Crystal structure and Hirshfeld surface analysis of N-(2-chloro­phenyl­carbamo­thio­yl)-4-fluoro­benzamide and N-(4-bromo­phenyl­carbamo­thio­yl)-4-fluoro­benzamide

Akhter, S.; Choudhary, M.I.; Siddiqui, H.; Yousuf, S.

doi:10.1107/S2056989019008569

research communications

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ISSN: 2056-9890

Volume 75| Part 7| July 2019| Pages 1026-1029

https://doi.org/10.1107/S2056989019008569

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Crystal structure and Hirshfeld surface analysis of N-(2-chlorophenylcarbamothioyl)-4-fluorobenzamide and N-(4-bromophenylcarbamothioyl)-4-fluorobenzamide

Sidra Akhter,^a Muhammad Iqbal Choudhary,^a Hina Siddiqui ^a and Sammer Yousuf ^a ^*

^aH.E.J. Research Institute Of Chemistry, International Center for Chemical and Biological Sciences, University of Karachi, Karachi 75270, Pakistan
^*Correspondence e-mail: dr.sammer.yousuf@gmail.com

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 15 February 2019; accepted 16 June 2019; online 21 June 2019)

The title compounds, C₁₄H₁₀ClFN₂OS (1) and C₁₄H₁₀BrFN₂OS (2), were synthesized by two-step reactions. The dihedral angles between the aromatic rings are 31.99 (3) and 9.17 (5)° for 1 and 2, respectively. Compound 1 features an intramolecular bifurcated N—H⋯(O,Cl) link due to the presence of the ortho-Cl atom on the benzene ring, whereas 2 features an intramolecular N—H⋯O hydrogen bond. In the crystal of 1, inversion dimers linked by pairs of N—H⋯S hydrogen bonds generate R₂²(8) loops. The extended structure of 2 features the same motif but an additional weak C—H⋯S interaction links the inversion dimers into [100] double columns. Hirshfeld surface analyses indicate that the most important contributors towards the crystal packing are H⋯H (26.6%), S⋯H/H.·S (13.8%) and Cl⋯H/H⋯Cl (9.5%) contacts for 1 and H⋯H (19.7%), C⋯H/H⋯C (14.8%) and Br⋯H/H⋯Br (12.4%) contacts for 2.

Keywords: Thiourea; benzamide derivative; crystal structure; Hirshfeld surface.

CCDC references: 1923234; 1923233

1. Chemical context

Thiourea and its derivatives show a broad range of biological activities (Solmaz et al., 2018 ; Saeed et al., 2018 ; Pandey et al., 2019 ). The crystal structures of many thiourea derivatives and their metal complexes have been reported (Lai et al.,2018 ; Contreras Aguilar et al., 2018 ; Fakhar et al., 2018 ; Mitoraj et al., 2018 ; Pervez et al., 2018 ; Hashim et al., 2017 Ghazal et al., 2019 ; Zhang et al., 2019 ). As part of our studies in this area, we now describe the syntheses, crystal structures and Hirshfeld surface analyses of the thiourea derivatives N-(2-chlorophenylcarbamothioyl)-4-fluorobenzamide (C₁₄H₁₀ClFN₂OS, 1) and N-(4-bromophenylcarbamothioyl)-4-fluorobenzamide (C₁₄H₁₀BrFN₂OS, 2). The biological activities of these compounds were previously reported by Khan et al. (2018 ).

2. Structural commentary

Compound 1 (Fig. 1) is composed of a para-fluoro-substituted [C—F = 1.3579 (16) Å] benzoyl ring linked to a ortho-chloro-substituted phenyl ring [C—Cl = 1.7387 (14) Å] in while in 2 (Fig. 2), a para-fluoro-substituted [C—F = 1.350 (2) Å] benzoyl ring is linked to a para-bromo-substituted phenyl ring [C—Br = 1.8991 (17) Å] via a thiourea (S1/N1/N2/C8) linkage. The benzoyl (O1/C1–C7) and phenyl rings (C9–C14) are arranged about the thiourea moiety in an anti fashion having torsion angles C8—N1—C7—C6 = −170.22 (13) and C9—N2—C8—S1 = 4.5 (2)° in compound 1, with corresponding values of −176.01 (16) and 3.8 (3)°, respectively, in compound 2. The dihedral angles between the phenyl rings are 31.99 (3) and 9.17 (5)° in 1 and 2, respectively. Compound 1 features an intramoleclar bifurcated N—H⋯(O,Cl) hydrogen bond (Table 1) due to the presence of the ortho-Cl atom whereas 2 has an intramolecular N—H⋯O link (Table 2). Both structures feature an intramolecular C—H⋯S bond, which closes an S(6) ring. These intramolecular hydrogen bonds may be responsible for the anti arrangement of the aromatic rings about the thiourea linker.

Table 1
Hydrogen-bond geometry (Å, °) for 1

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H10⋯S1	0.95	2.57	3.1945 (14)	124
N2—H1B⋯Cl	0.87 (2)	2.482 (19)	2.9246 (12)	112.3 (14)
N2—H1B⋯O1	0.87 (2)	1.924 (19)	2.6600 (14)	141.6 (17)
N1—H1A⋯S1ⁱ	0.85 (2)	2.67 (2)	3.4031 (13)	145.2 (16)
Symmetry code: (i) -x+1, -y+1, -z+1.

Table 2
Hydrogen-bond geometry (Å, °) for 2

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯S1ⁱ	0.88	2.69	3.5081 (15)	154
N2—H1B⋯O1	0.88	1.88	2.610 (2)	139
C10—H10⋯S1	0.95	2.65	3.2319 (18)	120
C1—H1⋯S1ⁱⁱ	0.95	2.81	3.7312 (18)	165
Symmetry codes: (i) -x+1, -y+1, -z; (ii) -x, -y+1, -z.

Figure 1
The molecular structure of 1 showing 50% displacement ellipsoids; the blue lines represent the intramolecular interactions.

Figure 2
The molecular structure of 2 showing 50% displacement ellipsoids; the blue lines represent the intramolecular interactions.

3. Supramolecular features

In the crystal of 1, inversion dimers linked by pairwise N1—H1A⋯S1 hydrogen bonds (Table 1) generate $[R_{2}^{2}]$ (8) loops (Fig. 3). The crystal of 2 features the same motif (Table 2), but an additional weak C—H⋯S bond links the dimers into double columns propagating in the [100] direction (Fig. 4).

Figure 3
Partial packing diagram for 1. Light-blue lines indicate directional interactions

Figure 4
Partial packing diagram for 2. Light-blue lines indicate directional interactions

4. Database survey

A search of Cambridge Structural Database (CSD version 5.39, update of February 2018) for compounds related to 1 and 2 yielded hits for N-{[4-chloro-3-(trifluoromethyl)phenyl]carbamothioyl}-3-methylbenzamide (CCDC deposition No. 1840069) and 4-chloro-N-{[4-chloro-3-(trifluoromethyl)phenyl]carbamothioyl}benzamide (CCDC 1587395) (Zhang et al., 2019): these compounds have the same skeleton as the title compounds but with different substituents attached to the phenyl rings. In both compounds, pairwise N—H⋯S hydrogen bonds are responsible for the formation of inversion dimers with an $[R_{2}^{2}]$ (8) motif, as also observed in title compounds.

5. Hirshfeld surface analysis

In order to further analyse the close contacts and intermolecular interactions in the crystals of 1 and 2, Hirshfeld surfaces (mapped over d_norm, curvedness and shape-index) (Fig. 5) and two-dimensional fingerprint plots (Figs. 6 and 7) were generated using CrystalExplorer3.1 (Mackenzie et al., 2017 ). The fingerprint plot for 1 decomposed into individual contact types indicates that the the most significant contributions are from H⋯H (van der Waals) (26.6%) contacts, followed by S⋯H/H⋯S (13.8%), Cl⋯H/H⋯Cl (9.5%) O⋯H/H⋯O (6.7%), F⋯H/H⋯F (6.6%), Cl⋯F/F⋯Cl (3.7%) and F⋯C/C⋯F (3.1%) interactions. In compound 2, H⋯H (19.7%) (van der Waals contacts) are the most significant, followed by C⋯H/H⋯C (14.8%), S⋯H/H⋯S (12.6%), Br⋯H/H⋯Br (12.4%), C⋯C (9.9%) and O⋯N/N⋯O (7.9%) interactions.

Figure 5
The Hirshfeld surfaces of 1 and 2.

Figure 6
Two dimensional fingerprint plots for 1.

Figure 7
Two dimensional fingerprint plots for 2.

6. Synthesis and Crystallization

Compounds 1 and 2 were synthesized by adopting a literature procedure (Binzet et al., 2018 ) with slight modification: we refluxed the reactants in distilled solvents for 20 min. instead of refluxing them in anhydrous solvents for 4 h. In the first step, 4-fluorobenzoyle chloride (1 mmol) and potassium thiocyanate (1 mmol) were dissolved in acetone (10 ml) at room temperature with constant stirring for 20 minutes to obtain a white precipitate of 4-fluorophenyl isothiocyanate. In the second step, 1 mmol of 2-chloro phenyl aniline (for 1) or 4-bromophenyl aniline (for 2) were added to the mixture and refluxed at 343 K. Hydrochloric acid (0.5 N, 10 ml) was added and the solution was filtered to obtain the desired products: 1 in 69% yield and 2 in 80% yield. For recrystallization, compound 1 was dissolved in a mixture of dichloromethane and methanol (1:1) while compound 2 was dissolved in dichloromethane and left for slow evaporation at room temperature to obtain colourless prisms of 1 and colourless plates of 2

7. Data collection and Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. The C-bound H atoms atoms were positioned with idealized geometry (C—H = 0.93–0.97 Å) and refined as riding atoms. In 1, the N-bound H atoms were located in difference-Fourier maps and their positions were freely refined; in 2, the N-bound H atoms were located in difference-Fourier maps and refined as riding atoms in their as-found relative positions. The constraint U_iso(H) = 1.2U_eq(carrier) was applied in all cases.

Table 3
Experimental details

	1	2
Crystal data
Chemical formula	C₁₄H₁₀ClFN₂OS	C₁₄H₁₀BrFN₂OS
M_r	308.75	353.19
Crystal system, space group	Monoclinic, P2₁/c	Triclinic, P $[\overline{1}]$
Temperature (K)	100	100
a, b, c (Å)	8.0785 (2), 12.4230 (3), 13.0772 (3)	3.8733 (2), 13.0776 (5), 13.2628 (6)
α, β, γ (°)	90, 90.551 (1), 90	98.817 (1), 94.714 (1), 94.727 (1)
V (Å³)	1312.36 (5)	658.54 (5)
Z	4	2
Radiation type	Cu Kα	Cu Kα
μ (mm⁻¹)	4.15	5.83
Crystal size (mm)	0.11 × 0.07 × 0.03	0.35 × 0.05 × 0.04

Data collection
Diffractometer	Bruker APEXII CCD	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2000 )	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.682, 0.895	0.612, 0.946
No. of measured, independent and observed [I > 2σ(I)] reflections	18686, 2362, 2269	20701, 2384, 2381
R_int	0.023	0.025
(sin θ/λ)_max (Å⁻¹)	0.602	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.025, 0.069, 1.05	0.025, 0.110, 1.10
No. of reflections	2362	2384
No. of parameters	189	181
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.25	0.45, −1.46
Computer programs: APEX2 and SAINT (Bruker, 2000), SHELXT2014 (Sheldrick, 2015 a), SHELXL2016 (Sheldrick, 2015b) and SHELXTL (Sheldrick, 2008 ).

Supporting information

CCDC references: 1923234; 1923233

Crystal structure: contains datablocks global, 1, 2. DOI: https://doi.org/10.1107/S2056989019008569/hb7804sup1.cif

Structure factors: contains datablock 2. DOI: https://doi.org/10.1107/S2056989019008569/hb78042sup3.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989019008569/hb78041sup4.cml

Structure factors: contains datablock 1. DOI: https://doi.org/10.1107/S2056989019008569/hb78041sup4.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989019008569/hb78042sup5.cml

checkCIF report

Computing details top

For both structures, data collection: APEX2 (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015b); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

N-(2-Chlorophenylcarbamothioyl)-4-fluorobenzamide (1) top

Crystal data top

C₁₄H₁₀ClFN₂OS	F(000) = 632
M_r = 308.75	D_x = 1.563 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54178 Å
a = 8.0785 (2) Å	Cell parameters from 9977 reflections
b = 12.4230 (3) Å	θ = 4.9–68.3°
c = 13.0772 (3) Å	µ = 4.15 mm⁻¹
β = 90.551 (1)°	T = 100 K
V = 1312.36 (5) Å³	Prism, colourless
Z = 4	0.11 × 0.07 × 0.03 mm

Data collection top

Bruker APEXII CCD diffractometer	2269 reflections with I > 2σ(I)
ω scans	R_int = 0.023
Absorption correction: multi-scan (SADABS; Bruker, 2000)	θ_max = 68.3°, θ_min = 4.9°
T_min = 0.682, T_max = 0.895	h = −9→9
18686 measured reflections	k = −14→14
2362 independent reflections	l = −15→15

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.025	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.069	w = 1/[σ²(F_o²) + (0.0347P)² + 0.7594P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
2362 reflections	Δρ_max = 0.22 e Å⁻³
189 parameters	Δρ_min = −0.24 e Å⁻³
0 restraints

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
S1	0.73325 (5)	0.47025 (3)	0.56374 (3)	0.02331 (12)
Cl	0.83162 (5)	0.03157 (3)	0.58416 (3)	0.02495 (11)
F1	0.18907 (12)	0.30493 (8)	0.01782 (7)	0.0314 (2)
O1	0.54889 (12)	0.15637 (8)	0.42244 (7)	0.0192 (2)
N1	0.56777 (15)	0.33824 (10)	0.44484 (9)	0.0179 (3)
N2	0.70992 (14)	0.25311 (9)	0.57516 (9)	0.0157 (2)
C1	0.43467 (17)	0.36712 (11)	0.24179 (10)	0.0177 (3)
H1	0.493438	0.425890	0.271153	0.021*
C2	0.35330 (18)	0.38022 (12)	0.14870 (11)	0.0206 (3)
H2	0.355095	0.447218	0.113699	0.025*
C3	0.26979 (18)	0.29291 (12)	0.10866 (10)	0.0211 (3)
C4	0.26446 (18)	0.19359 (12)	0.15557 (11)	0.0224 (3)
H4	0.206152	0.135158	0.125243	0.027*
C5	0.34669 (18)	0.18165 (11)	0.24822 (11)	0.0199 (3)
H5	0.345811	0.113881	0.281860	0.024*
C6	0.43099 (16)	0.26820 (11)	0.29281 (10)	0.0156 (3)
C7	0.51917 (16)	0.24761 (11)	0.39152 (10)	0.0160 (3)
C8	0.67071 (16)	0.34671 (11)	0.53083 (10)	0.0162 (3)
C9	0.80473 (16)	0.23264 (11)	0.66453 (10)	0.0148 (3)
C10	0.83157 (17)	0.30697 (11)	0.74300 (10)	0.0184 (3)
H10	0.789298	0.378033	0.736600	0.022*
C11	0.91962 (17)	0.27772 (12)	0.83031 (11)	0.0213 (3)
H11	0.938625	0.329427	0.882642	0.026*
C12	0.98017 (18)	0.17407 (12)	0.84215 (11)	0.0224 (3)
H12	1.040289	0.154849	0.902214	0.027*
C13	0.95246 (18)	0.09856 (12)	0.76576 (11)	0.0217 (3)
H13	0.992398	0.027057	0.773432	0.026*
C14	0.86603 (17)	0.12824 (11)	0.67813 (10)	0.0170 (3)
H1B	0.672 (2)	0.1970 (16)	0.5432 (14)	0.028 (5)*
H1A	0.528 (2)	0.3988 (16)	0.4260 (14)	0.031 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0331 (2)	0.01172 (18)	0.0249 (2)	−0.00054 (13)	−0.01311 (15)	−0.00095 (12)
Cl	0.0406 (2)	0.01417 (18)	0.01996 (19)	0.00501 (14)	−0.00550 (15)	−0.00194 (12)
F1	0.0374 (5)	0.0388 (5)	0.0178 (4)	0.0005 (4)	−0.0147 (4)	0.0016 (4)
O1	0.0267 (5)	0.0138 (5)	0.0170 (5)	−0.0006 (4)	−0.0048 (4)	0.0011 (4)
N1	0.0248 (6)	0.0126 (6)	0.0161 (6)	0.0039 (5)	−0.0079 (5)	−0.0007 (4)
N2	0.0206 (6)	0.0125 (6)	0.0141 (6)	0.0000 (5)	−0.0046 (4)	−0.0015 (4)
C1	0.0208 (7)	0.0165 (6)	0.0158 (7)	0.0002 (5)	−0.0008 (5)	−0.0019 (5)
C2	0.0257 (7)	0.0196 (7)	0.0166 (7)	0.0034 (6)	−0.0016 (6)	0.0024 (5)
C3	0.0209 (7)	0.0304 (8)	0.0119 (7)	0.0041 (6)	−0.0042 (5)	−0.0015 (6)
C4	0.0241 (7)	0.0243 (8)	0.0188 (7)	−0.0040 (6)	−0.0045 (6)	−0.0048 (6)
C5	0.0240 (7)	0.0170 (7)	0.0187 (7)	−0.0012 (6)	−0.0017 (5)	−0.0007 (5)
C6	0.0158 (6)	0.0171 (7)	0.0137 (6)	0.0017 (5)	−0.0004 (5)	−0.0012 (5)
C7	0.0171 (6)	0.0152 (7)	0.0158 (7)	0.0000 (5)	−0.0002 (5)	−0.0011 (5)
C8	0.0184 (6)	0.0150 (6)	0.0152 (6)	0.0020 (5)	−0.0023 (5)	−0.0010 (5)
C9	0.0139 (6)	0.0169 (6)	0.0135 (6)	−0.0009 (5)	−0.0008 (5)	0.0022 (5)
C10	0.0208 (7)	0.0169 (7)	0.0175 (7)	−0.0002 (5)	−0.0020 (5)	−0.0003 (5)
C11	0.0221 (7)	0.0250 (7)	0.0167 (7)	−0.0030 (6)	−0.0034 (5)	−0.0019 (6)
C12	0.0211 (7)	0.0292 (8)	0.0169 (7)	0.0001 (6)	−0.0055 (5)	0.0048 (6)
C13	0.0226 (7)	0.0211 (7)	0.0215 (7)	0.0039 (6)	−0.0024 (6)	0.0053 (6)
C14	0.0189 (6)	0.0160 (7)	0.0161 (6)	0.0000 (5)	−0.0001 (5)	−0.0007 (5)

Geometric parameters (Å, º) top

S1—C8	1.6709 (14)	C4—C5	1.384 (2)
Cl—C14	1.7387 (14)	C4—H4	0.9500
F1—C3	1.3579 (16)	C5—C6	1.3972 (19)
O1—C7	1.2264 (17)	C5—H5	0.9500
N1—C7	1.3794 (18)	C6—C7	1.4904 (18)
N1—C8	1.3961 (17)	C9—C10	1.3959 (19)
N1—H1A	0.85 (2)	C9—C14	1.3990 (19)
N2—C8	1.3360 (18)	C10—C11	1.3879 (19)
N2—C9	1.4141 (17)	C10—H10	0.9500
N2—H1B	0.87 (2)	C11—C12	1.385 (2)
C1—C2	1.3875 (19)	C11—H11	0.9500
C1—C6	1.3987 (19)	C12—C13	1.387 (2)
C1—H1	0.9500	C12—H12	0.9500
C2—C3	1.378 (2)	C13—C14	1.3860 (19)
C2—H2	0.9500	C13—H13	0.9500
C3—C4	1.379 (2)

C7—N1—C8	129.28 (12)	O1—C7—N1	122.26 (12)
C7—N1—H1A	117.8 (13)	O1—C7—C6	122.32 (12)
C8—N1—H1A	112.8 (13)	N1—C7—C6	115.41 (12)
C8—N2—C9	129.75 (12)	N2—C8—N1	114.89 (12)
C8—N2—H1B	114.1 (12)	N2—C8—S1	128.15 (10)
C9—N2—H1B	116.1 (12)	N1—C8—S1	116.94 (10)
C2—C1—C6	120.64 (13)	C10—C9—C14	117.87 (12)
C2—C1—H1	119.7	C10—C9—N2	124.58 (12)
C6—C1—H1	119.7	C14—C9—N2	117.39 (12)
C3—C2—C1	117.84 (13)	C11—C10—C9	120.42 (13)
C3—C2—H2	121.1	C11—C10—H10	119.8
C1—C2—H2	121.1	C9—C10—H10	119.8
F1—C3—C2	118.37 (13)	C12—C11—C10	120.86 (13)
F1—C3—C4	118.09 (13)	C12—C11—H11	119.6
C2—C3—C4	123.54 (13)	C10—C11—H11	119.6
C3—C4—C5	117.94 (13)	C11—C12—C13	119.58 (13)
C3—C4—H4	121.0	C11—C12—H12	120.2
C5—C4—H4	121.0	C13—C12—H12	120.2
C4—C5—C6	120.72 (13)	C14—C13—C12	119.47 (13)
C4—C5—H5	119.6	C14—C13—H13	120.3
C6—C5—H5	119.6	C12—C13—H13	120.3
C5—C6—C1	119.30 (12)	C13—C14—C9	121.78 (13)
C5—C6—C7	117.15 (12)	C13—C14—Cl	118.45 (11)
C1—C6—C7	123.49 (12)	C9—C14—Cl	119.76 (10)

C6—C1—C2—C3	−0.1 (2)	C9—N2—C8—S1	4.5 (2)
C1—C2—C3—F1	179.70 (12)	C7—N1—C8—N2	−9.6 (2)
C1—C2—C3—C4	−0.7 (2)	C7—N1—C8—S1	168.84 (11)
F1—C3—C4—C5	−179.92 (12)	C8—N2—C9—C10	22.4 (2)
C2—C3—C4—C5	0.5 (2)	C8—N2—C9—C14	−162.20 (13)
C3—C4—C5—C6	0.6 (2)	C14—C9—C10—C11	1.4 (2)
C4—C5—C6—C1	−1.3 (2)	N2—C9—C10—C11	176.73 (13)
C4—C5—C6—C7	−178.72 (13)	C9—C10—C11—C12	−1.1 (2)
C2—C1—C6—C5	1.1 (2)	C10—C11—C12—C13	0.0 (2)
C2—C1—C6—C7	178.32 (13)	C11—C12—C13—C14	0.7 (2)
C8—N1—C7—O1	8.6 (2)	C12—C13—C14—C9	−0.3 (2)
C8—N1—C7—C6	−170.22 (13)	C12—C13—C14—Cl	−179.45 (11)
C5—C6—C7—O1	15.54 (19)	C10—C9—C14—C13	−0.7 (2)
C1—C6—C7—O1	−161.73 (13)	N2—C9—C14—C13	−176.39 (12)
C5—C6—C7—N1	−165.60 (12)	C10—C9—C14—Cl	178.42 (10)
C1—C6—C7—N1	17.14 (19)	N2—C9—C14—Cl	2.72 (17)
C9—N2—C8—N1	−177.23 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10···S1	0.95	2.57	3.1945 (14)	124
N2—H1B···Cl	0.87 (2)	2.482 (19)	2.9246 (12)	112.3 (14)
N2—H1B···O1	0.87 (2)	1.924 (19)	2.6600 (14)	141.6 (17)
N1—H1A···S1ⁱ	0.85 (2)	2.67 (2)	3.4031 (13)	145.2 (16)

Symmetry code: (i) −x+1, −y+1, −z+1.

N-(4-Bromophenylcarbamothioyl)-4-fluorobenzamide (2) top

Crystal data top

C₁₄H₁₀BrFN₂OS	Z = 2
M_r = 353.19	F(000) = 348
Triclinic, P1	D_x = 1.771 Mg m⁻³
a = 3.8733 (2) Å	Cu Kα radiation, λ = 1.54178 Å
b = 13.0776 (5) Å	Cell parameters from 9945 reflections
c = 13.2628 (6) Å	θ = 3.4–68.2°
α = 98.817 (1)°	µ = 5.83 mm⁻¹
β = 94.714 (1)°	T = 100 K
γ = 94.727 (1)°	Plate, colourless
V = 658.54 (5) Å³	0.35 × 0.05 × 0.04 mm

Data collection top

Bruker APEXII CCD diffractometer	2381 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.025
Absorption correction: multi-scan (SADABS; Bruker, 2000)	θ_max = 68.2°, θ_min = 3.4°
T_min = 0.612, T_max = 0.946	h = −4→4
20701 measured reflections	k = −15→15
2384 independent reflections	l = −15→15

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.025	H-atom parameters constrained
wR(F²) = 0.110	w = 1/[σ²(F_o²) + (0.1P)²] where P = (F_o² + 2F_c²)/3
S = 1.10	(Δ/σ)_max = 0.001
2384 reflections	Δρ_max = 0.45 e Å⁻³
181 parameters	Δρ_min = −1.46 e Å⁻³
0 restraints

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Br1	−0.39350 (4)	0.11758 (2)	0.46689 (2)	0.01272 (16)
O1	0.4560 (4)	0.66092 (11)	0.32207 (10)	0.0175 (3)
N1	0.3835 (4)	0.58122 (12)	0.15534 (11)	0.0106 (3)
H1A	0.419261	0.590591	0.092584	0.013*
N2	0.1544 (4)	0.47331 (12)	0.26027 (11)	0.0111 (3)
H1B	0.187274	0.531645	0.304308	0.013*
F1	0.9679 (3)	1.04344 (9)	0.12214 (9)	0.0205 (3)
S1	0.18617 (10)	0.38973 (3)	0.06266 (3)	0.00989 (18)
C1	0.5195 (4)	0.78724 (14)	0.09959 (14)	0.0092 (4)
H1	0.376290	0.737919	0.050359	0.011*
C2	0.6398 (5)	0.88103 (14)	0.07394 (14)	0.0129 (4)
H2	0.581012	0.896819	0.007460	0.016*
C3	0.8466 (5)	0.95143 (15)	0.14634 (15)	0.0146 (4)
C4	0.9345 (5)	0.93323 (14)	0.24544 (14)	0.0137 (4)
H4	1.074144	0.983856	0.294279	0.016*
C5	0.8117 (5)	0.83897 (14)	0.27036 (14)	0.0116 (4)
H5	0.866416	0.824564	0.337592	0.014*
C6	0.6063 (5)	0.76392 (14)	0.19744 (13)	0.0101 (4)
C7	0.4782 (5)	0.66558 (14)	0.23084 (14)	0.0105 (4)
C9	0.0233 (4)	0.38653 (13)	0.30136 (13)	0.0086 (4)
C8	0.2378 (4)	0.48253 (14)	0.16562 (13)	0.0085 (4)
C10	−0.1837 (5)	0.30056 (14)	0.24536 (13)	0.0115 (4)
H10	−0.240925	0.296827	0.173769	0.014*
C11	−0.3051 (4)	0.22064 (14)	0.29513 (13)	0.0105 (4)
H11	−0.444455	0.161739	0.257544	0.013*
C12	−0.2224 (5)	0.22707 (13)	0.39998 (14)	0.0102 (4)
C13	−0.0217 (5)	0.31221 (13)	0.45694 (13)	0.0109 (4)
H13	0.031180	0.315998	0.528723	0.013*
C14	0.0999 (5)	0.39136 (15)	0.40755 (14)	0.0114 (4)
H14	0.237633	0.450144	0.445916	0.014*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0169 (2)	0.0096 (2)	0.0125 (2)	−0.00227 (13)	0.00215 (13)	0.00588 (13)
O1	0.0312 (8)	0.0122 (7)	0.0076 (7)	−0.0065 (6)	0.0033 (6)	0.0011 (5)
N1	0.0154 (8)	0.0108 (8)	0.0057 (7)	0.0005 (6)	0.0007 (6)	0.0022 (6)
N2	0.0170 (8)	0.0073 (7)	0.0090 (7)	−0.0001 (6)	0.0021 (6)	0.0019 (6)
F1	0.0328 (7)	0.0078 (6)	0.0213 (7)	−0.0054 (5)	0.0078 (5)	0.0051 (5)
S1	0.0140 (3)	0.0082 (3)	0.0069 (3)	−0.00094 (19)	0.00084 (19)	0.00050 (19)
C1	0.0092 (8)	0.0080 (9)	0.0102 (8)	−0.0004 (6)	0.0023 (6)	0.0005 (7)
C2	0.0161 (9)	0.0103 (9)	0.0133 (9)	0.0022 (7)	0.0031 (7)	0.0031 (7)
C3	0.0197 (9)	0.0068 (9)	0.0194 (10)	0.0022 (7)	0.0119 (8)	0.0033 (7)
C4	0.0149 (9)	0.0097 (9)	0.0148 (9)	−0.0026 (7)	0.0020 (7)	−0.0021 (7)
C5	0.0144 (8)	0.0095 (9)	0.0093 (8)	−0.0016 (7)	−0.0006 (7)	−0.0012 (7)
C6	0.0106 (8)	0.0103 (9)	0.0089 (9)	−0.0002 (7)	0.0008 (6)	0.0008 (7)
C7	0.0118 (8)	0.0104 (9)	0.0098 (9)	−0.0013 (7)	0.0013 (6)	0.0037 (7)
C9	0.0120 (8)	0.0070 (9)	0.0086 (8)	0.0005 (7)	0.0048 (6)	0.0047 (6)
C8	0.0103 (8)	0.0086 (8)	0.0071 (8)	0.0020 (7)	−0.0002 (6)	0.0026 (6)
C10	0.0137 (8)	0.0120 (9)	0.0088 (8)	0.0001 (7)	−0.0005 (7)	0.0028 (6)
C11	0.0116 (8)	0.0092 (9)	0.0097 (8)	−0.0028 (6)	0.0007 (6)	0.0004 (6)
C12	0.0128 (8)	0.0080 (9)	0.0112 (8)	0.0005 (6)	0.0023 (7)	0.0056 (6)
C13	0.0138 (8)	0.0132 (9)	0.0067 (8)	−0.0003 (7)	0.0018 (7)	0.0048 (6)
C14	0.0130 (8)	0.0092 (9)	0.0112 (9)	−0.0007 (6)	0.0011 (7)	0.0002 (6)

Geometric parameters (Å, º) top

Br1—C12	1.8991 (17)	C4—C5	1.382 (3)
O1—C7	1.230 (2)	C4—H4	0.9500
N1—C7	1.374 (2)	C5—C6	1.409 (2)
N1—C8	1.396 (2)	C5—H5	0.9500
N1—H1A	0.8800	C6—C7	1.484 (3)
N2—C8	1.342 (2)	C9—C10	1.399 (2)
N2—C9	1.408 (2)	C9—C14	1.406 (3)
N2—H1B	0.8800	C10—C11	1.390 (3)
F1—C3	1.350 (2)	C10—H10	0.9500
S1—C8	1.6687 (18)	C11—C12	1.389 (2)
C1—C2	1.377 (3)	C11—H11	0.9500
C1—C6	1.399 (3)	C12—C13	1.385 (3)
C1—H1	0.9500	C13—C14	1.379 (3)
C2—C3	1.375 (3)	C13—H13	0.9500
C2—H2	0.9500	C14—H14	0.9500
C3—C4	1.391 (3)

C7—N1—C8	128.20 (16)	O1—C7—N1	122.08 (17)
C7—N1—H1A	115.9	O1—C7—C6	121.00 (17)
C8—N1—H1A	115.9	N1—C7—C6	116.92 (16)
C8—N2—C9	131.19 (16)	C10—C9—C14	119.30 (16)
C8—N2—H1B	114.4	C10—C9—N2	124.87 (15)
C9—N2—H1B	114.4	C14—C9—N2	115.78 (16)
C2—C1—C6	120.62 (17)	N2—C8—N1	114.66 (16)
C2—C1—H1	119.7	N2—C8—S1	126.92 (15)
C6—C1—H1	119.7	N1—C8—S1	118.43 (13)
C3—C2—C1	118.79 (17)	C11—C10—C9	119.57 (16)
C3—C2—H2	120.6	C11—C10—H10	120.2
C1—C2—H2	120.6	C9—C10—H10	120.2
F1—C3—C2	119.46 (18)	C12—C11—C10	119.85 (16)
F1—C3—C4	117.55 (18)	C12—C11—H11	120.1
C2—C3—C4	122.98 (18)	C10—C11—H11	120.1
C5—C4—C3	117.70 (18)	C13—C12—C11	121.42 (16)
C5—C4—H4	121.1	C13—C12—Br1	119.31 (13)
C3—C4—H4	121.1	C11—C12—Br1	119.27 (13)
C4—C5—C6	120.91 (18)	C14—C13—C12	118.76 (16)
C4—C5—H5	119.5	C14—C13—H13	120.6
C6—C5—H5	119.5	C12—C13—H13	120.6
C1—C6—C5	118.97 (17)	C13—C14—C9	121.10 (17)
C1—C6—C7	123.33 (17)	C13—C14—H14	119.5
C5—C6—C7	117.62 (16)	C9—C14—H14	119.5

C6—C1—C2—C3	−0.1 (3)	C8—N2—C9—C10	−28.7 (3)
C1—C2—C3—F1	179.66 (16)	C8—N2—C9—C14	154.04 (18)
C1—C2—C3—C4	−1.4 (3)	C9—N2—C8—N1	−175.93 (16)
F1—C3—C4—C5	−179.80 (16)	C9—N2—C8—S1	3.8 (3)
C2—C3—C4—C5	1.2 (3)	C7—N1—C8—N2	6.3 (3)
C3—C4—C5—C6	0.4 (3)	C7—N1—C8—S1	−173.53 (14)
C2—C1—C6—C5	1.6 (3)	C14—C9—C10—C11	−1.1 (3)
C2—C1—C6—C7	178.38 (16)	N2—C9—C10—C11	−178.32 (16)
C4—C5—C6—C1	−1.8 (3)	C9—C10—C11—C12	0.5 (3)
C4—C5—C6—C7	−178.72 (16)	C10—C11—C12—C13	0.4 (3)
C8—N1—C7—O1	3.4 (3)	C10—C11—C12—Br1	179.54 (13)
C8—N1—C7—C6	−176.01 (16)	C11—C12—C13—C14	−0.6 (3)
C1—C6—C7—O1	−154.97 (17)	Br1—C12—C13—C14	−179.76 (13)
C5—C6—C7—O1	21.9 (3)	C12—C13—C14—C9	0.0 (3)
C1—C6—C7—N1	24.4 (2)	C10—C9—C14—C13	0.9 (3)
C5—C6—C7—N1	−158.75 (16)	N2—C9—C14—C13	178.36 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···S1ⁱ	0.88	2.69	3.5081 (15)	154
N2—H1B···O1	0.88	1.88	2.610 (2)	139
C10—H10···S1	0.95	2.65	3.2319 (18)	120
C1—H1···S1ⁱⁱ	0.95	2.81	3.7312 (18)	165

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

Funding information

The authors thank the Higher Education Commission of Pakistan (HEC) for financial support through research project No. 20-2830 under the National Research Program for Universities.

References

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Volume 75| Part 7| July 2019| Pages 1026-1029

https://doi.org/10.1107/S2056989019008569

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research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Crystal structure and Hirshfeld surface analysis of N-(2-chloro­phenyl­carbamo­thio­yl)-4-fluoro­benzamide and N-(4-bromo­phenyl­carbamo­thio­yl)-4-fluoro­benzamide

1. Chemical context

2. Structural commentary

3. Supra­molecular features

4. Database survey

5. Hirshfeld surface analysis

6. Synthesis and Crystallization

7. Data collection and Refinement

Supporting information

Funding information

References

research communications

Crystal structure and Hirshfeld surface analysis of N-(2-chlorophenylcarbamothioyl)-4-fluorobenzamide and N-(4-bromophenylcarbamothioyl)-4-fluorobenzamide

3. Supramolecular features