2-Cyclo­heptyl­idene-N-phenyl­hydrazine­carbo­thio­amide

In the title compound, C₁₄H₁₉N₃S, the seven-membered cyclo­heptane ring adopts a chair conformation. An intra­molecular N—H...N hydrogen bond [graph-set motif S(5)] is present in the N—N—C—N chain between the ring systems. An intra­molecular C—H...S contact also occurs. In the crystal, pairs of mol­ecules form centrosymmetric dimers through N—H...S hydrogen bonds [graph-set R₂²(8)]. These dimers are connected by C—H...S inter­actions with an R₂²(14) motif.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.030
• wR factor = 0.077
• Data-to-parameter ratio = 15.7

checkCIF/PLATON results

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Alert level B
PLAT230_ALERT_2_B Hirshfeld Test Diff for    S1     --  C7      ..        7.5 su

Alert level C
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          7 Why ?

Alert level G
PLAT005_ALERT_5_G No _iucr_refine_instructions_details  in the CIF     Please Do !
PLAT066_ALERT_1_G Predicted and Reported Tmin&Tmax Range Identical          ? Check
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         27 Note

   0 ALERT level A = Most likely a serious problem - resolve or explain
   1 ALERT level B = A potentially serious problem, consider carefully
   1 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   3 ALERT level G = General information/check it is not something unexpected

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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S1. Comment

Thiosemicarbazones constitute an important class of N, S-donor ligands, and their coordination chemistry was initially explored in the early sixties (Gingras et al., 1961; Ali & Livingstone, 1974; Lobana et al., 2009). On other hand, depending on the parent aldehyde or ketone, the corresponding thiosemicarbazone scaffolds have been evaluated over the last 50 years as anti-viral, anti-bacterial and anti-cancer therapeutic agents (Hu et al., 2006; Du et al., 2002; Lovejoy & Richardson, 2002). Based on these facts and following our study of cyclization reactions of thiosemicarbazides we report the synthesis and crystal structure of the title compound.

In this compound (Fig. 1), the cycloheptane ring (C8–C14) adopts a chair conformation [puckering parameters (Cremer & Pople, 1975) are Q(2) = 0.4493 (14) Å, φ(2) = 126.68 (18)° and Q(3) = 0.6604 (14) Å, φ(3) = 102.94 (12)°]. The C1–N1–C7–S1, C1–N1–C7–N2 and N1–C7–N2–N3 torsion angles are 3.8 (2), -176.94 (12) and -2.53 (16) °, respectively.

The molecular conformation of the title compound is stabilized by a cyclic intramolecular N1—H1N···N3 hydrogen bond, forming a graph set S(5) (Table 1; Bernstein et al., 1995).

In the crystal, pairs of molecules form centrosymmetric dimers through intermolecular N—H···S hydrogen bonds [graph-set R₂²(8)]. These dimers are also connected by C—H···S interactions with an R₂²(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).

S2. Experimental

A solution of 1 mmol (112 mg) of cycloheptanone in 5 ml DMSO was added dropwise to a solution of 1 mmol (167 mg) of N-phenylhydrazinecarbothioamide in 5 ml of DMSO. The reaction mixture was stirred for 2 h at ambient temperature and then left to stand overnight. The resulting mixture was poured into 250 ml of ice/water to give a white precipitate. The crude product was filtered off, washed with cold ethanol and recystallized from ethanol to furnish colourless crystals suitable for X-ray diffraction. M.p. 379 K.

S3. Refinement

All H atoms were found in a difference map. All C-bonded H-atoms were positioned geometrically and refined using a riding model [C—H = 0.95 (aromatic H) and 0.99 Å (methylene H)], with U_iso(H) = 1.2 U_iso(C). The N-bonded H-atoms were refined freely.

Computing details

Data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); 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).

Figures

	Fig. 1. The molecular structure of the title compound with 50% probability displacement ellipsoids.
	Fig. 2. View of the centrosymmetric R2^2(8) dimers of the title compound viewed down b-axis. H atoms not involved in hydrogen bonding have been omitted for clarity.

2-Cycloheptylidene-N-phenylhydrazinecarbothioamide

Crystal data

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) Å^3	0.20 × 0.08 × 0.04 mm
Z = 8

Data collection

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

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.030	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.077	w = 1/[σ^2(Fo^2) + (0.0368P)^2 + 2.2793P] where P = (Fo^2 + 2Fc^2)/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

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	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*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

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)

Hydrogen-bond geometry (Å, º)

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···S1^i	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···S1^i	0.99	2.69	3.3141 (13)	121

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