Di-n-butyl­bis­[N-(2-meth­oxy­eth­yl)-N-methyl­dithio­carbamato-κ2S,S′]tin(IV): crystal structure and Hirshfeld surface analysis

Mohamad, R.; Awang, N.; Kamaludin, N.F.; Jotani, M.M.; Tiekink, E.R.T.

doi:10.1107/S2056989017001098

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 73| Part 2| February 2017| Pages 260-265

https://doi.org/10.1107/S2056989017001098

Open

access

Di-n-butylbis[N-(2-methoxyethyl)-N-methyldithiocarbamato-κ²S,S′]tin(IV): crystal structure and Hirshfeld surface analysis

Rapidah Mohamad,^a Normah Awang,^b ‡ Nurul F. Kamaludin,^b Mukesh M. Jotani ^c and Edward R. T. Tiekink ^d ^*

^aBiomedical Science Programme, School of Diagnostic and Applied Health Sciences, Faculty of Health Sciences, Universiti Kebangsaan Malaysia, Jalan Raja Muda Abdul Aziz, 50300 Kuala Lumpur, Malaysia, ^bEnvironmental Health and Industrial Safety Programme, School of Diagnostic and Applied Health Sciences, Faculty of Health Sciences, Universiti Kebangsaan Malaysia, Jalan Raja Muda Abdul Aziz, 50300 Kuala Lumpur, Malaysia, ^cDepartment of Physics, Bhavan's Sheth R. A. College of Science, Ahmedabad, Gujarat 380 001, India, and ^dResearch Centre for Chemical Crystallography, School of Science and Technology, Sunway University, 47500 Bandar Sunway, Selangor Darul Ehsan, Malaysia
^*Correspondence e-mail: edwardt@sunway.edu.my

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 19 January 2017; accepted 22 January 2017; online 27 January 2017)

The complete molecule of the title compound, [Sn(C₄H₉)₂(C₅H₁₀NOS₂)₂], is generated by a crystallographic mirror plane, with the Sn^IV atom and the two inner methylene C atoms of the butyl ligands lying on the mirror plane; statistical disorder is noted in the two terminal ethyl groups, which deviate from mirror symmetry. The dithiocarbamate ligand coordinates to the metal atom in an asymmetric mode with the resulting C₂S₄ donor set defining a skew trapezoidal bipyramidal geometry; the n-butyl groups are disposed to lie over the longer Sn—S bonds. Supramolecular chains aligned along the a-axis direction and sustained by methylene-C—H⋯S(weakly coordinating) interactions feature in the molecular packing. A Hirshfeld surface analysis reveals the dominance of H⋯H contacts in the crystal.

Keywords: crystal structure; organotin; dithiocarbamate; Hirshfeld surface analysis.

CCDC reference: 1528948

1. Chemical context

The structural chemistry of molecules with the general formula R₂Sn(S₂CNRR′)₂ is diverse with coordination geometries ranging from five, as in trigonal bipyramid (t-Bu)₂Sn(S₂CNMe₂)₂ (Kim et al., 1987 ), to seven, as in pentagonal bipyramidal [MeOC(=O)CH₂CH₂]₂Sn(S₂CNMe)₂ (Ng et al., 1989 ). However, the overwhelming majority of structures are comprised of a six-coordinate Sn^IV atom, being based on either skew trapezoidal bipyramidal or octahedral coordination geometries (Tiekink, 2008 ). In the former, the dithiocarbamate ligands are coordinating in an asymmetric mode and lie in a plane, with the Sn-bound organic substituents orientated over the weaker Sn—S bonds. In the octahedral molecules, the Sn-bound substituents occupy mutually cis-positions. As a general observation, compounds with Sn-bound aryl groups are octahedral and those with Sn-bound alkyl groups are skew trapezoidal bipyramidal. However, the capricious nature of the ultimate structure adopted in the solid state is nicely illustrated in a recent study whereby Ph₂Sn[S₂CN(CH₂CH₂OMe)Me]₂, with a dithiocarbamate ligand with dissimilar substituents, was found to be octahedral but, Ph₂Sn[S₂CN(CH₂CH₂OMe)₂]₂, with the dithiocarbamate ligand having similar substituents, was skew trapezoidal bipyramidal (Mohamad, Awang, Jotani et al., 2016 ). The structural interest notwithstanding, organotin dithiocarbamates have potential biological applications, with recent investigations focusing upon biocidal activities, e.g. anti-fungal (Yu et al., 2014 ) and anti-bacterial (Ferreira et al., 2012 ), and, especially, as anti-cancer agents (Ferreira et al., 2014 ; Kadu et al., 2015 ), the focus of our interest (Khan et al., 2014 , 2015 ). During the course of the latter studies, crystals of the title compound, n-Bu₂Sn[S₂CN(CH₂CH₂OMe)Me]₂, (I), became available. Herein, the crystal and molecular structures of (I) are described along with a detailed analysis of the molecular packing via an analysis of the Hirshfeld surface.

1.1. Structural commentary

The asymmetric unit of (I) comprises half a molecule being located on a crystallographic mirror plane with the Sn atom along with the two inner C atoms of the n-butyl groups lying on the plane, Fig. 1. The dithiocarbamate ligand coordinates the Sn atom in an asymmetric fashion with the Δ(Sn—S), i.e. the difference between the Sn—S_long and Sn—S_short distances, being ca 0.39 Å, Table 1. This asymmetry is reflected in the associated C—S bond lengths with the short Sn—S bond being correlated with a long C—S bond length, Table 1. The coordination environment is completed by two α-C atoms of the n-butyl groups. The four S atoms are co-planar and define a skewed trapezoidal plane, and the α-C atoms are disposed over the weaker Sn—S bonds so that the C₂S₄ donor set defines a skew trapezoidal bipyramidal geometry.

Table 1
Selected bond lengths (Å)

Sn—S1	2.5425 (5)	Sn—C10	2.138 (3)
Sn—S2	2.9318 (5)	S1—C1	1.7443 (18)
Sn—C6	2.146 (3)	S2—C1	1.6974 (19)

Figure 1
The molecular structure of (I)

, showing the atom-labelling scheme and displacement ellipsoids at the 70% probability level. Unlabelled atoms are related by the symmetry operation (x, $[{1\over 2}]$ − y, z). Only one component of each of the disordered n-butyl groups is shown.

2. Supramolecular features

The only notable contacts identified in the molecular packing are methylene-C—H⋯S(weakly coordinating) interactions that assemble molecules into linear supramolecular chains propagating along the a-axis direction, Fig. 2a and Table 2. The chains pack in the crystal with no specific interactions between them, Fig. 2b. In order to ascertain more information of the nature of interactions between molecules, the molecular packing and its Hirshfeld surface was analysed, as discussed in Hirshfeld surface analysis.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4B⋯S2ⁱ	0.99	2.96	3.608 (2)	124
Symmetry code: (i) x-1, y, z.

Figure 2
The molecular packing in (I)

: (a) supramolecular chain along the a axis sustained by methylene-C—H⋯S interactions shown as orange dashed lines and (b) a view of the unit cell contents in projection down the a axis. Only one component of each of the disordered n-butyl groups is shown.

3. Hirshfeld surface analysis

The Hirshfeld surface analysis for (I) was performed as described recently for organotin dithiocarbamates (Mohamad, Awang, Kamaludin et al., 2016 ). From the views of the Hirshfeld surface mapped over d_norm, in the range −0.298 to +1.346 au, in Fig. 3, the pairs of bright-red spots near hydrogen atoms H9C and H13B of the disordered methyl groups, i.e. deviating from mirror symmetry, indicate their participation in specific intermolecular H⋯H interactions. In the crystal, these lead to a supramolecular chain along the c axis. The presence of this dihydrogen interaction, resulting from disparate charges on respective hydrogen atoms, can also be viewed by the different curvatures and electrostatic potentials around these atoms on the Hirshfeld surface mapped over the electrostatic potential in the range −0.082 to +0.163 au, Fig. 4. Fig. 5 illustrates the immediate environment around a reference molecule within its Hirshfeld surface mapped over d_norm, highlighting the intermolecular C—H⋯S and H⋯H interactions.

Figure 3
Two views of the Hirshfeld surface mapped over d_norm for (I)

. The disorder component has been retained in the images.

Figure 4
Two views of the Hirshfeld surfaces mapped over the electrostatic potential highlighting the disparate charge about the terminal hydrogen atoms (the red and blue regions represent negative and positive electrostatic potentials, respectively) for (I)

Figure 5
A view of the Hirshfeld surface mapped over d_norm for a reference molecule in contact with nearest neighbouring molecules and highlighting intermolecular C—H⋯S and H⋯H interactions, shown as white and black dashed lines, respectively.

From the overall two dimensional fingerprint plot, Fig. 6a, and those delineated (McKinnon et al., 2007 ) into H⋯H, C⋯H/H⋯C, S⋯H/H⋯S, O⋯H/H⋯O and N⋯H/H⋯N contacts, illustrated in Fig. 6b–f, it is interesting to note that each of the specified interatomic contacts involves the participation of H atoms to the Hirshfeld surfaces. The quantitative summary showing the relative contributions from all interatomic contacts, given in Table 3, reinforces this fact.

Table 3
Percentage contribution of the different intermolecular contacts to the Hirshfeld surface in (I)

Contact	% contribution in (I)
H⋯H	74.5
S⋯H/H⋯S	16.2
O⋯H/H⋯O	4.9
C⋯H/H⋯C	3.2
N⋯H/H⋯N	1.2

Figure 6
Views of the (a) full two-dimensional fingerprint plot for (I)

, and plots delineated into (b) H⋯H, (c) C⋯H/H⋯C, (d) S⋯H/H⋯S, (e) O⋯H/H⋯O and (f) N⋯H/H⋯N contacts.

In the fingerprint plot delineated into H⋯H contacts, Fig. 6b, a long and distinctive spike at d_e + d_i ∼ 1.8 Å represents H⋯H bonding described above, Table 4, i.e. between methyl-H9B and -H13B atoms. The major contribution from these contacts to the Hirshfeld surface, i.e. 74.5%, and the essentially same shape of overall and H⋯H delineated fingerprint plots in the upper (d_e, d_i) region, Fig. 6a and b, show the dominance of these interactions in the molecular packing. The peak in the plot corresponding to a second short interatomic H⋯H contact, i.e. between methyl-H2B and methylene-H10A, Table 4, is diminished within the plot due to H9B⋯H13B interaction. The dihydrogen H⋯H bonding also results in short interatomic C⋯H/H⋯C contacts, Table 4, leading to a pair of short peaks at d_e + d_i ∼ 2.8 Å in the delineated fingerprint plot, Fig. 6c; the other interatomic short C⋯H/H⋯C contact is merged within the plot. The presence of the weak C—H⋯S interactions, Table 2, is seen from the fingerprint plot corresponding to S⋯H/H⋯S contacts, Fig. 6d, and is evident as a pair of broad peaks at d_e + d_i ∼ 2.9 Å. The fingerprint plots delineated into O⋯H/H⋯O and N⋯H/H⋯N contacts, Fig. 6e and f, contribute in a minor fashion to the Hirshfeld surface and their characteristic points are longer than their respective van der Waals separations, i.e. longer than 2.72 and 2.75 Å, respectively, and hence it is likely they do not make any significant contribution to the molecular packing.

Table 4
Short interatomic contacts in (I)

Contact	distance	symmetry operation
H9C⋯H13B	1.85	x, y, 1 + z
H2B⋯H10A	2.27	1 − x, −y, 1 − z
C9⋯H13B	2.72	x, y, 1 + z
C13⋯H9C	2.73	x, y, −1 + z
C1⋯H2A	2.86	1 − x, −y, 1 − z
S2⋯H4B	2.96	1 + x, y, z

A comment on the relationship of the modelled disorder, the contribution of H⋯H contacts to the Hirshfeld surface and the nature of the H⋯H contacts is warranted. In the statistical disorder model for (I), it might be normally assumed (as done in Fig. 2b) that that H atoms adopt positions as far apart from each other as possible rather than participate in `non-bonded steric repulsion' (Matta et al., 2003 ). In (I), this does not appear to the case but, rather is an example where H⋯H contacts contribute to the stabilization of the molecular packing. In examples where dihydrogen H⋯H contacts are formed intramolecularly, energies of stabilization up to 10 kcal mol⁻¹ have been suggested (Matta et al., 2003).

4. Database survey

The interest in organotin dithiocarbamates is reflected in the relatively large number of crystal structures available in the crystallographic literature (Groom et al., 2016 ). An example of this interest is twenty structures conforming to the general formula n-Bu₂Sn(S₂CNRR')₂. One structure, i.e. R = R′ = i-Pr (Farina et al., 2000 ), conforms to crystallographic mm2 symmetry (implying disorder in the terminal residues), seven, i.e. R = Me, R′ = n-Bu (Ramasamy et al., 2013 ), R = Me, R′ = CH₂C(H)Me₂ (Ferreira et al., 2012), R = Me, R′ = methylene-1,3-dioxolan-2-yl (Ferreira et al., 2012), R = Et, R′ = methylene-4-pyridyl (Barba et al., 2012 ), NR,R′ = piperidine (Khan et al., 2015), NRR′ = morpholine (Vrábel & Kellö, 1993 ) and NRR′ = 4-(2-methoxyphenyl)piperazine (Zia-ur-Rehman et al., 2012 ), have twofold symmetry with the remainder having no crystallographically imposed symmetry. This implies the structure of (I) is the first of this type to have crystallographic m symmetry. Two structures, i.e. R = R′ = Et (Vrábel et al., 1992 ) and R = R′ = n-Bu (Ramasamy et al., 2013), have two independent molecules in the crystallographic unit and, remarkably, one, i.e. R = i-Pr and R′ = benzyl (Awang, Baba, Yousof et al., 2010 ), has Z′ = 5. In all, there are 26 independent dithiocarbamate ligands in n-Bu₂Sn(S₂CNRR′)₂.

The first noteworthy comment to be made on the structures of n-Bu₂Sn(S₂CNRR′)₂ is that they all conform to the same structural motif as adopted for (I). The Sn—S_short bond lengths in these structures span a relatively narrow range of 2.51 to 2.55 Å and cluster around 2.53 Å. As might be anticipated, a wider range is exhibited by the Sn—S_long bonds, i.e. 2.83 to 3.08 Å and these cluster around 2.96 Å. Given the range of Sn—S_short bond lengths is 0.04 Å and that for Sn—S_long is 0.25 Å, the observation that differences between the average values of Sn—S_short and Sn—S_long span a range of 0.43 Å indicates no specific correlations exist between Sn—S_short and Sn—S_long bond lengths. The S_short—Sn—S_short, S_long—Sn—S_long and C—Sn—C angles cluster around 83, 147 and 136°, respectively. However, these angles span ranges of 8° (range: 80 to 88°), 10° (140 to 151°) and 18° (127 to 145°), respectively. The disparity in the S—Sn—S angles is as expected from the adopted coordination geometry. While, generally, the S_long—Sn—S_long angles are wider than the C—Sn—C angles, there are three exceptional structures, namely R = R′ = Et (Vrábel et al., 1992), R = Et and R′ = Cy (Awang, Baba, Yamin et al., 2010 ) and R = benzyl and R′ = methylene-4-pyridyl (Gupta et al., 2015 ) have C—Sn—C which are marginally wider, by ca 1°, than the S_long—Sn—S_long angles. The fact of non-systematic variations in the geometric parameters in organotin dithiocarbamates has been commented upon previously (Buntine et al., 1998 ; Muthalib et al., 2014 ).

The homogeneity in the n-Bu₂Sn(S₂CNRR′)₂ structural motif does not translate to the diphenyl analogues, i.e. Ph₂Sn(S₂CNRR′)₂. Of the 19 structures conforming to this general formula, seven resemble the skew trapezoidal bipyramidal motif with the majority, i.e. twelve, having a cis-disposition of the tin-bound phenyl substituents. In this context, it is noteworthy that all structures of the general formula Sn(S₂CNRR′)₂X₂, where X = halide, are invariably cis-S₄X₂ octahedral (Tiekink, 2008). Given the electronegativity of a phenyl group is intermediate between that of an alkyl group and a halide, it seems that there is a fine balance between adopting one structural motif over the other for Ph₂Sn(S₂CNRR′)₂ compounds.

5. Synthesis and crystallization

(2-Methoxyethyl)methylamine (10 mmol) dissolved in ethanol (30 ml) was stirred in an ice bath (ca 277 K) for 30 min. 25% Ammonia solution (ca 2 ml) was added to make the solution basic. Then, a cold ethanol solution of carbon disulfide (10 mmol) was added to the solution followed by stirring for about 2 h. Next, di-n-butyltin(IV) dichloride (5 mmol), dissolved in ethanol (30 ml), was added to the solution which was further stirred for 2 h. The precipitate that formed was filtered and then washed three times with cold ethanol to remove any impurities. The precipitate was then dried in a dessicator. The compound was crystallized in a mixture of chloroform and ethanol (1:2 v/v) at room temperature to give colourless slabs. Yield: 66%, m.p. 333–336 K. Analysis. Found C, 40.3; H, 7.3; N, 5.0; S, 22.8. C₁₈H₃₈N₂O₂S₄Sn requires: C, 38.5; H, 6.8; N, 5.0; S, 23.7. IR (cm⁻¹): 1490 ν(C—N), 991 ν(C—S), 553 ν(Sn—C), 420 ν(Sn—S). ¹H NMR (CDCl₃): 7.40–7.74 (15H, Sn–Ph), 4.07 (2H, OCH₂), 3.71 (2H, NCH₂), 3.46 (3H, OCH₃), 3.40 (3H, NCH₃), 2.04 (2H, SnCH₂), 1.92 (2H, SNCH₂CH₂), 1.44 (2H, CH₂CH₃), 0.98 (3H, CH₂CH₃). ¹³C{¹H} NMR (CDCl₃): δ 201.2 (S₂C), 70.1 (OCH₂), 59.1 (NCH₂), 56.6 (OCH₃), 44.5 (NCH₃), 34.3 (SnCH₂), 28.6 (SnCH₂CH₂), 26.5 (CH₂CH₃), 13.9 (CH₂CH₃). ¹¹⁹Sn{¹H} NMR (CDCl₃): 338.6.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 5. Carbon-bound H atoms were placed in calculated positions (C—H = 0.98–0.99 Å) and were included in the refinement in the riding model approximation, with U_iso(H) set to 1.2–1.5U_eq(C). The molecule has crystallographic mirror symmetry with the Sn atom and n-butyl-C atoms lying on the plane. The terminal CH₂CH₃ residue of each n-butyl group is statistically disordered across this plane. Owing to poor agreement, three reflections, i.e. (172), (124) and (155), were omitted from the final cycles of refinement.

Table 5
Experimental details

Crystal data
Chemical formula	[Sn(C₄H₉)₂(C₅H₁₀NOS₂)₂]
M_r	561.43
Crystal system, space group	Monoclinic, P2₁/m
Temperature (K)	148
a, b, c (Å)	7.1021 (4), 18.0761 (8), 10.8809 (7)
β (°)	108.877 (7)
V (Å³)	1321.74 (14)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	1.30
Crystal size (mm)	0.50 × 0.42 × 0.40

Data collection
Diffractometer	Agilent Technologies SuperNova Dual diffractometer with an Atlas detector
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2015 )
T_min, T_max	0.482, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	10631, 4063, 3712
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.739

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.072, 1.12
No. of reflections	4063
No. of parameters	147
No. of restraints	2
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.68, −0.56
Computer programs: CrysAlis PRO (Agilent, 2015), SHELXL97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), ORTEP-3 for Windows (Farrugia, 2012 ), DIAMOND (Brandenburg, 2006 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1528948

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2056989017001098/hb7654sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989017001098/hb7654Isup2.hkl

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Agilent, 2015); cell refinement: CrysAlis PRO (Agilent, 2015); data reduction: CrysAlis PRO (Agilent, 2015); program(s) used to solve structure: SHELXL97 (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).

Di-n-butylbis[N-(2-methoxyethyl)-N-methyldithiocarbamato-κ²S,S']tin(IV) top

Crystal data top

[Sn(C₄H₉)₂(C₅H₁₀NOS₂)₂]	F(000) = 580
M_r = 561.43	D_x = 1.411 Mg m⁻³
Monoclinic, P2₁/m	Mo Kα radiation, λ = 0.71073 Å
a = 7.1021 (4) Å	Cell parameters from 6472 reflections
b = 18.0761 (8) Å	θ = 4.5–31.4°
c = 10.8809 (7) Å	µ = 1.30 mm⁻¹
β = 108.877 (7)°	T = 148 K
V = 1321.74 (14) Å³	Block, colourless
Z = 2	0.50 × 0.42 × 0.40 mm

Data collection top

Agilent Technologies SuperNova Dual diffractometer with an Atlas detector	4063 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	3712 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.022
Detector resolution: 10.4041 pixels mm^-1	θ_max = 31.7°, θ_min = 3.8°
ω scan	h = −6→10
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2015)	k = −26→25
T_min = 0.482, T_max = 1.000	l = −15→12
10631 measured reflections

Refinement top

Refinement on F²	2 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.027	H-atom parameters constrained
wR(F²) = 0.072	w = 1/[σ²(F_o²) + (0.0308P)² + 0.5383P] where P = (F_o² + 2F_c²)/3
S = 1.12	(Δ/σ)_max = 0.002
4063 reflections	Δρ_max = 0.68 e Å⁻³
147 parameters	Δρ_min = −0.56 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	Occ. (<1)
Sn	0.63209 (3)	0.2500	0.65708 (2)	0.02489 (6)
S1	0.36767 (7)	0.15500 (2)	0.65625 (5)	0.02861 (11)
S2	0.76229 (7)	0.09574 (3)	0.66305 (5)	0.02966 (11)
O1	0.3352 (2)	−0.06447 (9)	0.86623 (16)	0.0396 (3)
N1	0.4586 (2)	0.01192 (8)	0.66892 (16)	0.0266 (3)
C1	0.5266 (3)	0.08039 (10)	0.66318 (17)	0.0234 (3)
C2	0.5918 (3)	−0.05193 (11)	0.6850 (2)	0.0341 (4)
H2A	0.6388	−0.0555	0.6099	0.051*
H2B	0.5197	−0.0972	0.6916	0.051*
H2C	0.7059	−0.0458	0.7642	0.051*
C3	0.2511 (3)	−0.00359 (11)	0.6614 (2)	0.0298 (4)
H3A	0.2103	−0.0516	0.6170	0.036*
H3B	0.1637	0.0351	0.6080	0.036*
C4	0.2207 (3)	−0.00634 (11)	0.7922 (2)	0.0325 (4)
H4A	0.2615	0.0413	0.8380	0.039*
H4B	0.0781	−0.0144	0.7807	0.039*
C5	0.2984 (4)	−0.07280 (17)	0.9863 (3)	0.0531 (7)
H5A	0.3355	−0.0272	1.0371	0.080*
H5B	0.3776	−0.1141	1.0350	0.080*
H5C	0.1568	−0.0829	0.9697	0.080*
C6	0.8488 (4)	0.2500	0.8477 (3)	0.0309 (6)
H6A	0.8300	0.2943	0.8959	0.037*	0.5
H6B	0.8300	0.2057	0.8959	0.037*	0.5
C7	1.0587 (5)	0.2500	0.8393 (3)	0.0453 (8)
H7A	1.0830	0.2982	0.8039	0.054*	0.5
H7B	1.0677	0.2111	0.7773	0.054*	0.5
C8	1.2246 (7)	0.2366 (3)	0.9707 (5)	0.0471 (18)	0.5
H8A	1.1858	0.1960	1.0186	0.056*	0.5
H8B	1.3502	0.2226	0.9557	0.056*	0.5
C9	1.2526 (10)	0.3068 (4)	1.0476 (7)	0.0674 (16)*	0.5
H9A	1.2572	0.3488	0.9916	0.101*	0.5
H9B	1.3776	0.3043	1.1202	0.101*	0.5
H9C	1.1413	0.3133	1.0813	0.101*	0.5
C10	0.6376 (4)	0.2500	0.4618 (3)	0.0278 (5)
H10A	0.5652	0.2058	0.4167	0.033*	0.5
H10B	0.5652	0.2942	0.4167	0.033*	0.5
C11	0.8436 (5)	0.2500	0.4497 (3)	0.0442 (8)
H11A	0.9132	0.2039	0.4883	0.053*	0.5
H11B	0.9200	0.2923	0.4994	0.053*	0.5
C12	0.8384 (7)	0.2556 (15)	0.3070 (4)	0.059 (3)	0.5
H12A	0.7967	0.2074	0.2637	0.071*	0.5
H12B	0.7378	0.2929	0.2615	0.071*	0.5
C13	1.0384 (9)	0.2771 (5)	0.2943 (6)	0.086 (3)	0.5
H13A	1.0801	0.3251	0.3361	0.129*	0.5
H13B	1.0263	0.2805	0.2021	0.129*	0.5
H13C	1.1378	0.2395	0.3364	0.129*	0.5

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Sn	0.02457 (10)	0.02545 (9)	0.02660 (10)	0.000	0.01098 (7)	0.000
S1	0.0263 (2)	0.0217 (2)	0.0407 (3)	0.00326 (16)	0.0147 (2)	0.00337 (18)
S2	0.0279 (2)	0.0278 (2)	0.0364 (3)	0.00582 (17)	0.0146 (2)	0.00320 (18)
O1	0.0414 (8)	0.0371 (8)	0.0389 (9)	0.0048 (6)	0.0112 (7)	0.0136 (7)
N1	0.0304 (8)	0.0225 (7)	0.0267 (8)	0.0017 (6)	0.0091 (7)	−0.0005 (6)
C1	0.0269 (8)	0.0243 (8)	0.0194 (8)	0.0017 (6)	0.0080 (7)	−0.0005 (6)
C2	0.0412 (11)	0.0221 (8)	0.0390 (11)	0.0061 (8)	0.0132 (9)	−0.0005 (8)
C3	0.0290 (9)	0.0254 (8)	0.0314 (10)	−0.0022 (7)	0.0048 (8)	0.0023 (7)
C4	0.0303 (9)	0.0318 (9)	0.0358 (11)	0.0016 (7)	0.0113 (8)	0.0071 (8)
C5	0.0475 (14)	0.0690 (17)	0.0420 (14)	−0.0079 (12)	0.0134 (11)	0.0210 (12)
C6	0.0325 (14)	0.0377 (14)	0.0241 (13)	0.000	0.0115 (11)	0.000
C7	0.0279 (14)	0.074 (2)	0.0311 (16)	0.000	0.0051 (13)	0.000
C8	0.044 (2)	0.045 (6)	0.043 (2)	0.003 (2)	0.0020 (18)	0.001 (2)
C10	0.0330 (13)	0.0241 (11)	0.0263 (13)	0.000	0.0096 (11)	0.000
C11	0.0391 (17)	0.066 (2)	0.0323 (17)	0.000	0.0185 (14)	0.000
C12	0.059 (2)	0.091 (8)	0.0343 (19)	0.021 (7)	0.0253 (19)	−0.006 (6)
C13	0.070 (4)	0.148 (10)	0.061 (4)	−0.013 (4)	0.048 (3)	−0.011 (4)

Geometric parameters (Å, º) top

Sn—S1	2.5425 (5)	C6—C7	1.523 (4)
Sn—S2	2.9318 (5)	C6—H6A	0.9900
Sn—S1ⁱ	2.5425 (5)	C6—H6B	0.9900
Sn—S2ⁱ	2.9318 (5)	C7—C8	1.550 (5)
Sn—C6	2.146 (3)	C7—H7A	0.9900
Sn—C10	2.138 (3)	C7—H7B	0.9900
S1—C1	1.7443 (18)	C8—C9	1.498 (7)
S2—C1	1.6974 (19)	C8—H8A	0.9900
O1—C4	1.411 (2)	C8—H8B	0.9900
O1—C5	1.421 (3)	C9—H9A	0.9800
N1—C1	1.337 (2)	C9—H9B	0.9800
N1—C2	1.466 (2)	C9—H9C	0.9800
N1—C3	1.476 (2)	C10—C11	1.511 (4)
C2—H2A	0.9800	C10—H10A	0.9900
C2—H2B	0.9800	C10—H10B	0.9900
C2—H2C	0.9800	C11—C12	1.545 (5)
C3—C4	1.508 (3)	C11—H11A	0.9900
C3—H3A	0.9900	C11—H11B	0.9900
C3—H3B	0.9900	C12—C13	1.521 (8)
C4—H4A	0.9900	C12—H12A	0.9900
C4—H4B	0.9900	C12—H12B	0.9900
C5—H5A	0.9800	C13—H13A	0.9800
C5—H5B	0.9800	C13—H13B	0.9800
C5—H5C	0.9800	C13—H13C	0.9800

C10—Sn—C6	136.27 (11)	C7—C6—H6B	109.5
C10—Sn—S1	104.32 (6)	Sn—C6—H6B	109.5
C6—Sn—S1	107.55 (5)	H6A—C6—H6B	108.1
C10—Sn—S1ⁱ	104.32 (6)	C6—C7—C8	114.3 (3)
C6—Sn—S1ⁱ	107.55 (5)	C6—C7—H7A	108.7
S1—Sn—S1ⁱ	84.97 (2)	C8—C7—H7A	108.7
C10—Sn—S2	85.12 (2)	C6—C7—H7B	108.7
C6—Sn—S2	81.73 (2)	C8—C7—H7B	108.7
S1—Sn—S2	65.482 (14)	H7A—C7—H7B	107.6
S1ⁱ—Sn—S2	150.431 (15)	C9—C8—C7	107.9 (4)
C1—S1—Sn	93.17 (6)	C9—C8—H8A	110.1
C1—S2—Sn	81.45 (6)	C7—C8—H8A	110.1
C4—O1—C5	111.11 (19)	C9—C8—H8B	110.1
C1—N1—C2	120.35 (16)	C7—C8—H8B	110.1
C1—N1—C3	122.84 (15)	H8A—C8—H8B	108.4
C2—N1—C3	116.80 (15)	C8—C9—H9A	109.5
N1—C1—S2	121.49 (14)	C8—C9—H9B	109.5
N1—C1—S1	118.64 (14)	H9A—C9—H9B	109.5
S2—C1—S1	119.87 (10)	C8—C9—H9C	109.5
N1—C2—H2A	109.5	H9A—C9—H9C	109.5
N1—C2—H2B	109.5	H9B—C9—H9C	109.5
H2A—C2—H2B	109.5	C11—C10—Sn	114.6 (2)
N1—C2—H2C	109.5	C11—C10—H10A	108.6
H2A—C2—H2C	109.5	Sn—C10—H10A	108.6
H2B—C2—H2C	109.5	C11—C10—H10B	108.6
N1—C3—C4	113.55 (16)	Sn—C10—H10B	108.6
N1—C3—H3A	108.9	H10A—C10—H10B	107.6
C4—C3—H3A	108.9	C10—C11—C12	112.3 (3)
N1—C3—H3B	108.9	C10—C11—H11A	109.2
C4—C3—H3B	108.9	C12—C11—H11A	109.2
H3A—C3—H3B	107.7	C10—C11—H11B	109.2
O1—C4—C3	109.33 (17)	C12—C11—H11B	109.2
O1—C4—H4A	109.8	H11A—C11—H11B	107.9
C3—C4—H4A	109.8	C13—C12—C11	112.9 (5)
O1—C4—H4B	109.8	C13—C12—H12A	109.0
C3—C4—H4B	109.8	C11—C12—H12A	109.0
H4A—C4—H4B	108.3	C13—C12—H12B	109.0
O1—C5—H5A	109.5	C11—C12—H12B	109.0
O1—C5—H5B	109.5	H12A—C12—H12B	107.8
H5A—C5—H5B	109.5	C12—C13—H13A	109.5
O1—C5—H5C	109.5	C12—C13—H13B	109.5
H5A—C5—H5C	109.5	H13A—C13—H13B	109.5
H5B—C5—H5C	109.5	C12—C13—H13C	109.5
C7—C6—Sn	110.60 (19)	H13A—C13—H13C	109.5
C7—C6—H6A	109.5	H13B—C13—H13C	109.5
Sn—C6—H6A	109.5

C2—N1—C1—S2	4.5 (3)	C1—N1—C3—C4	−91.6 (2)
C3—N1—C1—S2	−176.29 (14)	C2—N1—C3—C4	87.6 (2)
C2—N1—C1—S1	−175.26 (14)	C5—O1—C4—C3	−175.28 (18)
C3—N1—C1—S1	3.9 (2)	N1—C3—C4—O1	−62.2 (2)
Sn—S2—C1—N1	−178.28 (16)	Sn—C6—C7—C8	−170.1 (2)
Sn—S2—C1—S1	1.51 (10)	C6—C7—C8—C9	−76.4 (5)
Sn—S1—C1—N1	178.07 (14)	Sn—C10—C11—C12	−175.9 (11)
Sn—S1—C1—S2	−1.72 (11)	C10—C11—C12—C13	164.0 (11)

Symmetry code: (i) x, −y+1/2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4B···S2ⁱⁱ	0.99	2.96	3.608 (2)	124

Symmetry code: (ii) x−1, y, z.

Percentage contribution of the different intermolecular contacts to the Hirshfeld surface in (I) top

Contact	% contribution in (I)
H···H	74.5
S···H/H···S	16.2
O···H/H···O	4.9
C···H/H···C	3.2
N···H/H···N	1.2

Short interatomic contacts in (I) top

Contact	distance	symmetry operation
H9C···H13B	1.85	x, y, 1 + z
H2B···H10A	2.27	1-x, -y, 1 - z
C9···H13B	2.72	x, y, 1 + z
C13···H9C	2.73	x, y, -1 + z
C1···H2A	2.86	1-x, -y, 1 - z
S2···H4B	2.96	1 + x, y, z

Footnotes

‡Additional correspondence author, e-mail: awang_normah@yahoo.com.

Acknowledgements

This work was supported by grant GGPM-2016-061. We gratefully acknowledge the School of Chemical Science and Food Technology, Universiti Kebangsaan Malaysia for providing the essential laboratory facilities. We would also like to acknowledge the technical support from the laboratory assistants of the Faculty of Science and Technology, Universiti Kebangsaan Malaysia. Intensity data were collected in the University of Malaya crystallographic laboratory.

Funding information

Funding for this research was provided by: Universiti Kebangsaan Malaysia (award No. GGPM-2016-061).

References

Agilent (2015). CrysAlis PRO. Agilent Technologies Inc., Santa Clara, CA, USA. Google Scholar
Awang, N., Baba, I., Yousof, N. S. A. M. & Kamaludin, N. F. (2010). Am. J. Appl. Sci. 7, 1047–1052. CSD CrossRef CAS Google Scholar
Awang, N., Baba, I., Yamin, B. M. & Ng, S. W. (2010). Acta Cryst. E66, m938. Web of Science CSD CrossRef IUCr Journals Google Scholar
Barba, V., Arenaza, B., Guerrero, J. & Reyes, R. (2012). Heteroat. Chem. 23, 422–428. Web of Science CSD CrossRef CAS Google Scholar
Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Buntine, M. A., Hall, V. J., Kosovel, F. J. & Tiekink, E. R. T. (1998). J. Phys. Chem. A, 102, 2472–2482. Web of Science CSD CrossRef CAS Google Scholar
Farina, Y., Baba, I., Othman, A. H. & Ng, S. W. (2000). Main Group Met. Chem. 23, 795–796. CrossRef CAS Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Ferreira, I. P., de Lima, G. M., Paniago, E. B., Rocha, W. R., Takahashi, J. A., Pinheiro, C. B. & Ardisson, J. D. (2012). Eur. J. Med. Chem. 58, 493–503. Web of Science CSD CrossRef CAS PubMed Google Scholar
Ferreira, I. P., de Lima, G. M., Paniago, E. B., Rocha, W. R., Takahashi, J. A., Pinheiro, C. B. & Ardisson, J. D. (2014). Polyhedron, 79, 161–169. Web of Science CSD CrossRef CAS Google Scholar
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CSD CrossRef IUCr Journals Google Scholar
Gupta, A. N., Kumar, V., Singh, V., Rajput, A., Prasad, L. B., Drew, M. G. B. & Singh, N. (2015). J. Organomet. Chem. 787, 65–72. CSD CrossRef CAS Google Scholar
Kadu, R., Roy, H. & Singh, V. K. (2015). Appl. Organomet. Chem. 29, 746–755. Web of Science CrossRef CAS Google Scholar
Khan, M. D., Akhtar, J., Malik, M. A., Akhtar, M. & Revaprasadu, N. (2015). New J. Chem. 39, 9569–9574. CSD CrossRef CAS Google Scholar
Khan, N., Farina, Y., Mun, L. K., Rajab, N. F. & Awang, N. (2014). J. Mol. Struct. 1076, 403–410. Web of Science CSD CrossRef CAS Google Scholar
Kim, K., Ibers, J. A., Jung, O.-S. & Sohn, Y. S. (1987). Acta Cryst. C43, 2317–2319. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Matta, C. F., Hernández-Trujillo, J., Tang, T.-H. & Bader, R. F. W. (2003). Chem. Eur. J. pp. 1940–1951. CrossRef Google Scholar
McKinnon, J. J., Jayatilaka, D. & Spackman, M. A. (2007). Chem. Commun. pp. 3814–3816. Web of Science CrossRef Google Scholar
Mohamad, R., Awang, N., Jotani, M. M. & Tiekink, E. R. T. (2016). Acta Cryst. E72, 1130–1137. Web of Science CSD CrossRef IUCr Journals Google Scholar
Mohamad, R., Awang, N., Kamaludin, N. F., Jotani, M. M. & Tiekink, E. R. T. (2016). Acta Cryst. E72, 1480–1487. CSD CrossRef IUCr Journals Google Scholar
Muthalib, A. F. A., Baba, I., Khaledi, H., Ali, H. M. & Tiekink, E. R. T. (2014). Z. Kristallogr. 229, 39–46. Google Scholar
Ng, S. W., Wei, C., Kumar Das, V. G., Jameson, G. B. & Butcher, R. J. (1989). J. Organomet. Chem. 365, 75–82. CSD CrossRef CAS Web of Science Google Scholar
Ramasamy, K., Kuznetsov, V. L., Gopal, K., Malik, M. A., Raftery, J., Edwards, P. P. & O'Brien, P. (2013). Chem. Mater. 25, 266–276. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Tiekink, E. R. T. (2008). Appl. Organomet. Chem. 22, 533–550. Web of Science CrossRef CAS Google Scholar
Vrábel, V. & Kellö, E. (1993). Acta Cryst. C49, 873–875. CSD CrossRef Web of Science IUCr Journals Google Scholar
Vrábel, V., Lokaj, J., Kellö, E., Garaj, J., Batsanov, A. C. & Struchkov, Yu. T. (1992). Acta Cryst. C48, 633–635. CSD CrossRef IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Yu, Y., Yang, H., Wei, Z.-W. & Tang, L.-F. (2014). Heteroat. Chem. 25, 274–281. Web of Science CSD CrossRef CAS Google Scholar
Zia-ur-Rehman, Muhammad, N., Shah, A., Ali, S., Butler, I. S. & Meetsma, A. (2012). J. Coord. Chem. 65, 3238–3253. 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.