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

Nichol, G.S.; Gunawan, S.; Dietrich, J.; Hulme, C.

doi:10.1107/S1600536810005477

organic compounds

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ISSN: 2056-9890

Volume 66| Part 3| March 2010| Page o625

doi:10.1107/S1600536810005477

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

Gary S. Nichol,^a ^* Steven Gunawan,^b Justin Dietrich ^b and Christopher Hulme ^b

^aDepartment of Chemistry and Biochemistry, The University of Arizona, 1306 E. University Boulevard, Tucson, AZ 85721, USA, and ^bSouthwest Center for Drug Discovery and Development, College of Pharmacy, BIO5 Institute, University of Arizona, Tucson, AZ 85721, USA
^*Correspondence e-mail: gsnichol@email.arizona.edu

(Received 29 January 2010; accepted 9 February 2010; online 13 February 2010)

The title compound, C₂₁H₂₁N₃O₂, 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 (CH₂ 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 R¹₂(6) motif formed by one of the carbonyl O atoms acting as a bifurcated acceptor in an N—H⋯O and C—H⋯O interaction. 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_r = 347.41
Monoclinic, P 2₁ /n
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
θ_max = 24.1°

Refinement

R[F² > 2σ(F²)] = 0.065
wR(F²) = 0.181
S = 1.03
2724 reflections
239 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.71 e Å⁻³
Δρ_min = −0.29 e Å⁻³

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) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

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.

Supporting information

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

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

checkCIF report

Comment top

We recently investigated a three step solution phase protocol for the synthesis of arrays of tricyclic fused hydantoin-benzodiazepines as part of broader research on multi-component reactions (Figure 1). Interestingly, the major product of this unique synthetic route was the tautomer 5 derived from the originally desired product 4, the structure being confirmed by X-ray crystallography. The methodology employs ortho-N-Boc benzylamines 1 and phenylglyoxaldehydes 2 in the rarely used five component Ugi reaction with CO₂ to assemble desired diversity in product 3 (Hulme et al., 2000). Acid treatment unmasks an internal amino nucleophile and promotes rapid formation of the diazepine ring of generic structure 4. Subsequent base treatment employs the amidic NH of the Ugi scaffold as a second internal nucleophile promoting hydantoin formation and an unexpected 1,3-H shift to give 5. As such the methodology represents an example of a post-condensation Ugi modification (Hulme & Gore, 2003) that employs two internal nucleophiles in distinct operations, generating a novel scaffold of high complexity in three succinct functional operations.

Two types of crystals were formed: very fine yellow needles together with a few slightly larger rod-shaped pale yellow crystals. The needles did not give any measurable diffraction and the rod crystals showed weak diffraction with 60 second exposure times; a resolution cutoff of 0.87Å was applied to the dataset. The identity of the needle crystals was not established. The molecular structure of 5 is shown in Figure 2. Molecular dimensions are unexceptional. The amine hydrogen atom was located in a difference Fourier map and its presence is confirmed by participation in hydrogen bonding discussed below. The central 7-membered heterocyclic ring adopts a conformation that is perhaps best described as a distorted boat with the H-bearing (C3 and N3) atoms lying well out of a least squares mean plane fitted through the other five atoms in the ring [r.m.s. deviation 0.075 Å; C3 deviates by 0.679 (5) Å and N3 deviates by 0.301 (4) Å]. The compound packs as a twisted chain which propagates along the b axis by means of an R¹₂(6) motif (Bernstein et al., 1995) formed by one of the carbonyl oxygen atoms acting as bifurcated acceptor in an N–H···O and C–H···O interaction (Figure 3).

Related literature top

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 top

Ugi reaction (For R₁, R₂=H, R₃= n-butyl)

CO₂ gas was bubbled through a stirring solution of MeOH for 25 minutes to generate methyl carbonic acid. In a separate 25 ml flask, phenyl glyoxal 2 (226 mg, 1.687 mmol) was added to BOC-2-aminobenyzlamine 1 (250 mg, 1.125 mmol). Methyl carbonic acid (10 ml) and N-butyl isonitrile (0.237 ml, 2.252 mmol) were then added to the latter flask. The reaction was stirred at room temperature under an atmosphere of CO₂ for 16 h. The solvent was evaporated in vacuo and the crude product purified with a Biotage Isolera4^TMsystem (hexane/EtOAc 10-30%) to afford the Ugi product 3 (218 mg, 0.438 mmol, 39%) as a yellow oil.

De-BOC and Cyclization

3 (0.180 g, 0.362 mmol) was treated with a 5 ml 10% TFA solution in 1,2-dichloroethane which was irradiated in a Biotage InitiatorTM at 80°C for 20 min. The resulting orange solution was washed with 1M NaHCO₃ (4 × 2.5 ml) and the organic layer dried (Na₂SO₄), filtered and evaporated in vacuo. MeOH (1.5 ml), THF (0.75 ml), H₂O (0.5 ml) were added to the crude product 4 (0.102 g, 0.269 mmol) followed by a 1 g/1 ml solution of KOH in H₂O (0.03 ml). The solution was irradiated at 100°C for 20 min and resultant orange solution partitioned between EtOAc (5 ml) and 1M NaHCO₃ (5 ml). The organic layer was dried (Na₂SO₄), filtered and evaporated in vacuo. Final crude product was purified with a Biotage Isolera4^TM (hexane/EtOAc 30%) to afford the final product 5 (0.074 g, 0.214 mmol, 80%) as a yellow solid. FT-ICR calculated for C₂₁H₂₂N₃O₂ [M+H]⁺: 348.1707, found: 348.1707.

Computing details top

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

Figures top

	Fig. 1. Synthetic route to 5.
	Fig. 2. The molecular structure of 5 with displacement ellipsoids at the 50% probability level.
	Fig. 3. An a-axis projection of 5 showing the twisted hydrogen-bonded chain (blue dotted lines; red dotted lines indicate continuation).

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

Crystal data top

C₂₁H₂₁N₃O₂	F(000) = 736
M_r = 347.41	D_x = 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

Data collection top

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 monochromator	R_int = 0.067
ϕ and ω scans	θ_max = 24.1°, θ_min = 1.9°
Absorption correction: numerical (SADABS; Sheldrick, 1996)	h = −14→14
T_min = 0.975, T_max = 0.993	k = −8→5
14047 measured reflections	l = −21→21

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)] = 0.065	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(F_o²) + (0.1146P)² + 0.6555P] where P = (F_o² + 2F_c²)/3
2724 reflections	(Δ/σ)_max = 0.001
239 parameters	Δρ_max = 0.71 e Å⁻³
0 restraints	Δρ_min = −0.29 e Å⁻³
0 constraints

Crystal data top

C₂₁H₂₁N₃O₂	V = 1716.1 (9) Å³
M_r = 347.41	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 12.192 (4) Å	µ = 0.09 mm⁻¹
b = 7.638 (2) Å	T = 100 K
c = 18.514 (6) Å	0.29 × 0.14 × 0.08 mm
β = 95.494 (5)°

Data collection top

Bruker Kappa APEXII DUO CCD diffractometer	2724 independent reflections
Absorption correction: numerical (SADABS; Sheldrick, 1996)	1908 reflections with I > 2σ(I)
T_min = 0.975, T_max = 0.993	R_int = 0.067
14047 measured reflections	θ_max = 24.1°

Refinement top

R[F² > 2σ(F²)] = 0.065	0 restraints
wR(F²) = 0.181	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.71 e Å⁻³
2724 reflections	Δρ_min = −0.29 e Å⁻³
239 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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) −x+3/2, y+1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₂₁H₂₁N₃O₂
M_r	347.41
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	12.192 (4), 7.638 (2), 18.514 (6)
β (°)	95.494 (5)
V (Å³)	1716.1 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.29 × 0.14 × 0.08

Data collection
Diffractometer	Bruker Kappa APEXII DUO CCD diffractometer
Absorption correction	Numerical (SADABS; Sheldrick, 1996)
T_min, T_max	0.975, 0.993
No. of measured, independent and observed [I > 2σ(I)] reflections	14047, 2724, 1908
R_int	0.067
θ_max (°)	24.1
(sin θ/λ)_max (Å⁻¹)	0.575

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.065, 0.181, 1.03
No. of reflections	2724
No. of parameters	239
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.71, −0.29

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Macrae et al., 2008), SHELXTL (Sheldrick, 2008) and local programs.

Hydrogen-bond geometry (Å, º) top

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)	136.3

Symmetry code: (i) −x+3/2, y+1/2, −z+3/2.

Acknowledgements

The diffractometer was purchased with funding from NSF grant No. CHE-0741837.

References

Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Hulme, C. & Gore, V. (2003). Curr. Med. Chem. 10, 51–80. Web of Science CrossRef PubMed CAS Google Scholar
Hulme, C., Ma, L., Romano, J. J., Morton, G., Tang, S.-Y., Cherrier, M.-P., Choi, S., Salvino, J. & Labaudiniere, R. (2000). Tetrahedron Lett. 41, 1889–1893. Web of Science CrossRef CAS Google Scholar
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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

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Experimental

Crystal data

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Refinement

Supporting information

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References

organic compounds

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