5-Chloro-1-[(E)-3-(dimethyl-amino)-acrylo-yl]-3-methyl-1H-benzimidazol-2(3H)-one-6-chloro-1-[(E)-3-(dimethyl-amino)-acrylo-yl]-3-methyl-1H-benzimid-azol-2(3H)-one (4/1).

In the reaction of 7-chloro-1,5-benzodiazepine-2,4-dione with N,N-dimethyl-formamide/dimethyl-acetal, the diazepine seven-membered ring undergoes a contraction to form the five-membered ring. The reaction yields two isomers the title compound, C(13)H(14)ClN(3)O(2); the major component has the chlorine-atom substituent in the 5-position of the benzimidazolone ring and the minor component has the chlorine atom in the 6-position. The two isomers form a disordered co-crystal, the chloro-methyl-benzimidazolone portion of both components are disordered with respect to each other in a 4:1 ratio [the refined ratio is 0.816 (5):0.184 (5)]; the dimethyl-amino-cryloyl substitutent is ordered. The double bond of the dimethyl-amino-acryloyl substituent has an E configuration.

Related literature

For the structure of the 7-chloro-1,5-benzodiazepine-2,4-dione reactant, see: Mondieig et al. (2007 ▶).

Experimental

Crystal data

C13H14ClN3O2

M = 279.72

Orthorhombic,

a = 7.3145 (2) Å

b = 14.2903 (3) Å

c = 25.1512 (6) Å

V = 2628.96 (11) Å3

Z = 8

Mo Kα radiation

μ = 0.29 mm−1

T = 293 K

0.30 × 0.25 × 0.05 mm

Data collection

Bruker APEXII diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.918, T max = 0.986

32296 measured reflections

2684 independent reflections

2103 reflections with I > 2σ(I)

R int = 0.053

Refinement

R[F 2 > 2σ(F 2)] = 0.067

wR(F 2) = 0.204

S = 1.15

2684 reflections

189 parameters

82 restraints

H-atom parameters constrained

Δρmax = 0.35 e Å−3

Δρmin = −0.45 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: X-SEED (Barbour, 2001 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811024706/xu5248sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811024706/xu5248Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811024706/xu5248Isup3.cml

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

C13H14ClN3O2	F(000) = 1168
Mr = 279.72	Dx = 1.413 Mg m−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 5721 reflections
a = 7.3145 (2) Å	θ = 2.9–26.2°
b = 14.2903 (3) Å	µ = 0.29 mm−1
c = 25.1512 (6) Å	T = 293 K
V = 2628.96 (11) Å3	Plate, brown
Z = 8	0.30 × 0.25 × 0.05 mm

Bruker APEXII diffractometer	2684 independent reflections
Radiation source: fine-focus sealed tube	2103 reflections with I > 2σ(I)
graphite	Rint = 0.053
φ and ω scans	θmax = 26.4°, θmin = 4.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→9
Tmin = 0.918, Tmax = 0.986	k = −14→17
32296 measured reflections	l = −31→31

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) = 0.204	H-atom parameters constrained
S = 1.15	w = 1/[σ2(Fo2) + (0.092P)2 + 3.0624P] where P = (Fo2 + 2Fc2)/3
2684 reflections	(Δ/σ)max = 0.001
189 parameters	Δρmax = 0.35 e Å−3
82 restraints	Δρmin = −0.45 e Å−3

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cl1	0.52676 (17)	0.77941 (8)	0.11089 (4)	0.0493 (4)	0.816 (5)
O1	0.5389 (12)	0.7581 (9)	0.4050 (3)	0.0492 (11)	0.816 (5)
N1	0.5117 (6)	0.8034 (3)	0.31659 (15)	0.0341 (8)	0.816 (5)
N2	0.6106 (9)	0.6599 (2)	0.33224 (15)	0.0335 (8)	0.816 (5)
C1	0.6049 (4)	0.67203 (15)	0.27723 (8)	0.0252 (8)	0.816 (5)
C2	0.6483 (5)	0.61571 (14)	0.23398 (10)	0.0316 (8)	0.816 (5)
H2	0.6929	0.5555	0.2394	0.038*	0.816 (5)
C3	0.6252 (5)	0.64935 (17)	0.18256 (9)	0.0372 (9)	0.816 (5)
H3	0.6543	0.6117	0.1536	0.045*	0.816 (5)
C4	0.5586 (6)	0.73931 (19)	0.17439 (9)	0.0376 (10)	0.816 (5)
C5	0.5152 (5)	0.79563 (15)	0.21764 (11)	0.0349 (10)	0.816 (5)
H5	0.4706	0.8558	0.2122	0.042*	0.816 (5)
C6	0.5383 (4)	0.76199 (15)	0.26906 (10)	0.0286 (8)	0.816 (5)
C7	0.4443 (8)	0.8980 (3)	0.32573 (18)	0.0418 (12)	0.816 (5)
H7A	0.3302	0.9063	0.3074	0.063*	0.816 (5)
H7B	0.5318	0.9424	0.3126	0.063*	0.816 (5)
H7C	0.4264	0.9076	0.3631	0.063*	0.816 (5)
C8	0.5526 (9)	0.7426 (3)	0.3577 (2)	0.0367 (10)	0.816 (5)
Cl1'	0.6682 (7)	0.6174 (3)	0.13514 (17)	0.0493 (4)	0.184
O1'	0.532 (5)	0.766 (5)	0.4135 (13)	0.0492 (11)	0.184
N1'	0.500 (3)	0.8135 (16)	0.3296 (7)	0.0341 (8)	0.184
N2'	0.609 (4)	0.6657 (9)	0.3400 (7)	0.0335 (8)	0.184
C1'	0.588 (2)	0.6955 (10)	0.2875 (4)	0.0252 (8)	0.184
C2'	0.632 (3)	0.6387 (9)	0.2445 (6)	0.0316 (8)	0.184
H2'	0.6760	0.5785	0.2502	0.038*	0.184 (5)
C3'	0.609 (3)	0.6718 (12)	0.1930 (5)	0.0372 (9)	0.184
C4'	0.542 (3)	0.7617 (13)	0.1845 (5)	0.0376 (10)	0.184
H4'	0.5271	0.7839	0.1500	0.045*	0.184 (5)
C5'	0.499 (3)	0.8186 (9)	0.2275 (7)	0.0349 (10)	0.184
H5'	0.4549	0.8787	0.2218	0.042*	0.184 (5)
C6'	0.5221 (18)	0.7855 (9)	0.2790 (5)	0.0286 (8)	0.184
C7'	0.431 (4)	0.9061 (17)	0.3435 (11)	0.0418 (12)	0.184
H7'A	0.4976	0.9528	0.3241	0.063*	0.184 (5)
H7'B	0.4466	0.9163	0.3810	0.063*	0.184 (5)
H7'C	0.3036	0.9100	0.3347	0.063*	0.184 (5)
C8'	0.548 (3)	0.7466 (13)	0.3669 (11)	0.0367 (10)	0.184
O2	0.6605 (4)	0.50518 (15)	0.32831 (9)	0.0496 (7)
N3	0.7521 (4)	0.4747 (2)	0.48942 (11)	0.0491 (8)
C9	0.6537 (4)	0.5735 (2)	0.35780 (13)	0.0369 (8)
C10	0.6877 (4)	0.5726 (2)	0.41357 (13)	0.0385 (8)
H10	0.6848	0.6278	0.4331	0.046*
C11	0.7244 (5)	0.4893 (2)	0.43769 (13)	0.0419 (8)
H11	0.7309	0.4371	0.4157	0.050*
C12	0.7832 (7)	0.3809 (3)	0.51016 (17)	0.0679 (13)
H12A	0.7952	0.3377	0.4811	0.102*
H12B	0.6816	0.3627	0.5320	0.102*
H12C	0.8931	0.3803	0.5310	0.102*
C13	0.7423 (6)	0.5493 (3)	0.52792 (14)	0.0616 (11)
H13A	0.6539	0.5948	0.5165	0.092*
H13B	0.8599	0.5786	0.5311	0.092*
H13C	0.7064	0.5243	0.5618	0.092*

	U11	U22	U33	U12	U13	U23
Cl1	0.0640 (7)	0.0447 (6)	0.0391 (6)	−0.0008 (5)	0.0014 (5)	0.0036 (4)
O1	0.0615 (18)	0.041 (3)	0.045 (3)	0.0082 (17)	0.0003 (18)	−0.012 (2)
N1	0.0370 (16)	0.0230 (17)	0.042 (2)	0.0014 (12)	0.0022 (15)	−0.0035 (15)
N2	0.0343 (14)	0.0272 (13)	0.0391 (18)	−0.0006 (12)	−0.0039 (15)	−0.0031 (12)
C1	0.0230 (15)	0.0169 (17)	0.0357 (18)	−0.0020 (14)	0.0010 (14)	−0.0065 (14)
C2	0.0322 (18)	0.0241 (19)	0.039 (2)	−0.0012 (16)	−0.0007 (16)	−0.0060 (14)
C3	0.038 (2)	0.036 (2)	0.038 (2)	−0.0052 (18)	0.0046 (17)	−0.0077 (16)
C4	0.037 (2)	0.038 (3)	0.038 (2)	−0.0075 (19)	0.0018 (17)	−0.0005 (16)
C5	0.0281 (18)	0.0218 (19)	0.055 (3)	−0.0007 (16)	−0.0005 (17)	0.0045 (18)
C6	0.0223 (16)	0.016 (2)	0.047 (2)	−0.0009 (15)	0.0009 (14)	−0.0027 (14)
C7	0.049 (2)	0.0284 (18)	0.048 (3)	0.0036 (16)	0.003 (2)	−0.008 (2)
C8	0.0359 (18)	0.0306 (16)	0.044 (3)	0.0020 (14)	−0.0027 (18)	−0.0055 (16)
Cl1'	0.0640 (7)	0.0447 (6)	0.0391 (6)	−0.0008 (5)	0.0014 (5)	0.0036 (4)
O1'	0.0615 (18)	0.041 (3)	0.045 (3)	0.0082 (17)	0.0003 (18)	−0.012 (2)
N1'	0.0370 (16)	0.0230 (17)	0.042 (2)	0.0014 (12)	0.0022 (15)	−0.0035 (15)
N2'	0.0343 (14)	0.0272 (13)	0.0391 (18)	−0.0006 (12)	−0.0039 (15)	−0.0031 (12)
C1'	0.0230 (15)	0.0169 (17)	0.0357 (18)	−0.0020 (14)	0.0010 (14)	−0.0065 (14)
C2'	0.0322 (18)	0.0241 (19)	0.039 (2)	−0.0012 (16)	−0.0007 (16)	−0.0060 (14)
C3'	0.038 (2)	0.036 (2)	0.038 (2)	−0.0052 (18)	0.0046 (17)	−0.0077 (16)
C4'	0.037 (2)	0.038 (3)	0.038 (2)	−0.0075 (19)	0.0018 (17)	−0.0005 (16)
C5'	0.0281 (18)	0.0218 (19)	0.055 (3)	−0.0007 (16)	−0.0005 (17)	0.0045 (18)
C6'	0.0223 (16)	0.016 (2)	0.047 (2)	−0.0009 (15)	0.0009 (14)	−0.0027 (14)
C7'	0.049 (2)	0.0284 (18)	0.048 (3)	0.0036 (16)	0.003 (2)	−0.008 (2)
C8'	0.0359 (18)	0.0306 (16)	0.044 (3)	0.0020 (14)	−0.0027 (18)	−0.0055 (16)
O2	0.0705 (18)	0.0299 (12)	0.0483 (14)	0.0076 (12)	−0.0090 (12)	−0.0024 (10)
N3	0.0491 (18)	0.0548 (19)	0.0433 (16)	0.0079 (15)	0.0003 (14)	0.0081 (13)
C9	0.0320 (17)	0.0316 (16)	0.0470 (18)	0.0005 (13)	−0.0020 (13)	0.0020 (14)
C10	0.0364 (17)	0.0352 (16)	0.0439 (17)	0.0012 (14)	−0.0004 (14)	−0.0024 (14)
C11	0.0386 (19)	0.0417 (18)	0.0453 (18)	0.0013 (15)	−0.0004 (14)	0.0015 (14)
C12	0.071 (3)	0.074 (3)	0.059 (2)	0.018 (2)	0.011 (2)	0.029 (2)
C13	0.063 (3)	0.080 (3)	0.0422 (19)	−0.003 (2)	−0.0037 (19)	−0.0049 (19)

Cl1—C4	1.713 (2)	N2'—C9	1.430 (9)
O1—C8	1.213 (5)	C1'—C2'	1.3900
N1—C6	1.348 (3)	C1'—C6'	1.3900
N1—C8	1.383 (5)	C2'—C3'	1.3900
N1—C7	1.458 (5)	C2'—H2'	0.9300
N2—C1	1.395 (3)	C3'—C4'	1.3900
N2—C8	1.409 (4)	C4'—C5'	1.3900
N2—C9	1.427 (4)	C4'—H4'	0.9300
C1—C2	1.3900	C5'—C6'	1.3900
C1—C6	1.3900	C5'—H5'	0.9300
C2—C3	1.3900	C7'—H7'A	0.9600
C2—H2	0.9300	C7'—H7'B	0.9600
C3—C4	1.3900	C7'—H7'C	0.9600
C3—H3	0.9300	O2—C9	1.227 (4)
C4—C5	1.3900	N3—C11	1.333 (4)
C5—C6	1.3900	N3—C13	1.442 (5)
C5—H5	0.9300	N3—C12	1.457 (5)
C7—H7A	0.9600	C9—C10	1.424 (5)
C7—H7B	0.9600	C10—C11	1.363 (5)
C7—H7C	0.9600	C10—H10	0.9300
Cl1'—C3'	1.705 (8)	C11—H11	0.9300
O1'—C8'	1.213 (10)	C12—H12A	0.9600
N1'—C6'	1.343 (10)	C12—H12B	0.9600
N1'—C8'	1.385 (10)	C12—H12C	0.9600
N1'—C7'	1.458 (10)	C13—H13A	0.9600
N2'—C1'	1.395 (9)	C13—H13B	0.9600
N2'—C8'	1.410 (10)	C13—H13C	0.9600
C6—N1—C8	110.9 (4)	C5'—C4'—H4'	120.0
C6—N1—C7	126.6 (4)	C3'—C4'—H4'	120.0
C8—N1—C7	122.5 (3)	C4'—C5'—C6'	120.0
C1—N2—C8	109.7 (3)	C4'—C5'—H5'	120.0
C1—N2—C9	124.1 (3)	C6'—C5'—H5'	120.0
C8—N2—C9	125.9 (4)	N1'—C6'—C5'	140.1 (15)
C2—C1—C6	120.0	N1'—C6'—C1'	99.9 (15)
C2—C1—N2	134.2 (2)	C5'—C6'—C1'	120.0
C6—C1—N2	105.8 (2)	N1'—C7'—H7'A	109.5
C3—C2—C1	120.0	N1'—C7'—H7'B	109.5
C3—C2—H2	120.0	H7'A—C7'—H7'B	109.5
C1—C2—H2	120.0	N1'—C7'—H7'C	109.5
C4—C3—C2	120.0	H7'A—C7'—H7'C	109.5
C4—C3—H3	120.0	H7'B—C7'—H7'C	109.5
C2—C3—H3	120.0	O1'—C8'—N1'	118 (4)
C5—C4—C3	120.0	O1'—C8'—N2'	133 (4)
C5—C4—Cl1	120.32 (15)	N1'—C8'—N2'	109 (2)
C3—C4—Cl1	119.67 (15)	C11—N3—C13	122.1 (3)
C4—C5—C6	120.0	C11—N3—C12	121.2 (3)
C4—C5—H5	120.0	C13—N3—C12	116.6 (3)
C6—C5—H5	120.0	O2—C9—C10	125.5 (3)
N1—C6—C5	131.0 (3)	O2—C9—N2	115.1 (3)
N1—C6—C1	109.0 (3)	C10—C9—N2	119.3 (3)
C5—C6—C1	120.0	O2—C9—N2'	123.6 (8)
O1—C8—N1	126.9 (8)	C10—C9—N2'	110.9 (8)
O1—C8—N2	128.5 (8)	C11—C10—C9	118.7 (3)
N1—C8—N2	104.6 (4)	C11—C10—H10	120.6
C6'—N1'—C8'	114 (2)	C9—C10—H10	120.6
C6'—N1'—C7'	122.7 (19)	N3—C11—C10	127.0 (3)
C8'—N1'—C7'	123.5 (16)	N3—C11—H11	116.5
C1'—N2'—C8'	99.7 (15)	C10—C11—H11	116.5
C1'—N2'—C9	127.0 (15)	N3—C12—H12A	109.5
C8'—N2'—C9	132.6 (15)	N3—C12—H12B	109.5
C2'—C1'—C6'	120.0	H12A—C12—H12B	109.5
C2'—C1'—N2'	122.3 (12)	N3—C12—H12C	109.5
C6'—C1'—N2'	117.7 (12)	H12A—C12—H12C	109.5
C1'—C2'—C3'	120.0	H12B—C12—H12C	109.5
C1'—C2'—H2'	120.0	N3—C13—H13A	109.5
C3'—C2'—H2'	120.0	N3—C13—H13B	109.5
C2'—C3'—C4'	120.0	H13A—C13—H13B	109.5
C2'—C3'—Cl1'	127.5 (11)	N3—C13—H13C	109.5
C4'—C3'—Cl1'	112.3 (11)	H13A—C13—H13C	109.5
C5'—C4'—C3'	120.0	H13B—C13—H13C	109.5
C8—N2—C1—C2	178.9 (2)	Cl1'—C3'—C4'—C5'	−175.6 (11)
C9—N2—C1—C2	−6.1 (7)	C3'—C4'—C5'—C6'	0.0
C8—N2—C1—C6	−1.5 (3)	C8'—N1'—C6'—C5'	180.0 (3)
C9—N2—C1—C6	173.4 (5)	C7'—N1'—C6'—C5'	0.1 (8)
C6—C1—C2—C3	0.0	C8'—N1'—C6'—C1'	−0.1 (5)
N2—C1—C2—C3	179.5 (3)	C7'—N1'—C6'—C1'	−180.0 (5)
C1—C2—C3—C4	0.0	C4'—C5'—C6'—N1'	180.0 (4)
C2—C3—C4—C5	0.0	C4'—C5'—C6'—C1'	0.0
C2—C3—C4—Cl1	−178.8 (3)	C2'—C1'—C6'—N1'	−180.0 (3)
C3—C4—C5—C6	0.0	N2'—C1'—C6'—N1'	0.0 (4)
Cl1—C4—C5—C6	178.8 (3)	C2'—C1'—C6'—C5'	0.0
C8—N1—C6—C5	180.0 (2)	N2'—C1'—C6'—C5'	−180.0 (3)
C7—N1—C6—C5	1.7 (5)	C6'—N1'—C8'—O1'	−180.0 (6)
C8—N1—C6—C1	−2.1 (3)	C7'—N1'—C8'—O1'	−0.1 (10)
C7—N1—C6—C1	179.6 (3)	C6'—N1'—C8'—N2'	0.1 (7)
C4—C5—C6—N1	177.7 (3)	C7'—N1'—C8'—N2'	180.0 (6)
C4—C5—C6—C1	0.0	C1'—N2'—C8'—O1'	−180.0 (7)
C2—C1—C6—N1	−178.2 (2)	C9—N2'—C8'—O1'	9(3)
N2—C1—C6—N1	2.2 (3)	C1'—N2'—C8'—N1'	0.0 (6)
C2—C1—C6—C5	0.0	C9—N2'—C8'—N1'	−172 (2)
N2—C1—C6—C5	−179.6 (2)	C1—N2—C9—O2	−10.2 (7)
C6—N1—C8—O1	−178.3 (4)	C8—N2—C9—O2	164.0 (4)
C7—N1—C8—O1	0.1 (7)	C1—N2—C9—C10	168.9 (4)
C6—N1—C8—N2	1.1 (4)	C8—N2—C9—C10	−17.0 (6)
C7—N1—C8—N2	179.5 (4)	C1—N2—C9—N2'	178 (9)
C1—N2—C8—O1	179.7 (4)	C8—N2—C9—N2'	−8(9)
C9—N2—C8—O1	4.8 (8)	C1'—N2'—C9—O2	−8(2)
C1—N2—C8—N1	0.3 (4)	C8'—N2'—C9—O2	161.0 (11)
C9—N2—C8—N1	−174.5 (5)	C1'—N2'—C9—C10	171.9 (12)
C8'—N2'—C1'—C2'	−180.0 (3)	C8'—N2'—C9—C10	−19 (2)
C9—N2'—C1'—C2'	−8(2)	C1'—N2'—C9—N2	0(7)
C8'—N2'—C1'—C6'	0.0 (5)	C8'—N2'—C9—N2	170 (10)
C9—N2'—C1'—C6'	172 (2)	O2—C9—C10—C11	−2.6 (5)
C6'—C1'—C2'—C3'	0.0	N2—C9—C10—C11	178.5 (4)
N2'—C1'—C2'—C3'	180.0 (3)	N2'—C9—C10—C11	177.1 (12)
C1'—C2'—C3'—C4'	0.0	C13—N3—C11—C10	1.3 (6)
C1'—C2'—C3'—Cl1'	174.9 (13)	C12—N3—C11—C10	177.6 (4)
C2'—C3'—C4'—C5'	0.0	C9—C10—C11—N3	−177.1 (3)