organic compounds
N-phenyl-1,3,4-oxadiazol-2-amine
of 5-(furan-2-yl)-aDepartment of Chemistry, Banaras Hindu University, Varanasi 221 005, India, and bSchool of Studies in Chemistry, Jiwaji University, Gwalior 474 011, India
*Correspondence e-mail: manoj_vns2005@yahoo.co.in
The title compound, C12H9N3O2, was obtained as a cyclized oxadiazole derivative from substituted thiosemicarbazide in the presence of manganese(II) acetate. The furan ring is disordered over two orientations, with occupancies of 0.76 (2) and 0.24 (2). The dihedral angles between the central oxadiazole ring and the pendant phenyl ring and furan ring (major disorder component) are 3.34 (18) and 5.7 (6)°, respectively. A short intramolecular C—H⋯O contact generates an S(6) ring. In the crystal, inversion dimers linked by pairs of N—H⋯N hydrogen bonds generate R22[8] loops. The dimers are linked by C—H⋯π and π–π interactions [range of centroid–centroid distances = 3.291 (2)–3.460 (8) Å], generating a three-dimensional network.
Keywords: crystal structure; cyclized oxadiazole derivative; hydrogen bonding; C—H⋯π interactions; π–π interactions.
CCDC reference: 1431289
1. Related literature
For heterocyclic ligands that form metal complexes, see: Tarafder et al. (2001); Ali & Ali (2007); Singh et al. (2007); Zhao et al. (2007); Zhang et al. (2007); Amin et al. (2004). For applications in medicine and agriculture, see: Pachhamia & Parikh (1988); Xu et al. (2002). For related structures, see: Foks et al. (2002); Dani et al. (2013).
2. Experimental
2.1. Crystal data
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2.3. Refinement
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Data collection: CrysAlis PRO (Agilent, 2011); cell CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.
Supporting information
CCDC reference: 1431289
https://doi.org/10.1107/S2056989015019453/hb7522sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015019453/hb7522Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2056989015019453/hb7522Isup3.cml
1,3,4-Oxadiazole-2-thiones, an important class of heterocyclic ligands in the field of coordination chemistry (Tarafder et al., 2001; Ali & Ali, 2007; Singh et al., 2007; Zhao et al., 2007; Zhang et al., 2007; Amin et al., 2004) have wide applications both in medicine and agriculture (Pachhamia & Parikh, 1988; Xu et al., 2002). The
of 3-acyldithiocarbazate N-aroyldithiocarbazates and their salts to the corresponding 1,3,4-oxadiazole in the presence of base is reported in the literature (Foks et al., 2002). Further, 5-benzyl-N- phenyl-1,3,4-thiadiazole-2-amine and 2-(5-phenyl-1,3,4-thiadiazol-2-yl)pyridine have also been reported in the presence of managnese(II) nitrate via loss of H2O (Dani et al., 2013). It is known that in the presence of strong acid, N-acylhydrazine carbodithioate is converted into thiadiazole but in presence of weak acid or base they are cyclized into oxadiazole. In the present case, managanese(II) acetate behaves like a weak acid and thus converts thiosemicarbazide into oxadiazole via loss of H2S.In the title compound (Fig. 2), the mean plane of the central oxadiazole ring (O2/C5/N1/N2/C6) forms dihedral angles of 5.65 and 3.34° with the furan (O1/C1–C4) and phenyl rings (C7–C12), respectively. Both the furan and phenyl rings are twisted by an angle of 7.51°. The C–N bond lengths, N1–C5 1.290 (4) and N2–C6 1.302 (4) Å, are similar to standard C ═N 1.28 Å. The distances found within the oxadiazole ring are intermediate between single and double bond, suggesting considerable delocalization in the ring. In the crystal, pairs of intermolecular N—H···N hydrogen bonds between the oxadiazole ring and the amine group forming dimers with an R22[8] ring motif (Fig. 3, Table 1) and an intramolecular C—H···O interaction is also found. Molecules are further linked by weak C—H···N and two C—H···π interactions, involving (C7–C12) and (O1/C1–C4) rings. In addition, weak π···π intermolecular stacking interactions [Cg1···Cg2 (x, 1+y, z) = 3.460 (8)Å; Cg2···Cg2 (1–x, 1–y, 1–z) = 3.291 (2)Å; Cg2···Cg3 (x, –1+y, z) = 3.431 (4)Å; Cg1: O1/C1–C4; Cg2: O2/C5/N1/N2/C6; Cg3: O1A/C1A–C4A] are present and influences the crystal packing. The furan ring is disordered over two positions, with occupancies of 0.76 (2) and 0.24 (2).
Referring to Fig. 1, a mixture of furan-2-carboxylic acid hydrazide (1.260 g, 10 mmol) and phenyl isothiocyanate (1.2 ml, 10 mmol) in absolute ethanol (20 mL) was refluxed for 4 h. The solid N-(furan-2-carbonyl)-4-phenylthiosemicarbazide obtained upon cooling was filtered off and washed with water and ether (50:50 v/v). A mixture of methanolic solution of N-(furan-2-carbonyl)-4-phenylthiosemicarbazide (0.261 g, 1.00 mmol) and Mn(OAc)2.4H2O (0.246 g, 1 mmol) was stirred for 4 h. A clear yellow solution obtained was filtered off and kept for crystallization. Colourless needles were obtained after 10 days. Yield: 60%; m.p.: 476–478 K. Anal. Calc. for C12H9N3O2(%):C 63.43, H 3.99, N 18.49. Found: C 63.68, H 4.05, N 18.61. 1H NMR (DMSO-d6): δ [ppm] = 11.60 (s, 1H, NH), 8.80–7.31 (m, 3H, furan), 7.80–6.76 (m, 5H, Phenyl). 13C NMR (DMSO-d6): δ [ppm] = 161.3 (C6), 162.0 (C5), 153.7 (C4), 146.9 (C1), 144.8 (C3), 140.7 (C2) (furan C); 120.6–145.2 (phenyl C) (Fig. 2). IR (selected, KBr): 3210 [ν(N– H)], 1605 [ν(C═N)], 1076 [ν(N – N)] cm-1.
The H atom bonded to N3 was located in a difference Fourier map and refined freely; N3–H3N3 = 1.02 (3) Å. Other H atoms were positioned geometrically and allowed to ride on their parent atoms, with C—H = 0.93 Å, and with Uiso(H) = 1.2Ueq(C). The ISOR restraint and EADP constraint commands in the SHELXL2014 software were used for the disordered atoms.
1,3,4-Oxadiazole-2-thiones, an important class of heterocyclic ligands in the field of coordination chemistry (Tarafder et al., 2001; Ali & Ali, 2007; Singh et al., 2007; Zhao et al., 2007; Zhang et al., 2007; Amin et al., 2004) have wide applications both in medicine and agriculture (Pachhamia & Parikh, 1988; Xu et al., 2002). The
of 3-acyldithiocarbazate N-aroyldithiocarbazates and their salts to the corresponding 1,3,4-oxadiazole in the presence of base is reported in the literature (Foks et al., 2002). Further, 5-benzyl-N- phenyl-1,3,4-thiadiazole-2-amine and 2-(5-phenyl-1,3,4-thiadiazol-2-yl)pyridine have also been reported in the presence of managnese(II) nitrate via loss of H2O (Dani et al., 2013). It is known that in the presence of strong acid, N-acylhydrazine carbodithioate is converted into thiadiazole but in presence of weak acid or base they are cyclized into oxadiazole. In the present case, managanese(II) acetate behaves like a weak acid and thus converts thiosemicarbazide into oxadiazole via loss of H2S.In the title compound (Fig. 2), the mean plane of the central oxadiazole ring (O2/C5/N1/N2/C6) forms dihedral angles of 5.65 and 3.34° with the furan (O1/C1–C4) and phenyl rings (C7–C12), respectively. Both the furan and phenyl rings are twisted by an angle of 7.51°. The C–N bond lengths, N1–C5 1.290 (4) and N2–C6 1.302 (4) Å, are similar to standard C ═N 1.28 Å. The distances found within the oxadiazole ring are intermediate between single and double bond, suggesting considerable delocalization in the ring. In the crystal, pairs of intermolecular N—H···N hydrogen bonds between the oxadiazole ring and the amine group forming dimers with an R22[8] ring motif (Fig. 3, Table 1) and an intramolecular C—H···O interaction is also found. Molecules are further linked by weak C—H···N and two C—H···π interactions, involving (C7–C12) and (O1/C1–C4) rings. In addition, weak π···π intermolecular stacking interactions [Cg1···Cg2 (x, 1+y, z) = 3.460 (8)Å; Cg2···Cg2 (1–x, 1–y, 1–z) = 3.291 (2)Å; Cg2···Cg3 (x, –1+y, z) = 3.431 (4)Å; Cg1: O1/C1–C4; Cg2: O2/C5/N1/N2/C6; Cg3: O1A/C1A–C4A] are present and influences the crystal packing. The furan ring is disordered over two positions, with occupancies of 0.76 (2) and 0.24 (2).
Referring to Fig. 1, a mixture of furan-2-carboxylic acid hydrazide (1.260 g, 10 mmol) and phenyl isothiocyanate (1.2 ml, 10 mmol) in absolute ethanol (20 mL) was refluxed for 4 h. The solid N-(furan-2-carbonyl)-4-phenylthiosemicarbazide obtained upon cooling was filtered off and washed with water and ether (50:50 v/v). A mixture of methanolic solution of N-(furan-2-carbonyl)-4-phenylthiosemicarbazide (0.261 g, 1.00 mmol) and Mn(OAc)2.4H2O (0.246 g, 1 mmol) was stirred for 4 h. A clear yellow solution obtained was filtered off and kept for crystallization. Colourless needles were obtained after 10 days. Yield: 60%; m.p.: 476–478 K. Anal. Calc. for C12H9N3O2(%):C 63.43, H 3.99, N 18.49. Found: C 63.68, H 4.05, N 18.61. 1H NMR (DMSO-d6): δ [ppm] = 11.60 (s, 1H, NH), 8.80–7.31 (m, 3H, furan), 7.80–6.76 (m, 5H, Phenyl). 13C NMR (DMSO-d6): δ [ppm] = 161.3 (C6), 162.0 (C5), 153.7 (C4), 146.9 (C1), 144.8 (C3), 140.7 (C2) (furan C); 120.6–145.2 (phenyl C) (Fig. 2). IR (selected, KBr): 3210 [ν(N– H)], 1605 [ν(C═N)], 1076 [ν(N – N)] cm-1.
For heterocyclic ligands that form metal complexes, see: Tarafder et al. (2001); Ali & Ali (2007); Singh et al. (2007); Zhao et al. (2007); Zhang et al. (2007); Amin et al. (2004). For applications in medicine and agriculture, see: Pachhamia & Parikh (1988); Xu et al. (2002). For related structures, see: Foks et al. (2002); Dani et al. (2013).
detailsThe H atom bonded to N3 was located in a difference Fourier map and refined freely; N3–H3N3 = 1.02 (3) Å. Other H atoms were positioned geometrically and allowed to ride on their parent atoms, with C—H = 0.93 Å, and with Uiso(H) = 1.2Ueq(C). The ISOR restraint and EADP constraint commands in the SHELXL2014 software were used for the disordered atoms.
Data collection: CrysAlis PRO (Agilent, 2011); cell
CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).Fig. 1. Scheme showing the synthesis of the title compound. | |
Fig. 2. The molecular structure of (I) showing 50% probability displacement ellipsoids. | |
Fig. 3. The molecular packing of the title compound, viewed along the b-axis. Dashed lines indicate weak N—H···N intermolecular hydrogen bonding between the oxadiazole ring and the amine group, forming dimers with an R22[8] ring motif. |
C12H9N3O2 | F(000) = 472 |
Mr = 227.22 | Dx = 1.424 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 13.195 (3) Å | Cell parameters from 594 reflections |
b = 5.6162 (8) Å | θ = 3.1–29.0° |
c = 14.958 (3) Å | µ = 0.10 mm−1 |
β = 107.00 (2)° | T = 293 K |
V = 1060.0 (3) Å3 | Needle, colourless |
Z = 4 | 0.4 × 0.3 × 0.15 mm |
Agilent Xcalibur Eos diffractometer | 2405 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 1057 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.039 |
Detector resolution: 16.0938 pixels mm-1 | θmax = 29.1°, θmin = 3.2° |
ω scans | h = −18→13 |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011) | k = −7→7 |
Tmin = 0.941, Tmax = 1.000 | l = −19→17 |
4305 measured reflections |
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)] = 0.064 | Hydrogen site location: mixed |
wR(F2) = 0.142 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0308P)2] where P = (Fo2 + 2Fc2)/3 |
2405 reflections | (Δ/σ)max < 0.001 |
174 parameters | Δρmax = 0.19 e Å−3 |
40 restraints | Δρmin = −0.21 e Å−3 |
C12H9N3O2 | V = 1060.0 (3) Å3 |
Mr = 227.22 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 13.195 (3) Å | µ = 0.10 mm−1 |
b = 5.6162 (8) Å | T = 293 K |
c = 14.958 (3) Å | 0.4 × 0.3 × 0.15 mm |
β = 107.00 (2)° |
Agilent Xcalibur Eos diffractometer | 2405 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011) | 1057 reflections with I > 2σ(I) |
Tmin = 0.941, Tmax = 1.000 | Rint = 0.039 |
4305 measured reflections |
R[F2 > 2σ(F2)] = 0.064 | 40 restraints |
wR(F2) = 0.142 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | Δρmax = 0.19 e Å−3 |
2405 reflections | Δρmin = −0.21 e Å−3 |
174 parameters |
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 on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs 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 | Occ. (<1) | |
O2 | 0.65450 (17) | 0.5460 (3) | 0.46696 (13) | 0.0425 (6) | |
N1 | 0.6233 (2) | 0.5577 (4) | 0.60530 (17) | 0.0463 (7) | |
N2 | 0.5682 (2) | 0.7470 (4) | 0.54975 (17) | 0.0445 (7) | |
N3 | 0.5544 (2) | 0.8799 (4) | 0.39788 (17) | 0.0449 (7) | |
H3N3 | 0.512 (2) | 1.014 (5) | 0.4150 (19) | 0.067 (11)* | |
O1 | 0.7733 (7) | 0.1580 (16) | 0.5086 (4) | 0.0560 (14) | 0.76 (2) |
C1 | 0.8374 (6) | −0.0405 (14) | 0.5478 (9) | 0.057 (2) | 0.76 (2) |
H1A | 0.8716 | −0.1392 | 0.5158 | 0.068* | 0.76 (2) |
C2 | 0.8412 (7) | −0.0643 (15) | 0.6370 (8) | 0.062 (2) | 0.76 (2) |
H2A | 0.8780 | −0.1815 | 0.6776 | 0.074* | 0.76 (2) |
C3 | 0.7797 (8) | 0.1194 (18) | 0.6598 (6) | 0.0470 (17) | 0.76 (2) |
H3A | 0.7692 | 0.1477 | 0.7177 | 0.056* | 0.76 (2) |
C4 | 0.740 (2) | 0.244 (4) | 0.5812 (9) | 0.0395 (13) | 0.76 (2) |
O1A | 0.790 (3) | 0.093 (5) | 0.5177 (17) | 0.0560 (14) | 0.24 (2) |
C1A | 0.844 (3) | −0.073 (5) | 0.587 (2) | 0.057 (2) | 0.24 (2) |
H1AA | 0.8868 | −0.1956 | 0.5766 | 0.068* | 0.24 (2) |
C2A | 0.826 (3) | −0.029 (5) | 0.6672 (18) | 0.062 (2) | 0.24 (2) |
H2AA | 0.8545 | −0.1113 | 0.7226 | 0.074* | 0.24 (2) |
C3A | 0.755 (3) | 0.163 (6) | 0.655 (2) | 0.0470 (17) | 0.24 (2) |
H3AA | 0.7244 | 0.2242 | 0.6989 | 0.056* | 0.24 (2) |
C4A | 0.741 (8) | 0.238 (13) | 0.568 (3) | 0.0395 (13) | 0.24 (2) |
C5 | 0.6717 (3) | 0.4467 (5) | 0.5543 (2) | 0.0411 (8) | |
C6 | 0.5901 (3) | 0.7321 (5) | 0.4705 (2) | 0.0409 (8) | |
C7 | 0.5742 (3) | 0.8830 (5) | 0.3105 (2) | 0.0408 (8) | |
C8 | 0.5304 (3) | 1.0704 (5) | 0.2521 (2) | 0.0515 (9) | |
H8A | 0.4916 | 1.1860 | 0.2722 | 0.062* | |
C9 | 0.5436 (3) | 1.0878 (6) | 0.1647 (2) | 0.0627 (11) | |
H9A | 0.5129 | 1.2139 | 0.1259 | 0.075* | |
C10 | 0.6013 (3) | 0.9215 (6) | 0.1342 (2) | 0.0607 (11) | |
H10A | 0.6097 | 0.9332 | 0.0748 | 0.073* | |
C11 | 0.6470 (3) | 0.7360 (6) | 0.1925 (2) | 0.0593 (10) | |
H11A | 0.6876 | 0.6238 | 0.1727 | 0.071* | |
C12 | 0.6330 (3) | 0.7158 (5) | 0.2798 (2) | 0.0518 (9) | |
H12A | 0.6633 | 0.5889 | 0.3183 | 0.062* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O2 | 0.0432 (14) | 0.0445 (12) | 0.0412 (12) | 0.0048 (11) | 0.0147 (11) | 0.0035 (9) |
N1 | 0.0496 (18) | 0.0517 (15) | 0.0372 (15) | −0.0012 (15) | 0.0123 (14) | −0.0020 (12) |
N2 | 0.0463 (18) | 0.0501 (16) | 0.0384 (15) | 0.0039 (14) | 0.0146 (14) | 0.0015 (12) |
N3 | 0.0511 (19) | 0.0456 (16) | 0.0418 (16) | 0.0102 (14) | 0.0192 (15) | 0.0040 (12) |
O1 | 0.061 (3) | 0.044 (4) | 0.065 (2) | 0.017 (3) | 0.022 (2) | 0.006 (2) |
C1 | 0.049 (3) | 0.036 (3) | 0.081 (6) | 0.014 (2) | 0.014 (4) | 0.012 (4) |
C2 | 0.060 (4) | 0.064 (3) | 0.055 (5) | 0.001 (3) | 0.007 (4) | 0.014 (4) |
C3 | 0.043 (5) | 0.048 (4) | 0.042 (2) | 0.017 (3) | −0.001 (3) | 0.017 (2) |
C4 | 0.042 (2) | 0.043 (2) | 0.035 (4) | −0.0025 (17) | 0.013 (5) | −0.002 (4) |
O1A | 0.061 (3) | 0.044 (4) | 0.065 (2) | 0.017 (3) | 0.022 (2) | 0.006 (2) |
C1A | 0.049 (3) | 0.036 (3) | 0.081 (6) | 0.014 (2) | 0.014 (4) | 0.012 (4) |
C2A | 0.060 (4) | 0.064 (3) | 0.055 (5) | 0.001 (3) | 0.007 (4) | 0.014 (4) |
C3A | 0.043 (5) | 0.048 (4) | 0.042 (2) | 0.017 (3) | −0.001 (3) | 0.017 (2) |
C4A | 0.042 (2) | 0.043 (2) | 0.035 (4) | −0.0025 (17) | 0.013 (5) | −0.002 (4) |
C5 | 0.042 (2) | 0.0453 (18) | 0.0321 (17) | −0.0056 (17) | 0.0056 (16) | 0.0040 (14) |
C6 | 0.039 (2) | 0.0412 (18) | 0.0430 (19) | −0.0004 (16) | 0.0122 (16) | −0.0018 (15) |
C7 | 0.041 (2) | 0.0437 (18) | 0.0377 (18) | −0.0019 (17) | 0.0112 (16) | 0.0004 (14) |
C8 | 0.062 (2) | 0.0446 (19) | 0.052 (2) | 0.0121 (18) | 0.023 (2) | 0.0051 (16) |
C9 | 0.079 (3) | 0.062 (2) | 0.052 (2) | 0.020 (2) | 0.026 (2) | 0.0165 (17) |
C10 | 0.073 (3) | 0.070 (2) | 0.047 (2) | 0.010 (2) | 0.030 (2) | 0.0091 (18) |
C11 | 0.070 (3) | 0.061 (2) | 0.056 (2) | 0.013 (2) | 0.033 (2) | −0.0006 (18) |
C12 | 0.058 (2) | 0.0509 (19) | 0.051 (2) | 0.0180 (19) | 0.0230 (19) | 0.0114 (16) |
O2—C6 | 1.358 (3) | C1A—C2A | 1.321 (16) |
O2—C5 | 1.376 (3) | C1A—H1AA | 0.9300 |
N1—C5 | 1.290 (4) | C2A—C3A | 1.397 (16) |
N1—N2 | 1.413 (3) | C2A—H2AA | 0.9300 |
N2—C6 | 1.302 (4) | C3A—C4A | 1.335 (16) |
N3—C6 | 1.339 (3) | C3A—H3AA | 0.9300 |
N3—C7 | 1.406 (4) | C4A—C5 | 1.46 (2) |
N3—H3N3 | 1.02 (3) | C7—C12 | 1.379 (4) |
O1—C4 | 1.375 (6) | C7—C8 | 1.382 (4) |
O1—C1 | 1.418 (6) | C8—C9 | 1.371 (4) |
C1—C2 | 1.328 (7) | C8—H8A | 0.9300 |
C1—H1A | 0.9300 | C9—C10 | 1.365 (4) |
C2—C3 | 1.414 (7) | C9—H9A | 0.9300 |
C2—H2A | 0.9300 | C10—C11 | 1.379 (4) |
C3—C4 | 1.337 (6) | C10—H10A | 0.9300 |
C3—H3A | 0.9300 | C11—C12 | 1.376 (4) |
C4—C5 | 1.433 (8) | C11—H11A | 0.9300 |
O1A—C4A | 1.387 (16) | C12—H12A | 0.9300 |
O1A—C1A | 1.418 (16) | ||
C6—O2—C5 | 101.9 (2) | C3A—C4A—O1A | 112.9 (16) |
C5—N1—N2 | 105.9 (2) | C3A—C4A—C5 | 107 (2) |
C6—N2—N1 | 105.9 (3) | O1A—C4A—C5 | 140 (3) |
C6—N3—C7 | 130.2 (3) | N1—C5—O2 | 113.1 (3) |
C6—N3—H3N3 | 110.1 (16) | N1—C5—C4 | 126.5 (5) |
C7—N3—H3N3 | 119.5 (16) | O2—C5—C4 | 120.3 (5) |
C4—O1—C1 | 103.9 (5) | N1—C5—C4A | 134.6 (14) |
C2—C1—O1 | 109.7 (5) | O2—C5—C4A | 112.2 (13) |
C2—C1—H1A | 125.1 | N2—C6—N3 | 125.4 (3) |
O1—C1—H1A | 125.1 | N2—C6—O2 | 113.2 (3) |
C1—C2—C3 | 108.3 (5) | N3—C6—O2 | 121.4 (3) |
C1—C2—H2A | 125.9 | C12—C7—C8 | 118.7 (3) |
C3—C2—H2A | 125.9 | C12—C7—N3 | 125.2 (3) |
C4—C3—C2 | 106.1 (5) | C8—C7—N3 | 116.1 (3) |
C4—C3—H3A | 127.0 | C9—C8—C7 | 120.7 (3) |
C2—C3—H3A | 127.0 | C9—C8—H8A | 119.6 |
C3—C4—O1 | 112.1 (6) | C7—C8—H8A | 119.6 |
C3—C4—C5 | 135.8 (8) | C10—C9—C8 | 120.6 (3) |
O1—C4—C5 | 112.1 (8) | C10—C9—H9A | 119.7 |
C4A—O1A—C1A | 102.0 (14) | C8—C9—H9A | 119.7 |
C2A—C1A—O1A | 110.6 (15) | C9—C10—C11 | 119.2 (3) |
C2A—C1A—H1AA | 124.7 | C9—C10—H10A | 120.4 |
O1A—C1A—H1AA | 124.7 | C11—C10—H10A | 120.4 |
C1A—C2A—C3A | 108.7 (16) | C12—C11—C10 | 120.5 (3) |
C1A—C2A—H2AA | 125.6 | C12—C11—H11A | 119.8 |
C3A—C2A—H2AA | 125.6 | C10—C11—H11A | 119.8 |
C4A—C3A—C2A | 105.5 (16) | C11—C12—C7 | 120.3 (3) |
C4A—C3A—H3AA | 127.3 | C11—C12—H12A | 119.9 |
C2A—C3A—H3AA | 127.3 | C7—C12—H12A | 119.9 |
C5—N1—N2—C6 | −0.7 (3) | C3—C4—C5—O2 | 173 (3) |
C4—O1—C1—C2 | −0.7 (18) | O1—C4—C5—O2 | −6 (3) |
O1—C1—C2—C3 | −0.2 (11) | C3A—C4A—C5—N1 | −2 (12) |
C1—C2—C3—C4 | 1.1 (19) | O1A—C4A—C5—N1 | 173 (9) |
C2—C3—C4—O1 | −2 (3) | C3A—C4A—C5—O2 | 178 (5) |
C2—C3—C4—C5 | 179 (3) | O1A—C4A—C5—O2 | −7 (15) |
C1—O1—C4—C3 | 1 (3) | N1—N2—C6—N3 | −179.4 (3) |
C1—O1—C4—C5 | −179.2 (18) | N1—N2—C6—O2 | 0.9 (3) |
C4A—O1A—C1A—C2A | 1 (7) | C7—N3—C6—N2 | 178.8 (3) |
O1A—C1A—C2A—C3A | 2 (5) | C7—N3—C6—O2 | −1.5 (5) |
C1A—C2A—C3A—C4A | −5 (7) | C5—O2—C6—N2 | −0.7 (3) |
C2A—C3A—C4A—O1A | 6 (10) | C5—O2—C6—N3 | 179.6 (3) |
C2A—C3A—C4A—C5 | −177 (5) | C6—N3—C7—C12 | 4.1 (5) |
C1A—O1A—C4A—C3A | −5 (9) | C6—N3—C7—C8 | −175.8 (3) |
C1A—O1A—C4A—C5 | −180 (12) | C12—C7—C8—C9 | 1.1 (5) |
N2—N1—C5—O2 | 0.2 (3) | N3—C7—C8—C9 | −178.9 (3) |
N2—N1—C5—C4 | 178.7 (18) | C7—C8—C9—C10 | −0.8 (6) |
N2—N1—C5—C4A | −180 (7) | C8—C9—C10—C11 | −0.4 (6) |
C6—O2—C5—N1 | 0.3 (3) | C9—C10—C11—C12 | 1.3 (6) |
C6—O2—C5—C4 | −178.3 (17) | C10—C11—C12—C7 | −0.9 (6) |
C6—O2—C5—C4A | −180 (5) | C8—C7—C12—C11 | −0.3 (5) |
C3—C4—C5—N1 | −5 (5) | N3—C7—C12—C11 | 179.8 (3) |
O1—C4—C5—N1 | 175.9 (13) |
Cg1 and Cg4 are the centroids of the O1A/C1/C2/C3/C4 and C7–C12 five- and six-membered rings, respectively. |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3N3···N2i | 1.02 (3) | 1.87 (3) | 2.892 (3) | 178 (2) |
C12—H12A···O2 | 0.93 | 2.27 | 2.892 (4) | 123 |
C9—H9A···Cg1ii | 0.93 | 3.00 | 3.653 (4) | 129 |
C2—H2A···Cg4iii | 0.93 | 2.93 | 3.664 (5) | 137 |
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) x−1/2, −y−1/2, z−1/2; (iii) x−3/2, −y+1/2, z−3/2. |
Cg1 and Cg4 are the centroids of the O1A/C1/C2/C3/C4 and C7–C12 five- and six-membered rings, respectively. |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3N3···N2i | 1.02 (3) | 1.87 (3) | 2.892 (3) | 178 (2) |
C12—H12A···O2 | 0.93 | 2.27 | 2.892 (4) | 123 |
C9—H9A···Cg1ii | 0.93 | 3.00 | 3.653 (4) | 129 |
C2—H2A···Cg4iii | 0.93 | 2.93 | 3.664 (5) | 137 |
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) x−1/2, −y−1/2, z−1/2; (iii) x−3/2, −y+1/2, z−3/2. |
Acknowledgements
This work was supported by the Department of Science and Technology (DST), New Delhi, India (Young Scientist Project No. SR/FT/CS-63/2011). We express our sincere thanks to Professor Ray J. Butcher for useful discussions.
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