3-(Adamantan-1-yl)-4-methyl-1-[(4-phenyl­piperazin-1-yl)meth­yl]-1H-1,2,4-triazole-5(4H)-thione dichloro­methane hemisolvate

El-Emam, A.A.; Al-Omar, M.A.; Al-Tamimi, A.-M.S.; Ng, S.W.; Tiekink, E.R.T.

doi:10.1107/S1600536812021393

organic compounds

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ISSN: 2056-9890

Volume 68| Part 6| June 2012| Pages o1772-o1773

doi:10.1107/S1600536812021393

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3-(Adamantan-1-yl)-4-methyl-1-[(4-phenylpiperazin-1-yl)methyl]-1H-1,2,4-triazole-5(4H)-thione dichloromethane hemisolvate

Ali A. El-Emam,^a ‡ Mohamed A. Al-Omar,^a Abdul-Malek S. Al-Tamimi,^a Seik Weng Ng ^b,^c and Edward R. T. Tiekink ^b ^*

^aDepartment of Pharmaceutical Chemistry, College of Pharmacy, King Saud University, Riyadh 11451, Saudi Arabia, ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia, and ^cChemistry Department, Faculty of Science, King Abdulaziz University, PO Box 80203 Jeddah, Saudi Arabia
^*Correspondence e-mail: edward.tiekink@gmail.com

(Received 10 May 2012; accepted 11 May 2012; online 19 May 2012)

The asymmetric unit of the title dichloromethane hemisolvate, C₂₄H₃₃N₅S·0.5CH₂Cl₂, comprises an adamantanyl/triazole derivative and half a CH₂Cl₂ molecule of crystallization; the latter is disordered about a twofold axis of symmetry. The piperazine ring has a chair conformation and the two N-bound substituents occupy equatorial positions. The piperazine residue is almost normal to the triazole ring [N—N—C—N torsion angle = −79.9 (3)°] so that to a first approximation, the molecule has an L-shape. Linear supramolecular chains parallel to [001] are formed via C—H⋯S interactions. Two such chains are linked into a double chain via C—H⋯Cl interactions involving the disordered CH₂Cl₂ molecules of solvation.

Related literature

For the diverse biological activities of adamantane derivatives, see: Al-Deeb et al. (2006 ); Al-Omar et al. (2010 ). For related adamantanyl structural studies, see: El-Emam et al. (2012a ,b ). For the preparation of one of the precursor molecules, see: El-Emam & Ibrahim (1991 ).

Experimental

Crystal data

2C₂₄H₃₃N₅S·CH₂Cl₂
M_r = 932.17
Orthorhombic, F d d 2
a = 66.8490 (16) Å
b = 22.1076 (4) Å
c = 6.5109 (1) Å
V = 9622.3 (3) Å³
Z = 8
Cu Kα radiation
μ = 2.38 mm⁻¹
T = 100 K
0.30 × 0.20 × 0.10 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ) T_min = 0.752, T_max = 1.000
18884 measured reflections
4509 independent reflections
4437 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.126
S = 1.09
4509 reflections
299 parameters
19 restraints
H-atom parameters constrained
Δρ_max = 0.41 e Å⁻³
Δρ_min = −1.00 e Å⁻³
Absolute structure: Flack (1983 ), 1772 Friedel pairs
Flack parameter: −0.002 (17)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C14—H14A⋯S1ⁱ	0.99	2.85	3.803 (3)	162
C16—H16A⋯Cl1	0.99	2.73	3.589 (4)	146
Symmetry code: (i) x, y, z-1.

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and DIAMOND (Brandenburg, 2006 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812021393/hg5226sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812021393/hg5226Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812021393/hg5226Isup3.cml

checkCIF report

Comment top

In continuation of our interest in the chemical and pharmacological properties of adamantane derivatives, motivated by their putative biological activities (Al-Deeb et al., 2006; Al-Omar et al., 2010), and as part of on-going structural studies (El-Emam et al., 2012a,b), we synthesized the title compound (I) as a potential chemotherapeutic agent. Herein, we describe the crystal and molecular structure of (I).

The asymmetric unit of (I), Fig. 1, comprises an adamantanyl/triazole derivative and half a CH₂Cl₂ molecule of crystallization. In the organic molecule, the piperazinyl ring has a chair conformation and the two N-bound substituents occupy equatorial positions. The piperazinyl residue is almost normal to the triazole ring with the N2—N3—C14—N4 torsion angle being -79.9 (3)°. To a first approximation, the molecule has an L-shape, as found recently in the 2-hydroxybenzylideneamino derivative (El-Emam et al., 2012a).

In the crystal packing, linear supramolecular chains parallel to [001] are formed via C—H···S interactions, Table 1. These are linked into a double chain via C—H···Cl interactions involving the disordered CH₂Cl₂ molecules of solvation, Fig. 2 and Table 1.

Related literature top

For the diverse biological activities of adamantane derivatives, see: Al-Deeb et al. (2006); Al-Omar et al. (2010). For related adamantanyl structural studies, see: El-Emam et al. (2012a,b). For the preparation of one of the precursor molecules, see: El-Emam & Ibrahim (1991).

Experimental top

A mixture of 3-(1-adamantyl)-4-methyl-4H-1,2,4-triazole-5-thiol (499 mg, 2 mmol), prepared according to the literature method (El-Emam & Ibrahim, 1991), 1-phenylpiperazine (325 mg, 2 mmol) and 37% formaldehyde solution (1 ml), in ethanol (8 ml), was heated under reflux for 15 min. when a clear solution was obtained. Stirring was continued for 12 h. at room temperature and the mixture was allowed to stand overnight. Cold water (5 ml) was slowly added and the mixture was stirred for 20 min. The precipitated crude product was filtered, washed with water, dried, and crystallized from ethanol to yield 635 mg (75%) of the title compound as colourless crystals. M.pt: 423–425 K. Single crystals suitable for X-ray analysis were obtained by slow evaporation of its CH₂Cl₂:EtOH solution held at room temperature (1:1; 5 ml). ¹H NMR (CDCl₃, 500.13 MHz): δ 1.77–1.84 (m, 6H, adamantane-H), 2.14 (s, 6H, adamantane-H), 2.27 (s, 3H, adamantane-H), 3.05 (s, 4H, piperazine-H), 3.27 (s, 4H, piperazine-H), 3.82 (s, 3H, CH₃), 5.20 (s, 2H, CH₂), 6.85–6.93 (m, 3H, Ar—H), 7.25–7.33 (m, 2H, Ar—H). ¹³C NMR (CDCl₃, 125.76 MHz): δ 27.84, 33.97, 36.31, 39.02 (adamantane-C), 31.58 (CH₃), 49.34, 50.40 (piperazine-C), 69.23 (CH₂), 116.27, 119.86, 129.10, 151.33 (Ar—C), 156.31 (triazole C-5), 169.53 (C═S).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular structures of the molecules comprising (I) showing the atom-labelling scheme and displacement ellipsoids at the 70% probability level. The CH₂Cl₂ molecule has 50% occupancy, being disordered over a twofold axis.
	Fig. 2. A view of the linear supramolecular double chain in (I). The C—H···S and C—H···Cl contacts are shown as orange and blue dashed lines, respectively. The CH₂Cl₂ molecule is disordered over two position; both orientations are displayed.

3-(Adamantan-1-yl)-4-methyl-1-[(4-phenylpiperazin-1-yl)methyl]-1H- 1,2,4-triazole-5(4H)-thione dichloromethane hemisolvate top

Crystal data top

2C₂₄H₃₃N₅S·CH₂Cl₂	F(000) = 3984
M_r = 932.17	D_x = 1.287 Mg m⁻³
Orthorhombic, Fdd2	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: F 2 -2d	Cell parameters from 10015 reflections
a = 66.8490 (16) Å	θ = 2.6–76.4°
b = 22.1076 (4) Å	µ = 2.38 mm⁻¹
c = 6.5109 (1) Å	T = 100 K
V = 9622.3 (3) Å³	Prism, colourless
Z = 8	0.30 × 0.20 × 0.10 mm

Data collection top

Agilent SuperNova Dual diffractometer with an Atlas detector	4509 independent reflections
Radiation source: SuperNova (Cu) X-ray Source	4437 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.025
Detector resolution: 10.4041 pixels mm^-1	θ_max = 76.6°, θ_min = 2.6°
ω scan	h = −84→80
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −25→27
T_min = 0.752, T_max = 1.000	l = −7→8
18884 measured reflections

Refinement top

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)] = 0.045	H-atom parameters constrained
wR(F²) = 0.126	w = 1/[σ²(F_o²) + (0.0825P)² + 16.7617P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max = 0.002
4509 reflections	Δρ_max = 0.41 e Å⁻³
299 parameters	Δρ_min = −1.00 e Å⁻³
19 restraints	Absolute structure: Flack (1983), 1772 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.002 (17)

Crystal data top

2C₂₄H₃₃N₅S·CH₂Cl₂	V = 9622.3 (3) Å³
M_r = 932.17	Z = 8
Orthorhombic, Fdd2	Cu Kα radiation
a = 66.8490 (16) Å	µ = 2.38 mm⁻¹
b = 22.1076 (4) Å	T = 100 K
c = 6.5109 (1) Å	0.30 × 0.20 × 0.10 mm

Data collection top

Agilent SuperNova Dual diffractometer with an Atlas detector	4509 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	4437 reflections with I > 2σ(I)
T_min = 0.752, T_max = 1.000	R_int = 0.025
18884 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	H-atom parameters constrained
wR(F²) = 0.126	w = 1/[σ²(F_o²) + (0.0825P)² + 16.7617P] where P = (F_o² + 2F_c²)/3
S = 1.09	Δρ_max = 0.41 e Å⁻³
4509 reflections	Δρ_min = −1.00 e Å⁻³
299 parameters	Absolute structure: Flack (1983), 1772 Friedel pairs
19 restraints	Absolute structure parameter: −0.002 (17)

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
S1	0.106131 (8)	0.22602 (2)	0.50061 (10)	0.02473 (15)
N1	0.09696 (3)	0.34338 (8)	0.4049 (3)	0.0198 (4)
N2	0.08323 (3)	0.33690 (8)	0.0966 (3)	0.0218 (4)
N3	0.08877 (3)	0.28044 (8)	0.1693 (3)	0.0219 (4)
N4	0.06533 (3)	0.20162 (8)	0.0489 (3)	0.0223 (4)
N5	0.02334 (3)	0.19119 (9)	0.1251 (3)	0.0256 (4)
C1	0.08658 (3)	0.44216 (9)	0.2235 (3)	0.0183 (4)
C2	0.07497 (4)	0.45691 (10)	0.0251 (4)	0.0256 (5)
H2A	0.0818	0.4383	−0.0939	0.031*
H2B	0.0613	0.4396	0.0337	0.031*
C3	0.07361 (4)	0.52562 (10)	−0.0064 (5)	0.0262 (5)
H3	0.0661	0.5343	−0.1362	0.031*
C4	0.09476 (4)	0.55174 (10)	−0.0222 (4)	0.0252 (5)
H4A	0.0941	0.5960	−0.0450	0.030*
H4B	0.1019	0.5333	−0.1400	0.030*
C5	0.10617 (4)	0.53843 (11)	0.1778 (4)	0.0252 (5)
H5	0.1199	0.5560	0.1685	0.030*
C6	0.09524 (5)	0.56653 (11)	0.3591 (5)	0.0356 (6)
H6A	0.0945	0.6110	0.3413	0.043*
H6B	0.1026	0.5579	0.4875	0.043*
C7	0.07398 (5)	0.54031 (11)	0.3735 (5)	0.0342 (6)
H7	0.0668	0.5591	0.4924	0.041*
C8	0.07510 (4)	0.47116 (10)	0.4044 (5)	0.0282 (5)
H8A	0.0614	0.4541	0.4118	0.034*
H8B	0.0820	0.4620	0.5352	0.034*
C9	0.10775 (3)	0.46982 (10)	0.2081 (4)	0.0220 (5)
H9A	0.1153	0.4610	0.3351	0.026*
H9B	0.1150	0.4516	0.0909	0.026*
C10	0.06261 (4)	0.55420 (11)	0.1747 (5)	0.0345 (6)
H10A	0.0489	0.5377	0.1834	0.041*
H10B	0.0617	0.5985	0.1550	0.041*
C11	0.08839 (3)	0.37444 (9)	0.2426 (4)	0.0199 (4)
C12	0.09709 (3)	0.28280 (10)	0.3552 (4)	0.0212 (4)
C13	0.10506 (4)	0.36501 (10)	0.5994 (4)	0.0245 (5)
H13A	0.1079	0.4084	0.5892	0.037*
H13B	0.1175	0.3432	0.6308	0.037*
H13C	0.0953	0.3580	0.7091	0.037*
C14	0.08542 (3)	0.22529 (9)	0.0446 (4)	0.0227 (5)
H14A	0.0890	0.2344	−0.0997	0.027*
H14B	0.0947	0.1934	0.0935	0.027*
C15	0.05794 (4)	0.18967 (13)	0.2540 (5)	0.0345 (6)
H15A	0.0564	0.2283	0.3293	0.041*
H15B	0.0677	0.1644	0.3292	0.041*
C16	0.03797 (4)	0.15741 (15)	0.2457 (6)	0.0427 (8)
H16A	0.0398	0.1168	0.1842	0.051*
H16B	0.0328	0.1519	0.3870	0.051*
C17	0.03096 (4)	0.20593 (11)	−0.0794 (4)	0.0278 (5)
H17A	0.0212	0.2321	−0.1518	0.033*
H17B	0.0326	0.1683	−0.1602	0.033*
C18	0.05105 (4)	0.23845 (11)	−0.0635 (4)	0.0261 (5)
H18A	0.0563	0.2468	−0.2030	0.031*
H18B	0.0492	0.2776	0.0078	0.031*
C19	0.00324 (4)	0.17111 (11)	0.1365 (4)	0.0281 (5)
C20	−0.01038 (4)	0.17995 (14)	−0.0246 (5)	0.0366 (6)
H20	−0.0061	0.1985	−0.1485	0.044*
C21	−0.03030 (4)	0.16163 (14)	−0.0037 (6)	0.0426 (7)
H21	−0.0393	0.1678	−0.1147	0.051*
C22	−0.03716 (4)	0.13510 (14)	0.1726 (6)	0.0404 (7)
H22	−0.0507	0.1227	0.1841	0.048*
C23	−0.02392 (4)	0.12670 (14)	0.3341 (6)	0.0421 (7)
H23	−0.0285	0.1087	0.4578	0.051*
C24	−0.00399 (4)	0.14421 (14)	0.3179 (5)	0.0365 (6)
H24	0.0048	0.1380	0.4304	0.044*
Cl1	0.02109 (2)	0.01531 (9)	0.0431 (3)	0.0562 (4)	0.50
Cl2	0.0020 (2)	−0.0144 (4)	−0.3345 (6)	0.143 (3)	0.50
C25	0.00259 (15)	−0.0235 (4)	−0.0659 (17)	0.073 (2)	0.50
H25A	−0.0103	−0.0100	−0.0076	0.088*	0.50
H25B	0.0042	−0.0670	−0.0331	0.088*	0.50

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0326 (3)	0.0149 (2)	0.0267 (3)	0.0043 (2)	0.0009 (2)	0.0027 (2)
N1	0.0249 (9)	0.0129 (8)	0.0214 (10)	0.0011 (6)	−0.0011 (7)	−0.0014 (7)
N2	0.0278 (9)	0.0130 (8)	0.0248 (11)	−0.0014 (7)	0.0005 (8)	0.0021 (8)
N3	0.0324 (10)	0.0115 (8)	0.0218 (10)	−0.0020 (7)	0.0025 (8)	0.0002 (7)
N4	0.0244 (9)	0.0159 (8)	0.0266 (11)	−0.0011 (7)	0.0011 (8)	0.0007 (8)
N5	0.0237 (9)	0.0280 (9)	0.0252 (11)	0.0024 (8)	−0.0004 (8)	0.0046 (9)
C1	0.0202 (9)	0.0136 (9)	0.0212 (12)	0.0006 (7)	0.0027 (8)	0.0024 (8)
C2	0.0285 (11)	0.0162 (10)	0.0323 (14)	0.0006 (8)	−0.0061 (10)	0.0003 (10)
C3	0.0293 (11)	0.0166 (10)	0.0328 (14)	0.0045 (8)	−0.0026 (10)	0.0035 (10)
C4	0.0341 (12)	0.0160 (9)	0.0256 (13)	0.0007 (8)	0.0031 (10)	0.0045 (9)
C5	0.0311 (12)	0.0173 (10)	0.0274 (13)	−0.0061 (8)	−0.0017 (10)	0.0043 (9)
C6	0.0644 (18)	0.0135 (10)	0.0288 (15)	−0.0043 (10)	−0.0054 (13)	−0.0001 (10)
C7	0.0535 (16)	0.0183 (10)	0.0308 (15)	0.0140 (10)	0.0160 (12)	0.0015 (10)
C8	0.0339 (12)	0.0184 (10)	0.0323 (15)	0.0062 (9)	0.0139 (10)	0.0059 (10)
C9	0.0211 (10)	0.0189 (10)	0.0259 (14)	−0.0019 (7)	0.0023 (8)	0.0045 (9)
C10	0.0377 (13)	0.0223 (11)	0.0436 (16)	0.0123 (10)	0.0102 (12)	0.0069 (11)
C11	0.0197 (9)	0.0166 (9)	0.0234 (12)	−0.0002 (7)	0.0010 (8)	0.0011 (9)
C12	0.0250 (10)	0.0136 (9)	0.0252 (12)	−0.0006 (8)	0.0027 (9)	−0.0018 (9)
C13	0.0323 (12)	0.0175 (10)	0.0239 (12)	0.0049 (8)	−0.0056 (10)	−0.0023 (9)
C14	0.0293 (11)	0.0151 (9)	0.0239 (13)	−0.0028 (8)	0.0054 (9)	−0.0037 (9)
C15	0.0240 (11)	0.0448 (14)	0.0348 (15)	−0.0005 (10)	−0.0018 (11)	0.0222 (13)
C16	0.0234 (11)	0.0544 (17)	0.0504 (19)	−0.0021 (11)	−0.0016 (12)	0.0336 (16)
C17	0.0292 (12)	0.0297 (12)	0.0244 (12)	−0.0018 (9)	−0.0028 (9)	0.0004 (10)
C18	0.0327 (12)	0.0231 (10)	0.0224 (12)	−0.0025 (9)	−0.0018 (9)	0.0044 (9)
C19	0.0243 (11)	0.0265 (11)	0.0335 (15)	0.0049 (9)	0.0024 (10)	−0.0044 (10)
C20	0.0304 (12)	0.0439 (14)	0.0356 (17)	0.0019 (11)	−0.0042 (11)	0.0003 (13)
C21	0.0277 (12)	0.0500 (16)	0.0500 (19)	0.0048 (11)	−0.0068 (13)	−0.0122 (15)
C22	0.0241 (12)	0.0406 (15)	0.057 (2)	−0.0005 (10)	0.0028 (12)	−0.0154 (14)
C23	0.0312 (13)	0.0454 (16)	0.0498 (19)	−0.0028 (11)	0.0101 (13)	0.0008 (14)
C24	0.0279 (12)	0.0425 (15)	0.0391 (17)	−0.0006 (10)	0.0028 (11)	0.0028 (13)
Cl1	0.0308 (7)	0.0813 (11)	0.0563 (11)	0.0133 (7)	−0.0006 (6)	−0.0114 (9)
Cl2	0.150 (5)	0.182 (8)	0.096 (2)	−0.015 (6)	0.001 (3)	−0.007 (3)
C25	0.074 (5)	0.059 (4)	0.086 (6)	0.008 (4)	−0.001 (5)	−0.005 (4)

Geometric parameters (Å, º) top

S1—C12	1.684 (2)	C8—H8A	0.9900
N1—C12	1.378 (3)	C8—H8B	0.9900
N1—C11	1.384 (3)	C9—H9A	0.9900
N1—C13	1.458 (3)	C9—H9B	0.9900
N2—C11	1.308 (3)	C10—H10A	0.9900
N2—N3	1.386 (2)	C10—H10B	0.9900
N3—C12	1.333 (3)	C13—H13A	0.9800
N3—C14	1.482 (3)	C13—H13B	0.9800
N4—C14	1.442 (3)	C13—H13C	0.9800
N4—C15	1.448 (3)	C14—H14A	0.9900
N4—C18	1.453 (3)	C14—H14B	0.9900
N5—C19	1.417 (3)	C15—C16	1.515 (3)
N5—C16	1.460 (3)	C15—H15A	0.9900
N5—C17	1.462 (3)	C15—H15B	0.9900
C1—C11	1.507 (3)	C16—H16A	0.9900
C1—C2	1.542 (3)	C16—H16B	0.9900
C1—C9	1.545 (3)	C17—C18	1.526 (3)
C1—C8	1.545 (3)	C17—H17A	0.9900
C2—C3	1.536 (3)	C17—H17B	0.9900
C2—H2A	0.9900	C18—H18A	0.9900
C2—H2B	0.9900	C18—H18B	0.9900
C3—C10	1.527 (4)	C19—C20	1.403 (4)
C3—C4	1.531 (3)	C19—C24	1.408 (4)
C3—H3	1.0000	C20—C21	1.398 (4)
C4—C5	1.538 (4)	C20—H20	0.9500
C4—H4A	0.9900	C21—C22	1.368 (5)
C4—H4B	0.9900	C21—H21	0.9500
C5—C6	1.521 (4)	C22—C23	1.386 (5)
C5—C9	1.533 (3)	C22—H22	0.9500
C5—H5	1.0000	C23—C24	1.392 (4)
C6—C7	1.538 (4)	C23—H23	0.9500
C6—H6A	0.9900	C24—H24	0.9500
C6—H6B	0.9900	Cl1—C25	1.664 (10)
C7—C10	1.532 (4)	Cl2—C25	1.761 (12)
C7—C8	1.544 (3)	C25—H25A	0.9900
C7—H7	1.0000	C25—H25B	0.9900

C12—N1—C11	107.82 (19)	C3—C10—H10B	109.8
C12—N1—C13	121.3 (2)	C7—C10—H10B	109.8
C11—N1—C13	130.84 (18)	H10A—C10—H10B	108.3
C11—N2—N3	104.64 (19)	N2—C11—N1	110.43 (18)
C12—N3—N2	112.72 (18)	N2—C11—C1	123.3 (2)
C12—N3—C14	126.35 (19)	N1—C11—C1	126.1 (2)
N2—N3—C14	120.92 (19)	N3—C12—N1	104.39 (19)
C14—N4—C15	113.7 (2)	N3—C12—S1	129.11 (17)
C14—N4—C18	113.51 (18)	N1—C12—S1	126.51 (19)
C15—N4—C18	110.06 (19)	N1—C13—H13A	109.5
C19—N5—C16	116.5 (2)	N1—C13—H13B	109.5
C19—N5—C17	116.6 (2)	H13A—C13—H13B	109.5
C16—N5—C17	111.7 (2)	N1—C13—H13C	109.5
C11—C1—C2	108.64 (18)	H13A—C13—H13C	109.5
C11—C1—C9	108.97 (17)	H13B—C13—H13C	109.5
C2—C1—C9	108.83 (19)	N4—C14—N3	115.42 (19)
C11—C1—C8	112.89 (18)	N4—C14—H14A	108.4
C2—C1—C8	107.53 (19)	N3—C14—H14A	108.4
C9—C1—C8	109.89 (19)	N4—C14—H14B	108.4
C3—C2—C1	110.5 (2)	N3—C14—H14B	108.4
C3—C2—H2A	109.5	H14A—C14—H14B	107.5
C1—C2—H2A	109.5	N4—C15—C16	110.7 (2)
C3—C2—H2B	109.5	N4—C15—H15A	109.5
C1—C2—H2B	109.5	C16—C15—H15A	109.5
H2A—C2—H2B	108.1	N4—C15—H15B	109.5
C10—C3—C4	109.9 (2)	C16—C15—H15B	109.5
C10—C3—C2	109.5 (2)	H15A—C15—H15B	108.1
C4—C3—C2	109.13 (18)	N5—C16—C15	111.7 (2)
C10—C3—H3	109.4	N5—C16—H16A	109.3
C4—C3—H3	109.4	C15—C16—H16A	109.3
C2—C3—H3	109.4	N5—C16—H16B	109.3
C3—C4—C5	109.2 (2)	C15—C16—H16B	109.3
C3—C4—H4A	109.8	H16A—C16—H16B	107.9
C5—C4—H4A	109.8	N5—C17—C18	110.5 (2)
C3—C4—H4B	109.8	N5—C17—H17A	109.6
C5—C4—H4B	109.8	C18—C17—H17A	109.6
H4A—C4—H4B	108.3	N5—C17—H17B	109.6
C6—C5—C9	109.7 (2)	C18—C17—H17B	109.6
C6—C5—C4	109.9 (2)	H17A—C17—H17B	108.1
C9—C5—C4	109.4 (2)	N4—C18—C17	110.37 (19)
C6—C5—H5	109.3	N4—C18—H18A	109.6
C9—C5—H5	109.3	C17—C18—H18A	109.6
C4—C5—H5	109.3	N4—C18—H18B	109.6
C5—C6—C7	109.7 (2)	C17—C18—H18B	109.6
C5—C6—H6A	109.7	H18A—C18—H18B	108.1
C7—C6—H6A	109.7	C20—C19—C24	117.6 (2)
C5—C6—H6B	109.7	C20—C19—N5	122.2 (3)
C7—C6—H6B	109.7	C24—C19—N5	120.1 (2)
H6A—C6—H6B	108.2	C21—C20—C19	120.3 (3)
C10—C7—C6	109.4 (2)	C21—C20—H20	119.8
C10—C7—C8	109.4 (2)	C19—C20—H20	119.8
C6—C7—C8	109.7 (2)	C22—C21—C20	121.7 (3)
C10—C7—H7	109.5	C22—C21—H21	119.2
C6—C7—H7	109.5	C20—C21—H21	119.2
C8—C7—H7	109.5	C21—C22—C23	118.7 (3)
C7—C8—C1	109.6 (2)	C21—C22—H22	120.7
C7—C8—H8A	109.8	C23—C22—H22	120.7
C1—C8—H8A	109.8	C22—C23—C24	121.1 (3)
C7—C8—H8B	109.8	C22—C23—H23	119.5
C1—C8—H8B	109.8	C24—C23—H23	119.5
H8A—C8—H8B	108.2	C23—C24—C19	120.6 (3)
C5—C9—C1	109.71 (18)	C23—C24—H24	119.7
C5—C9—H9A	109.7	C19—C24—H24	119.7
C1—C9—H9A	109.7	Cl1—C25—Cl2	112.3 (8)
C5—C9—H9B	109.7	Cl1—C25—H25A	109.1
C1—C9—H9B	109.7	Cl2—C25—H25A	109.1
H9A—C9—H9B	108.2	Cl1—C25—H25B	109.1
C3—C10—C7	109.3 (2)	Cl2—C25—H25B	109.1
C3—C10—H10A	109.8	H25A—C25—H25B	107.9
C7—C10—H10A	109.8

C11—N2—N3—C12	0.2 (2)	C2—C1—C11—N1	−176.7 (2)
C11—N2—N3—C14	−179.6 (2)	C9—C1—C11—N1	64.9 (3)
C11—C1—C2—C3	−177.29 (19)	C8—C1—C11—N1	−57.5 (3)
C9—C1—C2—C3	−58.8 (2)	N2—N3—C12—N1	−0.1 (2)
C8—C1—C2—C3	60.2 (2)	N2—N3—C12—S1	−179.48 (17)
C1—C2—C3—C10	−60.5 (3)	C14—N3—C12—S1	0.3 (3)
C1—C2—C3—C4	59.9 (3)	C11—N1—C12—N3	0.0 (2)
C10—C3—C4—C5	59.7 (2)	C13—N1—C12—N3	−179.56 (19)
C2—C3—C4—C5	−60.5 (3)	C11—N1—C12—S1	179.40 (17)
C3—C4—C5—C6	−59.3 (2)	C13—N1—C12—S1	−0.2 (3)
C3—C4—C5—C9	61.3 (2)	C15—N4—C14—N3	−54.9 (3)
C9—C5—C6—C7	−60.9 (3)	C18—N4—C14—N3	71.9 (3)
C4—C5—C6—C7	59.5 (3)	C12—N3—C14—N4	100.3 (3)
C5—C6—C7—C10	−59.8 (3)	N2—N3—C14—N4	−79.9 (3)
C5—C6—C7—C8	60.2 (3)	C14—N4—C15—C16	−172.6 (2)
C10—C7—C8—C1	61.3 (3)	C18—N4—C15—C16	58.8 (3)
C6—C7—C8—C1	−58.6 (3)	C19—N5—C16—C15	−169.1 (3)
C11—C1—C8—C7	179.8 (2)	C17—N5—C16—C15	53.3 (3)
C2—C1—C8—C7	−60.4 (3)	N4—C15—C16—N5	−55.6 (3)
C9—C1—C8—C7	57.9 (3)	C19—N5—C17—C18	168.7 (2)
C6—C5—C9—C1	60.0 (3)	C16—N5—C17—C18	−53.8 (3)
C4—C5—C9—C1	−60.6 (3)	C14—N4—C18—C17	171.5 (2)
C11—C1—C9—C5	177.2 (2)	C15—N4—C18—C17	−59.8 (3)
C2—C1—C9—C5	58.9 (2)	N5—C17—C18—N4	57.1 (3)
C8—C1—C9—C5	−58.6 (3)	C16—N5—C19—C20	−152.3 (3)
C4—C3—C10—C7	−60.4 (3)	C17—N5—C19—C20	−16.8 (3)
C2—C3—C10—C7	59.5 (3)	C16—N5—C19—C24	31.2 (4)
C6—C7—C10—C3	59.9 (3)	C17—N5—C19—C24	166.7 (2)
C8—C7—C10—C3	−60.2 (3)	C24—C19—C20—C21	−0.9 (4)
N3—N2—C11—N1	−0.1 (2)	N5—C19—C20—C21	−177.4 (2)
N3—N2—C11—C1	175.2 (2)	C19—C20—C21—C22	0.4 (5)
C12—N1—C11—N2	0.1 (3)	C20—C21—C22—C23	0.4 (5)
C12—N1—C11—C1	−175.1 (2)	C21—C22—C23—C24	−0.6 (5)
C13—N1—C11—C1	4.4 (4)	C22—C23—C24—C19	0.1 (5)
C2—C1—C11—N2	8.7 (3)	C20—C19—C24—C23	0.6 (4)
C9—C1—C11—N2	−109.8 (2)	N5—C19—C24—C23	177.2 (3)
C8—C1—C11—N2	127.9 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14A···S1ⁱ	0.99	2.85	3.803 (3)	162
C16—H16A···Cl1	0.99	2.73	3.589 (4)	146

Symmetry code: (i) x, y, z−1.

Experimental details

Crystal data
Chemical formula	2C₂₄H₃₃N₅S·CH₂Cl₂
M_r	932.17
Crystal system, space group	Orthorhombic, Fdd2
Temperature (K)	100
a, b, c (Å)	66.8490 (16), 22.1076 (4), 6.5109 (1)
V (Å³)	9622.3 (3)
Z	8
Radiation type	Cu Kα
µ (mm⁻¹)	2.38
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2011)
T_min, T_max	0.752, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	18884, 4509, 4437
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.631

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.126, 1.09
No. of reflections	4509
No. of parameters	299
No. of restraints	19
H-atom treatment	H-atom parameters constrained
	w = 1/[σ²(F_o²) + (0.0825P)² + 16.7617P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	0.41, −1.00
Absolute structure	Flack (1983), 1772 Friedel pairs
Absolute structure parameter	−0.002 (17)

Computer programs: CrysAlis PRO (Agilent, 2011), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14A···S1ⁱ	0.99	2.85	3.803 (3)	162
C16—H16A···Cl1	0.99	2.73	3.589 (4)	146

Symmetry code: (i) x, y, z−1.

Footnotes

‡Additional correspondence author, e-mail: elemam5@hotmail.com.

Acknowledgements

The financial support of the Deanship of Scientific Research and the Research Center of the College of Pharmacy, King Saud University is greatly appreciated. We also thank the Ministry of Higher Education (Malaysia) for funding structural studies through the High-Impact Research scheme (UM.C/HIR/MOHE/SC/12).

References

Agilent (2011). CrysAlis PRO. Agilent Technologies, Yarnton, England. Google Scholar
Al-Deeb, O. A., Al-Omar, M. A., El-Brollosy, N. R., Habib, E. E., Ibrahim, T. M. & El-Emam, A. A. (2006). Arzneim. Forsch. Drug. Res. 56, 40–47. CAS Google Scholar
Al-Omar, M. A., Al-Abdullah, E. S., Shehata, I. A., Habib, E. E., Ibrahim, T. M. & El-Emam, A. A. (2010). Molecules, 15, 2526–2550. Web of Science CAS PubMed Google Scholar
Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
El-Emam, A. A., Al-Omar, M. A., Al-Tamimi, A.-M. S., Ng, S. W. & Tiekink, E. R. T. (2012a). Acta Cryst. E68, o1766–o1767. CSD CrossRef IUCr Journals Google Scholar
El-Emam, A. A., Alrashood, K. A., Al-Tamimi, A.-M. S., Ng, S. W. & Tiekink, E. R. T. (2012b). Acta Cryst. E68, o657–o658. CSD CrossRef IUCr Journals Google Scholar
El-Emam, A. A. & Ibrahim, T. M. (1991). Arzneim. Forsch. Drug. Res. 41, 1260–1264. CAS Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

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Volume 68| Part 6| June 2012| Pages o1772-o1773

doi:10.1107/S1600536812021393

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

3-(Adamantan-1-yl)-4-methyl-1-[(4-phenyl­piperazin-1-yl)meth­yl]-1H-1,2,4-triazole-5(4H)-thione di­chloro­methane hemisolvate

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Experimental

Crystal data

Data collection

Refinement

Supporting information

Footnotes

Acknowledgements

References

organic compounds

3-(Adamantan-1-yl)-4-methyl-1-[(4-phenylpiperazin-1-yl)methyl]-1H-1,2,4-triazole-5(4H)-thione dichloromethane hemisolvate