organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 68| Part 9| September 2012| Pages o2606-o2607

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

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[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.]). For ring conformations, see: Cremer & Pople (1975[Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354-1358.]). For a related structure, see: Nakano et al. (1987[Nakano, Y., Igarashi, M. & Sato, S. (1987). Acta Cryst. C43, 738-740.]). For background to 2-aza­bicyclo­[2.2.2]octa-2,5-diene derivatives, see: Igarashi et al. (1987[Igarashi, M., Nakano, Y., Takezawa, K., Watanabe, T. & Sata, S. (1987). Synthesis, pp. 68-70.]); Nakano et al. (1999[Nakano, Y., Kaneko, Y. & Fen, W. A. (1999). Heterocycles, 51, 169-177.]). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986[Cosier, J. & Glazer, A. M. (1986). J. Appl. Cryst. 19, 105-107.]).

[Scheme 1]

Experimental

Crystal data
  • C14H18N4O

  • Mr = 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[Bruker (2009). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.970, Tmax = 0.993

  • 23432 measured reflections

  • 6248 independent reflections

  • 5008 reflections with I > 2σ(I)

  • Rint = 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

  • Δρmax = 0.39 e Å−3

  • Δρmin = −0.26 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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⋯O1Biv 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[Bruker (2009). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2009[Bruker (2009). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]).

Supporting information


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.

Refinement top

Amino H atoms were located in a Fourier difference map and isotropically refined. The remaining H atoms were positioned geometrically and allowed to ride on their parent atoms, with d(C—H) = 0.99 Å for CH2 and 0.98 Å for CH3 atoms. The Uiso values were constrained to be 1.5Ueq of the carrier atom for methyl H atoms and 1.2Ueq for the remaining H atoms. A rotating group model was used for the methyl groups.

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
[Figure 1] Fig. 1. The molecular structure of the title compound, showing 40% probability displacement ellipsoids.
[Figure 2] 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
C14H18N4OZ = 4
Mr = 258.32F(000) = 552
Triclinic, P1Dx = 1.264 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 9.1115 (1) ÅCell parameters from 6248 reflections
b = 12.4407 (2) Åθ = 1.8–27.6°
c = 13.4945 (2) ŵ = 0.08 mm1
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 tube5008 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.041
ϕ and ω scansθmax = 27.6°, θmin = 1.7°
Absorption correction: multi-scan
(SADABS; Bruker, 2009)
h = 1111
Tmin = 0.970, Tmax = 0.993k = 1616
23432 measured reflectionsl = 1617
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.047Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.109H atoms treated by a mixture of independent and constrained refinement
S = 1.05 w = 1/[σ2(Fo2) + (0.0415P)2 + 0.6407P]
where P = (Fo2 + 2Fc2)/3
6248 reflections(Δ/σ)max < 0.001
367 parametersΔρmax = 0.39 e Å3
0 restraintsΔρmin = 0.26 e Å3
Crystal data top
C14H18N4Oγ = 89.339 (1)°
Mr = 258.32V = 1357.30 (4) Å3
Triclinic, P1Z = 4
a = 9.1115 (1) ÅMo Kα radiation
b = 12.4407 (2) ŵ = 0.08 mm1
c = 13.4945 (2) ÅT = 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)
Tmin = 0.970, Tmax = 0.993Rint = 0.041
23432 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0470 restraints
wR(F2) = 0.109H atoms treated by a mixture of independent and constrained refinement
S = 1.05Δρmax = 0.39 e Å3
6248 reflectionsΔρmin = 0.26 e Å3
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
xyzUiso*/Ueq
O1A0.51622 (11)0.81541 (9)0.93597 (8)0.0146 (2)
N1A0.68788 (13)0.88613 (11)0.78197 (10)0.0140 (3)
N2A0.64063 (15)1.19295 (12)0.82159 (11)0.0161 (3)
N3A0.31531 (14)1.04786 (12)0.93804 (11)0.0213 (3)
N4A1.00936 (15)1.21629 (13)0.65912 (12)0.0235 (3)
C1A0.58254 (15)0.90145 (13)0.84112 (12)0.0131 (3)
C2A0.51981 (15)1.02696 (13)0.80102 (12)0.0134 (3)
C3A0.65055 (15)1.11279 (13)0.78038 (12)0.0135 (3)
C4A0.76098 (15)1.09834 (13)0.71388 (12)0.0144 (3)
C5A0.72908 (16)1.00115 (13)0.67865 (12)0.0144 (3)
C6A0.58991 (16)1.03710 (14)0.61325 (12)0.0162 (3)
H6AA0.56190.97210.59480.019*
H6AB0.61191.11150.54230.019*
C7A0.45923 (16)1.05909 (14)0.68268 (12)0.0156 (3)
C8A0.32783 (17)0.97506 (16)0.70002 (14)0.0235 (4)
H8AA0.29460.99120.62740.035*
H8AB0.24730.98930.74500.035*
H8AC0.35740.89090.73880.035*
C9A0.41209 (18)1.19086 (15)0.62827 (13)0.0221 (3)
H9AA0.37781.21130.55490.033*
H9AB0.49621.24390.61920.033*
H9AC0.33221.20160.67580.033*
C10A0.57397 (17)0.69428 (13)0.97043 (13)0.0179 (3)
H10A0.67710.69220.98930.021*
H10B0.57190.67160.90910.021*
C11A0.47834 (16)0.60812 (14)1.07080 (13)0.0180 (3)
H11A0.51280.52581.09470.027*
H11B0.37620.61231.05160.027*
H11C0.48350.63001.13160.027*
C12A0.40365 (16)1.03563 (13)0.87895 (13)0.0149 (3)
C13A0.89753 (16)1.16370 (13)0.68368 (12)0.0162 (3)
C14A0.85776 (16)0.97961 (14)0.61147 (13)0.0185 (3)
H14A0.94350.95610.65550.028*
H14B0.88191.05390.54230.028*
H14C0.83090.91500.59330.028*
O1B0.00455 (11)0.68930 (9)0.05704 (8)0.0147 (2)
N1B0.14158 (13)0.61679 (11)0.21120 (10)0.0145 (3)
N2B0.09705 (14)0.30548 (12)0.17838 (11)0.0157 (3)
N3B0.19771 (14)0.45877 (12)0.05722 (11)0.0206 (3)
N4B0.43461 (15)0.28183 (13)0.33393 (12)0.0240 (3)
C1B0.04928 (15)0.60238 (13)0.15241 (12)0.0135 (3)
C2B0.02378 (15)0.47844 (13)0.19317 (12)0.0135 (3)
C3B0.10078 (15)0.38876 (13)0.21586 (12)0.0135 (3)
C4B0.19768 (16)0.40264 (13)0.28067 (12)0.0145 (3)
C5B0.15887 (16)0.50179 (13)0.31466 (12)0.0145 (3)
C6B0.00466 (16)0.46929 (14)0.38005 (12)0.0157 (3)
H6BA0.01010.39440.45090.019*
H6BB0.02640.53490.39870.019*
C7B0.11103 (16)0.45074 (14)0.31062 (12)0.0155 (3)
C8B0.23621 (17)0.53982 (16)0.29022 (14)0.0224 (3)
H8BA0.28920.52440.36180.034*
H8BB0.30440.52950.24240.034*
H8BC0.19520.62260.25340.034*
C9B0.17408 (17)0.32157 (15)0.36637 (13)0.0216 (3)
H9BA0.22430.30390.43930.032*
H9BB0.09390.26530.37640.032*
H9BC0.24440.31260.31920.032*
C10B0.06840 (17)0.80957 (13)0.02335 (13)0.0177 (3)
H10C0.17610.81040.00560.021*
H10D0.05050.83220.08470.021*
C11B0.00375 (16)0.89715 (13)0.07808 (13)0.0179 (3)
H11D0.03670.97870.10240.027*
H11E0.11020.89550.05960.027*
H11F0.01520.87420.13840.027*
C12B0.12256 (16)0.47068 (13)0.11584 (12)0.0149 (3)
C13B0.32758 (16)0.33519 (14)0.31065 (12)0.0162 (3)
C14B0.27220 (16)0.52006 (14)0.38244 (13)0.0179 (3)
H14D0.36830.54080.33910.027*
H14E0.27930.44550.45190.027*
H14F0.24230.58570.40010.027*
H1NA0.573 (2)1.1790 (18)0.8807 (18)0.035 (5)*
H2NA0.713 (2)1.2426 (18)0.8112 (15)0.024 (5)*
H1NB0.172 (2)0.2538 (19)0.1900 (17)0.032 (5)*
H2NB0.046 (2)0.3204 (17)0.1204 (16)0.024 (5)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O1A0.0143 (5)0.0113 (5)0.0163 (5)0.0015 (4)0.0003 (4)0.0050 (4)
N1A0.0134 (6)0.0122 (6)0.0157 (6)0.0012 (5)0.0026 (5)0.0057 (5)
N2A0.0158 (6)0.0149 (6)0.0194 (7)0.0016 (5)0.0001 (5)0.0097 (5)
N3A0.0178 (6)0.0224 (7)0.0240 (7)0.0011 (5)0.0002 (6)0.0111 (6)
N4A0.0165 (7)0.0224 (7)0.0301 (8)0.0005 (6)0.0002 (6)0.0111 (6)
C1A0.0119 (6)0.0128 (7)0.0146 (7)0.0010 (5)0.0043 (5)0.0058 (6)
C2A0.0111 (6)0.0134 (7)0.0155 (7)0.0021 (5)0.0014 (5)0.0065 (6)
C3A0.0132 (7)0.0106 (7)0.0140 (7)0.0030 (5)0.0051 (5)0.0028 (6)
C4A0.0128 (7)0.0130 (7)0.0158 (7)0.0016 (5)0.0026 (5)0.0050 (6)
C5A0.0139 (7)0.0145 (7)0.0141 (7)0.0023 (5)0.0014 (5)0.0057 (6)
C6A0.0160 (7)0.0182 (7)0.0153 (7)0.0017 (6)0.0023 (6)0.0082 (6)
C7A0.0137 (7)0.0186 (7)0.0152 (7)0.0029 (6)0.0042 (6)0.0077 (6)
C8A0.0159 (7)0.0334 (9)0.0247 (9)0.0010 (7)0.0039 (6)0.0160 (7)
C9A0.0204 (8)0.0237 (8)0.0201 (8)0.0096 (6)0.0067 (6)0.0077 (7)
C10A0.0191 (7)0.0116 (7)0.0208 (8)0.0033 (6)0.0003 (6)0.0059 (6)
C11A0.0170 (7)0.0151 (7)0.0194 (8)0.0005 (6)0.0005 (6)0.0058 (6)
C12A0.0132 (7)0.0129 (7)0.0187 (7)0.0010 (5)0.0044 (6)0.0068 (6)
C13A0.0169 (7)0.0148 (7)0.0155 (7)0.0041 (6)0.0026 (6)0.0054 (6)
C14A0.0179 (7)0.0174 (8)0.0192 (8)0.0028 (6)0.0013 (6)0.0081 (6)
O1B0.0157 (5)0.0113 (5)0.0160 (5)0.0008 (4)0.0043 (4)0.0048 (4)
N1B0.0142 (6)0.0141 (6)0.0149 (6)0.0019 (5)0.0019 (5)0.0062 (5)
N2B0.0155 (6)0.0155 (6)0.0184 (7)0.0054 (5)0.0057 (5)0.0091 (5)
N3B0.0175 (6)0.0222 (7)0.0239 (7)0.0031 (5)0.0054 (6)0.0117 (6)
N4B0.0207 (7)0.0266 (8)0.0293 (8)0.0076 (6)0.0099 (6)0.0158 (6)
C1B0.0133 (7)0.0133 (7)0.0140 (7)0.0024 (5)0.0003 (5)0.0065 (6)
C2B0.0122 (6)0.0136 (7)0.0154 (7)0.0024 (5)0.0022 (5)0.0071 (6)
C3B0.0129 (7)0.0114 (7)0.0136 (7)0.0007 (5)0.0004 (5)0.0037 (6)
C4B0.0138 (7)0.0134 (7)0.0144 (7)0.0018 (5)0.0018 (5)0.0048 (6)
C5B0.0149 (7)0.0141 (7)0.0147 (7)0.0012 (5)0.0034 (5)0.0064 (6)
C6B0.0158 (7)0.0182 (7)0.0132 (7)0.0007 (6)0.0012 (6)0.0074 (6)
C7B0.0134 (7)0.0187 (7)0.0145 (7)0.0001 (6)0.0003 (6)0.0078 (6)
C8B0.0172 (7)0.0314 (9)0.0217 (8)0.0076 (7)0.0017 (6)0.0150 (7)
C9B0.0194 (8)0.0230 (8)0.0193 (8)0.0045 (6)0.0007 (6)0.0072 (7)
C10B0.0203 (7)0.0115 (7)0.0208 (8)0.0013 (6)0.0057 (6)0.0063 (6)
C11B0.0169 (7)0.0148 (7)0.0203 (8)0.0012 (6)0.0037 (6)0.0061 (6)
C12B0.0136 (7)0.0132 (7)0.0165 (7)0.0022 (5)0.0001 (6)0.0058 (6)
C13B0.0176 (7)0.0162 (7)0.0155 (7)0.0005 (6)0.0037 (6)0.0075 (6)
C14B0.0178 (7)0.0185 (8)0.0180 (8)0.0010 (6)0.0054 (6)0.0083 (6)
Geometric parameters (Å, º) top
O1A—C1A1.3391 (17)O1B—C1B1.3417 (17)
O1A—C10A1.4654 (17)O1B—C10B1.4638 (17)
N1A—C1A1.2671 (18)N1B—C1B1.2684 (19)
N1A—C5A1.4986 (18)N1B—C5B1.4947 (18)
N2A—C3A1.3440 (19)N2B—C3B1.3456 (19)
N2A—H1NA0.92 (2)N2B—H1NB0.91 (2)
N2A—H2NA0.87 (2)N2B—H2NB0.89 (2)
N3A—C12A1.145 (2)N3B—C12B1.146 (2)
N4A—C13A1.158 (2)N4B—C13B1.155 (2)
C1A—C2A1.5226 (19)C1B—C2B1.522 (2)
C2A—C12A1.469 (2)C2B—C12B1.467 (2)
C2A—C3A1.530 (2)C2B—C3B1.5305 (19)
C2A—C7A1.603 (2)C2B—C7B1.6029 (19)
C3A—C4A1.359 (2)C3B—C4B1.356 (2)
C4A—C13A1.420 (2)C4B—C13B1.419 (2)
C4A—C5A1.525 (2)C4B—C5B1.528 (2)
C5A—C14A1.5202 (19)C5B—C14B1.517 (2)
C5A—C6A1.548 (2)C5B—C6B1.551 (2)
C6A—C7A1.554 (2)C6B—C7B1.550 (2)
C6A—H6AA0.9900C6B—H6BA0.9900
C6A—H6AB0.9900C6B—H6BB0.9900
C7A—C8A1.531 (2)C7B—C9B1.526 (2)
C7A—C9A1.533 (2)C7B—C8B1.533 (2)
C8A—H8AA0.9800C8B—H8BA0.9800
C8A—H8AB0.9800C8B—H8BB0.9800
C8A—H8AC0.9800C8B—H8BC0.9800
C9A—H9AA0.9800C9B—H9BA0.9800
C9A—H9AB0.9800C9B—H9BB0.9800
C9A—H9AC0.9800C9B—H9BC0.9800
C10A—C11A1.501 (2)C10B—C11B1.505 (2)
C10A—H10A0.9900C10B—H10C0.9900
C10A—H10B0.9900C10B—H10D0.9900
C11A—H11A0.9800C11B—H11D0.9800
C11A—H11B0.9800C11B—H11E0.9800
C11A—H11C0.9800C11B—H11F0.9800
C14A—H14A0.9800C14B—H14D0.9800
C14A—H14B0.9800C14B—H14E0.9800
C14A—H14C0.9800C14B—H14F0.9800
C1A—O1A—C10A114.77 (11)C1B—O1B—C10B114.72 (11)
C1A—N1A—C5A111.14 (12)C1B—N1B—C5B110.77 (12)
C3A—N2A—H1NA119.3 (13)C3B—N2B—H1NB119.6 (13)
C3A—N2A—H2NA121.5 (12)C3B—N2B—H2NB118.6 (12)
H1NA—N2A—H2NA115.6 (18)H1NB—N2B—H2NB116.8 (17)
N1A—C1A—O1A125.80 (13)N1B—C1B—O1B125.50 (13)
N1A—C1A—C2A118.51 (13)N1B—C1B—C2B118.90 (13)
O1A—C1A—C2A115.65 (12)O1B—C1B—C2B115.55 (12)
C12A—C2A—C1A113.79 (12)C12B—C2B—C1B114.18 (12)
C12A—C2A—C3A111.62 (12)C12B—C2B—C3B111.54 (12)
C1A—C2A—C3A106.25 (11)C1B—C2B—C3B106.50 (11)
C12A—C2A—C7A111.29 (11)C12B—C2B—C7B111.31 (11)
C1A—C2A—C7A105.59 (11)C1B—C2B—C7B105.00 (11)
C3A—C2A—C7A107.90 (11)C3B—C2B—C7B107.89 (11)
N2A—C3A—C4A129.35 (14)N2B—C3B—C4B129.14 (14)
N2A—C3A—C2A119.54 (13)N2B—C3B—C2B119.52 (13)
C4A—C3A—C2A110.99 (13)C4B—C3B—C2B111.18 (13)
C3A—C4A—C13A123.22 (14)C3B—C4B—C13B123.34 (14)
C3A—C4A—C5A114.30 (13)C3B—C4B—C5B114.15 (13)
C13A—C4A—C5A122.42 (13)C13B—C4B—C5B122.45 (13)
N1A—C5A—C14A109.48 (12)N1B—C5B—C14B109.98 (12)
N1A—C5A—C4A108.12 (11)N1B—C5B—C4B108.41 (12)
C14A—C5A—C4A113.69 (12)C14B—C5B—C4B113.42 (12)
N1A—C5A—C6A105.84 (11)N1B—C5B—C6B105.86 (11)
C14A—C5A—C6A111.55 (12)C14B—C5B—C6B111.21 (12)
C4A—C5A—C6A107.80 (12)C4B—C5B—C6B107.64 (12)
C5A—C6A—C7A111.07 (12)C7B—C6B—C5B111.13 (12)
C5A—C6A—H6AA109.4C7B—C6B—H6BA109.4
C7A—C6A—H6AA109.4C5B—C6B—H6BA109.4
C5A—C6A—H6AB109.4C7B—C6B—H6BB109.4
C7A—C6A—H6AB109.4C5B—C6B—H6BB109.4
H6AA—C6A—H6AB108.0H6BA—C6B—H6BB108.0
C8A—C7A—C9A110.00 (13)C9B—C7B—C8B109.86 (12)
C8A—C7A—C6A110.68 (12)C9B—C7B—C6B111.77 (13)
C9A—C7A—C6A112.01 (12)C8B—C7B—C6B111.21 (13)
C8A—C7A—C2A109.42 (12)C9B—C7B—C2B109.64 (12)
C9A—C7A—C2A109.39 (12)C8B—C7B—C2B108.93 (12)
C6A—C7A—C2A105.21 (11)C6B—C7B—C2B105.29 (11)
C7A—C8A—H8AA109.5C7B—C8B—H8BA109.5
C7A—C8A—H8AB109.5C7B—C8B—H8BB109.5
H8AA—C8A—H8AB109.5H8BA—C8B—H8BB109.5
C7A—C8A—H8AC109.5C7B—C8B—H8BC109.5
H8AA—C8A—H8AC109.5H8BA—C8B—H8BC109.5
H8AB—C8A—H8AC109.5H8BB—C8B—H8BC109.5
C7A—C9A—H9AA109.5C7B—C9B—H9BA109.5
C7A—C9A—H9AB109.5C7B—C9B—H9BB109.5
H9AA—C9A—H9AB109.5H9BA—C9B—H9BB109.5
C7A—C9A—H9AC109.5C7B—C9B—H9BC109.5
H9AA—C9A—H9AC109.5H9BA—C9B—H9BC109.5
H9AB—C9A—H9AC109.5H9BB—C9B—H9BC109.5
O1A—C10A—C11A107.60 (11)O1B—C10B—C11B107.68 (12)
O1A—C10A—H10A110.2O1B—C10B—H10C110.2
C11A—C10A—H10A110.2C11B—C10B—H10C110.2
O1A—C10A—H10B110.2O1B—C10B—H10D110.2
C11A—C10A—H10B110.2C11B—C10B—H10D110.2
H10A—C10A—H10B108.5H10C—C10B—H10D108.5
C10A—C11A—H11A109.5C10B—C11B—H11D109.5
C10A—C11A—H11B109.5C10B—C11B—H11E109.5
H11A—C11A—H11B109.5H11D—C11B—H11E109.5
C10A—C11A—H11C109.5C10B—C11B—H11F109.5
H11A—C11A—H11C109.5H11D—C11B—H11F109.5
H11B—C11A—H11C109.5H11E—C11B—H11F109.5
N3A—C12A—C2A176.79 (15)N3B—C12B—C2B176.58 (15)
N4A—C13A—C4A179.54 (16)N4B—C13B—C4B178.95 (18)
C5A—C14A—H14A109.5C5B—C14B—H14D109.5
C5A—C14A—H14B109.5C5B—C14B—H14E109.5
H14A—C14A—H14B109.5H14D—C14B—H14E109.5
C5A—C14A—H14C109.5C5B—C14B—H14F109.5
H14A—C14A—H14C109.5H14D—C14B—H14F109.5
H14B—C14A—H14C109.5H14E—C14B—H14F109.5
C5A—N1A—C1A—O1A177.02 (13)C5B—N1B—C1B—O1B177.00 (12)
C5A—N1A—C1A—C2A0.75 (18)C5B—N1B—C1B—C2B0.39 (17)
C10A—O1A—C1A—N1A0.4 (2)C10B—O1B—C1B—N1B1.5 (2)
C10A—O1A—C1A—C2A177.40 (12)C10B—O1B—C1B—C2B175.93 (11)
N1A—C1A—C2A—C12A176.91 (13)N1B—C1B—C2B—C12B176.98 (12)
O1A—C1A—C2A—C12A5.09 (18)O1B—C1B—C2B—C12B5.38 (17)
N1A—C1A—C2A—C3A53.69 (17)N1B—C1B—C2B—C3B53.43 (16)
O1A—C1A—C2A—C3A128.31 (13)O1B—C1B—C2B—C3B128.93 (13)
N1A—C1A—C2A—C7A60.75 (16)N1B—C1B—C2B—C7B60.84 (16)
O1A—C1A—C2A—C7A117.25 (13)O1B—C1B—C2B—C7B116.80 (13)
C12A—C2A—C3A—N2A7.51 (19)C12B—C2B—C3B—N2B8.73 (18)
C1A—C2A—C3A—N2A132.08 (13)C1B—C2B—C3B—N2B133.91 (13)
C7A—C2A—C3A—N2A115.07 (14)C7B—C2B—C3B—N2B113.81 (14)
C12A—C2A—C3A—C4A176.11 (12)C12B—C2B—C3B—C4B175.44 (13)
C1A—C2A—C3A—C4A51.54 (16)C1B—C2B—C3B—C4B50.26 (15)
C7A—C2A—C3A—C4A61.31 (15)C7B—C2B—C3B—C4B62.02 (15)
N2A—C3A—C4A—C13A6.0 (2)N2B—C3B—C4B—C13B7.6 (2)
C2A—C3A—C4A—C13A178.06 (13)C2B—C3B—C4B—C13B177.03 (13)
N2A—C3A—C4A—C5A176.84 (14)N2B—C3B—C4B—C5B175.05 (14)
C2A—C3A—C4A—C5A0.91 (17)C2B—C3B—C4B—C5B0.27 (17)
C1A—N1A—C5A—C14A178.74 (13)C1B—N1B—C5B—C14B178.68 (12)
C1A—N1A—C5A—C4A54.39 (15)C1B—N1B—C5B—C4B54.17 (15)
C1A—N1A—C5A—C6A60.89 (15)C1B—N1B—C5B—C6B61.09 (15)
C3A—C4A—C5A—N1A53.95 (16)C3B—C4B—C5B—N1B54.80 (16)
C13A—C4A—C5A—N1A123.23 (14)C13B—C4B—C5B—N1B122.53 (14)
C3A—C4A—C5A—C14A175.75 (13)C3B—C4B—C5B—C14B177.24 (13)
C13A—C4A—C5A—C14A1.4 (2)C13B—C4B—C5B—C14B0.1 (2)
C3A—C4A—C5A—C6A60.05 (16)C3B—C4B—C5B—C6B59.29 (16)
C13A—C4A—C5A—C6A122.77 (14)C13B—C4B—C5B—C6B123.38 (14)
N1A—C5A—C6A—C7A61.10 (15)N1B—C5B—C6B—C7B60.54 (15)
C14A—C5A—C6A—C7A179.90 (12)C14B—C5B—C6B—C7B179.96 (12)
C4A—C5A—C6A—C7A54.41 (15)C4B—C5B—C6B—C7B55.24 (15)
C5A—C6A—C7A—C8A121.52 (14)C5B—C6B—C7B—C9B116.77 (13)
C5A—C6A—C7A—C9A115.33 (14)C5B—C6B—C7B—C8B120.04 (13)
C5A—C6A—C7A—C2A3.42 (16)C5B—C6B—C7B—C2B2.20 (16)
C12A—C2A—C7A—C8A57.10 (16)C12B—C2B—C7B—C9B62.71 (15)
C1A—C2A—C7A—C8A66.83 (14)C1B—C2B—C7B—C9B173.27 (12)
C3A—C2A—C7A—C8A179.88 (12)C3B—C2B—C7B—C9B59.97 (15)
C12A—C2A—C7A—C9A63.47 (15)C12B—C2B—C7B—C8B57.54 (16)
C1A—C2A—C7A—C9A172.60 (12)C1B—C2B—C7B—C8B66.48 (14)
C3A—C2A—C7A—C9A59.31 (14)C3B—C2B—C7B—C8B179.78 (12)
C12A—C2A—C7A—C6A176.04 (12)C12B—C2B—C7B—C6B176.91 (12)
C1A—C2A—C7A—C6A52.11 (14)C1B—C2B—C7B—C6B52.88 (14)
C3A—C2A—C7A—C6A61.18 (14)C3B—C2B—C7B—C6B60.41 (14)
C1A—O1A—C10A—C11A174.53 (12)C1B—O1B—C10B—C11B174.73 (12)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2A—H1NA···O1Ai0.92 (2)2.57 (2)3.4202 (17)153.7 (17)
N2A—H2NA···N1Bii0.87 (2)2.10 (2)2.958 (2)170 (2)
N2B—H1NB···N1Aiii0.91 (2)2.06 (2)2.951 (2)169 (2)
N2B—H2NB···O1Biv0.887 (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 formulaC14H18N4O
Mr258.32
Crystal system, space groupTriclinic, 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)
V3)1357.30 (4)
Z4
Radiation typeMo Kα
µ (mm1)0.08
Crystal size (mm)0.37 × 0.15 × 0.09
Data collection
DiffractometerBruker APEXII CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2009)
Tmin, Tmax0.970, 0.993
No. of measured, independent and
observed [I > 2σ(I)] reflections
23432, 6248, 5008
Rint0.041
(sin θ/λ)max1)0.651
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.047, 0.109, 1.05
No. of reflections6248
No. of parameters367
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)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···AD—HH···AD···AD—H···A
N2A—H1NA···O1Ai0.92 (2)2.57 (2)3.4202 (17)153.7 (17)
N2A—H2NA···N1Bii0.87 (2)2.10 (2)2.958 (2)170 (2)
N2B—H1NB···N1Aiii0.91 (2)2.06 (2)2.951 (2)169 (2)
N2B—H2NB···O1Biv0.887 (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

First citationAllen, 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
First citationBruker (2009). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.
First citationCosier, J. & Glazer, A. M. (1986). J. Appl. Cryst. 19, 105–107.  CrossRef CAS Web of Science IUCr Journals
First citationCremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358.  CrossRef CAS Web of Science
First citationIgarashi, M., Nakano, Y., Takezawa, K., Watanabe, T. & Sata, S. (1987). Synthesis, pp. 68–70.  CrossRef
First citationNakano, Y., Igarashi, M. & Sato, S. (1987). Acta Cryst. C43, 738–740.  CSD CrossRef CAS Web of Science IUCr Journals
First citationNakano, Y., Kaneko, Y. & Fen, W. A. (1999). Heterocycles, 51, 169–177.  CrossRef CAS
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals
First citationSpek, A. L. (2009). Acta Cryst. D65, 148–155.  Web of Science CrossRef CAS IUCr Journals

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.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 68| Part 9| September 2012| Pages o2606-o2607
Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds