trans-Di­chlorido­bis­(dimethyl sulfoxide-κO)bis­(4-fluoro­benzyl-κC1)tin(IV): crystal structure and Hirshfeld surface analysis

Amin, N.A.B.M.; Hussen, R.S.D.; Lee, S.M.; Halcovitch, N.R.; Jotani, M.M.; Tiekink, E.R.T.

doi:10.1107/S2056989017005072

research communications

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ISSN: 2056-9890

Volume 73| Part 5| May 2017| Pages 667-672

https://doi.org/10.1107/S2056989017005072

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trans-Dichloridobis(dimethyl sulfoxide-κO)bis(4-fluorobenzyl-κC¹)tin(IV): crystal structure and Hirshfeld surface analysis

Nur Adibah Binti Mohd Amin,^a Rusnah Syahila Duali Hussen,^a See Mun Lee,^b Nathan R. Halcovitch,^c Mukesh M. Jotani ^d ‡ and Edward R. T. Tiekink ^b ^*

^aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia, ^bResearch Centre for Crystalline Materials, School of Science and Technology, Sunway University, 47500 Bandar Sunway, Selangor Darul Ehsan, Malaysia, ^cDepartment of Chemistry, Lancaster University, Lancaster LA1 4YB, United Kingdom, and ^dDepartment of Physics, Bhavan's Sheth R. A. College of Science, Ahmedabad, Gujarat 380001, India
^*Correspondence e-mail: edwardt@sunway.edu.my

Edited by M. Weil, Vienna University of Technology, Austria (Received 30 March 2017; accepted 2 April 2017; online 7 April 2017)

The Sn^IV atom in the title diorganotin compound, [Sn(C₇H₆F)₂Cl₂(C₂H₆OS)₂], is located on a centre of inversion, resulting in the C₂Cl₂O₂ donor set having an all-trans disposition of like atoms. The coordination geometry approximates an octahedron. The crystal features C—H⋯F, C—H⋯Cl and C—H⋯π interactions, giving rise to a three-dimensional network. The respective influences of the Cl⋯H/H⋯Cl and F⋯H/H⋯F contacts to the molecular packing are clearly evident from the analysis of the Hirshfeld surface.

Keywords: crystal structure; organotin; C—H⋯F interactions; Hirshfeld surface analysis.

CCDC reference: 1541712

1. Chemical context

The structural chemistry of organotin(IV) compounds with multidentate Schiff base ligands has been of interest since the observation of the diversity in their supramolecular association patterns (Teoh et al., 1997 ; Dey et al., 1999 ). Typically, these multidentate ligands bind to the tin atom through the phenolic-O, imine-N, oxime-O or even oxime-N atoms. In view of this, the coordination of these multidentate ligands to (organo)tin may lead to more thermodynamically stable organotin complexes, in contrast to those with monodentate ligands (Vallet et al., 2003 ; Contreras et al., 2009 ), a feature which could potentially be useful in catalytic studies (Yearwood et al., 2002 ). In consideration of this and as part of on-going work with multidentate ligands of organotin compounds (Lee et al., 2004 ), an attempt to synthesize an adduct of the potentially tetradentate Schiff base N,N-1,1,2,2-dinitrilevinylenebis(5-bromosalicylaldiminato) with di(p-fluorobenzyl)tin(IV) dichloride was made.

The complex was obtained as an orange powder and was successfully characterized using various spectroscopic methods including ¹H NMR spectroscopy. Upon interaction with DMSO-d₆, in the context of NMR studies, colourless crystals were obtained after several weeks standing. The formation of the new title compound, (I), is likely due to degradation of the complex while stored in the NMR tube. In the present contribution, the crystal and molecular structures of (I) are described as well as a detailed analysis of the intermolecular association through a Hirshfeld surface analysis.

2. Structural commentary

The molecular structure of (I), Fig. 1, has the Sn^IV atom situated on a crystallographic centre of inversion. The Sn^IV atom is coordinated by monodentate ligands, i.e. chloride, sulfoxide-O and methylene-C atoms. From symmetry, each donor is trans to a like atom resulting in an all-trans-C₂Cl₂O₂ donor set about the Sn^IV atom. The donor set defines a distorted octahedral geometry owing, in part, to the disparate Sn—donor atom bond lengths, Table 1. The angles about the Sn^IV atom differ relatively little from the ideal octahedral angles with the maximum deviation of ca 6° noted for the C1—Sn—O1 angle, Table 1.

Table 1
Selected geometric parameters (Å, °)

Sn—C1	2.1628 (16)	Sn—Cl1	2.5599 (4)
Sn—O1	2.2332 (11)

C1—Sn—O1	95.99 (5)	C1—Sn—Cl1ⁱ	89.95 (5)
C1—Sn—Cl1	90.05 (5)	O1—Sn—Cl1	90.44 (3)
C1—Sn—O1ⁱ	84.01 (5)	O1—Sn—Cl1ⁱ	89.56 (3)
Symmetry code: (i) -x+1, -y+1, -z+1.

Figure 1
The molecular structure of (I)

, showing the atom-labelling scheme and displacement ellipsoids at the 70% probability level. The Sn^IV atom lies on a centre of inversion; unlabelled atoms are related by the symmetry operation 1 − x, 1 − y, 1 − z.

3. Supramolecular features

The molecular packing in (I) comprises C—H⋯F, C—H⋯Cl and C—H⋯π interactions which combine to generate a three-dimensional network, Table 2. The chloride atom participates in phenyl-C6—H⋯Cl1 and methyl-C8—H⋯Cl1 interactions. As each chloride atom is involved in two C—H⋯Cl interactions and there are two chloride atoms per molecule, the C—H⋯Cl interactions extend laterally to give rise to a supramolecular layer in the bc plane, Fig. 2a. Layers are connected along the a axis by phenyl-C3—H⋯F1 and methyl-C9—H⋯π(phenyl) interactions to consolidate the molecular packing, Fig. 2b.

Table 2
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C2–C7 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯F1ⁱⁱ	0.95	2.49	3.333 (2)	147
C6—H6⋯Cl1ⁱⁱⁱ	0.95	2.77	3.6129 (18)	148
C8—H8B⋯Cl1^iv	0.98	2.76	3.6379 (17)	150
C9—H9C⋯Cg1^v	0.98	2.67	3.3887 (19)	130
Symmetry codes: (ii) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[x, -y-{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iv) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (v) x+1, y, z.

Figure 2
The molecular packing in (I)

: (a) supramolecular layer in the bc plane sustained by C—H⋯Cl interactions and (b) a view of the unit-cell contents in projection down the c axis. The C—H⋯Cl, C—H⋯F and C—H⋯π interactions are shown as orange, blue and purple dashed lines, respectively.

4. Hirshfeld surface analysis

The Hirshfeld surface analysis on the structure of (I) provides more insight into the molecular packing and was performed as described recently (Wardell et al., 2016 ). It is evident from the bright-red spots appearing near the chloride and fluoride atoms on the Hirshfeld surface mapped over d_norm in Fig. 3 that these atoms play a significant role in the molecular packing. Thus, the bright-red spots near phenyl-H6, methyl-H8B and a pair near Cl1 in Fig. 3 indicate the presence of bifurcated C—H⋯Cl interactions formed by each of the chloride atoms. Similarly, the pair of red spots near phenyl-H3 and F1 atoms are associated with the donor and acceptor of C—H⋯F interactions, respectively. The donors and acceptors of C—H⋯Cl and C—H⋯F interactions are also represented with blue (positive potential) and red regions (negative potential), respectively, on the Hirshfeld surface mapped over the electrostatic potential in Fig. 4. In addition to above, the Cl1 and F1 atoms also participate in short interatomic contacts with methyl-H atoms, Table 3. The presence of faint-red spots near the phenyl-C4 and methyl-C9 atoms in Fig. 3 indicate their participation in a short interatomic C⋯C contact, Table 3, which compliments the methyl-C—H⋯π(phenyl) contact described above. The presence of the C—H⋯π interaction is also evident from the view of Hirshfeld surface mapped over the electrostatic potential around participating atoms, Fig. 4; the donors and acceptors of these interactions are viewed as the convex surface around atoms of the methyl-C9 groups and the concave surface above the (C2–C7) phenyl ring, respectively. The immediate environments about a reference molecule within d_norm- and shape-index-mapped Hirshfeld surfaces highlighting the various C—H⋯Cl, C—H⋯F and C—H⋯π interactions are illustrated in Fig. 5a–c, respectively.

Table 3
Summary of short interatomic contacts (Å) in (I)

Contact	distance	symmetry operation
C4⋯C9	3.371 (2)	−1 + x, y, z
F1⋯H8A	2.66	1 − x, −y, 1 − z
Cl1⋯H9B	2.91	1 − x, $[{1\over 2}]$ + y, $[{1\over 2}]$ − z
Note: (a) the Sn^IV atom is located on a centre of inversion.

Figure 3
A view of the Hirshfeld surface for (I)

mapped over d_norm over the range −0.049 to 1.356 au.

Figure 4
A view of the Hirshfeld surface for (I)

mapped over the electrostatic potential in the range ±0.095 au.

Figure 5
Views of the Hirshfeld surfaces about a reference molecule mapped over (a) shape-index, (b) d_norm and (c) shape-index, highlighting (a) C—H⋯F and short interatomic F⋯H/H⋯F contacts as black and red dashed lines, respectively, (b) C—H⋯Cl and short interatomic Cl⋯H/H⋯Cl contacts as black and red dashed lines, respectively, and (c) C—H⋯π and short interatomic C⋯C contacts as white and red dashed lines, respectively.

The overall two-dimensional fingerprint plot and those delineated into H⋯H, Cl⋯H/H⋯Cl, F⋯H/H⋯F, C⋯H/H⋯C and O⋯H/H⋯O contacts (McKinnon et al., 2007 ) are illustrated in Fig. 6a–f, respectively, and their relative contributions to the Hirshfeld surfaces are summarized in Table 4. It is clear from the fingerprint plot delineated into H⋯H contacts, Fig. 6b, that although these contacts have the greatest contribution, i.e. 45.7%, to the Hirshfeld surface, the dispersion forces acting between them keep these atoms at the distances greater than the sum of their van der Waals radii, hence they do not contribute significantly to the molecular packing. The comparatively greater contribution of F⋯H/H⋯F contacts to the Hirshfeld surface cf. Cl⋯H/H⋯Cl contacts, Table 4, is due to the relative positions of the chloride and fluoride atoms in the molecule, the fluoride atoms being at the extremities and the chloride atoms near the tin(IV) atom. However, the Cl⋯H/H⋯Cl contacts have a greater influence on the molecular packing as viewed from the delineated fingerprint plot in Fig. 6c. The forceps-like distribution of points in the plot with tips at d_e + d_i ∼2.8 Å result from the bifurcated C—H⋯Cl interactions, and points at positions less than the sum of their van der Waals radii are ascribed to the short interatomic Cl⋯H/H⋯Cl contacts, the green appearance due to high density of interactions. Similarly, a pair of short spikes at d_e + d_i ∼2.5 Å in the fingerprint plot delineated into F⋯H/H⋯F contacts, Fig. 6d, are indicative of intermolecular C—H⋯F interactions with the short interatomic F⋯H/H⋯F contacts merged within the fingerprint plot. It is important to note from the fingerprint plot delineated into C⋯H/H⋯C contacts, Fig. 6e, that even though their interatomic distances are equal to or greater than the sum of their van der Waals radii, i.e. 2.9 Å, the 12.8% contribution from these to the Hirshfeld surfaces are indicative of the presence of C—H⋯π interactions in the structure. This is also justified from the presence of short interatomic C⋯C contacts, Fig. 5c and Table 3. The 4.1% contribution from O⋯H/H⋯O contributions to Hirshfeld surfaces, Fig. 6f, and the small contributions from the other contacts listed in Table 2 have a negligible effect on the packing.

Table 4
Percentage contribution of interatomic contacts to the Hirshfeld surface for (I)

Contact	percentage contribution
H⋯H	45.7
Cl⋯H/H⋯Cl	15.1
F⋯H/H⋯F	19.8
C⋯H/H⋯C	12.8
O⋯H/H⋯O	4.1
S⋯H/H⋯S	1.7
Cl⋯F/F⋯Cl	0.6
C⋯Cl/Cl⋯C	0.1
F⋯F	0.1

Figure 6
Fingerprint plots for (I)

: (a) overall and those delineated into (b) H⋯H, (c) Cl⋯H/H⋯Cl, (d) F⋯H/H⋯F, (e) C⋯H/H⋯C and (f) O⋯H/H⋯O contacts.

5. Database survey

There are three related structures of the general formula R₂SnX₂(DMSO)₂ in the crystallographic literature (Groom et al., 2016 ). Key bond angles for these are listed in Table 5. The Me₂SnBr₂(DMSO)₂ compound (Aslanov et al., 1978 ) is analogous to (I) in that the Sn^IV atom is located on a centre of inversion and hence, is an all-trans isomer. The two remaining structures have a different arrangements of donor atoms with the common feature being the trans-disposition of the Sn-bound organic groups, with the halides and DMSO-O atoms being mutually cis, i.e. R = Me and X = Cl (Aslanov et al., 1978; Isaacs & Kennard, 1970 ) and R = Ph and X = Cl (Sadiq-ur-Rehman et al., 2007 ). Clearly, further studies are required to ascertain the factor(s) determining the adoption of one coordination geometry over another.

Table 5
Selected geometric parameters (Å, °) for molecules of the general formula R₂SnX₂(DMSO)₂

Compound	X—Sn—X	O—Sn—O	C—Sn—C	Reference
Me₂SnBr₂(DMSO)₂	180	180	180	Aslanov et al. (1978)
Me₂SnCl₂(DMSO)₂	95.2 (3)	83.7 (5)	172.7 (3)	Aslanov et al. (1978)
Ph₂SnCl₂(DMSO)₂	97.43 (3)	79.34 (9)	172.17 (14)	Sadiq-ur-Rehman et al. (2007)
(4-FC₆H₄CH₂)₂SnCl₂(DMSO)₂	180	180	180	This work

6. Synthesis and crystallization

All chemicals and solvents were used as purchased without purification. Di(p-fluorobenzyl)tin dichloride was prepared in accordance with the literature method (Sisido et al., 1961 ). All reactions were carried out under ambient conditions. The melting point was determined using an Electrothermal digital melting point apparatus and was uncorrected. The IR spectrum was obtained on a Perkin Elmer Spectrum 400 FT Mid-IR/Far-IR spectrophotometer in the range 4000 to 400 cm⁻¹. The ¹H NMR spectrum was recorded at room temperature in CDCl₃ solution on a Jeol ECA 400 MHz FT–NMR spectrometer.

N,N′-1,1,2,2-Dinitrilevinylenebis(5-bromosalicylaldiminato) (1.0 mmol, 0.401 g; prepared by the condensation reaction between diaminomaleonitrile and 5-bromosalicylaldehyde in a 2:1 molar ratio in ethanol) and triethylamine (1.0 mmol, 0.14 ml) in ethyl acetate (25 ml) was added to di(p-fluorobenzyl)tin dichloride (1.0 mmol, 0.183 g) in ethyl acetate (10 ml). The resulting mixture was stirred and refluxed for 4 h. The filtrate was evaporated until a dark-orange precipitate was obtained. The precipitate was dissolved in DMSO-d₆ solution in a NMR tube for ¹H NMR spectroscopic characterization. After the analysis, the tube was set aside for a month and colourless crystals of (I) suitable for X-ray crystallographic studies were obtained from the slow evaporation. Yield: 0.060 g, 11%; m.p: 399 K. IR (cm⁻¹): 1595(m) ν(C=C), 1504(s) ν(S=O), 1161(m), 578(w), 508(m) ν(Sn—O). ¹H NMR (in CDCl₃): 6.90–7.11, 7.35–7.40 (m, 8H, aromatic-H), 3.11 (s, 6H, –CH₃), 2.17 (m, 4H, –CH₂).

7. Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 6. Carbon-bound H-atoms were placed in calculated positions (C—H = 0.95–0.99 Å) and were included in the refinement in the riding model approximation, with U_iso(H) set to 1.2–1.5U_eq(C).

Table 6
Experimental details

Crystal data
Chemical formula	[Sn(C₇H₆F)₂Cl₂(C₂H₆OS)₂]
M_r	564.08
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	8.2363 (1), 12.7020 (2), 11.4038 (1)
β (°)	110.391 (2)
V (Å³)	1118.28 (3)
Z	2
Radiation type	Cu Kα
μ (mm⁻¹)	13.28
Crystal size (mm)	0.24 × 0.12 × 0.10

Data collection
Diffractometer	Agilent SuperNova, Dual, Cu at zero, AtlasS2
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku Oxford Diffraction, 2015 $[Rigaku Oxford Diffraction (2015). CrysAlis PRO. Agilent Technologies Inc., Santa Clara, CA, USA.]$ )
T_min, T_max	0.636, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	7792, 2292, 2228
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.631

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.018, 0.046, 1.08
No. of reflections	2292
No. of parameters	126
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.76
Computer programs: CrysAlis PRO (Rigaku Oxford Diffraction, 2015 $[Rigaku Oxford Diffraction (2015). CrysAlis PRO. Agilent Technologies Inc., Santa Clara, CA, USA.]$ ), SHELXS (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), ORTEP-3 for Windows (Farrugia, 2012 ), DIAMOND (Brandenburg, 2006 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1541712

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2056989017005072/wm5381sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989017005072/wm5381Isup2.hkl

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Rigaku Oxford Diffraction, 2015); cell refinement: CrysAlis PRO (Rigaku Oxford Diffraction, 2015); data reduction: CrysAlis PRO (Rigaku Oxford Diffraction, 2015); program(s) used to solve structure: SHELXS (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

trans-Dichloridobis(dimethyl sulfoxide-κO)bis(4-fluorobenzyl-κC¹)tin(IV) top

Crystal data top

[Sn(C₇H₆F)₂Cl₂(C₂H₆OS)₂]	F(000) = 564
M_r = 564.08	D_x = 1.675 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54184 Å
a = 8.2363 (1) Å	Cell parameters from 6127 reflections
b = 12.7020 (2) Å	θ = 5.4–76.3°
c = 11.4038 (1) Å	µ = 13.28 mm⁻¹
β = 110.391 (2)°	T = 100 K
V = 1118.28 (3) Å³	Prism, colourless
Z = 2	0.24 × 0.12 × 0.10 mm

Data collection top

Agilent SuperNova, Dual, Cu at zero, AtlasS2 diffractometer	2292 independent reflections
Radiation source: micro-focus sealed X-ray tube, SuperNova (Cu) X-ray Source	2228 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.020
ω scans	θ_max = 76.5°, θ_min = 5.4°
Absorption correction: multi-scan (CrysAlis PRO; Rigaku Oxford Diffraction, 2015)	h = −10→9
T_min = 0.636, T_max = 1.000	k = −15→15
7792 measured reflections	l = −14→14

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.018	H-atom parameters constrained
wR(F²) = 0.046	w = 1/[σ²(F_o²) + (0.0233P)² + 0.7527P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max < 0.001
2292 reflections	Δρ_max = 0.35 e Å⁻³
126 parameters	Δρ_min = −0.76 e Å⁻³

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
Sn	0.5000	0.5000	0.5000	0.00673 (6)
Cl1	0.44665 (6)	0.48762 (3)	0.26545 (4)	0.01508 (10)
S1	0.55778 (5)	0.24628 (3)	0.43015 (3)	0.00881 (9)
F1	0.06456 (15)	0.03219 (9)	0.34347 (11)	0.0248 (2)
O1	0.60349 (15)	0.33583 (9)	0.52752 (10)	0.0106 (2)
C1	0.2332 (2)	0.45714 (13)	0.46551 (16)	0.0130 (3)
H1A	0.2054	0.4746	0.5410	0.016*
H1B	0.1583	0.5013	0.3962	0.016*
C2	0.1878 (2)	0.34437 (13)	0.43339 (15)	0.0098 (3)
C3	0.1093 (2)	0.31260 (13)	0.30871 (15)	0.0111 (3)
H3	0.0838	0.3637	0.2440	0.013*
C4	0.0679 (2)	0.20772 (14)	0.27783 (15)	0.0134 (3)
H4	0.0147	0.1868	0.1930	0.016*
C5	0.1058 (2)	0.13487 (13)	0.37280 (16)	0.0140 (3)
C6	0.1822 (2)	0.16192 (14)	0.49747 (16)	0.0144 (3)
H6	0.2062	0.1101	0.5613	0.017*
C7	0.2229 (2)	0.26727 (14)	0.52668 (15)	0.0121 (3)
H7	0.2758	0.2873	0.6118	0.014*
C8	0.6371 (2)	0.13286 (13)	0.52466 (15)	0.0154 (3)
H8A	0.7576	0.1447	0.5786	0.023*
H8B	0.6312	0.0718	0.4708	0.023*
H8C	0.5662	0.1197	0.5766	0.023*
C9	0.7181 (2)	0.25482 (14)	0.35875 (16)	0.0159 (3)
H9A	0.7035	0.3209	0.3118	0.024*
H9B	0.7055	0.1952	0.3017	0.024*
H9C	0.8335	0.2530	0.4235	0.024*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Sn	0.00785 (9)	0.00543 (9)	0.00565 (8)	0.00005 (4)	0.00078 (6)	−0.00080 (4)
Cl1	0.0208 (2)	0.0153 (2)	0.00719 (18)	0.00143 (14)	0.00249 (16)	0.00013 (13)
S1	0.00860 (18)	0.00802 (18)	0.00877 (16)	0.00079 (13)	0.00171 (14)	−0.00157 (13)
F1	0.0250 (6)	0.0089 (5)	0.0328 (6)	−0.0026 (4)	0.0006 (5)	−0.0014 (5)
O1	0.0135 (6)	0.0067 (5)	0.0095 (5)	0.0016 (4)	0.0012 (4)	−0.0021 (4)
C1	0.0082 (7)	0.0131 (9)	0.0172 (8)	−0.0007 (6)	0.0039 (6)	−0.0030 (6)
C2	0.0059 (7)	0.0112 (8)	0.0122 (7)	0.0000 (6)	0.0032 (6)	−0.0012 (6)
C3	0.0087 (7)	0.0129 (8)	0.0105 (7)	0.0005 (6)	0.0018 (6)	0.0023 (6)
C4	0.0115 (8)	0.0152 (9)	0.0117 (7)	−0.0004 (6)	0.0020 (6)	−0.0028 (6)
C5	0.0110 (8)	0.0078 (8)	0.0211 (8)	−0.0014 (6)	0.0030 (6)	−0.0018 (6)
C6	0.0117 (8)	0.0151 (8)	0.0152 (8)	0.0015 (6)	0.0032 (6)	0.0065 (6)
C7	0.0089 (8)	0.0176 (8)	0.0090 (7)	−0.0006 (6)	0.0022 (6)	0.0000 (6)
C8	0.0228 (9)	0.0080 (8)	0.0141 (8)	0.0027 (6)	0.0049 (7)	0.0002 (6)
C9	0.0166 (9)	0.0175 (9)	0.0167 (8)	0.0005 (6)	0.0097 (7)	−0.0019 (6)

Geometric parameters (Å, º) top

Sn—C1	2.1628 (16)	C3—C4	1.390 (2)
Sn—C1ⁱ	2.1628 (16)	C3—H3	0.9500
Sn—O1	2.2332 (11)	C4—C5	1.375 (2)
Sn—O1ⁱ	2.2332 (11)	C4—H4	0.9500
Sn—Cl1ⁱ	2.5599 (4)	C5—C6	1.383 (2)
Sn—Cl1	2.5599 (4)	C6—C7	1.392 (2)
S1—O1	1.5417 (11)	C6—H6	0.9500
S1—C9	1.7796 (17)	C7—H7	0.9500
S1—C8	1.7815 (17)	C8—H8A	0.9800
F1—C5	1.360 (2)	C8—H8B	0.9800
C1—C2	1.494 (2)	C8—H8C	0.9800
C1—H1A	0.9900	C9—H9A	0.9800
C1—H1B	0.9900	C9—H9B	0.9800
C2—C7	1.400 (2)	C9—H9C	0.9800
C2—C3	1.401 (2)

C1—Sn—C1ⁱ	180.0	C4—C3—C2	121.27 (15)
C1—Sn—O1	95.99 (5)	C4—C3—H3	119.4
C1—Sn—Cl1	90.05 (5)	C2—C3—H3	119.4
C1—Sn—Cl1ⁱ	89.95 (5)	C5—C4—C3	118.50 (15)
C1—Sn—O1ⁱ	84.01 (5)	C5—C4—H4	120.8
C1—Sn—Cl1ⁱ	89.95 (5)	C3—C4—H4	120.8
O1—Sn—Cl1	90.44 (3)	F1—C5—C4	118.88 (15)
O1—Sn—Cl1ⁱ	89.56 (3)	F1—C5—C6	118.46 (15)
C1ⁱ—Sn—O1	84.01 (5)	C4—C5—C6	122.66 (16)
C1ⁱ—Sn—O1ⁱ	95.99 (5)	C5—C6—C7	118.07 (15)
O1—Sn—O1ⁱ	180.0	C5—C6—H6	121.0
C1ⁱ—Sn—Cl1ⁱ	90.05 (5)	C7—C6—H6	121.0
O1ⁱ—Sn—Cl1ⁱ	90.44 (3)	C6—C7—C2	121.47 (15)
O1ⁱ—Sn—Cl1	89.56 (3)	C6—C7—H7	119.3
Cl1ⁱ—Sn—Cl1	180.000 (18)	C2—C7—H7	119.3
O1—S1—C9	104.51 (8)	S1—C8—H8A	109.5
O1—S1—C8	102.41 (7)	S1—C8—H8B	109.5
C9—S1—C8	98.73 (8)	H8A—C8—H8B	109.5
S1—O1—Sn	127.03 (6)	S1—C8—H8C	109.5
C2—C1—Sn	115.97 (11)	H8A—C8—H8C	109.5
C2—C1—H1A	108.3	H8B—C8—H8C	109.5
Sn—C1—H1A	108.3	S1—C9—H9A	109.5
C2—C1—H1B	108.3	S1—C9—H9B	109.5
Sn—C1—H1B	108.3	H9A—C9—H9B	109.5
H1A—C1—H1B	107.4	S1—C9—H9C	109.5
C7—C2—C3	118.03 (15)	H9A—C9—H9C	109.5
C7—C2—C1	121.12 (14)	H9B—C9—H9C	109.5
C3—C2—C1	120.85 (15)

C9—S1—O1—Sn	92.64 (10)	C3—C4—C5—F1	179.52 (15)
C8—S1—O1—Sn	−164.80 (9)	C3—C4—C5—C6	0.4 (3)
Sn—C1—C2—C7	81.29 (17)	F1—C5—C6—C7	−179.60 (15)
Sn—C1—C2—C3	−98.42 (16)	C4—C5—C6—C7	−0.5 (3)
C7—C2—C3—C4	−0.3 (2)	C5—C6—C7—C2	0.1 (3)
C1—C2—C3—C4	179.42 (15)	C3—C2—C7—C6	0.2 (2)
C2—C3—C4—C5	0.0 (2)	C1—C2—C7—C6	−179.50 (15)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C2–C7 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···F1ⁱⁱ	0.95	2.49	3.333 (2)	147
C6—H6···Cl1ⁱⁱⁱ	0.95	2.77	3.6129 (18)	148
C8—H8B···Cl1^iv	0.98	2.76	3.6379 (17)	150
C9—H9C···Cg1^v	0.98	2.67	3.3887 (19)	130

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

Summary of short interatomic contacts (Å) in (I) top

Contact	distance	symmetry operation
C4···C9	3.371 (2)	-1 + x, y, z
F1···H8A	2.66	1 - x, -y, 1 - z
Cl1···H9B	2.91	1 - x, 1/2 + y, 1/2 - z

Note: (a) the Sn^IV atom is located on a centre of inversion.

Percentage contribution of interatomic contacts to the Hirshfeld surface for (I) top

Contact	percentage contribution
H···H	45.7
Cl···H/H···Cl	15.1
F···H/H···F	19.8
C···H/H···C	12.8
O···H/H···O	4.1
S···H/H···S	1.7
Cl···F/F···Cl	0.6
C···Cl/Cl···C	0.1
F···F	0.1

Selected geometric parameters (Å, °) for molecules of the general formula R₂SnX₂(DMSO)₂ top

Compound	X—Sn—X	O—Sn—O	C—Sn—C	Reference
Me₂SnBr₂(DMSO)₂	180	180	180	Aslanov et al. (1978)
Me₂SnCl₂(DMSO)₂	95.2 (3)	83.7 (5)	172.7 (3)	Aslanov et al. (1978)
Ph₂SnCl₂(DMSO)₂	97.43 (3)	79.34 (9)	172.17 (14)	Sadiq-ur-Rehman et al. (2007)
(4-FC₆H₄CH₂)₂SnCl₂(DMSO)₂	180	180	180	This work

Footnotes

‡Additional correspondence author, e-mail: mmjotani@rediffmail.com.

Funding information

Funding for this research was provided by: Sunway University (award No. INT-RRO-2017–096); University of Malaya (award Nos. RP017A-2014AFR, PG239–2016\#65532;A); Ministry of Higher Education, Malaysia (MOHE) Fundamental Research Grant Scheme (award No. FP033–2014B).

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