5-Amino-3-eth­oxy-1,8,8-trimethyl-2-aza­bicyclo­[2.2.2]octa-2,5-diene-4,6-dicarbo­nitrile

Chantrapromma, S.; Suwunwong, T.; Ruanwas, P.; Boonnak, N.; Fun, H.-K.

doi:10.1107/S1600536812032990

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 9| September 2012| Pages o2606-o2607

doi:10.1107/S1600536812032990

Open

access

5-Amino-3-ethoxy-1,8,8-trimethyl-2-azabicyclo[2.2.2]octa-2,5-diene-4,6-dicarbonitrile

Suchada Chantrapromma,^a ^*‡ Thitipone Suwunwong,^b Pumsak Ruanwas,^a Nawong Boonnak ^a and Hoong-Kun Fun ^c §

^aCrystal Materials Research Unit, Department of Chemistry, Faculty of Science, Prince of Songkla University, Hat-Yai, Songkhla 90112, Thailand, ^bDepartment of Chemistry and Center of Excellence for Innovation in Chemistry, Faculty of Science, Prince of Songkla University, Hat-Yai, Songkhla 90112, Thailand, and ^cX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia
^*Correspondence e-mail: suchada.c@psu.ac.th

(Received 6 July 2012; accepted 20 July 2012; online 1 August 2012)

The title 2-azabicyclo[2.2.2]octa-2,5-diene derivative, C₁₄H₁₈N₄O, crystallized out with two independent molecules with similar conformations in the asymmetric unit. In each molecule, the three six-membered rings adopt boat conformations. The molecules exist in the enamine form. In the crystal, molecules are linked by N—H⋯O and N—H⋯N hydrogen bonds into a two-dimensional network parallel to the ab plane.

Related literature

For bond-length data, see: Allen et al. (1987 ). For ring conformations, see: Cremer & Pople (1975 ). For a related structure, see: Nakano et al. (1987 ). For background to 2-azabicyclo[2.2.2]octa-2,5-diene derivatives, see: Igarashi et al. (1987 ); Nakano et al. (1999 ). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ).

Experimental

Crystal data

C₁₄H₁₈N₄O
M_r = 258.32
Triclinic, $[P \overline 1]$
a = 9.1115 (1) Å
b = 12.4407 (2) Å
c = 13.4945 (2) Å
α = 62.945 (1)°
β = 85.382 (1)°
γ = 89.339 (1)°
V = 1357.30 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 100 K
0.37 × 0.15 × 0.09 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.970, T_max = 0.993
23432 measured reflections
6248 independent reflections
5008 reflections with I > 2σ(I)
R_int = 0.041

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.109
S = 1.05
6248 reflections
367 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2A—H1NA⋯O1Aⁱ	0.92 (2)	2.57 (2)	3.4202 (17)	153.7 (17)
N2A—H2NA⋯N1Bⁱⁱ	0.87 (2)	2.10 (2)	2.958 (2)	170 (2)
N2B—H1NB⋯N1Aⁱⁱⁱ	0.91 (2)	2.06 (2)	2.951 (2)	169 (2)
N2B—H2NB⋯O1B^iv	0.887 (19)	2.53 (2)	3.3524 (17)	154.4 (18)
Symmetry codes: (i) -x+1, -y+2, -z+2; (ii) -x+1, -y+2, -z+1; (iii) -x+1, -y+1, -z+1; (iv) -x, -y+1, -z.

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); 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 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812032990/rz2787sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812032990/rz2787Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812032990/rz2787Isup3.cml

checkCIF report

Comment top

There are several reports showing that alkylidenemalononitriles can undergo self-condensation in the presence of alkoxide to give 2-azabicyclo[2.2.2]octa-2,5-diene derivatives (Igarashi et al., 1987; Nakano & Igarashi, 1987; Nakano et al., 1999). Herein we report the crystal structure of a new 2-azabicyclo[2.2.2]octa-2,5-diene derivative which was obtained from the self-condensation of malononitrile with acetone in the presence of sodium ethoxide.

The asymmetric of the title compound contains two crystallographic independent molecules A and B with similar conformation but differences in bond angles (Fig. 1). In both molecules A and B, the three six-membered rings are in boat conformation (Cremer & Pople, 1975). The molecules exist in the enamine form as indicated by the two H atoms attached to atom N2 and the C3 ═C4 is double bond [1.359 (1) Å in molecule A and 1.356 (2) Å in molecule B]. The angles around atom C1 indicate a sp₂ hybridization [115.65(12 - 125.80 (13)° in molecule A; 115.55 (12) - 125.50 (13)° in molecule B]. The orientation of the ethoxy substituent can be indicated by the torsion angle C1–O1–C10–C11 = -174.53 (12)° in molecule A [-174.73 (12)° in molecule B]. The bond distances agree with the literature values (Allen et al., 1987) and are comparable with those reported for a related structure (Nakano & Igarashi, 1987).

In the crystal packing (Fig. 2), the molecules are linked by intermolecular N—H···N and N—H···O hydrogen bonds (Table 1) into two dimensional networks parallel to the ab plane.

Related literature top

For bond-length data, see: Allen et al. (1987). For ring conformations, see: Cremer & Pople (1975). For a related structure, see: Nakano et al. (1987). For background to 2-azabicyclo[2.2.2]octa-2,5-diene derivatives, see: Igarashi et al. (1987); Nakano et al. (1999). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986).

Experimental top

The title compound was obtained by the condensation reaction of malononitrile (1.5 mmol) with acetone (20 ml) in the presence of freshly prepared sodium ethoxide (1.0 mmol of sodium in 20 ml of ethanol). The mixture was continuously stirred at room temperature until a precipitate was formed. The resulting solid was filtered. Colourless block-shaped single crystals of the title compound suitable for X-ray structure determination were recrystalized from acetone/methanol (1:1 v/v) by the slow evaporation of the solvent at room temperature after several days.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound, showing 40% probability displacement ellipsoids.
	Fig. 2. The crystal packing of the title compound viewed along the b axis, showing the two-dimensional networks. Only H atoms involved in hydrogen bonds (dashed lines) are shown.

5-Amino-3-ethoxy-1,8,8-trimethyl-2-azabicyclo[2.2.2]octa-2,5-diene-4,6- dicarbonitrile top

Crystal data top

C₁₄H₁₈N₄O	Z = 4
M_r = 258.32	F(000) = 552
Triclinic, P1	D_x = 1.264 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.1115 (1) Å	Cell parameters from 6248 reflections
b = 12.4407 (2) Å	θ = 1.8–27.6°
c = 13.4945 (2) Å	µ = 0.08 mm⁻¹
α = 62.945 (1)°	T = 100 K
β = 85.382 (1)°	Block, colourles
γ = 89.339 (1)°	0.37 × 0.15 × 0.09 mm
V = 1357.30 (4) Å³

Data collection top

Bruker APEXII CCD area-detector diffractometer	6248 independent reflections
Radiation source: sealed tube	5008 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.041
ϕ and ω scans	θ_max = 27.6°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −11→11
T_min = 0.970, T_max = 0.993	k = −16→16
23432 measured reflections	l = −16→17

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.109	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0415P)² + 0.6407P] where P = (F_o² + 2F_c²)/3
6248 reflections	(Δ/σ)_max < 0.001
367 parameters	Δρ_max = 0.39 e Å⁻³
0 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

C₁₄H₁₈N₄O	γ = 89.339 (1)°
M_r = 258.32	V = 1357.30 (4) Å³
Triclinic, P1	Z = 4
a = 9.1115 (1) Å	Mo Kα radiation
b = 12.4407 (2) Å	µ = 0.08 mm⁻¹
c = 13.4945 (2) Å	T = 100 K
α = 62.945 (1)°	0.37 × 0.15 × 0.09 mm
β = 85.382 (1)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	6248 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	5008 reflections with I > 2σ(I)
T_min = 0.970, T_max = 0.993	R_int = 0.041
23432 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.109	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.39 e Å⁻³
6248 reflections	Δρ_min = −0.26 e Å⁻³
367 parameters

Special details top

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

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.

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

	x	y	z	U_iso*/U_eq
O1A	0.51622 (11)	0.81541 (9)	0.93597 (8)	0.0146 (2)
N1A	0.68788 (13)	0.88613 (11)	0.78197 (10)	0.0140 (3)
N2A	0.64063 (15)	1.19295 (12)	0.82159 (11)	0.0161 (3)
N3A	0.31531 (14)	1.04786 (12)	0.93804 (11)	0.0213 (3)
N4A	1.00936 (15)	1.21629 (13)	0.65912 (12)	0.0235 (3)
C1A	0.58254 (15)	0.90145 (13)	0.84112 (12)	0.0131 (3)
C2A	0.51981 (15)	1.02696 (13)	0.80102 (12)	0.0134 (3)
C3A	0.65055 (15)	1.11279 (13)	0.78038 (12)	0.0135 (3)
C4A	0.76098 (15)	1.09834 (13)	0.71388 (12)	0.0144 (3)
C5A	0.72908 (16)	1.00115 (13)	0.67865 (12)	0.0144 (3)
C6A	0.58991 (16)	1.03710 (14)	0.61325 (12)	0.0162 (3)
H6AA	0.5619	0.9721	0.5948	0.019*
H6AB	0.6119	1.1115	0.5423	0.019*
C7A	0.45923 (16)	1.05909 (14)	0.68268 (12)	0.0156 (3)
C8A	0.32783 (17)	0.97506 (16)	0.70002 (14)	0.0235 (4)
H8AA	0.2946	0.9912	0.6274	0.035*
H8AB	0.2473	0.9893	0.7450	0.035*
H8AC	0.3574	0.8909	0.7388	0.035*
C9A	0.41209 (18)	1.19086 (15)	0.62827 (13)	0.0221 (3)
H9AA	0.3778	1.2113	0.5549	0.033*
H9AB	0.4962	1.2439	0.6192	0.033*
H9AC	0.3322	1.2016	0.6758	0.033*
C10A	0.57397 (17)	0.69428 (13)	0.97043 (13)	0.0179 (3)
H10A	0.6771	0.6922	0.9893	0.021*
H10B	0.5719	0.6716	0.9091	0.021*
C11A	0.47834 (16)	0.60812 (14)	1.07080 (13)	0.0180 (3)
H11A	0.5128	0.5258	1.0947	0.027*
H11B	0.3762	0.6123	1.0516	0.027*
H11C	0.4835	0.6300	1.1316	0.027*
C12A	0.40365 (16)	1.03563 (13)	0.87895 (13)	0.0149 (3)
C13A	0.89753 (16)	1.16370 (13)	0.68368 (12)	0.0162 (3)
C14A	0.85776 (16)	0.97961 (14)	0.61147 (13)	0.0185 (3)
H14A	0.9435	0.9561	0.6555	0.028*
H14B	0.8819	1.0539	0.5423	0.028*
H14C	0.8309	0.9150	0.5933	0.028*
O1B	0.00455 (11)	0.68930 (9)	0.05704 (8)	0.0147 (2)
N1B	0.14158 (13)	0.61679 (11)	0.21120 (10)	0.0145 (3)
N2B	0.09705 (14)	0.30548 (12)	0.17838 (11)	0.0157 (3)
N3B	−0.19771 (14)	0.45877 (12)	0.05722 (11)	0.0206 (3)
N4B	0.43461 (15)	0.28183 (13)	0.33393 (12)	0.0240 (3)
C1B	0.04928 (15)	0.60238 (13)	0.15241 (12)	0.0135 (3)
C2B	−0.02378 (15)	0.47844 (13)	0.19317 (12)	0.0135 (3)
C3B	0.10078 (15)	0.38876 (13)	0.21586 (12)	0.0135 (3)
C4B	0.19768 (16)	0.40264 (13)	0.28067 (12)	0.0145 (3)
C5B	0.15887 (16)	0.50179 (13)	0.31466 (12)	0.0145 (3)
C6B	0.00466 (16)	0.46929 (14)	0.38005 (12)	0.0157 (3)
H6BA	0.0101	0.3944	0.4509	0.019*
H6BB	−0.0264	0.5349	0.3987	0.019*
C7B	−0.11103 (16)	0.45074 (14)	0.31062 (12)	0.0155 (3)
C8B	−0.23621 (17)	0.53982 (16)	0.29022 (14)	0.0224 (3)
H8BA	−0.2892	0.5244	0.3618	0.034*
H8BB	−0.3044	0.5295	0.2424	0.034*
H8BC	−0.1952	0.6226	0.2534	0.034*
C9B	−0.17408 (17)	0.32157 (15)	0.36637 (13)	0.0216 (3)
H9BA	−0.2243	0.3039	0.4393	0.032*
H9BB	−0.0939	0.2653	0.3764	0.032*
H9BC	−0.2444	0.3126	0.3192	0.032*
C10B	0.06840 (17)	0.80957 (13)	0.02335 (13)	0.0177 (3)
H10C	0.1761	0.8104	0.0056	0.021*
H10D	0.0505	0.8322	0.0847	0.021*
C11B	−0.00375 (16)	0.89715 (13)	−0.07808 (13)	0.0179 (3)
H11D	0.0367	0.9787	−0.1024	0.027*
H11E	−0.1102	0.8955	−0.0596	0.027*
H11F	0.0152	0.8742	−0.1384	0.027*
C12B	−0.12256 (16)	0.47068 (13)	0.11584 (12)	0.0149 (3)
C13B	0.32758 (16)	0.33519 (14)	0.31065 (12)	0.0162 (3)
C14B	0.27220 (16)	0.52006 (14)	0.38244 (13)	0.0179 (3)
H14D	0.3683	0.5408	0.3391	0.027*
H14E	0.2793	0.4455	0.4519	0.027*
H14F	0.2423	0.5857	0.4001	0.027*
H1NA	0.573 (2)	1.1790 (18)	0.8807 (18)	0.035 (5)*
H2NA	0.713 (2)	1.2426 (18)	0.8112 (15)	0.024 (5)*
H1NB	0.172 (2)	0.2538 (19)	0.1900 (17)	0.032 (5)*
H2NB	0.046 (2)	0.3204 (17)	0.1204 (16)	0.024 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1A	0.0143 (5)	0.0113 (5)	0.0163 (5)	0.0015 (4)	0.0003 (4)	−0.0050 (4)
N1A	0.0134 (6)	0.0122 (6)	0.0157 (6)	0.0012 (5)	−0.0026 (5)	−0.0057 (5)
N2A	0.0158 (6)	0.0149 (6)	0.0194 (7)	−0.0016 (5)	0.0001 (5)	−0.0097 (5)
N3A	0.0178 (6)	0.0224 (7)	0.0240 (7)	0.0011 (5)	−0.0002 (6)	−0.0111 (6)
N4A	0.0165 (7)	0.0224 (7)	0.0301 (8)	−0.0005 (6)	0.0002 (6)	−0.0111 (6)
C1A	0.0119 (6)	0.0128 (7)	0.0146 (7)	0.0010 (5)	−0.0043 (5)	−0.0058 (6)
C2A	0.0111 (6)	0.0134 (7)	0.0155 (7)	0.0021 (5)	−0.0014 (5)	−0.0065 (6)
C3A	0.0132 (7)	0.0106 (7)	0.0140 (7)	0.0030 (5)	−0.0051 (5)	−0.0028 (6)
C4A	0.0128 (7)	0.0130 (7)	0.0158 (7)	0.0016 (5)	−0.0026 (5)	−0.0050 (6)
C5A	0.0139 (7)	0.0145 (7)	0.0141 (7)	0.0023 (5)	−0.0014 (5)	−0.0057 (6)
C6A	0.0160 (7)	0.0182 (7)	0.0153 (7)	0.0017 (6)	−0.0023 (6)	−0.0082 (6)
C7A	0.0137 (7)	0.0186 (7)	0.0152 (7)	0.0029 (6)	−0.0042 (6)	−0.0077 (6)
C8A	0.0159 (7)	0.0334 (9)	0.0247 (9)	−0.0010 (7)	−0.0039 (6)	−0.0160 (7)
C9A	0.0204 (8)	0.0237 (8)	0.0201 (8)	0.0096 (6)	−0.0067 (6)	−0.0077 (7)
C10A	0.0191 (7)	0.0116 (7)	0.0208 (8)	0.0033 (6)	0.0003 (6)	−0.0059 (6)
C11A	0.0170 (7)	0.0151 (7)	0.0194 (8)	0.0005 (6)	−0.0005 (6)	−0.0058 (6)
C12A	0.0132 (7)	0.0129 (7)	0.0187 (7)	0.0010 (5)	−0.0044 (6)	−0.0068 (6)
C13A	0.0169 (7)	0.0148 (7)	0.0155 (7)	0.0041 (6)	−0.0026 (6)	−0.0054 (6)
C14A	0.0179 (7)	0.0174 (8)	0.0192 (8)	0.0028 (6)	0.0013 (6)	−0.0081 (6)
O1B	0.0157 (5)	0.0113 (5)	0.0160 (5)	0.0008 (4)	−0.0043 (4)	−0.0048 (4)
N1B	0.0142 (6)	0.0141 (6)	0.0149 (6)	0.0019 (5)	−0.0019 (5)	−0.0062 (5)
N2B	0.0155 (6)	0.0155 (6)	0.0184 (7)	0.0054 (5)	−0.0057 (5)	−0.0091 (5)
N3B	0.0175 (6)	0.0222 (7)	0.0239 (7)	0.0031 (5)	−0.0054 (6)	−0.0117 (6)
N4B	0.0207 (7)	0.0266 (8)	0.0293 (8)	0.0076 (6)	−0.0099 (6)	−0.0158 (6)
C1B	0.0133 (7)	0.0133 (7)	0.0140 (7)	0.0024 (5)	−0.0003 (5)	−0.0065 (6)
C2B	0.0122 (6)	0.0136 (7)	0.0154 (7)	0.0024 (5)	−0.0022 (5)	−0.0071 (6)
C3B	0.0129 (7)	0.0114 (7)	0.0136 (7)	0.0007 (5)	0.0004 (5)	−0.0037 (6)
C4B	0.0138 (7)	0.0134 (7)	0.0144 (7)	0.0018 (5)	−0.0018 (5)	−0.0048 (6)
C5B	0.0149 (7)	0.0141 (7)	0.0147 (7)	0.0012 (5)	−0.0034 (5)	−0.0064 (6)
C6B	0.0158 (7)	0.0182 (7)	0.0132 (7)	0.0007 (6)	−0.0012 (6)	−0.0074 (6)
C7B	0.0134 (7)	0.0187 (7)	0.0145 (7)	0.0001 (6)	−0.0003 (6)	−0.0078 (6)
C8B	0.0172 (7)	0.0314 (9)	0.0217 (8)	0.0076 (7)	−0.0017 (6)	−0.0150 (7)
C9B	0.0194 (8)	0.0230 (8)	0.0193 (8)	−0.0045 (6)	0.0007 (6)	−0.0072 (7)
C10B	0.0203 (7)	0.0115 (7)	0.0208 (8)	−0.0013 (6)	−0.0057 (6)	−0.0063 (6)
C11B	0.0169 (7)	0.0148 (7)	0.0203 (8)	0.0012 (6)	−0.0037 (6)	−0.0061 (6)
C12B	0.0136 (7)	0.0132 (7)	0.0165 (7)	0.0022 (5)	−0.0001 (6)	−0.0058 (6)
C13B	0.0176 (7)	0.0162 (7)	0.0155 (7)	0.0005 (6)	−0.0037 (6)	−0.0075 (6)
C14B	0.0178 (7)	0.0185 (8)	0.0180 (8)	0.0010 (6)	−0.0054 (6)	−0.0083 (6)

Geometric parameters (Å, º) top

O1A—C1A	1.3391 (17)	O1B—C1B	1.3417 (17)
O1A—C10A	1.4654 (17)	O1B—C10B	1.4638 (17)
N1A—C1A	1.2671 (18)	N1B—C1B	1.2684 (19)
N1A—C5A	1.4986 (18)	N1B—C5B	1.4947 (18)
N2A—C3A	1.3440 (19)	N2B—C3B	1.3456 (19)
N2A—H1NA	0.92 (2)	N2B—H1NB	0.91 (2)
N2A—H2NA	0.87 (2)	N2B—H2NB	0.89 (2)
N3A—C12A	1.145 (2)	N3B—C12B	1.146 (2)
N4A—C13A	1.158 (2)	N4B—C13B	1.155 (2)
C1A—C2A	1.5226 (19)	C1B—C2B	1.522 (2)
C2A—C12A	1.469 (2)	C2B—C12B	1.467 (2)
C2A—C3A	1.530 (2)	C2B—C3B	1.5305 (19)
C2A—C7A	1.603 (2)	C2B—C7B	1.6029 (19)
C3A—C4A	1.359 (2)	C3B—C4B	1.356 (2)
C4A—C13A	1.420 (2)	C4B—C13B	1.419 (2)
C4A—C5A	1.525 (2)	C4B—C5B	1.528 (2)
C5A—C14A	1.5202 (19)	C5B—C14B	1.517 (2)
C5A—C6A	1.548 (2)	C5B—C6B	1.551 (2)
C6A—C7A	1.554 (2)	C6B—C7B	1.550 (2)
C6A—H6AA	0.9900	C6B—H6BA	0.9900
C6A—H6AB	0.9900	C6B—H6BB	0.9900
C7A—C8A	1.531 (2)	C7B—C9B	1.526 (2)
C7A—C9A	1.533 (2)	C7B—C8B	1.533 (2)
C8A—H8AA	0.9800	C8B—H8BA	0.9800
C8A—H8AB	0.9800	C8B—H8BB	0.9800
C8A—H8AC	0.9800	C8B—H8BC	0.9800
C9A—H9AA	0.9800	C9B—H9BA	0.9800
C9A—H9AB	0.9800	C9B—H9BB	0.9800
C9A—H9AC	0.9800	C9B—H9BC	0.9800
C10A—C11A	1.501 (2)	C10B—C11B	1.505 (2)
C10A—H10A	0.9900	C10B—H10C	0.9900
C10A—H10B	0.9900	C10B—H10D	0.9900
C11A—H11A	0.9800	C11B—H11D	0.9800
C11A—H11B	0.9800	C11B—H11E	0.9800
C11A—H11C	0.9800	C11B—H11F	0.9800
C14A—H14A	0.9800	C14B—H14D	0.9800
C14A—H14B	0.9800	C14B—H14E	0.9800
C14A—H14C	0.9800	C14B—H14F	0.9800

C1A—O1A—C10A	114.77 (11)	C1B—O1B—C10B	114.72 (11)
C1A—N1A—C5A	111.14 (12)	C1B—N1B—C5B	110.77 (12)
C3A—N2A—H1NA	119.3 (13)	C3B—N2B—H1NB	119.6 (13)
C3A—N2A—H2NA	121.5 (12)	C3B—N2B—H2NB	118.6 (12)
H1NA—N2A—H2NA	115.6 (18)	H1NB—N2B—H2NB	116.8 (17)
N1A—C1A—O1A	125.80 (13)	N1B—C1B—O1B	125.50 (13)
N1A—C1A—C2A	118.51 (13)	N1B—C1B—C2B	118.90 (13)
O1A—C1A—C2A	115.65 (12)	O1B—C1B—C2B	115.55 (12)
C12A—C2A—C1A	113.79 (12)	C12B—C2B—C1B	114.18 (12)
C12A—C2A—C3A	111.62 (12)	C12B—C2B—C3B	111.54 (12)
C1A—C2A—C3A	106.25 (11)	C1B—C2B—C3B	106.50 (11)
C12A—C2A—C7A	111.29 (11)	C12B—C2B—C7B	111.31 (11)
C1A—C2A—C7A	105.59 (11)	C1B—C2B—C7B	105.00 (11)
C3A—C2A—C7A	107.90 (11)	C3B—C2B—C7B	107.89 (11)
N2A—C3A—C4A	129.35 (14)	N2B—C3B—C4B	129.14 (14)
N2A—C3A—C2A	119.54 (13)	N2B—C3B—C2B	119.52 (13)
C4A—C3A—C2A	110.99 (13)	C4B—C3B—C2B	111.18 (13)
C3A—C4A—C13A	123.22 (14)	C3B—C4B—C13B	123.34 (14)
C3A—C4A—C5A	114.30 (13)	C3B—C4B—C5B	114.15 (13)
C13A—C4A—C5A	122.42 (13)	C13B—C4B—C5B	122.45 (13)
N1A—C5A—C14A	109.48 (12)	N1B—C5B—C14B	109.98 (12)
N1A—C5A—C4A	108.12 (11)	N1B—C5B—C4B	108.41 (12)
C14A—C5A—C4A	113.69 (12)	C14B—C5B—C4B	113.42 (12)
N1A—C5A—C6A	105.84 (11)	N1B—C5B—C6B	105.86 (11)
C14A—C5A—C6A	111.55 (12)	C14B—C5B—C6B	111.21 (12)
C4A—C5A—C6A	107.80 (12)	C4B—C5B—C6B	107.64 (12)
C5A—C6A—C7A	111.07 (12)	C7B—C6B—C5B	111.13 (12)
C5A—C6A—H6AA	109.4	C7B—C6B—H6BA	109.4
C7A—C6A—H6AA	109.4	C5B—C6B—H6BA	109.4
C5A—C6A—H6AB	109.4	C7B—C6B—H6BB	109.4
C7A—C6A—H6AB	109.4	C5B—C6B—H6BB	109.4
H6AA—C6A—H6AB	108.0	H6BA—C6B—H6BB	108.0
C8A—C7A—C9A	110.00 (13)	C9B—C7B—C8B	109.86 (12)
C8A—C7A—C6A	110.68 (12)	C9B—C7B—C6B	111.77 (13)
C9A—C7A—C6A	112.01 (12)	C8B—C7B—C6B	111.21 (13)
C8A—C7A—C2A	109.42 (12)	C9B—C7B—C2B	109.64 (12)
C9A—C7A—C2A	109.39 (12)	C8B—C7B—C2B	108.93 (12)
C6A—C7A—C2A	105.21 (11)	C6B—C7B—C2B	105.29 (11)
C7A—C8A—H8AA	109.5	C7B—C8B—H8BA	109.5
C7A—C8A—H8AB	109.5	C7B—C8B—H8BB	109.5
H8AA—C8A—H8AB	109.5	H8BA—C8B—H8BB	109.5
C7A—C8A—H8AC	109.5	C7B—C8B—H8BC	109.5
H8AA—C8A—H8AC	109.5	H8BA—C8B—H8BC	109.5
H8AB—C8A—H8AC	109.5	H8BB—C8B—H8BC	109.5
C7A—C9A—H9AA	109.5	C7B—C9B—H9BA	109.5
C7A—C9A—H9AB	109.5	C7B—C9B—H9BB	109.5
H9AA—C9A—H9AB	109.5	H9BA—C9B—H9BB	109.5
C7A—C9A—H9AC	109.5	C7B—C9B—H9BC	109.5
H9AA—C9A—H9AC	109.5	H9BA—C9B—H9BC	109.5
H9AB—C9A—H9AC	109.5	H9BB—C9B—H9BC	109.5
O1A—C10A—C11A	107.60 (11)	O1B—C10B—C11B	107.68 (12)
O1A—C10A—H10A	110.2	O1B—C10B—H10C	110.2
C11A—C10A—H10A	110.2	C11B—C10B—H10C	110.2
O1A—C10A—H10B	110.2	O1B—C10B—H10D	110.2
C11A—C10A—H10B	110.2	C11B—C10B—H10D	110.2
H10A—C10A—H10B	108.5	H10C—C10B—H10D	108.5
C10A—C11A—H11A	109.5	C10B—C11B—H11D	109.5
C10A—C11A—H11B	109.5	C10B—C11B—H11E	109.5
H11A—C11A—H11B	109.5	H11D—C11B—H11E	109.5
C10A—C11A—H11C	109.5	C10B—C11B—H11F	109.5
H11A—C11A—H11C	109.5	H11D—C11B—H11F	109.5
H11B—C11A—H11C	109.5	H11E—C11B—H11F	109.5
N3A—C12A—C2A	176.79 (15)	N3B—C12B—C2B	176.58 (15)
N4A—C13A—C4A	179.54 (16)	N4B—C13B—C4B	178.95 (18)
C5A—C14A—H14A	109.5	C5B—C14B—H14D	109.5
C5A—C14A—H14B	109.5	C5B—C14B—H14E	109.5
H14A—C14A—H14B	109.5	H14D—C14B—H14E	109.5
C5A—C14A—H14C	109.5	C5B—C14B—H14F	109.5
H14A—C14A—H14C	109.5	H14D—C14B—H14F	109.5
H14B—C14A—H14C	109.5	H14E—C14B—H14F	109.5

C5A—N1A—C1A—O1A	177.02 (13)	C5B—N1B—C1B—O1B	177.00 (12)
C5A—N1A—C1A—C2A	−0.75 (18)	C5B—N1B—C1B—C2B	−0.39 (17)
C10A—O1A—C1A—N1A	−0.4 (2)	C10B—O1B—C1B—N1B	−1.5 (2)
C10A—O1A—C1A—C2A	177.40 (12)	C10B—O1B—C1B—C2B	175.93 (11)
N1A—C1A—C2A—C12A	−176.91 (13)	N1B—C1B—C2B—C12B	−176.98 (12)
O1A—C1A—C2A—C12A	5.09 (18)	O1B—C1B—C2B—C12B	5.38 (17)
N1A—C1A—C2A—C3A	−53.69 (17)	N1B—C1B—C2B—C3B	−53.43 (16)
O1A—C1A—C2A—C3A	128.31 (13)	O1B—C1B—C2B—C3B	128.93 (13)
N1A—C1A—C2A—C7A	60.75 (16)	N1B—C1B—C2B—C7B	60.84 (16)
O1A—C1A—C2A—C7A	−117.25 (13)	O1B—C1B—C2B—C7B	−116.80 (13)
C12A—C2A—C3A—N2A	−7.51 (19)	C12B—C2B—C3B—N2B	−8.73 (18)
C1A—C2A—C3A—N2A	−132.08 (13)	C1B—C2B—C3B—N2B	−133.91 (13)
C7A—C2A—C3A—N2A	115.07 (14)	C7B—C2B—C3B—N2B	113.81 (14)
C12A—C2A—C3A—C4A	176.11 (12)	C12B—C2B—C3B—C4B	175.44 (13)
C1A—C2A—C3A—C4A	51.54 (16)	C1B—C2B—C3B—C4B	50.26 (15)
C7A—C2A—C3A—C4A	−61.31 (15)	C7B—C2B—C3B—C4B	−62.02 (15)
N2A—C3A—C4A—C13A	6.0 (2)	N2B—C3B—C4B—C13B	7.6 (2)
C2A—C3A—C4A—C13A	−178.06 (13)	C2B—C3B—C4B—C13B	−177.03 (13)
N2A—C3A—C4A—C5A	−176.84 (14)	N2B—C3B—C4B—C5B	−175.05 (14)
C2A—C3A—C4A—C5A	−0.91 (17)	C2B—C3B—C4B—C5B	0.27 (17)
C1A—N1A—C5A—C14A	178.74 (13)	C1B—N1B—C5B—C14B	178.68 (12)
C1A—N1A—C5A—C4A	54.39 (15)	C1B—N1B—C5B—C4B	54.17 (15)
C1A—N1A—C5A—C6A	−60.89 (15)	C1B—N1B—C5B—C6B	−61.09 (15)
C3A—C4A—C5A—N1A	−53.95 (16)	C3B—C4B—C5B—N1B	−54.80 (16)
C13A—C4A—C5A—N1A	123.23 (14)	C13B—C4B—C5B—N1B	122.53 (14)
C3A—C4A—C5A—C14A	−175.75 (13)	C3B—C4B—C5B—C14B	−177.24 (13)
C13A—C4A—C5A—C14A	1.4 (2)	C13B—C4B—C5B—C14B	0.1 (2)
C3A—C4A—C5A—C6A	60.05 (16)	C3B—C4B—C5B—C6B	59.29 (16)
C13A—C4A—C5A—C6A	−122.77 (14)	C13B—C4B—C5B—C6B	−123.38 (14)
N1A—C5A—C6A—C7A	61.10 (15)	N1B—C5B—C6B—C7B	60.54 (15)
C14A—C5A—C6A—C7A	−179.90 (12)	C14B—C5B—C6B—C7B	179.96 (12)
C4A—C5A—C6A—C7A	−54.41 (15)	C4B—C5B—C6B—C7B	−55.24 (15)
C5A—C6A—C7A—C8A	−121.52 (14)	C5B—C6B—C7B—C9B	116.77 (13)
C5A—C6A—C7A—C9A	115.33 (14)	C5B—C6B—C7B—C8B	−120.04 (13)
C5A—C6A—C7A—C2A	−3.42 (16)	C5B—C6B—C7B—C2B	−2.20 (16)
C12A—C2A—C7A—C8A	−57.10 (16)	C12B—C2B—C7B—C9B	62.71 (15)
C1A—C2A—C7A—C8A	66.83 (14)	C1B—C2B—C7B—C9B	−173.27 (12)
C3A—C2A—C7A—C8A	−179.88 (12)	C3B—C2B—C7B—C9B	−59.97 (15)
C12A—C2A—C7A—C9A	63.47 (15)	C12B—C2B—C7B—C8B	−57.54 (16)
C1A—C2A—C7A—C9A	−172.60 (12)	C1B—C2B—C7B—C8B	66.48 (14)
C3A—C2A—C7A—C9A	−59.31 (14)	C3B—C2B—C7B—C8B	179.78 (12)
C12A—C2A—C7A—C6A	−176.04 (12)	C12B—C2B—C7B—C6B	−176.91 (12)
C1A—C2A—C7A—C6A	−52.11 (14)	C1B—C2B—C7B—C6B	−52.88 (14)
C3A—C2A—C7A—C6A	61.18 (14)	C3B—C2B—C7B—C6B	60.41 (14)
C1A—O1A—C10A—C11A	−174.53 (12)	C1B—O1B—C10B—C11B	−174.73 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2A—H1NA···O1Aⁱ	0.92 (2)	2.57 (2)	3.4202 (17)	153.7 (17)
N2A—H2NA···N1Bⁱⁱ	0.87 (2)	2.10 (2)	2.958 (2)	170 (2)
N2B—H1NB···N1Aⁱⁱⁱ	0.91 (2)	2.06 (2)	2.951 (2)	169 (2)
N2B—H2NB···O1B^iv	0.887 (19)	2.53 (2)	3.3524 (17)	154.4 (18)

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

Experimental details

Crystal data
Chemical formula	C₁₄H₁₈N₄O
M_r	258.32
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	9.1115 (1), 12.4407 (2), 13.4945 (2)
α, β, γ (°)	62.945 (1), 85.382 (1), 89.339 (1)
V (Å³)	1357.30 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.37 × 0.15 × 0.09

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.970, 0.993
No. of measured, independent and observed [I > 2σ(I)] reflections	23432, 6248, 5008
R_int	0.041
(sin θ/λ)_max (Å⁻¹)	0.651

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.109, 1.05
No. of reflections	6248
No. of parameters	367
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.39, −0.26

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2A—H1NA···O1Aⁱ	0.92 (2)	2.57 (2)	3.4202 (17)	153.7 (17)
N2A—H2NA···N1Bⁱⁱ	0.87 (2)	2.10 (2)	2.958 (2)	170 (2)
N2B—H1NB···N1Aⁱⁱⁱ	0.91 (2)	2.06 (2)	2.951 (2)	169 (2)
N2B—H2NB···O1B^iv	0.887 (19)	2.53 (2)	3.3524 (17)	154.4 (18)

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

Footnotes

‡Thomson Reuters ResearcherID: A-5085-2009.

§Additional correspondence author, e-mail: hkfun@usm.my. Thomson Reuters ResearcherID: A-3561-2009.

Acknowledgements

Financial support by Prince of Songkla University through the Crystal Materials Research Unit is greatfully acknowledged. TS thanks the Center of Excellence for Innovation in Chemistry (PERCH-CIC), Office of the Higher Education, Ministry of Education, Thailand, for financial support. NB thanks Prince of Songkla University for a postdoctoral fellowship. The authors also thank Universiti Sains Malaysia for the Research University Grant No. 1001/PFIZIK/811160.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Bruker (2009). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cosier, J. & Glazer, A. M. (1986). J. Appl. Cryst. 19, 105–107. CrossRef CAS Web of Science IUCr Journals Google Scholar
Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358. CrossRef CAS Web of Science Google Scholar
Igarashi, M., Nakano, Y., Takezawa, K., Watanabe, T. & Sata, S. (1987). Synthesis, pp. 68–70. CrossRef Google Scholar
Nakano, Y., Igarashi, M. & Sato, S. (1987). Acta Cryst. C43, 738–740. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Nakano, Y., Kaneko, Y. & Fen, W. A. (1999). Heterocycles, 51, 169–177. 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

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.