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The central Ge atoms in the structures of 3-(2-fluorophenyl)-3-(triphenylgermyl)propionic acid, [Ge(C6H5)3(C9H8FO2)], 3-(2-tolyl)-3-(tri-4-tolylgermyl)propionic acid, [Ge(C7H7)3(C10H11O2)], and 3-(4-tolyl)-3-(tribenzylgermyl)propionic acid, [Ge(C7H7)3(C10H11O2)], are four-coordinate with slightly distorted tetrahedral geometry. The Ge-Csp3 distances [1.970 (3)-1.997 (3) Å] are significantly longer than the Ge-Caromatic distances [1.940 (3)-1.959 (2) Å]. In all three structures, the molecules form dimeric pairs about inversion centres through strong hydrogen-bonding interactions between carboxylic acid groups.
Supporting information
CCDC references: 199415; 199416; 199417
Compounds (I)-(III) were prepared following the standard methods described by
Choudhary et al. (2002). Crystals suitable for X-ray analysis were
grown by dissolving the respective compound (0.5 g) in chloroform (5.0 ml), to
which a few drops of acetone were added. Slow evaporation of the solvent at
room temperature over several days yielded fine crystals which were
subsequently washed with acetone.
For the three structures, the H atoms were located from difference Fourier
syntheses and were included in the refinements at idealized positions, with
Uiso(H) = 1.5Ueq(OH) and 1.2Ueq(C). Default C—H
and O—H distances were allowed for the various types of H atoms, as set by
the program SHELXL97 (Sheldrick, 1997). One of the phenyl rings in
(III) is disordered over sites C19—C24 and C19'-C24' with unequal site
occupancy factors of 0.65 (4) and 0.35 (4), respectively. The final difference
maps were free of any chemically significant features in the three structures.
For all compounds, data collection: COLLECT (Nonius, 1998); cell refinement: HKL DENZO (Otwinowski & Minor, 1997); data reduction: SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SAPI91 (Fan, 1991); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.
(I) 3-(2-fluorophenyl)-3-(triphenylgermyl)propionic acid
top
Crystal data top
[Ge(C6H5)3(C9H8FO2)] | F(000) = 968 |
Mr = 471.04 | Dx = 1.420 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 9816 reflections |
a = 9.7278 (10) Å | θ = 1.0–27.5° |
b = 17.907 (3) Å | µ = 1.42 mm−1 |
c = 13.541 (2) Å | T = 170 K |
β = 110.907 (8)° | Block, colourless |
V = 2203.5 (6) Å3 | 0.20 × 0.15 × 0.14 mm |
Z = 4 | |
Data collection top
Nonius KappaCCD area-detector diffractometer | 5026 independent reflections |
Radiation source: fine-focus sealed tube | 4338 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.017 |
ω and ϕ scans | θmax = 27.5°, θmin = 3.2° |
Absorption correction: multi-scan (SORTAV; Blessing, 1997) | h = −12→12 |
Tmin = 0.711, Tmax = 0.820 | k = −23→23 |
9816 measured reflections | l = −17→17 |
Refinement top
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)] = 0.028 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.070 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0332P)2 + 0.8526P] where P = (Fo2 + 2Fc2)/3 |
5026 reflections | (Δ/σ)max = 0.002 |
281 parameters | Δρmax = 0.30 e Å−3 |
0 restraints | Δρmin = −0.44 e Å−3 |
Crystal data top
[Ge(C6H5)3(C9H8FO2)] | V = 2203.5 (6) Å3 |
Mr = 471.04 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.7278 (10) Å | µ = 1.42 mm−1 |
b = 17.907 (3) Å | T = 170 K |
c = 13.541 (2) Å | 0.20 × 0.15 × 0.14 mm |
β = 110.907 (8)° | |
Data collection top
Nonius KappaCCD area-detector diffractometer | 5026 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1997) | 4338 reflections with I > 2σ(I) |
Tmin = 0.711, Tmax = 0.820 | Rint = 0.017 |
9816 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.028 | 0 restraints |
wR(F2) = 0.070 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.30 e Å−3 |
5026 reflections | Δρmin = −0.44 e Å−3 |
281 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Ge1 | 0.839925 (17) | 0.183673 (9) | 0.828679 (12) | 0.02017 (6) | |
F1 | 0.61906 (12) | 0.00707 (6) | 0.69416 (9) | 0.0392 (3) | |
O1 | 0.88991 (12) | 0.02038 (6) | 0.56415 (9) | 0.0279 (3) | |
O2 | 1.07267 (14) | 0.09183 (7) | 0.55351 (10) | 0.0341 (3) | |
H2 | 1.0824 | 0.0565 | 0.5158 | 0.051* | |
C1 | 0.96590 (17) | 0.07620 (9) | 0.58850 (12) | 0.0231 (3) | |
C2 | 0.95146 (18) | 0.13483 (9) | 0.66445 (13) | 0.0260 (3) | |
H2A | 0.9301 | 0.1836 | 0.6277 | 0.031* | |
H2B | 1.0465 | 0.1393 | 0.7241 | 0.031* | |
C3 | 0.83045 (16) | 0.11711 (9) | 0.70813 (12) | 0.0225 (3) | |
H3 | 0.8481 | 0.0650 | 0.7365 | 0.027* | |
C4 | 0.67724 (17) | 0.11887 (9) | 0.62599 (12) | 0.0220 (3) | |
C5 | 0.6257 (2) | 0.17702 (10) | 0.55313 (14) | 0.0304 (4) | |
H5 | 0.6911 | 0.2160 | 0.5513 | 0.036* | |
C6 | 0.4808 (2) | 0.17886 (11) | 0.48336 (15) | 0.0392 (5) | |
H6 | 0.4479 | 0.2194 | 0.4354 | 0.047* | |
C7 | 0.3844 (2) | 0.12260 (12) | 0.48314 (14) | 0.0401 (5) | |
H7 | 0.2860 | 0.1238 | 0.4343 | 0.048* | |
C8 | 0.43100 (19) | 0.06432 (11) | 0.55400 (14) | 0.0348 (4) | |
H8 | 0.3656 | 0.0253 | 0.5553 | 0.042* | |
C9 | 0.57508 (18) | 0.06432 (9) | 0.62294 (13) | 0.0269 (3) | |
C11 | 0.66775 (17) | 0.15948 (9) | 0.86442 (12) | 0.0224 (3) | |
C12 | 0.52581 (18) | 0.16953 (10) | 0.78972 (13) | 0.0267 (4) | |
H12 | 0.5136 | 0.1934 | 0.7245 | 0.032* | |
C13 | 0.40272 (19) | 0.14504 (11) | 0.80971 (15) | 0.0348 (4) | |
H13 | 0.3074 | 0.1507 | 0.7575 | 0.042* | |
C14 | 0.4194 (2) | 0.11243 (12) | 0.90557 (15) | 0.0401 (5) | |
H14 | 0.3354 | 0.0959 | 0.9196 | 0.048* | |
C15 | 0.5585 (2) | 0.10372 (12) | 0.98131 (15) | 0.0386 (4) | |
H15 | 0.5694 | 0.0818 | 1.0476 | 0.046* | |
C16 | 0.68217 (19) | 0.12679 (10) | 0.96110 (13) | 0.0294 (4) | |
H16 | 0.7772 | 0.1203 | 1.0134 | 0.035* | |
C18 | 1.02127 (17) | 0.16128 (9) | 0.94756 (12) | 0.0231 (3) | |
C19 | 1.06854 (18) | 0.08792 (9) | 0.97522 (13) | 0.0270 (3) | |
H19 | 1.0147 | 0.0478 | 0.9330 | 0.032* | |
C20 | 1.19301 (19) | 0.07254 (11) | 1.06353 (14) | 0.0335 (4) | |
H20 | 1.2228 | 0.0223 | 1.0813 | 0.040* | |
C21 | 1.2733 (2) | 0.13015 (12) | 1.12541 (15) | 0.0395 (4) | |
H21 | 1.3577 | 0.1198 | 1.1861 | 0.047* | |
C22 | 1.2295 (2) | 0.20313 (12) | 1.09784 (16) | 0.0433 (5) | |
H22 | 1.2854 | 0.2430 | 1.1394 | 0.052* | |
C23 | 1.1049 (2) | 0.21889 (10) | 1.01034 (14) | 0.0335 (4) | |
H23 | 1.0761 | 0.2693 | 0.9930 | 0.040* | |
C25 | 0.83946 (18) | 0.28931 (9) | 0.79274 (12) | 0.0246 (3) | |
C26 | 0.7291 (2) | 0.33745 (10) | 0.79790 (14) | 0.0318 (4) | |
H26 | 0.6522 | 0.3183 | 0.8185 | 0.038* | |
C27 | 0.7298 (2) | 0.41287 (11) | 0.77340 (15) | 0.0402 (5) | |
H27 | 0.6538 | 0.4448 | 0.7771 | 0.048* | |
C28 | 0.8411 (2) | 0.44124 (11) | 0.74363 (15) | 0.0414 (5) | |
H28 | 0.8410 | 0.4926 | 0.7261 | 0.050* | |
C29 | 0.9525 (2) | 0.39507 (11) | 0.73934 (15) | 0.0379 (4) | |
H29 | 1.0295 | 0.4148 | 0.7194 | 0.045* | |
C30 | 0.9521 (2) | 0.31984 (9) | 0.76410 (14) | 0.0302 (4) | |
H30 | 1.0297 | 0.2886 | 0.7615 | 0.036* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Ge1 | 0.01820 (9) | 0.02157 (10) | 0.02182 (10) | −0.00053 (6) | 0.00844 (7) | −0.00249 (6) |
F1 | 0.0352 (6) | 0.0321 (6) | 0.0454 (6) | −0.0083 (5) | 0.0083 (5) | 0.0083 (5) |
O1 | 0.0255 (6) | 0.0278 (6) | 0.0346 (6) | −0.0037 (5) | 0.0159 (5) | −0.0092 (5) |
O2 | 0.0371 (7) | 0.0284 (7) | 0.0488 (8) | −0.0086 (5) | 0.0300 (6) | −0.0135 (6) |
C1 | 0.0191 (7) | 0.0248 (8) | 0.0259 (8) | 0.0013 (6) | 0.0088 (6) | −0.0018 (6) |
C2 | 0.0218 (8) | 0.0263 (8) | 0.0328 (8) | −0.0037 (6) | 0.0134 (7) | −0.0084 (7) |
C3 | 0.0197 (7) | 0.0231 (8) | 0.0262 (8) | −0.0006 (6) | 0.0100 (6) | −0.0029 (6) |
C4 | 0.0213 (7) | 0.0257 (8) | 0.0218 (7) | 0.0004 (6) | 0.0111 (6) | −0.0044 (6) |
C5 | 0.0334 (9) | 0.0326 (10) | 0.0286 (9) | 0.0013 (7) | 0.0153 (8) | 0.0029 (7) |
C6 | 0.0349 (10) | 0.0476 (12) | 0.0315 (10) | 0.0115 (9) | 0.0075 (8) | 0.0102 (8) |
C7 | 0.0245 (9) | 0.0603 (13) | 0.0302 (9) | 0.0054 (9) | 0.0033 (7) | −0.0043 (9) |
C8 | 0.0245 (9) | 0.0421 (11) | 0.0369 (10) | −0.0078 (8) | 0.0099 (8) | −0.0102 (8) |
C9 | 0.0275 (8) | 0.0274 (9) | 0.0262 (8) | −0.0013 (7) | 0.0101 (7) | −0.0015 (6) |
C11 | 0.0224 (8) | 0.0226 (8) | 0.0243 (8) | 0.0002 (6) | 0.0107 (6) | −0.0034 (6) |
C12 | 0.0227 (8) | 0.0343 (9) | 0.0254 (8) | 0.0027 (7) | 0.0116 (7) | 0.0006 (7) |
C13 | 0.0218 (8) | 0.0478 (11) | 0.0358 (9) | −0.0013 (8) | 0.0116 (7) | −0.0017 (8) |
C14 | 0.0329 (10) | 0.0528 (12) | 0.0420 (10) | −0.0102 (9) | 0.0225 (9) | −0.0013 (9) |
C15 | 0.0400 (10) | 0.0498 (12) | 0.0305 (9) | −0.0056 (9) | 0.0183 (8) | 0.0059 (8) |
C16 | 0.0275 (9) | 0.0357 (10) | 0.0248 (8) | 0.0009 (7) | 0.0090 (7) | 0.0003 (7) |
C18 | 0.0197 (7) | 0.0274 (8) | 0.0241 (8) | −0.0017 (6) | 0.0102 (6) | −0.0029 (6) |
C19 | 0.0254 (8) | 0.0265 (9) | 0.0301 (8) | −0.0019 (7) | 0.0111 (7) | −0.0002 (7) |
C20 | 0.0271 (9) | 0.0370 (10) | 0.0364 (9) | 0.0044 (7) | 0.0113 (8) | 0.0089 (8) |
C21 | 0.0243 (9) | 0.0554 (13) | 0.0334 (9) | 0.0007 (8) | 0.0036 (7) | 0.0044 (9) |
C22 | 0.0327 (10) | 0.0462 (12) | 0.0400 (11) | −0.0092 (9) | −0.0006 (8) | −0.0111 (9) |
C23 | 0.0325 (9) | 0.0274 (9) | 0.0357 (9) | −0.0033 (7) | 0.0062 (8) | −0.0066 (7) |
C25 | 0.0278 (8) | 0.0232 (8) | 0.0216 (7) | −0.0011 (7) | 0.0073 (6) | −0.0028 (6) |
C26 | 0.0300 (9) | 0.0302 (9) | 0.0346 (9) | 0.0015 (7) | 0.0107 (7) | −0.0030 (7) |
C27 | 0.0415 (11) | 0.0285 (10) | 0.0416 (11) | 0.0083 (8) | 0.0040 (9) | −0.0048 (8) |
C28 | 0.0531 (12) | 0.0244 (9) | 0.0356 (10) | −0.0060 (9) | 0.0022 (9) | 0.0007 (8) |
C29 | 0.0469 (11) | 0.0321 (10) | 0.0348 (10) | −0.0121 (9) | 0.0146 (9) | −0.0014 (8) |
C30 | 0.0336 (9) | 0.0274 (9) | 0.0313 (9) | −0.0043 (7) | 0.0137 (8) | −0.0039 (7) |
Geometric parameters (Å, º) top
Ge1—C11 | 1.951 (2) | C13—H13 | 0.9500 |
Ge1—C25 | 1.953 (2) | C14—C15 | 1.384 (3) |
Ge1—C18 | 1.959 (2) | C14—H14 | 0.9500 |
Ge1—C3 | 1.997 (2) | C15—C16 | 1.388 (2) |
F1—C9 | 1.367 (2) | C15—H15 | 0.9500 |
O1—C1 | 1.217 (2) | C16—H16 | 0.9500 |
O2—C1 | 1.316 (2) | C18—C19 | 1.398 (2) |
O2—H2 | 0.8400 | C18—C23 | 1.398 (2) |
C1—C2 | 1.511 (2) | C19—C20 | 1.392 (2) |
C2—C3 | 1.527 (2) | C19—H19 | 0.9500 |
C2—H2A | 0.9900 | C20—C21 | 1.382 (3) |
C2—H2B | 0.9900 | C20—H20 | 0.9500 |
C3—C4 | 1.509 (2) | C21—C22 | 1.384 (3) |
C3—H3 | 1.0000 | C21—H21 | 0.9500 |
C4—C9 | 1.383 (2) | C22—C23 | 1.388 (3) |
C4—C5 | 1.399 (2) | C22—H22 | 0.9500 |
C5—C6 | 1.390 (3) | C23—H23 | 0.9500 |
C5—H5 | 0.9500 | C25—C30 | 1.397 (2) |
C6—C7 | 1.375 (3) | C25—C26 | 1.398 (2) |
C6—H6 | 0.9500 | C26—C27 | 1.391 (3) |
C7—C8 | 1.380 (3) | C26—H26 | 0.9500 |
C7—H7 | 0.9500 | C27—C28 | 1.380 (3) |
C8—C9 | 1.379 (2) | C27—H27 | 0.9500 |
C8—H8 | 0.9500 | C28—C29 | 1.381 (3) |
C11—C16 | 1.395 (2) | C28—H28 | 0.9500 |
C11—C12 | 1.402 (2) | C29—C30 | 1.389 (3) |
C12—C13 | 1.389 (2) | C29—H29 | 0.9500 |
C12—H12 | 0.9500 | C30—H30 | 0.9500 |
C13—C14 | 1.379 (3) | | |
| | | |
C11—Ge1—C25 | 110.55 (7) | C14—C13—H13 | 120.1 |
C11—Ge1—C18 | 110.60 (6) | C12—C13—H13 | 120.1 |
C25—Ge1—C18 | 108.93 (7) | C13—C14—C15 | 120.06 (17) |
C11—Ge1—C3 | 106.08 (6) | C13—C14—H14 | 120.0 |
C25—Ge1—C3 | 112.29 (7) | C15—C14—H14 | 120.0 |
C18—Ge1—C3 | 108.35 (6) | C14—C15—C16 | 120.46 (17) |
C1—O2—H2 | 109.5 | C14—C15—H15 | 119.8 |
O1—C1—O2 | 123.93 (14) | C16—C15—H15 | 119.8 |
O1—C1—C2 | 124.07 (14) | C15—C16—C11 | 120.39 (16) |
O2—C1—C2 | 111.98 (13) | C15—C16—H16 | 119.8 |
C1—C2—C3 | 113.01 (13) | C11—C16—H16 | 119.8 |
C1—C2—H2A | 109.0 | C19—C18—C23 | 117.79 (15) |
C3—C2—H2A | 109.0 | C19—C18—Ge1 | 121.75 (12) |
C1—C2—H2B | 109.0 | C23—C18—Ge1 | 120.42 (13) |
C3—C2—H2B | 109.0 | C20—C19—C18 | 121.21 (16) |
H2A—C2—H2B | 107.8 | C20—C19—H19 | 119.4 |
C4—C3—C2 | 113.91 (13) | C18—C19—H19 | 119.4 |
C4—C3—Ge1 | 109.60 (10) | C21—C20—C19 | 120.22 (17) |
C2—C3—Ge1 | 112.05 (10) | C21—C20—H20 | 119.9 |
C4—C3—H3 | 107.0 | C19—C20—H20 | 119.9 |
C2—C3—H3 | 107.0 | C20—C21—C22 | 119.22 (17) |
Ge1—C3—H3 | 107.0 | C20—C21—H21 | 120.4 |
C9—C4—C5 | 115.59 (15) | C22—C21—H21 | 120.4 |
C9—C4—C3 | 121.16 (14) | C21—C22—C23 | 120.89 (18) |
C5—C4—C3 | 123.13 (15) | C21—C22—H22 | 119.6 |
C6—C5—C4 | 121.23 (17) | C23—C22—H22 | 119.6 |
C6—C5—H5 | 119.4 | C22—C23—C18 | 120.66 (18) |
C4—C5—H5 | 119.4 | C22—C23—H23 | 119.7 |
C7—C6—C5 | 120.62 (17) | C18—C23—H23 | 119.7 |
C7—C6—H6 | 119.7 | C30—C25—C26 | 117.71 (16) |
C5—C6—H6 | 119.7 | C30—C25—Ge1 | 121.05 (13) |
C6—C7—C8 | 119.87 (17) | C26—C25—Ge1 | 121.22 (13) |
C6—C7—H7 | 120.1 | C27—C26—C25 | 121.15 (18) |
C8—C7—H7 | 120.1 | C27—C26—H26 | 119.4 |
C9—C8—C7 | 118.21 (17) | C25—C26—H26 | 119.4 |
C9—C8—H8 | 120.9 | C28—C27—C26 | 119.89 (18) |
C7—C8—H8 | 120.9 | C28—C27—H27 | 120.1 |
F1—C9—C8 | 117.64 (15) | C26—C27—H27 | 120.1 |
F1—C9—C4 | 117.88 (14) | C27—C28—C29 | 120.09 (18) |
C8—C9—C4 | 124.47 (16) | C27—C28—H28 | 120.0 |
C16—C11—C12 | 118.32 (15) | C29—C28—H28 | 120.0 |
C16—C11—Ge1 | 121.22 (12) | C28—C29—C30 | 120.03 (18) |
C12—C11—Ge1 | 120.29 (12) | C28—C29—H29 | 120.0 |
C13—C12—C11 | 120.96 (16) | C30—C29—H29 | 120.0 |
C13—C12—H12 | 119.5 | C29—C30—C25 | 121.12 (17) |
C11—C12—H12 | 119.5 | C29—C30—H30 | 119.4 |
C14—C13—C12 | 119.77 (17) | C25—C30—H30 | 119.4 |
| | | |
O1—C1—C2—C3 | −0.1 (2) | C12—C13—C14—C15 | −0.4 (3) |
O2—C1—C2—C3 | −178.73 (14) | C13—C14—C15—C16 | −0.8 (3) |
C1—C2—C3—C4 | −66.29 (18) | C14—C15—C16—C11 | 0.4 (3) |
C1—C2—C3—Ge1 | 168.58 (11) | C12—C11—C16—C15 | 1.2 (3) |
C11—Ge1—C3—C4 | 47.19 (12) | Ge1—C11—C16—C15 | −174.07 (14) |
C25—Ge1—C3—C4 | −73.68 (12) | C11—Ge1—C18—C19 | 73.15 (14) |
C18—Ge1—C3—C4 | 165.96 (10) | C25—Ge1—C18—C19 | −165.16 (13) |
C11—Ge1—C3—C2 | 174.66 (11) | C3—Ge1—C18—C19 | −42.73 (14) |
C25—Ge1—C3—C2 | 53.79 (13) | C11—Ge1—C18—C23 | −104.30 (14) |
C18—Ge1—C3—C2 | −66.56 (13) | C25—Ge1—C18—C23 | 17.39 (15) |
C2—C3—C4—C9 | 136.78 (15) | C3—Ge1—C18—C23 | 139.82 (13) |
Ge1—C3—C4—C9 | −96.80 (15) | C23—C18—C19—C20 | 1.3 (2) |
C2—C3—C4—C5 | −47.4 (2) | Ge1—C18—C19—C20 | −176.26 (13) |
Ge1—C3—C4—C5 | 78.99 (16) | C18—C19—C20—C21 | −0.5 (3) |
C9—C4—C5—C6 | 0.3 (2) | C19—C20—C21—C22 | −0.7 (3) |
C3—C4—C5—C6 | −175.71 (16) | C20—C21—C22—C23 | 1.2 (3) |
C4—C5—C6—C7 | −1.0 (3) | C21—C22—C23—C18 | −0.4 (3) |
C5—C6—C7—C8 | 1.2 (3) | C19—C18—C23—C22 | −0.8 (3) |
C6—C7—C8—C9 | −0.5 (3) | Ge1—C18—C23—C22 | 176.77 (15) |
C7—C8—C9—F1 | 178.72 (16) | C11—Ge1—C25—C30 | −179.87 (13) |
C7—C8—C9—C4 | −0.2 (3) | C18—Ge1—C25—C30 | 58.41 (15) |
C5—C4—C9—F1 | −178.60 (14) | C3—Ge1—C25—C30 | −61.61 (15) |
C3—C4—C9—F1 | −2.5 (2) | C11—Ge1—C25—C26 | 2.13 (15) |
C5—C4—C9—C8 | 0.3 (2) | C18—Ge1—C25—C26 | −119.59 (14) |
C3—C4—C9—C8 | 176.41 (15) | C3—Ge1—C25—C26 | 120.39 (13) |
C25—Ge1—C11—C16 | −124.11 (14) | C30—C25—C26—C27 | 1.2 (3) |
C18—Ge1—C11—C16 | −3.38 (16) | Ge1—C25—C26—C27 | 179.28 (14) |
C3—Ge1—C11—C16 | 113.91 (14) | C25—C26—C27—C28 | −0.2 (3) |
C25—Ge1—C11—C12 | 60.74 (15) | C26—C27—C28—C29 | −0.7 (3) |
C18—Ge1—C11—C12 | −178.53 (13) | C27—C28—C29—C30 | 0.6 (3) |
C3—Ge1—C11—C12 | −61.24 (14) | C28—C29—C30—C25 | 0.5 (3) |
C16—C11—C12—C13 | −2.4 (2) | C26—C25—C30—C29 | −1.4 (3) |
Ge1—C11—C12—C13 | 172.91 (14) | Ge1—C25—C30—C29 | −179.48 (13) |
C11—C12—C13—C14 | 2.0 (3) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O1i | 0.84 | 1.83 | 2.6689 (16) | 178 |
C8—H8···O1ii | 0.95 | 2.57 | 3.323 (2) | 137 |
C3—H3···F1 | 1.00 | 2.34 | 2.805 (2) | 108 |
Symmetry codes: (i) −x+2, −y, −z+1; (ii) −x+1, −y, −z+1. |
(II) 3-(2-tolyl)-3-(tri-4-tolylgermyl)propionic acid
top
Crystal data top
[Ge(C7H7)3(C10H11O2)] | F(000) = 1064 |
Mr = 509.16 | Dx = 1.213 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 10731 reflections |
a = 10.984 (3) Å | θ = 1.0–27.5° |
b = 13.710 (4) Å | µ = 1.12 mm−1 |
c = 20.245 (5) Å | T = 293 K |
β = 113.857 (14)° | Prismatic, colourless |
V = 2788.3 (13) Å3 | 0.20 × 0.17 × 0.13 mm |
Z = 4 | |
Data collection top
Nonius KappaCCD area-detector diffractometer | 6346 independent reflections |
Radiation source: fine-focus sealed tube | 4185 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.025 |
ω and ϕ scans | θmax = 27.5°, θmin = 4.0° |
Absorption correction: multi-scan (SORTAV; Blessing, 1997) | h = −14→14 |
Tmin = 0.749, Tmax = 0.864 | k = −16→17 |
10731 measured reflections | l = −26→26 |
Refinement top
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)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.115 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.047P)2 + 0.8585P] where P = (Fo2 + 2Fc2)/3 |
6346 reflections | (Δ/σ)max = 0.002 |
308 parameters | Δρmax = 0.38 e Å−3 |
0 restraints | Δρmin = −0.42 e Å−3 |
Crystal data top
[Ge(C7H7)3(C10H11O2)] | V = 2788.3 (13) Å3 |
Mr = 509.16 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.984 (3) Å | µ = 1.12 mm−1 |
b = 13.710 (4) Å | T = 293 K |
c = 20.245 (5) Å | 0.20 × 0.17 × 0.13 mm |
β = 113.857 (14)° | |
Data collection top
Nonius KappaCCD area-detector diffractometer | 6346 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1997) | 4185 reflections with I > 2σ(I) |
Tmin = 0.749, Tmax = 0.864 | Rint = 0.025 |
10731 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
wR(F2) = 0.115 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.38 e Å−3 |
6346 reflections | Δρmin = −0.42 e Å−3 |
308 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Ge1 | 0.39820 (2) | 0.22013 (2) | 0.916746 (13) | 0.05927 (12) | |
O1 | 0.0505 (2) | 0.0675 (2) | 0.94832 (13) | 0.1132 (9) | |
O2 | 0.1742 (2) | 0.0017 (2) | 1.05274 (12) | 0.1025 (8) | |
H2 | 0.1007 | −0.0120 | 1.0516 | 0.154* | |
C1 | 0.1601 (3) | 0.0526 (2) | 0.99729 (15) | 0.0661 (7) | |
C2 | 0.2845 (3) | 0.0900 (2) | 0.99328 (15) | 0.0665 (7) | |
H2A | 0.3114 | 0.0447 | 0.9656 | 0.080* | |
H2B | 0.3527 | 0.0943 | 1.0413 | 0.080* | |
C3 | 0.2659 (2) | 0.19052 (19) | 0.95768 (13) | 0.0600 (6) | |
H3 | 0.1825 | 0.1839 | 0.9167 | 0.072* | |
C4 | 0.2549 (3) | 0.2736 (2) | 1.00368 (15) | 0.0654 (7) | |
C5 | 0.3500 (4) | 0.2842 (3) | 1.07418 (18) | 0.0881 (9) | |
H5 | 0.4187 | 0.2359 | 1.0933 | 0.106* | |
C6 | 0.3461 (5) | 0.3626 (4) | 1.1169 (2) | 0.1227 (15) | |
H6 | 0.4101 | 0.3687 | 1.1659 | 0.147* | |
C7 | 0.2499 (7) | 0.4317 (4) | 1.0886 (4) | 0.142 (2) | |
H7 | 0.2486 | 0.4878 | 1.1167 | 0.171* | |
C8 | 0.1567 (6) | 0.4220 (3) | 1.0208 (4) | 0.1273 (16) | |
H8 | 0.0892 | 0.4712 | 1.0020 | 0.153* | |
C9 | 0.1541 (3) | 0.3436 (3) | 0.9758 (2) | 0.0901 (9) | |
C10 | 0.0462 (4) | 0.3376 (3) | 0.9011 (2) | 0.1234 (14) | |
H10A | −0.0133 | 0.3919 | 0.8930 | 0.148* | |
H10B | −0.0027 | 0.2778 | 0.8950 | 0.148* | |
H10C | 0.0867 | 0.3399 | 0.8671 | 0.148* | |
C11 | 0.3877 (3) | 0.1113 (2) | 0.85285 (13) | 0.0634 (7) | |
C12 | 0.5015 (3) | 0.0706 (2) | 0.85117 (15) | 0.0763 (8) | |
H12 | 0.5867 | 0.0994 | 0.8790 | 0.092* | |
C13 | 0.4952 (3) | −0.0114 (3) | 0.80993 (17) | 0.0897 (10) | |
H13 | 0.5756 | −0.0378 | 0.8092 | 0.108* | |
C14 | 0.3762 (4) | −0.0558 (2) | 0.76907 (16) | 0.0836 (9) | |
C15 | 0.2625 (4) | −0.0155 (3) | 0.76972 (16) | 0.0883 (10) | |
H15 | 0.1779 | −0.0439 | 0.7404 | 0.106* | |
C16 | 0.2673 (3) | 0.0671 (3) | 0.81019 (16) | 0.0817 (9) | |
H16 | 0.1851 | 0.0915 | 0.8099 | 0.098* | |
C17 | 0.3732 (5) | −0.1474 (3) | 0.7262 (2) | 0.1250 (15) | |
H17A | 0.2830 | −0.1692 | 0.7011 | 0.150* | |
H17B | 0.4242 | −0.1972 | 0.7591 | 0.150* | |
H17C | 0.4112 | −0.1342 | 0.6920 | 0.150* | |
C18 | 0.5818 (3) | 0.2322 (2) | 0.98661 (14) | 0.0626 (6) | |
C19 | 0.6641 (3) | 0.2995 (3) | 0.97437 (18) | 0.0973 (11) | |
H19 | 0.6276 | 0.3427 | 0.9337 | 0.117* | |
C20 | 0.7980 (3) | 0.3043 (3) | 1.0189 (2) | 0.1192 (15) | |
H20 | 0.8560 | 0.3495 | 1.0096 | 0.143* | |
C21 | 0.8543 (3) | 0.2468 (3) | 1.0781 (2) | 0.0964 (11) | |
C22 | 0.7734 (3) | 0.1802 (3) | 1.09125 (18) | 0.0885 (9) | |
H22 | 0.8116 | 0.1371 | 1.1319 | 0.106* | |
C23 | 0.6396 (3) | 0.1729 (2) | 1.04638 (15) | 0.0719 (7) | |
H23 | 0.5857 | 0.1266 | 1.0580 | 0.086* | |
C24 | 1.0011 (4) | 0.2551 (4) | 1.1269 (3) | 0.162 (2) | |
H24A | 1.0406 | 0.3057 | 1.1093 | 0.194* | |
H24B | 1.0442 | 0.1941 | 1.1270 | 0.194* | |
H24C | 1.0116 | 0.2706 | 1.1752 | 0.194* | |
C25 | 0.3440 (3) | 0.3417 (2) | 0.86385 (14) | 0.0650 (7) | |
C26 | 0.2784 (3) | 0.3438 (2) | 0.78938 (15) | 0.0813 (8) | |
H26 | 0.2665 | 0.2842 | 0.7626 | 0.098* | |
C27 | 0.2318 (4) | 0.4314 (3) | 0.75303 (19) | 0.1026 (12) | |
H27 | 0.1884 | 0.4315 | 0.7013 | 0.123* | |
C28 | 0.2486 (4) | 0.5176 (3) | 0.7886 (2) | 0.1040 (12) | |
C29 | 0.3158 (4) | 0.5167 (3) | 0.8623 (2) | 0.0992 (11) | |
H29 | 0.3303 | 0.5770 | 0.8886 | 0.119* | |
C30 | 0.3620 (3) | 0.4304 (2) | 0.89941 (17) | 0.0838 (9) | |
H30 | 0.4092 | 0.4322 | 0.9510 | 0.101* | |
C31 | 0.1958 (6) | 0.6114 (3) | 0.7468 (3) | 0.164 (2) | |
H31A | 0.1526 | 0.5960 | 0.6964 | 0.197* | |
H31B | 0.2676 | 0.6561 | 0.7545 | 0.197* | |
H31C | 0.1328 | 0.6409 | 0.7626 | 0.197* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Ge1 | 0.04470 (16) | 0.0744 (2) | 0.05520 (17) | −0.00848 (13) | 0.01654 (11) | 0.00079 (13) |
O1 | 0.0560 (13) | 0.159 (2) | 0.1050 (17) | −0.0269 (14) | 0.0122 (12) | 0.0545 (16) |
O2 | 0.0617 (13) | 0.145 (2) | 0.0912 (15) | −0.0257 (14) | 0.0213 (11) | 0.0361 (15) |
C1 | 0.0532 (15) | 0.0749 (17) | 0.0665 (16) | −0.0116 (13) | 0.0203 (13) | 0.0038 (14) |
C2 | 0.0529 (14) | 0.0701 (16) | 0.0781 (17) | −0.0061 (13) | 0.0282 (13) | 0.0050 (14) |
C3 | 0.0443 (13) | 0.0717 (16) | 0.0614 (14) | −0.0071 (11) | 0.0186 (11) | 0.0002 (12) |
C4 | 0.0594 (15) | 0.0697 (17) | 0.0747 (17) | −0.0065 (13) | 0.0351 (14) | −0.0004 (14) |
C5 | 0.084 (2) | 0.103 (3) | 0.079 (2) | −0.0117 (19) | 0.0344 (17) | −0.0114 (19) |
C6 | 0.139 (4) | 0.139 (4) | 0.104 (3) | −0.042 (3) | 0.063 (3) | −0.053 (3) |
C7 | 0.167 (5) | 0.111 (4) | 0.192 (6) | −0.026 (4) | 0.117 (5) | −0.059 (4) |
C8 | 0.129 (4) | 0.087 (3) | 0.198 (5) | 0.014 (3) | 0.100 (4) | −0.010 (3) |
C9 | 0.077 (2) | 0.086 (2) | 0.121 (3) | 0.0065 (18) | 0.054 (2) | 0.004 (2) |
C10 | 0.076 (2) | 0.135 (3) | 0.149 (4) | 0.037 (2) | 0.036 (2) | 0.034 (3) |
C11 | 0.0533 (14) | 0.0801 (18) | 0.0537 (13) | −0.0054 (13) | 0.0187 (11) | 0.0011 (13) |
C12 | 0.0605 (17) | 0.096 (2) | 0.0684 (17) | 0.0013 (15) | 0.0222 (14) | −0.0028 (16) |
C13 | 0.079 (2) | 0.108 (3) | 0.079 (2) | 0.0178 (19) | 0.0300 (17) | −0.0034 (19) |
C14 | 0.105 (3) | 0.081 (2) | 0.0625 (17) | 0.0037 (19) | 0.0325 (17) | 0.0002 (15) |
C15 | 0.088 (2) | 0.104 (3) | 0.0666 (18) | −0.024 (2) | 0.0245 (16) | −0.0170 (18) |
C16 | 0.0625 (18) | 0.104 (2) | 0.0751 (18) | −0.0105 (16) | 0.0242 (15) | −0.0160 (18) |
C17 | 0.166 (4) | 0.101 (3) | 0.100 (3) | 0.005 (3) | 0.045 (3) | −0.019 (2) |
C18 | 0.0488 (13) | 0.0755 (17) | 0.0596 (14) | −0.0095 (13) | 0.0180 (11) | 0.0017 (13) |
C19 | 0.0564 (17) | 0.129 (3) | 0.088 (2) | −0.0212 (18) | 0.0099 (15) | 0.040 (2) |
C20 | 0.058 (2) | 0.138 (3) | 0.129 (3) | −0.033 (2) | 0.004 (2) | 0.050 (3) |
C21 | 0.0510 (17) | 0.106 (2) | 0.103 (2) | −0.0149 (17) | 0.0004 (16) | 0.023 (2) |
C22 | 0.0636 (18) | 0.094 (2) | 0.087 (2) | 0.0016 (17) | 0.0094 (15) | 0.0262 (18) |
C23 | 0.0555 (16) | 0.0711 (17) | 0.0829 (18) | −0.0065 (13) | 0.0216 (14) | 0.0151 (15) |
C24 | 0.066 (2) | 0.179 (4) | 0.170 (4) | −0.029 (3) | −0.025 (3) | 0.057 (4) |
C25 | 0.0494 (14) | 0.0791 (18) | 0.0608 (14) | −0.0130 (13) | 0.0162 (11) | 0.0054 (14) |
C26 | 0.0742 (19) | 0.090 (2) | 0.0668 (17) | −0.0145 (17) | 0.0153 (14) | 0.0076 (17) |
C27 | 0.104 (3) | 0.109 (3) | 0.0708 (19) | −0.017 (2) | 0.0100 (18) | 0.024 (2) |
C28 | 0.107 (3) | 0.087 (2) | 0.101 (3) | −0.015 (2) | 0.025 (2) | 0.024 (2) |
C29 | 0.111 (3) | 0.077 (2) | 0.099 (3) | −0.013 (2) | 0.031 (2) | 0.006 (2) |
C30 | 0.087 (2) | 0.083 (2) | 0.0723 (18) | −0.0155 (17) | 0.0220 (16) | 0.0032 (17) |
C31 | 0.200 (5) | 0.105 (3) | 0.150 (4) | −0.002 (3) | 0.033 (4) | 0.050 (3) |
Geometric parameters (Å, º) top
Ge1—C25 | 1.940 (3) | C15—C16 | 1.386 (4) |
Ge1—C18 | 1.946 (3) | C15—H15 | 0.9601 |
Ge1—C11 | 1.948 (3) | C16—H16 | 0.9600 |
Ge1—C3 | 1.984 (2) | C17—H17A | 0.9600 |
O1—C1 | 1.228 (3) | C17—H17B | 0.9599 |
O2—C1 | 1.276 (3) | C17—H17C | 0.9601 |
O2—H2 | 0.8200 | C18—C23 | 1.381 (4) |
C1—C2 | 1.493 (4) | C18—C19 | 1.381 (4) |
C2—C3 | 1.530 (4) | C19—C20 | 1.382 (4) |
C2—H2A | 0.9600 | C19—H19 | 0.9599 |
C2—H2B | 0.9600 | C20—C21 | 1.357 (5) |
C3—C4 | 1.507 (4) | C20—H20 | 0.9600 |
C3—H3 | 0.9600 | C21—C22 | 1.373 (5) |
C4—C5 | 1.394 (4) | C21—C24 | 1.517 (5) |
C4—C9 | 1.400 (4) | C22—C23 | 1.383 (4) |
C5—C6 | 1.391 (5) | C22—H22 | 0.9599 |
C5—H5 | 0.9600 | C23—H23 | 0.9601 |
C6—C7 | 1.361 (7) | C24—H24A | 0.9599 |
C6—H6 | 0.9601 | C24—H24B | 0.9601 |
C7—C8 | 1.345 (7) | C24—H24C | 0.9601 |
C7—H7 | 0.9600 | C25—C26 | 1.384 (4) |
C8—C9 | 1.402 (6) | C25—C30 | 1.387 (4) |
C8—H8 | 0.9601 | C26—C27 | 1.393 (5) |
C9—C10 | 1.499 (5) | C26—H26 | 0.9600 |
C10—H10A | 0.9600 | C27—C28 | 1.358 (5) |
C10—H10B | 0.9601 | C27—H27 | 0.9600 |
C10—H10C | 0.9600 | C28—C29 | 1.371 (5) |
C11—C12 | 1.381 (4) | C28—C31 | 1.520 (5) |
C11—C16 | 1.393 (4) | C29—C30 | 1.383 (5) |
C12—C13 | 1.386 (4) | C29—H29 | 0.9600 |
C12—H12 | 0.9600 | C30—H30 | 0.9601 |
C13—C14 | 1.374 (5) | C31—H31A | 0.9600 |
C13—H13 | 0.9600 | C31—H31B | 0.9601 |
C14—C15 | 1.370 (5) | C31—H31C | 0.9600 |
C14—C17 | 1.520 (5) | | |
| | | |
C25—Ge1—C18 | 108.93 (11) | C14—C15—H15 | 119.3 |
C25—Ge1—C11 | 111.67 (11) | C16—C15—H15 | 119.5 |
C18—Ge1—C11 | 108.26 (11) | C15—C16—C11 | 121.4 (3) |
C25—Ge1—C3 | 107.07 (11) | C15—C16—H16 | 118.1 |
C18—Ge1—C3 | 115.63 (11) | C11—C16—H16 | 120.5 |
C11—Ge1—C3 | 105.31 (11) | C14—C17—H17A | 109.8 |
C1—O2—H2 | 109.5 | C14—C17—H17B | 108.7 |
O1—C1—O2 | 122.1 (3) | H17A—C17—H17B | 109.5 |
O1—C1—C2 | 121.2 (3) | C14—C17—H17C | 109.9 |
O2—C1—C2 | 116.6 (2) | H17A—C17—H17C | 109.5 |
C1—C2—C3 | 112.7 (2) | H17B—C17—H17C | 109.5 |
C1—C2—H2A | 108.3 | C23—C18—C19 | 116.6 (3) |
C3—C2—H2A | 108.7 | C23—C18—Ge1 | 124.1 (2) |
C1—C2—H2B | 108.8 | C19—C18—Ge1 | 119.1 (2) |
C3—C2—H2B | 108.8 | C18—C19—C20 | 121.1 (3) |
H2A—C2—H2B | 109.5 | C18—C19—H19 | 119.3 |
C4—C3—C2 | 114.7 (2) | C20—C19—H19 | 119.6 |
C4—C3—Ge1 | 111.04 (17) | C21—C20—C19 | 122.2 (3) |
C2—C3—Ge1 | 113.61 (17) | C21—C20—H20 | 116.5 |
C4—C3—H3 | 108.6 | C19—C20—H20 | 121.3 |
C2—C3—H3 | 102.7 | C20—C21—C22 | 117.3 (3) |
Ge1—C3—H3 | 105.2 | C20—C21—C24 | 121.1 (3) |
C5—C4—C9 | 119.0 (3) | C22—C21—C24 | 121.6 (3) |
C5—C4—C3 | 119.8 (3) | C21—C22—C23 | 121.3 (3) |
C9—C4—C3 | 121.1 (3) | C21—C22—H22 | 118.8 |
C6—C5—C4 | 121.2 (4) | C23—C22—H22 | 119.9 |
C6—C5—H5 | 119.9 | C18—C23—C22 | 121.5 (3) |
C4—C5—H5 | 118.8 | C18—C23—H23 | 119.5 |
C7—C6—C5 | 119.3 (4) | C22—C23—H23 | 118.9 |
C7—C6—H6 | 119.6 | C21—C24—H24A | 109.5 |
C5—C6—H6 | 121.1 | C21—C24—H24B | 109.2 |
C8—C7—C6 | 120.1 (5) | H24A—C24—H24B | 109.5 |
C8—C7—H7 | 119.8 | C21—C24—H24C | 109.8 |
C6—C7—H7 | 120.1 | H24A—C24—H24C | 109.5 |
C7—C8—C9 | 123.1 (5) | H24B—C24—H24C | 109.5 |
C7—C8—H8 | 118.8 | C26—C25—C30 | 116.7 (3) |
C9—C8—H8 | 118.1 | C26—C25—Ge1 | 121.9 (2) |
C4—C9—C8 | 117.2 (4) | C30—C25—Ge1 | 121.3 (2) |
C4—C9—C10 | 122.9 (3) | C25—C26—C27 | 120.8 (3) |
C8—C9—C10 | 119.9 (4) | C25—C26—H26 | 119.2 |
C9—C10—H10A | 109.6 | C27—C26—H26 | 120.0 |
C9—C10—H10B | 110.4 | C28—C27—C26 | 121.9 (3) |
H10A—C10—H10B | 109.5 | C28—C27—H27 | 118.6 |
C9—C10—H10C | 108.3 | C26—C27—H27 | 119.5 |
H10A—C10—H10C | 109.5 | C27—C28—C29 | 117.9 (3) |
H10B—C10—H10C | 109.5 | C27—C28—C31 | 120.1 (4) |
C12—C11—C16 | 116.8 (3) | C29—C28—C31 | 122.0 (4) |
C12—C11—Ge1 | 121.0 (2) | C28—C29—C30 | 121.1 (3) |
C16—C11—Ge1 | 122.1 (2) | C28—C29—H29 | 119.3 |
C11—C12—C13 | 121.1 (3) | C30—C29—H29 | 119.6 |
C11—C12—H12 | 119.8 | C29—C30—C25 | 121.7 (3) |
C13—C12—H12 | 119.1 | C29—C30—H30 | 119.1 |
C14—C13—C12 | 121.7 (3) | C25—C30—H30 | 119.2 |
C14—C13—H13 | 118.8 | C28—C31—H31A | 108.6 |
C12—C13—H13 | 119.5 | C28—C31—H31B | 110.2 |
C15—C14—C13 | 117.7 (3) | H31A—C31—H31B | 109.5 |
C15—C14—C17 | 122.0 (4) | C28—C31—H31C | 109.5 |
C13—C14—C17 | 120.3 (4) | H31A—C31—H31C | 109.5 |
C14—C15—C16 | 121.2 (3) | H31B—C31—H31C | 109.5 |
| | | |
O1—C1—C2—C3 | 36.9 (4) | C17—C14—C15—C16 | 178.8 (3) |
O2—C1—C2—C3 | −145.4 (3) | C14—C15—C16—C11 | −1.3 (5) |
C1—C2—C3—C4 | 73.4 (3) | C12—C11—C16—C15 | 1.9 (4) |
C1—C2—C3—Ge1 | −157.31 (19) | Ge1—C11—C16—C15 | −174.4 (2) |
C25—Ge1—C3—C4 | −56.2 (2) | C25—Ge1—C18—C23 | 160.3 (2) |
C18—Ge1—C3—C4 | 65.4 (2) | C11—Ge1—C18—C23 | −78.1 (3) |
C11—Ge1—C3—C4 | −175.13 (18) | C3—Ge1—C18—C23 | 39.7 (3) |
C25—Ge1—C3—C2 | 172.76 (18) | C25—Ge1—C18—C19 | −24.2 (3) |
C18—Ge1—C3—C2 | −65.7 (2) | C11—Ge1—C18—C19 | 97.4 (3) |
C11—Ge1—C3—C2 | 53.8 (2) | C3—Ge1—C18—C19 | −144.8 (3) |
C2—C3—C4—C5 | 50.8 (3) | C23—C18—C19—C20 | 1.9 (6) |
Ge1—C3—C4—C5 | −79.7 (3) | Ge1—C18—C19—C20 | −173.9 (3) |
C2—C3—C4—C9 | −132.4 (3) | C18—C19—C20—C21 | −2.9 (7) |
Ge1—C3—C4—C9 | 97.1 (3) | C19—C20—C21—C22 | 2.2 (7) |
C9—C4—C5—C6 | 0.1 (5) | C19—C20—C21—C24 | −178.7 (5) |
C3—C4—C5—C6 | 177.0 (3) | C20—C21—C22—C23 | −0.7 (7) |
C4—C5—C6—C7 | −1.9 (6) | C24—C21—C22—C23 | −179.9 (4) |
C5—C6—C7—C8 | 2.5 (8) | C19—C18—C23—C22 | −0.5 (5) |
C6—C7—C8—C9 | −1.3 (8) | Ge1—C18—C23—C22 | 175.1 (3) |
C5—C4—C9—C8 | 1.1 (5) | C21—C22—C23—C18 | −0.1 (6) |
C3—C4—C9—C8 | −175.8 (3) | C18—Ge1—C25—C26 | 133.1 (2) |
C5—C4—C9—C10 | −178.9 (3) | C11—Ge1—C25—C26 | 13.6 (3) |
C3—C4—C9—C10 | 4.2 (5) | C3—Ge1—C25—C26 | −101.2 (2) |
C7—C8—C9—C4 | −0.5 (6) | C18—Ge1—C25—C30 | −51.0 (3) |
C7—C8—C9—C10 | 179.5 (5) | C11—Ge1—C25—C30 | −170.5 (2) |
C25—Ge1—C11—C12 | 106.1 (2) | C3—Ge1—C25—C30 | 74.7 (3) |
C18—Ge1—C11—C12 | −13.8 (3) | C30—C25—C26—C27 | −0.9 (5) |
C3—Ge1—C11—C12 | −138.0 (2) | Ge1—C25—C26—C27 | 175.2 (3) |
C25—Ge1—C11—C16 | −77.7 (3) | C25—C26—C27—C28 | 0.1 (6) |
C18—Ge1—C11—C16 | 162.3 (2) | C26—C27—C28—C29 | 1.2 (6) |
C3—Ge1—C11—C16 | 38.1 (3) | C26—C27—C28—C31 | −179.8 (4) |
C16—C11—C12—C13 | −1.3 (4) | C27—C28—C29—C30 | −1.7 (6) |
Ge1—C11—C12—C13 | 175.1 (2) | C31—C28—C29—C30 | 179.4 (4) |
C11—C12—C13—C14 | 0.0 (5) | C28—C29—C30—C25 | 0.9 (6) |
C12—C13—C14—C15 | 0.6 (5) | C26—C25—C30—C29 | 0.4 (5) |
C12—C13—C14—C17 | −178.2 (3) | Ge1—C25—C30—C29 | −175.7 (3) |
C13—C14—C15—C16 | 0.0 (5) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O1i | 0.82 | 1.83 | 2.637 (3) | 169 |
C3—H3···O1 | 0.96 | 2.41 | 2.849 (4) | 107 |
Symmetry code: (i) −x, −y, −z+2. |
(III) 3-(tribenzylgermyl)-3-(4-tolyl)propionic acid
top
Crystal data top
[Ge(C7H7)3(C10H11O2)] | F(000) = 1064 |
Mr = 509.16 | Dx = 1.308 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 16881 reflections |
a = 10.476 (2) Å | θ = 1.0–25.0° |
b = 16.337 (3) Å | µ = 1.21 mm−1 |
c = 15.119 (5) Å | T = 123 K |
β = 92.018 (8)° | Prism, colourless |
V = 2586.0 (11) Å3 | 0.12 × 0.10 × 0.10 mm |
Z = 4 | |
Data collection top
Nonius KappaCCD area-detector diffractometer | 4533 independent reflections |
Radiation source: fine-focus sealed tube | 3586 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.054 |
ω and ϕ scans | θmax = 25.0°, θmin = 3.5° |
Absorption correction: multi-scan (SORTAV; Blessing, 1997) | h = −12→12 |
Tmin = 0.769, Tmax = 0.886 | k = −19→19 |
16881 measured reflections | l = −17→17 |
Refinement top
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)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.094 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.042P)2 + 1.7P] where P = (Fo2 + 2Fc2)/3 |
4533 reflections | (Δ/σ)max = 0.001 |
339 parameters | Δρmax = 0.64 e Å−3 |
2 restraints | Δρmin = −0.33 e Å−3 |
Crystal data top
[Ge(C7H7)3(C10H11O2)] | V = 2586.0 (11) Å3 |
Mr = 509.16 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 10.476 (2) Å | µ = 1.21 mm−1 |
b = 16.337 (3) Å | T = 123 K |
c = 15.119 (5) Å | 0.12 × 0.10 × 0.10 mm |
β = 92.018 (8)° | |
Data collection top
Nonius KappaCCD area-detector diffractometer | 4533 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1997) | 3586 reflections with I > 2σ(I) |
Tmin = 0.769, Tmax = 0.886 | Rint = 0.054 |
16881 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.037 | 2 restraints |
wR(F2) = 0.094 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.64 e Å−3 |
4533 reflections | Δρmin = −0.33 e Å−3 |
339 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Ge1 | 0.22676 (3) | 0.183568 (18) | 0.818794 (17) | 0.03043 (11) | |
O1 | 0.0586 (2) | 0.01191 (15) | 0.59993 (13) | 0.0490 (6) | |
O2 | 0.0365 (2) | 0.10915 (14) | 0.49876 (14) | 0.0497 (6) | |
H2 | 0.0022 | 0.0709 | 0.4694 | 0.075* | |
C1 | 0.0691 (3) | 0.08333 (19) | 0.57577 (19) | 0.0359 (7) | |
C2 | 0.1186 (3) | 0.14847 (19) | 0.64045 (19) | 0.0400 (7) | |
H2A | 0.1602 | 0.1925 | 0.6068 | 0.048* | |
H2B | 0.0452 | 0.1730 | 0.6704 | 0.048* | |
C3 | 0.2132 (2) | 0.11599 (18) | 0.71010 (17) | 0.0328 (6) | |
H3 | 0.1767 | 0.0626 | 0.7294 | 0.039* | |
C4 | 0.3410 (2) | 0.09469 (17) | 0.67203 (16) | 0.0296 (6) | |
C5 | 0.3876 (3) | 0.01564 (18) | 0.67800 (18) | 0.0373 (7) | |
H5 | 0.3396 | −0.0249 | 0.7073 | 0.045* | |
C6 | 0.5033 (3) | −0.00578 (19) | 0.64199 (19) | 0.0423 (7) | |
H6 | 0.5322 | −0.0608 | 0.6465 | 0.051* | |
C7 | 0.5768 (3) | 0.0512 (2) | 0.59986 (18) | 0.0390 (7) | |
C8 | 0.5321 (3) | 0.1310 (2) | 0.59508 (19) | 0.0404 (7) | |
H8 | 0.5818 | 0.1717 | 0.5674 | 0.048* | |
C9 | 0.4154 (3) | 0.15268 (18) | 0.63023 (18) | 0.0342 (6) | |
H9 | 0.3864 | 0.2077 | 0.6256 | 0.041* | |
C10 | 0.7025 (3) | 0.0271 (3) | 0.5605 (2) | 0.0602 (10) | |
H10A | 0.7409 | 0.0751 | 0.5331 | 0.072* | |
H10B | 0.6873 | −0.0154 | 0.5156 | 0.072* | |
H10C | 0.7606 | 0.0060 | 0.6074 | 0.072* | |
C11 | 0.2007 (3) | 0.30143 (18) | 0.7963 (2) | 0.0400 (7) | |
H11A | 0.1117 | 0.3098 | 0.7740 | 0.048* | |
H11B | 0.2109 | 0.3310 | 0.8533 | 0.048* | |
C12 | 0.2891 (3) | 0.33909 (17) | 0.73165 (19) | 0.0381 (7) | |
C13 | 0.2479 (3) | 0.35592 (19) | 0.6448 (2) | 0.0479 (8) | |
H13 | 0.1618 | 0.3456 | 0.6262 | 0.058* | |
C14 | 0.3341 (5) | 0.3881 (2) | 0.5852 (2) | 0.0655 (11) | |
H14 | 0.3061 | 0.3996 | 0.5261 | 0.079* | |
C15 | 0.4583 (5) | 0.4032 (2) | 0.6112 (3) | 0.0735 (13) | |
H15 | 0.5165 | 0.4242 | 0.5701 | 0.088* | |
C16 | 0.4981 (4) | 0.3877 (2) | 0.6968 (3) | 0.0663 (11) | |
H16 | 0.5840 | 0.3990 | 0.7151 | 0.080* | |
C17 | 0.4154 (3) | 0.3561 (2) | 0.7569 (2) | 0.0495 (8) | |
H17 | 0.4448 | 0.3459 | 0.8160 | 0.059* | |
C18 | 0.3925 (3) | 0.1615 (2) | 0.87966 (17) | 0.0433 (8) | |
H18A | 0.4343 | 0.1145 | 0.8512 | 0.052* | |
H18B | 0.4487 | 0.2098 | 0.8746 | 0.052* | |
C19 | 0.3742 (15) | 0.1426 (7) | 0.9756 (3) | 0.030 (3) | 0.65 (4) |
C20 | 0.3750 (10) | 0.2006 (6) | 1.0429 (6) | 0.040 (2) | 0.65 (4) |
H20 | 0.3830 | 0.2571 | 1.0292 | 0.048* | 0.65 (4) |
C21 | 0.3641 (9) | 0.1760 (11) | 1.1303 (4) | 0.060 (4) | 0.65 (4) |
H21 | 0.3647 | 0.2157 | 1.1763 | 0.072* | 0.65 (4) |
C22 | 0.3524 (9) | 0.0934 (12) | 1.1505 (4) | 0.071 (4) | 0.65 (4) |
H22 | 0.3449 | 0.0766 | 1.2102 | 0.085* | 0.65 (4) |
C23 | 0.3516 (11) | 0.0354 (8) | 1.0832 (9) | 0.073 (3) | 0.65 (4) |
H23 | 0.3436 | −0.0211 | 1.0969 | 0.087* | 0.65 (4) |
C24 | 0.3624 (15) | 0.0600 (6) | 0.9958 (8) | 0.049 (2) | 0.65 (4) |
H24 | 0.3619 | 0.0204 | 0.9498 | 0.058* | 0.65 (4) |
C19' | 0.395 (3) | 0.1424 (15) | 0.9769 (4) | 0.035 (5) | 0.35 (4) |
C20' | 0.386 (3) | 0.2143 (14) | 1.0255 (16) | 0.075 (7) | 0.35 (4) |
H20' | 0.3958 | 0.2657 | 0.9973 | 0.090* | 0.35 (4) |
C21' | 0.363 (2) | 0.211 (2) | 1.1153 (16) | 0.095 (8) | 0.35 (4) |
H21' | 0.3564 | 0.2599 | 1.1485 | 0.114* | 0.35 (4) |
C22' | 0.3485 (16) | 0.135 (3) | 1.1566 (6) | 0.072 (9) | 0.35 (4) |
H22' | 0.3325 | 0.1331 | 1.2180 | 0.086* | 0.35 (4) |
C23' | 0.358 (2) | 0.064 (2) | 1.1080 (14) | 0.074 (7) | 0.35 (4) |
H23' | 0.3481 | 0.0122 | 1.1362 | 0.089* | 0.35 (4) |
C24' | 0.381 (2) | 0.0671 (13) | 1.0182 (14) | 0.049 (5) | 0.35 (4) |
H24' | 0.3875 | 0.0180 | 0.9850 | 0.059* | 0.35 (4) |
C25 | 0.0925 (2) | 0.1486 (2) | 0.89873 (18) | 0.0373 (7) | |
H25A | 0.0976 | 0.0884 | 0.9059 | 0.045* | |
H25B | 0.1101 | 0.1735 | 0.9576 | 0.045* | |
C26 | −0.0411 (3) | 0.17073 (17) | 0.86840 (18) | 0.0338 (7) | |
C27 | −0.0977 (3) | 0.2432 (2) | 0.8926 (2) | 0.0494 (8) | |
H27 | −0.0526 | 0.2806 | 0.9302 | 0.059* | |
C28 | −0.2245 (3) | 0.2619 (2) | 0.8608 (3) | 0.0606 (10) | |
H28 | −0.2648 | 0.3111 | 0.8783 | 0.073* | |
C29 | −0.2879 (3) | 0.2082 (3) | 0.8047 (3) | 0.0641 (11) | |
H29 | −0.3713 | 0.2212 | 0.7824 | 0.077* | |
C30 | −0.2325 (3) | 0.1370 (3) | 0.7811 (3) | 0.0617 (10) | |
H30 | −0.2773 | 0.1002 | 0.7426 | 0.074* | |
C31 | −0.1115 (3) | 0.1178 (2) | 0.8128 (2) | 0.0487 (8) | |
H31 | −0.0748 | 0.0671 | 0.7964 | 0.058* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Ge1 | 0.02815 (16) | 0.03580 (19) | 0.02762 (16) | −0.00188 (13) | 0.00492 (11) | −0.00239 (13) |
O1 | 0.0562 (14) | 0.0572 (16) | 0.0332 (11) | −0.0055 (11) | −0.0044 (10) | 0.0032 (10) |
O2 | 0.0608 (14) | 0.0464 (14) | 0.0417 (12) | −0.0093 (11) | −0.0033 (11) | −0.0045 (10) |
C1 | 0.0284 (14) | 0.0372 (18) | 0.0422 (17) | −0.0010 (13) | 0.0036 (12) | 0.0006 (14) |
C2 | 0.0378 (16) | 0.0416 (18) | 0.0406 (16) | 0.0022 (14) | 0.0014 (13) | −0.0053 (14) |
C3 | 0.0304 (14) | 0.0333 (16) | 0.0349 (14) | −0.0019 (12) | 0.0034 (12) | −0.0029 (12) |
C4 | 0.0292 (14) | 0.0330 (16) | 0.0265 (13) | −0.0005 (12) | 0.0003 (11) | −0.0040 (12) |
C5 | 0.0414 (16) | 0.0322 (17) | 0.0388 (15) | −0.0014 (13) | 0.0057 (13) | −0.0009 (13) |
C6 | 0.0478 (18) | 0.0355 (18) | 0.0435 (17) | 0.0109 (14) | 0.0009 (14) | −0.0034 (14) |
C7 | 0.0315 (15) | 0.052 (2) | 0.0336 (15) | 0.0112 (14) | 0.0013 (12) | −0.0028 (14) |
C8 | 0.0352 (16) | 0.0461 (19) | 0.0403 (16) | 0.0002 (14) | 0.0085 (13) | 0.0067 (14) |
C9 | 0.0343 (15) | 0.0296 (15) | 0.0388 (15) | 0.0011 (12) | 0.0037 (12) | 0.0003 (13) |
C10 | 0.0416 (18) | 0.084 (3) | 0.055 (2) | 0.0197 (19) | 0.0090 (16) | −0.008 (2) |
C11 | 0.0395 (16) | 0.0388 (18) | 0.0423 (16) | 0.0007 (13) | 0.0119 (13) | −0.0077 (13) |
C12 | 0.0478 (18) | 0.0239 (16) | 0.0439 (17) | 0.0013 (13) | 0.0191 (14) | −0.0084 (13) |
C13 | 0.066 (2) | 0.0293 (17) | 0.0494 (18) | 0.0055 (16) | 0.0104 (16) | −0.0032 (15) |
C14 | 0.117 (4) | 0.032 (2) | 0.049 (2) | 0.013 (2) | 0.030 (2) | −0.0002 (16) |
C15 | 0.098 (3) | 0.036 (2) | 0.090 (3) | 0.003 (2) | 0.064 (3) | 0.000 (2) |
C16 | 0.057 (2) | 0.040 (2) | 0.105 (3) | −0.0070 (17) | 0.035 (2) | −0.001 (2) |
C17 | 0.0508 (19) | 0.0367 (18) | 0.062 (2) | −0.0052 (16) | 0.0129 (16) | −0.0056 (16) |
C18 | 0.0310 (15) | 0.061 (2) | 0.0377 (16) | −0.0021 (14) | 0.0051 (13) | −0.0026 (15) |
C19 | 0.012 (5) | 0.049 (6) | 0.030 (4) | 0.004 (4) | −0.003 (2) | 0.000 (4) |
C20 | 0.030 (3) | 0.061 (5) | 0.030 (4) | −0.012 (3) | 0.002 (3) | −0.011 (3) |
C21 | 0.034 (4) | 0.121 (9) | 0.026 (4) | −0.022 (5) | 0.009 (3) | −0.004 (5) |
C22 | 0.038 (5) | 0.124 (13) | 0.051 (6) | −0.007 (6) | −0.015 (4) | 0.026 (6) |
C23 | 0.048 (5) | 0.077 (6) | 0.092 (7) | −0.002 (5) | −0.006 (5) | 0.046 (6) |
C24 | 0.034 (5) | 0.057 (5) | 0.054 (4) | 0.004 (4) | −0.012 (5) | 0.015 (3) |
C19' | 0.008 (7) | 0.046 (11) | 0.050 (10) | −0.010 (6) | 0.009 (5) | 0.002 (8) |
C20' | 0.074 (13) | 0.108 (16) | 0.044 (9) | 0.013 (11) | 0.021 (8) | −0.011 (9) |
C21' | 0.068 (12) | 0.16 (2) | 0.054 (11) | 0.028 (14) | −0.014 (9) | −0.025 (12) |
C22' | 0.032 (7) | 0.14 (3) | 0.047 (9) | 0.007 (11) | 0.023 (6) | 0.044 (9) |
C23' | 0.042 (9) | 0.103 (16) | 0.077 (13) | −0.016 (10) | −0.014 (9) | 0.044 (14) |
C24' | 0.029 (8) | 0.063 (9) | 0.053 (8) | −0.011 (6) | −0.024 (7) | 0.012 (8) |
C25 | 0.0315 (15) | 0.0494 (19) | 0.0311 (14) | 0.0002 (14) | 0.0037 (12) | 0.0008 (14) |
C26 | 0.0298 (14) | 0.0389 (18) | 0.0332 (14) | −0.0041 (13) | 0.0078 (12) | 0.0049 (13) |
C27 | 0.0504 (19) | 0.049 (2) | 0.0505 (19) | −0.0013 (16) | 0.0210 (16) | −0.0020 (16) |
C28 | 0.057 (2) | 0.059 (2) | 0.068 (2) | 0.0213 (19) | 0.0191 (19) | 0.010 (2) |
C29 | 0.0323 (18) | 0.085 (3) | 0.076 (3) | −0.0044 (19) | 0.0077 (18) | 0.012 (2) |
C30 | 0.044 (2) | 0.069 (3) | 0.071 (2) | −0.0188 (19) | −0.0096 (18) | 0.010 (2) |
C31 | 0.0448 (18) | 0.046 (2) | 0.0544 (19) | −0.0119 (15) | −0.0036 (15) | 0.0036 (16) |
Geometric parameters (Å, º) top
Ge1—C18 | 1.970 (3) | C18—C19 | 1.502 (4) |
Ge1—C25 | 1.971 (3) | C18—C19' | 1.502 (5) |
Ge1—C11 | 1.973 (3) | C18—H18A | 0.9900 |
Ge1—C3 | 1.981 (3) | C18—H18B | 0.9900 |
O1—C1 | 1.229 (4) | C19—C20 | 1.3900 |
O2—C1 | 1.274 (3) | C19—C24 | 1.3900 |
O2—H2 | 0.8400 | C20—C21 | 1.3900 |
C1—C2 | 1.524 (4) | C20—H20 | 0.9500 |
C2—C3 | 1.516 (4) | C21—C22 | 1.3900 |
C2—H2A | 0.9900 | C21—H21 | 0.9500 |
C2—H2B | 0.9900 | C22—C23 | 1.3900 |
C3—C4 | 1.516 (4) | C22—H22 | 0.9500 |
C3—H3 | 1.0000 | C23—C24 | 1.3900 |
C4—C5 | 1.383 (4) | C23—H23 | 0.9500 |
C4—C9 | 1.393 (4) | C24—H24 | 0.9500 |
C5—C6 | 1.391 (4) | C19'—C20' | 1.3900 |
C5—H5 | 0.9500 | C19'—C24' | 1.3900 |
C6—C7 | 1.378 (4) | C20'—C21' | 1.3900 |
C6—H6 | 0.9500 | C20'—H20' | 0.9500 |
C7—C8 | 1.388 (4) | C21'—C22' | 1.4000 |
C7—C10 | 1.515 (4) | C21'—H21' | 0.9500 |
C8—C9 | 1.396 (4) | C22'—C23' | 1.3796 |
C8—H8 | 0.9500 | C22'—H22' | 0.9500 |
C9—H9 | 0.9500 | C23'—C24' | 1.3900 |
C10—H10A | 0.9800 | C23'—H23' | 0.9500 |
C10—H10B | 0.9800 | C24'—H24' | 0.9500 |
C10—H10C | 0.9800 | C25—C26 | 1.502 (4) |
C11—C12 | 1.502 (4) | C25—H25A | 0.9900 |
C11—H11A | 0.9900 | C25—H25B | 0.9900 |
C11—H11B | 0.9900 | C26—C27 | 1.380 (4) |
C12—C17 | 1.392 (4) | C26—C31 | 1.398 (4) |
C12—C13 | 1.395 (4) | C27—C28 | 1.430 (5) |
C13—C14 | 1.401 (5) | C27—H27 | 0.9500 |
C13—H13 | 0.9500 | C28—C29 | 1.374 (5) |
C14—C15 | 1.368 (6) | C28—H28 | 0.9500 |
C14—H14 | 0.9500 | C29—C30 | 1.353 (6) |
C15—C16 | 1.370 (6) | C29—H29 | 0.9500 |
C15—H15 | 0.9500 | C30—C31 | 1.375 (5) |
C16—C17 | 1.377 (5) | C30—H30 | 0.9500 |
C16—H16 | 0.9500 | C31—H31 | 0.9500 |
C17—H17 | 0.9500 | | |
| | | |
C18—Ge1—C25 | 107.26 (11) | C19—C18—C19' | 8.5 (15) |
C18—Ge1—C11 | 111.93 (14) | C19—C18—Ge1 | 110.4 (6) |
C25—Ge1—C11 | 106.94 (13) | C19'—C18—Ge1 | 118.8 (11) |
C18—Ge1—C3 | 108.79 (12) | C19—C18—H18A | 109.6 |
C25—Ge1—C3 | 108.38 (12) | C19'—C18—H18A | 105.7 |
C11—Ge1—C3 | 113.30 (12) | Ge1—C18—H18A | 109.6 |
C1—O2—H2 | 109.5 | C19—C18—H18B | 109.6 |
O1—C1—O2 | 124.2 (3) | C19'—C18—H18B | 104.5 |
O1—C1—C2 | 120.3 (3) | Ge1—C18—H18B | 109.6 |
O2—C1—C2 | 115.4 (3) | H18A—C18—H18B | 108.1 |
C3—C2—C1 | 113.6 (3) | C20—C19—C24 | 120.0 |
C3—C2—H2A | 108.8 | C20—C19—C18 | 124.7 (8) |
C1—C2—H2A | 108.8 | C24—C19—C18 | 115.2 (8) |
C3—C2—H2B | 108.8 | C21—C20—C19 | 120.0 |
C1—C2—H2B | 108.8 | C21—C20—H20 | 120.0 |
H2A—C2—H2B | 107.7 | C19—C20—H20 | 120.0 |
C2—C3—C4 | 112.4 (2) | C20—C21—C22 | 120.0 |
C2—C3—Ge1 | 114.04 (19) | C20—C21—H21 | 120.0 |
C4—C3—Ge1 | 113.84 (17) | C22—C21—H21 | 120.0 |
C2—C3—H3 | 105.2 | C23—C22—C21 | 120.0 |
C4—C3—H3 | 105.2 | C23—C22—H22 | 120.0 |
Ge1—C3—H3 | 105.2 | C21—C22—H22 | 120.0 |
C5—C4—C9 | 117.6 (2) | C24—C23—C22 | 120.0 |
C5—C4—C3 | 120.3 (2) | C24—C23—H23 | 120.0 |
C9—C4—C3 | 122.1 (3) | C22—C23—H23 | 120.0 |
C4—C5—C6 | 121.3 (3) | C23—C24—C19 | 120.0 |
C4—C5—H5 | 119.3 | C23—C24—H24 | 120.0 |
C6—C5—H5 | 119.3 | C19—C24—H24 | 120.0 |
C7—C6—C5 | 121.3 (3) | C20'—C19'—C24' | 120.0 |
C7—C6—H6 | 119.3 | C20'—C19'—C18 | 110.0 (17) |
C5—C6—H6 | 119.3 | C24'—C19'—C18 | 128.6 (16) |
C6—C7—C8 | 117.7 (3) | C21'—C20'—C19' | 120.0 |
C6—C7—C10 | 120.9 (3) | C21'—C20'—H20' | 120.0 |
C8—C7—C10 | 121.3 (3) | C19'—C20'—H20' | 120.0 |
C7—C8—C9 | 121.1 (3) | C20'—C21'—C22' | 120.0 |
C7—C8—H8 | 119.4 | C20'—C21'—H21' | 120.0 |
C9—C8—H8 | 119.4 | C22'—C21'—H21' | 120.0 |
C4—C9—C8 | 120.8 (3) | C21'—C22'—C23' | 120.0 |
C4—C9—H9 | 119.6 | C21'—C22'—H22' | 120.0 |
C8—C9—H9 | 119.6 | C23'—C22'—H22' | 120.0 |
C7—C10—H10A | 109.5 | C22'—C23'—C24' | 120.0 |
C7—C10—H10B | 109.5 | C22'—C23'—H23' | 120.0 |
H10A—C10—H10B | 109.5 | C24'—C23'—H23' | 120.0 |
C7—C10—H10C | 109.5 | C23'—C24'—C19' | 120.0 |
H10A—C10—H10C | 109.5 | C23'—C24'—H24' | 120.0 |
H10B—C10—H10C | 109.5 | C19'—C24'—H24' | 120.0 |
C12—C11—Ge1 | 115.31 (19) | C26—C25—Ge1 | 114.86 (19) |
C12—C11—H11A | 108.4 | C26—C25—H25A | 108.6 |
Ge1—C11—H11A | 108.4 | Ge1—C25—H25A | 108.6 |
C12—C11—H11B | 108.4 | C26—C25—H25B | 108.6 |
Ge1—C11—H11B | 108.4 | Ge1—C25—H25B | 108.6 |
H11A—C11—H11B | 107.5 | H25A—C25—H25B | 107.5 |
C17—C12—C13 | 118.6 (3) | C27—C26—C31 | 117.8 (3) |
C17—C12—C11 | 120.4 (3) | C27—C26—C25 | 122.1 (3) |
C13—C12—C11 | 121.0 (3) | C31—C26—C25 | 120.1 (3) |
C12—C13—C14 | 119.6 (3) | C26—C27—C28 | 119.8 (3) |
C12—C13—H13 | 120.2 | C26—C27—H27 | 120.1 |
C14—C13—H13 | 120.2 | C28—C27—H27 | 120.1 |
C15—C14—C13 | 120.8 (4) | C29—C28—C27 | 119.6 (3) |
C15—C14—H14 | 119.6 | C29—C28—H28 | 120.2 |
C13—C14—H14 | 119.6 | C27—C28—H28 | 120.2 |
C14—C15—C16 | 119.5 (3) | C30—C29—C28 | 120.6 (3) |
C14—C15—H15 | 120.2 | C30—C29—H29 | 119.7 |
C16—C15—H15 | 120.2 | C28—C29—H29 | 119.7 |
C15—C16—C17 | 121.0 (4) | C29—C30—C31 | 120.1 (4) |
C15—C16—H16 | 119.5 | C29—C30—H30 | 119.9 |
C17—C16—H16 | 119.5 | C31—C30—H30 | 119.9 |
C16—C17—C12 | 120.6 (4) | C30—C31—C26 | 122.0 (3) |
C16—C17—H17 | 119.7 | C30—C31—H31 | 119.0 |
C12—C17—H17 | 119.7 | C26—C31—H31 | 119.0 |
| | | |
O1—C1—C2—C3 | 31.0 (4) | C25—Ge1—C18—C19' | −13.5 (11) |
O2—C1—C2—C3 | −151.4 (3) | C11—Ge1—C18—C19' | 103.5 (11) |
C1—C2—C3—C4 | 71.3 (3) | C3—Ge1—C18—C19' | −130.6 (11) |
C1—C2—C3—Ge1 | −157.19 (19) | C19'—C18—C19—C20 | 85 (9) |
C18—Ge1—C3—C2 | −157.9 (2) | Ge1—C18—C19—C20 | −90.1 (10) |
C25—Ge1—C3—C2 | 85.8 (2) | C19'—C18—C19—C24 | −92 (9) |
C11—Ge1—C3—C2 | −32.7 (2) | Ge1—C18—C19—C24 | 93.3 (6) |
C18—Ge1—C3—C4 | −27.2 (2) | C24—C19—C20—C21 | 0.0 |
C25—Ge1—C3—C4 | −143.5 (2) | C18—C19—C20—C21 | −176.4 (12) |
C11—Ge1—C3—C4 | 98.0 (2) | C19—C20—C21—C22 | 0.0 |
C2—C3—C4—C5 | −120.1 (3) | C20—C21—C22—C23 | 0.0 |
Ge1—C3—C4—C5 | 108.3 (3) | C21—C22—C23—C24 | 0.0 |
C2—C3—C4—C9 | 59.8 (3) | C22—C23—C24—C19 | 0.0 |
Ge1—C3—C4—C9 | −71.7 (3) | C20—C19—C24—C23 | 0.0 |
C9—C4—C5—C6 | −1.3 (4) | C18—C19—C24—C23 | 176.8 (11) |
C3—C4—C5—C6 | 178.7 (3) | C19—C18—C19'—C20' | −85 (9) |
C4—C5—C6—C7 | 0.8 (4) | Ge1—C18—C19'—C20' | −79.5 (13) |
C5—C6—C7—C8 | 0.5 (4) | C19—C18—C19'—C24' | 82 (9) |
C5—C6—C7—C10 | −179.7 (3) | Ge1—C18—C19'—C24' | 87.0 (18) |
C6—C7—C8—C9 | −1.2 (4) | C24'—C19'—C20'—C21' | 0.0 |
C10—C7—C8—C9 | 179.0 (3) | C18—C19'—C20'—C21' | 167.9 (19) |
C5—C4—C9—C8 | 0.6 (4) | C19'—C20'—C21'—C22' | 0.0 |
C3—C4—C9—C8 | −179.4 (2) | C20'—C21'—C22'—C23' | 0.0 |
C7—C8—C9—C4 | 0.7 (4) | C21'—C22'—C23'—C24' | 0.0 |
C18—Ge1—C11—C12 | 66.5 (3) | C22'—C23'—C24'—C19' | 0.0 |
C25—Ge1—C11—C12 | −176.3 (2) | C20'—C19'—C24'—C23' | 0.0 |
C3—Ge1—C11—C12 | −56.9 (3) | C18—C19'—C24'—C23' | −165 (2) |
Ge1—C11—C12—C17 | −75.7 (3) | C18—Ge1—C25—C26 | 172.4 (2) |
Ge1—C11—C12—C13 | 102.7 (3) | C11—Ge1—C25—C26 | 52.2 (3) |
C17—C12—C13—C14 | 1.0 (4) | C3—Ge1—C25—C26 | −70.3 (2) |
C11—C12—C13—C14 | −177.5 (3) | Ge1—C25—C26—C27 | −91.0 (3) |
C12—C13—C14—C15 | 0.0 (5) | Ge1—C25—C26—C31 | 88.0 (3) |
C13—C14—C15—C16 | −0.9 (5) | C31—C26—C27—C28 | 0.0 (4) |
C14—C15—C16—C17 | 0.9 (6) | C25—C26—C27—C28 | 179.1 (3) |
C15—C16—C17—C12 | 0.1 (5) | C26—C27—C28—C29 | −1.5 (5) |
C13—C12—C17—C16 | −1.0 (5) | C27—C28—C29—C30 | 1.6 (5) |
C11—C12—C17—C16 | 177.5 (3) | C28—C29—C30—C31 | −0.3 (6) |
C25—Ge1—C18—C19 | −12.7 (5) | C29—C30—C31—C26 | −1.2 (5) |
C11—Ge1—C18—C19 | 104.3 (5) | C27—C26—C31—C30 | 1.3 (4) |
C3—Ge1—C18—C19 | −129.7 (5) | C25—C26—C31—C30 | −177.8 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O1i | 0.84 | 1.81 | 2.651 (3) | 175 |
C3—H3···O1 | 1.00 | 2.42 | 2.845 (4) | 105 |
Symmetry code: (i) −x, −y, −z+1. |
Experimental details
| (I) | (II) | (III) |
Crystal data |
Chemical formula | [Ge(C6H5)3(C9H8FO2)] | [Ge(C7H7)3(C10H11O2)] | [Ge(C7H7)3(C10H11O2)] |
Mr | 471.04 | 509.16 | 509.16 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, P21/c | Monoclinic, P21/n |
Temperature (K) | 170 | 293 | 123 |
a, b, c (Å) | 9.7278 (10), 17.907 (3), 13.541 (2) | 10.984 (3), 13.710 (4), 20.245 (5) | 10.476 (2), 16.337 (3), 15.119 (5) |
β (°) | 110.907 (8) | 113.857 (14) | 92.018 (8) |
V (Å3) | 2203.5 (6) | 2788.3 (13) | 2586.0 (11) |
Z | 4 | 4 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 1.42 | 1.12 | 1.21 |
Crystal size (mm) | 0.20 × 0.15 × 0.14 | 0.20 × 0.17 × 0.13 | 0.12 × 0.10 × 0.10 |
|
Data collection |
Diffractometer | Nonius KappaCCD area-detector diffractometer | Nonius KappaCCD area-detector diffractometer | Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (SORTAV; Blessing, 1997) | Multi-scan (SORTAV; Blessing, 1997) | Multi-scan (SORTAV; Blessing, 1997) |
Tmin, Tmax | 0.711, 0.820 | 0.749, 0.864 | 0.769, 0.886 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9816, 5026, 4338 | 10731, 6346, 4185 | 16881, 4533, 3586 |
Rint | 0.017 | 0.025 | 0.054 |
(sin θ/λ)max (Å−1) | 0.650 | 0.650 | 0.595 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.028, 0.070, 1.03 | 0.043, 0.115, 1.01 | 0.037, 0.094, 1.04 |
No. of reflections | 5026 | 6346 | 4533 |
No. of parameters | 281 | 308 | 339 |
No. of restraints | 0 | 0 | 2 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.30, −0.44 | 0.38, −0.42 | 0.64, −0.33 |
Selected geometric parameters (Å, º) for (I) topGe1—C11 | 1.951 (2) | F1—C9 | 1.367 (2) |
Ge1—C25 | 1.953 (2) | O1—C1 | 1.217 (2) |
Ge1—C18 | 1.959 (2) | O2—C1 | 1.316 (2) |
Ge1—C3 | 1.997 (2) | | |
| | | |
C11—Ge1—C25 | 110.55 (7) | C11—Ge1—C3 | 106.08 (6) |
C11—Ge1—C18 | 110.60 (6) | C25—Ge1—C3 | 112.29 (7) |
C25—Ge1—C18 | 108.93 (7) | C18—Ge1—C3 | 108.35 (6) |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O1i | 0.84 | 1.83 | 2.6689 (16) | 178 |
C8—H8···O1ii | 0.95 | 2.57 | 3.323 (2) | 137 |
C3—H3···F1 | 1.00 | 2.34 | 2.805 (2) | 108 |
Symmetry codes: (i) −x+2, −y, −z+1; (ii) −x+1, −y, −z+1. |
Selected geometric parameters (Å, º) for (II) topGe1—C25 | 1.940 (3) | Ge1—C3 | 1.984 (2) |
Ge1—C18 | 1.946 (3) | O1—C1 | 1.228 (3) |
Ge1—C11 | 1.948 (3) | O2—C1 | 1.276 (3) |
| | | |
C25—Ge1—C18 | 108.93 (11) | C25—Ge1—C3 | 107.07 (11) |
C25—Ge1—C11 | 111.67 (11) | C18—Ge1—C3 | 115.63 (11) |
C18—Ge1—C11 | 108.26 (11) | C11—Ge1—C3 | 105.31 (11) |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O1i | 0.82 | 1.83 | 2.637 (3) | 169 |
C3—H3···O1 | 0.96 | 2.41 | 2.849 (4) | 107 |
Symmetry code: (i) −x, −y, −z+2. |
Selected geometric parameters (Å, º) for (III) topGe1—C18 | 1.970 (3) | Ge1—C3 | 1.981 (3) |
Ge1—C25 | 1.971 (3) | O1—C1 | 1.229 (4) |
Ge1—C11 | 1.973 (3) | O2—C1 | 1.274 (3) |
| | | |
C18—Ge1—C25 | 107.26 (11) | C18—Ge1—C3 | 108.79 (12) |
C18—Ge1—C11 | 111.93 (14) | C25—Ge1—C3 | 108.38 (12) |
C25—Ge1—C11 | 106.94 (13) | C11—Ge1—C3 | 113.30 (12) |
Hydrogen-bond geometry (Å, º) for (III) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O1i | 0.84 | 1.81 | 2.651 (3) | 175 |
C3—H3···O1 | 1.00 | 2.42 | 2.845 (4) | 105 |
Symmetry code: (i) −x, −y, −z+1. |
Subscribe to Acta Crystallographica Section C: Structural Chemistry
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There has been considerable interest in recent years in the chemistry of germanium compounds, due to their diverse applications in the fields of medicine, electronics and optics, and as radiation detectors. A number of reports have been published regarding the structural chemistry of these compounds and their applications (Mackay, 1995; Westaway & Joly, 1995). In order to develop new kinds of organogermanium compounds with potential therapeutic properties, we have synthesized three derivatives of triorganogermyl propionic acid, 3-(2-fluorophenyl)-3-(triphenylgermyl)propionic acid, (I), 3-(2-tolyl)-3-(tri-4-tolylgermyl)propionic acid, (II) and 3-(tribenzylgermyl)-3-(4-tolyl)propionic acid, (III), and characterized them using X-ray diffraction methods, and the results are presented in this paper. The crystal structure of 2-methyl-3-phenyl-3-[(tri-p-tolyl)germylpropionic acid has recently been reported by our group (Imtiaz-ud-Din et al., 2002). \sch
Figs. 1–3 show the structures of (I)-(III), respectively. The central Ge atom in each compound is four-coordinate and the geometry about the Ge atoms is slightly distorted from tetrahedral, with C—Ge—C angles in the three compounds in the ranges 106.08 (6)–112.29 (7)° in (I), 105.31 (11)–115.63 (11)° in (II) and 106.94 (13)–113.30 (12)° in (III). The Ge-Csp3 distances (Ge—C3) in (I) and (II) are significantly longer [1.997 (2) and 1.984 (2) Å, respectively] than the Ge—Caromatic distances, which are identical to within 3σ limits in each of the two structures, with mean values of 1.954 (2) and 1.945 (2) Å, respectively. On the other hand, the Ge—C3 distance of 1.981 (3) Å in (III) is barely longer than the Ge—Cbenzyl distances, which are also identical with a mean value of 1.971 (1) Å. These Ge—Caromatic distances are in agreement with those reported in the related structures (C9H11)3GeCN·0.5C4H8O, (C9H11)3GeNCS and (C9H11)3GeN3 (Hihara et al., 2000), Ph3GeOH (Ferguson et al., 1992), (C7H7)4Ge (Belsky et al., 1984), and (C6H5)4Ge (Karipides & Haller, 1972).
The propionate moiety in (I) (O1/O2/C1/C2/C3) is essentially planar, with atom Ge1 lying 0.380 (2)° out of the plane formed by these atoms, and is inclined at an angle of 88.11 (5)° with the mean plane of the phenyl ring C4—C9 atoms. The mean planes of the phenyl rings C11—C16 (ring 1), C18—C23 (ring 2) and C25—C30 (ring 3) bonded to atom Ge1 are inclined with respect to each other at angles of 69.09 (6), 59.92 (7) and 68.21 (5)° for the pairs of rings 1/2, 1/3 and 2/3, respectively.
The propionate moiety in (II) is not planar, in contrast to (I). In this case, only atoms O1, O2, C1 and C2 are planar to within 0.012 (3) Å, while atoms C3 and Ge1 lie 0.679 (5) and 0.086 (7) Å, respectively, out of the plane of these atoms. The mean planes of the phenyl rings [rings 1–3, as defined for (I)] bonded to atom Ge1 are inclined with respect to each other at angles of 80.90 (10), 64.21 (12) and 67.42 (12)° for the pairs of rings 1/2, 1/3 and 2/3, respectively.
The propionate moiety in (III) is also non-planar, as observed in (II), wherein only atoms O1, O2, C1 and C2 are planar to within 0.012 (3) Å, while atoms C3 and Ge1 are 0.814 (5) and 0.277 (8) Å, respectively, out of the plane of these atoms. The mean planes of the benzyl rings [rings 1–3, as defined for (I)] bonded to atom Ge1 are inclined with respect to each other at angles of 71.7 (4), 74.3 (3) and 84.7 (1)° for the pairs of rings 1/2, 1/3 and 2/3, respectively. One of the phenyl rings in (III) is disordered over sites C19—C24 and C19'-C24' with site occupancy factors of 0.65 (4) and 0.35 (4), respectively, and with the mean planes of these rings lying at 7.0 (5)° with respect to each other.
In all three structures, the molecules form dimeric pairs about inversion centres through strong hydrogen-bonding interactions between carboxylate groups. These hydrogen-bonding interactions can be described in terms of graph-set presentations of R22(8) (Bernstein et al., 1994). In addition, there are short intermolecular C—H···O interactions (involving atoms C8 and O1) and intramolecular C3—H3···F1 contacts present in (I). The structure of (II) exhibits short intermolecular H8···H8i interactions involving adjacent molecules [2.08 Å; symmetry code: (ii) -x, 1 - y, 2 - z], resulting in a phenyl ring of the phenylpropionate ligand with C—C distances spanning a wide range; the shortest distance is C7—C8. Intramolecular C3—H3···O1 contacts are also observed in (II) and (III). Details of the hydrogen-bonding geometry for (I)-(III) are given in Tables 2, 4 and 6, respectively.