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

Reem I Al-Wabli; Ali A El-Emam; Obaid S Alroqi; C S Chidan Kumar; Hoong-Kun Fun

doi:10.1107/S2056989015000596

. 2015 Jan 17;71(Pt 2):o115–o116. doi: 10.1107/S2056989015000596

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

Reem I Al-Wabli ^a, Ali A El-Emam ^a,^b,^*, Obaid S Alroqi ^a, C S Chidan Kumar ^c,^d,^‡, Hoong-Kun Fun ^a,^c,^*,^§

PMCID: PMC4384613 PMID: 25878859

Abstract

The title compound, C₁₈H₂₀ClN₃S, is a functionalized triazoline-3-thione derivative. The benzene ring is almost perpendicular 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 triazolethione ring. In the crystal, N—H⋯S hydrogen-bonding interactions link the molecules into chains extending along the c-axis direction. The crystal packing is further stabilized by weak C—H⋯π interactions 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.

Keywords: crystal structure; adamantane; 1,2,4-triazole; starting material; hydrogen bonding

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 _r = 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
Δρ_max = 0.53 e Å⁻³
Δρ_min = −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 ▸).

Supplementary Material

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

e-71-0o115-sup1.cif^{(3MB, cif)}

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

e-71-0o115-Isup2.hkl^{(624.7KB, hkl)}

Click here for additional data file.^{(6.5KB, cml)}

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

Click here for additional data file.^{(1.4MB, tif)}

. 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.^{(2.4MB, tif)}

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

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

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

The financial support of the Deanship of Scientific Research and the Research Centre for Female Scientific and Medical Colleges, King Saud University, is greatly appreciated. CSCK thanks Universiti Sains Malaysia (USM) for a postdoctoral research fellowship.

supplementary crystallographic information

S1. Chemical context

Adamantane derivatives have long been known for their diverse biological activities (Wang et al., 2013) including antiviral activity against influenza (Vernier et al., 1969) and HIV viruses (El-Emam et al., 2004; Balzarini et al., 2009). In addition, adamantane derivatives are known to exhibit marked antibacterial activity (Kadi et al., 2010; Protopopova et al., 2005). In an earlier publication, we reported the synthesis and potent antimicrobial and anti-inflammatory activities of the title compound and its related derivatives (Al-Deeb et al., 2006).

S2. Structural commentary

In the title compound (Fig. 1), the 1,2,4-triazole (N1—N3/C7/C8) ring is nearly planar with a maximum deviation of -0.007 (1) Å at atom N1. The phenyl (C1–C6) ring is almost perpendicular to the near planar 1,2,4-triazole ring with a dihedral angle of 89.61 (5) Å between them. An adamantane group is substituted at the 3-position of the triazolethione ring. The crystal studied was an inversion twin with a 0.50 (3):0.50 (3) domain ratio.

S3. Supramolecular features

In the crystal packing (Fig. 2), the molecules are linked by intermolecular N3–H1N3···S1 hydrogen bonding interactions forming chains extending along along the c axis direction. The crystal packing is further stabilized by weak C–H···π (phenyl) interactions (Table 1) that link the adjacent chains into a two dimensional structure in the bc plane.

S4. Synthesis and crystallization

The title compound was prepared by a literature procedure (Al-Deeb et al., 2006) and crystallized from EtOH/CHCl₃ (1:1) to yield colorless crystals. M·P.: >300 °C.

¹H NMR (CDCl₃, 700.17 MHz): δ 1.55-1.70 (m, 6H, Adamantane-H), 1.86-2.05 (m, 9H, Adamantane-H), 7.25 (d, 2H, Ar—H, J = 8.5 Hz), 7.45 (d, 2H, Ar—H, J = 8.5 Hz), 11.90 (br. s, 1H, NH). 13C NMR (CDCl₃, 176.08 MHz): δ 27.68, 36.03, 36.44, 39.80 (Adamantane-C), 129.95, 131.02, 134.23, 136.42 (Ar—C), 158.41 (C=N), 170.0 (C=S).

S5. Refinement details

The nitrogen-bound H-atom was located in a difference Fourier map and its coordinates and isotropic displacement parameter were refined freely with d(N–H) = 0.92 (2) Å. Other H atoms were positioned geometrically (d(C–H) 0.93–0.98 Å) and refined using a riding model with U_iso(H) = 1.2 U_eq(C). The crystal studied was an inversion twin with a 0.50 (3):0.50 (3) domain ratio.