Dimethyl 9-benzyl-3-cyano-9H-pyrrolo[1,2-a]benzimidazole-1,2-dicarboxyl-ate.

The title compound, C(22)H(17)N(3)O(4), was prepared through 1,3-dipolar cyclo-addition: the dihedral angle between the benzimidazole and benzene rings is 80.93 (6)°. The crystal structure is stabilized by weak π-π inter-actions between the planar pyrrolobenzimidazole rings (r.m.s. deviation = 0.0293 Å) of neighbouring mol-ecules, forming chains along the c axis. The perpendicular distance is 3.47 (2) Å and the centroid-centroid distances are in the range of 3.590 (3)-3.944 (3) Å.

Related literature

For the use of 1,3-dipolar cyclo­addition reactions of azomethine ylides in the construction of five-membered nitro­gen heteroaromatic ring systems, see: Berry et al. (2007 ▶). For the applications of nitro­gen heteroaromatic ring systems, see: Ansari & Lal (2009 ▶); Shen et al. (2006 ▶, 2008 ▶); Zhang et al. (2009 ▶). For the synthesis, see: Wang et al. (2000 ▶).

Experimental

Crystal data

C22H17N3O4

M = 387.39

Monoclinic,

a = 9.8681 (15) Å

b = 24.766 (2) Å

c = 7.6551 (11) Å

β = 91.973 (3)°

V = 1869.7 (4) Å3

Z = 4

Mo Kα radiation

μ = 0.10 mm−1

T = 291 K

0.26 × 0.22 × 0.20 mm

Data collection

Bruker SMART APEX CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T min = 0.97, T max = 0.98

13898 measured reflections

3615 independent reflections

2699 reflections with I > 2σ(I)

R int = 0.057

Refinement

R[F 2 > 2σ(F 2)] = 0.056

wR(F 2) = 0.125

S = 1.03

3615 reflections

264 parameters

H-atom parameters constrained

Δρmax = 0.19 e Å−3

Δρmin = −0.19 e Å−3

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809048867/zq2016sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809048867/zq2016Isup2.hkl

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

C22H17N3O4	F(000) = 808
Mr = 387.39	Dx = 1.376 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1791 reflections
a = 9.8681 (15) Å	θ = 2.6–25.2°
b = 24.766 (2) Å	µ = 0.10 mm−1
c = 7.6551 (11) Å	T = 291 K
β = 91.973 (3)°	Block, colorless
V = 1869.7 (4) Å3	0.26 × 0.22 × 0.20 mm
Z = 4

Bruker SMART APEX CCD diffractometer	3615 independent reflections
Radiation source: sealed tube	2699 reflections with I > 2σ(I)
graphite	Rint = 0.057
phi and ω scans	θmax = 26.0°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −12→12
Tmin = 0.97, Tmax = 0.98	k = −26→30
13898 measured reflections	l = −9→9

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)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.125	H-atom parameters constrained
S = 1.02	w = 1/[σ2(Fo2) + (0.05P)2 + 0.66P] where P = (Fo2 + 2Fc2)/3
3615 reflections	(Δ/σ)max < 0.001
264 parameters	Δρmax = 0.19 e Å−3
0 restraints	Δρmin = −0.19 e Å−3

Experimental. 1H-NMR (CDCl3, 400 MHz) δ: 3.81 (s, 3H, –COOCH3), 4.00 (s, 3H, –COOCH3), 5.92 (s, 2H, –CH2Ph), 7.20–7.41 (m, 8H, ArH), 8.07 (d, 1H, J = 7.9 Hz, ArH)

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. Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)-0.0001(0.0049) x + 11.1526(0.0083)y + 6.8309(0.0017) z = 16.2473 (0.0105)* 0.0370 (0.0017) C1 * 0.0187 (0.0017) C2 * -0.0329 (0.0017) C3 * -0.0312 (0.0019) C4 * -0.0132 (0.0017) C5 * 0.0115 (0.0017) C6 * 0.0056 (0.0017) C7 * -0.0396 (0.0016) C8 * -0.0420 (0.0016) C9 * 0.0128 (0.0016) C10 * 0.0392 (0.0015) N1 * 0.0341 (0.0015) N2Rms deviation of fitted atoms = 0.02937.9901(0.0063)x + 10.7417(0.0233)y - 3.2379(0.0071)z = 12.8495 (0.0190)Angle to previous plane (with approximate e.s.d.) = 80.93 (0.06)* 0.0109 (0.0016) C13 * -0.0131 (0.0017) C14 * 0.0058 (0.0018) C15 * 0.0036 (0.0019) C16 * -0.0055 (0.0019) C17 * -0.0016 (0.0017) C18Rms deviation of fitted atoms = 0.0078

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	1.0019 (2)	1.00932 (8)	0.7360 (3)	0.0272 (4)
C2	1.0476 (2)	1.05587 (9)	0.6574 (3)	0.0342 (5)
H2	1.1394	1.0634	0.6481	0.041*
C3	0.9480 (3)	1.09034 (10)	0.5935 (3)	0.0403 (6)
H3	0.9727	1.1219	0.5367	0.048*
C4	0.8095 (2)	1.07867 (9)	0.6128 (3)	0.0387 (6)
H4	0.7450	1.1033	0.5710	0.046*
C5	0.7662 (2)	1.03148 (10)	0.6925 (3)	0.0359 (5)
H5	0.6746	1.0239	0.7042	0.043*
C6	0.8651 (2)	0.99690 (9)	0.7526 (3)	0.0283 (5)
C7	0.9829 (2)	0.92732 (8)	0.8653 (3)	0.0252 (4)
C8	1.0572 (2)	0.88306 (9)	0.9310 (3)	0.0283 (5)
C9	1.1957 (2)	0.89723 (9)	0.9075 (3)	0.0301 (5)
C10	1.2040 (2)	0.94775 (9)	0.8330 (3)	0.0288 (5)
C11	1.3184 (2)	0.97791 (9)	0.7903 (3)	0.0333 (5)
C12	0.7257 (2)	0.91558 (10)	0.8516 (3)	0.0326 (5)
H12A	0.6509	0.9402	0.8692	0.039*
H12B	0.7325	0.8913	0.9509	0.039*
C13	0.69949 (19)	0.88336 (9)	0.6848 (3)	0.0292 (5)
C14	0.6168 (2)	0.90361 (10)	0.5555 (3)	0.0394 (6)
H14	0.5747	0.9368	0.5706	0.047*
C15	0.5946 (3)	0.87514 (11)	0.4004 (3)	0.0463 (7)
H15	0.5403	0.8898	0.3108	0.056*
C16	0.6539 (3)	0.82453 (12)	0.3795 (3)	0.0493 (7)
H16	0.6382	0.8055	0.2761	0.059*
C17	0.7340 (3)	0.80288 (12)	0.5082 (3)	0.0466 (6)
H17	0.7729	0.7690	0.4944	0.056*
C18	0.7576 (2)	0.83240 (10)	0.6629 (3)	0.0411 (6)
H18	0.8125	0.8179	0.7521	0.049*
C19	1.0032 (2)	0.83746 (9)	1.0316 (3)	0.0336 (5)
C20	1.0629 (3)	0.76423 (12)	1.2133 (4)	0.0577 (8)
H20A	1.0048	0.7778	1.3013	0.087*
H20B	1.1420	0.7482	1.2682	0.087*
H20C	1.0150	0.7376	1.1441	0.087*
C21	1.3202 (2)	0.86405 (10)	0.9391 (3)	0.0376 (5)
C22	1.4343 (3)	0.78357 (12)	0.8747 (4)	0.0528 (7)
H22A	1.5076	0.7961	0.8061	0.079*
H22B	1.4102	0.7475	0.8400	0.079*
H22C	1.4619	0.7838	0.9962	0.079*
N1	1.07206 (16)	0.96508 (7)	0.8086 (2)	0.0243 (4)
N2	0.85368 (17)	0.94658 (7)	0.8381 (2)	0.0278 (4)
N3	1.41453 (19)	1.00265 (9)	0.7614 (3)	0.0411 (5)
O1	1.10343 (16)	0.80841 (7)	1.1015 (2)	0.0403 (4)
O2	0.88636 (17)	0.82715 (7)	1.0552 (2)	0.0449 (5)
O3	1.31742 (17)	0.81903 (7)	0.8471 (2)	0.0451 (5)
O4	1.4114 (2)	0.87751 (9)	1.0281 (3)	0.0648 (6)

	U11	U22	U33	U12	U13	U23
C1	0.0323 (11)	0.0244 (11)	0.0247 (10)	−0.0022 (9)	−0.0037 (8)	−0.0041 (8)
C2	0.0466 (13)	0.0273 (12)	0.0285 (11)	−0.0057 (10)	0.0002 (10)	−0.0019 (9)
C3	0.0513 (15)	0.0310 (13)	0.0385 (13)	0.0007 (11)	0.0013 (11)	−0.0045 (10)
C4	0.0433 (14)	0.0249 (12)	0.0473 (14)	0.0040 (10)	−0.0059 (11)	−0.0014 (10)
C5	0.0323 (12)	0.0352 (13)	0.0399 (13)	0.0041 (10)	−0.0055 (10)	−0.0037 (10)
C6	0.0274 (10)	0.0230 (11)	0.0343 (11)	0.0022 (9)	−0.0014 (9)	−0.0041 (9)
C7	0.0232 (10)	0.0269 (11)	0.0254 (10)	−0.0068 (8)	0.0006 (8)	−0.0034 (8)
C8	0.0264 (10)	0.0329 (12)	0.0257 (10)	−0.0025 (9)	0.0022 (8)	−0.0034 (9)
C9	0.0301 (11)	0.0342 (13)	0.0255 (10)	−0.0010 (9)	−0.0045 (9)	−0.0033 (9)
C10	0.0238 (10)	0.0337 (13)	0.0284 (10)	0.0024 (9)	−0.0040 (8)	−0.0013 (9)
C11	0.0260 (11)	0.0289 (12)	0.0448 (13)	0.0028 (9)	−0.0003 (10)	−0.0014 (10)
C12	0.0189 (10)	0.0365 (13)	0.0428 (13)	−0.0071 (9)	0.0074 (9)	−0.0026 (10)
C13	0.0175 (9)	0.0341 (12)	0.0361 (12)	−0.0056 (9)	0.0054 (8)	0.0021 (9)
C14	0.0381 (13)	0.0348 (13)	0.0444 (13)	−0.0044 (10)	−0.0116 (10)	−0.0010 (11)
C15	0.0522 (15)	0.0540 (17)	0.0316 (13)	−0.0098 (13)	−0.0143 (11)	0.0006 (11)
C16	0.0535 (16)	0.0536 (17)	0.0406 (14)	−0.0132 (13)	−0.0033 (12)	−0.0178 (12)
C17	0.0485 (15)	0.0460 (15)	0.0457 (15)	−0.0021 (12)	0.0038 (12)	−0.0133 (12)
C18	0.0398 (13)	0.0361 (14)	0.0466 (14)	0.0050 (11)	−0.0073 (11)	−0.0077 (11)
C19	0.0377 (13)	0.0303 (13)	0.0321 (12)	0.0005 (10)	−0.0074 (10)	−0.0015 (9)
C20	0.076 (2)	0.0544 (18)	0.0425 (15)	0.0009 (15)	0.0044 (14)	0.0349 (13)
C21	0.0348 (12)	0.0373 (14)	0.0403 (13)	0.0018 (10)	−0.0031 (10)	0.0009 (11)
C22	0.0480 (15)	0.0571 (18)	0.0535 (16)	0.0282 (13)	0.0064 (13)	−0.0133 (13)
N1	0.0211 (8)	0.0270 (9)	0.0249 (9)	−0.0030 (7)	0.0014 (7)	−0.0028 (7)
N2	0.0221 (8)	0.0295 (10)	0.0319 (9)	−0.0045 (7)	0.0000 (7)	−0.0004 (7)
N3	0.0303 (10)	0.0528 (14)	0.0404 (11)	−0.0052 (10)	0.0049 (8)	0.0129 (10)
O1	0.0418 (9)	0.0435 (10)	0.0356 (9)	0.0077 (8)	0.0030 (7)	0.0184 (7)
O2	0.0395 (10)	0.0547 (11)	0.0399 (9)	−0.0098 (8)	−0.0049 (7)	0.0225 (8)
O3	0.0467 (10)	0.0461 (11)	0.0422 (9)	0.0157 (8)	−0.0041 (8)	−0.0152 (8)
O4	0.0576 (12)	0.0899 (16)	0.0452 (11)	0.0140 (11)	−0.0211 (10)	−0.0184 (11)

C1—C2	1.384 (3)	C12—H12B	0.9700
C1—C6	1.394 (3)	C13—C14	1.357 (3)
C1—N1	1.401 (3)	C13—C18	1.398 (3)
C2—C3	1.379 (3)	C14—C15	1.392 (3)
C2—H2	0.9300	C14—H14	0.9300
C3—C4	1.410 (4)	C15—C16	1.395 (4)
C3—H3	0.9300	C15—H15	0.9300
C4—C5	1.392 (3)	C16—C17	1.352 (4)
C4—H4	0.9300	C16—H16	0.9300
C5—C6	1.366 (3)	C17—C18	1.405 (3)
C5—H5	0.9300	C17—H17	0.9300
C6—N2	1.414 (3)	C18—H18	0.9300
C7—N1	1.365 (3)	C19—O2	1.201 (3)
C7—N2	1.371 (3)	C19—O1	1.321 (3)
C7—C8	1.402 (3)	C20—O1	1.454 (3)
C8—C9	1.429 (3)	C20—H20A	0.9600
C8—C19	1.477 (3)	C20—H20B	0.9600
C9—C10	1.378 (3)	C20—H20C	0.9600
C9—C21	1.491 (3)	C21—O4	1.159 (3)
C10—N1	1.378 (3)	C21—O3	1.318 (3)
C10—C11	1.401 (3)	C22—O3	1.459 (3)
C11—N3	1.157 (3)	C22—H22A	0.9600
C12—N2	1.485 (3)	C22—H22B	0.9600
C12—C13	1.520 (3)	C22—H22C	0.9600
C12—H12A	0.9700
C2—C1—C6	123.7 (2)	C13—C14—H14	119.7
C2—C1—N1	131.3 (2)	C15—C14—H14	119.7
C6—C1—N1	104.97 (17)	C14—C15—C16	119.9 (2)
C3—C2—C1	115.5 (2)	C14—C15—H15	120.0
C3—C2—H2	122.2	C16—C15—H15	120.0
C1—C2—H2	122.2	C17—C16—C15	120.7 (2)
C2—C3—C4	121.2 (2)	C17—C16—H16	119.7
C2—C3—H3	119.4	C15—C16—H16	119.7
C4—C3—H3	119.4	C16—C17—C18	118.9 (3)
C5—C4—C3	122.1 (2)	C16—C17—H17	120.5
C5—C4—H4	118.9	C18—C17—H17	120.5
C3—C4—H4	118.9	C13—C18—C17	121.0 (2)
C6—C5—C4	116.5 (2)	C13—C18—H18	119.5
C6—C5—H5	121.7	C17—C18—H18	119.5
C4—C5—H5	121.7	O2—C19—O1	122.2 (2)
C5—C6—C1	120.9 (2)	O2—C19—C8	127.4 (2)
C5—C6—N2	129.9 (2)	O1—C19—C8	110.4 (2)
C1—C6—N2	109.22 (17)	O1—C20—H20A	109.5
N1—C7—N2	108.65 (18)	O1—C20—H20B	109.5
N1—C7—C8	108.36 (18)	H20A—C20—H20B	109.5
N2—C7—C8	142.99 (19)	O1—C20—H20C	109.5
C7—C8—C9	104.67 (19)	H20A—C20—H20C	109.5
C7—C8—C19	126.24 (19)	H20B—C20—H20C	109.5
C9—C8—C19	128.1 (2)	O4—C21—O3	124.0 (2)
C10—C9—C8	110.22 (19)	O4—C21—C9	123.7 (2)
C10—C9—C21	120.5 (2)	O3—C21—C9	112.17 (19)
C8—C9—C21	129.1 (2)	O3—C22—H22A	109.5
N1—C10—C9	105.65 (18)	O3—C22—H22B	109.5
N1—C10—C11	124.6 (2)	H22A—C22—H22B	109.5
C9—C10—C11	129.77 (19)	O3—C22—H22C	109.5
N3—C11—C10	177.5 (2)	H22A—C22—H22C	109.5
N2—C12—C13	109.47 (17)	H22B—C22—H22C	109.5
N2—C12—H12A	109.8	C7—N1—C10	111.09 (17)
C13—C12—H12A	109.8	C7—N1—C1	110.29 (17)
N2—C12—H12B	109.8	C10—N1—C1	138.55 (18)
C13—C12—H12B	109.8	C7—N2—C6	106.77 (16)
H12A—C12—H12B	108.2	C7—N2—C12	126.79 (18)
C14—C13—C18	119.0 (2)	C6—N2—C12	124.71 (17)
C14—C13—C12	120.0 (2)	C19—O1—C20	115.5 (2)
C18—C13—C12	121.1 (2)	C21—O3—C22	115.44 (19)
C13—C14—C15	120.6 (2)