4-[(4-Fluoro-benzyl-idene)amino]-3-[1-(4-isobutyl-phen-yl)eth-yl]-1H-1,2,4-triazole-5(4H)-thione.

In the title compound, C(21)H(23)FN(4)S, the benzene rings of the isobutyl-phenyl and fluoro-benzene units form dihedral angles of 75.89 (7) and 13.26 (7)°, respectively, with the triazole ring. An intra-molecular C-H⋯S hydrogen-bonding contact generates an S(6) ring motif. In the crystal packing, pairs of N-H⋯S hydrogen bonds link neighbouring mol-ecules into inversion dimers, forming R(2) (2)(8) ring motifs. The crystal structure is further stabilized by C-H⋯π inter-actions.

Related literature

For pharmacological activity of triazoles, see: Göknur et al. (2005 ▶). For the anti-tumor activity of triazole derivatives, see: Demirbas et al. (2002 ▶, 2004 ▶). For the synthesis of related heterocyclic compounds, see: Fun et al. (2008 ▶, 2009a ▶). For a related structure, see: Fun et al. (2009b ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C21H23FN4S

M = 382.49

Triclinic,

a = 5.7883 (1) Å

b = 9.9001 (1) Å

c = 18.4972 (3) Å

α = 98.132 (1)°

β = 97.087 (1)°

γ = 105.997 (1)°

V = 993.90 (3) Å3

Z = 2

Mo Kα radiation

μ = 0.19 mm−1

T = 100 K

0.46 × 0.20 × 0.07 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (; Bruker, 2005 ▶) T min = 0.919, T max = 0.987

31031 measured reflections

7460 independent reflections

5798 reflections with I > 2σ(I)

R int = 0.037

Refinement

R[F 2 > 2σ(F 2)] = 0.048

wR(F 2) = 0.135

S = 1.06

7460 reflections

336 parameters

All H-atom parameters refined

Δρmax = 0.63 e Å−3

Δρmin = −0.29 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680903030X/tk2518sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680903030X/tk2518Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C21H23FN4S	Z = 2
Mr = 382.49	F(000) = 404
Triclinic, P1	Dx = 1.278 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.7883 (1) Å	Cell parameters from 8265 reflections
b = 9.9001 (1) Å	θ = 2.3–32.9°
c = 18.4972 (3) Å	µ = 0.19 mm−1
α = 98.132 (1)°	T = 100 K
β = 97.087 (1)°	Plate, colourless
γ = 105.997 (1)°	0.46 × 0.20 × 0.07 mm
V = 993.90 (3) Å3

Bruker SMART APEXII CCD area-detector diffractometer	7460 independent reflections
Radiation source: fine-focus sealed tube	5798 reflections with I > 2σ(I)
graphite	Rint = 0.037
φ and ω scans	θmax = 33.1°, θmin = 1.1°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −8→8
Tmin = 0.919, Tmax = 0.987	k = −13→15
31031 measured reflections	l = −28→28

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.135	All H-atom parameters refined
S = 1.06	w = 1/[σ2(Fo2) + (0.0657P)2 + 0.2752P] where P = (Fo2 + 2Fc2)/3
7460 reflections	(Δ/σ)max = 0.001
336 parameters	Δρmax = 0.63 e Å−3
0 restraints	Δρmin = −0.29 e Å−3

Experimental. The crystal was placed in the cold stream of an Oxford Cyrosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

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.

	x	y	z	Uiso*/Ueq
S1	−0.23157 (6)	0.40057 (3)	0.062645 (17)	0.02273 (9)
F1	1.07698 (17)	0.46076 (11)	0.34727 (5)	0.0384 (2)
N2	0.09265 (19)	0.67553 (11)	0.11123 (6)	0.0200 (2)
N3	−0.2432 (2)	0.66569 (12)	0.04603 (6)	0.0240 (2)
N4	−0.1117 (2)	0.80841 (12)	0.06196 (6)	0.0262 (2)
C1	0.7243 (2)	0.63478 (14)	0.23907 (7)	0.0230 (2)
C2	0.9179 (2)	0.61374 (15)	0.28295 (8)	0.0265 (3)
C3	0.8872 (3)	0.48191 (16)	0.30420 (8)	0.0275 (3)
C4	0.6725 (3)	0.37142 (15)	0.28390 (8)	0.0291 (3)
C5	0.4798 (3)	0.39514 (15)	0.24054 (8)	0.0270 (3)
C6	0.5020 (2)	0.52512 (13)	0.21738 (7)	0.0220 (2)
C7	0.2896 (2)	0.54128 (14)	0.17189 (7)	0.0239 (2)
N1	0.29999 (19)	0.65984 (12)	0.15103 (6)	0.0219 (2)
C8	−0.1269 (2)	0.57973 (13)	0.07367 (6)	0.0207 (2)
C9	0.0928 (2)	0.81133 (13)	0.10125 (7)	0.0227 (2)
C10	0.3012 (3)	0.94216 (14)	0.13560 (7)	0.0248 (3)
C11	0.2842 (2)	0.98403 (13)	0.21717 (7)	0.0210 (2)
C12	0.4468 (2)	0.96157 (14)	0.27274 (7)	0.0226 (2)
C13	0.4346 (2)	1.00047 (13)	0.34731 (7)	0.0215 (2)
C14	0.2607 (2)	1.06384 (13)	0.36891 (7)	0.0198 (2)
C15	0.0957 (2)	1.08449 (14)	0.31282 (7)	0.0230 (2)
C16	0.1051 (2)	1.04396 (14)	0.23829 (7)	0.0239 (2)
C17	0.2509 (2)	1.11216 (14)	0.44918 (7)	0.0232 (2)
C18	0.3959 (2)	1.26943 (14)	0.48054 (7)	0.0231 (2)
C19	0.3044 (3)	1.06203 (16)	0.09161 (9)	0.0338 (3)
C20	0.6693 (3)	1.29519 (17)	0.48410 (9)	0.0302 (3)
C21	0.3413 (3)	1.31418 (18)	0.55751 (8)	0.0324 (3)
H1A	0.739 (3)	0.725 (2)	0.2216 (10)	0.031 (4)*
H2A	1.074 (4)	0.684 (2)	0.2993 (11)	0.042 (5)*
H4A	0.661 (4)	0.277 (2)	0.3010 (11)	0.042 (5)*
H5A	0.325 (4)	0.318 (2)	0.2259 (11)	0.038 (5)*
H7A	0.142 (4)	0.462 (2)	0.1596 (11)	0.037 (5)*
H10A	0.470 (4)	0.922 (2)	0.1304 (11)	0.035 (5)*
H12A	0.570 (3)	0.9154 (18)	0.2584 (9)	0.023 (4)*
H13A	0.545 (3)	0.985 (2)	0.3849 (11)	0.035 (5)*
H15A	−0.026 (3)	1.1270 (19)	0.3265 (10)	0.030 (4)*
H16A	−0.007 (4)	1.058 (2)	0.2033 (11)	0.040 (5)*
H17A	0.314 (3)	1.0534 (19)	0.4791 (10)	0.028 (4)*
H17B	0.078 (3)	1.0959 (18)	0.4546 (9)	0.024 (4)*
H18A	0.347 (3)	1.331 (2)	0.4477 (11)	0.035 (5)*
H19A	0.140 (4)	1.092 (2)	0.0910 (11)	0.044 (5)*
H19B	0.452 (4)	1.149 (2)	0.1147 (12)	0.047 (6)*
H19C	0.323 (4)	1.027 (2)	0.0392 (11)	0.040 (5)*
H20A	0.761 (4)	1.396 (2)	0.5032 (12)	0.047 (6)*
H20B	0.714 (4)	1.268 (2)	0.4370 (12)	0.041 (5)*
H20C	0.723 (4)	1.237 (2)	0.5162 (12)	0.043 (5)*
H21A	0.164 (4)	1.299 (2)	0.5562 (12)	0.048 (6)*
H21B	0.421 (4)	1.416 (2)	0.5753 (12)	0.042 (5)*
H21C	0.394 (4)	1.258 (2)	0.5923 (11)	0.036 (5)*
H1N3	−0.384 (4)	0.641 (2)	0.0196 (11)	0.038 (5)*

	U11	U22	U33	U12	U13	U23
S1	0.02380 (15)	0.01846 (14)	0.01925 (15)	−0.00197 (10)	0.00281 (11)	−0.00094 (10)
F1	0.0338 (5)	0.0443 (5)	0.0371 (5)	0.0151 (4)	−0.0013 (4)	0.0066 (4)
N2	0.0209 (5)	0.0188 (5)	0.0150 (4)	−0.0010 (4)	0.0017 (3)	0.0006 (3)
N3	0.0234 (5)	0.0201 (5)	0.0210 (5)	−0.0009 (4)	−0.0016 (4)	−0.0004 (4)
N4	0.0311 (6)	0.0190 (5)	0.0210 (5)	−0.0011 (4)	−0.0011 (4)	0.0012 (4)
C1	0.0241 (6)	0.0198 (5)	0.0216 (6)	0.0017 (4)	0.0074 (4)	−0.0004 (4)
C2	0.0224 (6)	0.0273 (6)	0.0250 (6)	0.0024 (5)	0.0057 (5)	−0.0021 (5)
C3	0.0287 (6)	0.0307 (7)	0.0225 (6)	0.0101 (5)	0.0038 (5)	0.0011 (5)
C4	0.0341 (7)	0.0237 (6)	0.0285 (7)	0.0065 (5)	0.0055 (5)	0.0056 (5)
C5	0.0279 (6)	0.0217 (6)	0.0265 (6)	0.0007 (5)	0.0039 (5)	0.0027 (5)
C6	0.0235 (6)	0.0202 (5)	0.0192 (5)	0.0023 (4)	0.0054 (4)	0.0002 (4)
C7	0.0236 (6)	0.0216 (6)	0.0217 (6)	−0.0002 (4)	0.0041 (5)	0.0017 (4)
N1	0.0207 (5)	0.0236 (5)	0.0171 (5)	0.0009 (4)	0.0028 (4)	0.0015 (4)
C8	0.0211 (5)	0.0209 (5)	0.0143 (5)	−0.0014 (4)	0.0039 (4)	−0.0006 (4)
C9	0.0273 (6)	0.0192 (5)	0.0159 (5)	−0.0012 (4)	0.0024 (4)	0.0020 (4)
C10	0.0281 (6)	0.0208 (6)	0.0174 (5)	−0.0035 (5)	0.0018 (5)	0.0013 (4)
C11	0.0227 (5)	0.0161 (5)	0.0178 (5)	−0.0029 (4)	0.0007 (4)	0.0018 (4)
C12	0.0233 (6)	0.0199 (5)	0.0211 (6)	0.0033 (4)	0.0020 (4)	0.0005 (4)
C13	0.0232 (6)	0.0198 (5)	0.0189 (5)	0.0049 (4)	−0.0007 (4)	0.0024 (4)
C14	0.0198 (5)	0.0175 (5)	0.0182 (5)	0.0004 (4)	0.0015 (4)	0.0020 (4)
C15	0.0183 (5)	0.0237 (6)	0.0246 (6)	0.0038 (4)	0.0007 (4)	0.0036 (5)
C16	0.0209 (6)	0.0245 (6)	0.0215 (6)	0.0016 (4)	−0.0035 (4)	0.0052 (5)
C17	0.0230 (6)	0.0245 (6)	0.0199 (6)	0.0039 (5)	0.0038 (4)	0.0029 (5)
C18	0.0235 (6)	0.0239 (6)	0.0198 (6)	0.0073 (4)	0.0004 (4)	0.0000 (4)
C19	0.0446 (9)	0.0252 (7)	0.0250 (7)	−0.0006 (6)	0.0034 (6)	0.0071 (5)
C20	0.0236 (6)	0.0323 (7)	0.0277 (7)	0.0019 (5)	0.0037 (5)	−0.0040 (6)
C21	0.0293 (7)	0.0391 (8)	0.0261 (7)	0.0126 (6)	0.0033 (5)	−0.0062 (6)

S1—C8	1.6821 (13)	C11—C12	1.3904 (18)
F1—C3	1.3577 (16)	C11—C16	1.3976 (19)
N2—C9	1.3824 (16)	C12—C13	1.3945 (18)
N2—N1	1.3870 (15)	C12—H12A	0.989 (16)
N2—C8	1.3888 (15)	C13—C14	1.3935 (17)
N3—C8	1.3389 (17)	C13—H13A	0.941 (19)
N3—N4	1.3772 (15)	C14—C15	1.3980 (17)
N3—H1N3	0.85 (2)	C14—C17	1.5071 (17)
N4—C9	1.3011 (17)	C15—C16	1.3923 (19)
C1—C2	1.382 (2)	C15—H15A	0.958 (18)
C1—C6	1.4055 (18)	C16—H16A	0.91 (2)
C1—H1A	0.977 (18)	C17—C18	1.5392 (19)
C2—C3	1.387 (2)	C17—H17A	0.968 (18)
C2—H2A	0.96 (2)	C17—H17B	0.988 (17)
C3—C4	1.379 (2)	C18—C20	1.524 (2)
C4—C5	1.385 (2)	C18—C21	1.5272 (19)
C4—H4A	1.01 (2)	C18—H18A	0.989 (19)
C5—C6	1.3908 (19)	C19—H19A	1.07 (2)
C5—H5A	0.98 (2)	C19—H19B	1.03 (2)
C6—C7	1.4618 (19)	C19—H19C	1.01 (2)
C7—N1	1.2747 (17)	C20—H20A	0.98 (2)
C7—H7A	0.97 (2)	C20—H20B	0.96 (2)
C9—C10	1.5013 (17)	C20—H20C	0.97 (2)
C10—C19	1.528 (2)	C21—H21A	0.99 (2)
C10—C11	1.5299 (18)	C21—H21B	0.97 (2)
C10—H10A	1.059 (19)	C21—H21C	0.98 (2)
C9—N2—N1	118.18 (10)	C11—C12—H12A	118.7 (10)
C9—N2—C8	108.16 (11)	C13—C12—H12A	120.3 (10)
N1—N2—C8	133.59 (11)	C14—C13—C12	121.45 (11)
C8—N3—N4	114.43 (11)	C14—C13—H13A	117.7 (12)
C8—N3—H1N3	127.2 (13)	C12—C13—H13A	120.9 (12)
N4—N3—H1N3	118.4 (13)	C13—C14—C15	117.37 (11)
C9—N4—N3	103.92 (11)	C13—C14—C17	122.28 (11)
C2—C1—C6	120.41 (13)	C15—C14—C17	120.33 (11)
C2—C1—H1A	121.3 (11)	C16—C15—C14	121.37 (12)
C6—C1—H1A	118.2 (11)	C16—C15—H15A	120.0 (11)
C1—C2—C3	118.32 (13)	C14—C15—H15A	118.7 (11)
C1—C2—H2A	124.2 (12)	C15—C16—C11	120.84 (12)
C3—C2—H2A	117.5 (12)	C15—C16—H16A	119.0 (13)
F1—C3—C4	118.41 (13)	C11—C16—H16A	120.2 (13)
F1—C3—C2	118.51 (13)	C14—C17—C18	114.35 (11)
C4—C3—C2	123.08 (13)	C14—C17—H17A	109.5 (10)
C3—C4—C5	117.71 (13)	C18—C17—H17A	107.9 (11)
C3—C4—H4A	119.6 (12)	C14—C17—H17B	108.3 (10)
C5—C4—H4A	122.6 (12)	C18—C17—H17B	109.7 (10)
C4—C5—C6	121.40 (13)	H17A—C17—H17B	106.9 (14)
C4—C5—H5A	119.0 (11)	C20—C18—C21	109.98 (11)
C6—C5—H5A	119.6 (11)	C20—C18—C17	111.77 (11)
C5—C6—C1	119.08 (13)	C21—C18—C17	110.13 (12)
C5—C6—C7	117.86 (12)	C20—C18—H18A	107.0 (11)
C1—C6—C7	123.06 (12)	C21—C18—H18A	108.4 (11)
N1—C7—C6	119.92 (12)	C17—C18—H18A	109.4 (12)
N1—C7—H7A	121.5 (11)	C10—C19—H19A	111.1 (11)
C6—C7—H7A	118.5 (11)	C10—C19—H19B	109.4 (12)
C7—N1—N2	119.06 (11)	H19A—C19—H19B	109.8 (16)
N3—C8—N2	102.50 (10)	C10—C19—H19C	107.9 (11)
N3—C8—S1	126.62 (10)	H19A—C19—H19C	109.8 (15)
N2—C8—S1	130.88 (10)	H19B—C19—H19C	108.7 (17)
N4—C9—N2	110.96 (11)	C18—C20—H20A	111.5 (12)
N4—C9—C10	126.38 (12)	C18—C20—H20B	113.4 (12)
N2—C9—C10	122.59 (12)	H20A—C20—H20B	108.1 (18)
C9—C10—C19	110.48 (11)	C18—C20—H20C	109.1 (13)
C9—C10—C11	108.88 (10)	H20A—C20—H20C	109.1 (17)
C19—C10—C11	113.34 (11)	H20B—C20—H20C	105.5 (17)
C9—C10—H10A	110.3 (11)	C18—C21—H21A	111.1 (13)
C19—C10—H10A	103.0 (11)	C18—C21—H21B	110.1 (13)
C11—C10—H10A	110.7 (11)	H21A—C21—H21B	106.5 (17)
C12—C11—C16	117.98 (12)	C18—C21—H21C	110.7 (11)
C12—C11—C10	120.42 (12)	H21A—C21—H21C	107.5 (17)
C16—C11—C10	121.60 (11)	H21B—C21—H21C	110.9 (17)
C11—C12—C13	120.95 (12)
C8—N3—N4—C9	−0.39 (15)	C8—N2—C9—N4	1.56 (14)
C6—C1—C2—C3	0.56 (19)	N1—N2—C9—C10	−3.85 (17)
C1—C2—C3—F1	179.96 (12)	C8—N2—C9—C10	178.80 (11)
C1—C2—C3—C4	−0.3 (2)	N4—C9—C10—C19	−26.92 (19)
F1—C3—C4—C5	179.39 (12)	N2—C9—C10—C19	156.28 (13)
C2—C3—C4—C5	−0.3 (2)	N4—C9—C10—C11	98.16 (15)
C3—C4—C5—C6	0.8 (2)	N2—C9—C10—C11	−78.64 (15)
C4—C5—C6—C1	−0.5 (2)	C9—C10—C11—C12	107.13 (14)
C4—C5—C6—C7	−179.87 (13)	C19—C10—C11—C12	−129.48 (14)
C2—C1—C6—C5	−0.16 (19)	C9—C10—C11—C16	−72.11 (15)
C2—C1—C6—C7	179.16 (12)	C19—C10—C11—C16	51.28 (17)
C5—C6—C7—N1	178.23 (12)	C16—C11—C12—C13	−1.31 (18)
C1—C6—C7—N1	−1.1 (2)	C10—C11—C12—C13	179.42 (11)
C6—C7—N1—N2	−176.62 (11)	C11—C12—C13—C14	−0.41 (19)
C9—N2—N1—C7	167.93 (12)	C12—C13—C14—C15	1.20 (18)
C8—N2—N1—C7	−15.5 (2)	C12—C13—C14—C17	−177.44 (12)
N4—N3—C8—N2	1.29 (14)	C13—C14—C15—C16	−0.28 (18)
N4—N3—C8—S1	−178.22 (9)	C17—C14—C15—C16	178.39 (12)
C9—N2—C8—N3	−1.65 (13)	C14—C15—C16—C11	−1.5 (2)
N1—N2—C8—N3	−178.43 (12)	C12—C11—C16—C15	2.23 (18)
C9—N2—C8—S1	177.83 (10)	C10—C11—C16—C15	−178.51 (11)
N1—N2—C8—S1	1.1 (2)	C13—C14—C17—C18	92.42 (15)
N3—N4—C9—N2	−0.73 (14)	C15—C14—C17—C18	−86.18 (14)
N3—N4—C9—C10	−177.84 (12)	C14—C17—C18—C20	−66.53 (15)
N1—N2—C9—N4	178.91 (11)	C14—C17—C18—C21	170.91 (11)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H1N3···S1i	0.85 (2)	2.43 (2)	3.2763 (12)	172.3 (18)
C7—H7A···S1	0.96 (2)	2.50 (2)	3.2415 (13)	133.2 (16)
C4—H4A···Cg1ii	1.01 (2)	2.85 (2)	3.6276 (16)	133.8 (17)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H1N3⋯S1i	0.85 (2)	2.43 (2)	3.2763 (12)	172.3 (18)
C7—H7A⋯S1	0.96 (2)	2.50 (2)	3.2415 (13)	133.2 (16)
C4—H4A⋯Cg1ii	1.01 (2)	2.85 (2)	3.6276 (16)	133.8 (17)

Symmetry codes: (i) ; (ii) . Cg1 is the centroid of the C11–C16 ring.