2-(2,3,4,9-Tetra­hydro-1H-carbazol-1-ylidene)propane­dinitrile

Archana, R.; Prabakaran, K.; Rajendra Prasad, K.J.; Thiruvalluvar, A.; Butcher, R.J.

doi:10.1107/S1600536810022671

organic compounds

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ISSN: 2056-9890

Volume 66| Part 7| July 2010| Page o1713

doi:10.1107/S1600536810022671

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2-(2,3,4,9-Tetrahydro-1H-carbazol-1-ylidene)propanedinitrile

R. Archana,^a K. Prabakaran,^b K. J. Rajendra Prasad,^b A. Thiruvalluvar ^a ^* and R. J. Butcher ^c

^aPG Research Department of Physics, Rajah Serfoji Government College (Autonomous), Thanjavur 613 005, Tamilnadu, India, ^bDepartment of Chemistry, Bharathiar University, Coimbatore 641 046, Tamilnadu, India, and ^cDepartment of Chemistry, Howard University, 525 College Street NW, Washington, DC 20059, USA
^*Correspondence e-mail: athiru@vsnl.net

(Received 4 June 2010; accepted 13 June 2010; online 18 June 2010)

In the title molecule, C₁₅H₁₁N₃, the dihedral angle between the benzene ring and the fused pyrrole ring is 1.07 (5)°. The cyclohexene ring adopts an envelope conformation: the dicyanomethylene group at position 1 has a coplanar orientation. An intramolecular N—H⋯N hydrogen bond generates an S(7) ring motif. Intermolecular N—H⋯N hydrogen bonds form an R₂²(14) ring in the crystal. A C—H⋯π interaction involving the benzene ring is also found in the structure.

Related literature

For naturally occurring carbazole alkaloids see: Scott et al. (2006 ). For the biological activity of carbazole alkaloids see: Ramsewak et al.(1999 ); Tachibana et al. (2001 ); Nakahara et al. (2002 ). For the crystal structures of substituted carbazole derivatives see: Gunaseelan et al. (2007a ,b , 2009 ); Thiruvalluvar et al. (2007 ); Sridharan et al. (2008 ). For ring conformations, see: Cremer & Pople (1975 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₁₅H₁₁N₃
M_r = 233.27
Monoclinic, P 2₁ /n
a = 8.4794 (3) Å
b = 10.5542 (4) Å
c = 13.0575 (5) Å
β = 97.366 (3)°
V = 1158.92 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 110 K
0.53 × 0.38 × 0.31 mm

Data collection

Oxford Diffraction Xcalibur Ruby Gemini diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.939, T_max = 1.000
8311 measured reflections
3822 independent reflections
2854 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.115
S = 0.98
3822 reflections
167 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C4B,C5–C8,C8A ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N9—H9⋯N13	0.913 (14)	2.508 (14)	3.2626 (12)	140.3 (11)
N9—H9⋯N13ⁱ	0.913 (14)	2.553 (14)	3.2267 (12)	131.1 (11)
C2—H2A⋯Cg1ⁱⁱ	0.99	2.79	3.6244 (10)	142
Symmetry codes: (i) -x+1, -y+1, -z; (ii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810022671/dn2576sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810022671/dn2576Isup2.hkl

checkCIF report

Comment top

Tetrahydrocarbazolones have been used extensively as advanced intermediates in synthetic efforts toward a number of naturally occurring carbazole alkaloids (Scott et al., 2006). Carbazole alkaloids possess various biological activities such as anti-tumor, anti-oxidative, anti-mutagenic, and anti-inflammatory activities (Ramsewak et al., 1999; Tachibana et al., 2001; Nakahara et al., 2002). Since it is known that carbazole alkaloids possess anti-tumor activity, the identification of alkaloids that are cytotoxic against tumor cells could lead to the development of a chemopreventive agent for tumor treatment.

Gunaseelan et al. (2007a,b), Gunaseelan et al. (2009), Thiruvalluvar et al. (2007) and Sridharan et al. (2008) have reported the crystal structures of substituted carbazole derivatives, in which the carbazole units are not planar. In the title molecule (Scheme I, Fig. 1), C₁₅H₁₁N₃, the carbazole unit is not planar. The dihedral angle between the benzene ring and the fused pyrrole ring is 1.07 (5)°. The r.m.s. deviation of a mean plane fitted through all non hydrogen atoms excluding C3 of the carbazole unit is 0.0263 Å; C3 deviates from this plane by 0.576 (1) Å. The cyclohexene ring adopts an envelope conformation. The puckering parameters (Cremer & Pople, 1975) are q2=0.3482 (10) Å, q3=-0.2564 (10) Å, Q=0.4324 (10) Å, θ=126.37 (13)° and ϕ=293.46 (16)°. The dicyanomethylene group at position 1 has a coplanar orientation. An intramolecular hydrogen contact N9—H9···N13 generates a ring of graph-set motif S(7) (Bernstein et al., 1995)(Table 1, Fig. 1). Intermolecular N9—H9···N13 hydrogen bonds form a R²₂(14)(Bernstein et al., 1995) ring in the crystal structure (Table 1, Fig. 2). A C2—H2A···π interaction involving the benzene (C4B,C5—C8,C8A) ring is also found in the structure(Table 1).

Related literature top

For naturally occurring carbazole alkaloids see: Scott et al. (2006). For the biological activity of carbazole alkaloids see: Ramsewak et al.(1999); Tachibana et al. (2001); Nakahara et al. (2002). For the crystal structures of substituted carbazole derivatives see: Gunaseelan et al. (2007a,b, 2009); Thiruvalluvar et al. (2007); Sridharan et al. (2008). For ring conformations, see: Cremer & Pople (1975). For hydrogen-bond motifs, see: Bernstein et al. (1995).

Experimental top

A mixture of 2,3,4,9-tetrahydro-1H-carbazol-1-one (0.199 g, 0.001 mol), malononitrile (0.066 g, 0.001 mol), ammonium acetate (0.092 g, 0.0012 mol) and few drops of acetic acid in 5 ml of toluene was refluxed at 383 K for 6 h. On cooling, the precipitate that formed was filtered off, washed with petroleum ether and dried. The crude product thus obtained was purified by column chromatography over silica gel using petroleum ether: ethyl acetate (99:1, v/v) to yield the titled product (0.173 g, 74%). This was recrystallized from ethyl acetate.

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound, showing the atom-numbering scheme and displacement ellipsoids drawn at the 50% probability level. H atoms are shown as small spheres of arbitrary radius.
	Fig. 2. A part of the crystal structure of (I), viewed along c axis, showing the formation of a R²₂(14) ring.

2-(2,3,4,9-Tetrahydro-1H-carbazol-1-ylidene)propanedinitrile top

Crystal data top

C₁₅H₁₁N₃	F(000) = 488
M_r = 233.27	D_x = 1.337 Mg m⁻³
Monoclinic, P2₁/n	Melting point: 470 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 8.4794 (3) Å	Cell parameters from 4130 reflections
b = 10.5542 (4) Å	θ = 4.7–32.6°
c = 13.0575 (5) Å	µ = 0.08 mm⁻¹
β = 97.366 (3)°	T = 110 K
V = 1158.92 (8) Å³	Prism, pale-yellow
Z = 4	0.53 × 0.38 × 0.31 mm

Data collection top

Oxford Diffraction Xcalibur Ruby Gemini diffractometer	3822 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2854 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
Detector resolution: 10.5081 pixels mm^-1	θ_max = 32.6°, θ_min = 4.7°
ω scans	h = −12→12
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	k = −15→15
T_min = 0.939, T_max = 1.000	l = −19→16
8311 measured 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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.115	H atoms treated by a mixture of independent and constrained refinement
S = 0.98	w = 1/[σ²(F_o²) + (0.0736P)²] where P = (F_o² + 2F_c²)/3
3822 reflections	(Δ/σ)_max = 0.001
167 parameters	Δρ_max = 0.40 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₁₅H₁₁N₃	V = 1158.92 (8) Å³
M_r = 233.27	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 8.4794 (3) Å	µ = 0.08 mm⁻¹
b = 10.5542 (4) Å	T = 110 K
c = 13.0575 (5) Å	0.53 × 0.38 × 0.31 mm
β = 97.366 (3)°

Data collection top

Oxford Diffraction Xcalibur Ruby Gemini diffractometer	3822 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	2854 reflections with I > 2σ(I)
T_min = 0.939, T_max = 1.000	R_int = 0.021
8311 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.115	H atoms treated by a mixture of independent and constrained refinement
S = 0.98	Δρ_max = 0.40 e Å⁻³
3822 reflections	Δρ_min = −0.24 e Å⁻³
167 parameters

Special details top

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 > 2σ(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
N9	0.20402 (9)	0.52842 (7)	0.07142 (6)	0.0170 (2)
N12	0.27359 (12)	0.01410 (9)	−0.03875 (8)	0.0333 (3)
N13	0.42310 (11)	0.40137 (9)	−0.08917 (7)	0.0351 (3)
C1	0.14687 (10)	0.29269 (9)	0.07178 (6)	0.0152 (2)
C2	0.05668 (11)	0.19571 (9)	0.12634 (7)	0.0194 (2)
C3	−0.09527 (10)	0.24541 (10)	0.16360 (7)	0.0219 (3)
C4	−0.06619 (11)	0.36476 (10)	0.22890 (7)	0.0212 (3)
C4A	0.03186 (10)	0.45589 (9)	0.17735 (6)	0.0166 (2)
C4B	0.04943 (10)	0.58875 (9)	0.19177 (7)	0.0179 (2)
C5	−0.01638 (11)	0.67652 (10)	0.25578 (8)	0.0238 (3)
C6	0.02314 (12)	0.80254 (10)	0.24880 (8)	0.0275 (3)
C7	0.12868 (12)	0.84267 (10)	0.18004 (8)	0.0264 (3)
C8	0.19716 (11)	0.75911 (9)	0.11745 (7)	0.0221 (2)
C8A	0.15696 (10)	0.63122 (9)	0.12427 (7)	0.0173 (2)
C9A	0.12894 (10)	0.42084 (8)	0.10364 (6)	0.0151 (2)
C11	0.24383 (10)	0.25207 (9)	0.00157 (7)	0.0178 (2)
C12	0.25910 (11)	0.12004 (10)	−0.02084 (7)	0.0222 (3)
C13	0.34255 (11)	0.33496 (10)	−0.04916 (7)	0.0226 (2)
H2A	0.12768	0.16285	0.18658	0.0232*
H2B	0.02872	0.12377	0.07880	0.0232*
H3A	−0.17457	0.26402	0.10301	0.0262*
H3B	−0.14007	0.17888	0.20485	0.0262*
H4A	−0.16918	0.40435	0.23835	0.0255*
H4B	−0.01056	0.34246	0.29787	0.0255*
H5	−0.08640	0.64936	0.30266	0.0286*
H6	−0.02115	0.86313	0.29074	0.0330*
H7	0.15343	0.93025	0.17673	0.0317*
H8	0.26848	0.78727	0.07176	0.0265*
H9	0.2890 (16)	0.5317 (13)	0.0351 (11)	0.043 (4)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N9	0.0188 (3)	0.0158 (4)	0.0172 (3)	−0.0019 (3)	0.0052 (3)	−0.0004 (3)
N12	0.0414 (5)	0.0225 (4)	0.0389 (5)	−0.0017 (4)	0.0158 (4)	−0.0055 (4)
N13	0.0396 (5)	0.0323 (5)	0.0383 (5)	−0.0131 (4)	0.0240 (4)	−0.0134 (4)
C1	0.0148 (4)	0.0166 (4)	0.0140 (4)	−0.0015 (3)	0.0007 (3)	0.0009 (3)
C2	0.0228 (4)	0.0177 (4)	0.0181 (4)	−0.0047 (3)	0.0046 (3)	0.0012 (4)
C3	0.0198 (4)	0.0262 (5)	0.0205 (4)	−0.0062 (4)	0.0057 (3)	0.0006 (4)
C4	0.0185 (4)	0.0271 (5)	0.0194 (4)	−0.0021 (4)	0.0074 (3)	−0.0002 (4)
C4A	0.0144 (4)	0.0204 (4)	0.0149 (4)	0.0006 (3)	0.0018 (3)	0.0004 (3)
C4B	0.0149 (4)	0.0208 (4)	0.0176 (4)	0.0022 (3)	0.0002 (3)	−0.0015 (4)
C5	0.0179 (4)	0.0290 (5)	0.0240 (4)	0.0059 (4)	0.0007 (3)	−0.0076 (4)
C6	0.0250 (5)	0.0263 (5)	0.0293 (5)	0.0096 (4)	−0.0040 (4)	−0.0107 (4)
C7	0.0292 (5)	0.0179 (4)	0.0290 (5)	0.0037 (4)	−0.0081 (4)	−0.0037 (4)
C8	0.0255 (4)	0.0175 (4)	0.0218 (4)	−0.0003 (4)	−0.0028 (3)	0.0007 (4)
C8A	0.0181 (4)	0.0169 (4)	0.0160 (4)	0.0014 (3)	−0.0013 (3)	−0.0009 (3)
C9A	0.0153 (4)	0.0157 (4)	0.0143 (4)	−0.0015 (3)	0.0023 (3)	0.0013 (3)
C11	0.0189 (4)	0.0166 (4)	0.0183 (4)	−0.0025 (3)	0.0044 (3)	−0.0026 (3)
C12	0.0238 (4)	0.0220 (5)	0.0219 (4)	−0.0014 (4)	0.0067 (3)	−0.0026 (4)
C13	0.0236 (4)	0.0221 (4)	0.0238 (4)	−0.0037 (4)	0.0097 (4)	−0.0081 (4)

Geometric parameters (Å, º) top

N9—C8A	1.3723 (12)	C6—C7	1.4115 (15)
N9—C9A	1.3929 (11)	C7—C8	1.3801 (14)
N12—C12	1.1521 (14)	C8—C8A	1.3978 (13)
N13—C13	1.1499 (14)	C11—C12	1.4331 (14)
N9—H9	0.913 (14)	C11—C13	1.4307 (13)
C1—C2	1.5099 (13)	C2—H2A	0.9900
C1—C11	1.3760 (12)	C2—H2B	0.9900
C1—C9A	1.4289 (13)	C3—H3A	0.9900
C2—C3	1.5273 (13)	C3—H3B	0.9900
C3—C4	1.5234 (14)	C4—H4A	0.9900
C4—C4A	1.4876 (13)	C4—H4B	0.9900
C4A—C9A	1.3943 (12)	C5—H5	0.9500
C4A—C4B	1.4201 (13)	C6—H6	0.9500
C4B—C5	1.4099 (14)	C7—H7	0.9500
C4B—C8A	1.4196 (13)	C8—H8	0.9500
C5—C6	1.3775 (15)

N9···N13	3.2626 (12)	C8A···H2A^vii	2.9000
N9···C13	2.9158 (13)	C9A···H3A	3.0600
N9···N13ⁱ	3.2267 (12)	C11···H9	3.001 (14)
N9···C9Aⁱⁱ	3.4392 (11)	C12···H2A	3.0900
N12···C3ⁱⁱⁱ	3.4371 (14)	C12···H2B	2.4800
N13···N9	3.2626 (12)	C13···H9	2.420 (14)
N13···N9ⁱ	3.2267 (12)	H2A···C12	3.0900
N13···N13ⁱ	3.2679 (13)	H2A···H7^iv	2.4700
N12···H2Bⁱⁱⁱ	2.9400	H2A···C4B^vi	3.0800
N12···H8^iv	2.8000	H2A···C8^vi	2.9700
N13···H9	2.508 (14)	H2A···C8A^vi	2.9000
N13···H9ⁱ	2.553 (14)	H2B···C12	2.4800
N13···H3B^v	2.8100	H2B···H7^iv	2.5600
C1···C6^vi	3.4129 (13)	H2B···N12ⁱⁱⁱ	2.9400
C1···C7^vi	3.5806 (13)	H3A···C9A	3.0600
C1···C8Aⁱⁱ	3.4849 (12)	H3A···C8ⁱⁱ	2.8700
C3···N12ⁱⁱⁱ	3.4371 (14)	H3A···H8ⁱⁱ	2.3800
C4A···C7^vi	3.4360 (13)	H3B···C5^viii	3.0200
C6···C9A^vii	3.5380 (13)	H3B···H5^viii	2.3300
C6···C1^vii	3.4129 (13)	H3B···N13^x	2.8100
C7···C9A^vii	3.3756 (13)	H4B···C8^vi	2.8800
C7···C1^vii	3.5806 (13)	H4B···H8^vi	2.5600
C7···C4A^vii	3.4360 (13)	H5···C3^ix	2.9700
C8A···C1ⁱⁱ	3.4849 (12)	H5···H3B^ix	2.3300
C9A···N9ⁱⁱ	3.4392 (11)	H7···C2^xi	2.9700
C9A···C6^vi	3.5380 (13)	H7···H2A^xi	2.4700
C9A···C7^vi	3.3756 (13)	H7···H2B^xi	2.5600
C13···N9	2.9158 (13)	H7···C4A^vii	3.0900
C2···H7^iv	2.9700	H8···N12^xi	2.8000
C3···H5^viii	2.9700	H8···H4B^vii	2.5600
C4A···H7^vi	3.0900	H8···H3Aⁱⁱ	2.3800
C4B···H2A^vii	3.0800	H9···N13	2.508 (14)
C5···H3B^ix	3.0200	H9···C11	3.001 (14)
C8···H3Aⁱⁱ	2.8700	H9···C13	2.420 (14)
C8···H2A^vii	2.9700	H9···N13ⁱ	2.553 (14)
C8···H4B^vii	2.8800

C8A—N9—C9A	108.60 (7)	C12—C11—C13	115.24 (8)
C9A—N9—H9	127.6 (9)	N12—C12—C11	179.07 (10)
C8A—N9—H9	122.1 (9)	N13—C13—C11	179.33 (10)
C2—C1—C11	119.03 (8)	C1—C2—H2A	109.00
C2—C1—C9A	115.16 (7)	C1—C2—H2B	109.00
C9A—C1—C11	125.72 (8)	C3—C2—H2A	109.00
C1—C2—C3	114.61 (8)	C3—C2—H2B	109.00
C2—C3—C4	112.31 (8)	H2A—C2—H2B	108.00
C3—C4—C4A	109.95 (7)	C2—C3—H3A	109.00
C4—C4A—C9A	123.68 (8)	C2—C3—H3B	109.00
C4B—C4A—C9A	107.00 (8)	C4—C3—H3A	109.00
C4—C4A—C4B	129.32 (8)	C4—C3—H3B	109.00
C5—C4B—C8A	119.68 (9)	H3A—C3—H3B	108.00
C4A—C4B—C5	133.21 (8)	C3—C4—H4A	110.00
C4A—C4B—C8A	107.11 (8)	C3—C4—H4B	110.00
C4B—C5—C6	118.49 (9)	C4A—C4—H4A	110.00
C5—C6—C7	120.75 (10)	C4A—C4—H4B	110.00
C6—C7—C8	122.29 (10)	H4A—C4—H4B	108.00
C7—C8—C8A	117.05 (9)	C4B—C5—H5	121.00
N9—C8A—C4B	108.30 (8)	C6—C5—H5	121.00
N9—C8A—C8	129.97 (8)	C5—C6—H6	120.00
C4B—C8A—C8	121.72 (8)	C7—C6—H6	120.00
N9—C9A—C1	127.87 (8)	C6—C7—H7	119.00
C1—C9A—C4A	123.12 (8)	C8—C7—H7	119.00
N9—C9A—C4A	108.99 (8)	C7—C8—H8	121.00
C1—C11—C13	123.57 (9)	C8A—C8—H8	121.00
C1—C11—C12	121.09 (8)

C9A—N9—C8A—C4B	−0.03 (12)	C4—C4A—C4B—C8A	179.76 (8)
C9A—N9—C8A—C8	−178.67 (9)	C9A—C4A—C4B—C5	−179.41 (10)
C8A—N9—C9A—C1	−177.78 (8)	C9A—C4A—C4B—C8A	0.72 (10)
C8A—N9—C9A—C4A	0.48 (10)	C4—C4A—C9A—N9	−179.85 (8)
C9A—C1—C2—C3	28.90 (11)	C4—C4A—C9A—C1	−1.49 (13)
C11—C1—C2—C3	−154.52 (8)	C4B—C4A—C9A—N9	−0.75 (9)
C2—C1—C9A—N9	176.14 (8)	C4B—C4A—C9A—C1	177.62 (8)
C2—C1—C9A—C4A	−1.90 (12)	C4A—C4B—C5—C6	−178.23 (10)
C11—C1—C9A—N9	−0.17 (14)	C8A—C4B—C5—C6	1.62 (14)
C11—C1—C9A—C4A	−178.21 (8)	C4A—C4B—C8A—N9	−0.44 (10)
C2—C1—C11—C12	0.52 (13)	C4A—C4B—C8A—C8	178.34 (8)
C2—C1—C11—C13	−175.65 (8)	C5—C4B—C8A—N9	179.67 (8)
C9A—C1—C11—C12	176.71 (8)	C5—C4B—C8A—C8	−1.55 (14)
C9A—C1—C11—C13	0.54 (14)	C4B—C5—C6—C7	−0.78 (15)
C1—C2—C3—C4	−52.67 (10)	C5—C6—C7—C8	−0.22 (16)
C2—C3—C4—C4A	46.84 (10)	C6—C7—C8—C8A	0.34 (15)
C3—C4—C4A—C4B	159.52 (9)	C7—C8—C8A—N9	179.04 (9)
C3—C4—C4A—C9A	−21.59 (12)	C7—C8—C8A—C4B	0.55 (14)
C4—C4A—C4B—C5	−0.37 (17)

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

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C4B,C5–C8,C8A ring.

D—H···A	D—H	H···A	D···A	D—H···A
N9—H9···N13	0.913 (14)	2.508 (14)	3.2626 (12)	140.3 (11)
N9—H9···N13ⁱ	0.913 (14)	2.553 (14)	3.2267 (12)	131.1 (11)
C2—H2A···Cg1^vi	0.99	2.79	3.6244 (10)	142

Symmetry codes: (i) −x+1, −y+1, −z; (vi) −x+1/2, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₅H₁₁N₃
M_r	233.27
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	110
a, b, c (Å)	8.4794 (3), 10.5542 (4), 13.0575 (5)
β (°)	97.366 (3)
V (Å³)	1158.92 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.53 × 0.38 × 0.31

Data collection
Diffractometer	Oxford Diffraction Xcalibur Ruby Gemini diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)
T_min, T_max	0.939, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	8311, 3822, 2854
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.758

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.115, 0.98
No. of reflections	3822
No. of parameters	167
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.40, −0.24

Computer programs: CrysAlis PRO (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C4B,C5–C8,C8A ring.

D—H···A	D—H	H···A	D···A	D—H···A
N9—H9···N13	0.913 (14)	2.508 (14)	3.2626 (12)	140.3 (11)
N9—H9···N13ⁱ	0.913 (14)	2.553 (14)	3.2267 (12)	131.1 (11)
C2—H2A···Cg1ⁱⁱ	0.99	2.79	3.6244 (10)	142

Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+1/2, y−1/2, −z+1/2.

Acknowledgements

RJB acknowledges the NSF MRI program (grant No. CHE-0619278) for funds to purchase an X-ray diffractometer.

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
Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358. CrossRef CAS Web of Science Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Gunaseelan, A. T., Prabakaran, K., Prasad, K. J. R., Thiruvalluvar, A. & Butcher, R. J. (2009). Acta Cryst. E65, o1946–o1947. Web of Science CSD CrossRef IUCr Journals Google Scholar
Gunaseelan, A. T., Thiruvalluvar, A., Martin, A. E. & Prasad, K. J. R. (2007a). Acta Cryst. E63, o2413–o2414. Web of Science CSD CrossRef IUCr Journals Google Scholar
Gunaseelan, A. T., Thiruvalluvar, A., Martin, A. E. & Prasad, K. J. R. (2007b). Acta Cryst. E63, o2729–o2730. Web of Science CSD CrossRef IUCr Journals Google Scholar
Nakahara, K., Trakoontivakorn, G., Alzoreky, N. S., Ono, H., Onishi-Kameyama, M. & Yoshida, M. (2002). J. Agric. Food Chem. 50, 4796–4802. Web of Science CrossRef PubMed CAS Google Scholar
Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England. Google Scholar
Ramsewak, R. S., Nair, M. G., Strasburg, G. M., DeWitt, D. L. & Nitiss, J. L. (1999). J. Agric. Food Chem. 47, 444–447. Web of Science CrossRef PubMed CAS Google Scholar
Scott, T. L., Yu, X., Gorugantula, S. P., Carrero-Martinez, G. & Söderberg, B. C. G. (2006). Tetrahedron, 62, 10835–10842. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sridharan, M., Prasad, K. J. R., Gunaseelan, A. T., Thiruvalluvar, A. & Linden, A. (2008). Acta Cryst. E64, o763–o764. Web of Science CSD CrossRef IUCr Journals Google Scholar
Tachibana, Y., Kikuzaki, H., Lajis, N. H. & Nakatani, N. (2001). J. Agric. Food Chem. 49, 5589–5594. Web of Science CrossRef PubMed CAS Google Scholar
Thiruvalluvar, A., Gunaseelan, A. T., Martin, A. E., Prasad, K. J. R. & Butcher, R. J. (2007). Acta Cryst. E63, o3524. Web of Science CSD CrossRef IUCr Journals Google Scholar

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Volume 66| Part 7| July 2010| Page o1713

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