2-{3-Methyl-2-[(2Z)-pent-2-en-1-yl]cyclo­pent-2-en-1-yl­idene}-N-phenylhydrazinecarbo­thio­amide

The hydro­chloric acid-catalyzed equimolar reaction between cis-jasmone and 4-phenyl­thio­semicarbazide yielded the title compound, C₁₈H₂₃N₃S (common name: cis-jasmone 4-phenyl­thio­semicarbazone). Concerning the hydrogen bonding, an N—H...N intra­molecular inter­action is observed, forming a ring with graph-set motif S(5). In the crystal, the mol­ecules are connected into centrosymmetric dimers by pairs of N—H...S and C—H...S inter­actions, forming rings of graph-set motifs R₂²(8) and R₂¹(7), with the sulfur atoms acting as double acceptors. The thio­semicarbazone entity is approximately planar, with the maximum deviation from the mean plane through the N/N/C/S/N atoms being 0.0376 (9) Å (the r.m.s.d. amounts to 0.0234 Å). The mol­ecule is substantially twisted as indicated by the dihedral angle between the thio­semicarbazone fragment and the phenyl ring, which amounts to 56.1 (5)°, and because of the jasmone fragment, which bears a chain with sp³-hybridized carbon atoms in the structure. The Hirshfeld surface analysis indicates that the major contributions for the crystal cohesion are: H...H (65.3%), H...C/C...H (16.2%), H...S/S...H (10.9%) and H...N/N...H (5.5%).

Key indicators

Structure: I

• Single-crystal X-ray study
• T = 123 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.039
• wR factor = 0.095
• Data-to-parameter ratio = 18.6

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT911_ALERT_3_C Missing FCF Refl Between Thmin & STh/L=    0.600          6 Report

Alert level G
PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms ..............          2 Report
PLAT013_ALERT_1_G N.O.K.   _shelx_hkl_checksum Found in CIF ......     Please Check
PLAT199_ALERT_1_G Reported _cell_measurement_temperature ..... (K)        293 Check
PLAT200_ALERT_1_G Reported   _diffrn_ambient_temperature ..... (K)        293 Check
PLAT480_ALERT_4_G Long H...A H-Bond Reported H2B      ..S1       .       2.96 Ang.
PLAT802_ALERT_4_G CIF Input Record(s) with more than 80 Characters          1 Info
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min).          3 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600          9 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.         11 Info

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

   3 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
   2 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

---

Computing details

2-{3-Methyl-2-[(2Z)-pent-2-en-1-yl]cyclopent-2-en-1-ylidene}-N-phenylhydrazinecarbothioamide

Crystal data

C18H23N3S	F(000) = 672
Mr = 313.45	Dx = 1.267 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 13.6565 (3) Å	Cell parameters from 63134 reflections
b = 5.8286 (2) Å	θ = 2.9–27.5°
c = 20.6721 (6) Å	µ = 0.20 mm^−1
β = 92.751 (2)°	T = 123 K
V = 1643.57 (8) Å^3	Fragment, colourless
Z = 4	0.22 × 0.13 × 0.05 mm

Data collection

Enraf–Nonius FR590 Kappa CCD diffractometer	2857 reflections with I > 2σ(I)
Radiation source: sealed X-ray tube, Enraf–Nonius FR590	Rint = 0.064
Detector resolution: 9 pixels mm^-1	θmax = 27.5°, θmin = 3.0°
CCD rotation images, thick slices, κ–goniostat scans	h = −17→17
26959 measured reflections	k = −7→7
3751 independent reflections	l = −26→26

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.039	w = 1/[σ^2(Fo^2) + (0.0359P)^2 + 0.7368P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.095	(Δ/σ)max < 0.001
S = 1.06	Δρmax = 0.28 e Å^−3
3751 reflections	Δρmin = −0.25 e Å^−3
202 parameters	Extinction correction: SHELXL-2018/3 (Sheldrick 2015), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0053 (9)
Primary atom site location: structure-invariant direct methods

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. An absorption correction was not performed, as the crystal data analysis suggested that the absorption effects were not significant for the structure refinement. Hydrogen atoms were located in a difference-Fourier map, but were positioned with idealized geometry and refined isotropically using a riding model (HFIX command). Methyl H atoms were allowed to rotate but not to tip to best fit the experimental electron density. Thus, for the methyl H atoms [U_iso(H) = 1.5 U_eq(C)], the C—H bond lengths were set to 0.96 Å. The other C—H bond lengths were also set according to the H atom neighbourhood [U_iso(H) = 1.2 U_eq(C)]. For the phenyl H atoms and for the other H atoms attached to sp²-hybridized carbon atoms (C7 and C8), the C—H bond lengths were set 0.93 Å. For the H atoms of the —CH₂— fragments (C2, C3, C6 and C9), the C—H bond lengths were set to 0.97 Å. Finally, the N—H bond lengths [U_iso(H) = 1.2 U_eq(N)] were set to 0.86 Å.

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

	x	y	z	Uiso*/Ueq
C1	0.38987 (11)	0.5560 (3)	−0.10461 (7)	0.0182 (3)
C2	0.45778 (11)	0.4298 (3)	−0.14766 (8)	0.0207 (3)
H2A	0.436900	0.272027	−0.154050	0.025*
H2B	0.524485	0.431089	−0.129277	0.025*
C3	0.45002 (12)	0.5646 (3)	−0.21191 (8)	0.0239 (4)
H3A	0.513393	0.625665	−0.222395	0.029*
H3B	0.425872	0.466784	−0.247139	0.029*
C4	0.37868 (11)	0.7559 (3)	−0.20041 (8)	0.0205 (3)
C5	0.34692 (11)	0.7526 (3)	−0.13988 (7)	0.0189 (3)
C6	0.27920 (11)	0.9155 (3)	−0.10790 (8)	0.0220 (3)
H6A	0.274508	1.055634	−0.133179	0.026*
H6B	0.307436	0.954690	−0.065378	0.026*
C7	0.17720 (12)	0.8219 (3)	−0.10048 (8)	0.0255 (4)
H7	0.165822	0.670153	−0.112577	0.031*
C8	0.10260 (12)	0.9383 (3)	−0.07815 (9)	0.0277 (4)
H8	0.043700	0.859385	−0.075799	0.033*
C9	0.10293 (12)	1.1834 (3)	−0.05628 (9)	0.0275 (4)
H9A	0.159387	1.260861	−0.072846	0.033*
H9B	0.109126	1.188208	−0.009357	0.033*
C10	0.01004 (13)	1.3102 (3)	−0.07920 (10)	0.0337 (4)
H10A	0.006058	1.315650	−0.125670	0.051*
H10B	0.011733	1.463645	−0.062278	0.051*
H10C	−0.046191	1.231343	−0.064102	0.051*
C11	0.35163 (13)	0.9202 (3)	−0.25364 (8)	0.0266 (4)
H11A	0.304018	1.027255	−0.239068	0.040*
H11B	0.324443	0.837326	−0.290397	0.040*
H11C	0.409031	1.001812	−0.265701	0.040*
C12	0.36853 (11)	0.2620 (3)	0.04217 (7)	0.0182 (3)
C13	0.24371 (11)	0.3876 (3)	0.11856 (7)	0.0189 (3)
C14	0.18756 (11)	0.1912 (3)	0.12727 (8)	0.0214 (3)
H14	0.190844	0.068671	0.098647	0.026*
C15	0.12685 (11)	0.1804 (3)	0.17895 (8)	0.0235 (4)
H15	0.088949	0.050178	0.184838	0.028*
C16	0.12210 (11)	0.3623 (3)	0.22203 (8)	0.0241 (4)
H16	0.081198	0.353730	0.256649	0.029*
C17	0.17823 (12)	0.5562 (3)	0.21342 (8)	0.0232 (4)
H17	0.175481	0.677598	0.242474	0.028*
C18	0.23886 (11)	0.5702 (3)	0.16133 (8)	0.0215 (3)
H18	0.276003	0.701443	0.155225	0.026*
N1	0.36550 (9)	0.5130 (2)	−0.04654 (6)	0.0189 (3)
N2	0.40538 (9)	0.3219 (2)	−0.01525 (6)	0.0195 (3)
H2	0.451694	0.244307	−0.031612	0.023*
N3	0.30211 (9)	0.4113 (2)	0.06367 (6)	0.0201 (3)
H3	0.294026	0.535658	0.041653	0.024*
S1	0.40757 (3)	0.02358 (7)	0.08139 (2)	0.02292 (12)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0171 (8)	0.0187 (8)	0.0187 (8)	−0.0025 (6)	0.0011 (6)	−0.0009 (6)
C2	0.0207 (8)	0.0204 (8)	0.0210 (8)	0.0008 (6)	0.0031 (6)	0.0008 (6)
C3	0.0267 (9)	0.0242 (8)	0.0212 (8)	0.0006 (7)	0.0063 (7)	0.0007 (7)
C4	0.0193 (8)	0.0204 (8)	0.0216 (8)	−0.0030 (6)	0.0006 (6)	0.0015 (6)
C5	0.0180 (8)	0.0174 (8)	0.0212 (8)	−0.0024 (6)	0.0015 (6)	−0.0003 (6)
C6	0.0231 (8)	0.0177 (8)	0.0254 (9)	0.0008 (6)	0.0037 (7)	−0.0001 (7)
C7	0.0259 (9)	0.0192 (8)	0.0318 (10)	−0.0013 (7)	0.0047 (7)	−0.0009 (7)
C8	0.0236 (9)	0.0238 (9)	0.0361 (10)	−0.0022 (7)	0.0053 (7)	−0.0004 (7)
C9	0.0272 (9)	0.0252 (9)	0.0302 (9)	0.0012 (7)	0.0027 (7)	−0.0026 (7)
C10	0.0309 (10)	0.0251 (9)	0.0452 (12)	0.0030 (7)	0.0022 (8)	0.0007 (8)
C11	0.0294 (9)	0.0271 (9)	0.0231 (9)	−0.0017 (7)	−0.0006 (7)	0.0048 (7)
C12	0.0192 (8)	0.0180 (8)	0.0174 (8)	−0.0028 (6)	−0.0003 (6)	−0.0013 (6)
C13	0.0180 (8)	0.0207 (8)	0.0181 (8)	0.0030 (6)	0.0019 (6)	0.0030 (6)
C14	0.0234 (8)	0.0204 (8)	0.0205 (8)	−0.0004 (6)	0.0010 (7)	0.0003 (6)
C15	0.0213 (8)	0.0239 (8)	0.0255 (9)	−0.0034 (7)	0.0032 (7)	0.0051 (7)
C16	0.0203 (8)	0.0317 (9)	0.0207 (8)	0.0034 (7)	0.0042 (7)	0.0043 (7)
C17	0.0239 (8)	0.0244 (9)	0.0216 (8)	0.0048 (7)	0.0026 (7)	−0.0026 (6)
C18	0.0214 (8)	0.0199 (8)	0.0234 (8)	−0.0004 (6)	0.0027 (6)	0.0010 (6)
N1	0.0213 (7)	0.0165 (6)	0.0189 (7)	−0.0007 (5)	0.0010 (5)	0.0019 (5)
N2	0.0216 (7)	0.0183 (6)	0.0188 (7)	0.0029 (5)	0.0034 (5)	0.0011 (5)
N3	0.0240 (7)	0.0171 (6)	0.0195 (7)	0.0018 (5)	0.0057 (5)	0.0036 (5)
S1	0.0255 (2)	0.0203 (2)	0.0233 (2)	0.00340 (16)	0.00521 (16)	0.00501 (16)

Geometric parameters (Å, º)

C1—N1	1.286 (2)	C10—H10B	0.9600
C1—C5	1.466 (2)	C10—H10C	0.9600
C1—C2	1.507 (2)	C11—H11A	0.9600
C2—C3	1.542 (2)	C11—H11B	0.9600
C2—H2A	0.9700	C11—H11C	0.9600
C2—H2B	0.9700	C12—N3	1.348 (2)
C3—C4	1.507 (2)	C12—N2	1.357 (2)
C3—H3A	0.9700	C12—S1	1.6827 (16)
C3—H3B	0.9700	C13—C18	1.387 (2)
C4—C5	1.344 (2)	C13—C14	1.394 (2)
C4—C11	1.492 (2)	C13—N3	1.425 (2)
C5—C6	1.501 (2)	C14—C15	1.385 (2)
C6—C7	1.511 (2)	C14—H14	0.9300
C6—H6A	0.9700	C15—C16	1.388 (2)
C6—H6B	0.9700	C15—H15	0.9300
C7—C8	1.325 (2)	C16—C17	1.382 (2)
C7—H7	0.9300	C16—H16	0.9300
C8—C9	1.498 (2)	C17—C18	1.392 (2)
C8—H8	0.9300	C17—H17	0.9300
C9—C10	1.524 (2)	C18—H18	0.9300
C9—H9A	0.9700	N1—N2	1.3863 (18)
C9—H9B	0.9700	N2—H2	0.8600
C10—H10A	0.9600	N3—H3	0.8600
N1—C1—C5	120.09 (14)	C9—C10—H10B	109.5
N1—C1—C2	130.57 (14)	H10A—C10—H10B	109.5
C5—C1—C2	109.32 (13)	C9—C10—H10C	109.5
C1—C2—C3	103.95 (12)	H10A—C10—H10C	109.5
C1—C2—H2A	111.0	H10B—C10—H10C	109.5
C3—C2—H2A	111.0	C4—C11—H11A	109.5
C1—C2—H2B	111.0	C4—C11—H11B	109.5
C3—C2—H2B	111.0	H11A—C11—H11B	109.5
H2A—C2—H2B	109.0	C4—C11—H11C	109.5
C4—C3—C2	105.03 (13)	H11A—C11—H11C	109.5
C4—C3—H3A	110.7	H11B—C11—H11C	109.5
C2—C3—H3A	110.7	N3—C12—N2	113.96 (13)
C4—C3—H3B	110.7	N3—C12—S1	125.25 (12)
C2—C3—H3B	110.7	N2—C12—S1	120.78 (12)
H3A—C3—H3B	108.8	C18—C13—C14	120.27 (14)
C5—C4—C11	128.03 (15)	C18—C13—N3	118.60 (14)
C5—C4—C3	112.11 (14)	C14—C13—N3	121.01 (14)
C11—C4—C3	119.85 (14)	C15—C14—C13	119.37 (15)
C4—C5—C1	109.55 (14)	C15—C14—H14	120.3
C4—C5—C6	129.38 (15)	C13—C14—H14	120.3
C1—C5—C6	121.06 (14)	C14—C15—C16	120.55 (15)
C5—C6—C7	114.00 (13)	C14—C15—H15	119.7
C5—C6—H6A	108.8	C16—C15—H15	119.7
C7—C6—H6A	108.8	C17—C16—C15	119.91 (15)
C5—C6—H6B	108.8	C17—C16—H16	120.0
C7—C6—H6B	108.8	C15—C16—H16	120.0
H6A—C6—H6B	107.6	C16—C17—C18	120.12 (15)
C8—C7—C6	125.32 (15)	C16—C17—H17	119.9
C8—C7—H7	117.3	C18—C17—H17	119.9
C6—C7—H7	117.3	C13—C18—C17	119.78 (15)
C7—C8—C9	127.02 (16)	C13—C18—H18	120.1
C7—C8—H8	116.5	C17—C18—H18	120.1
C9—C8—H8	116.5	C1—N1—N2	118.59 (13)
C8—C9—C10	112.23 (15)	C12—N2—N1	117.45 (12)
C8—C9—H9A	109.2	C12—N2—H2	121.3
C10—C9—H9A	109.2	N1—N2—H2	121.3
C8—C9—H9B	109.2	C12—N3—C13	127.68 (13)
C10—C9—H9B	109.2	C12—N3—H3	116.2
H9A—C9—H9B	107.9	C13—N3—H3	116.2
C9—C10—H10A	109.5
N1—C1—C2—C3	177.17 (16)	C18—C13—C14—C15	0.1 (2)
C5—C1—C2—C3	−1.15 (17)	N3—C13—C14—C15	−175.86 (14)
C1—C2—C3—C4	0.01 (16)	C13—C14—C15—C16	−0.4 (2)
C2—C3—C4—C5	1.26 (18)	C14—C15—C16—C17	0.1 (2)
C2—C3—C4—C11	−178.74 (14)	C15—C16—C17—C18	0.5 (2)
C11—C4—C5—C1	177.96 (15)	C14—C13—C18—C17	0.5 (2)
C3—C4—C5—C1	−2.03 (18)	N3—C13—C18—C17	176.55 (14)
C11—C4—C5—C6	−2.6 (3)	C16—C17—C18—C13	−0.8 (2)
C3—C4—C5—C6	177.45 (15)	C5—C1—N1—N2	178.18 (13)
N1—C1—C5—C4	−176.51 (14)	C2—C1—N1—N2	0.0 (2)
C2—C1—C5—C4	2.01 (18)	N3—C12—N2—N1	−5.15 (19)
N1—C1—C5—C6	4.0 (2)	S1—C12—N2—N1	176.26 (10)
C2—C1—C5—C6	−177.53 (13)	C1—N1—N2—C12	−171.07 (14)
C4—C5—C6—C7	104.92 (19)	N2—C12—N3—C13	173.62 (14)
C1—C5—C6—C7	−75.65 (19)	S1—C12—N3—C13	−7.9 (2)
C5—C6—C7—C8	−174.86 (17)	C18—C13—N3—C12	132.16 (16)
C6—C7—C8—C9	0.4 (3)	C14—C13—N3—C12	−51.8 (2)
C7—C8—C9—C10	138.6 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2B···S1^i	0.97	2.96	3.4640 (16)	113
N2—H2···S1^i	0.86	2.72	3.5757 (13)	177
N3—H3···N1	0.86	2.11	2.5457 (18)	111

Symmetry code: (i) −x+1, −y, −z.