(11aS)-8-Hydr-oxy-7-meth-oxy-2,3,5,10,11,11a-hexa-hydro-1H-pyrrolo[2,1-c][1,4]benzodiazepine-3,11-dione.

The title chiral compound, C(13)H(14)N(2)O(4), was prepared by an intra-cyclization reaction of methyl (S)-1-(4-hydr-oxy-5-meth-oxy-2-nitro-benz-yl)-5-oxopyrrolidine-2-carboxyl-ate in the presence of ethanol and iron. The five-membered substituted pyrrole ring adopts an approximate envelope conformation, while the seven-membered substituted diazepine ring displays a twist-boat conformation. Inter-molecular O-H⋯O and N-H⋯O hydrogen bonding helps to stabilize the crystal structure.

Related literature

For general background, see: Bose et al. (1992 ▶); Hu et al. (2001 ▶); Kamal et al. (2002 ▶); Thurston & Bose (1994 ▶). For a related structure, see: Cheng et al. (2007 ▶).

Experimental

Crystal data

C13H14N2O4

M = 262.26

Monoclinic,

a = 6.3819 (7) Å

b = 9.3139 (10) Å

c = 10.3673 (11) Å

β = 103.621 (1)°

V = 598.90 (11) Å3

Z = 2

Mo Kα radiation

μ = 0.11 mm−1

T = 187 (2) K

0.48 × 0.26 × 0.15 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer

Absorption correction: none

3169 measured reflections

1168 independent reflections

1149 reflections with I > 2σ(I)

R int = 0.013

Refinement

R[F 2 > 2σ(F 2)] = 0.030

wR(F 2) = 0.074

S = 1.12

1168 reflections

174 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.14 e Å−3

Δρmin = −0.19 e Å−3

Data collection: SMART (Bruker, 1997 ▶); cell refinement: SAINT (Bruker, 1999 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ▶); molecular graphics: SHELXTL-Plus (Siemens, 1990 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807066056/xu2391sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807066056/xu2391Isup2.hkl

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

C13H14N2O4	F000 = 276
Mr = 262.26	Dx = 1.454 Mg m−3
Monoclinic, P21	Mo Kα radiation λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 2332 reflections
a = 6.3819 (7) Å	θ = 3.0–25.3º
b = 9.3139 (10) Å	µ = 0.11 mm−1
c = 10.3673 (11) Å	T = 187 (2) K
β = 103.621 (1)º	Block, colorless
V = 598.90 (11) Å3	0.48 × 0.26 × 0.15 mm
Z = 2

Bruker SMART APEX CCD area-detector diffractometer	1149 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.013
Monochromator: graphite	θmax = 25.3º
T = 187(2) K	θmin = 3.0º
φ and ω scans	h = −7→7
Absorption correction: none	k = −5→11
3169 measured reflections	l = −12→11
1168 independent reflections

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)] = 0.030	H-atom parameters constrained
wR(F2) = 0.074	w = 1/[σ2(Fo2) + (0.0425P)2 + 0.0991P] where P = (Fo2 + 2Fc2)/3
S = 1.12	(Δ/σ)max = 0.004
1168 reflections	Δρmax = 0.14 e Å−3
174 parameters	Δρmin = −0.19 e Å−3
1 restraint	Extinction correction: none
Primary atom site location: structure-invariant direct methods

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
C1	−0.1968 (3)	0.3136 (2)	0.6150 (2)	0.0254 (4)
C2	0.0218 (3)	0.2900 (2)	0.6730 (2)	0.0283 (5)
C3	0.1550 (3)	0.4061 (3)	0.7152 (2)	0.0290 (5)
H3	0.3026	0.3905	0.7566	0.035*
C4	0.0751 (3)	0.5463 (3)	0.6978 (2)	0.0275 (5)
C5	−0.1437 (3)	0.5676 (2)	0.6429 (2)	0.0263 (4)
C6	−0.2799 (4)	0.4511 (3)	0.6011 (2)	0.0280 (5)
H6	−0.4289	0.4662	0.5632	0.034*
C7	0.3005 (4)	0.1165 (3)	0.7439 (3)	0.0375 (5)
H7A	0.3303	0.1447	0.8375	0.056*
H7B	0.3962	0.1695	0.6995	0.056*
H7C	0.3253	0.0132	0.7374	0.056*
C8	−0.1959 (3)	0.8199 (2)	0.7104 (2)	0.0281 (5)
C9	0.2252 (3)	0.6725 (2)	0.7329 (2)	0.0304 (5)
H9A	0.3751	0.6369	0.7620	0.037*
H9B	0.2159	0.7322	0.6528	0.037*
C10	−0.0465 (3)	0.7914 (3)	0.8459 (2)	0.0280 (5)
H10	−0.1028	0.7076	0.8878	0.034*
C11	−0.0166 (3)	0.9189 (3)	0.9420 (2)	0.0360 (5)
H11A	−0.1253	0.9172	0.9962	0.043*
H11B	−0.0277	1.0112	0.8935	0.043*
C12	0.2116 (4)	0.8965 (3)	1.0287 (2)	0.0402 (6)
H12A	0.2842	0.9897	1.0540	0.048*
H12B	0.2073	0.8425	1.1103	0.048*
C13	0.3266 (3)	0.8111 (3)	0.9419 (2)	0.0310 (5)
N1	−0.2336 (3)	0.7085 (2)	0.62395 (18)	0.0314 (4)
H1A	−0.3508	0.7192	0.5458	0.038*
N2	0.1759 (3)	0.76080 (19)	0.83733 (17)	0.0267 (4)
O1	−0.3329 (2)	0.20085 (17)	0.57207 (15)	0.0316 (4)
H1	−0.2729	0.1238	0.6029	0.047*
O2	0.0812 (2)	0.14895 (17)	0.68141 (17)	0.0352 (4)
O3	0.5206 (2)	0.7896 (2)	0.96020 (16)	0.0416 (4)
O4	−0.2877 (3)	0.93534 (18)	0.68144 (17)	0.0373 (4)

	U11	U22	U33	U12	U13	U23
C1	0.0268 (10)	0.0274 (11)	0.0211 (9)	−0.0026 (9)	0.0038 (8)	−0.0001 (9)
C2	0.0280 (11)	0.0297 (11)	0.0279 (11)	0.0021 (9)	0.0078 (8)	0.0001 (9)
C3	0.0229 (10)	0.0323 (12)	0.0309 (11)	0.0032 (9)	0.0047 (8)	−0.0027 (10)
C4	0.0264 (10)	0.0303 (11)	0.0253 (10)	−0.0007 (9)	0.0055 (8)	−0.0016 (9)
C5	0.0284 (10)	0.0255 (11)	0.0228 (9)	0.0015 (9)	0.0017 (8)	0.0005 (9)
C6	0.0255 (10)	0.0311 (12)	0.0247 (10)	−0.0005 (9)	0.0003 (8)	0.0023 (9)
C7	0.0272 (11)	0.0336 (12)	0.0514 (14)	0.0057 (9)	0.0092 (9)	0.0039 (11)
C8	0.0219 (9)	0.0255 (11)	0.0353 (11)	−0.0025 (9)	0.0036 (8)	0.0026 (10)
C9	0.0271 (10)	0.0322 (12)	0.0320 (11)	−0.0021 (9)	0.0070 (9)	−0.0034 (9)
C10	0.0236 (10)	0.0306 (11)	0.0296 (11)	−0.0027 (9)	0.0059 (8)	0.0006 (9)
C11	0.0305 (11)	0.0423 (14)	0.0357 (11)	−0.0042 (11)	0.0086 (9)	−0.0097 (11)
C12	0.0354 (12)	0.0521 (16)	0.0309 (11)	−0.0078 (11)	0.0035 (9)	−0.0089 (11)
C13	0.0272 (10)	0.0333 (12)	0.0295 (10)	−0.0055 (9)	0.0010 (8)	0.0034 (10)
N1	0.0294 (9)	0.0277 (10)	0.0304 (9)	0.0014 (9)	−0.0066 (7)	0.0029 (9)
N2	0.0216 (8)	0.0298 (10)	0.0273 (9)	−0.0013 (7)	0.0027 (7)	−0.0013 (7)
O1	0.0300 (8)	0.0249 (8)	0.0350 (8)	−0.0020 (7)	−0.0019 (6)	0.0021 (7)
O2	0.0277 (8)	0.0272 (9)	0.0477 (10)	0.0039 (7)	0.0029 (7)	−0.0019 (7)
O3	0.0246 (8)	0.0513 (11)	0.0437 (10)	−0.0034 (8)	−0.0021 (7)	−0.0010 (9)
O4	0.0328 (9)	0.0254 (8)	0.0482 (9)	0.0019 (7)	−0.0013 (7)	0.0036 (7)

C1—O1	1.369 (3)	C8—C10	1.524 (3)
C1—C6	1.381 (3)	C9—N2	1.452 (3)
C1—C2	1.400 (3)	C9—H9A	0.9900
C2—O2	1.364 (3)	C9—H9B	0.9900
C2—C3	1.382 (3)	C10—N2	1.471 (3)
C3—C4	1.398 (3)	C10—C11	1.532 (3)
C3—H3	0.9500	C10—H10	1.0000
C4—C5	1.392 (3)	C11—C12	1.535 (3)
C4—C9	1.506 (3)	C11—H11A	0.9900
C5—C6	1.394 (3)	C11—H11B	0.9900
C5—N1	1.427 (3)	C12—C13	1.514 (3)
C6—H6	0.9500	C12—H12A	0.9900
C7—O2	1.429 (3)	C12—H12B	0.9900
C7—H7A	0.9800	C13—O3	1.224 (3)
C7—H7B	0.9800	C13—N2	1.353 (3)
C7—H7C	0.9800	N1—H1A	0.9699
C8—O4	1.228 (3)	O1—H1	0.8400
C8—N1	1.355 (3)
O1—C1—C6	118.58 (18)	C4—C9—H9B	109.1
O1—C1—C2	120.7 (2)	H9A—C9—H9B	107.8
C6—C1—C2	120.7 (2)	N2—C10—C8	112.39 (17)
O2—C2—C3	126.32 (19)	N2—C10—C11	102.46 (16)
O2—C2—C1	114.37 (19)	C8—C10—C11	114.80 (19)
C3—C2—C1	119.3 (2)	N2—C10—H10	109.0
C2—C3—C4	120.79 (18)	C8—C10—H10	109.0
C2—C3—H3	119.6	C11—C10—H10	109.0
C4—C3—H3	119.6	C10—C11—C12	103.35 (19)
C5—C4—C3	119.1 (2)	C10—C11—H11A	111.1
C5—C4—C9	120.5 (2)	C12—C11—H11A	111.1
C3—C4—C9	120.41 (19)	C10—C11—H11B	111.1
C6—C5—C4	120.5 (2)	C12—C11—H11B	111.1
C6—C5—N1	118.15 (18)	H11A—C11—H11B	109.1
C4—C5—N1	121.28 (19)	C13—C12—C11	104.43 (18)
C1—C6—C5	119.54 (19)	C13—C12—H12A	110.9
C1—C6—H6	120.2	C11—C12—H12A	110.9
C5—C6—H6	120.2	C13—C12—H12B	110.9
O2—C7—H7A	109.5	C11—C12—H12B	110.9
O2—C7—H7B	109.5	H12A—C12—H12B	108.9
H7A—C7—H7B	109.5	O3—C13—N2	124.7 (2)
O2—C7—H7C	109.5	O3—C13—C12	127.5 (2)
H7A—C7—H7C	109.5	N2—C13—C12	107.80 (18)
H7B—C7—H7C	109.5	C8—N1—C5	127.59 (17)
O4—C8—N1	120.58 (19)	C8—N1—H1A	117.1
O4—C8—C10	122.5 (2)	C5—N1—H1A	114.5
N1—C8—C10	116.85 (19)	C13—N2—C9	123.76 (18)
N2—C9—C4	112.66 (17)	C13—N2—C10	113.48 (18)
N2—C9—H9A	109.1	C9—N2—C10	122.48 (16)
C4—C9—H9A	109.1	C1—O1—H1	109.5
N2—C9—H9B	109.1	C2—O2—C7	117.41 (18)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O4i	0.84	1.95	2.707 (2)	150
N1—H1A···O1ii	0.97	2.11	3.023 (2)	157.2

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O4i	0.84	1.95	2.707 (2)	150
N1—H1A⋯O1ii	0.97	2.11	3.023 (2)	157

Symmetry codes: (i) ; (ii) .