Methyl 2,4,5,10-tetra­hydro­pyrazolo[3,4-a]carbazole-3-carboxyl­ate acetic acid solvate at 160 K

Gunaseelan, A.T.; Thiruvalluvar, A.; Martin, A.E.; Prasad, K.J.R.

doi:10.1107/S1600536807020491

Methyl 2,4,5,10-tetrahydropyrazolo[3,4-a]carbazole-3-carboxylate acetic acid solvate at 160 K

A. T. Gunaseelan, A. Thiruvalluvar, A. E. Martin and K. J. R. Prasad

The heterofused carbazole unit of the title compound, C₁₅H₁₃N₃O₂, is not planar. The planar pyrazole ring forms dihedral angles of 2.52 (8)°, 3.18 (7)° and 2.22 (6)° with the pyrrole ring, the benzene ring and the attached carboxylate group respectively. The cyclohexene ring adopts a half-chair conformation. In the crystal structure, the molecules are stabilized by intermolecular N—H

O and O—H

N hydrogen bonds.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807020491/bq2014sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807020491/bq2014Isup2.hkl Contains datablock I

CCDC reference: 647730

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Key indicators

Single-crystal X-ray study
T = 160 K
Mean (C-C) = 0.002 Å
R factor = 0.054
wR factor = 0.152
Data-to-parameter ratio = 19.5

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No syntax errors found



Alert level C
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.25
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.13

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

The emerging importance towards the various strategies applied to prepare carbazoles and its derivatives were due to their diverse pharmacological properties (Bhattacharayya et al., 1987; Chakraborty et al., 1991; Chakraborty, 1993; Hewlins et al., 1984). Development of new methods for the synthesis of functionalized carbazoles in particular, is attracting organic chemists due to the discovery of many carbazole alkaloids with varied pharmacological properties (Pinder, 1990; Danish, & Rajendra Prasad, 2004; Ebenezer Martin, & Rajendra Prasad, 2006a; Balamurali, & Rajendra Prasad, 2001; Joule, 1984; Kapil, 1971). Identification of promising antineoplastic activity of ellipticine, tetracyclic compounds of the pyridocarbazole type, have stimulated considerable interest in the field of fused systems (Haider, 2002). In addition, pyridocarbazoles were reported to elicit anti-HIV properties (Hirata et al., 1999; Wang et al., 2005).

At this context, we planned to utilize an intermediate, methyl 2-(1-oxo-2,3,4,9-tetrahydro-1H-carbazol-2-yl)-2-oxoacetate (1) to construct newer fused carbazole. The reaction of (1) with hydrazine hydrate yielded pyrazolocarbazole, either methyl 2,4,5,10-tetrahydropyrazolo[3,4-a]carbazole-3-carboxylate (2) or methyl 1,4,5,10-tetrahydropyrazolo[3,4-a]carbazole-3-carboxylate (3) (Ebenezer Martin & Rajendra Prasad, 2006b). We present here the X-ray crystal and molecular structure of (2).

The molecular structure of (I), with atomic numbering scheme, is shown in Fig. 1. The pyrazolocarbazole unit is not planar. The carboxylate group at position 3 has a 2.22 (6)° tilt with that of the pyrazole ring. The cyclohexene ring adopts a half-chair conformation. Molecules are linked by intermolecular N—H···O and O—H···N hydrogen bonds. The N2—H2···O31 forms an infinite chain. The O3—H3···N1 and N10—H10···O2 hydrogen bonds between the heterofused carbazole units and the acetic acid solvent molecules form a 9-membered ring closure networks (Fig. 2).

Related literature top

For related literature, see: Balamurali & Rajendra Prasad (2001); Bhattacharayya & Chakraborty (1987); Chakraborty (1993); Chakraborty & Roy (1991); Danish & Rajendra Prasad (2004); Ebenezer & Rajendra Prasad (2006a,b); Haider (2002); Hewlins et al. (1984); Hirata et al. (1999); Joule (1984); Kapil (1971); Pinder (1990); Wang et al. (2005).

Experimental top

The methyl 2-(1-oxo-2,3,4,9-tetrahydro-1H-carbazol-2-yl)-2-oxoacetate (243 mg, 0.001 mol) in glacial acetic acid (15 ml) was added hydrazine hydrate (0.1 ml, 0.002 mol) and refluxed on oil bath for 1 h. The reaction was monitored by TLC. After the completion of the reaction it was poured into crushed ice. The precipitate was filtered, washed with water and dried. It was purified by column chromatography over silica gel using petroleum ether: ethyl acetate (85:15) as eluant. The product was characterized as (I). The yield of the isolated product was 181 g (68%).

Structure description top

Computing details top

Data collection: COLLECT (Nonius, 2000); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: PLATON (Spek, 2003).

Figures top

	Fig. 1. The molecular structure of (I), showing the atom-numbering scheme and displacement ellipsoids drawn at the 50% probability level. H atoms involved in hydrogen bonding are labelled.
	Fig. 2. The packing of (I), viewed down the a axis. Dashed lines indicate hydrogen bonds. H atoms not involved in hydrogen bonding have been omitted.

Methyl 2,4,5,10-tetrahydropyrazolo[3,4-a]carbazole-3-carboxylate acetic acid solvate top

Crystal data top

C₁₅H₁₃N₃O₂·C₂H₄O₂	Z = 2
M_r = 327.34	F(000) = 344
Triclinic, P1	D_x = 1.396 Mg m⁻³
Hall symbol: -P 1	Melting point: 512(1) K
a = 7.1379 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.0450 (4) Å	Cell parameters from 4376 reflections
c = 11.5179 (4) Å	θ = 2.0–30.0°
α = 117.252 (1)°	µ = 0.10 mm⁻¹
β = 100.046 (2)°	T = 160 K
γ = 95.486 (2)°	Block, colourless
V = 778.75 (5) Å³	0.3 × 0.2 × 0.13 mm

Data collection top

Nonius KappaCCD area-detector diffractometer	3773 reflections with I > 2σ(I)
Radiation source: Nonius FR590 sealed tube generator	R_int = 0.054
Horizontally mounted graphite crystal monochromator	θ_max = 30.0°, θ_min = 2.1°
Detector resolution: 9 pixels mm^-1	h = −10→10
φ and ω scans with κ offsets	k = −15→15
24031 measured reflections	l = −16→15
4507 independent reflections

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)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.152	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0862P)² + 0.2457P] where P = (F_o² + 2F_c²)/3
4507 reflections	(Δ/σ)_max = 0.001
231 parameters	Δρ_max = 0.55 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₁₅H₁₃N₃O₂·C₂H₄O₂	γ = 95.486 (2)°
M_r = 327.34	V = 778.75 (5) Å³
Triclinic, P1	Z = 2
a = 7.1379 (2) Å	Mo Kα radiation
b = 11.0450 (4) Å	µ = 0.10 mm⁻¹
c = 11.5179 (4) Å	T = 160 K
α = 117.252 (1)°	0.3 × 0.2 × 0.13 mm
β = 100.046 (2)°

Data collection top

Nonius KappaCCD area-detector diffractometer	3773 reflections with I > 2σ(I)
24031 measured reflections	R_int = 0.054
4507 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.055	0 restraints
wR(F²) = 0.152	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.55 e Å⁻³
4507 reflections	Δρ_min = −0.24 e Å⁻³
231 parameters

Special details top

Experimental. Solvent used: Cooling Device: Oxford Cryosystems Cryostream 700 Crystal mount: glued on a glass fibre Mosaicity (°.): 0.939 (2) Frames collected: 486 Seconds exposure per frame: 127 Degrees rotation per frame: 1.7 Crystal-Detector distance (mm): 30.0

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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.

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

	x	y	z	U_iso*/U_eq
O31	0.34994 (16)	0.82581 (10)	0.39653 (10)	0.0314 (3)
O32	0.20500 (14)	0.68331 (9)	0.17749 (9)	0.0264 (3)
N1	0.43529 (15)	1.12962 (10)	0.28289 (10)	0.0206 (3)
N2	0.42196 (16)	1.04370 (11)	0.33625 (10)	0.0217 (3)
N10	0.36245 (16)	1.21943 (11)	0.06189 (11)	0.0219 (3)
C3	0.32604 (17)	0.91281 (12)	0.24179 (12)	0.0196 (3)
C3A	0.27148 (16)	0.91219 (12)	0.12022 (11)	0.0173 (3)
C4	0.15818 (18)	0.80167 (12)	−0.01701 (12)	0.0209 (3)
C5	0.15172 (19)	0.84277 (13)	−0.12920 (12)	0.0228 (3)
C5A	0.21838 (17)	0.99373 (12)	−0.08205 (11)	0.0183 (3)
C5B	0.21568 (17)	1.06733 (13)	−0.15717 (12)	0.0197 (3)
C6	0.1484 (2)	1.02927 (15)	−0.29372 (13)	0.0264 (4)
C7	0.1741 (2)	1.12956 (16)	−0.33302 (15)	0.0323 (4)
C8	0.2638 (2)	1.26784 (16)	−0.23907 (15)	0.0325 (4)
C9	0.3301 (2)	1.30847 (14)	−0.10401 (14)	0.0280 (4)
C9A	0.30722 (18)	1.20748 (13)	−0.06413 (13)	0.0214 (3)
C10A	0.31031 (17)	1.08946 (12)	0.04899 (11)	0.0179 (3)
C11	0.34203 (17)	1.04983 (12)	0.15214 (11)	0.0179 (3)
C31	0.29712 (18)	0.80540 (13)	0.28174 (12)	0.0219 (3)
C32	0.1711 (3)	0.57044 (15)	0.20758 (16)	0.0375 (4)
O2	0.39202 (19)	0.54902 (11)	0.70226 (11)	0.0403 (3)
O3	0.33632 (16)	0.61547 (11)	0.54596 (10)	0.0326 (3)
C1	0.1918 (2)	0.38672 (15)	0.48456 (15)	0.0355 (4)
C2	0.31737 (19)	0.52438 (13)	0.58875 (13)	0.0250 (3)
H2	0.482 (3)	1.070 (2)	0.422 (2)	0.036 (5)*
H4A	0.02342	0.77694	−0.01285	0.0251*
H4B	0.21548	0.71766	−0.04202	0.0251*
H5A	0.23310	0.78999	−0.18831	0.0274*
H5B	0.01653	0.81341	−0.18472	0.0274*
H6	0.08625	0.93623	−0.35802	0.0317*
H7	0.13016	1.10437	−0.42534	0.0387*
H8	0.27922	1.33456	−0.26888	0.0389*
H9	0.38939	1.40228	−0.04033	0.0336*
H10	0.436 (3)	1.298 (2)	0.139 (2)	0.043 (5)*
H32A	0.29511	0.55974	0.25030	0.0561*
H32B	0.11044	0.48403	0.12389	0.0561*
H32C	0.08493	0.59121	0.26892	0.0561*
H1A	0.06179	0.38137	0.50082	0.0532*
H1B	0.18255	0.37707	0.39471	0.0532*
H1C	0.24908	0.31175	0.49005	0.0532*
H3	0.412 (4)	0.706 (3)	0.613 (3)	0.077 (8)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O31	0.0460 (6)	0.0263 (5)	0.0190 (4)	−0.0040 (4)	−0.0014 (4)	0.0140 (4)
O32	0.0369 (5)	0.0179 (4)	0.0204 (4)	−0.0042 (4)	−0.0002 (4)	0.0102 (3)
N1	0.0278 (5)	0.0163 (5)	0.0155 (5)	0.0004 (4)	0.0011 (4)	0.0082 (4)
N2	0.0305 (5)	0.0175 (5)	0.0143 (5)	−0.0014 (4)	−0.0002 (4)	0.0085 (4)
N10	0.0267 (5)	0.0175 (5)	0.0181 (5)	−0.0035 (4)	−0.0014 (4)	0.0096 (4)
C3	0.0236 (6)	0.0172 (5)	0.0165 (5)	0.0003 (4)	0.0022 (4)	0.0086 (4)
C3A	0.0189 (5)	0.0154 (5)	0.0156 (5)	0.0003 (4)	0.0027 (4)	0.0069 (4)
C4	0.0248 (6)	0.0170 (5)	0.0154 (5)	−0.0031 (4)	−0.0002 (4)	0.0065 (4)
C5	0.0310 (6)	0.0174 (5)	0.0142 (5)	−0.0011 (4)	−0.0006 (4)	0.0061 (4)
C5A	0.0195 (5)	0.0174 (5)	0.0162 (5)	0.0001 (4)	0.0012 (4)	0.0084 (4)
C5B	0.0197 (5)	0.0216 (5)	0.0174 (5)	0.0004 (4)	0.0009 (4)	0.0112 (4)
C6	0.0291 (6)	0.0290 (7)	0.0185 (6)	−0.0010 (5)	−0.0013 (5)	0.0132 (5)
C7	0.0363 (7)	0.0390 (8)	0.0237 (6)	−0.0004 (6)	−0.0014 (5)	0.0214 (6)
C8	0.0353 (7)	0.0361 (8)	0.0321 (7)	−0.0014 (6)	0.0006 (6)	0.0258 (6)
C9	0.0315 (7)	0.0241 (6)	0.0289 (7)	−0.0033 (5)	0.0002 (5)	0.0174 (5)
C9A	0.0216 (6)	0.0222 (6)	0.0208 (6)	−0.0003 (4)	0.0010 (4)	0.0131 (5)
C10A	0.0202 (5)	0.0164 (5)	0.0152 (5)	−0.0009 (4)	0.0002 (4)	0.0083 (4)
C11	0.0204 (5)	0.0163 (5)	0.0155 (5)	0.0011 (4)	0.0021 (4)	0.0078 (4)
C31	0.0266 (6)	0.0192 (5)	0.0177 (5)	−0.0003 (4)	0.0016 (4)	0.0095 (5)
C32	0.0542 (9)	0.0213 (6)	0.0342 (8)	−0.0051 (6)	0.0025 (7)	0.0165 (6)
O2	0.0606 (7)	0.0225 (5)	0.0254 (5)	−0.0078 (5)	−0.0083 (5)	0.0109 (4)
O3	0.0442 (6)	0.0228 (5)	0.0222 (5)	−0.0078 (4)	−0.0027 (4)	0.0103 (4)
C1	0.0420 (8)	0.0213 (6)	0.0267 (7)	−0.0074 (5)	−0.0018 (6)	0.0043 (5)
C2	0.0290 (6)	0.0184 (5)	0.0209 (6)	0.0006 (4)	0.0028 (5)	0.0060 (5)

Geometric parameters (Å, º) top

O31—C31	1.2157 (16)	C5B—C9A	1.419 (2)
O32—C31	1.3284 (17)	C6—C7	1.384 (3)
O32—C32	1.449 (2)	C7—C8	1.404 (2)
O2—C2	1.2127 (17)	C8—C9	1.382 (2)
O3—C2	1.313 (2)	C9—C9A	1.394 (2)
O3—H3	0.97 (3)	C10A—C11	1.4338 (18)
N1—C11	1.3455 (15)	C4—H4B	0.9900
N1—N2	1.3508 (18)	C4—H4A	0.9900
N2—C3	1.3612 (18)	C5—H5B	0.9900
N10—C9A	1.3765 (18)	C5—H5A	0.9900
N10—C10A	1.380 (2)	C6—H6	0.9500
N2—H2	0.90 (2)	C7—H7	0.9500
N10—H10	0.93 (2)	C8—H8	0.9500
C3—C31	1.466 (2)	C9—H9	0.9500
C3—C3A	1.3831 (17)	C32—H32C	0.9800
C3A—C11	1.406 (2)	C32—H32B	0.9800
C3A—C4	1.4969 (17)	C32—H32A	0.9800
C4—C5	1.5487 (19)	C1—C2	1.500 (2)
C5—C5A	1.493 (2)	C1—H1A	0.9800
C5A—C10A	1.3736 (16)	C1—H1B	0.9800
C5A—C5B	1.432 (2)	C1—H1C	0.9800
C5B—C6	1.4048 (18)

O2···N10ⁱ	2.8480 (17)	C11···C5A^vi	3.3978 (17)
O3···C2ⁱⁱ	3.2828 (18)	C31···C7^vii	3.598 (2)
O3···N1ⁱ	2.7183 (16)	C31···C8^vi	3.373 (2)
O31···N2ⁱ	2.8181 (14)	C2···H5A^iv	3.0900
O31···N2	2.8207 (18)	C2···H10ⁱ	2.93 (2)
O32···C4	3.0568 (17)	C5A···H4A^vii	3.0900
O2···H8ⁱⁱⁱ	2.6100	C5B···H4A^vii	2.8900
O2···H5A^iv	2.8200	C6···H7^viii	3.0700
O2···H32Aⁱⁱ	2.7200	C7···H7^viii	3.0600
O2···H10ⁱ	1.92 (2)	C9A···H4A^vii	2.6600
O3···H1A^v	2.8100	C10A···H5B^vii	3.0400
O31···H32A	2.5800	C10A···H4A^vii	2.9900
O31···H2	2.64 (2)	C11···H5B^vii	3.0900
O31···H2ⁱ	1.95 (2)	C11···H3ⁱ	2.90 (3)
O31···H32C	2.6600	C31···H2ⁱ	3.07 (2)
O32···H4B	2.7400	H1A···O3^v	2.8100
N1···O3ⁱ	2.7183 (16)	H1B···H5B^ix	2.4200
N1···N10	3.1117 (17)	H2···C31ⁱ	3.07 (2)
N2···O31	2.8207 (18)	H2···O31	2.64 (2)
N2···O31ⁱ	2.8181 (14)	H2···O31ⁱ	1.95 (2)
N2···C6^vi	3.3060 (19)	H3···N2ⁱ	2.65 (4)
N10···N1	3.1117 (17)	H3···N1ⁱ	1.76 (3)
N10···O2ⁱ	2.8480 (17)	H3···C11ⁱ	2.90 (3)
N1···H3ⁱ	1.76 (3)	H4A···N10^vii	2.7200
N2···H3ⁱ	2.65 (4)	H4A···C5A^vii	3.0900
N10···H4A^vii	2.7200	H4A···C9A^vii	2.6600
C2···O3ⁱⁱ	3.2828 (18)	H4A···C10A^vii	2.9900
C2···C2ⁱⁱ	3.5195 (19)	H4A···H32B^ix	2.5500
C3···C5B^vi	3.5874 (18)	H4A···C5B^vii	2.8900
C3···C9A^vi	3.5846 (18)	H4B···O32	2.7400
C3A···C9A^vi	3.4443 (18)	H5A···O2^x	2.8200
C3A···C5B^vi	3.5836 (17)	H5A···C2^x	3.0900
C3A···C5B^vii	3.5920 (17)	H5B···H1B^ix	2.4200
C4···O32	3.0568 (17)	H5B···C11^vii	3.0900
C5A···C11^vi	3.3978 (17)	H5B···C10A^vii	3.0400
C5A···C10A^vi	3.5737 (18)	H6···H7^viii	2.5100
C5B···C3A^vii	3.5920 (17)	H7···C7^viii	3.0600
C5B···C3A^vi	3.5836 (17)	H7···C6^viii	3.0700
C5B···C3^vi	3.5874 (18)	H7···H6^viii	2.5100
C5B···C11^vi	3.5257 (18)	H7···H7^viii	2.4800
C6···N2^vi	3.3060 (19)	H8···O2^xi	2.6100
C7···C31^vii	3.598 (2)	H9···H9^xii	2.2400
C8···C31^vi	3.373 (2)	H10···C2ⁱ	2.93 (2)
C9A···C3^vi	3.5846 (18)	H10···O2ⁱ	1.92 (2)
C9A···C3A^vi	3.4443 (18)	H32A···O31	2.5800
C10A···C10A^vi	3.5439 (18)	H32A···O2ⁱⁱ	2.7200
C10A···C5A^vi	3.5737 (18)	H32B···H4A^ix	2.5500
C11···C5B^vi	3.5257 (18)	H32C···O31	2.6600

C31—O32—C32	115.61 (11)	O31—C31—C3	124.08 (13)
C2—O3—H3	115 (2)	O32—C31—C3	111.81 (11)
N2—N1—C11	104.48 (11)	O31—C31—O32	124.11 (14)
N1—N2—C3	111.79 (10)	C3A—C4—H4A	109.00
C9A—N10—C10A	107.60 (11)	C3A—C4—H4B	109.00
N1—N2—H2	122.3 (16)	C5—C4—H4B	109.00
C3—N2—H2	125.5 (16)	H4A—C4—H4B	108.00
C9A—N10—H10	125.8 (14)	C5—C4—H4A	109.00
C10A—N10—H10	126.2 (14)	C4—C5—H5B	108.00
N2—C3—C31	119.39 (11)	C5A—C5—H5A	108.00
C3A—C3—C31	132.85 (12)	C5A—C5—H5B	108.00
N2—C3—C3A	107.76 (12)	H5A—C5—H5B	107.00
C3—C3A—C11	103.67 (11)	C4—C5—H5A	108.00
C4—C3A—C11	123.81 (11)	C5B—C6—H6	121.00
C3—C3A—C4	132.48 (13)	C7—C6—H6	121.00
C3A—C4—C5	114.64 (12)	C8—C7—H7	119.00
C4—C5—C5A	115.76 (10)	C6—C7—H7	119.00
C5—C5A—C5B	129.99 (11)	C9—C8—H8	119.00
C5—C5A—C10A	123.74 (12)	C7—C8—H8	119.00
C5B—C5A—C10A	106.14 (12)	C8—C9—H9	121.00
C6—C5B—C9A	118.86 (14)	C9A—C9—H9	121.00
C5A—C5B—C9A	106.79 (11)	O32—C32—H32A	109.00
C5A—C5B—C6	134.34 (14)	O32—C32—H32B	109.00
C5B—C6—C7	118.90 (14)	H32A—C32—H32B	109.00
C6—C7—C8	121.27 (14)	H32A—C32—H32C	109.00
C7—C8—C9	121.10 (17)	H32B—C32—H32C	109.00
C8—C9—C9A	117.89 (15)	O32—C32—H32C	109.00
N10—C9A—C9	129.59 (13)	O2—C2—C1	122.75 (15)
C5B—C9A—C9	121.97 (12)	O3—C2—C1	113.74 (12)
N10—C9A—C5B	108.44 (13)	O2—C2—O3	123.51 (14)
N10—C10A—C5A	111.01 (11)	C2—C1—H1A	109.00
N10—C10A—C11	127.96 (11)	C2—C1—H1B	109.00
C5A—C10A—C11	121.03 (13)	C2—C1—H1C	109.00
N1—C11—C3A	112.30 (11)	H1A—C1—H1B	109.00
C3A—C11—C10A	119.70 (10)	H1A—C1—H1C	109.00
N1—C11—C10A	128.01 (13)	H1B—C1—H1C	109.00

C32—O32—C31—O31	−0.8 (2)	C4—C5—C5A—C5B	−174.14 (12)
C32—O32—C31—C3	179.64 (13)	C4—C5—C5A—C10A	10.59 (18)
C11—N1—N2—C3	1.00 (14)	C10A—C5A—C5B—C6	178.22 (15)
N2—N1—C11—C3A	−1.05 (14)	C5—C5A—C5B—C9A	−176.44 (13)
N2—N1—C11—C10A	179.08 (12)	C5B—C5A—C10A—C11	−178.67 (11)
N1—N2—C3—C31	−179.77 (11)	C10A—C5A—C5B—C9A	−0.53 (14)
N1—N2—C3—C3A	−0.60 (15)	C5—C5A—C5B—C6	2.3 (2)
C9A—N10—C10A—C11	178.46 (12)	C5B—C5A—C10A—N10	1.18 (14)
C10A—N10—C9A—C5B	0.99 (15)	C5—C5A—C10A—N10	177.41 (12)
C9A—N10—C10A—C5A	−1.38 (15)	C5—C5A—C10A—C11	−2.44 (19)
C10A—N10—C9A—C9	−179.06 (14)	C9A—C5B—C6—C7	0.2 (2)
C31—C3—C3A—C4	1.4 (2)	C5A—C5B—C6—C7	−178.45 (14)
C31—C3—C3A—C11	178.96 (14)	C5A—C5B—C9A—N10	−0.29 (14)
N2—C3—C3A—C11	−0.06 (13)	C5A—C5B—C9A—C9	179.76 (13)
C3A—C3—C31—O32	2.4 (2)	C6—C5B—C9A—C9	0.8 (2)
N2—C3—C31—O31	1.8 (2)	C6—C5B—C9A—N10	−179.26 (12)
N2—C3—C3A—C4	−177.63 (13)	C5B—C6—C7—C8	−0.7 (2)
C3A—C3—C31—O31	−177.14 (14)	C6—C7—C8—C9	0.2 (2)
N2—C3—C31—O32	−178.66 (11)	C7—C8—C9—C9A	0.8 (2)
C3—C3A—C11—N1	0.70 (14)	C8—C9—C9A—N10	178.82 (14)
C3—C3A—C11—C10A	−179.41 (11)	C8—C9—C9A—C5B	−1.2 (2)
C11—C3A—C4—C5	9.58 (18)	N10—C10A—C11—N1	−2.5 (2)
C3—C3A—C4—C5	−173.26 (13)	C5A—C10A—C11—C3A	−2.53 (18)
C4—C3A—C11—N1	178.55 (11)	N10—C10A—C11—C3A	177.65 (12)
C4—C3A—C11—C10A	−1.57 (18)	C5A—C10A—C11—N1	177.33 (12)
C3A—C4—C5—C5A	−13.28 (16)

Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) −x+1, −y+1, −z+1; (iii) x, y−1, z+1; (iv) x, y, z+1; (v) −x, −y+1, −z+1; (vi) −x+1, −y+2, −z; (vii) −x, −y+2, −z; (viii) −x, −y+2, −z−1; (ix) −x, −y+1, −z; (x) x, y, z−1; (xi) x, y+1, z−1; (xii) −x+1, −y+3, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O31ⁱ	0.90 (2)	1.95 (2)	2.8181 (14)	163 (2)
O3—H3···N1ⁱ	0.97 (3)	1.76 (3)	2.7183 (16)	172 (3)
N10—H10···O2ⁱ	0.93 (2)	1.92 (2)	2.8480 (17)	175 (2)

Symmetry code: (i) −x+1, −y+2, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₅H₁₃N₃O₂·C₂H₄O₂
M_r	327.34
Crystal system, space group	Triclinic, P1
Temperature (K)	160
a, b, c (Å)	7.1379 (2), 11.0450 (4), 11.5179 (4)
α, β, γ (°)	117.252 (1), 100.046 (2), 95.486 (2)
V (Å³)	778.75 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.3 × 0.2 × 0.13

Data collection
Diffractometer	Nonius KappaCCD area-detector
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	24031, 4507, 3773
R_int	0.054
(sin θ/λ)_max (Å⁻¹)	0.703

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.055, 0.152, 1.05
No. of reflections	4507
No. of parameters	231
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.55, −0.24

Computer programs: COLLECT (Nonius, 2000), DENZO-SMN (Otwinowski & Minor, 1997), DENZO-SMN and SCALEPACK (Otwinowski & Minor, 1997), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), PLATON (Spek, 2003).