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A new three-dimensional open-framework germanate, namely ethylenediamine bis(ethylenediammonium) tetrahydroxooctadecaoxononagermanate, (C2H8N2)(C2H10N2)2[Ge9O18(OH)4], has been synthesized hydrothermally and its structure determined by single-crystal X-ray diffraction. The framework is built of [Ge9O22(OH)4] units formed by four-, five- and six-oxygen-coordinated germanium and templated by ethylenediamine. Three types of intersecting channels are formed in the framework, one by eight-membered rings running along the b axis and the other two by ten-membered rings running parallel to the a and c axes, respectively.
Supporting information
CCDC reference: 150768
Data collection: EXPOSE (Stoe & Cie, 1997b); cell refinement: CELL (Stoe & Cie, 1997b); data reduction: INTEGRATE (Stoe & Cie, 1997b); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Bergerhoff, 1996).
Crystal data top
(C2H8N2)(C2H10N2)2[H4Ge9O22] | F(000) = 1148 |
Mr = 1193.68 | Dx = 2.961 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 10.1958 (15) Å | Cell parameters from 5000 reflections |
b = 9.9753 (10) Å | θ = 2.9–26.0° |
c = 13.1655 (19) Å | µ = 10.06 mm−1 |
β = 90.695 (17)° | T = 293 K |
V = 1338.9 (3) Å3 | Prism, colourless |
Z = 2 | 0.06 × 0.04 × 0.04 mm |
Data collection top
STOE IPDS diffractometer | 2598 independent reflections |
Radiation source: fine-focus sealed tube | 2077 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.058 |
Detector resolution: 6.0 pixels mm-1 | θmax = 26.0°, θmin = 2.9° |
φ–oscill., φ–incr. = 1.5°; 133 exposures scans | h = −12→12 |
Absorption correction: numerical (XRED; Stoe & Cie, 1997a) | k = −11→12 |
Tmin = 0.577, Tmax = 0.721 | l = −16→16 |
10190 measured reflections | |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.027 | H-atom parameters constrained |
wR(F2) = 0.058 | w = 1/[σ2(Fo2) + (0.0315P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.96 | (Δ/σ)max = 0.041 |
2598 reflections | Δρmax = 0.80 e Å−3 |
204 parameters | Δρmin = −0.63 e Å−3 |
3 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.00047 (18) |
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 | x | y | z | Uiso*/Ueq | |
Ge1 | 0.5000 | 0.0000 | 0.0000 | 0.00530 (14) | |
Ge2 | 0.66385 (4) | 0.11685 (4) | 0.22083 (3) | 0.00670 (12) | |
Ge3 | 0.38181 (4) | 0.16338 (4) | 0.22955 (3) | 0.00800 (12) | |
Ge4 | 0.37016 (4) | 0.17895 (4) | −0.16785 (3) | 0.00633 (12) | |
Ge5 | 0.66835 (4) | 0.13366 (4) | −0.16933 (3) | 0.00673 (12) | |
O1 | 0.3862 (3) | 0.1442 (3) | −0.0388 (2) | 0.0099 (6) | |
O2 | 0.5145 (3) | 0.0677 (3) | 0.1338 (2) | 0.0073 (6) | |
O3 | 0.7882 (3) | 0.1684 (3) | 0.3194 (2) | 0.0113 (6) | |
O4 | 0.6463 (3) | 0.1004 (3) | −0.0407 (2) | 0.0102 (6) | |
O5 | 0.2897 (3) | 0.0122 (3) | 0.2377 (2) | 0.0143 (7) | |
O6 | 0.7432 (3) | 0.2095 (3) | 0.1243 (2) | 0.0139 (7) | |
H1 | 0.7163 | 0.1846 | 0.0685 | 0.017* | |
O7 | 0.5342 (3) | 0.1864 (3) | 0.2947 (2) | 0.0129 (7) | |
O8 | 0.5254 (3) | 0.2072 (3) | −0.2226 (2) | 0.0128 (6) | |
O9 | 0.3406 (3) | 0.2767 (3) | 0.1307 (2) | 0.0173 (7) | |
H2 | 0.3454 | 0.2383 | 0.0758 | 0.021* | |
O10 | 0.2939 (3) | 0.2503 (3) | 0.3284 (2) | 0.0132 (7) | |
O11 | 0.7151 (3) | −0.0528 (3) | 0.2336 (2) | 0.0127 (7) | |
C1 | 0.5575 (5) | 0.4524 (5) | 0.0077 (4) | 0.0273 (12) | |
H1A | 0.5368 | 0.3653 | −0.0209 | 0.033* | |
H1B | 0.6346 | 0.4871 | −0.0258 | 0.033* | |
N1 | 0.5825 (5) | 0.4405 (5) | 0.1180 (3) | 0.0293 (11) | |
H1C | 0.6178 | 0.5164 | 0.1411 | 0.035* | |
H1D | 0.6376 | 0.3729 | 0.1297 | 0.035* | |
H1E | 0.5073 | 0.4251 | 0.1495 | 0.035* | |
C2 | 0.4830 (7) | 0.0688 (7) | 0.5199 (5) | 0.0409 (16) | |
H2A | 0.4136 | 0.1064 | 0.4777 | 0.049* | |
H2B | 0.4494 | 0.0598 | 0.5882 | 0.049* | |
N2 | 0.5918 (6) | 0.1605 (6) | −0.4781 (4) | 0.0471 (15) | |
H2C | 0.6557 | 0.1274 | −0.4388 | 0.057* | |
H2D | 0.5658 | 0.2390 | −0.4533 | 0.057* | |
H2E | 0.6214 | 0.1719 | −0.5408 | 0.057* | |
C3 | 0.5232 (13) | 0.5073 (10) | −0.4518 (6) | 0.092 (4) | |
H3A | 0.4699 | 0.5747 | −0.4188 | 0.110* | |
H3B | 0.6114 | 0.5432 | −0.4558 | 0.110* | |
N3 | 0.5281 (6) | 0.3920 (7) | −0.3866 (5) | 0.0487 (15) | |
H3C | 0.449 (3) | 0.366 (7) | −0.366 (4) | 0.058* | |
H3D | 0.580 (5) | 0.402 (8) | −0.331 (3) | 0.058* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Ge1 | 0.0061 (3) | 0.0048 (3) | 0.0050 (3) | −0.0004 (2) | −0.0009 (2) | 0.0004 (2) |
Ge2 | 0.0065 (2) | 0.0050 (2) | 0.0086 (2) | −0.00009 (16) | −0.00103 (16) | −0.00059 (17) |
Ge3 | 0.0073 (2) | 0.0067 (2) | 0.0100 (2) | 0.00070 (16) | −0.00015 (17) | −0.00085 (18) |
Ge4 | 0.0077 (2) | 0.0043 (2) | 0.0069 (2) | 0.00008 (16) | −0.00225 (16) | 0.00046 (17) |
Ge5 | 0.0071 (2) | 0.0062 (2) | 0.0069 (2) | −0.00028 (16) | 0.00108 (17) | 0.00076 (17) |
O1 | 0.0113 (15) | 0.0091 (16) | 0.0092 (15) | 0.0027 (12) | −0.0003 (12) | 0.0030 (12) |
O2 | 0.0066 (14) | 0.0101 (16) | 0.0052 (14) | 0.0014 (11) | 0.0007 (11) | 0.0004 (12) |
O3 | 0.0124 (15) | 0.0070 (16) | 0.0144 (15) | −0.0017 (12) | −0.0084 (12) | 0.0020 (12) |
O4 | 0.0098 (15) | 0.0119 (16) | 0.0088 (15) | −0.0044 (12) | −0.0020 (12) | 0.0027 (12) |
O5 | 0.0145 (16) | 0.0105 (17) | 0.0180 (16) | −0.0040 (12) | 0.0078 (13) | −0.0047 (13) |
O6 | 0.0185 (16) | 0.0157 (17) | 0.0075 (15) | −0.0092 (13) | −0.0025 (12) | 0.0005 (13) |
O7 | 0.0079 (14) | 0.0180 (18) | 0.0126 (15) | 0.0019 (13) | −0.0019 (12) | −0.0091 (13) |
O8 | 0.0125 (15) | 0.0146 (17) | 0.0113 (15) | 0.0004 (13) | 0.0005 (12) | 0.0055 (13) |
O9 | 0.0241 (18) | 0.0136 (18) | 0.0143 (16) | 0.0096 (14) | −0.0009 (14) | 0.0010 (13) |
O10 | 0.0154 (16) | 0.0126 (17) | 0.0115 (16) | 0.0047 (12) | −0.0006 (13) | −0.0015 (13) |
O11 | 0.0126 (16) | 0.0088 (16) | 0.0165 (16) | 0.0007 (12) | −0.0090 (13) | −0.0010 (13) |
C1 | 0.030 (3) | 0.018 (3) | 0.033 (3) | 0.004 (2) | −0.013 (2) | 0.001 (2) |
N1 | 0.036 (3) | 0.017 (2) | 0.035 (3) | −0.0064 (19) | −0.020 (2) | 0.006 (2) |
C2 | 0.046 (4) | 0.048 (4) | 0.029 (3) | −0.003 (3) | −0.004 (3) | 0.006 (3) |
N2 | 0.057 (4) | 0.053 (4) | 0.031 (3) | −0.008 (3) | 0.008 (3) | −0.004 (3) |
C3 | 0.178 (12) | 0.058 (6) | 0.040 (4) | −0.013 (7) | −0.011 (6) | 0.015 (4) |
N3 | 0.036 (3) | 0.062 (4) | 0.048 (3) | −0.004 (3) | −0.003 (3) | 0.015 (3) |
Geometric parameters (Å, º) top
Ge1—O4 | 1.880 (3) | O5—Ge5i | 1.766 (3) |
Ge1—O4i | 1.880 (3) | O6—H1 | 0.8200 |
Ge1—O2i | 1.890 (3) | O9—H2 | 0.8200 |
Ge1—O2 | 1.890 (3) | O10—Ge5v | 1.726 (3) |
Ge1—O1i | 1.914 (3) | O11—Ge4i | 1.752 (3) |
Ge1—O1 | 1.914 (3) | C1—N1 | 1.475 (7) |
Ge2—O6 | 1.774 (3) | C1—C1vi | 1.520 (10) |
Ge2—O11 | 1.778 (3) | C1—H1A | 0.9700 |
Ge2—O7 | 1.790 (3) | C1—H1B | 0.9700 |
Ge2—O3 | 1.874 (3) | N1—H1C | 0.8900 |
Ge2—O2 | 1.957 (3) | N1—H1D | 0.8900 |
Ge2—Ge3 | 2.9165 (7) | N1—H1E | 0.8900 |
Ge3—O9 | 1.770 (3) | C2—N2vii | 1.438 (9) |
Ge3—O7 | 1.781 (3) | C2—C2viii | 1.511 (14) |
Ge3—O5 | 1.781 (3) | C2—H2A | 0.9700 |
Ge3—O10 | 1.810 (3) | C2—H2B | 0.9700 |
Ge3—O2 | 2.091 (3) | N2—C2ix | 1.438 (9) |
Ge4—O1 | 1.739 (3) | N2—H2C | 0.8900 |
Ge4—O3ii | 1.744 (3) | N2—H2D | 0.8900 |
Ge4—O11i | 1.752 (3) | N2—H2E | 0.8900 |
Ge4—O8 | 1.770 (3) | C3—C3x | 1.357 (16) |
Ge5—O10iii | 1.726 (3) | C3—N3 | 1.436 (10) |
Ge5—O4 | 1.743 (3) | C3—H3A | 0.9700 |
Ge5—O5i | 1.766 (3) | C3—H3B | 0.9700 |
Ge5—O8 | 1.769 (3) | N3—H3C | 0.90 (2) |
O3—Ge4iv | 1.744 (3) | N3—H3D | 0.90 (2) |
| | | |
O4—Ge1—O4i | 180.0 (2) | O10iii—Ge5—O5i | 111.06 (15) |
O4—Ge1—O2i | 88.74 (13) | O4—Ge5—O5i | 111.91 (15) |
O4i—Ge1—O2i | 91.26 (13) | O10iii—Ge5—O8 | 108.81 (15) |
O4—Ge1—O2 | 91.26 (13) | O4—Ge5—O8 | 110.41 (14) |
O4i—Ge1—O2 | 88.74 (13) | O5i—Ge5—O8 | 110.05 (15) |
O2i—Ge1—O2 | 180.00 (6) | Ge4—O1—Ge1 | 117.40 (16) |
O4—Ge1—O1i | 89.76 (13) | Ge1—O2—Ge2 | 133.36 (15) |
O4i—Ge1—O1i | 90.24 (13) | Ge1—O2—Ge3 | 132.93 (15) |
O2i—Ge1—O1i | 91.18 (12) | Ge2—O2—Ge3 | 92.13 (11) |
O2—Ge1—O1i | 88.82 (12) | Ge4iv—O3—Ge2 | 128.73 (17) |
O4—Ge1—O1 | 90.24 (13) | Ge5—O4—Ge1 | 119.40 (16) |
O4i—Ge1—O1 | 89.76 (13) | Ge5i—O5—Ge3 | 122.40 (17) |
O2i—Ge1—O1 | 88.82 (12) | Ge2—O6—H1 | 109.5 |
O2—Ge1—O1 | 91.18 (12) | Ge3—O7—Ge2 | 109.51 (15) |
O1i—Ge1—O1 | 180.0 (2) | Ge4—O8—Ge5 | 120.59 (17) |
O6—Ge2—O11 | 115.28 (15) | Ge3—O9—H2 | 109.5 |
O6—Ge2—O7 | 122.21 (15) | Ge5v—O10—Ge3 | 135.03 (18) |
O11—Ge2—O7 | 122.41 (15) | Ge4i—O11—Ge2 | 119.56 (16) |
O6—Ge2—O3 | 92.42 (14) | N1—C1—C1vi | 107.8 (6) |
O11—Ge2—O3 | 90.02 (13) | N1—C1—H1A | 110.1 |
O7—Ge2—O3 | 90.87 (13) | C1vi—C1—H1A | 110.1 |
O6—Ge2—O2 | 93.97 (13) | N1—C1—H1B | 110.1 |
O11—Ge2—O2 | 92.45 (13) | C1vi—C1—H1B | 110.1 |
O7—Ge2—O2 | 80.84 (12) | H1A—C1—H1B | 108.5 |
O3—Ge2—O2 | 171.39 (13) | C1—N1—H1C | 109.5 |
O6—Ge2—Ge3 | 113.80 (11) | C1—N1—H1D | 109.5 |
O11—Ge2—Ge3 | 115.89 (10) | H1C—N1—H1D | 109.5 |
O7—Ge2—Ge3 | 35.14 (9) | C1—N1—H1E | 109.5 |
O3—Ge2—Ge3 | 126.00 (10) | H1C—N1—H1E | 109.5 |
O2—Ge2—Ge3 | 45.76 (8) | H1D—N1—H1E | 109.5 |
O9—Ge3—O7 | 118.00 (16) | N2vii—C2—C2viii | 113.8 (7) |
O9—Ge3—O5 | 117.69 (16) | N2vii—C2—H2A | 108.8 |
O7—Ge3—O5 | 122.55 (15) | C2viii—C2—H2A | 108.8 |
O9—Ge3—O10 | 96.15 (14) | N2vii—C2—H2B | 108.8 |
O7—Ge3—O10 | 91.65 (14) | C2viii—C2—H2B | 108.8 |
O5—Ge3—O10 | 95.52 (14) | H2A—C2—H2B | 107.7 |
O9—Ge3—O2 | 89.87 (13) | C2ix—N2—H2C | 109.5 |
O7—Ge3—O2 | 77.42 (12) | C2ix—N2—H2D | 109.5 |
O5—Ge3—O2 | 89.74 (13) | H2C—N2—H2D | 109.5 |
O10—Ge3—O2 | 169.04 (12) | C2ix—N2—H2E | 109.5 |
O9—Ge3—Ge2 | 107.35 (11) | H2C—N2—H2E | 109.5 |
O7—Ge3—Ge2 | 35.35 (10) | H2D—N2—H2E | 109.5 |
O5—Ge3—Ge2 | 112.86 (10) | C3x—C3—N3 | 118.8 (11) |
O10—Ge3—Ge2 | 126.99 (10) | C3x—C3—H3A | 107.6 |
O2—Ge3—Ge2 | 42.12 (8) | N3—C3—H3A | 107.6 |
O1—Ge4—O3ii | 107.91 (14) | C3x—C3—H3B | 107.6 |
O1—Ge4—O11i | 112.28 (14) | N3—C3—H3B | 107.6 |
O3ii—Ge4—O11i | 110.18 (14) | H3A—C3—H3B | 107.0 |
O1—Ge4—O8 | 110.84 (14) | C3—N3—H3C | 113 (5) |
O3ii—Ge4—O8 | 104.57 (14) | C3—N3—H3D | 115 (5) |
O11i—Ge4—O8 | 110.75 (15) | H3C—N3—H3D | 107 (3) |
O10iii—Ge5—O4 | 104.43 (14) | | |
Symmetry codes: (i) −x+1, −y, −z; (ii) x−1/2, −y+1/2, z−1/2; (iii) x+1/2, −y+1/2, z−1/2; (iv) x+1/2, −y+1/2, z+1/2; (v) x−1/2, −y+1/2, z+1/2; (vi) −x+1, −y+1, −z; (vii) x, y, z+1; (viii) −x+1, −y, −z+1; (ix) x, y, z−1; (x) −x+1, −y+1, −z−1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O6—H1···O4 | 0.82 | 1.81 | 2.614 (4) | 169 |
O9—H2···O1 | 0.82 | 1.83 | 2.641 (4) | 170 |
N1—H1C···O3xi | 0.89 | 1.87 | 2.750 (5) | 172 |
N1—H1E···O9 | 0.89 | 2.27 | 2.965 (6) | 135 |
N1—H1D···O6 | 0.89 | 1.96 | 2.828 (6) | 166 |
N1—H1D···O11xi | 0.89 | 2.45 | 2.826 (5) | 106 |
N2—H2C···O9iii | 0.89 | 2.29 | 2.965 (7) | 132 |
N2—H2D···N3 | 0.89 | 1.80 | 2.687 (9) | 171 |
N2—H2E···O7ix | 0.89 | 2.34 | 3.053 (6) | 138 |
N2—H2E···O3ix | 0.89 | 2.52 | 3.355 (6) | 156 |
N3—H3C···O6ii | 0.90 (2) | 2.23 (3) | 3.081 (7) | 158 (5) |
N3—H3D···O5iii | 0.90 (2) | 2.47 (4) | 3.256 (7) | 146 (5) |
Symmetry codes: (ii) x−1/2, −y+1/2, z−1/2; (iii) x+1/2, −y+1/2, z−1/2; (ix) x, y, z−1; (xi) −x+3/2, y+1/2, −z+1/2. |
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