![](/logos/buttonlogos/cross.png)
![](/logos/buttonlogos/cross.png)
organic compounds
2,6-Diphenyl-4-(2-thienyl)-1,4-dihydropyridine-3,5-dicarbonitrile
aDepartment of Chemistry, Xuzhou Medical College, Jiangsu 221004, People's Republic of China, and bCollege of Chemistry and Chemical Engineering, Xuzhou Normal University, Xuzhou 221116, People's Republic of China
*Correspondence e-mail: laotu2001@263.net
The 23H15N3S, contains two crystallographically independent molecules. The pyridine rings adopt envelope conformations. The thiophene rings are oriented at dihedral angles of 77.97 (4)/53.53 (4) and 78.44 (4)/57.11 (4)° with respect to the phenyl rings, while the dihedral angles between the phenyl rings are 48.51 (4) and 44.49 (4)°. In the intermolecular N—H⋯N hydrogen bonds link the molecules into chains along the c axis. The S, C and H atoms of one of the thiophene rings are disordered over two orientations, with occupancy ratios of 0.314 (15):0.686 (15).
of the title compound, CRelated literature
For general background to the synthesis of pyridines with a multi-aryl substitution pattern, see: Adib et al. (2006); Cave & Raston (2000
); Kobayashi et al. (1991
); Kröhnke (1963
, 1976
); Kumar et al. (2006
); Tu et al. (2005a
,b
).
Experimental
Crystal data
|
Refinement
|
|
Data collection: SMART (Bruker, 2001); cell SAINT (Bruker, 2001
); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008
); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008
); molecular graphics: SHELXTL (Sheldrick, 2008
); software used to prepare material for publication: SHELXTL.
Supporting information
10.1107/S1600536809033339/hk2755sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536809033339/hk2755Isup2.hkl
The title compound was prepared in 10-ml vial, 3-oxo-3-phenylpropanenitrile (0.15 g, 1 mmol), thiophene-2-carbaldehyde (0.11 g, 1 mmol), ammonium acetate (0.5 g) and water (2.0 ml) were mixed, and then capped. The mixture was irradiated for 16 min at 423 K (initial power 150 W and maximum power 250 W).
H atoms were positioned geometrically with N-H = 0.86 Å (for NH) and C-H = 0.93 and 0.98 Å for aromatic and methine H atoms, respectively, and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C,N). S2, C37, C38, C39, H37, H38 and H39 atoms of the thiophene ring attached at C26 are disordered over two orientations. During the
process, the disordered S2, C37, C38, C39, H37, H38, H39 and S2', C37', C38', C39', H37', H38', H39' atoms were refined with occupancies of 0.314 (15) and 0.686 (15), respectively.Data collection: SMART (Bruker, 2001); cell
SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).C23H15N3S | Z = 4 |
Mr = 365.44 | F(000) = 760 |
Triclinic, P1 | Dx = 1.261 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 11.2726 (14) Å | Cell parameters from 2139 reflections |
b = 11.8903 (15) Å | θ = 2.3–24.9° |
c = 14.5544 (17) Å | µ = 0.18 mm−1 |
α = 86.571 (2)° | T = 298 K |
β = 88.755 (2)° | Block, yellow |
γ = 81.249 (1)° | 0.40 × 0.31 × 0.30 mm |
V = 1924.5 (4) Å3 |
Bruker SMART CCD area-detector diffractometer | 6647 independent reflections |
Radiation source: fine-focus sealed tube | 3520 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.026 |
ϕ and ω scans | θmax = 25.0°, θmin = 1.7° |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | h = −8→13 |
Tmin = 0.932, Tmax = 0.948 | k = −12→14 |
10076 measured reflections | l = −15→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)] = 0.068 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.199 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0913P)2] where P = (Fo2 + 2Fc2)/3 |
6647 reflections | (Δ/σ)max = 0.001 |
524 parameters | Δρmax = 0.57 e Å−3 |
0 restraints | Δρmin = −0.50 e Å−3 |
C23H15N3S | γ = 81.249 (1)° |
Mr = 365.44 | V = 1924.5 (4) Å3 |
Triclinic, P1 | Z = 4 |
a = 11.2726 (14) Å | Mo Kα radiation |
b = 11.8903 (15) Å | µ = 0.18 mm−1 |
c = 14.5544 (17) Å | T = 298 K |
α = 86.571 (2)° | 0.40 × 0.31 × 0.30 mm |
β = 88.755 (2)° |
Bruker SMART CCD area-detector diffractometer | 6647 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | 3520 reflections with I > 2σ(I) |
Tmin = 0.932, Tmax = 0.948 | Rint = 0.026 |
10076 measured reflections |
R[F2 > 2σ(F2)] = 0.068 | 0 restraints |
wR(F2) = 0.199 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.57 e Å−3 |
6647 reflections | Δρmin = −0.50 e Å−3 |
524 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 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 | Occ. (<1) | |
S1 | 1.15432 (13) | 0.07649 (11) | 1.06543 (10) | 0.0921 (5) | |
S2 | 0.4086 (13) | 0.1479 (9) | 0.7278 (7) | 0.133 (4) | 0.314 (15) |
S2' | 0.4830 (7) | 0.0834 (5) | 0.5978 (5) | 0.131 (2) | 0.686 (15) |
N1 | 0.8726 (3) | 0.2896 (2) | 0.94731 (17) | 0.0443 (7) | |
H1 | 0.8320 | 0.2821 | 0.8993 | 0.053* | |
N2 | 0.8246 (3) | 0.2069 (3) | 1.2711 (2) | 0.0662 (9) | |
N3 | 1.2341 (3) | 0.4398 (3) | 0.9984 (2) | 0.0646 (9) | |
N4 | 0.6938 (3) | 0.2732 (2) | 0.44938 (17) | 0.0507 (8) | |
H4 | 0.7373 | 0.2546 | 0.4018 | 0.061* | |
N5 | 0.7532 (3) | 0.2538 (3) | 0.7749 (2) | 0.0673 (10) | |
N6 | 0.2860 (3) | 0.4465 (3) | 0.4966 (2) | 0.0709 (10) | |
C1 | 0.8299 (3) | 0.2556 (3) | 1.0316 (2) | 0.0402 (8) | |
C2 | 0.8961 (3) | 0.2574 (3) | 1.1076 (2) | 0.0407 (8) | |
C3 | 1.0226 (3) | 0.2887 (3) | 1.1043 (2) | 0.0428 (8) | |
H3 | 1.0246 | 0.3478 | 1.1480 | 0.051* | |
C4 | 1.0467 (3) | 0.3400 (3) | 1.0091 (2) | 0.0418 (8) | |
C5 | 0.9770 (3) | 0.3352 (3) | 0.9359 (2) | 0.0429 (8) | |
C6 | 0.7073 (3) | 0.2246 (3) | 1.0299 (2) | 0.0441 (8) | |
C7 | 0.6763 (4) | 0.1307 (3) | 1.0811 (2) | 0.0599 (10) | |
H7 | 0.7327 | 0.0854 | 1.1184 | 0.072* | |
C8 | 0.5609 (4) | 0.1051 (4) | 1.0764 (3) | 0.0722 (12) | |
H8 | 0.5401 | 0.0421 | 1.1103 | 0.087* | |
C9 | 0.4776 (4) | 0.1718 (4) | 1.0224 (3) | 0.0711 (12) | |
H9 | 0.4001 | 0.1542 | 1.0202 | 0.085* | |
C10 | 0.5065 (4) | 0.2637 (3) | 0.9715 (3) | 0.0623 (11) | |
H10 | 0.4493 | 0.3087 | 0.9347 | 0.075* | |
C11 | 0.6212 (3) | 0.2898 (3) | 0.9749 (2) | 0.0514 (9) | |
H11 | 0.6411 | 0.3523 | 0.9397 | 0.062* | |
C12 | 0.8522 (3) | 0.2293 (3) | 1.1969 (2) | 0.0472 (9) | |
C13 | 1.1162 (3) | 0.1895 (3) | 1.1329 (2) | 0.0514 (9) | |
C14 | 1.1826 (4) | 0.1745 (3) | 1.2162 (3) | 0.0629 (11) | |
H14 | 1.1763 | 0.2254 | 1.2628 | 0.075* | |
C15 | 1.2610 (4) | 0.0671 (5) | 1.2155 (4) | 0.0915 (16) | |
H15 | 1.3123 | 0.0400 | 1.2638 | 0.110* | |
C16 | 1.2544 (4) | 0.0088 (4) | 1.1400 (4) | 0.0870 (15) | |
H16 | 1.3005 | −0.0614 | 1.1304 | 0.104* | |
C17 | 1.1503 (4) | 0.3958 (3) | 1.0003 (2) | 0.0466 (9) | |
C18 | 0.9985 (3) | 0.3797 (3) | 0.8404 (2) | 0.0482 (9) | |
C19 | 0.9072 (4) | 0.4475 (3) | 0.7920 (2) | 0.0568 (10) | |
H19 | 0.8337 | 0.4696 | 0.8210 | 0.068* | |
C20 | 0.9240 (5) | 0.4825 (3) | 0.7014 (3) | 0.0739 (13) | |
H20 | 0.8623 | 0.5282 | 0.6694 | 0.089* | |
C21 | 1.0329 (6) | 0.4495 (4) | 0.6583 (3) | 0.0845 (15) | |
H21 | 1.0442 | 0.4724 | 0.5969 | 0.101* | |
C22 | 1.1238 (5) | 0.3836 (4) | 0.7049 (3) | 0.0860 (15) | |
H22 | 1.1972 | 0.3627 | 0.6755 | 0.103* | |
C23 | 1.1080 (4) | 0.3474 (4) | 0.7958 (3) | 0.0678 (11) | |
H23 | 1.1703 | 0.3016 | 0.8271 | 0.081* | |
C24 | 0.7442 (3) | 0.2505 (3) | 0.5357 (2) | 0.0468 (9) | |
C25 | 0.6731 (3) | 0.2670 (3) | 0.6107 (2) | 0.0456 (9) | |
C26 | 0.5381 (3) | 0.2973 (3) | 0.6072 (2) | 0.0557 (10) | |
H26 | 0.5144 | 0.3601 | 0.6477 | 0.067* | |
C27 | 0.5019 (3) | 0.3403 (3) | 0.5100 (2) | 0.0476 (9) | |
C28 | 0.5775 (3) | 0.3242 (3) | 0.4368 (2) | 0.0453 (8) | |
C29 | 0.8750 (3) | 0.2102 (3) | 0.5369 (2) | 0.0514 (9) | |
C30 | 0.9234 (4) | 0.1189 (4) | 0.5951 (3) | 0.0726 (12) | |
H30 | 0.8735 | 0.0818 | 0.6341 | 0.087* | |
C31 | 1.0459 (5) | 0.0831 (5) | 0.5952 (3) | 0.0967 (16) | |
H31 | 1.0781 | 0.0209 | 0.6333 | 0.116* | |
C32 | 1.1197 (5) | 0.1388 (6) | 0.5395 (4) | 0.1023 (17) | |
H32 | 1.2023 | 0.1158 | 0.5410 | 0.123* | |
C33 | 1.0726 (4) | 0.2285 (5) | 0.4814 (3) | 0.0879 (15) | |
H33 | 1.1232 | 0.2655 | 0.4430 | 0.106* | |
C34 | 0.9508 (4) | 0.2643 (4) | 0.4795 (3) | 0.0677 (11) | |
H34 | 0.9193 | 0.3250 | 0.4396 | 0.081* | |
C35 | 0.7223 (3) | 0.2582 (3) | 0.7005 (2) | 0.0505 (9) | |
C36 | 0.4766 (4) | 0.2004 (5) | 0.6415 (3) | 0.0850 (15) | |
C37 | 0.492 (4) | 0.111 (4) | 0.568 (3) | 0.097 (11) | 0.314 (15) |
H37 | 0.5270 | 0.1204 | 0.5100 | 0.117* | 0.314 (15) |
C37' | 0.4036 (13) | 0.2143 (13) | 0.7245 (9) | 0.104 (4) | 0.686 (15) |
H37' | 0.3899 | 0.2784 | 0.7590 | 0.125* | 0.686 (15) |
C38 | 0.442 (2) | 0.008 (3) | 0.6026 (17) | 0.106 (9) | 0.314 (15) |
H38 | 0.4446 | −0.0579 | 0.5711 | 0.128* | 0.314 (15) |
C38' | 0.3546 (15) | 0.1055 (15) | 0.7434 (10) | 0.123 (4) | 0.686 (15) |
H38' | 0.3035 | 0.0924 | 0.7927 | 0.147* | 0.686 (15) |
C39 | 0.390 (16) | 0.025 (15) | 0.691 (11) | 0.11 (3) | 0.314 (15) |
H39 | 0.3508 | −0.0272 | 0.7244 | 0.130* | 0.314 (15) |
C39' | 0.395 (7) | 0.024 (7) | 0.678 (5) | 0.115 (18) | 0.686 (15) |
H39' | 0.3765 | −0.0495 | 0.6782 | 0.138* | 0.686 (15) |
C40 | 0.3836 (4) | 0.3998 (3) | 0.4991 (2) | 0.0507 (9) | |
C41 | 0.5466 (3) | 0.3632 (3) | 0.3408 (2) | 0.0475 (9) | |
C42 | 0.4461 (4) | 0.3353 (3) | 0.2997 (3) | 0.0656 (11) | |
H42 | 0.3964 | 0.2914 | 0.3328 | 0.079* | |
C43 | 0.4195 (5) | 0.3726 (4) | 0.2094 (3) | 0.0792 (14) | |
H43 | 0.3510 | 0.3552 | 0.1823 | 0.095* | |
C44 | 0.4940 (5) | 0.4350 (4) | 0.1603 (3) | 0.0795 (15) | |
H44 | 0.4766 | 0.4586 | 0.0993 | 0.095* | |
C45 | 0.5935 (5) | 0.4630 (3) | 0.1995 (3) | 0.0716 (13) | |
H45 | 0.6432 | 0.5062 | 0.1657 | 0.086* | |
C46 | 0.6204 (4) | 0.4267 (3) | 0.2904 (2) | 0.0592 (10) | |
H46 | 0.6884 | 0.4454 | 0.3172 | 0.071* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0863 (10) | 0.0734 (8) | 0.1132 (10) | 0.0033 (7) | −0.0117 (8) | −0.0120 (7) |
S2 | 0.149 (8) | 0.130 (10) | 0.123 (6) | −0.051 (8) | 0.024 (5) | 0.031 (7) |
S2' | 0.164 (4) | 0.096 (4) | 0.148 (5) | −0.078 (3) | −0.014 (4) | 0.014 (3) |
N1 | 0.0490 (18) | 0.0587 (17) | 0.0283 (14) | −0.0186 (15) | −0.0033 (12) | 0.0004 (12) |
N2 | 0.060 (2) | 0.099 (3) | 0.0362 (18) | −0.0057 (19) | 0.0060 (15) | 0.0059 (16) |
N3 | 0.057 (2) | 0.078 (2) | 0.061 (2) | −0.017 (2) | 0.0030 (17) | −0.0001 (17) |
N4 | 0.052 (2) | 0.0696 (19) | 0.0288 (15) | −0.0018 (16) | −0.0001 (13) | −0.0033 (13) |
N5 | 0.086 (3) | 0.082 (2) | 0.0387 (18) | −0.027 (2) | −0.0131 (17) | −0.0002 (15) |
N6 | 0.059 (2) | 0.089 (3) | 0.061 (2) | −0.001 (2) | −0.0012 (18) | 0.0019 (18) |
C1 | 0.044 (2) | 0.0445 (19) | 0.0316 (18) | −0.0061 (16) | 0.0029 (15) | −0.0032 (14) |
C2 | 0.043 (2) | 0.050 (2) | 0.0287 (17) | −0.0051 (16) | 0.0019 (15) | −0.0001 (14) |
C3 | 0.048 (2) | 0.049 (2) | 0.0325 (17) | −0.0087 (17) | −0.0016 (15) | −0.0049 (14) |
C4 | 0.044 (2) | 0.0458 (19) | 0.0361 (18) | −0.0089 (17) | 0.0008 (16) | −0.0025 (14) |
C5 | 0.048 (2) | 0.0453 (19) | 0.0368 (18) | −0.0106 (17) | 0.0044 (16) | −0.0031 (14) |
C6 | 0.046 (2) | 0.055 (2) | 0.0321 (17) | −0.0134 (18) | 0.0011 (15) | 0.0000 (15) |
C7 | 0.060 (3) | 0.074 (3) | 0.047 (2) | −0.020 (2) | −0.0070 (19) | 0.0119 (19) |
C8 | 0.070 (3) | 0.084 (3) | 0.068 (3) | −0.037 (3) | −0.004 (2) | 0.015 (2) |
C9 | 0.057 (3) | 0.095 (3) | 0.067 (3) | −0.029 (3) | −0.002 (2) | −0.003 (2) |
C10 | 0.051 (3) | 0.073 (3) | 0.063 (3) | −0.008 (2) | −0.008 (2) | −0.002 (2) |
C11 | 0.050 (2) | 0.058 (2) | 0.046 (2) | −0.0087 (19) | 0.0017 (17) | 0.0020 (17) |
C12 | 0.047 (2) | 0.060 (2) | 0.033 (2) | −0.0029 (18) | −0.0006 (16) | −0.0023 (16) |
C13 | 0.047 (2) | 0.055 (2) | 0.053 (2) | −0.0143 (19) | −0.0028 (17) | 0.0066 (17) |
C14 | 0.056 (3) | 0.072 (3) | 0.056 (2) | 0.001 (2) | −0.017 (2) | 0.0124 (19) |
C15 | 0.070 (3) | 0.109 (4) | 0.086 (4) | 0.000 (3) | −0.018 (3) | 0.041 (3) |
C16 | 0.073 (3) | 0.068 (3) | 0.112 (4) | 0.002 (3) | 0.003 (3) | 0.028 (3) |
C17 | 0.049 (2) | 0.052 (2) | 0.0379 (19) | −0.007 (2) | 0.0013 (17) | 0.0018 (15) |
C18 | 0.061 (3) | 0.052 (2) | 0.0356 (19) | −0.0237 (19) | 0.0055 (18) | −0.0029 (15) |
C19 | 0.074 (3) | 0.059 (2) | 0.039 (2) | −0.021 (2) | −0.0046 (19) | 0.0040 (17) |
C20 | 0.112 (4) | 0.068 (3) | 0.046 (2) | −0.030 (3) | −0.013 (3) | 0.0098 (19) |
C21 | 0.127 (5) | 0.090 (3) | 0.044 (2) | −0.046 (3) | 0.007 (3) | 0.007 (2) |
C22 | 0.097 (4) | 0.114 (4) | 0.053 (3) | −0.035 (3) | 0.030 (3) | −0.009 (3) |
C23 | 0.071 (3) | 0.086 (3) | 0.046 (2) | −0.015 (2) | 0.011 (2) | −0.002 (2) |
C24 | 0.054 (2) | 0.057 (2) | 0.0306 (18) | −0.0107 (18) | −0.0064 (16) | 0.0010 (15) |
C25 | 0.057 (2) | 0.052 (2) | 0.0295 (18) | −0.0136 (18) | −0.0056 (16) | 0.0013 (14) |
C26 | 0.063 (3) | 0.069 (2) | 0.0342 (19) | −0.007 (2) | 0.0037 (17) | −0.0001 (17) |
C27 | 0.052 (2) | 0.054 (2) | 0.0367 (19) | −0.0095 (19) | −0.0072 (17) | 0.0033 (15) |
C28 | 0.049 (2) | 0.052 (2) | 0.0349 (19) | −0.0094 (18) | −0.0035 (16) | 0.0006 (15) |
C29 | 0.054 (2) | 0.067 (2) | 0.0339 (19) | −0.010 (2) | −0.0088 (17) | −0.0008 (16) |
C30 | 0.064 (3) | 0.089 (3) | 0.059 (3) | 0.002 (3) | −0.008 (2) | 0.012 (2) |
C31 | 0.078 (4) | 0.121 (4) | 0.080 (3) | 0.016 (3) | −0.015 (3) | 0.015 (3) |
C32 | 0.061 (3) | 0.153 (5) | 0.088 (4) | 0.005 (4) | −0.008 (3) | −0.012 (4) |
C33 | 0.058 (3) | 0.133 (4) | 0.074 (3) | −0.020 (3) | −0.003 (2) | −0.001 (3) |
C34 | 0.059 (3) | 0.087 (3) | 0.057 (2) | −0.012 (2) | −0.007 (2) | 0.001 (2) |
C35 | 0.061 (2) | 0.059 (2) | 0.035 (2) | −0.0192 (19) | −0.0027 (17) | 0.0023 (16) |
C36 | 0.066 (3) | 0.114 (4) | 0.071 (3) | −0.021 (3) | −0.011 (2) | 0.051 (3) |
C37 | 0.098 (17) | 0.09 (2) | 0.11 (2) | −0.041 (16) | 0.004 (15) | 0.040 (15) |
C37' | 0.117 (8) | 0.092 (8) | 0.092 (6) | −0.014 (8) | 0.030 (5) | 0.059 (7) |
C38 | 0.108 (18) | 0.11 (2) | 0.103 (17) | −0.028 (15) | 0.010 (14) | 0.017 (15) |
C38' | 0.108 (10) | 0.121 (11) | 0.138 (11) | −0.038 (9) | 0.004 (8) | 0.050 (8) |
C39 | 0.11 (5) | 0.11 (7) | 0.11 (4) | −0.04 (4) | −0.02 (3) | 0.03 (4) |
C39' | 0.11 (3) | 0.11 (3) | 0.13 (3) | −0.05 (2) | −0.03 (2) | 0.06 (2) |
C40 | 0.056 (3) | 0.060 (2) | 0.0370 (19) | −0.012 (2) | 0.0009 (18) | 0.0019 (16) |
C41 | 0.056 (2) | 0.053 (2) | 0.0319 (18) | −0.0024 (19) | −0.0012 (17) | −0.0003 (15) |
C42 | 0.069 (3) | 0.081 (3) | 0.046 (2) | −0.007 (2) | −0.012 (2) | −0.0040 (19) |
C43 | 0.084 (3) | 0.098 (3) | 0.051 (3) | 0.009 (3) | −0.028 (2) | −0.008 (2) |
C44 | 0.105 (4) | 0.083 (3) | 0.037 (2) | 0.028 (3) | −0.010 (3) | 0.003 (2) |
C45 | 0.095 (4) | 0.067 (3) | 0.044 (2) | 0.007 (3) | 0.014 (2) | 0.0105 (19) |
C46 | 0.070 (3) | 0.063 (2) | 0.042 (2) | −0.004 (2) | 0.0002 (19) | 0.0006 (18) |
S1—C16 | 1.664 (5) | C21—C22 | 1.359 (7) |
S1—C13 | 1.708 (4) | C21—H21 | 0.9300 |
S2—C36 | 1.603 (11) | C22—C23 | 1.382 (5) |
S2—C39 | 1.62 (17) | C22—H22 | 0.9300 |
S2'—C36 | 1.555 (10) | C23—H23 | 0.9300 |
S2'—C39' | 1.70 (8) | C24—C25 | 1.346 (5) |
N1—C1 | 1.370 (4) | C24—C29 | 1.479 (5) |
N1—C5 | 1.372 (4) | C25—C35 | 1.423 (5) |
N1—H1 | 0.8600 | C25—C26 | 1.511 (5) |
N2—C12 | 1.145 (4) | C26—C36 | 1.488 (6) |
N3—C17 | 1.146 (4) | C26—C27 | 1.518 (4) |
N4—C28 | 1.369 (4) | C26—H26 | 0.9800 |
N4—C24 | 1.385 (4) | C27—C28 | 1.354 (5) |
N4—H4 | 0.8600 | C27—C40 | 1.419 (5) |
N5—C35 | 1.140 (4) | C28—C41 | 1.477 (4) |
N6—C40 | 1.155 (5) | C29—C34 | 1.384 (5) |
C1—C2 | 1.350 (4) | C29—C30 | 1.387 (5) |
C1—C6 | 1.484 (5) | C30—C31 | 1.381 (6) |
C2—C12 | 1.421 (4) | C30—H30 | 0.9300 |
C2—C3 | 1.526 (5) | C31—C32 | 1.365 (7) |
C3—C13 | 1.504 (5) | C31—H31 | 0.9300 |
C3—C4 | 1.516 (4) | C32—C33 | 1.370 (7) |
C3—H3 | 0.9800 | C32—H32 | 0.9300 |
C4—C5 | 1.346 (4) | C33—C34 | 1.374 (6) |
C4—C17 | 1.429 (5) | C33—H33 | 0.9300 |
C5—C18 | 1.485 (4) | C34—H34 | 0.9300 |
C6—C11 | 1.383 (5) | C36—C37' | 1.450 (15) |
C6—C7 | 1.390 (5) | C36—C37 | 1.54 (6) |
C7—C8 | 1.383 (5) | C37—C38 | 1.48 (5) |
C7—H7 | 0.9300 | C37—H37 | 0.9300 |
C8—C9 | 1.364 (5) | C37'—C38' | 1.49 (3) |
C8—H8 | 0.9300 | C37'—H37' | 0.9300 |
C9—C10 | 1.360 (5) | C38—C39 | 1.42 (15) |
C9—H9 | 0.9300 | C38—H38 | 0.9300 |
C10—C11 | 1.377 (5) | C38'—C39' | 1.42 (7) |
C10—H10 | 0.9300 | C38'—H38' | 0.9300 |
C11—H11 | 0.9300 | C39—H39 | 0.9300 |
C13—C14 | 1.426 (5) | C39'—H39' | 0.9300 |
C14—C15 | 1.439 (6) | C41—C46 | 1.377 (5) |
C14—H14 | 0.9300 | C41—C42 | 1.386 (5) |
C15—C16 | 1.344 (7) | C42—C43 | 1.386 (5) |
C15—H15 | 0.9300 | C42—H42 | 0.9300 |
C16—H16 | 0.9300 | C43—C44 | 1.366 (7) |
C18—C19 | 1.384 (5) | C43—H43 | 0.9300 |
C18—C23 | 1.394 (5) | C44—C45 | 1.364 (7) |
C19—C20 | 1.378 (5) | C44—H44 | 0.9300 |
C19—H19 | 0.9300 | C45—C46 | 1.392 (5) |
C20—C21 | 1.379 (7) | C45—H45 | 0.9300 |
C20—H20 | 0.9300 | C46—H46 | 0.9300 |
C16—S1—C13 | 93.3 (3) | C24—C25—C35 | 121.1 (3) |
C36—S2—C39 | 101 (6) | C24—C25—C26 | 123.9 (3) |
C36—S2'—C39' | 97 (3) | C35—C25—C26 | 115.0 (3) |
C1—N1—C5 | 123.1 (3) | C36—C26—C25 | 112.0 (3) |
C1—N1—H1 | 118.5 | C36—C26—C27 | 112.5 (3) |
C5—N1—H1 | 118.5 | C25—C26—C27 | 109.1 (3) |
C28—N4—C24 | 122.6 (3) | C36—C26—H26 | 107.7 |
C28—N4—H4 | 118.7 | C25—C26—H26 | 107.7 |
C24—N4—H4 | 118.7 | C27—C26—H26 | 107.7 |
C2—C1—N1 | 120.0 (3) | C28—C27—C40 | 120.9 (3) |
C2—C1—C6 | 125.8 (3) | C28—C27—C26 | 122.6 (3) |
N1—C1—C6 | 114.2 (3) | C40—C27—C26 | 116.5 (3) |
C1—C2—C12 | 121.7 (3) | C27—C28—N4 | 120.1 (3) |
C1—C2—C3 | 123.1 (3) | C27—C28—C41 | 124.8 (3) |
C12—C2—C3 | 115.2 (3) | N4—C28—C41 | 115.0 (3) |
C13—C3—C4 | 112.7 (3) | C34—C29—C30 | 119.1 (4) |
C13—C3—C2 | 112.4 (3) | C34—C29—C24 | 119.8 (3) |
C4—C3—C2 | 109.0 (3) | C30—C29—C24 | 121.0 (4) |
C13—C3—H3 | 107.5 | C31—C30—C29 | 120.0 (5) |
C4—C3—H3 | 107.5 | C31—C30—H30 | 120.0 |
C2—C3—H3 | 107.5 | C29—C30—H30 | 120.0 |
C5—C4—C17 | 120.5 (3) | C32—C31—C30 | 120.2 (5) |
C5—C4—C3 | 123.8 (3) | C32—C31—H31 | 119.9 |
C17—C4—C3 | 115.7 (3) | C30—C31—H31 | 119.9 |
C4—C5—N1 | 119.6 (3) | C31—C32—C33 | 120.2 (5) |
C4—C5—C18 | 126.3 (3) | C31—C32—H32 | 119.9 |
N1—C5—C18 | 114.1 (3) | C33—C32—H32 | 119.9 |
C11—C6—C7 | 118.6 (3) | C32—C33—C34 | 120.4 (5) |
C11—C6—C1 | 119.4 (3) | C32—C33—H33 | 119.8 |
C7—C6—C1 | 122.0 (3) | C34—C33—H33 | 119.8 |
C8—C7—C6 | 119.6 (4) | C33—C34—C29 | 120.1 (4) |
C8—C7—H7 | 120.2 | C33—C34—H34 | 119.9 |
C6—C7—H7 | 120.2 | C29—C34—H34 | 119.9 |
C9—C8—C7 | 120.4 (4) | N5—C35—C25 | 174.9 (4) |
C9—C8—H8 | 119.8 | C37'—C36—C26 | 117.7 (8) |
C7—C8—H8 | 119.8 | C37'—C36—C37 | 133.3 (15) |
C10—C9—C8 | 120.7 (4) | C26—C36—C37 | 108.1 (13) |
C10—C9—H9 | 119.6 | C37'—C36—S2' | 115.5 (7) |
C8—C9—H9 | 119.6 | C26—C36—S2' | 126.7 (5) |
C9—C10—C11 | 119.5 (4) | C26—C36—S2 | 144.7 (6) |
C9—C10—H10 | 120.2 | C37—C36—S2 | 107.0 (12) |
C11—C10—H10 | 120.2 | S2'—C36—S2 | 87.6 (5) |
C10—C11—C6 | 121.1 (3) | C38—C37—C36 | 110 (3) |
C10—C11—H11 | 119.5 | C38—C37—H37 | 125.0 |
C6—C11—H11 | 119.5 | C36—C37—H37 | 125.0 |
N2—C12—C2 | 175.2 (4) | C36—C37'—C38' | 106.5 (13) |
C14—C13—C3 | 126.9 (3) | C36—C37'—H37' | 126.8 |
C14—C13—S1 | 111.4 (3) | C38'—C37'—H37' | 126.8 |
C3—C13—S1 | 121.8 (2) | C39—C38—C37 | 110 (8) |
C13—C14—C15 | 108.1 (4) | C39—C38—H38 | 125.1 |
C13—C14—H14 | 126.0 | C37—C38—H38 | 125.1 |
C15—C14—H14 | 126.0 | C39'—C38'—C37' | 112 (4) |
C16—C15—C14 | 114.9 (4) | C39'—C38'—H38' | 123.9 |
C16—C15—H15 | 122.5 | C37'—C38'—H38' | 123.9 |
C14—C15—H15 | 122.5 | C38—C39—S2 | 112 (10) |
C15—C16—S1 | 112.3 (4) | C38—C39—H39 | 124.0 |
C15—C16—H16 | 123.8 | S2—C39—H39 | 124.0 |
S1—C16—H16 | 123.8 | C38'—C39'—S2' | 109 (5) |
N3—C17—C4 | 176.3 (4) | C38'—C39'—H39' | 125.6 |
C19—C18—C23 | 118.9 (3) | S2'—C39'—H39' | 125.6 |
C19—C18—C5 | 120.4 (3) | N6—C40—C27 | 175.3 (4) |
C23—C18—C5 | 120.6 (3) | C46—C41—C42 | 119.2 (3) |
C20—C19—C18 | 120.6 (4) | C46—C41—C28 | 119.5 (3) |
C20—C19—H19 | 119.7 | C42—C41—C28 | 121.3 (3) |
C18—C19—H19 | 119.7 | C41—C42—C43 | 120.2 (4) |
C19—C20—C21 | 119.6 (4) | C41—C42—H42 | 119.9 |
C19—C20—H20 | 120.2 | C43—C42—H42 | 119.9 |
C21—C20—H20 | 120.2 | C44—C43—C42 | 119.8 (4) |
C22—C21—C20 | 120.5 (4) | C44—C43—H43 | 120.1 |
C22—C21—H21 | 119.8 | C42—C43—H43 | 120.1 |
C20—C21—H21 | 119.8 | C45—C44—C43 | 120.8 (4) |
C21—C22—C23 | 120.5 (5) | C45—C44—H44 | 119.6 |
C21—C22—H22 | 119.7 | C43—C44—H44 | 119.6 |
C23—C22—H22 | 119.7 | C44—C45—C46 | 119.7 (4) |
C22—C23—C18 | 119.8 (4) | C44—C45—H45 | 120.2 |
C22—C23—H23 | 120.1 | C46—C45—H45 | 120.2 |
C18—C23—H23 | 120.1 | C41—C46—C45 | 120.3 (4) |
C25—C24—N4 | 118.9 (3) | C41—C46—H46 | 119.9 |
C25—C24—C29 | 125.3 (3) | C45—C46—H46 | 119.9 |
N4—C24—C29 | 115.8 (3) | ||
C5—N1—C1—C2 | −5.5 (5) | C36—C26—C27—C28 | −109.4 (4) |
C5—N1—C1—C6 | 171.6 (3) | C25—C26—C27—C28 | 15.5 (5) |
N1—C1—C2—C12 | 176.2 (3) | C36—C26—C27—C40 | 71.0 (4) |
C6—C1—C2—C12 | −0.5 (5) | C25—C26—C27—C40 | −164.1 (3) |
N1—C1—C2—C3 | −4.1 (5) | C40—C27—C28—N4 | 175.7 (3) |
C6—C1—C2—C3 | 179.2 (3) | C26—C27—C28—N4 | −3.9 (5) |
C1—C2—C3—C13 | −113.5 (3) | C40—C27—C28—C41 | −1.0 (5) |
C12—C2—C3—C13 | 66.2 (4) | C26—C27—C28—C41 | 179.5 (3) |
C1—C2—C3—C4 | 12.1 (4) | C24—N4—C28—C27 | −9.1 (5) |
C12—C2—C3—C4 | −168.1 (3) | C24—N4—C28—C41 | 167.9 (3) |
C13—C3—C4—C5 | 112.6 (4) | C25—C24—C29—C34 | −134.3 (4) |
C2—C3—C4—C5 | −12.8 (4) | N4—C24—C29—C34 | 45.1 (5) |
C13—C3—C4—C17 | −67.3 (4) | C25—C24—C29—C30 | 45.4 (5) |
C2—C3—C4—C17 | 167.2 (3) | N4—C24—C29—C30 | −135.2 (4) |
C17—C4—C5—N1 | −174.7 (3) | C34—C29—C30—C31 | −0.1 (6) |
C3—C4—C5—N1 | 5.4 (5) | C24—C29—C30—C31 | −179.8 (4) |
C17—C4—C5—C18 | 2.5 (5) | C29—C30—C31—C32 | 1.4 (8) |
C3—C4—C5—C18 | −177.4 (3) | C30—C31—C32—C33 | −1.8 (8) |
C1—N1—C5—C4 | 4.9 (5) | C31—C32—C33—C34 | 0.9 (8) |
C1—N1—C5—C18 | −172.6 (3) | C32—C33—C34—C29 | 0.4 (7) |
C2—C1—C6—C11 | 136.5 (4) | C30—C29—C34—C33 | −0.8 (6) |
N1—C1—C6—C11 | −40.4 (4) | C24—C29—C34—C33 | 178.9 (4) |
C2—C1—C6—C7 | −44.3 (5) | C25—C26—C36—C37' | 115.4 (7) |
N1—C1—C6—C7 | 138.8 (3) | C27—C26—C36—C37' | −121.2 (7) |
C11—C6—C7—C8 | −0.3 (6) | C25—C26—C36—C37 | −73.3 (19) |
C1—C6—C7—C8 | −179.5 (3) | C27—C26—C36—C37 | 50.0 (19) |
C6—C7—C8—C9 | −0.4 (6) | C25—C26—C36—S2' | −64.0 (6) |
C7—C8—C9—C10 | 0.7 (7) | C27—C26—C36—S2' | 59.3 (6) |
C8—C9—C10—C11 | −0.2 (6) | C25—C26—C36—S2 | 100.2 (11) |
C9—C10—C11—C6 | −0.6 (6) | C27—C26—C36—S2 | −136.5 (10) |
C7—C6—C11—C10 | 0.8 (5) | C39'—S2'—C36—C37' | −1 (3) |
C1—C6—C11—C10 | 180.0 (3) | C39'—S2'—C36—C26 | 178 (3) |
C4—C3—C13—C14 | 127.8 (4) | C39'—S2'—C36—C37 | −155 (7) |
C2—C3—C13—C14 | −108.6 (4) | C39'—S2'—C36—S2 | 7 (3) |
C4—C3—C13—S1 | −53.0 (4) | C39—S2—C36—C37' | 158 (7) |
C2—C3—C13—S1 | 70.6 (3) | C39—S2—C36—C26 | −174 (6) |
C16—S1—C13—C14 | −0.3 (3) | C39—S2—C36—C37 | 0 (7) |
C16—S1—C13—C3 | −179.5 (3) | C39—S2—C36—S2' | −6 (6) |
C3—C13—C14—C15 | 179.2 (3) | C37'—C36—C37—C38 | −16 (4) |
S1—C13—C14—C15 | 0.0 (4) | C26—C36—C37—C38 | 175 (2) |
C13—C14—C15—C16 | 0.4 (6) | S2'—C36—C37—C38 | 17 (3) |
C14—C15—C16—S1 | −0.6 (6) | S2—C36—C37—C38 | −1 (3) |
C13—S1—C16—C15 | 0.5 (4) | C36—C37—C38—C39 | 3 (8) |
C4—C5—C18—C19 | −131.2 (4) | C37—C38—C39—S2 | −3 (12) |
N1—C5—C18—C19 | 46.1 (4) | C36—S2—C39—C38 | 2 (11) |
C4—C5—C18—C23 | 53.4 (5) | C26—C36—C37'—C38' | −179.3 (7) |
N1—C5—C18—C23 | −129.2 (4) | C37—C36—C37'—C38' | 12 (3) |
C23—C18—C19—C20 | 0.0 (5) | S2'—C36—C37'—C38' | 0.2 (12) |
C5—C18—C19—C20 | −175.5 (3) | S2—C36—C37'—C38' | −17.5 (15) |
C18—C19—C20—C21 | 0.2 (6) | C36—C37'—C38'—C39' | 1 (4) |
C19—C20—C21—C22 | −0.6 (7) | C37'—C38'—C39'—S2' | −2 (5) |
C20—C21—C22—C23 | 0.9 (7) | C36—S2'—C39'—C38' | 2 (5) |
C21—C22—C23—C18 | −0.7 (6) | C27—C28—C41—C46 | 128.1 (4) |
C19—C18—C23—C22 | 0.3 (6) | N4—C28—C41—C46 | −48.7 (4) |
C5—C18—C23—C22 | 175.7 (3) | C27—C28—C41—C42 | −53.3 (5) |
C28—N4—C24—C25 | 7.7 (5) | N4—C28—C41—C42 | 129.9 (4) |
C28—N4—C24—C29 | −171.7 (3) | C46—C41—C42—C43 | −1.0 (6) |
N4—C24—C25—C35 | −172.4 (3) | C28—C41—C42—C43 | −179.7 (3) |
C29—C24—C25—C35 | 7.0 (5) | C41—C42—C43—C44 | 1.4 (6) |
N4—C24—C25—C26 | 6.8 (5) | C42—C43—C44—C45 | −1.2 (7) |
C29—C24—C25—C26 | −173.8 (3) | C43—C44—C45—C46 | 0.7 (7) |
C24—C25—C26—C36 | 108.1 (4) | C42—C41—C46—C45 | 0.5 (5) |
C35—C25—C26—C36 | −72.7 (4) | C28—C41—C46—C45 | 179.2 (3) |
C24—C25—C26—C27 | −17.1 (5) | C44—C45—C46—C41 | −0.3 (6) |
C35—C25—C26—C27 | 162.1 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···N5 | 0.86 | 2.10 | 2.956 (3) | 173 |
N4—H4···N2i | 0.86 | 2.19 | 3.042 (3) | 172 |
Symmetry code: (i) x, y, z−1. |
Experimental details
Crystal data | |
Chemical formula | C23H15N3S |
Mr | 365.44 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 298 |
a, b, c (Å) | 11.2726 (14), 11.8903 (15), 14.5544 (17) |
α, β, γ (°) | 86.571 (2), 88.755 (2), 81.249 (1) |
V (Å3) | 1924.5 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.18 |
Crystal size (mm) | 0.40 × 0.31 × 0.30 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2001) |
Tmin, Tmax | 0.932, 0.948 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10076, 6647, 3520 |
Rint | 0.026 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.068, 0.199, 1.07 |
No. of reflections | 6647 |
No. of parameters | 524 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.57, −0.50 |
Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···N5 | 0.86 | 2.10 | 2.956 (3) | 173 |
N4—H4···N2i | 0.86 | 2.19 | 3.042 (3) | 172 |
Symmetry code: (i) x, y, z−1. |
Acknowledgements
The authors are grateful to the Foundation of Xuzhou Medical College (grant No.08 K J06) for financial support.
References
Adib, M., Tahermansouri, H., Koloogani, S. A., Mohammadia, B. & Bijanzadeh, H. R. (2006). Tetrahedron Lett. 47, 5957–5960. Web of Science CrossRef CAS Google Scholar
Bruker (2001). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cave, G. W. V. & Raston, C. L. (2000). Chem. Commun. pp. 2199–2200. Web of Science CrossRef Google Scholar
Kobayashi, T., Kakiuchi, H. & Kato, H. (1991). Bull. Chem. Soc. Jpn, 64, 392–395. CrossRef CAS Web of Science Google Scholar
Kröhnke, F. (1963). Angew. Chem. Int. Ed. Engl. 2, 380–393. Google Scholar
Kröhnke, F. (1976). Synthesis, pp. 1–24. Google Scholar
Kumar, A., Koul, S., Razdan, T. K. & Kapoor, K. K. (2006). Tetrahedron Lett. 47, 837–842. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Tu, S., Li, T., Shi, F., Fang, F., Zhu, S., Wei, X. & Zong, Z. (2005a). Chem. Lett. 34, 732–733. Web of Science CSD CrossRef CAS Google Scholar
Tu, S., Li, T., Shi, F., Wang, Q., Zhang, J., Xu, J., Zhu, X., Zhang, X., Zhu, S. & Shi, D. (2005b). Synthesis, pp. 3045–3050. Web of Science CrossRef 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.
Pyridines are of interest because of the occurrence of their saturated and partially saturated derivatives in biologically active compounds and natural products such as NAD nucleotides, pyridoxol (vitamin B6), and pyridine alkaloids. Pyridines with a multi-aryl substitution pattern have been synthesized using various methods and procedures. Traditionally, these compounds have been synthesized through the reaction of N-phenacylpyridinium salts with unsaturated ketones in the presence of ammonium acetate (Kröhnke, 1963; Kröhnke, 1976). More recently, several new improved methods and procedures have been developed for the syntheses of these pyridines (Kobayashi et al., 1991; Kumar et al. 2006), including solvent-free condition (Adib et al., 2006; Cave & Raston, 2000) and microwave heating (Tu et al., 2005a; Tu et al., 2005b). We report herein the crystal structure of the title compound.
The asymmetric unit of the title compound contains two crystallographically independent molecules, in which they are linked through the intramolecular N-H···N hydrogen bond (Table 1, Fig. 1). The pyridine rings A (N1/C1-C5) and E (N4/C24-C28) adopt envelope conformations with atoms C3 and C26 displaced by 0.180 (3) and 0.238 (3) Å from the planes of the other ring atoms, respectively. Rings B (C6-C11), C (S1/C13-C16), D (C18-C23) and F (C29-C34), G (S2/C36-C39), H (C41-C46) are, of course, planar and they are oriented at dihedral angles of B/C = 77.97 (4), B/D = 48.51 (4), C/D = 53.53 (4) ° and F/G = 78.44 (4), F/H = 44.49 (4) °, G/H = 57.11 (4) °.
In the crystal structure, intra- and intermolecular N-H···N hydrogen bonds (Table 1) link the molecules into chains along the c axis (Fig. 2), in which they may be effective in the stabilization of the structure.