Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101009258/da1190sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101009258/da1190Isup2.hkl |
CCDC reference: 173345
A solution of K2[Ge(C2O4)3]·H2O (0.440 g, 1.02 mmol) in warm water (ca 15 ml) and a solution of Ph4PBr (0.853 g, 2.03 mmol) in methanol (ca 15 ml) were mixed, producing a white precipitate. The solid white product was separated by filtration, washed with water:methanol (1:1 v/v), dried and dissolved in boiling methanol. X-ray quality crystals of (I) were obtained as part of the second batch of crystals formed when the methanolic solution was allowed to cool to room temperature.
The asymmetric unit of (I) consists of one cation and half of one anion. The A single ring was used to model all four phenyl rings, with their location and orientation as variables. H atoms were included in calculated positions and were not refined. The thermal motion of each phenyl ring was described by a 12 parameter TL model (where T is the translation tensor and L is the libration tensor).
Data collection: CAD-4 Operations Manual (Enraf-Nonius, 1977); cell refinement: CAD-4 Operations Manual; data reduction: local programs; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: RAELS (Rae, 1989); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: local programs.
2C24H20P+·C6O12Ge2− | F(000) = 2088.0 |
Mr = 1015.4 | Dx = 1.42 Mg m−3 |
Monoclinic, C2/c | Cu Kα radiation, λ = 1.5418 Å |
a = 22.759 (5) Å | Cell parameters from 10 reflections |
b = 13.618 (2) Å | θ = 25–27° |
c = 15.813 (3) Å | µ = 2.04 mm−1 |
β = 104.34 (1)° | T = 294 K |
V = 4748 (2) Å3 | Plate, colourless |
Z = 4 | 0.15 × 0.13 × 0.06 mm |
Nonius CAD-4 diffractometer | Rint = 0.017 |
ω/2θ scans | θmax = 70° |
Absorption correction: analytical (de Meulenaer & Tompa, 1965) | h = −27→27 |
Tmin = 0.64, Tmax = 0.90 | k = −16→0 |
4616 measured reflections | l = 0→19 |
4439 independent reflections | 1 standard reflections every 30min min |
3646 reflections with I > 3σ(I) | intensity decay: none |
Refinement on F | H-atom parameters not refined |
R[F2 > 2σ(F2)] = 0.034 | w = 1/[σ2(F) + 0.0016F2] |
wR(F2) = 0.050 | (Δ/σ)max = 0.013 |
S = 1.78 | Δρmax = 0.38 e Å−3 |
3646 reflections | Δρmin = −0.40 e Å−3 |
174 parameters |
2C24H20P+·C6O12Ge2− | V = 4748 (2) Å3 |
Mr = 1015.4 | Z = 4 |
Monoclinic, C2/c | Cu Kα radiation |
a = 22.759 (5) Å | µ = 2.04 mm−1 |
b = 13.618 (2) Å | T = 294 K |
c = 15.813 (3) Å | 0.15 × 0.13 × 0.06 mm |
β = 104.34 (1)° |
Nonius CAD-4 diffractometer | 3646 reflections with I > 3σ(I) |
Absorption correction: analytical (de Meulenaer & Tompa, 1965) | Rint = 0.017 |
Tmin = 0.64, Tmax = 0.90 | 1 standard reflections every 30min min |
4616 measured reflections | intensity decay: none |
4439 independent reflections |
R[F2 > 2σ(F2)] = 0.034 | 174 parameters |
wR(F2) = 0.050 | H-atom parameters not refined |
S = 1.78 | Δρmax = 0.38 e Å−3 |
3646 reflections | Δρmin = −0.40 e Å−3 |
x | y | z | Uiso*/Ueq | ||
Ge | 0.50000 (1) | 0.67883 (3) | 0.25000 (1) | 0.0390 (1) | |
O1Ox1 | 0.3675 (1) | 0.5235 (2) | 0.2879 (2) | 0.0875 (7) | |
O2Ox1 | 0.4597 (1) | 0.5879 (1) | 0.3033 (1) | 0.0542 (4) | |
O3Ox1 | 0.3365 (1) | 0.6153 (2) | 0.1224 (2) | 0.0941 (8) | |
O4Ox1 | 0.4307 (1) | 0.6750 (1) | 0.1569 (1) | 0.0532 (4) | |
C1Ox1 | 0.4027 (1) | 0.5720 (2) | 0.2605 (2) | 0.0553 (6) | |
C2Ox1 | 0.3860 (1) | 0.6225 (2) | 0.1720 (2) | 0.0570 (6) | |
O1Ox2 | 0.5217 (1) | 0.9419 (2) | 0.1738 (2) | 0.108 (1) | |
O2Ox2 | 0.5293 (1) | 0.7799 (1) | 0.1906 (1) | 0.0531 (4) | |
COx2 | 0.5141 (1) | 0.8670 (2) | 0.2114 (2) | 0.0637 (8) | |
P | 0.3387 (1) | 0.2199 (1) | 0.1827 (1) | 0.0404 (2) | |
C1 | 0.3836 (1) | 0.2781 (1) | 0.1193 (1) | 0.0427 (5) | |
C2 | 0.4276 (1) | 0.3466 (1) | 0.1573 (1) | 0.0545 (5) | |
C3 | 0.4579 (1) | 0.3989 (1) | 0.1059 (1) | 0.0652 (6) | |
C4 | 0.4444 (1) | 0.3831 (2) | 0.0169 (1) | 0.0656 (7) | |
C5 | 0.4008 (1) | 0.3153 (2) | −0.0213 (1) | 0.0687 (8) | |
C6 | 0.3703 (1) | 0.2626 (1) | 0.0296 (1) | 0.0566 (6) | |
C7 | 0.3201 (1) | 0.0988 (1) | 0.1382 (1) | 0.0471 (6) | |
C8 | 0.3665 (1) | 0.0384 (1) | 0.1254 (1) | 0.0600 (6) | |
C9 | 0.3531 (1) | −0.0545 (1) | 0.0900 (1) | 0.0774 (9) | |
C10 | 0.2939 (1) | −0.0872 (1) | 0.0674 (1) | 0.0817 (9) | |
C11 | 0.2476 (1) | −0.0277 (2) | 0.0799 (1) | 0.0775 (7) | |
C12 | 0.2605 (1) | 0.0653 (1) | 0.1153 (1) | 0.0604 (6) | |
C13 | 0.3794 (1) | 0.2167 (1) | 0.2950 (1) | 0.0426 (6) | |
C14 | 0.4232 (1) | 0.1451 (1) | 0.3256 (1) | 0.0566 (6) | |
C15 | 0.4550 (1) | 0.1448 (1) | 0.4126 (1) | 0.0644 (8) | |
C16 | 0.4434 (1) | 0.2155 (1) | 0.4689 (1) | 0.0611 (8) | |
C17 | 0.4001 (1) | 0.2867 (2) | 0.4390 (1) | 0.0712 (9) | |
C18 | 0.3680 (1) | 0.2876 (1) | 0.3522 (1) | 0.0607 (7) | |
C19 | 0.2722 (1) | 0.2923 (1) | 0.1770 (1) | 0.0453 (5) | |
C20 | 0.2292 (1) | 0.2618 (1) | 0.2203 (1) | 0.0547 (4) | |
C21 | 0.1792 (1) | 0.3203 (2) | 0.2194 (1) | 0.0675 (5) | |
C22 | 0.1721 (1) | 0.4088 (1) | 0.1756 (1) | 0.0711 (6) | |
C23 | 0.2146 (1) | 0.4396 (1) | 0.1324 (1) | 0.0675 (7) | |
C24 | 0.2647 (1) | 0.3816 (1) | 0.1329 (1) | 0.0547 (5) | |
HC2 | 0.4374 | 0.3581 | 0.2218 | 0.069 | |
HC3 | 0.4895 | 0.4481 | 0.1332 | 0.087 | |
HC4 | 0.4663 | 0.4210 | −0.0200 | 0.079 | |
HC5 | 0.3913 | 0.3042 | −0.0858 | 0.093 | |
HC6 | 0.3387 | 0.2135 | 0.0018 | 0.072 | |
HC8 | 0.4094 | 0.0620 | 0.1418 | 0.069 | |
HC9 | 0.3864 | −0.0979 | 0.0808 | 0.100 | |
HC10 | 0.2844 | −0.1542 | 0.0419 | 0.102 | |
HC11 | 0.2048 | −0.0518 | 0.0634 | 0.100 | |
HC12 | 0.2270 | 0.1083 | 0.1243 | 0.070 | |
HC14 | 0.4317 | 0.0939 | 0.2849 | 0.079 | |
HC15 | 0.4865 | 0.0934 | 0.4345 | 0.090 | |
HC16 | 0.4664 | 0.2150 | 0.5315 | 0.072 | |
HC17 | 0.3918 | 0.3377 | 0.4801 | 0.104 | |
HC18 | 0.3366 | 0.3393 | 0.3307 | 0.084 | |
HC20 | 0.2343 | 0.1977 | 0.2522 | 0.061 | |
HC21 | 0.1483 | 0.2984 | 0.2506 | 0.083 | |
HC22 | 0.1360 | 0.4508 | 0.1751 | 0.086 | |
HC23 | 0.2092 | 0.5038 | 0.1007 | 0.083 | |
HC24 | 0.2955 | 0.4040 | 0.1015 | 0.061 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ge | 0.0409 (2) | 0.0421 (2) | 0.0328 (2) | 0.0000 (1) | 0.0066 (1) | 0.0000 (1) |
O1Ox1 | 0.089 (2) | 0.086 (2) | 0.098 (2) | −0.030 (1) | 0.042 (1) | 0.007 (1) |
O2Ox1 | 0.058 (1) | 0.054 (1) | 0.053 (1) | 0.0044 (8) | 0.0178 (8) | 0.0165 (8) |
O3Ox1 | 0.057 (1) | 0.128 (2) | 0.084 (2) | −0.034 (1) | −0.007 (1) | 0.004 (2) |
O4Ox1 | 0.0479 (9) | 0.066 (1) | 0.0402 (9) | −0.0165 (8) | 0.0001 (7) | 0.0046 (8) |
C1Ox1 | 0.060 (1) | 0.047 (1) | 0.064 (2) | −0.008 (1) | 0.025 (1) | −0.003 (1) |
C2Ox1 | 0.052 (1) | 0.062 (2) | 0.055 (2) | −0.011 (1) | 0.008 (1) | −0.006 (1) |
O1Ox2 | 0.089 (2) | 0.061 (1) | 0.169 (3) | −0.014 (1) | 0.021 (2) | 0.043 (2) |
O2Ox2 | 0.0494 (9) | 0.054 (1) | 0.054 (1) | −0.0112 (7) | 0.0105 (8) | 0.0070 (8) |
COx2 | 0.041 (1) | 0.051 (1) | 0.089 (2) | −0.009 (1) | −0.004 (1) | 0.011 (2) |
P | 0.0379 (3) | 0.0484 (3) | 0.0340 (3) | −0.0029 (2) | 0.0075 (2) | −0.0019 (2) |
C1 | 0.0387 (7) | 0.0481 (8) | 0.0398 (7) | −0.0036 (7) | 0.0066 (6) | −0.0047 (6) |
C2 | 0.0534 (8) | 0.0621 (9) | 0.0496 (6) | −0.0189 (7) | 0.0157 (6) | −0.0129 (6) |
C3 | 0.070 (1) | 0.069 (1) | 0.0622 (9) | −0.0274 (8) | 0.0274 (9) | −0.0146 (8) |
C4 | 0.069 (1) | 0.074 (1) | 0.0580 (8) | −0.020 (1) | 0.0243 (8) | −0.0022 (8) |
C5 | 0.068 (1) | 0.094 (1) | 0.0453 (6) | −0.0253 (9) | 0.0157 (7) | −0.0018 (7) |
C6 | 0.0534 (9) | 0.076 (1) | 0.0397 (7) | −0.0178 (7) | 0.0098 (6) | −0.0061 (6) |
C7 | 0.0509 (9) | 0.0527 (7) | 0.038 (1) | −0.0080 (5) | 0.0106 (7) | −0.0027 (6) |
C8 | 0.0677 (8) | 0.0581 (7) | 0.054 (1) | 0.0024 (7) | 0.0152 (8) | −0.0085 (7) |
C9 | 0.105 (1) | 0.0590 (7) | 0.067 (1) | 0.0035 (8) | 0.018 (1) | −0.0137 (7) |
C10 | 0.120 (2) | 0.0580 (7) | 0.062 (1) | −0.0186 (7) | 0.013 (1) | −0.0125 (8) |
C11 | 0.091 (1) | 0.0695 (9) | 0.067 (1) | −0.0329 (9) | 0.010 (1) | −0.0126 (9) |
C12 | 0.0587 (8) | 0.0653 (8) | 0.055 (1) | −0.0212 (6) | 0.0105 (8) | −0.0080 (7) |
C13 | 0.0453 (8) | 0.0458 (8) | 0.0376 (6) | −0.0002 (7) | 0.0119 (5) | 0.0003 (5) |
C14 | 0.0637 (9) | 0.0540 (8) | 0.0457 (6) | 0.0108 (7) | 0.0016 (6) | −0.0007 (5) |
C15 | 0.073 (1) | 0.062 (1) | 0.0480 (7) | 0.0072 (8) | −0.0035 (7) | 0.0030 (6) |
C16 | 0.068 (1) | 0.071 (1) | 0.0400 (6) | −0.0042 (9) | 0.0046 (6) | 0.0020 (5) |
C17 | 0.080 (1) | 0.088 (1) | 0.0410 (6) | 0.0148 (9) | 0.0058 (6) | −0.0127 (6) |
C18 | 0.067 (1) | 0.071 (1) | 0.0410 (6) | 0.0155 (7) | 0.0079 (6) | −0.0108 (6) |
C19 | 0.0412 (6) | 0.0538 (8) | 0.040 (1) | −0.0040 (5) | 0.0082 (6) | −0.0030 (7) |
C20 | 0.0439 (6) | 0.0672 (8) | 0.056 (1) | −0.0051 (6) | 0.0175 (7) | −0.0052 (6) |
C21 | 0.0466 (6) | 0.085 (1) | 0.074 (1) | 0.0009 (7) | 0.0199 (7) | −0.0130 (9) |
C22 | 0.0521 (7) | 0.082 (1) | 0.075 (2) | 0.0123 (8) | 0.0083 (8) | −0.015 (1) |
C23 | 0.0626 (9) | 0.0677 (8) | 0.067 (1) | 0.0141 (8) | 0.0066 (8) | −0.0013 (7) |
C24 | 0.0545 (7) | 0.0566 (8) | 0.051 (1) | 0.0037 (6) | 0.0089 (6) | 0.0025 (7) |
Ge—O2Ox1 | 1.862 (2) | P—C1 | 1.784 (2) |
Ge—O4Ox1 | 1.873 (2) | P—C7 | 1.802 (2) |
Ge—O2Ox2 | 1.879 (2) | P—C13 | 1.789 (2) |
O1Ox1—C1Ox1 | 1.200 (3) | P—C19 | 1.789 (2) |
O2Ox1—C1Ox1 | 1.323 (3) | C1—C2 | 1.392 (1) |
O3Ox1—C2Ox1 | 1.207 (3) | C1—C6 | 1.392 (1) |
O4Ox1—C2Ox1 | 1.312 (3) | C2—C3 | 1.386 (1) |
C1Ox1—C2Ox1 | 1.520 (4) | C3—C4 | 1.380 (1) |
O1Ox2—COx2 | 1.214 (3) | C4—C5 | 1.380 (1) |
O2Ox2—COx2 | 1.300 (3) | C5—C6 | 1.386 (1) |
COx2—COx2i | 1.514 (6) | ||
O2Ox1—Ge—O4Ox1 | 85.6 (1) | O2Ox2—COx2—COx2i | 113.3 (2) |
O2Ox1—Ge—O2Ox2 | 171.3 (1) | C1—P—C7 | 107.4 (1) |
O2Ox1—Ge—O2Ox1i | 96.7 (1) | C1—P—C13 | 109.9 (1) |
O2Ox1—Ge—O4Ox1i | 92.3 (1) | C1—P—C19 | 108.8 (1) |
O2Ox1—Ge—O2Ox2i | 89.2 (1) | C7—P—C13 | 112.3 (1) |
O4Ox1—Ge—O2Ox2 | 87.8 (1) | C7—P—C19 | 111.7 (1) |
O4Ox1—Ge—O2Ox1i | 92.3 (1) | C13—P—C19 | 106.7 (1) |
O4Ox1—Ge—O4Ox1i | 176.8 (1) | P—C1—C2 | 120.4 (1) |
O4Ox1—Ge—O2Ox2i | 94.5 (1) | P—C1—C6 | 119.7 (1) |
O2Ox2—Ge—O2Ox2i | 85.8 (1) | C2—C1—C6 | 119.6 (1) |
Ge—O2Ox1—C1Ox1 | 114.1 (2) | C1—C2—C3 | 120.0 (1) |
Ge—O4Ox1—C2Ox1 | 114.3 (2) | C2—C3—C4 | 120.1 (1) |
O1Ox1—C1Ox1—O2Ox1 | 124.2 (3) | C3—C4—C5 | 120.3 (1) |
O1Ox1—C1Ox1—C2Ox1 | 123.0 (3) | C4—C5—C6 | 120.1 (1) |
O2Ox1—C1Ox1—C2Ox1 | 112.8 (2) | C1—C6—C5 | 120.0 (1) |
O3Ox1—C2Ox1—O4Ox1 | 124.6 (3) | P—C7—C8 | 119.0 (1) |
O3Ox1—C2Ox1—C1Ox1 | 122.8 (3) | P—C7—C12 | 121.5 (1) |
O4Ox1—C2Ox1—C1Ox1 | 112.7 (2) | P—C13—C14 | 120.8 (1) |
Ge—O2Ox2—COx2 | 113.2 (2) | P—C13—C18 | 119.6 (1) |
O1Ox2—COx2—O2Ox2 | 124.3 (3) | P—C19—C20 | 120.1 (1) |
O1Ox2—COx2—COx2i | 122.4 (2) | P—C19—C24 | 120.3 (1) |
Symmetry code: (i) −x+1, y, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | 2C24H20P+·C6O12Ge2− |
Mr | 1015.4 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 294 |
a, b, c (Å) | 22.759 (5), 13.618 (2), 15.813 (3) |
β (°) | 104.34 (1) |
V (Å3) | 4748 (2) |
Z | 4 |
Radiation type | Cu Kα |
µ (mm−1) | 2.04 |
Crystal size (mm) | 0.15 × 0.13 × 0.06 |
Data collection | |
Diffractometer | Nonius CAD-4 diffractometer |
Absorption correction | Analytical (de Meulenaer & Tompa, 1965) |
Tmin, Tmax | 0.64, 0.90 |
No. of measured, independent and observed [I > 3σ(I)] reflections | 4616, 4439, 3646 |
Rint | 0.017 |
(sin θ/λ)max (Å−1) | 0.609 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.050, 1.78 |
No. of reflections | 3646 |
No. of parameters | 174 |
No. of restraints | ? |
H-atom treatment | H-atom parameters not refined |
Δρmax, Δρmin (e Å−3) | 0.38, −0.40 |
Computer programs: CAD-4 Operations Manual (Enraf-Nonius, 1977), CAD-4 Operations Manual, local programs, SIR92 (Altomare et al., 1994), RAELS (Rae, 1989), ORTEPII (Johnson, 1976).
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As part of a study of the packing of salts of phenylphosphonium cations (Dance & Scudder, 1995, 1996, 1998; Hasselgren et al., 1997), we have characterized the new salt (PPh4)2[Ge(C2O4)3], (I). The structure consists of recognizable PPh4+ cations and [Ge(C2O4)3]2- anions, the latter having crystallographic twofold symmetry (Fig. 1). The structure is almost isostructural with that of (AsPh4)2[Tc(C2O4)3] (Colmanet et al., 1987). \sch
The bond distances and angles within the anion (Fig. 1 and Table 1) can be compared with those found in K2[Ge(C2O4)3]·H2O, (II) (Jorgensen & Weakley, 1980). The s.u.s found for (I) are smaller than those found for (II). In no case do the bond distances or ligand bite angles observed for the anion in (I) differ significantly from those observed in (II). In addition, the C—Oterminal distances of (I) do not differ significantly from each other, even though atom O1Ox1 appears to be involved in an Anion···Cation interaction, as discussed below.
The cations in (I) are linked into pairs, closest approach 6.229 (1) Å, by a sixfold phenyl embrace, or 6PE, which is an attractive interaction (Dance & Scudder, 1995, 1996, 1998). In addition, each cation is linked to a further cation at a distance of 7.118 (1) Å by a fourfold phenyl embrace, or 4PE (Dance & Scudder, 1998). This 4PE is unusual in that it is made up of two offset face-to-face interactions, with a twofold axis bisecting the P···P vector, instead of the more commonly found centre of inversion at its midpoint. The P···P···P angle is 131.4 (1)°. In this way, infinite zigzag chains of alternating 6- and 4PEs are formed. However, the longer P···P distance is associated not only with the 4PE, but also with cation-anion interactions.
The single shortest P···O interaction at each P atom is 4.444 (2) Å. While this is longer than the sum of the van der Waals radii (3.35 Å; Bondi, 1964), the near-linearity of O1Ox1, P and the distal carbon [O···P—Cdistal 175.0 (1)°] is reminiscent of the near-linearity of P···P—Cdistal that characterizes the 6PE (Dance & Scudder, 1995, 1996). As in the 6PE, the linearity is presumably indicative of an attractive interaction. A study of [MePh3P]2[Cr2O7] shows that such attraction occurs via C—H···O hydrogen bonding (Lorenzo et al., 1999). In the present case, the shortest H···O distances are 2.74 and 3.09 Å, compared with values of 2.39–3.15 Å in [MePh3P]2[Cr2O7]. The twofold axis referred to above leads to two identical P···O interactions emanating from a single anion spanning each 4PE (Fig. 2). Similarly modified zigzag chains occur in (AsPh4)2[Tc(C2O4)3], where the As···As distances are 6.27 and 7.23 Å, the As···O distance is 4.35 Å and the O···As—C angle is 174.3°. Related chains also occur in (AsPh4)2[Zn(S2C2O2)2] (Golic et al., 1986). In this Zn salt there are two chains, one with As···As distances of 6.48 and 7.26 Å, the other with distances of 6.06 and 8.06 Å. Each chain is associated with one end of the anion to form two different O···As contacts, at 4.49 and 5.16 Å, the corresponding O···As—Cdistal angles being 163.6 and 167.5°.
In summary, the structure of (I) has allowed the recognition of an unusual chain structure of the cations occurring here and in some other EPh4+ salts of oxygen-bearing anions.