Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270111009383/em3039sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270111009383/em3039Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270111009383/em3039IIsup3.hkl |
CCDC references: 824040; 824041
For the preparation of ligand L, KOH (1.40 g, 25 mmol) was added, with stirring, to a solution of 1,2-bis(2-bromomethylphenoxy)ethane (2.00 g, 5 mmol) and imidazole (0.69 g, 10 mmol) in anhydrous tetrahydrofuran (50 ml) at ambient temperature. The mixture was stirred for 720 min at ambient temperature. After removal of the solvent under vacuum, the residue was purified on a silica-gel column using DCM–MeOH (20:1 v/v) as the eluent to afford L as a white crystalline solid (yield 1.07 g, 2.86 mmol, 57.6%). Spectroscopic analysis: IR (KBr pellet, ν, cm-1): 3094 (m), 2948 (w), 2884 (w), 1601 (m), 1589 (m), 1502 (vs), 1473 (s), 1453 (s), 1430 (s), 1388 (w), 1355 (w), 1339 (w), 1286 (m), 1247 (vs), 1223 (s), 1190 (m), 1156 (w), 1112 (s), 1087 (s), 1055 (s), 1039 (m), 908 (w), 840 (w), 814 (s), 774 (s), 751 (vs), 686 (s), 661 (s), 631 (s), 575 (m), 453 (w); 1H NMR (300 MHz, CDCl3, TMS, δ, p.p.m.): 7.50 (s, 2H, –C3H3N2), 7.33 (t, 2H, –C6H4–), 7.07 (d, 2H, –C6H4–), 6.98 (t, 2H, –C3H3N2), 6.97 (t, 2H, –C6H4–), 6.96 (s, 2H, –C3H3N2), 6.90 (s, 2H, –C6H4–), 5.08 (s, 4H, –CH2–), 4.30 (s, 4H, –CH2–). Elemental analysis, calculated for C22H22N4O2: C 70.59, H 5.88, N 14.97%; found: C 70.52, H 5.78, N 15.09%.
For the preparation of (I), L (3.74 mg, 0.01 mmol), Cd(NO3)2.4H2O (3.08 mg, 0.01 mmol), H2bdc (1.66 mg, 0.01 mmol) and water (2 ml) were sealed in a 5 ml glass tube. The mixture was heated at 453 K for 4320 min under autogenous pressure. After the mixture had been allowed to cool to room temperature (over a period of 3000 min), colourless cubic [Yellow bar given in CIF - please check] crystals were isolated in 58.2% yield. Spectroscopic analysis: IR (KBr pellet, ν, cm-1): 3135 (w), 3120 (w), 2950 (w), 2930 (w), 2875 (w), 1625 (m), 1602 (s), 1544 (vs), 1495 (s), 1451 (m), 1438 (m), 1387 (vs), 1293 (m), 1252 (s), 1232 (m), 1175 (w), 1111 (m), 1086 (s), 1067 (w), 1052 (w), 1035 (w), 1013 (w), 942 (m), 886 (w), 840 (s), 750 (vs), 711 (w), 657 (m), 643 (w), 531 (w), 435 (w). Elemental analysis, calculated for C30H30CdN4O8: C 52.45, H 4.40, N 8.16%; found: C 52.32, H 4.49, N 8.25%.
For the synthesis of (II), L (3.74 mg, 0.01 mmol), Co(NO3)2.6H2O (3.37 mg, 0.01 mmol), H2bdc (1.66 mg, 0.01 mmol) and water (2 ml) were sealed in a 5 ml glass tube. The mixture was heated at 423 K for 4320 min under autogenous pressure. After the mixture had been allowed to cool to room temperature (over a period of 2160 min), red crystals were isolated in 61.3% yield. Spectroscopic analysis: IR (KBr pellet, cm-1): 3139 (w), 3124 (w), 2953 (w), 2931 (w), 2878 (w), 1627 (m), 1603 (m), 1546 (vs), 1495 (s), 1451 (m), 1438 (m), 1401 (vs), 1293 (m), 1252 (s), 1235 (m), 1179 (w), 1108 (m), 1088 (m), 1069 (s), 1053 (w),1034 (w), 1013 (w), 946 (m), 886 (w), 837 (m), 750 (vs), 711 (w), 659 (m), 647 (w), 532 (w), 435 (w). Elemental analysis, calculated for C30H30CoN4O8: C 56.88, H 4.77, N 8.84%; found: C 56.79, H 4.85, N 8.91%.
H atoms attached to C atoms were placed in geometrically idealized positions and included as riding atoms, with C—H = 0.97 (CH2) or 0.93 Å (CH) and Uiso(H) = 1.2Ueq(C), while for water O atoms, O—H = 0.85 Å and Uiso(H) = 1.2Ueq(O).
For both compounds, data collection: SMART (Bruker, 2003); cell refinement: SMART (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
[Cd(C8H4O4)(C22H22N4O2)]·2H2O | F(000) = 1400 |
Mr = 686.98 | Dx = 1.522 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 2111 reflections |
a = 17.450 (10) Å | θ = 2.6–21.8° |
b = 15.480 (8) Å | µ = 0.79 mm−1 |
c = 12.636 (7) Å | T = 298 K |
β = 118.545 (7)° | Bar, yellow |
V = 2998 (3) Å3 | 0.26 × 0.16 × 0.09 mm |
Z = 4 |
Bruker SMART CCD area-detector diffractometer | 2944 independent reflections |
Radiation source: fine-focus sealed tube | 2081 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.034 |
ϕ and ω scans | θmax = 26.0°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Bruker, 2003) | h = −21→18 |
Tmin = 0.822, Tmax = 0.933 | k = −19→13 |
8061 measured reflections | l = −15→15 |
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)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.097 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0491P)2] where P = (Fo2 + 2Fc2)/3 |
2944 reflections | (Δ/σ)max = 0.001 |
195 parameters | Δρmax = 0.51 e Å−3 |
0 restraints | Δρmin = −0.26 e Å−3 |
[Cd(C8H4O4)(C22H22N4O2)]·2H2O | V = 2998 (3) Å3 |
Mr = 686.98 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 17.450 (10) Å | µ = 0.79 mm−1 |
b = 15.480 (8) Å | T = 298 K |
c = 12.636 (7) Å | 0.26 × 0.16 × 0.09 mm |
β = 118.545 (7)° |
Bruker SMART CCD area-detector diffractometer | 2944 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2003) | 2081 reflections with I > 2σ(I) |
Tmin = 0.822, Tmax = 0.933 | Rint = 0.034 |
8061 measured reflections |
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.097 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.51 e Å−3 |
2944 reflections | Δρmin = −0.26 e Å−3 |
195 parameters |
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. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.6155 (2) | 0.8386 (2) | 0.2543 (3) | 0.0683 (10) | |
H1 | 0.6511 | 0.8459 | 0.3367 | 0.082* | |
C2 | 0.6153 (3) | 0.7683 (2) | 0.1914 (3) | 0.0680 (10) | |
H2 | 0.6494 | 0.7189 | 0.2211 | 0.082* | |
C3 | 0.5210 (2) | 0.8621 (2) | 0.0724 (3) | 0.0627 (9) | |
H3 | 0.4779 | 0.8879 | 0.0029 | 0.075* | |
C4 | 0.5235 (3) | 0.7233 (2) | −0.0252 (3) | 0.0740 (11) | |
H4A | 0.5720 | 0.6877 | −0.0163 | 0.089* | |
H4B | 0.5021 | 0.7549 | −0.1003 | 0.089* | |
C5 | 0.4522 (3) | 0.6661 (2) | −0.0309 (3) | 0.0600 (9) | |
C6 | 0.4321 (2) | 0.5920 (2) | −0.1015 (3) | 0.0600 (9) | |
C7 | 0.3654 (3) | 0.5381 (3) | −0.1128 (3) | 0.0735 (11) | |
H7 | 0.3517 | 0.4889 | −0.1607 | 0.088* | |
C8 | 0.3196 (3) | 0.5578 (3) | −0.0526 (4) | 0.0806 (12) | |
H8 | 0.2749 | 0.5214 | −0.0602 | 0.097* | |
C9 | 0.3383 (3) | 0.6295 (3) | 0.0179 (3) | 0.0793 (11) | |
H9 | 0.3073 | 0.6420 | 0.0588 | 0.095* | |
C10 | 0.4048 (3) | 0.6837 (2) | 0.0275 (3) | 0.0719 (10) | |
H10 | 0.4175 | 0.7332 | 0.0747 | 0.086* | |
C11 | 0.4669 (3) | 0.50619 (19) | −0.2295 (4) | 0.0772 (12) | |
H11A | 0.4088 | 0.5089 | −0.2979 | 0.093* | |
H11B | 0.4716 | 0.4540 | −0.1843 | 0.093* | |
C12 | 0.3686 (2) | 1.1113 (2) | 0.1336 (3) | 0.0588 (8) | |
C13 | 0.3053 (2) | 1.1823 (2) | 0.0640 (3) | 0.0550 (8) | |
C14 | 0.2562 (2) | 1.1788 (2) | −0.0604 (3) | 0.0636 (9) | |
H14 | 0.2602 | 1.1308 | −0.1016 | 0.076* | |
C15 | 0.2983 (2) | 1.2540 (2) | 0.1233 (3) | 0.0643 (9) | |
H15 | 0.3309 | 1.2572 | 0.2068 | 0.077* | |
Cd1 | 0.5000 | 0.999407 (19) | 0.2500 | 0.05662 (15) | |
N1 | 0.55581 (19) | 0.89788 (17) | 0.1793 (3) | 0.0610 (7) | |
N2 | 0.55440 (19) | 0.78475 (18) | 0.0749 (2) | 0.0595 (7) | |
O1 | 0.48294 (17) | 0.57990 (14) | −0.15526 (19) | 0.0719 (7) | |
O2 | 0.38346 (15) | 1.05354 (15) | 0.07587 (19) | 0.0663 (6) | |
O3 | 0.40546 (17) | 1.11282 (15) | 0.2465 (2) | 0.0708 (7) | |
O4 | 0.3005 (2) | 0.9244 (2) | −0.1301 (3) | 0.1235 (12) | |
H4C | 0.3331 | 0.9213 | −0.1623 | 0.185* | |
H4D | 0.3204 | 0.9594 | −0.0690 | 0.185* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.054 (2) | 0.082 (3) | 0.066 (2) | −0.003 (2) | 0.0270 (19) | −0.013 (2) |
C2 | 0.065 (3) | 0.064 (2) | 0.080 (3) | 0.0090 (18) | 0.039 (2) | 0.0001 (19) |
C3 | 0.066 (2) | 0.062 (2) | 0.063 (2) | −0.0012 (18) | 0.0330 (19) | 0.0026 (18) |
C4 | 0.097 (3) | 0.069 (2) | 0.075 (2) | −0.028 (2) | 0.056 (2) | −0.021 (2) |
C5 | 0.071 (3) | 0.057 (2) | 0.0578 (19) | −0.0102 (18) | 0.0351 (18) | −0.0015 (16) |
C6 | 0.077 (3) | 0.050 (2) | 0.0516 (18) | −0.0089 (17) | 0.0295 (18) | 0.0062 (15) |
C7 | 0.091 (3) | 0.061 (2) | 0.061 (2) | −0.014 (2) | 0.030 (2) | 0.0000 (19) |
C8 | 0.067 (3) | 0.078 (3) | 0.085 (3) | −0.019 (2) | 0.027 (2) | 0.013 (2) |
C9 | 0.073 (3) | 0.089 (3) | 0.087 (3) | −0.008 (2) | 0.047 (2) | 0.004 (2) |
C10 | 0.079 (3) | 0.072 (2) | 0.079 (2) | −0.013 (2) | 0.049 (2) | −0.0100 (19) |
C11 | 0.127 (4) | 0.047 (2) | 0.064 (2) | −0.013 (2) | 0.050 (2) | −0.0060 (17) |
C12 | 0.055 (2) | 0.051 (2) | 0.080 (2) | −0.0017 (16) | 0.040 (2) | 0.0095 (18) |
C13 | 0.051 (2) | 0.0510 (19) | 0.071 (2) | −0.0031 (15) | 0.0349 (18) | 0.0056 (16) |
C14 | 0.065 (2) | 0.053 (2) | 0.074 (2) | 0.0012 (17) | 0.034 (2) | −0.0035 (17) |
C15 | 0.063 (2) | 0.067 (2) | 0.063 (2) | 0.0063 (18) | 0.0295 (18) | 0.0040 (18) |
Cd1 | 0.0636 (3) | 0.0437 (2) | 0.0695 (2) | 0.000 | 0.0375 (2) | 0.000 |
N1 | 0.064 (2) | 0.0553 (17) | 0.0684 (18) | −0.0040 (15) | 0.0357 (16) | −0.0091 (15) |
N2 | 0.071 (2) | 0.0536 (18) | 0.0672 (18) | −0.0131 (14) | 0.0434 (18) | −0.0114 (14) |
O1 | 0.107 (2) | 0.0567 (15) | 0.0660 (14) | −0.0192 (13) | 0.0531 (15) | −0.0143 (11) |
O2 | 0.0702 (17) | 0.0588 (16) | 0.0749 (15) | 0.0097 (12) | 0.0387 (13) | 0.0060 (12) |
O3 | 0.0794 (18) | 0.0673 (16) | 0.0662 (15) | 0.0190 (13) | 0.0352 (13) | 0.0126 (12) |
O4 | 0.110 (3) | 0.163 (3) | 0.120 (2) | 0.005 (2) | 0.074 (2) | 0.003 (2) |
C1—C2 | 1.346 (4) | C9—H9 | 0.9300 |
C1—N1 | 1.372 (4) | C10—H10 | 0.9300 |
C1—H1 | 0.9300 | C11—O1 | 1.417 (4) |
C2—N2 | 1.366 (4) | C11—C11i | 1.476 (9) |
C2—H2 | 0.9300 | C11—H11A | 0.9700 |
C3—N1 | 1.310 (4) | C11—H11B | 0.9700 |
C3—N2 | 1.325 (4) | C12—O3 | 1.254 (4) |
C3—H3 | 0.9300 | C12—O2 | 1.257 (4) |
C4—N2 | 1.464 (4) | C12—C13 | 1.507 (5) |
C4—C5 | 1.501 (5) | C12—Cd1 | 2.683 (4) |
C4—H4A | 0.9700 | C13—C15 | 1.378 (4) |
C4—H4B | 0.9700 | C13—C14 | 1.385 (4) |
C5—C10 | 1.375 (5) | C14—C15ii | 1.377 (5) |
C5—C6 | 1.391 (4) | C14—H14 | 0.9300 |
C6—O1 | 1.363 (4) | C15—H15 | 0.9300 |
C6—C7 | 1.382 (5) | Cd1—N1 | 2.247 (3) |
C7—C8 | 1.376 (5) | Cd1—O2 | 2.324 (2) |
C7—H7 | 0.9300 | Cd1—O3 | 2.395 (3) |
C8—C9 | 1.362 (5) | Cd1—C12iii | 2.683 (4) |
C8—H8 | 0.9300 | O4—H4C | 0.8430 |
C9—C10 | 1.388 (5) | O4—H4D | 0.8686 |
C2—C1—N1 | 110.3 (3) | C14—C13—C12 | 121.1 (3) |
C2—C1—H1 | 124.9 | C15ii—C14—C13 | 120.5 (3) |
N1—C1—H1 | 124.9 | C15ii—C14—H14 | 119.7 |
C1—C2—N2 | 105.4 (3) | C13—C14—H14 | 119.7 |
C1—C2—H2 | 127.3 | C14ii—C15—C13 | 120.7 (3) |
N2—C2—H2 | 127.3 | C14ii—C15—H15 | 119.6 |
N1—C3—N2 | 112.0 (3) | C13—C15—H15 | 119.6 |
N1—C3—H3 | 124.0 | N1—Cd1—N1iii | 91.22 (14) |
N2—C3—H3 | 124.0 | N1—Cd1—O2iii | 106.21 (10) |
N2—C4—C5 | 112.3 (3) | N1iii—Cd1—O2iii | 103.02 (10) |
N2—C4—H4A | 109.1 | N1—Cd1—O2 | 103.02 (10) |
C5—C4—H4A | 109.1 | N1iii—Cd1—O2 | 106.21 (10) |
N2—C4—H4B | 109.1 | O2iii—Cd1—O2 | 137.74 (12) |
C5—C4—H4B | 109.1 | N1—Cd1—O3iii | 95.42 (10) |
H4A—C4—H4B | 107.9 | N1iii—Cd1—O3iii | 158.60 (10) |
C10—C5—C6 | 118.5 (3) | O2iii—Cd1—O3iii | 55.59 (9) |
C10—C5—C4 | 123.7 (3) | O2—Cd1—O3iii | 92.10 (9) |
C6—C5—C4 | 117.8 (3) | N1—Cd1—O3 | 158.60 (10) |
O1—C6—C7 | 125.6 (3) | N1iii—Cd1—O3 | 95.42 (10) |
O1—C6—C5 | 114.1 (3) | O2iii—Cd1—O3 | 92.10 (9) |
C7—C6—C5 | 120.4 (3) | O2—Cd1—O3 | 55.59 (8) |
C8—C7—C6 | 119.4 (4) | O3iii—Cd1—O3 | 85.72 (13) |
C8—C7—H7 | 120.3 | N1—Cd1—C12iii | 104.48 (11) |
C6—C7—H7 | 120.3 | N1iii—Cd1—C12iii | 130.76 (12) |
C9—C8—C7 | 121.5 (4) | O2iii—Cd1—C12iii | 27.91 (9) |
C9—C8—H8 | 119.3 | O2—Cd1—C12iii | 114.73 (11) |
C7—C8—H8 | 119.3 | O3iii—Cd1—C12iii | 27.86 (9) |
C8—C9—C10 | 118.6 (4) | O3—Cd1—C12iii | 86.44 (10) |
C8—C9—H9 | 120.7 | N1—Cd1—C12 | 130.76 (12) |
C10—C9—H9 | 120.7 | N1iii—Cd1—C12 | 104.48 (11) |
C5—C10—C9 | 121.6 (4) | O2iii—Cd1—C12 | 114.73 (11) |
C5—C10—H10 | 119.2 | O2—Cd1—C12 | 27.91 (9) |
C9—C10—H10 | 119.2 | O3iii—Cd1—C12 | 86.44 (10) |
O1—C11—C11i | 107.0 (3) | O3—Cd1—C12 | 27.86 (9) |
O1—C11—H11A | 110.3 | C12iii—Cd1—C12 | 99.61 (15) |
C11i—C11—H11A | 110.3 | C3—N1—C1 | 104.7 (3) |
O1—C11—H11B | 110.3 | C3—N1—Cd1 | 129.1 (3) |
C11i—C11—H11B | 110.3 | C1—N1—Cd1 | 121.6 (2) |
H11A—C11—H11B | 108.6 | C3—N2—C2 | 107.5 (3) |
O3—C12—O2 | 122.5 (3) | C3—N2—C4 | 126.2 (3) |
O3—C12—C13 | 119.0 (3) | C2—N2—C4 | 125.8 (3) |
O2—C12—C13 | 118.5 (3) | C6—O1—C11 | 118.0 (3) |
O3—C12—Cd1 | 63.19 (18) | C12—O2—H4D | 143.2 |
O2—C12—Cd1 | 59.97 (17) | C12—O2—Cd1 | 92.1 (2) |
C13—C12—Cd1 | 170.5 (2) | H4D—O2—Cd1 | 114.6 |
C15—C13—C14 | 118.8 (3) | C12—O3—Cd1 | 88.9 (2) |
C15—C13—C12 | 120.1 (3) | H4C—O4—H4D | 112.9 |
N1—C1—C2—N2 | 0.4 (4) | C12—Cd1—N1—C3 | −18.6 (3) |
N2—C4—C5—C10 | 16.9 (6) | N1iii—Cd1—N1—C1 | −60.2 (2) |
N2—C4—C5—C6 | −164.5 (3) | O2iii—Cd1—N1—C1 | 43.7 (3) |
C10—C5—C6—O1 | −179.7 (3) | O2—Cd1—N1—C1 | −167.2 (3) |
C4—C5—C6—O1 | 1.6 (5) | O3iii—Cd1—N1—C1 | 99.4 (3) |
C10—C5—C6—C7 | 0.4 (5) | O3—Cd1—N1—C1 | −168.5 (2) |
C4—C5—C6—C7 | −178.2 (3) | C12iii—Cd1—N1—C1 | 72.6 (3) |
O1—C6—C7—C8 | 179.5 (3) | C12—Cd1—N1—C1 | −170.6 (2) |
C5—C6—C7—C8 | −0.7 (5) | N1—C3—N2—C2 | 0.1 (4) |
C6—C7—C8—C9 | 0.1 (6) | N1—C3—N2—C4 | 172.5 (3) |
C7—C8—C9—C10 | 0.6 (6) | C1—C2—N2—C3 | −0.3 (4) |
C6—C5—C10—C9 | 0.3 (6) | C1—C2—N2—C4 | −172.7 (3) |
C4—C5—C10—C9 | 178.9 (4) | C5—C4—N2—C3 | −87.1 (4) |
C8—C9—C10—C5 | −0.8 (6) | C5—C4—N2—C2 | 83.8 (4) |
O3—C12—C13—C15 | 9.7 (5) | C7—C6—O1—C11 | 0.1 (5) |
O2—C12—C13—C15 | −169.0 (3) | C5—C6—O1—C11 | −179.7 (3) |
O3—C12—C13—C14 | −173.3 (3) | C11i—C11—O1—C6 | −177.1 (3) |
O2—C12—C13—C14 | 8.0 (5) | O3—C12—O2—H4D | 128.7 |
C15—C13—C14—C15ii | 0.0 (6) | C13—C12—O2—H4D | −52.6 |
C12—C13—C14—C15ii | −177.0 (3) | Cd1—C12—O2—H4D | 138.1 |
C14—C13—C15—C14ii | 0.0 (6) | O3—C12—O2—Cd1 | −9.4 (3) |
C12—C13—C15—C14ii | 177.0 (3) | C13—C12—O2—Cd1 | 169.3 (2) |
O3—C12—Cd1—N1 | 178.34 (17) | N1—Cd1—O2—C12 | −174.41 (19) |
O2—C12—Cd1—N1 | 7.2 (2) | N1iii—Cd1—O2—C12 | 90.4 (2) |
O3—C12—Cd1—N1iii | 73.8 (2) | O2iii—Cd1—O2—C12 | −41.53 (17) |
O2—C12—Cd1—N1iii | −97.37 (19) | O3iii—Cd1—O2—C12 | −78.35 (19) |
O3—C12—Cd1—O2iii | −38.3 (2) | O3—Cd1—O2—C12 | 5.01 (18) |
O2—C12—Cd1—O2iii | 150.60 (15) | C12iii—Cd1—O2—C12 | −61.5 (2) |
O3—C12—Cd1—O2 | 171.1 (3) | N1—Cd1—O2—H4D | 31.7 |
O3—C12—Cd1—O3iii | −87.6 (2) | N1iii—Cd1—O2—H4D | −63.4 |
O2—C12—Cd1—O3iii | 101.29 (19) | O2iii—Cd1—O2—H4D | 164.6 |
O2—C12—Cd1—O3 | −171.1 (3) | O3iii—Cd1—O2—H4D | 127.8 |
O3—C12—Cd1—C12iii | −62.93 (18) | O3—Cd1—O2—H4D | −148.9 |
O2—C12—Cd1—C12iii | 125.9 (2) | C12iii—Cd1—O2—H4D | 144.6 |
N2—C3—N1—C1 | 0.1 (4) | C12—Cd1—O2—H4D | −153.9 |
N2—C3—N1—Cd1 | −155.6 (2) | O2—C12—O3—Cd1 | 9.1 (3) |
C2—C1—N1—C3 | −0.3 (4) | C13—C12—O3—Cd1 | −169.6 (3) |
C2—C1—N1—Cd1 | 157.6 (2) | N1—Cd1—O3—C12 | −3.5 (4) |
N1iii—Cd1—N1—C3 | 91.8 (3) | N1iii—Cd1—O3—C12 | −111.0 (2) |
O2iii—Cd1—N1—C3 | −164.2 (3) | O2iii—Cd1—O3—C12 | 145.7 (2) |
O2—Cd1—N1—C3 | −15.1 (3) | O2—Cd1—O3—C12 | −5.02 (18) |
O3iii—Cd1—N1—C3 | −108.5 (3) | O3iii—Cd1—O3—C12 | 90.48 (19) |
O3—Cd1—N1—C3 | −16.4 (5) | C12iii—Cd1—O3—C12 | 118.4 (2) |
C12iii—Cd1—N1—C3 | −135.3 (3) |
Symmetry codes: (i) −x+1, y, −z−1/2; (ii) −x+1/2, −y+5/2, −z; (iii) −x+1, y, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H4D···O2 | 0.87 | 2.18 | 3.044 (4) | 172 |
O4—H4C···O3iv | 0.84 | 2.14 | 2.973 (4) | 168 |
Symmetry code: (iv) x, −y+2, z−1/2. |
[Co(C8H4O4)(C22H22N4O2)]·2H2O | F(000) = 1316 |
Mr = 633.51 | Dx = 1.453 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 1214 reflections |
a = 17.612 (3) Å | θ = 2.7–19.9° |
b = 14.896 (3) Å | µ = 0.65 mm−1 |
c = 12.711 (3) Å | T = 298 K |
β = 119.724 (3)° | Block, red |
V = 2896.0 (10) Å3 | 0.26 × 0.16 × 0.09 mm |
Z = 4 |
Bruker SMART CCD area-detector diffractometer | 2547 independent reflections |
Radiation source: fine-focus sealed tube | 1861 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.049 |
ϕ and ω scans | θmax = 25.0°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Bruker, 2003) | h = −20→10 |
Tmin = 0.849, Tmax = 0.944 | k = −17→17 |
7231 measured reflections | l = −15→15 |
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) = 0.127 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0651P)2] where P = (Fo2 + 2Fc2)/3 |
2547 reflections | (Δ/σ)max = 0.001 |
195 parameters | Δρmax = 0.36 e Å−3 |
0 restraints | Δρmin = −0.29 e Å−3 |
[Co(C8H4O4)(C22H22N4O2)]·2H2O | V = 2896.0 (10) Å3 |
Mr = 633.51 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 17.612 (3) Å | µ = 0.65 mm−1 |
b = 14.896 (3) Å | T = 298 K |
c = 12.711 (3) Å | 0.26 × 0.16 × 0.09 mm |
β = 119.724 (3)° |
Bruker SMART CCD area-detector diffractometer | 2547 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2003) | 1861 reflections with I > 2σ(I) |
Tmin = 0.849, Tmax = 0.944 | Rint = 0.049 |
7231 measured reflections |
R[F2 > 2σ(F2)] = 0.052 | 0 restraints |
wR(F2) = 0.127 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.36 e Å−3 |
2547 reflections | Δρmin = −0.29 e Å−3 |
195 parameters |
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. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.6175 (2) | 0.8515 (2) | 0.2664 (3) | 0.0526 (9) | |
H1 | 0.6531 | 0.8592 | 0.3495 | 0.063* | |
C2 | 0.6193 (2) | 0.7806 (2) | 0.2026 (3) | 0.0539 (9) | |
H2 | 0.6554 | 0.7305 | 0.2330 | 0.065* | |
C3 | 0.5215 (2) | 0.8749 (2) | 0.0821 (3) | 0.0486 (9) | |
H3 | 0.4773 | 0.9011 | 0.0119 | 0.058* | |
C4 | 0.5289 (3) | 0.7326 (2) | −0.0149 (3) | 0.0539 (9) | |
H4A | 0.5780 | 0.6961 | −0.0036 | 0.065* | |
H4B | 0.5077 | 0.7654 | −0.0901 | 0.065* | |
C5 | 0.4568 (2) | 0.6719 (2) | −0.0238 (3) | 0.0463 (8) | |
C6 | 0.4356 (2) | 0.5968 (2) | −0.0986 (3) | 0.0470 (8) | |
C7 | 0.3691 (3) | 0.5401 (2) | −0.1118 (3) | 0.0563 (10) | |
H7 | 0.3544 | 0.4903 | −0.1624 | 0.068* | |
C8 | 0.3249 (3) | 0.5572 (3) | −0.0504 (4) | 0.0638 (11) | |
H8 | 0.2809 | 0.5184 | −0.0589 | 0.077* | |
C9 | 0.3447 (3) | 0.6307 (3) | 0.0230 (4) | 0.0634 (10) | |
H9 | 0.3143 | 0.6420 | 0.0641 | 0.076* | |
C10 | 0.4106 (2) | 0.6881 (2) | 0.0356 (3) | 0.0556 (10) | |
H10 | 0.4238 | 0.7384 | 0.0850 | 0.067* | |
C11 | 0.4664 (3) | 0.5113 (2) | −0.2308 (3) | 0.0593 (11) | |
H11A | 0.4083 | 0.5164 | −0.3009 | 0.071* | |
H11B | 0.4694 | 0.4561 | −0.1884 | 0.071* | |
C12 | 0.3733 (2) | 1.1107 (2) | 0.1391 (4) | 0.0483 (9) | |
C13 | 0.3076 (2) | 1.1814 (2) | 0.0665 (3) | 0.0415 (8) | |
C14 | 0.2577 (2) | 1.1756 (2) | −0.0581 (3) | 0.0524 (9) | |
H14 | 0.2629 | 1.1255 | −0.0978 | 0.063* | |
C15 | 0.2997 (2) | 1.2567 (2) | 0.1243 (3) | 0.0512 (9) | |
H15 | 0.3332 | 1.2616 | 0.2081 | 0.061* | |
Co1 | 0.5000 | 1.00653 (4) | 0.2500 | 0.0436 (2) | |
N1 | 0.55500 (18) | 0.91105 (17) | 0.1900 (3) | 0.0469 (7) | |
N2 | 0.55827 (18) | 0.79594 (17) | 0.0849 (2) | 0.0451 (7) | |
O1 | 0.48445 (17) | 0.58633 (14) | −0.1531 (2) | 0.0562 (7) | |
O2 | 0.39016 (16) | 1.04909 (16) | 0.0851 (2) | 0.0557 (6) | |
O3 | 0.41257 (17) | 1.11396 (15) | 0.2520 (2) | 0.0607 (7) | |
O4 | 0.2984 (2) | 0.9234 (3) | −0.1337 (3) | 0.1167 (12) | |
H4C | 0.3310 | 0.9203 | −0.1659 | 0.175* | |
H4D | 0.3183 | 0.9584 | −0.0726 | 0.175* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.041 (2) | 0.062 (2) | 0.045 (2) | 0.0008 (17) | 0.0139 (18) | −0.0090 (18) |
C2 | 0.054 (2) | 0.046 (2) | 0.066 (3) | 0.0080 (17) | 0.033 (2) | 0.0046 (19) |
C3 | 0.052 (2) | 0.0411 (19) | 0.052 (2) | 0.0009 (16) | 0.0252 (19) | 0.0007 (16) |
C4 | 0.076 (3) | 0.045 (2) | 0.054 (2) | −0.0143 (18) | 0.042 (2) | −0.0125 (17) |
C5 | 0.055 (2) | 0.0434 (19) | 0.043 (2) | −0.0029 (16) | 0.0268 (18) | 0.0010 (15) |
C6 | 0.060 (2) | 0.0402 (18) | 0.0391 (19) | −0.0013 (16) | 0.0234 (19) | 0.0067 (15) |
C7 | 0.067 (3) | 0.046 (2) | 0.050 (2) | −0.0133 (19) | 0.024 (2) | −0.0059 (17) |
C8 | 0.053 (2) | 0.066 (3) | 0.067 (3) | −0.0136 (19) | 0.025 (2) | 0.007 (2) |
C9 | 0.056 (2) | 0.072 (3) | 0.070 (3) | −0.001 (2) | 0.037 (2) | 0.002 (2) |
C10 | 0.062 (3) | 0.054 (2) | 0.059 (2) | −0.0048 (18) | 0.036 (2) | −0.0065 (18) |
C11 | 0.100 (3) | 0.0373 (19) | 0.046 (2) | −0.0054 (18) | 0.041 (2) | −0.0037 (15) |
C12 | 0.050 (2) | 0.0391 (19) | 0.064 (3) | −0.0012 (16) | 0.034 (2) | 0.0071 (18) |
C13 | 0.0379 (18) | 0.0391 (18) | 0.052 (2) | 0.0013 (14) | 0.0258 (17) | 0.0061 (15) |
C14 | 0.058 (2) | 0.0400 (19) | 0.063 (2) | 0.0036 (16) | 0.034 (2) | −0.0011 (17) |
C15 | 0.049 (2) | 0.051 (2) | 0.048 (2) | 0.0027 (16) | 0.0200 (18) | 0.0030 (16) |
Co1 | 0.0478 (4) | 0.0352 (4) | 0.0487 (4) | 0.000 | 0.0246 (3) | 0.000 |
N1 | 0.0491 (18) | 0.0397 (15) | 0.0521 (18) | −0.0025 (13) | 0.0253 (15) | −0.0069 (14) |
N2 | 0.0571 (19) | 0.0380 (15) | 0.0481 (18) | −0.0046 (13) | 0.0321 (16) | −0.0047 (13) |
O1 | 0.0877 (19) | 0.0422 (13) | 0.0516 (15) | −0.0132 (12) | 0.0444 (15) | −0.0112 (11) |
O2 | 0.0630 (17) | 0.0493 (15) | 0.0594 (16) | 0.0148 (12) | 0.0338 (14) | 0.0089 (12) |
O3 | 0.0677 (17) | 0.0471 (14) | 0.0552 (17) | 0.0134 (12) | 0.0213 (14) | 0.0052 (12) |
O4 | 0.094 (3) | 0.158 (4) | 0.106 (3) | 0.014 (2) | 0.056 (2) | 0.010 (2) |
C1—C2 | 1.342 (4) | C9—H9 | 0.9300 |
C1—N1 | 1.371 (4) | C10—H10 | 0.9300 |
C1—H1 | 0.9300 | C11—O1 | 1.419 (4) |
C2—N2 | 1.361 (4) | C11—C11i | 1.488 (8) |
C2—H2 | 0.9300 | C11—H11A | 0.9700 |
C3—N1 | 1.310 (4) | C11—H11B | 0.9700 |
C3—N2 | 1.335 (4) | C12—O3 | 1.247 (4) |
C3—H3 | 0.9300 | C12—O2 | 1.266 (4) |
C4—N2 | 1.455 (4) | C12—C13 | 1.497 (5) |
C4—C5 | 1.516 (5) | C12—Co1 | 2.501 (3) |
C4—H4A | 0.9700 | C13—C14 | 1.381 (5) |
C4—H4B | 0.9700 | C13—C15 | 1.385 (4) |
C5—C10 | 1.379 (5) | C14—C15ii | 1.380 (4) |
C5—C6 | 1.394 (4) | C14—H14 | 0.9300 |
C6—O1 | 1.354 (4) | C15—H15 | 0.9300 |
C6—C7 | 1.385 (5) | Co1—N1 | 2.068 (3) |
C7—C8 | 1.372 (5) | Co1—O2 | 2.125 (2) |
C7—H7 | 0.9300 | Co1—O3 | 2.230 (2) |
C8—C9 | 1.366 (5) | Co1—C12iii | 2.501 (4) |
C8—H8 | 0.9300 | O4—H4C | 0.8546 |
C9—C10 | 1.385 (5) | O4—H4D | 0.8535 |
C2—C1—N1 | 109.4 (3) | C15—C13—C12 | 119.5 (3) |
C2—C1—H1 | 125.3 | C15ii—C14—C13 | 120.7 (3) |
N1—C1—H1 | 125.3 | C15ii—C14—H14 | 119.7 |
C1—C2—N2 | 106.8 (3) | C13—C14—H14 | 119.7 |
C1—C2—H2 | 126.6 | C14ii—C15—C13 | 120.3 (3) |
N2—C2—H2 | 126.6 | C14ii—C15—H15 | 119.8 |
N1—C3—N2 | 111.9 (3) | C13—C15—H15 | 119.8 |
N1—C3—H3 | 124.1 | N1iii—Co1—N1 | 93.09 (15) |
N2—C3—H3 | 124.1 | N1iii—Co1—O2iii | 101.85 (10) |
N2—C4—C5 | 112.0 (3) | N1—Co1—O2iii | 101.84 (10) |
N2—C4—H4A | 109.2 | N1iii—Co1—O2 | 101.84 (10) |
C5—C4—H4A | 109.2 | N1—Co1—O2 | 101.85 (10) |
N2—C4—H4B | 109.2 | O2iii—Co1—O2 | 145.28 (13) |
C5—C4—H4B | 109.2 | N1iii—Co1—O3iii | 161.86 (11) |
H4A—C4—H4B | 107.9 | N1—Co1—O3iii | 92.12 (10) |
C10—C5—C6 | 118.9 (3) | O2iii—Co1—O3iii | 60.06 (9) |
C10—C5—C4 | 123.7 (3) | O2—Co1—O3iii | 94.06 (9) |
C6—C5—C4 | 117.4 (3) | N1iii—Co1—O3 | 92.12 (10) |
O1—C6—C7 | 125.6 (3) | N1—Co1—O3 | 161.86 (10) |
O1—C6—C5 | 114.7 (3) | O2iii—Co1—O3 | 94.06 (9) |
C7—C6—C5 | 119.7 (3) | O2—Co1—O3 | 60.06 (9) |
C8—C7—C6 | 120.1 (3) | O3iii—Co1—O3 | 88.26 (13) |
C8—C7—H7 | 119.9 | N1iii—Co1—C12iii | 131.99 (12) |
C6—C7—H7 | 119.9 | N1—Co1—C12iii | 100.64 (10) |
C9—C8—C7 | 120.8 (4) | O2iii—Co1—C12iii | 30.40 (10) |
C9—C8—H8 | 119.6 | O2—Co1—C12iii | 119.49 (11) |
C7—C8—H8 | 119.6 | O3iii—Co1—C12iii | 29.88 (9) |
C8—C9—C10 | 119.3 (4) | O3—Co1—C12iii | 88.64 (10) |
C8—C9—H9 | 120.3 | N1iii—Co1—C12 | 100.64 (10) |
C10—C9—H9 | 120.3 | N1—Co1—C12 | 131.99 (12) |
C5—C10—C9 | 121.1 (3) | O2iii—Co1—C12 | 119.49 (11) |
C5—C10—H10 | 119.5 | O2—Co1—C12 | 30.40 (10) |
C9—C10—H10 | 119.5 | O3iii—Co1—C12 | 88.64 (10) |
O1—C11—C11i | 106.7 (3) | O3—Co1—C12 | 29.88 (9) |
O1—C11—H11A | 110.4 | C12iii—Co1—C12 | 103.29 (16) |
C11i—C11—H11A | 110.4 | C3—N1—C1 | 105.2 (3) |
O1—C11—H11B | 110.4 | C3—N1—Co1 | 128.2 (2) |
C11i—C11—H11B | 110.4 | C1—N1—Co1 | 122.8 (2) |
H11A—C11—H11B | 108.6 | C3—N2—C2 | 106.7 (3) |
O3—C12—O2 | 120.4 (3) | C3—N2—C4 | 126.2 (3) |
O3—C12—C13 | 120.0 (3) | C2—N2—C4 | 126.5 (3) |
O2—C12—C13 | 119.6 (3) | C6—O1—C11 | 117.8 (3) |
O3—C12—Co1 | 62.93 (18) | C12—O2—Co1 | 91.5 (2) |
O2—C12—Co1 | 58.15 (17) | C12—O2—H4D | 138.5 |
C13—C12—Co1 | 170.1 (2) | Co1—O2—H4D | 122.8 |
C14—C13—C15 | 119.0 (3) | C12—O3—Co1 | 87.2 (2) |
C14—C13—C12 | 121.4 (3) | H4C—O4—H4D | 113.5 |
N1—C1—C2—N2 | 0.7 (4) | C12—Co1—N1—C3 | −15.8 (3) |
N2—C4—C5—C10 | 14.3 (5) | N1iii—Co1—N1—C1 | −63.3 (2) |
N2—C4—C5—C6 | −167.0 (3) | O2iii—Co1—N1—C1 | 39.5 (3) |
C10—C5—C6—O1 | −180.0 (3) | O2—Co1—N1—C1 | −166.1 (2) |
C4—C5—C6—O1 | 1.3 (4) | O3iii—Co1—N1—C1 | 99.3 (3) |
C10—C5—C6—C7 | −0.1 (5) | O3—Co1—N1—C1 | −169.8 (3) |
C4—C5—C6—C7 | −178.8 (3) | C12iii—Co1—N1—C1 | 70.4 (3) |
O1—C6—C7—C8 | 179.1 (3) | C12—Co1—N1—C1 | −170.6 (2) |
C5—C6—C7—C8 | −0.7 (5) | N1—C3—N2—C2 | 0.1 (4) |
C6—C7—C8—C9 | 0.9 (6) | N1—C3—N2—C4 | 171.1 (3) |
C7—C8—C9—C10 | −0.3 (6) | C1—C2—N2—C3 | −0.5 (4) |
C6—C5—C10—C9 | 0.7 (5) | C1—C2—N2—C4 | −171.4 (3) |
C4—C5—C10—C9 | 179.3 (3) | C5—C4—N2—C3 | −84.2 (4) |
C8—C9—C10—C5 | −0.6 (6) | C5—C4—N2—C2 | 85.0 (4) |
O3—C12—C13—C14 | −174.4 (3) | C7—C6—O1—C11 | 0.3 (5) |
O2—C12—C13—C14 | 7.2 (5) | C5—C6—O1—C11 | −179.9 (3) |
O3—C12—C13—C15 | 9.1 (5) | C11i—C11—O1—C6 | −175.0 (3) |
O2—C12—C13—C15 | −169.2 (3) | O3—C12—O2—Co1 | −9.6 (3) |
C15—C13—C14—C15ii | −0.5 (5) | C13—C12—O2—Co1 | 168.8 (3) |
C12—C13—C14—C15ii | −176.9 (3) | O3—C12—O2—H4D | 138.2 |
C14—C13—C15—C14ii | 0.5 (5) | C13—C12—O2—H4D | −43.5 |
C12—C13—C15—C14ii | 177.0 (3) | Co1—C12—O2—H4D | 147.7 |
O3—C12—Co1—N1iii | 75.4 (2) | N1iii—Co1—O2—C12 | 90.9 (2) |
O2—C12—Co1—N1iii | −95.3 (2) | N1—Co1—O2—C12 | −173.36 (19) |
O3—C12—Co1—N1 | 179.50 (18) | O2iii—Co1—O2—C12 | −41.24 (17) |
O2—C12—Co1—N1 | 8.8 (2) | O3iii—Co1—O2—C12 | −80.3 (2) |
O3—C12—Co1—O2iii | −34.8 (2) | O3—Co1—O2—C12 | 5.30 (18) |
O2—C12—Co1—O2iii | 154.45 (15) | C12iii—Co1—O2—C12 | −63.8 (3) |
O3—C12—Co1—O2 | 170.7 (3) | N1iii—Co1—O2—H4D | −64.2 |
O3—C12—Co1—O3iii | −88.9 (2) | N1—Co1—O2—H4D | 31.5 |
O2—C12—Co1—O3iii | 100.39 (19) | O2iii—Co1—O2—H4D | 163.7 |
O2—C12—Co1—O3 | −170.7 (3) | O3iii—Co1—O2—H4D | 124.6 |
O3—C12—Co1—C12iii | −62.61 (18) | O3—Co1—O2—H4D | −149.8 |
O2—C12—Co1—C12iii | 126.6 (2) | C12iii—Co1—O2—H4D | 141.1 |
N2—C3—N1—C1 | 0.4 (4) | C12—Co1—O2—H4D | −155.1 |
N2—C3—N1—Co1 | −157.9 (2) | O2—C12—O3—Co1 | 9.1 (3) |
C2—C1—N1—C3 | −0.7 (4) | C13—C12—O3—Co1 | −169.2 (3) |
C2—C1—N1—Co1 | 159.0 (2) | N1iii—Co1—O3—C12 | −107.8 (2) |
N1iii—Co1—N1—C3 | 91.5 (3) | N1—Co1—O3—C12 | −1.2 (4) |
O2iii—Co1—N1—C3 | −165.8 (3) | O2iii—Co1—O3—C12 | 150.1 (2) |
O2—Co1—N1—C3 | −11.3 (3) | O2—Co1—O3—C12 | −5.39 (18) |
O3iii—Co1—N1—C3 | −105.9 (3) | O3iii—Co1—O3—C12 | 90.3 (2) |
O3—Co1—N1—C3 | −15.0 (5) | C12iii—Co1—O3—C12 | 120.2 (2) |
C12iii—Co1—N1—C3 | −134.8 (3) |
Symmetry codes: (i) −x+1, y, −z−1/2; (ii) −x+1/2, −y+5/2, −z; (iii) −x+1, y, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H4D···O2 | 0.85 | 2.22 | 3.066 (4) | 171 |
O4—H4C···O3iv | 0.85 | 2.21 | 3.059 (4) | 170 |
Symmetry code: (iv) x, −y+2, z−1/2. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | [Cd(C8H4O4)(C22H22N4O2)]·2H2O | [Co(C8H4O4)(C22H22N4O2)]·2H2O |
Mr | 686.98 | 633.51 |
Crystal system, space group | Monoclinic, C2/c | Monoclinic, C2/c |
Temperature (K) | 298 | 298 |
a, b, c (Å) | 17.450 (10), 15.480 (8), 12.636 (7) | 17.612 (3), 14.896 (3), 12.711 (3) |
β (°) | 118.545 (7) | 119.724 (3) |
V (Å3) | 2998 (3) | 2896.0 (10) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.79 | 0.65 |
Crystal size (mm) | 0.26 × 0.16 × 0.09 | 0.26 × 0.16 × 0.09 |
Data collection | ||
Diffractometer | Bruker SMART CCD area-detector diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2003) | Multi-scan (SADABS; Bruker, 2003) |
Tmin, Tmax | 0.822, 0.933 | 0.849, 0.944 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8061, 2944, 2081 | 7231, 2547, 1861 |
Rint | 0.034 | 0.049 |
(sin θ/λ)max (Å−1) | 0.617 | 0.595 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.097, 1.00 | 0.052, 0.127, 1.01 |
No. of reflections | 2944 | 2547 |
No. of parameters | 195 | 195 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.51, −0.26 | 0.36, −0.29 |
Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H4D···O2 | 0.87 | 2.18 | 3.044 (4) | 171.8 |
O4—H4C···O3i | 0.84 | 2.14 | 2.973 (4) | 168.2 |
Symmetry code: (i) x, −y+2, z−1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H4D···O2 | 0.85 | 2.22 | 3.066 (4) | 170.6 |
O4—H4C···O3i | 0.85 | 2.21 | 3.059 (4) | 169.7 |
Symmetry code: (i) x, −y+2, z−1/2. |
The construction of coordination frameworks through crystal engineering has attracted considerable attention, not only because of their fascinating structure topologies (Abrahams et al., 2004), but also due to their potential application as functional materials (Noveron et al., 2002). In principle, some control over the type and topology of the polymer generated from the self-assembly of organic ligands and inorganic metal ions can be achieved by consideration of the functionality of the ligand (Munakata et al., 1997). Flexible N-donor ligands are good candidates for the assembly of versatile structures, owing to their diversity (Qi, Che et al., 2008 or Qi, Luo et al., 2008 ?).
It is well known that flexible ligands with imidazole are very useful organic building blocks for constructing metal–organic frameworks (MOFs) with versatile topologies (Cui et al., 2005). Using these ligands, many intriguing varieties of interpenetrating architectures and topologies have been constructed. Organic aromatic polycarboxylate ligands, especially benzene-1,4-dicarboxylic acid (H2bdc), have been extensively applied in the construction of a rich variety of MOFs because of their diverse coordination modes and high structural stability (Lan et al., 2009).
Recently, we reported several polymers generated from two novel flexible open-chain polyether-bridged organic ligands (Dong et al., 2007; Jiang et al., 2009). To research the coordination chemistry of the flexible open-chain polyether-bridged ligands with imidazole and a rigid aromatic polycarboxylate acid, we synthesized the novel ligand 1,2-bis[2-(1H-1,3-imidazol-1-ylmethyl)phenoxy]ethane (L) and investigated the self-assembly of L with CdII and CoII under hydrothermal conditions in the presence of H2bdc. Two MOFs with the same architectures and topologies were obtained, viz. {[Cd(bdc)(L)].2H2O}n, (I), and {[Co(bdc)(L)].2H2O}n, (II).
Complexes (I) (M = Cd) and (II) (M = Co) crystallize with one unique six-coordinated MII centre. Each MII cation lies in a distorted octahedral environment coordinated by four carboxylic O atoms [O2, O3, O2iii and O3iii; symmetry code: (iii) -x + 1, y, -z + 1/2] from two bdc2- dianions and two N atoms (N1 and N1iii) from two L ligands. This coordination environment is similar to those observed in the structures of [Cd(oba)(1,4-bix)], (III), and [Co(bpea)(bbi)].H2O [oba is 4,4'-oxybis(benzoate), bpea is biphenylethene-4,4'-dicarboxylate, 1,4-bix is 1,4-bis(imidazol-1-ylmethyl)benzene and bbi is 1,1'-(1,4-butanediyl)bis(imidazole); Yang et al., 2009]. The freedom of rotation around the central C—C single bond in L gives rise to cis or trans conformations. In these structures, L adopts the cis conformation (Figs. 1a and 1b). The O1—C11—C11i—O1i torsion angles [symmetry code: (i) -x + 1, y, -z - 1/2] in L are -65.3 (6) and -69.4 (5)° in (I) and (II), respectively. The dihedral angles between the two terminal imidazole rings in L at the metal atom are 49.48 (10) and 55.22 (10)°, while the dihedral angles between the two benzene rings are 63.25 (14) and 65.59 (13)° in (I) and (II), respectively. All the M—O/N bond lengths are consistent with values reported for the M–carboxylate and M–imidazole complexes [Co(1,4-bdc)(L)] and [Cd2(1,3-bdc)2(L)2] (Qi, Che et al., 2008 or Qi, Luo et al., 2008 ?).
In the extended structures of (I) and (II), each bdc2- dianion acts in a bis-bidentate chelating mode to bridge adjacent MII cations to form zigzag one-dimensional chains. These chains are linked by L ligands into a two-dimensional wave-like sheet (Fig. 2) in the ac plane. Although a large four-membered ring formed by four CdII ions, two L ligands and two bdc2- dianions exists in a single net, they are interpenetrated by other nets. These two-dimensional sheets are packed in the ab plane to form a threefold interpenetrated two-dimensional framework in a parallel fashion (Batten, 2001; Figs. 3 and 4). Each sheet is penetrated by two others (one above and one below) which have parallel but not coincident mean planes, leading to an overall three-dimensional entanglement architecture. The interpenetrated structure forms square channels when viewed down the c axis. Each square channel is formed by four MII cations and four bdc2- dianions and filled by L ligands.
The water molecules are linked to the framework via O4—H4C···O3 and O4—H4D···O2 hydrogen bonds. Although the two-dimensional framework topologies and the way they interpenetrate are similar to those in complex (III) (Yang et al., 2009), there are some significant differences in their structures. In (III), there are interpenetrating channels and the nodes of adjacent sheets are parallel. For (I) and (II), however, there are square channels which are not interpenetrated, and the nodes of the adjacent sheets are in a line.
In summary, the most interesting feature in (I) and (II) is the presence of a threefold interpenetrated framework with square channels formed by L ligands and bdc2- dianions. This behaviour may offer a route to new types of two-dimensional framework structures.