Benzene-1,3,5-tricarbonyl trichloride

Fan, X.; Wang, Y.; Jin, C.; Jin, L.

doi:10.1107/S1600536812012895

organic compounds

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ISSN: 2056-9890

Volume 68| Part 4| April 2012| Page o1260

doi:10.1107/S1600536812012895

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Benzene-1,3,5-tricarbonyl trichloride

Xin Fan,^a Yanrong Wang,^a Chengzhi Jin ^a and Longfei Jin ^a ^*

^aCollege of Chemistry and Material Science, South-Central University for Nationalities, Wuhan 430074, People's Republic of China
^*Correspondence e-mail: longfei.jin@yahoo.com

(Received 19 March 2012; accepted 24 March 2012; online 31 March 2012)

In the title molecule, C₉H₃Cl₃O₃, there are three short interactions involving the benzene H atoms and the chloroformyl Cl atoms. In the crystal, molecules stack along the a axis with no significant non-bonded interactions.

Related literature

For the preparation of the title compound, see: Hamel et al. (1968 ). For applications of 1,3,5-tri(chloroformyl)benzene, see: Buch et al. (2008 ); Li et al. (2007 ). For related structures and hydrogen bonding, see: Leser & Rabinovich (1978a ,b ); Jeffrey et al. (1985 ).

Experimental

Crystal data

C₉H₃Cl₃O₃
M_r = 265.46
Orthorhombic, P 2₁ 2₁ 2₁
a = 6.0230 (13) Å
b = 8.3306 (18) Å
c = 21.314 (5) Å
V = 1069.4 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.84 mm⁻¹
T = 298 K
0.30 × 0.20 × 0.20 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.787, T_max = 0.851
6552 measured reflections
2338 independent reflections
2267 reflections with I > 2σ(I)
R_int = 0.088

Refinement

R[F² > 2σ(F²)] = 0.065
wR(F²) = 0.170
S = 1.22
2338 reflections
136 parameters
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.28 e Å⁻³
Absolute structure: Flack (1983 ), 952 Friedel pairs
Flack parameter: 0.13 (15)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯Cl1	0.93	2.64	3.047 (5)	107
C4—H4⋯Cl2	0.93	2.62	3.036 (4)	108
C6—H6⋯Cl3	0.93	2.62	3.037 (4)	108

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812012895/vm2166sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812012895/vm2166Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812012895/vm2166Isup3.cml

checkCIF report

Comment top

1,3,5-Tri(chloroformyl)benzene is a commonly used monomer, mainly used in the preparation of reverse osmosis membranes and polyamide nanofiltration membranes (Buch et al., 2008; Li et al., 2007), which has good application prospects in the rapid development of today's film industry. As part of our ongoing studies, the preparation and X-ray structure determination of the title compound, (I), was undertaken.

The molecular structure of the title compound is shown in Figure 1. Bond lengths and angles in (I) show normal values. The geometric parameters of the title molecule agree well with those reported for similar structures (Leser & Rabinovich, 1978a,b). The non-hydrogen atoms of the molecule lie in a nearly plane with an r.m.s deviation of 0.1118 Å. Three intramolecular hydrogen bonds are observed between the C—H of phenyl group and the Cl atom of the chloroformyl group (Jeffrey et al., 1985) (Figure 1 and Table 1). The shortest contacts in the crystal packing are O1···C2ⁱ [3.094 (6) Å], O2···Cl3ⁱⁱ [3.191 (5) Å] and O3···C9ⁱⁱⁱ [3.216 (6) Å] [symmetry code (i): -x,1/2 + y,1/2 - z; (ii): 1 + x,1 + y,z; (iii): 1/2 + x,3/2 - y,-z].

Related literature top

For the preparation of the title compound, see: Hamel et al. (1968). For applications of 1,3,5-tri(chloroformyl)benzene, see: Buch et al. (2008); Li et al. (2007). For related structures and hydrogen bonding, see: Leser & Rabinovich (1978a,b); Jeffrey et al. (1985).

Experimental top

Compound (I) was synthesized according to the literature procedure of Hamel et al. (1968). Single crystals suitable for X-ray diffraction were grown by slow evaporation from 4:1 (V/V) mixed solution of petroleum ether and chloroform at room temperature.

Structure description top

For the preparation of the title compound, see: Hamel et al. (1968). For applications of 1,3,5-tri(chloroformyl)benzene, see: Buch et al. (2008); Li et al. (2007). For related structures and hydrogen bonding, see: Leser & Rabinovich (1978a,b); Jeffrey et al. (1985).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of (I), showing 30% probability displacement ellipsoids. Dashed lines indicate hydrogen bonds.

Benzene-1,3,5-tricarbonyl trichloride top

Crystal data top

C₉H₃Cl₃O₃	F(000) = 528
M_r = 265.46	D_x = 1.649 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 3613 reflections
a = 6.0230 (13) Å	θ = 2.4–28.2°
b = 8.3306 (18) Å	µ = 0.84 mm⁻¹
c = 21.314 (5) Å	T = 298 K
V = 1069.4 (4) Å³	Block, colorless
Z = 4	0.30 × 0.20 × 0.20 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	2338 independent reflections
Radiation source: fine-focus sealed tube	2267 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.088
phi and ω scans	θ_max = 27.0°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→5
T_min = 0.787, T_max = 0.851	k = −9→10
6552 measured reflections	l = −27→27

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.065	H-atom parameters constrained
wR(F²) = 0.170	w = 1/[σ²(F_o²) + (0.0522P)² + 0.5279P] where P = (F_o² + 2F_c²)/3
S = 1.22	(Δ/σ)_max < 0.001
2338 reflections	Δρ_max = 0.31 e Å⁻³
136 parameters	Δρ_min = −0.28 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 952 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.13 (15)

Crystal data top

C₉H₃Cl₃O₃	V = 1069.4 (4) Å³
M_r = 265.46	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 6.0230 (13) Å	µ = 0.84 mm⁻¹
b = 8.3306 (18) Å	T = 298 K
c = 21.314 (5) Å	0.30 × 0.20 × 0.20 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	2338 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2267 reflections with I > 2σ(I)
T_min = 0.787, T_max = 0.851	R_int = 0.088
6552 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.065	H-atom parameters constrained
wR(F²) = 0.170	Δρ_max = 0.31 e Å⁻³
S = 1.22	Δρ_min = −0.28 e Å⁻³
2338 reflections	Absolute structure: Flack (1983), 952 Friedel pairs
136 parameters	Absolute structure parameter: 0.13 (15)
0 restraints

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
C1	0.4413 (7)	0.7665 (6)	0.83052 (18)	0.0582 (10)
C2	0.3612 (7)	0.9176 (6)	0.84269 (18)	0.0582 (9)
H2	0.2326	0.9534	0.8230	0.070*
C3	0.4728 (7)	1.0170 (5)	0.88445 (19)	0.0545 (9)
C4	0.6638 (6)	0.9669 (5)	0.91364 (18)	0.0497 (8)
H4	0.7392	1.0352	0.9408	0.060*
C5	0.7435 (6)	0.8124 (5)	0.90207 (17)	0.0482 (8)
C6	0.6328 (7)	0.7132 (5)	0.86085 (19)	0.0553 (9)
H6	0.6860	0.6102	0.8532	0.066*
C7	0.3370 (9)	0.6507 (8)	0.7862 (3)	0.0834 (16)
C8	0.3650 (9)	1.1749 (6)	0.8981 (3)	0.0764 (14)
C9	0.9471 (7)	0.7645 (5)	0.9372 (2)	0.0565 (9)
Cl1	0.1090 (3)	0.7279 (3)	0.74344 (9)	0.1188 (7)
Cl2	0.5232 (3)	1.30825 (15)	0.94387 (9)	0.0934 (5)
Cl3	1.0317 (2)	0.56293 (13)	0.92527 (7)	0.0775 (4)
O1	0.3901 (9)	0.5166 (6)	0.7783 (2)	0.1201 (18)
O2	0.1848 (8)	1.2126 (6)	0.8830 (3)	0.130 (2)
O3	1.0513 (6)	0.8462 (4)	0.97113 (18)	0.0759 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.058 (2)	0.072 (3)	0.0452 (17)	0.0009 (19)	0.0046 (17)	−0.0110 (19)
C2	0.058 (2)	0.066 (2)	0.0502 (19)	0.008 (2)	−0.0014 (17)	0.0023 (19)
C3	0.058 (2)	0.0495 (19)	0.056 (2)	0.0058 (17)	0.0010 (18)	0.0014 (16)
C4	0.0481 (17)	0.0480 (18)	0.0530 (18)	0.0037 (15)	0.0025 (15)	0.0009 (16)
C5	0.0486 (18)	0.0464 (18)	0.0495 (18)	0.0055 (16)	0.0044 (15)	0.0063 (16)
C6	0.060 (2)	0.048 (2)	0.058 (2)	0.0056 (17)	0.0147 (18)	−0.0070 (17)
C7	0.076 (3)	0.103 (4)	0.070 (3)	0.003 (3)	−0.002 (2)	−0.034 (3)
C8	0.082 (3)	0.058 (2)	0.090 (3)	0.018 (2)	−0.029 (3)	−0.009 (2)
C9	0.0507 (19)	0.0460 (19)	0.073 (2)	0.0127 (16)	0.0077 (18)	0.0032 (19)
Cl1	0.1086 (11)	0.1431 (17)	0.1046 (11)	−0.0062 (12)	−0.0484 (10)	−0.0267 (12)
Cl2	0.0915 (9)	0.0520 (6)	0.1365 (13)	0.0142 (6)	−0.0241 (9)	−0.0208 (7)
Cl3	0.0730 (7)	0.0567 (6)	0.1028 (9)	0.0245 (5)	−0.0030 (6)	−0.0003 (6)
O1	0.123 (3)	0.112 (4)	0.125 (4)	0.020 (3)	−0.018 (3)	−0.076 (3)
O2	0.112 (3)	0.093 (3)	0.185 (5)	0.051 (3)	−0.071 (3)	−0.041 (3)
O3	0.0646 (18)	0.0658 (19)	0.097 (2)	0.0090 (15)	−0.0232 (18)	−0.0087 (19)

Geometric parameters (Å, º) top

C1—C2	1.373 (6)	C5—C6	1.378 (6)
C1—C6	1.394 (6)	C5—C9	1.491 (5)
C1—C7	1.489 (7)	C6—H6	0.9300
C2—C3	1.388 (6)	C7—O1	1.174 (7)
C2—H2	0.9300	C7—Cl1	1.769 (6)
C3—C4	1.373 (6)	C8—O2	1.175 (6)
C3—C8	1.496 (6)	C8—Cl2	1.758 (5)
C4—C5	1.396 (5)	C9—O3	1.174 (5)
C4—H4	0.9300	C9—Cl3	1.773 (4)

C2—C1—C6	119.6 (4)	C4—C5—C9	116.1 (4)
C2—C1—C7	124.4 (4)	C5—C6—C1	120.3 (4)
C6—C1—C7	115.9 (4)	C5—C6—H6	119.8
C1—C2—C3	119.9 (4)	C1—C6—H6	119.8
C1—C2—H2	120.1	O1—C7—C1	126.3 (6)
C3—C2—H2	120.1	O1—C7—Cl1	118.9 (5)
C4—C3—C2	121.0 (4)	C1—C7—Cl1	114.8 (4)
C4—C3—C8	122.8 (4)	O2—C8—C3	125.6 (5)
C2—C3—C8	116.1 (4)	O2—C8—Cl2	118.9 (4)
C3—C4—C5	119.2 (4)	C3—C8—Cl2	115.4 (3)
C3—C4—H4	120.4	O3—C9—C5	126.4 (4)
C5—C4—H4	120.4	O3—C9—Cl3	118.9 (3)
C6—C5—C4	119.9 (4)	C5—C9—Cl3	114.7 (3)
C6—C5—C9	123.9 (4)

C6—C1—C2—C3	0.8 (6)	C2—C1—C7—O1	−173.6 (6)
C7—C1—C2—C3	−179.3 (4)	C6—C1—C7—O1	6.4 (9)
C1—C2—C3—C4	0.5 (6)	C2—C1—C7—Cl1	5.3 (7)
C1—C2—C3—C8	−175.9 (4)	C6—C1—C7—Cl1	−174.8 (3)
C2—C3—C4—C5	−1.5 (6)	C4—C3—C8—O2	−166.4 (7)
C8—C3—C4—C5	174.7 (4)	C2—C3—C8—O2	10.0 (9)
C3—C4—C5—C6	1.2 (6)	C4—C3—C8—Cl2	10.6 (6)
C3—C4—C5—C9	−177.8 (3)	C2—C3—C8—Cl2	−173.0 (4)
C4—C5—C6—C1	0.1 (6)	C6—C5—C9—O3	177.2 (4)
C9—C5—C6—C1	179.0 (4)	C4—C5—C9—O3	−3.8 (6)
C2—C1—C6—C5	−1.1 (6)	C6—C5—C9—Cl3	−3.1 (5)
C7—C1—C6—C5	179.0 (4)	C4—C5—C9—Cl3	175.9 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···Cl1	0.93	2.64	3.047 (5)	107
C4—H4···Cl2	0.93	2.62	3.036 (4)	108
C6—H6···Cl3	0.93	2.62	3.037 (4)	108

Experimental details

Crystal data
Chemical formula	C₉H₃Cl₃O₃
M_r	265.46
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	298
a, b, c (Å)	6.0230 (13), 8.3306 (18), 21.314 (5)
V (Å³)	1069.4 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.84
Crystal size (mm)	0.30 × 0.20 × 0.20

Data collection
Diffractometer	Bruker SMART CCD area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.787, 0.851
No. of measured, independent and observed [I > 2σ(I)] reflections	6552, 2338, 2267
R_int	0.088
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.065, 0.170, 1.22
No. of reflections	2338
No. of parameters	136
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.28
Absolute structure	Flack (1983), 952 Friedel pairs
Absolute structure parameter	0.13 (15)

Computer programs: SMART (Bruker, 2001), SAINT-Plus (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···Cl1	0.93	2.64	3.047 (5)	107.3
C4—H4···Cl2	0.93	2.62	3.036 (4)	107.7
C6—H6···Cl3	0.93	2.62	3.037 (4)	108.1

Acknowledgements

This work was supported by the Key Project of the Natural Science Foundation of Hubei Province, China (2008CDA067) and the Graduate Student Research Funds of South-Central University for Nationalities.

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