Crystal structure and Hirshfeld surface analysis of (E)-2-(5-bromo-2-hy­droxy­benzyl­idene)hydrazine­carbo­thio­amide di­methyl sulfoxide monosolvate

Sivajeyanthi, P.; Jeevaraj, M.; Edison, B.; Balasubramani, K.

doi:10.1107/S2056989018000233

research communications

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ISSN: 2056-9890

Volume 74| Part 2| February 2018| Pages 119-123

https://doi.org/10.1107/S2056989018000233

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Crystal structure and Hirshfeld surface analysis of (E)-2-(5-bromo-2-hydroxybenzylidene)hydrazinecarbothioamide dimethyl sulfoxide monosolvate

Palaniyappan Sivajeyanthi,^a Muthaiah Jeevaraj,^a Bellarmin Edison ^a and Kasthuri Balasubramani ^a ^*

^aDepartment of Chemistry, Government Arts College (Autonomous), Thanthonimalai, Karur- 639 005, Tamil Nadu, India
^*Correspondence e-mail: manavaibala@gmail.com

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 8 December 2017; accepted 4 January 2018; online 9 January 2018)

The molecule of the title Schiff base, C₈H₈BrN₃OS·C₂H₆OS, which crystallizes as a dimethyl sulfoxide (DMSO) monosolvate, displays an E configuration with respect to the C=N bond, with a dihedral angle of 14.54 (11)° between the benzene ring and the mean plane of the N—N—C(N)=S unit. In the crystal, molecules are linked by N—H⋯O hydrogen bonds, forming chains propagating along the b-axis direction. Within the chains there are R²₃(11) ring motifs, which are reinforced by C—H⋯O_DMSO hydrogen bonds enclosing secondary R¹₂(6) and R²₃(9) loops. The chains are linked by O—H_hydroxyl⋯S hydrogen bonds, forming layers parallel to (011). Inversion-related layers are linked by short Br⋯Br interactions [3.5585 (5) Å], forming slabs parallel to (011). The intermolecular interactions have been investigated using Hirshfeld surface studies and two-dimensional fingerprint plots. The crystal structure of the unsolvated form of the title compound has been reported previously [Kargar et al. (2010). Acta Cryst. E66, o2999], and its solid-state structure is compared with that of the title solvated form.

Keywords: crystal structure; Schiff base; hydrazinecarbothioamide; hydrogen bonding; Hirshfeld surface analysis.

CCDC reference: 1587285

1. Chemical context

Schiff bases are nitrogen-containing active organic compounds that play a vital role in enzymatic reactions involving interaction of an enzyme with a carbonyl group of a substrate (Tidwell, 2008 ). Thiosemicarbazones exhibit interesting pharmacological properties and biological activities. Thiosemicarbazone derivatives have gained special importance because of their role in drug development; for example they are used as antiviral, antitubercular, anti-bacterial infection, analgesic and antiallergic agents and in the treatment of central nervous system disorders and as sodium channel blockers and show antitumorous activity. The pharmacological versatility of semicarbazones, thiosemicarbazones and their metal complexes have been reviewed by Beraldo & Gambino (2004 ).

Thiosemicarbazones are formed by the condensation of thiosemicarbazides with aldehydes or ketones (Sriram et al., 2006 ; Scovill et al., 1982 ). They are also used in most branches of chemistry, for example, as dyes, photographic films, plastics and in the textile industry. These types of compounds also act as ligands for a variety of transition metals, often as high propensity multi-dentate chelating agents (Al-Karawi et al., 2009 ). Herein, we report on the crystal structure of the title thiosemicarbazone that crystallizes as a dimethyl sulfoxide monosolvate. The crystal structure of the unsolvated form of the title Schiff base has been reported previously (Kargar et al., 2010a ), and its solid-state structure is compared with that of the title solvated form.

2. Structural commentary

The molecular structure of the title compound is shown in Fig. 1. The thiosemicarbazone molecule has an E configurationabout the C7=N1 bond. The molecule is twisted with a dihedral angle of 14.54 (11)° between the benzene ring and the mean plane of the N1/N2/C8/N3/S1 unit. The C8—-S1 bond distance of 1.698 (2) Å is close to that expected for a C=S bond (Cambridge Structural Database; Groom et al., 2016 ). This confirms the existence of the compound in the thioamido form in the solid state, similar to the situation observed in some related compounds, viz. (E)-2-(2,4-dihydroxybenzylidene)thiosemicarbazone and (E)-2-[(1H-indol-3-yl)methylene]thiosemicarbazone (Yıldız et al., 2009 ). The C1—N7 bond distance is 1.278 (3) Å, close to that of a C=N double bond, confirming the azomethine bond formation, again similar to the situation observed in related compounds, viz. (E)-1-[4-(dimethylamino)benzylidene]thiosemicarbazide (Sun et al. 2009 ) and 2-[(2-hydroxynaphthalen-1-yl)methylene]hydrazinecarbothioamide (Sivajeyanthi et al. 2017 ).

Figure 1
A view of the molecular structure of the title compound, with the atom labelling. Displacement ellipsoids are drawn at the 50% probability level.

In the molecular structure of the unsolvated form of the title compound (Kargar et al., 2010a), an intramolecular O—H⋯N hydrogen bond is present enclosing an S(6) ring motif. Comparing the two molecules, as shown in the structural overlay of Fig. 2, it can be seen that the benzene ring of the title solvated compound is rotated by ca. 180° with respect to that in the unsolvated form of the molecule. The bond lengths and bond angles of the two molecules are similar. In the title compound, the dihedral angle between the benzene ring and the mean plane of the N—N—C(N)=S hydrazinecarbothioamide unit is 14.54 (11)° compared to ca 7.05° in the unsolvated phase. Kargar et al. (2010b ) have also reported the crystal structure of the unsolvated chloro-substituted analogue. This molecule has the same conformation as the unsolvated bromo-substituted analogue (Kargar et al., 2010a), but in contrast it crystallizes in the monoclinic space group P2₁/c, while the unsolvated bromo compound crystallizes in the chiral orthorhombic space group P2₁2₁2₁.

Figure 2
The structural overlay of the title molecule with that of the unsolvated form (CEDPAE; Kargar et al., 2010a

), showing the presence of the intramolecular O—H⋯N hydrogen bond (dashed line) in CEDPAE.

3. Supramolecular features

In the crystal, the Schiff base hydrazone is hydrogen bonded (see Table 1) to the dimethyl sulfoxide solvate molecule, forming a chain propagating along the b-axis direction, as shown in Fig. 3. Within the chains there are R₃²(11) ring motifs, which are reinforced by C—H⋯O_DMSO hydrogen bonds enclosing secondary R₂¹(6) and R₃²(9) ring motifs (Table 1). The R₃²(11) ring motif is formed by N2—H2⋯O2ⁱⁱ, N3—H3A⋯O1ⁱⁱⁱ and N3—H3B⋯O2^iv hydrogen-bonding interactions, and the R₂¹(6) ring motif is formed via C7—H7⋯O2ⁱⁱ and N2—H2⋯O2ⁱⁱ hydrogen-bonding interactions. Hence, atom O2 of the dimethyl sulfoxide acts as a trifurcated acceptor (Fig. 3, Table 1). The chains are linked by O1—H1⋯Sⁱ hydrogen bonds, forming layers parallel to plane (011); see Fig. 4 and Table 1. Inversion-related layers are linked by short Br⋯Br(−x, −y + 1, −z + 1) interactions of 3.5585 (5) Å, forming slabs parallel to (011), as illustrated in Fig. 5.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯S1ⁱ	0.82	2.40	3.1655 (17)	157
N2—H2⋯O2ⁱⁱ	0.86	2.10	2.897 (2)	155
N3—H3A⋯O1ⁱⁱⁱ	0.86	2.37	3.048 (2)	136
N3—H3B⋯O2^iv	0.86	2.11	2.930 (3)	160
C7—H7⋯O2ⁱⁱ	0.93	2.53	3.315 (3)	142
Symmetry codes: (i) x-1, y+1, z; (ii) x+1, y, z; (iii) x, y-1, z; (iv) x+1, y-1, z.

Figure 3
A partial view, almost normal to the (011) plane, of the hydrogen-bonded chain (dashed lines; see Table 1

) propagating along the [010] direction. In this and subsequent figures, only the H atoms involved in hydrogen bonding have been included.

Figure 4
A view, almost normal to (011), of the hydrogen-bonded sheets parallel to (011). The hydrogen bonds are shown as dashed lines and details are given in Table 1

Figure 5
A view along the b axis of the crystal packing of the title compound. The hydrogen bonds (see Table 1

) and the short Br⋯Br interactions are shown as dashed lines.

4. Hirshfeld surface analysis

The three-dimensional d_norm surface is a useful tool to analyse and visualize the inter-molecular interactions. d_norm takes negative or positive values depending on whether the intermolecular contact is shorter or longer than the van der Waals radii (Spackman & Jayatilaka, 2009 ; McKinnon et al., 2007 ). The three-dimensional d_norm surface of the title compound is shown in Fig. 6. The red points, which represent closer contacts and negative d_norm values on the surface, correspond to the N—H⋯O, O—H⋯S and C—H⋯O interactions. The percentage contributions of various contacts to the total Hirshfeld surface are as follows: H⋯H (32.9%), S⋯H/H⋯S (18.8%), O⋯H/H⋯O (13.3%), Br⋯H/H⋯Br (11.6), C⋯H/H⋯C (8.8%), N⋯H/H⋯N (3.4%), C⋯C (2.8%), Br⋯N/N⋯Br (2.0%), Br⋯Br (1.5%), Br⋯O/O⋯Br (1.1%), Br⋯C/C⋯Br (1.1%), C⋯N/N⋯C (1.0%), S⋯S (0.7%), S⋯N/N⋯S (0.6%) and S⋯C/C⋯S (0.2%), as shown in the two-dimensional fingerprint plots in Fig. 7.

Figure 6
Hirshfeld surfaces mapped over d_norm for the title compound.

Figure 7
Two-dimensional fingerprint plots of the crystal and the relative contributions of the atom pairs to the Hirshfeld surface.

5. Database survey

A search of the Cambridge Structural Database (Version 5.38, update May 2017; Groom et al., 2016) for the 2-hydroxybenzaldehyde thiosemicarbazone skeleton (or salicylaldehyde thiosemicarbazone) yielded 25 hits. These include the unsolvated bromo- and chloro-substituted analogues of the title compound mentioned above, viz. 5-bromo-2-hydroxybenzaldehyde thiosemicarbazone (CEDPAE; Kargar et al., 2010a) and 2-(5-chloro-2-hydroxybenzylidene)hydrazinecarbothioamide (VACGUD; Kargar et al., 2010b). The crystal structure of salicylaldehyde thiosemicarbazone has also been reported at 295 K (GEXKID; Chattopadhyay et al., 1988 ) and at 100 K (GEXKID01; Novaković et al., 2007 ). The crystal structures of various hydrated forms of salicylaldehydethiosemicarbazone [(E)-2-(2-hydroxybenzylidene)hydrazinecarbothioamide hydrate] have been reported at 100 K (UJIPIN) and 203 K (UJIPOT and UJIPUZ) by Monfared et al. (2010 ). In the majority of the hits, the 2-hydroxy group forms an intramolecular O—H⋯N hydrogen bond, as shown for CEDPAE in Fig. 2. Consequently, in the compounds mentioned above, the dihedral angle between the benzene ring and the mean plane of the N—N—C(N)=S hydrazinecarbothioamide unit is relatively small, varying from ca 5.62 to 10.10°, compared to 14.54 (11)° in the title compound.

6. Synthesis and crystallization

The title compound was synthesized by refluxing for 8 h a 1:1 molar ratio of a hot ethanolic solution (20 ml) of thiosemicarbazide (0.091 mg, Aldrich) and a hot ethanolic solution of 5-bromosalicylaldehyde (0.196 mg, Aldrich). The solution was then cooled and kept at room temperature. The precipitate that formed was filtered off and recrystallized from dimethyl sulfoxide. Colourless block-like crystals, suitable for the X-ray analysis, were obtained in a few days on slow evaporation of the solvent.

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The hydrogen atoms were fixed geometrically (O—H = 0.82, N—H = 0.86, C—H = 0.93–0.96 Å) and allowed to ride on their parent atoms with U_iso(H) = 1.5U_eq(O-hydroxyl, C-methyl) and 1.2U_eq(N,C) for other H atoms.

Table 2
Experimental details

Crystal data
Chemical formula	C₈H₈BrN₃OS·C₂H₆OS
M_r	352.26
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	296
a, b, c (Å)	6.5411 (4), 7.3889 (6), 15.0662 (12)
α, β, γ (°)	78.772 (3), 86.872 (3), 87.376 (3)
V (Å³)	712.71 (9)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	3.17
Crystal size (mm)	0.30 × 0.20 × 0.20

Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2004 )
T_min, T_max	0.449, 0.569
No. of measured, independent and observed [I > 2σ(I)] reflections	6030, 3299, 2661
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.666

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.106, 0.79
No. of reflections	3299
No. of parameters	165
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.34
Computer programs: APEX2, SAINT and XPREP (Bruker, 2004), SIR92 (Altomare et al., 1993 ), SHELXL2017/1 (Sheldrick, 2015 ), PLATON (Spek 2009 ), Mercury (Macrae et al., 2008 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1587285

Crystal structure: contains datablocks global, I, 1. DOI: https://doi.org/10.1107/S2056989018000233/su5414sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989018000233/su5414Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989018000233/su5414Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 and SAINT (Bruker, 2004); data reduction: SAINT and XPREP (Bruker, 2004); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL2017/1 (Sheldrick, 2015); molecular graphics: PLATON (Spek 2009) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2017/1 (Sheldrick, 2015), PLATON (Spek 2009) and publCIF (Westrip, 2010).

(E)-2-(5-Bromo-2-hydroxybenzylidene)hydrazinecarbothioamide dimethyl sulfoxide monosolvate top

Crystal data top

C₈H₈BrN₃OS·C₂H₆OS	Z = 2
M_r = 352.26	F(000) = 356
Triclinic, P1	D_x = 1.637 Mg m⁻³
a = 6.5411 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.3889 (6) Å	Cell parameters from 2934 reflections
c = 15.0662 (12) Å	θ = 5.5–55.9°
α = 78.772 (3)°	µ = 3.17 mm⁻¹
β = 86.872 (3)°	T = 296 K
γ = 87.376 (3)°	Block, colourless
V = 712.71 (9) Å³	0.30 × 0.20 × 0.20 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	2661 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.018
ω and φ scan	θ_max = 28.3°, θ_min = 3.4°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −8→6
T_min = 0.449, T_max = 0.569	k = −9→9
6030 measured reflections	l = −17→19
3299 independent reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.106	H-atom parameters constrained
S = 0.79	w = 1/[σ²(F_o²) + (0.1P)²] where P = (F_o² + 2F_c²)/3
3299 reflections	(Δ/σ)_max = 0.001
165 parameters	Δρ_max = 0.27 e Å⁻³
0 restraints	Δρ_min = −0.34 e Å⁻³

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
Br1	0.20262 (4)	0.63938 (4)	0.51812 (2)	0.0512 (1)
S1	1.36501 (8)	0.37819 (8)	0.83370 (4)	0.0359 (2)
S2	0.24643 (10)	0.89596 (8)	0.93448 (4)	0.0421 (2)
O1	0.6312 (2)	1.1359 (2)	0.71559 (12)	0.0382 (5)
N1	0.8705 (3)	0.6223 (3)	0.72520 (13)	0.0300 (5)
N2	1.0553 (3)	0.5884 (2)	0.76701 (13)	0.0305 (5)
N3	1.0303 (3)	0.2820 (3)	0.76421 (15)	0.0389 (6)
C1	0.6169 (3)	0.8495 (3)	0.66806 (14)	0.0267 (6)
O2	0.1487 (3)	0.9012 (2)	0.84564 (14)	0.0512 (6)
C2	0.5325 (3)	1.0274 (3)	0.66902 (15)	0.0287 (6)
C3	0.3559 (3)	1.0884 (3)	0.62389 (16)	0.0346 (7)
C4	0.2574 (4)	0.9727 (3)	0.57957 (17)	0.0385 (7)
C5	0.3383 (3)	0.7961 (3)	0.58003 (15)	0.0325 (6)
C6	0.5159 (3)	0.7339 (3)	0.62232 (15)	0.0309 (6)
C7	0.8054 (3)	0.7906 (3)	0.71317 (15)	0.0300 (6)
C8	1.1348 (3)	0.4159 (3)	0.78513 (14)	0.0274 (6)
C9	0.5074 (4)	0.8287 (4)	0.9172 (2)	0.0493 (9)
C10	0.1671 (5)	0.6884 (4)	1.0067 (2)	0.0578 (10)
H1	0.54961	1.21258	0.73121	0.0570*
H2	1.11849	0.67747	0.78122	0.0360*
H3	0.30338	1.20764	0.62341	0.0410*
H3A	0.91417	0.30700	0.73958	0.0470*
H3B	1.07844	0.17008	0.77525	0.0470*
H4	0.13811	1.01311	0.54976	0.0460*
H6	0.56908	0.61567	0.62069	0.0370*
H7	0.88039	0.87680	0.73376	0.0360*
H9A	0.51533	0.72024	0.89072	0.0740*
H9B	0.57191	0.80243	0.97422	0.0740*
H9C	0.57610	0.92693	0.87721	0.0740*
H10A	0.02145	0.69522	1.01827	0.0870*
H10B	0.23443	0.67244	1.06288	0.0870*
H10C	0.20263	0.58551	0.97788	0.0870*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0489 (2)	0.0567 (2)	0.0538 (2)	−0.0095 (1)	−0.0172 (1)	−0.0193 (1)
S1	0.0323 (3)	0.0315 (3)	0.0469 (4)	0.0088 (2)	−0.0164 (2)	−0.0132 (2)
S2	0.0571 (4)	0.0295 (3)	0.0432 (4)	−0.0032 (3)	−0.0125 (3)	−0.0124 (3)
O1	0.0344 (8)	0.0356 (8)	0.0498 (10)	0.0071 (7)	−0.0122 (7)	−0.0203 (7)
N1	0.0244 (8)	0.0301 (9)	0.0365 (10)	0.0043 (7)	−0.0081 (7)	−0.0086 (7)
N2	0.0273 (9)	0.0241 (8)	0.0417 (11)	0.0023 (7)	−0.0132 (7)	−0.0082 (7)
N3	0.0374 (10)	0.0260 (9)	0.0566 (14)	0.0019 (8)	−0.0182 (9)	−0.0123 (9)
C1	0.0254 (10)	0.0273 (10)	0.0267 (10)	0.0031 (8)	−0.0038 (7)	−0.0040 (8)
O2	0.0724 (13)	0.0296 (8)	0.0554 (12)	0.0027 (8)	−0.0339 (10)	−0.0099 (8)
C2	0.0294 (10)	0.0280 (10)	0.0288 (11)	0.0017 (8)	−0.0032 (8)	−0.0057 (8)
C3	0.0341 (11)	0.0302 (11)	0.0390 (13)	0.0091 (9)	−0.0089 (9)	−0.0059 (9)
C4	0.0303 (11)	0.0460 (13)	0.0373 (13)	0.0063 (10)	−0.0115 (9)	−0.0024 (10)
C5	0.0314 (10)	0.0377 (11)	0.0289 (11)	−0.0033 (9)	−0.0054 (8)	−0.0063 (9)
C6	0.0328 (11)	0.0306 (10)	0.0297 (11)	0.0012 (8)	−0.0047 (8)	−0.0063 (9)
C7	0.0306 (11)	0.0290 (10)	0.0314 (11)	0.0008 (8)	−0.0039 (8)	−0.0084 (8)
C8	0.0283 (10)	0.0249 (10)	0.0301 (11)	0.0030 (8)	−0.0031 (8)	−0.0083 (8)
C9	0.0524 (16)	0.0504 (15)	0.0462 (16)	−0.0097 (12)	−0.0098 (12)	−0.0079 (12)
C10	0.0619 (18)	0.0567 (17)	0.0521 (18)	−0.0143 (14)	0.0035 (13)	−0.0025 (14)

Geometric parameters (Å, º) top

Br1—C5	1.898 (2)	N3—H3B	0.8600
S1—C8	1.698 (2)	C3—C4	1.383 (3)
S2—C10	1.780 (3)	N3—H3A	0.8600
S2—O2	1.508 (2)	C4—C5	1.384 (3)
S2—C9	1.776 (3)	C5—C6	1.373 (3)
O1—C2	1.367 (3)	C3—H3	0.9300
N1—N2	1.384 (3)	C4—H4	0.9300
N1—C7	1.278 (3)	C6—H6	0.9300
O1—H1	0.8200	C7—H7	0.9300
N2—C8	1.338 (3)	C9—H9A	0.9600
N3—C8	1.324 (3)	C9—H9B	0.9600
C1—C7	1.449 (3)	C9—H9C	0.9600
C1—C2	1.405 (3)	C10—H10A	0.9600
C1—C6	1.404 (3)	C10—H10B	0.9600
C2—C3	1.385 (3)	C10—H10C	0.9600
N2—H2	0.8600

C9—S2—C10	97.89 (14)	S1—C8—N2	118.69 (16)
O2—S2—C9	105.88 (12)	N2—C8—N3	118.41 (19)
O2—S2—C10	105.84 (12)	S1—C8—N3	122.90 (18)
N2—N1—C7	114.45 (19)	C2—C3—H3	120.00
C2—O1—H1	110.00	C4—C3—H3	120.00
N1—N2—C8	119.44 (18)	C5—C4—H4	120.00
C2—C1—C7	119.58 (19)	C3—C4—H4	120.00
C2—C1—C6	118.62 (19)	C1—C6—H6	120.00
C6—C1—C7	121.8 (2)	C5—C6—H6	120.00
O1—C2—C3	122.0 (2)	N1—C7—H7	119.00
C1—C2—C3	120.5 (2)	C1—C7—H7	119.00
N1—N2—H2	120.00	S2—C9—H9A	109.00
C8—N2—H2	120.00	S2—C9—H9B	110.00
O1—C2—C1	117.53 (18)	S2—C9—H9C	109.00
H3A—N3—H3B	120.00	H9A—C9—H9B	109.00
C2—C3—C4	120.3 (2)	H9A—C9—H9C	109.00
C8—N3—H3B	120.00	H9B—C9—H9C	109.00
C8—N3—H3A	120.00	S2—C10—H10A	109.00
C3—C4—C5	119.3 (2)	S2—C10—H10B	109.00
Br1—C5—C6	119.57 (17)	S2—C10—H10C	109.00
Br1—C5—C4	118.85 (17)	H10A—C10—H10B	109.00
C4—C5—C6	121.6 (2)	H10A—C10—H10C	109.00
C1—C6—C5	119.8 (2)	H10B—C10—H10C	109.00
N1—C7—C1	121.2 (2)

C7—N1—N2—C8	178.2 (2)	C2—C1—C7—N1	169.6 (2)
N2—N1—C7—C1	178.29 (19)	C6—C1—C7—N1	−10.9 (3)
N1—N2—C8—S1	178.26 (15)	O1—C2—C3—C4	−178.3 (2)
N1—N2—C8—N3	−1.7 (3)	C1—C2—C3—C4	1.9 (3)
C6—C1—C2—O1	178.65 (19)	C2—C3—C4—C5	−0.7 (4)
C6—C1—C2—C3	−1.5 (3)	C3—C4—C5—Br1	−179.52 (18)
C7—C1—C2—O1	−1.9 (3)	C3—C4—C5—C6	−1.0 (4)
C7—C1—C2—C3	178.0 (2)	Br1—C5—C6—C1	179.90 (16)
C2—C1—C6—C5	−0.1 (3)	C4—C5—C6—C1	1.4 (3)
C7—C1—C6—C5	−179.6 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···S1ⁱ	0.82	2.40	3.1655 (17)	157
N2—H2···O2ⁱⁱ	0.86	2.10	2.897 (2)	155
N3—H3A···O1ⁱⁱⁱ	0.86	2.37	3.048 (2)	136
N3—H3A···N1	0.86	2.30	2.648 (3)	104
N3—H3B···O2^iv	0.86	2.11	2.930 (3)	160
C7—H7···O1	0.93	2.44	2.752 (3)	100
C7—H7···O2ⁱⁱ	0.93	2.53	3.315 (3)	142

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

Funding information

KB and PS thank the Department of Science and Technology (DST–SERB), grant No. SB/FT/CS-058/2013, New Delhi, India, for financial support.

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