N-[(4-Carbamoylphen-yl)carbamothio-yl]-2,3,4,5-tetra-fluoro-benzamide.

In the title compound, C(15)H(9)F(4)N(3)O(2)S, the N,N'-disubstituted thio-urea fragment adopts a cis,trans geometry, stabilized by an intra-molecular N-H⋯O hydrogen bond to the carbonyl O atom of the tetra-fluoro-benzoyl group. The central thio-urea group makes dihedral angles of 47.79 (7) and 35.54 (8)° with the two aromatic rings. In the crystal, mol-ecules are linked via N-H⋯O and N-H⋯S hydrogen bonds into two-dimensional polymeric structures parallel to (100). In turn, π-π stacking inter-actions between tetra-fluoro-benzene and benzene units [centroid-centroid distance = 3.996 (10) Å; dihedral angle = 13.60 (8)°] organize these two-dimensional assemblies into a three-dimensional framework.

Related literature

For the biological activity of thio­urea derivatives, see: Zeng et al. (2003 ▶); Saeed et al. (2010 ▶). For the synthesis of thio­urea derivatives, see: Nosova et al. (2007 ▶). For related structures, see: Saeed et al. (2008 ▶, 2009 ▶).

Experimental

Crystal data

C15H9F4N3O2S

M = 371.31

Monoclinic,

a = 7.4246 (3) Å

b = 20.3368 (7) Å

c = 9.8954 (4) Å

β = 95.554 (3)°

V = 1487.12 (9) Å3

Z = 4

Mo Kα radiation

μ = 0.28 mm−1

T = 294 K

0.38 × 0.30 × 0.26 mm

Data collection

Oxford Diffraction Xcalibur E CCD diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2006 ▶) T min = 0.860, T max = 1.0

6598 measured reflections

3031 independent reflections

2263 reflections with I > 2σ(I)

R int = 0.014

Refinement

R[F 2 > 2σ(F 2)] = 0.036

wR(F 2) = 0.103

S = 1.13

3031 reflections

226 parameters

H-atom parameters constrained

Δρmax = 0.31 e Å−3

Δρmin = −0.34 e Å−3

Data collection: CrysAlis PRO (Oxford Diffraction, 2006 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: OLEX2 (Dolomanov et al., 2009 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: OLEX2.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811005915/gk2335sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811005915/gk2335Isup2.hkl

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

C15H9F4N3O2S	F(000) = 752
Mr = 371.31	Dx = 1.658 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.7107 Å
Hall symbol: -P 2ybc	Cell parameters from 3669 reflections
a = 7.4246 (3) Å	θ = 3.3–29.2°
b = 20.3368 (7) Å	µ = 0.28 mm−1
c = 9.8954 (4) Å	T = 294 K
β = 95.554 (3)°	Block, colourless
V = 1487.12 (9) Å3	0.38 × 0.30 × 0.26 mm
Z = 4

Oxford Diffraction Xcalibur E CCD diffractometer	3031 independent reflections
Radiation source: fine-focus sealed tube	2263 reflections with I > 2σ(I)
graphite	Rint = 0.014
Detector resolution: 16.0874 pixels mm-1	θmax = 26.4°, θmin = 3.4°
ω scans	h = −9→9
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2006)	k = −25→21
Tmin = 0.860, Tmax = 1.0	l = −11→12
6598 measured reflections

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.103	H-atom parameters constrained
S = 1.13	w = 1/[σ2(Fo2) + (0.056P)2] where P = (Fo2 + 2Fc2)/3
3031 reflections	(Δ/σ)max < 0.001
226 parameters	Δρmax = 0.31 e Å−3
0 restraints	Δρmin = −0.34 e Å−3

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	0.41600 (7)	0.40876 (2)	0.28889 (6)	0.05125 (18)
F	0.98701 (18)	0.10215 (6)	−0.07009 (12)	0.0623 (4)
F1	0.66951 (14)	0.21050 (5)	0.34645 (9)	0.0445 (3)
F2	0.72451 (16)	0.08149 (5)	0.33952 (12)	0.0543 (3)
F3	0.87569 (17)	0.02540 (5)	0.12899 (13)	0.0635 (4)
O1	0.66762 (17)	0.73716 (6)	0.33958 (11)	0.0386 (3)
O2	0.91223 (18)	0.33325 (6)	0.09914 (14)	0.0471 (3)
N1	0.7405 (2)	0.75363 (7)	0.12865 (14)	0.0434 (4)
H1B	0.7340	0.7956	0.1382	0.052*
H1A	0.7683	0.7373	0.0532	0.052*
N2	0.7175 (2)	0.43553 (7)	0.17165 (14)	0.0390 (4)
H2	0.8046	0.4200	0.1300	0.047*
N3	0.64026 (19)	0.32604 (7)	0.18763 (14)	0.0356 (3)
H3	0.5580	0.2981	0.2036	0.043*
C1	0.7076 (2)	0.71401 (8)	0.23066 (16)	0.0304 (4)
C2	0.7164 (2)	0.64135 (8)	0.21097 (16)	0.0286 (4)
C3	0.7548 (3)	0.61151 (9)	0.09123 (18)	0.0392 (4)
H3A	0.7823	0.6372	0.0182	0.047*
C4	0.7524 (3)	0.54374 (9)	0.07970 (18)	0.0425 (5)
H4	0.7771	0.5241	−0.0013	0.051*
C5	0.7133 (2)	0.50499 (8)	0.18833 (17)	0.0343 (4)
C6	0.6795 (2)	0.53412 (8)	0.30877 (17)	0.0367 (4)
H6	0.6566	0.5083	0.3828	0.044*
C7	0.6796 (2)	0.60191 (8)	0.31958 (16)	0.0329 (4)
H7	0.6546	0.6214	0.4007	0.039*
C8	0.6006 (2)	0.39170 (8)	0.21371 (17)	0.0345 (4)
C9	0.7920 (2)	0.30012 (9)	0.14025 (17)	0.0338 (4)
C10	0.8043 (2)	0.22623 (8)	0.14010 (16)	0.0315 (4)
C11	0.8887 (2)	0.19686 (9)	0.03581 (18)	0.0369 (4)
H11	0.9315	0.2228	−0.0316	0.044*
C12	0.9089 (2)	0.13022 (9)	0.03208 (19)	0.0410 (4)
C13	0.8521 (3)	0.09051 (8)	0.1325 (2)	0.0414 (5)
C14	0.7735 (2)	0.11852 (8)	0.23825 (18)	0.0369 (4)
C15	0.7476 (2)	0.18583 (8)	0.24020 (16)	0.0326 (4)

	U11	U22	U33	U12	U13	U23
S1	0.0543 (3)	0.0289 (3)	0.0750 (4)	0.0028 (2)	0.0295 (3)	−0.0031 (2)
F	0.0717 (9)	0.0532 (7)	0.0638 (8)	0.0202 (6)	0.0162 (6)	−0.0171 (6)
F1	0.0550 (7)	0.0402 (6)	0.0394 (6)	0.0026 (5)	0.0093 (5)	0.0001 (5)
F2	0.0617 (8)	0.0366 (6)	0.0643 (7)	−0.0022 (5)	0.0052 (6)	0.0184 (5)
F3	0.0688 (8)	0.0237 (6)	0.0975 (10)	0.0083 (5)	0.0051 (7)	−0.0067 (6)
O1	0.0568 (8)	0.0293 (7)	0.0305 (6)	0.0036 (6)	0.0085 (6)	−0.0027 (5)
O2	0.0453 (8)	0.0312 (7)	0.0677 (9)	−0.0037 (6)	0.0199 (7)	0.0007 (6)
N1	0.0702 (11)	0.0250 (8)	0.0374 (8)	−0.0013 (7)	0.0174 (8)	0.0019 (7)
N2	0.0480 (9)	0.0228 (7)	0.0488 (9)	−0.0001 (7)	0.0181 (7)	−0.0001 (7)
N3	0.0392 (8)	0.0215 (7)	0.0481 (9)	0.0008 (6)	0.0145 (7)	0.0009 (6)
C1	0.0333 (9)	0.0274 (9)	0.0303 (9)	0.0002 (7)	0.0031 (7)	0.0003 (7)
C2	0.0310 (9)	0.0245 (9)	0.0303 (8)	0.0002 (7)	0.0028 (7)	0.0005 (7)
C3	0.0559 (12)	0.0280 (9)	0.0359 (10)	−0.0041 (8)	0.0166 (9)	0.0013 (8)
C4	0.0614 (12)	0.0293 (10)	0.0398 (10)	−0.0009 (9)	0.0206 (9)	−0.0057 (8)
C5	0.0409 (10)	0.0213 (9)	0.0416 (10)	−0.0004 (7)	0.0075 (8)	0.0002 (7)
C6	0.0509 (11)	0.0273 (9)	0.0319 (9)	−0.0022 (8)	0.0037 (8)	0.0056 (7)
C7	0.0432 (10)	0.0288 (9)	0.0269 (8)	−0.0004 (7)	0.0042 (7)	−0.0007 (7)
C8	0.0434 (10)	0.0233 (9)	0.0371 (9)	0.0023 (7)	0.0060 (8)	0.0010 (7)
C9	0.0368 (10)	0.0271 (9)	0.0377 (9)	0.0016 (7)	0.0045 (7)	0.0004 (7)
C10	0.0310 (9)	0.0252 (9)	0.0380 (9)	0.0018 (7)	0.0015 (7)	−0.0003 (7)
C11	0.0342 (9)	0.0341 (10)	0.0426 (10)	0.0040 (8)	0.0043 (8)	0.0013 (8)
C12	0.0387 (10)	0.0364 (10)	0.0475 (11)	0.0104 (8)	0.0022 (8)	−0.0113 (9)
C13	0.0389 (10)	0.0221 (9)	0.0612 (12)	0.0040 (8)	−0.0061 (9)	−0.0046 (9)
C14	0.0350 (10)	0.0275 (9)	0.0469 (10)	−0.0027 (7)	−0.0032 (8)	0.0060 (8)
C15	0.0296 (9)	0.0313 (9)	0.0366 (9)	0.0018 (7)	0.0022 (7)	−0.0011 (8)

S1—C8	1.6583 (18)	C2—C7	1.389 (2)
F—C12	1.341 (2)	C3—H3A	0.9300
F1—C15	1.3458 (18)	C3—C4	1.383 (2)
F2—C14	1.332 (2)	C4—H4	0.9300
F3—C13	1.3365 (18)	C4—C5	1.386 (2)
O1—C1	1.2383 (18)	C5—C6	1.376 (2)
O2—C9	1.219 (2)	C6—H6	0.9300
N1—H1B	0.8600	C6—C7	1.383 (2)
N1—H1A	0.8600	C7—H7	0.9300
N1—C1	1.333 (2)	C9—C10	1.505 (2)
N2—H2	0.8600	C10—C11	1.393 (2)
N2—C5	1.423 (2)	C10—C15	1.384 (2)
N2—C8	1.338 (2)	C11—H11	0.9300
N3—H3	0.8600	C11—C12	1.364 (2)
N3—C8	1.397 (2)	C12—C13	1.378 (3)
N3—C9	1.367 (2)	C13—C14	1.370 (3)
C1—C2	1.493 (2)	C14—C15	1.383 (2)
C2—C3	1.385 (2)
F—C12—C11	119.99 (18)	C4—C3—H3A	119.8
F—C12—C13	118.62 (16)	C4—C5—N2	117.77 (15)
F1—C15—C10	121.45 (14)	C5—N2—H2	116.5
F1—C15—C14	116.81 (15)	C5—C4—H4	119.8
F2—C14—C13	120.47 (15)	C5—C6—H6	120.1
F2—C14—C15	120.04 (16)	C5—C6—C7	119.84 (15)
F3—C13—C12	120.80 (18)	C6—C5—N2	122.40 (15)
F3—C13—C14	119.87 (18)	C6—C5—C4	119.77 (15)
O1—C1—N1	120.43 (15)	C6—C7—C2	120.96 (15)
O1—C1—C2	120.47 (14)	C6—C7—H7	119.5
O2—C9—N3	123.76 (16)	C7—C2—C1	117.15 (14)
O2—C9—C10	120.32 (15)	C7—C6—H6	120.1
N1—C1—C2	119.09 (14)	C8—N2—H2	116.5
H1B—N1—H1A	120.0	C8—N2—C5	127.09 (15)
N2—C8—S1	126.10 (13)	C8—N3—H3	115.6
N2—C8—N3	115.14 (15)	C9—N3—H3	115.6
N3—C8—S1	118.75 (12)	C9—N3—C8	128.85 (14)
N3—C9—C10	115.92 (14)	C10—C11—H11	119.9
C1—N1—H1B	120.0	C11—C10—C9	117.41 (15)
C1—N1—H1A	120.0	C11—C12—C13	121.38 (17)
C2—C3—H3A	119.8	C12—C11—C10	120.29 (17)
C2—C7—H7	119.5	C12—C11—H11	119.9
C3—C2—C1	124.10 (15)	C13—C14—C15	119.49 (16)
C3—C2—C7	118.74 (15)	C14—C13—C12	119.32 (15)
C3—C4—H4	119.8	C14—C15—C10	121.71 (15)
C3—C4—C5	120.31 (16)	C15—C10—C9	124.72 (15)
C4—C3—C2	120.34 (16)	C15—C10—C11	117.75 (15)
F—C12—C13—F3	0.6 (3)	C5—N2—C8—N3	−178.02 (15)
F—C12—C13—C14	179.40 (16)	C5—C6—C7—C2	−1.1 (3)
F2—C14—C15—F1	−1.0 (2)	C7—C2—C3—C4	1.4 (3)
F2—C14—C15—C10	177.00 (15)	C8—N2—C5—C4	−138.63 (19)
F3—C13—C14—F2	1.7 (3)	C8—N2—C5—C6	44.1 (3)
F3—C13—C14—C15	−179.20 (15)	C8—N3—C9—O2	−8.1 (3)
O1—C1—C2—C3	178.02 (16)	C8—N3—C9—C10	172.27 (16)
O1—C1—C2—C7	−0.5 (2)	C9—N3—C8—S1	−172.62 (14)
O2—C9—C10—C11	−33.5 (2)	C9—N3—C8—N2	8.7 (3)
O2—C9—C10—C15	142.48 (18)	C9—C10—C11—C12	178.10 (15)
N1—C1—C2—C3	−0.9 (3)	C9—C10—C15—F1	2.2 (2)
N1—C1—C2—C7	−179.44 (15)	C9—C10—C15—C14	−175.74 (15)
N2—C5—C6—C7	179.11 (16)	C10—C11—C12—F	178.65 (16)
N3—C9—C10—C11	146.16 (16)	C10—C11—C12—C13	−2.0 (3)
N3—C9—C10—C15	−37.9 (2)	C11—C10—C15—F1	178.11 (14)
C1—C2—C3—C4	−177.14 (16)	C11—C10—C15—C14	0.2 (2)
C1—C2—C7—C6	178.11 (16)	C11—C12—C13—F3	−178.74 (16)
C2—C3—C4—C5	−0.6 (3)	C11—C12—C13—C14	0.1 (3)
C3—C2—C7—C6	−0.5 (3)	C12—C13—C14—F2	−177.14 (15)
C3—C4—C5—N2	−178.38 (17)	C12—C13—C14—C15	2.0 (3)
C3—C4—C5—C6	−1.0 (3)	C13—C14—C15—F1	179.87 (15)
C4—C5—C6—C7	1.9 (3)	C13—C14—C15—C10	−2.1 (3)
C5—N2—C8—S1	3.4 (3)	C15—C10—C11—C12	1.9 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···S1i	0.86	2.69	3.4861 (16)	155
N1—H1A···O1ii	0.86	2.23	2.8654 (17)	130
N2—H2···O2	0.86	1.97	2.6708 (18)	138
N3—H3···F1	0.86	2.37	2.8234 (17)	113
N3—H3···O1iii	0.86	2.09	2.9062 (18)	157

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1B⋯S1i	0.86	2.69	3.4861 (16)	155
N1—H1A⋯O1ii	0.86	2.23	2.8654 (17)	130
N2—H2⋯O2	0.86	1.97	2.6708 (18)	138
N3—H3⋯O1iii	0.86	2.09	2.9062 (18)	157

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