![cross.png](/logos/buttonlogos/cross.png)
![cross.png](/logos/buttonlogos/cross.png)
research communications
![Open Access](/logos/open.png)
Di-n-butylbis[N-(2-methoxyethyl)-N-methyldithiocarbamato-κ2S,S′]tin(IV): and Hirshfeld surface analysis
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
The complete molecule of the title compound, [Sn(C4H9)2(C5H10NOS2)2], is generated by a crystallographic mirror plane, with the SnIV 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.
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 SnIV 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 are octahedral and those with Sn-bound 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 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—Slong and Sn—Sshort 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.
|
![]() | Figure 1 The molecular structure of (I) ![]() ![]() |
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. 2
b. 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.
|
![]() | Figure 2 The molecular packing in (I) ![]() |
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 dnorm, 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 dnorm, highlighting the intermolecular C—H⋯S and H⋯H interactions.
![]() | Figure 3 Two views of the Hirshfeld surface mapped over dnorm for (I) ![]() |
![]() | 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 dnorm 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. 6
b–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.
|
![]() | Figure 6 Views of the (a) full two-dimensional fingerprint plot for (I) ![]() |
In the fingerprint plot delineated into H⋯H contacts, Fig. 6b, a long and distinctive spike at de + di ∼ 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 (de, di) region, Fig. 6
a 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 de + di ∼ 2.8 Å in the delineated fingerprint plot, Fig. 6
c; 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. 6
d, and is evident as a pair of broad peaks at de + di ∼ 2.9 Å. The fingerprint plots delineated into O⋯H/H⋯O and N⋯H/H⋯N contacts, Fig. 6
e 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.
|
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. 2
b) 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—Sshort 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—Slong bonds, i.e. 2.83 to 3.08 Å and these cluster around 2.96 Å. Given the range of Sn—Sshort bond lengths is 0.04 Å and that for Sn—Slong is 0.25 Å, the observation that differences between the average values of Sn—Sshort and Sn—Slong span a range of 0.43 Å indicates no specific correlations exist between Sn—Sshort and Sn—Slong bond lengths. The Sshort—Sn—Sshort, Slong—Sn—Slong 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 Slong—Sn—Slong 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 Slong—Sn—Slong 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 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 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 . Carbon-bound H atoms were placed in calculated positions (C—H = 0.98–0.99 Å) and were included in the in the riding model approximation, with Uiso(H) set to 1.2–1.5Ueq(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.
|
Supporting information
CCDC reference: 1528948
https://doi.org/10.1107/S2056989017001098/hb7654sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989017001098/hb7654Isup2.hkl
Data collection: CrysAlis PRO (Agilent, 2015); cell
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).[Sn(C4H9)2(C5H10NOS2)2] | F(000) = 580 |
Mr = 561.43 | Dx = 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 |
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 | Rint = 0.022 |
Detector resolution: 10.4041 pixels mm-1 | θmax = 31.7°, θmin = 3.8° |
ω scan | h = −6→10 |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2015) | k = −26→25 |
Tmin = 0.482, Tmax = 1.000 | l = −15→12 |
10631 measured reflections |
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(Fo2) + (0.0308P)2 + 0.5383P] where P = (Fo2 + 2Fc2)/3 |
S = 1.12 | (Δ/σ)max = 0.002 |
4063 reflections | Δρmax = 0.68 e Å−3 |
147 parameters | Δρmin = −0.56 e Å−3 |
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. |
x | y | z | Uiso*/Ueq | 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 |
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) |
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. |
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. |
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 |
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.
![Open Access](/logos/open.png)