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The structure of the title compound, [GeCl4(C6H7N)2], (I), is the first example of an addition compound of GeCl4 with two aromatic nitrogen bases. The molecule, with essential D2h symmetry, has crystallographic C2h symmetry. The environment around the Ge atom can be described as a slightly distorted octahedron with the 4-methylpyridine ligands occupying axial positions and the four chloro ligands in the equatorial plane. The structure of (I) is isomorphous with the corresponding silicon halides.
Supporting information
CCDC reference: 153931
Data collection: SMART (Siemens, 1995); cell refinement: SMART; data reduction: SAINT (Siemens, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: SHELXL97.
Crystal data top
[GeCl4(C6H7N)2] | Dx = 1.707 Mg m−3 |
Mr = 400.64 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pmna | Cell parameters from 2407 reflections |
a = 7.154 (2) Å | θ = 1–25° |
b = 7.933 (2) Å | µ = 2.64 mm−1 |
c = 13.731 (3) Å | T = 173 K |
V = 779.3 (3) Å3 | Block, colourless |
Z = 2 | 0.60 × 0.20 × 0.20 mm |
F(000) = 400 | |
Data collection top
Siemens CCD three-circle diffractometer | 1036 independent reflections |
Radiation source: fine-focus sealed tube | 895 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.031 |
ω scans | θmax = 28.3°, θmin = 2.6° |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | h = −9→5 |
Tmin = 0.301, Tmax = 0.621 | k = −10→8 |
3722 measured reflections | l = −17→16 |
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)] = 0.026 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.062 | w = 1/[σ2(Fo2) + (0.0334P)2 + 0.1042P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max < 0.001 |
1036 reflections | Δρmax = 0.41 e Å−3 |
57 parameters | Δρmin = −0.51 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0063 (14) |
Special details top
Experimental. ; |
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 | Occ. (<1) |
Cl1 | 0.72510 (7) | 0.16635 (6) | 0.43468 (3) | 0.02974 (16) | |
Ge1 | 0.5000 | 0.0000 | 0.5000 | 0.01699 (14) | |
N1 | 0.5000 | 0.1450 (3) | 0.62414 (15) | 0.0186 (4) | |
C2 | 0.5000 | 0.3149 (3) | 0.6175 (2) | 0.0230 (6) | |
H2 | 0.5000 | 0.3659 | 0.5549 | 0.028* | |
C3 | 0.5000 | 0.4162 (3) | 0.6989 (2) | 0.0240 (6) | |
H3 | 0.5000 | 0.5354 | 0.6919 | 0.029* | |
C4 | 0.5000 | 0.3445 (3) | 0.79128 (19) | 0.0205 (5) | |
C41 | 0.5000 | 0.4504 (4) | 0.8814 (2) | 0.0285 (6) | |
H41A | 0.5000 | 0.5623 | 0.8628 | 0.043* | 0.50 |
H41B | 0.3975 | 0.4180 | 0.9215 | 0.043* | 0.50 |
H41C | 0.5000 | 0.3836 | 0.9399 | 0.043* | 0.50 |
H41D | 0.3929 | 0.5179 | 0.8789 | 0.043* | 0.50 |
C5 | 0.5000 | 0.1696 (3) | 0.79704 (19) | 0.0230 (5) | |
H5 | 0.5000 | 0.1156 | 0.8588 | 0.028* | |
C6 | 0.5000 | 0.0748 (3) | 0.71332 (19) | 0.0220 (5) | |
H6 | 0.5000 | −0.0446 | 0.7186 | 0.026* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl1 | 0.0322 (3) | 0.0279 (3) | 0.0291 (3) | −0.01187 (19) | 0.0090 (2) | −0.00667 (19) |
Ge1 | 0.0192 (2) | 0.01502 (19) | 0.0167 (2) | 0.000 | 0.000 | −0.00263 (14) |
N1 | 0.0210 (11) | 0.0165 (9) | 0.0183 (11) | 0.000 | 0.000 | −0.0028 (8) |
C2 | 0.0272 (14) | 0.0195 (12) | 0.0224 (14) | 0.000 | 0.000 | 0.0010 (10) |
C3 | 0.0272 (14) | 0.0158 (12) | 0.0288 (14) | 0.000 | 0.000 | −0.0032 (10) |
C4 | 0.0155 (12) | 0.0234 (12) | 0.0226 (13) | 0.000 | 0.000 | −0.0064 (11) |
C41 | 0.0313 (15) | 0.0290 (13) | 0.0251 (15) | 0.000 | 0.000 | −0.0112 (11) |
C5 | 0.0252 (14) | 0.0258 (13) | 0.0181 (13) | 0.000 | 0.000 | −0.0006 (11) |
C6 | 0.0261 (13) | 0.0178 (12) | 0.0221 (13) | 0.000 | 0.000 | 0.0018 (10) |
Geometric parameters (Å, º) top
Cl1—Ge1 | 2.2670 (6) | C3—H3 | 0.9500 |
Ge1—N1 | 2.057 (2) | C4—C5 | 1.390 (4) |
Ge1—N1i | 2.057 (2) | C4—C41 | 1.495 (4) |
Ge1—Cl1ii | 2.2670 (6) | C41—H41A | 0.9240 |
Ge1—Cl1i | 2.2670 (6) | C41—H41B | 0.9530 |
Ge1—Cl1iii | 2.2670 (6) | C41—H41C | 0.9620 |
N1—C6 | 1.345 (3) | C41—H41D | 0.9355 |
N1—C2 | 1.350 (3) | C5—C6 | 1.373 (4) |
C2—C3 | 1.377 (4) | C5—H5 | 0.9500 |
C2—H2 | 0.9500 | C6—H6 | 0.9500 |
C3—C4 | 1.390 (4) | | |
| | | |
N1—Ge1—N1i | 180.0 | C2—C3—H3 | 119.9 |
N1—Ge1—Cl1 | 90.13 (4) | C4—C3—H3 | 119.9 |
N1i—Ge1—Cl1 | 89.87 (4) | C3—C4—C5 | 117.4 (2) |
N1—Ge1—Cl1ii | 90.13 (4) | C3—C4—C41 | 121.7 (2) |
N1i—Ge1—Cl1ii | 89.87 (4) | C5—C4—C41 | 120.9 (2) |
Cl1—Ge1—Cl1ii | 90.53 (3) | C4—C41—H41A | 108.2 |
N1—Ge1—Cl1i | 89.87 (4) | C4—C41—H41B | 109.1 |
N1i—Ge1—Cl1i | 90.13 (4) | H41A—C41—H41B | 114.8 |
Cl1—Ge1—Cl1i | 180.0 | C4—C41—H41C | 112.4 |
Cl1ii—Ge1—Cl1i | 89.47 (3) | H41A—C41—H41C | 139.4 |
N1—Ge1—Cl1iii | 89.87 (4) | H41B—C41—H41C | 50.8 |
N1i—Ge1—Cl1iii | 90.13 (4) | C4—C41—H41D | 107.0 |
Cl1—Ge1—Cl1iii | 89.47 (3) | H41A—C41—H41D | 55.9 |
Cl1ii—Ge1—Cl1iii | 180.0 | H41B—C41—H41D | 62.9 |
Cl1i—Ge1—Cl1iii | 90.53 (3) | H41C—C41—H41D | 110.2 |
C6—N1—C2 | 118.3 (2) | C6—C5—C4 | 119.9 (2) |
C6—N1—Ge1 | 121.53 (17) | C6—C5—H5 | 120.0 |
C2—N1—Ge1 | 120.14 (17) | C4—C5—H5 | 120.0 |
N1—C2—C3 | 121.9 (2) | N1—C6—C5 | 122.4 (2) |
N1—C2—H2 | 119.1 | N1—C6—H6 | 118.8 |
C3—C2—H2 | 119.1 | C5—C6—H6 | 118.8 |
C2—C3—C4 | 120.1 (2) | | |
| | | |
N1i—Ge1—N1—C6 | 0.0 (3) | C6—N1—C2—C3 | 0.0 |
Cl1—Ge1—N1—C6 | −134.736 (16) | Ge1—N1—C2—C3 | 180.0 |
Cl1ii—Ge1—N1—C6 | 134.736 (16) | N1—C2—C3—C4 | 0.0 |
Cl1i—Ge1—N1—C6 | 45.264 (17) | C2—C3—C4—C5 | 0.0 |
Cl1iii—Ge1—N1—C6 | −45.264 (16) | C2—C3—C4—C41 | 180.0 |
N1i—Ge1—N1—C2 | 180.0 (3) | C3—C4—C5—C6 | 0.0 |
Cl1—Ge1—N1—C2 | 45.264 (17) | C41—C4—C5—C6 | 180.0 |
Cl1ii—Ge1—N1—C2 | −45.264 (16) | C2—N1—C6—C5 | 0.0 |
Cl1i—Ge1—N1—C2 | −134.736 (17) | Ge1—N1—C6—C5 | 180.0 |
Cl1iii—Ge1—N1—C2 | 134.736 (17) | C4—C5—C6—N1 | 0.0 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+1, y, z; (iii) x, −y, −z+1. |
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