organic compounds
2-Cycloheptylidene-N-phenylhydrazinecarbothioamide
aDepartment of Physics, Faculty of Sciences, Erciyes University, 38039 Kayseri, Turkey, bChemistry and Environmental Division, Manchester Metropolitan University, Manchester M1 5GD, England, cChemistry Department, Faculty of Science, Minia University, 61519 El-Minia, Egypt, dDepartment of Chemistry, Tulane University, New Orleans, LA 70118, USA, and eKirkuk University, College of Science, Department of Chemistry, Kirkuk, Iraq
*Correspondence e-mail: shaabankamel@yahoo.com
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.
CCDC reference: 988001
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
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Data collection: APEX2 (Bruker, 2013); cell 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).
Supporting information
CCDC reference: 988001
10.1107/S1600536814003948/bt6964sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536814003948/bt6964Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536814003948/bt6964Isup3.cml
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.
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 Uiso(H) = 1.2 Uiso(C). The N-bonded H-atoms were refined freely.
Data collection: APEX2 (Bruker, 2013); cell
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).Fig. 1. The molecular structure of the title compound with 50% probability displacement ellipsoids. | |
Fig. 2. View of the centrosymmetric R22(8) dimers of the title compound viewed down b-axis. H atoms not involved in hydrogen bonding have been omitted for clarity. |
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 |
C14H19N3S | V = 2743.61 (10) Å3 |
Mr = 261.39 | Z = 8 |
Monoclinic, C2/c | Cu Kα radiation |
a = 22.1371 (4) Å | µ = 1.97 mm−1 |
b = 6.1079 (1) Å | T = 100 K |
c = 22.0796 (5) Å | 0.20 × 0.08 × 0.04 mm |
β = 113.219 (2)° |
Bruker D8 VENTURE PHOTON 100 CMOS diffractometer | 2693 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2013) | 2460 reflections with I > 2σ(I) |
Tmin = 0.83, Tmax = 0.93 | Rint = 0.023 |
11263 measured reflections |
R[F2 > 2σ(F2)] = 0.030 | 0 restraints |
wR(F2) = 0.077 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | Δρmax = 0.24 e Å−3 |
2693 reflections | Δρmin = −0.24 e Å−3 |
171 parameters |
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 |
Symmetry code: (i) −x+1/2, −y+3/2, −z. |
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) −x+1/2, −y+3/2, −z. |
Acknowledgements
We gratefully acknowledge Manchester Metropolitan University, Tulane University and Erciyes University for supporting this study. The support of NSF–MRI grant No. 1228232 for the purchase of the diffractometer is gratefully acknowledged.
References
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
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.