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Molecules of diphenyl(2-thioxo-1,3-dithiole-4,5-dithiolato-
S,
S′)plumbane, [Pb(C
3S
5)(C
6H
5)
2], are linked into sheets
via two intermolecular Pb
S
thione interactions of 3.322 (4) and 3.827 (4) Å; the Pb centre has a distorted octahedral geometry. In contrast, molecules of diphenyl(2-thioxo-1,3-dithiole-4,5-dithiolato-
S,
S′)stannane, [Sn(C
3S
5)(C
6H
5)
2], are linked into chains
via a single intermolecular Sn—S
thione interaction of 2.8174 (9) Å; the Sn centre has a distorted trigonal-bipyramidal geometry.
Supporting information
CCDC references: 169918; 169919
Compounds (III) (Doidge-Harrison, Irvine, Spencer et al., 1996) and (IV)
(Doidge-Harrison, Irvine, Khan et al., 1996) were prepared by published
routes and recrystallized from EtOH. Crystals of (III) formed very thin plates
and data were collected at room temperature; consequently, the data for (III)
were of poorer quality than those for (IV), which were collected at 150 K on
larger crystals.
All H atoms were placed in geometrical positions and refined using a riding
model, with C—H = 0.93–0.95 Å. The number of Friedel-related reflections
for each compound was 1825 for (III) and 1623 for (IV).
Data collection: SMART (Bruker, 1999) for (III); DENZO (Otwinowski and Minor, 1997) and COLLECT (Nonius, 1998) for (IV). Cell refinement: SAINT (Bruker, 1999) for (III); DENZO and COLLECT for (IV). Data reduction: SAINT for (III); DENZO and COLLECT for (IV). For both compounds, program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997). Molecular graphics: ORTEX in OSCAIL (McArdle, 1994, 2000) and ORTEP-3 for Windows (Farrugia, 1997) for (III); ORTEX in OSCAIL (McArdle, 1994, 2000), ORTEP-3 for Windows (Farrugia, 1997) for (IV). For both compounds, software used to prepare material for publication: CIFTAB (Sheldrick, 1997).
(III) (2-thioxo-1,3-dithiole-4,5-dithiolato-
S,
S')diphenylplumbane
top
Crystal data top
[Pb(C3S5)(C6H5)2] | F(000) = 1048 |
Mr = 557.73 | Dx = 2.152 Mg m−3 |
Orthorhombic, Pna21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2c -2n | Cell parameters from 4683 reflections |
a = 17.5109 (9) Å | θ = 2.3–30.1° |
b = 9.5222 (5) Å | µ = 10.40 mm−1 |
c = 10.3232 (5) Å | T = 295 K |
V = 1721.31 (15) Å3 | Plate, dark red |
Z = 4 | 0.25 × 0.18 × 0.02 mm |
Data collection top
Bruker SMART CCD area-detector diffractometer | 5088 independent reflections |
Radiation source: fine-focus sealed tube | 3310 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.10 |
ϕ/ω scans | θmax = 32.5°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Bruker, 1999) | h = −26→26 |
Tmin = 0.181, Tmax = 0.819 | k = −14→12 |
16869 measured reflections | l = −12→15 |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.055 | H-atom parameters constrained |
wR(F2) = 0.140 | w = 1/[σ2(Fo2) + (0.0573P)2 + 8.9418P] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max < 0.001 |
5088 reflections | Δρmax = 1.89 e Å−3 |
190 parameters | Δρmin = −2.04 e Å−3 |
1 restraint | Absolute structure: (Flack, 1983) |
Primary atom site location: heavy-atom method | Absolute structure parameter: 0.015 (14) |
Crystal data top
[Pb(C3S5)(C6H5)2] | V = 1721.31 (15) Å3 |
Mr = 557.73 | Z = 4 |
Orthorhombic, Pna21 | Mo Kα radiation |
a = 17.5109 (9) Å | µ = 10.40 mm−1 |
b = 9.5222 (5) Å | T = 295 K |
c = 10.3232 (5) Å | 0.25 × 0.18 × 0.02 mm |
Data collection top
Bruker SMART CCD area-detector diffractometer | 5088 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1999) | 3310 reflections with I > 2σ(I) |
Tmin = 0.181, Tmax = 0.819 | Rint = 0.10 |
16869 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.055 | H-atom parameters constrained |
wR(F2) = 0.140 | Δρmax = 1.89 e Å−3 |
S = 1.01 | Δρmin = −2.04 e Å−3 |
5088 reflections | Absolute structure: (Flack, 1983) |
190 parameters | Absolute structure parameter: 0.015 (14) |
1 restraint | |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell e.s.d.'s are taken
into account individually in the estimation of e.s.d.'s in distances, angles
and torsion angles; correlations between e.s.d.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s.
planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor
wR and goodness of fit S are based on F2, conventional
R-factors R are based on F, with F set to zero for
negative F2. The threshold expression of F2 >
σ(F2) is used only for calculating R-factors(gt) etc.
and is not relevant to the choice of reflections for refinement.
R-factors based on F2 are statistically about twice as large
as those based on F, and R- factors based on ALL data will be
even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Pb1 | 0.08628 (2) | 0.13212 (3) | −0.00325 (8) | 0.03829 (13) | |
S1 | 0.1517 (2) | 0.2027 (4) | 0.2122 (3) | 0.0436 (7) | |
S2 | 0.1990 (2) | 0.2470 (4) | −0.1204 (4) | 0.0467 (8) | |
C1 | 0.2274 (7) | 0.2957 (11) | 0.1439 (12) | 0.032 (2) | |
C2 | 0.2460 (7) | 0.3119 (12) | 0.0162 (17) | 0.038 (3) | |
S3 | 0.28893 (19) | 0.3763 (3) | 0.2535 (3) | 0.0410 (7) | |
S4 | 0.32587 (17) | 0.4180 (3) | −0.0129 (5) | 0.0431 (7) | |
C3 | 0.3496 (7) | 0.4526 (13) | 0.1441 (14) | 0.042 (3) | |
S5 | 0.4263 (2) | 0.5511 (5) | 0.1844 (4) | 0.0575 (10) | |
C4 | 0.1033 (6) | −0.0949 (10) | 0.009 (2) | 0.033 (3) | |
C5 | 0.1673 (9) | −0.1433 (14) | 0.0732 (14) | 0.047 (3) | |
H5 | 0.1994 | −0.0808 | 0.1160 | 0.056* | |
C6 | 0.1832 (10) | −0.2850 (15) | 0.0733 (16) | 0.057 (4) | |
H6 | 0.2267 | −0.3184 | 0.1148 | 0.068* | |
C7 | 0.1343 (12) | −0.3775 (13) | 0.012 (3) | 0.073 (6) | |
H7 | 0.1465 | −0.4724 | 0.0069 | 0.087* | |
C8 | 0.0685 (9) | −0.3300 (13) | −0.0422 (15) | 0.053 (4) | |
H8 | 0.0337 | −0.3943 | −0.0753 | 0.063* | |
C9 | 0.0520 (8) | −0.1884 (12) | −0.0489 (14) | 0.044 (3) | |
H9 | 0.0082 | −0.1564 | −0.0905 | 0.053* | |
C10 | −0.0077 (6) | 0.2859 (10) | −0.0212 (14) | 0.033 (3) | |
C11 | −0.0379 (10) | 0.3305 (17) | −0.1341 (19) | 0.045 (4) | |
H11 | −0.0197 | 0.2943 | −0.2119 | 0.054* | |
C12 | −0.0940 (9) | 0.427 (2) | −0.135 (2) | 0.057 (5) | |
H12 | −0.1150 | 0.4542 | −0.2142 | 0.069* | |
C13 | −0.1208 (8) | 0.4854 (15) | −0.023 (2) | 0.059 (5) | |
H13 | −0.1591 | 0.5530 | −0.0271 | 0.070* | |
C14 | −0.0919 (10) | 0.445 (2) | 0.094 (2) | 0.064 (6) | |
H14 | −0.1097 | 0.4852 | 0.1706 | 0.077* | |
C15 | −0.0335 (11) | 0.3404 (19) | 0.096 (2) | 0.052 (4) | |
H15 | −0.0131 | 0.3092 | 0.1740 | 0.063* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Pb1 | 0.03712 (19) | 0.02808 (14) | 0.0497 (2) | 0.00494 (15) | −0.0089 (3) | −0.0037 (4) |
S1 | 0.0466 (18) | 0.0458 (15) | 0.0383 (18) | −0.0138 (14) | −0.0006 (14) | −0.0028 (13) |
S2 | 0.049 (2) | 0.058 (2) | 0.0335 (18) | −0.0018 (16) | 0.0024 (15) | −0.0090 (15) |
C1 | 0.034 (6) | 0.033 (5) | 0.030 (6) | −0.001 (5) | 0.000 (5) | −0.003 (4) |
C2 | 0.032 (5) | 0.045 (5) | 0.038 (9) | −0.002 (4) | 0.000 (6) | −0.012 (6) |
S3 | 0.0404 (16) | 0.0501 (16) | 0.0326 (16) | −0.0116 (14) | −0.0012 (12) | −0.0051 (13) |
S4 | 0.0383 (13) | 0.0511 (13) | 0.040 (2) | −0.0023 (11) | 0.0042 (18) | −0.0010 (19) |
C3 | 0.037 (7) | 0.041 (6) | 0.049 (8) | −0.003 (5) | 0.001 (6) | −0.002 (5) |
S5 | 0.050 (2) | 0.067 (2) | 0.056 (2) | −0.0265 (18) | 0.0096 (17) | −0.0075 (18) |
C4 | 0.031 (5) | 0.033 (4) | 0.035 (7) | 0.007 (3) | 0.008 (7) | −0.001 (6) |
C5 | 0.051 (8) | 0.048 (7) | 0.042 (8) | 0.008 (6) | −0.004 (6) | 0.001 (6) |
C6 | 0.058 (9) | 0.052 (7) | 0.060 (10) | 0.028 (7) | −0.010 (7) | −0.009 (7) |
C7 | 0.113 (14) | 0.034 (5) | 0.071 (13) | 0.012 (7) | 0.027 (14) | 0.004 (8) |
C8 | 0.067 (9) | 0.031 (5) | 0.060 (11) | −0.007 (6) | 0.013 (7) | −0.010 (5) |
C9 | 0.041 (7) | 0.035 (5) | 0.057 (9) | −0.003 (5) | 0.006 (6) | −0.006 (5) |
C10 | 0.034 (5) | 0.031 (4) | 0.034 (8) | 0.006 (4) | −0.001 (5) | −0.002 (5) |
C11 | 0.040 (8) | 0.040 (7) | 0.055 (10) | 0.008 (6) | −0.001 (7) | 0.003 (6) |
C12 | 0.048 (10) | 0.052 (9) | 0.072 (14) | 0.003 (7) | −0.012 (9) | −0.005 (8) |
C13 | 0.043 (7) | 0.053 (7) | 0.079 (15) | 0.017 (6) | −0.001 (9) | −0.001 (9) |
C14 | 0.066 (12) | 0.059 (11) | 0.068 (14) | 0.028 (9) | 0.015 (9) | −0.012 (10) |
C15 | 0.054 (10) | 0.052 (9) | 0.051 (10) | 0.005 (7) | 0.007 (7) | −0.002 (7) |
Geometric parameters (Å, º) top
Pb1—C4 | 2.185 (10) | C6—C7 | 1.38 (3) |
Pb1—C10 | 2.210 (10) | C6—H6 | 0.9300 |
Pb1—S2 | 2.561 (4) | C7—C8 | 1.36 (3) |
Pb1—S1 | 2.591 (4) | C7—H7 | 0.9300 |
Pb1—S5i | 3.322 (4) | C8—C9 | 1.380 (17) |
Pb1—S5ii | 3.827 (4) | C8—H8 | 0.9300 |
S1—C1 | 1.742 (12) | C9—H9 | 0.9300 |
S2—C2 | 1.746 (16) | C10—C11 | 1.35 (2) |
C1—C2 | 1.37 (2) | C10—C15 | 1.39 (2) |
C1—S3 | 1.741 (13) | C11—C12 | 1.34 (3) |
C2—S4 | 1.752 (12) | C11—H11 | 0.9300 |
S3—C3 | 1.713 (14) | C12—C13 | 1.37 (3) |
S4—C3 | 1.706 (15) | C12—H12 | 0.9300 |
C3—S5 | 1.690 (13) | C13—C14 | 1.37 (3) |
C4—C5 | 1.384 (19) | C13—H13 | 0.9300 |
C4—C9 | 1.397 (18) | C14—C15 | 1.43 (3) |
C5—C6 | 1.378 (19) | C14—H14 | 0.9300 |
C5—H5 | 0.9300 | C15—H15 | 0.9300 |
| | | |
C4—Pb1—C10 | 139.6 (4) | C6—C5—H5 | 120.3 |
C4—Pb1—S2 | 110.2 (4) | C4—C5—H5 | 120.3 |
C10—Pb1—S2 | 104.5 (3) | C5—C6—C7 | 119.9 (15) |
C4—Pb1—S1 | 98.5 (5) | C5—C6—H6 | 120.1 |
C10—Pb1—S1 | 103.3 (3) | C7—C6—H6 | 120.1 |
S2—Pb1—S1 | 87.33 (11) | C8—C7—C6 | 120.1 (11) |
C4—Pb1—S5i | 80.5 (5) | C8—C7—H7 | 120.0 |
C10—Pb1—S5i | 91.3 (4) | C6—C7—H7 | 120.0 |
S2—Pb1—S5i | 72.07 (12) | C7—C8—C9 | 121.7 (14) |
S1—Pb1—S5i | 157.32 (11) | C7—C8—H8 | 119.2 |
C4—Pb1—S5ii | 67.7 (4) | C9—C8—H8 | 119.2 |
C10—Pb1—S5ii | 78.5 (3) | C8—C9—C4 | 117.8 (14) |
S2—Pb1—S5ii | 176.61 (11) | C8—C9—H9 | 121.1 |
S1—Pb1—S5ii | 90.44 (11) | C4—C9—H9 | 121.1 |
S5i—Pb1—S5ii | 109.68 (6) | C11—C10—C15 | 120.5 (11) |
C1—S1—Pb1 | 96.9 (4) | C11—C10—Pb1 | 124.9 (11) |
C2—S2—Pb1 | 97.6 (5) | C15—C10—Pb1 | 114.6 (11) |
C2—C1—S3 | 115.5 (9) | C12—C11—C10 | 120.7 (18) |
C2—C1—S1 | 129.0 (10) | C12—C11—H11 | 119.7 |
S3—C1—S1 | 115.6 (7) | C10—C11—H11 | 119.7 |
C1—C2—S2 | 128.9 (10) | C11—C12—C13 | 121 (2) |
C1—C2—S4 | 114.9 (11) | C11—C12—H12 | 119.3 |
S2—C2—S4 | 116.2 (10) | C13—C12—H12 | 119.3 |
C3—S3—C1 | 98.2 (6) | C12—C13—C14 | 120.5 (13) |
C3—S4—C2 | 98.2 (7) | C12—C13—H13 | 119.7 |
S5—C3—S4 | 122.3 (8) | C14—C13—H13 | 119.7 |
S5—C3—S3 | 124.5 (9) | C13—C14—C15 | 118.1 (18) |
S4—C3—S3 | 113.1 (7) | C13—C14—H14 | 120.9 |
C5—C4—C9 | 120.9 (11) | C15—C14—H14 | 120.9 |
C5—C4—Pb1 | 117.8 (9) | C10—C15—C14 | 118.8 (18) |
C9—C4—Pb1 | 121.3 (10) | C10—C15—H15 | 120.6 |
C6—C5—C4 | 119.4 (14) | C14—C15—H15 | 120.6 |
Symmetry codes: (i) −x+1/2, y−1/2, z−1/2; (ii) x−1/2, −y+1/2, z. |
(IV) (2-thioxo-1,3-dithiole-4,5-dithiolato-
S,
S')diphenylstannane
top
Crystal data top
[Sn(C3S5)(C6H5)2] | F(000) = 920 |
Mr = 469.23 | Dx = 1.875 Mg m−3 |
Orthorhombic, Pna21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2c -2n | Cell parameters from 6500 reflections |
a = 17.3574 (5) Å | θ = 2.9–27.5° |
b = 9.2270 (2) Å | µ = 2.15 mm−1 |
c = 10.3775 (2) Å | T = 150 K |
V = 1662.03 (7) Å3 | Needle, orange-red |
Z = 4 | 0.48 × 0.10 × 0.06 mm |
Data collection top
Nonius KappaCCD area-detector diffractometer | 3622 independent reflections |
Radiation source: fine-focus sealed tube | 3405 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.039 |
ϕ/ω scans | θmax = 27.5°, θmin = 3.2° |
Absorption correction: empirical (using intensity measurements) (SORTAV; Blessing, 1995, 1997) | h = −22→19 |
Tmin = 0.425, Tmax = 0.882 | k = −11→11 |
11483 measured reflections | l = −13→13 |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.028 | H-atom parameters constrained |
wR(F2) = 0.061 | w = 1/[σ2(Fo2) + (0.0284P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max < 0.001 |
3622 reflections | Δρmax = 0.68 e Å−3 |
190 parameters | Δρmin = −1.25 e Å−3 |
1 restraint | Absolute structure: (Flack, 1983) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.004 (19) |
Crystal data top
[Sn(C3S5)(C6H5)2] | V = 1662.03 (7) Å3 |
Mr = 469.23 | Z = 4 |
Orthorhombic, Pna21 | Mo Kα radiation |
a = 17.3574 (5) Å | µ = 2.15 mm−1 |
b = 9.2270 (2) Å | T = 150 K |
c = 10.3775 (2) Å | 0.48 × 0.10 × 0.06 mm |
Data collection top
Nonius KappaCCD area-detector diffractometer | 3622 independent reflections |
Absorption correction: empirical (using intensity measurements) (SORTAV; Blessing, 1995, 1997) | 3405 reflections with I > 2σ(I) |
Tmin = 0.425, Tmax = 0.882 | Rint = 0.039 |
11483 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.028 | H-atom parameters constrained |
wR(F2) = 0.061 | Δρmax = 0.68 e Å−3 |
S = 1.08 | Δρmin = −1.25 e Å−3 |
3622 reflections | Absolute structure: (Flack, 1983) |
190 parameters | Absolute structure parameter: −0.004 (19) |
1 restraint | |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell e.s.d.'s are taken
into account individually in the estimation of e.s.d.'s in distances, angles
and torsion angles; correlations between e.s.d.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s.
planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor
wR and goodness of fit S are based on F2, conventional
R-factors R are based on F, with F set to zero for
negative F2. The threshold expression of F2 >
σ(F2) is used only for calculating R-factors(gt) etc.
and is not relevant to the choice of reflections for refinement.
R-factors based on F2 are statistically about twice as large
as those based on F, and R- factors based on ALL data will be
even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Sn1 | 0.101604 (10) | 0.16708 (2) | −0.01258 (3) | 0.01963 (8) | |
S1 | 0.15889 (5) | 0.22305 (10) | 0.20630 (8) | 0.02618 (18) | |
S2 | 0.20835 (5) | 0.30346 (10) | −0.10939 (9) | 0.02471 (19) | |
C1 | 0.2330 (2) | 0.3346 (3) | 0.1525 (4) | 0.0195 (7) | |
C2 | 0.25333 (18) | 0.3662 (4) | 0.0302 (3) | 0.0195 (7) | |
S3 | 0.28947 (5) | 0.41349 (9) | 0.27232 (7) | 0.02238 (18) | |
S4 | 0.33083 (5) | 0.48353 (9) | 0.01353 (7) | 0.0260 (2) | |
C3 | 0.34947 (19) | 0.5097 (4) | 0.1743 (3) | 0.0239 (7) | |
S5 | 0.42116 (5) | 0.61976 (11) | 0.22192 (8) | 0.0286 (2) | |
C4 | 0.10113 (16) | −0.0625 (4) | 0.0153 (3) | 0.0209 (8) | |
C5 | 0.1555 (2) | −0.1267 (4) | 0.0932 (3) | 0.0237 (7) | |
H5 | 0.1917 | −0.0683 | 0.1383 | 0.028* | |
C6 | 0.1577 (2) | −0.2763 (4) | 0.1062 (4) | 0.0328 (9) | |
H6 | 0.1970 | −0.3205 | 0.1564 | 0.039* | |
C7 | 0.1024 (2) | −0.3614 (5) | 0.0455 (5) | 0.0368 (10) | |
H7 | 0.1033 | −0.4638 | 0.0551 | 0.044* | |
C8 | 0.0463 (2) | −0.2964 (4) | −0.0288 (4) | 0.0339 (9) | |
H8 | 0.0076 | −0.3538 | −0.0687 | 0.041* | |
C9 | 0.0463 (2) | −0.1474 (4) | −0.0455 (3) | 0.0260 (8) | |
H9 | 0.0086 | −0.1032 | −0.0988 | 0.031* | |
C10 | −0.00310 (17) | 0.2880 (3) | −0.0017 (4) | 0.0211 (6) | |
C11 | −0.0392 (2) | 0.3451 (4) | −0.1098 (4) | 0.0259 (9) | |
H11 | −0.0193 | 0.3254 | −0.1933 | 0.031* | |
C12 | −0.1045 (2) | 0.4312 (5) | −0.0957 (4) | 0.0327 (10) | |
H12 | −0.1289 | 0.4710 | −0.1697 | 0.039* | |
C13 | −0.1338 (2) | 0.4585 (4) | 0.0237 (4) | 0.0330 (9) | |
H13 | −0.1782 | 0.5179 | 0.0324 | 0.040* | |
C14 | −0.0995 (2) | 0.4010 (5) | 0.1318 (5) | 0.0418 (11) | |
H14 | −0.1208 | 0.4187 | 0.2146 | 0.050* | |
C15 | −0.0337 (2) | 0.3168 (4) | 0.1186 (4) | 0.0313 (10) | |
H15 | −0.0094 | 0.2785 | 0.1933 | 0.038* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Sn1 | 0.02078 (12) | 0.01665 (12) | 0.02147 (13) | 0.00217 (8) | −0.00251 (10) | −0.00229 (10) |
S1 | 0.0325 (5) | 0.0270 (4) | 0.0190 (4) | −0.0096 (4) | −0.0022 (3) | −0.0003 (4) |
S2 | 0.0286 (5) | 0.0293 (5) | 0.0162 (4) | −0.0022 (4) | −0.0007 (3) | −0.0030 (3) |
C1 | 0.0190 (18) | 0.0171 (18) | 0.0224 (18) | 0.0023 (12) | −0.0013 (14) | −0.0032 (12) |
C2 | 0.0183 (17) | 0.0192 (17) | 0.0211 (17) | −0.0005 (14) | −0.0018 (12) | −0.0017 (13) |
S3 | 0.0245 (4) | 0.0247 (4) | 0.0180 (4) | −0.0053 (3) | 0.0001 (3) | −0.0032 (3) |
S4 | 0.0270 (4) | 0.0307 (5) | 0.0204 (5) | −0.0052 (4) | 0.0024 (3) | −0.0024 (3) |
C3 | 0.0237 (18) | 0.0210 (18) | 0.0271 (18) | 0.0003 (15) | 0.0012 (13) | −0.0017 (13) |
S5 | 0.0290 (5) | 0.0344 (5) | 0.0225 (4) | −0.0116 (4) | 0.0057 (4) | −0.0064 (4) |
C4 | 0.0212 (17) | 0.0141 (16) | 0.027 (2) | 0.0018 (11) | 0.0057 (12) | −0.0044 (13) |
C5 | 0.0240 (18) | 0.0205 (18) | 0.0266 (18) | 0.0004 (15) | 0.0018 (14) | −0.0021 (15) |
C6 | 0.042 (2) | 0.021 (2) | 0.036 (2) | 0.0039 (17) | 0.0010 (17) | 0.0034 (17) |
C7 | 0.052 (3) | 0.019 (2) | 0.039 (2) | −0.0010 (16) | 0.0072 (17) | 0.0031 (18) |
C8 | 0.038 (2) | 0.0292 (19) | 0.034 (2) | −0.0146 (16) | 0.0032 (19) | −0.0129 (19) |
C9 | 0.0253 (18) | 0.0257 (18) | 0.027 (2) | −0.0032 (14) | 0.0045 (13) | −0.0054 (13) |
C10 | 0.0212 (15) | 0.0152 (14) | 0.0268 (18) | −0.0008 (12) | 0.0009 (14) | 0.0002 (16) |
C11 | 0.025 (2) | 0.029 (2) | 0.023 (2) | 0.0036 (15) | −0.0013 (15) | −0.0049 (14) |
C12 | 0.028 (2) | 0.028 (2) | 0.042 (3) | 0.0066 (15) | −0.0080 (15) | −0.0036 (18) |
C13 | 0.0211 (18) | 0.033 (2) | 0.045 (3) | 0.0076 (15) | 0.0022 (16) | −0.0079 (16) |
C14 | 0.035 (3) | 0.047 (3) | 0.043 (3) | 0.0057 (18) | 0.0156 (17) | −0.005 (2) |
C15 | 0.030 (2) | 0.035 (2) | 0.029 (2) | 0.0041 (16) | 0.0048 (17) | 0.0053 (16) |
Geometric parameters (Å, º) top
Sn1—C10 | 2.135 (3) | C6—C7 | 1.392 (6) |
Sn1—C4 | 2.138 (3) | C6—H6 | 0.9500 |
Sn1—S2 | 2.4547 (10) | C7—C8 | 1.379 (6) |
Sn1—S1 | 2.5327 (9) | C7—H7 | 0.9500 |
Sn1—S5i | 2.8174 (9) | C8—C9 | 1.386 (5) |
Sn1—S5ii | 4.7683 (10) | C8—H8 | 0.9500 |
S1—C1 | 1.740 (4) | C9—H9 | 0.9500 |
S2—C2 | 1.745 (3) | C10—C15 | 1.383 (6) |
C1—C2 | 1.349 (5) | C10—C11 | 1.389 (5) |
C1—S3 | 1.742 (4) | C11—C12 | 1.393 (5) |
C2—S4 | 1.735 (3) | C11—H11 | 0.9500 |
S3—C3 | 1.705 (3) | C12—C13 | 1.363 (6) |
S4—C3 | 1.717 (3) | C12—H12 | 0.9500 |
C3—S5 | 1.681 (3) | C13—C14 | 1.375 (6) |
S5—Sn1iii | 2.8175 (9) | C13—H13 | 0.9500 |
C4—C5 | 1.377 (5) | C14—C15 | 1.389 (6) |
C4—C9 | 1.383 (5) | C14—H14 | 0.9500 |
C5—C6 | 1.387 (4) | C15—H15 | 0.9500 |
C5—H5 | 0.9500 | | |
| | | |
C10—Sn1—C4 | 120.47 (11) | C4—C5—H5 | 119.9 |
C10—Sn1—S2 | 113.34 (8) | C6—C5—H5 | 119.9 |
C4—Sn1—S2 | 124.49 (8) | C5—C6—C7 | 119.9 (4) |
C10—Sn1—S1 | 100.38 (10) | C5—C6—H6 | 120.0 |
C4—Sn1—S1 | 94.72 (9) | C7—C6—H6 | 120.0 |
S2—Sn1—S1 | 88.06 (3) | C8—C7—C6 | 119.6 (4) |
C10—Sn1—S5i | 90.77 (11) | C8—C7—H7 | 120.2 |
C4—Sn1—S5i | 88.74 (9) | C6—C7—H7 | 120.2 |
S2—Sn1—S5i | 77.59 (3) | C7—C8—C9 | 120.1 (4) |
S1—Sn1—S5i | 164.51 (3) | C7—C8—H8 | 120.0 |
C10—Sn1—S5ii | 72.77 (8) | C9—C8—H8 | 120.0 |
C4—Sn1—S5ii | 51.58 (8) | C4—C9—C8 | 120.3 (4) |
S2—Sn1—S5ii | 171.57 (3) | C4—C9—H9 | 119.8 |
S1—Sn1—S5ii | 85.03 (2) | C8—C9—H9 | 119.8 |
S5i—Sn1—S5ii | 108.722 (16) | C15—C10—C11 | 118.9 (3) |
C1—S1—Sn1 | 97.09 (13) | C15—C10—Sn1 | 118.4 (3) |
C2—S2—Sn1 | 99.67 (11) | C11—C10—Sn1 | 122.6 (3) |
C2—C1—S1 | 128.5 (3) | C10—C11—C12 | 119.9 (4) |
C2—C1—S3 | 115.7 (3) | C10—C11—H11 | 120.1 |
S1—C1—S3 | 115.7 (2) | C12—C11—H11 | 120.1 |
C1—C2—S4 | 115.6 (3) | C13—C12—C11 | 120.3 (4) |
C1—C2—S2 | 126.3 (3) | C13—C12—H12 | 119.8 |
S4—C2—S2 | 118.10 (18) | C11—C12—H12 | 119.8 |
C3—S3—C1 | 97.78 (16) | C12—C13—C14 | 120.6 (3) |
C3—S4—C2 | 97.86 (16) | C12—C13—H13 | 119.7 |
S5—C3—S3 | 126.3 (2) | C14—C13—H13 | 119.7 |
S5—C3—S4 | 120.7 (2) | C13—C14—C15 | 119.4 (4) |
S3—C3—S4 | 113.05 (19) | C13—C14—H14 | 120.3 |
C3—S5—Sn1iii | 106.11 (12) | C15—C14—H14 | 120.3 |
C5—C4—C9 | 119.7 (3) | C10—C15—C14 | 120.8 (4) |
C5—C4—Sn1 | 120.2 (2) | C10—C15—H15 | 119.6 |
C9—C4—Sn1 | 120.1 (2) | C14—C15—H15 | 119.6 |
C4—C5—C6 | 120.2 (3) | | |
Symmetry codes: (i) −x+1/2, y−1/2, z−1/2; (ii) x−1/2, −y+1/2, z; (iii) −x+1/2, y+1/2, z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5···S1 | 0.95 | 2.84 | 3.434 (4) | 122 |
C11—H11···S5i | 0.95 | 2.70 | 3.401 (4) | 131 |
Symmetry code: (i) −x+1/2, y−1/2, z−1/2. |
Experimental details
| (III) | (IV) |
Crystal data |
Chemical formula | [Pb(C3S5)(C6H5)2] | [Sn(C3S5)(C6H5)2] |
Mr | 557.73 | 469.23 |
Crystal system, space group | Orthorhombic, Pna21 | Orthorhombic, Pna21 |
Temperature (K) | 295 | 150 |
a, b, c (Å) | 17.5109 (9), 9.5222 (5), 10.3232 (5) | 17.3574 (5), 9.2270 (2), 10.3775 (2) |
V (Å3) | 1721.31 (15) | 1662.03 (7) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 10.40 | 2.15 |
Crystal size (mm) | 0.25 × 0.18 × 0.02 | 0.48 × 0.10 × 0.06 |
|
Data collection |
Diffractometer | Bruker SMART CCD area-detector diffractometer | Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 1999) | Empirical (using intensity measurements) (SORTAV; Blessing, 1995, 1997) |
Tmin, Tmax | 0.181, 0.819 | 0.425, 0.882 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 16869, 5088, 3310 | 11483, 3622, 3405 |
Rint | 0.10 | 0.039 |
(sin θ/λ)max (Å−1) | 0.756 | 0.650 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.055, 0.140, 1.01 | 0.028, 0.061, 1.08 |
No. of reflections | 5088 | 3622 |
No. of parameters | 190 | 190 |
No. of restraints | 1 | 1 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.89, −2.04 | 0.68, −1.25 |
Absolute structure | (Flack, 1983) | (Flack, 1983) |
Absolute structure parameter | 0.015 (14) | −0.004 (19) |
Hydrogen-bond geometry (Å, º) for (IV) top
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5···S1 | 0.95 | 2.84 | 3.434 (4) | 122 |
C11—H11···S5i | 0.95 | 2.70 | 3.401 (4) | 131 |
Symmetry code: (i) −x+1/2, y−1/2, z−1/2. |
Selected geometric parameters for (III) and (IV) (Å, °) top | (III) at 295 K | (IV) at 150 K |
M-C4 | 2.185 (10) | 2.138 (3) |
M-C10 | 2.210 (10) | 2.135 (3) |
M-S1 | 2.591 (4) | 2.5327 (9) |
M-S2 | 2.561 (4) | 2.4547 (10) |
M-S5i | 3.322 (4) | 2.8174 (9) |
M-S5ii | 3.827 (4) | |
| | |
S1-M1-S2 | 87.33 (11) | 88.06 (3) |
C4-M1-S1 | 98.5 (5) | 94.72 (5) |
C10-M1-S1 | 103.3 (3) | 100.38 (10) |
C4-M1-S2 | 110.2 (4) | 124.49 (8) |
C10-M1-S2 | 104.5 (3) | 113.34 (9) |
C4-M1-C10 | 139.6 (4) | 120.47 (11) |
C4-M1-S5i | 80.5 (5) | 88.74 (9) |
C10-M1-S5i | 91.3 (4) | 90.77 (11) |
S1-M1-S5i | 157.32 (11) | 164.51 (3) |
S2-M1-S5i | 72.07 (12) | 77.59 (3) |
C4-M1-S5ii | 67.7 (4) | |
C10-M1-S5ii | 78.5 (3) | |
S2-M1-S5ii | 176.61 (11) | |
S1-M1-S5ii | 90.44 (11) | |
S5i-M1-S5ii | 109.68 (6) | |
C3i-S5i-M1 | 108.4 (5) | 106.11 (12) |
Symmetry codes: (i) 1/2 - x, y - 1/2, z - 1/2; (ii) x - 1/2, 1/2 - y, z |
Comparison of selected parameters in five-coordinate R2Sn(dmit)
compounds (Å, °) topCompound | Intermolecular Sn-S | C═S-Sn | C-Sn-C | Temperature (K) |
Me2Sn(dmit)a | 3.001 (2) | 116.4 (3) | 126.3 (3) | 150 |
| 2.960 (2) | 114.1 (3) | 119.5 (5) | |
Et2Sn(dmit)a | 3.037 (4) | 112.1 (5) | 128.7 (8) | 295 |
orthorhombica | 3.0083 (15) | 111.1 (2) | 130.8 (2) | 150 |
MePhSn(dmit)b | 3.139 (1) | 113.1 (1) | 115.8 (1) | 295 |
Ph2Sn(dmit)c | 2.8174 (9) | 106.11 (12) | 120.47 (11) | 150 |
a Allan et al. (2001); b Doidge-Harrison, Irvine, Khan et al., 1996;
c this work. |
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While structures of various neutral diorganotin 1,2-dithiolates, (I), are listed in the Cambridge Structural Database (Allen & Kennard, 1993) at the chemical database service of the EPSRC (Fletcher et al., 1996), there are no entries for diorganolead derivatives, (II). In order to compare related diorganolead- and diorganotin-1,2-dithiolato complexes, the structures of (2-thioxo-1,3-dithiole-4,5-dithiolato-S,S')diphenyllead, Ph2Pb(dmit), (III), and of (2-thioxo-1,3-dithiole-4,5-dithiolato-S,S')diphenyltin, Ph2Sn(dmit), (IV), have been determined. \sch
The two compounds are isostructural in the sense that they crystallize in the same space group and that the atomic coordinates and cell dimensions are similar. However, the two molecules exhibit differences in the geometries at the metal atom centre and in the intermolecular interactions. The atom-labelling schemes for (III) and (IV) are shown in Figs. 1 and 2, respectively, and selected geometric parameters are listed in Table 1.
Molecules of (III) are linked into sheets via secondary Pb···Sthione intermolecular interactions [Pb···S5i 3.322 (4) and Pb···S5ii 3.827 (4) Å; symmetry codes: (i) 1/2 - x, y - 1/2, z - 1/2; (ii) x - 1/2, 1/2 - y, z; Fig. 3a]. Thus, the Pb centre is six coordinate, with a distorted octahedral geometry, as shown by the bond angles at Pb (Table 1). The chelate bite angle is 87.33 (11)°. The secondary Pb···S bonds are considerably longer than the primary and intramolecular Pb···S bonds [2.561 (4) and 2.591 (4) Å], but are both within the van der Waals radii sum of 4.14 Å for Pb and S. The shorter Pb···S5i bond links molecules into zigzag chains, while the longer Pb···S5ii bond links the chains into sheets. S···S separations [S2···S5i 3.515 (6) Å], at just less than the van der Waals radii sum of 3.60 Å, further augment the chain formation.
The six-coordinate structure of (III) has similiarities with that of molecule B in monoclinic Et2Sn(dmit) (Allan et al., 2001), in which the Sn centre forms one secondary bond [Sn···S 3.555 (2) Å] and a much longer second Sn···S contact at 3.927 (2) Å, the latter just being within the van der Waals radii sum of 4.05 Å.
In contrast with (III), molecules of (IV) are solely linked into chains via a single secondary Sn···Sthione intermolecular interaction [Sn—S5i 2.8174 (9) Å: symmetry code: (i) 1/2 - x, y - 1/2, z - 1/2; Fig. 3 b]. The next shortest Sn···S separation is at a distance of 4.7683 (10) Å [symmetry code: x - 1/2, 1/2 - y, z], which is much longer than the sum of the van der Waals radii of 4.05 Å for Sn and S. Thus, the Sn centre in (IV) is five-coordinate, with a distorted trigonal bipyramidal geometry (Fig. 2). The degree of distortion along the pathway from trigonal bipyramidal toward square planar is calculated to be 33%, using the τ parameter of Addison et al. (1984), or 23%, using the Berry pseudorotational coordinate of Holmes (1984). The axial sites are occupied by the intermolecular thione S and S1 [Sn—S1 2.5327 (9) Å]. The equatorial Sn—S2 bond length is shorter, as expected, at 2.4547 (10) Å. PLATON (Spek, 1994) recognized the two hydrogen bonds in (IV) (Table 2).
Compound (IV) has a similar chain structure to those reported for orthorhombic Et2Sn(dmit), Me2Sn(dmit) and PhMeSn(dmit) (Allan et al., 2001; Doidge-Harrison, Irvine, Khan et al., 1996), although both Et2Sn(dmit) and Me2Sn(dmit) also possess interchain S···S interactions of less than 3.60 Å (Allan et al., 2001), while neither PhMeSn(dmit) (Doidge-Harrison, Irvine, Khan et al., 1996) nor (IV) exhibit these. Comparisons of selected geometric parameters of the four compounds are shown in Table 3. The variations in the intermolecular Sn—Sthione bond lengths follow from no obvious steric or electronic property of the organic groups. There are also significant differences in the molecular C—Sn—C and the intermolecular C═S···Sn angles in the four compounds.