSubset: true FirstChar: 40 LastChar: 93 FontDescriptor: FontName: JZKDWD+CMR10 Flags: Symbolic FontBBox: -40, -250, 1009, 750 FontFile: true Font: BaseFont: 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