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Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 71| Part 6| June 2015| Pages 687-689

Crystal structure of 4-(tri­methyl­germ­yl)benzoic acid

aFakultät für Chemie und Chemische Biologie, Technische Universität Dortmund, Otto-Hahn-Strasse 6, 44227 Dortmund, Germany
*Correspondence e-mail: carsten.strohmann@tu-dortmund.de

Edited by M. Weil, Vienna University of Technology, Austria (Received 30 April 2015; accepted 13 May 2015; online 23 May 2015)

The title compound, [Ge(CH3)3(C7H5O2)], was obtained as a by-product in the synthesis of the corresponding aldehyde. Two slightly different mol­ecules are present in the asymmetric unit. In both mol­ecules, the geometry of the aromatic ring plane is distorted by varying intensities. Additionally, the Ge atoms deviate from the mean aromatic ring planes. Whereas the distance of the Ge atom to the ring plane is only 0.101 (4) Å in the first mol­ecule, this distance is increased to 0.210 (4) Å in the second. In the crystal structure, centrosymmetric O—H⋯O hydrogen-bonded dimers are formed. The title compound is isostructural with the Si analogue [Haberecht et al. (2004[Haberecht, M. C., Vitze, H., Lerner, H.-W. & Bolte, M. (2004). Acta Cryst. E60, o329-o330.]). Acta Cryst. E60, o329–0330].

1. Chemical context

The application of 1,4-di­hydro­pyridines (DHPs) as a pharmaceutical tool represents a novel and promising approach in the therapy of autoimmune diseases, cancer and other illnesses. The effect of drugs containing DHPs is based on the inter­action with the Transforming Growth Factor β (TGFβ). The title compound, [Ge(CH3)3(C7H5O2)], (I)[link], was obtained as a side-product in the synthesis of the corresponding aldehyde, which can be employed in the synthesis of DHPs (Längle et al., 2015[Längle, D., Marquardt, V., Heider, E., Vigante, B., Duburs, G., Luntena, I., Flötgen, D., Golz, C., Strohmann, C., Koch, O. & Schade, D. (2015). Eur. J. Med. Chem. 95, 249-266.]).

[Scheme 1]

2. Structural commentary

The asymmetric unit of (I)[link] contains two mol­ecules (Fig. 1[link]), which exhibit different deformations of the aromatic plane. This deformation may be caused by the sterically demanding substituents in 1- and 4-positions. In the first mol­ecule, the opposite carbon atoms C2 and C5 deviate from the mean aromatic ring plane by −0.015 (2) Å, which leads to a boat-shaped deformation (Table 1[link]). The distance of the germanium atom Ge1 to this plane is −0.210 (4) Å. Corresponding to this boat-shaped deformation, the bond lengths of the aromatic ring are not equidistant, but can be divided into three pairs of similar distances: the bonds C5—C4 [1.393 (4) Å] and C5—C6 [1.398 (4) Å] are slightly elongated, C2—C3 [1.383 (4) Å] and C2—C7 [1.384 (4) Å] lie in a medium range, and C3—C4 [1.368 (4) Å] and C6—C7 [1.379 (4) Å] are the shortest. In the second mol­ecule, the aromatic ring exhibits a nearly planar geometry (Table 1[link]). Similar to the first mol­ecule, the Ge2 atom deviates from the mean aromatic ring plane by 0.101 (4) Å. Additionally, elongated bond lengths at C12 and C15 can be observed [C12—C13 1.385 (4), C12—C17 1.381 (4), C15—C14 1.393 (4), C15—C16 1.398 (4) Å].

Table 1
Deviation of atoms from the benzene ring least-squares planes (Å)

Atom Deviation Atom Deviation
C2 −0.015 (2) C12 0.004 (2)
C3 0.007 (2) C13 −0.003 (2)
C4 0.008 (2) C14 −0.003 (2)
C5 −0.015 (2) C15 0.007 (2)
C6 0.007 (2) C16 −0.006 (2)
C7 0.007 (2) C17 0.000 (4)
Ge1* −0.210 (4) Ge2* 0.101 (4)
Note: (*) not used in the least-squares-plane calculation.
[Figure 1]
Figure 1
The structures and atom numbering of the two independent mol­ecules in the title compound. Displacement ellipsoids are drawn at the 30% probability level.

All in all, the degree of deformation in the second mol­ecule is smaller compared to the first mol­ecule. This difference may be the reason for the presence of two mol­ecules in the asymmetric unit. The deformations described above may be caused by the sterically demanding substituents attached to the aromatic ring in 1- and 4-positions, or may be traced back to packing effects.

3. Supra­molecular features

The mol­ecules in the title compound crystallize as centrosymmetric hydrogen-bonded dimers (Fig. 2[link], Table 2[link]). Considering the donor⋯acceptor bond lengths of 2.626 (3) Å [O2—H2⋯O1] and 2.635 (3) Å [O4—H4A⋯O3], the strength of the hydrogen bonds can be classified as moderate according to Jeffrey (1997[Jeffrey, G. A. (1997). In An Introduction to Hydrogen Bonding. Oxford University Press.]).

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
O2—H2⋯O1i 0.93 (5) 1.71 (5) 2.626 (3) 170 (5)
O4—H4A⋯O3ii 0.93 (5) 1.70 (5) 2.635 (3) 179 (4)
Symmetry codes: (i) -x, -y+2, -z; (ii) -x+2, -y+1, -z+1.
[Figure 2]
Figure 2
Illustration of the hydrogen-bonded dimers in the unit cell. Hydrogen bonds are represented as dashed lines.

4. Database survey

In the isotypic structure containing silicon instead of germanium, similar distortions can be observed (Haberecht et al., 2004[Haberecht, M. C., Vitze, H., Lerner, H.-W. & Bolte, M. (2004). Acta Cryst. E60, o329-o330.]). In this structure, the asymmetric unit also contains two differently deformed mol­ecules. In the first mol­ecule, a nearly planar geometry of the aromatic ring plane is exhibited. The second mol­ecule shows the same boat-shaped deformation of the aromatic ring as described for the Ge compound. The atoms equal to C12 and C15 deviate by −0.016 (1) Å and −0.017 (1) Å, respectively. The silicon atoms Si1 and Si2 exhibit distances to the aromatic ring plane of 0.088 (3) and −0.219 (2) Å, respectively. A comparison of these distances to those reported for the title compound reveals that the observed distortions occur in similar dimensions for both structures. This points to a comparable steric demand of the tri­methyl­germyl and tri­methyl­silyl moieties.

5. Synthesis and crystallization

To a solution of 1,4-di­bromo­benzene (1.50 g, 6.36 mmol) in Et2O (13 ml) was added n-BuLi (6.36 mmol, 2.5 M in hexa­ne) at 195 K and the mixture stirred at this temperature for 4 h. Then chloro­tri­methyl­germane (1.10 g, 7.00 mmol) was added to the reaction mixture at 195 K, stirred at this temperature for 10 min, followed by stirring over night at room temperature. After addition of H2O, the organic phase was separated and the aqueous phase was extracted with Et2O three times. The combined organic phases were washed with brine and dried over Na2SO4. Removal of the solvent under reduced pressure afforded (4-bromo­phen­yl)tri­methyl­germane (1.67 g, 6.12 mmol, 96%) as a colorless liquid. The reaction product was used in following syntheses without further purification.

To a solution of (4-bromo­phen­yl)tri­methyl­germane (1.67 g, 6.12 mmol) in THF (38 ml) was added n-BuLi (6.73 mmol, 2.5 M in hexa­ne) at 195 K and the mixture was stirred at this temperature for 15 minutes. Then di­methyl­formamide (1.34 g, 18.4 mmol) was added to the reaction mixture at 195 K, and it was allowed to warm to room temperature over night. After addition of a saturated aqueous NH4Cl solution, the organic phase was separated and the aqueous phase extracted three times with Et2O. The combined organic phases were washed with water and brine and dried over Na2SO4. Removal of the solvent under reduced pressure and subsequent silica gel chromatography (pentane, penta­ne/Et2O = 100:1 → 50:1) afforded 4-(tri­methyl­germ­yl)benzaldehyde, which oxidized at ambient air conditions to give 4-(tri­methyl­germ­yl)benzoic acid, (I)[link], (1.05 g, 4.70 mmol, 77%) as a colorless solid. A schematic representation of the synthetic procedure is shown in Fig. 3[link].

[Figure 3]
Figure 3
Schematic representation of the synthesis of compound (I)[link].

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3[link]. Hydrogen atoms were located from difference Fourier maps. They were refined with ideal­ized positions in a riding model with Uiso(H) = 1.2Ueq(C) and C—H = 0.95 Å for aromatic hydrogen atoms, and with Uiso(H) = 1.5Ueq(C) and C—H = 0.98 Å for methyl hydrogen atoms. All CH3 hydrogen atoms were allowed to rotate but not to tip. Hydroxyl hydrogen atoms were located from difference Fourier maps and were refined freely.

Table 3
Experimental details

Crystal data
Chemical formula [Ge(CH3)3(C7H5O2)]
Mr 238.80
Crystal system, space group Triclinic, P[\overline{1}]
Temperature (K) 173
a, b, c (Å) 6.3560 (4), 12.3927 (6), 14.2084 (7)
α, β, γ (°) 96.348 (4), 92.846 (4), 93.246 (4)
V3) 1108.76 (10)
Z 4
Radiation type Mo Kα
μ (mm−1) 2.73
Crystal size (mm) 0.08 × 0.08 × 0.02
 
Data collection
Diffractometer Agilent Xcalibur Sapphire3
Absorption correction Multi-scan (CrysAlis PRO; Agilent, 2014[Agilent (2014). CrysAlis PRO. Agilent Technologies UK Ltd, Yarnton, England.])
Tmin, Tmax 0.794, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections 15667, 4781, 3261
Rint 0.044
(sin θ/λ)max−1) 0.639
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.036, 0.083, 1.02
No. of reflections 4781
No. of parameters 249
H-atom treatment H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3) 0.54, −0.31
Computer programs: CrysAlis PRO (Agilent, 2014[Agilent (2014). CrysAlis PRO. Agilent Technologies UK Ltd, Yarnton, England.]), SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]), SHELXL2014 (Sheldrick, 2015[Sheldrick, G. M. (2015). Acta Cryst. C71, 3-8.]) and OLEX2 (Dolomanov et al., 2009[Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339-341.]).

Supporting information


Chemical context top

The application of 1,4-di­hydro­pyridines (DHPs) as a pharmaceutical tool represents a novel and promising approach in the therapy of autoimmune diseases, cancer and other illnesses. The effect of drugs containing DHPs is based on the inter­action with the Transforming Growth Factor β (TGFβ). The title compound, [Ge(CH3)3(C7H5O2)], (I), was obtained as a side-product in the synthesis of the corresponding aldehyde, which can be employed in the synthesis of DHPs (Längle et al., 2015).

Structural commentary top

The asymmetric unit of (I) contains two molecules (Fig. 1), which exhibit different deformations of the aromatic plane. This deformation may be caused by the sterically demanding substituents in 1- and 4-positions. In the first molecule, the opposite carbon atoms C2 and C5 deviate from the mean aromatic ring plane by -0.015 (2) Å, which leads to a boat-shaped deformation (Table 1). The distance of the germanium atom Ge1 to this plane is -0.210 (4) Å. Corresponding to this boat-shaped deformation, the bond lengths of the aromatic ring are not equidistant, but can be divided into three pairs of similar distances: the bonds C5—C4 [1.393 (4) Å] and C5—C6 [1.398 (4) Å] are slightly elongated, C2—C3 [1.383 (4) Å] and C2—C7 [1.384 (4) Å] lie in a medium range, and C3—C4 [1.368 (4) Å] and C6—C7 [1.379 (4) Å] are the shortest. In the second molecule, the aromatic ring exhibits a nearly planar geometry (Table 1). Similar to the first molecule, the Ge2 atom deviates from the mean aromatic ring plane by 0.101 (4) Å. Additionally, elongated bond lengths at C12 and C15 can be observed [C12—C13 1.385 (4), C12—C17 1.381 (4), C15—C14 1.393 (4), C15—C16 1.398 (4) Å].

All in all, the degree of deformation in the second molecule is smaller compared to the first molecule. This difference may be the reason for the presence of two molecules in the asymmetric unit. The deformations described above may be caused by the sterically demanding substituents attached to the aromatic ring in 1- and 4-positions, or may be traced back to packing effects.

Supra­molecular features top

The molecules in the title compound crystallize as centrosymmetric hydrogen-bonded dimers (Fig. 2, Table 2). Considering the donor···acceptor bond lengths of 2.626 (3) Å [O2—H2···O1] and 2.635 (3) Å [O4—H4A···O3], the strength of the hydrogen bonds can be classified as moderate according to Jeffrey (1997).

Database survey top

In the isotypic structure containing silicon instead of germanium, similar distortions can be observed (Haberecht et al., 2004). In this structure, the asymmetric unit also contains two differently deformed molecules. In the first molecule, a nearly planar geometry of the aromatic ring plane is exhibited. The second molecule shows the same boat-shaped deformation of the aromatic ring as described for the Ge compound. The atoms equal to C12 and C15 deviate by -0.016 (1) Å and -0.017 (1) Å, respectively. The silicon atoms Si1 and Si2 exhibit distances to the aromatic ring plane of 0.088 (3) and -0.219 (2) Å, respectively. A comparison of these distances to those reported for the title compound reveals that the observed distortions occur in similar dimensions for both structures. This points to a comparable steric demand of the tri­methyl­germyl and tri­methyl­silyl moieties.

Synthesis and crystallization top

To a solution of 1,4-di­bromo­benzene (1.50 g, 6.36 mmol) in Et2O (13 ml) was added n-BuLi (6.36 mmol, 2.5 M in hexane) at 195 K and the mixture stirred at this temperature for 4 h. Then chloro­tri­methyl­germane (1.10 g, 7.00 mmol) was added to the reaction mixture at 195 K, stirred at this temperature for 10 min, followed by stirring over night at room temperature. After addition of H2O, the organic phase was separated and the aqueous phase was extracted with Et2O three times. The combined organic phases were washed with brine and dried over Na2SO4. Removal of the solvent under reduced pressure afforded (4-bromo­phenyl)­tri­methyl­germane (1.67 g, 6.12 mmol, 96%) as a colorless liquid. The reaction product was used in following syntheses without further purification.

To a solution of (4-bromo­phenyl)­tri­methyl­germane (1.67 g, 6.12 mmol) in THF (38 ml) was added n-BuLi (6.73 mmol, 2.5 M in hexane) at 195 K and the mixture was stirred at this temperature for 15 minutes. Then di­methyl­formamide (1.34 g, 18.4 mmol) was added to the reaction mixture at 195 K, and it was allowed to warm to room temperature over night. After addition of a saturated aqueous NH4Cl solution, the organic phase was separated and the aqueous phase extracted three times with Et2O. The combined organic phases were washed with water and brine and dried over Na2SO4. Removal of the solvent under reduced pressure and subsequent silica gel chromatography (pentane, pentane/Et2O = 100:1 50:1) afforded 4-(tri­methyl­germyl)benzaldehyde, which oxidized at ambient air conditions to give 4-(tri­methyl­germyl)benzoic acid, (I), (1.05 g, 4.70 mmol, 77%) as a colorless solid. A schematic representation of the synthetic procedure is shown in Fig. 3.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 3. Hydrogen atoms were located from difference Fourier maps. They were refined with idealized positions in a riding model with Uiso(H) = 1.2Ueq(C) and C—H = 0.95 Å for aromatic hydrogen atoms, and with Uiso(H) = 1.5Ueq(C) and C—H = 0.98 Å for methyl hydrogen atoms. All CH3 hydrogen atoms were allowed to rotate but not to tip. Hydroxyl hydrogen atoms were located from difference Fourier maps and were refined freely.

Related literature top

For related literature, see: Haberecht et al. (2004); Jeffrey (1997); Längle et al. (2015).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2014); cell refinement: CrysAlis PRO (Agilent, 2014); data reduction: CrysAlis PRO (Agilent, 2014); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Figures top
[Figure 1] Fig. 1. The structures and atom numbering of the two independent molecules in the title compound. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] Fig. 2. Illustration of the hydrogen-bonded dimers in the unit cell. Hydrogen bonds are represented as dashed lines.
[Figure 3] Fig. 3. Schematic representation of the synthesis of compound (I).
4-(Trimethylgermyl)benzoic acid top
Crystal data top
[Ge(CH3)3(C7H5O2)]Z = 4
Mr = 238.80F(000) = 488
Triclinic, P1Dx = 1.431 Mg m3
a = 6.3560 (4) ÅMo Kα radiation, λ = 0.71073 Å
b = 12.3927 (6) ÅCell parameters from 4611 reflections
c = 14.2084 (7) Åθ = 2.9–28.4°
α = 96.348 (4)°µ = 2.73 mm1
β = 92.846 (4)°T = 173 K
γ = 93.246 (4)°Plate, clear colourless
V = 1108.76 (10) Å30.08 × 0.08 × 0.02 mm
Data collection top
Agilent Xcalibur Sapphire3
diffractometer
4781 independent reflections
Radiation source: Enhance (Mo) X-ray Source3261 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.044
Detector resolution: 16.0560 pixels mm-1θmax = 27.0°, θmin = 2.3°
ω scansh = 88
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2014)
k = 1515
Tmin = 0.794, Tmax = 1.000l = 1818
15667 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.036H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.083 w = 1/[σ2(Fo2) + (0.0332P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.01(Δ/σ)max < 0.001
4781 reflectionsΔρmax = 0.54 e Å3
249 parametersΔρmin = 0.31 e Å3
0 restraints
Crystal data top
[Ge(CH3)3(C7H5O2)]γ = 93.246 (4)°
Mr = 238.80V = 1108.76 (10) Å3
Triclinic, P1Z = 4
a = 6.3560 (4) ÅMo Kα radiation
b = 12.3927 (6) ŵ = 2.73 mm1
c = 14.2084 (7) ÅT = 173 K
α = 96.348 (4)°0.08 × 0.08 × 0.02 mm
β = 92.846 (4)°
Data collection top
Agilent Xcalibur Sapphire3
diffractometer
4781 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2014)
3261 reflections with I > 2σ(I)
Tmin = 0.794, Tmax = 1.000Rint = 0.044
15667 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0360 restraints
wR(F2) = 0.083H atoms treated by a mixture of independent and constrained refinement
S = 1.01Δρmax = 0.54 e Å3
4781 reflectionsΔρmin = 0.31 e Å3
249 parameters
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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ge10.34904 (5)0.43946 (2)0.19617 (2)0.02258 (10)
O10.1858 (3)0.90478 (18)0.01761 (15)0.0386 (6)
O20.0693 (4)0.9178 (2)0.08546 (16)0.0369 (6)
H20.124 (7)0.976 (4)0.060 (3)0.13 (2)*
C10.0846 (5)0.8712 (3)0.0511 (2)0.0268 (7)
C20.1569 (5)0.7738 (2)0.0910 (2)0.0237 (7)
C30.3337 (5)0.7244 (3)0.0588 (2)0.0309 (8)
H30.41400.75590.01310.037*
C40.3942 (5)0.6307 (3)0.0920 (2)0.0306 (8)
H40.51640.59850.06880.037*
C50.2814 (4)0.5813 (2)0.1589 (2)0.0230 (7)
C60.1072 (4)0.6339 (2)0.1931 (2)0.0259 (7)
H60.02910.60390.24040.031*
C70.0460 (5)0.7283 (2)0.1598 (2)0.0262 (7)
H70.07320.76240.18430.031*
C80.2619 (5)0.4263 (3)0.3237 (2)0.0355 (8)
H8A0.30640.35760.34380.053*
H8B0.10790.42750.32440.053*
H8C0.32730.48720.36720.053*
C90.1964 (5)0.3288 (3)0.1066 (2)0.0324 (8)
H9A0.23460.33880.04210.049*
H9B0.04420.33510.11150.049*
H9C0.23340.25650.12130.049*
C100.6506 (4)0.4247 (3)0.1914 (2)0.0361 (8)
H10A0.72410.47010.24530.054*
H10B0.69910.44800.13200.054*
H10C0.68080.34840.19450.054*
Ge20.64145 (5)1.05828 (3)0.30054 (2)0.02464 (10)
O30.7978 (3)0.54301 (17)0.43295 (15)0.0338 (5)
O41.0933 (4)0.6355 (2)0.49737 (16)0.0376 (6)
H4A1.133 (7)0.573 (4)0.522 (3)0.116 (19)*
C110.9143 (5)0.6285 (3)0.4488 (2)0.0267 (7)
C120.8508 (5)0.7298 (3)0.4112 (2)0.0250 (7)
C130.6552 (5)0.7320 (2)0.3641 (2)0.0276 (7)
H130.56200.66860.35510.033*
C140.5962 (5)0.8266 (2)0.3304 (2)0.0275 (7)
H140.46180.82710.29810.033*
C150.7279 (5)0.9214 (2)0.3421 (2)0.0244 (7)
C160.9254 (5)0.9163 (3)0.3887 (2)0.0306 (8)
H161.02050.97900.39680.037*
C170.9849 (5)0.8226 (2)0.4229 (2)0.0278 (7)
H171.11950.82150.45490.033*
C180.4858 (5)1.1327 (3)0.4005 (2)0.0401 (9)
H18A0.38841.08010.42540.060*
H18B0.40551.18900.37460.060*
H18C0.58511.16650.45170.060*
C190.8925 (5)1.1465 (3)0.2791 (2)0.0383 (9)
H19A0.97151.16900.33980.057*
H19B0.85171.21100.25030.057*
H19C0.98131.10390.23650.057*
C200.4583 (5)1.0264 (3)0.1866 (2)0.0404 (9)
H20A0.52490.97600.14080.061*
H20B0.43461.09400.15880.061*
H20C0.32290.99320.20240.061*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ge10.02235 (19)0.02012 (19)0.02573 (19)0.00270 (14)0.00329 (14)0.00304 (14)
O10.0510 (15)0.0342 (14)0.0335 (13)0.0061 (12)0.0093 (12)0.0124 (11)
O20.0398 (14)0.0324 (14)0.0416 (14)0.0141 (12)0.0061 (12)0.0108 (12)
C10.0287 (18)0.0262 (19)0.0240 (17)0.0001 (14)0.0020 (14)0.0015 (14)
C20.0280 (17)0.0190 (16)0.0232 (16)0.0010 (13)0.0015 (13)0.0000 (13)
C30.0338 (18)0.033 (2)0.0291 (18)0.0054 (15)0.0141 (15)0.0104 (15)
C40.0319 (18)0.0303 (19)0.0329 (18)0.0105 (15)0.0142 (15)0.0078 (15)
C50.0235 (16)0.0242 (17)0.0206 (16)0.0005 (13)0.0003 (13)0.0012 (13)
C60.0297 (17)0.0253 (18)0.0240 (16)0.0025 (14)0.0102 (14)0.0048 (14)
C70.0258 (16)0.0241 (17)0.0298 (17)0.0061 (13)0.0058 (14)0.0042 (14)
C80.045 (2)0.0308 (19)0.0326 (19)0.0042 (16)0.0076 (16)0.0084 (15)
C90.0279 (18)0.0293 (19)0.0386 (19)0.0012 (14)0.0035 (15)0.0016 (15)
C100.0236 (17)0.039 (2)0.046 (2)0.0056 (15)0.0030 (15)0.0063 (17)
Ge20.02168 (19)0.0210 (2)0.0313 (2)0.00206 (14)0.00119 (14)0.00386 (15)
O30.0441 (14)0.0212 (12)0.0352 (13)0.0003 (11)0.0028 (11)0.0024 (10)
O40.0411 (15)0.0338 (15)0.0379 (14)0.0072 (12)0.0082 (11)0.0060 (12)
C110.0357 (19)0.0264 (19)0.0187 (16)0.0078 (15)0.0043 (14)0.0010 (14)
C120.0315 (18)0.0261 (18)0.0173 (15)0.0040 (14)0.0043 (13)0.0011 (13)
C130.0284 (17)0.0234 (17)0.0302 (18)0.0018 (14)0.0000 (14)0.0020 (14)
C140.0237 (17)0.0269 (18)0.0320 (18)0.0025 (14)0.0028 (14)0.0052 (14)
C150.0257 (17)0.0225 (17)0.0250 (17)0.0037 (13)0.0019 (13)0.0018 (14)
C160.0299 (18)0.0241 (18)0.0363 (19)0.0045 (14)0.0038 (15)0.0020 (15)
C170.0250 (17)0.0258 (18)0.0321 (18)0.0041 (14)0.0059 (14)0.0030 (14)
C180.035 (2)0.040 (2)0.044 (2)0.0114 (16)0.0014 (17)0.0034 (17)
C190.0310 (19)0.032 (2)0.054 (2)0.0012 (15)0.0039 (17)0.0172 (17)
C200.042 (2)0.040 (2)0.039 (2)0.0076 (17)0.0100 (17)0.0072 (17)
Geometric parameters (Å, º) top
Ge1—C51.955 (3)Ge2—C151.955 (3)
Ge1—C81.942 (3)Ge2—C181.949 (3)
Ge1—C91.945 (3)Ge2—C191.938 (3)
Ge1—C101.939 (3)Ge2—C201.937 (3)
O1—C11.289 (3)O3—C111.250 (4)
O2—H20.93 (5)O4—H4A0.93 (5)
O2—C11.256 (3)O4—C111.295 (4)
C1—C21.476 (4)C11—C121.486 (4)
C2—C31.383 (4)C12—C131.385 (4)
C2—C71.384 (4)C12—C171.381 (4)
C3—H30.9500C13—H130.9500
C3—C41.368 (4)C13—C141.379 (4)
C4—H40.9500C14—H140.9500
C4—C51.393 (4)C14—C151.393 (4)
C5—C61.398 (4)C15—C161.398 (4)
C6—H60.9500C16—H160.9500
C6—C71.379 (4)C16—C171.374 (4)
C7—H70.9500C17—H170.9500
C8—H8A0.9800C18—H18A0.9800
C8—H8B0.9800C18—H18B0.9800
C8—H8C0.9800C18—H18C0.9800
C9—H9A0.9800C19—H19A0.9800
C9—H9B0.9800C19—H19B0.9800
C9—H9C0.9800C19—H19C0.9800
C10—H10A0.9800C20—H20A0.9800
C10—H10B0.9800C20—H20B0.9800
C10—H10C0.9800C20—H20C0.9800
C8—Ge1—C5109.93 (12)C18—Ge2—C15108.31 (13)
C8—Ge1—C9109.99 (13)C19—Ge2—C15108.52 (13)
C9—Ge1—C5107.50 (13)C19—Ge2—C18110.01 (15)
C10—Ge1—C5109.30 (13)C20—Ge2—C15108.88 (13)
C10—Ge1—C8109.89 (14)C20—Ge2—C18109.23 (14)
C10—Ge1—C9110.19 (13)C20—Ge2—C19111.81 (15)
C1—O2—H2122 (3)C11—O4—H4A116 (3)
O1—C1—C2117.5 (3)O3—C11—O4123.6 (3)
O2—C1—O1123.2 (3)O3—C11—C12120.3 (3)
O2—C1—C2119.3 (3)O4—C11—C12116.0 (3)
C3—C2—C1120.8 (3)C13—C12—C11120.0 (3)
C3—C2—C7118.6 (3)C17—C12—C11120.6 (3)
C7—C2—C1120.6 (3)C17—C12—C13119.3 (3)
C2—C3—H3119.6C12—C13—H13120.1
C4—C3—C2120.8 (3)C14—C13—C12119.7 (3)
C4—C3—H3119.6C14—C13—H13120.1
C3—C4—H4119.1C13—C14—H14119.0
C3—C4—C5121.7 (3)C13—C14—C15122.0 (3)
C5—C4—H4119.1C15—C14—H14119.0
C4—C5—Ge1121.8 (2)C14—C15—Ge2122.6 (2)
C4—C5—C6116.8 (3)C14—C15—C16117.0 (3)
C6—C5—Ge1121.2 (2)C16—C15—Ge2120.4 (2)
C5—C6—H6119.3C15—C16—H16119.3
C7—C6—C5121.5 (3)C17—C16—C15121.4 (3)
C7—C6—H6119.3C17—C16—H16119.3
C2—C7—H7119.8C12—C17—H17119.7
C6—C7—C2120.4 (3)C16—C17—C12120.6 (3)
C6—C7—H7119.8C16—C17—H17119.7
Ge1—C8—H8A109.5Ge2—C18—H18A109.5
Ge1—C8—H8B109.5Ge2—C18—H18B109.5
Ge1—C8—H8C109.5Ge2—C18—H18C109.5
H8A—C8—H8B109.5H18A—C18—H18B109.5
H8A—C8—H8C109.5H18A—C18—H18C109.5
H8B—C8—H8C109.5H18B—C18—H18C109.5
Ge1—C9—H9A109.5Ge2—C19—H19A109.5
Ge1—C9—H9B109.5Ge2—C19—H19B109.5
Ge1—C9—H9C109.5Ge2—C19—H19C109.5
H9A—C9—H9B109.5H19A—C19—H19B109.5
H9A—C9—H9C109.5H19A—C19—H19C109.5
H9B—C9—H9C109.5H19B—C19—H19C109.5
Ge1—C10—H10A109.5Ge2—C20—H20A109.5
Ge1—C10—H10B109.5Ge2—C20—H20B109.5
Ge1—C10—H10C109.5Ge2—C20—H20C109.5
H10A—C10—H10B109.5H20A—C20—H20B109.5
H10A—C10—H10C109.5H20A—C20—H20C109.5
H10B—C10—H10C109.5H20B—C20—H20C109.5
Ge1—C5—C6—C7173.3 (2)Ge2—C15—C16—C17176.5 (2)
O1—C1—C2—C33.4 (4)O3—C11—C12—C134.5 (4)
O1—C1—C2—C7175.0 (3)O3—C11—C12—C17175.6 (3)
O2—C1—C2—C3176.0 (3)O4—C11—C12—C13175.5 (3)
O2—C1—C2—C75.6 (5)O4—C11—C12—C174.4 (4)
C1—C2—C3—C4176.4 (3)C11—C12—C13—C14179.3 (3)
C1—C2—C7—C6176.4 (3)C11—C12—C17—C16179.6 (3)
C2—C3—C4—C50.1 (5)C12—C13—C14—C150.1 (5)
C3—C2—C7—C62.0 (5)C13—C12—C17—C160.3 (4)
C3—C4—C5—Ge1173.2 (2)C13—C14—C15—Ge2176.8 (2)
C3—C4—C5—C62.1 (5)C13—C14—C15—C161.0 (4)
C4—C5—C6—C72.1 (4)C14—C15—C16—C171.3 (4)
C5—C6—C7—C20.0 (5)C15—C16—C17—C120.7 (5)
C7—C2—C3—C42.0 (5)C17—C12—C13—C140.6 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2···O1i0.93 (5)1.71 (5)2.626 (3)170 (5)
O4—H4A···O3ii0.93 (5)1.70 (5)2.635 (3)179 (4)
Symmetry codes: (i) x, y+2, z; (ii) x+2, y+1, z+1.
Deviation of atoms from the benzene ring least-squares planes (Å) top
AtomDeviationAtomDeviation
C2-0.015 (2)C120.004 (2)
C30.007 (2)C13-0.003 (2)
C40.008C14-0.003 (2)
C5-0.015 (2)C150.007 (2)
C60.007 (2)C16-0.006
C70.007 (2)C170.000 (4)
Ge1*-0.210 (4)Ge2*0.101 (4)
Note: (*) not used in the least-squares-plane calculation.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2···O1i0.93 (5)1.71 (5)2.626 (3)170 (5)
O4—H4A···O3ii0.93 (5)1.70 (5)2.635 (3)179 (4)
Symmetry codes: (i) x, y+2, z; (ii) x+2, y+1, z+1.

Experimental details

Crystal data
Chemical formula[Ge(CH3)3(C7H5O2)]
Mr238.80
Crystal system, space groupTriclinic, P1
Temperature (K)173
a, b, c (Å)6.3560 (4), 12.3927 (6), 14.2084 (7)
α, β, γ (°)96.348 (4), 92.846 (4), 93.246 (4)
V3)1108.76 (10)
Z4
Radiation typeMo Kα
µ (mm1)2.73
Crystal size (mm)0.08 × 0.08 × 0.02
Data collection
DiffractometerAgilent Xcalibur Sapphire3
diffractometer
Absorption correctionMulti-scan
(CrysAlis PRO; Agilent, 2014)
Tmin, Tmax0.794, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections
15667, 4781, 3261
Rint0.044
(sin θ/λ)max1)0.639
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.036, 0.083, 1.01
No. of reflections4781
No. of parameters249
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.54, 0.31

Computer programs: CrysAlis PRO (Agilent, 2014), SHELXS97 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015), OLEX2 (Dolomanov et al., 2009).

 

Acknowledgements

We are grateful to the Deutsche Forschungsgemeinschaft (DFG) for financial support.

References

First citationAgilent (2014). CrysAlis PRO. Agilent Technologies UK Ltd, Yarnton, England.  Google Scholar
First citationDolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationHaberecht, M. C., Vitze, H., Lerner, H.-W. & Bolte, M. (2004). Acta Cryst. E60, o329–o330.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationJeffrey, G. A. (1997). In An Introduction to Hydrogen Bonding. Oxford University Press.  Google Scholar
First citationLängle, D., Marquardt, V., Heider, E., Vigante, B., Duburs, G., Luntena, I., Flötgen, D., Golz, C., Strohmann, C., Koch, O. & Schade, D. (2015). Eur. J. Med. Chem. 95, 249–266.  PubMed Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSheldrick, G. M. (2015). Acta Cryst. C71, 3–8.  Web of Science CrossRef IUCr Journals Google Scholar

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Volume 71| Part 6| June 2015| Pages 687-689
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