Crystal structure of 4-fluoro-N-[2-(4-fluoro-benzo-yl)hydra-zine-1-carbono-thio-yl]benzamide.

In the title compound, C15H11F2N3O2S, the dihedral angle between the fluoro-benzene rings is 88.43 (10)° and that between the central semithiocarbazide grouping is 47.00 (11)°. The dihedral angle between the amide group and attached fluoro-benzene ring is 50.52 (11)°; the equivalent angle between the carbonyl-thio-amide group and its attached ring is 12.98 (10)°. The major twists in the mol-ecule occur about the C-N-N-C bonds [torsion angle = -138.7 (2)°] and the Car-Car-C-N (ar = aromatic) bonds [-132.0 (2)°]. An intra-molecular N-H⋯O hydrogen bond occurs, which generates an S(6) ring. In the crystal, the mol-ecules are linked by N-H⋯O and N-H⋯S hydrogen bonds, generating (001) sheets. Weak C-H⋯O and C-H⋯F inter-actions are also observed.

Related literature

For further synthetic details and the crystal structures of related thio­urea derivatives, see: Yamin & Yusof (2003a ▶,b ▶); Yusof et al. (2003 ▶); For a metal complex with a similar ligand, see: Ke et al. (2007 ▶).

Experimental

Crystal data

C15H11F2N3O2S

M = 335.33

Orthorhombic,

a = 11.6172 (6) Å

b = 8.4086 (5) Å

c = 30.0002 (16) Å

V = 2930.6 (3) Å3

Z = 8

Mo Kα radiation

μ = 0.26 mm−1

T = 296 K

0.50 × 0.12 × 0.08 mm

Data collection

Bruker SMART APEX CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T min = 0.883, T max = 0.980

76830 measured reflections

2886 independent reflections

2024 reflections with I > 2σ(I)

R int = 0.137

Refinement

R[F 2 > 2σ(F 2)] = 0.046

wR(F 2) = 0.099

S = 1.04

2886 reflections

208 parameters

H-atom parameters constrained

Δρmax = 0.27 e Å−3

Δρmin = −0.21 e Å−3

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536814015761/hb7245sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814015761/hb7245Isup2.hkl

Click here for additional data file.

. DOI: 10.1107/S1600536814015761/hb7245fig1.tif

Mol­ecular structure of (I) with 50% probability displacement ellipsoids. The dashes line indicates the intra­molecular hydrogen bond.

Click here for additional data file.

. DOI: 10.1107/S1600536814015761/hb7245fig2.tif

Unit-cell packing for (I) in the unit cell viewed down a axis. The dashes lines indicate hydrogen bonds.

CCDC reference: 1012471

Additional supporting information: crystallographic information; 3D view; checkCIF report

C15H11F2N3O2S	Z = 8
Mr = 335.33	F(000) = 1376
Orthorhombic, Pbca	Dx = 1.520 Mg m−3
Hall symbol: -P 2ac 2ab	Mo Kα radiation, λ = 0.71073 Å
a = 11.6172 (6) Å	µ = 0.26 mm−1
b = 8.4086 (5) Å	T = 296 K
c = 30.0002 (16) Å	Block, colorless
V = 2930.6 (3) Å3	0.50 × 0.12 × 0.08 mm

Bruker SMART APEX CCD diffractometer	2886 independent reflections
Radiation source: fine-focus sealed tube	2024 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.137
ω scans	θmax = 26.0°, θmin = 3.1°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −14→14
Tmin = 0.883, Tmax = 0.980	k = −10→10
76830 measured reflections	l = −37→37

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.099	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.0354P)2 + 2.0394P] where P = (Fo2 + 2Fc2)/3
2886 reflections	(Δ/σ)max = 0.001
208 parameters	Δρmax = 0.27 e Å−3
0 restraints	Δρmin = −0.21 e Å−3

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. 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 > 2sigma(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	0.98887 (5)	0.15863 (8)	0.73680 (2)	0.04054 (19)
O1	0.69608 (15)	0.4074 (2)	0.80598 (6)	0.0585 (6)
O2	0.64343 (13)	0.34844 (18)	0.67414 (5)	0.0328 (4)
N1	0.88035 (15)	0.3239 (2)	0.79937 (6)	0.0283 (4)
H1A	0.9472	0.3290	0.8116	0.034*
N2	0.76928 (15)	0.2357 (2)	0.74100 (6)	0.0308 (5)
H2A	0.7137	0.2871	0.7533	0.037*
N3	0.74823 (15)	0.1473 (2)	0.70307 (5)	0.0278 (4)
H3	0.7784	0.0548	0.6995	0.033*
C1	0.7245 (2)	0.5302 (3)	0.88928 (8)	0.0444 (7)
H1	0.6558	0.5469	0.8741	0.053*
C2	0.7347 (2)	0.5802 (3)	0.93299 (8)	0.0511 (7)
H2	0.6738	0.6303	0.9474	0.061*
C3	0.8362 (2)	0.5540 (3)	0.95425 (8)	0.0430 (7)
C4	0.9276 (2)	0.4826 (3)	0.93441 (8)	0.0479 (7)
H4	0.9959	0.4667	0.9500	0.057*
C5	0.9171 (2)	0.4339 (3)	0.89050 (8)	0.0402 (6)
H5	0.9792	0.3861	0.8762	0.048*
C6	0.81520 (19)	0.4557 (3)	0.86779 (7)	0.0300 (5)
C7	0.79209 (19)	0.3964 (3)	0.82191 (7)	0.0315 (5)
C8	0.87407 (18)	0.2428 (3)	0.75895 (7)	0.0258 (5)
C9	0.67935 (17)	0.2104 (3)	0.67201 (7)	0.0254 (5)
C10	0.64585 (18)	0.1018 (3)	0.63505 (7)	0.0263 (5)
C11	0.6553 (2)	0.1549 (3)	0.59144 (7)	0.0383 (6)
H11	0.6838	0.2563	0.5858	0.046*
C12	0.6228 (2)	0.0589 (3)	0.55647 (8)	0.0481 (7)
H12	0.6300	0.0931	0.5271	0.058*
C13	0.5797 (2)	−0.0878 (3)	0.56616 (9)	0.0503 (7)
C15	0.6004 (2)	−0.0473 (3)	0.64350 (8)	0.0360 (6)
H15	0.5929	−0.0828	0.6727	0.043*
F1	0.84583 (15)	0.6012 (2)	0.99733 (5)	0.0681 (5)
F2	0.54797 (19)	−0.1828 (2)	0.53146 (6)	0.0870 (7)
C14	0.5660 (2)	−0.1434 (3)	0.60860 (9)	0.0491 (7)
H14	0.5344	−0.2433	0.6139	0.059*

	U11	U22	U33	U12	U13	U23
S1	0.0271 (3)	0.0533 (4)	0.0412 (4)	0.0032 (3)	−0.0018 (3)	−0.0162 (3)
O1	0.0387 (11)	0.0887 (16)	0.0482 (11)	0.0263 (10)	−0.0169 (9)	−0.0332 (11)
O2	0.0344 (9)	0.0280 (9)	0.0359 (9)	0.0044 (8)	−0.0042 (7)	−0.0043 (7)
N1	0.0248 (9)	0.0357 (11)	0.0242 (9)	−0.0003 (8)	−0.0042 (8)	−0.0055 (8)
N2	0.0269 (10)	0.0392 (12)	0.0262 (10)	0.0057 (9)	−0.0042 (8)	−0.0118 (9)
N3	0.0280 (9)	0.0286 (10)	0.0270 (10)	0.0032 (9)	−0.0059 (8)	−0.0073 (8)
C1	0.0390 (15)	0.0567 (18)	0.0374 (14)	0.0123 (13)	−0.0061 (12)	−0.0095 (13)
C2	0.0505 (17)	0.0635 (19)	0.0394 (15)	0.0131 (15)	0.0054 (13)	−0.0154 (14)
C3	0.0531 (17)	0.0494 (17)	0.0265 (13)	−0.0062 (14)	−0.0001 (12)	−0.0112 (12)
C4	0.0389 (14)	0.067 (2)	0.0377 (15)	0.0004 (14)	−0.0096 (12)	−0.0118 (14)
C5	0.0347 (14)	0.0535 (17)	0.0323 (13)	0.0045 (12)	−0.0021 (11)	−0.0116 (12)
C6	0.0316 (13)	0.0303 (13)	0.0280 (12)	−0.0002 (10)	−0.0017 (10)	−0.0027 (11)
C7	0.0300 (12)	0.0332 (14)	0.0314 (13)	0.0042 (10)	−0.0046 (10)	−0.0026 (11)
C8	0.0294 (12)	0.0253 (12)	0.0228 (11)	−0.0025 (10)	−0.0034 (10)	0.0009 (9)
C9	0.0214 (11)	0.0280 (13)	0.0267 (12)	−0.0014 (10)	0.0019 (9)	−0.0010 (10)
C10	0.0233 (11)	0.0289 (13)	0.0267 (12)	0.0027 (10)	−0.0056 (9)	−0.0036 (10)
C11	0.0464 (14)	0.0374 (15)	0.0313 (13)	−0.0068 (13)	−0.0024 (11)	0.0013 (12)
C12	0.0634 (18)	0.0546 (18)	0.0261 (13)	−0.0020 (15)	−0.0060 (12)	−0.0041 (13)
C13	0.0603 (18)	0.0505 (18)	0.0399 (16)	−0.0067 (15)	−0.0182 (13)	−0.0189 (14)
C15	0.0390 (14)	0.0368 (15)	0.0321 (13)	−0.0051 (12)	−0.0082 (11)	0.0020 (11)
F1	0.0741 (11)	0.0980 (14)	0.0322 (8)	−0.0006 (10)	−0.0036 (8)	−0.0258 (9)
F2	0.1324 (18)	0.0781 (14)	0.0506 (11)	−0.0280 (12)	−0.0284 (11)	−0.0258 (10)
C14	0.0589 (18)	0.0370 (16)	0.0514 (17)	−0.0158 (14)	−0.0154 (14)	−0.0037 (13)

S1—C8	1.650 (2)	C4—C5	1.385 (3)
O1—C7	1.217 (3)	C4—H4	0.9300
O2—C9	1.235 (3)	C5—C6	1.378 (3)
N1—C7	1.371 (3)	C5—H5	0.9300
N1—C8	1.393 (3)	C6—C7	1.488 (3)
N1—H1A	0.8600	C9—C10	1.488 (3)
N2—C8	1.333 (3)	C10—C15	1.384 (3)
N2—N3	1.381 (2)	C10—C11	1.387 (3)
N2—H2A	0.8600	C11—C12	1.377 (3)
N3—C9	1.338 (3)	C11—H11	0.9300
N3—H3	0.8600	C12—C13	1.362 (4)
C1—C2	1.382 (3)	C12—H12	0.9300
C1—C6	1.385 (3)	C13—F2	1.363 (3)
C1—H1	0.9300	C13—C14	1.366 (4)
C2—C3	1.359 (4)	C15—C14	1.381 (3)
C2—H2	0.9300	C15—H15	0.9300
C3—F1	1.357 (3)	C14—H14	0.9300
C3—C4	1.358 (4)
C7—N1—C8	127.43 (18)	O1—C7—N1	121.7 (2)
C7—N1—H1A	116.3	O1—C7—C6	120.2 (2)
C8—N1—H1A	116.3	N1—C7—C6	118.04 (19)
C8—N2—N3	121.27 (18)	N2—C8—N1	114.95 (18)
C8—N2—H2A	119.4	N2—C8—S1	123.80 (16)
N3—N2—H2A	119.4	N1—C8—S1	121.23 (15)
C9—N3—N2	117.80 (18)	O2—C9—N3	122.6 (2)
C9—N3—H3	121.1	O2—C9—C10	121.8 (2)
N2—N3—H3	121.1	N3—C9—C10	115.58 (19)
C2—C1—C6	121.0 (2)	C15—C10—C11	119.7 (2)
C2—C1—H1	119.5	C15—C10—C9	121.3 (2)
C6—C1—H1	119.5	C11—C10—C9	119.0 (2)
C3—C2—C1	118.0 (2)	C12—C11—C10	120.5 (2)
C3—C2—H2	121.0	C12—C11—H11	119.7
C1—C2—H2	121.0	C10—C11—H11	119.7
F1—C3—C4	118.8 (2)	C13—C12—C11	118.0 (2)
F1—C3—C2	118.1 (2)	C13—C12—H12	121.0
C4—C3—C2	123.0 (2)	C11—C12—H12	121.0
C3—C4—C5	118.6 (2)	C12—C13—F2	117.8 (2)
C3—C4—H4	120.7	C12—C13—C14	123.5 (2)
C5—C4—H4	120.7	F2—C13—C14	118.7 (3)
C6—C5—C4	120.5 (2)	C14—C15—C10	120.1 (2)
C6—C5—H5	119.8	C14—C15—H15	119.9
C4—C5—H5	119.8	C10—C15—H15	119.9
C5—C6—C1	118.9 (2)	C13—C14—C15	118.2 (3)
C5—C6—C7	124.6 (2)	C13—C14—H14	120.9
C1—C6—C7	116.4 (2)	C15—C14—H14	120.9
C8—N2—N3—C9	−138.7 (2)	C7—N1—C8—N2	−0.5 (3)
C6—C1—C2—C3	0.0 (4)	C7—N1—C8—S1	−178.67 (18)
C1—C2—C3—F1	−179.2 (3)	N2—N3—C9—O2	6.9 (3)
C1—C2—C3—C4	0.5 (5)	N2—N3—C9—C10	−171.47 (17)
F1—C3—C4—C5	179.6 (3)	O2—C9—C10—C15	−127.2 (2)
C2—C3—C4—C5	−0.1 (4)	N3—C9—C10—C15	51.2 (3)
C3—C4—C5—C6	−0.9 (4)	O2—C9—C10—C11	49.5 (3)
C4—C5—C6—C1	1.4 (4)	N3—C9—C10—C11	−132.0 (2)
C4—C5—C6—C7	−175.0 (2)	C15—C10—C11—C12	−1.9 (4)
C2—C1—C6—C5	−1.0 (4)	C9—C10—C11—C12	−178.6 (2)
C2—C1—C6—C7	175.7 (3)	C10—C11—C12—C13	1.1 (4)
C8—N1—C7—O1	−6.0 (4)	C11—C12—C13—F2	−179.8 (3)
C8—N1—C7—C6	171.2 (2)	C11—C12—C13—C14	0.7 (4)
C5—C6—C7—O1	172.8 (3)	C11—C10—C15—C14	0.9 (4)
C1—C6—C7—O1	−3.6 (4)	C9—C10—C15—C14	177.6 (2)
C5—C6—C7—N1	−4.4 (4)	C12—C13—C14—C15	−1.7 (4)
C1—C6—C7—N1	179.1 (2)	F2—C13—C14—C15	178.8 (3)
N3—N2—C8—N1	−174.21 (18)	C10—C15—C14—C13	0.8 (4)
N3—N2—C8—S1	3.9 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1	0.86	1.89	2.571 (2)	135
N2—H2A···S1i	0.86	2.84	3.3875 (18)	123
N1—H1A···O2ii	0.86	2.33	3.165 (2)	165
N3—H3···O2iii	0.86	2.10	2.942 (2)	166
C4—H4···F1iv	0.93	2.49	3.409 (3)	169
C5—H5···O2ii	0.93	2.45	3.345 (3)	160

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O1	0.86	1.89	2.571 (2)	135
N2—H2A⋯S1i	0.86	2.84	3.3875 (18)	123
N1—H1A⋯O2ii	0.86	2.33	3.165 (2)	165
N3—H3⋯O2iii	0.86	2.10	2.942 (2)	166
C4—H4⋯F1iv	0.93	2.49	3.409 (3)	169
C5—H5⋯O2ii	0.93	2.45	3.345 (3)	160

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .