Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807020016/hy2056sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807020016/hy2056Isup2.hkl |
CCDC reference: 650510
Compound (I) was prepared by the hydrothermal reaction of Co(C2O4).2H2O(0.130 g, 0.71 mmol), (R)-(+)-1-phenylethylamine (0.062 g, 0.51 mmol) and water (0.6 ml) at 383 K for 3 d in a sealed thick-walled Pyrex tube. Light pink crystals of (I) were obtained in 40–50% yield.
H atoms on C and N atoms were positioned geometrically and refined as riding atoms, with C—H = 0.93Å (aryl), 0.98Å (CH) and 0.96Å (CH3) and N—H = 0.89 Å and Uiso(H) = 1.2Ueq(C,N). H atoms on water molecules were located in a difference Fourier map and fixed with Uiso(H) = 1.2Ueq(O).
The crystal structure of the title compound, (I)(Fig. 1), consists of bicobalt oxalate complex anions [Co2(C2O4)3(H2O)4]2- and organic cations (C8H12N)+, joined into a two-dimensional sheet by hydrogen bonds. Owing to the presence of the chiral organic cation, the compound crystallizes in the polar space group C2. In the anion, there are two types of oxalates. One as tetradentate ligand bridges two Co atoms, each is coordinated by another type of oxalate as bidentate ligand in the same plane. Each Co atom is also bonded by two water molecules above and below the equatorial plane to produce a negative step-lamella. The bond angles around the Co atom range from 81.01 (9)° to 100.2 (2) °, and from 178.1 (2)° to 178.7 (2)°. The Co—O distances span from 2.062 (5)Å to 2.114 (3) Å. The organic cation contains a stereogenic center in its R configuration and has a normal structure similar to that described elsewhere (Shan & Huang, 2001). The cations are anchored in the pockets on the both faces of the puckered anionic lamella through hydrogen bonds with the distances ranging from 2.678 (8)Å to 2.976 (7)Å (Table 1), thus resulting in the formation of cation–anion–cation slab-sandwich layers with an arrangement of the cations held together by close C–H···π(aryl) interactions in a herring bone motif (Fig.2).
For related structure, see: Shan & Huang (2001).
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL.
(C8H12N)2[Co2(C2O4)3(H2O)4] | F(000) = 720 |
Mr = 698.36 | Dx = 1.639 Mg m−3 |
Monoclinic, C2 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: C 2y | Cell parameters from 4453 reflections |
a = 10.973 (2) Å | θ = 1.2–27.1° |
b = 7.5560 (15) Å | µ = 1.25 mm−1 |
c = 17.067 (3) Å | T = 296 K |
β = 90.33 (3)° | Plate, pink |
V = 1415.0 (5) Å3 | 0.24 × 0.12 × 0.04 mm |
Z = 2 |
Siemens Quantum CCD diffractometer | 1938 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.020 |
Graphite monochromator | θmax = 25.5°, θmin = 1.2° |
ω scans | h = −13→10 |
3658 measured reflections | k = −9→8 |
2268 independent reflections | l = −20→19 |
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)] = 0.033 | H-atom parameters constrained |
wR(F2) = 0.102 | w = 1/[σ2(Fo2) + (0.0589P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.13 | (Δ/σ)max < 0.001 |
2268 reflections | Δρmax = 0.45 e Å−3 |
193 parameters | Δρmin = −0.52 e Å−3 |
38 restraints | Absolute structure: Flack (1983), 850 Fridel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.11 (3) |
(C8H12N)2[Co2(C2O4)3(H2O)4] | V = 1415.0 (5) Å3 |
Mr = 698.36 | Z = 2 |
Monoclinic, C2 | Mo Kα radiation |
a = 10.973 (2) Å | µ = 1.25 mm−1 |
b = 7.5560 (15) Å | T = 296 K |
c = 17.067 (3) Å | 0.24 × 0.12 × 0.04 mm |
β = 90.33 (3)° |
Siemens Quantum CCD diffractometer | 1938 reflections with I > 2σ(I) |
3658 measured reflections | Rint = 0.020 |
2268 independent reflections |
R[F2 > 2σ(F2)] = 0.033 | H-atom parameters constrained |
wR(F2) = 0.102 | Δρmax = 0.45 e Å−3 |
S = 1.13 | Δρmin = −0.52 e Å−3 |
2268 reflections | Absolute structure: Flack (1983), 850 Fridel pairs |
193 parameters | Absolute structure parameter: 0.11 (3) |
38 restraints |
x | y | z | Uiso*/Ueq | ||
Co | 0.29291 (4) | 0.98018 (18) | 0.41036 (3) | 0.02253 (17) | |
O1 | 0.4159 (6) | 0.8027 (5) | 0.4631 (3) | 0.0242 (13) | |
O2 | 0.4163 (5) | 1.1583 (6) | 0.4624 (3) | 0.0266 (13) | |
O3 | 0.1732 (5) | 1.1586 (6) | 0.3606 (3) | 0.0262 (14) | |
O4 | 0.1735 (6) | 0.8017 (6) | 0.3563 (3) | 0.0286 (15) | |
O5 | −0.0023 (6) | 0.8057 (7) | 0.2907 (3) | 0.0379 (16) | |
O6 | −0.0019 (5) | 1.1607 (6) | 0.2925 (3) | 0.0341 (15) | |
O7 | 0.3966 (2) | 0.9858 (9) | 0.30858 (15) | 0.0317 (6) | |
H7A | 0.4480 | 0.8882 | 0.2992 | 0.038* | |
H7B | 0.4491 | 1.0760 | 0.3010 | 0.038* | |
O8 | 0.1915 (2) | 0.9809 (10) | 0.51531 (15) | 0.0314 (6) | |
H8A | 0.1465 | 1.0892 | 0.5220 | 0.038* | |
H8B | 0.1487 | 0.8760 | 0.5244 | 0.038* | |
N1 | 0.2561 (3) | 0.4834 (10) | 0.28541 (18) | 0.0278 (7) | |
H1A | 0.3371 | 0.4822 | 0.2833 | 0.042* | |
H1B | 0.2306 | 0.3950 | 0.3156 | 0.042* | |
H1C | 0.2312 | 0.5860 | 0.3054 | 0.042* | |
C1 | 0.5000 | 0.8799 (16) | 0.5000 | 0.019 (2) | |
C2 | 0.5000 | 1.0861 (15) | 0.5000 | 0.021 (3) | |
C4 | 0.0833 (8) | 0.8815 (10) | 0.3241 (4) | 0.0194 (16) | |
C3 | 0.0844 (9) | 1.0873 (11) | 0.3269 (5) | 0.0275 (19) | |
C9 | 0.3493 (6) | 0.6631 (9) | 0.1348 (3) | 0.0599 (19) | |
H9 | 0.4134 | 0.5978 | 0.1560 | 0.072* | |
C8 | 0.3753 (9) | 0.8048 (11) | 0.0842 (4) | 0.081 (2) | |
H8 | 0.4553 | 0.8345 | 0.0722 | 0.098* | |
C7 | 0.2813 (10) | 0.8964 (11) | 0.0536 (5) | 0.086 (3) | |
H7 | 0.2975 | 0.9898 | 0.0198 | 0.103* | |
C6 | 0.1660 (9) | 0.8583 (11) | 0.0701 (4) | 0.083 (3) | |
H6 | 0.1033 | 0.9241 | 0.0477 | 0.100* | |
C5 | 0.1388 (7) | 0.7174 (10) | 0.1216 (4) | 0.067 (2) | |
H5 | 0.0582 | 0.6921 | 0.1337 | 0.080* | |
C10 | 0.2306 (8) | 0.6182 (9) | 0.1538 (4) | 0.0395 (18) | |
C11 | 0.2044 (4) | 0.4618 (12) | 0.2043 (2) | 0.0307 (12) | |
H11 | 0.1157 | 0.4517 | 0.2089 | 0.037* | |
C12 | 0.2513 (8) | 0.2897 (8) | 0.1688 (4) | 0.045 (2) | |
H12A | 0.2189 | 0.2763 | 0.1168 | 0.068* | |
H12B | 0.2258 | 0.1917 | 0.2005 | 0.068* | |
H12C | 0.3387 | 0.2928 | 0.1667 | 0.068* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co | 0.0218 (3) | 0.0158 (3) | 0.0299 (3) | −0.0009 (6) | −0.00417 (19) | 0.0013 (6) |
O1 | 0.034 (3) | 0.010 (3) | 0.029 (3) | −0.001 (3) | −0.008 (3) | 0.003 (2) |
O2 | 0.018 (3) | 0.023 (3) | 0.039 (3) | 0.002 (3) | −0.006 (2) | 0.005 (3) |
O3 | 0.023 (3) | 0.018 (3) | 0.038 (3) | −0.004 (2) | −0.007 (3) | 0.002 (2) |
O4 | 0.033 (4) | 0.016 (3) | 0.037 (3) | −0.001 (3) | −0.007 (3) | −0.001 (2) |
O5 | 0.038 (4) | 0.031 (4) | 0.044 (3) | −0.004 (3) | −0.020 (3) | 0.005 (3) |
O6 | 0.032 (4) | 0.021 (3) | 0.050 (3) | 0.010 (3) | −0.006 (3) | 0.000 (3) |
O7 | 0.0339 (13) | 0.0203 (14) | 0.0412 (15) | −0.001 (3) | 0.0077 (11) | 0.007 (3) |
O8 | 0.0361 (13) | 0.0150 (12) | 0.0432 (15) | −0.001 (3) | 0.0063 (11) | −0.002 (3) |
N1 | 0.0297 (15) | 0.0213 (15) | 0.0323 (16) | −0.002 (4) | 0.0005 (13) | 0.003 (4) |
C1 | 0.011 (5) | 0.029 (5) | 0.017 (4) | 0.000 | −0.001 (4) | 0.000 |
C2 | 0.030 (6) | 0.005 (4) | 0.029 (5) | 0.000 | 0.004 (5) | 0.000 |
C4 | 0.014 (4) | 0.024 (4) | 0.019 (4) | 0.001 (3) | −0.002 (3) | 0.000 (3) |
C3 | 0.039 (5) | 0.015 (3) | 0.029 (4) | 0.004 (4) | 0.002 (4) | −0.001 (3) |
C9 | 0.073 (5) | 0.070 (5) | 0.037 (3) | −0.032 (4) | 0.000 (3) | 0.005 (3) |
C8 | 0.109 (6) | 0.082 (5) | 0.053 (4) | −0.043 (5) | 0.008 (4) | 0.003 (4) |
C7 | 0.149 (7) | 0.053 (4) | 0.056 (4) | −0.010 (5) | 0.007 (5) | −0.001 (3) |
C6 | 0.132 (7) | 0.062 (4) | 0.056 (4) | 0.045 (5) | −0.011 (5) | 0.010 (4) |
C5 | 0.086 (5) | 0.064 (4) | 0.050 (4) | 0.038 (4) | −0.003 (4) | 0.009 (4) |
C10 | 0.055 (4) | 0.031 (4) | 0.033 (3) | −0.003 (3) | −0.007 (3) | −0.008 (3) |
C11 | 0.0267 (18) | 0.032 (4) | 0.034 (2) | −0.005 (3) | −0.0019 (16) | 0.001 (3) |
C12 | 0.076 (5) | 0.027 (4) | 0.033 (4) | 0.002 (4) | −0.003 (4) | −0.010 (3) |
Co—O3 | 2.062 (5) | C1—C2 | 1.558 (6) |
Co—O7 | 2.083 (3) | C2—O2i | 1.243 (7) |
Co—O4 | 2.091 (5) | C4—C3 | 1.556 (5) |
Co—O1 | 2.102 (5) | C9—C10 | 1.387 (10) |
Co—O2 | 2.103 (6) | C9—C8 | 1.406 (10) |
Co—O8 | 2.114 (3) | C9—H9 | 0.9300 |
O1—C1 | 1.257 (8) | C8—C7 | 1.345 (12) |
O2—C2 | 1.243 (7) | C8—H8 | 0.9300 |
O3—C3 | 1.250 (10) | C7—C6 | 1.329 (12) |
O4—C4 | 1.281 (9) | C7—H7 | 0.9300 |
O5—C4 | 1.237 (9) | C6—C5 | 1.414 (11) |
O6—C3 | 1.242 (10) | C6—H6 | 0.9300 |
O7—H7A | 0.9420 | C5—C10 | 1.368 (10) |
O7—H7B | 0.9020 | C5—H5 | 0.9300 |
O8—H8A | 0.9630 | C10—C11 | 1.491 (11) |
O8—H8B | 0.9349 | C11—C12 | 1.525 (11) |
N1—C11 | 1.503 (5) | C11—H11 | 0.9800 |
N1—H1A | 0.8900 | C12—H12A | 0.9600 |
N1—H1B | 0.8900 | C12—H12B | 0.9600 |
N1—H1C | 0.8900 | C12—H12C | 0.9600 |
C1—O1i | 1.257 (8) | ||
O3—Co—O7 | 89.6 (2) | O5—C4—O4 | 124.3 (8) |
O3—Co—O4 | 81.01 (9) | O5—C4—C3 | 118.9 (9) |
O7—Co—O4 | 89.4 (2) | O4—C4—C3 | 116.8 (9) |
O3—Co—O1 | 178.7 (2) | O6—C3—O3 | 128.0 (8) |
O7—Co—O1 | 91.0 (2) | O6—C3—C4 | 115.2 (9) |
O4—Co—O1 | 100.2 (2) | O3—C3—C4 | 116.8 (9) |
O3—Co—O2 | 99.4 (2) | C10—C9—C8 | 121.6 (8) |
O7—Co—O2 | 89.2 (2) | C10—C9—H9 | 119.2 |
O4—Co—O2 | 178.5 (3) | C8—C9—H9 | 119.2 |
O1—Co—O2 | 79.45 (9) | C7—C8—C9 | 118.2 (8) |
O3—Co—O8 | 90.6 (2) | C7—C8—H8 | 120.9 |
O7—Co—O8 | 178.1 (2) | C9—C8—H8 | 120.9 |
O4—Co—O8 | 92.5 (2) | C6—C7—C8 | 122.4 (8) |
O1—Co—O8 | 88.7 (2) | C6—C7—H7 | 118.8 |
O2—Co—O8 | 88.9 (2) | C8—C7—H7 | 118.8 |
C1—O1—Co | 112.7 (6) | C7—C6—C5 | 119.9 (8) |
C2—O2—Co | 114.2 (6) | C7—C6—H6 | 120.0 |
C3—O3—Co | 113.6 (5) | C5—C6—H6 | 120.0 |
C4—O4—Co | 111.5 (5) | C10—C5—C6 | 120.4 (8) |
Co—O7—H7A | 117.1 | C10—C5—H5 | 119.8 |
Co—O7—H7B | 119.1 | C6—C5—H5 | 119.8 |
H7A—O7—H7B | 100.6 | C5—C10—C9 | 117.5 (7) |
Co—O8—H8A | 112.0 | C5—C10—C11 | 121.5 (7) |
Co—O8—H8B | 113.9 | C9—C10—C11 | 120.9 (7) |
H8A—O8—H8B | 116.2 | C10—C11—N1 | 111.9 (6) |
C11—N1—H1A | 109.5 | C10—C11—C12 | 112.3 (4) |
C11—N1—H1B | 109.5 | N1—C11—C12 | 109.4 (6) |
H1A—N1—H1B | 109.5 | C10—C11—H11 | 107.7 |
C11—N1—H1C | 109.5 | N1—C11—H11 | 107.7 |
H1A—N1—H1C | 109.5 | C12—C11—H11 | 107.7 |
H1B—N1—H1C | 109.5 | C11—C12—H12A | 109.5 |
O1—C1—O1i | 124.7 (12) | C11—C12—H12B | 109.5 |
O1—C1—C2 | 117.6 (6) | H12A—C12—H12B | 109.5 |
O1i—C1—C2 | 117.6 (6) | C11—C12—H12C | 109.5 |
O2i—C2—O2 | 128.0 (12) | H12A—C12—H12C | 109.5 |
O2i—C2—C1 | 116.0 (6) | H12B—C12—H12C | 109.5 |
O2—C2—C1 | 116.0 (6) |
Symmetry code: (i) −x+1, y, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1C···O4 | 0.89 | 1.95 | 2.843 (8) | 176 |
N1—H1B···O3ii | 0.89 | 2.05 | 2.918 (8) | 166 |
N1—H1A···O6iii | 0.89 | 2.23 | 2.976 (7) | 141 |
N1—H1A···O5iii | 0.89 | 2.21 | 2.973 (7) | 143 |
O8—H8B···O2iv | 0.93 | 1.81 | 2.737 (9) | 172 |
O8—H8A···O1v | 0.96 | 1.77 | 2.728 (9) | 172 |
O7—H7B···O5vi | 0.90 | 1.82 | 2.678 (8) | 157 |
O7—H7A···O6iii | 0.94 | 1.81 | 2.712 (8) | 159 |
Symmetry codes: (ii) x, y−1, z; (iii) x+1/2, y−1/2, z; (iv) −x+1/2, y−1/2, −z+1; (v) −x+1/2, y+1/2, −z+1; (vi) x+1/2, y+1/2, z. |
Experimental details
Crystal data | |
Chemical formula | (C8H12N)2[Co2(C2O4)3(H2O)4] |
Mr | 698.36 |
Crystal system, space group | Monoclinic, C2 |
Temperature (K) | 296 |
a, b, c (Å) | 10.973 (2), 7.5560 (15), 17.067 (3) |
β (°) | 90.33 (3) |
V (Å3) | 1415.0 (5) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.25 |
Crystal size (mm) | 0.24 × 0.12 × 0.04 |
Data collection | |
Diffractometer | Siemens Quantum CCD |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3658, 2268, 1938 |
Rint | 0.020 |
(sin θ/λ)max (Å−1) | 0.606 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.033, 0.102, 1.13 |
No. of reflections | 2268 |
No. of parameters | 193 |
No. of restraints | 38 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.45, −0.52 |
Absolute structure | Flack (1983), 850 Fridel pairs |
Absolute structure parameter | 0.11 (3) |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2001), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1C···O4 | 0.89 | 1.95 | 2.843 (8) | 176 |
N1—H1B···O3i | 0.89 | 2.05 | 2.918 (8) | 166 |
N1—H1A···O6ii | 0.89 | 2.23 | 2.976 (7) | 141 |
N1—H1A···O5ii | 0.89 | 2.21 | 2.973 (7) | 143 |
O8—H8B···O2iii | 0.93 | 1.81 | 2.737 (9) | 172 |
O8—H8A···O1iv | 0.96 | 1.77 | 2.728 (9) | 172 |
O7—H7B···O5v | 0.90 | 1.82 | 2.678 (8) | 157 |
O7—H7A···O6ii | 0.94 | 1.81 | 2.712 (8) | 159 |
Symmetry codes: (i) x, y−1, z; (ii) x+1/2, y−1/2, z; (iii) −x+1/2, y−1/2, −z+1; (iv) −x+1/2, y+1/2, −z+1; (v) x+1/2, y+1/2, z. |
The crystal structure of the title compound, (I)(Fig. 1), consists of bicobalt oxalate complex anions [Co2(C2O4)3(H2O)4]2- and organic cations (C8H12N)+, joined into a two-dimensional sheet by hydrogen bonds. Owing to the presence of the chiral organic cation, the compound crystallizes in the polar space group C2. In the anion, there are two types of oxalates. One as tetradentate ligand bridges two Co atoms, each is coordinated by another type of oxalate as bidentate ligand in the same plane. Each Co atom is also bonded by two water molecules above and below the equatorial plane to produce a negative step-lamella. The bond angles around the Co atom range from 81.01 (9)° to 100.2 (2) °, and from 178.1 (2)° to 178.7 (2)°. The Co—O distances span from 2.062 (5)Å to 2.114 (3) Å. The organic cation contains a stereogenic center in its R configuration and has a normal structure similar to that described elsewhere (Shan & Huang, 2001). The cations are anchored in the pockets on the both faces of the puckered anionic lamella through hydrogen bonds with the distances ranging from 2.678 (8)Å to 2.976 (7)Å (Table 1), thus resulting in the formation of cation–anion–cation slab-sandwich layers with an arrangement of the cations held together by close C–H···π(aryl) interactions in a herring bone motif (Fig.2).