2,6-Diphenyl-4-(2-thien­yl)-1,4-dihydro­pyridine-3,5-dicarbonitrile

Zhu, X.-T.; Zhang, G.; Ma, N.

doi:10.1107/S1600536809033339

organic compounds

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ISSN: 2056-9890

Volume 65| Part 9| September 2009| Page o2246

doi:10.1107/S1600536809033339

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2,6-Diphenyl-4-(2-thienyl)-1,4-dihydropyridine-3,5-dicarbonitrile

Xiao-Tong Zhu,^a ^* Ge Zhang ^b and Ning Ma ^b

^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

(Received 10 August 2009; accepted 21 August 2009; online 26 August 2009)

The asymmetric unit of the title compound, C₂₃H₁₅N₃S, 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 crystal structure, 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).

Related 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

C₂₃H₁₅N₃S
M_r = 365.44
Triclinic, $[P \overline 1]$
a = 11.2726 (14) Å
b = 11.8903 (15) Å
c = 14.5544 (17) Å
α = 86.571 (2)°
β = 88.755 (2)°
γ = 81.249 (1)°
V = 1924.5 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.18 mm⁻¹
T = 298 K
0.40 × 0.31 × 0.30 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.932, T_max = 0.948
10076 measured reflections
6647 independent reflections
3520 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.068
wR(F²) = 0.199
S = 1.07
6647 reflections
524 parameters
H-atom parameters constrained
Δρ_max = 0.57 e Å⁻³
Δρ_min = −0.50 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

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.

Data collection: SMART (Bruker, 2001); cell refinement: 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

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809033339/hk2755sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809033339/hk2755Isup2.hkl

checkCIF report

Comment top

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.

Related literature top

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 top

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).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: 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).

Figures top

	Fig. 1. The molecular structure of the title molecule with the atom-numbering scheme. Hydrogen bond is shown as dashed line.
	Fig. 2. A partial packing diagram. Hydrogen bonds are shown as dashed lines. Hydrogen atoms not involved in hydrogen bonding are omitted for clarity.

2,6-Diphenyl-4-(2-thienyl)-1,4-dihydropyridine-3,5-dicarbonitrile top

Crystal data top

C₂₃H₁₅N₃S	Z = 4
M_r = 365.44	F(000) = 760
Triclinic, P1	D_x = 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

Data collection top

Bruker SMART CCD area-detector diffractometer	6647 independent reflections
Radiation source: fine-focus sealed tube	3520 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
ϕ and ω scans	θ_max = 25.0°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −8→13
T_min = 0.932, T_max = 0.948	k = −12→14
10076 measured reflections	l = −15→17

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.068	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.199	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0913P)²] where P = (F_o² + 2F_c²)/3
6647 reflections	(Δ/σ)_max = 0.001
524 parameters	Δρ_max = 0.57 e Å⁻³
0 restraints	Δρ_min = −0.50 e Å⁻³

Crystal data top

C₂₃H₁₅N₃S	γ = 81.249 (1)°
M_r = 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)°

Data collection top

Bruker SMART CCD area-detector diffractometer	6647 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	3520 reflections with I > 2σ(I)
T_min = 0.932, T_max = 0.948	R_int = 0.026
10076 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.068	0 restraints
wR(F²) = 0.199	H-atom parameters constrained
S = 1.07	Δρ_max = 0.57 e Å⁻³
6647 reflections	Δρ_min = −0.50 e Å⁻³
524 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq	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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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
M_r	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)
T_min, T_max	0.932, 0.948
No. of measured, independent and observed [I > 2σ(I)] reflections	10076, 6647, 3520
R_int	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
Δρ_max, Δρ_min (e Å⁻³)	0.57, −0.50

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

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
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