2-Cyclo-heptyl-idene-N-phenyl-hydrazine-carbo-thio-amide.

In the title compound, C14H19N3S, the seven-membered cyclo-heptane ring adopts a chair conformation. An intra-molecular N-H⋯N hydrogen bond [graph-set motif S(5)] is present in the N-N-C-N chain between the ring systems. An intra-molecular C-H⋯S contact also occurs. In the crystal, pairs of mol-ecules form centrosymmetric dimers through N-H⋯S hydrogen bonds [graph-set R 2 (2)(8)]. These dimers are connected by C-H⋯S inter-actions with an R 2 (2)(14) motif.

Related literature

For the coordination chemistry of thio­semicarbazones, see: Gingras et al. (1961 ▶); Ali & Livingstone (1974 ▶); Lobana et al. (2009 ▶). For general biological properties of thio­semicarbazone scaffold compounds, see: Hu et al. (2006 ▶); Du et al. (2002 ▶); Lovejoy & Richardson (2002 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For ring-puckering parameters, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C14H19N3S

M = 261.39

Monoclinic,

a = 22.1371 (4) Å

b = 6.1079 (1) Å

c = 22.0796 (5) Å

β = 113.219 (2)°

V = 2743.61 (10) Å3

Z = 8

Cu Kα radiation

μ = 1.97 mm−1

T = 100 K

0.20 × 0.08 × 0.04 mm

Data collection

Bruker D8 VENTURE PHOTON 100 CMOS diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2013 ▶) T min = 0.83, T max = 0.93

11263 measured reflections

2693 independent reflections

2460 reflections with I > 2σ(I)

R int = 0.023

Refinement

R[F 2 > 2σ(F 2)] = 0.030

wR(F 2) = 0.077

S = 1.07

2693 reflections

171 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.24 e Å−3

Δρmin = −0.24 e Å−3

Data collection: APEX2 (Bruker, 2013 ▶); cell refinement: SAINT (Bruker, 2013 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶) and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536814003948/bt6964sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814003948/bt6964Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814003948/bt6964Isup3.cml

CCDC reference: 988001

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

C14H19N3S	F(000) = 1120
Mr = 261.39	Dx = 1.266 Mg m−3
Monoclinic, C2/c	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -C 2yc	Cell parameters from 8726 reflections
a = 22.1371 (4) Å	θ = 4.4–72.4°
b = 6.1079 (1) Å	µ = 1.97 mm−1
c = 22.0796 (5) Å	T = 100 K
β = 113.219 (2)°	Parallelepiped, colourless
V = 2743.61 (10) Å3	0.20 × 0.08 × 0.04 mm
Z = 8

Bruker D8 VENTURE PHOTON 100 CMOS diffractometer	2693 independent reflections
Radiation source: INCOATEC IµS micro–focus source	2460 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.023
Detector resolution: 10.4167 pixels mm-1	θmax = 72.4°, θmin = 4.4°
ω scans	h = −25→27
Absorption correction: multi-scan (SADABS; Bruker, 2013)	k = −7→7
Tmin = 0.83, Tmax = 0.93	l = −27→27
11263 measured reflections

Refinement on F2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.030	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.077	w = 1/[σ2(Fo2) + (0.0368P)2 + 2.2793P] where P = (Fo2 + 2Fc2)/3
S = 1.07	(Δ/σ)max < 0.001
2693 reflections	Δρmax = 0.24 e Å−3
171 parameters	Δρmin = −0.24 e Å−3

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs 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	0.17859 (2)	0.78279 (5)	0.04498 (2)	0.0211 (1)
N1	0.11142 (5)	0.39799 (19)	0.02178 (5)	0.0198 (3)
N2	0.17477 (5)	0.46222 (18)	−0.03562 (5)	0.0198 (3)
N3	0.15155 (5)	0.26265 (17)	−0.06567 (5)	0.0194 (3)
C1	0.07507 (6)	0.4095 (2)	0.06186 (6)	0.0184 (3)
C2	0.07037 (6)	0.5909 (2)	0.09770 (6)	0.0238 (4)
C3	0.03058 (6)	0.5801 (2)	0.13315 (7)	0.0255 (4)
C4	−0.00440 (6)	0.3922 (2)	0.13341 (6)	0.0246 (4)
C5	0.00110 (7)	0.2115 (2)	0.09818 (7)	0.0260 (4)
C6	0.04086 (6)	0.2191 (2)	0.06301 (6)	0.0226 (4)
C7	0.15252 (6)	0.5377 (2)	0.01003 (6)	0.0187 (3)
C8	0.17441 (6)	0.1871 (2)	−0.10668 (6)	0.0186 (3)
C9	0.22606 (6)	0.3024 (2)	−0.12320 (6)	0.0201 (3)
C10	0.24745 (6)	0.1938 (2)	−0.17382 (6)	0.0221 (4)
C11	0.19353 (7)	0.1805 (2)	−0.24352 (6)	0.0254 (4)
C12	0.14582 (7)	−0.0109 (2)	−0.25458 (6)	0.0261 (4)
C13	0.10499 (6)	−0.0088 (2)	−0.21264 (6)	0.0259 (4)
C14	0.14621 (6)	−0.0277 (2)	−0.13788 (6)	0.0217 (4)
H1N	0.1062 (8)	0.280 (3)	−0.0007 (8)	0.023 (4)*
H2	0.09410	0.72090	0.09800	0.0290*
H2N	0.2057 (8)	0.535 (3)	−0.0405 (8)	0.025 (4)*
H3	0.02730	0.70410	0.15770	0.0310*
H4	−0.03180	0.38760	0.15740	0.0300*
H5	−0.02250	0.08150	0.09810	0.0310*
H6	0.04480	0.09350	0.03950	0.0270*
H9A	0.26550	0.32090	−0.08190	0.0240*
H9B	0.20950	0.45070	−0.13950	0.0240*
H10A	0.26290	0.04360	−0.15860	0.0270*
H10B	0.28510	0.27640	−0.17570	0.0270*
H11A	0.16810	0.31870	−0.25300	0.0300*
H11B	0.21460	0.16830	−0.27540	0.0300*
H12A	0.11540	−0.01210	−0.30160	0.0310*
H12B	0.17130	−0.14880	−0.24570	0.0310*
H13A	0.07340	−0.13190	−0.22650	0.0310*
H13B	0.07930	0.12880	−0.22130	0.0310*
H14A	0.11820	−0.08710	−0.11620	0.0260*
H14B	0.18260	−0.13250	−0.13040	0.0260*

	U11	U22	U33	U12	U13	U23
S1	0.0234 (2)	0.0197 (2)	0.0226 (2)	−0.0056 (1)	0.0116 (1)	−0.0035 (1)
N1	0.0235 (5)	0.0191 (6)	0.0189 (5)	−0.0053 (4)	0.0106 (4)	−0.0042 (4)
N2	0.0225 (5)	0.0195 (6)	0.0209 (5)	−0.0054 (4)	0.0122 (4)	−0.0025 (4)
N3	0.0215 (5)	0.0183 (5)	0.0188 (5)	−0.0021 (4)	0.0084 (4)	−0.0008 (4)
C1	0.0151 (5)	0.0240 (7)	0.0148 (5)	−0.0009 (5)	0.0046 (4)	0.0016 (5)
C2	0.0252 (6)	0.0235 (7)	0.0249 (6)	−0.0062 (5)	0.0123 (5)	−0.0032 (5)
C3	0.0280 (7)	0.0277 (7)	0.0242 (6)	−0.0015 (6)	0.0138 (6)	−0.0035 (5)
C4	0.0209 (6)	0.0323 (8)	0.0238 (6)	0.0001 (5)	0.0122 (5)	0.0031 (6)
C5	0.0229 (6)	0.0249 (7)	0.0326 (7)	−0.0038 (5)	0.0136 (6)	0.0026 (6)
C6	0.0216 (6)	0.0222 (7)	0.0247 (6)	−0.0023 (5)	0.0099 (5)	−0.0013 (5)
C7	0.0173 (6)	0.0213 (6)	0.0162 (5)	−0.0001 (5)	0.0051 (5)	0.0018 (5)
C8	0.0180 (6)	0.0203 (6)	0.0179 (6)	0.0000 (5)	0.0074 (5)	0.0024 (5)
C9	0.0214 (6)	0.0199 (6)	0.0202 (6)	−0.0035 (5)	0.0095 (5)	0.0004 (5)
C10	0.0219 (6)	0.0251 (7)	0.0234 (6)	−0.0027 (5)	0.0133 (5)	0.0002 (5)
C11	0.0295 (7)	0.0293 (7)	0.0208 (6)	−0.0028 (6)	0.0136 (5)	0.0005 (5)
C12	0.0267 (6)	0.0314 (8)	0.0215 (6)	−0.0038 (6)	0.0109 (5)	−0.0052 (6)
C13	0.0218 (6)	0.0310 (7)	0.0257 (7)	−0.0057 (5)	0.0103 (5)	−0.0080 (6)
C14	0.0230 (6)	0.0217 (7)	0.0251 (6)	−0.0045 (5)	0.0146 (5)	−0.0025 (5)

S1—C7	1.6788 (13)	C12—C13	1.528 (2)
N1—C1	1.4132 (18)	C13—C14	1.5437 (17)
N1—C7	1.3451 (18)	C2—H2	0.9500
N2—N3	1.3861 (15)	C3—H3	0.9500
N2—C7	1.3648 (17)	C4—H4	0.9500
N3—C8	1.2846 (17)	C5—H5	0.9500
N1—H1N	0.857 (18)	C6—H6	0.9500
N2—H2N	0.858 (19)	C9—H9A	0.9900
C1—C6	1.3935 (18)	C9—H9B	0.9900
C1—C2	1.3891 (18)	C10—H10A	0.9900
C2—C3	1.392 (2)	C10—H10B	0.9900
C3—C4	1.3858 (18)	C11—H11A	0.9900
C4—C5	1.3830 (18)	C11—H11B	0.9900
C5—C6	1.385 (2)	C12—H12A	0.9900
C8—C14	1.4988 (17)	C12—H12B	0.9900
C8—C9	1.5051 (19)	C13—H13A	0.9900
C9—C10	1.5267 (18)	C13—H13B	0.9900
C10—C11	1.5334 (18)	C14—H14A	0.9900
C11—C12	1.529 (2)	C14—H14B	0.9900
C1—N1—C7	133.21 (11)	C6—C5—H5	120.00
N3—N2—C7	118.48 (11)	C1—C6—H6	120.00
N2—N3—C8	118.59 (11)	C5—C6—H6	120.00
C7—N1—H1N	111.7 (12)	C8—C9—H9A	108.00
C1—N1—H1N	115.1 (12)	C8—C9—H9B	108.00
C7—N2—H2N	117.1 (12)	C10—C9—H9A	108.00
N3—N2—H2N	124.0 (12)	C10—C9—H9B	108.00
N1—C1—C2	125.84 (12)	H9A—C9—H9B	107.00
C2—C1—C6	119.47 (12)	C9—C10—H10A	109.00
N1—C1—C6	114.68 (11)	C9—C10—H10B	109.00
C1—C2—C3	119.26 (12)	C11—C10—H10A	109.00
C2—C3—C4	121.35 (12)	C11—C10—H10B	109.00
C3—C4—C5	119.04 (13)	H10A—C10—H10B	108.00
C4—C5—C6	120.32 (12)	C10—C11—H11A	109.00
C1—C6—C5	120.54 (12)	C10—C11—H11B	109.00
S1—C7—N2	118.81 (10)	C12—C11—H11A	109.00
N1—C7—N2	113.37 (11)	C12—C11—H11B	109.00
S1—C7—N1	127.82 (10)	H11A—C11—H11B	108.00
N3—C8—C9	123.42 (11)	C11—C12—H12A	108.00
N3—C8—C14	115.47 (12)	C11—C12—H12B	108.00
C9—C8—C14	121.12 (11)	C13—C12—H12A	108.00
C8—C9—C10	117.30 (10)	C13—C12—H12B	108.00
C9—C10—C11	114.48 (12)	H12A—C12—H12B	107.00
C10—C11—C12	114.59 (10)	C12—C13—H13A	109.00
C11—C12—C13	115.67 (11)	C12—C13—H13B	109.00
C12—C13—C14	113.95 (11)	C14—C13—H13A	109.00
C8—C14—C13	112.92 (10)	C14—C13—H13B	109.00
C1—C2—H2	120.00	H13A—C13—H13B	108.00
C3—C2—H2	120.00	C8—C14—H14A	109.00
C2—C3—H3	119.00	C8—C14—H14B	109.00
C4—C3—H3	119.00	C13—C14—H14A	109.00
C3—C4—H4	120.00	C13—C14—H14B	109.00
C5—C4—H4	120.00	H14A—C14—H14B	108.00
C4—C5—H5	120.00
C7—N1—C1—C2	5.0 (2)	C1—C2—C3—C4	0.0 (2)
C7—N1—C1—C6	−176.19 (13)	C2—C3—C4—C5	0.7 (2)
C1—N1—C7—S1	3.8 (2)	C3—C4—C5—C6	−0.2 (2)
C1—N1—C7—N2	−176.94 (12)	C4—C5—C6—C1	−0.9 (2)
C7—N2—N3—C8	−177.23 (12)	N3—C8—C9—C10	−178.99 (12)
N3—N2—C7—S1	−178.15 (9)	C14—C8—C9—C10	1.11 (17)
N3—N2—C7—N1	2.53 (16)	N3—C8—C14—C13	113.26 (13)
N2—N3—C8—C14	−179.13 (10)	C9—C8—C14—C13	−66.84 (16)
N2—N3—C8—C9	0.97 (18)	C8—C9—C10—C11	65.39 (14)
N1—C1—C2—C3	177.64 (12)	C9—C10—C11—C12	−81.85 (14)
C2—C1—C6—C5	1.6 (2)	C10—C11—C12—C13	62.65 (16)
C6—C1—C2—C3	−1.15 (19)	C11—C12—C13—C14	−63.37 (14)
N1—C1—C6—C5	−177.31 (12)	C12—C13—C14—C8	82.43 (14)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···N3	0.857 (18)	2.052 (18)	2.5599 (16)	117.2 (16)
N2—H2N···S1i	0.858 (19)	2.830 (19)	3.6790 (13)	170.5 (15)
C2—H2···S1	0.95	2.60	3.2660 (15)	128
C9—H9A···S1i	0.99	2.69	3.3141 (13)	121

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯N3	0.857 (18)	2.052 (18)	2.5599 (16)	117.2 (16)
N2—H2N⋯S1i	0.858 (19)	2.830 (19)	3.6790 (13)	170.5 (15)
C2—H2⋯S1	0.95	2.60	3.2660 (15)	128
C9—H9A⋯S1i	0.99	2.69	3.3141 (13)	121

Symmetry code: (i) .