A second crystalline modification of 2-{3-methyl-2-[(2Z)-pent-2-en-1-yl]cyclo­pent-2-en-1-yl­idene}hydrazinecarbo­thio­amide

A second crystalline modification of the title compound, C₁₂H₁₉N₃S [common name: cis-jasmone thio­semicarbazone] was crystallized from tetra­hydro­furane at room temperature. There is one crystallographic independent mol­ecule in the asymmetric unit, showing disorder in the cis-jasmone chain [site-occupancy ratio = 0.590 (14):0.410 (14)]. The thio­semicarbazone entity is approximately planar, with the maximum deviation from the mean plane through the N/N/C/S/N atoms being 0.0463 (14) Å [r.m.s.d. = 0.0324 Å], while for the five-membered ring of the jasmone fragment, the maximum deviation from the mean plane through the carbon atoms amounts to 0.0465 (15) Å [r.m.s.d. = 0.0338 Å]. The mol­ecule is not planar due to the dihedral angle between these two fragments, which is 8.93 (1)°, and due to the sp³-hybridized carbon atoms in the jasmone fragment chain. In the crystal, the mol­ecules are connected by N—H...S and C—H...S inter­actions, with graph-set motifs R₂²(8) and R₂¹(7), building mono-periodic hydrogen-bonded ribbons along [010]. A Hirshfeld surface analysis indicates that the major contributions for the crystal cohesion are H...H (67.8%), H...S/S...H (15.0%), H...C/C...H (8.5%) and H...N/N...H (5.6%) [only non-disordered atoms and those with the highest s.o.f. were considered]. This work reports the second crystalline modification of the cis-jasmone thio­semicarbazone structure, the first one being published recently [Orsoni et al. (2020). Int. J. Mol. Sci. 21, 8681–8697] with the crystals obtained in ethanol at 273 K.

Key indicators

Structure: I

• Single-crystal X-ray study
• T = 123 K
• Mean [sigma](C-C) = 0.003 Å
• Disorder in main residue
• R factor = 0.054
• wR factor = 0.143
• Data-to-parameter ratio = 14.2

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT220_ALERT_2_C NonSolvent   Resd 1  C   Ueq(max)/Ueq(min) Range        4.1 Ratio
PLAT222_ALERT_3_C NonSolvent Resd 1  H   Uiso(max)/Uiso(min) Range        5.6 Ratio
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          1 Note
              C12 H19 N3 S
PLAT906_ALERT_3_C Large K Value in the Analysis of Variance ......      3.373 Check
PLAT934_ALERT_3_C Number of (Iobs-Icalc)/Sigma(W) > 10 Outliers ..          1 Check
                0  0  6,

Alert level G
PLAT301_ALERT_3_G Main Residue  Disorder ..............(Resd  1  )        13% Note
PLAT380_ALERT_4_G Incorrectly? Oriented X(sp2)-Methyl Moiety .....        C11 Check
PLAT410_ALERT_2_G Short Intra H...H Contact  H6B      ..H9B2     .       2.10 Ang.
                                                      x,y,z  =      1_555 Check
PLAT480_ALERT_4_G Long H...A H-Bond Reported H2B      ..S1       .       2.93 Ang.
PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels ..........          4 Note
              H9A1    H9A2    H9B1    H9B2
PLAT899_ALERT_4_G SHELXL2018 is Deprecated and Succeeded by SHELXL     2019/3 Note
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min).          3 Note
                1  0  0,   1  1  0,   2  0  0,
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         21 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          1 Info

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   5 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

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

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Computing details

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

Crystal data

C12H19N3S	F(000) = 512
Mr = 237.36	Dx = 1.207 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 15.0159 (7) Å	Cell parameters from 60208 reflections
b = 8.0595 (3) Å	θ = 2.9–27.5°
c = 10.8243 (5) Å	µ = 0.23 mm^−1
β = 94.372 (3)°	T = 123 K
V = 1306.15 (10) Å^3	Plate, colourless
Z = 4	0.17 × 0.14 × 0.05 mm

Data collection

Enraf–Nonius FR590 Kappa CCD diffractometer	3002 independent reflections
Radiation source: sealed X-ray tube, Enraf Nonius FR590	2241 reflections with I > 2σ(I)
Horizontally mounted graphite crystal monochromator	Rint = 0.083
Detector resolution: 9 pixels mm^-1	θmax = 27.6°, θmin = 3.2°
CCD rotation images, thick slices, κ–goniostat scans	h = −19→19
Absorption correction: multi-scan (Blessing, 1995)	k = −10→10
Tmin = 0.922, Tmax = 0.998	l = −13→14
24176 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.054	Hydrogen site location: mixed
wR(F^2) = 0.143	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ^2(Fo^2) + (0.069P)^2 + 0.7307P] where P = (Fo^2 + 2Fc^2)/3
3002 reflections	(Δ/σ)max < 0.001
212 parameters	Δρmax = 0.59 e Å^−3
0 restraints	Δρmin = −0.45 e Å^−3

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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
S1	0.49279 (4)	−0.38063 (6)	0.29692 (5)	0.02576 (19)
N1	0.35988 (12)	−0.5052 (2)	−0.01509 (16)	0.0239 (4)
N2	0.40985 (12)	−0.5194 (2)	0.09773 (17)	0.0235 (4)
H1	0.4271 (17)	−0.617 (3)	0.133 (2)	0.030 (7)*
N3	0.42480 (14)	−0.2376 (2)	0.09074 (19)	0.0275 (5)
H2	0.3988 (18)	−0.242 (4)	0.016 (3)	0.039 (5)*
H3	0.4455 (19)	−0.149 (4)	0.126 (3)	0.039 (5)*
C1	0.32864 (14)	−0.6392 (3)	−0.0662 (2)	0.0224 (5)
C2	0.33976 (16)	−0.8181 (3)	−0.0266 (2)	0.0251 (5)
H2A	0.3276 (15)	−0.833 (3)	0.065 (2)	0.024 (4)*
H2B	0.4031 (17)	−0.853 (3)	−0.036 (2)	0.024 (4)*
C3	0.27458 (17)	−0.9129 (3)	−0.1170 (2)	0.0295 (5)
H3A	0.3041 (16)	−1.002 (4)	−0.156 (2)	0.035 (5)*
H3B	0.2234 (17)	−0.961 (3)	−0.074 (2)	0.035 (5)*
C4	0.24066 (15)	−0.7858 (3)	−0.2109 (2)	0.0269 (5)
C5	0.27121 (15)	−0.6322 (3)	−0.1810 (2)	0.0253 (5)
C6	0.25021 (17)	−0.4704 (3)	−0.2465 (2)	0.0299 (5)
H6A	0.3013 (19)	−0.413 (4)	−0.246 (3)	0.039 (5)*
H6B	0.2284 (17)	−0.490 (3)	−0.337 (3)	0.039 (5)*
C7	0.18173 (18)	−0.3701 (3)	−0.1851 (2)	0.0349 (6)
H7	0.1977 (18)	−0.347 (3)	−0.097 (3)	0.041 (8)*
C8	0.1055 (2)	−0.3144 (4)	−0.2354 (3)	0.0520 (8)
H8A	0.077777	−0.233393	−0.190673	0.062*	0.590 (14)
H8B	0.059808	−0.292155	−0.184493	0.062*	0.410 (14)
C9A	0.0569 (4)	−0.3651 (9)	−0.3570 (6)	0.0381 (17)	0.590 (14)
H9A1	0.014033	−0.451696	−0.342863	0.046*	0.590 (14)
H9A2	0.099214	−0.408217	−0.412357	0.046*	0.590 (14)
C10A	0.0088 (6)	−0.2146 (8)	−0.4159 (9)	0.0420 (18)	0.590 (14)
H10A	−0.034413	−0.174691	−0.362002	0.063*	0.590 (14)
H10B	−0.020921	−0.245795	−0.494084	0.063*	0.590 (14)
H10C	0.051400	−0.128624	−0.428493	0.063*	0.590 (14)
C11	0.17972 (19)	−0.8356 (4)	−0.3194 (3)	0.0371 (6)
H11A	0.161 (2)	−0.743 (4)	−0.376 (3)	0.051 (5)*
H11B	0.125 (2)	−0.877 (4)	−0.291 (3)	0.051 (5)*
H11C	0.206 (2)	−0.916 (4)	−0.370 (3)	0.051 (5)*
C12	0.43977 (14)	−0.3783 (2)	0.1527 (2)	0.0221 (4)
C9B	0.0882 (7)	−0.2831 (15)	−0.3810 (7)	0.043 (3)	0.410 (14)
H9B1	0.108084	−0.172234	−0.400126	0.052*	0.410 (14)
H9B2	0.120614	−0.362544	−0.427766	0.052*	0.410 (14)
C10B	−0.0104 (10)	−0.290 (3)	−0.4108 (15)	0.090 (6)	0.410 (14)
H10D	−0.034871	−0.381309	−0.367063	0.135*	0.410 (14)
H10E	−0.022841	−0.306245	−0.498360	0.135*	0.410 (14)
H10F	−0.037061	−0.188515	−0.386266	0.135*	0.410 (14)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0399 (4)	0.0149 (3)	0.0215 (3)	−0.0017 (2)	−0.0048 (2)	−0.0004 (2)
N1	0.0299 (10)	0.0203 (9)	0.0208 (9)	−0.0005 (8)	−0.0020 (7)	0.0003 (7)
N2	0.0330 (10)	0.0148 (9)	0.0215 (9)	−0.0010 (7)	−0.0045 (8)	−0.0010 (7)
N3	0.0414 (12)	0.0160 (9)	0.0241 (11)	−0.0025 (8)	−0.0047 (9)	−0.0005 (8)
C1	0.0252 (11)	0.0207 (11)	0.0215 (11)	−0.0015 (8)	0.0023 (8)	−0.0016 (9)
C2	0.0298 (12)	0.0174 (10)	0.0275 (12)	−0.0013 (9)	−0.0023 (9)	−0.0026 (9)
C3	0.0343 (13)	0.0249 (12)	0.0289 (12)	−0.0053 (10)	−0.0004 (10)	−0.0040 (10)
C4	0.0252 (11)	0.0303 (12)	0.0250 (11)	−0.0026 (9)	0.0014 (9)	−0.0039 (10)
C5	0.0265 (11)	0.0266 (11)	0.0226 (11)	0.0005 (9)	0.0009 (9)	−0.0002 (9)
C6	0.0339 (13)	0.0299 (12)	0.0253 (12)	0.0003 (10)	−0.0026 (10)	0.0028 (10)
C7	0.0506 (16)	0.0272 (13)	0.0261 (13)	0.0051 (11)	−0.0020 (11)	−0.0040 (10)
C8	0.0579 (19)	0.0569 (18)	0.0405 (16)	0.0247 (15)	−0.0007 (14)	−0.0123 (15)
C9A	0.032 (3)	0.033 (3)	0.048 (3)	0.003 (2)	−0.003 (2)	−0.004 (3)
C10A	0.041 (4)	0.038 (3)	0.046 (4)	0.006 (2)	−0.007 (3)	0.003 (3)
C11	0.0353 (15)	0.0436 (15)	0.0316 (14)	−0.0105 (12)	−0.0024 (11)	−0.0053 (12)
C12	0.0258 (11)	0.0156 (10)	0.0249 (11)	0.0009 (8)	0.0019 (9)	−0.0006 (9)
C9B	0.047 (5)	0.046 (5)	0.037 (4)	0.004 (4)	0.003 (3)	0.005 (3)
C10B	0.047 (7)	0.173 (19)	0.050 (6)	0.012 (10)	0.001 (5)	0.021 (11)

Geometric parameters (Å, º)

S1—C12	1.698 (2)	C7—C8	1.308 (4)
N1—C1	1.285 (3)	C7—H7	0.98 (3)
N1—N2	1.388 (2)	C8—C9A	1.512 (6)
N2—C12	1.345 (3)	C8—C9B	1.598 (8)
N2—H1	0.90 (3)	C8—H8A	0.9300
N3—C12	1.328 (3)	C8—H8B	0.9300
N3—H2	0.87 (3)	C9A—C10A	1.526 (10)
N3—H3	0.85 (3)	C9A—H9A1	0.9700
C1—C5	1.458 (3)	C9A—H9A2	0.9700
C1—C2	1.510 (3)	C10A—H10A	0.9600
C2—C3	1.534 (3)	C10A—H10B	0.9600
C2—H2A	1.03 (2)	C10A—H10C	0.9600
C2—H2B	1.00 (2)	C11—H11A	1.00 (3)
C3—C4	1.504 (3)	C11—H11B	0.96 (3)
C3—H3A	0.96 (3)	C11—H11C	0.95 (3)
C3—H3B	1.00 (3)	C9B—C10B	1.49 (2)
C4—C5	1.351 (3)	C9B—H9B1	0.9700
C4—C11	1.489 (3)	C9B—H9B2	0.9700
C5—C6	1.506 (3)	C10B—H10D	0.9600
C6—C7	1.502 (4)	C10B—H10E	0.9600
C6—H6A	0.90 (3)	C10B—H10F	0.9600
C6—H6B	1.02 (3)
C1—N1—N2	117.67 (18)	C7—C8—C9B	122.4 (4)
C12—N2—N1	117.32 (18)	C7—C8—H8A	115.9
C12—N2—H1	118.2 (16)	C9A—C8—H8A	115.9
N1—N2—H1	124.3 (16)	C7—C8—H8B	118.8
C12—N3—H2	118.8 (19)	C9B—C8—H8B	118.8
C12—N3—H3	116.3 (19)	C8—C9A—C10A	109.3 (5)
H2—N3—H3	125 (3)	C8—C9A—H9A1	109.8
N1—C1—C5	120.47 (19)	C10A—C9A—H9A1	109.8
N1—C1—C2	130.6 (2)	C8—C9A—H9A2	109.8
C5—C1—C2	108.90 (18)	C10A—C9A—H9A2	109.8
C1—C2—C3	104.07 (18)	H9A1—C9A—H9A2	108.3
C1—C2—H2A	111.4 (14)	C9A—C10A—H10A	109.5
C3—C2—H2A	113.8 (13)	C9A—C10A—H10B	109.5
C1—C2—H2B	108.9 (13)	H10A—C10A—H10B	109.5
C3—C2—H2B	111.0 (13)	C9A—C10A—H10C	109.5
H2A—C2—H2B	107.6 (19)	H10A—C10A—H10C	109.5
C4—C3—C2	105.00 (19)	H10B—C10A—H10C	109.5
C4—C3—H3A	110.8 (15)	C4—C11—H11A	114.3 (18)
C2—C3—H3A	111.1 (15)	C4—C11—H11B	109.3 (18)
C4—C3—H3B	110.1 (15)	H11A—C11—H11B	104 (2)
C2—C3—H3B	111.7 (14)	C4—C11—H11C	112.3 (18)
H3A—C3—H3B	108 (2)	H11A—C11—H11C	105 (3)
C5—C4—C11	127.8 (2)	H11B—C11—H11C	111 (3)
C5—C4—C3	111.8 (2)	N3—C12—N2	117.47 (19)
C11—C4—C3	120.4 (2)	N3—C12—S1	121.54 (17)
C4—C5—C1	109.67 (19)	N2—C12—S1	120.98 (16)
C4—C5—C6	128.7 (2)	C10B—C9B—C8	107.0 (10)
C1—C5—C6	121.56 (19)	C10B—C9B—H9B1	107.9
C7—C6—C5	112.6 (2)	C8—C9B—H9B1	109.0
C7—C6—H6A	109.3 (18)	C10B—C9B—H9B2	113.0
C5—C6—H6A	107.2 (18)	C8—C9B—H9B2	111.1
C7—C6—H6B	109.0 (15)	H9B1—C9B—H9B2	108.7
C5—C6—H6B	111.1 (16)	C9B—C10B—H10D	109.5
H6A—C6—H6B	108 (2)	C9B—C10B—H10E	109.5
C8—C7—C6	127.4 (2)	H10D—C10B—H10E	109.5
C8—C7—H7	118.7 (16)	C9B—C10B—H10F	109.5
C6—C7—H7	113.9 (16)	H10D—C10B—H10F	109.5
C7—C8—C9A	128.2 (3)	H10E—C10B—H10F	109.5
C1—N1—N2—C12	−177.82 (19)	C2—C1—C5—C4	4.5 (3)
N2—N1—C1—C5	176.34 (19)	N1—C1—C5—C6	3.0 (3)
N2—N1—C1—C2	−2.8 (4)	C2—C1—C5—C6	−177.7 (2)
N1—C1—C2—C3	171.8 (2)	C4—C5—C6—C7	100.2 (3)
C5—C1—C2—C3	−7.4 (2)	C1—C5—C6—C7	−77.0 (3)
C1—C2—C3—C4	7.3 (3)	C5—C6—C7—C8	−123.5 (3)
C2—C3—C4—C5	−5.1 (3)	C6—C7—C8—C9A	14.5 (7)
C2—C3—C4—C11	175.9 (2)	C6—C7—C8—C9B	−24.3 (7)
C11—C4—C5—C1	179.4 (2)	C7—C8—C9A—C10A	−145.8 (5)
C3—C4—C5—C1	0.5 (3)	N1—N2—C12—N3	−4.8 (3)
C11—C4—C5—C6	1.9 (4)	N1—N2—C12—S1	174.04 (15)
C3—C4—C5—C6	−177.1 (2)	C7—C8—C9B—C10B	156.7 (12)
N1—C1—C5—C4	−174.7 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1···S1^i	0.90 (3)	2.53 (3)	3.4142 (19)	166 (2)
N3—H3···S1^ii	0.85 (3)	2.48 (3)	3.325 (2)	173 (3)
C2—H2B···S1^i	1.00 (2)	2.93 (2)	3.436 (2)	112.2 (16)

Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) −x+1, y+1/2, −z+1/2.