Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100014153/qa0420sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100014153/qa0420Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100014153/qa0420IIsup3.hkl |
CCDC references: 153932; 153933
For both compounds, 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.
[GeBr4(C6H7N)2] | F(000) = 544 |
Mr = 578.48 | Dx = 2.302 Mg m−3 |
Orthorhombic, Pmna | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2 | Cell parameters from 5051 reflections |
a = 7.360 (1) Å | θ = 1–25° |
b = 8.360 (1) Å | µ = 11.40 mm−1 |
c = 13.561 (1) Å | T = 173 K |
V = 834.40 (16) Å3 | Needle, yellow |
Z = 2 | 0.36 × 0.16 × 0.10 mm |
Siemens CCD three-circle diffractometer | 1122 independent reflections |
Radiation source: fine-focus sealed tube | 869 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.074 |
ω scans | θmax = 28.3°, θmin = 2.4° |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | h = −9→9 |
Tmin = 0.089, Tmax = 0.319 | k = −11→11 |
14794 measured reflections | l = −18→18 |
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) = 0.056 | w = 1/[σ2(Fo2) + (0.0202P)2 + 1.2129P] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max < 0.001 |
1122 reflections | Δρmax = 0.48 e Å−3 |
57 parameters | Δρmin = −0.64 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: 0.0027 (3) |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Br1 | 0.73632 (5) | 0.16531 (4) | 0.42513 (3) | 0.03106 (13) | |
Ge1 | 0.5000 | 0.0000 | 0.5000 | 0.01701 (16) | |
N1 | 0.5000 | 0.1469 (4) | 0.6241 (3) | 0.0178 (8) | |
C2 | 0.5000 | 0.3075 (5) | 0.6141 (3) | 0.0222 (10) | |
H2 | 0.5000 | 0.3522 | 0.5497 | 0.027* | |
C3 | 0.5000 | 0.4082 (6) | 0.6938 (4) | 0.0255 (11) | |
H3 | 0.5000 | 0.5208 | 0.6840 | 0.031* | |
C4 | 0.5000 | 0.3459 (6) | 0.7891 (3) | 0.0223 (10) | |
C41 | 0.5000 | 0.4520 (6) | 0.8782 (3) | 0.0292 (11) | |
H41A | 0.5000 | 0.5639 | 0.8596 | 0.044* | 0.50 |
H41B | 0.3975 | 0.4196 | 0.9183 | 0.044* | 0.50 |
H41C | 0.5000 | 0.3852 | 0.9367 | 0.044* | 0.50 |
H41D | 0.3929 | 0.5195 | 0.8757 | 0.044* | 0.50 |
C5 | 0.5000 | 0.1803 (6) | 0.7984 (3) | 0.0240 (10) | |
H5 | 0.5000 | 0.1328 | 0.8620 | 0.029* | |
C6 | 0.5000 | 0.0850 (6) | 0.7158 (3) | 0.0221 (10) | |
H6 | 0.5000 | −0.0279 | 0.7237 | 0.027* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0313 (2) | 0.02804 (19) | 0.0338 (2) | −0.01124 (16) | 0.00933 (15) | −0.00716 (16) |
Ge1 | 0.0182 (3) | 0.0142 (3) | 0.0186 (3) | 0.000 | 0.000 | −0.0030 (3) |
N1 | 0.0200 (18) | 0.0126 (18) | 0.0208 (18) | 0.000 | 0.000 | −0.0046 (15) |
C2 | 0.027 (2) | 0.018 (2) | 0.022 (2) | 0.000 | 0.000 | 0.0002 (19) |
C3 | 0.030 (3) | 0.013 (2) | 0.034 (3) | 0.000 | 0.000 | −0.004 (2) |
C4 | 0.017 (2) | 0.024 (2) | 0.025 (2) | 0.000 | 0.000 | −0.009 (2) |
C41 | 0.037 (3) | 0.025 (3) | 0.026 (3) | 0.000 | 0.000 | −0.010 (2) |
C5 | 0.030 (2) | 0.021 (2) | 0.021 (2) | 0.000 | 0.000 | −0.002 (2) |
C6 | 0.030 (2) | 0.015 (2) | 0.021 (2) | 0.000 | 0.000 | −0.0016 (19) |
Br1—Ge1 | 2.4425 (4) | C3—H3 | 0.9500 |
Ge1—N1 | 2.083 (3) | C4—C5 | 1.391 (6) |
Ge1—N1i | 2.083 (3) | C4—C41 | 1.498 (6) |
Ge1—Br1i | 2.4425 (4) | C41—H41A | 0.9693 |
Ge1—Br1ii | 2.4425 (4) | C41—H41B | 0.9693 |
Ge1—Br1iii | 2.4425 (4) | C41—H41C | 0.9699 |
N1—C6 | 1.347 (6) | C41—H41D | 0.9701 |
N1—C2 | 1.350 (5) | C5—C6 | 1.374 (6) |
C2—C3 | 1.369 (6) | C5—H5 | 0.9500 |
C2—H2 | 0.9500 | C6—H6 | 0.9500 |
C3—C4 | 1.394 (7) | ||
N1—Ge1—N1i | 180.0 | C2—C3—H3 | 119.9 |
N1—Ge1—Br1 | 90.14 (7) | C4—C3—H3 | 119.9 |
N1i—Ge1—Br1 | 89.86 (7) | C5—C4—C3 | 117.1 (4) |
N1—Ge1—Br1i | 89.86 (7) | C5—C4—C41 | 121.1 (4) |
N1i—Ge1—Br1i | 90.14 (7) | C3—C4—C41 | 121.8 (4) |
Br1—Ge1—Br1i | 180.0 | C4—C41—H41A | 111.2 |
N1—Ge1—Br1ii | 89.86 (7) | C4—C41—H41B | 106.7 |
N1i—Ge1—Br1ii | 90.14 (7) | H41A—C41—H41B | 114.6 |
Br1—Ge1—Br1ii | 89.19 (2) | C4—C41—H41C | 108.6 |
Br1i—Ge1—Br1ii | 90.81 (2) | H41A—C41—H41C | 140.2 |
N1—Ge1—Br1iii | 90.14 (7) | H41B—C41—H41C | 51.7 |
N1i—Ge1—Br1iii | 89.86 (7) | C4—C41—H41D | 108.5 |
Br1—Ge1—Br1iii | 90.81 (2) | H41A—C41—H41D | 55.2 |
Br1i—Ge1—Br1iii | 89.19 (2) | H41B—C41—H41D | 63.2 |
Br1ii—Ge1—Br1iii | 180.000 (15) | H41C—C41—H41D | 111.3 |
C6—N1—C2 | 118.3 (4) | C6—C5—C4 | 120.2 (4) |
C6—N1—Ge1 | 121.3 (3) | C6—C5—H5 | 119.9 |
C2—N1—Ge1 | 120.3 (3) | C4—C5—H5 | 119.9 |
N1—C2—C3 | 122.2 (4) | N1—C6—C5 | 122.0 (4) |
N1—C2—H2 | 118.9 | N1—C6—H6 | 119.0 |
C3—C2—H2 | 118.9 | C5—C6—H6 | 119.0 |
C2—C3—C4 | 120.1 (4) | ||
N1i—Ge1—N1—C6 | 180.0 (6) | C6—N1—C2—C3 | 0.000 (2) |
Br1—Ge1—N1—C6 | −134.594 (10) | Ge1—N1—C2—C3 | 180.000 (1) |
Br1i—Ge1—N1—C6 | 45.406 (10) | N1—C2—C3—C4 | 0.000 (2) |
Br1ii—Ge1—N1—C6 | −45.406 (10) | C2—C3—C4—C5 | 0.000 (2) |
Br1iii—Ge1—N1—C6 | 134.594 (10) | C2—C3—C4—C41 | 180.000 (2) |
N1i—Ge1—N1—C2 | 0 (100) | C3—C4—C5—C6 | 0.000 (2) |
Br1—Ge1—N1—C2 | 45.406 (10) | C41—C4—C5—C6 | 180.000 (2) |
Br1i—Ge1—N1—C2 | −134.594 (10) | C2—N1—C6—C5 | 0.000 (2) |
Br1ii—Ge1—N1—C2 | 134.594 (10) | Ge1—N1—C6—C5 | 180.000 (1) |
Br1iii—Ge1—N1—C2 | −45.406 (10) | C4—C5—C6—N1 | 0.000 (2) |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) x, −y, −z+1; (iii) −x+1, y, z. |
[GeBr4(C7H9N)2] | Dx = 2.276 Mg m−3 |
Mr = 606.53 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Cmca | Cell parameters from 3846 reflections |
a = 7.477 (1) Å | θ = 1–25° |
b = 17.942 (5) Å | µ = 10.76 mm−1 |
c = 13.194 (3) Å | T = 173 K |
V = 1770.0 (7) Å3 | Plate, yellow |
Z = 4 | 0.22 × 0.12 × 0.05 mm |
F(000) = 1152 |
Siemens CCD three-circle diffractometer | 1134 independent reflections |
Radiation source: fine-focus sealed tube | 898 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.099 |
ω scans | θmax = 27.8°, θmin = 2.8° |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | h = −9→9 |
Tmin = 0.200, Tmax = 0.580 | k = −23→23 |
12371 measured reflections | l = −17→17 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.036 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.077 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0315P)2 + 6.1521P] where P = (Fo2 + 2Fc2)/3 |
1134 reflections | (Δ/σ)max < 0.001 |
62 parameters | Δρmax = 0.62 e Å−3 |
0 restraints | Δρmin = −0.78 e Å−3 |
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. |
x | y | z | Uiso*/Ueq | ||
Ge1 | 0.5000 | 0.5000 | 0.5000 | 0.0149 (2) | |
Br1 | 0.73194 (6) | 0.42244 (2) | 0.42398 (3) | 0.02444 (15) | |
N1 | 0.5000 | 0.4321 (3) | 0.6297 (4) | 0.0165 (10) | |
C2 | 0.5000 | 0.3577 (3) | 0.6207 (5) | 0.0183 (13) | |
H2 | 0.5000 | 0.3369 | 0.5544 | 0.022* | |
C3 | 0.5000 | 0.3095 (3) | 0.7025 (4) | 0.0172 (12) | |
C31 | 0.5000 | 0.2267 (3) | 0.6870 (5) | 0.0267 (15) | |
H31A | 0.5000 | 0.2152 | 0.6144 | 0.040* | |
H31B | 0.3932 | 0.2051 | 0.7185 | 0.040* | |
C4 | 0.5000 | 0.3412 (3) | 0.8010 (5) | 0.0180 (13) | |
C41 | 0.5000 | 0.2930 (4) | 0.8943 (5) | 0.0243 (14) | |
H41A | 0.5000 | 0.3245 | 0.9550 | 0.036* | |
H41B | 0.3933 | 0.2613 | 0.8941 | 0.036* | |
C5 | 0.5000 | 0.4181 (3) | 0.8085 (5) | 0.0219 (13) | |
H5 | 0.5000 | 0.4407 | 0.8737 | 0.026* | |
C6 | 0.5000 | 0.4626 (3) | 0.7236 (5) | 0.0239 (14) | |
H6 | 0.5000 | 0.5153 | 0.7309 | 0.029* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ge1 | 0.0177 (4) | 0.0132 (4) | 0.0137 (4) | 0.000 | 0.000 | 0.0004 (4) |
Br1 | 0.0261 (2) | 0.0223 (2) | 0.0249 (2) | 0.00582 (19) | 0.00608 (19) | 0.00143 (19) |
N1 | 0.018 (2) | 0.019 (3) | 0.013 (3) | 0.000 | 0.000 | 0.000 (2) |
C2 | 0.024 (3) | 0.015 (3) | 0.015 (3) | 0.000 | 0.000 | −0.008 (2) |
C3 | 0.019 (3) | 0.018 (3) | 0.015 (3) | 0.000 | 0.000 | −0.002 (3) |
C31 | 0.047 (4) | 0.018 (3) | 0.015 (3) | 0.000 | 0.000 | 0.000 (3) |
C4 | 0.017 (3) | 0.020 (3) | 0.017 (3) | 0.000 | 0.000 | 0.005 (3) |
C41 | 0.035 (4) | 0.020 (3) | 0.018 (3) | 0.000 | 0.000 | 0.001 (3) |
C5 | 0.030 (3) | 0.021 (3) | 0.015 (3) | 0.000 | 0.000 | −0.007 (3) |
C6 | 0.034 (4) | 0.015 (3) | 0.023 (4) | 0.000 | 0.000 | 0.000 (3) |
Ge1—N1 | 2.101 (5) | C3—C31 | 1.501 (8) |
Ge1—N1i | 2.101 (5) | C31—H31A | 0.9800 |
Ge1—Br1ii | 2.4392 (5) | C31—H31B | 0.9800 |
Ge1—Br1i | 2.4392 (5) | C4—C5 | 1.384 (8) |
Ge1—Br1 | 2.4392 (5) | C4—C41 | 1.504 (8) |
Ge1—Br1iii | 2.4392 (5) | C41—H41A | 0.9799 |
N1—C2 | 1.341 (7) | C41—H41B | 0.9801 |
N1—C6 | 1.354 (8) | C5—C6 | 1.376 (9) |
C2—C3 | 1.383 (8) | C5—H5 | 0.9500 |
C2—H2 | 0.9500 | C6—H6 | 0.9500 |
C3—C4 | 1.419 (8) | ||
N1—Ge1—N1i | 180.0 | C3—C2—H2 | 118.2 |
N1—Ge1—Br1ii | 89.76 (9) | C2—C3—C4 | 117.7 (5) |
N1i—Ge1—Br1ii | 90.24 (9) | C2—C3—C31 | 120.8 (5) |
N1—Ge1—Br1i | 89.76 (9) | C4—C3—C31 | 121.5 (5) |
N1i—Ge1—Br1i | 90.24 (9) | C3—C31—H31A | 110.0 |
Br1ii—Ge1—Br1i | 90.63 (3) | C3—C31—H31B | 109.4 |
N1—Ge1—Br1 | 90.24 (9) | H31A—C31—H31B | 109.4 |
N1i—Ge1—Br1 | 89.76 (9) | C5—C4—C3 | 117.7 (5) |
Br1ii—Ge1—Br1 | 89.37 (3) | C5—C4—C41 | 121.0 (6) |
Br1i—Ge1—Br1 | 180.0 | C3—C4—C41 | 121.3 (5) |
N1—Ge1—Br1iii | 90.24 (9) | C4—C41—H41A | 109.7 |
N1i—Ge1—Br1iii | 89.76 (9) | C4—C41—H41B | 109.4 |
Br1ii—Ge1—Br1iii | 180.0 | H41A—C41—H41B | 109.7 |
Br1i—Ge1—Br1iii | 89.37 (3) | C6—C5—C4 | 121.3 (6) |
Br1—Ge1—Br1iii | 90.63 (3) | C6—C5—H5 | 119.3 |
C2—N1—C6 | 119.0 (5) | C4—C5—H5 | 119.3 |
C2—N1—Ge1 | 120.3 (4) | N1—C6—C5 | 120.7 (6) |
C6—N1—Ge1 | 120.7 (4) | N1—C6—H6 | 119.6 |
N1—C2—C3 | 123.5 (5) | C5—C6—H6 | 119.6 |
N1—C2—H2 | 118.2 | ||
N1i—Ge1—N1—C2 | 1 (100) | N1—C2—C3—C4 | 0.000 (2) |
Br1ii—Ge1—N1—C2 | −134.686 (13) | N1—C2—C3—C31 | 180.000 (2) |
Br1i—Ge1—N1—C2 | 134.686 (13) | C2—C3—C4—C5 | 0.000 (2) |
Br1—Ge1—N1—C2 | −45.314 (13) | C31—C3—C4—C5 | 180.000 (2) |
Br1iii—Ge1—N1—C2 | 45.313 (13) | C2—C3—C4—C41 | 180.000 (2) |
N1i—Ge1—N1—C6 | −179 (100) | C31—C3—C4—C41 | 0.000 (2) |
Br1ii—Ge1—N1—C6 | 45.314 (13) | C3—C4—C5—C6 | 0.000 (3) |
Br1i—Ge1—N1—C6 | −45.314 (13) | C41—C4—C5—C6 | 180.000 (2) |
Br1—Ge1—N1—C6 | 134.686 (13) | C2—N1—C6—C5 | 0.000 (3) |
Br1iii—Ge1—N1—C6 | −134.687 (13) | Ge1—N1—C6—C5 | 180.000 (2) |
C6—N1—C2—C3 | 0.000 (2) | C4—C5—C6—N1 | 0.000 (3) |
Ge1—N1—C2—C3 | 180.000 (2) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, −y+1, −z+1; (iii) −x+1, y, z. |