2-Butyl-11-phenyl-5,10-dihydro-1H-benzo[e]imidazo[1,5-a][1,4]diazepine-1,3(2H)-dione.

The title compound, C(21)H(21)N(3)O(2), was obtained following a five-step synthetic procedure yielding weakly diffracting rod and needle-shaped crystals which crystallized concomitantly. Structural analysis of a rod-shaped crystal showed that the central seven-membered heterocyclic ring adopts a conformation that is perhaps best described as a distorted boat, with the H-bearing (CH(2) and NH) atoms lying well out of the least-squares mean plane fitted through the other five atoms in the ring (r.m.s. deviation 0.075 Å). In the crystal, the compound packs as a twisted chain, which propagates along the b axis by means of an R(1) (2)(6) motif formed by one of the carbonyl O atoms acting as a bifurcated acceptor in an N-H⋯O and C-H⋯O inter-action. No diffraction was observed from the needle-shaped crystals.

Related literature

For background to the synthetic procedure, see: Hulme & Gore (2003 ▶); Hulme et al. (2000 ▶). For graph-set analysis of hydrogen-bond networks, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C21H21N3O2

M = 347.41

Monoclinic,

a = 12.192 (4) Å

b = 7.638 (2) Å

c = 18.514 (6) Å

β = 95.494 (5)°

V = 1716.1 (9) Å3

Z = 4

Mo Kα radiation

μ = 0.09 mm−1

T = 100 K

0.29 × 0.14 × 0.08 mm

Data collection

Bruker Kappa APEXII DUO CCD diffractometer

Absorption correction: numerical (SADABS; Sheldrick, 1996 ▶) T min = 0.975, T max = 0.993

14047 measured reflections

2724 independent reflections

1908 reflections with I > 2σ(I)

R int = 0.067

θmax = 24.1°

Refinement

R[F 2 > 2σ(F 2)] = 0.065

wR(F 2) = 0.181

S = 1.03

2724 reflections

239 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.71 e Å−3

Δρmin = −0.29 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXTL and local programs.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810005477/bh2272sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810005477/bh2272Isup2.hkl

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

C21H21N3O2	F(000) = 736
Mr = 347.41	Dx = 1.345 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2525 reflections
a = 12.192 (4) Å	θ = 2.2–24.8°
b = 7.638 (2) Å	µ = 0.09 mm−1
c = 18.514 (6) Å	T = 100 K
β = 95.494 (5)°	Rod, yellow
V = 1716.1 (9) Å3	0.29 × 0.14 × 0.08 mm
Z = 4

Bruker Kappa APEXII DUO CCD diffractometer	2724 independent reflections
Radiation source: fine-focus sealed tube with Miracol optics	1908 reflections with I > 2σ(I)
graphite	Rint = 0.067
φ and ω scans	θmax = 24.1°, θmin = 1.9°
Absorption correction: numerical (SADABS; Sheldrick, 1996)	h = −14→14
Tmin = 0.975, Tmax = 0.993	k = −8→5
14047 measured reflections	l = −21→21

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)] = 0.065	Hydrogen site location: difference Fourier map
wR(F2) = 0.181	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ2(Fo2) + (0.1146P)2 + 0.6555P] where P = (Fo2 + 2Fc2)/3
2724 reflections	(Δ/σ)max = 0.001
239 parameters	Δρmax = 0.71 e Å−3
0 restraints	Δρmin = −0.29 e Å−3
0 constraints

Experimental. 1H NMR (300 MHz, CDCl3) δ ppm 0.89 (t, J = 7.2 Hz, 3H), 1.28 (m, 2H), 1.56 (m, 2H), 3.49 (t, J = 7.3 Hz, 2H), 4.98 (s, 2H), 5.95 (s, 1H), 6.89 (d, J = 7.8 Hz, 1H), 7.06 (t, J = 7.2 Hz, 1H), 7.28 (t, J = 7.7 Hz, 1H), 7.34 (d, J = 7.5 Hz, 1H), 7.52 (m, 5H).13C NMR (75 MHz, CDCl3) δ ppm 14.1, 20.5, 30.7, 39.0, 45.7, 109.4, 120.7, 123.9, 126.4, 129.1, 129.6, 129.7, 130.5, 130.6, 134.6, 135.4, 142.5, 153.7, 161.9.

	x	y	z	Uiso*/Ueq
O1	0.88328 (17)	0.0841 (3)	0.87585 (11)	0.0267 (6)
O2	0.61570 (19)	0.1425 (3)	1.03172 (11)	0.0346 (6)
N1	0.7648 (2)	0.0891 (4)	0.96528 (13)	0.0249 (6)
N2	0.62702 (19)	0.2468 (3)	0.91468 (13)	0.0221 (6)
N3	0.6120 (2)	0.4044 (4)	0.76450 (14)	0.0253 (7)
H3N	0.625 (3)	0.466 (5)	0.7271 (19)	0.030*
C1	0.7968 (3)	0.1375 (4)	0.89869 (16)	0.0243 (8)
C2	0.6618 (3)	0.1580 (5)	0.97655 (17)	0.0282 (8)
C3	0.5292 (3)	0.3561 (5)	0.90814 (17)	0.0290 (8)
H3A	0.5519	0.4803	0.9130	0.035*
H3B	0.4843	0.3285	0.9485	0.035*
C4	0.4598 (2)	0.3329 (5)	0.83796 (17)	0.0272 (8)
C5	0.3498 (3)	0.2811 (5)	0.83711 (18)	0.0308 (8)
H5	0.3222	0.2501	0.8816	0.037*
C6	0.2800 (3)	0.2733 (5)	0.77408 (18)	0.0316 (8)
H6	0.2060	0.2351	0.7752	0.038*
C7	0.3188 (3)	0.3216 (5)	0.70925 (18)	0.0295 (8)
H7	0.2707	0.3223	0.6658	0.035*
C8	0.4285 (3)	0.3690 (4)	0.70802 (17)	0.0274 (8)
H8	0.4551	0.4017	0.6634	0.033*
C9	0.4995 (2)	0.3694 (4)	0.77089 (17)	0.0241 (8)
C10	0.7038 (2)	0.3312 (4)	0.80057 (16)	0.0239 (8)
C11	0.7095 (2)	0.2491 (4)	0.86567 (16)	0.0215 (7)
C12	0.8299 (3)	−0.0207 (5)	1.01778 (16)	0.0291 (8)
H12A	0.8060	0.0008	1.0666	0.035*
H12B	0.9083	0.0136	1.0189	0.035*
C13	0.8194 (3)	−0.2160 (5)	1.00075 (16)	0.0290 (8)
H13A	0.7411	−0.2509	0.9997	0.035*
H13B	0.8435	−0.2381	0.9520	0.035*
C14	0.8874 (3)	−0.3268 (5)	1.05583 (17)	0.0297 (8)
H14A	0.8702	−0.2937	1.1052	0.036*
H14B	0.9666	−0.3032	1.0523	0.036*
C15	0.8653 (3)	−0.5210 (5)	1.04422 (19)	0.0377 (9)
H15A	0.7890	−0.5471	1.0531	0.057*
H15B	0.9157	−0.5887	1.0779	0.057*
H15C	0.8768	−0.5525	0.9942	0.057*
C16	0.8047 (2)	0.3506 (4)	0.76174 (16)	0.0231 (7)
C17	0.8030 (2)	0.2989 (5)	0.68966 (16)	0.0256 (8)
H17	0.7377	0.2506	0.6654	0.031*
C18	0.8963 (3)	0.3177 (5)	0.65308 (16)	0.0279 (8)
H18	0.8943	0.2830	0.6037	0.033*
C19	0.9920 (3)	0.3863 (5)	0.68772 (17)	0.0292 (8)
H19	1.0559	0.3979	0.6625	0.035*
C20	0.9944 (3)	0.4382 (4)	0.75934 (17)	0.0272 (8)
H20	1.0601	0.4852	0.7835	0.033*
C21	0.9005 (2)	0.4217 (4)	0.79611 (17)	0.0256 (8)
H21	0.9022	0.4594	0.8451	0.031*

	U11	U22	U33	U12	U13	U23
O1	0.0233 (12)	0.0323 (14)	0.0259 (12)	0.0001 (10)	0.0093 (9)	−0.0012 (10)
O2	0.0315 (13)	0.0513 (17)	0.0230 (12)	−0.0006 (11)	0.0132 (10)	0.0038 (11)
N1	0.0252 (14)	0.0305 (17)	0.0200 (13)	0.0005 (12)	0.0063 (11)	0.0030 (11)
N2	0.0193 (13)	0.0305 (17)	0.0179 (13)	0.0017 (11)	0.0093 (10)	0.0011 (11)
N3	0.0213 (14)	0.0332 (18)	0.0226 (14)	−0.0016 (12)	0.0080 (11)	0.0057 (12)
C1	0.0251 (17)	0.028 (2)	0.0209 (16)	−0.0040 (14)	0.0075 (13)	−0.0026 (14)
C2	0.0274 (18)	0.034 (2)	0.0242 (18)	−0.0042 (15)	0.0092 (14)	−0.0018 (15)
C3	0.0250 (17)	0.036 (2)	0.0281 (17)	0.0057 (14)	0.0145 (14)	−0.0007 (15)
C4	0.0240 (17)	0.035 (2)	0.0244 (17)	0.0043 (14)	0.0109 (13)	−0.0012 (14)
C5	0.0239 (17)	0.041 (2)	0.0297 (18)	0.0028 (15)	0.0147 (14)	0.0035 (15)
C6	0.0176 (16)	0.044 (2)	0.0348 (19)	−0.0002 (15)	0.0084 (14)	0.0032 (16)
C7	0.0222 (17)	0.038 (2)	0.0293 (18)	0.0033 (15)	0.0059 (13)	0.0009 (15)
C8	0.0256 (17)	0.031 (2)	0.0274 (17)	0.0024 (14)	0.0093 (14)	0.0030 (14)
C9	0.0223 (16)	0.023 (2)	0.0285 (17)	0.0013 (13)	0.0112 (13)	0.0003 (14)
C10	0.0216 (17)	0.026 (2)	0.0253 (17)	0.0004 (13)	0.0084 (13)	−0.0035 (14)
C11	0.0197 (16)	0.027 (2)	0.0193 (15)	−0.0018 (13)	0.0082 (12)	−0.0033 (13)
C12	0.0282 (18)	0.038 (2)	0.0221 (16)	0.0009 (15)	0.0079 (13)	0.0041 (15)
C13	0.0294 (18)	0.040 (2)	0.0183 (16)	−0.0014 (15)	0.0059 (13)	0.0011 (14)
C14	0.0256 (17)	0.036 (2)	0.0279 (17)	0.0005 (15)	0.0063 (14)	0.0023 (15)
C15	0.040 (2)	0.038 (2)	0.036 (2)	−0.0037 (17)	0.0099 (16)	−0.0002 (17)
C16	0.0218 (16)	0.027 (2)	0.0207 (16)	0.0008 (13)	0.0058 (12)	0.0031 (13)
C17	0.0219 (16)	0.034 (2)	0.0220 (16)	0.0008 (14)	0.0060 (13)	0.0016 (14)
C18	0.0276 (17)	0.037 (2)	0.0199 (16)	0.0041 (15)	0.0078 (13)	0.0012 (15)
C19	0.0289 (18)	0.031 (2)	0.0299 (18)	0.0049 (15)	0.0152 (14)	0.0062 (15)
C20	0.0238 (17)	0.030 (2)	0.0285 (17)	−0.0012 (14)	0.0045 (13)	0.0048 (14)
C21	0.0266 (17)	0.029 (2)	0.0227 (16)	0.0023 (14)	0.0091 (13)	0.0024 (14)

O1—C1	1.241 (4)	C10—C11	1.355 (4)
O2—C2	1.218 (4)	C10—C16	1.491 (4)
N1—C1	1.379 (4)	C12—H12A	0.990
N1—C2	1.396 (4)	C12—H12B	0.990
N1—C12	1.459 (4)	C12—C13	1.528 (5)
N2—C2	1.363 (4)	C13—H13A	0.990
N2—C3	1.452 (4)	C13—H13B	0.990
N2—C11	1.417 (4)	C13—C14	1.510 (5)
N3—H3N	0.86 (4)	C14—H14A	0.990
N3—C9	1.413 (4)	C14—H14B	0.990
N3—C10	1.367 (4)	C14—C15	1.519 (5)
C1—C11	1.453 (5)	C15—H15A	0.980
C3—H3A	0.990	C15—H15B	0.980
C3—H3B	0.990	C15—H15C	0.980
C3—C4	1.492 (5)	C16—C17	1.390 (4)
C4—C5	1.396 (5)	C16—C21	1.387 (5)
C4—C9	1.403 (4)	C17—H17	0.950
C5—H5	0.950	C17—C18	1.386 (4)
C5—C6	1.379 (5)	C18—H18	0.950
C6—H6	0.950	C18—C19	1.380 (5)
C6—C7	1.382 (5)	C19—H19	0.950
C7—H7	0.950	C19—C20	1.381 (5)
C7—C8	1.387 (4)	C20—H20	0.950
C8—H8	0.950	C20—C21	1.392 (4)
C8—C9	1.383 (5)	C21—H21	0.950
C1—N1—C2	111.6 (3)	C1—C11—C10	128.3 (3)
C1—N1—C12	124.5 (3)	N1—C12—H12A	108.9
C2—N1—C12	123.8 (2)	N1—C12—H12B	108.9
C2—N2—C3	122.9 (2)	N1—C12—C13	113.2 (3)
C2—N2—C11	111.2 (2)	H12A—C12—H12B	107.7
C3—N2—C11	124.5 (3)	H12A—C12—C13	108.9
H3N—N3—C9	115 (2)	H12B—C12—C13	108.9
H3N—N3—C10	115 (2)	C12—C13—H13A	109.2
C9—N3—C10	129.6 (3)	C12—C13—H13B	109.2
O1—C1—N1	122.6 (3)	C12—C13—C14	112.2 (3)
O1—C1—C11	131.4 (3)	H13A—C13—H13B	107.9
N1—C1—C11	105.9 (3)	H13A—C13—C14	109.2
O2—C2—N1	125.6 (3)	H13B—C13—C14	109.2
O2—C2—N2	128.5 (3)	C13—C14—H14A	109.2
N1—C2—N2	105.9 (2)	C13—C14—H14B	109.2
N2—C3—H3A	108.9	C13—C14—C15	111.9 (3)
N2—C3—H3B	108.9	H14A—C14—H14B	107.9
N2—C3—C4	113.4 (3)	H14A—C14—C15	109.2
H3A—C3—H3B	107.7	H14B—C14—C15	109.2
H3A—C3—C4	108.9	C14—C15—H15A	109.5
H3B—C3—C4	108.9	C14—C15—H15B	109.5
C3—C4—C5	120.5 (3)	C14—C15—H15C	109.5
C3—C4—C9	122.2 (3)	H15A—C15—H15B	109.5
C5—C4—C9	117.3 (3)	H15A—C15—H15C	109.5
C4—C5—H5	118.8	H15B—C15—H15C	109.5
C4—C5—C6	122.5 (3)	C10—C16—C17	119.8 (3)
H5—C5—C6	118.8	C10—C16—C21	121.0 (3)
C5—C6—H6	120.4	C17—C16—C21	119.1 (3)
C5—C6—C7	119.2 (3)	C16—C17—H17	119.9
H6—C6—C7	120.4	C16—C17—C18	120.1 (3)
C6—C7—H7	120.2	H17—C17—C18	119.9
C6—C7—C8	119.7 (3)	C17—C18—H18	119.7
H7—C7—C8	120.2	C17—C18—C19	120.6 (3)
C7—C8—H8	119.6	H18—C18—C19	119.7
C7—C8—C9	120.9 (3)	C18—C19—H19	120.2
H8—C8—C9	119.6	C18—C19—C20	119.6 (3)
N3—C9—C4	122.1 (3)	H19—C19—C20	120.2
N3—C9—C8	117.7 (3)	C19—C20—H20	120.0
C4—C9—C8	120.2 (3)	C19—C20—C21	120.1 (3)
N3—C10—C11	126.4 (3)	H20—C20—C21	120.0
N3—C10—C16	113.5 (3)	C16—C21—C20	120.5 (3)
C11—C10—C16	120.1 (3)	C16—C21—H21	119.8
N2—C11—C1	105.0 (2)	C20—C21—H21	119.8
N2—C11—C10	126.6 (3)
C2—N1—C1—O1	−176.4 (3)	C9—N3—C10—C16	158.5 (3)
C2—N1—C1—C11	1.5 (4)	N3—C10—C11—N2	−10.9 (6)
C12—N1—C1—O1	3.5 (5)	N3—C10—C11—C1	165.3 (3)
C12—N1—C1—C11	−178.5 (3)	C16—C10—C11—N2	168.2 (3)
C3—N2—C2—O2	6.5 (5)	C16—C10—C11—C1	−15.6 (5)
C3—N2—C2—N1	−172.0 (3)	C2—N2—C11—C1	5.7 (4)
C11—N2—C2—O2	173.7 (3)	C2—N2—C11—C10	−177.3 (3)
C11—N2—C2—N1	−4.8 (4)	C3—N2—C11—C1	172.7 (3)
C1—N1—C2—O2	−176.7 (3)	C3—N2—C11—C10	−10.4 (5)
C1—N1—C2—N2	2.0 (4)	O1—C1—C11—N2	173.5 (3)
C12—N1—C2—O2	3.4 (5)	O1—C1—C11—C10	−3.4 (6)
C12—N1—C2—N2	−178.0 (3)	N1—C1—C11—N2	−4.2 (3)
C2—N2—C3—C4	−136.8 (3)	N1—C1—C11—C10	178.9 (3)
C11—N2—C3—C4	57.7 (4)	C1—N1—C12—C13	−80.8 (4)
N2—C3—C4—C5	121.8 (3)	C2—N1—C12—C13	99.1 (3)
N2—C3—C4—C9	−61.3 (4)	N1—C12—C13—C14	−180.0 (2)
C3—C4—C5—C6	174.0 (3)	C12—C13—C14—C15	172.6 (3)
C9—C4—C5—C6	−3.1 (5)	N3—C10—C16—C17	−52.2 (4)
C4—C5—C6—C7	−1.3 (5)	N3—C10—C16—C21	127.0 (3)
C5—C6—C7—C8	3.1 (5)	C11—C10—C16—C17	128.6 (3)
C6—C7—C8—C9	−0.3 (5)	C11—C10—C16—C21	−52.2 (5)
C7—C8—C9—N3	174.6 (3)	C10—C16—C17—C18	179.6 (3)
C7—C8—C9—C4	−4.3 (5)	C21—C16—C17—C18	0.3 (5)
C3—C4—C9—N3	9.9 (5)	C16—C17—C18—C19	0.5 (5)
C3—C4—C9—C8	−171.2 (3)	C17—C18—C19—C20	−0.6 (5)
C5—C4—C9—N3	−173.1 (3)	C18—C19—C20—C21	−0.2 (5)
C5—C4—C9—C8	5.8 (5)	C10—C16—C21—C20	179.7 (3)
C10—N3—C9—C4	37.7 (5)	C17—C16—C21—C20	−1.1 (5)
C10—N3—C9—C8	−141.3 (3)	C19—C20—C21—C16	1.1 (5)
C9—N3—C10—C11	−22.3 (6)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3N···O1i	0.86 (4)	2.10 (4)	2.944 (3)	165 (3)
C8—H8···O1i	0.95	2.57	3.326 (4)	136

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3N⋯O1i	0.86 (4)	2.10 (4)	2.944 (3)	165 (3)
C8—H8⋯O1i	0.95	2.57	3.326 (4)	136

Symmetry code: (i) .