organic compounds
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
The title 2-azabicyclo[2.2.2]octa-2,5-diene derivative, C14H18N4O, crystallized out with two independent molecules with similar conformations in the 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
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Refinement
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Data collection: APEX2 (Bruker, 2009); cell 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
10.1107/S1600536812032990/rz2787sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812032990/rz2787Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812032990/rz2787Isup3.cml
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
were recrystalized from acetone/methanol (1:1 v/v) by the slow evaporation of the solvent at room temperature after several days.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
for methyl H atoms and 1.2Ueq for the remaining H atoms. A rotating group model was used for the methyl groups.Data collection: APEX2 (Bruker, 2009); cell
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).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. |
C14H18N4O | Z = 4 |
Mr = 258.32 | F(000) = 552 |
Triclinic, P1 | Dx = 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 |
Bruker APEXII CCD area-detector diffractometer | 6248 independent reflections |
Radiation source: sealed tube | 5008 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.041 |
ϕ and ω scans | θmax = 27.6°, θmin = 1.7° |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | h = −11→11 |
Tmin = 0.970, Tmax = 0.993 | k = −16→16 |
23432 measured reflections | l = −16→17 |
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(Fo2) + (0.0415P)2 + 0.6407P] where P = (Fo2 + 2Fc2)/3 |
6248 reflections | (Δ/σ)max < 0.001 |
367 parameters | Δρmax = 0.39 e Å−3 |
0 restraints | Δρmin = −0.26 e Å−3 |
C14H18N4O | γ = 89.339 (1)° |
Mr = 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)° |
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 = 0.993 | Rint = 0.041 |
23432 measured reflections |
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 | Δρmax = 0.39 e Å−3 |
6248 reflections | Δρmin = −0.26 e Å−3 |
367 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
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)* |
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) |
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) |
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···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. |
Experimental details
Crystal data | |
Chemical formula | C14H18N4O |
Mr | 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) |
Tmin, Tmax | 0.970, 0.993 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 23432, 6248, 5008 |
Rint | 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 |
Δρmax, Δρmin (e Å−3) | 0.39, −0.26 |
Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).
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···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. |
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
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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.
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.