5-(Adamantan-1-yl)-N-methyl-1,3,4-thia­diazol-2-amine

Abstract

In the title compound, C₁₃H₁₉N₃S, the methyl­amine substituent is coplanar with the thia­diazole ring to which it is attached [C—N—C—S torsion angle = 175.9 (2)°] and the amine H atom is syn to the thia­diazole S atom. Supra­molecular chains along [101], sustained by N—H⋯N hydrogen bonding, feature in the crystal packing.

Related literature  

For the biological activity of 1,3,4-thia­diazol-2-amine derivatives, see: Carvalho et al. (2008 ▶); Foroumadi et al. (1999 ▶), and of adamantane derivatives, see: Togo et al. (1968 ▶); El-Emam et al. (2004 ▶). For related structures, see: El-Emam et al. (2012 ▶); Almutairi et al. (2012 ▶). For the synthesis of the title compound, see: El-Emam & Lehmann (1994 ▶).

Experimental  

Crystal data  

• C₁₃H₁₉N₃S

• M _r = 249.37

• Monoclinic,

• a = 10.4394 (12) Å

• b = 13.0910 (13) Å

• c = 10.8871 (15) Å

• β = 118.008 (16)°

• V = 1313.6 (3) ų

• Z = 4

• Mo Kα radiation

• μ = 0.23 mm⁻¹

• T = 295 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, 2012 ▶) T _min = 0.887, T _max = 1.000

• 6791 measured reflections

• 3027 independent reflections

• 1975 reflections with I > 2σ(I)

• R _int = 0.039

Refinement  

• R[F ² > 2σ(F ²)] = 0.054

• wR(F ²) = 0.144

• S = 1.04

• 3027 reflections

• 159 parameters

• 1 restraint

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.24 e Å⁻³

• Δρ_min = −0.22 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2012 ▶); 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 for Windows (Farrugia, 2012 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3⋯N1i	0.87 (1)	2.15 (1)	3.021 (3)	179 (2)

Symmetry code: (i) .

supplementary crystallographic information

Comment

Derivatives of adamantane have long been known for their diverse biological activities including anti-viral activity against influenza (Togo et al., 1968) and HIV viruses (El-Emam et al., 2004). Moreover, 1,3,4-thiadiazole derivatives were reported to exhibit marked anti-trypanosomal (Carvalho et al., 2008) and anti-microbial activities (Foroumadi et al., 1999). In continuation of our interest in the chemical and pharmacological properties of adamantane derivatives, and as part of on-going structural studies of these (El-Emam et al., 2012; Almutairi et al., 2012), we report herein the X-ray crystallographic data of the title compound, (I).

In (I), Fig. 1, the five-membered ring is planar (r.m.s. deviation = 0.009 Å) and the methylamine substituent is co-planar: the C13—N3—C2—S1 torsion angle is 175.9 (2)°. The amine-H atom is syn to the thiadiazole-S1 atom. N—H···N hydrogen bonds feature in the crystal packing, leading to supramolecular chains along [1 0 1], Fig. 2 and Table 1. Chains pack with no specific intermolecular interactions between them. Globally, the crystal structure comprises alternating layers of hydrophilic and hydrophobic regions, Fig. 3.

Experimental

The title compound was prepared by dehydrative cyclization of 1-(1-adamantylcarbonyl)-4-methylthiosemicarbazide using sulfuric acid at room temperature for 24 h as previously described (El-Emam & Lehmann, 1994). Single crystals were obtained by slow evaporation from its CHCl₃:EtOH solution at room temperature; M.pt: 441–443 K.

Refinement

The C-bound H-atoms were placed in calculated positions [C—H = 0.96 to 0.98 Å, U_iso(H) = 1.2 or 1.5U_eq(C)] and were included in the refinement in the riding model approximation. The N-bound H-atom was refined with N—H = 0.88±0.01 Å.

Figures

Fig. 1.

The molecular structure of (I) showing the atom-labelling scheme and displacement ellipsoids at the 35% probability level.

Fig. 2.

A view of the supramolecular chain in (I) sustained by N—H···N hydrogen bonds shown as orange dashed lines.

Fig. 3.

A view in projection down the b axis of the unit-cell contents for (I).

Crystal data

C13H19N3S	F(000) = 536
Mr = 249.37	Dx = 1.261 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1515 reflections
a = 10.4394 (12) Å	θ = 3.1–27.5°
b = 13.0910 (13) Å	µ = 0.23 mm−1
c = 10.8871 (15) Å	T = 295 K
β = 118.008 (16)°	Prism, colourless
V = 1313.6 (3) Å3	0.30 × 0.20 × 0.10 mm
Z = 4

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector	3027 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	1975 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.039
Detector resolution: 10.4041 pixels mm-1	θmax = 27.6°, θmin = 3.1°
ω scan	h = −13→13
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	k = −16→17
Tmin = 0.887, Tmax = 1.000	l = −13→14
6791 measured reflections

Refinement

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)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.144	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ2(Fo2) + (0.0539P)2 + 0.1967P] where P = (Fo2 + 2Fc2)/3
3027 reflections	(Δ/σ)max < 0.001
159 parameters	Δρmax = 0.24 e Å−3
1 restraint	Δρmin = −0.22 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
S1	0.21237 (6)	0.64435 (5)	0.41269 (6)	0.0480 (2)
N1	0.45652 (19)	0.66351 (15)	0.62872 (19)	0.0446 (5)
N2	0.43886 (18)	0.75355 (15)	0.55520 (19)	0.0455 (5)
N3	0.2711 (2)	0.83210 (16)	0.3481 (2)	0.0514 (5)
H3	0.1801 (12)	0.8326 (19)	0.2850 (19)	0.047 (7)*
C1	0.3500 (2)	0.60016 (19)	0.5713 (2)	0.0398 (5)
C2	0.3152 (2)	0.75433 (18)	0.4397 (2)	0.0404 (5)
C3	0.3392 (2)	0.49988 (18)	0.6325 (2)	0.0398 (5)
C4	0.4805 (3)	0.4770 (2)	0.7646 (3)	0.0614 (7)
H4A	0.5016	0.5321	0.8308	0.074*
H4B	0.5598	0.4725	0.7420	0.074*
C5	0.4676 (3)	0.3761 (2)	0.8298 (3)	0.0698 (9)
H5	0.5580	0.3627	0.9150	0.084*
C6	0.3426 (3)	0.3824 (3)	0.8635 (3)	0.0744 (9)
H6A	0.3359	0.3190	0.9062	0.089*
H6B	0.3600	0.4373	0.9292	0.089*
C7	0.2019 (3)	0.4013 (2)	0.7331 (3)	0.0614 (7)
H7	0.1221	0.4047	0.7564	0.074*
C8	0.2149 (3)	0.5035 (2)	0.6717 (3)	0.0566 (7)
H8A	0.2337	0.5575	0.7391	0.068*
H8B	0.1242	0.5188	0.5896	0.068*
C9	0.3080 (3)	0.4115 (2)	0.5300 (3)	0.0605 (7)
H9A	0.3848	0.4073	0.5040	0.073*
H9B	0.2175	0.4242	0.4465	0.073*
C10	0.2977 (3)	0.3098 (2)	0.5956 (3)	0.0682 (8)
H10	0.2792	0.2540	0.5294	0.082*
C11	0.1735 (3)	0.3176 (2)	0.6301 (3)	0.0675 (8)
H11A	0.0840	0.3314	0.5459	0.081*
H11B	0.1625	0.2533	0.6683	0.081*
C12	0.4399 (3)	0.2912 (3)	0.7263 (4)	0.0807 (10)
H12A	0.4358	0.2262	0.7671	0.097*
H12B	0.5187	0.2882	0.7028	0.097*
C13	0.3567 (3)	0.9237 (2)	0.3810 (3)	0.0619 (7)
H13A	0.3160	0.9693	0.3028	0.093*
H13B	0.4544	0.9068	0.4020	0.093*
H13C	0.3570	0.9562	0.4602	0.093*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
S1	0.0374 (3)	0.0496 (4)	0.0422 (4)	−0.0049 (3)	0.0063 (3)	0.0015 (3)
N1	0.0365 (9)	0.0478 (12)	0.0403 (11)	0.0009 (9)	0.0105 (8)	0.0020 (9)
N2	0.0361 (9)	0.0460 (12)	0.0435 (11)	−0.0023 (9)	0.0096 (8)	0.0033 (10)
N3	0.0380 (10)	0.0503 (13)	0.0490 (13)	−0.0012 (10)	0.0063 (9)	0.0077 (11)
C1	0.0314 (10)	0.0487 (14)	0.0366 (12)	0.0015 (10)	0.0138 (9)	−0.0020 (11)
C2	0.0327 (10)	0.0455 (14)	0.0396 (12)	0.0020 (10)	0.0142 (9)	0.0001 (11)
C3	0.0366 (11)	0.0435 (13)	0.0388 (12)	0.0010 (10)	0.0171 (9)	0.0007 (11)
C4	0.0435 (13)	0.0650 (18)	0.0611 (17)	−0.0039 (13)	0.0125 (12)	0.0184 (14)
C5	0.0500 (14)	0.070 (2)	0.0689 (19)	−0.0026 (15)	0.0110 (14)	0.0242 (17)
C6	0.089 (2)	0.081 (2)	0.0559 (18)	−0.0179 (18)	0.0364 (17)	0.0018 (16)
C7	0.0560 (15)	0.073 (2)	0.0647 (18)	−0.0040 (14)	0.0364 (14)	0.0026 (15)
C8	0.0556 (14)	0.0574 (17)	0.0643 (17)	0.0008 (13)	0.0344 (13)	−0.0009 (14)
C9	0.0785 (18)	0.0535 (16)	0.0597 (17)	−0.0018 (14)	0.0408 (15)	−0.0035 (14)
C10	0.095 (2)	0.0474 (16)	0.070 (2)	−0.0086 (16)	0.0448 (18)	−0.0112 (15)
C11	0.0611 (16)	0.0589 (18)	0.075 (2)	−0.0128 (15)	0.0254 (15)	0.0020 (16)
C12	0.081 (2)	0.066 (2)	0.115 (3)	0.0235 (18)	0.062 (2)	0.034 (2)
C13	0.0534 (14)	0.0537 (17)	0.0642 (18)	−0.0072 (13)	0.0157 (13)	0.0063 (14)

Geometric parameters (Å, º)

S1—C2	1.737 (2)	C6—H6B	0.9700
S1—C1	1.747 (2)	C7—C11	1.495 (4)
N1—C1	1.289 (3)	C7—C8	1.530 (4)
N1—N2	1.388 (3)	C7—H7	0.9800
N2—C2	1.313 (3)	C8—H8A	0.9700
N3—C2	1.346 (3)	C8—H8B	0.9700
N3—C13	1.437 (3)	C9—C10	1.538 (4)
N3—H3	0.872 (9)	C9—H9A	0.9700
C1—C3	1.500 (3)	C9—H9B	0.9700
C3—C4	1.530 (3)	C10—C11	1.513 (4)
C3—C9	1.532 (3)	C10—C12	1.518 (4)
C3—C8	1.545 (3)	C10—H10	0.9800
C4—C5	1.535 (4)	C11—H11A	0.9700
C4—H4A	0.9700	C11—H11B	0.9700
C4—H4B	0.9700	C12—H12A	0.9700
C5—C12	1.511 (4)	C12—H12B	0.9700
C5—C6	1.514 (4)	C13—H13A	0.9600
C5—H5	0.9800	C13—H13B	0.9600
C6—C7	1.509 (4)	C13—H13C	0.9600
C6—H6A	0.9700
C2—S1—C1	87.21 (11)	C11—C7—H7	109.5
C1—N1—N2	114.59 (18)	C6—C7—H7	109.5
C2—N2—N1	111.34 (18)	C8—C7—H7	109.5
C2—N3—C13	119.4 (2)	C7—C8—C3	110.6 (2)
C2—N3—H3	117.1 (16)	C7—C8—H8A	109.5
C13—N3—H3	120.7 (16)	C3—C8—H8A	109.5
N1—C1—C3	125.1 (2)	C7—C8—H8B	109.5
N1—C1—S1	112.82 (18)	C3—C8—H8B	109.5
C3—C1—S1	122.04 (16)	H8A—C8—H8B	108.1
N2—C2—N3	123.8 (2)	C3—C9—C10	110.7 (2)
N2—C2—S1	114.02 (17)	C3—C9—H9A	109.5
N3—C2—S1	122.18 (16)	C10—C9—H9A	109.5
C1—C3—C4	110.38 (18)	C3—C9—H9B	109.5
C1—C3—C9	111.84 (19)	C10—C9—H9B	109.5
C4—C3—C9	108.5 (2)	H9A—C9—H9B	108.1
C1—C3—C8	110.08 (19)	C11—C10—C12	110.7 (2)
C4—C3—C8	108.1 (2)	C11—C10—C9	108.1 (2)
C9—C3—C8	107.8 (2)	C12—C10—C9	108.9 (2)
C3—C4—C5	110.3 (2)	C11—C10—H10	109.7
C3—C4—H4A	109.6	C12—C10—H10	109.7
C5—C4—H4A	109.6	C9—C10—H10	109.7
C3—C4—H4B	109.6	C7—C11—C10	110.1 (2)
C5—C4—H4B	109.6	C7—C11—H11A	109.6
H4A—C4—H4B	108.1	C10—C11—H11A	109.6
C12—C5—C6	109.6 (2)	C7—C11—H11B	109.6
C12—C5—C4	108.4 (3)	C10—C11—H11B	109.6
C6—C5—C4	109.8 (3)	H11A—C11—H11B	108.1
C12—C5—H5	109.7	C5—C12—C10	109.9 (2)
C6—C5—H5	109.7	C5—C12—H12A	109.7
C4—C5—H5	109.7	C10—C12—H12A	109.7
C7—C6—C5	110.5 (2)	C5—C12—H12B	109.7
C7—C6—H6A	109.6	C10—C12—H12B	109.7
C5—C6—H6A	109.6	H12A—C12—H12B	108.2
C7—C6—H6B	109.6	N3—C13—H13A	109.5
C5—C6—H6B	109.6	N3—C13—H13B	109.5
H6A—C6—H6B	108.1	H13A—C13—H13B	109.5
C11—C7—C6	110.4 (3)	N3—C13—H13C	109.5
C11—C7—C8	109.9 (2)	H13A—C13—H13C	109.5
C6—C7—C8	108.0 (2)	H13B—C13—H13C	109.5
C1—N1—N2—C2	−0.7 (3)	C12—C5—C6—C7	−58.7 (3)
N2—N1—C1—C3	−177.1 (2)	C4—C5—C6—C7	60.3 (3)
N2—N1—C1—S1	1.3 (2)	C5—C6—C7—C11	58.9 (3)
C2—S1—C1—N1	−1.21 (18)	C5—C6—C7—C8	−61.2 (3)
C2—S1—C1—C3	177.24 (19)	C11—C7—C8—C3	−59.0 (3)
N1—N2—C2—N3	−179.5 (2)	C6—C7—C8—C3	61.4 (3)
N1—N2—C2—S1	−0.3 (2)	C1—C3—C8—C7	179.5 (2)
C13—N3—C2—N2	−5.0 (4)	C4—C3—C8—C7	−59.9 (3)
C13—N3—C2—S1	175.9 (2)	C9—C3—C8—C7	57.3 (3)
C1—S1—C2—N2	0.84 (18)	C1—C3—C9—C10	179.9 (2)
C1—S1—C2—N3	−180.0 (2)	C4—C3—C9—C10	57.9 (3)
N1—C1—C3—C4	−6.8 (3)	C8—C3—C9—C10	−58.9 (3)
S1—C1—C3—C4	174.97 (17)	C3—C9—C10—C11	61.2 (3)
N1—C1—C3—C9	−127.7 (2)	C3—C9—C10—C12	−59.1 (3)
S1—C1—C3—C9	54.0 (3)	C6—C7—C11—C10	−58.0 (3)
N1—C1—C3—C8	112.5 (2)	C8—C7—C11—C10	60.9 (3)
S1—C1—C3—C8	−65.8 (2)	C12—C10—C11—C7	57.7 (3)
C1—C3—C4—C5	178.1 (2)	C9—C10—C11—C7	−61.5 (3)
C9—C3—C4—C5	−59.0 (3)	C6—C5—C12—C10	57.9 (3)
C8—C3—C4—C5	57.7 (3)	C4—C5—C12—C10	−61.9 (3)
C3—C4—C5—C12	61.2 (3)	C11—C10—C12—C5	−57.8 (3)
C3—C4—C5—C6	−58.5 (3)	C9—C10—C12—C5	61.0 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···N1i	0.87 (1)	2.15 (1)	3.021 (3)	179 (2)

Symmetry code: (i) x−1/2, −y+3/2, z−1/2.