Crystal structures and Hirshfeld surface analyses of bis­[N,N-bis­(2-meth­oxy­eth­yl)di­thio­carbamato-κ2S,S′]di-n-butyl­tin(IV) and [N-(2-meth­oxy­eth­yl)-N-methyl­dithio­carbamato-κ2S,S′]tri­phenyl­tin(IV)

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

doi:10.1107/S2056989018001901

research communications

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 74| Part 3| March 2018| Pages 302-308

https://doi.org/10.1107/S2056989018001901

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Crystal structures and Hirshfeld surface analyses of bis[N,N-bis(2-methoxyethyl)dithiocarbamato-κ²S,S′]di-n-butyltin(IV) and [N-(2-methoxyethyl)-N-methyldithiocarbamato-κ²S,S′]triphenyltin(IV)

Rapidah Mohamad,^a Normah Awang,^b ‡ Nurul Farahana 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 30 January 2018; accepted 31 January 2018; online 7 February 2018)

The crystal and molecular structures of the two title organotin dithiocarbamate compounds, [Sn(C₄H₉)₂(C₇H₁₄NO₂S₂)₂], (I), and [Sn(C₆H₅)₃(C₅H₁₀NOS₂)], (II), are described. Both structures feature asymmetrically bound dithiocarbamate ligands leading to a skew-trapezoidal bipyramidal geometry for the metal atom in (I) and a distorted tetrahedral geometry in (II). The complete molecule of (I) is generated by a crystallographic twofold axis (Sn site symmetry 2). In the crystal of (I), molecules self-assemble into a supramolecular array parallel to (10-1) via methylene-C—H⋯O(methoxy) interactions. In the crystal of (II), supramolecular dimers are formed via pairs of weak phenyl-C—H⋯π(phenyl) contacts. In each of (I) and (II), the specified assemblies connect into a three-dimensional architecture without directional interactions between them. Hirshfeld surface analyses confirm the importance of H⋯H contacts in the molecular packing of each of (I) and (II), and in the case of (I), highlight the importance of short methoxy-H⋯H(butyl) contacts between layers.

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

CCDC references: 1821129; 1821128

1. Chemical context

While formerly the purview of all-alkyl substituents (Hogarth, 2005 ; Heard, 2005 ), recent work in the chemistry of dithiocarbamate ligands, ⁻S₂CN(R)R′, has increasingly seen the inclusion of oxygen atoms in these N-bound groups (Hogarth et al., 2009 ), leading to different chemistry/biochemistry. Oxygen can be present as a hydroxyl group, giving rise to supramolecular aggregation patterns based on hydrogen bonding for otherwise non-aggregating species (Tan et al., 2016 ; Jotani et al., 2017 ) or as an ether, giving rise to compounds with biological activity (Ferreira et al., 2012 ). Organotin dithiocarbamates have long been known to possess biological activity, in particular as anti-tumour and anti-bacterial agents (Tiekink, 2008 ). In keeping with the aforementioned, several recent studies have appeared investigating the biological activity of metal dithiocarbamates where the ligand contains at least one 2-methoxyethyl substituent (Khan et al., 2013 , 2016 ), including anti-bacterial potential of organotins (Mohamad, Awang, Kamaludin & Abu Bakar, 2016 ; Mohamad, Awang & Kamaludin, 2016 ). The latter studies have been augmented by several structural investigations in recent times (Mohamad, Awang, Jotani & Tiekink, 2016 ; Mohamad, Awang, Kamaludin, Jotani et al., 2016 ; Mohamad et al., 2017 ). In a continuation of these structural studies, herein, the crystal and molecular structures of (n-Bu)₂Sn[S₂CN(CH₂CH₂OCH₃)₂]₂ (I) and (C₆H₅)₃Sn[S₂CN(CH₃)CH₂CH₂OCH₃] (II) are reported along with a Hirshfeld surface analysis to provide more details on the molecular packing, which generally lacks directional intermolecular interactions.

1.1. Structural commentary

The tin atom in (I), Fig. 1a, lies on a crystallographic twofold axis so that the asymmetric unit comprises half a molecule. The dithiocarbamate ligand coordinates to the tin atom with quite disparate Sn—S bond lengths with Δ(Sn—S) = d(Sn—S_long) − (Sn—S)_short = 0.38 Å, Table 1. The disparity in the Sn—S bond lengths is reflected in systematic differences in the C—S bonds lengths with the bond associated with the stronger Sn—S1 bond being significantly longer, i.e. by about 0.03 Å, than the C—S bond associated with the weaker Sn—S2 bond. The coordination environment is completed by two α-carbon atoms of the n-butyl substituents. The resultant C₂S₄ donor set defines a skew-trapezoidal bipyramidal geometry with the tin-bound organic substituents lying over the weaker Sn—S2 bonds, which subtend an angle at the tin atom approximately 50° wider than that subtended by the S1 atoms, Table 1. The 2-methoxyethyl groups lie to either side of the S₂CN residue and have very similar conformations, as seen in the values of the C1—N1—C2—C3, N1—C2—C3—O1 and C2—C3—O1—C4 torsion angles of −94.1 (4), −67.4 (4) and −177.1 (3)°, indicating that − anti-clinal, − syn-clinal and − anti-periplanar descriptors, respectively, are in effect. For the O2-methoxyethyl group, the equivalent torsion angles are −82.0 (4), −70.3 (4) and −169.1 (3)°. The independent n-butyl substituent has an all-trans (+ anti-periplanar) conformation, as seen in the values of the Sn—C8—C9—C10 and C8—C9—C10— C11 torsion angles of 172.9 (2) and 176.3 (3)°, respectively.

Table 1
Selected geometric parameters (Å, °) for (I)

Sn—S1	2.5503 (9)	S1—C1	1.736 (3)
Sn—S2	2.9300 (9)	S2—C1	1.702 (3)
Sn—C8	2.131 (3)

S1—Sn—S2	65.13 (3)	S2—Sn—C8	83.95 (9)
S1—Sn—S1ⁱ	87.95 (4)	S1—Sn—C8ⁱ	104.64 (9)
S2—Sn—S2ⁱ	141.79 (3)	S2—Sn—C8ⁱ	82.96 (9)
S1—Sn—C8	104.38 (9)	C8—Sn—C8ⁱ	139.25 (17)
Symmetry code: (i) $[-x, y, -z+{\script{1\over 2}}]$ .

Figure 1
The molecular structures of (a) (I)

and (b) (II)

, showing the atom-labelling schemes and displacement ellipsoids at the 50% probability level. Unlabelled atoms in (a) are related by the symmetry operation x, y, $[{1\over 2}]$ − z.

The molecule in (II), Fig. 1b, lies on a general position and has a quite distinct coordination geometry owing to the presence of three tin-bound phenyl groups. As for (I), the dithiocarbamate ligand coordinates in an asymmetric mode with Δ(Sn—S) being 0.55 Å. Consistent with the greater disparity in Sn—S bond lengths, the difference in the associated C—S bond lengths in (II) is greater cf. (I), i.e. nearly 0.07 Å, Table 2. The increased asymmetry in the mode of coordination of the dithiocarbamate ligand in (II), cf. (I), is correlated with the reduced Lewis acidity of the tin atom in the triorganotin compound, (II), compared with that in the diorganotin compound, (I). The angles subtended at the tin atom vary from a narrow 64.37 (2)° for the S1—Sn—S2 chelate angle to 155.54 (8)° for S2—Sn—C11. The C₃S₂ donor set approximates a trigonal–bipyramidal geometry with the value of τ, an indicator of a five-coordinate coordination geometry, being 0.61, cf. 1.0 for an ideal trigonal bipyramid and 0.0 for an ideal square pyramid (Addison et al., 1984 ). If the coordination geometry is considered as being based on a C₃S donor set, the range of tetrahedral angles is 91.17 (8)°, for S1—Sn—C11, to 119.09 (7)°, for S1—Sn—C31. The C21—Sn—C31 angle, at 115.55 (10)°, is wider by 10° than the other C—Sn—C angles, a result correlated with the close approach of the S2 atom. The 2-methoxyethyl group has a very similar conformation to the O1-methoxyethyl group in (I), with the values of the C1—N1—C3—C4, N1—C3—C4—O1 and C5—O1—C4—C3 torsion angles being 95.1 (3), 81.8 (3) and 178.7 (3)°, respectively.

Table 2
Selected geometric parameters (Å, °) for (II)

Sn—S1	2.4711 (7)	Sn—C11	2.162 (3)
Sn—S2	3.0180 (7)	Sn—C21	2.136 (3)
S1—C1	1.755 (3)	Sn—C31	2.133 (2)
S2—C1	1.686 (3)

S1—Sn—S2	64.37 (2)	S2—Sn—C21	87.38 (7)
S1—Sn—C11	91.17 (8)	S2—Sn—C31	87.83 (7)
S1—Sn—C21	115.84 (7)	C11—Sn—C21	104.11 (10)
S1—Sn—C31	119.09 (7)	C11—Sn—C31	105.78 (10)
S2—Sn—C11	155.54 (8)	C21—Sn—C31	115.55 (10)

2. Supramolecular features

Geometric parameters characterizing the intermolecular interactions operating in the crystal structures of (I) and (II) are collected in Tables 3 and 4, respectively. The molecular packing of (I) is dominated by methylene-C—H⋯O(methoxy) interactions whereby each methoxy-oxygen atom accepts a single interaction. Supramolecular chains form about the twofold axis along b so that a supramolecular array is formed parallel to (10 $[\overline{1}]$ ), Fig. 2a. Layers stack with no directional interactions between them, Fig. 2b.

Table 3
Hydrogen-bond geometry (Å, °) for (I)

Cg1 is the centroid of the N4/C5–C9 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4A⋯O2ⁱⁱ	0.98	2.55	3.423 (5)	149
C6—H6B⋯O1ⁱⁱⁱ	0.99	2.57	3.553 (4)	175
Symmetry codes: (ii) $[-x+{\script{1\over 2}}, -y-{\script{1\over 2}}, -z+1]$ ; (iii) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ .

Table 4
Hydrogen-bond geometry (Å, °) for (II)

Cg1 is the centroid of the C21–C26 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C35—H35⋯Cg1ⁱ	0.95	2.99	3.760 (3)	139
Symmetry code: (i) -x+1, -y, -z+1.

Figure 2
Molecular packing in the crystal of (I)

: (a) supramolecular layer parallel to (10 $[\overline{1}]$ ) sustained by methylene-C—H⋯O(methoxy) interactions shown as orange dashed lines and (b) a view of the unit-cell contents in projection down the b axis, with one layer highlighted in space-filling mode.

The molecular packing in (II) is largely devoid of directional interactions with the only contact rated in PLATON (Spek, 2009 ) being a phenyl-C—H⋯π(phenyl) contact. These occur between centrosymmetrically related molecules to form dimeric aggregates which assemble into columns parallel to the a axis, Fig. 3

Figure 3
Molecular packing in the crystal of (II)

: a view of the unit-cell contents in projection down the a axis. The phenyl-C—H⋯π(phenyl) interactions are shown as purple dashed lines.

3. Hirshfeld surface analysis

The Hirshfeld surface calculations for the organotin derivatives (I) and (II) were performed in accord with recent work on related organotin dithiocarbamate compounds (Mohamad et al., 2017), and these exhibit different intermolecular environments as described below.

The bright-red spots near each of the methoxy-O1 and -O2, and methylene-H4A and H6B atoms lying on both the sides of twofold symmetry axis on the Hirshfeld surfaces mapped over d_norm for (I) in Fig. 4a and b represent the dominant intermolecular C—H⋯O contacts, Table 3. In addition, the bright-red spots appearing near the methoxy-H8B and butyl-H8A atoms in Fig. 4c indicate the significant influence of intra-layer H⋯H contacts, Table 5. On the Hirshfeld surface mapped over the electrostatic potential for (I) shown in Fig. 5a and b, the donors and acceptors are represented with blue and red regions around the respective atoms corresponding to positive and negative potentials, respectively.

Table 5
Summary of short interatomic contacts (Å) in (I)

Contact	Distance	Symmetry operation
(I)
H4B⋯H8A	2.00	−x, − y, 1 − z
H5A⋯H6B	2.21	$[{1\over 2}]$ − x, $[{1\over 2}]$ − y, 1 − z
H8B⋯H10B	2.37	−x, 1 − y, 1 − z
H10B⋯H10B	2.37	−x, 1 − y, 1 − z
(II)
H14⋯H33	2.37	1 + x, 1 + y, z
H16⋯H33	2.25	x, 1 + y, z
H22⋯H34	2.33	x, 1 + y, z
C1⋯H3B	2.86	−x, − y, 2 − z
C14⋯H4A	2.85	1 − x, 1 − y, 2 − z

Figure 4
Views of Hirshfeld surface for (I)

mapped over d_norm in the range −0.163 to +1.302, highlighting (a) and (b) intermolecular methylene-C—H⋯O(methoxy) interactions and (c) short intra-layer H⋯H contacts between methoxy- and butyl-hydrogen atoms H4B and H8A as sky-blue dashed lines.

Figure 5
Views of Hirshfeld surface mapped over the electrostatic potential (the red and blue regions represent negative and positive electrostatic potentials, respectively) for: (a) and (b) a molecule of (I)

in the range −0.054 to +0.036 au and (c) a molecule of (II)

in the range ±0.036 au.

The Hirshfeld surfaces mapped over d_norm for (II) (not shown), indicate the absence of significant directional interactions operating in the crystal as no characteristic red spots appear on the surface. The blue and red regions on the Hirshfeld surface mapped over electrostatic potential for (II) in Fig. 5c are due to polarization of charges near the respective functional groups and do not represent any significant interaction in the crystal. The weak intermolecular C—H⋯π contact and intra-layer interatomic H⋯H contacts (Table 5) present in the crystal of (II) are illustrated in Fig. 6.

Figure 6
Views of the Hirshfeld surface for (II)

mapped with the shape-index property showing (a) intermolecular C—H⋯π/π⋯H—C contacts and (b) short interatomic H⋯H contacts through black-dashed lines.

The overall two-dimensional fingerprint plots for (I) and (II), Fig. 7a and b, reveal the distinct supramolecular associations in their crystals. The terminal methoxy-ethyl and coordinated n-butyl substituents in (I) form significant intra-layer H⋯H contacts in comparison to (II), Table 5. This fact is also indicated in the fingerprint plots delineated into H⋯H contacts (McKinnon et al., 2007 ), showing a short thick spike at d_e + d_i ∼ 2.0 Å and the distribution of points with greater density in (d_e, d_i) range ∼1.0 to 1.2 Å for (I) in Fig. 7a, and a small peak at d_e + d_i ∼ 2.2 Å with relatively few points at d_e + d_i < 2.4 Å for (II) in Fig. 7b. The fingerprint plot delineated into O⋯H/H⋯O contacts for (I), Fig. 7a, characterizes intermolecular C—H⋯O interactions as the pair of forceps-like tips at d_e + d_i ∼ 2.5 Å. A low percentage contribution due to O⋯H/H⋯O contacts is noted for (II), as summarized in Table 6. The relatively high, i.e. 29.1%, contribution from C⋯H/H⋯C contacts to the Hirshfeld surfaces of (II) is due to the presence of tin-bound phenyl substituents and the resulting short interatomic C⋯H/H⋯C contacts, Table 5, and intermolecular C—H⋯π contact, Table 4, viewed as the pair of peaks at d_e + d_i ∼ 2.8 Å and the distribution of points around d_e + d_i ∼ 2.9 Å in both the wings of its delineated fingerprint plot, Fig. 7b. Although S⋯H/H⋯S contacts have significant contributions to the Hirshfeld surfaces of (I) and (II), as summarized in Table 6, their interatomic distances are farther than sum of their van der Waals radii, i.e. d_e + d_i > 3.0 Å, Fig. 7, and hence do not have a structure-directing influence on the molecular packing. The small contributions from other contacts in (I) and (II) also have negligible impact in the respective crystals.

Table 6
Percentage contributions of interatomic contacts to the Hirshfeld surface for (I) and (II)

Contact	% contribution in (I)	% contribution in (II)
H⋯H	77.9	58.9
S⋯H/H⋯S	12.2	7.3
C⋯H/H⋯C	1.6	29.1
O⋯H/H⋯O	7.9	2.5
N⋯H/H⋯N	0.4	0.7
C⋯S/S⋯C	0.0	1.3
S⋯O/O⋯S	0.0	0.1
Sn⋯H/N⋯Sn	0.0	0.1

Figure 7
Comparison of the full two-dimensional fingerprint plots for (I)

and (II)

, and the plots delineated into (a) H⋯H, O⋯H/H⋯O and S⋯H/H⋯S contacts and (b) H⋯H, C⋯H/H⋯C and S⋯H/H⋯S contacts.

4. Database survey

It is well documented that organotin dithiocarbamates, R′′_xSn(S₂CNRR′)_4–x, can adopt a variety of coordination geometries, especially for x = 2 (Tiekink, 2008). The structural motifs for the x = 2 series were recently summarized (Zaldi et al., 2017 ) and four structural motifs recognized. With a trapezoidal bipyramidal geometry being observed in (I), this structure conforms to the common motif for the x = 2 structures. There is one other diorganotin structure with the same dithiocarbamate ligand, viz. the R′′ = C₆H₅ compound (Mohamad, Awang, Jotani et al., 2016). This, too, adopts the common trapezoidal bipyramidal geometry although a good number of other derivatives with R′′ = Ph adopt octahedral geometries, such as in (C₆H₅)₂Sn[S₂CN(CH₃)CH₂CH₂OCH₃]₂ (Muthalib et al., 2014 ) featuring the same dithiocarbamate ligand as in (II). The observed anisobidentate mode of coordination for the dithiocarbamate ligand in (II) is as expected and in fact is the norm for x = 3 structures which may be described as having 4 + 1 coordination geometries (Tiekink, 2008).

5. Synthesis and crystallization

All chemicals and solvents were used as purchased without purification. The melting points were determined using an automated melting point apparatus (MPA 120 EZ-Melt). Carbon, hydrogen, nitrogen and sulfur analyses were performed on a Leco CHNS-932 Elemental Analyzer. The IR spectra were obtained on a Perkin Elmer Spectrum GX from 4000 to 400 cm⁻¹. NMR spectra were recorded at room temperature on Bruker AVANCE 400 lll HD in CDCl₃.

Synthesis of (I): bis(2-methoxyethyl)amine (Aldrich; 1.48 ml, 10 mmol) dissolved in ethanol (30 ml) was stirred for 30 min. Then, carbon disulfide (0.6 ml, 10 mmol) in cold ethanol was added and the resulting mixture was stirred for 2 h. A 25% ammonia solution (1–2 ml) was added to generate basic conditions. Then, di-n-butyltin(IV) dichloride (Aldrich; 1.52 g, 5 mmol) dissolved in ethanol (20–30 ml) was added dropwise into the solution and stirring was continued for 2 h. All reactions were carried out at 277 K. The precipitate that formed was dried and collected. Colourless prisms were harvested from the slow evaporation of its chloroform:ethanol (2:1 v/v) solution. Yield: 72%. M.p. 341–342 K. Elemental analysis: calculated (%): C 40.68, H 7.14, N 4.31, S 19.75. Found (%): C 41.76, H 6.07, N 4.91, S 19.25. IR (KBr cm⁻¹): 1487 ν(C—N), 992 ν(C—S), 544 ν(Sn—C), 386 ν(Sn—S). ¹H NMR (CDCl₃): δ 4.13 (2H, O—CH₂); 3.70 (2H, N—CH₂); 3.35 (3H, O—CH₃); 1.45–2.05 (6H, Sn—CH₂—CH₂—CH₂–), 0.94 (3H, CH₂—CH₃). ¹³C NMR (CDCl₃): δ 201.52 (NCS₂); 70.07 (O—CH₂); 55.59 (N—CH₂); 59.01 (O—CH₃); 34.26 Sn—CH₂; 28.55 Sn—CH₂CH₂; 26.41 Sn—CH₂CH₂CH₂; 13.87 CH₂CH₃. ¹¹⁹Sn NMR (CDCl₃): δ −335.5.

Synthesis of (II): The synthesis of (II) was carried out in the same manner as for (I) using (2-methoxyethyl)methylamine (Santa Cruz Biotechnology; 1.1 ml, 10 mmol) and triphenyltin(IV) chloride (Merck; 3.85 g, 10 mmol). Crystallization in the form of colourless slabs was from its chloroform:ethanol (1:2 v/v) solution. Yield: 78%. M.p. 366-367 K. Elemental analysis: calculated (%): C 53.71, H 4.89, N 2.72, S 12.47. Found (%): C 54.28, H 5.26, N 2.73, S 12.5. IR (KBr cm⁻¹): 1477 ν(C—N), 997 ν(C—S), 527 ν(Sn—C), 451 ν(Sn—S). ¹H NMR (CDCl₃): δ 7.41–7.82 (15H, Sn—C₆H₅); 4.05 (2H, O—CH₂); 3.71 (2H, N—CH₂); 3.51 (3H, O—CH₃); 3.38 (3H, N—CH₃). ¹³C NMR (CDCl₃): δ 196.97 (NCS₂); 128.25–142.28 (C-aromatic); 70.09 (O—CH₂); 59.06 (N—CH₂); 58.10 (O—CH₃); 45.81 (N—CH₃);. ¹¹⁹Sn NMR (CDCl₃): δ −183.8.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 7. 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). For (I), the maximum and minimum residual electron density peaks of 2.18 and 0.88 e Å⁻³, respectively, were located 0.88 and 1.03 Å from the S1 and Sn atoms, respectively. For (II), the maximum and minimum residual electron density peaks of 2.21 and 1.82 e Å⁻³, respectively, were located 0.96 and 0.76 Å from the Sn atom.

Table 7
Experimental details

	(I)	(II)
Crystal data
Chemical formula	[Sn(C₄H₉)₂(C₇H₁₄NO₂S₂)₂]	[Sn(C₆H₅)₃(C₅H₁₀NOS₂)]
M_r	649.54	514.25
Crystal system, space group	Monoclinic, C2/c	Triclinic, P $[\overline{1}]$
Temperature (K)	173	148
a, b, c (Å)	25.8819 (17), 7.1272 (4), 16.4146 (11)	7.6258 (3), 10.2178 (3), 14.8621 (6)
α, β, γ (°)	90, 97.282 (6), 90	91.976 (3), 90.655 (3), 107.875 (3)
V (Å³)	3003.5 (3)	1101.19 (7)
Z	4	2
Radiation type	Mo Kα	Mo Kα
μ (mm⁻¹)	1.16	1.36
Crystal size (mm)	0.30 × 0.15 × 0.05	0.50 × 0.30 × 0.30

Data collection
Diffractometer	Agilent Technologies SuperNova Dual diffractometer with Atlas detector	Agilent Technologies SuperNova Dual diffractometer with Atlas detector
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2015 )	Multi-scan (CrysAlis PRO; Agilent, 2015)
T_min, T_max	0.247, 1.000	0.479, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	18349, 4631, 3678	11916, 6547, 6089
R_int	0.054	0.046
(sin θ/λ)_max (Å⁻¹)	0.738	0.739

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.128, 1.05	0.040, 0.114, 1.09
No. of reflections	4631	6547
No. of parameters	153	255
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	2.18, −0.88	2.21, −1.82
Computer programs: CrysAlis PRO (Agilent, 2015), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), ORTEP-3 for Windows (Farrugia, 2012 ), DIAMOND (Brandenburg, 2006 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC references: 1821129; 1821128

Crystal structure: contains datablocks I, II, global. DOI: https://doi.org/10.1107/S2056989018001901/hb7731sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989018001901/hb7731Isup2.hkl

Structure factors: contains datablock II. DOI: https://doi.org/10.1107/S2056989018001901/hb7731IIsup3.hkl

checkCIF report

Computing details top

For both structures, data collection: CrysAlis PRO (Agilent, 2015); cell refinement: CrysAlis PRO (Agilent, 2015); data reduction: CrysAlis PRO (Agilent, 2015); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015). Molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg, 2006) for (I); ORTEP-3 for Windows (Farrugia, 2012) for (II). For both structures, software used to prepare material for publication: publCIF (Westrip, 2010).

Bis[N,N-bis(2-methoxyethyl)dithiocarbamato-κ²S,S']di-n-butyltin(IV) (I) top

Crystal data top

[Sn(C₄H₉)₂(C₇H₁₄NO₂S₂)₂]	F(000) = 1352
M_r = 649.54	D_x = 1.436 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 25.8819 (17) Å	Cell parameters from 5103 reflections
b = 7.1272 (4) Å	θ = 3.9–30.2°
c = 16.4146 (11) Å	µ = 1.16 mm⁻¹
β = 97.282 (6)°	T = 173 K
V = 3003.5 (3) Å³	Prism, colourless
Z = 4	0.30 × 0.15 × 0.05 mm

Data collection top

Agilent Technologies SuperNova Dual diffractometer with Atlas detector	4631 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	3678 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.054
Detector resolution: 10.4041 pixels mm^-1	θ_max = 31.6°, θ_min = 3.3°
ω scan	h = −36→37
Absorption correction: multi-scan (CrysAlis Pro; Agilent, 2015)	k = −9→9
T_min = 0.247, T_max = 1.000	l = −18→23
18349 measured reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.048	H-atom parameters constrained
wR(F²) = 0.128	w = 1/[σ²(F_o²) + (0.0581P)² + 4.9909P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
4631 reflections	Δρ_max = 2.18 e Å⁻³
153 parameters	Δρ_min = −0.88 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.

Refinement. The maximum and minimum residual electron density peaks of 2.18 and 0.88 eÅ^-3, respectively, were located 0.88 Å and 1.03 Å from the S1 and Sn atoms, respectively.

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

	x	y	z	U_iso*/U_eq
Sn	0.0000	0.22626 (4)	0.2500	0.03003 (11)
S1	0.06302 (3)	−0.03124 (11)	0.30644 (5)	0.03538 (19)
S2	0.09910 (3)	0.36081 (12)	0.33633 (5)	0.03628 (19)
O1	0.18723 (10)	−0.1322 (4)	0.54586 (15)	0.0420 (6)
O2	0.26265 (10)	0.1284 (4)	0.34048 (17)	0.0468 (6)
N1	0.15552 (10)	0.0612 (4)	0.38750 (16)	0.0307 (5)
C1	0.11053 (12)	0.1264 (4)	0.34726 (18)	0.0300 (6)
C2	0.16660 (13)	−0.1410 (5)	0.4000 (2)	0.0348 (7)
H2A	0.2041	−0.1635	0.3970	0.042*
H2B	0.1465	−0.2127	0.3550	0.042*
C3	0.15321 (15)	−0.2133 (5)	0.4811 (2)	0.0378 (7)
H3A	0.1167	−0.1807	0.4872	0.045*
H3B	0.1566	−0.3516	0.4830	0.045*
C4	0.17861 (15)	−0.2007 (6)	0.6240 (2)	0.0444 (9)
H4A	0.1816	−0.3378	0.6247	0.067*
H4B	0.1437	−0.1645	0.6351	0.067*
H4C	0.2046	−0.1473	0.6662	0.067*
C5	0.19574 (13)	0.1927 (5)	0.42487 (19)	0.0329 (7)
H5A	0.2181	0.1273	0.4695	0.039*
H5B	0.1785	0.2983	0.4498	0.039*
C6	0.22976 (13)	0.2705 (5)	0.3646 (2)	0.0342 (7)
H6A	0.2076	0.3201	0.3157	0.041*
H6B	0.2511	0.3751	0.3903	0.041*
C7	0.30157 (16)	0.2029 (6)	0.2963 (3)	0.0475 (9)
H7A	0.3247	0.2850	0.3323	0.071*
H7B	0.2851	0.2752	0.2492	0.071*
H7C	0.3219	0.1000	0.2767	0.071*
C8	−0.03139 (13)	0.3304 (5)	0.35511 (19)	0.0311 (6)
H8A	−0.0673	0.2822	0.3543	0.037*
H8B	−0.0104	0.2810	0.4051	0.037*
C9	−0.03254 (13)	0.5440 (4)	0.36019 (19)	0.0323 (6)
H9A	0.0036	0.5920	0.3684	0.039*
H9B	−0.0498	0.5949	0.3075	0.039*
C10	−0.06123 (13)	0.6138 (5)	0.42990 (19)	0.0341 (7)
H10A	−0.0980	0.5726	0.4197	0.041*
H10B	−0.0454	0.5562	0.4821	0.041*
C11	−0.05949 (17)	0.8260 (5)	0.4386 (2)	0.0454 (9)
H11A	−0.0752	0.8838	0.3872	0.068*
H11B	−0.0232	0.8671	0.4510	0.068*
H11C	−0.0790	0.8639	0.4834	0.068*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Sn	0.03662 (18)	0.02227 (17)	0.03257 (17)	0.000	0.00965 (12)	0.000
S1	0.0400 (4)	0.0212 (4)	0.0445 (4)	−0.0060 (3)	0.0036 (3)	−0.0035 (3)
S2	0.0399 (4)	0.0252 (4)	0.0433 (4)	−0.0045 (3)	0.0037 (3)	0.0006 (3)
O1	0.0456 (14)	0.0362 (15)	0.0443 (13)	−0.0097 (11)	0.0063 (11)	0.0091 (11)
O2	0.0485 (15)	0.0295 (14)	0.0657 (16)	−0.0004 (11)	0.0197 (12)	0.0066 (12)
N1	0.0393 (14)	0.0201 (13)	0.0338 (13)	−0.0038 (10)	0.0094 (11)	−0.0006 (10)
C1	0.0391 (16)	0.0268 (16)	0.0267 (13)	−0.0013 (12)	0.0148 (12)	0.0008 (11)
C2	0.0406 (17)	0.0218 (16)	0.0433 (17)	0.0027 (12)	0.0102 (14)	−0.0027 (13)
C3	0.0461 (19)	0.0186 (16)	0.0496 (19)	−0.0032 (12)	0.0101 (15)	0.0015 (13)
C4	0.044 (2)	0.037 (2)	0.052 (2)	−0.0035 (15)	0.0053 (16)	0.0186 (16)
C5	0.0356 (16)	0.0309 (18)	0.0314 (15)	−0.0100 (12)	0.0011 (12)	0.0012 (12)
C6	0.0376 (17)	0.0263 (17)	0.0384 (17)	−0.0085 (12)	0.0038 (13)	0.0054 (12)
C7	0.044 (2)	0.043 (2)	0.058 (2)	−0.0004 (16)	0.0157 (17)	0.0078 (18)
C8	0.0376 (16)	0.0239 (15)	0.0337 (15)	−0.0023 (12)	0.0117 (12)	0.0002 (12)
C9	0.0403 (17)	0.0241 (16)	0.0338 (15)	−0.0014 (12)	0.0093 (13)	−0.0002 (12)
C10	0.0401 (17)	0.0281 (17)	0.0355 (15)	0.0019 (13)	0.0104 (13)	−0.0005 (12)
C11	0.067 (2)	0.0281 (19)	0.0429 (19)	0.0084 (16)	0.0138 (17)	−0.0051 (15)

Geometric parameters (Å, º) top

Sn—S1	2.5503 (9)	C4—H4C	0.9800
Sn—S1ⁱ	2.5504 (9)	C5—C6	1.511 (4)
Sn—S2	2.9300 (9)	C5—H5A	0.9900
Sn—S2ⁱ	2.9300 (9)	C5—H5B	0.9900
Sn—C8	2.131 (3)	C6—H6A	0.9900
Sn—C8ⁱ	2.131 (3)	C6—H6B	0.9900
S1—C1	1.736 (3)	C7—H7A	0.9800
S2—C1	1.702 (3)	C7—H7B	0.9800
O1—C3	1.415 (4)	C7—H7C	0.9800
O1—C4	1.416 (4)	C8—C9	1.526 (4)
O2—C6	1.412 (4)	C8—H8A	0.9900
O2—C7	1.417 (4)	C8—H8B	0.9900
N1—C1	1.347 (4)	C9—C10	1.524 (4)
N1—C5	1.475 (4)	C9—H9A	0.9900
N1—C2	1.479 (4)	C9—H9B	0.9900
C2—C3	1.508 (5)	C10—C11	1.519 (5)
C2—H2A	0.9900	C10—H10A	0.9900
C2—H2B	0.9900	C10—H10B	0.9900
C3—H3A	0.9900	C11—H11A	0.9800
C3—H3B	0.9900	C11—H11B	0.9800
C4—H4A	0.9800	C11—H11C	0.9800
C4—H4B	0.9800

S1—Sn—S2	65.13 (3)	C6—C5—H5A	108.9
S1—Sn—S1ⁱ	87.95 (4)	N1—C5—H5B	108.9
S2—Sn—S2ⁱ	141.79 (3)	C6—C5—H5B	108.9
S1—Sn—C8	104.38 (9)	H5A—C5—H5B	107.7
S2—Sn—C8	83.95 (9)	O2—C6—C5	110.0 (3)
S1—Sn—C8ⁱ	104.64 (9)	O2—C6—H6A	109.7
C8—Sn—S1ⁱ	104.64 (9)	C5—C6—H6A	109.7
C8ⁱ—Sn—S1ⁱ	104.38 (9)	O2—C6—H6B	109.7
S2—Sn—C8ⁱ	82.96 (9)	C5—C6—H6B	109.7
S1—Sn—S2ⁱ	153.08 (3)	H6A—C6—H6B	108.2
C8—Sn—C8ⁱ	139.25 (17)	O2—C7—H7A	109.5
C1—S1—Sn	93.64 (11)	O2—C7—H7B	109.5
C1—S2—Sn	81.93 (11)	H7A—C7—H7B	109.5
C3—O1—C4	112.6 (3)	O2—C7—H7C	109.5
C6—O2—C7	111.6 (3)	H7A—C7—H7C	109.5
C1—N1—C5	120.4 (3)	H7B—C7—H7C	109.5
C1—N1—C2	123.0 (3)	C9—C8—Sn	113.8 (2)
C5—N1—C2	116.6 (3)	C9—C8—H8A	108.8
N1—C1—S2	121.2 (2)	Sn—C8—H8A	108.8
N1—C1—S1	119.5 (2)	C9—C8—H8B	108.8
S2—C1—S1	119.31 (19)	Sn—C8—H8B	108.8
N1—C2—C3	113.2 (3)	H8A—C8—H8B	107.7
N1—C2—H2A	108.9	C10—C9—C8	112.4 (3)
C3—C2—H2A	108.9	C10—C9—H9A	109.1
N1—C2—H2B	108.9	C8—C9—H9A	109.1
C3—C2—H2B	108.9	C10—C9—H9B	109.1
H2A—C2—H2B	107.8	C8—C9—H9B	109.1
O1—C3—C2	109.4 (3)	H9A—C9—H9B	107.9
O1—C3—H3A	109.8	C11—C10—C9	112.6 (3)
C2—C3—H3A	109.8	C11—C10—H10A	109.1
O1—C3—H3B	109.8	C9—C10—H10A	109.1
C2—C3—H3B	109.8	C11—C10—H10B	109.1
H3A—C3—H3B	108.2	C9—C10—H10B	109.1
O1—C4—H4A	109.5	H10A—C10—H10B	107.8
O1—C4—H4B	109.5	C10—C11—H11A	109.5
H4A—C4—H4B	109.5	C10—C11—H11B	109.5
O1—C4—H4C	109.5	H11A—C11—H11B	109.5
H4A—C4—H4C	109.5	C10—C11—H11C	109.5
H4B—C4—H4C	109.5	H11A—C11—H11C	109.5
N1—C5—C6	113.6 (3)	H11B—C11—H11C	109.5
N1—C5—H5A	108.9

C5—N1—C1—S2	1.4 (4)	C5—N1—C2—C3	83.2 (3)
C2—N1—C1—S2	178.6 (2)	C4—O1—C3—C2	−177.1 (3)
C5—N1—C1—S1	−178.1 (2)	N1—C2—C3—O1	−67.4 (4)
C2—N1—C1—S1	−0.8 (4)	C1—N1—C5—C6	−82.0 (4)
Sn—S2—C1—N1	−179.6 (2)	C2—N1—C5—C6	100.6 (3)
Sn—S2—C1—S1	−0.11 (15)	C7—O2—C6—C5	−169.1 (3)
Sn—S1—C1—N1	179.6 (2)	N1—C5—C6—O2	−70.3 (4)
Sn—S1—C1—S2	0.12 (17)	Sn—C8—C9—C10	172.9 (2)
C1—N1—C2—C3	−94.1 (4)	C8—C9—C10—C11	176.3 (3)

Symmetry code: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the N4/C5–C9 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4A···O2ⁱⁱ	0.98	2.55	3.423 (5)	149
C6—H6B···O1ⁱⁱⁱ	0.99	2.57	3.553 (4)	175

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

[N-(2-Methoxyethyl)-N-methyldithiocarbamato-κ²S,S']triphenyltin(IV) (II) top

Crystal data top

[Sn(C₆H₅)₃(C₅H₁₀NOS₂)]	Z = 2
M_r = 514.25	F(000) = 520
Triclinic, P1	D_x = 1.551 Mg m⁻³
a = 7.6258 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.2178 (3) Å	Cell parameters from 8110 reflections
c = 14.8621 (6) Å	θ = 4.1–31.4°
α = 91.976 (3)°	µ = 1.36 mm⁻¹
β = 90.655 (3)°	T = 148 K
γ = 107.875 (3)°	Slab, colourless
V = 1101.19 (7) Å³	0.50 × 0.30 × 0.30 mm

Data collection top

Agilent Technologies SuperNova Dual diffractometer with Atlas detector	6547 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	6089 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.046
Detector resolution: 10.4041 pixels mm^-1	θ_max = 31.7°, θ_min = 3.5°
ω scan	h = −11→11
Absorption correction: multi-scan (CrysAlis Pro; Agilent, 2015)	k = −15→14
T_min = 0.479, T_max = 1.000	l = −20→20
11916 measured reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.040	H-atom parameters constrained
wR(F²) = 0.114	w = 1/[σ²(F_o²) + (0.0671P)² + 0.2783P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max = 0.001
6547 reflections	Δρ_max = 2.21 e Å⁻³
255 parameters	Δρ_min = −1.82 e Å⁻³

Special details top

Refinement. The maximum and minimum residual electron density peaks of 2.21 and 1.82 eÅ^-3, respectively, were located 0.96 Å and 0.76 Å from the Sn atom.

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

	x	y	z	U_iso*/U_eq
Sn	0.33155 (2)	0.17167 (2)	0.71926 (2)	0.01646 (7)
S1	0.22626 (10)	0.21030 (8)	0.87168 (5)	0.02514 (15)
S2	−0.04590 (10)	−0.01260 (7)	0.76544 (5)	0.02473 (15)
O1	−0.3089 (3)	0.2686 (2)	1.02520 (19)	0.0379 (6)
N1	−0.1129 (3)	0.0832 (3)	0.92564 (17)	0.0254 (5)
C1	0.0058 (4)	0.0900 (3)	0.85949 (19)	0.0211 (5)
C2	−0.3028 (4)	−0.0073 (4)	0.9179 (3)	0.0358 (7)
H2A	−0.3842	0.0464	0.9015	0.054*
H2B	−0.3399	−0.0496	0.9757	0.054*
H2C	−0.3118	−0.0794	0.8713	0.054*
C3	−0.0635 (4)	0.1730 (4)	1.0074 (2)	0.0302 (6)
H3A	0.0717	0.2002	1.0174	0.036*
H3B	−0.1218	0.1203	1.0596	0.036*
C4	−0.1216 (4)	0.3017 (3)	1.0033 (2)	0.0293 (6)
H4A	−0.0459	0.3734	1.0464	0.035*
H4B	−0.1032	0.3380	0.9421	0.035*
C5	−0.3705 (6)	0.3865 (4)	1.0244 (3)	0.0456 (9)
H5A	−0.2985	0.4559	1.0689	0.068*
H5B	−0.5011	0.3603	1.0395	0.068*
H5C	−0.3542	0.4246	0.9644	0.068*
C11	0.5881 (4)	0.3348 (3)	0.74340 (19)	0.0210 (5)
C12	0.7602 (4)	0.3153 (3)	0.7336 (2)	0.0249 (6)
H12	0.7669	0.2264	0.7169	0.030*
C13	0.9229 (4)	0.4240 (4)	0.7479 (2)	0.0321 (7)
H13	1.0389	0.4091	0.7404	0.039*
C14	0.9145 (4)	0.5536 (3)	0.7729 (2)	0.0308 (6)
H14	1.0250	0.6279	0.7821	0.037*
C15	0.7455 (4)	0.5753 (3)	0.7846 (2)	0.0299 (6)
H15	0.7397	0.6641	0.8021	0.036*
C16	0.5846 (4)	0.4662 (3)	0.7704 (2)	0.0262 (6)
H16	0.4691	0.4814	0.7793	0.031*
C21	0.2016 (4)	0.2414 (3)	0.61084 (18)	0.0188 (5)
C22	0.2874 (4)	0.3708 (3)	0.5777 (2)	0.0262 (6)
H22	0.3998	0.4270	0.6050	0.031*
C23	0.2114 (5)	0.4192 (4)	0.5050 (2)	0.0345 (7)
H23	0.2704	0.5083	0.4838	0.041*
C24	0.0504 (5)	0.3373 (4)	0.4643 (2)	0.0370 (7)
H24	−0.0018	0.3700	0.4148	0.044*
C25	−0.0359 (5)	0.2075 (4)	0.4951 (2)	0.0344 (7)
H25	−0.1463	0.1509	0.4663	0.041*
C26	0.0387 (4)	0.1600 (3)	0.5682 (2)	0.0263 (6)
H26	−0.0219	0.0712	0.5894	0.032*
C31	0.4062 (3)	−0.0098 (3)	0.69017 (18)	0.0175 (5)
C32	0.3456 (4)	−0.1288 (3)	0.7390 (2)	0.0272 (6)
H32	0.2659	−0.1323	0.7881	0.033*
C33	0.4018 (5)	−0.2424 (3)	0.7156 (3)	0.0360 (8)
H33	0.3608	−0.3231	0.7493	0.043*
C34	0.5168 (4)	−0.2389 (3)	0.6439 (3)	0.0312 (7)
H34	0.5535	−0.3173	0.6281	0.037*
C35	0.5782 (4)	−0.1216 (3)	0.5952 (2)	0.0255 (6)
H35	0.6573	−0.1190	0.5460	0.031*
C36	0.5237 (4)	−0.0067 (3)	0.61873 (19)	0.0212 (5)
H36	0.5673	0.0745	0.5857	0.025*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Sn	0.01712 (11)	0.01286 (10)	0.01959 (11)	0.00482 (7)	0.00283 (7)	0.00054 (7)
S1	0.0219 (3)	0.0277 (3)	0.0224 (3)	0.0028 (3)	0.0036 (2)	−0.0031 (3)
S2	0.0239 (3)	0.0231 (3)	0.0250 (3)	0.0041 (3)	0.0038 (3)	0.0000 (3)
O1	0.0331 (12)	0.0285 (11)	0.0553 (16)	0.0134 (10)	0.0124 (11)	0.0057 (11)
N1	0.0239 (12)	0.0295 (12)	0.0249 (12)	0.0108 (10)	0.0072 (9)	0.0043 (10)
C1	0.0216 (12)	0.0201 (12)	0.0233 (13)	0.0085 (10)	0.0035 (10)	0.0037 (10)
C2	0.0258 (15)	0.0372 (17)	0.0429 (19)	0.0065 (13)	0.0144 (13)	0.0060 (14)
C3	0.0348 (16)	0.0395 (17)	0.0213 (13)	0.0183 (14)	0.0079 (11)	0.0027 (12)
C4	0.0316 (15)	0.0277 (14)	0.0259 (14)	0.0051 (12)	0.0076 (12)	0.0003 (11)
C5	0.047 (2)	0.0374 (19)	0.060 (3)	0.0249 (17)	−0.0004 (18)	−0.0011 (18)
C11	0.0195 (12)	0.0174 (11)	0.0248 (13)	0.0038 (10)	0.0036 (10)	0.0029 (9)
C12	0.0225 (13)	0.0212 (13)	0.0316 (15)	0.0079 (11)	0.0026 (11)	−0.0024 (11)
C13	0.0185 (13)	0.0373 (17)	0.0381 (17)	0.0052 (12)	0.0043 (12)	−0.0009 (13)
C14	0.0248 (14)	0.0289 (15)	0.0293 (15)	−0.0053 (12)	0.0018 (12)	−0.0011 (12)
C15	0.0336 (16)	0.0176 (12)	0.0348 (16)	0.0025 (11)	0.0007 (12)	−0.0020 (11)
C16	0.0243 (14)	0.0192 (13)	0.0344 (16)	0.0059 (11)	0.0022 (11)	−0.0018 (11)
C21	0.0201 (12)	0.0178 (11)	0.0201 (12)	0.0077 (10)	0.0060 (9)	0.0021 (9)
C22	0.0267 (14)	0.0212 (13)	0.0312 (15)	0.0075 (11)	0.0026 (11)	0.0054 (11)
C23	0.0418 (18)	0.0308 (16)	0.0348 (17)	0.0155 (14)	0.0069 (14)	0.0137 (13)
C24	0.0381 (18)	0.050 (2)	0.0303 (16)	0.0225 (16)	0.0043 (13)	0.0139 (15)
C25	0.0301 (16)	0.0466 (19)	0.0252 (15)	0.0096 (14)	−0.0025 (12)	0.0034 (13)
C26	0.0234 (13)	0.0285 (14)	0.0242 (14)	0.0035 (11)	0.0018 (11)	0.0027 (11)
C31	0.0161 (11)	0.0140 (10)	0.0219 (12)	0.0039 (9)	0.0019 (9)	0.0016 (9)
C32	0.0269 (14)	0.0191 (13)	0.0389 (16)	0.0103 (11)	0.0141 (12)	0.0109 (11)
C33	0.0344 (17)	0.0191 (13)	0.059 (2)	0.0131 (12)	0.0178 (15)	0.0148 (14)
C34	0.0271 (14)	0.0196 (13)	0.0492 (19)	0.0111 (11)	0.0036 (13)	−0.0033 (13)
C35	0.0233 (13)	0.0269 (14)	0.0271 (14)	0.0094 (11)	0.0042 (11)	−0.0049 (11)
C36	0.0212 (12)	0.0199 (12)	0.0220 (12)	0.0054 (10)	0.0036 (10)	0.0006 (10)

Geometric parameters (Å, º) top

Sn—S1	2.4711 (7)	C13—H13	0.9500
Sn—S2	3.0180 (7)	C14—C15	1.385 (5)
S1—C1	1.755 (3)	C14—H14	0.9500
S2—C1	1.686 (3)	C15—C16	1.390 (4)
Sn—C11	2.162 (3)	C15—H15	0.9500
Sn—C21	2.136 (3)	C16—H16	0.9500
Sn—C31	2.133 (2)	C21—C22	1.393 (4)
O1—C4	1.408 (4)	C21—C26	1.396 (4)
O1—C5	1.420 (4)	C22—C23	1.395 (4)
N1—C1	1.333 (4)	C22—H22	0.9500
N1—C2	1.460 (4)	C23—C24	1.375 (5)
N1—C3	1.470 (4)	C23—H23	0.9500
C2—H2A	0.9800	C24—C25	1.384 (5)
C2—H2B	0.9800	C24—H24	0.9500
C2—H2C	0.9800	C25—C26	1.389 (4)
C3—C4	1.514 (4)	C25—H25	0.9500
C3—H3A	0.9900	C26—H26	0.9500
C3—H3B	0.9900	C31—C36	1.392 (4)
C4—H4A	0.9900	C31—C32	1.393 (4)
C4—H4B	0.9900	C32—C33	1.389 (4)
C5—H5A	0.9800	C32—H32	0.9500
C5—H5B	0.9800	C33—C34	1.383 (5)
C5—H5C	0.9800	C33—H33	0.9500
C11—C12	1.395 (4)	C34—C35	1.379 (5)
C11—C16	1.396 (4)	C34—H34	0.9500
C12—C13	1.396 (4)	C35—C36	1.395 (4)
C12—H12	0.9500	C35—H35	0.9500
C13—C14	1.383 (5)	C36—H36	0.9500

S1—Sn—S2	64.37 (2)	C14—C13—C12	119.8 (3)
S1—Sn—C11	91.17 (8)	C14—C13—H13	120.1
S1—Sn—C21	115.84 (7)	C12—C13—H13	120.1
S1—Sn—C31	119.09 (7)	C13—C14—C15	120.2 (3)
S2—Sn—C11	155.54 (8)	C13—C14—H14	119.9
S2—Sn—C21	87.38 (7)	C15—C14—H14	119.9
S2—Sn—C31	87.83 (7)	C14—C15—C16	119.5 (3)
C11—Sn—C21	104.11 (10)	C14—C15—H15	120.2
C11—Sn—C31	105.78 (10)	C16—C15—H15	120.2
C21—Sn—C31	115.55 (10)	C15—C16—C11	121.8 (3)
C1—S1—Sn	96.57 (10)	C15—C16—H16	119.1
C1—S2—Sn	79.96 (10)	C11—C16—H16	119.1
C4—O1—C5	111.3 (3)	C22—C21—C26	118.1 (3)
C1—N1—C2	121.6 (3)	C22—C21—Sn	118.9 (2)
C1—N1—C3	121.8 (3)	C26—C21—Sn	122.9 (2)
C2—N1—C3	116.4 (2)	C21—C22—C23	121.1 (3)
N1—C1—S2	122.9 (2)	C21—C22—H22	119.4
N1—C1—S1	118.3 (2)	C23—C22—H22	119.4
S2—C1—S1	118.72 (16)	C24—C23—C22	119.7 (3)
N1—C2—H2A	109.5	C24—C23—H23	120.2
N1—C2—H2B	109.5	C22—C23—H23	120.2
H2A—C2—H2B	109.5	C23—C24—C25	120.3 (3)
N1—C2—H2C	109.5	C23—C24—H24	119.9
H2A—C2—H2C	109.5	C25—C24—H24	119.9
H2B—C2—H2C	109.5	C24—C25—C26	120.1 (3)
N1—C3—C4	113.6 (3)	C24—C25—H25	120.0
N1—C3—H3A	108.8	C26—C25—H25	120.0
C4—C3—H3A	108.8	C25—C26—C21	120.7 (3)
N1—C3—H3B	108.8	C25—C26—H26	119.6
C4—C3—H3B	108.8	C21—C26—H26	119.6
H3A—C3—H3B	107.7	C36—C31—C32	119.1 (2)
O1—C4—C3	108.7 (3)	C36—C31—Sn	117.20 (19)
O1—C4—H4A	109.9	C32—C31—Sn	123.70 (19)
C3—C4—H4A	109.9	C33—C32—C31	119.9 (3)
O1—C4—H4B	109.9	C33—C32—H32	120.0
C3—C4—H4B	109.9	C31—C32—H32	120.0
H4A—C4—H4B	108.3	C34—C33—C32	120.6 (3)
O1—C5—H5A	109.5	C34—C33—H33	119.7
O1—C5—H5B	109.5	C32—C33—H33	119.7
H5A—C5—H5B	109.5	C35—C34—C33	120.0 (3)
O1—C5—H5C	109.5	C35—C34—H34	120.0
H5A—C5—H5C	109.5	C33—C34—H34	120.0
H5B—C5—H5C	109.5	C34—C35—C36	119.7 (3)
C12—C11—C16	117.5 (3)	C34—C35—H35	120.1
C12—C11—Sn	123.0 (2)	C36—C35—H35	120.1
C16—C11—Sn	119.5 (2)	C31—C36—C35	120.6 (3)
C11—C12—C13	121.2 (3)	C31—C36—H36	119.7
C11—C12—H12	119.4	C35—C36—H36	119.7
C13—C12—H12	119.4

C2—N1—C1—S2	−5.0 (4)	C12—C11—C16—C15	1.9 (5)
C3—N1—C1—S2	179.3 (2)	Sn—C11—C16—C15	−178.3 (2)
C2—N1—C1—S1	175.7 (2)	C26—C21—C22—C23	1.3 (4)
C3—N1—C1—S1	0.0 (4)	Sn—C21—C22—C23	177.9 (2)
Sn—S2—C1—N1	175.2 (2)	C21—C22—C23—C24	−1.1 (5)
Sn—S2—C1—S1	−5.46 (14)	C22—C23—C24—C25	0.0 (5)
Sn—S1—C1—N1	−174.0 (2)	C23—C24—C25—C26	0.8 (5)
Sn—S1—C1—S2	6.62 (16)	C24—C25—C26—C21	−0.6 (5)
C1—N1—C3—C4	95.1 (3)	C22—C21—C26—C25	−0.4 (4)
C2—N1—C3—C4	−80.8 (3)	Sn—C21—C26—C25	−176.9 (2)
C5—O1—C4—C3	178.7 (3)	C36—C31—C32—C33	−0.4 (5)
N1—C3—C4—O1	81.8 (3)	Sn—C31—C32—C33	−179.7 (3)
C16—C11—C12—C13	−1.7 (5)	C31—C32—C33—C34	−0.4 (5)
Sn—C11—C12—C13	178.5 (2)	C32—C33—C34—C35	0.6 (6)
C11—C12—C13—C14	0.5 (5)	C33—C34—C35—C36	0.0 (5)
C12—C13—C14—C15	0.6 (5)	C32—C31—C36—C35	0.9 (4)
C13—C14—C15—C16	−0.4 (5)	Sn—C31—C36—C35	−179.7 (2)
C14—C15—C16—C11	−0.9 (5)	C34—C35—C36—C31	−0.8 (4)

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C21–C26 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C35—H35···Cg1ⁱ	0.95	2.99	3.760 (3)	139

Symmetry code: (i) −x+1, −y, −z+1.

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

Contact	Distance	Symmetry operation
(I)
H4B···H8A	2.00	-x, - y, 1 - z
H5A···H6B	2.21	1/2 - x, 1/2 - y, 1 - z
H8B···H10B	2.37	-x, 1 - y, 1 - z
H10B···H10B	2.37	-x, 1 - y, 1 - z
(II)
H14···H33	2.37	1 + x, 1 + y, z
H16···H33	2.25	x, 1 + y, z
H22···H34	2.33	x, 1 + y, z
C1···H3B	2.86	-x, - y, 2 - z
C14···H4A	2.85	1 - x, 1 - y, 2 - z

Percentage contributions of interatomic contacts to the Hirshfeld surface for (I) and (II) top

Contact	% contribution in (I)	% contribution in (II)
H···H	77.9	58.9
S···H/H···S	12.2	7.3
C···H/H···C	1.6	29.1
O···H/H···O	7.9	2.5
N···H/H···N	0.4	0.7
C···S/S···C	0.0	1.3
S···O/O···S	0.0	0.1
Sn···H/N···Sn	0.0	0.1

Footnotes

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

Acknowledgements

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 thank the technical support received from the laboratory assistants of Faculty Science and Technology, Universiti Kebangsaan Malaysia. Intensity data were collected in the University of Malaya's crystallographic laboratory.

Funding information

This work was supported by grant No. GGP-2017-081 awarded by Universiti Kebangsaan Malaysia.

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