Structural investigation of N-[2-(4-fluoro-3-phen­oxy­benzo­yl)hydrazinecarbo­thio­yl]benzamide and N-[2-(4-fluoro-3-phen­oxy­benzo­yl)hydrazinecarbo­thio­yl]-4-meth­oxy­benzamide

Dey, D.; Shruti, I.; Chopra, D.; Mohan, T.P.

doi:10.1107/S2056989021001900

research communications

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 77| Part 3| March 2021| Pages 277-281

https://doi.org/10.1107/S2056989021001900

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Structural investigation of N-[2-(4-fluoro-3-phenoxybenzoyl)hydrazinecarbothioyl]benzamide and N-[2-(4-fluoro-3-phenoxybenzoyl)hydrazinecarbothioyl]-4-methoxybenzamide

Dhananjay Dey,^a I. Shruti,^a Deepak Chopra ^a ^* and T. P. Mohan ^b

^aDepartment of Chemistry, Indian Institute of Science Education and Research, Bhopal, Bhauri, Bhopal 462066, India, and ^bRallis India Ltd, Bangalore 560091, Karnataka, India
^*Correspondence e-mail: dchopra@iiserb.ac.in

Edited by G. Diaz de Delgado, Universidad de Los Andes, Venezuela (Received 2 February 2021; accepted 16 February 2021; online 19 February 2021)

The compound N-[2-(4-fluoro-3-phenoxybenzoyl)hydrazinecarbothioyl]benzamide, C₂₁H₁₆FN₃O₃S, crystallizes in the monoclinic centrosymmetric space group P2₁/c and its molecular conformation is stabilized via an intramolecular N—H⋯O hydrogen bond. The corresponding para-methoxy derivative, namely, N-[2-(4-fluoro-3-phenoxybenzoyl)hydrazinecarbothioyl]-4-methoxybenzamide, C₂₂H₁₈FN₃O₄S, crystallizes in the monoclinic centrosymmetric space group C2/c. The supramolecular network mainly comprises N—H⋯O, N—H⋯S and C—H⋯O hydrogen bonds, which contribute towards the formation of the crystal structures for the two molecules. The different intermolecular interactions have been further analysed using Hirshfeld surface analysis and fingerprint plots.

Keywords: crystal structure; drug; hydrogen bonds; molecular conformation; chalcogen-centered interactions.

CCDC references: 2063226; 2063225

1. Chemical context

Substituted thiosemicarbazides (TSCs) constitute an important class of organic compounds with the general formula R–(C=O)–NH–NH–(C=S)–R′ and find application in the synthesis of five- and six-membered heterocyclic compounds (Gazieva & Kravchenko, 2012 ) and transition-metal complexes (Campbell, 1975 ). The chemical diversity of thiosemicarbazides, and their synthesis, including their role in biological applications, is nicely summarized in a recent review article (Acharya et al., 2021 ). Dibenzoylated TSCs have been synthesized and explored for their antibacterial activity (Qandil et al., 2006 ). Furthermore, molecular modelling studies establish the relevance of both geometry and electron-density distribution in the observed antibacterial activity (Paneth et al., 2016 ). Piperidin-4-yl-based TSCs have been examined for cytotoxicity in breast cancer cell lines in addition to being possible potential topoisomerase inhibitors (Siwek et al., 2014 ). 1-(2-Hydroxybenzoyl)-thiosemicarbazides have been observed to exhibit antimicrobial activity and structure–activity relationship (SARs) studies establish that the 2-hydroxybenzoyl group plays an important role in enzyme inhibition, in addition to these exhibiting low cytotoxicity (Ameryckx et al., 2018 ). Furthermore, triazole-substituted benzoylthiosemicarbazides have been synthesized and their effect on the inhibition of corrosion on mild steel has been investigated (Yan et al., 2018 ). Keeping in mind the above-mentioned applications of substituted TSCs, we have performed the synthesis and crystal structure analysis of two compounds, namely N-[2-(4-fluoro-3-phenoxybenzoyl)hydrazinecarbothioyl]benzamide (A1) and N-[2-(4-fluoro-3-phenoxybenzoyl)hydrazinecarbothioyl]-4-methoxybenzamide (A2) in the current study. The molecular conformations have been studied with respect to the various flexible bonds and the occurrence of various intermolecular interactions that contribute towards the stability of the molecules in the crystalline lattice has been investigated in detail via an investigation of the crystal packing and quantitative insights from Hirshfeld surface analysis.

2. Structural commentary

Compound A1 crystallizes in the centrosymmetric monoclinic P2₁/c space group and A2 crystallizes in the centrosymmetric monoclinic C2/c space group. The molecular structure comprises one fluoro-substituted phenoxybenzoyl ring, a rigid and planar (C=O)—NH—NH—(C=S) moiety and a benzamide ring. The bond lengths and bond angles are in accordance with the magnitudes in the literature. The molecular conformations of A1 (Fig. 1) and A2 (Fig. 2) are both conformationally locked via the presence of an N—H⋯O hydrogen bond (involving H2N and O3), the N2⋯O3 distance being 2.555 (2) and 2.589 (4) Å in A1 and A2, respectively. The molecular structure possesses four conformational degrees of freedom due to the free rotation with respect to the N1—N2, C7—O1, O1—C1 and C15—C16 single bonds. The torsion angles C13—N1—N2—C14, C8—C7—O1—C1, C7—O1—C1—C2 and N3—C15—C16—C21 are 163.27 (16)/-143.5 (4)°, 97.3 (2)/149.6 (5)°, 167.18 (18)/148.1 (4)° and −160.26 (15)/-174.7 (3)° in A1/A2, respectively.

Figure 1
Ellipsoid plot of A1 drawn with 50% ellipsoidal probability. The cyan line indicates the intramolecular N—H⋯O hydrogen bond.

Figure 2
Ellipsoid plot of A2 drawn with 50% ellipsoidal probability. The cyan line indicates the intramolecular N—H⋯O hydrogen bond.

3. Supramolecular features

In the crystal structure of A1, the molecules are primarily assembled through the presence of N3—H3N⋯O2 and C18—H18⋯O3 hydrogen bonds (Table 1), forming molecular chains along the c-axis direction utilizing the c-glide as the symmetry element (Fig. 3). Adjacent layers are held together via C20—H20⋯O1 and C19—H19⋯S1 hydrogen bonds. The crystal packing of A2 (Fig. 4) primarily consists of N1—H1⋯O2 hydrogen bonds (Table 2), forming molecular chains along the b-axis direction. Two such adjacent layers are held via N3—H3N⋯S1 and C17—H17⋯S1 hydrogen bonds. In addition S1⋯C17 contacts (S⋯π type), [3.384 (4) Å, 174.9 (1)°, −x + 1, y + 1, −z + $[{1\over 2}]$ ] chalcogen-centered contacts are also present in the crystal packing (Fig. 4). Intermolecular contacts involving chalcogens are well-recognized in the literature [Pramanik & Chopra, 2020 ]. Furthermore, additional C21—H21⋯O3 hydrogen bonds form centrosymmetric dimers and provide additional stability to the crystal packing.

Table 1
Hydrogen-bond geometry (Å, °) for A1

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2N⋯O3	0.86	1.88	2.555 (2)	135
C18—H18⋯O3ⁱ	0.93	2.45	3.218 (2)	141
N3—H3N⋯O2ⁱ	0.86	2.28	3.067 (2)	152
C19—H19⋯S1ⁱⁱ	0.93	2.98	3.778 (2)	145
C20—H20⋯O1ⁱⁱⁱ	0.93	2.77	3.510 (3)	138
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{5\over 2}}]$ ; (iii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Table 2
Hydrogen-bond geometry (Å, °) for A2

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2N⋯O3	0.86	1.92	2.589 (4)	134
N3—H3N⋯S1ⁱ	0.86	2.80	3.615 (3)	159
C17—H17⋯S1ⁱ	0.93	2.69	3.614 (4)	174
N1—H1⋯O2ⁱⁱ	0.86	2.15	2.915 (4)	148
C21—H21⋯O3ⁱⁱⁱ	0.93	2.57	3.399 (4)	148
Symmetry codes: (i) $[-x+1, y, -z+{\script{1\over 2}}]$ ; (ii) x, y+1, z; (iii) .

Figure 3
Crystal packing of A1 showing the formation of the crystal structure primarily via N—H⋯O and C—H⋯O intermolecular interactions.

Figure 4
Crystal packing of A2 showing the formation of the crystal structure primarily via N—H⋯O, N—H⋯S, C—H⋯S and S⋯C intermolecular interactions.

4. Database survey

A search for the dibenzoylthiosemicarbazide skeleton, Ph–(C=O)–NH–NH–(C=S)–NH–(C=O)–Ph was carried out in the Cambridge Structural Database (CSD version 5.40, updates of Aug 2019; Groom et al., 2016 ) . No hits were obtained. Thus, further systematic studies related to the investigation of the role of differently substituted thiosemicarbazide molecules towards the crystal packing, including a detailed investigation of polymorphism in this class of compounds, is of relevance.

5. Hirshfeld surface analysis and fingerprint plots

The relevance of different intermolecular interactions can be established via Hirshfeld surface analysis (Spackman & Jayatilaka, 2009 ). These surfaces, along with the two-dimensional fingerprint plots, were evaluated using Crystal Explorer 17.5 (Turner et al., 2017 ). The surfaces mapped over d_norm for A1, Fig. 5(a), and A2, Fig. 5(b) and 5(c), show the important hydrogen bonds. The red and blue spots correspond to intermolecular interactions that are less or greater than the sum of the van der Waals radii. The fingerprint plots depict the individual contributions of the different interactions. The fingerprint plots for A1/A2 (Figs. 6 and 7) show that the greatest contributions are from H⋯H (31.3/32%) contacts, followed by C⋯H/H⋯C (23.2/23.2%), O⋯H/H⋯O (14.3/16.7%), S⋯H/H⋯S (7/5.7%), S⋯C/C⋯S (4.9/2.8%) and F⋯H/H⋯F (8.8/6.9%) contacts. The O⋯H/H⋯O contribution is slightly higher in the case of A2 (16.7%) due to the presence of an additional methoxy group in the molecule. Further interactions, involving F⋯H/H⋯F, contributing around 7–9% (A1: 8.8% and A2: 6.9%) and S⋯H (A1: 7.0% and A2: 5.7%) correspond to the presence of highly directional interactions, involving fluorine and sulfur in A2, and are important; this is clearly illustrated in the fingerprint plot (Fig. 7). The percentage contribution of S⋯C/C⋯S contacts in A2 is 2.8% lower than in A1. However, the relevance of this contact is greater in A2 on account of the presence of the highly directional C—S⋯π intermolecular contact and this feature is also clearly visible in the 2D fingerprint plot (Fig. 7).

Figure 5
The Hirshfeld surface mapped over d_norm for (a) A1, (b) A2 depicting N—H⋯O hydrogen bonds and (c) A2 depicting C—S⋯π interactions.

Figure 6
The fingerprint plots for A1 showing the different contributions derived from the H⋯H, C⋯H/H⋯C, O⋯H/H⋯O, H⋯F/F⋯H,S⋯H/S⋯H and C⋯S/S⋯C contacts.

Figure 7
The fingerprint plots for A2 showing the different contributions derived from the H⋯H, C⋯H/H⋯C, O⋯H/H⋯O, H⋯F/F⋯H,S⋯H/S⋯H and C⋯S/S⋯C contacts.

6. Synthesis and Crystallization

The title compounds were synthesized in accordance with the procedure reported in the literature (Mohan, 2006 ). Crystallization was performed in 5.0 ml beakers at room temperature via the slow evaporation method from methanol solvent.

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. H atoms were placed in idealized positions (N—H = 0.86 Å, C—H = 0.93 Å) and refined using a riding model with U_iso(H) = 1.2U_eq(C, N) or 1.5U_eq(C-methyl).

Table 3
Experimental details

	A1	A2
Crystal data
Chemical formula	C₂₁H₁₆FN₃O₃S	C₂₂H₁₈FN₃O₄S
M_r	409.43	439.45
Crystal system, space group	Monoclinic, P2₁/c	Monoclinic, C2/c
Temperature (K)	298	298
a, b, c (Å)	18.3849 (13), 7.7063 (6), 13.9216 (10)	47.298 (3), 4.8054 (3), 18.4939 (10)
β (°)	100.136 (5)	100.429 (6)
V (Å³)	1941.6 (2)	4134.0 (4)
Z	4	8
Radiation type	Mo Kα	Mo Kα
μ (mm⁻¹)	0.20	0.20
Crystal size (mm)	0.27 × 0.20 × 0.14	0.25 × 0.17 × 0.10

Data collection
Diffractometer	Bruker APEXII CCD	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2008 )	Multi-scan (SADABS; Bruker, 2008)
No. of measured, independent and observed [I > 2σ(I)] reflections	31160, 4460, 2753	9841, 2188, 1751
R_int	0.043	0.062
θ_max (°)	27.7	20.9
(sin θ/λ)_max (Å⁻¹)	0.653	0.503

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.119, 1.04	0.046, 0.122, 1.06
No. of reflections	4460	2188
No. of parameters	262	281
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.15, −0.17	0.20, −0.16
Computer programs: APEX2 (Bruker, 2012 ), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008 ), SHELXL2018/3 (Sheldrick, 2015 ), Mercury (Macrae et al., 2020 ), WinGX (Farrugia, 2012 ) and PLATON (Spek, 2020 ).

Supporting information

CCDC references: 2063226; 2063225

Crystal structure: contains datablocks A1, A2. DOI: https://doi.org/10.1107/S2056989021001900/dj2021sup1.cif

Structure factors: contains datablock A1. DOI: https://doi.org/10.1107/S2056989021001900/dj2021A1sup2.hkl

Structure factors: contains datablock A2. DOI: https://doi.org/10.1107/S2056989021001900/dj2021A2sup3.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989021001900/dj2021A1sup4.cml

Supporting information file. DOI: https://doi.org/10.1107/S2056989021001900/dj2021A2sup5.cml

checkCIF report

Computing details top

For both structures, data collection: APEX2 (Bruker, 2012); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015); molecular graphics: Mercury (Macrae et al., 2020), WinGX (Farrugia, 2012); software used to prepare material for publication: PLATON (Spek, 2020).

N-[2-(4-Fluoro-3-phenoxybenzoyl)hydrazinecarbothioyl]benzamide (A1) top

Crystal data top

C₂₁H₁₆FN₃O₃S	F(000) = 848
M_r = 409.43	D_x = 1.401 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 18.3849 (13) Å	Cell parameters from 10485 reflections
b = 7.7063 (6) Å	θ = 2.2–28.6°
c = 13.9216 (10) Å	µ = 0.20 mm⁻¹
β = 100.136 (5)°	T = 298 K
V = 1941.6 (2) Å³	Plates, colorless
Z = 4	0.27 × 0.20 × 0.14 mm

Data collection top

Bruker APEXII CCD diffractometer	2753 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.043
Absorption correction: multi-scan (SADABS; Bruker, 2008)	θ_max = 27.7°, θ_min = 2.3°
	h = −23→21
31160 measured reflections	k = −10→10
4460 independent reflections	l = −18→18

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.043	H-atom parameters constrained
wR(F²) = 0.119	w = 1/[σ²(F_o²) + (0.0531P)² + 0.1773P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
4460 reflections	Δρ_max = 0.15 e Å⁻³
262 parameters	Δρ_min = −0.17 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
N2	0.35731 (8)	0.0786 (2)	0.88306 (10)	0.0603 (4)
H2N	0.398146	0.108884	0.865793	0.072*
O2	0.35727 (7)	0.08997 (19)	0.69344 (9)	0.0715 (4)
N1	0.30299 (8)	0.0015 (2)	0.81656 (10)	0.0635 (4)
H1	0.267495	−0.053998	0.835584	0.076*
C15	0.47522 (9)	0.2198 (2)	1.01326 (12)	0.0544 (4)
N3	0.40609 (7)	0.18548 (18)	1.03435 (9)	0.0538 (4)
H3N	0.398570	0.216229	1.091172	0.065*
C19	0.63953 (10)	0.4486 (3)	1.22873 (13)	0.0637 (5)
H19	0.675815	0.500499	1.274731	0.076*
C13	0.30627 (10)	0.0143 (2)	0.72070 (12)	0.0546 (4)
C11	0.24397 (10)	−0.0680 (2)	0.65341 (12)	0.0548 (4)
O3	0.48982 (7)	0.18773 (19)	0.93243 (8)	0.0737 (4)
C12	0.23455 (10)	−0.0202 (2)	0.55602 (12)	0.0587 (5)
H12	0.267655	0.056422	0.535242	0.070*
C18	0.58177 (10)	0.3634 (3)	1.25799 (13)	0.0651 (5)
H18	0.579476	0.355776	1.324057	0.078*
C16	0.53052 (9)	0.2979 (2)	1.09115 (11)	0.0509 (4)
C7	0.17640 (11)	−0.0857 (3)	0.48974 (13)	0.0650 (5)
C17	0.52695 (10)	0.2888 (2)	1.19000 (12)	0.0589 (5)
H17	0.487572	0.232436	1.210329	0.071*
O1	0.16903 (8)	−0.0470 (2)	0.39147 (9)	0.0815 (4)
C20	0.64377 (11)	0.4571 (3)	1.13081 (13)	0.0683 (5)
H20	0.683089	0.514503	1.110943	0.082*
C14	0.34729 (9)	0.1066 (2)	0.97367 (11)	0.0524 (4)
C1	0.13186 (10)	0.1053 (3)	0.35731 (13)	0.0658 (5)
C10	0.19555 (10)	−0.1858 (3)	0.68345 (14)	0.0678 (5)
H10	0.202440	−0.221053	0.748315	0.081*
C21	0.59024 (10)	0.3814 (3)	1.06281 (12)	0.0610 (5)
H21	0.593940	0.385998	0.997084	0.073*
C8	0.12811 (11)	−0.1982 (3)	0.52212 (15)	0.0755 (6)
F1	0.07018 (8)	−0.2577 (2)	0.45739 (10)	0.1157 (5)
C9	0.13740 (12)	−0.2507 (3)	0.61757 (16)	0.0828 (6)
H9	0.104704	−0.329362	0.637526	0.099*
C6	0.09068 (11)	0.2008 (3)	0.41052 (15)	0.0756 (6)
H6	0.086151	0.166959	0.473327	0.091*
C4	0.06114 (16)	0.3971 (4)	0.2770 (2)	0.1119 (9)
H4	0.036467	0.495305	0.249363	0.134*
C2	0.13978 (13)	0.1537 (3)	0.26449 (15)	0.0849 (7)
H2	0.169036	0.089353	0.229477	0.102*
C3	0.10316 (18)	0.3001 (4)	0.2249 (2)	0.1101 (9)
H3	0.107028	0.333605	0.161870	0.132*
C5	0.05585 (13)	0.3485 (4)	0.3694 (2)	0.0958 (7)
H5	0.028365	0.415792	0.405426	0.115*
S1	0.26986 (3)	0.05350 (8)	1.01272 (3)	0.07183 (19)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N2	0.0605 (9)	0.0788 (10)	0.0420 (8)	−0.0123 (8)	0.0097 (7)	−0.0069 (7)
O2	0.0662 (8)	0.0981 (10)	0.0499 (7)	−0.0220 (7)	0.0097 (6)	0.0030 (7)
N1	0.0659 (10)	0.0808 (11)	0.0435 (8)	−0.0197 (8)	0.0090 (7)	−0.0051 (8)
C15	0.0558 (10)	0.0637 (11)	0.0457 (9)	0.0021 (8)	0.0147 (8)	−0.0033 (8)
N3	0.0539 (8)	0.0702 (10)	0.0381 (7)	−0.0016 (7)	0.0100 (6)	−0.0055 (7)
C19	0.0562 (11)	0.0809 (13)	0.0525 (10)	−0.0022 (10)	0.0053 (8)	−0.0055 (10)
C13	0.0590 (11)	0.0618 (11)	0.0425 (9)	−0.0026 (9)	0.0076 (8)	0.0010 (8)
C11	0.0566 (10)	0.0612 (11)	0.0457 (9)	−0.0014 (9)	0.0070 (8)	−0.0016 (8)
O3	0.0684 (8)	0.1078 (11)	0.0495 (7)	−0.0126 (7)	0.0229 (6)	−0.0201 (7)
C12	0.0637 (11)	0.0683 (12)	0.0444 (9)	−0.0035 (9)	0.0107 (8)	−0.0032 (8)
C18	0.0610 (11)	0.0937 (14)	0.0408 (9)	0.0028 (10)	0.0095 (8)	−0.0040 (9)
C16	0.0512 (10)	0.0590 (10)	0.0433 (8)	0.0056 (8)	0.0104 (7)	−0.0012 (8)
C7	0.0693 (12)	0.0775 (13)	0.0450 (10)	0.0071 (10)	0.0012 (9)	−0.0073 (9)
C17	0.0540 (10)	0.0781 (12)	0.0467 (9)	−0.0011 (9)	0.0149 (8)	−0.0006 (9)
O1	0.0998 (11)	0.0991 (11)	0.0421 (7)	0.0170 (9)	0.0026 (7)	−0.0105 (7)
C20	0.0595 (11)	0.0891 (14)	0.0576 (11)	−0.0121 (10)	0.0136 (9)	0.0041 (10)
C14	0.0585 (11)	0.0573 (10)	0.0409 (8)	0.0019 (8)	0.0076 (8)	0.0015 (8)
C1	0.0568 (11)	0.0850 (14)	0.0496 (10)	−0.0092 (10)	−0.0068 (9)	−0.0020 (10)
C10	0.0663 (12)	0.0775 (13)	0.0573 (11)	−0.0110 (10)	0.0048 (9)	0.0084 (10)
C21	0.0609 (11)	0.0792 (13)	0.0443 (9)	−0.0033 (10)	0.0134 (8)	0.0014 (9)
C8	0.0648 (13)	0.0863 (15)	0.0666 (13)	−0.0101 (11)	−0.0126 (10)	−0.0100 (11)
F1	0.0972 (10)	0.1390 (12)	0.0957 (9)	−0.0334 (9)	−0.0246 (8)	−0.0135 (9)
C9	0.0714 (13)	0.0906 (15)	0.0824 (15)	−0.0234 (12)	0.0023 (11)	0.0080 (13)
C6	0.0658 (13)	0.0965 (17)	0.0625 (12)	0.0016 (11)	0.0058 (10)	−0.0011 (12)
C4	0.101 (2)	0.112 (2)	0.116 (2)	0.0046 (17)	0.0013 (18)	0.034 (2)
C2	0.0881 (16)	0.1073 (18)	0.0569 (12)	−0.0178 (14)	0.0063 (11)	−0.0009 (13)
C3	0.128 (2)	0.122 (2)	0.0745 (16)	−0.0238 (19)	0.0032 (16)	0.0288 (17)
C5	0.0718 (15)	0.1026 (19)	0.111 (2)	0.0045 (14)	0.0110 (14)	0.0038 (16)
S1	0.0630 (3)	0.1025 (4)	0.0515 (3)	−0.0143 (3)	0.0141 (2)	−0.0031 (3)

Geometric parameters (Å, º) top

N2—C14	1.3242 (19)	C7—O1	1.383 (2)
N2—N1	1.3718 (19)	C17—H17	0.9300
N2—H2N	0.8600	O1—C1	1.399 (2)
O2—C13	1.220 (2)	C20—C21	1.370 (3)
N1—C13	1.350 (2)	C20—H20	0.9300
N1—H1	0.8600	C14—S1	1.6617 (17)
C15—O3	1.2272 (18)	C1—C6	1.364 (3)
C15—N3	1.379 (2)	C1—C2	1.377 (3)
C15—C16	1.478 (2)	C10—C9	1.374 (3)
N3—C14	1.389 (2)	C10—H10	0.9300
N3—H3N	0.8600	C21—H21	0.9300
C19—C18	1.370 (3)	C8—F1	1.349 (2)
C19—C20	1.381 (2)	C8—C9	1.371 (3)
C19—H19	0.9300	C9—H9	0.9300
C13—C11	1.488 (2)	C6—C5	1.380 (3)
C11—C12	1.386 (2)	C6—H6	0.9300
C11—C10	1.387 (2)	C4—C5	1.360 (4)
C12—C7	1.379 (3)	C4—C3	1.370 (4)
C12—H12	0.9300	C4—H4	0.9300
C18—C17	1.381 (2)	C2—C3	1.378 (4)
C18—H18	0.9300	C2—H2	0.9300
C16—C21	1.389 (2)	C3—H3	0.9300
C16—C17	1.391 (2)	C5—H5	0.9300
C7—C8	1.372 (3)

C14—N2—N1	120.44 (14)	C21—C20—C19	120.23 (17)
C14—N2—H2N	119.8	C21—C20—H20	119.9
N1—N2—H2N	119.8	C19—C20—H20	119.9
C13—N1—N2	118.79 (14)	N2—C14—N3	115.25 (14)
C13—N1—H1	120.6	N2—C14—S1	122.85 (13)
N2—N1—H1	120.6	N3—C14—S1	121.90 (12)
O3—C15—N3	120.99 (16)	C6—C1—C2	121.6 (2)
O3—C15—C16	121.44 (15)	C6—C1—O1	123.55 (18)
N3—C15—C16	117.57 (13)	C2—C1—O1	114.8 (2)
C15—N3—C14	127.02 (13)	C9—C10—C11	120.14 (18)
C15—N3—H3N	116.5	C9—C10—H10	119.9
C14—N3—H3N	116.5	C11—C10—H10	119.9
C18—C19—C20	119.86 (17)	C20—C21—C16	120.58 (16)
C18—C19—H19	120.1	C20—C21—H21	119.7
C20—C19—H19	120.1	C16—C21—H21	119.7
O2—C13—N1	120.86 (16)	F1—C8—C9	119.7 (2)
O2—C13—C11	123.81 (15)	F1—C8—C7	118.42 (19)
N1—C13—C11	115.33 (15)	C9—C8—C7	121.84 (18)
C12—C11—C10	119.51 (17)	C8—C9—C10	119.28 (19)
C12—C11—C13	116.91 (16)	C8—C9—H9	120.4
C10—C11—C13	123.57 (16)	C10—C9—H9	120.4
C7—C12—C11	120.40 (18)	C1—C6—C5	118.7 (2)
C7—C12—H12	119.8	C1—C6—H6	120.6
C11—C12—H12	119.8	C5—C6—H6	120.6
C19—C18—C17	120.41 (16)	C5—C4—C3	119.4 (3)
C19—C18—H18	119.8	C5—C4—H4	120.3
C17—C18—H18	119.8	C3—C4—H4	120.3
C21—C16—C17	118.81 (16)	C1—C2—C3	118.1 (2)
C21—C16—C15	117.16 (14)	C1—C2—H2	120.9
C17—C16—C15	124.01 (15)	C3—C2—H2	120.9
C8—C7—C12	118.78 (17)	C4—C3—C2	121.1 (2)
C8—C7—O1	120.31 (18)	C4—C3—H3	119.4
C12—C7—O1	120.81 (18)	C2—C3—H3	119.4
C18—C17—C16	120.09 (16)	C4—C5—C6	121.0 (3)
C18—C17—H17	120.0	C4—C5—H5	119.5
C16—C17—H17	120.0	C6—C5—H5	119.5
C7—O1—C1	118.30 (15)

C14—N2—N1—C13	163.27 (16)	N1—N2—C14—S1	−0.5 (2)
O3—C15—N3—C14	3.4 (3)	C15—N3—C14—N2	−7.4 (2)
C16—C15—N3—C14	−177.17 (15)	C15—N3—C14—S1	173.17 (14)
N2—N1—C13—O2	1.4 (3)	C7—O1—C1—C6	−12.8 (3)
N2—N1—C13—C11	−178.11 (15)	C7—O1—C1—C2	167.18 (18)
O2—C13—C11—C12	−15.9 (3)	C12—C11—C10—C9	−1.9 (3)
N1—C13—C11—C12	163.59 (16)	C13—C11—C10—C9	177.23 (19)
O2—C13—C11—C10	164.89 (19)	C19—C20—C21—C16	1.1 (3)
N1—C13—C11—C10	−15.6 (3)	C17—C16—C21—C20	−1.5 (3)
C10—C11—C12—C7	1.7 (3)	C15—C16—C21—C20	179.92 (17)
C13—C11—C12—C7	−177.53 (17)	C12—C7—C8—F1	178.13 (18)
C20—C19—C18—C17	−1.2 (3)	O1—C7—C8—F1	−5.5 (3)
O3—C15—C16—C21	19.2 (3)	C12—C7—C8—C9	−1.9 (3)
N3—C15—C16—C21	−160.26 (15)	O1—C7—C8—C9	174.4 (2)
O3—C15—C16—C17	−159.26 (18)	F1—C8—C9—C10	−178.4 (2)
N3—C15—C16—C17	21.3 (3)	C7—C8—C9—C10	1.7 (4)
C11—C12—C7—C8	0.2 (3)	C11—C10—C9—C8	0.3 (3)
C11—C12—C7—O1	−176.13 (16)	C2—C1—C6—C5	0.5 (3)
C19—C18—C17—C16	0.8 (3)	O1—C1—C6—C5	−179.55 (18)
C21—C16—C17—C18	0.6 (3)	C6—C1—C2—C3	−1.7 (3)
C15—C16—C17—C18	179.02 (17)	O1—C1—C2—C3	178.36 (19)
C8—C7—O1—C1	97.3 (2)	C5—C4—C3—C2	0.4 (4)
C12—C7—O1—C1	−86.4 (2)	C1—C2—C3—C4	1.3 (4)
C18—C19—C20—C21	0.3 (3)	C3—C4—C5—C6	−1.6 (4)
N1—N2—C14—N3	−179.95 (15)	C1—C6—C5—C4	1.2 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···O3	0.86	1.88	2.555 (2)	135
C18—H18···O3ⁱ	0.93	2.45	3.218 (2)	141
N3—H3N···O2ⁱ	0.86	2.28	3.067 (2)	152
C19—H19···S1ⁱⁱ	0.93	2.98	3.778 (2)	145
C20—H20···O1ⁱⁱⁱ	0.93	2.77	3.510 (3)	138

Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) −x+1, y+1/2, −z+5/2; (iii) −x+1, y+1/2, −z+3/2.

N-[2-(4-Fluoro-3-phenoxybenzoyl)hydrazinecarbothioyl]-4-methoxybenzamide (A2) top

Crystal data top

C₂₂H₁₈FN₃O₄S	F(000) = 1824
M_r = 439.45	D_x = 1.412 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 47.298 (3) Å	Cell parameters from 9864 reflections
b = 4.8054 (3) Å	θ = 2.3–21.0°
c = 18.4939 (10) Å	µ = 0.20 mm⁻¹
β = 100.429 (6)°	T = 298 K
V = 4134.0 (4) Å³	Plates, colorless
Z = 8	0.25 × 0.17 × 0.10 mm

Data collection top

Bruker APEXII CCD diffractometer	1751 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.062
Absorption correction: multi-scan (SADABS; Bruker, 2008)	θ_max = 20.9°, θ_min = 2.3°
	h = −46→38
9841 measured reflections	k = −4→4
2188 independent reflections	l = −18→18

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.046	H-atom parameters constrained
wR(F²) = 0.122	w = 1/[σ²(F_o²) + (0.0421P)² + 7.4575P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
2188 reflections	Δρ_max = 0.20 e Å⁻³
281 parameters	Δρ_min = −0.16 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
S1	0.46155 (2)	0.5067 (2)	0.20257 (5)	0.0570 (4)
O3	0.48485 (5)	−0.1767 (5)	0.05581 (13)	0.0564 (7)
O2	0.40193 (5)	−0.2064 (6)	0.06269 (16)	0.0693 (8)
N3	0.49466 (6)	0.1596 (6)	0.14319 (15)	0.0476 (8)
H3N	0.508458	0.244009	0.171425	0.057*
O4	0.61871 (6)	−0.3864 (7)	0.15455 (17)	0.0846 (9)
N2	0.44651 (6)	0.1428 (6)	0.09635 (17)	0.0548 (8)
H2N	0.450510	0.022383	0.065314	0.066*
F1	0.28801 (5)	0.3872 (7)	0.11032 (16)	0.1091 (10)
C16	0.53329 (7)	−0.1387 (7)	0.11626 (18)	0.0431 (9)
N1	0.41856 (7)	0.2174 (7)	0.09631 (18)	0.0636 (9)
H1	0.414588	0.386840	0.105555	0.076*
C13	0.39757 (8)	0.0319 (9)	0.0822 (2)	0.0514 (10)
C11	0.36866 (8)	0.1329 (8)	0.0915 (2)	0.0516 (10)
C14	0.46729 (8)	0.2578 (7)	0.14456 (18)	0.0438 (9)
O1	0.29250 (6)	0.0013 (8)	0.01236 (19)	0.1023 (12)
C21	0.54221 (8)	−0.3385 (8)	0.0720 (2)	0.0547 (10)
H21	0.528867	−0.416711	0.034349	0.066*
C15	0.50265 (8)	−0.0588 (7)	0.10183 (19)	0.0441 (9)
C19	0.59029 (8)	−0.3153 (9)	0.1383 (2)	0.0576 (10)
C20	0.57034 (9)	−0.4253 (8)	0.0820 (2)	0.0603 (11)
H20	0.575894	−0.558120	0.050737	0.072*
C17	0.55367 (9)	−0.0281 (8)	0.1725 (2)	0.0601 (11)
H17	0.548250	0.107588	0.203190	0.072*
C12	0.34481 (8)	0.0178 (9)	0.0473 (2)	0.0638 (11)
H12	0.347192	−0.119851	0.013548	0.077*
C18	0.58180 (9)	−0.1171 (10)	0.1835 (2)	0.0678 (12)
H18	0.595147	−0.042543	0.221674	0.081*
C10	0.36521 (9)	0.3291 (9)	0.1432 (2)	0.0663 (11)
H10	0.381175	0.405703	0.173417	0.080*
C7	0.31751 (9)	0.1059 (10)	0.0528 (2)	0.0710 (12)
C8	0.31463 (9)	0.3024 (10)	0.1041 (3)	0.0714 (12)
C9	0.33763 (11)	0.4125 (10)	0.1500 (3)	0.0804 (14)
H9	0.334955	0.542017	0.185500	0.096*
C1	0.29108 (10)	−0.0900 (12)	−0.0591 (3)	0.0824 (15)
C22	0.62909 (10)	−0.5808 (11)	0.1078 (3)	0.0994 (17)
H22A	0.619623	−0.756318	0.110327	0.149*
H22B	0.649439	−0.604267	0.123394	0.149*
H22C	0.625228	−0.513264	0.058166	0.149*
C2	0.27240 (11)	−0.3041 (13)	−0.0798 (3)	0.1014 (17)
H2	0.262932	−0.386389	−0.045353	0.122*
C5	0.30114 (16)	−0.0664 (17)	−0.1801 (4)	0.120 (2)
H5	0.310776	0.012404	−0.214659	0.144*
C4	0.28168 (18)	−0.2822 (19)	−0.1998 (4)	0.128 (3)
H4	0.278282	−0.348577	−0.247824	0.153*
C6	0.30602 (11)	0.0306 (13)	−0.1075 (3)	0.1001 (17)
H6	0.319071	0.173145	−0.092598	0.120*
C3	0.26762 (14)	−0.3964 (17)	−0.1492 (5)	0.131 (2)
H3	0.254553	−0.539896	−0.162868	0.157*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0682 (7)	0.0481 (6)	0.0553 (6)	0.0142 (5)	0.0124 (5)	−0.0014 (5)
O3	0.0554 (16)	0.0545 (17)	0.0589 (16)	0.0012 (14)	0.0092 (13)	−0.0131 (14)
O2	0.0576 (17)	0.0393 (18)	0.109 (2)	0.0029 (14)	0.0092 (15)	−0.0124 (16)
N3	0.0473 (19)	0.0409 (18)	0.0556 (18)	−0.0008 (16)	0.0119 (14)	−0.0034 (16)
O4	0.0587 (19)	0.094 (2)	0.098 (2)	0.0215 (18)	0.0072 (16)	−0.0099 (19)
N2	0.047 (2)	0.0453 (19)	0.074 (2)	0.0059 (17)	0.0161 (17)	−0.0125 (17)
F1	0.0701 (18)	0.141 (3)	0.127 (2)	0.0232 (18)	0.0454 (15)	−0.0117 (19)
C16	0.051 (2)	0.036 (2)	0.045 (2)	0.0000 (19)	0.0154 (19)	0.0032 (18)
N1	0.050 (2)	0.036 (2)	0.107 (3)	0.0023 (18)	0.0183 (18)	−0.0086 (18)
C13	0.052 (3)	0.039 (3)	0.062 (2)	0.003 (2)	0.0088 (19)	0.003 (2)
C11	0.047 (2)	0.044 (2)	0.065 (2)	0.001 (2)	0.013 (2)	0.002 (2)
C14	0.050 (2)	0.036 (2)	0.047 (2)	0.000 (2)	0.0138 (19)	0.0088 (18)
O1	0.0447 (18)	0.159 (3)	0.104 (3)	−0.010 (2)	0.0170 (17)	−0.039 (2)
C21	0.055 (3)	0.053 (3)	0.058 (2)	0.001 (2)	0.0142 (19)	−0.006 (2)
C15	0.052 (2)	0.039 (2)	0.045 (2)	0.000 (2)	0.018 (2)	0.0040 (19)
C19	0.053 (3)	0.057 (3)	0.063 (3)	0.008 (2)	0.010 (2)	0.005 (2)
C20	0.065 (3)	0.052 (3)	0.068 (3)	0.007 (2)	0.022 (2)	−0.011 (2)
C17	0.063 (3)	0.060 (3)	0.059 (2)	0.005 (2)	0.015 (2)	−0.011 (2)
C12	0.051 (3)	0.064 (3)	0.079 (3)	0.003 (2)	0.020 (2)	−0.014 (2)
C18	0.056 (3)	0.080 (3)	0.064 (3)	0.008 (2)	0.002 (2)	−0.013 (2)
C10	0.060 (3)	0.066 (3)	0.075 (3)	−0.004 (2)	0.017 (2)	−0.010 (3)
C7	0.059 (3)	0.082 (3)	0.074 (3)	0.001 (3)	0.017 (2)	−0.003 (3)
C8	0.053 (3)	0.084 (3)	0.084 (3)	0.012 (3)	0.031 (3)	−0.001 (3)
C9	0.089 (4)	0.073 (3)	0.088 (3)	0.003 (3)	0.039 (3)	−0.017 (3)
C1	0.050 (3)	0.104 (4)	0.088 (4)	0.017 (3)	0.000 (3)	−0.024 (3)
C22	0.077 (3)	0.097 (4)	0.129 (4)	0.028 (3)	0.031 (3)	−0.010 (4)
C2	0.073 (3)	0.121 (5)	0.106 (4)	0.014 (4)	0.005 (3)	−0.023 (4)
C5	0.118 (5)	0.142 (6)	0.099 (5)	0.046 (5)	0.015 (4)	0.027 (5)
C4	0.128 (6)	0.151 (7)	0.091 (5)	0.056 (5)	−0.015 (5)	−0.018 (5)
C6	0.082 (4)	0.117 (5)	0.101 (4)	0.013 (3)	0.015 (3)	0.001 (4)
C3	0.100 (5)	0.158 (7)	0.125 (6)	0.022 (5)	−0.006 (5)	−0.039 (6)

Geometric parameters (Å, º) top

S1—C14	1.661 (4)	C20—H20	0.9300
O3—C15	1.223 (4)	C17—C18	1.377 (5)
O2—C13	1.229 (4)	C17—H17	0.9300
N3—C14	1.383 (4)	C12—C7	1.380 (5)
N3—C15	1.391 (4)	C12—H12	0.9300
N3—H3N	0.8600	C18—H18	0.9300
O4—C19	1.367 (4)	C10—C9	1.392 (6)
O4—C22	1.419 (5)	C10—H10	0.9300
N2—C14	1.322 (4)	C7—C8	1.362 (6)
N2—N1	1.369 (4)	C8—C9	1.360 (6)
N2—H2N	0.8600	C9—H9	0.9300
F1—C8	1.348 (4)	C1—C2	1.365 (7)
C16—C21	1.377 (5)	C1—C6	1.365 (7)
C16—C17	1.390 (5)	C22—H22A	0.9600
C16—C15	1.476 (5)	C22—H22B	0.9600
N1—C13	1.325 (5)	C22—H22C	0.9600
N1—H1	0.8600	C2—C3	1.338 (8)
C13—C11	1.490 (5)	C2—H2	0.9300
C11—C10	1.373 (5)	C5—C4	1.390 (9)
C11—C12	1.383 (5)	C5—C6	1.401 (8)
O1—C7	1.375 (5)	C5—H5	0.9300
O1—C1	1.383 (5)	C4—C3	1.359 (9)
C21—C20	1.374 (5)	C4—H4	0.9300
C21—H21	0.9300	C6—H6	0.9300
C19—C18	1.374 (5)	C3—H3	0.9300
C19—C20	1.378 (5)

C14—N3—C15	128.0 (3)	C11—C12—H12	119.8
C14—N3—H3N	116.0	C19—C18—C17	120.5 (4)
C15—N3—H3N	116.0	C19—C18—H18	119.8
C19—O4—C22	117.7 (3)	C17—C18—H18	119.8
C14—N2—N1	119.4 (3)	C11—C10—C9	119.4 (4)
C14—N2—H2N	120.3	C11—C10—H10	120.3
N1—N2—H2N	120.3	C9—C10—H10	120.3
C21—C16—C17	117.8 (3)	C8—C7—O1	116.6 (4)
C21—C16—C15	118.1 (3)	C8—C7—C12	118.5 (4)
C17—C16—C15	124.1 (3)	O1—C7—C12	124.9 (4)
C13—N1—N2	120.9 (3)	F1—C8—C9	118.9 (4)
C13—N1—H1	119.6	F1—C8—C7	118.8 (4)
N2—N1—H1	119.6	C9—C8—C7	122.3 (4)
O2—C13—N1	121.7 (3)	C8—C9—C10	119.3 (4)
O2—C13—C11	122.9 (4)	C8—C9—H9	120.4
N1—C13—C11	115.4 (4)	C10—C9—H9	120.4
C10—C11—C12	120.0 (4)	C2—C1—C6	121.5 (5)
C10—C11—C13	122.1 (4)	C2—C1—O1	115.1 (5)
C12—C11—C13	117.9 (4)	C6—C1—O1	123.4 (5)
N2—C14—N3	115.4 (3)	O4—C22—H22A	109.5
N2—C14—S1	123.2 (3)	O4—C22—H22B	109.5
N3—C14—S1	121.4 (3)	H22A—C22—H22B	109.5
C7—O1—C1	121.6 (4)	O4—C22—H22C	109.5
C20—C21—C16	121.7 (4)	H22A—C22—H22C	109.5
C20—C21—H21	119.2	H22B—C22—H22C	109.5
C16—C21—H21	119.2	C3—C2—C1	120.4 (7)
O3—C15—N3	120.7 (3)	C3—C2—H2	119.8
O3—C15—C16	122.3 (3)	C1—C2—H2	119.8
N3—C15—C16	116.9 (3)	C4—C5—C6	119.0 (7)
O4—C19—C18	115.0 (4)	C4—C5—H5	120.5
O4—C19—C20	125.6 (4)	C6—C5—H5	120.5
C18—C19—C20	119.3 (4)	C3—C4—C5	120.3 (7)
C21—C20—C19	119.9 (4)	C3—C4—H4	119.9
C21—C20—H20	120.0	C5—C4—H4	119.9
C19—C20—H20	120.0	C1—C6—C5	118.2 (6)
C18—C17—C16	120.8 (4)	C1—C6—H6	120.9
C18—C17—H17	119.6	C5—C6—H6	120.9
C16—C17—H17	119.6	C2—C3—C4	120.6 (7)
C7—C12—C11	120.5 (4)	C2—C3—H3	119.7
C7—C12—H12	119.8	C4—C3—H3	119.7

C14—N2—N1—C13	−143.5 (4)	C13—C11—C12—C7	−179.2 (4)
N2—N1—C13—O2	−6.2 (6)	O4—C19—C18—C17	180.0 (4)
N2—N1—C13—C11	173.9 (3)	C20—C19—C18—C17	−0.2 (6)
O2—C13—C11—C10	147.9 (4)	C16—C17—C18—C19	0.7 (6)
N1—C13—C11—C10	−32.2 (5)	C12—C11—C10—C9	−0.6 (6)
O2—C13—C11—C12	−30.6 (5)	C13—C11—C10—C9	−179.1 (4)
N1—C13—C11—C12	149.3 (4)	C1—O1—C7—C8	149.6 (5)
N1—N2—C14—N3	176.7 (3)	C1—O1—C7—C12	−33.4 (7)
N1—N2—C14—S1	−4.1 (5)	C11—C12—C7—C8	−1.8 (6)
C15—N3—C14—N2	−5.7 (5)	C11—C12—C7—O1	−178.8 (4)
C15—N3—C14—S1	175.2 (3)	O1—C7—C8—F1	−2.0 (6)
C17—C16—C21—C20	−0.7 (5)	C12—C7—C8—F1	−179.3 (4)
C15—C16—C21—C20	−179.7 (3)	O1—C7—C8—C9	176.8 (4)
C14—N3—C15—O3	5.9 (5)	C12—C7—C8—C9	−0.4 (7)
C14—N3—C15—C16	−174.1 (3)	F1—C8—C9—C10	−179.1 (4)
C21—C16—C15—O3	5.2 (5)	C7—C8—C9—C10	2.1 (7)
C17—C16—C15—O3	−173.8 (3)	C11—C10—C9—C8	−1.5 (7)
C21—C16—C15—N3	−174.7 (3)	C7—O1—C1—C2	148.1 (4)
C17—C16—C15—N3	6.3 (5)	C7—O1—C1—C6	−34.9 (7)
C22—O4—C19—C18	−177.2 (4)	C6—C1—C2—C3	−2.0 (8)
C22—O4—C19—C20	3.0 (6)	O1—C1—C2—C3	175.1 (5)
C16—C21—C20—C19	1.2 (6)	C6—C5—C4—C3	0.1 (9)
O4—C19—C20—C21	179.1 (4)	C2—C1—C6—C5	1.7 (8)
C18—C19—C20—C21	−0.7 (6)	O1—C1—C6—C5	−175.1 (4)
C21—C16—C17—C18	−0.2 (6)	C4—C5—C6—C1	−0.7 (8)
C15—C16—C17—C18	178.8 (3)	C1—C2—C3—C4	1.3 (9)
C10—C11—C12—C7	2.3 (6)	C5—C4—C3—C2	−0.4 (10)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···O3	0.86	1.92	2.589 (4)	134
N3—H3N···S1ⁱ	0.86	2.80	3.615 (3)	159
C17—H17···S1ⁱ	0.93	2.69	3.614 (4)	174
N1—H1···O2ⁱⁱ	0.86	2.15	2.915 (4)	148
C21—H21···O3ⁱⁱⁱ	0.93	2.57	3.399 (4)	148

Symmetry codes: (i) −x+1, y, −z+1/2; (ii) x, y+1, z; (iii) −x+1, −y−1, −z.

Acknowledgements

The authors are thankful to the CIF of IISER Bhopal for research facilities and infrastructure.

References

Acharya, P. T., Bhavsar, Z. A., Jethava, D., Patel, D. B. & Patel, H. D. (2021). J. Mol. Struct. 1226, 129268. CrossRef Google Scholar
Ameryckx, A., Thabault, L., Pochet, L., Leimanis, S., Poupaert, J. H., Wouters, J., Joris, B., Van Bambeke, F. & Frédérick, R. (2018). Eur. J. Med. Chem. 159, 324–338. CrossRef CAS PubMed Google Scholar
Bruker (2008). SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2012). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Campbell, M. J. M. (1975). Coord. Chem. Rev. 15, 279–319. CrossRef CAS Web of Science Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Gazieva, G. A. & Kravchenko, A. N. (2012). Russ. Chem. Rev. 81, 494–523. CrossRef CAS Google Scholar
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CrossRef IUCr Journals Google Scholar
Macrae, C. F., Sovago, I., Cottrell, S. J., Galek, P. T. A., McCabe, P., Pidcock, E., Platings, M., Shields, G. P., Stevens, J. S., Towler, M. & Wood, P. A. (2020). J. Appl. Cryst. 53, 226–235. Web of Science CrossRef CAS IUCr Journals Google Scholar
Mohan, T. P. (2006). PhD Thesis, Mangalore University, Mangalore, Karnataka, India. Google Scholar
Paneth, A., Stączek, P., Plech, T., Strzelczyk, A., Dzitko, K., Wujec, M., Kuśmierz, E., Kosikowska, U., Grzegorczyk, A. & Paneth, P. (2016). J. Enzyme Inhib. Med. Chem. 31, 14–22. CrossRef CAS PubMed Google Scholar
Pramanik, S. & Chopra, D. (2020). J. Indian Inst. Sci. 100, 43–59. CrossRef Google Scholar
Qandil, A. M., Tumah, H. N. & Hassan, M. A. (2006). Acta. Pharm. Sci. 48, 95–107. CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Siwek, A., Bielawska, A., Maciorkowska, E., Lepiarczyk, M., Bielawski, K., Trotsko, N. & Wujec, M. (2014). J. Enzyme Inhib. Med. Chem. 29, 243–248. CrossRef CAS PubMed Google Scholar
Spackman, M. A. & Jayatilaka, D. (2009). CrystEngComm, 11, 19–32. Web of Science CrossRef CAS Google Scholar
Spek, A. L. (2020). Acta Cryst. E76, 1–11. Web of Science CrossRef IUCr Journals Google Scholar
Turner, M. J., McKinnon, J. J., Wolff, S. K., Grimwood, D. J., Spackman, P. R., Jayatilaka, D. & Spackman, M. A. (2017). CrystalExplorer 17.5. University of Western Australia, Perth. Google Scholar
Yan, Y., Dai, L., Zhang, L., Zhong, S., Zhou, H., Wu, L. & Cai, L. (2018). Res. Chem. Intermed. 44, 3437–3454. CrossRef CAS Google Scholar

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Volume 77| Part 3| March 2021| Pages 277-281

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

Structural investigation of N-[2-(4-fluoro-3-phen­­oxy­benzo­yl)hydrazinecarbo­thio­yl]benzamide and N-[2-(4-fluoro-3-phen­­oxy­benzo­yl)hydrazinecarbo­thio­yl]-4-meth­­oxy­benzamide

1. Chemical context

2. Structural commentary

3. Supra­molecular features

4. Database survey

5. Hirshfeld surface analysis and fingerprint plots

6. Synthesis and Crystallization

7. Refinement

Supporting information

Acknowledgements

References

research communications

Structural investigation of N-[2-(4-fluoro-3-phenoxybenzoyl)hydrazinecarbothioyl]benzamide and N-[2-(4-fluoro-3-phenoxybenzoyl)hydrazinecarbothioyl]-4-methoxybenzamide

3. Supramolecular features