3-(Adamantan-1-yl)-4-benzyl-1H-1,2,4-triazole-5(4H)-thione.

The title compound, C19H23N3S, is a functionalized triazoline-3-thione derivative. The benzyl ring is almost normal to the planar 1,2,4-triazole ring (r.m.s. deviation = 0.007 Å) with a dihedral angle of 86.90 (7)°. In the crystal, molecules are linked by pairs of N-H⋯S hydrogen bonds, forming inversion dimers that enclose R 2 (2)(8) loops. The crystal packing is further stabilized by weak C-H⋯π inter-actions that link adjacent dimeric units into supra-molecular chains extending along the a-axis direction.

Related literature

For the biological activity of adamantane derivatives, see: Lorenzo et al. (2008 ▶); Al-Deeb et al. (2006 ▶); Wang et al. (2013 ▶); El-Emam et al. (2004 ▶); Kadi et al. (2010 ▶); Balzarini et al. (2009 ▶); Protopopova et al. (2005 ▶); Vernier et al. (1969 ▶). For related adamantyl-1,2,4-triazole structures, see: El-Emam et al. (2012 ▶), Al-Tamimi et al. (2013 ▶). For the synthesis of the title compound, see El-Emam & Ibrahim (1991 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C19H23N3S

M = 325.46

Triclinic,

a = 7.6407 (4) Å

b = 10.5150 (5) Å

c = 12.3434 (5) Å

α = 67.1806 (13)°

β = 72.9688 (13)°

γ = 70.0695 (14)°

V = 844.42 (7) Å3

Z = 2

Mo Kα radiation

μ = 0.20 mm−1

T = 293 K

0.60 × 0.48 × 0.34 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.891, T max = 0.937

43581 measured reflections

5166 independent reflections

4651 reflections with I > 2σ(I)

R int = 0.029

Refinement

R[F 2 > 2σ(F 2)] = 0.046

wR(F 2) = 0.127

S = 1.08

5166 reflections

212 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.31 e Å−3

Δρmin = −0.56 e Å−3

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); 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 and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536814013257/sj5408sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814013257/sj5408Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814013257/sj5408Isup3.cml

CCDC reference: 1007119

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

C19H23N3S	Z = 2
Mr = 325.46	F(000) = 348
Triclinic, P1	Dx = 1.280 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.6407 (4) Å	Cell parameters from 9608 reflections
b = 10.5150 (5) Å	θ = 2.9–30.6°
c = 12.3434 (5) Å	µ = 0.20 mm−1
α = 67.1806 (13)°	T = 293 K
β = 72.9688 (13)°	Block, colourless
γ = 70.0695 (14)°	0.60 × 0.48 × 0.34 mm
V = 844.42 (7) Å3

Bruker APEXII CCD diffractometer	5166 independent reflections
Radiation source: fine-focus sealed tube	4651 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
φ and ω scans	θmax = 30.6°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −10→10
Tmin = 0.891, Tmax = 0.937	k = −15→15
43581 measured reflections	l = −17→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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.127	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ2(Fo2) + (0.0747P)2 + 0.1424P] where P = (Fo2 + 2Fc2)/3
5166 reflections	(Δ/σ)max = 0.001
212 parameters	Δρmax = 0.31 e Å−3
0 restraints	Δρmin = −0.56 e Å−3

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
S1	1.05370 (4)	0.44991 (3)	0.32578 (3)	0.03965 (10)
N1	0.70863 (12)	0.63160 (9)	0.28216 (7)	0.02792 (16)
N2	0.74865 (14)	0.58334 (11)	0.45903 (8)	0.0360 (2)
N3	0.57266 (14)	0.67716 (11)	0.45231 (8)	0.0359 (2)
C1	0.75626 (15)	0.49115 (13)	0.03402 (10)	0.0363 (2)
H1A	0.8142	0.5555	−0.0302	0.044*
C2	0.71844 (19)	0.38114 (15)	0.01658 (13)	0.0471 (3)
H2A	0.7512	0.3719	−0.0593	0.057*
C3	0.6325 (2)	0.28550 (15)	0.11137 (15)	0.0522 (3)
H3A	0.6073	0.2118	0.0995	0.063*
C4	0.5840 (2)	0.29922 (14)	0.22381 (14)	0.0497 (3)
H4A	0.5253	0.2349	0.2876	0.060*
C5	0.62220 (17)	0.40876 (12)	0.24249 (10)	0.0390 (2)
H5A	0.5903	0.4169	0.3187	0.047*
C6	0.70774 (13)	0.50549 (10)	0.14754 (8)	0.02895 (19)
C7	0.75127 (15)	0.62875 (11)	0.15983 (8)	0.03048 (19)
H7A	0.8846	0.6242	0.1282	0.037*
H7B	0.6793	0.7175	0.1113	0.037*
C8	0.83679 (14)	0.55430 (10)	0.35740 (9)	0.03030 (19)
C9	0.54907 (13)	0.70511 (10)	0.34398 (8)	0.02803 (18)
C10	0.37568 (13)	0.81094 (10)	0.29687 (8)	0.02757 (18)
C11	0.22454 (18)	0.84649 (16)	0.40233 (11)	0.0460 (3)
H11A	0.1894	0.7604	0.4584	0.055*
H11B	0.2761	0.8830	0.4439	0.055*
C12	0.04846 (19)	0.95844 (17)	0.35680 (13)	0.0513 (3)
H12A	−0.0461	0.9806	0.4247	0.062*
C13	0.1044 (2)	1.09463 (16)	0.26935 (19)	0.0642 (4)
H13A	0.1566	1.1326	0.3094	0.077*
H13B	−0.0065	1.1663	0.2411	0.077*
C14	0.2523 (2)	1.05937 (13)	0.16312 (15)	0.0553 (4)
H14A	0.2873	1.1465	0.1064	0.066*
C15	0.1686 (2)	0.99973 (17)	0.10091 (13)	0.0546 (3)
H15A	0.0585	1.0705	0.0709	0.065*
H15B	0.2614	0.9773	0.0336	0.065*
C16	0.11210 (18)	0.86562 (14)	0.18917 (12)	0.0436 (3)
H16A	0.0581	0.8279	0.1488	0.052*
C17	0.28778 (16)	0.75284 (12)	0.23410 (11)	0.0380 (2)
H17A	0.3800	0.7290	0.1672	0.046*
H17B	0.2524	0.6667	0.2897	0.046*
C18	0.42886 (18)	0.94874 (12)	0.20848 (12)	0.0428 (3)
H18A	0.4818	0.9870	0.2479	0.051*
H18B	0.5239	0.9277	0.1415	0.051*
C19	−0.03504 (18)	0.90065 (16)	0.29388 (14)	0.0499 (3)
H19A	−0.1464	0.9712	0.2654	0.060*
H19B	−0.0728	0.8153	0.3493	0.060*
H1N2	0.798 (3)	0.5628 (19)	0.5188 (16)	0.056 (5)*

	U11	U22	U33	U12	U13	U23
S1	0.03414 (15)	0.04240 (16)	0.04517 (17)	0.00090 (11)	−0.01292 (11)	−0.02211 (12)
N1	0.0301 (4)	0.0295 (4)	0.0249 (3)	−0.0049 (3)	−0.0058 (3)	−0.0114 (3)
N2	0.0363 (4)	0.0423 (5)	0.0276 (4)	−0.0032 (4)	−0.0107 (3)	−0.0118 (3)
N3	0.0351 (4)	0.0435 (5)	0.0264 (4)	−0.0027 (4)	−0.0068 (3)	−0.0140 (3)
C1	0.0341 (5)	0.0463 (6)	0.0330 (5)	−0.0067 (4)	−0.0059 (4)	−0.0208 (4)
C2	0.0439 (6)	0.0582 (7)	0.0537 (7)	−0.0057 (5)	−0.0127 (5)	−0.0368 (6)
C3	0.0468 (7)	0.0482 (7)	0.0780 (9)	−0.0082 (5)	−0.0187 (6)	−0.0355 (7)
C4	0.0485 (7)	0.0399 (6)	0.0619 (8)	−0.0167 (5)	−0.0066 (6)	−0.0158 (5)
C5	0.0414 (6)	0.0381 (5)	0.0367 (5)	−0.0109 (4)	−0.0020 (4)	−0.0144 (4)
C6	0.0261 (4)	0.0323 (4)	0.0295 (4)	−0.0029 (3)	−0.0052 (3)	−0.0149 (3)
C7	0.0348 (5)	0.0337 (5)	0.0238 (4)	−0.0092 (4)	−0.0022 (3)	−0.0122 (3)
C8	0.0327 (4)	0.0295 (4)	0.0302 (4)	−0.0067 (3)	−0.0087 (3)	−0.0103 (3)
C9	0.0301 (4)	0.0295 (4)	0.0242 (4)	−0.0063 (3)	−0.0044 (3)	−0.0101 (3)
C10	0.0292 (4)	0.0276 (4)	0.0256 (4)	−0.0053 (3)	−0.0050 (3)	−0.0101 (3)
C11	0.0372 (5)	0.0618 (7)	0.0336 (5)	0.0026 (5)	−0.0053 (4)	−0.0240 (5)
C12	0.0377 (6)	0.0647 (8)	0.0516 (7)	0.0076 (5)	−0.0096 (5)	−0.0357 (6)
C13	0.0572 (8)	0.0428 (7)	0.1067 (13)	0.0107 (6)	−0.0372 (9)	−0.0429 (8)
C14	0.0536 (7)	0.0294 (5)	0.0729 (9)	−0.0095 (5)	−0.0244 (7)	0.0022 (5)
C15	0.0523 (7)	0.0577 (8)	0.0418 (6)	−0.0021 (6)	−0.0200 (6)	−0.0058 (6)
C16	0.0399 (6)	0.0473 (6)	0.0527 (7)	−0.0034 (5)	−0.0192 (5)	−0.0243 (5)
C17	0.0377 (5)	0.0351 (5)	0.0480 (6)	−0.0052 (4)	−0.0136 (4)	−0.0199 (4)
C18	0.0402 (6)	0.0310 (5)	0.0536 (7)	−0.0126 (4)	−0.0123 (5)	−0.0043 (4)
C19	0.0324 (5)	0.0551 (7)	0.0610 (8)	−0.0069 (5)	−0.0090 (5)	−0.0207 (6)

S1—C8	1.6784 (10)	C10—C17	1.5415 (14)
N1—C8	1.3735 (12)	C11—C12	1.5368 (18)
N1—C9	1.3915 (12)	C11—H11A	0.9700
N1—C7	1.4586 (12)	C11—H11B	0.9700
N2—C8	1.3351 (13)	C12—C19	1.517 (2)
N2—N3	1.3732 (13)	C12—C13	1.532 (3)
N2—H1N2	0.846 (19)	C12—H12A	0.9800
N3—C9	1.3065 (12)	C13—C14	1.535 (3)
C1—C2	1.3876 (16)	C13—H13A	0.9700
C1—C6	1.3946 (13)	C13—H13B	0.9700
C1—H1A	0.9300	C14—C15	1.525 (2)
C2—C3	1.378 (2)	C14—C18	1.5344 (18)
C2—H2A	0.9300	C14—H14A	0.9800
C3—C4	1.379 (2)	C15—C16	1.520 (2)
C3—H3A	0.9300	C15—H15A	0.9700
C4—C5	1.3929 (17)	C15—H15B	0.9700
C4—H4A	0.9300	C16—C19	1.5185 (19)
C5—C6	1.3840 (15)	C16—C17	1.5351 (16)
C5—H5A	0.9300	C16—H16A	0.9800
C6—C7	1.5131 (13)	C17—H17A	0.9700
C7—H7A	0.9700	C17—H17B	0.9700
C7—H7B	0.9700	C18—H18A	0.9700
C9—C10	1.5086 (13)	C18—H18B	0.9700
C10—C11	1.5396 (14)	C19—H19A	0.9700
C10—C18	1.5396 (14)	C19—H19B	0.9700
C8—N1—C9	108.06 (8)	C19—C12—C13	109.53 (12)
C8—N1—C7	121.22 (8)	C19—C12—C11	109.84 (11)
C9—N1—C7	130.71 (8)	C13—C12—C11	109.41 (12)
C8—N2—N3	113.41 (9)	C19—C12—H12A	109.3
C8—N2—H1N2	126.3 (12)	C13—C12—H12A	109.3
N3—N2—H1N2	119.1 (12)	C11—C12—H12A	109.3
C9—N3—N2	104.79 (8)	C12—C13—C14	109.13 (10)
C2—C1—C6	120.22 (11)	C12—C13—H13A	109.9
C2—C1—H1A	119.9	C14—C13—H13A	109.9
C6—C1—H1A	119.9	C12—C13—H13B	109.9
C3—C2—C1	120.15 (11)	C14—C13—H13B	109.9
C3—C2—H2A	119.9	H13A—C13—H13B	108.3
C1—C2—H2A	119.9	C15—C14—C18	109.88 (12)
C2—C3—C4	119.91 (11)	C15—C14—C13	109.38 (12)
C2—C3—H3A	120.0	C18—C14—C13	109.37 (13)
C4—C3—H3A	120.0	C15—C14—H14A	109.4
C3—C4—C5	120.43 (12)	C18—C14—H14A	109.4
C3—C4—H4A	119.8	C13—C14—H14A	109.4
C5—C4—H4A	119.8	C16—C15—C14	109.44 (11)
C6—C5—C4	119.92 (11)	C16—C15—H15A	109.8
C6—C5—H5A	120.0	C14—C15—H15A	109.8
C4—C5—H5A	120.0	C16—C15—H15B	109.8
C5—C6—C1	119.36 (10)	C14—C15—H15B	109.8
C5—C6—C7	123.23 (9)	H15A—C15—H15B	108.2
C1—C6—C7	117.40 (9)	C19—C16—C15	109.94 (11)
N1—C7—C6	114.42 (8)	C19—C16—C17	109.96 (11)
N1—C7—H7A	108.7	C15—C16—C17	109.53 (10)
C6—C7—H7A	108.7	C19—C16—H16A	109.1
N1—C7—H7B	108.7	C15—C16—H16A	109.1
C6—C7—H7B	108.7	C17—C16—H16A	109.1
H7A—C7—H7B	107.6	C16—C17—C10	109.85 (9)
N2—C8—N1	103.79 (9)	C16—C17—H17A	109.7
N2—C8—S1	129.01 (8)	C10—C17—H17A	109.7
N1—C8—S1	127.19 (8)	C16—C17—H17B	109.7
N3—C9—N1	109.93 (9)	C10—C17—H17B	109.7
N3—C9—C10	122.14 (9)	H17A—C17—H17B	108.2
N1—C9—C10	127.80 (8)	C14—C18—C10	109.81 (9)
C9—C10—C11	108.87 (8)	C14—C18—H18A	109.7
C9—C10—C18	109.22 (8)	C10—C18—H18A	109.7
C11—C10—C18	108.93 (10)	C14—C18—H18B	109.7
C9—C10—C17	112.77 (8)	C10—C18—H18B	109.7
C11—C10—C17	107.69 (9)	H18A—C18—H18B	108.2
C18—C10—C17	109.28 (9)	C12—C19—C16	109.24 (10)
C12—C11—C10	110.21 (10)	C12—C19—H19A	109.8
C12—C11—H11A	109.6	C16—C19—H19A	109.8
C10—C11—H11A	109.6	C12—C19—H19B	109.8
C12—C11—H11B	109.6	C16—C19—H19B	109.8
C10—C11—H11B	109.6	H19A—C19—H19B	108.3
H11A—C11—H11B	108.1
C8—N2—N3—C9	1.25 (13)	N3—C9—C10—C17	−132.65 (10)
C6—C1—C2—C3	0.06 (19)	N1—C9—C10—C17	51.96 (13)
C1—C2—C3—C4	0.0 (2)	C9—C10—C11—C12	177.91 (10)
C2—C3—C4—C5	−0.4 (2)	C18—C10—C11—C12	58.90 (14)
C3—C4—C5—C6	0.7 (2)	C17—C10—C11—C12	−59.52 (13)
C4—C5—C6—C1	−0.56 (17)	C10—C11—C12—C19	60.43 (15)
C4—C5—C6—C7	179.01 (11)	C10—C11—C12—C13	−59.83 (15)
C2—C1—C6—C5	0.21 (16)	C19—C12—C13—C14	−60.12 (15)
C2—C1—C6—C7	−179.39 (10)	C11—C12—C13—C14	60.33 (15)
C8—N1—C7—C6	85.08 (11)	C12—C13—C14—C15	59.48 (15)
C9—N1—C7—C6	−95.63 (12)	C12—C13—C14—C18	−60.91 (15)
C5—C6—C7—N1	4.38 (14)	C18—C14—C15—C16	60.57 (16)
C1—C6—C7—N1	−176.04 (9)	C13—C14—C15—C16	−59.51 (15)
N3—N2—C8—N1	−1.21 (12)	C14—C15—C16—C19	60.18 (14)
N3—N2—C8—S1	178.19 (8)	C14—C15—C16—C17	−60.75 (14)
C9—N1—C8—N2	0.70 (11)	C19—C16—C17—C10	−60.82 (13)
C7—N1—C8—N2	−179.87 (9)	C15—C16—C17—C10	60.09 (13)
C9—N1—C8—S1	−178.72 (7)	C9—C10—C17—C16	179.74 (9)
C7—N1—C8—S1	0.71 (14)	C11—C10—C17—C16	59.61 (12)
N2—N3—C9—N1	−0.74 (11)	C18—C10—C17—C16	−58.58 (12)
N2—N3—C9—C10	−176.86 (9)	C15—C14—C18—C10	−59.41 (15)
C8—N1—C9—N3	0.04 (11)	C13—C14—C18—C10	60.67 (14)
C7—N1—C9—N3	−179.32 (10)	C9—C10—C18—C14	−178.04 (10)
C8—N1—C9—C10	175.88 (9)	C11—C10—C18—C14	−59.25 (14)
C7—N1—C9—C10	−3.48 (16)	C17—C10—C18—C14	58.16 (13)
N3—C9—C10—C11	−13.20 (14)	C13—C12—C19—C16	60.51 (14)
N1—C9—C10—C11	171.41 (10)	C11—C12—C19—C16	−59.68 (15)
N3—C9—C10—C18	105.64 (11)	C15—C16—C19—C12	−60.60 (14)
N1—C9—C10—C18	−69.75 (12)	C17—C16—C19—C12	60.06 (14)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1N2···S1i	0.85 (2)	2.44 (2)	3.2753 (11)	169.1 (18)
C19—H19B···Cg1ii	0.97	2.85	3.7885 (17)	141

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the N1–N3/C8/C9 triazole ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1N2⋯S1i	0.85 (2)	2.44 (2)	3.2753 (11)	169.1 (18)
C19—H19B⋯Cg1ii	0.97	2.85	3.7885 (17)	141

Symmetry codes: (i) ; (ii) .