In the crystal of trimethyl 3,3',3''-(benzene-triyl)tripropynoate, a system of new hydrogen bond ring motifs involving C-H...O interactions give rise to layer formation of molecules while the layers are connected among each other via weak contacts of C---H...O and C---H...pi type to specifically complete the supramolecular packing structure

Gruber, Tobias

Katzsch, Felix

Weber, Edwin

In the title compound, C18H12O6, the alkyne bonds are distorted, featuring bond angles around the C—C[triple-bond]C—C group of 173.6 (1)/179.0 (1), 178.1 (1)/178.4 (1) and 174.9 (1)/175.9 (1)°, and the ester groups make angles of 3.5 (1), 13.8 (1) and 14.5 (1)° with the central benzene ring. In the crystal, molecules are connected in layers parallel to (131) by weak C—H...O hydrogen bonds, giving rise to a system of hydrogen-bonded ring motifs with graph sets R22(14) and R44(22). The layers are linked by C—H...O and C—H...π contacts

Felix Katzsch

Tobias Gruber

Edwin Weber

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Trimethyl 3,3′,3′′-(benzene-1,3,5-triyl)tripropynoate

University of Lincoln Institutional Repository

data report1publCIFTrimethyl 3,3′,3′′-(benzene-1,3,5-triyl)tripropynoate 1Felix Katzsch,a Tobias Gruberb and Edwin Webera* 2aInstitut für Organische Chemie, TU Bergakademie Freiberg, Leipziger Straße 29, D-09596 Freiberg/Sachsen, Germany, and bSchool of Pharmacy, 3University of Lincoln, Joseph Banks Laboratories, Green Lane, Lincoln, LN6 7DL, United Kingdom 4Correspondence email: edwin.weber@chemie.tu-freiberg.de 5Abstract6The title compound, C18H12O6, crystallizes in the triclinic space group P-1 with one molecule in the asymmetric unit. The 7alkyne bonds are distorted featuring bond angles around C—C≡C—C of 173.6 (1)/179.0 (1)°, 178.1 (1)/178.4 (1)° and 8174.9 (1)/175.9 (1)°, and the ester groups show interplanary angles of 3.5, 13.8 and 14.5° with reference to the plane of 9the central benzene ring, respectively. The molecules are connected in layers parallel to the (131)-plane by weak C—10H···O hydrogen bonds giving rise to a system of new hydrogen bond ring motifs with graph sets R22(14) and R44(22). The 11layers are linked among each other by interactions involving C—H···O and C—H···π contacts. 12Structure description13The title compound, C18H12O6, is an interesting synthetic intermediate for the preparation of application–oriented solid 14materials involving both porous coordination polymers (MacGillivray, 2010) or metal-organic frameworks (Noro & 15Kitagawa, 2010) and crystalline inclusion hosts (Weber, 1996; Katzsch et al., 2016). In the structure of the molecule (Fig. 161), the alkyne bonds are distorted which is shown by the corresponding bond angles [C2—C3—C4 173.6 (1)°, C3—C4—17C13 179.0 (1)°, C6—C7—C8 178.1 (1)°, C7—C8—C15 178.4 (1)°, C10—C11—C12 174.9 (1)°, C11—C12—C17 18175.9 (1)°] and the ester functions are not arranged in the benzene plane [interplanary angles: 3.5° (C2, O1, O2), 13.8° 19(C6, O3, O4), 14.5° (C10, O5, O10)]. The molecules are connected in layers parallel to the (131)-plane by weak C—20H···O hydrogen bonds (Desiraju & Steiner, 1999) (Table 1) giving rise to new hydrogen bond ring motifs with the graph 21sets (Bernstein et al., 1995) R22(14) and R44(22) (Fig. 2). The layers are stabilized among each other also by weak C—22H···O hydrogen bonds [d(C1···O6) 3.438 (1) Å] and additionally by C—H···π contacts (Desiraju & Steiner, 1999) 23[d(C1···Cg3) 3.551 (1) Å d(C9···Cg1) 3.630 (1) Å].24Synthesis and crystallization25The title compound was prepared from 1,3,5-triethynylbenzene (Münch et al., 2013) and methyl chloroformiate as 26described in the literature (Katzsch et al., 2016). Colorless single crystals of prismatic shape suitable for X-ray diffraction 27were obtained by slow crystallization from a solvent mixture of acetone, ethyl acetate and n-hexane. For the synthesis of 28a related compound, see: Welti & Diederich (2003).29Refinement details30Crystal data, data collection and structure refinement details are summarized in Table 2. The H atoms were included in 31calculated positions and treated as riding atoms.32Table 133Experimental details 3435 Crystal data36 Chemical formula C18H12O637 Mr 324.28data report2publCIF38 Crystal system, space group Triclinic, P139 Temperature (K) 10040 a, b, c (Å) 8.5765 (2), 9.8469 (2), 10.2677 (2)41 α, β, γ (°) 78.903 (1), 79.552 (1), 68.655 (1)42 V (Å3) 786.65 (3)43 Z 244 Radiation type Mo Kα45 µ (mm−1) 0.1046 Crystal size (mm) 0.54 × 0.43 × 0.374748 Data collection49 Diffractometer Bruker APEX-II CCD50 Absorption correction Multi-scan SADABS (Sheldrick, 2004)51 Tmin, Tmax 0.946, 0.96352 No. of measured, independent andobserved [I > 2σ(I)] reflections16379, 2769, 2558 53 Rint 0.02254 (sin θ/λ)max (Å−1) 0.5955556 Refinement57 R[F2 > 2σ(F2)], wR(F2), S 0.030, 0.082, 1.0858 No. of reflections 276959 No. of parameters 22060 H-atom treatment H-atom parameters constrained61 Δρmax, Δρmin (e Å−3) 0.15, −0.24Computer programs: Bruker APEX2, Bruker SAINT, SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), Bruker SHELXTL. 62Table 263Hydrogen-bond geometry (Å, º) 64Cg1 is the centroid of the atoms C13–C18 and Cg3 is the centroid of the atoms C7 and C8. 6566 D—H···A D—H H···A D···A D—H···A67 C1—H1C···O6i 0.98 2.70 3.4378 (15) 13368 C5—H5B···O5ii 0.98 2.66 3.4517 (15) 13869 C14—H14···O2iii 0.95 2.31 3.2278 (13) 16270 C16—H16···O6iv 0.95 2.35 3.2390 (13) 15571 C1—H1A···Cg3v 0.98 2.85 3.5506 (13) 13072 C9—H9A···Cg1vi 0.98 2.76 3.6302 (13) 148Symmetry codes: (i) x−1, y+1, z−1; (ii) x−1, y, z+1; (iii) −x+1, −y+1, −z+1; (iv) −x+3, −y, −z+2; (v) x, y, z−1; (vi) x+1, y, z. 73Acknowledgements74This work was supported from the Deutsche Forschungsgemeinschaft (DFG) under the program SPP 1362/1. 75References76Bernstein, J., Davies, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573.77Bruker (2008). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.78Desiraju, G. R. & Steiner, T. (1999). The Weak Hydrogen Bond in Structural Chemistry and Biology, pp. 29-121. New 79York: Oxford University Press Inc.80data report3publCIFFarrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854.81Katzsch, F., Gruber, T. & Weber, E. (2016). J. Mol. Struct. 1114, 48–64.82MacGillivray, L. R. (2010). Metal Organic Frameworks. Hoboken: Wiley.83Münch, A. S., Katzsch, F., Weber, E. & Mertens, F. O. R. L. (2013). J. Mol. Struct. 1043, 103–108.84Nishio, M. (2004). CrystEngComm, 6, 130–158.85Noro, S.-I. & Kitagawa, S. (2010). In The Supramolecular Chemistry of Organic-Inorganic Hybrid Materials, edited by 86Rurack. K. & Martinez-Manez, R., pp. 235-269. Hoboken: Wiley.87Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.88Weber, E. (1996). In Comprehensive Supramolecular Chemistry, Vol. 6, edited by MacNicol, D. D., Toda, F. & Bishop, 89R., pp. 535-592. Oxford: Elsevier.90Welti, R. & Diederich, F. (2003). Helv. Chim. Acta, 86, 494–503.91Figure 1 92A view of the molecular structure of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 9350% probability level.94Figure 2 95A partial view of the crystal packing of the title compound, showing the formation of the C—H···O bonded layer 96structure, enclosing the system of R22(14) and R44(22) ring motifs. Hydrogen bond contacts are indicated by dashed lines. 97data report4publCIFfull crystallographic data1Trimethyl 3,3′,3′′-(benzene-1,3,5-triyl)tripropynoate 2′Trimethyl 3,3′,3′′-(benzene-1,3,5-triyl)tripropynoate′ 3Crystal data 4C18H12O65 Mr = 324.286 Triclinic, P17 Hall symbol: -P 18 a = 8.5765 (2) Å9 b = 9.8469 (2) Å10 c = 10.2677 (2) Å11 α = 78.903 (1)°12 β = 79.552 (1)°13 γ = 68.655 (1)°14 V = 786.65 (3) Å315Z = 2F(000) = 336Dx = 1.369 Mg m−3Mo Kα radiation, λ = 0.71073 ÅCell parameters from 9912 reflectionsθ = 2.8–35.9°µ = 0.10 mm−1T = 100 KPrism, colourless0.54 × 0.43 × 0.37 mmData collection 16Bruker APEX-II CCD 17 diffractometerRadiation source: fine-focus sealed tube18 Graphite monochromator19 φ and ω scans20 Absorption correction: multi-scan 21 SADABS (Sheldrick, 2004)Tmin = 0.946, Tmax = 0.9632216379 measured reflections2769 independent reflections2558 reflections with I > 2σ(I)Rint = 0.022θmax = 25.0°, θmin = 2.0°h = −10→10k = −11→11l = −12→12Refinement 23Refinement on F224 Least-squares matrix: full25 R[F2 > 2σ(F2)] = 0.03026 wR(F2) = 0.08227 S = 1.0828 2769 reflections29 220 parameters30 0 restraints31 Primary atom site location: structure-invariant direct 32 methodsSecondary atom site location: difference Fourier mapHydrogen site location: inferred from neighbouring sitesH-atom parameters constrainedw = 1/[σ2(Fo2) + (0.0423P)2 + 0.2206P] where P = (Fo2 + 2Fc2)/3(Δ/σ)max = 0.001Δρmax = 0.15 e Å−3Δρmin = −0.24 e Å−3Special details 3334 Refinement Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) 3536 x y z Uiso*/Ueq37 O1 0.83566 (10) 0.52293 (9) 0.16775 (8) 0.0236 (2)38 O2 0.57685 (10) 0.57849 (10) 0.28339 (8) 0.0293 (2)data report5publCIF39 O3 0.65384 (9) 0.22546 (9) 1.31248 (7) 0.02084 (19)40 O4 0.41386 (10) 0.31372 (9) 1.21571 (8) 0.0268 (2)41 O5 1.77215 (9) −0.03869 (9) 0.67379 (8) 0.0236 (2)42 O6 1.70937 (10) −0.04808 (10) 0.89660 (8) 0.0299 (2)43 C1 0.75769 (16) 0.59765 (14) 0.04628 (11) 0.0278 (3)44 H1A 0.6774 0.5528 0.0338 0.042*45 H1B 0.8452 0.5882 −0.0308 0.042*46 H1C 0.6982 0.7021 0.0544 0.042*47 C2 0.72764 (14) 0.52404 (12) 0.27834 (11) 0.0190 (2)48 C3 0.81227 (13) 0.45041 (12) 0.39566 (11) 0.0194 (2)49 C4 0.86741 (13) 0.38829 (12) 0.49835 (11) 0.0185 (2)50 C5 0.55244 (15) 0.23382 (15) 1.44175 (11) 0.0278 (3)51 H5A 0.4759 0.3352 1.4466 0.042*52 H5B 0.6263 0.2036 1.5123 0.042*53 H5C 0.4865 0.1683 1.4539 0.042*54 C6 0.56511 (13) 0.26911 (12) 1.20822 (11) 0.0188 (2)55 C7 0.67830 (14) 0.25513 (12) 1.08442 (11) 0.0203 (2)56 C8 0.77122 (13) 0.24785 (11) 0.98194 (11) 0.0188 (2)57 C9 1.94875 (14) −0.09886 (14) 0.69328 (13) 0.0277 (3)58 H9A 1.9750 −0.0336 0.7404 0.042*59 H9B 2.0182 −0.1071 0.6062 0.042*60 H9C 1.9726 −0.1965 0.7465 0.042*61 C10 1.66647 (14) −0.01980 (12) 0.78696 (11) 0.0190 (2)62 C11 1.49194 (13) 0.04128 (12) 0.76135 (10) 0.0193 (2)63 C12 1.34504 (14) 0.09501 (12) 0.74997 (10) 0.0183 (2)64 C13 0.93204 (13) 0.31191 (12) 0.62162 (11) 0.0175 (2)65 C14 0.82157 (13) 0.31487 (12) 0.73950 (11) 0.0183 (2)66 H14 0.7041 0.3661 0.7379 0.022*67 C15 0.88415 (13) 0.24233 (12) 0.85995 (11) 0.0178 (2)68 C16 1.05675 (14) 0.16784 (12) 0.86244 (11) 0.0180 (2)69 H16 1.0992 0.1189 0.9445 0.022*70 C17 1.16685 (13) 0.16532 (11) 0.74421 (11) 0.0171 (2)71 C18 1.10490 (13) 0.23615 (12) 0.62325 (11) 0.0178 (2)72 H18 1.1797 0.2329 0.5425 0.021*Atomic displacement parameters (Å2) 7374 U11 U22 U33 U12 U13 U2375 O1 0.0233 (4) 0.0293 (4) 0.0145 (4) −0.0059 (3) −0.0046 (3) 0.0018 (3)76 O2 0.0194 (5) 0.0351 (5) 0.0271 (5) −0.0035 (4) −0.0074 (3) 0.0034 (4)77 O3 0.0171 (4) 0.0290 (4) 0.0140 (4) −0.0066 (3) −0.0007 (3) −0.0010 (3)78 O4 0.0179 (4) 0.0345 (5) 0.0225 (4) −0.0033 (4) −0.0029 (3) −0.0018 (3)79 O5 0.0146 (4) 0.0310 (4) 0.0222 (4) −0.0039 (3) −0.0028 (3) −0.0036 (3)80 O6 0.0230 (4) 0.0434 (5) 0.0209 (5) −0.0074 (4) −0.0089 (3) −0.0005 (4)81 C1 0.0363 (7) 0.0292 (6) 0.0153 (6) −0.0082 (5) −0.0099 (5) 0.0038 (5)82 C2 0.0204 (6) 0.0181 (5) 0.0186 (6) −0.0061 (4) −0.0053 (4) −0.0007 (4)83 C3 0.0162 (5) 0.0209 (5) 0.0196 (6) −0.0046 (4) −0.0020 (4) −0.0025 (4)84 C4 0.0153 (5) 0.0205 (5) 0.0185 (6) −0.0050 (4) −0.0015 (4) −0.0026 (4)85 C5 0.0248 (6) 0.0411 (7) 0.0133 (5) −0.0097 (5) 0.0017 (4) −0.0005 (5)86 C6 0.0191 (6) 0.0179 (5) 0.0177 (5) −0.0050 (4) −0.0023 (4) −0.0009 (4)87 C7 0.0203 (6) 0.0211 (6) 0.0187 (6) −0.0059 (4) −0.0048 (5) −0.0008 (4)88 C8 0.0186 (5) 0.0191 (5) 0.0178 (6) −0.0052 (4) −0.0042 (4) −0.0012 (4)data report6publCIF89 C9 0.0139 (5) 0.0309 (6) 0.0358 (7) −0.0024 (5) −0.0033 (5) −0.0090 (5)90 C10 0.0176 (5) 0.0185 (5) 0.0203 (6) −0.0055 (4) −0.0049 (4) −0.0002 (4)91 C11 0.0194 (6) 0.0225 (6) 0.0149 (5) −0.0070 (5) −0.0035 (4) 0.0008 (4)92 C12 0.0200 (6) 0.0201 (5) 0.0151 (5) −0.0076 (4) −0.0034 (4) −0.0003 (4)93 C13 0.0175 (5) 0.0185 (5) 0.0163 (5) −0.0057 (4) −0.0044 (4) −0.0009 (4)94 C14 0.0147 (5) 0.0193 (5) 0.0199 (6) −0.0039 (4) −0.0037 (4) −0.0026 (4)95 C15 0.0184 (5) 0.0190 (5) 0.0166 (5) −0.0071 (4) −0.0020 (4) −0.0024 (4)96 C16 0.0204 (6) 0.0188 (5) 0.0157 (5) −0.0073 (4) −0.0055 (4) −0.0005 (4)97 C17 0.0156 (5) 0.0174 (5) 0.0188 (5) −0.0053 (4) −0.0046 (4) −0.0015 (4)98 C18 0.0166 (5) 0.0207 (5) 0.0162 (5) −0.0070 (4) −0.0013 (4) −0.0021 (4)Geometric parameters (Å, º) 99100 O1—C2 1.3280 (14) C6—C7 1.4490 (15)101 O1—C1 1.4612 (13) C7—C8 1.1961 (16)102 O2—C2 1.2018 (14) C8—C15 1.4345 (15)103 O3—C6 1.3379 (13) C9—H9A 0.9800104 O3—C5 1.4478 (13) C9—H9B 0.9800105 O4—C6 1.2015 (13) C9—H9C 0.9800106 O5—C10 1.3359 (13) C10—C11 1.4485 (15)107 O5—C9 1.4478 (13) C11—C12 1.1938 (16)108 O6—C10 1.1980 (14) C12—C17 1.4371 (15)109 C1—H1A 0.9800 C13—C14 1.3931 (15)110 C1—H1B 0.9800 C13—C18 1.3978 (15)111 C1—H1C 0.9800 C14—C15 1.3963 (15)112 C2—C3 1.4496 (15) C14—H14 0.9500113 C3—C4 1.1965 (16) C15—C16 1.3950 (15)114 C4—C13 1.4351 (15) C16—C17 1.3945 (15)115 C5—H5A 0.9800 C16—H16 0.9500116 C5—H5B 0.9800 C17—C18 1.3955 (15)117 C5—H5C 0.9800 C18—H18 0.9500118119 C2—O1—C1 114.65 (9) H9A—C9—H9B 109.5120 C6—O3—C5 114.53 (8) O5—C9—H9C 109.5121 C10—O5—C9 114.15 (9) H9A—C9—H9C 109.5122 O1—C1—H1A 109.5 H9B—C9—H9C 109.5123 O1—C1—H1B 109.5 O6—C10—O5 124.66 (10)124 H1A—C1—H1B 109.5 O6—C10—C11 123.62 (10)125 O1—C1—H1C 109.5 O5—C10—C11 111.72 (9)126 H1A—C1—H1C 109.5 C12—C11—C10 174.86 (11)127 H1B—C1—H1C 109.5 C11—C12—C17 175.86 (11)128 O2—C2—O1 125.16 (10) C14—C13—C18 120.36 (10)129 O2—C2—C3 122.68 (10) C14—C13—C4 119.56 (9)130 O1—C2—C3 112.16 (9) C18—C13—C4 120.08 (10)131 C4—C3—C2 173.59 (11) C13—C14—C15 119.76 (10)132 C3—C4—C13 178.97 (12) C13—C14—H14 120.1133 O3—C5—H5A 109.5 C15—C14—H14 120.1134 O3—C5—H5B 109.5 C16—C15—C14 120.15 (10)135 H5A—C5—H5B 109.5 C16—C15—C8 119.93 (10)136 O3—C5—H5C 109.5 C14—C15—C8 119.90 (10)137 H5A—C5—H5C 109.5 C17—C16—C15 119.89 (10)138 H5B—C5—H5C 109.5 C17—C16—H16 120.1data report7publCIF139 O4—C6—O3 125.17 (10) C15—C16—H16 120.1140 O4—C6—C7 124.83 (10) C16—C17—C18 120.25 (9)141 O3—C6—C7 110.00 (9) C16—C17—C12 119.01 (9)142 C8—C7—C6 178.08 (11) C18—C17—C12 120.67 (10)143 C7—C8—C15 178.35 (11) C17—C18—C13 119.58 (10)144 O5—C9—H9A 109.5 C17—C18—H18 120.2145 O5—C9—H9B 109.5 C13—C18—H18 120.2146147 C1—O1—C2—O2 1.09 (16) C13—C14—C15—C8 178.64 (10)148 C1—O1—C2—C3 −179.11 (9) C14—C15—C16—C17 −0.29 (16)149 C5—O3—C6—O4 0.66 (16) C8—C15—C16—C17 −178.57 (9)150 C5—O3—C6—C7 −179.49 (9) C15—C16—C17—C18 −0.46 (16)151 C9—O5—C10—O6 0.41 (16) C15—C16—C17—C12 176.57 (9)152 C9—O5—C10—C11 179.68 (9) C16—C17—C18—C13 1.13 (15)153 C18—C13—C14—C15 0.32 (16) C12—C17—C18—C13 −175.85 (10)154 C4—C13—C14—C15 −179.16 (10) C14—C13—C18—C17 −1.06 (16)155 C13—C14—C15—C16 0.35 (16) C4—C13—C18—C17 178.42 (10)Hydrogen-bond geometry (Å, º) 156Cg1 is the centroid of the atoms C13–C18 and Cg3 is the centroid of the atoms C7 and C8. 157158 D—H···A D—H H···A D···A D—H···A159 C1—H1C···O6i 0.98 2.70 3.4378 (15) 133160 C5—H5B···O5ii 0.98 2.66 3.4517 (15) 138161 C14—H14···O2iii 0.95 2.31 3.2278 (13) 162162 C16—H16···O6iv 0.95 2.35 3.2390 (13) 155163 C1—H1A···Cg3v 0.98 2.85 3.5506 (13) 130164 C9—H9A···Cg1vi 0.98 2.76 3.6302 (13) 148Symmetry codes: (i) x−1, y+1, z−1; (ii) x−1, y, z+1; (iii) −x+1, −y+1, −z+1; (iv) −x+3, −y, −z+2; (v) x, y, z−1; (vi) x+1, y, z. 165

Trimethyl 3,3',3''-(benzene-1,3,5-triyl)tripropynoate

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