Different inter­molecular inter­actions in solvated and unsolvated isatin-based di­thio­carbazate imine derivatives

McKay, A.P.; Cordes, D.B.; Fatah Abdul Manan, M.A.

doi:10.1107/S2056989025011028

research communications

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ISSN: 2056-9890

Volume 82| Part 1| January 2026| Pages 72-76

https://doi.org/10.1107/S2056989025011028

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Different intermolecular interactions in solvated and unsolvated isatin-based dithiocarbazate imine derivatives

Aidan P. McKay,^a David B. Cordes ^a and Mohd Abdul Fatah Abdul Manan ^b ^*

^aEaStCHEM School of Chemistry, University of St Andrews, St Andrews, Fife KY16 9ST, United Kingdom, and ^bFaculty of Applied Sciences, Universiti Teknologi MARA, 40450 Shah Alam, Selangor, Malaysia
^*Correspondence e-mail: [email protected]

Edited by W. T. A. Harrison, University of Aberdeen, United Kingdom (Received 25 November 2025; accepted 5 December 2025; online 1 January 2026)

The syntheses and structures of 2-fluorobenzyl (Z)-2-(2-oxoindolin-3-ylidene)hydrazine-1-carbodithioate dimethyl sulfoxide monosolvate, C₁₆H₁₂FN₃OS₂·C₂H₆OS (1) and 2-fluorobenzyl (Z)-2-(5-bromo-2-oxoindolin-3-ylidene)hydrazine-1-carbodithioate, C₁₆H₁₁BrFN₃OS₂ (2) are reported. Both structures feature a Z-configuration with respect to the C=N bond and the fluorobenzyl ring is approximately orthogonal to the isatin moiety. For 1, the crystal packing features weak C_ar—H⋯S (ar = aromatic) hydrogen bonds that link adjacent molecules in a C(10) fashion to form pleated chains propagating along [001] and short S⋯O contacts between dimethyl sulfoxide solvent molecules forming chains along [010]. The N—H hydrogen bond donors in 1 form either intramolecular or discrete N—H⋯O_(DMSO) hydrogen bonds. In 2, alternating R²₂(8)-type pairwise N—H⋯O hydrogen bonds and short F⋯Br contacts link the molecules into chains propagating along [210]. The later unsolvated structure is of notably poorer quality and exhibits disorder in its o-fluorobenzyl group, with a 180° flip and a small twist around the S—C bond. These findings are consistent with the results of Hirshfeld surface analyses.

Keywords: crystal structure; isatin; hydrogen bonding; chalcogen bonding.

CCDC references: 2513536; 2513535

1. Chemical context

The use of solvent molecules in reducing structural disorder is an emerging theme in crystal engineering. Controlled solvation can enhance crystallographic quality and provides a means to fine-tune the chemical and physical properties of solid-state materials, including functional organic frameworks, coordination complexes and pharmaceuticals (for recent reviews, see: Werner & Swift, 2021 ; Bolla et al., 2022 ). The inclusion of a solvent such as dimethyl sulfoxide (DMSO), in the crystal fills void space, introduces additional hydrogen-bond acceptors, and stabilizes conformations, leading to more rigid and well-defined structural units of crystalline motifs (Klitou et al., 2020 ; Li et al., 2021 ). For example, our recent crystallographic study on 2-fluorobenzyl (Z)-2-(5-chloro-2-oxoindolin-3-ylidene) hydrazine-1-carbodithioate dimethyl sulfoxide monosolvate highlighted the role of DMSO as a hydrogen bond acceptor by forming discrete directional N—H⋯O_(DMSO) contacts and occupying voids in the crystal. The inclusion of the solvate increased packing complementarity, producing a more rigid asymmetric unit and fewer alternative conformers, resulting in a more stable molecular conformation (McKay et al., 2025 ).

Isatin-based imines have been widely recognized as versatile scaffolds, displaying a broad range of application domains (Liu et al., 2025 ; Tok et al., 2025 ; Topkaya et al., 2024 ). Their functionalization allows chemists to modulate steric and electronic properties for tuning solid-state architectures, which can exhibit profound implications on physical properties and applications (Wang et al., 2023 ; Venugopal & Pansare 2025 ).

As part of our ongoing studies of organosulfur imines and their solid-state behaviour, we report here the syntheses, crystal structures and Hirshfeld-surface analyses of 2-fluorobenzyl (Z)-2-(2-oxoindolin-3-ylidene)hydrazine-1-carbodithioate dimethyl sulfoxide monosolvate, C₁₆H₁₂FN₃OS₂·C₂H₆OS (1) and 2-fluorobenzyl (Z)-2-(5-bromo-2-oxoindolin-3-ylidene)hydrazine-1-carbodithioate, C₁₆H₁₁BrFN₃OS₂ (2).

2. Structural commentary

Compound 1 crystallizes in space group P2₁/c as a dimethyl sulfoxide solvate (Fig. 1), while compound 2 crystallizes in the space group P $[\overline{1}]$ , without any solvent of crystallization (Fig. 2). Both compounds display a Z configuration with respect to the C=N bond, resulting in the hydrazine (N4) hydrogen atom being directed towards the isatin (O2) oxygen atom generating an S(6) intramolecular N—H⋯O hydrogen bond (Tables 1 and 2) in the same manner as in previously reported related structures (Abdul Manan et al., 2023 ; Abdul Manan et al., 2024a ,b ,c ; McKay et al., 2025). In both structures, the thione sulfur atom (S10) is orientated syn to the γ-lactam oxygen atom while the S-2-fluorobenzyl moiety is orientated in the opposite direction. There is a small bow between the methylidenehydrazinecarbodithioate (MHT) and the γ-lactam moieties in both structures [6.70 (8) and 6.5 (3)° for 1 and 2, respectively] while the 2-fluorophenyl ring is twisted almost perpendicular to the MHT fragment [90.37 (7) and 72.5 (17)° for 1 and 2, respectively]. In compound 1, the H atom on the γ-lactam nitrogen atom (N1) forms a discrete N—H⋯O hydrogen bond to the DMSO solvent molecule (Table 1) in the same manner as the previously reported 5-chloro analogue (McKay et al., 2025).

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O21	0.78 (3)	2.05 (3)	2.820 (3)	174 (3)
N4—H4⋯O2	0.88 (3)	1.99 (3)	2.696 (3)	136 (3)
C7—H7⋯S10ⁱ	0.95	2.94	3.860 (3)	163
C21—H21C⋯O2ⁱⁱ	0.98	2.53	3.305 (3)	136
C22—H22C⋯O21ⁱⁱⁱ	0.98	2.48	3.457 (3)	172
Symmetry codes: (i) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) .

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2ⁱ	0.88	1.96	2.821 (15)	165
N4—H4⋯O2	0.88	2.09	2.777 (16)	134
C11—H11D⋯S10	0.99	2.56	3.221 (14)	124
Symmetry code: (i) .

Figure 1
The molecular structure of 1 with ellipsoids drawn at the 50% probability level. Hydrogen bonds are shown as blue dashed lines.

Figure 2
The molecular structure of 2 with ellipsoids drawn at 50% probability and the minor component of disorder omitted for clarity. Hydrogen bonds are shown as blue dashed lines.

3. Supramolecular features

In the extended structure of 1 the fused benzo-ring of the isatin moiety forms non-classical C_ar—H⋯S and C_ar—H⋯F hydrogen bonds to the thione and the fluorine atoms (Table 1). These interactions link adjacent molecules in a C(10) fashion (with respect to the C—H⋯S hydrogen bond) to form pleated chains propagating along [001] (Fig. 3). These pleated chains are similar to the pleated sheets reported in methyl (Z)-methyl 2-(−5-methyl-2-oxoindolin-3-ylidene)hydrazine-1-carbodithioate (Abdul Manan et al., 2024c), which are formed by non-classical C_ar—H⋯S hydrogen bonds between adjacent N—H⋯O hydrogen bonded dimers. The pleated chains in 1 further stack together through both weak π–π stacking (Corne et al., 2016 ) from the fused benzo (C4–C9) of the isatin moiety to the C3=N3 bond [centroid⋯centroid separation = 3.302 (3) Å], and additional weaker non-classical C_ar—H⋯S hydrogen bonds from C16 in the fluorobenzyl ring to the sulfide group (S11) of an adjacent molecule [H16⋯S11 = 3.0363 (6) Å, C16⋯S11 = 3.770 (3) Å]. This packing motif is supported by chains of chalcogen-bonded DMSO solvent molecules [S21⋯O21 = 3.188 (2) Å compared to a van der Waals separation of 3.32 Å; S21—O21⋯S21 = 169.37 (10)°] along [010], which are hydrogen-bonded to the γ-lactam nitrogen atoms to form sheets lying in the (100) plane.

Figure 3
The packing of 1 into pleated sheets (left to right) through classical and non-classical hydrogen bonds (blue dashed lines) with chalcogen bonded (green dashed lines) DMSO solvent molecules.

In contrast, 2 forms inversion dimers through reciprocal N—H⋯O hydrogen bonds in the typical R₂²(8) form (Table 2) between adjacent γ-lactam units in the same manner as previously reported related structures (Abdul Manan et al., 2023, 2024a,b,c). The dimers link together into chains (Fig. 4) propagating along [2 $[\overline{1}]$ 0] through Br⋯S halogen bonds (Br6⋯S11 = 3.405 (5) Å, C6—Br6⋯S11 = 158.7 (6)°). These chains pack together into sheets in (001) through a combination of edge-to-face stacking between the fused benzo rings (C8) and fluorophenyl rings [H8⋯centroid = 3.20 (2) and 3.22 (2) Å, C8⋯centroid 3.91 (3) and 3.98 (3) Å, for the major and minor disordered parts, respectively], π–π stacking between adjacent γ-lactam rings [centroid–centroid separation = 3.467 (13) Å], weaker non-classical C_ar—H⋯S [H⋯S = 2.956 (4)–3.211 (4) Å, C⋯S = 3.68 (3)–4.01 (4) Å] and C_ar—H⋯Br [H5⋯Br6 = 3.201 (2) Å; C5⋯Br6 = 4.138 (16) Å] hydrogen bonds, and, depending on the orientation of the o-fluorobenzyl ring, either very weak Type IV (Saha et al., 2023 ) Br⋯F [Br6⋯F13A = 3.35 (3) Å compared to a van der Waals separation of 3.37 Å; C6—Br6⋯F13A = 96.0 (7)°; C13A—F13A⋯Br6 = 104 (2)°] halogen bonds or weak non-classical C_ar—H⋯F [H17B⋯F13B = 2.65 (2) Å; C17B⋯F13B = 3.26 (4) Å] hydrogen bonds. These sheets assemble into the overall structure through additional weaker C_ar—H⋯S and C_ar—H⋯F interactions.

Figure 4
The packing of 2 into chains through alternating pairwise N—H⋯O hydrogen bonds (blue dashed lines) and S⋯Br halogen bonds (green dashed lines).

4. Hirshfeld surface analysis

Hirshfeld surface analyses of 1 (with the DMSO solvent molecule external to the surface) and 2 (Fig. 5) both show sharp H⋯O and H⋯S contacts (5.9 and 7.5%, and 17.0 and 13.8% of the surfaces, respectively). The H⋯S fingerprints for both structures show broad tails, highlighting the diverse range of H⋯S contacts occurring beyond the discrete C—H⋯S non-classical hydrogen bonds mentioned above. The majority of these contacts are likely electrostatic/van der Waals in character. The fingerprint of H⋯Br contacts in 2 (8.3% of surface) shows a sharp contact which corresponds to a long C_ar—H⋯Br interaction [H5⋯Br6 = 3.201 (2) Å] supporting the halogen-bonding interaction. The surface of 1 shows sharp H⋯F contacts (7.5% of surface) which correspond to a weak C_ar—H⋯F interaction [H6⋯F13 = 2.6116 (15) Å; C6⋯F13 = 3.540 (3) Å] between the fused benzo ring of the istan grouping and an adjacent fluorobenzyl ring while the surface of 2 only shows diffuse H⋯F contacts (4.5% of surface), likely due to the disorder of the fluorobenzyl group. The surface of 2 also shows sharp S⋯Br contacts (2.9% of surface) consistent with the halogen bonds observed in the structure.

Figure 5
Hirshfeld surface fingerprint plots of 1 (left) and 2 (right) with various contacts highlighted.

5. Synthesis and crystallization

The 2-fluorobenzyl hydrazinecarbodithioate precursor was synthesized using our previously published methods (McKay et al., 2025).

To prepare 1, a solution of isatin (1.47 g, 10.0 mmol, 1 eq.) in hot ethanol (40 ml) was added to a solution of the dithiocarbazate precursor (2.16 g, 10.0 mmol, 1.0 e.q) in hot ethanol (40 ml). The mixture was heated (353 K) with continuous stirring for 15 min and later allowed to cool to room temperature and stand for about 20 min., until a precipitate formed, which was then collected by filtration and dried over silica gel. The crude solid was purified by recrystallization from ethanol solution to yield a yellow solid (yield: 2.87 g, 83%). m.p. 494–495 K; elemental analysis calculated for C₁₆H₁₂FN₃OS₂: C, 55.63; H, 3.50; N, 12.17%; found: C, 55.63; H, 3.12; N, 11.96%. FT–IR (KBr, ν, cm⁻¹): 3175 (NH), 1688 (C=O); 1613 (C=N); 1079 (C=S); 1143 (N—N); ¹H NMR (400 MHz, d₆-DMSO) δ: (ppm): 4.56 (s, 2H), 6.94 (d, J = 7.9 Hz, 1H) 7.04–7.08 (m, 1H), 7.17–7.26 (m, 2H), 7.35–7.42 (m, 2H), 7.53–7.58 (m, 2H), 11.38 (s, 1H), 13.97 (s, 1H). Crystals of the DMSO solvate suitable for X-ray diffraction were grown by slow evaporation of a dimethyl sulfoxide solution at room temperature.

Compound 2 was prepared as follows: a solution of 5-bromoisatin (2.26 g, 10.0 mmol, 1.0 eq.) in hot ethanol (40 ml) was added to a solution of the dithiocarbazate precursor (2.16 g, 10.0 mmol, 1.0 e.q) in hot ethanol (40 ml). The mixture was heated (353 K with continuous stirring for 15 min and later allowed to cool to room temperature and stand for about 20 min., until a precipitate formed, which was then collected by filteration and dried over silica gel. The crude solid was purified by recrystallization from ethanol solution to give a yellow solid (3.39 g, yield: 80%). m.p 499–500 K. Elemental analysis calculated for C₁₆H₁₁BrFN₃OS₂: C, 45.29; H, 2.61; N, 9.90%. Found: C, 45.60; H, 2.31; N, 9.74%. FT–IR (KBr, ν, cm⁻¹): 3157 (NH), 1694 (C=O); 1613 (C=N); 1068 (C=S); 1144 (N—N); ¹H NMR (400 MHz, d₆-DMSO) δ: (ppm): 4.56 (s, 2H), 6.90 (d, J = 8.2 Hz, 1H) 7.18–7.26 (m, 2H), 7.35–7.41 (m, 1H), 7.54–7.59 (m, 2H), 7.64 (d, J = 2.0 Hz, 1H), 11.48 (s, 1H), 13.89 (s, 1H). Crystals suitable for X-ray diffraction were grown by slow evaporation of an ethanolic solution at room temperature.

6. Refinement

Crystal data, data collection, and structure refinement details are summarized in Table 3. The N-bound H atoms in 1 were located in a difference map and refined isotropically without restraint. The C-bound H atoms, and N-bond H atoms in 2, were located geometrically (phenyl C—H = 0.95 Å, amide/thioamide N—H = 0.88 Å, methylene C—H = 0.99 Å, methyl C—H = 0.98 Å) and refined as riding atoms. The constraint U_iso(H) = 1.2 U_eq(carrier) or 1.5 U_eq(methyl C) was applied in all cases. Non-merohedral twinning in the structure of 2 with the twin matrix [–1.000 0.000 0.000 / 0.000 1.001 −0.005 / 0.000 0.333 −1.001] was processed using the TwinRotMat routine in PLATON (Spek, 2009 ) and refined as a two component twin with component 2 rotated by 0.26° around [061] (reciprocal) or [010] (direct), with a refined twin fraction of 0.417 (6). This structure also showed disorder in its o-fluorobenzyl group, with a 180° flip and a small (∼8°) twist around the S11—C11 bond. The aromatic ring and fluoro subsitutent was modelled in two parts with geometric and displacement-factor restraints retained on both major and minor parts in a 0.52 (3):0.48 (3) ratio.

Table 3
Experimental details

	1	2
Crystal data
Chemical formula	C₁₆H₁₂FN₃OS₂·C₂H₆OS	C₁₆H₁₁BrFN₃OS₂
M_r	423.53	424.31
Crystal system, space group	Monoclinic, P2₁/c	Triclinic, P $[\overline{1}]$
Temperature (K)	100	100
a, b, c (Å)	21.6312 (10), 4.6850 (2), 18.9579 (8)	6.6979 (7), 8.0075 (9), 15.880 (2)
α, β, γ (°)	90, 91.519 (4), 90	84.917 (10), 80.544 (10), 89.948 (9)
V (Å³)	1920.58 (14)	836.73 (17)
Z	4	2
Radiation type	Mo Kα	Cu Kα
μ (mm⁻¹)	0.41	5.86
Crystal size (mm)	0.27 × 0.02 × 0.01	0.1 × 0.01 × 0.01

Data collection
Diffractometer	Rigaku XtaLAB P200K	Rigaku XtaLAB P200K
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2024 )	Multi-scan (CrysAlis PRO; Rigaku OD, 2024)
T_min, T_max	0.588, 1.000	0.695, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	23801, 4647, 3366	12408, 3262, 1900
R_int	0.069	0.139

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.055, 0.114, 1.02	0.132, 0.319, 1.16
No. of reflections	4647	3262
No. of parameters	254	282
No. of restraints	0	130
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)	0.51, −0.32	1.39, −1.23
Computer programs: CrysAlis PRO (Rigaku OD, 2023 , 2024), SHELXT2018/2 (Sheldrick, 2015a ), SHELXL2019/3 (Sheldrick, 2015b ), Mercury (Macrae et al., 2020 ), enCIFer (Allen et al., 2004 ) publCIF (Westrip, 2010 ) and OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC references: 2513536; 2513535

Crystal structure: contains datablocks 1, 2, general. DOI: https://doi.org/10.1107/S2056989025011028/hb8175sup1.cif

Structure factors: contains datablock 1. DOI: https://doi.org/10.1107/S2056989025011028/hb81751sup2.hkl

Structure factors: contains datablock 2. DOI: https://doi.org/10.1107/S2056989025011028/hb81752sup3.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989025011028/hb81751sup4.cml

Supporting information file. DOI: https://doi.org/10.1107/S2056989025011028/hb81752sup5.cml

checkCIF report

Computing details top

2-Fluorobenzyl (Z)-2-(2-oxoindolin-3-ylidene)hydrazine-1-carbodithioate dimethyl sulfoxide monololvate (1) top

Crystal data top

C₁₆H₁₂FN₃OS₂·C₂H₆OS	F(000) = 880
M_r = 423.53	D_x = 1.465 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 21.6312 (10) Å	Cell parameters from 5747 reflections
b = 4.6850 (2) Å	θ = 2.2–26.9°
c = 18.9579 (8) Å	µ = 0.41 mm⁻¹
β = 91.519 (4)°	T = 100 K
V = 1920.58 (14) Å³	Needle, yellow
Z = 4	0.27 × 0.02 × 0.01 mm

Data collection top

Rigaku XtaLAB P200K diffractometer	4647 independent reflections
Radiation source: Rotating Anode, Rigaku FR-X	3366 reflections with I > 2σ(I)
Rigaku Osmic Confocal Optical System monochromator	R_int = 0.069
Detector resolution: 5.8140 pixels mm^-1	θ_max = 29.4°, θ_min = 2.2°
shutterless scans	h = −29→27
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2024)	k = −6→6
T_min = 0.588, T_max = 1.000	l = −25→24
23801 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.055	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.114	w = 1/[σ²(F_o²) + (0.0464P)² + 1.708P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max = 0.001
4647 reflections	Δρ_max = 0.51 e Å⁻³
254 parameters	Δρ_min = −0.32 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.

Refinement. Hydrogen atoms on N1 and N4 were located from the F_map and refined isotropically without restraint. DMSO solvate in the asymmetric unit is positioned outside the cell to clearly show discrete hydrogen bonding interaction between O21 and N1

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

	x	y	z	U_iso*/U_eq
S10	0.71801 (3)	−0.17029 (15)	0.13746 (3)	0.02101 (17)
S11	0.83457 (3)	0.09873 (15)	0.19938 (3)	0.02130 (17)
F13	0.93202 (7)	0.2497 (4)	0.04837 (8)	0.0317 (4)
O2	0.61299 (8)	0.3901 (4)	0.28556 (9)	0.0196 (4)
N1	0.63062 (11)	0.7489 (5)	0.36760 (12)	0.0188 (5)
H1	0.5968 (15)	0.793 (7)	0.3747 (17)	0.037 (10)*
N3	0.75269 (9)	0.3900 (5)	0.28429 (10)	0.0176 (5)
N4	0.72281 (10)	0.2053 (5)	0.23945 (11)	0.0184 (5)
H4	0.6820 (16)	0.196 (7)	0.2376 (16)	0.040 (9)*
C2	0.64701 (11)	0.5455 (5)	0.32149 (13)	0.0169 (5)
C3	0.71713 (11)	0.5460 (5)	0.32265 (12)	0.0156 (5)
C4	0.73668 (11)	0.7572 (5)	0.37423 (12)	0.0164 (5)
C5	0.79386 (12)	0.8519 (6)	0.39943 (13)	0.0211 (6)
H5	0.830912	0.776224	0.381188	0.025*
C6	0.79602 (12)	1.0589 (6)	0.45168 (14)	0.0238 (6)
H6	0.834959	1.123396	0.469705	0.029*
C7	0.74203 (13)	1.1734 (6)	0.47810 (14)	0.0231 (6)
H7	0.744531	1.313797	0.514229	0.028*
C8	0.68421 (12)	1.0844 (6)	0.45213 (13)	0.0213 (6)
H8	0.647223	1.164628	0.469411	0.026*
C9	0.68241 (11)	0.8767 (5)	0.40063 (12)	0.0163 (5)
C10	0.75457 (11)	0.0472 (5)	0.19318 (12)	0.0172 (5)
C11	0.86058 (12)	−0.1306 (6)	0.12843 (14)	0.0239 (6)
H11A	0.845435	−0.327976	0.135090	0.029*
H11B	0.844624	−0.059551	0.082264	0.029*
C12	0.93023 (12)	−0.1248 (6)	0.13096 (13)	0.0207 (6)
C13	0.96358 (12)	0.0615 (6)	0.09076 (14)	0.0226 (6)
C14	1.02731 (12)	0.0685 (6)	0.09125 (14)	0.0267 (6)
H14	1.048630	0.199412	0.062354	0.032*
C15	1.05949 (12)	−0.1200 (6)	0.13488 (15)	0.0271 (6)
H15	1.103426	−0.119825	0.136062	0.032*
C16	1.02768 (12)	−0.3084 (6)	0.17671 (15)	0.0264 (6)
H16	1.049759	−0.437167	0.206774	0.032*
C17	0.96361 (12)	−0.3096 (6)	0.17480 (14)	0.0237 (6)
H17	0.942143	−0.438896	0.203984	0.028*
S21	0.50131 (3)	1.27070 (14)	0.39185 (3)	0.01653 (16)
O21	0.50964 (8)	0.9499 (4)	0.38887 (9)	0.0216 (4)
C21	0.46100 (12)	1.3699 (6)	0.31267 (12)	0.0199 (6)
H21A	0.488204	1.345701	0.272589	0.030*
H21B	0.448170	1.570006	0.315740	0.030*
H21C	0.424392	1.248576	0.306044	0.030*
C22	0.43948 (11)	1.3253 (6)	0.45068 (13)	0.0226 (6)
H22A	0.403487	1.213317	0.434743	0.034*
H22B	0.428535	1.528252	0.451386	0.034*
H22C	0.452432	1.264394	0.498271	0.034*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S10	0.0165 (3)	0.0279 (4)	0.0185 (3)	−0.0028 (3)	−0.0018 (2)	−0.0033 (3)
S11	0.0125 (3)	0.0290 (4)	0.0224 (3)	−0.0004 (3)	0.0002 (2)	−0.0075 (3)
F13	0.0314 (10)	0.0376 (10)	0.0260 (9)	0.0043 (8)	−0.0014 (7)	0.0036 (8)
O2	0.0134 (9)	0.0255 (10)	0.0197 (9)	−0.0011 (8)	−0.0014 (7)	−0.0019 (8)
N1	0.0121 (11)	0.0216 (12)	0.0228 (12)	0.0015 (10)	0.0022 (9)	−0.0021 (10)
N3	0.0164 (11)	0.0197 (11)	0.0165 (10)	−0.0025 (9)	−0.0009 (8)	0.0010 (9)
N4	0.0126 (11)	0.0246 (13)	0.0178 (11)	−0.0019 (9)	−0.0012 (9)	−0.0017 (9)
C2	0.0139 (12)	0.0195 (14)	0.0173 (12)	0.0012 (11)	−0.0002 (10)	0.0039 (11)
C3	0.0125 (12)	0.0188 (13)	0.0157 (12)	0.0001 (10)	0.0007 (9)	0.0020 (11)
C4	0.0181 (13)	0.0181 (13)	0.0131 (12)	0.0005 (11)	0.0009 (10)	0.0009 (10)
C5	0.0172 (13)	0.0244 (15)	0.0217 (13)	0.0011 (11)	−0.0003 (10)	0.0020 (12)
C6	0.0219 (14)	0.0271 (16)	0.0221 (14)	−0.0054 (12)	−0.0038 (11)	−0.0006 (12)
C7	0.0279 (15)	0.0236 (15)	0.0177 (13)	−0.0037 (12)	0.0001 (11)	−0.0019 (11)
C8	0.0213 (14)	0.0232 (15)	0.0195 (13)	0.0001 (11)	0.0054 (10)	0.0015 (12)
C9	0.0151 (12)	0.0163 (13)	0.0176 (13)	−0.0004 (10)	0.0016 (9)	0.0032 (11)
C10	0.0156 (13)	0.0222 (14)	0.0139 (12)	−0.0002 (11)	0.0006 (10)	0.0040 (11)
C11	0.0178 (14)	0.0314 (16)	0.0224 (14)	0.0011 (12)	−0.0008 (10)	−0.0078 (12)
C12	0.0166 (13)	0.0264 (15)	0.0189 (13)	0.0041 (11)	−0.0007 (10)	−0.0087 (12)
C13	0.0221 (14)	0.0247 (15)	0.0209 (14)	0.0041 (12)	−0.0013 (11)	−0.0049 (12)
C14	0.0229 (15)	0.0321 (17)	0.0253 (15)	−0.0045 (13)	0.0061 (11)	−0.0058 (13)
C15	0.0157 (13)	0.0325 (17)	0.0331 (16)	0.0014 (12)	0.0007 (11)	−0.0099 (14)
C16	0.0194 (14)	0.0293 (16)	0.0302 (15)	0.0053 (12)	−0.0054 (11)	−0.0044 (13)
C17	0.0220 (14)	0.0262 (15)	0.0229 (14)	−0.0018 (12)	0.0004 (11)	−0.0039 (12)
S21	0.0130 (3)	0.0207 (4)	0.0158 (3)	0.0007 (3)	−0.0007 (2)	−0.0009 (3)
O21	0.0183 (10)	0.0216 (10)	0.0248 (10)	0.0020 (8)	0.0005 (7)	−0.0001 (8)
C21	0.0182 (13)	0.0252 (15)	0.0163 (13)	0.0024 (11)	−0.0003 (10)	−0.0002 (11)
C22	0.0178 (13)	0.0327 (16)	0.0175 (13)	0.0037 (12)	0.0026 (10)	0.0004 (12)

Geometric parameters (Å, º) top

S10—C10	1.654 (3)	C8—C9	1.378 (4)
S11—C10	1.748 (2)	C11—H11A	0.9900
S11—C11	1.822 (3)	C11—H11B	0.9900
F13—C13	1.364 (3)	C11—C12	1.506 (4)
O2—C2	1.228 (3)	C12—C13	1.376 (4)
N1—H1	0.78 (3)	C12—C17	1.389 (4)
N1—C2	1.347 (3)	C13—C14	1.379 (4)
N1—C9	1.403 (3)	C14—H14	0.9500
N3—N4	1.364 (3)	C14—C15	1.385 (4)
N3—C3	1.298 (3)	C15—H15	0.9500
N4—H4	0.88 (3)	C15—C16	1.382 (4)
N4—C10	1.350 (3)	C16—H16	0.9500
C2—C3	1.517 (3)	C16—C17	1.385 (4)
C3—C4	1.446 (3)	C17—H17	0.9500
C4—C5	1.387 (3)	S21—O21	1.5150 (19)
C4—C9	1.405 (3)	S21—C21	1.778 (2)
C5—H5	0.9500	S21—C22	1.783 (2)
C5—C6	1.386 (4)	C21—H21A	0.9800
C6—H6	0.9500	C21—H21B	0.9800
C6—C7	1.391 (4)	C21—H21C	0.9800
C7—H7	0.9500	C22—H22A	0.9800
C7—C8	1.396 (4)	C22—H22B	0.9800
C8—H8	0.9500	C22—H22C	0.9800

C10—S11—C11	101.15 (12)	H11A—C11—H11B	108.6
C2—N1—H1	125 (2)	C12—C11—S11	107.09 (18)
C2—N1—C9	111.8 (2)	C12—C11—H11A	110.3
C9—N1—H1	124 (2)	C12—C11—H11B	110.3
C3—N3—N4	115.4 (2)	C13—C12—C11	122.2 (2)
N3—N4—H4	121 (2)	C13—C12—C17	117.1 (2)
C10—N4—N3	120.8 (2)	C17—C12—C11	120.8 (3)
C10—N4—H4	118 (2)	F13—C13—C12	118.4 (2)
O2—C2—N1	128.0 (2)	F13—C13—C14	118.3 (2)
O2—C2—C3	126.4 (2)	C12—C13—C14	123.4 (3)
N1—C2—C3	105.6 (2)	C13—C14—H14	120.8
N3—C3—C2	126.8 (2)	C13—C14—C15	118.4 (3)
N3—C3—C4	126.7 (2)	C15—C14—H14	120.8
C4—C3—C2	106.6 (2)	C14—C15—H15	120.0
C5—C4—C3	133.9 (2)	C16—C15—C14	120.0 (3)
C5—C4—C9	119.7 (2)	C16—C15—H15	120.0
C9—C4—C3	106.3 (2)	C15—C16—H16	120.0
C4—C5—H5	120.6	C15—C16—C17	120.0 (3)
C6—C5—C4	118.9 (2)	C17—C16—H16	120.0
C6—C5—H5	120.6	C12—C17—H17	119.4
C5—C6—H6	119.5	C16—C17—C12	121.1 (3)
C5—C6—C7	121.0 (2)	C16—C17—H17	119.4
C7—C6—H6	119.5	O21—S21—C21	106.50 (12)
C6—C7—H7	119.6	O21—S21—C22	104.93 (12)
C6—C7—C8	120.7 (2)	C21—S21—C22	97.55 (12)
C8—C7—H7	119.6	S21—C21—H21A	109.5
C7—C8—H8	121.0	S21—C21—H21B	109.5
C9—C8—C7	118.0 (2)	S21—C21—H21C	109.5
C9—C8—H8	121.0	H21A—C21—H21B	109.5
N1—C9—C4	109.6 (2)	H21A—C21—H21C	109.5
C8—C9—N1	128.7 (2)	H21B—C21—H21C	109.5
C8—C9—C4	121.7 (2)	S21—C22—H22A	109.5
S10—C10—S11	125.71 (15)	S21—C22—H22B	109.5
N4—C10—S10	120.67 (19)	S21—C22—H22C	109.5
N4—C10—S11	113.62 (18)	H22A—C22—H22B	109.5
S11—C11—H11A	110.3	H22A—C22—H22C	109.5
S11—C11—H11B	110.3	H22B—C22—H22C	109.5

S11—C11—C12—C13	−93.9 (3)	C5—C4—C9—N1	179.9 (2)
S11—C11—C12—C17	85.9 (3)	C5—C4—C9—C8	−1.0 (4)
F13—C13—C14—C15	179.2 (2)	C5—C6—C7—C8	−0.6 (4)
O2—C2—C3—N3	2.5 (4)	C6—C7—C8—C9	1.2 (4)
O2—C2—C3—C4	−178.2 (2)	C7—C8—C9—N1	178.5 (2)
N1—C2—C3—N3	−177.4 (2)	C7—C8—C9—C4	−0.4 (4)
N1—C2—C3—C4	1.8 (3)	C9—N1—C2—O2	178.1 (2)
N3—N4—C10—S10	−178.38 (18)	C9—N1—C2—C3	−1.9 (3)
N3—N4—C10—S11	1.7 (3)	C9—C4—C5—C6	1.6 (4)
N3—C3—C4—C5	−1.8 (5)	C10—S11—C11—C12	−175.81 (19)
N3—C3—C4—C9	178.2 (2)	C11—S11—C10—S10	2.4 (2)
N4—N3—C3—C2	−1.0 (3)	C11—S11—C10—N4	−177.65 (19)
N4—N3—C3—C4	179.8 (2)	C11—C12—C13—F13	1.2 (4)
C2—N1—C9—C4	1.3 (3)	C11—C12—C13—C14	−179.0 (2)
C2—N1—C9—C8	−177.6 (2)	C11—C12—C17—C16	179.1 (2)
C2—C3—C4—C5	179.0 (3)	C12—C13—C14—C15	−0.6 (4)
C2—C3—C4—C9	−1.1 (3)	C13—C12—C17—C16	−1.1 (4)
C3—N3—N4—C10	175.0 (2)	C13—C14—C15—C16	−0.2 (4)
C3—C4—C5—C6	−178.5 (3)	C14—C15—C16—C17	0.3 (4)
C3—C4—C9—N1	−0.1 (3)	C15—C16—C17—C12	0.4 (4)
C3—C4—C9—C8	179.0 (2)	C17—C12—C13—F13	−178.6 (2)
C4—C5—C6—C7	−0.8 (4)	C17—C12—C13—C14	1.2 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O21	0.78 (3)	2.05 (3)	2.820 (3)	174 (3)
N4—H4···O2	0.88 (3)	1.99 (3)	2.696 (3)	136 (3)
C7—H7···S10ⁱ	0.95	2.94	3.860 (3)	163
C21—H21C···O2ⁱⁱ	0.98	2.53	3.305 (3)	136
C22—H22C···O21ⁱⁱⁱ	0.98	2.48	3.457 (3)	172

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

2-Fluorobenzyl (Z)-2-(5-bromo-2-oxoindolin-3-ylidene)hydrazine-1-carbodithioate (2) top

Crystal data top

C₁₆H₁₁BrFN₃OS₂	Z = 2
M_r = 424.31	F(000) = 424
Triclinic, P1	D_x = 1.684 Mg m⁻³
a = 6.6979 (7) Å	Cu Kα radiation, λ = 1.54184 Å
b = 8.0075 (9) Å	Cell parameters from 1932 reflections
c = 15.880 (2) Å	θ = 2.8–60.0°
α = 84.917 (10)°	µ = 5.86 mm⁻¹
β = 80.544 (10)°	T = 100 K
γ = 89.948 (9)°	Needle, orange
V = 836.73 (17) Å³	0.1 × 0.01 × 0.01 mm

Data collection top

Rigaku XtaLAB P200K diffractometer	3262 independent reflections
Radiation source: Rotating Anode, Rigaku MM-007HF	1900 reflections with I > 2σ(I)
Rigaku Osmic Confocal Optical System monochromator	R_int = 0.139
Detector resolution: 5.8140 pixels mm^-1	θ_max = 75.8°, θ_min = 2.8°
shutterless scans	h = −8→8
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2024)	k = −9→10
T_min = 0.695, T_max = 1.000	l = −19→19
12408 measured reflections

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)] = 0.132	H-atom parameters constrained
wR(F²) = 0.319	w = 1/[σ²(F_o²) + 14.5238P] where P = (F_o² + 2F_c²)/3
S = 1.16	(Δ/σ)_max < 0.001
3262 reflections	Δρ_max = 1.39 e Å⁻³
282 parameters	Δρ_min = −1.23 e Å⁻³
130 restraints

Special details top

Refinement. Refined as a 2-component twin at [-1 0 0 0 1.001 -0.005 0 0.333 -1.001] with HKLF5 generated by TWINROTMAT running in PLATON. Ortho-fluorobenzyl group was disordered with fluoro group fliped 180°. fluoro- phenyl ring was split in two parts and refined with C—F and aromatic C—C distances restrained, C12A/B thermal parameters linked with SIMU, and general thermal restraints on both parts.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Br6	0.0746 (3)	0.4658 (3)	0.34527 (14)	0.0526 (6)
S10	0.5773 (6)	0.2120 (6)	0.8720 (3)	0.0532 (12)
S11	0.2188 (6)	0.3262 (6)	0.7844 (3)	0.0493 (12)
F13A	−0.190 (3)	0.587 (3)	0.8641 (17)	0.063 (8)	0.48 (3)
F13B	0.423 (3)	0.628 (3)	0.9211 (15)	0.066 (7)	0.52 (3)
O2	0.8662 (15)	0.0741 (14)	0.5997 (7)	0.042 (3)
N1	0.7918 (17)	0.1135 (16)	0.4609 (9)	0.038 (3)
H1	0.897901	0.066037	0.432771	0.046*
N3	0.4653 (18)	0.2489 (16)	0.6398 (9)	0.040 (3)
N4	0.5546 (17)	0.2100 (17)	0.7094 (8)	0.040 (3)
H4	0.672455	0.159957	0.703457	0.048*
C2	0.759 (2)	0.124 (2)	0.5459 (13)	0.044 (4)
C3	0.560 (2)	0.2145 (19)	0.5670 (11)	0.038 (4)
C4	0.491 (2)	0.256 (2)	0.4859 (11)	0.040 (4)
C5	0.319 (2)	0.331 (2)	0.4627 (12)	0.044 (4)
H5	0.214241	0.367252	0.504814	0.053*
C6	0.303 (2)	0.350 (2)	0.3780 (14)	0.052 (5)
C7	0.444 (2)	0.287 (2)	0.3158 (11)	0.042 (4)
H7	0.425799	0.299914	0.257538	0.051*
C8	0.614 (2)	0.204 (2)	0.3380 (12)	0.044 (4)
H8	0.711650	0.159053	0.295954	0.053*
C9	0.633 (2)	0.189 (2)	0.4224 (11)	0.043 (4)
C10	0.465 (2)	0.247 (2)	0.7876 (13)	0.050 (5)
C11	0.134 (2)	0.3751 (17)	0.8932 (11)	0.044 (4)
H11A	−0.002943	0.326768	0.913682	0.052*	0.48 (3)
H11B	0.226375	0.323685	0.930561	0.052*	0.48 (3)
H11C	0.006433	0.313510	0.916922	0.052*	0.52 (3)
H11D	0.237024	0.339671	0.929080	0.052*	0.52 (3)
C12A	0.129 (7)	0.563 (3)	0.899 (7)	0.041 (9)	0.48 (3)
C12B	0.101 (7)	0.562 (3)	0.895 (7)	0.045 (9)	0.52 (3)
C13A	−0.028 (4)	0.667 (3)	0.881 (3)	0.048 (11)	0.48 (3)
C13B	0.242 (4)	0.681 (4)	0.905 (3)	0.044 (9)	0.52 (3)
C14A	−0.027 (6)	0.838 (4)	0.887 (3)	0.051 (10)	0.48 (3)
H14A	−0.141486	0.903603	0.878526	0.061*	0.48 (3)
C14B	0.201 (5)	0.849 (4)	0.913 (3)	0.053 (8)	0.52 (3)
H14B	0.298101	0.922374	0.927666	0.064*	0.52 (3)
C15A	0.145 (5)	0.910 (4)	0.906 (3)	0.055 (11)	0.48 (3)
H15A	0.156351	1.028798	0.905431	0.066*	0.48 (3)
C15B	0.015 (5)	0.905 (4)	0.898 (3)	0.051 (8)	0.52 (3)
H15B	−0.013716	1.020749	0.900113	0.061*	0.52 (3)
C16A	0.302 (6)	0.808 (4)	0.925 (3)	0.061 (11)	0.48 (3)
H16A	0.417329	0.858294	0.940689	0.073*	0.48 (3)
C16B	−0.131 (5)	0.798 (3)	0.880 (2)	0.049 (8)	0.52 (3)
H16B	−0.255576	0.837253	0.866029	0.059*	0.52 (3)
C17A	0.296 (6)	0.638 (4)	0.922 (3)	0.046 (9)	0.48 (3)
H17A	0.406788	0.571999	0.934537	0.056*	0.48 (3)
C17B	−0.085 (6)	0.631 (4)	0.884 (3)	0.044 (8)	0.52 (3)
H17B	−0.189861	0.554327	0.879354	0.053*	0.52 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br6	0.0318 (8)	0.0514 (12)	0.0740 (14)	0.0068 (8)	−0.0112 (8)	0.0025 (10)
S10	0.049 (2)	0.046 (3)	0.066 (3)	0.007 (2)	−0.016 (2)	−0.006 (2)
S11	0.046 (2)	0.042 (3)	0.059 (3)	0.0194 (19)	−0.006 (2)	−0.005 (2)
F13A	0.041 (11)	0.043 (12)	0.11 (2)	−0.002 (8)	−0.026 (11)	0.003 (12)
F13B	0.053 (11)	0.070 (14)	0.084 (16)	0.013 (9)	−0.026 (11)	−0.037 (12)
O2	0.035 (5)	0.039 (7)	0.053 (7)	0.012 (5)	−0.004 (5)	−0.012 (6)
N1	0.029 (6)	0.027 (7)	0.057 (9)	0.003 (5)	−0.003 (6)	−0.006 (6)
N3	0.038 (7)	0.025 (7)	0.056 (9)	0.003 (6)	−0.004 (6)	−0.008 (7)
N4	0.030 (6)	0.040 (8)	0.047 (8)	0.009 (6)	0.001 (6)	−0.009 (7)
C2	0.023 (7)	0.029 (9)	0.077 (14)	0.000 (6)	0.001 (8)	−0.002 (9)
C3	0.029 (7)	0.026 (8)	0.061 (11)	0.006 (6)	−0.002 (7)	−0.020 (8)
C4	0.031 (7)	0.036 (9)	0.050 (10)	−0.006 (7)	−0.002 (7)	0.003 (8)
C5	0.038 (8)	0.034 (9)	0.058 (11)	0.008 (7)	−0.001 (8)	−0.004 (8)
C6	0.019 (7)	0.037 (10)	0.096 (15)	0.013 (6)	−0.007 (8)	0.005 (10)
C7	0.031 (8)	0.040 (10)	0.056 (11)	−0.013 (7)	−0.014 (7)	0.008 (8)
C8	0.034 (8)	0.034 (9)	0.063 (12)	0.008 (7)	−0.004 (8)	−0.011 (9)
C9	0.032 (8)	0.045 (10)	0.053 (11)	−0.002 (7)	−0.008 (7)	−0.002 (9)
C10	0.039 (9)	0.025 (9)	0.081 (14)	0.010 (7)	−0.004 (9)	0.004 (9)
C11	0.048 (9)	0.031 (9)	0.049 (10)	0.001 (7)	0.002 (8)	−0.008 (8)
C12A	0.032 (14)	0.040 (14)	0.05 (2)	0.009 (10)	0.004 (14)	−0.001 (15)
C12B	0.039 (12)	0.042 (12)	0.05 (2)	0.002 (9)	−0.004 (13)	−0.003 (14)
C13A	0.036 (14)	0.032 (12)	0.08 (3)	0.005 (9)	−0.009 (15)	−0.007 (14)
C13B	0.039 (11)	0.044 (11)	0.05 (2)	−0.003 (8)	−0.002 (11)	0.004 (13)
C14A	0.051 (18)	0.034 (12)	0.07 (3)	0.005 (10)	−0.014 (18)	−0.008 (15)
C14B	0.053 (10)	0.049 (10)	0.059 (13)	−0.001 (7)	−0.012 (8)	−0.008 (9)
C15A	0.058 (19)	0.029 (14)	0.08 (3)	−0.003 (11)	−0.022 (17)	0.003 (17)
C15B	0.052 (10)	0.045 (10)	0.053 (12)	0.003 (7)	−0.006 (8)	−0.004 (9)
C16A	0.060 (18)	0.041 (14)	0.08 (3)	−0.002 (13)	−0.026 (19)	0.009 (16)
C16B	0.042 (13)	0.044 (11)	0.06 (2)	0.006 (9)	0.001 (14)	−0.011 (12)
C17A	0.049 (18)	0.038 (13)	0.05 (2)	−0.003 (12)	−0.013 (18)	0.020 (15)
C17B	0.042 (10)	0.043 (10)	0.049 (12)	0.005 (7)	−0.008 (9)	−0.008 (9)

Geometric parameters (Å, º) top

Br6—C6	1.910 (14)	C11—H11B	0.9900
S10—C10	1.644 (19)	C11—H11C	0.9900
S11—C10	1.774 (15)	C11—H11D	0.9900
S11—C11	1.804 (16)	C11—C12A	1.519 (19)
F13A—C13A	1.342 (19)	C11—C12B	1.516 (18)
F13B—C13B	1.339 (18)	C12A—C13A	1.390 (19)
O2—C2	1.246 (19)	C12A—C17A	1.38 (2)
N1—H1	0.8800	C12B—C13B	1.383 (19)
N1—C2	1.34 (2)	C12B—C17B	1.385 (19)
N1—C9	1.421 (19)	C13A—C14A	1.382 (19)
N3—N4	1.353 (18)	C13B—C14B	1.381 (19)
N3—C3	1.28 (2)	C14A—H14A	0.9500
N4—H4	0.8800	C14A—C15A	1.38 (2)
N4—C10	1.34 (2)	C14B—H14B	0.9500
C2—C3	1.517 (19)	C14B—C15B	1.372 (19)
C3—C4	1.45 (2)	C15A—H15A	0.9500
C4—C5	1.39 (2)	C15A—C16A	1.386 (19)
C4—C9	1.41 (2)	C15B—H15B	0.9500
C5—H5	0.9500	C15B—C16B	1.38 (2)
C5—C6	1.36 (3)	C16A—H16A	0.9500
C6—C7	1.38 (2)	C16A—C17A	1.369 (19)
C7—H7	0.9500	C16B—H16B	0.9500
C7—C8	1.39 (2)	C16B—C17B	1.370 (19)
C8—H8	0.9500	C17A—H17A	0.9500
C8—C9	1.36 (2)	C17B—H17B	0.9500
C11—H11A	0.9900

C10—S11—C11	103.1 (9)	C12A—C11—H11A	109.4
C2—N1—H1	124.5	C12A—C11—H11B	109.4
C2—N1—C9	111.0 (13)	C12B—C11—S11	110 (4)
C9—N1—H1	124.5	C12B—C11—H11C	109.7
C3—N3—N4	117.9 (13)	C12B—C11—H11D	109.7
N3—N4—H4	119.6	C13A—C12A—C11	125 (3)
C10—N4—N3	120.7 (12)	C17A—C12A—C11	118 (2)
C10—N4—H4	119.6	C17A—C12A—C13A	117 (2)
O2—C2—N1	128.7 (14)	C13B—C12B—C11	126 (3)
O2—C2—C3	124.4 (16)	C13B—C12B—C17B	113 (2)
N1—C2—C3	106.9 (14)	C17B—C12B—C11	121 (2)
N3—C3—C2	129.1 (16)	F13A—C13A—C12A	115 (2)
N3—C3—C4	124.8 (13)	F13A—C13A—C14A	121 (3)
C4—C3—C2	106.1 (14)	C14A—C13A—C12A	123 (2)
C5—C4—C3	134.1 (15)	F13B—C13B—C12B	118 (3)
C5—C4—C9	119.0 (16)	F13B—C13B—C14B	117 (3)
C9—C4—C3	106.7 (13)	C14B—C13B—C12B	124 (3)
C4—C5—H5	120.9	C13A—C14A—H14A	121.1
C6—C5—C4	118.2 (15)	C15A—C14A—C13A	118 (3)
C6—C5—H5	120.9	C15A—C14A—H14A	121.1
C5—C6—Br6	118.3 (13)	C13B—C14B—H14B	121.1
C5—C6—C7	122.4 (14)	C15B—C14B—C13B	118 (3)
C7—C6—Br6	119.3 (15)	C15B—C14B—H14B	121.1
C6—C7—H7	119.8	C14A—C15A—H15A	120.4
C6—C7—C8	120.3 (17)	C14A—C15A—C16A	119 (3)
C8—C7—H7	119.8	C16A—C15A—H15A	120.4
C7—C8—H8	121.3	C14B—C15B—H15B	119.1
C9—C8—C7	117.4 (16)	C14B—C15B—C16B	122 (3)
C9—C8—H8	121.3	C16B—C15B—H15B	119.1
C4—C9—N1	109.3 (14)	C15A—C16A—H16A	118.9
C8—C9—N1	128.2 (15)	C17A—C16A—C15A	122 (4)
C8—C9—C4	122.4 (15)	C17A—C16A—H16A	118.9
S10—C10—S11	127.5 (12)	C15B—C16B—H16B	121.9
N4—C10—S10	121.5 (11)	C17B—C16B—C15B	116 (3)
N4—C10—S11	110.9 (13)	C17B—C16B—H16B	121.9
S11—C11—H11A	109.4	C12A—C17A—H17A	120.1
S11—C11—H11B	109.4	C16A—C17A—C12A	120 (3)
S11—C11—H11C	109.7	C16A—C17A—H17A	120.1
S11—C11—H11D	109.7	C12B—C17B—H17B	116.9
H11A—C11—H11B	108.0	C16B—C17B—C12B	126 (3)
H11C—C11—H11D	108.2	C16B—C17B—H17B	116.9
C12A—C11—S11	111 (4)

Br6—C6—C7—C8	179.3 (12)	C6—C7—C8—C9	0 (2)
S11—C11—C12A—C13A	82 (9)	C7—C8—C9—N1	−178.7 (15)
S11—C11—C12A—C17A	−95 (7)	C7—C8—C9—C4	−1 (2)
S11—C11—C12B—C13B	−91 (9)	C9—N1—C2—O2	−179.0 (16)
S11—C11—C12B—C17B	88 (8)	C9—N1—C2—C3	0.1 (17)
F13A—C13A—C14A—C15A	180 (4)	C9—C4—C5—C6	−6 (2)
F13B—C13B—C14B—C15B	−179 (4)	C10—S11—C11—C12A	107.9 (17)
O2—C2—C3—N3	−3 (3)	C10—S11—C11—C12B	116.4 (16)
O2—C2—C3—C4	177.5 (15)	C11—S11—C10—S10	5.0 (14)
N1—C2—C3—N3	178.0 (15)	C11—S11—C10—N4	−177.6 (11)
N1—C2—C3—C4	−1.6 (17)	C11—C12A—C13A—F13A	6 (11)
N3—N4—C10—S10	−176.1 (12)	C11—C12A—C13A—C14A	−179 (7)
N3—N4—C10—S11	6.3 (19)	C11—C12A—C17A—C16A	177 (6)
N3—C3—C4—C5	−3 (3)	C11—C12B—C13B—F13B	−5 (11)
N3—C3—C4—C9	−177.2 (16)	C11—C12B—C13B—C14B	−175 (7)
N4—N3—C3—C2	4 (2)	C11—C12B—C17B—C16B	−176 (6)
N4—N3—C3—C4	−176.4 (14)	C12A—C13A—C14A—C15A	5 (9)
C2—N1—C9—C4	1.4 (18)	C12B—C13B—C14B—C15B	−9 (8)
C2—N1—C9—C8	179.6 (17)	C13A—C12A—C17A—C16A	0 (11)
C2—C3—C4—C5	176.7 (18)	C13A—C14A—C15A—C16A	−5 (7)
C2—C3—C4—C9	2.4 (17)	C13B—C12B—C17B—C16B	2 (11)
C3—N3—N4—C10	178.2 (15)	C13B—C14B—C15B—C16B	3 (6)
C3—C4—C5—C6	−179.8 (17)	C14A—C15A—C16A—C17A	3 (7)
C3—C4—C9—N1	−2.4 (18)	C14B—C15B—C16B—C17B	5 (6)
C3—C4—C9—C8	179.3 (15)	C15A—C16A—C17A—C12A	−1 (8)
C4—C5—C6—Br6	−176.1 (12)	C15B—C16B—C17B—C12B	−8 (8)
C4—C5—C6—C7	5 (3)	C17A—C12A—C13A—F13A	−177 (6)
C5—C4—C9—N1	−177.7 (14)	C17A—C12A—C13A—C14A	−2 (11)
C5—C4—C9—C8	4 (3)	C17B—C12B—C13B—F13B	176 (6)
C5—C6—C7—C8	−2 (3)	C17B—C12B—C13B—C14B	6 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2ⁱ	0.88	1.96	2.821 (15)	165
N4—H4···O2	0.88	2.09	2.777 (16)	134
C11—H11D···S10	0.99	2.56	3.221 (14)	124

Symmetry code: (i) −x+2, −y, −z+1.

Acknowledgements

The authors acknowledge Universiti Teknologi MARA for financial support.

References

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Volume 82| Part 1| January 2026| Pages 72-76

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

Different inter­molecular inter­actions in solvated and unsolvated isatin-based di­thio­carbazate imine derivatives

1. Chemical context

2. Structural commentary

3. Supra­molecular features

4. Hirshfeld surface analysis

5. Synthesis and crystallization

6. Refinement

Supporting information

Acknowledgements

References

research communications

Different intermolecular interactions in solvated and unsolvated isatin-based dithiocarbazate imine derivatives

3. Supramolecular features