N,N,N,N-Tetra-kis(2-chloro-ethyl)-3,4-dimethyl-thio-phene-2,5-dicarboxamide.

In the title compound, C(16)H(22)Cl(4)N(2)O(2)S, the two imide groups adopt a trans arrangement relative to the central thienyl ring, so the four terminal 2-chloro-ethyl arms adopt different orientations. In the crystal, mol-ecules are linked by weak C-H⋯Cl and C-H⋯O hydrogen bonds into a three-dimensional network.

Related literature

For general background to nitro­gen mustard agents as anti­tumor dugs, see: Zhuang et al. (2008 ▶). For the synthesis, see: Luo et al. (2007 ▶). For a related structure, see: Dong et al. (2006 ▶).

Experimental

Crystal data

C16H22Cl4N2O2S

M = 448.22

Monoclinic,

a = 7.9238 (4) Å

b = 21.1712 (11) Å

c = 12.6186 (7) Å

β = 99.2380 (10)°

V = 2089.39 (19) Å3

Z = 4

Mo Kα radiation

μ = 0.68 mm−1

T = 298 K

0.25 × 0.22 × 0.20 mm

Data collection

Bruker APEXII area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.849, T max = 0.876

13412 measured reflections

4008 independent reflections

3342 reflections with I > 2σ(I)

R int = 0.018

Refinement

R[F 2 > 2σ(F 2)] = 0.042

wR(F 2) = 0.126

S = 1.04

4008 reflections

228 parameters

H-atom parameters constrained

Δρmax = 0.88 e Å−3

Δρmin = −0.63 e Å−3

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; 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: n class="Gene">APEX2 (Bruker, 2004 ▶) and publCIF (Westrip, 2009 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809052374/ng2703sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809052374/ng2703Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C16H22Cl4N2O2S	F(000) = 928
Mr = 448.22	Dx = 1.425 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 7657 reflections
a = 7.9238 (4) Å	θ = 1.0–28.3°
b = 21.1712 (11) Å	µ = 0.68 mm−1
c = 12.6186 (7) Å	T = 298 K
β = 99.238 (1)°	Block, white
V = 2089.39 (19) Å3	0.25 × 0.22 × 0.20 mm
Z = 4

Bruker APEXII area-detector diffractometer	4008 independent reflections
Radiation source: fine-focus sealed tube	3342 reflections with I > 2σ(I)
graphite	Rint = 0.018
φ and ω scan	θmax = 26.0°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
Tmin = 0.849, Tmax = 0.876	k = −26→26
13412 measured reflections	l = −15→15

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.126	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.0694P)2 + 1.0128P] where P = (Fo2 + 2Fc2)/3
4008 reflections	(Δ/σ)max < 0.001
228 parameters	Δρmax = 0.88 e Å−3
0 restraints	Δρmin = −0.63 e Å−3

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.

	x	y	z	Uiso*/Ueq
C1	0.6440 (3)	0.16192 (11)	0.56639 (16)	0.0422 (5)
C2	0.4663 (3)	0.10478 (11)	0.41970 (16)	0.0443 (5)
C3	0.7314 (3)	0.11337 (11)	0.52879 (16)	0.0443 (5)
C4	0.6267 (3)	0.07973 (11)	0.44327 (16)	0.0452 (5)
C5	0.9129 (3)	0.09640 (14)	0.5718 (2)	0.0604 (7)
H5A	0.9596	0.1267	0.6251	0.091*
H5B	0.9788	0.0965	0.5142	0.091*
H5C	0.9166	0.0551	0.6034	0.091*
C6	0.6887 (4)	0.02243 (13)	0.3905 (2)	0.0622 (7)
H6A	0.5947	0.0033	0.3441	0.093*
H6B	0.7362	−0.0073	0.4445	0.093*
H6C	0.7749	0.0348	0.3491	0.093*
C7	0.3109 (3)	0.08236 (11)	0.34627 (17)	0.0458 (5)
C8	0.7126 (3)	0.21071 (11)	0.64859 (17)	0.0422 (5)
C9	0.6710 (3)	0.13373 (12)	0.79073 (18)	0.0500 (6)
H9A	0.7502	0.1203	0.8534	0.060*
H9B	0.6717	0.1022	0.7350	0.060*
C10	0.4939 (4)	0.13895 (13)	0.8188 (2)	0.0643 (7)
H10A	0.4128	0.1483	0.7547	0.077*
H10B	0.4904	0.1732	0.8694	0.077*
C11	0.7869 (4)	0.24259 (14)	0.8346 (2)	0.0575 (6)
H11A	0.7587	0.2291	0.9031	0.069*
H11B	0.7269	0.2819	0.8152	0.069*
C12	0.9744 (4)	0.25440 (18)	0.8472 (3)	0.0832 (10)
H12A	1.0070	0.2838	0.9059	0.100*
H12B	1.0009	0.2738	0.7822	0.100*
C13	0.4527 (3)	0.10073 (11)	0.18708 (17)	0.0459 (5)
H13A	0.4924	0.0670	0.1451	0.055*
H13B	0.5478	0.1132	0.2414	0.055*
C14	0.4016 (3)	0.15598 (12)	0.11482 (18)	0.0504 (6)
H14A	0.3109	0.1434	0.0577	0.060*
H14B	0.4985	0.1696	0.0824	0.060*
C15	0.1637 (3)	0.05019 (11)	0.17242 (19)	0.0497 (6)
H15A	0.1273	0.0125	0.2063	0.060*
H15B	0.1937	0.0379	0.1038	0.060*
C16	0.0165 (3)	0.09661 (13)	0.1536 (2)	0.0577 (6)
H16A	0.0514	0.1342	0.1190	0.069*
H16B	−0.0148	0.1089	0.2219	0.069*
Cl1	1.09507 (11)	0.18434 (6)	0.87299 (8)	0.0971 (3)
Cl2	0.43645 (12)	0.06673 (3)	0.87659 (6)	0.0720 (2)
Cl3	−0.16257 (10)	0.06186 (4)	0.07135 (7)	0.0781 (3)
Cl4	0.32971 (10)	0.22004 (3)	0.18815 (6)	0.0651 (2)
N1	0.3156 (2)	0.07637 (9)	0.24030 (14)	0.0420 (4)
N2	0.7258 (2)	0.19471 (9)	0.75320 (14)	0.0434 (4)
O1	0.1805 (3)	0.06964 (11)	0.38336 (14)	0.0699 (6)
O2	0.7529 (3)	0.26329 (8)	0.62021 (14)	0.0593 (5)
S1	0.43739 (8)	0.16811 (3)	0.50083 (4)	0.04896 (18)

	U11	U22	U33	U12	U13	U23
C1	0.0423 (12)	0.0513 (12)	0.0326 (10)	0.0084 (9)	0.0052 (8)	0.0022 (9)
C2	0.0492 (13)	0.0534 (13)	0.0302 (10)	0.0059 (10)	0.0066 (9)	−0.0019 (9)
C3	0.0471 (13)	0.0543 (13)	0.0321 (10)	0.0109 (10)	0.0082 (9)	0.0025 (9)
C4	0.0547 (14)	0.0508 (12)	0.0307 (10)	0.0123 (10)	0.0089 (9)	0.0026 (9)
C5	0.0496 (15)	0.0781 (18)	0.0526 (14)	0.0201 (13)	0.0054 (11)	−0.0018 (13)
C6	0.0777 (19)	0.0630 (16)	0.0451 (13)	0.0261 (14)	0.0073 (12)	−0.0057 (11)
C7	0.0508 (14)	0.0507 (12)	0.0361 (11)	0.0023 (10)	0.0072 (10)	0.0025 (9)
C8	0.0369 (12)	0.0505 (12)	0.0390 (11)	0.0072 (9)	0.0058 (9)	0.0011 (9)
C9	0.0589 (15)	0.0538 (13)	0.0373 (11)	0.0106 (11)	0.0077 (10)	0.0037 (10)
C10	0.0720 (19)	0.0531 (14)	0.0737 (17)	0.0027 (13)	0.0295 (14)	0.0103 (13)
C11	0.0556 (16)	0.0686 (16)	0.0464 (13)	0.0011 (12)	0.0026 (11)	−0.0132 (12)
C12	0.068 (2)	0.096 (2)	0.079 (2)	−0.0103 (17)	−0.0062 (16)	−0.0104 (18)
C13	0.0453 (13)	0.0577 (13)	0.0357 (11)	0.0011 (10)	0.0093 (9)	−0.0033 (9)
C14	0.0542 (15)	0.0603 (14)	0.0376 (11)	−0.0078 (11)	0.0100 (10)	−0.0009 (10)
C15	0.0568 (15)	0.0478 (12)	0.0435 (12)	−0.0091 (11)	0.0049 (10)	−0.0084 (10)
C16	0.0510 (15)	0.0590 (15)	0.0592 (15)	−0.0086 (12)	−0.0024 (11)	−0.0083 (12)
Cl1	0.0548 (5)	0.1416 (9)	0.0898 (6)	0.0198 (5)	−0.0041 (4)	0.0276 (6)
Cl2	0.1030 (6)	0.0533 (4)	0.0654 (4)	−0.0134 (3)	0.0309 (4)	−0.0015 (3)
Cl3	0.0515 (4)	0.1027 (6)	0.0773 (5)	−0.0200 (4)	0.0019 (3)	−0.0212 (4)
Cl4	0.0750 (5)	0.0475 (3)	0.0758 (5)	−0.0069 (3)	0.0213 (4)	−0.0027 (3)
N1	0.0468 (11)	0.0451 (10)	0.0340 (9)	−0.0025 (8)	0.0056 (8)	−0.0029 (7)
N2	0.0432 (11)	0.0517 (10)	0.0346 (9)	0.0023 (8)	0.0037 (7)	−0.0030 (8)
O1	0.0591 (12)	0.1096 (17)	0.0431 (9)	−0.0159 (11)	0.0148 (8)	0.0033 (10)
O2	0.0674 (12)	0.0544 (10)	0.0566 (10)	−0.0052 (8)	0.0112 (9)	0.0066 (8)
S1	0.0447 (3)	0.0604 (4)	0.0402 (3)	0.0135 (3)	0.0020 (2)	−0.0095 (2)

C1—C3	1.366 (3)	C10—H10A	0.9700
C1—C8	1.502 (3)	C10—H10B	0.9700
C1—S1	1.717 (2)	C11—N2	1.468 (3)
C2—C4	1.365 (3)	C11—C12	1.490 (4)
C2—C7	1.494 (3)	C11—H11A	0.9700
C2—S1	1.724 (2)	C11—H11B	0.9700
C3—C4	1.440 (3)	C12—Cl1	1.766 (4)
C3—C5	1.497 (3)	C12—H12A	0.9700
C4—C6	1.504 (3)	C12—H12B	0.9700
C5—H5A	0.9600	C13—N1	1.460 (3)
C5—H5B	0.9600	C13—C14	1.498 (3)
C5—H5C	0.9600	C13—H13A	0.9700
C6—H6A	0.9600	C13—H13B	0.9700
C6—H6B	0.9600	C14—Cl4	1.786 (3)
C6—H6C	0.9600	C14—H14A	0.9700
C7—O1	1.231 (3)	C14—H14B	0.9700
C7—N1	1.350 (3)	C15—N1	1.469 (3)
C8—O2	1.227 (3)	C15—C16	1.514 (4)
C8—N2	1.350 (3)	C15—H15A	0.9700
C9—N2	1.465 (3)	C15—H15B	0.9700
C9—C10	1.505 (4)	C16—Cl3	1.777 (3)
C9—H9A	0.9700	C16—H16A	0.9700
C9—H9B	0.9700	C16—H16B	0.9700
C10—Cl2	1.784 (3)
C3—C1—C8	127.6 (2)	N2—C11—H11A	108.8
C3—C1—S1	112.81 (17)	C12—C11—H11A	108.8
C8—C1—S1	119.44 (16)	N2—C11—H11B	108.8
C4—C2—C7	131.1 (2)	C12—C11—H11B	108.8
C4—C2—S1	112.36 (17)	H11A—C11—H11B	107.7
C7—C2—S1	116.12 (17)	C11—C12—Cl1	112.3 (3)
C1—C3—C4	111.6 (2)	C11—C12—H12A	109.1
C1—C3—C5	124.5 (2)	Cl1—C12—H12A	109.1
C4—C3—C5	123.9 (2)	C11—C12—H12B	109.1
C2—C4—C3	112.1 (2)	Cl1—C12—H12B	109.1
C2—C4—C6	125.2 (2)	H12A—C12—H12B	107.9
C3—C4—C6	122.7 (2)	N1—C13—C14	114.0 (2)
C3—C5—H5A	109.5	N1—C13—H13A	108.7
C3—C5—H5B	109.5	C14—C13—H13A	108.7
H5A—C5—H5B	109.5	N1—C13—H13B	108.7
C3—C5—H5C	109.5	C14—C13—H13B	108.7
H5A—C5—H5C	109.5	H13A—C13—H13B	107.6
H5B—C5—H5C	109.5	C13—C14—Cl4	110.80 (15)
C4—C6—H6A	109.5	C13—C14—H14A	109.5
C4—C6—H6B	109.5	Cl4—C14—H14A	109.5
H6A—C6—H6B	109.5	C13—C14—H14B	109.5
C4—C6—H6C	109.5	Cl4—C14—H14B	109.5
H6A—C6—H6C	109.5	H14A—C14—H14B	108.1
H6B—C6—H6C	109.5	N1—C15—C16	112.64 (19)
O1—C7—N1	121.0 (2)	N1—C15—H15A	109.1
O1—C7—C2	119.5 (2)	C16—C15—H15A	109.1
N1—C7—C2	119.6 (2)	N1—C15—H15B	109.1
O2—C8—N2	122.0 (2)	C16—C15—H15B	109.1
O2—C8—C1	120.3 (2)	H15A—C15—H15B	107.8
N2—C8—C1	117.7 (2)	C15—C16—Cl3	110.22 (18)
N2—C9—C10	110.34 (19)	C15—C16—H16A	109.6
N2—C9—H9A	109.6	Cl3—C16—H16A	109.6
C10—C9—H9A	109.6	C15—C16—H16B	109.6
N2—C9—H9B	109.6	Cl3—C16—H16B	109.6
C10—C9—H9B	109.6	H16A—C16—H16B	108.1
H9A—C9—H9B	108.1	C7—N1—C13	124.28 (19)
C9—C10—Cl2	110.00 (19)	C7—N1—C15	117.58 (19)
C9—C10—H10A	109.7	C13—N1—C15	117.75 (17)
Cl2—C10—H10A	109.7	C8—N2—C9	123.80 (19)
C9—C10—H10B	109.7	C8—N2—C11	118.4 (2)
Cl2—C10—H10B	109.7	C9—N2—C11	117.63 (19)
H10A—C10—H10B	108.2	C1—S1—C2	91.11 (11)
N2—C11—C12	113.7 (2)

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14B···O2i	0.97	2.45	3.257 (3)	141
C14—H14A···Cl1ii	0.97	2.80	3.632 (3)	145
C6—H6B···O1iii	0.96	2.54	3.474 (3)	166
C5—H5B···O1iv	0.96	2.54	3.477 (3)	165

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C14—H14B⋯O2i	0.97	2.45	3.257 (3)	141
C14—H14A⋯Cl1ii	0.97	2.80	3.632 (3)	145
C6—H6B⋯O1iii	0.96	2.54	3.474 (3)	166
C5—H5B⋯O1iv	0.96	2.54	3.477 (3)	165

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .