(11aS)-7-Bromo-2,3,5,10,11,11a-hexa-hydro-1H-pyrrolo-[2,1-c][1,4]benzodiazepine-3,11-dione.

The title compound, C(12)H(11)BrN(2)O(2), was prepared by an intra-cyclization reaction of (S)-1-(5-bromo-2-nitro-benz-yl)-5-oxopyrrolidine-2-carb-oxy-lic acid methyl ester in the presence of EtOH/Fe. The five-membered pyrrolidinone ring adopts an approximate envelope conformation, while the seven-membered diazepanone ring displays a twisted boat conformation. Inter-molecular classical N-H⋯O hydrogen bonds and weak C-H⋯O inter-actions help to stabilize the crystal structure.

Related literature

For applications of pyrrolo­[2,1-c][1,4]benzodiazepines, see: Bose et al. (1992 ▶); Hu et al. (2001 ▶); Jitendra et al. (2007 ▶); Kamal et al. (2002 ▶); Thurston & Bose (1994 ▶). For a related structure, see: Cheng et al. (2007 ▶).

Experimental

Crystal data

C12H11BrN2O2

M = 295.14

Orthorhombic,

a = 4.3880 (4) Å

b = 13.1210 (11) Å

c = 19.8722 (16) Å

V = 1144.14 (17) Å3

Z = 4

Mo Kα radiation

μ = 3.58 mm−1

T = 185 K

0.22 × 0.18 × 0.07 mm

Data collection

Bruker APEX CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T min = 0.506, T max = 0.788

7012 measured reflections

2244 independent reflections

2074 reflections with I > 2σ(I)

R int = 0.021

Refinement

R[F 2 > 2σ(F 2)] = 0.022

wR(F 2) = 0.057

S = 1.02

2244 reflections

154 parameters

H-atom parameters constrained

Δρmax = 0.49 e Å−3

Δρmin = −0.21 e Å−3

Absolute structure: Flack (1983 ▶), 884 Friedel pairs

Flack parameter: −0.007 (9)

Data collection: SMART (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: SHELXTL; software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811052962/xu5404sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811052962/xu5404Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811052962/xu5404Isup3.cml

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

C12H11BrN2O2	F(000) = 592
Mr = 295.14	Dx = 1.713 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 3967 reflections
a = 4.3880 (4) Å	θ = 2.6–26.0°
b = 13.1210 (11) Å	µ = 3.58 mm−1
c = 19.8722 (16) Å	T = 185 K
V = 1144.14 (17) Å3	Plate, colorless
Z = 4	0.22 × 0.18 × 0.07 mm

Bruker APEX CCD area-detector diffractometer	2244 independent reflections
Radiation source: fine-focus sealed tube	2074 reflections with I > 2σ(I)
graphite	Rint = 0.021
φ and ω scans	θmax = 26.0°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −5→5
Tmin = 0.506, Tmax = 0.788	k = −14→16
7012 measured reflections	l = −23→24

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.022	H-atom parameters constrained
wR(F2) = 0.057	w = 1/[σ2(Fo2) + (0.0236P)2] where P = (Fo2 + 2Fc2)/3
S = 1.02	(Δ/σ)max = 0.001
2244 reflections	Δρmax = 0.49 e Å−3
154 parameters	Δρmin = −0.21 e Å−3
0 restraints	Absolute structure: Flack (1983), 884 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: −0.007 (9)

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
Br1	0.25401 (6)	0.050666 (16)	0.521650 (10)	0.04269 (9)
O1	1.0495 (4)	0.02986 (12)	0.85625 (8)	0.0421 (4)
O2	0.9421 (4)	0.41192 (12)	0.82097 (8)	0.0443 (4)
N1	0.8206 (4)	0.16602 (12)	0.80547 (8)	0.0238 (4)
N2	0.7499 (5)	0.35871 (11)	0.72148 (7)	0.0275 (3)
H2	0.8076	0.4163	0.7027	0.033*
C1	0.8919 (5)	0.10757 (16)	0.85843 (11)	0.0301 (5)
C2	0.7399 (7)	0.15233 (16)	0.92027 (10)	0.0388 (5)
H2A	0.8826	0.1537	0.9588	0.047*
H2B	0.5574	0.1123	0.9329	0.047*
C3	0.6517 (5)	0.26009 (17)	0.89928 (10)	0.0322 (5)
H3A	0.8033	0.3101	0.9157	0.039*
H3B	0.4489	0.2785	0.9175	0.039*
C4	0.6457 (4)	0.25772 (15)	0.82215 (10)	0.0253 (5)
H4	0.4310	0.2502	0.8060	0.030*
C5	0.9226 (5)	0.14577 (17)	0.73654 (10)	0.0249 (4)
H5A	0.9572	0.0717	0.7312	0.030*
H5B	1.1195	0.1808	0.7289	0.030*
C6	0.6986 (4)	0.18057 (14)	0.68438 (9)	0.0214 (4)
C7	0.6198 (5)	0.28407 (15)	0.67832 (10)	0.0240 (4)
C8	0.7940 (5)	0.35007 (14)	0.78876 (10)	0.0276 (4)
C9	0.5797 (5)	0.11109 (15)	0.63852 (10)	0.0233 (4)
H9	0.6271	0.0407	0.6424	0.028*
C10	0.3923 (5)	0.14489 (17)	0.58721 (10)	0.0267 (4)
C11	0.3113 (5)	0.24598 (17)	0.58081 (10)	0.0295 (5)
H11	0.1805	0.2676	0.5455	0.035*
C12	0.4250 (5)	0.31536 (17)	0.62704 (11)	0.0291 (5)
H12	0.3692	0.3851	0.6237	0.035*

	U11	U22	U33	U12	U13	U23
Br1	0.06219 (16)	0.03517 (14)	0.03072 (13)	0.00004 (16)	−0.01668 (12)	−0.00718 (8)
O1	0.0678 (12)	0.0294 (9)	0.0292 (9)	0.0169 (9)	−0.0064 (8)	0.0009 (7)
O2	0.0671 (12)	0.0285 (9)	0.0374 (10)	−0.0143 (9)	−0.0088 (9)	−0.0034 (7)
N1	0.0321 (10)	0.0195 (8)	0.0199 (8)	0.0021 (7)	0.0005 (7)	−0.0026 (6)
N2	0.0391 (9)	0.0173 (7)	0.0262 (8)	−0.0044 (10)	0.0027 (9)	−0.0003 (6)
C1	0.0400 (12)	0.0244 (11)	0.0261 (12)	−0.0031 (10)	−0.0012 (10)	−0.0022 (9)
C2	0.0597 (13)	0.0332 (11)	0.0235 (10)	0.0038 (16)	0.0059 (14)	0.0014 (8)
C3	0.0411 (13)	0.0314 (12)	0.0241 (11)	0.0036 (9)	0.0040 (9)	−0.0054 (9)
C4	0.0293 (11)	0.0230 (10)	0.0236 (10)	0.0028 (8)	0.0022 (8)	−0.0028 (8)
C5	0.0268 (11)	0.0250 (10)	0.0229 (10)	0.0004 (9)	0.0013 (8)	−0.0031 (9)
C6	0.0230 (11)	0.0221 (9)	0.0190 (9)	0.0013 (8)	0.0077 (8)	0.0005 (7)
C7	0.0288 (10)	0.0202 (10)	0.0231 (10)	−0.0035 (8)	0.0048 (9)	0.0011 (8)
C8	0.0316 (12)	0.0195 (9)	0.0318 (11)	0.0024 (10)	0.0010 (9)	−0.0039 (8)
C9	0.0273 (10)	0.0202 (10)	0.0226 (10)	−0.0005 (8)	0.0028 (9)	−0.0010 (8)
C10	0.0313 (10)	0.0271 (11)	0.0218 (11)	−0.0033 (9)	0.0014 (9)	−0.0043 (9)
C11	0.0359 (13)	0.0320 (11)	0.0205 (10)	0.0047 (10)	−0.0015 (9)	0.0051 (8)
C12	0.0383 (12)	0.0219 (11)	0.0271 (12)	0.0035 (9)	0.0050 (10)	0.0029 (9)

Br1—C10	1.896 (2)	C3—H3B	0.9900
O1—C1	1.233 (3)	C4—C8	1.527 (3)
O2—C8	1.221 (2)	C4—H4	1.0000
N1—C1	1.339 (3)	C5—C6	1.500 (3)
N1—C4	1.465 (2)	C5—H5A	0.9900
N1—C5	1.465 (3)	C5—H5B	0.9900
N2—C8	1.356 (2)	C6—C9	1.391 (3)
N2—C7	1.422 (3)	C6—C7	1.406 (3)
N2—H2	0.8800	C7—C12	1.392 (3)
C1—C2	1.517 (3)	C9—C10	1.383 (3)
C2—C3	1.524 (3)	C9—H9	0.9500
C2—H2A	0.9900	C10—C11	1.379 (3)
C2—H2B	0.9900	C11—C12	1.386 (3)
C3—C4	1.533 (3)	C11—H11	0.9500
C3—H3A	0.9900	C12—H12	0.9500
C1—N1—C4	114.51 (16)	N1—C5—C6	113.00 (16)
C1—N1—C5	124.01 (17)	N1—C5—H5A	109.0
C4—N1—C5	121.36 (15)	C6—C5—H5A	109.0
C8—N2—C7	126.49 (16)	N1—C5—H5B	109.0
C8—N2—H2	116.8	C6—C5—H5B	109.0
C7—N2—H2	116.8	H5A—C5—H5B	107.8
O1—C1—N1	125.2 (2)	C9—C6—C7	118.99 (18)
O1—C1—C2	126.5 (2)	C9—C6—C5	119.95 (17)
N1—C1—C2	108.19 (18)	C7—C6—C5	120.95 (18)
C1—C2—C3	104.43 (17)	C12—C7—C6	119.90 (19)
C1—C2—H2A	110.9	C12—C7—N2	119.02 (18)
C3—C2—H2A	110.9	C6—C7—N2	120.98 (18)
C1—C2—H2B	110.9	O2—C8—N2	122.50 (19)
C3—C2—H2B	110.9	O2—C8—C4	121.76 (18)
H2A—C2—H2B	108.9	N2—C8—C4	115.73 (17)
C2—C3—C4	105.02 (17)	C10—C9—C6	119.74 (19)
C2—C3—H3A	110.7	C10—C9—H9	120.1
C4—C3—H3A	110.7	C6—C9—H9	120.1
C2—C3—H3B	110.7	C11—C10—C9	121.97 (19)
C4—C3—H3B	110.7	C11—C10—Br1	118.79 (15)
H3A—C3—H3B	108.8	C9—C10—Br1	119.20 (16)
N1—C4—C8	109.27 (16)	C10—C11—C12	118.56 (19)
N1—C4—C3	103.52 (16)	C10—C11—H11	120.7
C8—C4—C3	114.27 (17)	C12—C11—H11	120.7
N1—C4—H4	109.9	C11—C12—C7	120.8 (2)
C8—C4—H4	109.9	C11—C12—H12	119.6
C3—C4—H4	109.9	C7—C12—H12	119.6

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1i	0.88	2.00	2.864 (2)	169.
C5—H5A···O2ii	0.99	2.38	3.328 (3)	160.

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O1i	0.88	2.00	2.864 (2)	169
C5—H5A⋯O2ii	0.99	2.38	3.328 (3)	160

Symmetry codes: (i) ; (ii) .