6-Nitro-2,3-dihydro-1H-pyrrolo-[2,1-c][1,4]benzodiazepine-5,11(10H,11aH)-dione.

In the two mol-ecules of the asymmetric unit of the title compound, C(12)H(11)N(3)O(4), the seven-membered diazepine ring adopts a boat conformation (with the two phenyl-ene C atoms representing the stern and the methine C atom the prow). The five-membered pyrrole ring, which has an envelope conformation, makes dihedral angles of 60.47 (10) and 54.69 (9)° with the benzene ring of the benzodiazepine unit in the two mol-ecules. In the crystal, inter-molecular N-H⋯O hydrogen bonds and π-π stacking inter-actions [centroid-centroid distance = 3.8023 (7)-3.8946 (7) Å] lead to the formation of a three-dimensional framework.

Related literature

For the biological activity of pyrrolo­[2,1-c][1,4]benzodiazepine derivatives, see: Dervan (1986 ▶); Leimgruber et al. (1975 ▶); Da Settimo et al. (2007 ▶); Herpin et al. (2000 ▶); Arima et al. (1983 ▶).

Experimental

Crystal data

C12H11N3O4

M = 261.24

Monoclinic,

a = 10.7364 (2) Å

b = 6.8925 (1) Å

c = 16.3901 (3) Å

β = 101.870 (1)°

V = 1186.94 (4) Å3

Z = 4

Mo Kα radiation

μ = 0.11 mm−1

T = 296 K

0.23 × 0.20 × 0.15 mm

Data collection

Bruker APEXII CCD detector diffractometer

14768 measured reflections

2543 independent reflections

2452 reflections with I > 2σ(I)

R int = 0.021

Refinement

R[F 2 > 2σ(F 2)] = 0.030

wR(F 2) = 0.080

S = 1.04

2543 reflections

351 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.17 e Å−3

Δρmin = −0.16 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811024500/vm2102sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811024500/vm2102Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811024500/vm2102Isup3.cml

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

C12H11N3O4	F(000) = 544
Mr = 261.24	Dx = 1.462 Mg m−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 246 reflections
a = 10.7364 (2) Å	θ = 2.4–26.3°
b = 6.8925 (1) Å	µ = 0.11 mm−1
c = 16.3901 (3) Å	T = 296 K
β = 101.870 (1)°	Prism, colourless
V = 1186.94 (4) Å3	0.23 × 0.20 × 0.15 mm
Z = 4

Bruker APEXII CCD detector diffractometer	2452 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.021
graphite	θmax = 26.0°, θmin = 2.5°
ω and φ scans	h = −13→13
14768 measured reflections	k = −8→8
2543 independent reflections	l = −20→20

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.080	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ2(Fo2) + (0.0518P)2 + 0.1616P] where P = (Fo2 + 2Fc2)/3
2543 reflections	(Δ/σ)max < 0.001
351 parameters	Δρmax = 0.17 e Å−3
1 restraint	Δρmin = −0.16 e Å−3

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
C100	0.4871 (2)	0.4617 (3)	1.03240 (11)	0.0410 (4)
C101	0.3608 (2)	0.4649 (3)	0.99613 (13)	0.0445 (5)
C102	0.32175 (19)	0.4505 (3)	0.91009 (14)	0.0442 (5)
C103	0.41314 (17)	0.4215 (3)	0.86410 (11)	0.0359 (4)
C104	0.54297 (16)	0.4047 (3)	0.89854 (10)	0.0311 (4)
C105	0.58012 (18)	0.4374 (3)	0.98486 (10)	0.0336 (4)
C106	0.8095 (2)	0.5177 (3)	1.00041 (13)	0.0483 (5)
C107	0.63255 (16)	0.3127 (3)	0.85085 (10)	0.0316 (4)
C109	0.84963 (18)	0.3029 (4)	0.82441 (13)	0.0479 (5)
C110	0.9600 (2)	0.4396 (6)	0.8535 (2)	0.0749 (9)
C111	0.9040 (3)	0.6286 (5)	0.8754 (2)	0.0752 (9)
C112	0.7860 (2)	0.5679 (4)	0.90711 (14)	0.0485 (5)
C200	0.44163 (18)	0.4931 (3)	0.38760 (12)	0.0399 (4)
C201	0.40473 (19)	0.4968 (3)	0.46329 (13)	0.0440 (5)
C202	0.4948 (2)	0.5030 (3)	0.53689 (12)	0.0430 (4)
C203	0.62060 (19)	0.5134 (3)	0.53182 (11)	0.0374 (4)
C204	0.66333 (16)	0.5194 (3)	0.45691 (10)	0.0318 (4)
C205	0.57090 (16)	0.4986 (3)	0.38404 (10)	0.0318 (4)
C206	0.70022 (18)	0.4042 (3)	0.28050 (11)	0.0378 (4)
C207	0.79608 (17)	0.5876 (3)	0.45641 (11)	0.0360 (4)
C209	0.98134 (19)	0.5664 (4)	0.39103 (15)	0.0522 (6)
C210	1.0011 (2)	0.4484 (5)	0.31649 (15)	0.0655 (8)
C211	0.9243 (2)	0.2650 (4)	0.32000 (15)	0.0559 (6)
C212	0.80720 (17)	0.3350 (3)	0.35062 (11)	0.0369 (4)
H100	0.5118	0.4760	1.0899	0.049*
H101	0.3004	0.4767	1.0292	0.053*
H102	0.2362	0.4603	0.8845	0.053*
H10A	0.8258	0.2995	0.7640	0.058*
H10B	0.8700	0.1724	0.8451	0.058*
H10N	0.539 (3)	0.528 (5)	0.2657 (18)	0.056 (8)*
H112	0.7192	0.6665	0.8932	0.058*
H11A	0.8815	0.7115	0.8267	0.090*
H11B	0.9636	0.6972	0.9182	0.090*
H11C	1.0174	0.3867	0.9019	0.090*
H11D	1.0070	0.4595	0.8096	0.090*
H200	0.3803	0.4870	0.3385	0.048*
H201	0.3187	0.4950	0.4649	0.053*
H202	0.4709	0.5002	0.5883	0.052*
H20A	1.0469	0.5388	0.4399	0.063*
H20B	0.9812	0.7043	0.3793	0.063*
H20N	0.716 (2)	0.416 (5)	1.0780 (17)	0.058 (7)*
H212	0.7765	0.2341	0.3837	0.044*
H21A	0.9722	0.1718	0.3584	0.067*
H21B	0.9005	0.2058	0.2653	0.067*
H21C	0.9703	0.5183	0.2649	0.079*
H21D	1.0905	0.4183	0.3208	0.079*
N10	0.60011 (15)	0.4905 (3)	0.30409 (9)	0.0369 (4)
N11	0.71691 (17)	0.5079 (3)	0.61116 (9)	0.0464 (4)
N12	0.85585 (14)	0.5013 (3)	0.40290 (9)	0.0371 (4)
N20	0.70780 (16)	0.4399 (3)	1.02707 (10)	0.0413 (4)
N21	0.36959 (16)	0.4213 (3)	0.77185 (11)	0.0479 (4)
N22	0.74763 (15)	0.3889 (3)	0.86106 (10)	0.0380 (4)
O11	0.60185 (13)	0.1634 (2)	0.81012 (8)	0.0435 (4)
O12	0.91105 (16)	0.5401 (4)	1.04775 (12)	0.0739 (6)
O13	0.26234 (16)	0.3669 (4)	0.74408 (12)	0.0761 (6)
O14	0.44340 (18)	0.4853 (4)	0.73230 (10)	0.0743 (6)
O21	0.84147 (15)	0.7225 (3)	0.50119 (10)	0.0571 (4)
O22	0.70331 (15)	0.3858 (3)	0.20681 (8)	0.0581 (5)
O23	0.6951 (2)	0.5986 (4)	0.66967 (9)	0.0723 (6)
O24	0.80876 (17)	0.4033 (4)	0.61259 (10)	0.0725 (6)

	U11	U22	U33	U12	U13	U23
C100	0.0594 (12)	0.0344 (10)	0.0313 (8)	0.0026 (9)	0.0144 (8)	−0.0011 (8)
C101	0.0534 (12)	0.0395 (11)	0.0477 (11)	0.0024 (9)	0.0268 (9)	−0.0014 (9)
C102	0.0350 (9)	0.0462 (12)	0.0522 (11)	0.0019 (9)	0.0107 (8)	−0.0011 (10)
C103	0.0352 (9)	0.0384 (10)	0.0328 (8)	0.0023 (8)	0.0039 (7)	0.0010 (8)
C104	0.0335 (8)	0.0321 (9)	0.0275 (7)	−0.0022 (7)	0.0057 (6)	0.0010 (7)
C105	0.0420 (9)	0.0288 (9)	0.0290 (8)	0.0006 (8)	0.0054 (7)	−0.0002 (7)
C106	0.0483 (11)	0.0426 (11)	0.0478 (11)	−0.0081 (10)	−0.0043 (9)	−0.0095 (10)
C107	0.0311 (8)	0.0397 (10)	0.0225 (7)	−0.0023 (8)	0.0021 (6)	0.0011 (7)
C109	0.0339 (10)	0.0676 (15)	0.0441 (10)	0.0059 (10)	0.0124 (8)	0.0114 (11)
C110	0.0398 (12)	0.097 (2)	0.0907 (19)	−0.0091 (14)	0.0187 (12)	0.021 (2)
C111	0.0662 (17)	0.079 (2)	0.0801 (18)	−0.0344 (16)	0.0148 (14)	0.0114 (17)
C112	0.0483 (11)	0.0458 (12)	0.0499 (11)	−0.0153 (10)	0.0064 (9)	0.0005 (10)
C200	0.0364 (9)	0.0400 (10)	0.0417 (9)	−0.0023 (9)	0.0046 (7)	0.0022 (9)
C201	0.0381 (10)	0.0452 (11)	0.0519 (11)	−0.0033 (9)	0.0163 (8)	0.0039 (10)
C202	0.0537 (11)	0.0398 (10)	0.0407 (9)	0.0029 (10)	0.0217 (8)	0.0050 (9)
C203	0.0479 (10)	0.0353 (9)	0.0289 (8)	0.0061 (9)	0.0079 (7)	0.0014 (8)
C204	0.0358 (9)	0.0313 (9)	0.0282 (8)	0.0027 (7)	0.0059 (7)	0.0000 (7)
C205	0.0359 (9)	0.0294 (8)	0.0299 (8)	0.0005 (8)	0.0065 (7)	0.0018 (7)
C206	0.0412 (9)	0.0434 (10)	0.0273 (8)	−0.0008 (9)	0.0038 (7)	−0.0013 (8)
C207	0.0346 (9)	0.0420 (10)	0.0292 (8)	0.0010 (8)	0.0015 (7)	−0.0022 (8)
C209	0.0338 (10)	0.0653 (15)	0.0589 (12)	−0.0050 (10)	0.0124 (9)	−0.0021 (12)
C210	0.0449 (11)	0.100 (2)	0.0558 (13)	0.0031 (14)	0.0205 (10)	−0.0026 (15)
C211	0.0461 (12)	0.0721 (17)	0.0486 (11)	0.0161 (12)	0.0078 (9)	−0.0136 (12)
C212	0.0393 (10)	0.0408 (10)	0.0298 (8)	0.0036 (8)	0.0047 (7)	−0.0026 (8)
N10	0.0374 (8)	0.0469 (9)	0.0236 (7)	0.0050 (8)	−0.0001 (6)	0.0032 (7)
N11	0.0565 (10)	0.0552 (11)	0.0274 (7)	0.0124 (10)	0.0083 (7)	0.0032 (8)
N12	0.0316 (7)	0.0454 (9)	0.0339 (7)	−0.0014 (7)	0.0054 (6)	−0.0026 (8)
N20	0.0489 (9)	0.0438 (10)	0.0264 (7)	−0.0011 (8)	−0.0033 (6)	−0.0014 (7)
N21	0.0385 (9)	0.0599 (11)	0.0410 (8)	0.0143 (9)	−0.0017 (7)	−0.0011 (9)
N22	0.0335 (7)	0.0454 (9)	0.0350 (7)	−0.0040 (7)	0.0070 (6)	−0.0002 (7)
O11	0.0392 (7)	0.0551 (9)	0.0365 (7)	−0.0099 (7)	0.0085 (5)	−0.0170 (7)
O12	0.0528 (9)	0.0925 (16)	0.0643 (10)	−0.0183 (10)	−0.0158 (8)	−0.0133 (11)
O13	0.0474 (9)	0.1032 (18)	0.0660 (11)	0.0102 (11)	−0.0155 (8)	−0.0227 (12)
O14	0.0711 (11)	0.1173 (18)	0.0343 (7)	0.0125 (13)	0.0102 (7)	0.0148 (11)
O21	0.0456 (8)	0.0651 (11)	0.0592 (9)	−0.0130 (8)	0.0075 (7)	−0.0283 (9)
O22	0.0600 (9)	0.0874 (13)	0.0262 (6)	0.0125 (10)	0.0070 (6)	−0.0042 (8)
O23	0.0948 (13)	0.0859 (14)	0.0326 (7)	0.0271 (12)	0.0053 (8)	−0.0093 (9)
O24	0.0681 (10)	0.1011 (16)	0.0439 (8)	0.0377 (12)	0.0012 (7)	0.0013 (10)

C100—H100	0.9300	C203—N11	1.486 (2)
C100—C101	1.365 (3)	C203—C202	1.372 (3)
C101—H101	0.9300	C204—C207	1.502 (3)
C101—C102	1.390 (3)	C204—C203	1.397 (2)
C102—H102	0.9300	C204—C205	1.394 (2)
C103—N21	1.488 (2)	C205—N10	1.410 (2)
C103—C102	1.369 (3)	C205—C200	1.402 (3)
C104—C107	1.499 (2)	C206—N10	1.352 (3)
C104—C105	1.407 (2)	C206—O22	1.222 (2)
C104—C103	1.397 (2)	C207—O21	1.222 (3)
C105—N20	1.403 (2)	C209—H20B	0.9700
C105—C100	1.397 (3)	C209—H20A	0.9700
C106—N20	1.366 (3)	C209—C210	1.519 (4)
C106—O12	1.211 (3)	C210—H21D	0.9700
C107—N22	1.321 (2)	C210—H21C	0.9700
C107—O11	1.234 (2)	C211—H21B	0.9700
C109—H10B	0.9700	C211—H21A	0.9700
C109—H10A	0.9700	C211—C210	1.516 (5)
C109—C110	1.512 (4)	C212—H212	0.9800
C110—H11D	0.9700	C212—C211	1.525 (3)
C110—H11C	0.9700	C212—C206	1.525 (3)
C111—H11B	0.9700	N10—H10N	0.85 (3)
C111—H11A	0.9700	N11—O24	1.218 (3)
C111—C110	1.508 (5)	N11—O23	1.207 (2)
C112—H112	0.9800	N12—C209	1.470 (2)
C112—C106	1.537 (3)	N12—C212	1.462 (3)
C112—C111	1.524 (3)	N12—C207	1.329 (3)
C200—H200	0.9300	N20—H20N	0.84 (3)
C200—C201	1.378 (3)	N21—O13	1.208 (3)
C201—H201	0.9300	N21—O14	1.206 (3)
C202—H202	0.9300	N22—C109	1.477 (3)
C202—C201	1.383 (3)	N22—C112	1.461 (3)
C105—C100—H100	119.4	C204—C203—N11	118.34 (17)
C101—C100—H100	119.4	C202—C203—N11	117.53 (17)
C101—C100—C105	121.28 (18)	C202—C203—C204	124.06 (18)
C102—C101—H101	119.8	C203—C204—C207	119.82 (16)
C100—C101—H101	119.8	C205—C204—C207	122.44 (15)
C100—C101—C102	120.41 (17)	C205—C204—C203	116.44 (16)
C101—C102—H102	121.0	C200—C205—N10	116.68 (16)
C103—C102—H102	121.0	C204—C205—N10	123.03 (15)
C103—C102—C101	117.92 (18)	C204—C205—C200	120.24 (16)
C104—C103—N21	119.29 (16)	N10—C206—C212	116.22 (15)
C102—C103—N21	116.65 (17)	O22—C206—C212	122.90 (18)
C102—C103—C104	123.93 (17)	O22—C206—N10	120.88 (18)
C105—C104—C107	120.83 (16)	N12—C207—C204	116.80 (17)
C103—C104—C107	121.21 (15)	O21—C207—C204	119.76 (17)
C103—C104—C105	116.48 (16)	O21—C207—N12	123.36 (18)
N20—C105—C104	122.95 (17)	H20A—C209—H20B	109.1
C100—C105—C104	119.53 (18)	C210—C209—H20B	111.1
C100—C105—N20	117.48 (16)	N12—C209—H20B	111.1
N20—C106—C112	115.31 (17)	C210—C209—H20A	111.1
O12—C106—C112	123.4 (2)	N12—C209—H20A	111.1
O12—C106—N20	121.2 (2)	N12—C209—C210	103.11 (19)
N22—C107—C104	116.70 (17)	H21C—C210—H21D	108.9
O11—C107—C104	120.41 (16)	C209—C210—H21D	110.9
O11—C107—N22	122.60 (18)	C211—C210—H21D	110.9
H10A—C109—H10B	109.1	C209—C210—H21C	110.9
C110—C109—H10B	111.2	C211—C210—H21C	110.9
N22—C109—H10B	111.2	C211—C210—C209	104.39 (19)
C110—C109—H10A	111.2	H21A—C211—H21B	109.0
N22—C109—H10A	111.2	C212—C211—H21B	111.0
N22—C109—C110	102.7 (2)	C210—C211—H21B	111.0
H11C—C110—H11D	108.6	C212—C211—H21A	111.0
C109—C110—H11D	110.4	C210—C211—H21A	111.0
C111—C110—H11D	110.4	C210—C211—C212	103.9 (2)
C109—C110—H11C	110.4	C211—C212—H212	110.6
C111—C110—H11C	110.4	C206—C212—H212	110.6
C111—C110—C109	106.8 (2)	N12—C212—H212	110.6
H11A—C111—H11B	109.0	C206—C212—C211	113.29 (16)
C112—C111—H11B	110.9	N12—C212—C211	102.79 (17)
C110—C111—H11B	110.9	N12—C212—C206	108.64 (17)
C112—C111—H11A	110.9	C205—N10—H10N	113.2 (18)
C110—C111—H11A	110.9	C206—N10—H10N	117.2 (18)
C110—C111—C112	104.1 (2)	C206—N10—C205	128.68 (16)
C106—C112—H112	110.5	O24—N11—C203	116.55 (17)
C111—C112—H112	110.5	O23—N11—C203	117.90 (18)
N22—C112—H112	110.5	O23—N11—O24	125.44 (18)
C111—C112—C106	115.0 (2)	C212—N12—C209	112.85 (16)
N22—C112—C106	107.16 (18)	C207—N12—C209	122.05 (19)
N22—C112—C111	102.8 (2)	C207—N12—C212	125.10 (16)
C205—C200—H200	119.8	C105—N20—H20N	112.6 (18)
C201—C200—H200	119.8	C106—N20—H20N	117.8 (19)
C201—C200—C205	120.49 (18)	C106—N20—C105	127.69 (17)
C202—C201—H201	119.8	O13—N21—C103	117.34 (19)
C200—C201—H201	119.8	O14—N21—C103	116.24 (18)
C200—C201—C202	120.46 (18)	O14—N21—O13	126.3 (2)
C201—C202—H202	121.0	C112—N22—C109	113.29 (17)
C203—C202—H202	121.0	C107—N22—C109	122.77 (19)
C203—C202—C201	118.00 (18)	C107—N22—C112	123.91 (18)

D—H···A	D—H	H···A	D···A	D—H···A
N10—H10N···O11i	0.85 (3)	1.98 (3)	2.821 (2)	169 (3)
N20—H20N···O22ii	0.84 (3)	2.15 (3)	2.980 (2)	169 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N10—H10N⋯O11i	0.85 (3)	1.98 (3)	2.821 (2)	169 (3)
N20—H20N⋯O22ii	0.84 (3)	2.15 (3)	2.980 (2)	169 (2)

Symmetry codes: (i) ; (ii) .