Crystal structure of 3-(adamantan-1-yl)-4-(4-chloro-phen-yl)-1H-1,2,4-triazole-5(4H)-thione.

The title compound, C18H20ClN3S, is a functionalized triazoline-3-thione derivative. The benzene ring is almost perpendic-ular to the planar 1,2,4-triazole ring [maximum deviation = 0.007 (1) Å] with a dihedral angle of 89.61 (5)° between them and there is an adamantane substituent at the 3-position of the triazole-thione ring. In the crystal, N-H⋯S hydrogen-bonding inter-actions link the mol-ecules into chains extending along the c-axis direction. The crystal packing is further stabilized by weak C-H⋯π inter-actions that link adjacent chains into a two-dimensional structure in the bc plane. The crystal studied was an inversion twin with a 0.50 (3):0.50 (3) domain ratio.

Related literature

For the biological activity of adamantane derivatives, see: Lorenzo et al. (2008 ▸); Wang et al. (2013 ▸); Kadi et al. (2010 ▸); Balzarini et al. (2009 ▸); Protopopova et al. (2005 ▸); Vernier et al. (1969 ▸). For the biological activity of adamantyl-1,2,4-triazole derivatives, see: El-Emam & Ibrahim (1991 ▸); Al-Abdullah et al. (2014 ▸); El-Emam et al. (2004 ▸, 2013 ▸). For related adamantyl-1,2,4-triazole structures, see: El-Emam et al. (2012 ▸), Al-Tamimi et al. (2013 ▸), Al-Omary et al. (2014 ▸); Almutairi et al. (2012 ▸). For the synthesis of the title compound, see: Al-Deeb et al. (2006 ▸).

Experimental

Crystal data

C18H20ClN3S

M = 345.88

Tetragonal,

a = 23.1302 (5) Å

c = 6.4100 (2) Å

V = 3429.39 (18) Å3

Z = 8

Mo Kα radiation

μ = 0.35 mm−1

T = 150 K

0.68 × 0.29 × 0.26 mm

Data collection

Bruker APEXII CCD diffractometer

106262 measured reflections

11408 independent reflections

10584 reflections with I > 2σ(I)

R int = 0.033

Refinement

R[F 2 > 2σ(F 2)] = 0.030

wR(F 2) = 0.082

S = 1.06

11408 reflections

213 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.53 e Å−3

Δρmin = −0.31 e Å−3

Absolute structure: Flack (1983 ▸), 5353 Friedel pairs

Absolute structure parameter: 0.50 (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: SHELXL2013 (Sheldrick, 2015 ▸); molecular graphics: SHELXTL (Sheldrick, 2008 ▸); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▸).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989015000596/sj5439sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015000596/sj5439Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015000596/sj5439Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S2056989015000596/sj5439fig1.tif

The mol­ecular structure of the title compound with atom labels and 50% probability displacement ellipsoids.

Click here for additional data file.

c . DOI: 10.1107/S2056989015000596/sj5439fig2.tif

Crystal packing of the title compound, showing the N–H⋯S hydrogen bonding inter­actions (Table 1) as dashed lines linking the mol­ecules into chains extending along the c axis direction. Other H-atoms are omited for clarity.

CCDC reference: 1042916

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

C18H20ClN3S	Dx = 1.340 Mg m−3
Mr = 345.88	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I4	Cell parameters from 9155 reflections
a = 23.1302 (5) Å	θ = 2.5–40.8°
c = 6.4100 (2) Å	µ = 0.35 mm−1
V = 3429.39 (18) Å3	T = 150 K
Z = 8	Needle, colourless
F(000) = 1456	0.68 × 0.29 × 0.26 mm

Bruker APEXII CCD diffractometer	Rint = 0.033
φ and ω scans	θmax = 41.2°, θmin = 2.5°
106262 measured reflections	h = −42→42
11408 independent reflections	k = −42→42
10584 reflections with I > 2σ(I)	l = −11→11

Refinement on F2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.030	w = 1/[σ2(Fo2) + (0.0483P)2 + 0.551P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.082	(Δ/σ)max = 0.002
S = 1.06	Δρmax = 0.53 e Å−3
11408 reflections	Δρmin = −0.31 e Å−3
213 parameters	Absolute structure: Flack (1983), 5353 Friedel pairs
0 restraints	Absolute structure parameter: 0.50 (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. Refined as a 2-component inversion twin.

	x	y	z	Uiso*/Ueq
S1	0.25120 (2)	0.81338 (2)	0.20570 (4)	0.01558 (4)
Cl1	0.10286 (2)	0.98207 (2)	0.89359 (5)	0.03118 (7)
N1	0.15119 (3)	0.77326 (3)	0.38819 (12)	0.01309 (10)
N2	0.13872 (4)	0.68822 (4)	0.23712 (14)	0.01734 (13)
N3	0.18691 (3)	0.71564 (4)	0.16208 (13)	0.01642 (12)
C1	0.16658 (4)	0.83033 (4)	0.70574 (15)	0.01686 (13)
H1A	0.1901	0.8012	0.7588	0.020*
C2	0.15555 (5)	0.87980 (4)	0.82355 (16)	0.01990 (15)
H2A	0.1715	0.8840	0.9558	0.024*
C3	0.12041 (5)	0.92258 (4)	0.74046 (17)	0.01972 (15)
C4	0.09818 (5)	0.91871 (4)	0.53962 (19)	0.02225 (17)
H4A	0.0761	0.9486	0.4843	0.027*
C5	0.10952 (4)	0.86925 (4)	0.42249 (16)	0.01916 (15)
H5A	0.0953	0.8660	0.2874	0.023*
C6	0.14220 (4)	0.82486 (4)	0.50837 (14)	0.01374 (12)
C7	0.19637 (3)	0.76715 (4)	0.25068 (13)	0.01323 (12)
C8	0.11738 (4)	0.72353 (4)	0.37613 (14)	0.01404 (12)
C9	0.06417 (3)	0.70942 (4)	0.50180 (14)	0.01456 (12)
C10	0.04492 (5)	0.64750 (5)	0.4465 (2)	0.02441 (19)
H10A	0.0368	0.6450	0.2983	0.029*
H10B	0.0758	0.6206	0.4784	0.029*
C11	−0.00943 (6)	0.63104 (5)	0.5707 (2)	0.0292 (2)
H11A	−0.0214	0.5918	0.5330	0.035*
C12	−0.05832 (5)	0.67338 (6)	0.5199 (2)	0.0292 (2)
H12A	−0.0673	0.6716	0.3722	0.035*
H12B	−0.0928	0.6628	0.5971	0.035*
C13	−0.03997 (4)	0.73459 (6)	0.5782 (2)	0.02497 (19)
H13A	−0.0715	0.7615	0.5465	0.030*
C14	−0.02609 (5)	0.73732 (7)	0.8112 (2)	0.0307 (2)
H14A	−0.0145	0.7763	0.8487	0.037*
H14B	−0.0602	0.7274	0.8916	0.037*
C15	0.02267 (5)	0.69501 (7)	0.86116 (18)	0.0303 (3)
H15A	0.0313	0.6967	1.0107	0.036*
C16	0.07706 (4)	0.71160 (6)	0.73728 (16)	0.0253 (2)
H16A	0.1082	0.6850	0.7703	0.030*
H16B	0.0893	0.7503	0.7759	0.030*
C17	0.00415 (6)	0.63344 (7)	0.8040 (3)	0.0356 (3)
H17A	0.0349	0.6065	0.8369	0.043*
H17B	−0.0298	0.6226	0.8838	0.043*
C18	0.01416 (4)	0.75172 (5)	0.45273 (18)	0.02095 (16)
H18A	0.0256	0.7908	0.4888	0.025*
H18B	0.0055	0.7507	0.3047	0.025*
H1N3	0.2084 (9)	0.6995 (9)	0.057 (4)	0.029 (5)*

	U11	U22	U33	U12	U13	U23
S1	0.01413 (8)	0.01610 (8)	0.01653 (8)	−0.00195 (6)	0.00022 (6)	0.00131 (6)
Cl1	0.04393 (16)	0.01649 (9)	0.03312 (14)	0.00301 (9)	0.01278 (12)	−0.00681 (9)
N1	0.0119 (2)	0.0135 (2)	0.0139 (3)	0.00076 (19)	0.0009 (2)	−0.0017 (2)
N2	0.0145 (3)	0.0176 (3)	0.0200 (3)	−0.0026 (2)	0.0042 (2)	−0.0047 (2)
N3	0.0140 (3)	0.0175 (3)	0.0178 (3)	−0.0019 (2)	0.0040 (2)	−0.0052 (2)
C1	0.0189 (3)	0.0158 (3)	0.0158 (3)	0.0034 (2)	−0.0032 (3)	−0.0026 (3)
C2	0.0251 (4)	0.0178 (3)	0.0168 (4)	0.0013 (3)	−0.0005 (3)	−0.0038 (3)
C3	0.0226 (4)	0.0136 (3)	0.0230 (4)	0.0011 (3)	0.0052 (3)	−0.0030 (3)
C4	0.0248 (4)	0.0151 (3)	0.0269 (5)	0.0065 (3)	−0.0008 (3)	0.0000 (3)
C5	0.0211 (4)	0.0170 (3)	0.0193 (4)	0.0048 (3)	−0.0030 (3)	0.0002 (3)
C6	0.0133 (3)	0.0127 (3)	0.0152 (3)	0.0021 (2)	0.0000 (2)	−0.0015 (2)
C7	0.0117 (3)	0.0146 (3)	0.0134 (3)	0.0007 (2)	0.0000 (2)	−0.0005 (2)
C8	0.0120 (3)	0.0152 (3)	0.0149 (3)	0.0001 (2)	0.0010 (2)	−0.0016 (2)
C9	0.0113 (3)	0.0177 (3)	0.0146 (3)	−0.0002 (2)	0.0011 (2)	0.0002 (3)
C10	0.0227 (4)	0.0184 (4)	0.0322 (5)	−0.0046 (3)	0.0090 (4)	−0.0016 (3)
C11	0.0251 (5)	0.0242 (4)	0.0382 (6)	−0.0082 (4)	0.0103 (4)	0.0016 (4)
C12	0.0150 (4)	0.0438 (6)	0.0288 (5)	−0.0089 (4)	−0.0016 (3)	0.0016 (5)
C13	0.0125 (3)	0.0319 (5)	0.0305 (5)	0.0038 (3)	0.0031 (3)	0.0058 (4)
C14	0.0208 (4)	0.0435 (7)	0.0280 (5)	−0.0009 (4)	0.0101 (4)	−0.0069 (5)
C15	0.0181 (4)	0.0568 (8)	0.0161 (4)	−0.0046 (4)	0.0023 (3)	0.0064 (4)
C16	0.0140 (3)	0.0462 (6)	0.0157 (4)	−0.0035 (4)	−0.0010 (3)	0.0036 (4)
C17	0.0241 (5)	0.0438 (7)	0.0388 (7)	0.0009 (5)	0.0085 (5)	0.0235 (6)
C18	0.0134 (3)	0.0238 (4)	0.0256 (4)	0.0034 (3)	0.0018 (3)	0.0055 (3)

S1—C7	1.6836 (9)	C10—H10A	0.9700
Cl1—C3	1.7384 (10)	C10—H10B	0.9700
N1—C7	1.3744 (11)	C11—C17	1.529 (2)
N1—C8	1.3931 (11)	C11—C12	1.531 (2)
N1—C6	1.4355 (11)	C11—H11A	0.9800
N2—C8	1.3056 (12)	C12—C13	1.5246 (19)
N2—N3	1.3696 (11)	C12—H12A	0.9700
N3—C7	1.3379 (12)	C12—H12B	0.9700
N3—H1N3	0.92 (2)	C13—C14	1.529 (2)
C1—C6	1.3909 (13)	C13—C18	1.5399 (15)
C1—C2	1.3946 (13)	C13—H13A	0.9800
C1—H1A	0.9300	C14—C15	1.527 (2)
C2—C3	1.3869 (14)	C14—H14A	0.9700
C2—H2A	0.9300	C14—H14B	0.9700
C3—C4	1.3892 (16)	C15—C17	1.532 (2)
C4—C5	1.3933 (14)	C15—C16	1.5362 (15)
C4—H4A	0.9300	C15—H15A	0.9800
C5—C6	1.3889 (12)	C16—H16A	0.9700
C5—H5A	0.9300	C16—H16B	0.9700
C8—C9	1.5067 (12)	C17—H17A	0.9700
C9—C16	1.5394 (14)	C17—H17B	0.9700
C9—C10	1.5413 (14)	C18—H18A	0.9700
C9—C18	1.5473 (13)	C18—H18B	0.9700
C10—C11	1.5359 (15)
C7—N1—C8	107.83 (7)	C17—C11—H11A	109.4
C7—N1—C6	122.67 (7)	C12—C11—H11A	109.4
C8—N1—C6	129.42 (7)	C10—C11—H11A	109.4
C8—N2—N3	104.93 (7)	C13—C12—C11	109.64 (9)
C7—N3—N2	113.35 (7)	C13—C12—H12A	109.7
C7—N3—H1N3	125.9 (14)	C11—C12—H12A	109.7
N2—N3—H1N3	120.7 (14)	C13—C12—H12B	109.7
C6—C1—C2	119.54 (8)	C11—C12—H12B	109.7
C6—C1—H1A	120.2	H12A—C12—H12B	108.2
C2—C1—H1A	120.2	C12—C13—C14	109.65 (11)
C3—C2—C1	118.99 (9)	C12—C13—C18	109.72 (10)
C3—C2—H2A	120.5	C14—C13—C18	109.20 (9)
C1—C2—H2A	120.5	C12—C13—H13A	109.4
C2—C3—C4	121.80 (9)	C14—C13—H13A	109.4
C2—C3—Cl1	119.00 (8)	C18—C13—H13A	109.4
C4—C3—Cl1	119.20 (8)	C15—C14—C13	109.46 (10)
C3—C4—C5	118.85 (9)	C15—C14—H14A	109.8
C3—C4—H4A	120.6	C13—C14—H14A	109.8
C5—C4—H4A	120.6	C15—C14—H14B	109.8
C6—C5—C4	119.73 (9)	C13—C14—H14B	109.8
C6—C5—H5A	120.1	H14A—C14—H14B	108.2
C4—C5—H5A	120.1	C14—C15—C17	109.82 (10)
C5—C6—C1	120.93 (8)	C14—C15—C16	109.66 (11)
C5—C6—N1	118.74 (8)	C17—C15—C16	109.74 (11)
C1—C6—N1	120.33 (7)	C14—C15—H15A	109.2
N3—C7—N1	103.86 (7)	C17—C15—H15A	109.2
N3—C7—S1	128.03 (7)	C16—C15—H15A	109.2
N1—C7—S1	128.11 (7)	C15—C16—C9	109.88 (8)
N2—C8—N1	110.01 (8)	C15—C16—H16A	109.7
N2—C8—C9	122.57 (8)	C9—C16—H16A	109.7
N1—C8—C9	127.42 (8)	C15—C16—H16B	109.7
C8—C9—C16	111.04 (7)	C9—C16—H16B	109.7
C8—C9—C10	108.32 (7)	H16A—C16—H16B	108.2
C16—C9—C10	108.17 (9)	C11—C17—C15	108.97 (10)
C8—C9—C18	111.41 (8)	C11—C17—H17A	109.9
C16—C9—C18	108.87 (8)	C15—C17—H17A	109.9
C10—C9—C18	108.96 (8)	C11—C17—H17B	109.9
C11—C10—C9	110.34 (9)	C15—C17—H17B	109.9
C11—C10—H10A	109.6	H17A—C17—H17B	108.3
C9—C10—H10A	109.6	C13—C18—C9	109.81 (8)
C11—C10—H10B	109.6	C13—C18—H18A	109.7
C9—C10—H10B	109.6	C9—C18—H18A	109.7
H10A—C10—H10B	108.1	C13—C18—H18B	109.7
C17—C11—C12	109.66 (11)	C9—C18—H18B	109.7
C17—C11—C10	109.25 (11)	H18A—C18—H18B	108.2
C12—C11—C10	109.63 (10)
C8—N2—N3—C7	0.12 (11)	N1—C8—C9—C10	−175.22 (9)
C6—C1—C2—C3	−0.08 (15)	N2—C8—C9—C18	−115.92 (10)
C1—C2—C3—C4	−3.09 (16)	N1—C8—C9—C18	64.95 (12)
C1—C2—C3—Cl1	175.90 (8)	C8—C9—C10—C11	−179.89 (10)
C2—C3—C4—C5	2.89 (17)	C16—C9—C10—C11	59.67 (12)
Cl1—C3—C4—C5	−176.10 (9)	C18—C9—C10—C11	−58.54 (13)
C3—C4—C5—C6	0.48 (16)	C9—C10—C11—C17	−60.75 (14)
C4—C5—C6—C1	−3.62 (15)	C9—C10—C11—C12	59.44 (14)
C4—C5—C6—N1	177.30 (9)	C17—C11—C12—C13	59.98 (13)
C2—C1—C6—C5	3.41 (14)	C10—C11—C12—C13	−59.96 (14)
C2—C1—C6—N1	−177.52 (9)	C11—C12—C13—C14	−59.57 (12)
C7—N1—C6—C5	88.15 (11)	C11—C12—C13—C18	60.37 (13)
C8—N1—C6—C5	−88.12 (12)	C12—C13—C14—C15	59.55 (12)
C7—N1—C6—C1	−90.93 (11)	C18—C13—C14—C15	−60.70 (14)
C8—N1—C6—C1	92.80 (11)	C13—C14—C15—C17	−59.99 (13)
N2—N3—C7—N1	−0.81 (10)	C13—C14—C15—C16	60.67 (14)
N2—N3—C7—S1	178.68 (7)	C14—C15—C16—C9	−60.06 (15)
C8—N1—C7—N3	1.15 (9)	C17—C15—C16—C9	60.65 (14)
C6—N1—C7—N3	−175.82 (8)	C8—C9—C16—C15	−178.05 (10)
C8—N1—C7—S1	−178.34 (7)	C10—C9—C16—C15	−59.33 (13)
C6—N1—C7—S1	4.69 (12)	C18—C9—C16—C15	58.94 (13)
N3—N2—C8—N1	0.64 (10)	C12—C11—C17—C15	−59.90 (12)
N3—N2—C8—C9	−178.62 (8)	C10—C11—C17—C15	60.27 (13)
C7—N1—C8—N2	−1.17 (10)	C14—C15—C17—C11	60.10 (13)
C6—N1—C8—N2	175.53 (9)	C16—C15—C17—C11	−60.52 (13)
C7—N1—C8—C9	178.05 (8)	C12—C13—C18—C9	−59.95 (12)
C6—N1—C8—C9	−5.25 (15)	C14—C13—C18—C9	60.26 (13)
N2—C8—C9—C16	122.54 (11)	C8—C9—C18—C13	178.01 (9)
N1—C8—C9—C16	−56.58 (13)	C16—C9—C18—C13	−59.20 (12)
N2—C8—C9—C10	3.91 (13)	C10—C9—C18—C13	58.56 (12)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H1N3···S1i	0.92 (2)	2.46 (2)	3.3253 (9)	158.4 (19)
C13—H13A···Cg2ii	0.98	2.97	3.8881 (13)	156

Table 1

Hydrogen-bond geometry (, )

Cg2 is the centroid of the C1C6 phenyl ring.

DHA	DH	HA	D A	DHA
N3H1N3S1i	0.92(2)	2.46(2)	3.3253(9)	158.4(19)
C13H13A Cg2ii	0.98	2.97	3.8881(13)	156

Symmetry codes: (i) ; (ii) .