4-(2-Methyl­prop-2-enyl)-1-[3-(tri­fluoro­methyl)­phenyl]­thio­semicarbazide

The title compound, C₁₂H₁₄F₃N₃S, is a biologically active anti-implantation agent. Its crystal structure is stabilized by intermolecular N—H...S hydrogen bonds, which form dimers in a head-to-tail arrangement and link them into a polymeric chain.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.076
• wR factor = 0.249
• Data-to-parameter ratio = 14.9

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT241_ALERT_2_A Check High   U(eq) as Compared to Neighbors  for         F1

Author Response: Positional disorder of the trifluoromethyl group is responsible for the thermal parameter of fluorine being high compared to its neighbours.

PLAT242_ALERT_2_A Check Low    U(eq) as Compared to Neighbors  for         C7

Author Response: Positional disorder of the trifluoromethyl group is responsible for the thermal parameter of carbon being low compared to its neighbours.

Alert level B
PLAT222_ALERT_3_B Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       4.55 Ratio

Alert level C
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.06
PLAT213_ALERT_2_C Atom F3A     has ADP max/min Ratio .............       3.10 prolat
PLAT213_ALERT_2_C Atom F3      has ADP max/min Ratio .............       3.10 prolat
PLAT301_ALERT_3_C Main Residue  Disorder .........................      14.00 Perc.
PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          6
PLAT352_ALERT_3_C Short   N-H Bond (0.87A)   N2     -   H2N    ...       0.69 Ang.

   2 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   6 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

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

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Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SMART; data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and CAMERON (Watkin et al., 1993); software used to prepare material for publication: PLATON (Spek, 2003).

4-(2-Methylprop-2-enyl)-1-[3-(trifluoromethyl)phenyl]thiosemicarbazide

Crystal data

C12H14F3N3S	F(000) = 599.9
Mr = 289.31	Dx = 1.41 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 975 reflections
a = 14.964 (2) Å	θ = 1.4–25.2°
b = 6.0900 (8) Å	µ = 0.26 mm^−1
c = 15.754 (2) Å	T = 293 K
β = 108.387 (2)°	Block, orange
V = 1362.3 (3) Å^3	0.3 × 0.3 × 0.2 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer	2913 independent reflections
Radiation source: fine-focus sealed tube	1741 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.052
φ and ω scans	θmax = 27.7°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −18→18
Tmin = 0.913, Tmax = 0.941	k = −7→7
10483 measured reflections	l = −19→20

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)] = 0.076	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.249	H atoms treated by a mixture of independent and constrained refinement
S = 0.91	w = 1/[σ^2(Fo^2) + (0.2P)^2] where P = (Fo^2 + 2Fc^2)/3
2913 reflections	(Δ/σ)max < 0.001
195 parameters	Δρmax = 0.84 e Å^−3
0 restraints	Δρmin = −0.41 e Å^−3

Special details

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) 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	Occ. (<1)
F1	0.567 (2)	0.241 (6)	0.051 (2)	0.130 (4)	0.228 (9)
F2	0.5042 (18)	0.297 (4)	0.0411 (14)	0.094 (2)	0.228 (9)
F3	0.546 (2)	0.011 (4)	0.1180 (12)	0.113 (3)	0.228 (9)
F1A	0.5855 (5)	0.1167 (17)	0.0664 (6)	0.130 (4)	0.772 (9)
F2A	0.4561 (5)	0.2988 (9)	0.0586 (4)	0.094 (2)	0.772 (9)
F3A	0.4877 (6)	0.0197 (9)	0.1297 (3)	0.113 (3)	0.772 (9)
S1	0.59913 (8)	−0.26039 (17)	0.53618 (8)	0.0476 (4)
N1	0.6609 (3)	0.2936 (6)	0.4403 (2)	0.0408 (9)
N2	0.6126 (3)	0.1058 (6)	0.4521 (2)	0.0430 (9)
N3	0.7529 (3)	−0.0415 (6)	0.5329 (2)	0.0443 (9)
C1	0.6441 (3)	0.3650 (6)	0.3515 (3)	0.0367 (9)
C2	0.5944 (3)	0.2426 (6)	0.2768 (3)	0.0364 (9)
C3	0.5836 (3)	0.3252 (7)	0.1921 (3)	0.0386 (9)
C4	0.6208 (3)	0.5265 (7)	0.1801 (3)	0.0444 (10)
C5	0.6705 (3)	0.6460 (7)	0.2543 (3)	0.0444 (10)
C6	0.6827 (3)	0.5678 (6)	0.3392 (3)	0.0417 (10)
C7	0.5310 (4)	0.1970 (8)	0.1115 (3)	0.0498 (11)
C8	0.6596 (3)	−0.0543 (6)	0.5071 (2)	0.0342 (9)
C9	0.8170 (3)	−0.1715 (8)	0.6036 (3)	0.0502 (11)
C10	0.8445 (3)	−0.0670 (8)	0.6944 (3)	0.0482 (11)
C11	0.9105 (4)	−0.2019 (10)	0.7668 (3)	0.0667 (15)
C13	0.8142 (4)	0.1270 (10)	0.7094 (4)	0.0714 (15)
H1N	0.651 (3)	0.385 (7)	0.470 (3)	0.035 (12)*
H2N	0.565 (3)	0.116 (7)	0.447 (3)	0.022 (11)*
H3N	0.770 (3)	0.079 (8)	0.516 (3)	0.048 (13)*
H2	0.5687	0.1073	0.2836	0.044*
H4	0.6123	0.5803	0.1228	0.053*
H5	0.6962	0.7811	0.2469	0.053*
H6	0.7167	0.6498	0.3886	0.050*
H9A	0.8737	−0.1996	0.5879	0.060*
H9B	0.7877	−0.3121	0.6067	0.060*
H11A	0.9695	−0.2167	0.7555	0.100*
H11B	0.8837	−0.3447	0.7680	0.100*
H11C	0.9204	−0.1309	0.8235	0.100*
H13A	0.8336	0.1856	0.7668	0.086*
H13B	0.7732	0.2058	0.6625	0.086*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
F1	0.082 (4)	0.191 (10)	0.120 (5)	−0.015 (5)	0.039 (3)	−0.115 (7)
F2	0.069 (4)	0.104 (3)	0.075 (3)	0.031 (3)	−0.027 (3)	−0.027 (2)
F3	0.173 (7)	0.102 (3)	0.052 (2)	−0.104 (4)	0.018 (3)	−0.009 (2)
F1A	0.082 (4)	0.191 (10)	0.120 (5)	−0.015 (5)	0.039 (3)	−0.115 (7)
F2A	0.069 (4)	0.104 (3)	0.075 (3)	0.031 (3)	−0.027 (3)	−0.027 (2)
F3A	0.173 (7)	0.102 (3)	0.052 (2)	−0.104 (4)	0.018 (3)	−0.009 (2)
S1	0.0564 (7)	0.0402 (7)	0.0513 (7)	0.0022 (5)	0.0242 (5)	0.0056 (5)
N1	0.053 (2)	0.0335 (19)	0.0355 (18)	−0.0036 (15)	0.0137 (16)	−0.0022 (15)
N2	0.039 (2)	0.044 (2)	0.047 (2)	0.0020 (18)	0.0152 (17)	0.0092 (16)
N3	0.047 (2)	0.041 (2)	0.044 (2)	0.0016 (17)	0.0132 (16)	0.0009 (16)
C1	0.038 (2)	0.034 (2)	0.038 (2)	0.0049 (17)	0.0129 (16)	0.0041 (16)
C2	0.037 (2)	0.0306 (19)	0.042 (2)	−0.0037 (16)	0.0133 (16)	−0.0001 (16)
C3	0.038 (2)	0.036 (2)	0.040 (2)	0.0004 (16)	0.0099 (17)	−0.0014 (16)
C4	0.053 (3)	0.038 (2)	0.043 (2)	−0.0025 (19)	0.0162 (19)	0.0070 (18)
C5	0.052 (2)	0.030 (2)	0.053 (2)	−0.0015 (19)	0.020 (2)	0.0034 (18)
C6	0.044 (2)	0.037 (2)	0.045 (2)	−0.0030 (18)	0.0158 (18)	−0.0062 (17)
C7	0.062 (3)	0.043 (3)	0.039 (2)	−0.003 (2)	0.009 (2)	−0.0019 (18)
C8	0.042 (2)	0.034 (2)	0.0288 (18)	0.0004 (17)	0.0146 (16)	−0.0035 (15)
C9	0.045 (2)	0.050 (2)	0.052 (3)	0.012 (2)	0.010 (2)	0.000 (2)
C10	0.042 (2)	0.057 (3)	0.047 (2)	0.002 (2)	0.0162 (19)	0.002 (2)
C11	0.057 (3)	0.084 (4)	0.052 (3)	0.006 (3)	0.006 (2)	0.009 (3)
C13	0.085 (4)	0.073 (4)	0.053 (3)	0.007 (3)	0.019 (3)	−0.012 (3)

Geometric parameters (Å, º)

C7—F2A	1.321 (7)	C2—H2	0.9300
C7—F1A	1.333 (8)	C10—C13	1.314 (7)
C7—F3A	1.336 (7)	C10—C11	1.497 (6)
C7—C3	1.486 (6)	C10—C9	1.500 (6)
S1—C8	1.693 (4)	C9—H9A	0.9700
N3—C8	1.328 (5)	C9—H9B	0.9700
N3—C9	1.454 (5)	C6—C5	1.377 (6)
N3—H3N	0.85 (5)	C6—H6	0.9300
N1—N2	1.396 (5)	C4—C5	1.379 (6)
N1—C1	1.411 (5)	C4—H4	0.9300
N1—H1N	0.77 (5)	C5—H5	0.9300
N2—C8	1.346 (5)	C11—H11A	0.9600
N2—H2N	0.70 (4)	C11—H11B	0.9600
C3—C4	1.384 (6)	C11—H11C	0.9600
C3—C2	1.387 (6)	C13—H13A	0.9300
C1—C2	1.393 (5)	C13—H13B	0.9300
C1—C6	1.403 (6)
F2A—C7—F1A	112.1 (7)	C13—C10—C11	122.6 (5)
F2A—C7—F3A	98.2 (6)	C13—C10—C9	123.1 (4)
F1A—C7—F3A	103.7 (6)	C11—C10—C9	114.3 (4)
F2A—C7—C3	114.0 (4)	N3—C9—C10	114.6 (4)
F1A—C7—C3	113.6 (5)	N3—C9—H9A	108.6
F3A—C7—C3	113.8 (4)	C10—C9—H9A	108.6
C8—N3—C9	125.4 (4)	N3—C9—H9B	108.6
C8—N3—H3N	110 (3)	C10—C9—H9B	108.6
C9—N3—H3N	122 (3)	H9A—C9—H9B	107.6
N2—N1—C1	116.5 (3)	C5—C6—C1	120.3 (4)
N2—N1—H1N	108 (3)	C5—C6—H6	119.8
C1—N1—H1N	112 (3)	C1—C6—H6	119.8
C8—N2—N1	119.4 (4)	C5—C4—C3	119.0 (4)
C8—N2—H2N	116 (3)	C5—C4—H4	120.5
N1—N2—H2N	118 (4)	C3—C4—H4	120.5
C4—C3—C2	121.6 (4)	C6—C5—C4	120.8 (4)
C4—C3—C7	118.4 (4)	C6—C5—H5	119.6
C2—C3—C7	120.0 (4)	C4—C5—H5	119.6
N3—C8—N2	116.1 (4)	C10—C11—H11A	109.5
N3—C8—S1	124.1 (3)	C10—C11—H11B	109.5
N2—C8—S1	119.7 (3)	H11A—C11—H11B	109.5
C2—C1—C6	119.2 (4)	C10—C11—H11C	109.5
C2—C1—N1	123.6 (4)	H11A—C11—H11C	109.5
C6—C1—N1	117.1 (4)	H11B—C11—H11C	109.5
C3—C2—C1	119.2 (3)	C10—C13—H13A	120.0
C3—C2—H2	120.4	C10—C13—H13B	120.0
C1—C2—H2	120.4	H13A—C13—H13B	120.0
C3—C7—F1—F2	−110.7 (18)	C4—C3—C2—C1	−0.2 (6)
C1—N1—N2—C8	133.5 (4)	C7—C3—C2—C1	179.8 (4)
F2A—C7—C3—C4	−60.3 (7)	C6—C1—C2—C3	−0.5 (6)
F1A—C7—C3—C4	69.8 (7)	N1—C1—C2—C3	−178.5 (4)
F3A—C7—C3—C4	−171.8 (6)	C8—N3—C9—C10	−91.7 (5)
F2A—C7—C3—C2	119.7 (6)	C13—C10—C9—N3	−0.6 (7)
F1A—C7—C3—C2	−110.2 (7)	C11—C10—C9—N3	179.9 (4)
F3A—C7—C3—C2	8.1 (7)	C2—C1—C6—C5	0.8 (6)
C9—N3—C8—N2	168.5 (4)	N1—C1—C6—C5	178.9 (4)
C9—N3—C8—S1	−13.7 (6)	C2—C3—C4—C5	0.7 (6)
N1—N2—C8—N3	−12.9 (5)	C7—C3—C4—C5	−179.3 (4)
N1—N2—C8—S1	169.2 (3)	C1—C6—C5—C4	−0.3 (6)
N2—N1—C1—C2	−9.8 (6)	C3—C4—C5—C6	−0.4 (6)
N2—N1—C1—C6	172.2 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···S1^i	0.70 (5)	2.69 (5)	3.366 (5)	162 (5)
N1—H1N···S1^ii	0.77 (5)	2.62 (5)	3.375 (4)	167 (4)

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