Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010701459X/ln3043sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827010701459X/ln3043Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827010701459X/ln3043IIsup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827010701459X/ln3043IIIsup4.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827010701459X/ln3043IVsup5.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827010701459X/ln3043Vsup6.hkl |
CCDC references: 649070; 649071; 649072; 649073; 649074
For the synthesis of compound (I), equimolar quantities (1 mmol of each component) of beryllium sulfate tetrahydrate and 4-oxo-4H-pyran-2,6-dicarboxylic acid were dissolved in doubly distilled water (20 ml). Slow evaporation at ambient temperature yielded, after 19 d, pale-yellow prismatic crystals of (I) (yield 94%). Analysis for (I), found: C 32.0, H 3.8%; C7H10BeO10 requires: C 31.9, H 3.8%.
Compound (II) was unexpectedly obtained from the reaction between equimolar quantities (1 mmol of each component) of hydrazine hydrate and 4-oxo-4H-pyran-2,6-dicarboxylic acid in singly distilled water, followed by slow evaporation. Analysis for (II), found: C 36.0, H 2.9, N 5.8%; C14H8CaN2O14 requires: C 35.4, H 3.0, N 5.9%; IR (KBr, ν, cm-1): 3460, 3299, 3064, 1616, 1402, 1349, 1109.
For the synthesis of compound (III), a solution of manganese(II) acetate (1 mmol in 5 ml of water) was added to a solution of 4-oxo-4H-pyran-2,6-dicarboxylic acid (1 mmol in 15 ml of water). Slow evaporation at ambient temperature gave, after 12 d, yellow rhomboid crystals of (III) (yield 53%). Analysis for (III), found: C 26.0, H 3.0%; C7H14MnO12 requires: C 24.4, H 4.1%.
Compound (IV) was prepared by the portionwise addition of basic copper(II) carbonate (1 mmol, as a solid) to a hot (ca 350 K) solution of 4-oxo-4H-pyran-2,6-dicarboxylic acid (2 mmol in 40 ml of water). The solution was filtered hot and then allowed to cool to ambient temperature, when slow evaporation gave pale-green crystals of (IV) after 12 d (yield 80%). Analysis for (IV), found: C 26.1, H 3.2%; C7H10CuO10 requires: C 26.5, H 3.2%.
For the synthesis of compound (V), aqueous solutions of cadmium nitrate (1 mmol in 5 ml of water) and 4-oxo-4H-pyran-2,6-dicarboxylic acid (1 mmol in 15 ml of water) were mixed at ambient temperature. Subsequent slow evaporation at ambient temperature yielded, after 8 d, pale-yellow rhomboid crystals of (V) (yield 79%). Analysis for (V), found: C 24.4, H 2.1%; C7H8CdO9 requires: C 24.15, H 2.3%.
In every case, the crystals were collected by filtration and then washed with ice-cold water (ca 5 ml) prior to analysis.
For compound (I), the space group P21/n was uniquely assigned from the systematic absences. For compound (II), the systematic absences permitted Pc and P2/c as possible space groups; P2/c was selected, and confirmed by the successful structure analysis. Crystals of compounds (III)–(V) are all triclinic. The space group P1 was selected for compounds (III) and (IV), and P1 was selected for compound (V), and these selections were all confirmed by the subsequent structure analyses. All H atoms were located in difference maps and then treated as riding atoms. H atoms bonded to C atoms were placed in calculated positions, with C—H = 0.95 Å, and with Uiso(H) = 1.2Ueq(C). H atoms bonded to N or O atoms were permitted to ride at the locations deduced from the difference maps, giving N—H = 0.88–0.96 Å and O—H = 0.82–0.94 Å, with Uiso(H) = 1.2Ueq(N) or 1.5Ueq(O). The correct absolute configuration of the structure of compound (V) in the crystal selected for data collection was established by means of the Flack parameter (Flack, 1983).
For all compounds, data collection: COLLECT (Nonius, 1999); cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: OSCAIL and SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).
[Be(H2O)4](C7H2O6) | F(000) = 544 |
Mr = 263.16 | Dx = 1.594 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 2504 reflections |
a = 5.4331 (2) Å | θ = 3.7–27.5° |
b = 10.6173 (4) Å | µ = 0.15 mm−1 |
c = 19.1890 (5) Å | T = 120 K |
β = 97.771 (2)° | Block, colourless |
V = 1096.75 (6) Å3 | 0.28 × 0.24 × 0.11 mm |
Z = 4 |
Bruker Nonius KappaCCD area-detector diffractometer | 2504 independent reflections |
Radiation source: Bruker Nonius FR591 rotating anode | 2180 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.034 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 3.7° |
ϕ and ω scans | h = −7→7 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −13→13 |
Tmin = 0.968, Tmax = 0.984 | l = −24→24 |
11511 measured reflections |
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) = 0.118 | H-atom parameters constrained |
S = 1.15 | w = 1/[σ2(Fo2) + (0.0538P)2 + 0.5571P] where P = (Fo2 + 2Fc2)/3 |
2504 reflections | (Δ/σ)max < 0.001 |
163 parameters | Δρmax = 0.37 e Å−3 |
0 restraints | Δρmin = −0.34 e Å−3 |
[Be(H2O)4](C7H2O6) | V = 1096.75 (6) Å3 |
Mr = 263.16 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 5.4331 (2) Å | µ = 0.15 mm−1 |
b = 10.6173 (4) Å | T = 120 K |
c = 19.1890 (5) Å | 0.28 × 0.24 × 0.11 mm |
β = 97.771 (2)° |
Bruker Nonius KappaCCD area-detector diffractometer | 2504 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2180 reflections with I > 2σ(I) |
Tmin = 0.968, Tmax = 0.984 | Rint = 0.034 |
11511 measured reflections |
R[F2 > 2σ(F2)] = 0.037 | 0 restraints |
wR(F2) = 0.118 | H-atom parameters constrained |
S = 1.15 | Δρmax = 0.37 e Å−3 |
2504 reflections | Δρmin = −0.34 e Å−3 |
163 parameters |
x | y | z | Uiso*/Ueq | ||
Be1 | 0.9267 (4) | 0.82639 (19) | 0.70311 (10) | 0.0159 (4) | |
O11 | 0.7690 (2) | 0.72233 (11) | 0.73958 (6) | 0.0207 (3) | |
O12 | 1.0599 (2) | 0.74678 (11) | 0.64721 (6) | 0.0232 (3) | |
O13 | 1.1337 (2) | 0.89899 (10) | 0.75675 (5) | 0.0166 (2) | |
O14 | 0.7441 (2) | 0.93860 (11) | 0.66807 (6) | 0.0181 (3) | |
O1 | 0.40311 (19) | 0.33307 (10) | 0.60011 (5) | 0.0150 (2) | |
C2 | 0.5898 (3) | 0.38121 (14) | 0.56826 (7) | 0.0135 (3) | |
C21 | 0.7056 (3) | 0.49728 (14) | 0.60615 (8) | 0.0158 (3) | |
O21 | 0.6151 (2) | 0.53141 (11) | 0.65993 (6) | 0.0219 (3) | |
O22 | 0.8768 (2) | 0.54817 (11) | 0.57978 (6) | 0.0226 (3) | |
C3 | 0.6627 (3) | 0.33029 (14) | 0.51029 (8) | 0.0141 (3) | |
C4 | 0.5414 (3) | 0.21854 (14) | 0.47974 (7) | 0.0147 (3) | |
O4 | 0.6024 (2) | 0.16676 (11) | 0.42565 (6) | 0.0187 (3) | |
C5 | 0.3443 (3) | 0.16948 (15) | 0.51547 (8) | 0.0150 (3) | |
C6 | 0.2847 (3) | 0.22814 (14) | 0.57311 (8) | 0.0136 (3) | |
C61 | 0.0816 (3) | 0.18509 (15) | 0.61493 (8) | 0.0146 (3) | |
O61 | 0.0470 (2) | 0.24956 (11) | 0.66770 (6) | 0.0185 (3) | |
O62 | −0.0342 (2) | 0.08964 (11) | 0.59166 (6) | 0.0202 (3) | |
H11A | 0.7154 | 0.6595 | 0.7130 | 0.031* | |
H11B | 0.6794 | 0.7367 | 0.7775 | 0.031* | |
H12A | 0.9988 | 0.6801 | 0.6256 | 0.035* | |
H12B | 1.1678 | 0.7810 | 0.6217 | 0.035* | |
H13A | 1.0664 | 0.9449 | 0.7874 | 0.025* | |
H13B | 1.2387 | 0.8536 | 0.7864 | 0.025* | |
H14A | 0.6244 | 0.9146 | 0.6343 | 0.027* | |
H14B | 0.8245 | 0.9979 | 0.6391 | 0.027* | |
H3 | 0.7938 | 0.3678 | 0.4895 | 0.017* | |
H5 | 0.2568 | 0.0959 | 0.4983 | 0.018* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Be1 | 0.0188 (9) | 0.0161 (9) | 0.0141 (8) | −0.0038 (7) | 0.0062 (7) | −0.0015 (7) |
O11 | 0.0274 (6) | 0.0155 (6) | 0.0223 (6) | −0.0064 (5) | 0.0145 (5) | −0.0056 (4) |
O12 | 0.0284 (6) | 0.0202 (6) | 0.0248 (6) | −0.0122 (5) | 0.0169 (5) | −0.0102 (5) |
O13 | 0.0183 (5) | 0.0173 (6) | 0.0144 (5) | 0.0013 (4) | 0.0034 (4) | −0.0018 (4) |
O14 | 0.0183 (5) | 0.0186 (6) | 0.0170 (5) | −0.0056 (4) | 0.0013 (4) | 0.0009 (4) |
O1 | 0.0164 (5) | 0.0148 (5) | 0.0149 (5) | −0.0041 (4) | 0.0064 (4) | −0.0021 (4) |
C2 | 0.0126 (7) | 0.0140 (7) | 0.0141 (7) | −0.0021 (5) | 0.0020 (5) | 0.0026 (6) |
C21 | 0.0193 (7) | 0.0135 (7) | 0.0150 (7) | −0.0014 (6) | 0.0032 (6) | −0.0003 (6) |
O21 | 0.0304 (6) | 0.0180 (6) | 0.0198 (6) | −0.0085 (5) | 0.0127 (5) | −0.0058 (4) |
O22 | 0.0254 (6) | 0.0205 (6) | 0.0241 (6) | −0.0109 (5) | 0.0116 (5) | −0.0065 (5) |
C3 | 0.0140 (7) | 0.0148 (7) | 0.0139 (7) | −0.0030 (5) | 0.0030 (5) | 0.0017 (5) |
C4 | 0.0145 (7) | 0.0170 (7) | 0.0127 (7) | −0.0007 (6) | 0.0027 (5) | 0.0002 (6) |
O4 | 0.0188 (6) | 0.0220 (6) | 0.0166 (5) | −0.0063 (4) | 0.0073 (4) | −0.0064 (4) |
C5 | 0.0146 (7) | 0.0155 (7) | 0.0153 (7) | −0.0036 (6) | 0.0033 (5) | −0.0003 (6) |
C6 | 0.0134 (7) | 0.0124 (7) | 0.0152 (7) | −0.0022 (5) | 0.0022 (5) | 0.0017 (5) |
C61 | 0.0135 (7) | 0.0166 (7) | 0.0140 (7) | 0.0000 (5) | 0.0033 (5) | 0.0033 (5) |
O61 | 0.0178 (5) | 0.0218 (6) | 0.0174 (5) | −0.0033 (4) | 0.0072 (4) | −0.0021 (4) |
O62 | 0.0205 (6) | 0.0201 (6) | 0.0210 (6) | −0.0079 (5) | 0.0065 (4) | −0.0003 (4) |
Be1—O12 | 1.612 (2) | C2—C3 | 1.344 (2) |
Be1—O13 | 1.614 (2) | C2—C21 | 1.523 (2) |
Be1—O11 | 1.614 (2) | C21—O22 | 1.2413 (18) |
Be1—O14 | 1.636 (2) | C21—O21 | 1.2549 (18) |
O11—H11A | 0.8652 | C3—C4 | 1.443 (2) |
O11—H11B | 0.9418 | C3—H3 | 0.95 |
O12—H12A | 0.8635 | C4—O4 | 1.2579 (18) |
O12—H12B | 0.8908 | C4—C5 | 1.445 (2) |
O13—H13A | 0.8802 | C5—C6 | 1.347 (2) |
O13—H13B | 0.8906 | C5—H5 | 0.95 |
O14—H14A | 0.8911 | C6—C61 | 1.520 (2) |
O14—H14B | 0.9810 | C61—O62 | 1.2437 (19) |
O1—C2 | 1.3535 (17) | C61—O61 | 1.2572 (19) |
O1—C6 | 1.3540 (18) | ||
O12—Be1—O13 | 109.76 (13) | C3—C2—C21 | 124.90 (13) |
O12—Be1—O11 | 104.00 (13) | O1—C2—C21 | 112.10 (12) |
O13—Be1—O11 | 114.53 (13) | O22—C21—O21 | 127.43 (14) |
O12—Be1—O14 | 114.22 (13) | O22—C21—C2 | 116.19 (13) |
O13—Be1—O14 | 104.24 (12) | O21—C21—C2 | 116.37 (13) |
O11—Be1—O14 | 110.41 (13) | C2—C3—C4 | 119.86 (13) |
Be1—O11—H11A | 115.4 | C2—C3—H3 | 120.1 |
Be1—O11—H11B | 125.8 | C4—C3—H3 | 120.1 |
H11A—O11—H11B | 114.3 | O4—C4—C3 | 122.54 (13) |
Be1—O12—H12A | 124.9 | O4—C4—C5 | 121.93 (14) |
Be1—O12—H12B | 122.7 | C3—C4—C5 | 115.53 (13) |
H12A—O12—H12B | 108.0 | C6—C5—C4 | 119.95 (14) |
Be1—O13—H13A | 111.9 | C6—C5—H5 | 120.0 |
Be1—O13—H13B | 118.6 | C4—C5—H5 | 120.0 |
H13A—O13—H13B | 99.3 | C5—C6—O1 | 122.70 (13) |
Be1—O14—H14A | 115.7 | C5—C6—C61 | 124.55 (13) |
Be1—O14—H14B | 114.1 | O1—C6—C61 | 112.75 (12) |
H14A—O14—H14B | 96.2 | O62—C61—O61 | 127.53 (14) |
C2—O1—C6 | 118.96 (12) | O62—C61—C6 | 115.08 (13) |
C3—C2—O1 | 123.00 (13) | O61—C61—C6 | 117.38 (13) |
C6—O1—C2—C3 | 0.6 (2) | O4—C4—C5—C6 | −179.82 (14) |
C6—O1—C2—C21 | −178.87 (12) | C3—C4—C5—C6 | 0.2 (2) |
C3—C2—C21—O22 | 1.3 (2) | C4—C5—C6—O1 | −0.2 (2) |
O1—C2—C21—O22 | −179.20 (13) | C4—C5—C6—C61 | −179.90 (13) |
C3—C2—C21—O21 | −179.51 (14) | C2—O1—C6—C5 | −0.2 (2) |
O1—C2—C21—O21 | −0.02 (19) | C2—O1—C6—C61 | 179.50 (12) |
O1—C2—C3—C4 | −0.6 (2) | C5—C6—C61—O62 | −1.0 (2) |
C21—C2—C3—C4 | 178.87 (13) | O1—C6—C61—O62 | 179.29 (12) |
C2—C3—C4—O4 | −179.82 (14) | C5—C6—C61—O61 | −179.98 (14) |
C2—C3—C4—C5 | 0.1 (2) | O1—C6—C61—O61 | 0.28 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
O11—H11A···O21 | 0.86 | 1.74 | 2.6073 (16) | 179 |
O11—H11B···O61i | 0.94 | 1.73 | 2.6501 (16) | 165 |
O12—H12A···O22 | 0.86 | 1.74 | 2.6003 (16) | 178 |
O12—H12B···O4ii | 0.89 | 1.73 | 2.6187 (16) | 174 |
O13—H13A···O21iii | 0.88 | 1.76 | 2.6353 (15) | 171 |
O13—H13B···O61iii | 0.89 | 1.75 | 2.6360 (15) | 170 |
O14—H14A···O4iv | 0.89 | 1.79 | 2.6672 (16) | 168 |
O14—H14B···O62v | 0.98 | 1.60 | 2.5788 (16) | 177 |
Symmetry codes: (i) −x+1/2, y+1/2, −z+3/2; (ii) −x+2, −y+1, −z+1; (iii) −x+3/2, y+1/2, −z+3/2; (iv) −x+1, −y+1, −z+1; (v) x+1, y+1, z. |
(N2H6)[Ca(C7H2O6)2(H2O)2] | F(000) = 488 |
Mr = 474.35 | Dx = 1.843 Mg m−3 |
Monoclinic, P2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yc | Cell parameters from 1953 reflections |
a = 6.4669 (2) Å | θ = 3.1–27.5° |
b = 7.0797 (3) Å | µ = 0.46 mm−1 |
c = 18.8278 (6) Å | T = 120 K |
β = 97.372 (2)° | Lath, yellow |
V = 854.88 (5) Å3 | 0.26 × 0.18 × 0.08 mm |
Z = 2 |
Bruker Nonius KappaCCD area-detector diffractometer | 1953 independent reflections |
Radiation source: Bruker Nonius FR591 rotating anode | 1876 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.030 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 3.1° |
ϕ and ω scans | h = −8→7 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −9→9 |
Tmin = 0.909, Tmax = 0.964 | l = −24→24 |
9031 measured reflections |
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)] = 0.036 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.116 | H-atom parameters constrained |
S = 1.20 | w = 1/[σ2(Fo2) + (0.060P)2 + 0.7277P] where P = (Fo2 + 2Fc2)/3 |
1953 reflections | (Δ/σ)max < 0.001 |
141 parameters | Δρmax = 0.68 e Å−3 |
0 restraints | Δρmin = −0.54 e Å−3 |
(N2H6)[Ca(C7H2O6)2(H2O)2] | V = 854.88 (5) Å3 |
Mr = 474.35 | Z = 2 |
Monoclinic, P2/c | Mo Kα radiation |
a = 6.4669 (2) Å | µ = 0.46 mm−1 |
b = 7.0797 (3) Å | T = 120 K |
c = 18.8278 (6) Å | 0.26 × 0.18 × 0.08 mm |
β = 97.372 (2)° |
Bruker Nonius KappaCCD area-detector diffractometer | 1953 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 1876 reflections with I > 2σ(I) |
Tmin = 0.909, Tmax = 0.964 | Rint = 0.030 |
9031 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
wR(F2) = 0.116 | H-atom parameters constrained |
S = 1.20 | Δρmax = 0.68 e Å−3 |
1953 reflections | Δρmin = −0.54 e Å−3 |
141 parameters |
x | y | z | Uiso*/Ueq | ||
Ca1 | 0.5000 | 0.85706 (7) | 0.2500 | 0.01039 (17) | |
O1 | 0.51583 (19) | 0.74693 (18) | 0.11779 (6) | 0.0101 (3) | |
C2 | 0.6593 (3) | 0.8198 (2) | 0.07852 (9) | 0.0096 (3) | |
C21 | 0.8291 (3) | 0.9236 (3) | 0.12590 (9) | 0.0118 (3) | |
O21 | 0.7934 (2) | 0.95232 (19) | 0.18942 (7) | 0.0138 (3) | |
O22 | 0.9825 (2) | 0.9765 (2) | 0.09744 (7) | 0.0162 (3) | |
C3 | 0.6390 (3) | 0.8098 (2) | 0.00668 (9) | 0.0108 (3) | |
C4 | 0.4521 (3) | 0.7278 (2) | −0.03265 (9) | 0.0102 (3) | |
O4 | 0.4236 (2) | 0.71664 (19) | −0.09930 (6) | 0.0133 (3) | |
C5 | 0.3012 (3) | 0.6570 (2) | 0.01138 (9) | 0.0103 (4) | |
C6 | 0.3415 (3) | 0.6643 (2) | 0.08294 (9) | 0.0093 (3) | |
C61 | 0.2130 (3) | 0.5782 (2) | 0.13619 (9) | 0.0102 (3) | |
O61 | 0.2756 (2) | 0.60581 (19) | 0.20161 (7) | 0.0133 (3) | |
O62 | 0.0588 (2) | 0.4825 (2) | 0.11096 (7) | 0.0153 (3) | |
N3 | 0.0905 (2) | 0.3231 (2) | 0.27702 (8) | 0.0130 (3) | |
O2 | 0.3223 (2) | 1.09917 (19) | 0.18032 (7) | 0.0129 (3) | |
H3 | 0.7468 | 0.8562 | −0.0184 | 0.013* | |
H5 | 0.1731 | 0.6053 | −0.0105 | 0.012* | |
H3A | 0.1982 | 0.3794 | 0.2623 | 0.016* | |
H3B | 0.0510 | 0.3660 | 0.3218 | 0.016* | |
H3C | 0.1300 | 0.2046 | 0.2777 | 0.016* | |
H2A | 0.3847 | 1.1675 | 0.1538 | 0.019* | |
H2B | 0.2118 | 1.0582 | 0.1500 | 0.019* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ca1 | 0.0120 (3) | 0.0114 (3) | 0.0075 (3) | 0.000 | 0.00036 (18) | 0.000 |
O1 | 0.0094 (6) | 0.0130 (6) | 0.0082 (5) | −0.0044 (5) | 0.0020 (4) | −0.0016 (4) |
C2 | 0.0099 (8) | 0.0087 (7) | 0.0109 (8) | −0.0014 (6) | 0.0038 (6) | −0.0007 (6) |
C21 | 0.0121 (8) | 0.0119 (8) | 0.0110 (8) | −0.0009 (6) | 0.0006 (6) | −0.0010 (6) |
O21 | 0.0151 (6) | 0.0161 (7) | 0.0104 (6) | −0.0034 (5) | 0.0022 (5) | −0.0025 (5) |
O22 | 0.0124 (6) | 0.0222 (7) | 0.0144 (6) | −0.0066 (5) | 0.0035 (5) | −0.0025 (5) |
C3 | 0.0119 (8) | 0.0107 (8) | 0.0104 (8) | −0.0009 (6) | 0.0032 (6) | −0.0004 (6) |
C4 | 0.0129 (8) | 0.0083 (7) | 0.0093 (8) | 0.0010 (6) | 0.0013 (6) | 0.0004 (6) |
O4 | 0.0165 (6) | 0.0164 (7) | 0.0072 (6) | −0.0016 (5) | 0.0017 (5) | 0.0008 (5) |
C5 | 0.0097 (8) | 0.0110 (8) | 0.0102 (8) | −0.0009 (6) | 0.0011 (6) | 0.0002 (6) |
C6 | 0.0077 (7) | 0.0093 (8) | 0.0112 (8) | −0.0016 (6) | 0.0020 (6) | −0.0008 (6) |
C61 | 0.0105 (7) | 0.0112 (8) | 0.0093 (8) | −0.0017 (6) | 0.0027 (6) | 0.0007 (6) |
O61 | 0.0147 (6) | 0.0174 (7) | 0.0078 (6) | −0.0057 (5) | 0.0013 (5) | −0.0008 (5) |
O62 | 0.0141 (6) | 0.0213 (7) | 0.0104 (6) | −0.0093 (5) | 0.0003 (5) | 0.0007 (5) |
N3 | 0.0146 (8) | 0.0144 (7) | 0.0099 (7) | 0.0019 (6) | 0.0012 (6) | −0.0005 (6) |
O2 | 0.0129 (6) | 0.0158 (6) | 0.0102 (6) | −0.0005 (5) | 0.0017 (5) | 0.0034 (5) |
Ca1—O2i | 2.3649 (13) | C3—H3 | 0.95 |
Ca1—O2 | 2.3649 (13) | C4—O4 | 1.247 (2) |
Ca1—O61 | 2.4002 (13) | C4—C5 | 1.449 (2) |
Ca1—O61i | 2.4002 (13) | C5—C6 | 1.340 (2) |
Ca1—O21 | 2.4314 (13) | C5—H5 | 0.95 |
Ca1—O21i | 2.4314 (13) | C6—C61 | 1.510 (2) |
Ca1—O1 | 2.6230 (12) | C61—O62 | 1.248 (2) |
Ca1—O1i | 2.6231 (12) | C61—O61 | 1.261 (2) |
O1—C2 | 1.360 (2) | N3—N3ii | 1.449 (3) |
O1—C6 | 1.362 (2) | N3—H3A | 0.8774 |
C2—C3 | 1.344 (2) | N3—H3B | 0.9617 |
C2—C21 | 1.513 (2) | N3—H3C | 0.8768 |
C21—O22 | 1.244 (2) | O2—H2A | 0.8356 |
C21—O21 | 1.263 (2) | O2—H2B | 0.9040 |
C3—C4 | 1.455 (2) | ||
O2i—Ca1—O2 | 87.09 (7) | C3—C2—C21 | 126.06 (16) |
O2i—Ca1—O61 | 167.11 (4) | O1—C2—C21 | 110.97 (14) |
O2—Ca1—O61 | 95.71 (5) | O22—C21—O21 | 127.74 (17) |
O2i—Ca1—O61i | 95.71 (5) | O22—C21—C2 | 116.78 (15) |
O2—Ca1—O61i | 167.11 (4) | O21—C21—C2 | 115.42 (15) |
O61—Ca1—O61i | 84.35 (7) | C21—O21—Ca1 | 130.38 (11) |
O2i—Ca1—O21 | 72.92 (4) | C2—C3—C4 | 120.05 (16) |
O2—Ca1—O21 | 83.78 (5) | C2—C3—H3 | 120.0 |
O61—Ca1—O21 | 119.85 (4) | C4—C3—H3 | 120.0 |
O61i—Ca1—O21 | 85.03 (5) | O4—C4—C5 | 122.03 (16) |
O2i—Ca1—O21i | 83.78 (4) | O4—C4—C3 | 122.91 (16) |
O2—Ca1—O21i | 72.92 (4) | C5—C4—C3 | 115.05 (15) |
O61—Ca1—O21i | 85.03 (5) | C6—C5—C4 | 120.23 (15) |
O61i—Ca1—O21i | 119.85 (4) | C6—C5—H5 | 119.9 |
O21—Ca1—O21i | 147.79 (7) | C4—C5—H5 | 119.9 |
O2i—Ca1—O1 | 131.80 (4) | C5—C6—O1 | 122.90 (15) |
O2—Ca1—O1 | 76.37 (4) | C5—C6—C61 | 126.81 (15) |
O61—Ca1—O1 | 60.97 (4) | O1—C6—C61 | 110.23 (14) |
O61i—Ca1—O1 | 92.56 (4) | O62—C61—O61 | 126.62 (16) |
O21—Ca1—O1 | 60.62 (4) | O62—C61—C6 | 116.57 (15) |
O21i—Ca1—O1 | 130.95 (4) | O61—C61—C6 | 116.78 (15) |
O2i—Ca1—O1i | 76.37 (4) | C61—O61—Ca1 | 126.03 (11) |
O2—Ca1—O1i | 131.80 (4) | N3ii—N3—H3A | 112.4 |
O61—Ca1—O1i | 92.56 (4) | N3ii—N3—H3B | 109.6 |
O61i—Ca1—O1i | 60.97 (4) | H3A—N3—H3B | 116.3 |
O21—Ca1—O1i | 130.95 (4) | N3ii—N3—H3C | 102.6 |
O21i—Ca1—O1i | 60.62 (4) | H3A—N3—H3C | 101.4 |
O1—Ca1—O1i | 145.42 (6) | H3B—N3—H3C | 113.5 |
C2—O1—C6 | 118.79 (13) | Ca1—O2—H2A | 120.9 |
C2—O1—Ca1 | 121.03 (10) | Ca1—O2—H2B | 114.0 |
C6—O1—Ca1 | 117.02 (10) | H2A—O2—H2B | 102.2 |
C3—C2—O1 | 122.80 (15) | ||
O2i—Ca1—O1—C2 | 7.11 (14) | O21i—Ca1—O21—C21 | −117.74 (16) |
O2—Ca1—O1—C2 | 80.44 (12) | O1—Ca1—O21—C21 | 3.43 (14) |
O61—Ca1—O1—C2 | −174.98 (13) | O1i—Ca1—O21—C21 | 143.11 (14) |
O61i—Ca1—O1—C2 | −92.88 (12) | O1—C2—C3—C4 | 3.6 (3) |
O21—Ca1—O1—C2 | −10.04 (11) | C21—C2—C3—C4 | −171.27 (16) |
O21i—Ca1—O1—C2 | 132.81 (12) | C2—C3—C4—O4 | 179.16 (16) |
O1i—Ca1—O1—C2 | −130.62 (12) | C2—C3—C4—C5 | −1.6 (2) |
O2i—Ca1—O1—C6 | −152.55 (10) | O4—C4—C5—C6 | 177.13 (17) |
O2—Ca1—O1—C6 | −79.22 (11) | C3—C4—C5—C6 | −2.1 (2) |
O61—Ca1—O1—C6 | 25.36 (11) | C4—C5—C6—O1 | 4.2 (3) |
O61i—Ca1—O1—C6 | 107.46 (11) | C4—C5—C6—C61 | −172.81 (16) |
O21—Ca1—O1—C6 | −169.71 (13) | C2—O1—C6—C5 | −2.3 (2) |
O21i—Ca1—O1—C6 | −26.85 (13) | Ca1—O1—C6—C5 | 157.79 (14) |
O1i—Ca1—O1—C6 | 69.72 (11) | C2—O1—C6—C61 | 175.08 (14) |
C6—O1—C2—C3 | −1.7 (2) | Ca1—O1—C6—C61 | −24.78 (17) |
Ca1—O1—C2—C3 | −160.98 (13) | C5—C6—C61—O62 | 3.8 (3) |
C6—O1—C2—C21 | 173.86 (14) | O1—C6—C61—O62 | −173.46 (15) |
Ca1—O1—C2—C21 | 14.55 (18) | C5—C6—C61—O61 | −178.12 (17) |
C3—C2—C21—O22 | −13.2 (3) | O1—C6—C61—O61 | 4.6 (2) |
O1—C2—C21—O22 | 171.45 (16) | O62—C61—O61—Ca1 | −160.20 (14) |
C3—C2—C21—O21 | 164.21 (18) | C6—C61—O61—Ca1 | 22.0 (2) |
O1—C2—C21—O21 | −11.1 (2) | O2i—Ca1—O61—C61 | 147.9 (2) |
O22—C21—O21—Ca1 | 179.72 (14) | O2—Ca1—O61—C61 | 45.89 (15) |
C2—C21—O21—Ca1 | 2.6 (2) | O61i—Ca1—O61—C61 | −121.16 (16) |
O2i—Ca1—O21—C21 | −163.27 (16) | O21—Ca1—O61—C61 | −40.20 (16) |
O2—Ca1—O21—C21 | −74.41 (16) | O21i—Ca1—O61—C61 | 118.13 (15) |
O61—Ca1—O21—C21 | 18.62 (17) | O1—Ca1—O61—C61 | −25.06 (13) |
O61i—Ca1—O21—C21 | 99.19 (16) | O1i—Ca1—O61—C61 | 178.34 (14) |
Symmetry codes: (i) −x+1, y, −z+1/2; (ii) −x, y, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2A···O4iii | 0.84 | 1.89 | 2.7149 (18) | 167 |
O2—H2B···O22iv | 0.90 | 1.77 | 2.6717 (19) | 175 |
N3—H3A···O61 | 0.88 | 2.07 | 2.8091 (19) | 142 |
N3—H3B···O62ii | 0.96 | 1.74 | 2.679 (2) | 166 |
N3—H3C···O21v | 0.88 | 1.93 | 2.781 (2) | 162 |
Symmetry codes: (ii) −x, y, −z+1/2; (iii) −x+1, −y+2, −z; (iv) x−1, y, z; (v) −x+1, y−1, −z+1/2. |
[Mn2(C7H2O6)2(H2O)8]·4H2O | Z = 1 |
Mr = 690.24 | F(000) = 354 |
Triclinic, P1 | Dx = 1.809 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.4343 (2) Å | Cell parameters from 2877 reflections |
b = 10.1176 (3) Å | θ = 1.0–27.5° |
c = 10.2290 (3) Å | µ = 1.11 mm−1 |
α = 61.935 (2)° | T = 120 K |
β = 78.219 (3)° | Block, colourless |
γ = 69.061 (2)° | 0.47 × 0.21 × 0.10 mm |
V = 633.49 (3) Å3 |
Bruker Nonius KappaCCD area-detector diffractometer | 2914 independent reflections |
Radiation source: Bruker Nonius FR591 rotating anode | 2423 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.037 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.6°, θmin = 2.3° |
ϕ and ω scans | h = −9→9 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −13→13 |
Tmin = 0.625, Tmax = 0.898 | l = −13→13 |
14668 measured reflections |
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)] = 0.030 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.074 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0298P)2 + 0.4478P] where P = (Fo2 + 2Fc2)/3 |
2914 reflections | (Δ/σ)max = 0.001 |
181 parameters | Δρmax = 0.45 e Å−3 |
0 restraints | Δρmin = −0.40 e Å−3 |
[Mn2(C7H2O6)2(H2O)8]·4H2O | γ = 69.061 (2)° |
Mr = 690.24 | V = 633.49 (3) Å3 |
Triclinic, P1 | Z = 1 |
a = 7.4343 (2) Å | Mo Kα radiation |
b = 10.1176 (3) Å | µ = 1.11 mm−1 |
c = 10.2290 (3) Å | T = 120 K |
α = 61.935 (2)° | 0.47 × 0.21 × 0.10 mm |
β = 78.219 (3)° |
Bruker Nonius KappaCCD area-detector diffractometer | 2914 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2423 reflections with I > 2σ(I) |
Tmin = 0.625, Tmax = 0.898 | Rint = 0.037 |
14668 measured reflections |
R[F2 > 2σ(F2)] = 0.030 | 0 restraints |
wR(F2) = 0.074 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.45 e Å−3 |
2914 reflections | Δρmin = −0.40 e Å−3 |
181 parameters |
x | y | z | Uiso*/Ueq | ||
Mn1 | 0.31863 (4) | 0.76085 (3) | 0.36918 (3) | 0.01098 (9) | |
O11 | 0.10413 (19) | 0.67707 (15) | 0.54233 (14) | 0.0155 (3) | |
O12 | 0.54328 (18) | 0.84672 (14) | 0.20661 (14) | 0.0137 (3) | |
O13 | 0.11232 (19) | 0.85552 (15) | 0.19602 (14) | 0.0152 (3) | |
O14 | 0.20426 (19) | 0.98191 (15) | 0.37900 (15) | 0.0180 (3) | |
O1 | 0.72562 (18) | 0.44480 (14) | 0.87582 (14) | 0.0115 (3) | |
C2 | 0.6253 (2) | 0.5879 (2) | 0.77498 (19) | 0.0104 (4) | |
C21 | 0.5665 (3) | 0.5768 (2) | 0.6477 (2) | 0.0115 (4) | |
O21 | 0.5760 (2) | 0.44477 (15) | 0.66593 (15) | 0.0170 (3) | |
O22 | 0.50595 (18) | 0.70582 (14) | 0.53764 (14) | 0.0132 (3) | |
C3 | 0.5743 (3) | 0.7197 (2) | 0.7926 (2) | 0.0119 (4) | |
C4 | 0.6237 (3) | 0.7147 (2) | 0.9248 (2) | 0.0122 (4) | |
O4 | 0.5717 (2) | 0.83307 (15) | 0.94879 (14) | 0.0169 (3) | |
C5 | 0.7341 (3) | 0.5617 (2) | 1.0273 (2) | 0.0119 (4) | |
C6 | 0.7787 (2) | 0.4361 (2) | 0.99952 (19) | 0.0106 (4) | |
C61 | 0.8887 (3) | 0.2688 (2) | 1.1021 (2) | 0.0127 (4) | |
O61 | 0.9128 (2) | 0.16511 (15) | 1.06153 (15) | 0.0195 (3) | |
O62 | 0.9432 (2) | 0.25253 (15) | 1.21799 (15) | 0.0175 (3) | |
O15 | 0.1088 (2) | 0.37608 (17) | 0.67361 (18) | 0.0278 (4) | |
O16 | 0.2782 (2) | 1.07386 (16) | 0.57159 (15) | 0.0194 (3) | |
H11A | 0.1093 | 0.5831 | 0.5852 | 0.023* | |
H11B | 0.0938 | 0.6922 | 0.6165 | 0.023* | |
H12A | 0.5532 | 0.8347 | 0.1195 | 0.021* | |
H12B | 0.5191 | 0.9417 | 0.1794 | 0.021* | |
H13A | 0.0422 | 0.9589 | 0.1591 | 0.023* | |
H13B | 0.1467 | 0.8283 | 0.1240 | 0.023* | |
H14A | 0.2359 | 1.0063 | 0.4429 | 0.027* | |
H14B | 0.1232 | 1.0706 | 0.3228 | 0.027* | |
H3 | 0.5055 | 0.8167 | 0.7181 | 0.014* | |
H5 | 0.7755 | 0.5497 | 1.1152 | 0.014* | |
H15A | 0.2212 | 0.3116 | 0.7036 | 0.042* | |
H15B | 0.0224 | 0.3184 | 0.7118 | 0.042* | |
H16A | 0.3508 | 1.1363 | 0.5416 | 0.029* | |
H16B | 0.1565 | 1.1533 | 0.5581 | 0.029* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mn1 | 0.01369 (15) | 0.00878 (15) | 0.01055 (15) | −0.00173 (11) | −0.00393 (10) | −0.00411 (11) |
O11 | 0.0219 (7) | 0.0143 (7) | 0.0123 (7) | −0.0071 (5) | 0.0002 (5) | −0.0067 (6) |
O12 | 0.0210 (7) | 0.0091 (6) | 0.0109 (6) | −0.0039 (5) | −0.0016 (5) | −0.0042 (5) |
O13 | 0.0190 (7) | 0.0120 (6) | 0.0135 (7) | 0.0005 (5) | −0.0067 (5) | −0.0061 (5) |
O14 | 0.0242 (7) | 0.0103 (6) | 0.0188 (7) | 0.0037 (6) | −0.0113 (6) | −0.0082 (6) |
O1 | 0.0143 (6) | 0.0092 (6) | 0.0103 (6) | −0.0010 (5) | −0.0046 (5) | −0.0039 (5) |
C2 | 0.0097 (8) | 0.0084 (8) | 0.0102 (8) | −0.0012 (7) | −0.0023 (7) | −0.0020 (7) |
C21 | 0.0111 (8) | 0.0115 (9) | 0.0112 (9) | −0.0012 (7) | −0.0025 (7) | −0.0053 (7) |
O21 | 0.0266 (8) | 0.0096 (6) | 0.0168 (7) | −0.0017 (6) | −0.0078 (6) | −0.0074 (6) |
O22 | 0.0169 (7) | 0.0111 (6) | 0.0111 (6) | −0.0032 (5) | −0.0060 (5) | −0.0031 (5) |
C3 | 0.0132 (9) | 0.0104 (9) | 0.0098 (9) | −0.0025 (7) | −0.0026 (7) | −0.0024 (7) |
C4 | 0.0148 (9) | 0.0109 (9) | 0.0117 (9) | −0.0055 (7) | 0.0002 (7) | −0.0046 (7) |
O4 | 0.0277 (8) | 0.0107 (6) | 0.0129 (7) | −0.0039 (6) | −0.0038 (6) | −0.0059 (5) |
C5 | 0.0142 (9) | 0.0122 (9) | 0.0097 (9) | −0.0042 (7) | −0.0011 (7) | −0.0046 (7) |
C6 | 0.0107 (8) | 0.0128 (9) | 0.0073 (8) | −0.0036 (7) | −0.0018 (7) | −0.0030 (7) |
C61 | 0.0139 (9) | 0.0104 (9) | 0.0108 (9) | −0.0003 (7) | −0.0022 (7) | −0.0039 (7) |
O61 | 0.0285 (8) | 0.0111 (6) | 0.0167 (7) | 0.0017 (6) | −0.0100 (6) | −0.0063 (6) |
O62 | 0.0233 (7) | 0.0139 (7) | 0.0141 (7) | 0.0006 (5) | −0.0091 (6) | −0.0064 (6) |
O15 | 0.0189 (8) | 0.0178 (7) | 0.0398 (9) | −0.0065 (6) | −0.0054 (7) | −0.0048 (7) |
O16 | 0.0222 (7) | 0.0176 (7) | 0.0219 (7) | −0.0079 (6) | −0.0024 (6) | −0.0093 (6) |
Mn1—O21i | 2.1199 (13) | C2—C21 | 1.517 (2) |
Mn1—O14 | 2.1337 (13) | C21—O21 | 1.237 (2) |
Mn1—O22 | 2.1775 (12) | C21—O22 | 1.256 (2) |
Mn1—O11 | 2.1905 (13) | O21—Mn1i | 2.1199 (13) |
Mn1—O12 | 2.2030 (13) | C3—C4 | 1.447 (2) |
Mn1—O13 | 2.2068 (13) | C3—H3 | 0.95 |
O11—H11A | 0.8286 | C4—O4 | 1.246 (2) |
O11—H11B | 0.8254 | C4—C5 | 1.444 (2) |
O12—H12A | 0.9395 | C5—C6 | 1.343 (3) |
O12—H12B | 0.8240 | C5—H5 | 0.95 |
O13—H13A | 0.9097 | C6—C61 | 1.525 (2) |
O13—H13B | 0.8645 | C61—O61 | 1.245 (2) |
O14—H14A | 0.8941 | C61—O62 | 1.249 (2) |
O14—H14B | 0.8765 | O15—H15A | 0.8632 |
O1—C6 | 1.356 (2) | O15—H15B | 0.9256 |
O1—C2 | 1.361 (2) | O16—H16A | 0.8823 |
C2—C3 | 1.338 (3) | O16—H16B | 0.9536 |
O21i—Mn1—O14 | 173.56 (5) | C6—O1—C2 | 118.14 (14) |
O21i—Mn1—O22 | 102.25 (5) | C3—C2—O1 | 123.42 (16) |
O14—Mn1—O22 | 83.30 (5) | C3—C2—C21 | 124.58 (16) |
O21i—Mn1—O11 | 94.50 (5) | O1—C2—C21 | 111.85 (14) |
O14—Mn1—O11 | 88.72 (5) | O21—C21—O22 | 127.61 (17) |
O22—Mn1—O11 | 90.12 (5) | O21—C21—C2 | 117.13 (15) |
O21i—Mn1—O12 | 87.64 (5) | O22—C21—C2 | 115.19 (15) |
O14—Mn1—O12 | 89.50 (5) | C21—O21—Mn1i | 156.82 (13) |
O22—Mn1—O12 | 86.04 (5) | C21—O22—Mn1 | 127.91 (11) |
O11—Mn1—O12 | 175.93 (5) | C2—C3—C4 | 120.14 (16) |
O21i—Mn1—O13 | 86.92 (5) | C2—C3—H3 | 119.9 |
O14—Mn1—O13 | 87.46 (5) | C4—C3—H3 | 119.9 |
O22—Mn1—O13 | 170.70 (5) | O4—C4—C5 | 122.98 (16) |
O11—Mn1—O13 | 90.69 (5) | O4—C4—C3 | 122.24 (16) |
O12—Mn1—O13 | 92.89 (5) | C5—C4—C3 | 114.77 (15) |
Mn1—O11—H11A | 121.7 | C6—C5—C4 | 120.63 (16) |
Mn1—O11—H11B | 117.0 | C6—C5—H5 | 119.7 |
H11A—O11—H11B | 98.1 | C4—C5—H5 | 119.7 |
Mn1—O12—H12A | 114.3 | C5—C6—O1 | 122.86 (16) |
Mn1—O12—H12B | 109.9 | C5—C6—C61 | 124.97 (16) |
H12A—O12—H12B | 105.5 | O1—C6—C61 | 112.16 (15) |
Mn1—O13—H13A | 119.3 | O61—C61—O62 | 127.79 (17) |
Mn1—O13—H13B | 118.9 | O61—C61—C6 | 116.70 (16) |
H13A—O13—H13B | 108.6 | O62—C61—C6 | 115.50 (16) |
Mn1—O14—H14A | 126.0 | H15A—O15—H15B | 107.3 |
Mn1—O14—H14B | 131.2 | H16A—O16—H16B | 97.1 |
H14A—O14—H14B | 102.7 | ||
C6—O1—C2—C3 | −0.9 (3) | O1—C2—C3—C4 | −0.7 (3) |
C6—O1—C2—C21 | −176.66 (15) | C21—C2—C3—C4 | 174.50 (17) |
C3—C2—C21—O21 | −160.11 (18) | C2—C3—C4—O4 | −176.72 (17) |
O1—C2—C21—O21 | 15.6 (2) | C2—C3—C4—C5 | 2.1 (3) |
C3—C2—C21—O22 | 17.1 (3) | O4—C4—C5—C6 | 176.80 (18) |
O1—C2—C21—O22 | −167.24 (15) | C3—C4—C5—C6 | −2.0 (3) |
O22—C21—O21—Mn1i | 71.4 (4) | C4—C5—C6—O1 | 0.5 (3) |
C2—C21—O21—Mn1i | −111.9 (3) | C4—C5—C6—C61 | −177.98 (16) |
O21—C21—O22—Mn1 | 20.1 (3) | C2—O1—C6—C5 | 1.0 (3) |
C2—C21—O22—Mn1 | −156.77 (12) | C2—O1—C6—C61 | 179.68 (14) |
O21i—Mn1—O22—C21 | −39.88 (15) | C5—C6—C61—O61 | 177.81 (18) |
O14—Mn1—O22—C21 | 143.45 (15) | O1—C6—C61—O61 | −0.8 (2) |
O11—Mn1—O22—C21 | 54.75 (15) | C5—C6—C61—O62 | −1.8 (3) |
O12—Mn1—O22—C21 | −126.59 (15) | O1—C6—C61—O62 | 179.55 (16) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O11—H11A···O15 | 0.83 | 1.85 | 2.6784 (19) | 176 |
O11—H11B···O62ii | 0.83 | 1.96 | 2.7846 (18) | 175 |
O12—H12A···O4iii | 0.94 | 1.73 | 2.6670 (18) | 174 |
O12—H12B···O4iv | 0.82 | 1.95 | 2.7356 (18) | 158 |
O13—H13A···O61v | 0.91 | 1.81 | 2.7133 (18) | 172 |
O13—H13B···O61i | 0.86 | 2.00 | 2.7866 (18) | 151 |
O14—H14A···O16 | 0.89 | 1.86 | 2.7532 (19) | 174 |
O14—H14B···O62v | 0.88 | 1.82 | 2.6908 (18) | 176 |
O15—H15A···O12i | 0.86 | 1.93 | 2.7930 (19) | 173 |
O15—H15B···O13vi | 0.93 | 2.07 | 2.9814 (19) | 166 |
O16—H16A···O22iv | 0.88 | 2.00 | 2.8765 (19) | 175 |
O16—H16B···O11vii | 0.95 | 2.13 | 3.0423 (19) | 160 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y+1, −z+2; (iii) x, y, z−1; (iv) −x+1, −y+2, −z+1; (v) x−1, y+1, z−1; (vi) −x, −y+1, −z+1; (vii) −x, −y+2, −z+1. |
[Cu(C7H2O6)(H2O)4] | Z = 2 |
Mr = 317.70 | F(000) = 322 |
Triclinic, P1 | Dx = 2.086 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 4.9593 (6) Å | Cell parameters from 2264 reflections |
b = 9.8973 (14) Å | θ = 3.0–27.7° |
c = 10.4697 (12) Å | µ = 2.21 mm−1 |
α = 94.237 (9)° | T = 120 K |
β = 94.955 (9)° | Block, green |
γ = 97.353 (6)° | 0.12 × 0.12 × 0.10 mm |
V = 505.88 (11) Å3 |
Bruker Nonius KappaCCD area-detector diffractometer | 2264 independent reflections |
Radiation source: Bruker Nonius FR591 rotating anode | 2043 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.034 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.7°, θmin = 3.0° |
ϕ and ω scans | h = −6→6 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −12→12 |
Tmin = 0.777, Tmax = 0.809 | l = −13→13 |
6400 measured reflections |
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)] = 0.052 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.156 | H-atom parameters constrained |
S = 1.12 | w = 1/[σ2(Fo2) + (0.0763P)2 + 2.2295P] where P = (Fo2 + 2Fc2)/3 |
2264 reflections | (Δ/σ)max < 0.001 |
167 parameters | Δρmax = 1.42 e Å−3 |
0 restraints | Δρmin = −1.42 e Å−3 |
[Cu(C7H2O6)(H2O)4] | γ = 97.353 (6)° |
Mr = 317.70 | V = 505.88 (11) Å3 |
Triclinic, P1 | Z = 2 |
a = 4.9593 (6) Å | Mo Kα radiation |
b = 9.8973 (14) Å | µ = 2.21 mm−1 |
c = 10.4697 (12) Å | T = 120 K |
α = 94.237 (9)° | 0.12 × 0.12 × 0.10 mm |
β = 94.955 (9)° |
Bruker Nonius KappaCCD area-detector diffractometer | 2264 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2043 reflections with I > 2σ(I) |
Tmin = 0.777, Tmax = 0.809 | Rint = 0.034 |
6400 measured reflections |
R[F2 > 2σ(F2)] = 0.052 | 0 restraints |
wR(F2) = 0.156 | H-atom parameters constrained |
S = 1.12 | Δρmax = 1.42 e Å−3 |
2264 reflections | Δρmin = −1.42 e Å−3 |
167 parameters |
x | y | z | Uiso*/Ueq | ||
Cu1 | 0.0000 | 0.0000 | 0.5000 | 0.0106 (2) | |
O1A | 0.2978 (6) | −0.0275 (3) | 0.6286 (3) | 0.0144 (6) | |
O1B | 0.1358 (8) | −0.1487 (3) | 0.3266 (4) | 0.0238 (8) | |
Cu2 | 0.5000 | 0.0000 | 0.0000 | 0.0108 (2) | |
O2A | 0.3739 (7) | 0.1700 (3) | −0.0507 (3) | 0.0175 (7) | |
O2B | 0.2379 (6) | −0.0106 (3) | 0.1229 (3) | 0.0179 (7) | |
O1 | 0.5368 (6) | 0.2869 (3) | 0.2755 (3) | 0.0132 (6) | |
C2 | 0.3774 (8) | 0.3563 (4) | 0.3476 (4) | 0.0119 (8) | |
C21 | 0.2055 (9) | 0.2683 (4) | 0.4303 (4) | 0.0143 (8) | |
O21 | 0.2528 (6) | 0.1442 (3) | 0.4337 (3) | 0.0140 (6) | |
O22 | 0.0323 (8) | 0.3231 (4) | 0.4846 (4) | 0.0273 (8) | |
C3 | 0.3702 (9) | 0.4924 (4) | 0.3446 (4) | 0.0150 (8) | |
C4 | 0.5389 (10) | 0.5700 (4) | 0.2643 (5) | 0.0172 (9) | |
O4 | 0.5466 (9) | 0.6975 (4) | 0.2634 (4) | 0.0292 (9) | |
C5 | 0.7043 (9) | 0.4922 (5) | 0.1875 (5) | 0.0167 (9) | |
C6 | 0.6990 (8) | 0.3571 (4) | 0.1981 (4) | 0.0122 (8) | |
C61 | 0.8765 (8) | 0.2673 (4) | 0.1289 (4) | 0.0119 (8) | |
O61 | 0.8556 (6) | 0.1442 (3) | 0.1577 (3) | 0.0149 (6) | |
O62 | 1.0274 (7) | 0.3210 (3) | 0.0545 (3) | 0.0179 (7) | |
H11A | 0.4442 | −0.0615 | 0.6064 | 0.022* | |
H12A | 0.2531 | −0.0696 | 0.6963 | 0.022* | |
H11B | −0.0203 | −0.2028 | 0.3091 | 0.036* | |
H12B | 0.2808 | −0.1903 | 0.3401 | 0.036* | |
H21A | 0.2306 | 0.2025 | −0.0229 | 0.026* | |
H22A | 0.4215 | 0.2072 | −0.1206 | 0.026* | |
H21B | 0.1092 | 0.0428 | 0.1254 | 0.027* | |
H22B | 0.1985 | −0.0713 | 0.1781 | 0.027* | |
H3 | 0.2527 | 0.5364 | 0.3959 | 0.018* | |
H5 | 0.8165 | 0.5364 | 0.1296 | 0.020* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0075 (3) | 0.0116 (4) | 0.0133 (4) | 0.0006 (3) | 0.0033 (3) | 0.0042 (3) |
O1A | 0.0110 (13) | 0.0164 (15) | 0.0167 (15) | 0.0024 (11) | 0.0022 (11) | 0.0058 (12) |
O1B | 0.0273 (18) | 0.0173 (16) | 0.029 (2) | 0.0019 (14) | 0.0126 (15) | 0.0036 (14) |
Cu2 | 0.0090 (3) | 0.0124 (4) | 0.0123 (4) | 0.0028 (3) | 0.0042 (3) | 0.0032 (3) |
O2A | 0.0182 (15) | 0.0187 (16) | 0.0192 (17) | 0.0081 (12) | 0.0096 (13) | 0.0070 (13) |
O2B | 0.0155 (15) | 0.0210 (16) | 0.0211 (17) | 0.0093 (13) | 0.0078 (12) | 0.0098 (13) |
O1 | 0.0124 (14) | 0.0129 (14) | 0.0153 (15) | 0.0026 (11) | 0.0056 (12) | 0.0010 (12) |
C2 | 0.0120 (18) | 0.015 (2) | 0.0095 (19) | 0.0011 (15) | 0.0035 (15) | 0.0017 (15) |
C21 | 0.0140 (19) | 0.014 (2) | 0.015 (2) | −0.0009 (15) | 0.0058 (16) | 0.0019 (16) |
O21 | 0.0123 (13) | 0.0136 (14) | 0.0172 (16) | 0.0022 (11) | 0.0039 (11) | 0.0047 (12) |
O22 | 0.0300 (19) | 0.0164 (16) | 0.041 (2) | 0.0063 (14) | 0.0256 (17) | 0.0076 (15) |
C3 | 0.0152 (19) | 0.016 (2) | 0.015 (2) | 0.0053 (16) | 0.0036 (16) | 0.0017 (16) |
C4 | 0.023 (2) | 0.0099 (19) | 0.020 (2) | 0.0034 (16) | 0.0066 (18) | 0.0036 (16) |
O4 | 0.050 (2) | 0.0136 (16) | 0.029 (2) | 0.0093 (16) | 0.0218 (18) | 0.0053 (14) |
C5 | 0.019 (2) | 0.016 (2) | 0.016 (2) | 0.0031 (17) | 0.0083 (17) | 0.0033 (17) |
C6 | 0.0113 (18) | 0.014 (2) | 0.012 (2) | 0.0017 (15) | 0.0036 (15) | 0.0027 (15) |
C61 | 0.0100 (18) | 0.016 (2) | 0.010 (2) | 0.0041 (15) | 0.0015 (15) | −0.0009 (15) |
O61 | 0.0150 (14) | 0.0150 (15) | 0.0164 (16) | 0.0034 (12) | 0.0069 (12) | 0.0042 (12) |
O62 | 0.0205 (16) | 0.0170 (16) | 0.0190 (17) | 0.0048 (12) | 0.0122 (13) | 0.0047 (12) |
Cu1—O1A | 1.970 (3) | O2B—H21B | 0.8801 |
Cu1—O1Ai | 1.970 (3) | O2B—H22B | 0.88 |
Cu1—O21 | 1.982 (3) | O1—C2 | 1.353 (5) |
Cu1—O21i | 1.982 (3) | O1—C6 | 1.357 (5) |
Cu1—O1B | 2.447 (4) | C2—C3 | 1.355 (6) |
Cu1—O1Bi | 2.447 (4) | C2—C21 | 1.511 (6) |
O1A—H11A | 0.8797 | C21—O22 | 1.230 (6) |
O1A—H12A | 0.8794 | C21—O21 | 1.282 (5) |
O1B—H11B | 0.88 | C3—C4 | 1.432 (6) |
O1B—H12B | 0.8798 | C3—H3 | 0.95 |
Cu2—O2Aii | 1.961 (3) | C4—O4 | 1.258 (6) |
Cu2—O2A | 1.961 (3) | C4—C5 | 1.449 (6) |
Cu2—O2B | 1.906 (3) | C5—C6 | 1.346 (6) |
Cu2—O2Bii | 1.906 (3) | C5—H5 | 0.95 |
Cu2—O61 | 2.525 (3) | C6—C61 | 1.518 (6) |
Cu2—O61ii | 2.525 (3) | C61—O62 | 1.228 (6) |
O2A—H21A | 0.88 | C61—O61 | 1.271 (5) |
O2A—H22A | 0.8801 | ||
O1A—Cu1—O1Ai | 180.0 | O1—C2—C3 | 122.9 (4) |
O1A—Cu1—O21 | 88.68 (13) | O1—C2—C21 | 114.1 (4) |
O1Ai—Cu1—O21 | 91.32 (13) | C3—C2—C21 | 123.0 (4) |
O1A—Cu1—O21i | 91.32 (13) | O22—C21—O21 | 127.4 (4) |
O1Ai—Cu1—O21i | 88.68 (13) | O22—C21—C2 | 116.3 (4) |
O21—Cu1—O21i | 180.00 (13) | O21—C21—C2 | 116.3 (4) |
Cu1—O1A—H11A | 121.8 | C21—O21—Cu1 | 123.0 (3) |
Cu1—O1A—H12A | 117.6 | C2—C3—C4 | 120.2 (4) |
H11A—O1A—H12A | 104.6 | C2—C3—H3 | 119.9 |
H11B—O1B—H12B | 115.4 | C4—C3—H3 | 119.9 |
O2B—Cu2—O2Bii | 180.0 (3) | O4—C4—C3 | 122.0 (4) |
O2B—Cu2—O2Aii | 91.08 (13) | O4—C4—C5 | 122.7 (4) |
O2Bii—Cu2—O2Aii | 88.92 (13) | C3—C4—C5 | 115.3 (4) |
O2B—Cu2—O2A | 88.92 (13) | C6—C5—C4 | 120.0 (4) |
O2Bii—Cu2—O2A | 91.08 (13) | C6—C5—H5 | 120.0 |
O2Aii—Cu2—O2A | 180.00 (19) | C4—C5—H5 | 120.0 |
Cu2—O2A—H21A | 124.2 | C5—C6—O1 | 123.0 (4) |
Cu2—O2A—H22A | 122.0 | C5—C6—C61 | 124.5 (4) |
H21A—O2A—H22A | 111.2 | O1—C6—C61 | 112.4 (3) |
Cu2—O2B—H21B | 122.9 | O62—C61—O61 | 127.3 (4) |
Cu2—O2B—H22B | 131.3 | O62—C61—C6 | 117.4 (4) |
H21B—O2B—H22B | 105.2 | O61—C61—C6 | 115.3 (4) |
C2—O1—C6 | 118.5 (3) | ||
C6—O1—C2—C3 | 0.9 (6) | C2—C3—C4—O4 | −176.8 (5) |
C6—O1—C2—C21 | −179.9 (4) | C2—C3—C4—C5 | 1.6 (7) |
O1—C2—C21—O22 | −171.0 (4) | O4—C4—C5—C6 | 176.2 (5) |
C3—C2—C21—O22 | 8.2 (7) | C3—C4—C5—C6 | −2.2 (7) |
O1—C2—C21—O21 | 7.6 (6) | C4—C5—C6—O1 | 2.3 (7) |
C3—C2—C21—O21 | −173.2 (4) | C4—C5—C6—C61 | −176.0 (4) |
O22—C21—O21—Cu1 | 13.4 (7) | C2—O1—C6—C5 | −1.5 (6) |
C2—C21—O21—Cu1 | −165.0 (3) | C2—O1—C6—C61 | 176.9 (3) |
O1A—Cu1—O21—C21 | −121.0 (3) | C5—C6—C61—O62 | −2.9 (6) |
O1Ai—Cu1—O21—C21 | 59.0 (3) | O1—C6—C61—O62 | 178.7 (4) |
O1—C2—C3—C4 | −1.0 (7) | C5—C6—C61—O61 | 175.4 (4) |
C21—C2—C3—C4 | 179.8 (4) | O1—C6—C61—O61 | −3.0 (5) |
Symmetry codes: (i) −x, −y, −z+1; (ii) −x+1, −y, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1A—H11A···O21iii | 0.88 | 1.86 | 2.743 (4) | 176 |
O1A—H12A···O61iii | 0.88 | 1.84 | 2.715 (4) | 175 |
O1B—H11B···O4iv | 0.88 | 2.24 | 3.110 (6) | 169 |
O1B—H12B···O4v | 0.88 | 2.01 | 2.790 (5) | 147 |
O2A—H21A···O62vi | 0.88 | 1.83 | 2.672 (4) | 160 |
O2A—H22A···O4vii | 0.88 | 1.83 | 2.699 (5) | 168 |
O2B—H21B···O61vi | 0.88 | 1.75 | 2.618 (4) | 170 |
O2B—H22B···O1B | 0.88 | 1.82 | 2.666 (5) | 162 |
Symmetry codes: (iii) −x+1, −y, −z+1; (iv) x−1, y−1, z; (v) x, y−1, z; (vi) x−1, y, z; (vii) −x+1, −y+1, −z. |
[Cd(C7H2O6)(H2O)2]·H2O | Z = 1 |
Mr = 348.53 | F(000) = 170 |
Triclinic, P1 | Dx = 2.434 Mg m−3 |
Hall symbol: P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 5.3262 (2) Å | Cell parameters from 2108 reflections |
b = 6.2885 (2) Å | θ = 3.6–27.7° |
c = 8.1008 (3) Å | µ = 2.34 mm−1 |
α = 97.733 (2)° | T = 120 K |
β = 105.0554 (17)° | Block, colourless |
γ = 110.4356 (18)° | 0.10 × 0.04 × 0.04 mm |
V = 237.80 (2) Å3 |
Bruker Nonius KappaCCD area-detector diffractometer | 2108 independent reflections |
Radiation source: Bruker Nonius FR591 rotating anode | 2108 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.050 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.7°, θmin = 3.6° |
ϕ and ω scans | h = −6→6 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −8→8 |
Tmin = 0.781, Tmax = 0.912 | l = −10→10 |
7006 measured reflections |
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)] = 0.018 | H-atom parameters constrained |
wR(F2) = 0.042 | w = 1/[σ2(Fo2) + (0.0114P)2 + 0.0048P] where P = (Fo2 + 2Fc2)/3 |
S = 1.15 | (Δ/σ)max = 0.001 |
2108 reflections | Δρmax = 0.58 e Å−3 |
136 parameters | Δρmin = −0.98 e Å−3 |
3 restraints | Absolute structure: Flack (1983), with 1003 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.002 (17) |
[Cd(C7H2O6)(H2O)2]·H2O | γ = 110.4356 (18)° |
Mr = 348.53 | V = 237.80 (2) Å3 |
Triclinic, P1 | Z = 1 |
a = 5.3262 (2) Å | Mo Kα radiation |
b = 6.2885 (2) Å | µ = 2.34 mm−1 |
c = 8.1008 (3) Å | T = 120 K |
α = 97.733 (2)° | 0.10 × 0.04 × 0.04 mm |
β = 105.0554 (17)° |
Bruker Nonius KappaCCD area-detector diffractometer | 2108 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2108 reflections with I > 2σ(I) |
Tmin = 0.781, Tmax = 0.912 | Rint = 0.050 |
7006 measured reflections |
R[F2 > 2σ(F2)] = 0.018 | H-atom parameters constrained |
wR(F2) = 0.042 | Δρmax = 0.58 e Å−3 |
S = 1.15 | Δρmin = −0.98 e Å−3 |
2108 reflections | Absolute structure: Flack (1983), with 1003 Friedel pairs |
136 parameters | Absolute structure parameter: −0.002 (17) |
3 restraints |
x | y | z | Uiso*/Ueq | ||
Cd1 | 0.00000 (1) | 0.50000 (1) | 0.00000 (1) | 0.00988 (6) | |
O11 | −0.0137 (5) | 0.7926 (4) | −0.1443 (3) | 0.0143 (4) | |
O12 | −0.4494 (4) | 0.2331 (4) | −0.1384 (3) | 0.0162 (4) | |
O13 | 0.4510 (7) | 0.7778 (6) | 0.6771 (4) | 0.0165 (7) | |
O1 | 0.5050 (4) | 0.0405 (3) | 0.2331 (3) | 0.0096 (3) | |
C2 | 0.5019 (10) | 0.2251 (8) | 0.3401 (6) | 0.0097 (5) | |
C21 | 0.2943 (6) | 0.3182 (5) | 0.2507 (4) | 0.0104 (5) | |
O21 | 0.1374 (5) | 0.2152 (4) | 0.0927 (3) | 0.0116 (4) | |
O22 | 0.2975 (4) | 0.4995 (4) | 0.3360 (3) | 0.0142 (4) | |
C3 | 0.6760 (6) | 0.3164 (5) | 0.5079 (4) | 0.0099 (4) | |
C4 | 0.8828 (6) | 0.2263 (5) | 0.5826 (4) | 0.0096 (3) | |
O4 | 1.0493 (6) | 0.3090 (5) | 0.7377 (4) | 0.0131 (6) | |
C5 | 0.8833 (6) | 0.0358 (5) | 0.4631 (4) | 0.0097 (5) | |
C6 | 0.6983 (6) | −0.0471 (5) | 0.2967 (4) | 0.0099 (4) | |
C61 | 0.6863 (6) | −0.2438 (5) | 0.1608 (4) | 0.0097 (5) | |
O61 | 0.4763 (4) | −0.3306 (4) | 0.0227 (3) | 0.0120 (4) | |
O62 | 0.8958 (6) | −0.2957 (5) | 0.2016 (4) | 0.0138 (6) | |
H11A | −0.1770 | 0.7758 | −0.1936 | 0.021* | |
H11B | 0.0595 | 0.9165 | −0.0687 | 0.021* | |
H12A | −0.4789 | 0.0975 | −0.1811 | 0.024* | |
H12B | −0.6066 | 0.2366 | −0.1597 | 0.024* | |
H13A | 0.3396 | 0.7017 | 0.7217 | 0.025* | |
H13B | 0.3841 | 0.7135 | 0.5714 | 0.025* | |
H3 | 0.6629 | 0.4427 | 0.5788 | 0.012* | |
H5 | 1.0148 | −0.0323 | 0.5015 | 0.012* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cd1 | 0.01116 (9) | 0.01089 (9) | 0.00812 (9) | 0.00639 (6) | 0.00209 (6) | 0.00079 (6) |
O11 | 0.0189 (11) | 0.0092 (10) | 0.0119 (11) | 0.0060 (8) | 0.0013 (9) | −0.0003 (8) |
O12 | 0.0101 (9) | 0.0134 (10) | 0.0216 (12) | 0.0053 (8) | 0.0018 (9) | −0.0019 (9) |
O13 | 0.0201 (15) | 0.0155 (12) | 0.0102 (13) | 0.0035 (11) | 0.0059 (10) | −0.0002 (10) |
O1 | 0.0103 (7) | 0.0103 (8) | 0.0068 (8) | 0.0053 (6) | 0.0002 (6) | −0.0006 (6) |
C2 | 0.0106 (10) | 0.0105 (11) | 0.0102 (11) | 0.0069 (8) | 0.0036 (8) | 0.0020 (9) |
C21 | 0.0110 (12) | 0.0092 (13) | 0.0103 (13) | 0.0046 (10) | 0.0018 (10) | 0.0025 (10) |
O21 | 0.0134 (10) | 0.0124 (10) | 0.0085 (10) | 0.0080 (8) | −0.0004 (8) | 0.0012 (8) |
O22 | 0.0159 (10) | 0.0151 (11) | 0.0138 (11) | 0.0105 (8) | 0.0036 (8) | 0.0015 (8) |
C3 | 0.0108 (9) | 0.0093 (10) | 0.0103 (10) | 0.0056 (8) | 0.0033 (8) | 0.0010 (8) |
C4 | 0.0103 (7) | 0.0103 (8) | 0.0068 (8) | 0.0053 (6) | 0.0002 (6) | −0.0006 (6) |
O4 | 0.0120 (12) | 0.0147 (12) | 0.0095 (14) | 0.0077 (10) | −0.0014 (11) | −0.0034 (11) |
C5 | 0.0106 (10) | 0.0105 (11) | 0.0102 (11) | 0.0069 (8) | 0.0036 (8) | 0.0020 (9) |
C6 | 0.0108 (9) | 0.0093 (10) | 0.0103 (10) | 0.0056 (8) | 0.0033 (8) | 0.0010 (8) |
C61 | 0.0129 (13) | 0.0093 (13) | 0.0074 (13) | 0.0052 (11) | 0.0037 (11) | 0.0007 (10) |
O61 | 0.0099 (9) | 0.0137 (10) | 0.0077 (10) | 0.0031 (8) | 0.0002 (8) | −0.0021 (8) |
O62 | 0.0127 (13) | 0.0177 (13) | 0.0104 (15) | 0.0096 (10) | 0.0002 (11) | −0.0010 (11) |
Cd1—O62i | 2.242 (3) | C2—C3 | 1.341 (6) |
Cd1—O12 | 2.258 (2) | C2—C21 | 1.497 (6) |
Cd1—O21 | 2.302 (2) | C21—O22 | 1.243 (4) |
Cd1—O11 | 2.320 (2) | C21—O21 | 1.265 (4) |
Cd1—O61ii | 2.3284 (19) | C3—C4 | 1.443 (4) |
Cd1—O4iii | 2.419 (3) | C3—H3 | 0.95 |
O11—H11A | 0.82 | C4—O4 | 1.249 (4) |
O11—H11B | 0.82 | C4—C5 | 1.436 (4) |
O12—H12A | 0.82 | C5—C6 | 1.350 (4) |
O12—H12B | 0.82 | C5—H5 | 0.95 |
O13—H13A | 0.82 | C6—C61 | 1.512 (4) |
O13—H13B | 0.82 | C61—O62 | 1.246 (4) |
O1—C6 | 1.351 (3) | C61—O61 | 1.249 (4) |
O1—C2 | 1.360 (5) | ||
O62i—Cd1—O12 | 95.60 (9) | C3—C2—C21 | 124.2 (4) |
O62i—Cd1—O21 | 113.93 (9) | O1—C2—C21 | 113.5 (4) |
O12—Cd1—O21 | 90.83 (8) | O22—C21—O21 | 124.4 (3) |
O62i—Cd1—O11 | 83.99 (9) | O22—C21—C2 | 117.0 (3) |
O12—Cd1—O11 | 99.26 (8) | O21—C21—C2 | 118.6 (3) |
O21—Cd1—O11 | 158.60 (7) | C21—O21—Cd1 | 102.03 (17) |
O62i—Cd1—O61ii | 112.34 (9) | C2—C3—C4 | 121.2 (3) |
O12—Cd1—O61ii | 151.83 (7) | C2—C3—H3 | 119.4 |
O21—Cd1—O61ii | 81.34 (8) | C4—C3—H3 | 119.4 |
O11—Cd1—O61ii | 80.92 (8) | O4—C4—C5 | 122.9 (3) |
O62i—Cd1—O4iii | 167.51 (8) | O4—C4—C3 | 122.7 (3) |
O12—Cd1—O4iii | 79.30 (9) | C5—C4—C3 | 114.4 (2) |
O21—Cd1—O4iii | 77.76 (9) | C4—O4—Cd1iv | 131.0 (2) |
O11—Cd1—O4iii | 85.59 (9) | C6—C5—C4 | 120.5 (3) |
O61ii—Cd1—O4iii | 72.61 (9) | C6—C5—H5 | 119.8 |
Cd1—O11—H11A | 111.7 | C4—C5—H5 | 119.8 |
Cd1—O11—H11B | 107.2 | C5—C6—O1 | 123.1 (3) |
H11A—O11—H11B | 106.1 | C5—C6—C61 | 124.3 (3) |
Cd1—O12—H12A | 120.0 | O1—C6—C61 | 112.7 (2) |
Cd1—O12—H12B | 134.7 | O62—C61—O61 | 128.1 (3) |
H12A—O12—H12B | 105.3 | O62—C61—C6 | 114.3 (3) |
H13A—O13—H13B | 105.7 | O61—C61—C6 | 117.7 (2) |
C6—O1—C2 | 118.5 (3) | C61—O61—Cd1v | 127.30 (17) |
C3—C2—O1 | 122.3 (4) | C61—O62—Cd1vi | 121.8 (2) |
C6—O1—C2—C3 | −2.7 (6) | C5—C4—O4—Cd1iv | −151.7 (2) |
C6—O1—C2—C21 | 175.5 (3) | C3—C4—O4—Cd1iv | 29.1 (5) |
C3—C2—C21—O22 | 4.2 (6) | O4—C4—C5—C6 | 179.9 (3) |
O1—C2—C21—O22 | −173.9 (3) | C3—C4—C5—C6 | −0.8 (4) |
C3—C2—C21—O21 | −178.8 (4) | C4—C5—C6—O1 | −0.2 (4) |
O1—C2—C21—O21 | 3.0 (5) | C4—C5—C6—C61 | 178.9 (2) |
O22—C21—O21—Cd1 | 16.8 (3) | C2—O1—C6—C5 | 1.9 (5) |
C2—C21—O21—Cd1 | −159.9 (3) | C2—O1—C6—C61 | −177.3 (3) |
O62i—Cd1—O21—C21 | −40.9 (2) | C5—C6—C61—O62 | −13.3 (4) |
O12—Cd1—O21—C21 | −137.45 (18) | O1—C6—C61—O62 | 165.9 (3) |
O11—Cd1—O21—C21 | 104.0 (3) | C5—C6—C61—O61 | 168.0 (3) |
O61ii—Cd1—O21—C21 | 69.73 (18) | O1—C6—C61—O61 | −12.8 (4) |
O4iii—Cd1—O21—C21 | 143.69 (19) | O62—C61—O61—Cd1v | 124.3 (3) |
O1—C2—C3—C4 | 1.7 (6) | C6—C61—O61—Cd1v | −57.2 (3) |
C21—C2—C3—C4 | −176.3 (3) | O61—C61—O62—Cd1vi | 16.7 (5) |
C2—C3—C4—O4 | 179.3 (4) | C6—C61—O62—Cd1vi | −161.86 (19) |
C2—C3—C4—C5 | 0.1 (4) |
Symmetry codes: (i) x−1, y+1, z; (ii) x, y+1, z; (iii) x−1, y, z−1; (iv) x+1, y, z+1; (v) x, y−1, z; (vi) x+1, y−1, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O11—H11A···O13iii | 0.82 | 1.99 | 2.805 (4) | 172 |
O11—H11B···O21ii | 0.82 | 1.98 | 2.780 (3) | 165 |
O12—H12A···O13vii | 0.82 | 2.03 | 2.844 (4) | 171 |
O12—H12B···O4viii | 0.82 | 2.04 | 2.827 (3) | 162 |
O13—H13A···O61ix | 0.82 | 2.42 | 2.950 (4) | 124 |
O13—H13A···O4x | 0.82 | 2.46 | 3.169 (5) | 146 |
O13—H13B···O22 | 0.82 | 2.02 | 2.809 (4) | 162 |
Symmetry codes: (ii) x, y+1, z; (iii) x−1, y, z−1; (vii) x−1, y−1, z−1; (viii) x−2, y, z−1; (ix) x, y+1, z+1; (x) x−1, y, z. |
Experimental details
(I) | (II) | (III) | (IV) | |
Crystal data | ||||
Chemical formula | [Be(H2O)4](C7H2O6) | (N2H6)[Ca(C7H2O6)2(H2O)2] | [Mn2(C7H2O6)2(H2O)8]·4H2O | [Cu(C7H2O6)(H2O)4] |
Mr | 263.16 | 474.35 | 690.24 | 317.70 |
Crystal system, space group | Monoclinic, P21/n | Monoclinic, P2/c | Triclinic, P1 | Triclinic, P1 |
Temperature (K) | 120 | 120 | 120 | 120 |
a, b, c (Å) | 5.4331 (2), 10.6173 (4), 19.1890 (5) | 6.4669 (2), 7.0797 (3), 18.8278 (6) | 7.4343 (2), 10.1176 (3), 10.2290 (3) | 4.9593 (6), 9.8973 (14), 10.4697 (12) |
α, β, γ (°) | 90, 97.771 (2), 90 | 90, 97.372 (2), 90 | 61.935 (2), 78.219 (3), 69.061 (2) | 94.237 (9), 94.955 (9), 97.353 (6) |
V (Å3) | 1096.75 (6) | 854.88 (5) | 633.49 (3) | 505.88 (11) |
Z | 4 | 2 | 1 | 2 |
Radiation type | Mo Kα | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.15 | 0.46 | 1.11 | 2.21 |
Crystal size (mm) | 0.28 × 0.24 × 0.11 | 0.26 × 0.18 × 0.08 | 0.47 × 0.21 × 0.10 | 0.12 × 0.12 × 0.10 |
Data collection | ||||
Diffractometer | Bruker Nonius KappaCCD area-detector diffractometer | Bruker Nonius KappaCCD area-detector diffractometer | Bruker Nonius KappaCCD area-detector diffractometer | Bruker Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.968, 0.984 | 0.909, 0.964 | 0.625, 0.898 | 0.777, 0.809 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11511, 2504, 2180 | 9031, 1953, 1876 | 14668, 2914, 2423 | 6400, 2264, 2043 |
Rint | 0.034 | 0.030 | 0.037 | 0.034 |
(sin θ/λ)max (Å−1) | 0.650 | 0.650 | 0.651 | 0.655 |
Refinement | ||||
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.118, 1.15 | 0.036, 0.116, 1.20 | 0.030, 0.074, 1.08 | 0.052, 0.156, 1.12 |
No. of reflections | 2504 | 1953 | 2914 | 2264 |
No. of parameters | 163 | 141 | 181 | 167 |
No. of restraints | 0 | 0 | 0 | 0 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.37, −0.34 | 0.68, −0.54 | 0.45, −0.40 | 1.42, −1.42 |
Absolute structure | ? | ? | ? | ? |
Absolute structure parameter | ? | ? | ? | ? |
(V) | |
Crystal data | |
Chemical formula | [Cd(C7H2O6)(H2O)2]·H2O |
Mr | 348.53 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 120 |
a, b, c (Å) | 5.3262 (2), 6.2885 (2), 8.1008 (3) |
α, β, γ (°) | 97.733 (2), 105.0554 (17), 110.4356 (18) |
V (Å3) | 237.80 (2) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 2.34 |
Crystal size (mm) | 0.10 × 0.04 × 0.04 |
Data collection | |
Diffractometer | Bruker Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.781, 0.912 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7006, 2108, 2108 |
Rint | 0.050 |
(sin θ/λ)max (Å−1) | 0.653 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.018, 0.042, 1.15 |
No. of reflections | 2108 |
No. of parameters | 136 |
No. of restraints | 3 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.58, −0.98 |
Absolute structure | Flack (1983), with 1003 Friedel pairs |
Absolute structure parameter | −0.002 (17) |
Computer programs: COLLECT (Nonius, 1999), DENZO (Otwinowski & Minor, 1997) and COLLECT, DENZO and COLLECT, OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997), OSCAIL and SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), SHELXL97 and PRPKAPPA (Ferguson, 1999).
D—H···A | D—H | H···A | D···A | D—H···A |
O11—H11A···O21 | 0.86 | 1.74 | 2.6073 (16) | 179 |
O11—H11B···O61i | 0.94 | 1.73 | 2.6501 (16) | 165 |
O12—H12A···O22 | 0.86 | 1.74 | 2.6003 (16) | 178 |
O12—H12B···O4ii | 0.89 | 1.73 | 2.6187 (16) | 174 |
O13—H13A···O21iii | 0.88 | 1.76 | 2.6353 (15) | 171 |
O13—H13B···O61iii | 0.89 | 1.75 | 2.6360 (15) | 170 |
O14—H14A···O4iv | 0.89 | 1.79 | 2.6672 (16) | 168 |
O14—H14B···O62v | 0.98 | 1.60 | 2.5788 (16) | 177 |
Symmetry codes: (i) −x+1/2, y+1/2, −z+3/2; (ii) −x+2, −y+1, −z+1; (iii) −x+3/2, y+1/2, −z+3/2; (iv) −x+1, −y+1, −z+1; (v) x+1, y+1, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2A···O4i | 0.84 | 1.89 | 2.7149 (18) | 167 |
O2—H2B···O22ii | 0.90 | 1.77 | 2.6717 (19) | 175 |
N3—H3A···O61 | 0.88 | 2.07 | 2.8091 (19) | 142 |
N3—H3B···O62iii | 0.96 | 1.74 | 2.679 (2) | 166 |
N3—H3C···O21iv | 0.88 | 1.93 | 2.781 (2) | 162 |
Symmetry codes: (i) −x+1, −y+2, −z; (ii) x−1, y, z; (iii) −x, y, −z+1/2; (iv) −x+1, y−1, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O11—H11A···O15 | 0.83 | 1.85 | 2.6784 (19) | 176 |
O11—H11B···O62i | 0.83 | 1.96 | 2.7846 (18) | 175 |
O12—H12A···O4ii | 0.94 | 1.73 | 2.6670 (18) | 174 |
O12—H12B···O4iii | 0.82 | 1.95 | 2.7356 (18) | 158 |
O13—H13A···O61iv | 0.91 | 1.81 | 2.7133 (18) | 172 |
O13—H13B···O61v | 0.86 | 2.00 | 2.7866 (18) | 151 |
O14—H14A···O16 | 0.89 | 1.86 | 2.7532 (19) | 174 |
O14—H14B···O62iv | 0.88 | 1.82 | 2.6908 (18) | 176 |
O15—H15A···O12v | 0.86 | 1.93 | 2.7930 (19) | 173 |
O15—H15B···O13vi | 0.93 | 2.07 | 2.9814 (19) | 166 |
O16—H16A···O22iii | 0.88 | 2.00 | 2.8765 (19) | 175 |
O16—H16B···O11vii | 0.95 | 2.13 | 3.0423 (19) | 160 |
Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) x, y, z−1; (iii) −x+1, −y+2, −z+1; (iv) x−1, y+1, z−1; (v) −x+1, −y+1, −z+1; (vi) −x, −y+1, −z+1; (vii) −x, −y+2, −z+1. |
Cu1—O1A | 1.970 (3) | Cu2—O2A | 1.961 (3) |
Cu1—O21 | 1.982 (3) | Cu2—O2B | 1.906 (3) |
Cu1—O1B | 2.447 (4) | Cu2—O61 | 2.525 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1A—H11A···O21i | 0.88 | 1.86 | 2.743 (4) | 176 |
O1A—H12A···O61i | 0.88 | 1.84 | 2.715 (4) | 175 |
O1B—H11B···O4ii | 0.88 | 2.24 | 3.110 (6) | 169 |
O1B—H12B···O4iii | 0.88 | 2.01 | 2.790 (5) | 147 |
O2A—H21A···O62iv | 0.88 | 1.83 | 2.672 (4) | 160 |
O2A—H22A···O4v | 0.88 | 1.83 | 2.699 (5) | 168 |
O2B—H21B···O61iv | 0.88 | 1.75 | 2.618 (4) | 170 |
O2B—H22B···O1B | 0.88 | 1.82 | 2.666 (5) | 162 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) x−1, y−1, z; (iii) x, y−1, z; (iv) x−1, y, z; (v) −x+1, −y+1, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O11—H11A···O13i | 0.82 | 1.99 | 2.805 (4) | 172 |
O11—H11B···O21ii | 0.82 | 1.98 | 2.780 (3) | 165 |
O12—H12A···O13iii | 0.82 | 2.03 | 2.844 (4) | 171 |
O12—H12B···O4iv | 0.82 | 2.04 | 2.827 (3) | 162 |
O13—H13A···O61v | 0.82 | 2.42 | 2.950 (4) | 124 |
O13—H13A···O4vi | 0.82 | 2.46 | 3.169 (5) | 146 |
O13—H13B···O22 | 0.82 | 2.02 | 2.809 (4) | 162 |
Symmetry codes: (i) x−1, y, z−1; (ii) x, y+1, z; (iii) x−1, y−1, z−1; (iv) x−2, y, z−1; (v) x, y+1, z+1; (vi) x−1, y, z. |
4-Oxo-4H-pyran-2,6-dicarboxylic acid (chelidonic acid), (A), is one of the constituents of the greater celandine Chelidonium majus, which exhibits a wide range of therapeutic properties (Chevallier, 1996). It is also an inhibitor of dihydrodipicolinate synthase, a key enzyme in the biosynthesis of lysine via the diaminopimelate pathway (Borthwick et al., 1995). A pKa of about 2.4 for both carboxyl groups (Miyamoto & Brochmann-Hanssen, 1962) makes it a very effective chelating agent at physiological pH. However, while a number of metal complexes formed by the closely-related 4-oxo-1,4-dihydropyridine-2,6-dicarboxylic acid (chelidamic acid), (B), have been structurally characterized (Devereux et al., 2002; Burnett et al., 2003; Zhou et al., 2004; Cui et al., 2006; Gao et al., 2006), very few complexes derived from 4-oxo-4H-pyran-2,6-dicarboxylic acid have been structurally characterized. In pentaaqua(4-oxo-4H-pyran-2,6-dicarboxylato)copper(II) monohydrate, the organic ligand is coordinated to the Cu via the ketonic O atom only and the coordination polyhedron around Cu is completed by five water ligands. The carboxylate groups do not coordinate to Cu, but they participate in a complex hydrogen-bonding scheme which generates a three-dimensional framework structure (Manojlović-Muir et al., 1999). In the dicyclohexylammonium salt of tributyl(4-oxo-4H-pyran-2,6-dicarboxylato)stannate(IV), the 4-oxo-4H-pyran-2,6-dicarboxylato dianion acts as a bridging ligand, via two different carboxylate groups, between planar tributyltin(IV) units, so forming a chain polymer (Ng et al., 2000).
With this in mind, we report here the molecular and supramolecular structures of five metal complexes derived from 4-oxo-4H-pyran-2,6-dicarboxylic acid, namely tetraaquaberyllium 4-oxo-4H-pyran-2,6-dicarboxylate, (I), hydrazinium(2+) diaqua(4-oxo-4H-pyran-2,6-dicarboxylato)calcate, (II), tetraaqua(4-oxo-4H-pyran-2,6-dicarboxylato)manganese(II) dihydrate, (III), tetraaqua(4-oxo-4H-pyran-2,6-dicarboxylato)copper(II), (IV), and diaqua(4-oxo-4H-pyran-2,6-dicarboxylato)cadmium monohydrate, (V). Complexes (I), (III) and (V) were prepared straightforwardly by the reactions, in aqueous solution, of 4-oxo-4H-pyran-2,6-dicarboxylic acid with beryllium sulfate tetrahydrate, manganese(II) acetate and cadmium nitrate, respectively. Complex (IV) was similarly prepared using basic copper carbonate. Attempts to prepare the simple hydrazinium salt by a similar type of reaction consistently yielded only polycrystalline material when conducted in doubly distilled water, but the same procedure in singly distilled water unexpectedly gave the anionic complex, (II), where the calcium component has presumably arisen from the water employed. Attempts to isolate crystals of this material from solutions containing hydrazine, calcium nitrate and 4-oxo-4H-pyran-2,6-dicarboxylic acid have been uniformly unsuccessful: polycrystalline samples of (II) have been readily obtained in this manner, in yields of around 65–70%, but no crystals suitable for single-crystal X-ray diffraction have been obtained by this route.
In each of compounds (I)–(V), the organic component is present in dianionic form, C7H2O62-. This entity occurs as isolated ions in compound (I), which is a hydrated salt in which the metal is present as a simple aqua ion, thus [Be(H2O)4]2+·C7H2O62- (Fig. 1). In each of the coordination compounds (II)–(V), the 4-oxo-4H-pyran-2,6-dicarboxylate anion acts as a ligand towards the metal, and the coordination complexes are neutral in the cases of compounds (III)–(V) and anionic in compound (II). Compound (II) contains isolated mononuclear anions (Fig. 2), compound (III) contains isolated dimers which are neutral and centrosymmetric (Fig. 3), while both (IV) and (V) (Figs. 4 and 5) form coordination polymers, which are one-dimensional in the case of (IV) and three-dimensional in the case of (V). In all compounds, there is an extensive series of hydrogen bonds which link the metal-containing species. We note in particular here the contrast between the coordination polymer formed in the tetrahydrate, (IV), and the isolated mononuclear complexes formed in the corresponding hexahydrate (Manojlović-Muir et al., 1999).
In compound (II), the 4-oxo-4H-pyran-2,6-dicarboxylate anion acts as a tridentate ligand to the Ca2+ cation, coordinating via a pair of carboxylate O atoms and also via the ring O atom (Fig. 2). In each of compounds (III) and (IV), the organic anion acts as a bidentate ligand bridging a pair of metal centres. However, in the Mn complex, (III), the anion utilizes two O atoms from a single carboxylate group acting as donor to a pair of symmetry-related MnII cations, and the resulting aggregate is centrosymmetric (Fig. 3). By contrast, in the Cu complex, (IV), the anion utilizes one O atom from each carboxylate group as donors to two independent CuII cations, each of which lies on a centre of inversion (Fig. 4). Finally, in the Cd complex, (V), the organic ligand utilizes three carboxylate O atoms and the ketonic O atom as donors to four different Cd atoms (Fig. 5).
The bond lengths within the organic ligands are remarkably constant across the series (I)–(V). The C—O distances in the carboxylate groups are fully consistent with complete ionization in every case. The metal—O distances present only a few unexpected values. In the Ca complex, (II), the distance to the ring O atom [2.6231 (12) Å] is significantly longer than the distances [2.4002 (13) and 2.4314 (13) Å] to the adjacent carboxylate O atoms, purely for geometric reasons. In the Cd complex, (V), the Cd—O(carboxylate) distances range from 2.242 (3) to 2.3284 (19) Å, with the distances to the water O atoms both within this range, but the distance to the ketonic O atom is significantly longer, at 2.419 (3) Å. The most striking distances occur for the CuII complex, (IV), where the six-coordination of the two independent CuII cations is subject to Jahn–Teller distortion giving, for both ions, the typical (4 + 2) coordination having local D4h (4/mmm) point symmtry, with the two axial distances significantly longer than the four equatorial distances. However, for atom Cu1, the two axial sites are occupied by a pair of water molecules, while for atom Cu2, these sites are occupied by a pair of carboxylate ligands (Table 4).
The supramolecular structures of compounds (I)–(V) are all three-dimensional. In compounds (I)–(III), the three-dimensional frameworks are all built entirely from hydrogen bonds. Compound (IV) forms a one-dimensional polymer chain, and these chains are linked into a three-dimensional structure by hydrogen bonds, while compound (V) consists of the three-dimensional coordination polymer interwoven with a three-dimensional hydrogen-bonded framework.
Within the selected asymmetric unit of the hydrated salt, (I) (Fig. 1), the cation is linked to the anion by two nearly linear O—H···O hydrogen bonds (Table 1), where both acceptors are in the same carboxylate group. Ion pairs of this type are linked by six further O—H···O hydrogen bonds into a three-dimensional framework structure, whose formation is readily analysed in terms of simple sub-structures. The cation at (x, y, z) acts as hydrogen-bond donor via atom O11 to atom O61 in the anion at (1/2 - x, 1/2 + y, 3/2 - z), via atom O13 to atoms O21 and O61 in the anion at (3/2 - x, 1/2 + y, 3/2 - z), and via atom O14 to atom O62 in the anion at (1 + x, 1 + y, z), resulting in the formation of a complex sheet parallel to (001) generated by the 21 screw axes at z = 3/4 (Fig. 6). Successive (001) sheets are linked by two further hydrogen bonds. The cation at (x, y, z) is linked via atoms O12 and O14, respectively, to atoms O4 in the anions at (2 - x, 1 - y, 1 - z) and (1 - x, 1 - y, 1 - z), both of which lie in the (001) sheet generated by the 21 screw axes at y = 1/4. These two interactions together form a chain of alternating R44(18) (Bernstein et al., 1995) and R44(22) rings (Fig. 7), whose propagation by the space group thus links each (001) sheet to the two adjacent sheets. Hence, all of the component ions are linked into a single three-dimensional structure.
In the salt (II), N2H62+·[Ca(C7H2O6)2(H2O)2]2-, the Ca atom forms part of an isolated anion, which lies across a twofold rotation axis in space group P2/c. The hydrazinium cation likewise lies across a twofold axis. A combination of O—H···O and N—H···O hydrogen bonds (Table 2) links the component ions into a three-dimensional framework, but it is possible to identify a two-dimensional sub-structure built from anions only. The water atoms O2 at (x, y, z) and (1 - x, y, 1/2 - z) are components of the reference anion across the axis (1/2, y, 1/4). These two atoms act as hydrogen-bond donors via atom H2A to the ketonic atoms O4 at (1 - x, 2 - y, -z) and (x, 2 - y, 1/2 + z), respectively, which lie in the anions across (1/2, -y, 1/4) and (1/2, -y, 3/4), respectively. Similarly, the water atoms O2 at (x, y, z) and (1 - x, y, 1/2 - z) act as hydrogen-bond donors via atom H2B to the carboxylate atoms O22 at (-1 + x, y, z) and (2 - x, y, 1/2 - z), which form parts of the anions across (-1/2, y, 1/4) and (3/2, y, 1/4), respectively. Propagation of these two hydrogen bonds by translation, rotation and inversion then generates a sheet of anions lying parallel to (010) and containing three types of ring (Fig. 8). A single sheet of this type passes through each unit cell. The hydrazinium cations lie within one of the larger rings, and each cation forms six N—H···O hydrogen bonds, four of which (involving atoms H3A and H3B) lie within the reference (010) sheet, while the other two, involving atom H3C, serve to link the reference sheet to the two adjacent sheets, so linking all of the ions into a single three-dimensional framework.
The 4-oxo-4H-pyran-2,6-dicarboxylate ligand in the MnII complex, (III), acts as a bridging ligand between two symmetrically related metal centres, thereby forming a cyclic centrosymmetric aggregate containing an R24(8) (Starbuck et al., 1999) ring (Fig. 3), located for the sake of convenience across (1/2, 1/2, 1/2). The four water molecules coordinated to the metal form three internal O—H···O hydrogen bonds, one to a carboxylate O atom and the other two to the uncoordinated water molecules. In addition, the non-coordinated water atom O15 at (x, y, z) forms an internal hydrogen bond to the coordinated water atom O12 at (1 - x, 1 - y, 1 - z). In each dimeric aggregate, therefore, there are 16 O—H bonds available for the formation of hydrogen bonds between the aggregates (Table 3), and these link the metal complexes into a three-dimensional framework structure of considerable complexity. However, the three-dimensional nature of the supramolecular structure can be readily demonstrated using just four of the independent hydrogen bonds between the aggregates, which give rise to three simple one-dimensional sub-structures. In the first of these sub-structures, water atom O12 at (x, y, z) acts as hydrogen-bond donor, via atom H12A, to ketonic atom O4 at (x, y, -1 + z), so generating by translation a molecular ladder running parallel to the [001] direction, in which the uprights are formed by an antiparallel pair of C(8) chains, while the rungs of the ladder contain the R24(8) rings (Fig. 9). In addition, atom O12 at (x, y, z) also acts as donor to atom O4 at (1 - x, 2 - y, 1 - z), this time via atom H12B, and propagation of this interaction by inversion generates a chain of fused rings running parallel to the [010] direction (Fig. 10). Finally, water atoms O13 and O14 at (x, y, z) act as donors to, respectively, carboxylate atoms O61 and O62 at (-1 + x, 1 + y, -1 + z), so generating by translation a chain of fused rings running parallel to the [111] direction (Fig. 11). The combination of these [001], [010] and [111] chains suffices to generate a three-dimensional framework, whose structure is rendered considerably more complex by further hydrogen bonds involving both coordinated and non-coordinated water molecules (Table 3).
The two independent CuII ions in compound (IV) both lie on centres of inversion in space group P1, selected as those at (0, 0, 1/2) for Cu1 and (1/2, 0, 0) for Cu2. The 4-oxo-4H-pyran-2,6-dicarboxylate ligand lies in a general position, bridging the two Cu ions via a pair of carboxylate O atoms (Fig. 4). The action of the two independent inversion centres then generates a coordination polymer chain of alternating cations and anions, running parallel to the [101] direction (Fig. 12). The role of the 4-oxo-4H-pyran-2,6-dicarboxylate ligand in (IV) is thus similar to that in the polymer formed with tributyltin(IV) units (Ng et al., 2000), although in that instance the coordination polymer is anionic, whereas in (IV) it is neutral.
The coordination polymer chains are linked into a complex three-dimensional framework by no fewer than eight independent O—H···O hydrogen bonds (Table 5), but the three-dimensional nature of the supramolecular structure can most simply be demonstrated in terms of two one-dimensional hydrogen-bonded sub-structures involving just three of the hydrogen bonds. In the first of these sub-structures, water atom O1B at (x, y, z) acts as hydrogen-bond donor, via atom H12B, to ketonic atom O4 at (x, -1 + y, z), and propagation of this interaction by translation and inversion generates a chain of spiro-fused R46(18) rings running parallel to the [010] direction (Fig. 13). In the second hydrogen-bonded sub-structure, water atoms O2A and O2B at (x, y, z) act as donors to, respectively, atoms O62 and O61 at (-1 + x, y, z). Propagation of these interactions by translation and inversion then generates a complex chain of R44(8) and R46(8) rings running parallel to the [100] direction (Fig. 14). The combination of these [100], [010] and [101] chains is sufficient to generate a three-dimensional framework, with further complexity generated by the remaining hydrogen bonds.
Compound (V) is a coordination compound, [Cd(C7H2O6)(H2O)2]·H2O (Fig. 5), in which the Cd centre is coordinated by two water molecules, occupying cis sites, and four O atoms, one of them a ketonic O atom and three of them from carboxylate groups, which themselves form parts of four different anionic ligands. The six-coordination of the Cd ion is markedly distorted from regular octahedral. The third water molecule is not coordinated to the Cd ion, but instead forms hydrogen bonds to O atoms in three different anions via one two-centre O—H···O interaction and one three-centre O—H···(O)2 interaction (Table 6).
The Cd cations and the anions together form a three-dimensional coordination polymer, whose formation is very easily analysed in terms of two simple sub-structures, namely a two-dimensional sub-structure involving only carboxylate coordination and a one-dimensional sub-structure based on the coordination of the ketonic O atom to the Cd ion. The reference Cd ion at (x, y, z) is coordinated not only by atom O21 at (x, y, z), but also by atoms O61 and O62 in the anions at (x, 1 + y, z) and (-1 + x, 1 + y, z), respectively, and these interactions together generate a sheet parallel to (001) which takes the form of a (4,4) net (Batten & Robson, 1998) (Fig. 15). In the second sub-structure, the reference Cd ion is coordinated by ketonic atom O4 in the anion at (-1 + x, y, -1 + z), so forming a C(7) chain (Starbuck et al., 1999) running parallel to the [101] direction (Fig. 16). The combination of these [101] chains and (001) sheets suffices to generate a single three-dimensional coordination polymer.
In addition, the polymer framework is reinforced by an extensive series of hydrogen bonds (Table 6). These individually form chains parallel to [100], [010], [101], [201], [011] and [111], and their combination thereby forms a very complex three-dimensional hydrogen-bonded framework interwoven with the coordination polymer framework.
The range of the structures reported here, together with those reported previously (Manojlović-Muir et al., 1999, Ng et al., 2000), indicates the remarkably versatile coordination behaviour of the 4-oxo-4H-pyran-2,6-dicarboxylate dianion, which has led here to the characterization of cationic, neutral and anionic complexes, encompassing finite coordination species, both mononuclear and binuclear, as well as one- and three-dimensional coordination polymers.