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Acta Cryst. (2009). E65, m594    [ doi:10.1107/S1600536809014883 ]

Di-n-butylbis(N-n-butyl-N-ethyldithiocarbamato-[kappa]S)tin(IV)

I. Baba, N. N. Dzulkefli and S. W. Ng

Abstract top

The Sn atom in the title compound, [Sn(C4H9)2(C7H14NS2)2], exists in a tetrahedral C2S2Sn coordination geometry. The geometry is distorted towards skew-trapezoidal-bipyramidal owing to the proximity of the double-bond S atoms [Sn-S = 2.521 (2) and Sn...S = 2.933 (2) Å]. The Sn atom lies on a special position of mm2 site symmetry and the tin-bound n-butyl chain is disordered about a mirror plane. The ethyl and n-butyl groups of the dithiocarbamate unit are disordered about another mirror plane.

Related literature top

For other di-n-butyltin dithiocarbamates, see: Farina et al. (2000); Lokaj et al. (1986); Menezes et al. (2005); Vrábel et al. (1992a,b); Vrábel & Kellö (1993); Zia-ur-Rehman et al. (2006). For a review of the applications and structures of tin dithiocarbamates, see: Tiekink (2008).

Experimental top

Carbon disulfide (4 ml, 0.06 mol) was added to n-butylisopropylamine (8 ml, 0.06 mol) in ethanol (50 ml) at 277 K. Dibutyltin dichloride (9.1 g, 0.03 mol) dissolved in ethanol (50 ml) was added. The white solid that precipitated was collected and recrystallized from ethanol.

Refinement top

The tin-bound butyl chain was allowed to refined off the mirror plane, as were the ethyl and butyl groups of the dithiocarbamate anion. 1,2-Related carbon-carbon distances were restrained to 1.54±0.01 Å and the 1,3-related ones to 2.51±0.02 Å. The N1–C6 and N1–C6' pair of distances were restrained to 0.01 Å as were the N1–C8 and N1–C8' pair. The temperature factors of the primed atoms were restrained to those of the unprimed ones; the anisotropic displacement parameters of the primed atoms were restrained to be nearly isotropic.

Carbon-bound H-atoms were placed in calculated positions (C—H 0.95 to 0.99 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2 to 1.5U(C). The final difference Fourier map had a large peak in the vicinity of the C9' atom.

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2009).

Figures top
[Figure 1] Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of dibutyldi(N-butyl-N-ethylbutyldithiocarbamato)tin at the 70% probability level; the disorder is not shown. Unlabelled atoms are related by a 2-fold axis. Hydrogen atoms are drawn as spheres of arbitrary radius.
Di-n-butylbis(N-n-butyl-N-ethyldithiocarbamato- κS)tin(IV) top
Crystal data top
[Sn(C4H9)2(C7H14NS2)2]F(000) = 612
Mr = 585.54Dx = 1.163 Mg m−3
Orthorhombic, PmmnMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ab 2aCell parameters from 5407 reflections
a = 11.1317 (2) Åθ = 2.8–28.2°
b = 19.4349 (3) ŵ = 1.02 mm−1
c = 7.7262 (1) ÅT = 123 K
V = 1671.51 (5) Å3Block, colorless
Z = 20.30 × 0.25 × 0.20 mm
Data collection top
Bruker SMART APEX
diffractometer		2072 independent reflections
Radiation source: fine-focus sealed tube1667 reflections with I > 2σ(I)
graphiteRint = 0.024
ω scansθmax = 27.5°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −14→14
Tmin = 0.749, Tmax = 0.821k = −24→25
11224 measured reflectionsl = −10→9
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.066Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.239H-atom parameters constrained
S = 1.11 w = 1/[σ2(Fo2) + (0.1484P)2 + 2.8257P]
where P = (Fo2 + 2Fc2)/3
2072 reflections(Δ/σ)max = 0.001
131 parametersΔρmax = 1.03 e Å−3
55 restraintsΔρmin = −0.66 e Å−3
Crystal data top
[Sn(C4H9)2(C7H14NS2)2]V = 1671.51 (5) Å3
Mr = 585.54Z = 2
Orthorhombic, PmmnMo Kα radiation
a = 11.1317 (2) ŵ = 1.02 mm−1
b = 19.4349 (3) ÅT = 123 K
c = 7.7262 (1) Å0.30 × 0.25 × 0.20 mm
Data collection top
Bruker SMART APEX
diffractometer		2072 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		1667 reflections with I > 2σ(I)
Tmin = 0.749, Tmax = 0.821Rint = 0.024
11224 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.066H-atom parameters constrained
wR(F2) = 0.239Δρmax = 1.03 e Å−3
S = 1.11Δρmin = −0.66 e Å−3
2072 reflectionsAbsolute structure: ?
131 parametersFlack parameter: ?
55 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Sn10.75000.25000.43290 (7)0.0602 (4)
S10.75000.33480 (11)0.6798 (2)0.0659 (6)
S20.75000.39534 (11)0.3309 (3)0.0852 (9)
N10.75000.4700 (4)0.6210 (11)0.0661 (18)
C10.5831 (12)0.257 (4)0.3153 (12)0.085 (10)0.50
H1A0.53150.21900.35800.102*0.50
H1B0.54480.30080.34880.102*0.50
C20.5905 (11)0.2529 (13)0.1171 (11)0.100 (5)0.50
H2A0.64370.29010.07520.120*0.50
H2B0.62770.20850.08430.120*0.50
C30.4697 (14)0.2591 (17)0.0264 (19)0.107 (9)0.50
H3A0.48140.2581−0.10060.129*0.50
H3B0.43140.30340.05730.129*0.50
C40.3882 (18)0.1990 (16)0.082 (3)0.130 (9)0.50
H4A0.30750.20580.03450.195*0.50
H4B0.38390.19730.20870.195*0.50
H4C0.42150.15570.03840.195*0.50
C50.75000.4065 (5)0.5500 (10)0.0576 (18)
C60.744 (3)0.4806 (13)0.8169 (16)0.085 (4)0.25
H6A0.71810.52820.84260.102*0.25
H6B0.68490.44850.86780.102*0.25
C70.865 (3)0.4679 (13)0.8947 (16)0.049 (4)0.25
H7A0.86100.47551.02000.074*0.25
H7B0.92350.49960.84370.074*0.25
H7C0.88960.42040.87160.074*0.25
C6'0.732 (3)0.4781 (19)0.8168 (18)0.085 (4)0.25
H6'10.69800.43540.86680.102*0.25
H6'20.67640.51660.84150.102*0.25
C7'0.857 (3)0.4929 (13)0.895 (3)0.049 (4)0.25
H7'10.84990.49941.01990.074*0.25
H7'20.89040.53460.84190.074*0.25
H7'30.91080.45390.87110.074*0.25
C80.7479 (19)0.5360 (8)0.521 (3)0.083 (4)0.50
H8A0.72110.57390.59710.100*0.25
H8B0.69010.53210.42400.100*0.25
C90.8705 (19)0.5520 (8)0.451 (3)0.047 (4)0.25
H9A0.89420.51470.37060.056*0.25
H9B0.92830.55190.54830.056*0.25
C100.8813 (14)0.6206 (8)0.356 (3)0.042 (3)0.25
H10A0.94890.61860.27270.050*0.25
H10B0.89790.65790.43980.050*0.25
C110.764 (3)0.6359 (14)0.259 (4)0.102 (6)0.25
H11A0.76470.68370.21780.153*0.25
H11B0.69550.62910.33650.153*0.25
H11C0.75670.60480.15920.153*0.25
C8'0.734 (3)0.5340 (12)0.513 (5)0.083 (4)0.25
H8C0.67700.56550.57250.100*0.25
H8D0.69850.52150.39990.100*0.25
C9'0.8539 (19)0.5710 (11)0.485 (3)0.047 (4)0.25
H9C0.88730.58510.59820.056*0.25
H9D0.91140.53880.43020.056*0.25
C10'0.8399 (14)0.6346 (8)0.370 (3)0.042 (3)0.25
H10C0.85620.62180.24820.050*0.25
H10D0.89990.66960.40460.050*0.25
C11'0.7130 (18)0.6661 (16)0.383 (4)0.102 (6)0.25
H11D0.70180.69970.28980.153*0.25
H11E0.70370.68890.49510.153*0.25
H11F0.65280.62950.37170.153*0.25
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Sn10.1059 (7)0.0502 (5)0.0245 (4)0.0000.0000.000
S10.1097 (17)0.0588 (11)0.0292 (8)0.0000.000−0.0063 (7)
S20.172 (3)0.0471 (11)0.0367 (9)0.0000.000−0.0001 (8)
N10.080 (4)0.055 (4)0.064 (4)0.0000.000−0.018 (3)
C10.112 (9)0.08 (3)0.062 (6)0.03 (2)−0.015 (6)−0.007 (11)
C20.135 (11)0.112 (11)0.053 (5)0.075 (14)0.011 (7)0.029 (11)
C30.145 (13)0.11 (2)0.070 (7)0.041 (19)−0.030 (9)0.006 (12)
C40.137 (18)0.16 (2)0.089 (13)0.024 (18)−0.032 (12)0.002 (13)
C50.073 (5)0.057 (4)0.043 (4)0.0000.000−0.006 (3)
C60.086 (8)0.091 (6)0.077 (6)0.000 (8)−0.029 (8)−0.042 (5)
C70.048 (5)0.066 (11)0.034 (4)0.002 (9)−0.017 (4)0.016 (6)
C6'0.086 (8)0.091 (6)0.077 (6)0.000 (8)−0.029 (8)−0.042 (5)
C7'0.048 (5)0.066 (11)0.034 (4)0.002 (9)−0.017 (4)0.016 (6)
C80.068 (7)0.063 (5)0.118 (7)−0.021 (8)0.010 (9)0.001 (5)
C90.040 (6)0.057 (8)0.044 (7)0.002 (6)0.011 (5)0.013 (7)
C100.031 (8)0.035 (6)0.058 (6)0.010 (5)0.014 (6)0.005 (5)
C110.119 (11)0.092 (9)0.095 (9)0.039 (9)−0.007 (8)0.002 (7)
C8'0.068 (7)0.063 (5)0.118 (7)−0.021 (8)0.010 (9)0.001 (5)
C9'0.040 (6)0.057 (8)0.044 (7)0.002 (6)0.011 (5)0.013 (7)
C10'0.031 (8)0.035 (6)0.058 (6)0.010 (5)0.014 (6)0.005 (5)
C11'0.119 (11)0.092 (9)0.095 (9)0.039 (9)−0.007 (8)0.002 (7)
Geometric parameters (Å, °) top
Sn1—C12.073 (13)C7—H7B0.9800
Sn1—C1i2.073 (13)C7—H7C0.9800
Sn1—C1ii2.073 (13)C6'—C7'1.545 (10)
Sn1—C1iii2.073 (13)C6'—H6'10.9900
Sn1—S12.5211 (19)C6'—H6'20.9900
Sn1—S1iii2.5211 (19)C7'—H7'10.9800
S1—C51.718 (9)C7'—H7'20.9800
S2—C51.707 (8)C7'—H7'30.9800
N1—C51.350 (11)C8—C91.4998
N1—C81.499 (14)C8—H8A0.9900
N1—C8'1.508 (15)C8—H8B0.9900
N1—C8'ii1.508 (15)C9—C101.527 (9)
N1—C61.528 (14)C9—H9A0.9900
N1—C6ii1.528 (14)C9—H9B0.9900
N1—C6'ii1.534 (15)C10—C111.536 (10)
N1—C6'1.534 (15)C10—H10A0.9900
C1—C21.536 (9)C10—H10B0.9900
C1—H1A0.9900C11—H11A0.9800
C1—H1B0.9900C11—H11B0.9800
C2—C31.520 (9)C11—H11C0.9800
C2—H2A0.9900C8'—C9'1.536 (10)
C2—H2B0.9900C8'—H8C0.9900
C3—C41.540 (10)C8'—H8D0.9900
C3—H3A0.9900C9'—C10'1.529 (10)
C3—H3B0.9900C9'—H9C0.9900
C4—H4A0.9800C9'—H9D0.9900
C4—H4B0.9800C10'—C11'1.543 (10)
C4—H4C0.9800C10'—H10C0.9900
C6—C71.4925C10'—H10D0.9900
C6—H6A0.9900C11'—H11D0.9800
C6—H6B0.9900C11'—H11E0.9800
C7—H7A0.9800C11'—H11F0.9800
C1—Sn1—C1ii127.4 (9)C6—C7—H7A109.5
C1i—Sn1—C1ii128.0 (6)C6—C7—H7B109.5
C1—Sn1—C1iii128.0 (6)H7A—C7—H7B109.5
C1i—Sn1—C1iii127.4 (9)C6—C7—H7C109.5
C1—Sn1—S1106.9 (14)H7A—C7—H7C109.5
C1i—Sn1—S1111.9 (15)H7B—C7—H7C109.5
C1ii—Sn1—S1106.9 (14)N1—C6'—C7'106.5 (19)
C1iii—Sn1—S1111.9 (15)N1—C6'—H6'1110.4
C1—Sn1—S1iii111.9 (15)C7'—C6'—H6'1110.4
C1i—Sn1—S1iii106.9 (14)N1—C6'—H6'2110.4
C1ii—Sn1—S1iii111.9 (15)C7'—C6'—H6'2110.4
C1iii—Sn1—S1iii106.9 (14)H6'1—C6'—H6'2108.6
S1—Sn1—S1iii81.64 (10)C6'—C7'—H7'1109.5
C5—S1—Sn195.1 (3)C6'—C7'—H7'2109.5
C5—N1—C8124.9 (12)H7'1—C7'—H7'2109.5
C5—N1—C8'122.0 (17)C6'—C7'—H7'3109.5
C5—N1—C8'ii122.0 (17)H7'1—C7'—H7'3109.5
C5—N1—C6121.7 (12)H7'2—C7'—H7'3109.5
C8—N1—C6113.3 (14)N1—C8—C9110.5 (8)
C8'—N1—C6115.5 (18)N1—C8—H8A109.6
C8'ii—N1—C6116.1 (19)C9—C8—H8A109.6
C5—N1—C6ii121.7 (12)N1—C8—H8B109.6
C8—N1—C6ii113.4 (14)C9—C8—H8B109.6
C8'—N1—C6ii116.1 (19)H8A—C8—H8B108.1
C8'ii—N1—C6ii115.5 (18)C8—C9—C10115.2 (9)
C5—N1—C6'ii119.7 (16)C8—C9—H9A108.5
C8—N1—C6'ii115.1 (18)C10—C9—H9A108.5
C8'—N1—C6'ii118 (2)C8—C9—H9B108.5
C8'ii—N1—C6'ii116 (2)C10—C9—H9B108.5
C5—N1—C6'119.7 (16)H9A—C9—H9B107.5
C8—N1—C6'114.8 (18)C9—C10—C11109.7 (12)
C8'—N1—C6'116 (2)C9—C10—H10A109.7
C8'ii—N1—C6'118 (2)C11—C10—H10A109.7
C2—C1—Sn1112.7 (9)C9—C10—H10B109.7
C2—C1—H1A109.1C11—C10—H10B109.7
Sn1—C1—H1A109.1H10A—C10—H10B108.2
C2—C1—H1B109.1C10—C11—H11A109.5
Sn1—C1—H1B109.1C10—C11—H11B109.5
H1A—C1—H1B107.8H11A—C11—H11B109.5
C3—C2—C1114.1 (9)C10—C11—H11C109.5
C3—C2—H2A108.7H11A—C11—H11C109.5
C1—C2—H2A108.7H11B—C11—H11C109.5
C3—C2—H2B108.7N1—C8'—C9'111.1 (17)
C1—C2—H2B108.7N1—C8'—H8C109.4
H2A—C2—H2B107.6C9'—C8'—H8C109.4
C2—C3—C4109.4 (13)N1—C8'—H8D109.4
C2—C3—H3A109.8C9'—C8'—H8D109.4
C4—C3—H3A109.8H8C—C8'—H8D108.0
C2—C3—H3B109.8C10'—C9'—C8'111.9 (11)
C4—C3—H3B109.8C10'—C9'—H9C109.2
H3A—C3—H3B108.2C8'—C9'—H9C109.2
C3—C4—H4A109.5C10'—C9'—H9D109.2
C3—C4—H4B109.5C8'—C9'—H9D109.2
H4A—C4—H4B109.5H9C—C9'—H9D107.9
C3—C4—H4C109.5C9'—C10'—C11'112.1 (12)
H4A—C4—H4C109.5C9'—C10'—H10C109.2
H4B—C4—H4C109.5C11'—C10'—H10C109.2
N1—C5—S2121.3 (7)C9'—C10'—H10D109.2
N1—C5—S1120.3 (6)C11'—C10'—H10D109.2
S2—C5—S1118.4 (5)H10C—C10'—H10D107.9
C7—C6—N1109.8 (11)C10'—C11'—H11D109.5
C7—C6—H6A109.7C10'—C11'—H11E109.5
N1—C6—H6A109.7H11D—C11'—H11E109.5
C7—C6—H6B109.7C10'—C11'—H11F109.5
N1—C6—H6B109.7H11D—C11'—H11F109.5
H6A—C6—H6B108.2H11E—C11'—H11F109.5
C1—Sn1—S1—C5−69.5 (16)C6'ii—N1—C5—S18.7 (14)
C1i—Sn1—S1—C5−75.1 (16)C6'—N1—C5—S1−8.7 (14)
C1ii—Sn1—S1—C569.5 (16)Sn1—S1—C5—N1180.000 (3)
C1iii—Sn1—S1—C575.1 (16)Sn1—S1—C5—S20.000 (2)
S1iii—Sn1—S1—C5180.000 (2)C5—N1—C6—C778.1 (9)
C8—N1—C5—S21.1 (10)C8—N1—C6—C7−105.3 (10)
C8'—N1—C5—S28.2 (12)C8'—N1—C6—C7−112.2 (12)
C8'ii—N1—C5—S2−8.2 (12)C8'ii—N1—C6—C7−96.8 (13)
C6—N1—C5—S2177.2 (14)C6ii—N1—C6—C7−13.4 (4)
C6ii—N1—C5—S2−177.2 (14)C5—N1—C8—C9−78.2 (8)
C6'ii—N1—C5—S2−171.3 (14)C8'—N1—C8—C9−144 (19)
C6'—N1—C5—S2171.3 (14)C8'ii—N1—C8—C9−6(15)
C8—N1—C5—S1−178.9 (10)C6—N1—C8—C9105.4 (14)
C8'—N1—C5—S1−171.8 (12)C6ii—N1—C8—C9100.2 (14)
C8'ii—N1—C5—S1171.8 (12)C6'ii—N1—C8—C994.5 (15)
C6—N1—C5—S1−2.8 (14)C6'—N1—C8—C9111.1 (14)
C6ii—N1—C5—S12.8 (14)
Symmetry codes: (i) x, −y+1/2, z; (ii) −x+3/2, y, z; (iii) −x+3/2, −y+1/2, z.
Acknowledgements top

We thank Universiti Kebangsaan Malaysia and the University of Malaya for supporting this study.

references
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