N-Methyl-2-thio-cytisine.

The rings of the three-ring cytisine system in the title compound [systematic name: (1R,5S)-1,2,3,4,5,6-hexa-hydro-1,5-methano-8H-pyrido[1,2-a][1,5]diazo-cine-8-thione], C(12)H(16)N(2)S, have planar [maximum deviation 0.0170 (7) Å], half-chair and chair conformations. In the crystal structure, relatively short and directional C-H⋯π inter-actions and weaker secondary C-H⋯S contacts join the mol-ecules into helical chains along the [001] direction.

Related literature

For general literature on cytisine, see: Okuda et al. (1961 ▶). For synthetic methods, see: Marriere et al. (2000 ▶); Imming et al. (2001 ▶). For similar structures, see: Freer et al. (1987 ▶); Imming et al. (2001 ▶). For asymmetry parameters, see: Duax & Norton (1975 ▶). For C—H⋯π interactions, see: Desiraju & Steiner (1999 ▶); Braga et al. (1998 ▶). For a description of the Cambridge Structural Database, see: Allen (2002 ▶).

Experimental

Crystal data

C12H16N2S

M = 220.33

Orthorhombic,

a = 9.8530 (6) Å

b = 10.6964 (7) Å

c = 10.8226 (7) Å

V = 1140.61 (13) Å3

Z = 4

Mo Kα radiation

μ = 0.25 mm−1

T = 100 K

0.5 × 0.2 × 0.1 mm

Data collection

Xcalibur, Eos diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 ▶) T min = 0.921, T max = 1.000

13752 measured reflections

2744 independent reflections

2604 reflections with I > 2σ(I)

R int = 0.019

Refinement

R[F 2 > 2σ(F 2)] = 0.021

wR(F 2) = 0.056

S = 1.07

2744 reflections

200 parameters

All H-atom parameters refined

Δρmax = 0.25 e Å−3

Δρmin = −0.16 e Å−3

Absolute structure: Flack (1983 ▶), 1015 Friedel pairs

Flack parameter: 0.02 (4)

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SIR92 (Altomare et al., 1993 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: Stereochemical Workstation Operation Manual (Siemens, 1989 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810025870/nk2044sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810025870/nk2044Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C12H16N2S	F(000) = 472
Mr = 220.33	Dx = 1.283 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 11220 reflections
a = 9.8530 (6) Å	θ = 3.4–29.0°
b = 10.6964 (7) Å	µ = 0.25 mm−1
c = 10.8226 (7) Å	T = 100 K
V = 1140.61 (13) Å3	Prism, colourless
Z = 4	0.5 × 0.2 × 0.1 mm

Xcalibur, Eos diffractometer	2744 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2604 reflections with I > 2σ(I)
graphite	Rint = 0.019
Detector resolution: 16.1544 pixels mm-1	θmax = 29.0°, θmin = 3.4°
ω–scan	h = −12→12
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	k = −13→13
Tmin = 0.921, Tmax = 1.000	l = −14→14
13752 measured reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.021	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.056	w = 1/[σ2(Fo2) + (0.040P)2] where P = (Fo2 + 2Fc2)/3
S = 1.07	(Δ/σ)max = 0.001
2744 reflections	Δρmax = 0.25 e Å−3
200 parameters	Δρmin = −0.16 e Å−3
0 restraints	Absolute structure: Flack (1983), 1015 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.02 (4)

Experimental. For cytisine: EI—MS m/z: 190 (96%), m/z: 146 (100%), 147 (99%), 148 (42%), 134 (32%), 160 (29%), 109 (20%).For N-methylcytisine:EI—MS m/z: 204 (54%), m/z: 58 (100%), 146 (15%), 160 (9%). 13C-NMR: 163.5; 151.30; 138.5; 116.5; 104.6; 62.5; 62.1; 49.9; 46.2; 35.4; 35.4; 27.9; 25.4.For 1:EI—MS m/z 220 (92%), 162 (100%), 58 (47%), 189 (27), 176 (27%), 130 (23%)82 (17%), 117 (16%). 13C-NMR: 179.6; 133.5; 132.9; 154.4; 113.7; 62.6; 62.0; 58.4; 46.4; 36.3; 29.0. GC—MS analyses were performed on gas chromatograph CP3800 associated with mass spectrometer (4000MS, ion trap). The column was: VF-5 ms 30 m x 0.25 mm x 0.39 mm (Varian Part No. CP8944); carried gas was helium with flow 1 ml/min. Injector type 1177, std. on column, temp. 250 oC. Temperature program during GC—MS analysis: 80¯C/1¯C/1 min; 180¯C/20¯C/1 min/ 280¯C/10¯C/1 min, hold 20 minutes. NMR spectra were measured on a Bruker AVANCE 600 (600.31 MHz for 1H and 150.052 MHz for 13C) spectrometer.

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
N1	0.90884 (9)	0.93342 (8)	0.93639 (8)	0.01107 (18)
C2	0.93960 (11)	0.84480 (9)	0.84655 (9)	0.0124 (2)
S2	1.05611 (3)	0.87330 (3)	0.73429 (2)	0.01503 (7)
C3	0.86834 (12)	0.73023 (11)	0.85333 (10)	0.0161 (2)
H3	0.8883 (14)	0.6684 (13)	0.7933 (13)	0.021 (3)*
C4	0.77017 (12)	0.70978 (11)	0.94042 (11)	0.0195 (2)
H4	0.7145 (14)	0.6306 (15)	0.9409 (13)	0.027 (4)*
C5	0.74016 (12)	0.80336 (11)	1.02604 (10)	0.0174 (2)
H5	0.6694 (15)	0.7997 (14)	1.0879 (12)	0.024 (4)*
C6	0.80976 (11)	0.91409 (10)	1.02375 (9)	0.0129 (2)
C7	0.77873 (12)	1.01441 (11)	1.11690 (10)	0.0150 (2)
H7	0.6821 (15)	1.0028 (12)	1.1408 (12)	0.016 (3)*
C8	0.80632 (12)	1.14397 (11)	1.06434 (10)	0.0174 (2)
H8A	0.7864 (15)	1.2061 (15)	1.1303 (13)	0.026 (4)*
H8B	0.7486 (14)	1.1589 (14)	0.9908 (12)	0.023 (4)*
C9	0.95672 (12)	1.14670 (9)	1.03299 (10)	0.0150 (2)
H9	0.9853 (14)	1.2232 (14)	0.9994 (12)	0.019 (3)*
C10	0.98425 (12)	1.05431 (10)	0.92880 (10)	0.0137 (2)
H10A	0.9562 (15)	1.0889 (13)	0.8476 (12)	0.020 (3)*
H10B	1.0795 (16)	1.0292 (14)	0.9265 (13)	0.022 (4)*
C11	1.04178 (12)	1.12303 (11)	1.14906 (9)	0.0160 (2)
H11A	1.1421 (14)	1.1253 (14)	1.1292 (11)	0.018 (3)*
H11B	1.0252 (14)	1.1959 (13)	1.2076 (12)	0.022 (4)*
N12	1.00916 (10)	1.00157 (9)	1.20468 (8)	0.0139 (2)
C13	0.86495 (12)	0.99465 (10)	1.23364 (10)	0.0154 (2)
H13A	0.8353 (13)	1.0555 (12)	1.2962 (12)	0.015 (3)*
H13B	0.8429 (13)	0.9123 (13)	1.2648 (12)	0.020 (3)*
C14	1.08925 (14)	0.98412 (12)	1.31729 (11)	0.0202 (3)
H14A	1.0719 (14)	0.9084 (15)	1.3549 (13)	0.025 (4)*
H14B	1.1830 (16)	0.9908 (12)	1.2980 (12)	0.022 (4)*
H14C	1.0686 (18)	1.0426 (17)	1.3806 (15)	0.039 (5)*

	U11	U22	U33	U12	U13	U23
N1	0.0113 (4)	0.0105 (4)	0.0114 (4)	−0.0004 (3)	0.0001 (3)	0.0008 (3)
C2	0.0118 (5)	0.0134 (5)	0.0120 (4)	0.0027 (4)	−0.0021 (4)	0.0009 (3)
S2	0.01402 (13)	0.01866 (13)	0.01242 (12)	0.00195 (11)	0.00257 (9)	−0.00147 (10)
C3	0.0192 (6)	0.0131 (5)	0.0161 (5)	0.0004 (4)	−0.0022 (4)	−0.0024 (4)
C4	0.0222 (6)	0.0154 (5)	0.0208 (6)	−0.0067 (5)	−0.0026 (5)	0.0016 (4)
C5	0.0170 (6)	0.0195 (6)	0.0157 (5)	−0.0047 (4)	0.0021 (4)	0.0011 (4)
C6	0.0112 (5)	0.0164 (5)	0.0112 (5)	0.0003 (4)	−0.0007 (4)	0.0015 (4)
C7	0.0126 (6)	0.0187 (5)	0.0138 (5)	0.0018 (4)	0.0029 (4)	−0.0026 (4)
C8	0.0202 (6)	0.0158 (6)	0.0162 (5)	0.0059 (5)	−0.0004 (4)	−0.0017 (4)
C9	0.0213 (6)	0.0092 (5)	0.0144 (5)	−0.0012 (4)	0.0009 (4)	0.0000 (4)
C10	0.0151 (6)	0.0120 (5)	0.0141 (5)	−0.0028 (4)	0.0025 (4)	0.0009 (4)
C11	0.0197 (5)	0.0131 (5)	0.0153 (5)	−0.0033 (5)	−0.0002 (4)	−0.0005 (4)
N12	0.0165 (5)	0.0126 (4)	0.0126 (4)	−0.0005 (3)	−0.0012 (3)	0.0012 (3)
C13	0.0182 (6)	0.0167 (5)	0.0112 (5)	−0.0007 (4)	0.0027 (4)	−0.0005 (4)
C14	0.0253 (7)	0.0179 (6)	0.0176 (6)	−0.0012 (5)	−0.0061 (5)	0.0016 (4)

N1—C6	1.3747 (13)	C8—H8B	0.991 (14)
N1—C2	1.3913 (13)	C9—C10	1.5237 (15)
N1—C10	1.4936 (14)	C9—C11	1.5312 (14)
C2—C3	1.4143 (15)	C9—H9	0.939 (14)
C2—S2	1.6990 (11)	C10—H10A	0.993 (14)
C3—C4	1.3682 (16)	C10—H10B	0.976 (16)
C3—H3	0.948 (14)	C11—N12	1.4674 (14)
C4—C5	1.3957 (16)	C11—H11A	1.012 (13)
C4—H4	1.009 (16)	C11—H11B	1.018 (14)
C5—C6	1.3688 (16)	N12—C13	1.4570 (15)
C5—H5	0.968 (15)	N12—C14	1.4638 (15)
C6—C7	1.5037 (15)	C13—H13A	0.983 (13)
C7—C8	1.5225 (16)	C13—H13B	0.968 (14)
C7—C13	1.5371 (16)	C14—H14A	0.922 (16)
C7—H7	0.994 (14)	C14—H14B	0.950 (16)
C8—C9	1.5205 (16)	C14—H14C	0.950 (17)
C8—H8A	0.995 (15)
C6—N1—C2	122.20 (9)	C10—C9—C11	113.73 (9)
C6—N1—C10	121.42 (9)	C8—C9—H9	113.3 (9)
C2—N1—C10	116.29 (9)	C10—C9—H9	103.0 (8)
N1—C2—C3	116.48 (9)	C11—C9—H9	107.3 (8)
N1—C2—S2	121.65 (8)	N1—C10—C9	115.61 (9)
C3—C2—S2	121.87 (8)	N1—C10—H10A	103.5 (8)
C4—C3—C2	121.69 (10)	C9—C10—H10A	111.3 (8)
C4—C3—H3	120.5 (8)	N1—C10—H10B	104.0 (9)
C2—C3—H3	117.8 (8)	C9—C10—H10B	111.6 (8)
C3—C4—C5	119.50 (11)	H10A—C10—H10B	110.3 (12)
C3—C4—H4	121.5 (8)	N12—C11—C9	111.29 (9)
C5—C4—H4	118.9 (8)	N12—C11—H11A	108.8 (8)
C6—C5—C4	120.16 (11)	C9—C11—H11A	110.8 (7)
C6—C5—H5	114.1 (9)	N12—C11—H11B	112.8 (8)
C4—C5—H5	125.7 (9)	C9—C11—H11B	107.2 (8)
C5—C6—N1	119.89 (10)	H11A—C11—H11B	105.7 (11)
C5—C6—C7	120.23 (10)	C13—N12—C14	109.89 (9)
N1—C6—C7	119.88 (9)	C13—N12—C11	110.29 (9)
C6—C7—C8	111.27 (9)	C14—N12—C11	109.66 (9)
C6—C7—C13	109.91 (9)	N12—C13—C7	110.81 (9)
C8—C7—C13	109.48 (9)	N12—C13—H13A	113.8 (8)
C6—C7—H7	106.3 (8)	C7—C13—H13A	108.1 (8)
C8—C7—H7	112.4 (8)	N12—C13—H13B	109.9 (8)
C13—C7—H7	107.3 (8)	C7—C13—H13B	106.7 (8)
C9—C8—C7	105.96 (9)	H13A—C13—H13B	107.2 (10)
C9—C8—H8A	109.9 (9)	N12—C14—H14A	112.3 (9)
C7—C8—H8A	107.7 (8)	N12—C14—H14B	109.4 (8)
C9—C8—H8B	112.1 (8)	H14A—C14—H14B	110.0 (12)
C7—C8—H8B	110.1 (9)	N12—C14—H14C	113.7 (10)
H8A—C8—H8B	110.8 (12)	H14A—C14—H14C	102.7 (13)
C8—C9—C10	109.04 (9)	H14B—C14—H14C	108.5 (13)
C8—C9—C11	110.31 (9)
C6—N1—C2—C3	−3.20 (14)	N1—C6—C7—C13	−91.68 (11)
C10—N1—C2—C3	−179.95 (9)	C6—C7—C8—C9	−61.04 (12)
C6—N1—C2—S2	176.50 (8)	C13—C7—C8—C9	60.65 (11)
C10—N1—C2—S2	−0.25 (13)	C7—C8—C9—C10	65.86 (11)
N1—C2—C3—C4	2.75 (15)	C7—C8—C9—C11	−59.71 (11)
S2—C2—C3—C4	−176.95 (9)	C6—N1—C10—C9	7.35 (14)
C2—C3—C4—C5	−0.81 (17)	C2—N1—C10—C9	−175.87 (9)
C3—C4—C5—C6	−0.84 (18)	C8—C9—C10—N1	−39.82 (12)
C4—C5—C6—N1	0.42 (17)	C11—C9—C10—N1	83.75 (12)
C4—C5—C6—C7	−179.26 (11)	C8—C9—C11—N12	59.15 (12)
C2—N1—C6—C5	1.69 (15)	C10—C9—C11—N12	−63.71 (12)
C10—N1—C6—C5	178.28 (10)	C9—C11—N12—C13	−57.09 (12)
C2—N1—C6—C7	−178.62 (9)	C9—C11—N12—C14	−178.23 (9)
C10—N1—C6—C7	−2.04 (15)	C14—N12—C13—C7	179.28 (9)
C5—C6—C7—C8	−150.56 (10)	C11—N12—C13—C7	58.27 (12)
N1—C6—C7—C8	29.76 (14)	C6—C7—C13—N12	60.91 (12)
C5—C6—C7—C13	88.00 (13)	C8—C7—C13—N12	−61.59 (12)

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···S2i	0.968 (15)	2.893 (14)	3.6861 (12)	139.9 (11)
C7—H7···S2ii	0.994 (14)	2.879 (14)	3.7338 (12)	144.6 (10)
C13—H13A···Cg1ii	0.983 (13)	2.648 (13)	3.5717 (14)	156.5 (10)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5⋯S2i	0.968 (15)	2.893 (14)	3.6861 (12)	139.9 (11)
C7—H7⋯S2ii	0.994 (14)	2.879 (14)	3.7338 (12)	144.6 (10)
C13—H13A⋯Cg1ii	0.983 (13)	2.648 (13)	3.5717 (14)	156.5 (10)

Symmetry codes: (i) ; (ii) .