6-Benzyl-2-[(triphenyl-λ5-phosphanyl­idene)amino]-4,5,6,7-tetra­hydro­thieno[2,3-c]pyridine-3-carbonitrile

Chen, H.; Yan, K.

doi:10.1107/S1600536811035082

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 10| October 2011| Page o2548

https://doi.org/10.1107/S1600536811035082

Open

access

6-Benzyl-2-[(triphenyl-λ⁵-phosphanylidene)amino]-4,5,6,7-tetrahydrothieno[2,3-c]pyridine-3-carbonitrile

Hong Chen ^a ^* and Kai Yan ^b

^aCollege of Chemistry and Life Science, China Three Gorges University, Yichang 443002, People's Republic of China, and ^bHubei Key Laboratory of Natural Products Research and Development, China Three Gorges University, Yichang 443002, People's Republic of China
^*Correspondence e-mail: chenhong3736@sina.com

(Received 14 July 2011; accepted 27 August 2011; online 3 September 2011)

In the title compound, C₃₃H₂₈N₃PS, the P atom has a distorted tetrahedral PNC₃ environment, formed by the N atom and three aryl rings. No intermolecular hydrogen-bonding interactions or π–π stacking interactions are present in the crystal structure.

Related literature

For general background to the potential use of iminophosphoranes in the synthesis of N-heterocyclic compounds by means of an aza-Wittig reaction, see: Bräse et al. (2005 ); Ding et al. (2005 ); Huang et al. (2009a ,b ); Liu et al. (2008 ); Palacios et al. (2007 ). For a related structure, see: Muller (2011 ).

Experimental

Crystal data

C₃₃H₂₈N₃PS
M_r = 529.61
Monoclinic, P 2₁ /c
a = 8.926 (4) Å
b = 27.537 (12) Å
c = 11.719 (5) Å
β = 101.970 (4)°
V = 2818 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.20 mm⁻¹
T = 296 K
0.23 × 0.15 × 0.14 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.965, T_max = 0.973
25582 measured reflections
6415 independent reflections
5506 reflections with I > 2σ(I)
R_int = 0.078

Refinement

R[F² > 2σ(F²)] = 0.054
wR(F²) = 0.145
S = 1.09
6415 reflections
343 parameters
14 restraints
H-atom parameters constrained
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.40 e Å⁻³

Data collection: SMART (Bruker, 1997 ); cell refinement: SAINT (Bruker, 1997); 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536811035082/aa2019sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811035082/aa2019Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536811035082/aa2019Isup3.cml

checkCIF report

Comment top

Over the past twenty years, the aza-Wittig reactions of iminophosphoranes have received increasing attention in view of their utility in the synthesis of N-heterocyclic compounds (Bräse et al., 2005; Palacios et al., 2007). Annelation of ring systems with N-heterocycles by means of an aza-Wittig reaction has been widely utilized because of the availability of functionalized iminophosphoranes. Consequently, the discovery of novel functionalized iminophosphoranes is important in this respect. Recently we have become interested in the synthesis of thienopyrimidinone, quinazolinones, and imidazolinones by an aza-Wittig reaction, with the aim of evaluating their fungicidal activities (Ding et al., 2005; Huang et al., 2009a,b; Liu et al., 2008). Meanwhile, the title compound can be used as a new precursor for obtaining of bioactive molecules with fluorescence properties. Herein we wish to report the efficient synthesis, structural characterization of the title compound.

The molecular structure of the title compound is shown in Fig.1. The molecule has a benzyl substituent at the N6 atom of the thienopyridine ring and an nitrile group substituent at C3. Within the molecule, the bond lengths and bond angles present no unusual features. In the fused thienopyridine ring system, the thiophene ring is essentially coplanar, with maximum deviation of -0.0052 and 0.0059 Å for C8 and C9, respectively. The dihedral angle between plane (N6, C5, C7) and plane (C4, C5, C7) is 61.69°. The thiophene ring forms dihedral angles of 84.67, 73.58, 2.35 and 65.29° with the adjacent 6-membered rings C12–C17, C18–C23, C24–C29 and C33–C38, respectively. Meanwhile, the P atom has a distorted PNC₃ tetrahedral environment, formed by the N atom [P═N = 1.5782 (16) Å] and three aryl rings. The crystal packing is determined by van der Waals forces. No intermolecular hydrogen bonding interaction or π-π stacking interactions are present in the crystal structure.

Related literature top

For general background to the potential use of iminophosphoranes in the synthesis of N-heterocyclic compounds by means of an aza-Wittig reaction, see: Bräse et al. (2005); Ding et al. (2005); Huang et al. (2009a,b); Liu et al. (2008); Palacios et al. (2007). For a related structure, see: Muller (2011).

Experimental top

A well stirred mixture of 1-benzylpiperidin-4-one (1.89 g, 10 mmol), sulfur (0.32 g, 10 mmol), malononitrile (0.66 g, 10 mmol) in EtOH (10 ml) was cooled in an ice bath and treated dropwise with Et₃N (1.01 g, 10 mmol). When addition was complete, the reaction mixture was warmed to 333 K for 40 min and then stored in the cold place until crystallization occurred. The product, 2-amino-6-benzyl-4,5,6,7-tetrahydrothieno[2,3-c]pyridine-3-carbonitrile (2.29 g, yield 85%) was recrystallized from EtOH as colourless needles, M.p. 422–423 K.

To a mixture of 2-amino-6-benzyl-4,5,6,7-tetrahydrothieno[2,3-c]pyridine-3-carbonitrile (1.35 g, 5 mmol), PPh₃ (3.94 g, 15 mmol) and C₂Cl₆ (3.55 g, 15 mmol) in anhydrous CH₃CN (40 ml), were added dropwise Et₃N (2.42 g, 24 mmol) at room temperature. The color of the reaction mixture quickly turned yellow. After stirring for 4–6 h, the solvent was removed under reduced pressure and the residue was recrystallized from EtOH to give iminophosphorane in light yellow crystals, 3.63 g (83%), M.p. 463 K; IR (KBr), cm^-1 2190 (C≡N), 1490, 1346, 1100, 688; ¹H NMR(CDCl₃, 400 MHz) δ(p.p.m.): 7.78–7.23 (m, 20H, Ar—H), 3.62 (s, 2H, Ar—CH₂), 3.24 (s, 2H, NCH₂-thiophene), 2.75 (t, J = 8.7 Hz, 2H, NCH₂CH₂), 2.64 (t, J = 8.7 Hz, 2H, NCH₂CH₂); ESI-MS (m/z): 529.2 (M⁺), 530.2 ([M+H]⁺), 531.1 ([M+2H]⁺).

Structure description top

For general background to the potential use of iminophosphoranes in the synthesis of N-heterocyclic compounds by means of an aza-Wittig reaction, see: Bräse et al. (2005); Ding et al. (2005); Huang et al. (2009a,b); Liu et al. (2008); Palacios et al. (2007). For a related structure, see: Muller (2011).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); 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).

Figures top

	Fig. 1. Molecular structure of the title compound with 50% probability displacement ellipsoids.
	Fig. 2. Packing diagram of the title compound projected along the c axis direction. H atoms are omitted for clarity.
	Fig. 3. Reaction scheme.

6-Benzyl-2-[(triphenyl-λ⁵-phosphanylidene)amino]-4,5,6,7- tetrahydrothieno[2,3-c]pyridine-3-carbonitrile top

Crystal data top

C₃₃H₂₈N₃PS	F(000) = 1112
M_r = 529.61	D_x = 1.248 Mg m⁻³
Monoclinic, P2₁/c	Melting point: 463 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 8.926 (4) Å	Cell parameters from 6648 reflections
b = 27.537 (12) Å	θ = 2.7–27.5°
c = 11.719 (5) Å	µ = 0.20 mm⁻¹
β = 101.970 (4)°	T = 296 K
V = 2818 (2) Å³	Block, yellow
Z = 4	0.23 × 0.15 × 0.14 mm

Data collection top

Bruker SMART CCD diffractometer	6415 independent reflections
Radiation source: fine-focus sealed tube	5506 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.078
CCD Profile fitting scans	θ_max = 27.5°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→11
T_min = 0.965, T_max = 0.973	k = −35→35
25582 measured reflections	l = −15→15

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)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.145	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0593P)² + 0.6222P] where P = (F_o² + 2F_c²)/3
6415 reflections	(Δ/σ)_max = 0.001
343 parameters	Δρ_max = 0.35 e Å⁻³
14 restraints	Δρ_min = −0.40 e Å⁻³

Crystal data top

C₃₃H₂₈N₃PS	V = 2818 (2) Å³
M_r = 529.61	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.926 (4) Å	µ = 0.20 mm⁻¹
b = 27.537 (12) Å	T = 296 K
c = 11.719 (5) Å	0.23 × 0.15 × 0.14 mm
β = 101.970 (4)°

Data collection top

Bruker SMART CCD diffractometer	6415 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	5506 reflections with I > 2σ(I)
T_min = 0.965, T_max = 0.973	R_int = 0.078
25582 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	14 restraints
wR(F²) = 0.145	H-atom parameters constrained
S = 1.09	Δρ_max = 0.35 e Å⁻³
6415 reflections	Δρ_min = −0.40 e Å⁻³
343 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
S1	0.39018 (6)	0.490734 (17)	0.21538 (4)	0.04728 (14)
P11	0.32811 (5)	0.375360 (16)	0.10480 (4)	0.03695 (13)
C2	0.29442 (19)	0.44156 (6)	0.26335 (15)	0.0385 (4)
N10	0.26996 (18)	0.39751 (5)	0.21202 (13)	0.0430 (3)
C24	0.2666 (2)	0.31289 (7)	0.10029 (15)	0.0423 (4)
C3	0.2455 (2)	0.45503 (7)	0.36345 (15)	0.0409 (4)
C18	0.2416 (2)	0.40262 (7)	−0.03330 (16)	0.0433 (4)
C9	0.2855 (2)	0.50376 (7)	0.40134 (15)	0.0431 (4)
C4	0.2442 (3)	0.52902 (8)	0.50410 (17)	0.0533 (5)
H4A	0.2822	0.5103	0.5742	0.064*
H4B	0.1336	0.5310	0.4932	0.064*
C12	0.5327 (2)	0.37745 (7)	0.11612 (16)	0.0431 (4)
C8	0.3613 (2)	0.52716 (7)	0.32988 (17)	0.0467 (4)
C30	0.1641 (2)	0.42171 (7)	0.42103 (16)	0.0482 (4)
C19	0.1165 (2)	0.43269 (8)	−0.03768 (18)	0.0526 (5)
H19	0.0819	0.4395	0.0302	0.063*
N6	0.3003 (2)	0.60358 (7)	0.40430 (17)	0.0624 (5)
C7	0.4035 (3)	0.57978 (8)	0.3403 (2)	0.0613 (6)
H7A	0.5089	0.5835	0.3818	0.074*
H7B	0.3932	0.5941	0.2635	0.074*
C29	0.1868 (3)	0.29638 (8)	0.18196 (19)	0.0559 (5)
H29	0.1703	0.3171	0.2409	0.067*
N31	0.0979 (3)	0.39483 (8)	0.46615 (18)	0.0729 (6)
C13	0.6239 (2)	0.34442 (9)	0.18892 (19)	0.0573 (5)
H13	0.5789	0.3190	0.2221	0.069*
C5	0.3120 (3)	0.58015 (9)	0.5189 (2)	0.0666 (6)
H5A	0.2575	0.5994	0.5665	0.080*
H5B	0.4187	0.5784	0.5586	0.080*
C33	0.3007 (3)	0.67981 (8)	0.2956 (2)	0.0681 (6)
C27	0.1534 (3)	0.21872 (9)	0.0894 (3)	0.0765 (8)
H27	0.1140	0.1874	0.0849	0.092*
C23	0.2916 (3)	0.39258 (10)	−0.13584 (18)	0.0643 (6)
H23	0.3761	0.3726	−0.1341	0.077*
C25	0.2919 (3)	0.28159 (8)	0.0134 (2)	0.0628 (6)
H25	0.3471	0.2920	−0.0413	0.075*
C26	0.2338 (4)	0.23443 (9)	0.0087 (2)	0.0775 (8)
H26	0.2499	0.2134	−0.0498	0.093*
C17	0.6018 (3)	0.41492 (9)	0.0675 (2)	0.0630 (6)
H17	0.5420	0.4372	0.0184	0.076*
C16	0.7602 (3)	0.41936 (11)	0.0916 (3)	0.0805 (8)
H16	0.8063	0.4446	0.0587	0.097*
C36	0.2460 (5)	0.72224 (11)	0.0748 (3)	0.0943 (9)
H36	0.2282	0.7364	0.0012	0.113*
C15	0.8486 (3)	0.38665 (12)	0.1639 (3)	0.0797 (8)
H15	0.9546	0.3898	0.1803	0.096*
C14	0.7818 (3)	0.34928 (11)	0.2122 (2)	0.0748 (7)
H14	0.8427	0.3271	0.2607	0.090*
C28	0.1311 (3)	0.24919 (9)	0.1766 (3)	0.0753 (7)
H28	0.0786	0.2383	0.2324	0.090*
C22	0.2153 (3)	0.41234 (12)	−0.2402 (2)	0.0827 (9)
H22	0.2480	0.4053	−0.3087	0.099*
C20	0.0417 (3)	0.45287 (10)	−0.1435 (2)	0.0723 (7)
H20	−0.0416	0.4734	−0.1462	0.087*
C21	0.0922 (3)	0.44216 (12)	−0.2433 (2)	0.0802 (8)
H21	0.0420	0.4553	−0.3140	0.096*
C35	0.3784 (4)	0.72998 (12)	0.1508 (4)	0.0936 (10)
H35	0.4520	0.7499	0.1292	0.112*
C32	0.3298 (4)	0.65581 (9)	0.4136 (3)	0.0824 (8)
H32A	0.4353	0.6613	0.4526	0.099*
H32B	0.2643	0.6704	0.4607	0.099*
C38	0.1630 (3)	0.67270 (10)	0.2154 (3)	0.0808 (8)
H38	0.0867	0.6536	0.2358	0.097*
C34	0.4080 (3)	0.70931 (11)	0.2599 (3)	0.0888 (9)
H34	0.5013	0.7152	0.3103	0.107*
C37	0.1393 (4)	0.69361 (12)	0.1064 (3)	0.0931 (10)
H37	0.0478	0.6879	0.0537	0.112*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0532 (3)	0.0445 (3)	0.0489 (3)	−0.00073 (19)	0.0216 (2)	−0.00419 (18)
P11	0.0375 (2)	0.0411 (2)	0.0327 (2)	0.00167 (17)	0.00837 (17)	−0.00069 (16)
C2	0.0377 (8)	0.0432 (9)	0.0346 (8)	0.0036 (7)	0.0076 (7)	0.0006 (6)
N10	0.0485 (8)	0.0442 (8)	0.0386 (8)	−0.0012 (6)	0.0143 (7)	−0.0042 (6)
C24	0.0422 (9)	0.0443 (9)	0.0374 (9)	0.0003 (7)	0.0014 (7)	−0.0019 (7)
C3	0.0432 (9)	0.0476 (9)	0.0314 (8)	0.0064 (7)	0.0065 (7)	0.0001 (7)
C18	0.0415 (9)	0.0501 (10)	0.0376 (9)	−0.0001 (7)	0.0070 (7)	0.0037 (7)
C9	0.0423 (9)	0.0505 (10)	0.0348 (9)	0.0091 (8)	0.0040 (7)	−0.0045 (7)
C4	0.0608 (12)	0.0609 (12)	0.0356 (9)	0.0127 (9)	0.0040 (9)	−0.0081 (8)
C12	0.0400 (9)	0.0491 (10)	0.0406 (9)	0.0035 (7)	0.0094 (7)	−0.0051 (7)
C8	0.0450 (9)	0.0462 (9)	0.0492 (10)	0.0052 (8)	0.0104 (8)	−0.0090 (8)
C30	0.0582 (11)	0.0536 (10)	0.0339 (9)	0.0080 (9)	0.0119 (8)	0.0017 (7)
C19	0.0443 (10)	0.0608 (12)	0.0512 (11)	0.0049 (9)	0.0064 (9)	0.0052 (9)
N6	0.0780 (13)	0.0471 (9)	0.0629 (11)	0.0041 (9)	0.0170 (10)	−0.0168 (8)
C7	0.0602 (12)	0.0494 (11)	0.0773 (15)	−0.0018 (10)	0.0213 (11)	−0.0146 (10)
C29	0.0691 (13)	0.0484 (11)	0.0515 (11)	−0.0074 (9)	0.0158 (10)	0.0022 (8)
N31	0.0974 (16)	0.0704 (13)	0.0583 (12)	−0.0061 (11)	0.0330 (12)	0.0098 (9)
C13	0.0485 (11)	0.0683 (13)	0.0529 (12)	0.0064 (10)	0.0056 (9)	0.0076 (10)
C5	0.0779 (15)	0.0678 (14)	0.0499 (12)	0.0049 (12)	0.0036 (11)	−0.0212 (10)
C33	0.0764 (15)	0.0455 (11)	0.0805 (16)	0.0092 (10)	0.0119 (13)	−0.0187 (10)
C27	0.0892 (18)	0.0464 (12)	0.0819 (18)	−0.0119 (12)	−0.0100 (15)	0.0005 (11)
C23	0.0621 (13)	0.0937 (17)	0.0391 (11)	0.0135 (12)	0.0152 (10)	0.0084 (10)
C25	0.0818 (15)	0.0564 (12)	0.0504 (12)	0.0022 (11)	0.0143 (11)	−0.0109 (9)
C26	0.103 (2)	0.0541 (13)	0.0662 (16)	0.0051 (13)	−0.0043 (14)	−0.0223 (11)
C17	0.0470 (11)	0.0652 (13)	0.0806 (16)	0.0025 (10)	0.0220 (11)	0.0123 (11)
C16	0.0498 (13)	0.0850 (18)	0.112 (2)	−0.0080 (12)	0.0288 (14)	0.0093 (16)
C36	0.119 (3)	0.0695 (18)	0.095 (2)	0.0008 (18)	0.025 (2)	−0.0063 (15)
C15	0.0403 (11)	0.114 (2)	0.0847 (19)	−0.0037 (13)	0.0122 (12)	−0.0092 (16)
C14	0.0482 (12)	0.105 (2)	0.0668 (16)	0.0173 (13)	0.0017 (11)	0.0068 (14)
C28	0.0913 (18)	0.0535 (13)	0.0814 (17)	−0.0172 (12)	0.0187 (14)	0.0079 (12)
C22	0.0768 (17)	0.132 (3)	0.0392 (12)	−0.0004 (17)	0.0118 (12)	0.0154 (13)
C20	0.0526 (12)	0.0819 (16)	0.0743 (17)	0.0134 (12)	−0.0057 (12)	0.0194 (13)
C21	0.0652 (15)	0.113 (2)	0.0549 (15)	−0.0024 (15)	−0.0054 (12)	0.0301 (14)
C35	0.105 (2)	0.0723 (18)	0.115 (3)	−0.0176 (17)	0.048 (2)	−0.0176 (17)
C32	0.1019 (19)	0.0533 (13)	0.0851 (17)	0.0030 (13)	0.0036 (15)	−0.0268 (11)
C38	0.0603 (14)	0.0636 (15)	0.116 (2)	−0.0038 (12)	0.0126 (15)	0.0062 (15)
C34	0.0697 (16)	0.0736 (17)	0.117 (3)	−0.0124 (14)	0.0048 (17)	−0.0369 (17)
C37	0.086 (2)	0.0790 (19)	0.101 (2)	0.0032 (16)	−0.0105 (18)	0.0071 (17)

Geometric parameters (Å, º) top

S1—C8	1.737 (2)	C33—C34	1.385 (4)
S1—C2	1.7550 (19)	C33—C38	1.397 (4)
P11—N10	1.5782 (16)	C33—C32	1.506 (4)
P11—C24	1.803 (2)	C27—C28	1.368 (4)
P11—C12	1.804 (2)	C27—C26	1.371 (4)
P11—C18	1.8057 (19)	C27—H27	0.9300
C2—N10	1.351 (2)	C23—C22	1.382 (3)
C2—C3	1.385 (2)	C23—H23	0.9300
C24—C29	1.383 (3)	C25—C26	1.395 (3)
C24—C25	1.388 (3)	C25—H25	0.9300
C3—C30	1.424 (3)	C26—H26	0.9300
C3—C9	1.435 (3)	C17—C16	1.389 (3)
C18—C19	1.383 (3)	C17—H17	0.9300
C18—C23	1.394 (3)	C16—C15	1.369 (4)
C9—C8	1.345 (3)	C16—H16	0.9300
C9—C4	1.501 (2)	C36—C35	1.341 (5)
C4—C5	1.528 (3)	C36—C37	1.347 (5)
C4—H4A	0.9700	C36—H36	0.9300
C4—H4B	0.9700	C15—C14	1.369 (4)
C12—C17	1.384 (3)	C15—H15	0.9300
C12—C13	1.389 (3)	C14—H14	0.9300
C8—C7	1.496 (3)	C28—H28	0.9300
C30—N31	1.143 (3)	C22—C21	1.367 (4)
C19—C20	1.396 (3)	C22—H22	0.9300
C19—H19	0.9300	C20—C21	1.370 (4)
N6—C7	1.458 (3)	C20—H20	0.9300
N6—C32	1.462 (3)	C21—H21	0.9300
N6—C5	1.474 (3)	C35—C34	1.373 (5)
C7—H7A	0.9700	C35—H35	0.9300
C7—H7B	0.9700	C32—H32A	0.9700
C29—C28	1.388 (3)	C32—H32B	0.9700
C29—H29	0.9300	C38—C37	1.376 (4)
C13—C14	1.386 (3)	C38—H38	0.9300
C13—H13	0.9300	C34—H34	0.9300
C5—H5A	0.9700	C37—H37	0.9300
C5—H5B	0.9700

C8—S1—C2	92.17 (9)	C34—C33—C38	116.4 (3)
N10—P11—C24	104.09 (8)	C34—C33—C32	122.4 (3)
N10—P11—C12	115.09 (8)	C38—C33—C32	121.1 (3)
C24—P11—C12	109.28 (8)	C28—C27—C26	120.0 (2)
N10—P11—C18	113.76 (9)	C28—C27—H27	120.0
C24—P11—C18	107.42 (9)	C26—C27—H27	120.0
C12—P11—C18	106.90 (9)	C22—C23—C18	119.8 (2)
N10—C2—C3	124.56 (16)	C22—C23—H23	120.1
N10—C2—S1	126.48 (13)	C18—C23—H23	120.1
C3—C2—S1	108.96 (13)	C24—C25—C26	119.4 (2)
C2—N10—P11	130.67 (13)	C24—C25—H25	120.3
C29—C24—C25	119.31 (19)	C26—C25—H25	120.3
C29—C24—P11	119.39 (15)	C27—C26—C25	120.7 (2)
C25—C24—P11	121.24 (16)	C27—C26—H26	119.7
C2—C3—C30	120.69 (17)	C25—C26—H26	119.7
C2—C3—C9	114.23 (16)	C12—C17—C16	120.2 (2)
C30—C3—C9	125.07 (16)	C12—C17—H17	119.9
C19—C18—C23	119.18 (18)	C16—C17—H17	119.9
C19—C18—P11	118.30 (15)	C15—C16—C17	120.0 (3)
C23—C18—P11	122.44 (16)	C15—C16—H16	120.0
C8—C9—C3	112.36 (16)	C17—C16—H16	120.0
C8—C9—C4	121.09 (18)	C35—C36—C37	119.1 (3)
C3—C9—C4	126.47 (17)	C35—C36—H36	120.5
C9—C4—C5	111.13 (18)	C37—C36—H36	120.5
C9—C4—H4A	109.4	C16—C15—C14	120.4 (2)
C5—C4—H4A	109.4	C16—C15—H15	119.8
C9—C4—H4B	109.4	C14—C15—H15	119.8
C5—C4—H4B	109.4	C15—C14—C13	120.2 (2)
H4A—C4—H4B	108.0	C15—C14—H14	119.9
C17—C12—C13	119.13 (19)	C13—C14—H14	119.9
C17—C12—P11	121.62 (15)	C27—C28—C29	120.1 (3)
C13—C12—P11	118.64 (15)	C27—C28—H28	120.0
C9—C8—C7	124.33 (18)	C29—C28—H28	120.0
C9—C8—S1	112.26 (15)	C21—C22—C23	120.4 (2)
C7—C8—S1	123.18 (16)	C21—C22—H22	119.8
N31—C30—C3	179.3 (2)	C23—C22—H22	119.8
C18—C19—C20	120.3 (2)	C21—C20—C19	119.4 (2)
C18—C19—H19	119.8	C21—C20—H20	120.3
C20—C19—H19	119.8	C19—C20—H20	120.3
C7—N6—C32	110.9 (2)	C22—C21—C20	120.8 (2)
C7—N6—C5	109.80 (19)	C22—C21—H21	119.6
C32—N6—C5	112.64 (19)	C20—C21—H21	119.6
N6—C7—C8	107.58 (18)	C36—C35—C34	121.7 (3)
N6—C7—H7A	110.2	C36—C35—H35	119.1
C8—C7—H7A	110.2	C34—C35—H35	119.1
N6—C7—H7B	110.2	N6—C32—C33	111.7 (2)
C8—C7—H7B	110.2	N6—C32—H32A	109.3
H7A—C7—H7B	108.5	C33—C32—H32A	109.3
C24—C29—C28	120.5 (2)	N6—C32—H32B	109.3
C24—C29—H29	119.8	C33—C32—H32B	109.3
C28—C29—H29	119.8	H32A—C32—H32B	107.9
C14—C13—C12	120.0 (2)	C37—C38—C33	120.7 (3)
C14—C13—H13	120.0	C37—C38—H38	119.7
C12—C13—H13	120.0	C33—C38—H38	119.7
N6—C5—C4	110.37 (17)	C35—C34—C33	120.8 (3)
N6—C5—H5A	109.6	C35—C34—H34	119.6
C4—C5—H5A	109.6	C33—C34—H34	119.6
N6—C5—H5B	109.6	C36—C37—C38	121.2 (3)
C4—C5—H5B	109.6	C36—C37—H37	119.4
H5A—C5—H5B	108.1	C38—C37—H37	119.4

C8—S1—C2—N10	179.48 (17)	P11—C18—C19—C20	−177.18 (18)
C8—S1—C2—C3	−0.05 (14)	C32—N6—C7—C8	−177.4 (2)
C3—C2—N10—P11	−174.79 (14)	C5—N6—C7—C8	57.4 (2)
S1—C2—N10—P11	5.7 (3)	C9—C8—C7—N6	−22.4 (3)
C24—P11—N10—C2	173.39 (17)	S1—C8—C7—N6	151.68 (16)
C12—P11—N10—C2	53.8 (2)	C25—C24—C29—C28	−0.6 (3)
C18—P11—N10—C2	−70.01 (19)	P11—C24—C29—C28	176.58 (19)
N10—P11—C24—C29	0.25 (18)	C17—C12—C13—C14	0.1 (3)
C12—P11—C24—C29	123.69 (16)	P11—C12—C13—C14	−171.05 (19)
C18—P11—C24—C29	−120.68 (16)	C7—N6—C5—C4	−69.2 (2)
N10—P11—C24—C25	177.42 (17)	C32—N6—C5—C4	166.6 (2)
C12—P11—C24—C25	−59.14 (19)	C9—C4—C5—N6	39.9 (3)
C18—P11—C24—C25	56.49 (19)	C19—C18—C23—C22	−0.5 (4)
N10—C2—C3—C30	0.5 (3)	P11—C18—C23—C22	176.3 (2)
S1—C2—C3—C30	−179.95 (14)	C29—C24—C25—C26	1.3 (3)
N10—C2—C3—C9	179.89 (16)	P11—C24—C25—C26	−175.92 (18)
S1—C2—C3—C9	−0.57 (19)	C28—C27—C26—C25	−0.9 (4)
N10—P11—C18—C19	−11.62 (19)	C24—C25—C26—C27	−0.5 (4)
C24—P11—C18—C19	103.01 (17)	C13—C12—C17—C16	−0.2 (4)
C12—P11—C18—C19	−139.79 (16)	P11—C12—C17—C16	170.7 (2)
N10—P11—C18—C23	171.61 (18)	C12—C17—C16—C15	−0.1 (4)
C24—P11—C18—C23	−73.8 (2)	C17—C16—C15—C14	0.4 (5)
C12—P11—C18—C23	43.4 (2)	C16—C15—C14—C13	−0.5 (5)
C2—C3—C9—C8	1.1 (2)	C12—C13—C14—C15	0.2 (4)
C30—C3—C9—C8	−179.54 (17)	C26—C27—C28—C29	1.5 (4)
C2—C3—C9—C4	177.94 (17)	C24—C29—C28—C27	−0.8 (4)
C30—C3—C9—C4	−2.7 (3)	C18—C23—C22—C21	0.8 (4)
C8—C9—C4—C5	−5.3 (3)	C18—C19—C20—C21	0.8 (4)
C3—C9—C4—C5	178.09 (18)	C23—C22—C21—C20	−0.2 (5)
N10—P11—C12—C17	−94.91 (19)	C19—C20—C21—C22	−0.6 (4)
C24—P11—C12—C17	148.44 (18)	C37—C36—C35—C34	0.3 (5)
C18—P11—C12—C17	32.5 (2)	C7—N6—C32—C33	62.6 (3)
N10—P11—C12—C13	76.04 (18)	C5—N6—C32—C33	−173.9 (2)
C24—P11—C12—C13	−40.61 (18)	C34—C33—C32—N6	−127.8 (3)
C18—P11—C12—C13	−156.57 (16)	C38—C33—C32—N6	51.2 (3)
C3—C9—C8—C7	173.52 (19)	C34—C33—C38—C37	1.1 (4)
C4—C9—C8—C7	−3.5 (3)	C32—C33—C38—C37	−178.0 (3)
C3—C9—C8—S1	−1.1 (2)	C36—C35—C34—C33	−0.5 (5)
C4—C9—C8—S1	−178.14 (14)	C38—C33—C34—C35	−0.2 (4)
C2—S1—C8—C9	0.68 (15)	C32—C33—C34—C35	179.0 (3)
C2—S1—C8—C7	−174.02 (18)	C35—C36—C37—C38	0.7 (5)
C23—C18—C19—C20	−0.3 (3)	C33—C38—C37—C36	−1.4 (5)

Experimental details

Crystal data
Chemical formula	C₃₃H₂₈N₃PS
M_r	529.61
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	8.926 (4), 27.537 (12), 11.719 (5)
β (°)	101.970 (4)
V (Å³)	2818 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.20
Crystal size (mm)	0.23 × 0.15 × 0.14

Data collection
Diffractometer	Bruker SMART CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.965, 0.973
No. of measured, independent and observed [I > 2σ(I)] reflections	25582, 6415, 5506
R_int	0.078
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.145, 1.09
No. of reflections	6415
No. of parameters	343
No. of restraints	14
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.40

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXTL (Sheldrick, 2008).

Acknowledgements

This work was supported financially by the Science Foundation of Hubei Province Education Department, China (project No. D20091301) and the Excellent Fund for Scientific Research and Special Projects in China Three Gorges University, China (project No. KJ2009B004).

References

Bräse, S., Gil, C., Knepper, K. & Zimmermann, V. (2005). Angew. Chem. Int. Ed. 44, 5188–5240. Google Scholar
Bruker (1997). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Ding, M. W., Huang, N. Y. & He, H. W. (2005). Synthesis, 10, 1601–1604. Web of Science CrossRef Google Scholar
Huang, N. Y., Liang, Y. J., Ding, M. W., Fu, L. W. & He, H. W. (2009a). Bioorg. Med. Chem. Lett. 19, 831–833. Web of Science CrossRef PubMed CAS Google Scholar
Huang, N. Y., Liu, M. G. & Ding, M. W. (2009b). J. Org. Chem. 74, 6874–6877. Web of Science CSD CrossRef PubMed CAS Google Scholar
Liu, M. G., Hu, Y. G. & Ding, M. W. (2008). Tetrahedron, 64, 9052–9059. Web of Science CSD CrossRef CAS Google Scholar
Muller, A. (2011). Acta Cryst. E67, o45. Web of Science CSD CrossRef IUCr Journals Google Scholar
Palacios, F., Alonso, C., Aparicio, D., Rbbiales, G. & Santos, J. M. (2007). Tetrahedron, 63, 523–575. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals 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.