4-Phenyl-1,2,4-tri-aza-spiro-[4.4]non-1-ene-3-thione.

In the title compound, C12H13N3S, the 4,5-di-hydro-3H-1,2,4-triazole system is nearly planar [maximum deviation = 0.014 (2) Å], while the cyclo-pentane ring adopts a half-chair conformation. The dihedral angle between the mean plane of the 4,5-di-hydro-3H-1,2,4-triazole-3-thione ring and the phenyl ring is 85.49 (14)°, with the S atom 0.046 (1) Å out of the former plane. The crystal structure is stabilized only by van der Waals inter-actions. The investigated crystal was found to be a non-merohedral two-component twin by a 180° rotation about c*, with a refined value of the minor twin fraction of 0.12203 (18).

Related literature

For wide-spectrum medicinal applications of spiro compounds incorporating heterocyclic substructures, see: Sar et al. (2006 ▶); Park et al. (2007 ▶); Nakao et al. (2008 ▶); Obniska & Kamiński (2006 ▶); Kamiński et al. (2008 ▶); Obniska et al. (2006 ▶); Chin et al. (2008 ▶); Wang et al. (2007 ▶); Pawar et al. (2009 ▶); Thadhaney et al. (2010 ▶); (Chande et al., 2005 ▶); Shimakawa et al. (2003 ▶); Sarma et al. (2010 ▶). For industrial uses of heterocyclic spiro compounds, see: Rongbao et al. (2009 ▶); Hu et al. (2006 ▶); Méhes et al. (2012 ▶); Billah et al. (2008 ▶). For the crystal structure of a similar compound, see: Akkurt et al. (2013 ▶). For ring-puckering parameters, see: Cremer & Pople (1975 ▶). For the indexing program for twinned crystals, see: Sheldrick (2008a ▶).

Experimental

Crystal data

C12H13N3S

M = 231.32

Monoclinic,

a = 11.4780 (12) Å

b = 12.0452 (12) Å

c = 17.0439 (17) Å

β = 101.3060 (14)°

V = 2310.7 (4) Å3

Z = 8

Mo Kα radiation

μ = 0.26 mm−1

T = 150 K

0.15 × 0.13 × 0.12 mm

Data collection

Bruker SMART APEX CCD diffractometer

Absorption correction: multi-scan (TWINABS; Sheldrick, 2009 ▶) T min = 0.96, T max = 0.97

29725 measured reflections

29725 independent reflections

21519 reflections with I > 2σ(I)

R int = 0.050

Refinement

R[F 2 > 2σ(F 2)] = 0.059

wR(F 2) = 0.168

S = 1.05

29725 reflections

146 parameters

44 restraints

H-atom parameters constrained

Δρmax = 0.62 e Å−3

Δρmin = −0.65 e Å−3

Data collection: APEX2 (Bruker, 2013 ▶); cell refinement: SAINT (Bruker, 2013 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008b ▶); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2008b ▶); molecular graphics: DIAMOND (Brandenburg & Putz, 2012 ▶) and ORTEP-3 for Windows (Farrugia, 2012 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536814005418/rz5108sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814005418/rz5108Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814005418/rz5108Isup3.cml

CCDC reference: 990878

Additional supporting information: crystallographic information; 3D view; checkCIF report

C12H13N3S	F(000) = 976
Mr = 231.32	Dx = 1.330 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 8834 reflections
a = 11.4780 (12) Å	θ = 2.4–29.1°
b = 12.0452 (12) Å	µ = 0.26 mm−1
c = 17.0439 (17) Å	T = 150 K
β = 101.3060 (14)°	Block, orange
V = 2310.7 (4) Å3	0.15 × 0.13 × 0.12 mm
Z = 8

Bruker SMART APEX CCD diffractometer	29725 independent reflections
Radiation source: fine-focus sealed tube	21519 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.050
Detector resolution: 8.3660 pixels mm-1	θmax = 29.2°, θmin = 2.4°
φ and ω scans	h = −15→15
Absorption correction: multi-scan (TWINABS; Sheldrick, 2009)	k = −16→16
Tmin = 0.96, Tmax = 0.97	l = −23→23
29725 measured reflections

Refinement on F2	44 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.059	H-atom parameters constrained
wR(F2) = 0.168	w = 1/[σ2(Fo2) + (0.0674P)2 + 1.7625P] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max < 0.001
29725 reflections	Δρmax = 0.62 e Å−3
146 parameters	Δρmin = −0.65 e Å−3

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

	x	y	z	Uiso*/Ueq
S1	0.33502 (7)	0.94435 (6)	1.03564 (4)	0.0358 (2)
N1	0.42067 (18)	0.80829 (17)	0.93431 (12)	0.0221 (6)
N2	0.5566 (2)	0.7153 (2)	1.02559 (14)	0.0355 (8)
N3	0.5050 (2)	0.7828 (2)	1.06315 (14)	0.0364 (8)
C1	0.4168 (2)	0.8470 (2)	1.00689 (15)	0.0259 (8)
C2	0.5122 (2)	0.7230 (2)	0.93878 (15)	0.0252 (7)
C3	0.4680 (2)	0.6091 (2)	0.90472 (18)	0.0321 (9)
C4	0.5715 (3)	0.5557 (3)	0.8784 (3)	0.0627 (14)
C5	0.6575 (4)	0.6450 (3)	0.8686 (3)	0.0695 (16)
C6	0.6150 (2)	0.7526 (2)	0.89633 (17)	0.0321 (9)
C7	0.3486 (2)	0.8458 (2)	0.86065 (14)	0.0214 (7)
C8	0.2459 (2)	0.7876 (2)	0.82843 (16)	0.0289 (8)
C9	0.1807 (3)	0.8195 (3)	0.75431 (17)	0.0374 (9)
C10	0.2175 (3)	0.9075 (3)	0.71427 (16)	0.0389 (10)
C11	0.3174 (3)	0.9671 (2)	0.74808 (16)	0.0358 (9)
C12	0.3844 (2)	0.9370 (2)	0.82186 (16)	0.0280 (8)
H3A	0.44130	0.56350	0.94620	0.0380*
H3B	0.40080	0.61790	0.85890	0.0380*
H4A	0.60970	0.50130	0.91890	0.0750*
H4B	0.54480	0.51630	0.82710	0.0750*
H5A	0.66400	0.65090	0.81160	0.0840*
H5B	0.73710	0.62700	0.90030	0.0840*
H6A	0.58690	0.80240	0.85030	0.0380*
H6B	0.67980	0.79020	0.93380	0.0380*
H8	0.22050	0.72710	0.85660	0.0350*
H9	0.11060	0.78020	0.73130	0.0450*
H10	0.17400	0.92750	0.66290	0.0470*
H11	0.34040	1.02950	0.72060	0.0430*
H12	0.45330	0.97790	0.84520	0.0340*

	U11	U22	U33	U12	U13	U23
S1	0.0424 (4)	0.0413 (4)	0.0254 (4)	0.0049 (3)	0.0109 (3)	−0.0062 (3)
N1	0.0225 (10)	0.0259 (11)	0.0175 (10)	0.0026 (9)	0.0027 (8)	0.0011 (8)
N2	0.0318 (13)	0.0438 (14)	0.0288 (13)	0.0038 (11)	0.0009 (10)	0.0069 (11)
N3	0.0341 (13)	0.0498 (15)	0.0227 (12)	0.0028 (12)	−0.0006 (10)	0.0044 (11)
C1	0.0259 (13)	0.0331 (14)	0.0181 (12)	−0.0035 (11)	0.0030 (10)	0.0014 (10)
C2	0.0227 (12)	0.0273 (13)	0.0252 (13)	0.0043 (10)	0.0040 (11)	0.0036 (10)
C3	0.0322 (15)	0.0253 (14)	0.0392 (16)	0.0011 (11)	0.0082 (13)	0.0029 (12)
C4	0.042 (2)	0.050 (2)	0.101 (3)	−0.0047 (16)	0.026 (2)	−0.026 (2)
C5	0.070 (3)	0.049 (2)	0.107 (3)	−0.008 (2)	0.060 (3)	−0.016 (2)
C6	0.0243 (13)	0.0354 (16)	0.0385 (16)	0.0022 (11)	0.0110 (12)	0.0045 (12)
C7	0.0243 (12)	0.0245 (13)	0.0151 (11)	0.0056 (10)	0.0030 (9)	−0.0012 (9)
C8	0.0264 (13)	0.0304 (14)	0.0291 (14)	0.0015 (11)	0.0038 (11)	0.0004 (11)
C9	0.0290 (15)	0.0458 (18)	0.0329 (16)	0.0075 (13)	−0.0051 (12)	−0.0081 (13)
C10	0.0472 (18)	0.0466 (18)	0.0201 (13)	0.0245 (15)	−0.0004 (13)	−0.0006 (12)
C11	0.0524 (18)	0.0318 (16)	0.0253 (14)	0.0142 (14)	0.0130 (13)	0.0076 (11)
C12	0.0329 (14)	0.0266 (14)	0.0252 (14)	0.0027 (11)	0.0075 (11)	−0.0001 (10)

S1—C1	1.636 (3)	C10—C11	1.380 (5)
N1—C1	1.331 (3)	C11—C12	1.387 (4)
N1—C2	1.461 (3)	C3—H3A	0.9900
N1—C7	1.434 (3)	C3—H3B	0.9900
N2—N3	1.253 (3)	C4—H4A	0.9900
N2—C2	1.470 (3)	C4—H4B	0.9900
N3—C1	1.470 (3)	C5—H5A	0.9900
C2—C3	1.537 (3)	C5—H5B	0.9900
C2—C6	1.542 (3)	C6—H6A	0.9900
C3—C4	1.495 (4)	C6—H6B	0.9900
C4—C5	1.491 (6)	C8—H8	0.9500
C5—C6	1.494 (5)	C9—H9	0.9500
C7—C8	1.389 (3)	C10—H10	0.9500
C7—C12	1.385 (3)	C11—H11	0.9500
C8—C9	1.390 (4)	C12—H12	0.9500
C9—C10	1.371 (5)
C1—N1—C2	110.7 (2)	C4—C3—H3A	111.00
C1—N1—C7	125.8 (2)	C4—C3—H3B	111.00
C2—N1—C7	123.6 (2)	H3A—C3—H3B	109.00
N3—N2—C2	111.6 (2)	C3—C4—H4A	110.00
N2—N3—C1	110.0 (2)	C3—C4—H4B	110.00
S1—C1—N1	130.9 (2)	C5—C4—H4A	110.00
S1—C1—N3	122.94 (19)	C5—C4—H4B	110.00
N1—C1—N3	106.1 (2)	H4A—C4—H4B	108.00
N1—C2—N2	101.58 (19)	C4—C5—H5A	110.00
N1—C2—C3	115.3 (2)	C4—C5—H5B	110.00
N1—C2—C6	114.9 (2)	C6—C5—H5A	110.00
N2—C2—C3	110.3 (2)	C6—C5—H5B	110.00
N2—C2—C6	109.9 (2)	H5A—C5—H5B	108.00
C3—C2—C6	104.8 (2)	C2—C6—H6A	111.00
C2—C3—C4	105.9 (2)	C2—C6—H6B	111.00
C3—C4—C5	107.8 (3)	C5—C6—H6A	111.00
C4—C5—C6	109.0 (3)	C5—C6—H6B	111.00
C2—C6—C5	106.0 (2)	H6A—C6—H6B	109.00
N1—C7—C8	119.1 (2)	C7—C8—H8	121.00
N1—C7—C12	119.6 (2)	C9—C8—H8	121.00
C8—C7—C12	121.3 (2)	C8—C9—H9	120.00
C7—C8—C9	118.9 (2)	C10—C9—H9	120.00
C8—C9—C10	120.2 (3)	C9—C10—H10	120.00
C9—C10—C11	120.4 (3)	C11—C10—H10	120.00
C10—C11—C12	120.7 (2)	C10—C11—H11	120.00
C7—C12—C11	118.4 (2)	C12—C11—H11	120.00
C2—C3—H3A	111.00	C7—C12—H12	121.00
C2—C3—H3B	111.00	C11—C12—H12	121.00
C2—N1—C1—S1	177.9 (2)	N2—N3—C1—N1	1.5 (3)
C2—N1—C1—N3	−2.4 (3)	N1—C2—C3—C4	153.1 (3)
C7—N1—C1—S1	−0.4 (4)	N2—C2—C3—C4	−92.6 (3)
C7—N1—C1—N3	179.3 (2)	C6—C2—C3—C4	25.7 (3)
C1—N1—C2—N2	2.4 (3)	N1—C2—C6—C5	−149.9 (3)
C1—N1—C2—C3	121.7 (2)	N2—C2—C6—C5	96.3 (3)
C1—N1—C2—C6	−116.2 (2)	C3—C2—C6—C5	−22.2 (3)
C7—N1—C2—N2	−179.3 (2)	C2—C3—C4—C5	−19.6 (4)
C7—N1—C2—C3	−60.0 (3)	C3—C4—C5—C6	5.6 (5)
C7—N1—C2—C6	62.1 (3)	C4—C5—C6—C2	10.6 (4)
C1—N1—C7—C8	−96.5 (3)	N1—C7—C8—C9	−175.6 (2)
C1—N1—C7—C12	85.5 (3)	C12—C7—C8—C9	2.5 (4)
C2—N1—C7—C8	85.5 (3)	N1—C7—C12—C11	175.7 (2)
C2—N1—C7—C12	−92.6 (3)	C8—C7—C12—C11	−2.3 (4)
C2—N2—N3—C1	0.1 (3)	C7—C8—C9—C10	−0.4 (4)
N3—N2—C2—N1	−1.5 (3)	C8—C9—C10—C11	−1.9 (5)
N3—N2—C2—C3	−124.2 (2)	C9—C10—C11—C12	2.1 (5)
N3—N2—C2—C6	120.7 (2)	C10—C11—C12—C7	0.0 (4)
N2—N3—C1—S1	−178.8 (2)