supplementary materials


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

cf2186 scheme

Acta Cryst. (2008). E64, o692    [ doi:10.1107/S1600536808006132 ]

Bis(4-nitrophenyl) 1,3-phenylenedimethylene dicarbonate

S. Nawazish Ali, S. Begum, M. A. Winnik and A. J. Lough

Abstract top

In the title molecule, C22H16N2O10, the dihedral angles between the benzene rings of the 4-nitrophenyl groups and the central benzene ring are 32.7 (1) and 34.7 (1)°, while the dihedral angle between the two benzene rings of the 4-nitrophenyl groups is 3.6 (2)°. In the crystal structure, weak intermolecular C-H...O hydrogen bonds link molecules into centrosymmetric dimers.

Comment top

For background information and relevant references see Ali et al. (2008). In the title molecule (Fig. 1) the dihedral angles between the benzene rings of the p-nitrophenyl groups and the central benzene ring are 32.7 (1) (for C9—C14) and 34.7 (1)° (for C17—C22), while the dihedral angle between the two benzene rings of the p-nitrophenyl groups is 3.6 (2)°. In the crystal structure, weak intermolecluar C—H···O hydrogen bonds link molecules into centrosymmetric dimers (Fig. 2).

Related literature top

For related literature, see: Nawazish Ali et al. (2008).

Experimental top

A solution of 4-nitrophenylchloroformate (14.1 g, 70 mmol) in dry dichloromethane (70 ml) was added dropwise via a 250 ml separatory funnel to a solution of 1,3-phenylenedimethanol (4.82 g, 35 mmol) in anhydrous pyridine (5.38 g, 5.5 ml, 68.0 mmol) and dry dichloromethane (20 ml) in a 250 ml round-bottom flask. A white suspension appeared which was stirred gently at room temperature for 10 h. After this time more dry dichloromethane (50 ml) was added, which dissolved the suspension and then the reaction mixture was stirred for another 6 h. It was then quenched by adding deionized water (50 ml). The reaction mixture was transferred to a separatory funnel (500 ml), and the lower organic phase was removed. The aqueous phase was washed with dichloromethane (30 ml x 3), and all the dichloromethane solutions were combined. These were then washed with deionized water (40 ml x 3), a 1.0% solution of acetic acid (50 ml x 4) and once more with deionized water (40 ml x 3), and then dried over anhydrous magnesium sulfate and filtered. After filtration, the solvent was removed by rotary evaporator. The product was dried in air overnight in a fume hood and then in a vacuum oven for 24 h at room temperature (< 1 Torr). The desired product was obtained in a moderate yield (11.4 g, 70.0%) as a white solid; the product was recrystallized by dissolving in a mixture of dichloromethane and ethanol (95%) (1:1). The reaction mixture was heated at 358 K, and filtered after 40 minutes. X-ray quality crystals were obtained after slow evaporation of the solvent at room temperature.

Refinement top

Hydrogen atoms were placed in calculated positions with C—H = 0.95–1.00 Å and they were included in the refinement in the riding-model approximation with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: COLLECT (Nonius, 2002); cell refinement: DENZO–SMN (Otwinowski & Minor, 1997); data reduction: DENZO–SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound showing displacement ellipsoids drawn at the 30% probability level.
[Figure 2] Fig. 2. Part of the crystal structure with weak intermolecular C—H···O hydrogen bonds shown as dashed lines.
Bis(4-nitrophenyl) 1,3-phenylenedimethylene dicarbonate top
Crystal data top
C22H16N2O10Z = 2
Mr = 468.37F000 = 484
Triclinic, P1Dx = 1.525 Mg m−3
Hall symbol: -P 1Mo Kα radiation
λ = 0.71073 Å
a = 8.5956 (4) ÅCell parameters from 10107 reflections
b = 9.2367 (5) Åθ = 2.6–27.5º
c = 14.1550 (8) ŵ = 0.12 mm−1
α = 94.094 (2)ºT = 150 (1) K
β = 107.134 (3)ºBlock, colourless
γ = 105.674 (3)º0.34 × 0.20 × 0.20 mm
V = 1020.00 (10) Å3
Data collection top
Bruker–Nonius KappaCCD
diffractometer		4580 independent reflections
Radiation source: fine-focus sealed tube3182 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.054
Detector resolution: 9 pixels mm-1θmax = 27.5º
T = 150(2) Kθmin = 2.6º
φ scans and ω scans with κ offsetsh = −11→10
Absorption correction: multi-scan
(SORTAV; Blessing, 1995)		k = −11→11
Tmin = 0.808, Tmax = 0.980l = −18→18
10107 measured reflections
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.064  w = 1/[σ2(Fo2) + (0.035P)2 + 1.3721P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.166(Δ/σ)max < 0.001
S = 1.15Δρmax = 0.30 e Å−3
4580 reflectionsΔρmin = −0.26 e Å−3
308 parametersExtinction correction: SHELXTL (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.021 (4)
Secondary atom site location: difference Fourier map
Crystal data top
C22H16N2O10γ = 105.674 (3)º
Mr = 468.37V = 1020.00 (10) Å3
Triclinic, P1Z = 2
a = 8.5956 (4) ÅMo Kα
b = 9.2367 (5) ŵ = 0.12 mm−1
c = 14.1550 (8) ÅT = 150 (1) K
α = 94.094 (2)º0.34 × 0.20 × 0.20 mm
β = 107.134 (3)º
Data collection top
Bruker–Nonius KappaCCD
diffractometer		4580 independent reflections
Absorption correction: multi-scan
(SORTAV; Blessing, 1995)		3182 reflections with I > 2σ(I)
Tmin = 0.808, Tmax = 0.980Rint = 0.054
10107 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.064308 parameters
wR(F2) = 0.166H-atom parameters constrained
S = 1.15Δρmax = 0.30 e Å−3
4580 reflectionsΔρmin = −0.26 e Å−3
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

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 > σ(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) top
xyzUiso*/Ueq
O10.8872 (3)0.1353 (2)0.51451 (16)0.0340 (5)
O20.6463 (3)0.2045 (3)0.48906 (18)0.0406 (6)
O30.8682 (3)0.3232 (2)0.43660 (16)0.0339 (5)
O40.5734 (3)0.8621 (3)0.32218 (18)0.0493 (7)
O50.5700 (3)0.7631 (3)0.17823 (17)0.0453 (6)
O60.7702 (3)0.1855 (2)0.94414 (15)0.0321 (5)
O70.7572 (3)0.4000 (2)1.02591 (16)0.0346 (5)
O80.6017 (3)0.1596 (2)1.03074 (15)0.0304 (5)
O90.1915 (5)0.4431 (4)1.2504 (3)0.0781 (10)
O100.2930 (3)0.3121 (3)1.35819 (18)0.0490 (7)
N10.6000 (3)0.7673 (3)0.26870 (19)0.0343 (6)
N20.2722 (4)0.3547 (3)1.2770 (2)0.0413 (7)
C10.8609 (4)0.1437 (3)0.7314 (2)0.0289 (6)
H1A0.78260.19490.69960.035*
C20.9034 (4)0.0426 (3)0.6733 (2)0.0269 (6)
C31.0188 (4)−0.0314 (4)0.7203 (2)0.0326 (7)
H3A1.0505−0.09930.68140.039*
C41.0875 (4)−0.0059 (4)0.8237 (2)0.0388 (8)
H4A1.1658−0.05710.85560.047*
C51.0431 (4)0.0932 (4)0.8811 (2)0.0363 (7)
H5A1.08930.10820.95210.044*
C60.9314 (4)0.1712 (3)0.8356 (2)0.0313 (7)
C70.8208 (4)0.0058 (3)0.5615 (2)0.0333 (7)
H7A0.8443−0.08540.53540.040*
H7B0.6954−0.01730.54440.040*
C80.7845 (4)0.2182 (3)0.4820 (2)0.0300 (6)
C90.7965 (4)0.4351 (3)0.3983 (2)0.0288 (6)
C100.7170 (4)0.5092 (3)0.4481 (2)0.0311 (7)
H10A0.70520.48390.51000.037*
C110.6548 (4)0.6215 (3)0.4058 (2)0.0314 (7)
H11A0.60080.67580.43870.038*
C120.6728 (4)0.6530 (3)0.3153 (2)0.0287 (6)
C130.7562 (4)0.5817 (4)0.2664 (2)0.0320 (7)
H13A0.76910.60800.20490.038*
C140.8204 (4)0.4712 (3)0.3092 (2)0.0310 (7)
H14A0.87990.42080.27810.037*
C150.8850 (4)0.2793 (4)0.8979 (3)0.0382 (8)
H15A0.98870.34770.95010.046*
H15B0.82670.34240.85560.046*
C160.7147 (4)0.2644 (3)1.0016 (2)0.0269 (6)
C170.5156 (4)0.2113 (3)1.0894 (2)0.0261 (6)
C180.5105 (4)0.1426 (3)1.1723 (2)0.0284 (6)
H18A0.56210.06421.18650.034*
C190.4293 (4)0.1892 (3)1.2346 (2)0.0295 (6)
H19A0.42710.14611.29330.035*
C200.3518 (4)0.2999 (3)1.2088 (2)0.0294 (6)
C210.3483 (4)0.3636 (3)1.1233 (2)0.0312 (7)
H21A0.28980.43681.10670.037*
C220.4322 (4)0.3182 (3)1.0620 (2)0.0279 (6)
H22A0.43230.35971.00250.033*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0368 (12)0.0373 (12)0.0328 (11)0.0141 (10)0.0145 (10)0.0116 (9)
O20.0349 (13)0.0401 (13)0.0535 (15)0.0122 (10)0.0215 (11)0.0171 (11)
O30.0352 (12)0.0365 (12)0.0347 (12)0.0114 (10)0.0163 (10)0.0116 (10)
O40.0688 (18)0.0461 (15)0.0451 (14)0.0304 (14)0.0230 (13)0.0126 (12)
O50.0525 (15)0.0504 (15)0.0315 (12)0.0159 (12)0.0094 (11)0.0155 (11)
O60.0388 (12)0.0276 (11)0.0331 (11)0.0059 (9)0.0210 (10)0.0018 (9)
O70.0409 (12)0.0249 (12)0.0371 (12)0.0039 (9)0.0185 (10)0.0001 (9)
O80.0381 (12)0.0240 (11)0.0351 (11)0.0082 (9)0.0217 (10)0.0060 (9)
O90.110 (3)0.081 (2)0.102 (3)0.070 (2)0.078 (2)0.0417 (19)
O100.0583 (16)0.0476 (15)0.0417 (14)0.0040 (12)0.0308 (13)−0.0023 (11)
N10.0335 (14)0.0357 (15)0.0321 (14)0.0068 (12)0.0105 (12)0.0111 (12)
N20.0466 (17)0.0318 (15)0.0512 (18)0.0068 (13)0.0302 (15)0.0010 (13)
C10.0275 (15)0.0283 (15)0.0332 (16)0.0083 (12)0.0135 (13)0.0064 (13)
C20.0259 (15)0.0261 (15)0.0294 (15)0.0060 (12)0.0114 (12)0.0056 (12)
C30.0328 (16)0.0361 (17)0.0366 (17)0.0152 (14)0.0180 (14)0.0077 (14)
C40.0333 (17)0.050 (2)0.0390 (18)0.0189 (16)0.0137 (15)0.0152 (16)
C50.0319 (16)0.047 (2)0.0261 (15)0.0045 (15)0.0105 (13)0.0049 (14)
C60.0306 (16)0.0287 (16)0.0349 (16)0.0022 (13)0.0182 (14)0.0026 (13)
C70.0425 (18)0.0285 (16)0.0299 (16)0.0112 (14)0.0127 (14)0.0058 (13)
C80.0357 (17)0.0294 (16)0.0235 (14)0.0092 (13)0.0087 (13)0.0034 (12)
C90.0308 (15)0.0265 (15)0.0260 (14)0.0053 (12)0.0076 (12)0.0051 (12)
C100.0377 (17)0.0299 (16)0.0229 (14)0.0059 (13)0.0103 (13)0.0022 (12)
C110.0341 (16)0.0290 (16)0.0280 (15)0.0048 (13)0.0106 (13)0.0017 (12)
C120.0284 (15)0.0261 (15)0.0265 (15)0.0031 (12)0.0059 (12)0.0051 (12)
C130.0312 (16)0.0350 (17)0.0256 (15)0.0014 (13)0.0108 (13)0.0068 (13)
C140.0279 (15)0.0330 (17)0.0302 (15)0.0047 (13)0.0113 (13)0.0041 (13)
C150.0449 (19)0.0300 (17)0.0402 (18)0.0003 (14)0.0262 (16)0.0001 (14)
C160.0280 (15)0.0261 (16)0.0242 (14)0.0051 (12)0.0085 (12)0.0025 (12)
C170.0284 (15)0.0236 (14)0.0251 (14)0.0046 (12)0.0112 (12)−0.0005 (11)
C180.0316 (16)0.0245 (15)0.0301 (15)0.0077 (12)0.0118 (13)0.0067 (12)
C190.0314 (16)0.0290 (16)0.0276 (15)0.0038 (13)0.0132 (13)0.0067 (12)
C200.0299 (15)0.0250 (15)0.0330 (16)0.0028 (12)0.0164 (13)−0.0021 (12)
C210.0288 (15)0.0277 (16)0.0362 (17)0.0088 (13)0.0097 (13)0.0032 (13)
C220.0300 (15)0.0277 (15)0.0229 (14)0.0067 (12)0.0063 (12)0.0037 (12)
Geometric parameters (Å, °) top
O1—C81.324 (4)C5—H5A0.950
O1—C71.472 (4)C6—C151.494 (4)
O2—C81.195 (4)C7—H7A0.990
O3—C81.362 (3)C7—H7B0.990
O3—C91.404 (3)C9—C101.379 (4)
O4—N11.227 (3)C9—C141.385 (4)
O5—N11.225 (3)C10—C111.385 (4)
O6—C161.323 (3)C10—H10A0.950
O6—C151.467 (3)C11—C121.377 (4)
O7—C161.199 (3)C11—H11A0.950
O8—C161.355 (3)C12—C131.382 (4)
O8—C171.400 (3)C13—C141.382 (4)
O9—N21.219 (4)C13—H13A0.950
O10—N21.220 (4)C14—H14A0.950
N1—C121.468 (4)C15—H15A0.990
N2—C201.471 (4)C15—H15B0.990
C1—C21.391 (4)C17—C181.380 (4)
C1—C61.394 (4)C17—C221.383 (4)
C1—H1A0.950C18—C191.386 (4)
C2—C31.392 (4)C18—H18A0.950
C2—C71.501 (4)C19—C201.379 (4)
C3—C41.384 (4)C19—H19A0.950
C3—H3A0.950C20—C211.378 (4)
C4—C51.381 (4)C21—C221.389 (4)
C4—H4A0.950C21—H21A0.950
C5—C61.390 (4)C22—H22A0.950
C8—O1—C7116.3 (2)C9—C10—H10A120.7
C8—O3—C9119.8 (2)C11—C10—H10A120.7
C16—O6—C15114.3 (2)C12—C11—C10118.7 (3)
C16—O8—C17118.4 (2)C12—C11—H11A120.7
O5—N1—O4123.6 (3)C10—C11—H11A120.7
O5—N1—C12117.9 (3)C11—C12—C13122.9 (3)
O4—N1—C12118.5 (2)C11—C12—N1118.5 (3)
O9—N2—O10123.2 (3)C13—C12—N1118.6 (3)
O9—N2—C20118.2 (3)C12—C13—C14118.4 (3)
O10—N2—C20118.6 (3)C12—C13—H13A120.8
C2—C1—C6121.0 (3)C14—C13—H13A120.8
C2—C1—H1A119.5C13—C14—C9118.8 (3)
C6—C1—H1A119.5C13—C14—H14A120.6
C1—C2—C3119.2 (3)C9—C14—H14A120.6
C1—C2—C7121.4 (3)O6—C15—C6106.4 (2)
C3—C2—C7119.3 (3)O6—C15—H15A110.4
C4—C3—C2119.9 (3)C6—C15—H15A110.4
C4—C3—H3A120.0O6—C15—H15B110.4
C2—C3—H3A120.0C6—C15—H15B110.4
C5—C4—C3120.6 (3)H15A—C15—H15B108.6
C5—C4—H4A119.7O7—C16—O6128.0 (3)
C3—C4—H4A119.7O7—C16—O8126.2 (3)
C4—C5—C6120.4 (3)O6—C16—O8105.7 (2)
C4—C5—H5A119.8C18—C17—C22122.3 (3)
C6—C5—H5A119.8C18—C17—O8116.0 (2)
C5—C6—C1118.8 (3)C22—C17—O8121.6 (2)
C5—C6—C15120.2 (3)C17—C18—C19119.2 (3)
C1—C6—C15120.9 (3)C17—C18—H18A120.4
O1—C7—C2110.4 (2)C19—C18—H18A120.4
O1—C7—H7A109.6C20—C19—C18118.0 (3)
C2—C7—H7A109.6C20—C19—H19A121.0
O1—C7—H7B109.6C18—C19—H19A121.0
C2—C7—H7B109.6C21—C20—C19123.2 (3)
H7A—C7—H7B108.1C21—C20—N2118.6 (3)
O2—C8—O1128.1 (3)C19—C20—N2118.2 (3)
O2—C8—O3126.4 (3)C20—C21—C22118.5 (3)
O1—C8—O3105.5 (2)C20—C21—H21A120.8
C10—C9—C14122.6 (3)C22—C21—H21A120.8
C10—C9—O3122.7 (3)C17—C22—C21118.6 (3)
C14—C9—O3114.6 (3)C17—C22—H22A120.7
C9—C10—C11118.5 (3)C21—C22—H22A120.7
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C10—H10A···O10i0.952.553.134 (4)120
C15—H15B···O9i0.992.583.504 (4)155
C21—H21A···O7i0.952.503.264 (3)138
Symmetry codes: (i) −x+1, −y+1, −z+2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C10—H10A···O10i0.952.553.134 (4)120
C15—H15B···O9i0.992.583.504 (4)155
C21—H21A···O7i0.952.503.264 (3)138
Symmetry codes: (i) −x+1, −y+1, −z+2.
Acknowledgements top

The authors acknowledge the Higher Education Commission (HEC) of Pakistan, Materials and Manufacturing Ontario (MMO), Canada, NSERC Canada and the University of Toronto for funding.

references
References top

Nawazish Ali, S., Begum, S., Winnik, M. A. & Lough, A. J. (2008). Acta Cryst. E64, o281–?.

Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435–?.

Blessing, R. H. (1995). Acta Cryst. A51, 33–38.

Nonius (2002). COLLECT. Nonius BV, Delft, The Netherlands.

Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press.

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