Di­bromido­bis­(3-bromo­benzyl-κC)(4,7-diphenyl-1,10-phenanthroline-κ2N,N′)tin(IV)

Bhaskar, C.; Chandrasekar, S.; Mohandas, T.; Butcher, R.J.

doi:10.1107/S2414314619003365

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 4| Part 3| March 2019| x190336

https://doi.org/10.1107/S2414314619003365

Open

access

Dibromidobis(3-bromobenzyl-κC)(4,7-diphenyl-1,10-phenanthroline-κ²N,N′)tin(IV)

C. Bhaskar,^a ^* S. Chandrasekar,^b T. Mohandas ^c and Ray J. Butcher ^d

^aDepartment of Chemistry, K. Ramakrishnan College of Engineering, Samayapuram, Tiruchirappalli 621 112, Tamilnadu, India, ^bArignar Anna Government Arts College, Musiri, Tiruchirappalli 621 211, Tamilnadu, India, ^cDepartment of Physics, K. Ramakrishnan College of Engineering, Samayapuram, Tiruchirappalli 621 112, Tamilnadu, India, and ^dDepartment of Chemistry, Howard University, 525 College Street NW, Washington, DC 20059, USA
^*Correspondence e-mail: baskarvsp@gmail.com

Edited by E. R. T. Tiekink, Sunway University, Malaysia (Received 5 March 2019; accepted 8 March 2019; online 15 March 2019)

In the title compound, [SnBr₂(C₇H₆Br)₂(C₂₄H₁₆N₂)], the Sn atom is coordinated to a 4,7-diphenyl-1,10-phenanthroline, two 3-bromobenzyl and two bromide ligands, leading to a six-coordinate C₂Br₂N₂ donor set. The bromobenzyl ligands are trans to each other, while the Br anions are in a cis arrangement. One of the two 3-bromobenzyl ligands is disordered over two similar conformations, with occupancies of 0.7078 (18) and 0.2922 (18). In the crystal, molecules are linked into centrosymmetric dimers by Br⋯Br halogen bonds [3.5972 (12) Å], which are linked into a supramolecular layer in the ac plane by weak intermolecular C—H⋯Br interactions.

Keywords: crystal structure; organotin compound; 4,7-diphenyl-1,10-phenanthroline; 3-bromobenzyl.

CCDC reference: 1901922

Structure description

Organotin compounds are mostly known for their biocidal effects and have been used for multiple applications, being utilized as wood preservatives, acaricides, disinfectants, bactericides, fungicides, molluscicides, PVC stabilizers and marine antifouling products (Snoeij et al., 1987 ). In addition, much recent interest has focused on the potential applications of organotin compounds for their cytotoxicity and antitumour activities against various cell lines (Yadav et al., 2015 ; Varela-Ramirez et al., 2011 ). Metal complexes of 1,10-phenanthroline have also been found to show excellent biological activity, playing several roles, displaying both antimicrobial and antifungal activities (McCann et al., 2012a ) and anticancer potential (McCann et al., 2012b ). Several studies show that this ligand and a number of its complexes are effective against various strains of microorganisms (Josa Parada et al., 2017 ). Both diorgano- and triorganotin compounds have been confirmed to show cytotoxicity against various cancer cell lines (Yadav et al., 2015).

In light of these biological activities for both organotin compounds and metal complexes of phenanthroline derivatives, and the lack of such examples in the literature where both Sn and 4,7-diphenyl-1,10-phenanthroline were combined [the Cambridge Structural Database (CSD; Groom et al., 2016 ) gave two hits: (4,7-diphenyl-1,10-phenanthroline)dimethylbis(isothiocyanato)tin(IV) (Najafi et al., 2011 ) and di-n-butyl-dichlorido(4,7-diphenylphenanthroline)tin(IV) (Hu et al., 1989 )], it was decided to synthesize and structurally characterize the title compound, (I). Its biological activity will be reported elsewhere.

In (I), the Sn atom is coordinated by a 4,7-diphenyl-1,10-phenanthroline, two 3-bromobenzyl and two bromide ligands, leading to a six-coordinate C₂Br₂N₂ donor set (see Fig. 1). The bromobenzyl ligands are trans to each other, while the Br anions are in a cis arrangement. The geometry about the Sn atom is distorted octahedral due in part to the small bite distance of the 4,7-diphenyl-1,10-phenanthroline ligand. The cis angles range from 70.32 (11) to 94.2 (2)° and the trans angles range from 174.0 (3) to 161.60 (8)° (Table 1). One of the interesting aspects of the structure is the conformation adopted by the 3-bromobenzyl ligands. As indicated above, these are arranged in a trans fashion in the Sn coordination sphere. However, they are not arranged in the normal way to minimize steric repulsion, but rather are both tilted away from the SnN₂Br₂ plane, with a dihedral angle of 40.1 (2)° between them. The reason for this appears to be so that they can form intramolecular π–π interactions with the central phenanthroline moiety [Cg⋯Cg = 3.584 (2) and 3.694 (3) Å]. The 3-bromobenzyl rings and the phenanthroline ring are not mutually parallel, but make dihedral angles of 24.4 (2) and 21.7 (3)°. These values are about the closest these rings can approach each other while maintaining a tetrahedral (sp³) angle at the benzyl C atoms.

Table 1
Selected geometric parameters (Å, °)

Sn1—C25	2.211 (4)	Sn1—N2	2.353 (3)
Sn1—C32	2.218 (13)	Sn1—Br2	2.6355 (6)
Sn1—N1	2.320 (3)	Sn1—Br1	2.7059 (5)

C25—Sn1—C32	174.0 (3)	N1—Sn1—Br2	91.31 (8)
C25—Sn1—N1	91.65 (13)	N2—Sn1—Br2	161.60 (8)
C32—Sn1—N1	89.8 (2)	C25—Sn1—Br1	88.35 (10)
C25—Sn1—N2	88.03 (15)	C32—Sn1—Br1	88.7 (2)
C32—Sn1—N2	87.0 (2)	N1—Sn1—Br1	164.19 (8)
N1—Sn1—N2	70.32 (11)	N2—Sn1—Br1	93.89 (8)
C25—Sn1—Br2	91.60 (13)	Br2—Sn1—Br1	104.49 (2)
C32—Sn1—Br2	94.2 (2)

Figure 1
The molecular structure of (I), showing the folding of the 3-bromobenzyl rings in order to form π–π interactions with the 4,7-diphenyl-1,10-phenanthroline ligand. Displacement ellipsoids are drawn at the 30% probability level.

As far as comparisons with related structures are concerned, there is only one other structure which bears some resemblance to (I), namely dibromobis(pentafluoroethyl)(1,10-phenanthroline)tin(IV), (II) (Klosener et al., 2017 ). The phenanthroline bite angle for (II) is 72.40 (9)°, which is slightly wider that the value found for (I) of 70.32 (11)°

In the crystal, molecules are linked into centrosymmetric dimers (Fig. 2) by Br⋯Br halogen bonds [Br3⋯Br4 = 3.5972 (12) Å] and the dimers are linked into a supramolecular layer in the ac plane by weak intermolecular C—H⋯Br interactions (Table 2 and Fig. 3).

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1A⋯Br2	0.93	2.78	3.477 (4)	133
C12—H12A⋯Br1	0.93	2.97	3.656 (5)	132
C36—H36A⋯Br2ⁱ	0.93	3.00	3.883 (3)	159
Symmetry code: (i) x+1, y, z.

Figure 2
Diagram of (I) (major component only), showing the formation of R₂²(22) rings due to the formation of intermolecular Br⋯Br interactions (shown as dashed lines).

Figure 3
Packing diagram for (I), showing both the formation of R₂²(22) rings due to the formation of intermolecular Br⋯Br interactions, as well as the C—H⋯Br interactions linking these dimers into a two-dimensional layer (all interactions are shown as dashed lines).

Synthesis and crystallization

3-Bromobenzyl bromide, tin powder and 4,7-diphenyl-1,10-phenanthroline were purchased from Sigma–Aldrich and used without further purification. All solvents were dried according to standard procedures.

Synthesis of bis (3-bromobenzyl) tin dibromide. Tin powder (2 g, 16.8 mmol) and 3-bromobenzyl bromide (4.21 g, 16.8 mmol) in toluene (60 ml) were refluxed at 110 °C for 3 h. The crystallized products were extracted under vacuum, purified with chloroform and used for the synthesis of the complex.

Synthesis of dibromidobis(3-bromobenzyl)(4,7-diphenyl-1,10-phenanthroline)tin(IV), (I). Bis(3-bromobenzyl)tin dibromide (0.46 g, 0.752 mmol) in methanol (50 ml) was reacted with 4,7-diphenyl-1,10-phenanthroline (0.25 g, 0.752 mmol) at room temperature for 24 h. The yellow product was recrystallized by the vapour-diffusion method using chloroform as solvent and petroleum ether as antisolvent.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. One of the two 3-bromobenzyl ligands is disordered over two similar conformations, with occupancies of 0.7078 (18) and 0.2929 (18), and were constrained to have similar geometries using the SAME command in SHELXL2018 (Sheldrick, 2015b ). H atoms were idealized using a riding model, with U_iso(H) = 1.2U_eq(C). The maximum and minimum residual electron-density peaks of 1.14 and −1.47 Å⁻³, respectively, were located 0.71 and 0.77 Å from the C12 and Br3 atoms.

Table 3
Experimental details

Crystal data
Chemical formula	[SnBr₂(C₇H₆Br)₂(C₂₄H₁₆N₂)]
M_r	950.95
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	296
a, b, c (Å)	10.1328 (3), 11.2430 (3), 16.7726 (4)
α, β, γ (°)	83.216 (2), 72.639 (2), 71.787 (1)
V (Å³)	1731.72 (8)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	5.38
Crystal size (mm)	0.10 × 0.10 × 0.05

Data collection
Diffractometer	Bruker Kappa APEX3 CMOS
Absorption correction	Multi-scan (SADABS; Bruker, 2016 )
T_min, T_max	0.588, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	77114, 10637, 6920
R_int	0.056
(sin θ/λ)_max (Å⁻¹)	0.719

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.123, 1.04
No. of reflections	10637
No. of parameters	444
No. of restraints	342
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.14, −1.47
Computer programs: APEX3 (Bruker, 2016), SAINT (Bruker, 2016), XPREP (Bruker, 2016), SHELXT2014 (Sheldrick, 2015a ), SHELXL2018 (Sheldrick, 2015b) and ORTEP-3 (Farrugia, 2012 ).

Structural data

CCDC reference: 1901922

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314619003365/tk4055sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314619003365/tk4055Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2016); cell refinement: APEX3/SAINT (Bruker, 2016); data reduction: SAINT/XPREP (Bruker, 2016); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: ORTEP-3 (Farrugia, 2012); software used to prepare material for publication: SHELXL2018 (Sheldrick, 2015b).

Dibromidobis(3-bromobenzyl-κC)(4,7-diphenyl-1,10-phenanthroline-κ²N,N')tin(IV) top

Crystal data top

[SnBr₂(C₇H₆Br)₂(C₂₄H₁₆N₂)]	Z = 2
M_r = 950.95	F(000) = 920
Triclinic, P1	D_x = 1.824 Mg m⁻³
a = 10.1328 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.2430 (3) Å	Cell parameters from 9823 reflections
c = 16.7726 (4) Å	θ = 3.0–28.6°
α = 83.216 (2)°	µ = 5.38 mm⁻¹
β = 72.639 (2)°	T = 296 K
γ = 71.787 (1)°	Block, yellow
V = 1731.72 (8) Å³	0.10 × 0.10 × 0.05 mm

Data collection top

Bruker Kappa APEX3 CMOS diffractometer	6920 reflections with I > 2σ(I)
ω and φ scan	R_int = 0.056
Absorption correction: multi-scan (SADABS; Bruker, 2016)	θ_max = 30.7°, θ_min = 3.2°
T_min = 0.588, T_max = 0.746	h = −14→14
77114 measured reflections	k = −16→16
10637 independent reflections	l = −23→24

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.050	H-atom parameters constrained
wR(F²) = 0.123	w = 1/[σ²(F_o²) + (0.0373P)² + 5.1192P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
10637 reflections	Δρ_max = 1.14 e Å⁻³
444 parameters	Δρ_min = −1.47 e Å⁻³
342 restraints	Extinction correction: SHELXL2018 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0039 (4)

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	Occ. (<1)
Sn1	0.38752 (3)	0.17331 (3)	0.72938 (2)	0.03379 (10)
Br1	0.33777 (7)	0.02517 (5)	0.63249 (4)	0.06410 (18)
Br2	0.16984 (6)	0.19942 (6)	0.86610 (4)	0.06052 (16)
N1	0.4864 (4)	0.2968 (3)	0.7817 (2)	0.0308 (7)
N2	0.5998 (4)	0.1939 (3)	0.6302 (2)	0.0341 (7)
C1	0.4282 (5)	0.3489 (4)	0.8548 (3)	0.0366 (9)
H1A	0.341361	0.336726	0.887668	0.044*
C2	0.4896 (5)	0.4216 (4)	0.8856 (3)	0.0371 (9)
H2A	0.442692	0.458385	0.937283	0.045*
C3	0.6184 (4)	0.4389 (4)	0.8402 (2)	0.0319 (8)
C4	0.6838 (4)	0.3835 (3)	0.7609 (2)	0.0298 (8)
C5	0.6128 (4)	0.3139 (3)	0.7340 (2)	0.0281 (7)
C6	0.6732 (4)	0.2596 (3)	0.6529 (2)	0.0286 (8)
C7	0.8030 (4)	0.2756 (4)	0.6007 (2)	0.0328 (8)
C8	0.8698 (5)	0.3509 (4)	0.6294 (3)	0.0410 (10)
H8A	0.953686	0.365947	0.594406	0.049*
C9	0.8143 (5)	0.4001 (4)	0.7055 (3)	0.0395 (10)
H9A	0.862230	0.446305	0.722592	0.047*
C10	0.8584 (4)	0.2214 (4)	0.5210 (2)	0.0347 (9)
C11	0.7795 (5)	0.1564 (4)	0.4997 (3)	0.0426 (10)
H11A	0.811934	0.120607	0.447548	0.051*
C12	0.6517 (5)	0.1440 (4)	0.5558 (3)	0.0451 (11)
H12A	0.600943	0.098914	0.540185	0.054*
C13	0.9940 (5)	0.2357 (4)	0.4614 (2)	0.0357 (9)
C14	0.9906 (5)	0.2837 (4)	0.3814 (3)	0.0440 (10)
H14A	0.905237	0.304162	0.365872	0.053*
C15	1.1139 (6)	0.3008 (5)	0.3255 (3)	0.0537 (12)
H15A	1.111680	0.333651	0.272256	0.064*
C16	1.2389 (6)	0.2699 (5)	0.3477 (3)	0.0570 (14)
H16A	1.321496	0.283353	0.309874	0.068*
C17	1.2442 (5)	0.2190 (5)	0.4256 (4)	0.0565 (13)
H17A	1.330992	0.195671	0.439754	0.068*
C18	1.1215 (5)	0.2023 (5)	0.4826 (3)	0.0469 (11)
H18A	1.125085	0.168349	0.535556	0.056*
C19	0.6850 (5)	0.5157 (4)	0.8721 (2)	0.0359 (9)
C20	0.8143 (6)	0.4632 (5)	0.8906 (3)	0.0525 (12)
H20A	0.862273	0.378558	0.881796	0.063*
C21	0.8736 (7)	0.5360 (7)	0.9224 (4)	0.0700 (18)
H21A	0.960660	0.499760	0.935713	0.084*
C22	0.8050 (8)	0.6607 (7)	0.9343 (4)	0.077 (2)
H22A	0.845981	0.709600	0.954680	0.092*
C23	0.6777 (8)	0.7127 (6)	0.9163 (4)	0.0697 (18)
H23A	0.631127	0.797693	0.924707	0.084*
C24	0.6150 (6)	0.6415 (4)	0.8855 (3)	0.0481 (11)
H24A	0.526526	0.678099	0.873946	0.058*
Br3	0.17356 (10)	0.71660 (8)	0.85740 (6)	0.0998 (3)
C25	0.2648 (5)	0.3378 (4)	0.6683 (3)	0.0419 (10)
H25A	0.286528	0.321174	0.609603	0.050*
H25B	0.162171	0.349458	0.693184	0.050*
C26	0.2978 (4)	0.4559 (2)	0.67555 (18)	0.0470 (11)
C27	0.2270 (3)	0.5234 (3)	0.74818 (16)	0.0504 (12)
H27A	0.157510	0.496840	0.790011	0.060*
C28	0.2602 (4)	0.6307 (3)	0.75830 (17)	0.0594 (14)
C29	0.3642 (4)	0.6704 (3)	0.6958 (2)	0.0749 (19)
H29A	0.386364	0.742139	0.702556	0.090*
C30	0.4349 (4)	0.6028 (3)	0.62315 (19)	0.0682 (16)
H30A	0.504435	0.629389	0.581319	0.082*
C31	0.4017 (4)	0.4956 (3)	0.61303 (16)	0.0599 (14)
H31A	0.449046	0.450363	0.564427	0.072*
Br4	0.74161 (13)	0.12905 (11)	0.99659 (6)	0.0867 (4)	0.7078 (18)
C32	0.5264 (7)	0.0032 (13)	0.7775 (6)	0.0418 (14)	0.7078 (18)
H32A	0.467748	−0.025946	0.828296	0.050*	0.7078 (18)
H32D	0.559912	−0.061825	0.736771	0.050*	0.7078 (18)
C33	0.6549 (4)	0.0197 (5)	0.7958 (2)	0.0411 (12)	0.7078 (18)
C34	0.6406 (3)	0.0586 (5)	0.8744 (2)	0.0452 (13)	0.7078 (18)
H34A	0.552033	0.073368	0.914914	0.054*	0.7078 (18)
C35	0.7588 (4)	0.0755 (5)	0.8924 (2)	0.0522 (14)	0.7078 (18)
C36	0.8912 (4)	0.0534 (5)	0.8319 (3)	0.0576 (15)	0.7078 (18)
H36A	0.970292	0.064717	0.843903	0.069*	0.7078 (18)
C37	0.9055 (4)	0.0145 (5)	0.7533 (2)	0.0583 (16)	0.7078 (18)
H37A	0.994127	−0.000251	0.712761	0.070*	0.7078 (18)
C38	0.7874 (4)	−0.0024 (5)	0.73526 (19)	0.0489 (14)	0.7078 (18)
H38A	0.796916	−0.028410	0.682694	0.059*	0.7078 (18)
Br4'	1.0330 (2)	0.0096 (2)	0.73285 (14)	0.0682 (7)	0.2922 (18)
C32'	0.4920 (14)	0.010 (4)	0.7812 (12)	0.045 (3)	0.2922 (18)
H32B	0.420210	−0.019752	0.823919	0.054*	0.2922 (18)
H32C	0.537565	−0.051949	0.738235	0.054*	0.2922 (18)
C33'	0.6043 (6)	0.0184 (14)	0.8195 (6)	0.045 (2)	0.2922 (18)
C34'	0.7443 (7)	0.0041 (13)	0.7687 (5)	0.045 (2)	0.2922 (18)
H34B	0.768330	−0.016692	0.713079	0.054*	0.2922 (18)
C35'	0.8483 (5)	0.0208 (12)	0.8011 (4)	0.050 (2)	0.2922 (18)
C36'	0.8124 (7)	0.0519 (13)	0.8843 (4)	0.052 (2)	0.2922 (18)
H36B	0.881969	0.063077	0.905934	0.063*	0.2922 (18)
C37'	0.6724 (7)	0.0662 (13)	0.9350 (4)	0.057 (2)	0.2922 (18)
H37B	0.648295	0.086977	0.990655	0.069*	0.2922 (18)
C38'	0.5683 (6)	0.0495 (13)	0.9026 (5)	0.051 (2)	0.2922 (18)
H38B	0.474636	0.059043	0.936589	0.061*	0.2922 (18)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Sn1	0.03763 (16)	0.03340 (15)	0.03712 (16)	−0.01548 (11)	−0.01446 (12)	−0.00210 (11)
Br1	0.0924 (4)	0.0533 (3)	0.0721 (4)	−0.0312 (3)	−0.0480 (3)	−0.0061 (3)
Br2	0.0514 (3)	0.0794 (4)	0.0558 (3)	−0.0348 (3)	−0.0020 (2)	−0.0114 (3)
N1	0.0349 (17)	0.0314 (17)	0.0296 (16)	−0.0130 (14)	−0.0109 (14)	−0.0003 (13)
N2	0.0368 (18)	0.0363 (18)	0.0328 (17)	−0.0127 (15)	−0.0096 (14)	−0.0088 (14)
C1	0.035 (2)	0.039 (2)	0.039 (2)	−0.0182 (18)	−0.0082 (18)	0.0038 (17)
C2	0.039 (2)	0.043 (2)	0.030 (2)	−0.0129 (18)	−0.0060 (17)	−0.0088 (17)
C3	0.039 (2)	0.0291 (19)	0.0292 (19)	−0.0091 (16)	−0.0122 (16)	−0.0048 (15)
C4	0.035 (2)	0.0280 (18)	0.0278 (19)	−0.0086 (15)	−0.0092 (15)	−0.0062 (15)
C5	0.0321 (19)	0.0286 (18)	0.0253 (18)	−0.0079 (15)	−0.0099 (15)	−0.0039 (14)
C6	0.036 (2)	0.0269 (18)	0.0247 (18)	−0.0088 (15)	−0.0098 (15)	−0.0044 (14)
C7	0.038 (2)	0.034 (2)	0.0267 (19)	−0.0104 (17)	−0.0086 (16)	−0.0049 (15)
C8	0.042 (2)	0.049 (3)	0.034 (2)	−0.023 (2)	−0.0020 (18)	−0.0083 (19)
C9	0.042 (2)	0.045 (2)	0.036 (2)	−0.023 (2)	−0.0018 (18)	−0.0116 (18)
C10	0.038 (2)	0.034 (2)	0.028 (2)	−0.0054 (17)	−0.0073 (17)	−0.0040 (16)
C11	0.046 (2)	0.051 (3)	0.032 (2)	−0.016 (2)	−0.0057 (19)	−0.0146 (19)
C12	0.055 (3)	0.038 (2)	0.054 (3)	−0.017 (2)	−0.027 (2)	−0.008 (2)
C13	0.041 (2)	0.035 (2)	0.028 (2)	−0.0105 (17)	−0.0029 (17)	−0.0089 (16)
C14	0.049 (3)	0.042 (2)	0.038 (2)	−0.011 (2)	−0.010 (2)	−0.0022 (19)
C15	0.064 (3)	0.051 (3)	0.040 (3)	−0.020 (2)	−0.003 (2)	0.003 (2)
C16	0.054 (3)	0.055 (3)	0.053 (3)	−0.022 (2)	0.009 (2)	−0.013 (2)
C17	0.039 (3)	0.060 (3)	0.067 (4)	−0.011 (2)	−0.009 (2)	−0.016 (3)
C18	0.041 (2)	0.052 (3)	0.045 (3)	−0.008 (2)	−0.014 (2)	−0.005 (2)
C19	0.045 (2)	0.042 (2)	0.0265 (19)	−0.0201 (19)	−0.0087 (17)	−0.0046 (16)
C20	0.051 (3)	0.067 (3)	0.047 (3)	−0.020 (2)	−0.017 (2)	−0.016 (2)
C21	0.060 (3)	0.116 (5)	0.053 (3)	−0.044 (4)	−0.017 (3)	−0.020 (3)
C22	0.092 (5)	0.114 (6)	0.050 (3)	−0.075 (5)	−0.002 (3)	−0.027 (3)
C23	0.107 (5)	0.057 (3)	0.052 (3)	−0.052 (3)	0.002 (3)	−0.017 (3)
C24	0.065 (3)	0.043 (3)	0.038 (2)	−0.023 (2)	−0.008 (2)	−0.0061 (19)
Br3	0.1022 (6)	0.0841 (5)	0.1170 (7)	−0.0153 (4)	−0.0318 (5)	−0.0468 (5)
C25	0.051 (3)	0.038 (2)	0.047 (3)	−0.016 (2)	−0.028 (2)	0.0059 (19)
C26	0.054 (3)	0.039 (2)	0.050 (3)	−0.008 (2)	−0.025 (2)	0.006 (2)
C27	0.055 (3)	0.041 (3)	0.060 (3)	−0.014 (2)	−0.027 (2)	0.006 (2)
C28	0.065 (3)	0.044 (3)	0.075 (4)	−0.006 (2)	−0.038 (3)	−0.003 (3)
C29	0.088 (5)	0.042 (3)	0.108 (5)	−0.028 (3)	−0.046 (4)	0.019 (3)
C30	0.083 (4)	0.061 (4)	0.061 (4)	−0.027 (3)	−0.023 (3)	0.020 (3)
C31	0.076 (4)	0.054 (3)	0.053 (3)	−0.025 (3)	−0.021 (3)	0.013 (2)
Br4	0.1113 (9)	0.1036 (8)	0.0660 (6)	−0.0356 (6)	−0.0479 (6)	−0.0095 (5)
C32	0.039 (3)	0.032 (3)	0.060 (3)	−0.008 (4)	−0.026 (3)	0.000 (3)
C33	0.043 (3)	0.032 (2)	0.054 (3)	−0.012 (2)	−0.022 (2)	0.000 (2)
C34	0.046 (3)	0.042 (3)	0.054 (3)	−0.012 (2)	−0.024 (2)	0.003 (2)
C35	0.055 (3)	0.050 (3)	0.060 (3)	−0.013 (3)	−0.030 (3)	−0.004 (3)
C36	0.046 (3)	0.059 (3)	0.075 (4)	−0.013 (3)	−0.030 (3)	−0.003 (3)
C37	0.041 (3)	0.060 (3)	0.071 (4)	−0.009 (3)	−0.016 (3)	−0.005 (3)
C38	0.044 (3)	0.043 (3)	0.061 (3)	−0.007 (3)	−0.021 (3)	−0.006 (3)
Br4'	0.0440 (11)	0.0825 (15)	0.0820 (15)	−0.0203 (10)	−0.0192 (9)	−0.0073 (11)
C32'	0.043 (5)	0.036 (5)	0.062 (5)	−0.011 (6)	−0.025 (5)	0.000 (5)
C33'	0.044 (4)	0.036 (4)	0.057 (4)	−0.009 (4)	−0.022 (3)	0.002 (4)
C34'	0.043 (4)	0.041 (4)	0.056 (4)	−0.009 (4)	−0.023 (4)	0.000 (4)
C35'	0.046 (4)	0.047 (4)	0.063 (4)	−0.011 (4)	−0.025 (3)	−0.001 (4)
C36'	0.050 (4)	0.051 (4)	0.062 (4)	−0.013 (4)	−0.026 (4)	−0.004 (4)
C37'	0.057 (5)	0.058 (5)	0.059 (5)	−0.010 (4)	−0.027 (4)	−0.003 (4)
C38'	0.049 (4)	0.048 (4)	0.057 (4)	−0.011 (4)	−0.023 (4)	0.000 (4)

Geometric parameters (Å, º) top

Sn1—C32'	2.05 (4)	C22—C23	1.347 (10)
Sn1—C25	2.211 (4)	C22—H22A	0.9300
Sn1—C32	2.218 (13)	C23—C24	1.387 (7)
Sn1—N1	2.320 (3)	C23—H23A	0.9300
Sn1—N2	2.353 (3)	C24—H24A	0.9300
Sn1—Br2	2.6355 (6)	Br3—Br4ⁱ	3.5972 (12)
Sn1—Br1	2.7059 (5)	Br3—C28	1.856 (2)
N1—C1	1.310 (5)	C25—C26	1.493 (4)
N1—C5	1.350 (5)	C25—H25A	0.9700
N2—C12	1.317 (6)	C25—H25B	0.9700
N2—C6	1.351 (5)	C26—C27	1.3900
C1—C2	1.390 (6)	C26—C31	1.3900
C1—H1A	0.9300	C27—C28	1.3900
C2—C3	1.360 (6)	C27—H27A	0.9300
C2—H2A	0.9300	C28—C29	1.3900
C3—C4	1.417 (5)	C29—C30	1.3900
C3—C19	1.477 (5)	C29—H29A	0.9300
C4—C5	1.401 (5)	C30—C31	1.3900
C4—C9	1.424 (6)	C30—H30A	0.9300
C5—C6	1.435 (5)	C31—H31A	0.9300
C6—C7	1.398 (6)	Br4—C35	1.857 (2)
C7—C10	1.415 (5)	C32—C33	1.492 (4)
C7—C8	1.434 (6)	C32—H32A	0.9700
C8—C9	1.339 (6)	C32—H32D	0.9700
C8—H8A	0.9300	C33—C34	1.3900
C9—H9A	0.9300	C33—C38	1.3900
C10—C11	1.377 (6)	C34—C35	1.3900
C10—C13	1.481 (6)	C34—H34A	0.9300
C11—C12	1.392 (7)	C35—C36	1.3900
C11—H11A	0.9300	C36—C37	1.3900
C12—H12A	0.9300	C36—H36A	0.9300
C13—C18	1.370 (6)	C37—C38	1.3900
C13—C14	1.393 (6)	C37—H37A	0.9300
C14—C15	1.373 (7)	C38—H38A	0.9300
C14—H14A	0.9300	Br4'—C35'	1.854 (3)
C15—C16	1.356 (8)	C32'—C33'	1.493 (4)
C15—H15A	0.9300	C32'—H32B	0.9700
C16—C17	1.372 (8)	C32'—H32C	0.9700
C16—H16A	0.9300	C33'—C34'	1.3900
C17—C18	1.375 (7)	C33'—C38'	1.3900
C17—H17A	0.9300	C34'—C35'	1.3900
C18—H18A	0.9300	C34'—H34B	0.9300
C19—C20	1.370 (7)	C35'—C36'	1.3900
C19—C24	1.380 (6)	C36'—C37'	1.3900
C20—C21	1.385 (7)	C36'—H36B	0.9300
C20—H20A	0.9300	C37'—C38'	1.3900
C21—C22	1.365 (10)	C37'—H37B	0.9300
C21—H21A	0.9300	C38'—H38B	0.9300

C32'—Sn1—C25	174.2 (5)	C21—C20—H20A	120.0
C25—Sn1—C32	174.0 (3)	C22—C21—C20	120.3 (6)
C32'—Sn1—N1	94.2 (5)	C22—C21—H21A	119.9
C25—Sn1—N1	91.65 (13)	C20—C21—H21A	119.9
C32—Sn1—N1	89.8 (2)	C23—C22—C21	119.9 (5)
C32'—Sn1—N2	94.0 (4)	C23—C22—H22A	120.1
C25—Sn1—N2	88.03 (15)	C21—C22—H22A	120.1
C32—Sn1—N2	87.0 (2)	C22—C23—C24	120.9 (6)
N1—Sn1—N2	70.32 (11)	C22—C23—H23A	119.5
C32'—Sn1—Br2	88.2 (4)	C24—C23—H23A	119.5
C25—Sn1—Br2	91.60 (13)	C19—C24—C23	119.5 (5)
C32—Sn1—Br2	94.2 (2)	C19—C24—H24A	120.3
N1—Sn1—Br2	91.31 (8)	C23—C24—H24A	120.3
N2—Sn1—Br2	161.60 (8)	C26—C25—Sn1	113.4 (3)
C32'—Sn1—Br1	86.1 (5)	C26—C25—H25A	108.9
C25—Sn1—Br1	88.35 (10)	Sn1—C25—H25A	108.9
C32—Sn1—Br1	88.7 (2)	C26—C25—H25B	108.9
N1—Sn1—Br1	164.19 (8)	Sn1—C25—H25B	108.9
N2—Sn1—Br1	93.89 (8)	H25A—C25—H25B	107.7
Br2—Sn1—Br1	104.49 (2)	C27—C26—C31	120.0
C1—N1—C5	118.5 (3)	C27—C26—C25	118.7 (3)
C1—N1—Sn1	124.0 (3)	C31—C26—C25	121.3 (3)
C5—N1—Sn1	117.5 (2)	C28—C27—C26	120.0
C12—N2—C6	118.9 (4)	C28—C27—H27A	120.0
C12—N2—Sn1	124.4 (3)	C26—C27—H27A	120.0
C6—N2—Sn1	116.7 (2)	C29—C28—C27	120.0
N1—C1—C2	123.3 (4)	C29—C28—Br3	119.64 (18)
N1—C1—H1A	118.4	C27—C28—Br3	120.28 (18)
C2—C1—H1A	118.4	C28—C29—C30	120.0
C3—C2—C1	120.0 (4)	C28—C29—H29A	120.0
C3—C2—H2A	120.0	C30—C29—H29A	120.0
C1—C2—H2A	120.0	C31—C30—C29	120.0
C2—C3—C4	117.8 (4)	C31—C30—H30A	120.0
C2—C3—C19	120.7 (4)	C29—C30—H30A	120.0
C4—C3—C19	121.5 (4)	C30—C31—C26	120.0
C5—C4—C3	118.3 (4)	C30—C31—H31A	120.0
C5—C4—C9	118.3 (3)	C26—C31—H31A	120.0
C3—C4—C9	123.3 (3)	C33—C32—Sn1	115.4 (8)
N1—C5—C4	122.0 (3)	C33—C32—H32A	108.4
N1—C5—C6	118.0 (3)	Sn1—C32—H32A	108.4
C4—C5—C6	120.0 (3)	C33—C32—H32D	108.4
N2—C6—C7	122.3 (3)	Sn1—C32—H32D	108.4
N2—C6—C5	117.4 (3)	H32A—C32—H32D	107.5
C7—C6—C5	120.3 (3)	C34—C33—C38	120.0
C6—C7—C10	118.5 (4)	C34—C33—C32	119.2 (3)
C6—C7—C8	118.0 (3)	C38—C33—C32	120.8 (3)
C10—C7—C8	123.5 (4)	C33—C34—C35	120.0
C9—C8—C7	121.6 (4)	C33—C34—H34A	120.0
C9—C8—H8A	119.2	C35—C34—H34A	120.0
C7—C8—H8A	119.2	C36—C35—C34	120.0
C8—C9—C4	121.8 (4)	C36—C35—Br4	119.3 (2)
C8—C9—H9A	119.1	C34—C35—Br4	120.7 (2)
C4—C9—H9A	119.1	C37—C36—C35	120.0
C11—C10—C7	117.5 (4)	C37—C36—H36A	120.0
C11—C10—C13	120.7 (4)	C35—C36—H36A	120.0
C7—C10—C13	121.8 (4)	C36—C37—C38	120.0
C10—C11—C12	120.4 (4)	C36—C37—H37A	120.0
C10—C11—H11A	119.8	C38—C37—H37A	120.0
C12—C11—H11A	119.8	C37—C38—C33	120.0
N2—C12—C11	122.4 (4)	C37—C38—H38A	120.0
N2—C12—H12A	118.8	C33—C38—H38A	120.0
C11—C12—H12A	118.8	C33'—C32'—Sn1	116 (2)
C18—C13—C14	119.6 (4)	C33'—C32'—H32B	108.3
C18—C13—C10	122.0 (4)	Sn1—C32'—H32B	108.3
C14—C13—C10	118.4 (4)	C33'—C32'—H32C	108.3
C15—C14—C13	119.7 (5)	Sn1—C32'—H32C	108.3
C15—C14—H14A	120.2	H32B—C32'—H32C	107.4
C13—C14—H14A	120.2	C34'—C33'—C38'	120.0
C16—C15—C14	120.3 (5)	C34'—C33'—C32'	118.7 (4)
C16—C15—H15A	119.8	C38'—C33'—C32'	121.1 (4)
C14—C15—H15A	119.8	C33'—C34'—C35'	120.0
C15—C16—C17	120.3 (5)	C33'—C34'—H34B	120.0
C15—C16—H16A	119.8	C35'—C34'—H34B	120.0
C17—C16—H16A	119.8	C36'—C35'—C34'	120.0
C16—C17—C18	120.2 (5)	C36'—C35'—Br4'	119.5 (3)
C16—C17—H17A	119.9	C34'—C35'—Br4'	120.4 (3)
C18—C17—H17A	119.9	C37'—C36'—C35'	120.0
C13—C18—C17	119.9 (5)	C37'—C36'—H36B	120.0
C13—C18—H18A	120.1	C35'—C36'—H36B	120.0
C17—C18—H18A	120.1	C36'—C37'—C38'	120.0
C20—C19—C24	119.4 (4)	C36'—C37'—H37B	120.0
C20—C19—C3	120.8 (4)	C38'—C37'—H37B	120.0
C24—C19—C3	119.8 (4)	C37'—C38'—C33'	120.0
C19—C20—C21	120.1 (5)	C37'—C38'—H38B	120.0
C19—C20—H20A	120.0	C33'—C38'—H38B	120.0

C5—N1—C1—C2	0.3 (6)	C14—C13—C18—C17	1.5 (7)
Sn1—N1—C1—C2	179.3 (3)	C10—C13—C18—C17	−179.1 (4)
N1—C1—C2—C3	−1.6 (7)	C16—C17—C18—C13	0.5 (8)
C1—C2—C3—C4	1.5 (6)	C2—C3—C19—C20	115.5 (5)
C1—C2—C3—C19	−179.9 (4)	C4—C3—C19—C20	−66.0 (6)
C2—C3—C4—C5	−0.2 (6)	C2—C3—C19—C24	−63.0 (6)
C19—C3—C4—C5	−178.7 (4)	C4—C3—C19—C24	115.5 (5)
C2—C3—C4—C9	176.5 (4)	C24—C19—C20—C21	0.0 (7)
C19—C3—C4—C9	−2.0 (6)	C3—C19—C20—C21	−178.5 (5)
C1—N1—C5—C4	1.1 (6)	C19—C20—C21—C22	−1.0 (9)
Sn1—N1—C5—C4	−178.0 (3)	C20—C21—C22—C23	1.1 (9)
C1—N1—C5—C6	−178.1 (4)	C21—C22—C23—C24	−0.2 (9)
Sn1—N1—C5—C6	2.8 (4)	C20—C19—C24—C23	0.9 (7)
C3—C4—C5—N1	−1.2 (6)	C3—C19—C24—C23	179.4 (4)
C9—C4—C5—N1	−178.1 (4)	C22—C23—C24—C19	−0.8 (8)
C3—C4—C5—C6	178.0 (4)	Sn1—C25—C26—C27	−82.9 (3)
C9—C4—C5—C6	1.1 (6)	Sn1—C25—C26—C31	94.2 (3)
C12—N2—C6—C7	−0.6 (6)	C31—C26—C27—C28	0.0
Sn1—N2—C6—C7	178.2 (3)	C25—C26—C27—C28	177.1 (3)
C12—N2—C6—C5	179.3 (4)	C26—C27—C28—C29	0.0
Sn1—N2—C6—C5	−2.0 (5)	C26—C27—C28—Br3	−176.7 (3)
N1—C5—C6—N2	−0.6 (5)	C27—C28—C29—C30	0.0
C4—C5—C6—N2	−179.8 (4)	Br3—C28—C29—C30	176.7 (3)
N1—C5—C6—C7	179.3 (3)	C28—C29—C30—C31	0.0
C4—C5—C6—C7	0.1 (6)	C29—C30—C31—C26	0.0
N2—C6—C7—C10	0.3 (6)	C27—C26—C31—C30	0.0
C5—C6—C7—C10	−179.5 (4)	C25—C26—C31—C30	−177.1 (3)
N2—C6—C7—C8	177.7 (4)	Sn1—C32—C33—C34	88.1 (6)
C5—C6—C7—C8	−2.1 (6)	Sn1—C32—C33—C38	−91.4 (5)
C6—C7—C8—C9	3.1 (7)	C38—C33—C34—C35	0.0
C10—C7—C8—C9	−179.7 (4)	C32—C33—C34—C35	−179.5 (7)
C7—C8—C9—C4	−1.9 (7)	C33—C34—C35—C36	0.0
C5—C4—C9—C8	−0.2 (7)	C33—C34—C35—Br4	179.3 (4)
C3—C4—C9—C8	−176.9 (4)	C34—C35—C36—C37	0.0
C6—C7—C10—C11	0.5 (6)	Br4—C35—C36—C37	−179.4 (4)
C8—C7—C10—C11	−176.8 (4)	C35—C36—C37—C38	0.0
C6—C7—C10—C13	179.0 (4)	C36—C37—C38—C33	0.0
C8—C7—C10—C13	1.8 (6)	C34—C33—C38—C37	0.0
C7—C10—C11—C12	−1.0 (7)	C32—C33—C38—C37	179.4 (8)
C13—C10—C11—C12	−179.6 (4)	Sn1—C32'—C33'—C34'	−86.4 (12)
C6—N2—C12—C11	0.1 (7)	Sn1—C32'—C33'—C38'	88.6 (14)
Sn1—N2—C12—C11	−178.6 (3)	C38'—C33'—C34'—C35'	0.0
C10—C11—C12—N2	0.7 (7)	C32'—C33'—C34'—C35'	175 (2)
C11—C10—C13—C18	−126.2 (5)	C33'—C34'—C35'—C36'	0.0
C7—C10—C13—C18	55.2 (6)	C33'—C34'—C35'—Br4'	−177.0 (9)
C11—C10—C13—C14	53.2 (6)	C34'—C35'—C36'—C37'	0.0
C7—C10—C13—C14	−125.3 (4)	Br4'—C35'—C36'—C37'	177.0 (9)
C18—C13—C14—C15	−2.1 (7)	C35'—C36'—C37'—C38'	0.0
C10—C13—C14—C15	178.5 (4)	C36'—C37'—C38'—C33'	0.0
C13—C14—C15—C16	0.7 (7)	C34'—C33'—C38'—C37'	0.0
C14—C15—C16—C17	1.3 (8)	C32'—C33'—C38'—C37'	−175 (2)
C15—C16—C17—C18	−1.9 (8)

Symmetry code: (i) −x+1, −y+1, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···Br2	0.93	2.78	3.477 (4)	133
C12—H12A···Br1	0.93	2.97	3.656 (5)	132
C36—H36A···Br2ⁱⁱ	0.93	3.00	3.883 (3)	159

Symmetry code: (ii) x+1, y, z.

Acknowledgements

The authors thank SAIF, IIT Madras, for providing the intensity data collection.

References

Bruker (2016). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals 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
Hu, S.-Z., Lin, W., Wan, J. & Huang, Z. (1989). Jiegou Huaxue (Chin. J. Struct. Chem.), 8, 36–42. CAS Google Scholar
Klosener, J., Wiesemann, M., Niemann, M., Neumann, B., Stammler, H.-G. & Hoge, B. (2017). Chem. Eur. J. 23, 8295–8298. Google Scholar
McCann, M., Kellett, A., Kavanagh, K., Devereux, M. & Santos, A. L. (2012a). Curr. Med. Chem. 19, 2703–2714. CrossRef CAS Google Scholar
McCann, M., Santos, A. L. S., da Silva, B. A., Romanos, M. T. V., Pyrrho, A. S., Devereux, M., Kavanagh, K., Fichtner, I. & Kellett, A. (2012b). Toxicol. Res. 1, 47–54. CrossRef CAS Google Scholar
Najafi, E., Amini, M. M. & Ng, S. W. (2011). Acta Cryst. E67, m244. CrossRef IUCr Journals Google Scholar
Parada, J., Ana, M. A., Guillermo, W. E. R. & Gino, C. (2017). J. Chil. Chem. Soc. 62, 3746–3751. CrossRef CAS Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Snoeij, N. J., Penninks, A. H. & Seinen, W. (1987). Environ. Res. 44, 335–353. CrossRef CAS Google Scholar
Varela-Ramirez, A., Costanzo, M., Carrasco, Y. P., Pannell, K. H. & Aguilera, R. J. (2011). Cell Biol. Toxicol. 27, 159–168. CAS Google Scholar
Yadav, S., Yousuf, I., Usman, M., Ahmad, M. F., Arjmanda, F. & Tabassum, S. (2015). RSC Adv. 5, 50673–50690. CrossRef CAS Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.