Crystal structures and Hirshfeld surface analyses of (N-hexyl-N-methyl­dithio­carbamato-κ2S,S′)triphenyl­tin(IV) and [N-methyl-N-(2-phenyl­ethyl)­dithio­carbamato-κ2S,S′]tri­phenyl­tin(IV)

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

doi:10.1107/S2056989018005133

research communications

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ISSN: 2056-9890

Volume 74| Part 5| May 2018| Pages 630-637

https://doi.org/10.1107/S2056989018005133

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Crystal structures and Hirshfeld surface analyses of (N-hexyl-N-methyldithiocarbamato-κ²S,S′)triphenyltin(IV) and [N-methyl-N-(2-phenylethyl)dithiocarbamato-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, Faculty of Health Sciences, Universiti Kebangsaan Malaysia, Jalan Raja Muda Abdul Aziz, 50300 Kuala Lumpur, Malaysia, ^bEnvironmental Health and Industrial Safety Programme, 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 380001, India, and ^dResearch Centre for Crystalline Materials, 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 26 March 2018; accepted 30 March 2018; online 6 April 2018)

The crystal and molecular structures of two triphenyltin dithiocarbamate compounds, viz. [Sn(C₆H₅)₃(C₈H₁₆NS₂)], (I), and [Sn(C₆H₅)₃(C₁₀H₁₂NS₂)], (II), are described. The dithiocarbamate ligand in each molecule coordinates in an asymmetric fashion resulting in heavily distorted tetrahedral C₃S coordination geometries for the Sn atoms, with the distortions traced to the close approach of the non-coordinating thione-S atom. The molecular packing in both compounds features C—H⋯π(Sn-phenyl) interactions. In (I), the donors are Sn-phenyl-C—H groups leading to centrosymmetric aggregates, while in (II), the donors are both Sn-phenyl-C—H and methyl-C—H groups leading to supramolecular chains propagating along the b axis. The identified aggregates assemble into their respective crystals with no directional interactions between them. An analysis of the Hirshfeld surfaces show distinctive patterns, but an overwhelming predominance (>99% in each case) of H⋯H, C⋯H/H⋯C and S⋯H/H⋯S contacts on the respective Hirshfeld surface.

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

CCDC references: 1833664; 1833663

1. Chemical context

A vast array of different dithiocarbamate anions, ⁻S₂CNRR′, has been prepared, which stems simply from the ability to alter the substituents in the starting amines used to prepare them. A key interest in dithiocarbamate compounds of both transition metals and main-group elements relates to their biological activity (Hogarth, 2012 ). Of particular relevance to the present study is the anti-microbial potential exhibited by organotin dithiocarbamates (Tiekink, 2008 ). In an on-going study of biological potential, organotin(IV) species have been complexed with two non-symmetric dithiocarbamate ligands, namely, with R = Me and R′ = n-Hex and CH₂CH₂Ph. Previously, similar species, i.e. R = benzyl and R′ = CH₂CH₂Ph (Mohamad, Awang, Kamaludin & Abu Bakar, 2016 ; Segovia et al., 2002 ) and R = Me and R′ = n-Bu (Segovia et al. 2002) have been tested for their toxicity using a bioassay based on the inhibition of the growth of Escherichia coli with the latter compound being most toxic according to the EC₅₀ value measured in vitro (Segovia et al., 2002). These results gave rise to the suggestion that increasing the length of the alkyl chain leads to enhanced solubility/activity of the compound (Segovia et al., 2002). Complementing these biological investigations (Mohamad, Awang, Kamaludin & Abu Bakar, 2016; Mohamad, Awang & Kamaludin, 2016 ) are structural studies of organotin dithiocarbamates (Mohamad, Awang, Jotani & Tiekink, 2016 ; Mohamad, Awang, Kamaludin, Jotani et al., 2016 ; Mohamad et al., 2017 , 2018 ) and in continuation of the latter, herein, the crystal and molecular structures of (C₆H₅)₃Sn[S₂CN(Me)Hex] (I) and (C₆H₅)₃Sn[S₂CN(CH₃)CH₂CH₂Ph] (II) are reported along with a Hirshfeld surface analysis to provide more details on the molecular packing.

2. Structural commentary

The tin atom in (I), Fig. 1a, is coordinated by three ipso-carbon atoms along with a dithiocarbamate ligand. As seen from Table 1, the dithiocarbamate ligand forms quite disparate Sn—S1, S2 bond lengths, with Δ(Sn—S) = (Sn—S_long – Sn—S_short) being 0.64 Å. This asymmetry is confirmed in the differences in the C—S bond lengths with the C1—S1 bond associated with the short Sn—S1 contact, at 1.761 (4) Å, being significantly longer than the C1—S2 bond, i.e. 1.688 (4) Å, involving the weakly bound S2 atom. If the S2 atom is ignored, the coordination geometry about the tin atom is distorted C₃S tetrahedral with the range of angles being 90.00 (11)°, for S1—Sn—C31, to 121.53 (10)°, for S1—Sn—C11. The wide angle clearly reflects the influence of the close approach of the S2 atom, Fig. 1a and Table 1. If the S2 atom is considered a significant bonding interaction, the resultant C₃S₂ donor set is almost perfectly intermediate between ideal square-pyramidal (SP) and trigonal–bipyramidal (TP). This is quantified in the value of τ = 0.52, which compares with the ideal values for SP and TP geometries of τ = 0.0 and 1.0, respectively (Addison et al., 1984 ). In the latter description, the range of angles is wide with the S1—Sn—S2 chelate angle being acute [63.26 (3)°] and with the widest angle [152.54 (11)°] being for S2—Sn—C31. The n-hexyl chain is linear up to the terminal methyl group. Thus, the N1—C3—C4—C5, C3—C4—C5—C6 and C4—C5—C6—C7 torsion angles of 175.9 (4), 178.5 (4) and 178.9 (5)°, respectively, indicate + anti-periplanar descriptors but, that of C5—C6—C7—C8, i.e. −66.4 (8)°, indicative of a − syn-clinal disposition.

Table 1
Selected interatomic parameters (Å, °) for (I) and (II)

Parameter	(I)	(II)
Sn—S1	2.4672 (11)	2.4636 (9)
Sn⋯S2	3.1113 (11)	3.1066 (10)
C1—S1	1.761 (4)	1.761 (4)
C1—S2	1.688 (4)	1.678 (4)
C1—N1	1.330 (5)	1.342 (5)
S1—Sn⋯S2	63.26 (3)	63.42 (3)
S1—Sn⋯C11	121.53 (10)	111.30 (9)
S1—Sn⋯C31	90.00 (11)	92.68 (9)
C11—Sn—C21	114.88 (15)	119.27 (13)
S2—Sn⋯C31	152.54 (11)	155.43 (9)

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

and (b) (II)

, showing the atom-labelling schemes and displacement ellipsoids at the 50% probability level.

The molecular structure of (II), Fig. 1b, resembles closely that described for (I). Indeed, a comparison of the key bond lengths included in Table 1 show there are no chemically significant differences between the common parts of the molecules. In terms of bond angles, for a tetrahedral description, the range of angles in (II) is smaller, by 2°, than in (I), again, not chemically significant. If the five-coordinate C₃S₂ description pertains, the value of τ = 0.60 indicates a distortion towards TP. The phenylethyl chain is kinked as seen in the N1—C3—C4—C5 and C3—C4—C5—C6 torsion angles of −175.8 (3) and 91.9 (5)°, respectively.

3. Supramolecular features

Tables 2 and 3 list the geometric parameters characterizing the intermolecular interactions operating in the crystals of (I) and (II), respectively. The molecular packing of (I) features centrosymmetric dimeric aggregates sustained by four phenyl-C—H⋯π(phenyl) interactions whereby all of the participating groups are derived from Sn-bound phenyl rings, Fig. 2a. Such cooperative C—H⋯π(phenyl) embraces have been described for many phenyl-rich systems and in instances where six phenyl rings of two residues associate by edge-to-face interactions, i.e. a six-fold embrace, the energies of stabilization can resemble or even exceed that provided by strong conventional hydrogen bonding (Dance & Scudder, 2009 ). The supramolecular dimers stack parallel to the b axis with no directional interactions between successive aggregates. Globally, columns pack into layers in the ab plane. The layers inter-digitate along the c axis, again without specific interactions between proximate residues, Fig. 2b.

Table 2
Hydrogen-bond geometry (Å, °) for (I)

Cg1 and Cg2 are the centroids of the (C11–C16) and (C31–C36) rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C32—H32⋯Cg1ⁱ	0.95	2.88	3.630 (4)	137
C26—H26⋯Cg2ⁱ	0.95	2.99	3.641 (5)	127
Symmetry code: (i) -x+1, -y+1, -z.

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

Cg1 and Cg2 are the ring centroids of the (C11–C16) and (C31–C36) rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2B⋯Cg1ⁱ	0.98	2.99	3.779 (5)	138
C14—H14⋯Cg2ⁱⁱ	0.95	2.95	3.754 (5)	143
Symmetry codes: (i) -x+2, -y, -z+2; (ii) x, y-1, z.

Figure 2
Molecular packing in the crystal of (I)

: (a) supramolecular dimer sustained by a four-fold embrace of phenyl-C—H⋯π(phenyl) interactions shown as purple dashed lines (for clarity, the phenyl rings are shown as small spheres, the interacting phenyl rings are highlighted in purple and only the N-bound carbon atoms of the dithiocarbamate substituents are shown) and (b) a view of the unit-cell contents shown in projection down the b axis.

The molecular packing of (II) again features C—H⋯π interactions, as for (I), but with both methyl-H and Sn-bound-H hydrogen atoms as donors; the Sn-phenyl rings function as acceptors. As illustrated in Fig. 3a, the C—H⋯π interactions sustain a supramolecular chain aligned along the b axis. The chains pack into the three-dimensional architecture without directional interactions between then, Fig. 3b. As may be seen from Fig. 3b, centrosymmetrically related Ph₃Sn residues approach each other so as to form phenyl-embrace interactions as found in the molecular packing of (I), but none of the putative contacts are within the standard distance criteria assumed in PLATON (Spek, 2009 ).

Figure 3
Molecular packing in the crystal of (II)

: (a) supramolecular chain sustained by C—H⋯π(phenyl) interactions shown as purple dashed lines and (b) a view of the unit-cell contents in projection down the b axis. One chain is highlighted in space-filling mode.

4. Hirshfeld surface analysis

The Hirshfeld surface calculations for the triphenyltin dithiocarbamate derivatives (I) and (II) were performed in accord with recent work on related organotin dithiocarbamates (Mohamad et al., 2017). Despite the similarity in composition, the structures of (I) and (II) exhibit different intermolecular environments because of the presence of different substituents in the respective dithiocarbamate ligands, i.e. n-hexyl in the former and phenylethyl in the latter. These differences are readily discerned from the differently shaped Hirshfeld surfaces mapped over d_norm for (I), Fig. 4, and (II), Fig. 5, which reflect the influence of short interatomic H⋯H and C⋯H/H⋯C contacts, Table 4, and comparatively weak C—H⋯π interactions, Tables 2 and 3.

Table 4
Summary of short interatomic contacts (Å) in (I) and (II)

Contact	Distance	Symmetry operation
(I)
H2C⋯H7B	1.98	x, − 1 + y, z
H2C⋯C7	2.67	x, − 1 + y, z
H23⋯C32	2.57	−x, − 1 + y, − 1 + z
H26⋯C33	2.70	1 − x, − 1 − y, − z

(II)
H2A⋯H7	2.26	2 − x, $[{1\over 2}]$ + y, $[{3\over 2}]$ + z
H9⋯H23	2.29	1 + x, y, z
H2A⋯C7	2.68	2 − x, $[{1\over 2}]$ + y, $[{3\over 2}]$ + z
H2A⋯C8	2.74	2 − x, $[{1\over 2}]$ + y, $[{3\over 2}]$ + z
H2B⋯C11	2.70	2 − x, − y, 2 − z
H2B⋯C16	2.77	2 − x, − y, 2 − z
H22⋯C35	2.69	1 − x, − y, 2 − z

Figure 4
Views of Hirshfeld surface for (I)

mapped over d_norm in the range −0.133 to +1.538 au.

Figure 5
Views of Hirshfeld surface for (II)

mapped over d_norm in the range −0.075 to +1.363 au.

The faint-red spots near the phenyl-C33 and H26 atoms in Fig. 4a reflect the presence of a weak C—H⋯π interaction, as summarized in Table 4. In both images of Fig. 4, the bright-red spots appearing near Sn-bound phenyl atoms C32 and H23, methyl-H2C and n-hexyl atoms C7 and H7B are indicative of the short interatomic H⋯H and C⋯H/H⋯C contacts involving these atoms, as listed in Table 4. The presence of similar intermolecular interactions in the crystal of (II) cf. (I), but involving different atoms, is also characterized by bright and faint-red spots on the Hirshfeld surfaces mapped over d_norm in Fig. 5. Thus, the C—H⋯π interaction is seen from the presence of bright-red spots near methyl-H2B and phenyl-C11 together with the pair of faint-red spots near the methyl-H2B and phenyl-C16 atoms in Fig. 5a. The influence of other short interatomic C⋯H/H⋯C contacts summarized in Table 4 are viewed as diminutive and faint-red spots near the respective atoms in Fig. 5a,b. The involvement of different atoms in the intermolecular interactions in the crystals of (I) and (II) is also confirmed from the views of their Hirshfeld surfaces mapped over electrostatic potential, Fig. 6, through the appearance of blue and red regions corresponding to positive and negative electrostatic potentials around them. The different molecular environments about respective reference molecules are highlighted in Fig. 7.

Figure 6
Views of Hirshfeld surface mapped over the electrostatic potential (the red and blue regions represent negative and positive electrostatic potentials, respectively) for a molecule of: (a) (I)

in the range ±0.041 au and (b) (II)

in the range −0.033 to +0.049 au.

Figure 7
The immediate environment around reference molecules within d_norm-mapped Hirshfeld surfaces for (a) (I)

and (b) (II)

, highlighting short interatomic H⋯H and C⋯H/H⋯C contacts by yellow and blue dashed lines, respectively

The distinct distribution of points in the overall two-dimensional fingerprint plots for (I) and (II), Fig. 8a, also highlight the different molecular environments for the two molecules. The significant contributions from H⋯H, C⋯H/H⋯C and S⋯H/H⋯S contacts to the Hirshfeld surfaces of both (I) and (II) are evident from Table 5. The short interatomic H⋯H contact between the methyl-H2C and n-hexyl-H7B atoms in (I) is viewed as a pair of closely spaced overlapping peaks with their tips at d_e + d_i ∼2.0 Å in the delineated plot (McKinnon et al., 2007 ) Fig. 8b. A pair of well separated short peaks at d_e + d_i ∼2.2 Å observed in the corresponding fingerprint plot for (II) are due to the involvement of methyl-H2A and phenyl-H7, H9 and H23 atoms in comparatively weaker short interatomic H⋯H contacts, Table 4. The pair of very thin and long forceps-like tips at d_e + d_i ∼2.6 Å in the fingerprint plot delineated into C⋯H/H⋯C contacts for (I), Fig. 8c, is the result of a short interatomic contact between phenyl-C32 and -H23 atoms while the points corresponding to other short interatomic contacts are merged within the plot. The presence of a pair of twin forceps-like tips at d_e + d_i ∼ 2.7 Å in the C⋯H/H⋯C delineated plot for (II), Fig. 8c, also indicates the involvement of methyl-H2A and -H2B, and phenyl-C7, -C8, -C11, -C16 and -C35 atoms in short interatomic contacts, Table 4. Further, it is clear from the fingerprint plots delineated into S⋯H/H⋯S contacts, Fig. 8d, that the pair of spikes at d_e + d_i ∼ 3.0 Å for (I) show van der Waals contacts whereas the pair of peaks at d_e + d_i > 3.1 Å for (II) show contacts farther than van der Waals separation. The other interatomic contacts summarized in Table 5 make a negligible contribution to their Hirshfeld surfaces.

Table 5
Percentage contributions of interatomic contacts to the Hirshfeld surface for (I) and (II)

Contact	Percentage contribution
	(I)	(II)
H⋯H	66.1	57.8
C⋯H/H⋯C	25.6	33.7
S⋯H/H⋯S	7.6	7.6
N⋯H/H⋯N	0.4	0.6
C⋯N/N⋯C	0.2	0.0
S⋯N/N⋯S	0.1	0.0
C⋯S/S⋯C	0.0	0.3

Figure 8
A comparison of the (a) full two-dimensional fingerprint plots for (I)

and (II)

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

5. Database survey

The dithiocarbamate ligands reported in the present study are quite rare, despite the rather large number of crystal structures of dithiocarbamate ligands available in the crystallographic literature (Groom et al., 2016 ). Thus, the N-hexyl-N-methyldithiocarbamate ligand reported in (I), i.e. dtcI, has been reported in the crystal structures of Ph₂Sn(dtcI)₂ (Ramasamy et al., 2013 ), In(dtcI)₃ (Park et al., 2003 ), and in Bi(dtcI)₃ and its 1:1 1,10-phenanthroline adduct (Monteiro et al., 2001 ). The uniform motivation for these studies was for their evaluation as useful precursors for the deposition of heavy element sulfide nanomaterials. In terms of the molecular structures, no special features in the mode of coordination are noted in the tin (Tiekink, 2008), indium (Heard, 2005 ) and bismuth (Lai & Tiekink, 2007 ) compounds. The N-methyl-N-phenylethyldithiocarbamate ligand, i.e. dtcII, has been reported only in its binary mercury(II) compound, i.e. Hg(dtcII)₃ (Green et al., 2004 ), and again, its study was motivated by the desire to generate β–HgS thin films and its structure confirms to expectation (Jotani et al., 2016 ).

Reflecting the interest in organotin dithiocarbamates, including their biological activity, there are over 50 structures of general formula Ph₃Sn(S₂CNRR') in the Cambridge Structural Database (Groom et al., 2016). Of these, seven are binuclear and are better represented as Ph₃SnS₂CN–R–NCS₂SnPh₃. In all, there are 56 independent coordination geometries and all conform to the same structural motif as described above for (I) and (II). The average Sn—S_short bond length is 2.47 Å and the average Sn—S_long bond length is 3.04 Å. This gives rise to an average Δ(Sn—S) of 0.57 Å. These values indicate the structures of (I) and (II) are outliers in that the values of Sn—S_long are generally longer than usually observed. An analysis of the available crystallographic data showed the shortest Sn—S1 bond length occurred in the structure of Ph₃Sn(S₂CNEt₂) [(III); Hook et al. 1994 ] while the longest was found for one of the independent tin centres in binuclear Ph₃Sn[S₂CN(CH₂CH₂)₂C(H)(CH₂)₃C(H)(CH₂CH₂)₂NCS₂]SnPh₃ [(IV); Ali et al., 2014 ], i.e. spanning the range 2.43 to 2.52 Å, Table 6. The shortest and longest of the Sn⋯S2 separations were found in Ph₃Sn[S₂CN(CH₂Ph)CH₂CH₂Ph] [(V); Mohamad, Awang, Kamaludin, Jotani et al., 2016] and for one of the two independent molecules of Ph₃Sn{S₂CN[CH₂(3-pyridyl)]₂} [(VI); Gupta et al., 2015 ], i.e. spanning the range 2.91 to 3.22 Å, Table 6. The lack of systematic variations in these structural parameters is borne out by the disparity of the cited bonds with the second tin centre of non-symmetric (IV) and the second independent molecule of (VI). Thus, the range of Δ(Sn—S) for all structures was 0.40 to 0.74, with the correlation coefficient from the plot of Sn—S_short versus Sn—S_long being 0.52. Such a lack of correlation has often been noted in the structural chemistry of organotin dithiocarbamates and has been ascribed to the dictates of the molecular packing (Buntine et al., 1998 ; Tiekink et al., 1999 ; Muthalib et al., 2014 ).

Table 6
Selected interatomic parameters (Å) for Ph₃Sn(S₂CNRR′)

Compound	R	R′	Sn—S_short	Sn—S_long	Δ(Sn—S)	Reference
(III)	Et	Et	2.429 (3)	3.096 (3)	0.67	Hook et al. (1994)
(IV)^a	(CH₂CH₂)₂C(H)CH₂CH₂	(CH₂CH₂)₂C(H)CH₂	2.521 (3)	2.919 (3)	0.40	Ali et al. (2014)
			2.4735 (10)	2.9468 (10)	0.47
(V)	CH₂Ph	CH₂CH₂Ph	2.4885 (5)	2.9120 (5)	0.42	Mohamad, Awang, Kamaludin, Jotani et al. (2016)
(VI)^b	CH₂(3-pyridyl)	CH₂(3-pyridyl)	2.5165 (19)	3.2209 (19)	0.71	Gupta et al. (2015)
			2.4685 (19)	3.0397 (19)	0.57
Notes: (a) non-symmetric binuclear molecule; (b) two independent molecules in the asymmetric unit.

6. Synthesis and crystallization

All chemicals and solvents were used as purchased. The melting points were determined using an automated melting-point apparatus (MPA 120 EZ-Melt). C, H, N and S 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 in CDCl₃ at room temperature on a Bruker AVANCE 400 111 HD.

Synthesis of triphenyltin(IV) N-hexyl-N-methyldithiocarbamate (I): N-hexyl-N-methylamine (Aldrich; 1.52 ml, 10 mmol) dissolved in ethanol (30 ml) was stirred at 277 K before a cold ethanolic solution of carbon disulfide (0.6 ml, 10 mmol) was added dropwise. The resulting mixture was stirred for 2 h. Then, triphenyltin(IV) chloride (Merck; 3.85 g, 10 mmol) dissolved in ethanol (25 ml) was added dropwise into the solution and stirring was continued for 2 h. The precipitate formed was filtered, washed with cold ethanol and dried. Recrystallization was achieved by dissolving the compound in a chloroform and ethanol mixture (1:1 v/v). This solution was allowed to slowly evaporate at room temperature yielding colourless slabs of (I). Yield: 52%, m.p. 364.6–365.4 K. Elemental analysis: calculated (%): C 57.8, H 5.8, N 2.6, S 11.9. Found (%): C 56.5, H 6.2, N 2.5, S 11.7. IR (KBr cm⁻¹): 1429 ν(C—N), 983 ν(C—S), 559 ν(Sn—C), 425 ν(Sn—S). ¹H NMR (CDCl₃): δ 7.41–7.77 (15H, C₆H₅); 3.38 (2H, N—CH₂); 3.42 (3H, N—CH₃); 2.21 (2H, N—CH₂CH₂); 1.75 (2H, N—(CH₂)₂CH₂); 1.59 (2H, N—(CH₂)₃CH₂); 1.34 (2H, N—(CH₂)₄CH₂); 0.92 (3H, hexyl—CH₃). ¹³C NMR (CDCl₃): δ 196.04 (NCS₂); 128.52–142.53 (C-aromatic); 58.97 (NCH₂); 43.79 (NCH₃); 31.46 (N—CH₂CH₂); 26.98 [N—(CH₂)₂CH₂]; 26.39 [N—(CH₂)₃CH₂]; 22.6 [N—CH₂)₄CH₂]; 14.06 (hexyl—CH₃). ¹¹⁹Sn NMR (CDCl₃): −187.56.

Synthesis of triphenyltin(IV) N-methyl-N-phenylethyldithiocarbamate (II): compound (II) was prepared in essentially the same manner as for (I) but using N-methyl-N-phenylethylamine (Aldrich; 1.45 ml, 10 mmol) in place of N-hexyl-N-methylamine. Recrystallization was achieved by dissolving the compound in a chloroform/ethanol mixture (1:2 v/v). Yield: 67%, m.p. 387.5–388.3 K. Elemental analysis: calculated (%): C 60.0, H 4.9, N 2.5, S 11.4. Found (%): C 57.9, H 5.3, N 2.8, S 11.2. IR (KBr cm⁻¹): 1452 ν(C—N), 977 ν(C—S), 502 ν(Sn—C), 488 ν(Sn—S). ¹H NMR (CDCl₃): δ 7.43–7.77 (15H, Sn—C₆H₅); 7.24–7.35 [5H, N(CH₂)₂C₆H₅]; 4.06 (2H, NCH₂); 3.36 (3H, NCH₃); 3.09 (2H, NCH₂CH₂). ¹³C NMR (CDCl₃): δ 196.61 (NCS₂); 126.8–142.3 (C-aromatic); 60.25 (NCH₂); 44.59 (NCH₂CH₂); 33.12 (N—CH₃). ¹¹⁹Sn NMR (CDCl₃) = −183.84.

7. 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 1.75 and 1.51 e Å⁻³, respectively, are located 0.95 and 0.86 Å from the Sn atom. For (II), the maximum and minimum residual electron density peaks of 1.47 and 1.58 e Å⁻³, respectively, are located 0.96 and 0.68 Å from the C11 and Sn atoms, respectively.

Table 7
Experimental details

	(I)	(II)
Crystal data
Chemical formula	[Sn(C₆H₅)₃(C₈H₁₆NS₂)]	[Sn(C₆H₅)₃(C₁₀H₁₂NS₂)]
M_r	540.38	560.37
Crystal system, space group	Triclinic, P $[\overline{1}]$	Monoclinic, P2₁/c
Temperature (K)	173	173
a, b, c (Å)	9.8590 (6), 10.4256 (5), 14.3960 (8)	14.3682 (4), 9.4758 (2), 19.2747 (6)
α, β, γ (°)	110.557 (5), 94.057 (5), 110.730 (5)	90, 106.450 (3), 90
V (Å³)	1263.24 (13)	2516.84 (12)
Z	2	4
Radiation type	Cu Kα	Cu Kα
μ (mm⁻¹)	9.67	9.73
Crystal size (mm)	0.30 × 0.20 × 0.05	0.10 × 0.10 × 0.05

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	0.204, 1.000	0.206, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	8833, 5033, 4580	9741, 5054, 4431
R_int	0.057	0.040
(sin θ/λ)_max (Å⁻¹)	0.628	0.628

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.121, 1.06	0.039, 0.106, 1.02
No. of reflections	5033	5054
No. of parameters	273	290
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.75, −1.51	1.47, −1.58
Computer programs: CrysAlis PRO (Agilent, 2015), SIR92 (Altomare et al., 1993 ), SHELXL2014 (Sheldrick, 2015 ), ORTEP-3 for Windows (Farrugia, 2012 ), DIAMOND (Brandenburg, 2006 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC references: 1833664; 1833663

Crystal structure: contains datablocks I, II, global. DOI: https://doi.org/10.1107/S2056989018005133/hb7745sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989018005133/hb7745Isup2.hkl

Structure factors: contains datablock II. DOI: https://doi.org/10.1107/S2056989018005133/hb7745IIsup3.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: SIR92 (Altomare et al., 1993); 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).

(N-Hexyl-N-methyldithiocarbamato-κ²S,S')triphenyltin(IV) (I) top

Crystal data top

[Sn(C₆H₅)₃(C₈H₁₆NS₂)]	Z = 2
M_r = 540.38	F(000) = 552
Triclinic, P1	D_x = 1.421 Mg m⁻³
a = 9.8590 (6) Å	Cu Kα radiation, λ = 1.54184 Å
b = 10.4256 (5) Å	Cell parameters from 4558 reflections
c = 14.3960 (8) Å	θ = 4.7–75.4°
α = 110.557 (5)°	µ = 9.67 mm⁻¹
β = 94.057 (5)°	T = 173 K
γ = 110.730 (5)°	Prism, colourless
V = 1263.24 (13) Å³	0.30 × 0.20 × 0.05 mm

Data collection top

Agilent Technologies SuperNova Dual diffractometer with Atlas detector	5033 independent reflections
Radiation source: SuperNova (Cu) X-ray Source	4580 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.057
ω scan	θ_max = 75.4°, θ_min = 4.7°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2015)	h = −11→12
T_min = 0.204, T_max = 1.000	k = −12→13
8833 measured reflections	l = −17→17

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.043	H-atom parameters constrained
wR(F²) = 0.121	w = 1/[σ²(F_o²) + (0.0811P)²] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.001
5033 reflections	Δρ_max = 1.75 e Å⁻³
273 parameters	Δρ_min = −1.50 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 1.75 and 1.50 eÅ^-3, respectively, were located 0.95 Å and 0.86 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	0.42003 (3)	0.66365 (2)	0.17688 (2)	0.02940 (11)
S1	0.28273 (12)	0.69634 (11)	0.31417 (8)	0.0359 (2)
S2	0.46733 (12)	0.99031 (11)	0.31126 (8)	0.0375 (2)
N1	0.2964 (4)	0.9556 (4)	0.4439 (3)	0.0361 (7)
C1	0.3470 (4)	0.8930 (4)	0.3645 (3)	0.0311 (8)
C2	0.1843 (6)	0.8691 (6)	0.4837 (4)	0.0466 (11)
H2A	0.0966	0.7982	0.4288	0.070*
H2B	0.1561	0.9368	0.5374	0.070*
H2C	0.2248	0.8137	0.5119	0.070*
C3	0.3467 (5)	1.1182 (5)	0.4945 (3)	0.0413 (10)
H3A	0.4459	1.1674	0.4825	0.050*
H3B	0.3566	1.1477	0.5688	0.050*
C4	0.2394 (5)	1.1719 (5)	0.4560 (4)	0.0410 (9)
H4A	0.1386	1.1175	0.4634	0.049*
H4B	0.2351	1.1492	0.3828	0.049*
C5	0.2864 (6)	1.3392 (5)	0.5142 (4)	0.0506 (11)
H5A	0.3883	1.3936	0.5083	0.061*
H5B	0.2880	1.3617	0.5871	0.061*
C6	0.1802 (7)	1.3931 (6)	0.4730 (4)	0.0537 (12)
H6A	0.1801	1.3713	0.4003	0.064*
H6B	0.0781	1.3362	0.4774	0.064*
C7	0.2206 (9)	1.5598 (7)	0.5301 (5)	0.0694 (17)
H7A	0.3247	1.6157	0.5288	0.083*
H7B	0.1564	1.5891	0.4932	0.083*
C8	0.2058 (9)	1.6078 (7)	0.6395 (5)	0.0719 (18)
H8A	0.1058	1.5468	0.6426	0.108*
H8B	0.2218	1.7137	0.6672	0.108*
H8C	0.2800	1.5941	0.6795	0.108*
C11	0.6597 (4)	0.7469 (4)	0.2096 (3)	0.0304 (7)
C12	0.7510 (5)	0.8927 (5)	0.2260 (3)	0.0379 (9)
H12	0.7089	0.9628	0.2292	0.045*
C13	0.9038 (5)	0.9364 (5)	0.2376 (4)	0.0447 (10)
H13	0.9657	1.0367	0.2495	0.054*
C14	0.9665 (5)	0.8351 (6)	0.2318 (4)	0.0454 (10)
H14	1.0710	0.8654	0.2394	0.054*
C15	0.8759 (5)	0.6892 (6)	0.2148 (4)	0.0427 (10)
H15	0.9188	0.6195	0.2113	0.051*
C16	0.7237 (5)	0.6441 (5)	0.2028 (3)	0.0356 (8)
H16	0.6622	0.5433	0.1900	0.043*
C21	0.3260 (4)	0.7039 (4)	0.0583 (3)	0.0286 (7)
C22	0.1745 (5)	0.6661 (5)	0.0340 (4)	0.0404 (9)
H22	0.1116	0.6201	0.0704	0.048*
C23	0.1134 (6)	0.6942 (6)	−0.0422 (4)	0.0513 (12)
H23	0.0091	0.6666	−0.0583	0.062*
C24	0.2042 (6)	0.7626 (6)	−0.0950 (4)	0.0486 (11)
H24	0.1623	0.7819	−0.1474	0.058*
C25	0.3532 (6)	0.8021 (6)	−0.0721 (4)	0.0491 (11)
H25	0.4154	0.8502	−0.1079	0.059*
C26	0.4154 (5)	0.7723 (5)	0.0041 (3)	0.0396 (9)
H26	0.5196	0.7990	0.0190	0.047*
C31	0.3442 (4)	0.4284 (4)	0.1449 (3)	0.0300 (7)
C32	0.2560 (5)	0.3130 (5)	0.0524 (3)	0.0359 (8)
H32	0.2296	0.3366	−0.0024	0.043*
C33	0.2063 (5)	0.1638 (5)	0.0394 (4)	0.0468 (11)
H33	0.1433	0.0870	−0.0233	0.056*
C34	0.2475 (6)	0.1261 (5)	0.1167 (4)	0.0519 (12)
H34	0.2146	0.0240	0.1071	0.062*
C35	0.3367 (6)	0.2384 (6)	0.2077 (4)	0.0503 (12)
H35	0.3673	0.2135	0.2607	0.060*
C36	0.3824 (5)	0.3874 (5)	0.2229 (4)	0.0423 (10)
H36	0.4408	0.4634	0.2872	0.051*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Sn	0.02606 (15)	0.03203 (15)	0.03534 (16)	0.01310 (11)	0.00868 (10)	0.01771 (11)
S1	0.0372 (5)	0.0344 (4)	0.0426 (5)	0.0156 (4)	0.0165 (4)	0.0201 (4)
S2	0.0369 (5)	0.0362 (5)	0.0465 (5)	0.0170 (4)	0.0175 (4)	0.0208 (4)
N1	0.0326 (18)	0.0422 (18)	0.0386 (17)	0.0188 (15)	0.0119 (14)	0.0177 (15)
C1	0.0272 (18)	0.0334 (18)	0.0350 (18)	0.0149 (15)	0.0058 (15)	0.0139 (15)
C2	0.056 (3)	0.049 (2)	0.049 (2)	0.027 (2)	0.030 (2)	0.027 (2)
C3	0.041 (2)	0.042 (2)	0.039 (2)	0.0205 (19)	0.0047 (18)	0.0101 (18)
C4	0.038 (2)	0.040 (2)	0.049 (2)	0.0189 (18)	0.0124 (19)	0.0191 (19)
C5	0.053 (3)	0.040 (2)	0.060 (3)	0.020 (2)	0.017 (2)	0.019 (2)
C6	0.070 (3)	0.052 (3)	0.053 (3)	0.032 (3)	0.022 (2)	0.028 (2)
C7	0.095 (5)	0.055 (3)	0.084 (4)	0.041 (3)	0.044 (4)	0.042 (3)
C8	0.109 (6)	0.062 (3)	0.066 (4)	0.049 (4)	0.028 (4)	0.033 (3)
C11	0.0265 (18)	0.0358 (18)	0.0315 (17)	0.0131 (15)	0.0086 (14)	0.0155 (15)
C12	0.033 (2)	0.038 (2)	0.044 (2)	0.0159 (17)	0.0089 (17)	0.0158 (17)
C13	0.031 (2)	0.045 (2)	0.052 (2)	0.0098 (18)	0.0079 (19)	0.018 (2)
C14	0.026 (2)	0.056 (3)	0.049 (2)	0.0161 (19)	0.0061 (18)	0.017 (2)
C15	0.036 (2)	0.056 (3)	0.044 (2)	0.028 (2)	0.0103 (18)	0.020 (2)
C16	0.036 (2)	0.042 (2)	0.0357 (19)	0.0205 (17)	0.0106 (16)	0.0192 (17)
C21	0.0264 (18)	0.0300 (16)	0.0332 (17)	0.0134 (14)	0.0054 (14)	0.0154 (14)
C22	0.0256 (19)	0.052 (2)	0.050 (2)	0.0162 (17)	0.0109 (17)	0.026 (2)
C23	0.034 (2)	0.070 (3)	0.056 (3)	0.026 (2)	0.004 (2)	0.027 (2)
C24	0.056 (3)	0.058 (3)	0.044 (2)	0.033 (2)	0.005 (2)	0.024 (2)
C25	0.058 (3)	0.060 (3)	0.052 (3)	0.031 (2)	0.023 (2)	0.039 (2)
C26	0.030 (2)	0.052 (2)	0.047 (2)	0.0187 (18)	0.0131 (17)	0.027 (2)
C31	0.0247 (17)	0.0306 (17)	0.0366 (18)	0.0113 (14)	0.0093 (15)	0.0151 (15)
C32	0.030 (2)	0.041 (2)	0.042 (2)	0.0147 (17)	0.0176 (16)	0.0204 (17)
C33	0.042 (2)	0.035 (2)	0.049 (2)	0.0056 (18)	0.018 (2)	0.0105 (19)
C34	0.056 (3)	0.033 (2)	0.073 (3)	0.017 (2)	0.033 (3)	0.027 (2)
C35	0.059 (3)	0.052 (3)	0.063 (3)	0.030 (2)	0.026 (2)	0.039 (2)
C36	0.049 (3)	0.037 (2)	0.048 (2)	0.0188 (19)	0.010 (2)	0.0238 (18)

Geometric parameters (Å, º) top

Sn—C21	2.123 (4)	C11—C16	1.404 (6)
Sn—C31	2.156 (4)	C12—C13	1.389 (6)
Sn—C11	2.159 (4)	C12—H12	0.9500
Sn—S1	2.4672 (11)	C13—C14	1.383 (7)
Sn—S2	3.1113 (11)	C13—H13	0.9500
S1—C1	1.761 (4)	C14—C15	1.384 (7)
S2—C1	1.688 (4)	C14—H14	0.9500
N1—C1	1.330 (5)	C15—C16	1.382 (6)
N1—C2	1.453 (6)	C15—H15	0.9500
N1—C3	1.462 (6)	C16—H16	0.9500
C2—H2A	0.9800	C21—C22	1.386 (5)
C2—H2B	0.9800	C21—C26	1.392 (6)
C2—H2C	0.9800	C22—C23	1.382 (7)
C3—C4	1.514 (6)	C22—H22	0.9500
C3—H3A	0.9900	C23—C24	1.383 (8)
C3—H3B	0.9900	C23—H23	0.9500
C4—C5	1.518 (6)	C24—C25	1.358 (7)
C4—H4A	0.9900	C24—H24	0.9500
C4—H4B	0.9900	C25—C26	1.398 (6)
C5—C6	1.526 (7)	C25—H25	0.9500
C5—H5A	0.9900	C26—H26	0.9500
C5—H5B	0.9900	C31—C32	1.396 (6)
C6—C7	1.521 (8)	C31—C36	1.405 (6)
C6—H6A	0.9900	C32—C33	1.392 (6)
C6—H6B	0.9900	C32—H32	0.9500
C7—C8	1.510 (9)	C33—C34	1.385 (8)
C7—H7A	0.9900	C33—H33	0.9500
C7—H7B	0.9900	C34—C35	1.375 (8)
C8—H8A	0.9800	C34—H34	0.9500
C8—H8B	0.9800	C35—C36	1.385 (6)
C8—H8C	0.9800	C35—H35	0.9500
C11—C12	1.388 (6)	C36—H36	0.9500

C21—Sn—C31	112.73 (14)	C7—C8—H8C	109.5
C21—Sn—C11	114.88 (15)	H8A—C8—H8C	109.5
C31—Sn—C11	104.73 (15)	H8B—C8—H8C	109.5
C21—Sn—S1	109.94 (11)	C12—C11—C16	119.1 (4)
C31—Sn—S1	90.00 (11)	C12—C11—Sn	122.6 (3)
C11—Sn—S1	121.53 (10)	C16—C11—Sn	117.9 (3)
C21—Sn—S2	84.08 (10)	C11—C12—C13	120.2 (4)
C31—Sn—S2	152.54 (11)	C11—C12—H12	119.9
C11—Sn—S2	85.86 (11)	C13—C12—H12	119.9
S1—Sn—S2	63.26 (3)	C14—C13—C12	120.5 (4)
C1—S1—Sn	98.62 (14)	C14—C13—H13	119.7
C1—S2—Sn	78.80 (14)	C12—C13—H13	119.7
C1—N1—C2	123.0 (4)	C13—C14—C15	119.5 (4)
C1—N1—C3	121.5 (4)	C13—C14—H14	120.2
C2—N1—C3	115.4 (4)	C15—C14—H14	120.2
N1—C1—S2	124.0 (3)	C16—C15—C14	120.5 (4)
N1—C1—S1	116.7 (3)	C16—C15—H15	119.7
S2—C1—S1	119.3 (2)	C14—C15—H15	119.7
N1—C2—H2A	109.5	C15—C16—C11	120.1 (4)
N1—C2—H2B	109.5	C15—C16—H16	119.9
H2A—C2—H2B	109.5	C11—C16—H16	119.9
N1—C2—H2C	109.5	C22—C21—C26	118.0 (4)
H2A—C2—H2C	109.5	C22—C21—Sn	121.1 (3)
H2B—C2—H2C	109.5	C26—C21—Sn	120.9 (3)
N1—C3—C4	111.7 (4)	C23—C22—C21	121.2 (4)
N1—C3—H3A	109.3	C23—C22—H22	119.4
C4—C3—H3A	109.3	C21—C22—H22	119.4
N1—C3—H3B	109.3	C24—C23—C22	119.9 (4)
C4—C3—H3B	109.3	C24—C23—H23	120.1
H3A—C3—H3B	107.9	C22—C23—H23	120.1
C3—C4—C5	111.4 (4)	C25—C24—C23	120.1 (4)
C3—C4—H4A	109.3	C25—C24—H24	119.9
C5—C4—H4A	109.4	C23—C24—H24	119.9
C3—C4—H4B	109.3	C24—C25—C26	120.2 (5)
C5—C4—H4B	109.4	C24—C25—H25	119.9
H4A—C4—H4B	108.0	C26—C25—H25	119.9
C4—C5—C6	111.1 (4)	C21—C26—C25	120.5 (4)
C4—C5—H5A	109.4	C21—C26—H26	119.7
C6—C5—H5A	109.4	C25—C26—H26	119.7
C4—C5—H5B	109.4	C32—C31—C36	117.4 (4)
C6—C5—H5B	109.4	C32—C31—Sn	124.4 (3)
H5A—C5—H5B	108.0	C36—C31—Sn	118.2 (3)
C7—C6—C5	113.2 (5)	C33—C32—C31	120.8 (4)
C7—C6—H6A	108.9	C33—C32—H32	119.6
C5—C6—H6A	108.9	C31—C32—H32	119.6
C7—C6—H6B	108.9	C34—C33—C32	120.8 (4)
C5—C6—H6B	108.9	C34—C33—H33	119.6
H6A—C6—H6B	107.8	C32—C33—H33	119.6
C8—C7—C6	115.3 (5)	C35—C34—C33	119.1 (4)
C8—C7—H7A	108.4	C35—C34—H34	120.5
C6—C7—H7A	108.4	C33—C34—H34	120.5
C8—C7—H7B	108.4	C34—C35—C36	120.7 (5)
C6—C7—H7B	108.4	C34—C35—H35	119.7
H7A—C7—H7B	107.5	C36—C35—H35	119.7
C7—C8—H8A	109.5	C35—C36—C31	121.2 (4)
C7—C8—H8B	109.5	C35—C36—H36	119.4
H8A—C8—H8B	109.5	C31—C36—H36	119.4

C2—N1—C1—S2	175.2 (3)	C14—C15—C16—C11	−1.1 (7)
C3—N1—C1—S2	−2.3 (6)	C12—C11—C16—C15	1.5 (6)
C2—N1—C1—S1	−5.0 (5)	Sn—C11—C16—C15	174.7 (3)
C3—N1—C1—S1	177.6 (3)	C26—C21—C22—C23	0.5 (7)
Sn—S2—C1—N1	179.5 (4)	Sn—C21—C22—C23	179.0 (4)
Sn—S2—C1—S1	−0.32 (19)	C21—C22—C23—C24	−0.7 (8)
Sn—S1—C1—N1	−179.4 (3)	C22—C23—C24—C25	0.0 (8)
Sn—S1—C1—S2	0.4 (2)	C23—C24—C25—C26	0.8 (8)
C1—N1—C3—C4	96.6 (5)	C22—C21—C26—C25	0.2 (7)
C2—N1—C3—C4	−81.0 (5)	Sn—C21—C26—C25	−178.3 (4)
N1—C3—C4—C5	175.9 (4)	C24—C25—C26—C21	−0.9 (8)
C3—C4—C5—C6	178.5 (4)	C36—C31—C32—C33	1.2 (6)
C4—C5—C6—C7	178.9 (5)	Sn—C31—C32—C33	−177.2 (3)
C5—C6—C7—C8	−66.4 (8)	C31—C32—C33—C34	−2.3 (7)
C16—C11—C12—C13	−1.3 (6)	C32—C33—C34—C35	1.0 (8)
Sn—C11—C12—C13	−174.2 (3)	C33—C34—C35—C36	1.3 (8)
C11—C12—C13—C14	0.7 (7)	C34—C35—C36—C31	−2.5 (8)
C12—C13—C14—C15	−0.3 (7)	C32—C31—C36—C35	1.2 (7)
C13—C14—C15—C16	0.5 (7)	Sn—C31—C36—C35	179.6 (4)

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of the (C11–C16) and (C31–C36) rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C32—H32···Cg1ⁱ	0.95	2.88	3.630 (4)	137
C26—H26···Cg2ⁱ	0.95	2.99	3.641 (5)	127

Symmetry code: (i) −x+1, −y+1, −z.

[N-Methyl-N-(2-phenylethyl)dithiocarbamato-κ²S,S']triphenyltin(IV) (II) top

Crystal data top

[Sn(C₆H₅)₃(C₁₀H₁₂NS₂)]	F(000) = 1136
M_r = 560.37	D_x = 1.479 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54184 Å
a = 14.3682 (4) Å	Cell parameters from 4369 reflections
b = 9.4758 (2) Å	θ = 4.8–75.1°
c = 19.2747 (6) Å	µ = 9.73 mm⁻¹
β = 106.450 (3)°	T = 173 K
V = 2516.84 (12) Å³	Prism, colourless
Z = 4	0.10 × 0.10 × 0.05 mm

Data collection top

Agilent Technologies SuperNova Dual diffractometer with Atlas detector	5054 independent reflections
Radiation source: SuperNova (Cu) X-ray Source	4431 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.040
Detector resolution: 10.4041 pixels mm^-1	θ_max = 75.6°, θ_min = 4.8°
ω scan	h = −17→13
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2015)	k = −11→7
T_min = 0.206, T_max = 1.000	l = −22→24
9741 measured reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.039	H-atom parameters constrained
wR(F²) = 0.106	w = 1/[σ²(F_o²) + (0.0648P)²] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max = 0.003
5054 reflections	Δρ_max = 1.47 e Å⁻³
290 parameters	Δρ_min = −1.58 e Å⁻³

Special details top

Refinement. The maximum and minimum residual electron density peaks of 1.47 and 1.58 eÅ^-3, respectively, were located 0.96 Å and 0.68 Å from the C11 and Sn atoms, respectively.

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

	x	y	z	U_iso*/U_eq
Sn	0.68172 (2)	0.06519 (2)	0.97084 (2)	0.02404 (9)
S1	0.84111 (6)	0.17866 (9)	0.98902 (5)	0.0307 (2)
S2	0.78587 (7)	0.01259 (10)	0.85224 (5)	0.0350 (2)
N1	0.9625 (2)	0.1189 (3)	0.91290 (17)	0.0320 (7)
C1	0.8706 (3)	0.1012 (4)	0.91495 (19)	0.0279 (7)
C2	1.0356 (3)	0.1925 (4)	0.9697 (2)	0.0369 (8)
H2A	1.0283	0.2946	0.9619	0.055*
H2B	1.1005	0.1636	0.9683	0.055*
H2C	1.0270	0.1687	1.0170	0.055*
C3	0.9948 (3)	0.0678 (4)	0.8520 (2)	0.0344 (9)
H3A	0.9483	−0.0036	0.8248	0.041*
H3B	1.0589	0.0216	0.8705	0.041*
C4	1.0026 (3)	0.1877 (4)	0.8013 (2)	0.0427 (10)
H4A	0.9398	0.2383	0.7856	0.051*
H4B	1.0527	0.2555	0.8275	0.051*
C5	1.0287 (3)	0.1338 (4)	0.7357 (2)	0.0353 (8)
C6	0.9574 (3)	0.0996 (4)	0.6730 (2)	0.0386 (9)
H6	0.8911	0.1128	0.6709	0.046*
C7	0.9812 (3)	0.0467 (4)	0.6137 (2)	0.0400 (9)
H7	0.9311	0.0239	0.5712	0.048*
C8	1.0764 (3)	0.0264 (5)	0.6150 (2)	0.0401 (9)
H8	1.0924	−0.0106	0.5740	0.048*
C9	1.1483 (3)	0.0605 (6)	0.6769 (3)	0.0513 (13)
H9	1.2144	0.0472	0.6784	0.062*
C10	1.1254 (3)	0.1139 (6)	0.7368 (2)	0.0469 (11)
H10	1.1759	0.1372	0.7790	0.056*
C11	0.6968 (2)	−0.1552 (3)	0.9966 (2)	0.0245 (7)
C12	0.6890 (3)	−0.1965 (4)	1.0642 (2)	0.0311 (8)
H12	0.6760	−0.1278	1.0961	0.037*
C13	0.7002 (3)	−0.3379 (4)	1.0855 (2)	0.0392 (9)
H13	0.6963	−0.3644	1.1321	0.047*
C14	0.7168 (3)	−0.4394 (4)	1.0389 (3)	0.0377 (9)
H14	0.7242	−0.5356	1.0533	0.045*
C15	0.7227 (3)	−0.4001 (4)	0.9714 (2)	0.0344 (8)
H15	0.7331	−0.4699	0.9390	0.041*
C16	0.7137 (3)	−0.2591 (4)	0.9504 (2)	0.0308 (8)
H16	0.7190	−0.2334	0.9040	0.037*
C21	0.5674 (2)	0.1332 (3)	0.88077 (18)	0.0238 (7)
C22	0.5054 (3)	0.0368 (4)	0.8369 (2)	0.0351 (8)
H22	0.5164	−0.0613	0.8457	0.042*
C23	0.4274 (3)	0.0811 (5)	0.7804 (2)	0.0424 (10)
H23	0.3857	0.0136	0.7507	0.051*
C24	0.4107 (3)	0.2222 (5)	0.7676 (2)	0.0414 (10)
H24	0.3568	0.2528	0.7294	0.050*
C25	0.4718 (4)	0.3196 (4)	0.8099 (2)	0.0449 (10)
H25	0.4606	0.4174	0.8003	0.054*
C26	0.5496 (3)	0.2767 (4)	0.8665 (2)	0.0366 (9)
H26	0.5912	0.3450	0.8957	0.044*
C31	0.6570 (2)	0.1695 (4)	1.06344 (19)	0.0262 (7)
C32	0.7271 (3)	0.1666 (4)	1.1310 (2)	0.0311 (8)
H32	0.7863	0.1174	1.1362	0.037*
C33	0.7110 (3)	0.2349 (4)	1.1904 (2)	0.0331 (8)
H33	0.7588	0.2309	1.2360	0.040*
C34	0.6260 (3)	0.3084 (4)	1.1836 (2)	0.0328 (8)
H34	0.6152	0.3545	1.2244	0.039*
C35	0.5566 (3)	0.3150 (4)	1.1174 (2)	0.0348 (8)
H35	0.4986	0.3670	1.1125	0.042*
C36	0.5718 (3)	0.2455 (4)	1.0579 (2)	0.0284 (7)
H36	0.5232	0.2497	1.0127	0.034*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Sn	0.02450 (14)	0.02123 (14)	0.02577 (14)	0.00113 (8)	0.00611 (10)	−0.00044 (8)
S1	0.0308 (4)	0.0320 (4)	0.0324 (4)	−0.0046 (3)	0.0139 (4)	−0.0054 (3)
S2	0.0352 (5)	0.0397 (5)	0.0307 (5)	−0.0032 (4)	0.0104 (4)	−0.0035 (4)
N1	0.0303 (16)	0.0367 (17)	0.0309 (16)	0.0030 (13)	0.0117 (14)	0.0010 (13)
C1	0.0307 (19)	0.0294 (17)	0.0279 (17)	0.0023 (15)	0.0152 (15)	0.0038 (14)
C2	0.0300 (19)	0.044 (2)	0.036 (2)	0.0008 (17)	0.0076 (17)	0.0023 (17)
C3	0.031 (2)	0.037 (2)	0.042 (2)	0.0049 (15)	0.0213 (18)	0.0011 (16)
C4	0.056 (3)	0.038 (2)	0.039 (2)	0.0026 (19)	0.022 (2)	0.0010 (17)
C5	0.043 (2)	0.0305 (19)	0.035 (2)	0.0003 (16)	0.0158 (18)	0.0041 (15)
C6	0.033 (2)	0.039 (2)	0.044 (2)	0.0091 (17)	0.0105 (19)	0.0015 (18)
C7	0.037 (2)	0.041 (2)	0.038 (2)	0.0040 (17)	0.0031 (19)	−0.0035 (17)
C8	0.041 (2)	0.049 (2)	0.033 (2)	−0.0006 (19)	0.0169 (18)	0.0011 (18)
C9	0.029 (2)	0.086 (4)	0.041 (3)	−0.006 (2)	0.015 (2)	0.001 (2)
C10	0.036 (2)	0.073 (3)	0.031 (2)	−0.011 (2)	0.0091 (18)	−0.003 (2)
C11	0.0182 (15)	0.0191 (15)	0.0334 (18)	0.0001 (12)	0.0029 (14)	0.0021 (13)
C12	0.0356 (19)	0.0228 (16)	0.038 (2)	0.0012 (14)	0.0153 (17)	0.0001 (14)
C13	0.045 (2)	0.034 (2)	0.042 (2)	0.0025 (18)	0.0184 (19)	0.0113 (17)
C14	0.037 (2)	0.0227 (18)	0.057 (3)	0.0018 (14)	0.020 (2)	0.0058 (16)
C15	0.031 (2)	0.0254 (17)	0.048 (2)	−0.0052 (15)	0.0145 (18)	−0.0101 (16)
C16	0.0303 (18)	0.0284 (17)	0.0335 (19)	−0.0042 (15)	0.0087 (16)	−0.0026 (15)
C21	0.0246 (16)	0.0227 (16)	0.0241 (16)	0.0022 (13)	0.0067 (14)	0.0012 (12)
C22	0.040 (2)	0.0238 (17)	0.040 (2)	−0.0031 (16)	0.0078 (18)	0.0025 (15)
C23	0.033 (2)	0.051 (3)	0.035 (2)	−0.0049 (18)	−0.0032 (18)	−0.0001 (18)
C24	0.038 (2)	0.055 (3)	0.030 (2)	0.0156 (19)	0.0076 (18)	0.0075 (18)
C25	0.060 (3)	0.030 (2)	0.042 (2)	0.0186 (19)	0.010 (2)	0.0098 (17)
C26	0.048 (2)	0.0220 (17)	0.034 (2)	0.0027 (16)	0.0033 (18)	0.0005 (14)
C31	0.0257 (17)	0.0235 (16)	0.0295 (17)	−0.0039 (14)	0.0080 (15)	−0.0034 (13)
C32	0.0314 (18)	0.0293 (18)	0.0326 (19)	0.0040 (15)	0.0092 (16)	−0.0026 (15)
C33	0.0330 (19)	0.0358 (19)	0.0277 (18)	−0.0020 (16)	0.0043 (16)	−0.0078 (15)
C34	0.037 (2)	0.0248 (17)	0.041 (2)	−0.0015 (15)	0.0173 (17)	−0.0106 (15)
C35	0.0273 (18)	0.0295 (18)	0.050 (2)	0.0024 (15)	0.0149 (17)	−0.0056 (16)
C36	0.0216 (16)	0.0292 (17)	0.0318 (18)	−0.0008 (14)	0.0032 (14)	−0.0025 (14)

Geometric parameters (Å, º) top

Sn—C21	2.125 (3)	C12—C13	1.397 (5)
Sn—C11	2.143 (3)	C12—H12	0.9500
Sn—C31	2.156 (3)	C13—C14	1.382 (6)
Sn—S1	2.4636 (9)	C13—H13	0.9500
Sn—S2	3.1066 (10)	C14—C15	1.379 (6)
S1—C1	1.761 (4)	C14—H14	0.9500
S2—C1	1.678 (4)	C15—C16	1.392 (5)
N1—C1	1.342 (5)	C15—H15	0.9500
N1—C2	1.462 (5)	C16—H16	0.9500
N1—C3	1.462 (5)	C21—C22	1.384 (5)
C2—H2A	0.9800	C21—C26	1.396 (5)
C2—H2B	0.9800	C22—C23	1.389 (6)
C2—H2C	0.9800	C22—H22	0.9500
C3—C4	1.524 (5)	C23—C24	1.369 (6)
C3—H3A	0.9900	C23—H23	0.9500
C3—H3B	0.9900	C24—C25	1.373 (6)
C4—C5	1.505 (5)	C24—H24	0.9500
C4—H4A	0.9900	C25—C26	1.383 (6)
C4—H4B	0.9900	C25—H25	0.9500
C5—C6	1.384 (6)	C26—H26	0.9500
C5—C10	1.396 (6)	C31—C32	1.403 (5)
C6—C7	1.378 (6)	C31—C36	1.398 (5)
C6—H6	0.9500	C32—C33	1.391 (5)
C7—C8	1.375 (6)	C32—H32	0.9500
C7—H7	0.9500	C33—C34	1.379 (5)
C8—C9	1.376 (7)	C33—H33	0.9500
C8—H8	0.9500	C34—C35	1.380 (6)
C9—C10	1.383 (6)	C34—H34	0.9500
C9—H9	0.9500	C35—C36	1.392 (5)
C10—H10	0.9500	C35—H35	0.9500
C11—C12	1.397 (5)	C36—H36	0.9500
C11—C16	1.393 (5)

C21—Sn—C11	119.27 (13)	C12—C11—C16	118.2 (3)
C21—Sn—C31	105.46 (13)	C12—C11—Sn	117.4 (3)
C11—Sn—C31	106.56 (13)	C16—C11—Sn	124.4 (3)
C21—Sn—S1	117.16 (9)	C11—C12—C13	120.7 (3)
C11—Sn—S1	111.30 (9)	C11—C12—H12	119.7
C31—Sn—S1	92.68 (9)	C13—C12—H12	119.7
C21—Sn—S2	82.51 (9)	C14—C13—C12	120.2 (4)
C11—Sn—S2	88.60 (10)	C14—C13—H13	119.9
C31—Sn—S2	155.43 (9)	C12—C13—H13	119.9
S1—Sn—S2	63.42 (3)	C15—C14—C13	119.6 (3)
C1—S1—Sn	97.50 (13)	C15—C14—H14	120.2
C1—S2—Sn	78.01 (12)	C13—C14—H14	120.2
C1—N1—C2	122.8 (3)	C14—C15—C16	120.5 (4)
C1—N1—C3	121.4 (3)	C14—C15—H15	119.7
C2—N1—C3	115.8 (3)	C16—C15—H15	119.7
N1—C1—S2	124.1 (3)	C15—C16—C11	120.7 (4)
N1—C1—S1	115.9 (3)	C15—C16—H16	119.6
S2—C1—S1	120.0 (2)	C11—C16—H16	119.6
N1—C2—H2A	109.5	C22—C21—C26	118.2 (3)
N1—C2—H2B	109.5	C22—C21—Sn	120.9 (3)
H2A—C2—H2B	109.5	C26—C21—Sn	120.8 (3)
N1—C2—H2C	109.5	C23—C22—C21	121.1 (4)
H2A—C2—H2C	109.5	C23—C22—H22	119.4
H2B—C2—H2C	109.5	C21—C22—H22	119.4
N1—C3—C4	111.5 (3)	C24—C23—C22	119.9 (4)
N1—C3—H3A	109.3	C24—C23—H23	120.1
C4—C3—H3A	109.3	C22—C23—H23	120.1
N1—C3—H3B	109.3	C23—C24—C25	120.0 (4)
C4—C3—H3B	109.3	C23—C24—H24	120.0
H3A—C3—H3B	108.0	C25—C24—H24	120.0
C5—C4—C3	111.5 (3)	C24—C25—C26	120.6 (4)
C5—C4—H4A	109.3	C24—C25—H25	119.7
C3—C4—H4A	109.3	C26—C25—H25	119.7
C5—C4—H4B	109.3	C25—C26—C21	120.3 (4)
C3—C4—H4B	109.3	C25—C26—H26	119.9
H4A—C4—H4B	108.0	C21—C26—H26	119.9
C6—C5—C10	118.0 (4)	C32—C31—C36	117.6 (3)
C6—C5—C4	120.8 (4)	C32—C31—Sn	121.1 (2)
C10—C5—C4	121.2 (4)	C36—C31—Sn	121.3 (3)
C7—C6—C5	120.9 (4)	C31—C32—C33	120.8 (3)
C7—C6—H6	119.6	C31—C32—H32	119.6
C5—C6—H6	119.6	C33—C32—H32	119.6
C6—C7—C8	121.0 (4)	C34—C33—C32	120.3 (4)
C6—C7—H7	119.5	C34—C33—H33	119.8
C8—C7—H7	119.5	C32—C33—H33	119.8
C7—C8—C9	118.8 (4)	C35—C34—C33	120.0 (3)
C7—C8—H8	120.6	C35—C34—H34	120.0
C9—C8—H8	120.6	C33—C34—H34	120.0
C8—C9—C10	120.8 (4)	C34—C35—C36	120.0 (3)
C8—C9—H9	119.6	C34—C35—H35	120.0
C10—C9—H9	119.6	C36—C35—H35	120.0
C9—C10—C5	120.5 (4)	C35—C36—C31	121.2 (3)
C9—C10—H10	119.7	C35—C36—H36	119.4
C5—C10—H10	119.7	C31—C36—H36	119.4

C2—N1—C1—S2	−177.8 (3)	C11—C12—C13—C14	−1.5 (6)
C3—N1—C1—S2	3.7 (5)	C12—C13—C14—C15	0.2 (6)
C2—N1—C1—S1	2.4 (5)	C13—C14—C15—C16	1.1 (6)
C3—N1—C1—S1	−176.0 (3)	C14—C15—C16—C11	−1.1 (6)
Sn—S2—C1—N1	171.3 (3)	C12—C11—C16—C15	−0.2 (5)
Sn—S2—C1—S1	−9.00 (18)	Sn—C11—C16—C15	179.9 (3)
Sn—S1—C1—N1	−169.0 (3)	C26—C21—C22—C23	−0.2 (6)
Sn—S1—C1—S2	11.2 (2)	Sn—C21—C22—C23	176.5 (3)
C1—N1—C3—C4	102.6 (4)	C21—C22—C23—C24	−0.3 (7)
C2—N1—C3—C4	−76.0 (4)	C22—C23—C24—C25	0.9 (7)
N1—C3—C4—C5	−175.8 (3)	C23—C24—C25—C26	−1.1 (7)
C3—C4—C5—C6	91.9 (5)	C24—C25—C26—C21	0.5 (7)
C3—C4—C5—C10	−86.7 (5)	C22—C21—C26—C25	0.1 (6)
C10—C5—C6—C7	0.4 (6)	Sn—C21—C26—C25	−176.6 (3)
C4—C5—C6—C7	−178.2 (4)	C36—C31—C32—C33	1.2 (5)
C5—C6—C7—C8	0.0 (7)	Sn—C31—C32—C33	179.6 (3)
C6—C7—C8—C9	−0.3 (7)	C31—C32—C33—C34	−0.9 (6)
C7—C8—C9—C10	0.2 (7)	C32—C33—C34—C35	−0.3 (6)
C8—C9—C10—C5	0.2 (8)	C33—C34—C35—C36	1.1 (6)
C6—C5—C10—C9	−0.5 (7)	C34—C35—C36—C31	−0.7 (6)
C4—C5—C10—C9	178.1 (4)	C32—C31—C36—C35	−0.4 (5)
C16—C11—C12—C13	1.5 (5)	Sn—C31—C36—C35	−178.8 (3)
Sn—C11—C12—C13	−178.6 (3)

Hydrogen-bond geometry (Å, º) top

Hydrogen-bond geometry (Å, °) for (I). Cg1 and Cg2 are the ring centroids of the (C11–C16) and (C31–C36) rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2B···Cg1ⁱ	0.98	2.99	3.779 (5)	138
C14—H14···Cg2ⁱⁱ	0.95	2.95	3.754 (5)	143

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

Selected interatomic parameters (Å, °) for (I) and (II) top

Parameter	(I)	(II)
Sn—S1	2.4672 (11)	2.4636 (9)
Sn···S2	3.1113 (11)	3.1066 (10)
C1—S1	1.761 (4)	1.761 (4)
C1—S2	1.688 (4)	1.678 (4)
C1—N1	1.330 (5)	1.342 (5)
S1—Sn···S2	63.26 (3)	63.42 (3)
S1—Sn···C11	121.53 (10)	111.30 (9)
S1—Sn···C31	90.00 (11)	92.68 (9)
C11—Sn—C21	114.88 (15)	119.27 (13)
S2—Sn···C31	152.54 (11)	155.43 (9)

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

Contact	Distance	Symmetry operation
(I)
H2C···H7B	1.98	x, - 1 + y, z
H2C···C7	2.67	x, - 1 + y, z
H23···C32	2.57	- x, - 1 + y, - 1 + z
H26···C33	2.70	1 - x, - 1 - y, - z
(II)
H2A···H7	2.26	2 - x, 1/2 + y, 3/2 + z
H9···H23	2.29	1 + x, y, z
H2A···C7	2.68	2 - x, 1/2 + y, 3/2 + z
H2A···C8	2.74	2 - x, 1/2 + y, 3/2 + z
H2B···C11	2.70	2 - x, - y, 2 - z
H2B···C16	2.77	2 - x, - y, 2 - z
H22···C35	2.69	1 - x, - y, 2 - z

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

Contact	Percentage contribution
	(I)	(II)
H···H	66.1	57.8
C···H/H···C	25.6	33.7
S···H/H···S	7.6	7.6
N···H/H···N	0.4	0.6
C···N/N···C	0.2	0.0
S···N/N···S	0.1	0.0
C···S/S···C	0.0	0.3

Selected interatomic parameters (Å) for Ph₃Sn(S₂CNRR') top

Compound	R	R'	Sn—S_short	Sn—S_long	Δ(Sn—S)	Reference
(III)	Et	Et	2.429 (3)	3.096 (3)	0.67	Hook et al. (1994)
(IV)^a	(CH₂CH₂)₂C(H)CH₂CH₂	(CH₂CH₂)₂C(H)CH₂	2.521 (3)	2.919 (3)	0.40	Ali et al. (2014)
			2.4735 (10)	2.9468 (10)	0.47
(V)	CH₂Ph	CH₂CH₂Ph	2.4885 (5)	2.9120 (5)	0.42	Mohamad, Awang, Kamaludin, Jotani et al. (2016)
(VI)^b	CH₂(3-pyridyl)	CH₂(3-pyridyl)	2.5165 (19)	3.2209 (19)	0.71	Gupta et al. (2015)
			2.4685 (19)	3.0397 (19)	0.57

Notes: (a) non-symmetric binuclear molecule; (b) two independent molecules in the asymmetric unit.

Footnotes

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

Acknowledgements

We gratefully acknowledge the School of Chemical Sciences and Food Technology, Universiti Kebangsaan Malaysia, for providing the essential laboratory facilities. We would also like to thank the laboratory assistants of the Faculty of Science and Technology, Universiti Kebangsaan Malaysia, for technical support received. Intensity data were collected in the University of Malaya's crystallographic laboratory.

Funding information

This work was supported by the Fundamental Research Grant Scheme (FRGS/2/2013/SKK10/UKM/02/1) awarded by the Ministry of Education (MOE).

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