(4,6-Dibromo-m-phenyl­enedimethyl­idyne) tetra­acetate

Song, G.-L.; Liu, S.; Deng, S.-P.; Liu, Y.-Y.; Zhu, H.-J.

doi:10.1107/S1600536807063581

organic compounds

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ISSN: 2056-9890

Volume 64| Part 1| January 2008| Page o153

https://doi.org/10.1107/S1600536807063581

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(4,6-Dibromo-m-phenylenedimethylidyne) tetraacetate

Guang-Liang Song,^a Shan Liu,^a Shui-Ping Deng,^a Yuan-Yuan Liu ^a and Hong-Jun Zhu ^a ^*

^aDepartment of Applied Chemistry, College of Science, Nanjing University of Technology, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: zhuhj@njut.edu.cn

(Received 15 November 2007; accepted 26 November 2007; online 6 December 2007)

The title molecule, C₁₆H₁₆Br₂O₈, lies on a crystallographic twofold axis. Weak intramolecular C—H⋯O hydrogen bonds may, in part, control the conformation of the molecule. In the crystal structure, molecules are connected into a two-dimensional network via weak intermolecular C—H⋯O hydrogen bonds.

Related literature

For related literature, see: Allen et al. (1987 ); Mitchell et al. (1995 ).

Experimental

Crystal data

C₁₆H₁₆Br₂O₈
M_r = 496.09
Orthorhombic, P b c n
a = 20.639 (4) Å
b = 10.150 (2) Å
c = 9.0880 (18) Å
V = 1903.8 (6) Å³
Z = 4
Mo Kα radiation
μ = 4.30 mm⁻¹
T = 298 (2) K
0.40 × 0.30 × 0.20 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.278, T_max = 0.480 (expected range = 0.245–0.423)
3687 measured reflections
1877 independent reflections
805 reflections with I > 2σ(I)
R_int = 0.054
3 standard reflections every 200 reflections intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.067
wR(F²) = 0.130
S = 0.96
1877 reflections
107 parameters
29 restraints
H-atom parameters constrained
Δρ_max = 0.58 e Å⁻³
Δρ_min = −0.49 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4A⋯O3	0.93	2.46	2.815 (7)	103
C5—H5A⋯O2	0.98	2.34	2.693 (9)	100
C7—H7C⋯O2ⁱ	0.96	2.37	3.318 (11)	170
Symmetry code: (i) $[-x+{\script{3\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: CAD-4 Software (Enraf–Nonius, 1985 ); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536807063581/lh2578sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807063581/lh2578Isup2.hkl

checkCIF report

Comment top

The molecular structure of the title compound is shown in Fig. 1. The bond lengths and angles are within normal ranges (Allen et al., 1987).

The asymmetric unit contains one half-molecule; the full molecule being generated by a crystallographic twofold rotation axis. Weak intramolecular C—H···O hydrogen bonds may, in part, control the conformation of the molecule. In the crystal structure, molecules are connected into a two-dimensional network via weak intermolecular C—H···O hydrogen bonds. (Fig. 2).

Related literature top

For related literature, see: Allen et al. (1987); Mitchell et al. (1995).

Experimental top

The title compound was prepared by a previously reported method (Mitchell et al., 1995).

The crystals of the title compound, were obtained by dissolving (I) (2.00 g, 4.03 mmol) into acetone (50 ml), and evaporating the solvent slowly at room temperature for about 3 d.

Structure description top

The molecular structure of the title compound is shown in Fig. 1. The bond lengths and angles are within normal ranges (Allen et al., 1987).

For related literature, see: Allen et al. (1987); Mitchell et al. (1995).

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1985); cell refinement: CAD-4 Software (Enraf–Nonius, 1985); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL (Bruker, 2000).

Figures top

	Fig. 1. The molecular structure, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 40% probability level. Hydrogen bonds are shown by dashed lines. [Symmetry code: (A) -x + 1, y, -z + 1/2.]
	Fig. 2. The packing of the title compound with C—H···O hydrogen bonds are shown by dashed lines.

(4,6-Dibromo-m-phenylenedimethylidyne) tetraacetate top

Crystal data top

C₁₆H₁₆Br₂O₈	F(000) = 984
M_r = 496.09	D_x = 1.731 Mg m⁻³
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 25 reflections
a = 20.639 (4) Å	θ = 10–14°
b = 10.150 (2) Å	µ = 4.30 mm⁻¹
c = 9.0880 (18) Å	T = 298 K
V = 1903.8 (6) Å³	Plate, colourless
Z = 4	0.40 × 0.30 × 0.20 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	805 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.054
Graphite monochromator	θ_max = 26.0°, θ_min = 2.0°
ω/2θ scans	h = 0→25
Absorption correction: ψ scan (North et al., 1968)	k = 0→12
T_min = 0.278, T_max = 0.480	l = 0→11
3687 measured reflections	3 standard reflections every 200 reflections
1877 independent reflections	intensity decay: none

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.067	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.130	H-atom parameters constrained
S = 0.96	w = 1/[σ²(F_o²) + (0.02P)² + 0.0P] where P = (F_o² + 2F_c²)/3
1877 reflections	(Δ/σ)_max = 0.001
107 parameters	Δρ_max = 0.58 e Å⁻³
29 restraints	Δρ_min = −0.49 e Å⁻³

Crystal data top

C₁₆H₁₆Br₂O₈	V = 1903.8 (6) Å³
M_r = 496.09	Z = 4
Orthorhombic, Pbcn	Mo Kα radiation
a = 20.639 (4) Å	µ = 4.30 mm⁻¹
b = 10.150 (2) Å	T = 298 K
c = 9.0880 (18) Å	0.40 × 0.30 × 0.20 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	805 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.054
T_min = 0.278, T_max = 0.480	3 standard reflections every 200 reflections
3687 measured reflections	intensity decay: none
1877 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.067	29 restraints
wR(F²) = 0.130	H-atom parameters constrained
S = 0.96	Δρ_max = 0.58 e Å⁻³
1877 reflections	Δρ_min = −0.49 e Å⁻³
107 parameters

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

	x	y	z	U_iso*/U_eq
Br	0.61944 (4)	0.39329 (6)	0.10603 (9)	0.0671 (3)
O1	0.6622 (2)	0.6733 (4)	0.2433 (6)	0.0456 (11)
O2	0.7386 (3)	0.6717 (7)	0.0680 (7)	0.0852 (19)
O3	0.6065 (2)	0.8406 (5)	0.1438 (5)	0.049
O4	0.5702 (3)	0.8387 (5)	−0.0882 (6)	0.0750 (17)
C1	0.5000	0.4229 (8)	0.2500	0.042 (2)
H1A	0.5000	0.3313	0.2500	0.051*
C2	0.5520 (3)	0.4888 (6)	0.1917 (7)	0.0390 (16)
C3	0.5535 (3)	0.6316 (6)	0.1962 (7)	0.0414 (17)
C4	0.5000	0.6958 (9)	0.2500	0.037 (2)
H4A	0.5000	0.7874	0.2500	0.044*
C5	0.6135 (3)	0.6973 (7)	0.1474 (7)	0.041
H5A	0.6256	0.6652	0.0494	0.049*
C6	0.7244 (4)	0.6543 (8)	0.1961 (9)	0.052 (2)
C7	0.7671 (4)	0.6004 (9)	0.3066 (9)	0.084 (3)
H7A	0.8098	0.5906	0.2661	0.126*
H7B	0.7513	0.5159	0.3375	0.126*
H7C	0.7688	0.6588	0.3896	0.126*
C8	0.5877 (3)	0.8970 (7)	0.0164 (10)	0.063 (2)
C9	0.5899 (4)	1.0491 (6)	0.0331 (9)	0.060 (2)
H9A	0.5761	1.0896	−0.0571	0.090*
H9B	0.6334	1.0762	0.0552	0.090*
H9C	0.5616	1.0757	0.1116	0.090*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br	0.0785 (5)	0.0252 (4)	0.0977 (6)	0.0028 (4)	0.0283 (5)	−0.0106 (5)
O1	0.055 (3)	0.033 (2)	0.049 (3)	0.001 (2)	−0.007 (2)	−0.009 (3)
O2	0.064 (4)	0.107 (5)	0.084 (4)	−0.006 (4)	0.024 (3)	−0.001 (4)
O3	0.049	0.049	0.049	0.000	0.000	0.000
O4	0.095 (4)	0.051 (3)	0.080 (4)	−0.008 (3)	−0.023 (3)	0.005 (4)
C1	0.058 (5)	0.019 (4)	0.049 (5)	0.000	0.010 (5)	0.000
C2	0.051 (3)	0.013 (3)	0.053 (4)	−0.004 (3)	−0.011 (3)	−0.016 (3)
C3	0.058 (4)	0.022 (3)	0.045 (4)	−0.005 (3)	−0.008 (3)	−0.010 (3)
C4	0.051 (5)	0.021 (4)	0.040 (5)	0.000	0.005 (4)	0.000
C5	0.041	0.041	0.041	0.000	0.000	0.000
C6	0.058 (5)	0.052 (5)	0.046 (5)	−0.010 (4)	0.010 (4)	−0.018 (4)
C7	0.067 (5)	0.095 (8)	0.090 (7)	0.020 (6)	0.000 (5)	−0.012 (6)
C8	0.037 (3)	0.059 (5)	0.094 (6)	0.009 (4)	−0.011 (4)	−0.055 (6)
C9	0.077 (5)	0.018 (3)	0.084 (5)	−0.005 (4)	0.004 (5)	−0.001 (5)

Geometric parameters (Å, º) top

Br—C2	1.866 (6)	C3—C5	1.476 (9)
O1—C5	1.353 (7)	C4—C3ⁱ	1.372 (8)
O1—C6	1.366 (8)	C4—H4A	0.9300
O2—C6	1.213 (9)	C5—H5A	0.9800
O3—C8	1.349 (9)	C6—C7	1.445 (10)
O3—C5	1.461 (9)	C7—H7A	0.9600
O4—C8	1.177 (8)	C7—H7B	0.9600
C1—C2	1.371 (7)	C7—H7C	0.9600
C1—C2ⁱ	1.371 (7)	C8—C9	1.552 (8)
C1—H1A	0.9300	C9—H9A	0.9600
C2—C3	1.450 (8)	C9—H9B	0.9600
C3—C4	1.372 (8)	C9—H9C	0.9600

C5—O1—C6	121.4 (6)	C3—C5—H5A	109.6
C8—O3—C5	118.0 (5)	O2—C6—O1	120.5 (7)
C2—C1—C2ⁱ	121.6 (8)	O2—C6—C7	125.0 (7)
C2—C1—H1A	119.2	O1—C6—C7	114.1 (6)
C2ⁱ—C1—H1A	119.2	C6—C7—H7A	109.5
C1—C2—C3	119.6 (6)	C6—C7—H7B	109.5
C1—C2—Br	119.4 (4)	H7A—C7—H7B	109.5
C3—C2—Br	121.0 (5)	C6—C7—H7C	109.5
C4—C3—C2	117.9 (6)	H7A—C7—H7C	109.5
C4—C3—C5	124.6 (6)	H7B—C7—H7C	109.5
C2—C3—C5	117.5 (6)	O4—C8—O3	124.6 (7)
C3ⁱ—C4—C3	123.3 (8)	O4—C8—C9	126.0 (8)
C3ⁱ—C4—H4A	118.4	O3—C8—C9	109.3 (6)
C3—C4—H4A	118.4	C8—C9—H9A	109.5
O1—C5—O3	105.5 (5)	C8—C9—H9B	109.5
O1—C5—C3	110.4 (5)	H9A—C9—H9B	109.5
O3—C5—C3	112.0 (5)	C8—C9—H9C	109.5
O1—C5—H5A	109.6	H9A—C9—H9C	109.5
O3—C5—H5A	109.6	H9B—C9—H9C	109.5

C2ⁱ—C1—C2—C3	2.3 (4)	C8—O3—C5—O1	147.6 (5)
C2ⁱ—C1—C2—Br	−177.1 (5)	C8—O3—C5—C3	−92.3 (7)
C1—C2—C3—C4	−4.6 (9)	C4—C3—C5—O1	109.4 (6)
Br—C2—C3—C4	174.8 (3)	C2—C3—C5—O1	−68.3 (8)
C1—C2—C3—C5	173.3 (5)	C4—C3—C5—O3	−7.8 (8)
Br—C2—C3—C5	−7.3 (9)	C2—C3—C5—O3	174.5 (6)
C2—C3—C4—C3ⁱ	2.2 (4)	C5—O1—C6—O2	7.5 (12)
C5—C3—C4—C3ⁱ	−175.5 (7)	C5—O1—C6—C7	−166.4 (6)
C6—O1—C5—O3	−96.1 (7)	C5—O3—C8—O4	7.9 (10)
C6—O1—C5—C3	142.8 (6)	C5—O3—C8—C9	−174.6 (6)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4A···O3	0.93	2.46	2.815 (7)	103
C5—H5A···O2	0.98	2.34	2.693 (9)	100
C7—H7C···O2ⁱⁱ	0.96	2.37	3.318 (11)	170

Symmetry code: (ii) −x+3/2, −y+3/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₆H₁₆Br₂O₈
M_r	496.09
Crystal system, space group	Orthorhombic, Pbcn
Temperature (K)	298
a, b, c (Å)	20.639 (4), 10.150 (2), 9.0880 (18)
V (Å³)	1903.8 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	4.30
Crystal size (mm)	0.40 × 0.30 × 0.20

Data collection
Diffractometer	Enraf–Nonius CAD-4
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.278, 0.480
No. of measured, independent and observed [I > 2σ(I)] reflections	3687, 1877, 805
R_int	0.054
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.067, 0.130, 0.96
No. of reflections	1877
No. of parameters	107
No. of restraints	29
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.58, −0.49

Computer programs: CAD-4 Software (Enraf–Nonius, 1985), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2000).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4A···O3	0.9300	2.4600	2.815 (7)	103.00
C5—H5A···O2	0.9800	2.3400	2.693 (9)	100.00
C7—H7C···O2ⁱ	0.9600	2.3700	3.318 (11)	170.00

Symmetry code: (i) −x+3/2, −y+3/2, z+1/2.

Acknowledgements

The authors thank the Center of Testing and Analysis, Nanjing University, for support.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CSD CrossRef Web of Science Google Scholar
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North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef IUCr Journals Web of Science Google Scholar
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