supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers Open access

Acta Cryst. (2009). E65, o794    [ doi:10.1107/S1600536809009271 ]

Tetramethyl 4,4'-carbonylbis(benzene-1,2-dicarboxylate)

X.-Y. Zhu, G.-W. Gao, J. Men and S. W. Ng

Abstract top

In the molecule of the title compound, C21H18O9, the two aromatic rings are aligned at an angle of 49.7 (1)°.

Related literature top

For the parent acid monohydrate, see: Fitzgerald & Gerkin (1997). For related literature, see: Zhang et al. (2004).

Experimental top

3,3',4,4'-Tetracarboxybenzophenone (29.4 g, 0.1 mol) and p-toluenesulfonic acid (2.0 g, 0.01 mol) were heated in a mixture of toluene (100 ml) and methanol (50 ml) in a Dean-Stark apparatus for 20 h. Water (500 ml) was added to the mixture, the organic phase was separated and washed with saturated sodium carbonate. The toluene was removed and the product purified from ethanol to afford a white powder (34.7 g, 90% yield; m.p. 382–384 K). Colorless single crystals were obtained by recrystallization from toluene.

Refinement top

Carbon-bound H-atoms were placed in calculated positions (C—H 0.95 to 0.98 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2 to 1.5U(C).

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2009).

Figures top
[Figure 1] Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of C21H18O9 at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.
Tetramethyl 4,4'-carbonylbis(benzene-1,2-dicarboxylate) top
Crystal data top
C21H18O9F(000) = 864
Mr = 414.35Dx = 1.450 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 5155 reflections
a = 11.8627 (2) Åθ = 2.9–28.2°
b = 17.3678 (3) ŵ = 0.12 mm−1
c = 9.2506 (2) ÅT = 123 K
β = 95.150 (1)°Block, colorless
V = 1898.20 (6) Å30.45 × 0.15 × 0.05 mm
Z = 4
Data collection top
Bruker SMART APEX [APEXII?]
diffractometer		3596 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.024
graphiteθmax = 27.5°, θmin = 1.7°
ω scansh = −15→15
14279 measured reflectionsk = −22→22
4339 independent reflectionsl = −11→12
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.050Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.139H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.0704P)2 + 1.4144P]
where P = (Fo2 + 2Fc2)/3
4339 reflections(Δ/σ)max = 0.001
275 parametersΔρmax = 0.89 e Å−3
0 restraintsΔρmin = −0.50 e Å−3
Crystal data top
C21H18O9V = 1898.20 (6) Å3
Mr = 414.35Z = 4
Monoclinic, P21/cMo Kα radiation
a = 11.8627 (2) ŵ = 0.12 mm−1
b = 17.3678 (3) ÅT = 123 K
c = 9.2506 (2) Å0.45 × 0.15 × 0.05 mm
β = 95.150 (1)°
Data collection top
Bruker SMART APEX [APEXII?]
diffractometer		3596 reflections with I > 2σ(I)
14279 measured reflectionsRint = 0.024
4339 independent reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.050H-atom parameters constrained
wR(F2) = 0.139Δρmax = 0.89 e Å−3
S = 1.04Δρmin = −0.50 e Å−3
4339 reflectionsAbsolute structure: ?
275 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.82828 (10)0.56029 (7)0.93784 (12)0.0205 (3)
O21.01037 (11)0.56968 (8)0.88890 (13)0.0261 (3)
O30.89532 (11)0.62457 (7)0.42114 (13)0.0227 (3)
O40.87735 (13)0.65645 (7)0.65258 (14)0.0288 (3)
O50.47658 (11)0.33391 (8)0.30590 (16)0.0310 (3)
O60.38426 (16)0.22311 (10)0.2777 (3)0.0726 (7)
O70.50941 (16)0.09165 (11)0.19849 (17)0.0525 (5)
O80.42373 (14)0.05561 (10)0.38926 (19)0.0458 (4)
O90.85745 (11)0.25995 (7)0.79479 (13)0.0236 (3)
C10.82935 (13)0.36953 (9)0.64550 (17)0.0163 (3)
C20.85873 (13)0.42065 (9)0.75874 (17)0.0165 (3)
H20.86500.40260.85610.020*
C30.87895 (13)0.49763 (9)0.73051 (17)0.0160 (3)
C40.87127 (13)0.52414 (9)0.58682 (17)0.0158 (3)
C50.84754 (14)0.47205 (9)0.47349 (17)0.0180 (3)
H50.84630.48920.37590.022*
C60.82574 (14)0.39516 (9)0.50221 (17)0.0177 (3)
H60.80840.36020.42450.021*
C70.91496 (14)0.54819 (9)0.85827 (17)0.0173 (3)
C80.85333 (17)0.60385 (11)1.07015 (19)0.0262 (4)
H8A0.78260.62221.10530.039*
H8B0.90120.64801.05080.039*
H8C0.89320.57091.14400.039*
C90.88242 (14)0.60863 (9)0.55979 (17)0.0170 (3)
C100.90221 (18)0.70612 (10)0.3881 (2)0.0280 (4)
H10A0.82820.73020.39520.042*
H10B0.92460.71260.28940.042*
H10C0.95850.73060.45730.042*
C110.72742 (14)0.23959 (9)0.59007 (17)0.0168 (3)
C120.63715 (14)0.27188 (9)0.50347 (18)0.0187 (3)
H120.62680.32610.50240.022*
C130.56220 (14)0.22528 (10)0.41868 (19)0.0210 (4)
C140.57621 (15)0.14533 (10)0.42228 (19)0.0220 (4)
C150.66549 (15)0.11274 (10)0.50977 (19)0.0223 (4)
H150.67480.05840.51270.027*
C160.74083 (14)0.15960 (9)0.59265 (18)0.0189 (3)
H160.80190.13720.65150.023*
C170.46489 (16)0.25921 (11)0.3262 (2)0.0287 (4)
C180.38474 (18)0.37057 (13)0.2166 (2)0.0354 (5)
H18A0.37870.34770.11940.053*
H18B0.40010.42580.20940.053*
H18C0.31360.36290.26090.053*
C190.49327 (17)0.09303 (11)0.3372 (2)0.0300 (4)
C200.4158 (3)0.0543 (2)0.1117 (3)0.0687 (9)
H20A0.40900.00080.14360.103*
H20B0.43030.05520.00910.103*
H20C0.34520.08190.12420.103*
C210.80855 (14)0.28732 (9)0.68492 (17)0.0172 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0222 (6)0.0240 (6)0.0151 (5)0.0013 (5)−0.0003 (4)−0.0048 (5)
O20.0248 (7)0.0309 (7)0.0223 (6)−0.0094 (5)0.0005 (5)−0.0043 (5)
O30.0370 (7)0.0143 (6)0.0168 (6)−0.0020 (5)0.0027 (5)0.0017 (4)
O40.0485 (9)0.0173 (6)0.0217 (6)−0.0032 (6)0.0094 (6)−0.0037 (5)
O50.0251 (7)0.0254 (7)0.0403 (8)0.0007 (5)−0.0099 (6)0.0103 (6)
O60.0480 (11)0.0316 (9)0.1273 (19)−0.0056 (8)−0.0526 (12)0.0061 (10)
O70.0661 (12)0.0602 (11)0.0298 (8)−0.0355 (9)−0.0036 (8)−0.0023 (7)
O80.0378 (9)0.0433 (9)0.0561 (10)−0.0220 (7)0.0039 (7)−0.0106 (8)
O90.0298 (7)0.0194 (6)0.0205 (6)−0.0013 (5)−0.0032 (5)0.0045 (5)
C10.0158 (7)0.0157 (7)0.0171 (7)0.0003 (6)0.0003 (6)0.0000 (6)
C20.0172 (8)0.0178 (8)0.0141 (7)−0.0019 (6)−0.0004 (6)0.0013 (6)
C30.0149 (7)0.0177 (8)0.0154 (7)−0.0014 (6)0.0007 (6)−0.0014 (6)
C40.0158 (7)0.0157 (7)0.0160 (7)−0.0004 (6)0.0010 (6)0.0004 (6)
C50.0222 (8)0.0180 (8)0.0137 (7)−0.0007 (6)0.0016 (6)0.0014 (6)
C60.0215 (8)0.0164 (8)0.0150 (7)−0.0006 (6)0.0001 (6)−0.0030 (6)
C70.0215 (8)0.0159 (7)0.0140 (7)−0.0020 (6)−0.0006 (6)0.0018 (6)
C80.0336 (10)0.0275 (9)0.0173 (8)0.0032 (7)−0.0001 (7)−0.0071 (7)
C90.0172 (8)0.0167 (7)0.0169 (7)−0.0003 (6)0.0007 (6)0.0001 (6)
C100.0433 (11)0.0146 (8)0.0260 (9)−0.0018 (7)0.0029 (8)0.0046 (7)
C110.0185 (8)0.0154 (7)0.0168 (8)−0.0009 (6)0.0033 (6)−0.0005 (6)
C120.0186 (8)0.0145 (7)0.0231 (8)0.0004 (6)0.0032 (6)0.0013 (6)
C130.0186 (8)0.0186 (8)0.0257 (9)−0.0006 (6)0.0018 (7)0.0018 (6)
C140.0203 (8)0.0187 (8)0.0270 (9)−0.0035 (6)0.0013 (7)−0.0009 (7)
C150.0260 (9)0.0142 (8)0.0266 (9)−0.0009 (6)0.0028 (7)−0.0003 (6)
C160.0208 (8)0.0163 (8)0.0197 (8)0.0010 (6)0.0021 (6)0.0027 (6)
C170.0234 (9)0.0232 (9)0.0377 (11)0.0000 (7)−0.0063 (8)0.0000 (8)
C180.0290 (10)0.0345 (11)0.0404 (11)0.0064 (8)−0.0097 (9)0.0107 (9)
C190.0344 (11)0.0194 (9)0.0345 (10)−0.0007 (7)−0.0072 (8)−0.0004 (8)
C200.076 (2)0.084 (2)0.0432 (15)−0.0364 (17)−0.0131 (14)−0.0089 (14)
C210.0191 (8)0.0162 (8)0.0164 (7)0.0001 (6)0.0031 (6)0.0006 (6)
Geometric parameters (Å, °) top
O1—C71.334 (2)C8—H8A0.9800
O1—C81.447 (2)C8—H8B0.9800
O2—C71.201 (2)C8—H8C0.9800
O3—C91.334 (2)C10—H10A0.9800
O3—C101.453 (2)C10—H10B0.9800
O4—C91.200 (2)C10—H10C0.9800
O5—C171.320 (2)C11—C161.398 (2)
O5—C181.454 (2)C11—C121.396 (2)
O6—C171.197 (2)C11—C211.494 (2)
O7—C191.315 (3)C12—C131.391 (2)
O7—C201.463 (3)C12—H120.9500
O8—C191.186 (3)C13—C141.399 (2)
O9—C211.220 (2)C13—C171.495 (2)
C1—C21.393 (2)C14—C151.394 (2)
C1—C61.395 (2)C14—C191.508 (2)
C1—C211.500 (2)C15—C161.388 (2)
C2—C31.387 (2)C15—H150.9500
C2—H20.9500C16—H160.9500
C3—C41.402 (2)C18—H18A0.9800
C3—C71.503 (2)C18—H18B0.9800
C4—C51.394 (2)C18—H18C0.9800
C4—C91.496 (2)C20—H20A0.9800
C5—C61.390 (2)C20—H20B0.9800
C5—H50.9500C20—H20C0.9800
C6—H60.9500
C7—O1—C8116.05 (14)C16—C11—C12119.28 (15)
C9—O3—C10114.72 (13)C16—C11—C21118.36 (15)
C17—O5—C18115.37 (15)C12—C11—C21122.33 (14)
C19—O7—C20111.96 (19)C13—C12—C11120.56 (15)
C2—C1—C6119.69 (15)C13—C12—H12119.7
C2—C1—C21117.35 (14)C11—C12—H12119.7
C6—C1—C21122.89 (14)C12—C13—C14119.71 (16)
C3—C2—C1120.55 (14)C12—C13—C17121.00 (15)
C3—C2—H2119.7C14—C13—C17119.28 (16)
C1—C2—H2119.7C15—C14—C13119.97 (16)
C2—C3—C4119.83 (14)C15—C14—C19118.98 (15)
C2—C3—C7117.18 (14)C13—C14—C19121.01 (16)
C4—C3—C7122.91 (14)C16—C15—C14120.04 (15)
C5—C4—C3119.43 (14)C16—C15—H15120.0
C5—C4—C9121.71 (14)C14—C15—H15120.0
C3—C4—C9118.77 (14)C15—C16—C11120.44 (15)
C6—C5—C4120.53 (14)C15—C16—H16119.8
C6—C5—H5119.7C11—C16—H16119.8
C4—C5—H5119.7O6—C17—O5123.51 (18)
C5—C6—C1119.84 (14)O6—C17—C13123.94 (18)
C5—C6—H6120.1O5—C17—C13112.54 (15)
C1—C6—H6120.1O5—C18—H18A109.5
O2—C7—O1125.28 (15)O5—C18—H18B109.5
O2—C7—C3124.21 (15)H18A—C18—H18B109.5
O1—C7—C3110.31 (13)O5—C18—H18C109.5
O1—C8—H8A109.5H18A—C18—H18C109.5
O1—C8—H8B109.5H18B—C18—H18C109.5
H8A—C8—H8B109.5O8—C19—O7123.63 (19)
O1—C8—H8C109.5O8—C19—C14124.31 (19)
H8A—C8—H8C109.5O7—C19—C14112.02 (17)
H8B—C8—H8C109.5O7—C20—H20A109.5
O4—C9—O3124.16 (15)O7—C20—H20B109.5
O4—C9—C4123.26 (15)H20A—C20—H20B109.5
O3—C9—C4112.55 (13)O7—C20—H20C109.5
O3—C10—H10A109.5H20A—C20—H20C109.5
O3—C10—H10B109.5H20B—C20—H20C109.5
H10A—C10—H10B109.5O9—C21—C11120.40 (14)
O3—C10—H10C109.5O9—C21—C1119.80 (15)
H10A—C10—H10C109.5C11—C21—C1119.80 (13)
H10B—C10—H10C109.5
C6—C1—C2—C33.2 (2)C12—C13—C14—C15−0.5 (3)
C21—C1—C2—C3−179.84 (14)C17—C13—C14—C15−178.97 (17)
C1—C2—C3—C4−0.8 (2)C12—C13—C14—C19177.06 (17)
C1—C2—C3—C7−177.49 (15)C17—C13—C14—C19−1.4 (3)
C2—C3—C4—C5−2.4 (2)C13—C14—C15—C16−0.4 (3)
C7—C3—C4—C5174.02 (15)C19—C14—C15—C16−177.95 (17)
C2—C3—C4—C9174.17 (14)C14—C15—C16—C110.5 (3)
C7—C3—C4—C9−9.4 (2)C12—C11—C16—C150.2 (2)
C3—C4—C5—C63.4 (2)C21—C11—C16—C15178.04 (15)
C9—C4—C5—C6−173.13 (15)C18—O5—C17—O6−1.2 (3)
C4—C5—C6—C1−1.0 (2)C18—O5—C17—C13179.94 (17)
C2—C1—C6—C5−2.3 (2)C12—C13—C17—O6−162.3 (2)
C21—C1—C6—C5−179.05 (15)C14—C13—C17—O616.2 (3)
C8—O1—C7—O20.9 (2)C12—C13—C17—O516.6 (3)
C8—O1—C7—C3175.88 (13)C14—C13—C17—O5−164.95 (17)
C2—C3—C7—O2103.63 (19)C20—O7—C19—O814.0 (3)
C4—C3—C7—O2−72.9 (2)C20—O7—C19—C14−168.1 (2)
C2—C3—C7—O1−71.44 (18)C15—C14—C19—O873.0 (3)
C4—C3—C7—O1112.03 (17)C13—C14—C19—O8−104.6 (2)
C10—O3—C9—O4−0.5 (2)C15—C14—C19—O7−104.9 (2)
C10—O3—C9—C4177.76 (14)C13—C14—C19—O777.6 (2)
C5—C4—C9—O4162.70 (17)C16—C11—C21—O9−25.3 (2)
C3—C4—C9—O4−13.8 (2)C12—C11—C21—O9152.50 (16)
C5—C4—C9—O3−15.5 (2)C16—C11—C21—C1155.19 (15)
C3—C4—C9—O3167.94 (14)C12—C11—C21—C1−27.0 (2)
C16—C11—C12—C13−1.0 (2)C2—C1—C21—O9−29.0 (2)
C21—C11—C12—C13−178.79 (15)C6—C1—C21—O9147.90 (17)
C11—C12—C13—C141.2 (3)C2—C1—C21—C11150.56 (15)
C11—C12—C13—C17179.64 (16)C6—C1—C21—C11−32.6 (2)
Acknowledgements top

The authors thank the Undergraduates Innovative Experiment Project and the Experimental Technical Project of Sichuan University (grant No. 07-54), and the University of Malaya for supporting this study.

references
References top

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.

Bruker (2008). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Fitzgerald, L. J. & Gerkin, R. E. (1997). Acta Cryst. C53, 1267–1270.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Westrip, S. P. (2009). publCIF. In preparation.

Zhang, J., Li, Z.-J., Kang, Y., Cheng, J.-K. & Yao, Y.-G. (2004). Inorg. Chem. 43, 8085–8091.