Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107044010/bm3034sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107044010/bm3034Isup2.hkl |
CCDC reference: 665491
For related literature, see: Beatty (2003); Bu et al. (2000); Chen et al. (2007); Fun et al. (1997); Ge et al. (2006); Li et al. (2006); Liu et al. (2007); Mautner et al. (2004); Ochoa & Alexandre (2005); Qiu et al. (2006); Russell & Ward (1996); Vreshch et al. (2005); Yang et al. (2006).
Ligand L was prepared by condensation (Qiu et al., 2006; Yang et al., 2006). To a solution of L (51 mg, 0.2 mmol) in methanol (10 ml), cadmium nitrate tetrahydrate (60 mg, 0.2 mmol) was added slowly. After stirring for 1.5 h, the solution was filtered. Slow evaporation of the solution afforded yellow crystals suitable for X-ray diffraction.
H atoms in water molecules were located in difference Fourier maps and then allowed to ride on the O atoms with Uiso(H) values of 1.5Ueq(O). The other H atoms were placed in idealized positions and treated as riding with [C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C) for aromatic H atoms; C—H = 0.96 Å and Uiso(H) = 1.5Ueq(C) for methyl H atoms; and N—H = 0.86 Å and Uiso(H) = 1.2Ueq(N) for the imine group].
Data collection: TEXRAY (Molecular Structure Corporation, 1999); cell refinement: TEXRAY (Molecular Structure Corporation, 1999); data reduction: TEXSAN (Molecular Structure Corporation, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEX (McArdle, 1995); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
[Cd(C14H13N3O2)2(H2O)4](NO3)2 | F(000) = 836 |
Mr = 819.03 | Dx = 1.602 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 16376 reflections |
a = 8.062 (5) Å | θ = 3.1–27.5° |
b = 17.955 (8) Å | µ = 0.72 mm−1 |
c = 11.853 (6) Å | T = 293 K |
β = 98.26 (2)° | Prism, yellow |
V = 1697.9 (15) Å3 | 0.28 × 0.21 × 0.15 mm |
Z = 2 |
Rigaku Weissenberg IP diffractometer | 3892 independent reflections |
Radiation source: fine-focus sealed tube | 3210 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.031 |
scintillation counter scans | θmax = 27.5°, θmin = 3.1° |
Absorption correction: empirical (using intensity measurements) (TEXRAY; Molecular Structure Corporation, 1999) | h = −10→10 |
Tmin = 0.824, Tmax = 0.907 | k = −23→23 |
16376 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)] = 0.028 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.073 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0363P)2 + 0.6841P] where P = (Fo2 + 2Fc2)/3 |
3892 reflections | (Δ/σ)max < 0.001 |
232 parameters | Δρmax = 0.54 e Å−3 |
0 restraints | Δρmin = −0.35 e Å−3 |
[Cd(C14H13N3O2)2(H2O)4](NO3)2 | V = 1697.9 (15) Å3 |
Mr = 819.03 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 8.062 (5) Å | µ = 0.72 mm−1 |
b = 17.955 (8) Å | T = 293 K |
c = 11.853 (6) Å | 0.28 × 0.21 × 0.15 mm |
β = 98.26 (2)° |
Rigaku Weissenberg IP diffractometer | 3892 independent reflections |
Absorption correction: empirical (using intensity measurements) (TEXRAY; Molecular Structure Corporation, 1999) | 3210 reflections with I > 2σ(I) |
Tmin = 0.824, Tmax = 0.907 | Rint = 0.031 |
16376 measured reflections |
R[F2 > 2σ(F2)] = 0.028 | 0 restraints |
wR(F2) = 0.073 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.54 e Å−3 |
3892 reflections | Δρmin = −0.35 e Å−3 |
232 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 | ||
Cd1 | 0.5000 | 0.0000 | 0.5000 | 0.03016 (7) | |
N1 | 0.5471 (2) | 0.12516 (8) | 0.54394 (14) | 0.0335 (3) | |
N2 | 0.6850 (2) | 0.39910 (9) | 0.53496 (15) | 0.0420 (4) | |
H2N | 0.6271 | 0.3876 | 0.4706 | 0.050* | |
N3 | 0.7551 (3) | 0.46925 (9) | 0.55202 (16) | 0.0430 (4) | |
N4 | 0.1051 (3) | 0.09655 (11) | 0.71737 (18) | 0.0539 (5) | |
O1 | 0.7804 (2) | 0.36331 (8) | 0.71533 (13) | 0.0550 (5) | |
O2 | 0.6712 (4) | 0.59681 (11) | 0.27756 (18) | 0.0882 (8) | |
O3 | 0.0330 (3) | 0.07672 (13) | 0.62190 (16) | 0.0718 (6) | |
O4 | 0.2606 (3) | 0.09431 (16) | 0.7357 (2) | 0.0954 (8) | |
O5 | 0.0241 (3) | 0.11696 (15) | 0.79077 (16) | 0.0929 (9) | |
O6 | 0.2207 (2) | 0.02289 (11) | 0.46857 (16) | 0.0572 (4) | |
H6A | 0.1776 | 0.0404 | 0.5282 | 0.086* | |
H6B | 0.1467 | −0.0027 | 0.4290 | 0.086* | |
O7 | 0.4929 (2) | 0.02422 (10) | 0.30786 (13) | 0.0508 (4) | |
H7A | 0.5708 | 0.0043 | 0.2736 | 0.076* | |
H7B | 0.4234 | 0.0486 | 0.2654 | 0.076* | |
C1 | 0.4825 (3) | 0.18060 (12) | 0.47614 (18) | 0.0416 (5) | |
H1 | 0.4046 | 0.1691 | 0.4128 | 0.050* | |
C2 | 0.5267 (3) | 0.25424 (12) | 0.49630 (17) | 0.0412 (5) | |
H2 | 0.4789 | 0.2915 | 0.4476 | 0.049* | |
C3 | 0.6436 (3) | 0.27190 (10) | 0.59037 (16) | 0.0336 (4) | |
C4 | 0.7057 (3) | 0.21492 (11) | 0.66163 (18) | 0.0416 (5) | |
H4 | 0.7810 | 0.2249 | 0.7269 | 0.050* | |
C5 | 0.6553 (3) | 0.14303 (11) | 0.63555 (18) | 0.0411 (5) | |
H5 | 0.6990 | 0.1050 | 0.6843 | 0.049* | |
C6 | 0.7085 (3) | 0.34932 (10) | 0.61978 (17) | 0.0375 (4) | |
C7 | 0.7248 (3) | 0.51204 (11) | 0.4665 (2) | 0.0455 (5) | |
H7 | 0.6561 | 0.4952 | 0.4017 | 0.055* | |
C8 | 0.7948 (3) | 0.58685 (11) | 0.46696 (19) | 0.0406 (5) | |
C9 | 0.7633 (3) | 0.63043 (12) | 0.3692 (2) | 0.0477 (5) | |
C10 | 0.8263 (4) | 0.70238 (13) | 0.3683 (2) | 0.0554 (6) | |
H10 | 0.8028 | 0.7319 | 0.3035 | 0.067* | |
C11 | 0.9232 (4) | 0.72942 (14) | 0.4638 (3) | 0.0630 (7) | |
H11 | 0.9649 | 0.7777 | 0.4636 | 0.076* | |
C12 | 0.9599 (4) | 0.68623 (15) | 0.5601 (3) | 0.0701 (8) | |
H12 | 1.0281 | 0.7048 | 0.6239 | 0.084* | |
C13 | 0.8951 (4) | 0.61536 (13) | 0.5615 (2) | 0.0552 (6) | |
H13 | 0.9191 | 0.5863 | 0.6268 | 0.066* | |
C14 | 0.6214 (5) | 0.63733 (18) | 0.1781 (2) | 0.0757 (9) | |
H14D | 0.5581 | 0.6057 | 0.1224 | 0.114* | |
H14A | 0.7187 | 0.6556 | 0.1487 | 0.114* | |
H14B | 0.5531 | 0.6786 | 0.1947 | 0.114* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cd1 | 0.03183 (11) | 0.02169 (10) | 0.03528 (12) | −0.00205 (7) | −0.00087 (7) | 0.00060 (7) |
N1 | 0.0383 (8) | 0.0249 (7) | 0.0358 (8) | −0.0033 (6) | 0.0010 (7) | −0.0002 (7) |
N2 | 0.0605 (12) | 0.0251 (8) | 0.0371 (9) | −0.0098 (8) | −0.0045 (8) | 0.0010 (7) |
N3 | 0.0593 (11) | 0.0252 (8) | 0.0425 (10) | −0.0093 (8) | 0.0008 (8) | 0.0002 (8) |
N4 | 0.0641 (14) | 0.0461 (11) | 0.0476 (12) | 0.0079 (10) | −0.0048 (10) | −0.0065 (9) |
O1 | 0.0869 (13) | 0.0332 (7) | 0.0379 (8) | −0.0162 (8) | −0.0150 (8) | 0.0010 (7) |
O2 | 0.148 (2) | 0.0456 (10) | 0.0573 (12) | −0.0274 (12) | −0.0314 (13) | 0.0173 (9) |
O3 | 0.0585 (11) | 0.1015 (16) | 0.0543 (11) | −0.0095 (11) | 0.0047 (9) | −0.0310 (11) |
O4 | 0.0616 (14) | 0.117 (2) | 0.1009 (18) | −0.0146 (13) | −0.0103 (12) | −0.0120 (16) |
O5 | 0.1123 (19) | 0.1193 (19) | 0.0424 (10) | 0.0705 (16) | −0.0053 (11) | −0.0138 (11) |
O6 | 0.0347 (8) | 0.0708 (10) | 0.0641 (11) | 0.0033 (8) | 0.0003 (7) | −0.0228 (9) |
O7 | 0.0643 (11) | 0.0489 (8) | 0.0385 (8) | 0.0141 (8) | 0.0047 (7) | 0.0084 (7) |
C1 | 0.0512 (12) | 0.0290 (10) | 0.0399 (11) | −0.0026 (8) | −0.0096 (9) | −0.0011 (8) |
C2 | 0.0547 (14) | 0.0267 (10) | 0.0374 (11) | −0.0013 (8) | −0.0100 (10) | 0.0039 (8) |
C3 | 0.0420 (10) | 0.0254 (8) | 0.0324 (9) | −0.0039 (8) | 0.0015 (8) | −0.0001 (7) |
C4 | 0.0524 (12) | 0.0312 (10) | 0.0362 (10) | −0.0063 (9) | −0.0107 (9) | 0.0024 (8) |
C5 | 0.0520 (12) | 0.0283 (9) | 0.0389 (11) | −0.0037 (9) | −0.0069 (9) | 0.0067 (8) |
C6 | 0.0488 (12) | 0.0273 (9) | 0.0343 (10) | −0.0052 (8) | −0.0009 (8) | −0.0002 (8) |
C7 | 0.0633 (15) | 0.0305 (10) | 0.0402 (11) | −0.0083 (9) | −0.0015 (10) | 0.0014 (9) |
C8 | 0.0496 (12) | 0.0278 (9) | 0.0445 (11) | −0.0039 (8) | 0.0071 (9) | 0.0017 (9) |
C9 | 0.0616 (14) | 0.0329 (10) | 0.0479 (12) | −0.0053 (10) | 0.0053 (10) | 0.0022 (9) |
C10 | 0.0729 (17) | 0.0355 (11) | 0.0592 (15) | −0.0050 (11) | 0.0137 (13) | 0.0118 (11) |
C11 | 0.0755 (19) | 0.0333 (11) | 0.0809 (19) | −0.0182 (12) | 0.0134 (15) | 0.0003 (12) |
C12 | 0.090 (2) | 0.0458 (14) | 0.0696 (18) | −0.0259 (14) | −0.0064 (16) | −0.0049 (13) |
C13 | 0.0733 (17) | 0.0376 (11) | 0.0511 (14) | −0.0109 (11) | −0.0028 (12) | 0.0029 (10) |
C14 | 0.103 (3) | 0.0648 (18) | 0.0530 (16) | −0.0053 (17) | −0.0098 (16) | 0.0140 (14) |
Cd1—O6 | 2.267 (2) | C1—H1 | 0.9300 |
Cd1—O6i | 2.267 (2) | C2—C3 | 1.389 (3) |
Cd1—O7i | 2.3112 (19) | C2—H2 | 0.9300 |
Cd1—O7 | 2.3112 (19) | C3—C4 | 1.374 (3) |
Cd1—N1 | 2.3256 (18) | C3—C6 | 1.508 (3) |
Cd1—N1i | 2.3256 (18) | C4—C5 | 1.375 (3) |
N1—C5 | 1.331 (3) | C4—H4 | 0.9300 |
N1—C1 | 1.337 (3) | C5—H5 | 0.9300 |
N2—C6 | 1.338 (3) | C7—C8 | 1.457 (3) |
N2—N3 | 1.383 (2) | C7—H7 | 0.9300 |
N2—H2N | 0.8600 | C8—C13 | 1.382 (3) |
N3—C7 | 1.268 (3) | C8—C9 | 1.391 (3) |
N4—O5 | 1.217 (3) | C9—C10 | 1.388 (3) |
N4—O4 | 1.242 (3) | C10—C11 | 1.369 (4) |
N4—O3 | 1.247 (3) | C10—H10 | 0.9300 |
O1—C6 | 1.222 (2) | C11—C12 | 1.377 (4) |
O2—C9 | 1.365 (3) | C11—H11 | 0.9300 |
O2—C14 | 1.394 (3) | C12—C13 | 1.377 (3) |
O6—H6A | 0.8892 | C12—H12 | 0.9300 |
O6—H6B | 0.8405 | C13—H13 | 0.9300 |
O7—H7A | 0.8717 | C14—H14A | 0.9600 |
O7—H7B | 0.8234 | C14—H14A | 0.9600 |
C1—C2 | 1.381 (3) | C14—H14B | 0.9600 |
O6—Cd1—O6i | 180.0 | C4—C3—C6 | 117.42 (17) |
O6—Cd1—O7i | 94.56 (7) | C2—C3—C6 | 124.65 (17) |
O6i—Cd1—O7i | 85.44 (7) | C3—C4—C5 | 119.41 (18) |
O6—Cd1—O7 | 85.44 (7) | C3—C4—H4 | 120.3 |
O6i—Cd1—O7 | 94.56 (7) | C5—C4—H4 | 120.3 |
O7i—Cd1—O7 | 180.0 | N1—C5—C4 | 123.20 (18) |
O6—Cd1—N1 | 89.31 (7) | N1—C5—H5 | 118.4 |
O6i—Cd1—N1 | 90.69 (7) | C4—C5—H5 | 118.4 |
O7i—Cd1—N1 | 88.91 (6) | O1—C6—N2 | 123.79 (18) |
O7—Cd1—N1 | 91.09 (6) | O1—C6—C3 | 120.41 (18) |
O6—Cd1—N1i | 90.69 (7) | N2—C6—C3 | 115.79 (17) |
O6i—Cd1—N1i | 89.31 (7) | N3—C7—C8 | 121.7 (2) |
O7i—Cd1—N1i | 91.09 (6) | N3—C7—H7 | 119.1 |
O7—Cd1—N1i | 88.91 (6) | C8—C7—H7 | 119.1 |
N1—Cd1—N1i | 180.0 | C13—C8—C9 | 118.8 (2) |
C5—N1—C1 | 117.65 (17) | C13—C8—C7 | 121.7 (2) |
C5—N1—Cd1 | 118.85 (13) | C9—C8—C7 | 119.4 (2) |
C1—N1—Cd1 | 123.22 (13) | O2—C9—C10 | 124.2 (2) |
C6—N2—N3 | 119.19 (17) | O2—C9—C8 | 115.30 (19) |
C6—N2—H2N | 120.4 | C10—C9—C8 | 120.4 (2) |
N3—N2—H2N | 120.4 | C11—C10—C9 | 119.3 (2) |
C7—N3—N2 | 114.04 (18) | C11—C10—H10 | 120.4 |
O5—N4—O4 | 121.1 (2) | C9—C10—H10 | 120.4 |
O5—N4—O3 | 120.4 (2) | C10—C11—C12 | 121.0 (2) |
O4—N4—O3 | 118.4 (2) | C10—C11—H11 | 119.5 |
C9—O2—C14 | 120.0 (2) | C12—C11—H11 | 119.5 |
Cd1—O6—H6A | 115.2 | C13—C12—C11 | 119.6 (3) |
Cd1—O6—H6B | 127.0 | C13—C12—H12 | 120.2 |
H6A—O6—H6B | 108.1 | C11—C12—H12 | 120.2 |
Cd1—O7—H7A | 117.6 | C12—C13—C8 | 120.8 (2) |
Cd1—O7—H7B | 128.4 | C12—C13—H13 | 119.6 |
H7A—O7—H7B | 114.0 | C8—C13—H13 | 119.6 |
N1—C1—C2 | 122.69 (18) | O2—C14—H14D | 109.5 |
N1—C1—H1 | 118.7 | O2—C14—H14A | 109.5 |
C2—C1—H1 | 118.7 | H14D—C14—H14A | 109.5 |
C1—C2—C3 | 119.06 (18) | O2—C14—H14B | 109.5 |
C1—C2—H2 | 120.5 | H14D—C14—H14B | 109.5 |
C3—C2—H2 | 120.5 | H14A—C14—H14B | 109.5 |
C4—C3—C2 | 117.93 (18) | ||
O6—Cd1—N1—C5 | 134.67 (17) | C4—C3—C6—O1 | −17.0 (3) |
O6i—Cd1—N1—C5 | −45.33 (17) | C2—C3—C6—O1 | 163.4 (2) |
O7i—Cd1—N1—C5 | 40.10 (17) | C4—C3—C6—N2 | 161.6 (2) |
O7—Cd1—N1—C5 | −139.90 (17) | C2—C3—C6—N2 | −18.1 (3) |
O6—Cd1—N1—C1 | −51.63 (18) | N2—N3—C7—C8 | −177.1 (2) |
O6i—Cd1—N1—C1 | 128.37 (18) | N3—C7—C8—C13 | −1.3 (4) |
O7i—Cd1—N1—C1 | −146.20 (18) | N3—C7—C8—C9 | 177.4 (3) |
O7—Cd1—N1—C1 | 33.80 (18) | C14—O2—C9—C10 | −6.1 (5) |
C6—N2—N3—C7 | −179.8 (2) | C14—O2—C9—C8 | 175.0 (3) |
C5—N1—C1—C2 | 1.6 (3) | C13—C8—C9—O2 | 176.4 (3) |
Cd1—N1—C1—C2 | −172.21 (17) | C7—C8—C9—O2 | −2.2 (4) |
N1—C1—C2—C3 | 0.3 (4) | C13—C8—C9—C10 | −2.5 (4) |
C1—C2—C3—C4 | −2.3 (3) | C7—C8—C9—C10 | 178.8 (2) |
C1—C2—C3—C6 | 177.4 (2) | O2—C9—C10—C11 | −177.2 (3) |
C2—C3—C4—C5 | 2.3 (3) | C8—C9—C10—C11 | 1.6 (4) |
C6—C3—C4—C5 | −177.3 (2) | C9—C10—C11—C12 | 0.4 (5) |
C1—N1—C5—C4 | −1.5 (3) | C10—C11—C12—C13 | −1.5 (5) |
Cd1—N1—C5—C4 | 172.55 (19) | C11—C12—C13—C8 | 0.6 (5) |
C3—C4—C5—N1 | −0.5 (4) | C9—C8—C13—C12 | 1.4 (4) |
N3—N2—C6—O1 | 4.7 (4) | C7—C8—C13—C12 | −180.0 (3) |
N3—N2—C6—C3 | −173.84 (19) |
Symmetry code: (i) −x+1, −y, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O6—H6A···O3 | 0.89 | 1.84 | 2.705 (3) | 164 |
N2—H2N···O5ii | 0.86 | 2.18 | 3.011 (3) | 164 |
O6—H6B···O3iii | 0.84 | 1.99 | 2.811 (3) | 164 |
O7—H7A···O4i | 0.87 | 2.24 | 3.006 (4) | 146 |
O7—H7B···O1iv | 0.82 | 2.00 | 2.771 (2) | 156 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) x+1/2, −y+1/2, z−1/2; (iii) −x, −y, −z+1; (iv) x−1/2, −y+1/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | [Cd(C14H13N3O2)2(H2O)4](NO3)2 |
Mr | 819.03 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 8.062 (5), 17.955 (8), 11.853 (6) |
β (°) | 98.26 (2) |
V (Å3) | 1697.9 (15) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.72 |
Crystal size (mm) | 0.28 × 0.21 × 0.15 |
Data collection | |
Diffractometer | Rigaku Weissenberg IP diffractometer |
Absorption correction | Empirical (using intensity measurements) (TEXRAY; Molecular Structure Corporation, 1999) |
Tmin, Tmax | 0.824, 0.907 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 16376, 3892, 3210 |
Rint | 0.031 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.028, 0.073, 1.07 |
No. of reflections | 3892 |
No. of parameters | 232 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.54, −0.35 |
Computer programs: TEXRAY (Molecular Structure Corporation, 1999), TEXSAN (Molecular Structure Corporation, 1999), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEX (McArdle, 1995).
D—H···A | D—H | H···A | D···A | D—H···A |
O6—H6A···O3 | 0.89 | 1.84 | 2.705 (3) | 163.5 |
N2—H2N···O5i | 0.86 | 2.18 | 3.011 (3) | 163.8 |
O6—H6B···O3ii | 0.84 | 1.99 | 2.811 (3) | 163.6 |
O7—H7A···O4iii | 0.87 | 2.24 | 3.006 (4) | 146.0 |
O7—H7B···O1iv | 0.82 | 2.00 | 2.771 (2) | 156.4 |
Symmetry codes: (i) x+1/2, −y+1/2, z−1/2; (ii) −x, −y, −z+1; (iii) −x+1, −y, −z+1; (iv) x−1/2, −y+1/2, z−1/2. |
Complex | Cd1—O1 | Cd2—O2 | Δd e |
This work | 2.267 (2) | 2.311 (2) | 0.044 |
[Cd(pmtca)2(H2O)2]na | 2.277 (2) | 2.350 (2) | 0.073 |
[Cd(pmtca)2(H2O)4]a | 2.298 (2) | 2.347 (2) | 0.049 |
C54H70CdN12O16b | 2.299 (3) | 2.321 (2) | 0.022 |
[Cd(trtr)2(H2O)4](SiF6)c | 2.273 (2) | 2.289 (2) | 0.016 |
[Cd(9-EtGH)2(H2O)4]-2(NO3d) | 2.309 (3) | 2.324 (3) | 0.015 |
[Cd(9-MeGH)2(H2O)4]-2(NO3d) | 2.317 (3) | 2.331 (2) | 0.014 |
Notes: (a) Chen et al. (2007) [Hpmtca is 2-(3-pyridyl)-4-methylthiazole −5-carboxylic acid, Hptca is 2-(4-pyridyl)thiazole-4-carboxylic acid ptca IS NOT USED]; (b) Wei et al. (2006); (c) Liu et al. (2007) {trtr is 4-[3-(1,2,4-triazolyl)-1,2,4-triazole} PLEASE CHECK NAME - MISSING CLOSING BRACKET; (d) Ochoa & Alexandre (2005) (9-EtGH is 9-ethylguanine, 9-MeGH is 9-methylguanine); (e) Δd is the difference between Cd—O(water) bond distances in same complex. |
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Supramolecular assembly through hydrogen bonds has been extensively exploited to generate one-, two- and three-dimensional extended structures (Beatty, 2003; Li et al., 2006; Russell & Ward, 1996). It is interesting that polytoptic ligands based on isonicotinoylhydrazone have led to a number of complexes with multi-dimensional structure or extended multi-dimensional structures (Bu et al., 2000; Ge et al., 2006). We present here the synthesis and structural characterization of the cadmium complex (I), [Cd(C14H13N3O2)2(H2O)4](NO3)2, where C14H13N3O2 is neutral 2-methoxybenzldehyde isonicotinoylhydrazone, L.
As shown in Fig. 1, the title complex consists of one complex cation, [Cd(C14H13N3O2)2(H2O)4]2+, on an inversion centre and two NO3− anions. The cadmium centre is six-coordinated by two pyridine N atoms [N1 and N1i; symmetry code: (i) −x + 1, −y, −z + 1] of two L ligands and four coordinated water O atoms (O6, O7, O6i and O7i), conferring a slightly distorted octahedral coordination. The equatorial plane is formed by atoms O6, O7, O6i and O7i, while the axial positions are occupied by atoms N1and N1i. The Cd atom lies on a crystallographic inversion centre and the two hydrazone ligands are in a trans configuration.
As listed in Table 2, the Cd—O(coordinated water) bond lengths in the known cadmium complexes are from 2.273 (2) to 2.350 (2) Å (Chen et al., 2007; Liu et al., 2007; Ochoa & Alexandre, 2005; Wei et al., 2006). The Cd—O(coordinated water) bond lengths in (I) (Cd1—O6 and Cd—O7) are 2.267 (2) and 2.311 (2) Å, respectively, the former being the shortest Cd—O(water) value among the known cadmium complexes. It is interesting to note that the difference between Cd—O(coordinated water) bond lengths in same complex ranges from 0.014 (3) to 0.073 (2) Å. The Cd1—N1 bond distance of 2.326 (2) Å is in agreement with the values reported by Mautner et al. (2004) and Vreshch et al. (2005).
The structral parameters of L in the title complex are within normal ranges as reported by Qiu et al. (2006) and Yang et al. (2006). The C7═N3 bond distance of 1.268 (3) Å in (I) confirms the presence of a double bond; the corresponding bonds in the neutral [or `uncoordinated?'; `neutral' is used above to describe L in the title complex] ligand L are 1.277 (2) and 1.269 (7) Å (Qiu et al., 2006; Yang et al., 2006). The C6—N2 bond distance of 1.338 (3) Å in (I) is similar to the corresponding distances [1.340 (8) and 1.350 (2) Å] reported by Qiu et al. (2006) and Yang et al. (2006). The dihedral angle between the benzene (C8–C13) and pyridine (N1/C1–C5) rings is 18.8 (2)°; these rings are slightly more inclined than normal (Fun et al., 1997) and we attribute this to the steric effect of the C9 methoxy substituent.
As can be seen from Table 1, there are many hydrogen bonds in the title complex. Each [Cd(C14H13N3O2)2(H2O)4]2+ cation is connected to four NO3− anions by O—H(H2O)···O(NO3−)-type hydrogen bonds (O6—H6A···O3, O6—H6B···O3iii, O7—H7A···O4i; symmetry codes as in Table 1), forming an extended chain along the a axis (Fig. 2).
At the same time, every ligand L is coordinated to one Cd atom through its pyridine N atom (N1) and linked to another cadmium complex cation by an O7—H7B···O1iv hydrogen bond. This means that the hydrazone ligand acts as a bridging ligand. Therefore, four [Cd(C14H13N3O2)2(H2O)4]2+ units are combined by four hydrogen bonds, forming a 36-membered ring. Two such rings are presented in Fig. 3; one ring is composed of the four ligands with lightly shaded bonds (coloured cyan in the online version of the journal) and the other ring is composed of three more darkly shaded (pink online [this looks more like purple on the IUCr system]) and one lightly shaded (cyan online) ligands. These ring are then connected together to form an extended layer along the bc plane.
These layers and chains are linked together to obtain an extended three-dimensional network (see Fig. 4). O—H(water)···O(NO3−) and O—H(water)···O(carboxyl) hydrogen bonds play an important role in the formation of this network.