2-Chloro-N-(4-chloro-3-iodo­phen­yl)-4-(methyl­sulfon­yl)benzamide

Wang, D.-C.; Song, H.; Yang, C.; Huang, W.-C.; Yao, S.

doi:10.1107/S1600536811053633

organic compounds

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ISSN: 2056-9890

Volume 68| Part 1| January 2012| Page o189

doi:10.1107/S1600536811053633

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2-Chloro-N-(4-chloro-3-iodophenyl)-4-(methylsulfonyl)benzamide

Dao-Cai Wang,^a Hang Song,^a Chang Yang,^a Wen-Cai Huang ^a and Shun Yao ^a ^*

^aDepartment of Pharmaceutical and Biological Engineering, College of Chemical Engineering, Sichuan University, Chengdu 610065, People's Republic of China
^*Correspondence e-mail: cusack@scu.edu.cn

(Received 10 December 2011; accepted 13 December 2011; online 21 December 2011)

In the title compound, C₁₄H₁₀Cl₂INO₃S, the dihedral angle between the benzene rings is 52.13 (10)°. In the crystal, the components are linked by pairs of N—H⋯O(sulfonyl) hydrogen bonds into centrosymmetric dimers.

Related literature

For background to benzamides, see: Castanedo et al. (2010 ); Tremblay et al. (2010 ); Mahindroo et al. (2010 ). For the preparation of the title compound, see: Robarge et al. (2009 ).

Experimental

Crystal data

C₁₄H₁₀Cl₂INO₃S
M_r = 470.09
Triclinic, $[P \overline 1]$
a = 8.8694 (6) Å
b = 10.3837 (8) Å
c = 10.4288 (5) Å
α = 103.862 (5)°
β = 96.452 (5)°
γ = 114.949 (7)°
V = 820.25 (9) Å³
Z = 2
Mo Kα radiation
μ = 2.41 mm⁻¹
T = 290 K
0.30 × 0.30 × 0.25 mm

Data collection

Oxford Diffraction Xcalibur Eos diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2006 $[Oxford Diffraction (2006). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.887, T_max = 1.000
6770 measured reflections
3323 independent reflections
2957 reflections with I > 2σ(I)
R_int = 0.020

Refinement

R[F² > 2σ(F²)] = 0.028
wR(F²) = 0.067
S = 1.07
3323 reflections
200 parameters
H-atom parameters constrained
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.55 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2ⁱ	0.86	2.15	2.991 (3)	167
Symmetry code: (i) -x, -y+1, -z+3.

Data collection: CrysAlis PRO (Oxford Diffraction, 2006 $[Oxford Diffraction (2006). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009 ) and Mercury (Macrae et al., 2006 ); software used to prepare material for publication: OLEX2.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811053633/tk5034sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811053633/tk5034Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811053633/tk5034Isup3.cml

checkCIF report

Comment top

The benzamide moiety is the constituent of many biologically significant compounds including anticancer compounds (Castanedo et al., 2010; Tremblay et al., 2010; Mahindroo et al., 2010). The title compound is one of the key intermediates in our synthetic investigations of anticancer drugs. In this paper, we synthesized the title compound and report its crystal structure, Fig. 1. The dihedral angle between the two benzene rings is 52.13 (10)°. In the crystal, the molecules are connected via intermolecular N—H···O hydrogen bonds to form a centrosymmetric dimer, in which the amide H atom acts as a donor and the sulfonyl-O atom act as an acceptor, Table 1.

Related literature top

For background to benzamides, see: Castanedo et al. (2010); Tremblay et al. (2010); Mahindroo et al. (2010). For the preparation of the title compound, see: Robarge et al. (2009).

Experimental top

The title compound was prepared by a method similar to that of Robarge et al. (2009). Crystals were obtained by slow evaporation from its methanol-acetic acid (5:2) solution.

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2006); cell refinement: CrysAlis PRO (Oxford Diffraction, 2006); data reduction: CrysAlis PRO (Oxford Diffraction, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009) and Mercury (Macrae et al., 2006); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Figures top

Fig. 1. The molecular structure of the title compound, with displacement ellipsoids drawn at the 30% probability level.

2-Chloro-N-(4-chloro-3-iodophenyl)-4-(methylsulfonyl)benzamide top

Crystal data top

C₁₄H₁₀Cl₂INO₃S	Z = 2
M_r = 470.09	F(000) = 456
Triclinic, P1	D_x = 1.903 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.7107 Å
a = 8.8694 (6) Å	Cell parameters from 2872 reflections
b = 10.3837 (8) Å	θ = 2.9–26.3°
c = 10.4288 (5) Å	µ = 2.41 mm⁻¹
α = 103.862 (5)°	T = 290 K
β = 96.452 (5)°	Block, colourless
γ = 114.949 (7)°	0.30 × 0.30 × 0.25 mm
V = 820.25 (9) Å³

Data collection top

Oxford Diffraction Xcalibur Eos diffractometer	3323 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2957 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
Detector resolution: 16.0874 pixels mm^-1	θ_max = 26.4°, θ_min = 2.9°
ω scans	h = −11→11
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2006)	k = −12→12
T_min = 0.887, T_max = 1.000	l = −12→13
6770 measured reflections

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)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.067	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0257P)² + 0.4057P] where P = (F_o² + 2F_c²)/3
3323 reflections	(Δ/σ)_max = 0.001
200 parameters	Δρ_max = 0.43 e Å⁻³
0 restraints	Δρ_min = −0.55 e Å⁻³

Crystal data top

C₁₄H₁₀Cl₂INO₃S	γ = 114.949 (7)°
M_r = 470.09	V = 820.25 (9) Å³
Triclinic, P1	Z = 2
a = 8.8694 (6) Å	Mo Kα radiation
b = 10.3837 (8) Å	µ = 2.41 mm⁻¹
c = 10.4288 (5) Å	T = 290 K
α = 103.862 (5)°	0.30 × 0.30 × 0.25 mm
β = 96.452 (5)°

Data collection top

Oxford Diffraction Xcalibur Eos diffractometer	3323 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2006)	2957 reflections with I > 2σ(I)
T_min = 0.887, T_max = 1.000	R_int = 0.020
6770 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.028	0 restraints
wR(F²) = 0.067	H-atom parameters constrained
S = 1.07	Δρ_max = 0.43 e Å⁻³
3323 reflections	Δρ_min = −0.55 e Å⁻³
200 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
I1	0.61447 (3)	0.68561 (3)	0.77089 (2)	0.04648 (9)
Cl1	0.29725 (14)	0.32782 (12)	0.59427 (9)	0.0627 (3)
Cl2	0.29306 (15)	0.99624 (11)	1.34350 (10)	0.0603 (3)
S2	0.11153 (10)	0.80692 (9)	1.76536 (8)	0.03759 (19)
O1	0.4697 (3)	0.8156 (3)	1.2278 (2)	0.0620 (8)
O2	0.0367 (3)	0.6656 (3)	1.7893 (2)	0.0536 (7)
O3	0.0121 (4)	0.8840 (4)	1.7587 (3)	0.0676 (8)
N1	0.2439 (3)	0.5816 (3)	1.1495 (2)	0.0344 (6)
H1	0.1576	0.5214	1.1721	0.041*
C1	0.4083 (4)	0.5502 (4)	0.8367 (3)	0.0328 (7)
C2	0.2898 (4)	0.4068 (4)	0.7585 (3)	0.0390 (8)
C3	0.1603 (4)	0.3219 (4)	0.8106 (3)	0.0478 (9)
H3	0.0821	0.2240	0.7588	0.057*
C4	0.1467 (4)	0.3817 (4)	0.9391 (3)	0.0412 (8)
H4	0.0578	0.3246	0.9729	0.049*
C5	0.2643 (4)	0.5261 (3)	1.0182 (3)	0.0303 (6)
C6	0.3978 (4)	0.6101 (3)	0.9675 (3)	0.0326 (7)
H6	0.4798	0.7061	1.0210	0.039*
C7	0.3431 (4)	0.7173 (4)	1.2433 (3)	0.0370 (7)
C8	0.2843 (4)	0.7407 (3)	1.3728 (3)	0.0315 (7)
C9	0.2612 (4)	0.8646 (3)	1.4266 (3)	0.0346 (7)
C10	0.2081 (4)	0.8860 (3)	1.5459 (3)	0.0346 (7)
H10	0.1917	0.9691	1.5806	0.042*
C11	0.1800 (3)	0.7808 (3)	1.6127 (3)	0.0307 (6)
C12	0.2046 (4)	0.6571 (3)	1.5633 (3)	0.0332 (7)
H12	0.1865	0.5880	1.6099	0.040*
C13	0.2566 (4)	0.6382 (4)	1.4433 (3)	0.0336 (7)
H13	0.2734	0.5553	1.4090	0.040*
C14	0.3027 (5)	0.9225 (5)	1.8925 (3)	0.0601 (11)
H14A	0.2762	0.9474	1.9789	0.090*
H14B	0.3667	1.0126	1.8717	0.090*
H14C	0.3697	0.8705	1.8963	0.090*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I1	0.05672 (15)	0.05233 (16)	0.04928 (15)	0.02995 (12)	0.03477 (12)	0.02942 (12)
Cl1	0.0823 (7)	0.0685 (7)	0.0327 (4)	0.0349 (6)	0.0224 (5)	0.0051 (4)
Cl2	0.0951 (7)	0.0446 (5)	0.0564 (5)	0.0341 (5)	0.0333 (5)	0.0322 (4)
S2	0.0338 (4)	0.0384 (4)	0.0326 (4)	0.0090 (3)	0.0162 (3)	0.0088 (3)
O1	0.0644 (16)	0.0378 (14)	0.0517 (15)	−0.0044 (13)	0.0346 (13)	0.0034 (12)
O2	0.0539 (14)	0.0436 (15)	0.0454 (13)	0.0031 (12)	0.0266 (12)	0.0140 (11)
O3	0.0703 (18)	0.094 (2)	0.0684 (18)	0.0555 (18)	0.0411 (15)	0.0315 (16)
N1	0.0369 (13)	0.0297 (14)	0.0319 (13)	0.0082 (11)	0.0193 (11)	0.0108 (11)
C1	0.0395 (16)	0.0390 (18)	0.0308 (15)	0.0225 (14)	0.0159 (13)	0.0181 (14)
C2	0.0490 (18)	0.048 (2)	0.0240 (15)	0.0270 (17)	0.0120 (14)	0.0086 (14)
C3	0.0491 (19)	0.040 (2)	0.0351 (18)	0.0103 (17)	0.0068 (15)	0.0020 (15)
C4	0.0386 (16)	0.0398 (19)	0.0350 (17)	0.0075 (15)	0.0120 (14)	0.0134 (14)
C5	0.0358 (15)	0.0330 (16)	0.0258 (14)	0.0157 (13)	0.0129 (12)	0.0134 (12)
C6	0.0356 (15)	0.0292 (16)	0.0325 (15)	0.0128 (13)	0.0116 (13)	0.0117 (13)
C7	0.0403 (17)	0.0300 (17)	0.0345 (16)	0.0089 (14)	0.0156 (14)	0.0107 (14)
C8	0.0283 (14)	0.0296 (16)	0.0300 (15)	0.0065 (13)	0.0098 (12)	0.0104 (13)
C9	0.0421 (16)	0.0282 (16)	0.0324 (15)	0.0126 (14)	0.0123 (14)	0.0135 (13)
C10	0.0367 (16)	0.0297 (16)	0.0345 (16)	0.0132 (14)	0.0105 (13)	0.0083 (13)
C11	0.0267 (13)	0.0341 (17)	0.0260 (14)	0.0092 (13)	0.0078 (12)	0.0092 (12)
C12	0.0357 (15)	0.0314 (17)	0.0337 (15)	0.0135 (13)	0.0122 (13)	0.0147 (13)
C13	0.0390 (16)	0.0320 (17)	0.0332 (16)	0.0178 (14)	0.0142 (13)	0.0112 (13)
C14	0.056 (2)	0.051 (2)	0.0362 (19)	−0.0018 (19)	0.0054 (17)	0.0050 (17)

Geometric parameters (Å, º) top

I1—C1	2.090 (3)	C4—C5	1.382 (4)
Cl1—C2	1.735 (3)	C5—C6	1.391 (4)
Cl2—C9	1.731 (3)	C6—H6	0.9300
S2—O2	1.431 (3)	C7—C8	1.504 (4)
S2—O3	1.426 (3)	C8—C9	1.384 (4)
S2—C11	1.769 (3)	C8—C13	1.388 (4)
S2—C14	1.757 (4)	C9—C10	1.381 (4)
O1—C7	1.218 (4)	C10—H10	0.9300
N1—H1	0.8600	C10—C11	1.383 (4)
N1—C5	1.416 (4)	C11—C12	1.380 (4)
N1—C7	1.348 (4)	C12—H12	0.9300
C1—C2	1.375 (5)	C12—C13	1.381 (4)
C1—C6	1.388 (4)	C13—H13	0.9300
C2—C3	1.381 (5)	C14—H14A	0.9600
C3—H3	0.9300	C14—H14B	0.9600
C3—C4	1.378 (4)	C14—H14C	0.9600
C4—H4	0.9300

O2—S2—C11	107.98 (15)	O1—C7—N1	124.5 (3)
O2—S2—C14	106.74 (19)	O1—C7—C8	121.2 (3)
O3—S2—O2	118.76 (18)	N1—C7—C8	114.3 (2)
O3—S2—C11	108.53 (16)	C9—C8—C7	121.8 (3)
O3—S2—C14	109.7 (2)	C9—C8—C13	118.5 (3)
C14—S2—C11	104.21 (16)	C13—C8—C7	119.7 (3)
C5—N1—H1	116.0	C8—C9—Cl2	120.7 (2)
C7—N1—H1	116.0	C10—C9—Cl2	117.7 (3)
C7—N1—C5	128.0 (2)	C10—C9—C8	121.6 (3)
C2—C1—I1	123.1 (2)	C9—C10—H10	120.8
C2—C1—C6	120.3 (3)	C9—C10—C11	118.4 (3)
C6—C1—I1	116.6 (2)	C11—C10—H10	120.8
C1—C2—Cl1	121.8 (2)	C10—C11—S2	118.7 (2)
C1—C2—C3	119.8 (3)	C12—C11—S2	119.6 (2)
C3—C2—Cl1	118.3 (3)	C12—C11—C10	121.7 (3)
C2—C3—H3	119.9	C11—C12—H12	120.7
C4—C3—C2	120.3 (3)	C11—C12—C13	118.6 (3)
C4—C3—H3	119.9	C13—C12—H12	120.7
C3—C4—H4	119.8	C8—C13—H13	119.4
C3—C4—C5	120.4 (3)	C12—C13—C8	121.3 (3)
C5—C4—H4	119.8	C12—C13—H13	119.4
C4—C5—N1	117.9 (3)	S2—C14—H14A	109.5
C4—C5—C6	119.4 (3)	S2—C14—H14B	109.5
C6—C5—N1	122.7 (3)	S2—C14—H14C	109.5
C1—C6—C5	119.8 (3)	H14A—C14—H14B	109.5
C1—C6—H6	120.1	H14A—C14—H14C	109.5
C5—C6—H6	120.1	H14B—C14—H14C	109.5

I1—C1—C2—Cl1	−2.5 (4)	C4—C5—C6—C1	2.2 (5)
I1—C1—C2—C3	177.7 (3)	C5—N1—C7—O1	0.1 (6)
I1—C1—C6—C5	−179.8 (2)	C5—N1—C7—C8	179.6 (3)
Cl1—C2—C3—C4	−178.1 (3)	C6—C1—C2—Cl1	179.6 (2)
Cl2—C9—C10—C11	179.2 (2)	C6—C1—C2—C3	−0.2 (5)
S2—C11—C12—C13	179.4 (2)	C7—N1—C5—C4	179.5 (3)
O1—C7—C8—C9	51.1 (5)	C7—N1—C5—C6	0.2 (5)
O1—C7—C8—C13	−127.0 (4)	C7—C8—C9—Cl2	2.0 (4)
O2—S2—C11—C10	160.6 (2)	C7—C8—C9—C10	−179.6 (3)
O2—S2—C11—C12	−19.6 (3)	C7—C8—C13—C12	179.2 (3)
O3—S2—C11—C10	30.7 (3)	C8—C9—C10—C11	0.8 (5)
O3—S2—C11—C12	−149.6 (3)	C9—C8—C13—C12	1.0 (4)
N1—C5—C6—C1	−178.5 (3)	C9—C10—C11—S2	−179.9 (2)
N1—C7—C8—C9	−128.4 (3)	C9—C10—C11—C12	0.4 (4)
N1—C7—C8—C13	53.5 (4)	C10—C11—C12—C13	−0.8 (4)
C1—C2—C3—C4	1.8 (6)	C11—C12—C13—C8	0.1 (4)
C2—C1—C6—C5	−1.7 (5)	C13—C8—C9—Cl2	−179.8 (2)
C2—C3—C4—C5	−1.3 (6)	C13—C8—C9—C10	−1.5 (4)
C3—C4—C5—N1	−180.0 (3)	C14—S2—C11—C10	−86.2 (3)
C3—C4—C5—C6	−0.7 (5)	C14—S2—C11—C12	93.6 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2ⁱ	0.86	2.15	2.991 (3)	167

Symmetry code: (i) −x, −y+1, −z+3.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₀Cl₂INO₃S
M_r	470.09
Crystal system, space group	Triclinic, P1
Temperature (K)	290
a, b, c (Å)	8.8694 (6), 10.3837 (8), 10.4288 (5)
α, β, γ (°)	103.862 (5), 96.452 (5), 114.949 (7)
V (Å³)	820.25 (9)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	2.41
Crystal size (mm)	0.30 × 0.30 × 0.25

Data collection
Diffractometer	Oxford Diffraction Xcalibur Eos diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2006)
T_min, T_max	0.887, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	6770, 3323, 2957
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.067, 1.07
No. of reflections	3323
No. of parameters	200
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.43, −0.55

Computer programs: CrysAlis PRO (Oxford Diffraction, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), OLEX2 (Dolomanov et al., 2009) and Mercury (Macrae et al., 2006), OLEX2 (Dolomanov et al., 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2ⁱ	0.86	2.15	2.991 (3)	167

Symmetry code: (i) −x, −y+1, −z+3.

Acknowledgements

We thank the Analytical and Testing Center of Sichuan University for the X-ray measurements.

References

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