Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102005966/de1183sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102005966/de1183Isup2.hkl |
CCDC reference: 188592
Complex (I) was obtained as yellow crystals by the reaction between an aqueous solution (10 ml) of K3[Cr(CN)6] (0.2 mmol), 2-pyrrolidone (0.4 mmol) and an aqueous solution (10 ml) of [Dy(H2O)6]Cl3 (0.2 mmol) at room tempetature.
The coordinates of the water H atoms were found from difference Fourier maps and were normalized to have O—H distances of 0.88 Å. H atoms bound to C and N atoms were also visible in difference maps and were placed using the HFIX commands in SHELXL97 (Sheldrick, 1997). All H atoms were allowed for as riding atoms (C—H = 0.97 Å and N—H 0.86 Å). Residual peaks in the final Fourier map shows were adjacent (1.12 Å) to the Dy atom.
Data collection: COLLECT (Nonius, 1998); cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997); data reduction: HKL DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2002); software used to prepare material for publication: SHELXL97.
Fig. 1. A view of (I) with the atom-labelling scheme. Displacement ellipsoids are drawn at the 20% probability level. Hydrogen bonds within the asymmetric unit are indicated by dashed lines. |
[CrDy(C4H7NO)4(CN)6(H2O)3]·2H2O | Z = 2 |
Mr = 801.12 | F(000) = 804 |
Triclinic, P1 | Dx = 1.612 Mg m−3 |
a = 9.1442 (18) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 12.448 (3) Å | θ = 3.5–25.0° |
c = 14.518 (3) Å | µ = 2.64 mm−1 |
α = 90.19 (3)° | T = 293 K |
β = 92.40 (3)° | Platelet, yellow |
γ = 91.10 (3)° | 0.20 × 0.10 × 0.08 mm |
V = 1650.8 (6) Å3 |
Nonius KappaCCD area-detector diffractometer | 5798 independent reflections |
Radiation source: fine-focus sealed tube | 5457 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.046 |
Detector resolution: 0.76 pixels mm-1 | θmax = 25.0°, θmin = 3.5° |
CCD scans | h = −10→10 |
Absorption correction: empirical (using intensity measurements) (Blessing, 1995, 1997) | k = −14→14 |
Tmin = 0.625, Tmax = 0.812 | l = 0→17 |
9078 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)] = 0.029 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.074 | H-atom parameters constrained |
S = 1.13 | w = 1/[σ2(Fo2) + (0.0281P)2 + 3.8796P] where P = (Fo2 + 2Fc2)/3 |
5798 reflections | (Δ/σ)max = 0.001 |
389 parameters | Δρmax = 2.25 e Å−3 |
0 restraints | Δρmin = −0.95 e Å−3 |
[CrDy(C4H7NO)4(CN)6(H2O)3]·2H2O | γ = 91.10 (3)° |
Mr = 801.12 | V = 1650.8 (6) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.1442 (18) Å | Mo Kα radiation |
b = 12.448 (3) Å | µ = 2.64 mm−1 |
c = 14.518 (3) Å | T = 293 K |
α = 90.19 (3)° | 0.20 × 0.10 × 0.08 mm |
β = 92.40 (3)° |
Nonius KappaCCD area-detector diffractometer | 5798 independent reflections |
Absorption correction: empirical (using intensity measurements) (Blessing, 1995, 1997) | 5457 reflections with I > 2σ(I) |
Tmin = 0.625, Tmax = 0.812 | Rint = 0.046 |
9078 measured reflections |
R[F2 > 2σ(F2)] = 0.029 | 0 restraints |
wR(F2) = 0.074 | H-atom parameters constrained |
S = 1.13 | Δρmax = 2.25 e Å−3 |
5798 reflections | Δρmin = −0.95 e Å−3 |
389 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 | ||
Dy | 0.557981 (18) | 0.234345 (14) | 0.249405 (11) | 0.02406 (7) | |
Cr | 0.21126 (6) | −0.14059 (5) | 0.25114 (4) | 0.02209 (13) | |
O1 | 0.6484 (4) | 0.3850 (3) | 0.3299 (2) | 0.0543 (9) | |
O2 | 0.4831 (3) | 0.2048 (3) | 0.40197 (19) | 0.0375 (7) | |
O3 | 0.4588 (4) | 0.1971 (3) | 0.1015 (2) | 0.0594 (10) | |
O4 | 0.3229 (3) | 0.3073 (3) | 0.2551 (2) | 0.0525 (9) | |
O5 | 0.5930 (4) | 0.3839 (2) | 0.1488 (2) | 0.0404 (7) | |
O6 | 0.7567 (3) | 0.1824 (3) | 0.15911 (19) | 0.0429 (8) | |
O7 | 0.7513 (3) | 0.1570 (3) | 0.33933 (19) | 0.0483 (9) | |
N1 | 0.4533 (4) | 0.0510 (3) | 0.2503 (2) | 0.0379 (8) | |
N2 | 0.2270 (5) | −0.1762 (4) | 0.0324 (3) | 0.0589 (12) | |
N3 | 0.4579 (5) | −0.3197 (4) | 0.2634 (4) | 0.0635 (13) | |
N4 | −0.0446 (5) | −0.3199 (4) | 0.2494 (4) | 0.0711 (14) | |
N5 | 0.2279 (4) | −0.1323 (3) | 0.4716 (2) | 0.0460 (10) | |
N6 | −0.0214 (4) | 0.0515 (4) | 0.2428 (3) | 0.0498 (10) | |
N7 | 0.6979 (7) | 0.3761 (4) | 0.4842 (3) | 0.0765 (17) | |
H7 | 0.6722 | 0.3097 | 0.4904 | 0.092* | |
N8 | 0.2384 (5) | 0.1669 (4) | 0.4150 (3) | 0.0611 (12) | |
H8 | 0.2140 | 0.1765 | 0.3578 | 0.073* | |
N9 | 0.4174 (5) | 0.1295 (4) | −0.0435 (3) | 0.0669 (13) | |
H9 | 0.5077 | 0.1254 | −0.0572 | 0.080* | |
N10 | 0.2623 (5) | 0.4325 (4) | 0.1488 (4) | 0.0658 (13) | |
H10 | 0.3499 | 0.4475 | 0.1330 | 0.079* | |
C1 | 0.3725 (4) | −0.0196 (3) | 0.2497 (3) | 0.0301 (8) | |
C2 | 0.2162 (4) | −0.1592 (4) | 0.1088 (3) | 0.0343 (9) | |
C3 | 0.3696 (5) | −0.2561 (4) | 0.2593 (3) | 0.0361 (9) | |
C4 | 0.0467 (5) | −0.2566 (4) | 0.2520 (3) | 0.0392 (10) | |
C5 | 0.2190 (4) | −0.1334 (3) | 0.3934 (3) | 0.0310 (9) | |
C6 | 0.0582 (4) | −0.0182 (3) | 0.2442 (3) | 0.0315 (9) | |
C7 | 0.6885 (6) | 0.4252 (4) | 0.4049 (3) | 0.0439 (11) | |
C8 | 0.7326 (9) | 0.5391 (5) | 0.4202 (4) | 0.076 (2) | |
H8A | 0.6529 | 0.5861 | 0.4025 | 0.092* | |
H8B | 0.8167 | 0.5578 | 0.3845 | 0.092* | |
C9 | 0.7704 (11) | 0.5489 (5) | 0.5221 (4) | 0.094 (3) | |
H9A | 0.8700 | 0.5757 | 0.5323 | 0.112* | |
H9B | 0.7048 | 0.5980 | 0.5509 | 0.112* | |
C10 | 0.7544 (10) | 0.4410 (5) | 0.5609 (4) | 0.087 (2) | |
H10A | 0.8481 | 0.4149 | 0.5843 | 0.104* | |
H10B | 0.6866 | 0.4407 | 0.6106 | 0.104* | |
C11 | 0.3786 (5) | 0.1633 (4) | 0.0389 (3) | 0.0444 (11) | |
C12 | 0.2172 (7) | 0.1542 (7) | 0.0380 (5) | 0.087 (2) | |
H12A | 0.1865 | 0.1097 | 0.0887 | 0.105* | |
H12B | 0.1751 | 0.2246 | 0.0442 | 0.105* | |
C13 | 0.1688 (7) | 0.1051 (6) | −0.0504 (5) | 0.078 (2) | |
H13A | 0.0939 | 0.1480 | −0.0809 | 0.093* | |
H13B | 0.1288 | 0.0334 | −0.0409 | 0.093* | |
C14 | 0.3018 (7) | 0.1005 (6) | −0.1074 (4) | 0.0719 (17) | |
H14A | 0.3145 | 0.0288 | −0.1318 | 0.086* | |
H14B | 0.2955 | 0.1510 | −0.1581 | 0.086* | |
C15 | 0.3774 (5) | 0.1777 (4) | 0.4476 (3) | 0.0382 (10) | |
C16 | 0.3847 (7) | 0.1514 (6) | 0.5458 (4) | 0.0732 (18) | |
H16A | 0.4335 | 0.2084 | 0.5817 | 0.088* | |
H16B | 0.4360 | 0.0848 | 0.5568 | 0.088* | |
C17 | 0.2227 (10) | 0.1398 (6) | 0.5695 (6) | 0.105 (3) | |
H17A | 0.2067 | 0.0737 | 0.6031 | 0.126* | |
H17B | 0.1952 | 0.1995 | 0.6077 | 0.126* | |
C18 | 0.1333 (8) | 0.1383 (6) | 0.4817 (6) | 0.089 (2) | |
H18A | 0.0908 | 0.0675 | 0.4692 | 0.107* | |
H18B | 0.0556 | 0.1902 | 0.4829 | 0.107* | |
C19 | 0.2340 (5) | 0.3613 (4) | 0.2112 (3) | 0.0444 (11) | |
C20 | 0.0706 (6) | 0.3554 (6) | 0.2217 (5) | 0.0748 (19) | |
H20A | 0.0443 | 0.3868 | 0.2799 | 0.090* | |
H20B | 0.0346 | 0.2816 | 0.2186 | 0.090* | |
C21 | 0.0094 (7) | 0.4198 (6) | 0.1412 (6) | 0.096 (3) | |
H21A | −0.0302 | 0.3722 | 0.0929 | 0.115* | |
H21B | −0.0679 | 0.4658 | 0.1608 | 0.115* | |
C22 | 0.1335 (7) | 0.4852 (6) | 0.1074 (6) | 0.087 (2) | |
H22A | 0.1346 | 0.4837 | 0.0406 | 0.105* | |
H22B | 0.1287 | 0.5592 | 0.1280 | 0.105* | |
O8 | 0.6882 (4) | 0.5915 (3) | 0.1705 (2) | 0.0501 (8) | |
O9 | 0.5662 (5) | 0.3900 (3) | −0.0407 (3) | 0.0655 (10) | |
H51 | 0.6268 | 0.4488 | 0.1630 | 0.094* | |
H52 | 0.5930 | 0.3796 | 0.0883 | 0.094* | |
H61 | 0.8331 | 0.1428 | 0.1731 | 0.094* | |
H62 | 0.7616 | 0.1791 | 0.0988 | 0.094* | |
H71 | 0.8299 | 0.1203 | 0.3281 | 0.094* | |
H72 | 0.7396 | 0.1295 | 0.3943 | 0.094* | |
H81 | 0.6266 | 0.6097 | 0.2125 | 0.094* | |
H82 | 0.7803 | 0.6054 | 0.1870 | 0.094* | |
H91 | 0.6286 | 0.3406 | −0.0556 | 0.094* | |
H92 | 0.4758 | 0.3928 | −0.0638 | 0.094* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Dy | 0.02291 (10) | 0.02860 (11) | 0.02033 (10) | −0.00276 (7) | −0.00165 (6) | 0.00127 (7) |
Cr | 0.0228 (3) | 0.0265 (3) | 0.0170 (3) | −0.0005 (2) | 0.0011 (2) | −0.0005 (2) |
O1 | 0.086 (3) | 0.0430 (19) | 0.0316 (17) | −0.0200 (17) | −0.0101 (16) | −0.0031 (14) |
O2 | 0.0334 (16) | 0.0525 (19) | 0.0269 (15) | −0.0011 (13) | 0.0069 (12) | 0.0020 (13) |
O3 | 0.076 (3) | 0.061 (2) | 0.0371 (18) | −0.0250 (19) | −0.0300 (17) | 0.0049 (16) |
O4 | 0.0336 (17) | 0.081 (3) | 0.0438 (19) | 0.0156 (17) | 0.0037 (14) | 0.0176 (17) |
O5 | 0.060 (2) | 0.0311 (16) | 0.0298 (15) | −0.0085 (14) | 0.0007 (13) | 0.0047 (12) |
O6 | 0.0421 (17) | 0.068 (2) | 0.0195 (14) | 0.0189 (15) | 0.0055 (12) | 0.0020 (14) |
O7 | 0.0387 (17) | 0.086 (3) | 0.0212 (15) | 0.0286 (17) | 0.0023 (12) | 0.0089 (15) |
N1 | 0.042 (2) | 0.036 (2) | 0.035 (2) | −0.0107 (17) | 0.0027 (15) | −0.0006 (15) |
N2 | 0.054 (3) | 0.099 (4) | 0.024 (2) | 0.015 (2) | 0.0051 (17) | −0.004 (2) |
N3 | 0.061 (3) | 0.056 (3) | 0.075 (3) | 0.026 (2) | 0.003 (2) | −0.001 (2) |
N4 | 0.054 (3) | 0.071 (3) | 0.087 (4) | −0.031 (3) | 0.012 (2) | −0.012 (3) |
N5 | 0.053 (2) | 0.064 (3) | 0.022 (2) | 0.011 (2) | 0.0007 (16) | 0.0024 (17) |
N6 | 0.045 (2) | 0.057 (3) | 0.048 (2) | 0.020 (2) | −0.0014 (18) | −0.001 (2) |
N7 | 0.143 (5) | 0.042 (3) | 0.041 (3) | −0.024 (3) | −0.021 (3) | 0.006 (2) |
N8 | 0.039 (2) | 0.082 (3) | 0.063 (3) | −0.006 (2) | 0.007 (2) | −0.007 (2) |
N9 | 0.046 (3) | 0.084 (4) | 0.070 (3) | −0.007 (2) | 0.007 (2) | −0.017 (3) |
N10 | 0.041 (2) | 0.066 (3) | 0.091 (4) | 0.006 (2) | −0.006 (2) | 0.029 (3) |
C1 | 0.032 (2) | 0.034 (2) | 0.024 (2) | −0.0005 (17) | 0.0030 (15) | −0.0003 (16) |
C2 | 0.030 (2) | 0.046 (3) | 0.026 (2) | 0.0054 (17) | 0.0020 (16) | 0.0004 (18) |
C3 | 0.040 (2) | 0.037 (2) | 0.032 (2) | 0.0067 (19) | −0.0008 (17) | −0.0026 (18) |
C4 | 0.035 (2) | 0.045 (3) | 0.037 (2) | −0.009 (2) | 0.0049 (18) | −0.004 (2) |
C5 | 0.028 (2) | 0.036 (2) | 0.030 (2) | 0.0031 (16) | 0.0022 (16) | 0.0031 (17) |
C6 | 0.031 (2) | 0.039 (2) | 0.023 (2) | 0.0025 (18) | −0.0003 (15) | −0.0021 (16) |
C7 | 0.060 (3) | 0.038 (3) | 0.033 (2) | −0.009 (2) | −0.005 (2) | 0.0003 (19) |
C8 | 0.132 (6) | 0.046 (3) | 0.048 (3) | −0.022 (3) | −0.021 (3) | 0.001 (3) |
C9 | 0.163 (8) | 0.060 (4) | 0.055 (4) | −0.025 (4) | −0.021 (4) | −0.015 (3) |
C10 | 0.147 (7) | 0.071 (4) | 0.040 (3) | −0.022 (4) | −0.025 (4) | −0.001 (3) |
C11 | 0.055 (3) | 0.038 (3) | 0.038 (3) | −0.008 (2) | −0.012 (2) | 0.005 (2) |
C12 | 0.061 (4) | 0.125 (6) | 0.076 (4) | −0.016 (4) | 0.009 (3) | −0.039 (4) |
C13 | 0.050 (3) | 0.104 (5) | 0.077 (4) | 0.000 (3) | −0.023 (3) | −0.025 (4) |
C14 | 0.080 (4) | 0.089 (5) | 0.045 (3) | −0.015 (3) | −0.009 (3) | −0.019 (3) |
C15 | 0.040 (2) | 0.037 (2) | 0.039 (2) | 0.0035 (18) | 0.0153 (19) | −0.0013 (19) |
C16 | 0.076 (4) | 0.112 (5) | 0.033 (3) | 0.019 (4) | 0.011 (3) | 0.011 (3) |
C17 | 0.146 (8) | 0.083 (5) | 0.093 (6) | −0.018 (5) | 0.096 (6) | 0.003 (4) |
C18 | 0.060 (4) | 0.071 (4) | 0.140 (7) | −0.003 (3) | 0.052 (4) | 0.011 (4) |
C19 | 0.035 (2) | 0.050 (3) | 0.049 (3) | 0.007 (2) | 0.001 (2) | −0.003 (2) |
C20 | 0.031 (3) | 0.109 (5) | 0.085 (5) | 0.012 (3) | 0.001 (3) | 0.010 (4) |
C21 | 0.051 (4) | 0.087 (5) | 0.148 (8) | 0.019 (3) | −0.021 (4) | 0.023 (5) |
C22 | 0.069 (4) | 0.081 (5) | 0.112 (6) | 0.027 (4) | −0.018 (4) | 0.034 (4) |
O8 | 0.0438 (19) | 0.0431 (19) | 0.063 (2) | −0.0055 (14) | 0.0020 (16) | −0.0070 (16) |
O9 | 0.090 (3) | 0.063 (2) | 0.043 (2) | 0.007 (2) | 0.0016 (19) | −0.0001 (18) |
Dy—O1 | 2.326 (3) | N10—H10 | 0.86 |
Dy—O3 | 2.337 (3) | C7—C8 | 1.480 (7) |
Dy—O4 | 2.354 (3) | C8—C9 | 1.510 (8) |
Dy—O2 | 2.373 (3) | C8—H8A | 0.97 |
Dy—O7 | 2.374 (3) | C8—H8B | 0.97 |
Dy—O6 | 2.383 (3) | C9—C10 | 1.465 (9) |
Dy—O5 | 2.394 (3) | C9—H9A | 0.97 |
Dy—N1 | 2.458 (4) | C9—H9B | 0.97 |
Cr—C3 | 2.061 (4) | C10—H10A | 0.97 |
Cr—C5 | 2.064 (4) | C10—H10B | 0.97 |
Cr—C4 | 2.066 (4) | C11—C12 | 1.478 (8) |
Cr—C2 | 2.081 (4) | C12—C13 | 1.467 (8) |
Cr—C1 | 2.088 (4) | C12—H12A | 0.97 |
Cr—C6 | 2.088 (4) | C12—H12B | 0.97 |
O1—C7 | 1.236 (5) | C13—C14 | 1.502 (9) |
O2—C15 | 1.237 (5) | C13—H13A | 0.97 |
O3—C11 | 1.213 (5) | C13—H13B | 0.97 |
O4—C19 | 1.224 (6) | C14—H14A | 0.97 |
O5—H51 | 0.88 | C14—H14B | 0.97 |
O5—H52 | 0.88 | C15—C16 | 1.463 (7) |
O6—H61 | 0.88 | C16—C17 | 1.539 (10) |
O6—H62 | 0.88 | C16—H16A | 0.97 |
O7—H71 | 0.88 | C16—H16B | 0.97 |
O7—H72 | 0.88 | C17—C18 | 1.485 (12) |
N1—C1 | 1.138 (5) | C17—H17A | 0.97 |
N2—C2 | 1.137 (6) | C17—H17B | 0.97 |
N3—C3 | 1.141 (6) | C18—H18A | 0.97 |
N4—C4 | 1.137 (6) | C18—H18B | 0.97 |
N5—C5 | 1.136 (5) | C19—C20 | 1.509 (7) |
N6—C6 | 1.142 (6) | C20—C21 | 1.513 (9) |
N7—C7 | 1.306 (6) | C20—H20A | 0.97 |
N7—C10 | 1.446 (7) | C20—H20B | 0.97 |
N7—H7 | 0.86 | C21—C22 | 1.486 (10) |
N8—C15 | 1.341 (6) | C21—H21A | 0.97 |
N8—C18 | 1.434 (8) | C21—H21B | 0.97 |
N8—H8 | 0.86 | C22—H22A | 0.97 |
N9—C11 | 1.331 (7) | C22—H22B | 0.97 |
N9—C14 | 1.417 (7) | O8—H81 | 0.88 |
N9—H9 | 0.86 | O8—H82 | 0.88 |
N10—C19 | 1.300 (7) | O9—H91 | 0.88 |
N10—C22 | 1.467 (7) | O9—H92 | 0.88 |
O1—Dy—O3 | 136.65 (12) | C7—C8—H8B | 110.7 |
O1—Dy—O4 | 88.05 (14) | C9—C8—H8B | 110.7 |
O3—Dy—O4 | 77.80 (14) | H8A—C8—H8B | 108.8 |
O1—Dy—O2 | 76.31 (11) | C10—C9—C8 | 106.7 (5) |
O3—Dy—O2 | 135.47 (12) | C10—C9—H9A | 110.4 |
O4—Dy—O2 | 74.29 (11) | C8—C9—H9A | 110.4 |
O1—Dy—O7 | 79.61 (13) | C10—C9—H9B | 110.4 |
O3—Dy—O7 | 132.63 (13) | C8—C9—H9B | 110.4 |
O4—Dy—O7 | 144.12 (11) | H9A—C9—H9B | 108.6 |
O2—Dy—O7 | 70.10 (10) | N7—C10—C9 | 104.2 (5) |
O1—Dy—O6 | 103.88 (13) | N7—C10—H10A | 110.9 |
O3—Dy—O6 | 73.53 (13) | C9—C10—H10A | 110.9 |
O4—Dy—O6 | 148.46 (11) | N7—C10—H10B | 110.9 |
O2—Dy—O6 | 136.60 (10) | C9—C10—H10B | 110.9 |
O7—Dy—O6 | 67.39 (10) | H10A—C10—H10B | 108.9 |
O1—Dy—O5 | 68.44 (11) | O3—C11—N9 | 127.2 (5) |
O3—Dy—O5 | 69.05 (11) | O3—C11—C12 | 126.7 (5) |
O4—Dy—O5 | 81.61 (12) | N9—C11—C12 | 106.1 (4) |
O2—Dy—O5 | 137.63 (11) | C13—C12—C11 | 107.2 (5) |
O7—Dy—O5 | 123.17 (12) | C13—C12—H12A | 110.3 |
O6—Dy—O5 | 76.14 (11) | C11—C12—H12A | 110.3 |
O1—Dy—N1 | 149.59 (12) | C13—C12—H12B | 110.3 |
O3—Dy—N1 | 72.28 (12) | C11—C12—H12B | 110.3 |
O4—Dy—N1 | 90.87 (13) | H12A—C12—H12B | 108.5 |
O2—Dy—N1 | 74.17 (12) | C12—C13—C14 | 106.4 (5) |
O7—Dy—N1 | 83.68 (13) | C12—C13—H13A | 110.5 |
O6—Dy—N1 | 92.71 (13) | C14—C13—H13A | 110.5 |
O5—Dy—N1 | 141.33 (11) | C12—C13—H13B | 110.5 |
C3—Cr—C5 | 88.60 (16) | C14—C13—H13B | 110.5 |
C3—Cr—C4 | 91.26 (18) | H13A—C13—H13B | 108.6 |
C5—Cr—C4 | 90.87 (17) | N9—C14—C13 | 103.0 (5) |
C3—Cr—C2 | 86.29 (17) | N9—C14—H14A | 111.2 |
C5—Cr—C2 | 174.87 (16) | C13—C14—H14A | 111.2 |
C4—Cr—C2 | 88.73 (17) | N9—C14—H14B | 111.2 |
C3—Cr—C1 | 90.55 (17) | C13—C14—H14B | 111.2 |
C5—Cr—C1 | 89.26 (16) | H14A—C14—H14B | 109.1 |
C4—Cr—C1 | 178.18 (17) | O2—C15—N8 | 125.6 (4) |
C2—Cr—C1 | 91.30 (16) | O2—C15—C16 | 125.1 (5) |
C3—Cr—C6 | 177.40 (17) | N8—C15—C16 | 109.2 (4) |
C5—Cr—C6 | 90.80 (16) | C15—C16—C17 | 103.3 (5) |
C4—Cr—C6 | 91.27 (17) | C15—C16—H16A | 111.1 |
C2—Cr—C6 | 94.32 (16) | C17—C16—H16A | 111.1 |
C1—Cr—C6 | 86.91 (16) | C15—C16—H16B | 111.1 |
C7—O1—Dy | 147.6 (3) | C17—C16—H16B | 111.1 |
C15—O2—Dy | 143.3 (3) | H16A—C16—H16B | 109.1 |
C11—O3—Dy | 161.8 (4) | C18—C17—C16 | 108.0 (5) |
C19—O4—Dy | 142.7 (3) | C18—C17—H17A | 110.1 |
Dy—O5—H51 | 128.3 | C16—C17—H17A | 110.1 |
Dy—O5—H52 | 124.8 | C18—C17—H17B | 110.1 |
H51—O5—H52 | 105.7 | C16—C17—H17B | 110.1 |
Dy—O6—H61 | 130.8 | H17A—C17—H17B | 108.4 |
Dy—O6—H62 | 129.2 | N8—C18—C17 | 102.7 (5) |
H61—O6—H62 | 97.5 | N8—C18—H18A | 111.2 |
Dy—O7—H71 | 135.9 | C17—C18—H18A | 111.2 |
Dy—O7—H72 | 123.2 | N8—C18—H18B | 111.2 |
H71—O7—H72 | 95.2 | C17—C18—H18B | 111.2 |
C1—N1—Dy | 162.4 (3) | H18A—C18—H18B | 109.1 |
C7—N7—C10 | 115.3 (5) | O4—C19—N10 | 126.8 (5) |
C7—N7—H7 | 122.3 | O4—C19—C20 | 124.7 (5) |
C10—N7—H7 | 122.3 | N10—C19—C20 | 108.5 (5) |
C15—N8—C18 | 115.7 (6) | C19—C20—C21 | 104.0 (5) |
C15—N8—H8 | 122.2 | C19—C20—H20A | 111.0 |
C18—N8—H8 | 122.2 | C21—C20—H20A | 111.0 |
C11—N9—C14 | 116.4 (5) | C19—C20—H20B | 111.0 |
C11—N9—H9 | 121.8 | C21—C20—H20B | 111.0 |
C14—N9—H9 | 121.8 | H20A—C20—H20B | 109.0 |
C19—N10—C22 | 115.0 (5) | C22—C21—C20 | 106.3 (5) |
C19—N10—H10 | 122.5 | C22—C21—H21A | 110.5 |
C22—N10—H10 | 122.5 | C20—C21—H21A | 110.5 |
N1—C1—Cr | 175.4 (4) | C22—C21—H21B | 110.5 |
N2—C2—Cr | 174.2 (4) | C20—C21—H21B | 110.5 |
N3—C3—Cr | 179.5 (5) | H21A—C21—H21B | 108.7 |
N4—C4—Cr | 177.7 (5) | N10—C22—C21 | 103.1 (5) |
N5—C5—Cr | 177.2 (4) | N10—C22—H22A | 111.1 |
N6—C6—Cr | 177.0 (4) | C21—C22—H22A | 111.1 |
O1—C7—N7 | 126.6 (4) | N10—C22—H22B | 111.1 |
O1—C7—C8 | 125.3 (4) | C21—C22—H22B | 111.1 |
N7—C7—C8 | 108.1 (4) | H22A—C22—H22B | 109.1 |
C7—C8—C9 | 105.4 (5) | H81—O8—H82 | 113.3 |
C7—C8—H8A | 110.7 | H91—O9—H92 | 123.8 |
C9—C8—H8A | 110.7 | ||
O3—Dy—O1—C7 | 168.0 (6) | Dy—O1—C7—C8 | −175.6 (5) |
O4—Dy—O1—C7 | 98.2 (7) | C10—N7—C7—O1 | 177.4 (6) |
O2—Dy—O1—C7 | 23.9 (7) | C10—N7—C7—C8 | −3.5 (9) |
O7—Dy—O1—C7 | −48.0 (7) | O1—C7—C8—C9 | 179.4 (6) |
O6—Dy—O1—C7 | −111.4 (7) | N7—C7—C8—C9 | 0.3 (8) |
O5—Dy—O1—C7 | 179.9 (7) | C7—C8—C9—C10 | 2.8 (9) |
N1—Dy—O1—C7 | 9.8 (9) | C7—N7—C10—C9 | 5.2 (10) |
O1—Dy—O2—C15 | 133.1 (5) | C8—C9—C10—N7 | −4.5 (10) |
O3—Dy—O2—C15 | −11.9 (6) | Dy—O3—C11—N9 | −145.2 (10) |
O4—Dy—O2—C15 | 41.3 (5) | Dy—O3—C11—C12 | 36.7 (16) |
O7—Dy—O2—C15 | −143.2 (5) | C14—N9—C11—O3 | −175.8 (6) |
O6—Dy—O2—C15 | −131.1 (5) | C14—N9—C11—C12 | 2.7 (8) |
O5—Dy—O2—C15 | 99.0 (5) | O3—C11—C12—C13 | −177.7 (6) |
N1—Dy—O2—C15 | −54.3 (5) | N9—C11—C12—C13 | 3.8 (8) |
O1—Dy—O3—C11 | −131.5 (12) | C11—C12—C13—C14 | −8.3 (9) |
O4—Dy—O3—C11 | −57.7 (12) | C11—N9—C14—C13 | −7.8 (8) |
O2—Dy—O3—C11 | −5.7 (13) | C12—C13—C14—N9 | 9.4 (8) |
O7—Dy—O3—C11 | 100.3 (12) | Dy—O2—C15—N8 | −10.6 (8) |
O6—Dy—O3—C11 | 135.6 (12) | Dy—O2—C15—C16 | 168.7 (4) |
O5—Dy—O3—C11 | −143.3 (13) | C18—N8—C15—O2 | −177.9 (5) |
N1—Dy—O3—C11 | 37.2 (12) | C18—N8—C15—C16 | 2.7 (7) |
O1—Dy—O4—C19 | 95.0 (6) | O2—C15—C16—C17 | 172.2 (5) |
O3—Dy—O4—C19 | −43.7 (6) | N8—C15—C16—C17 | −8.4 (7) |
O2—Dy—O4—C19 | 171.4 (6) | C15—C16—C17—C18 | 11.1 (8) |
O7—Dy—O4—C19 | 164.3 (5) | C15—N8—C18—C17 | 4.5 (8) |
O6—Dy—O4—C19 | −18.8 (7) | C16—C17—C18—N8 | −9.5 (8) |
O5—Dy—O4—C19 | 26.6 (6) | Dy—O4—C19—N10 | −26.1 (10) |
N1—Dy—O4—C19 | −115.4 (6) | Dy—O4—C19—C20 | 154.1 (5) |
O1—Dy—N1—C1 | 91.9 (11) | C22—N10—C19—O4 | −179.9 (6) |
O3—Dy—N1—C1 | −72.6 (11) | C22—N10—C19—C20 | −0.1 (8) |
O4—Dy—N1—C1 | 4.3 (11) | O4—C19—C20—C21 | −169.4 (6) |
O2—Dy—N1—C1 | 77.7 (11) | N10—C19—C20—C21 | 10.8 (7) |
O7—Dy—N1—C1 | 148.7 (11) | C19—C20—C21—C22 | −17.1 (8) |
O6—Dy—N1—C1 | −144.4 (11) | C19—N10—C22—C21 | −10.8 (9) |
O5—Dy—N1—C1 | −73.3 (11) | C20—C21—C22—N10 | 16.8 (9) |
Dy—O1—C7—N7 | 3.4 (11) |
D—H···A | D—H | H···A | D···A | D—H···A |
N7—H7···O2 | 0.86 | 2.46 | 3.075 (6) | 129 |
N7—H7···N5i | 0.86 | 2.46 | 3.183 (7) | 142 |
N8—H8···O4 | 0.86 | 2.44 | 3.028 (6) | 126 |
N9—H9···N2ii | 0.86 | 2.51 | 3.290 (7) | 152 |
N10—H10···O5 | 0.86 | 2.38 | 3.096 (6) | 141 |
N10—H10···O9iii | 0.86 | 2.55 | 3.147 (6) | 127 |
O5—H51···O8 | 0.88 | 1.85 | 2.724 (4) | 170 |
O5—H52···O9 | 0.88 | 1.88 | 2.754 (5) | 169 |
O6—H61···N6iv | 0.88 | 2.01 | 2.861 (5) | 162 |
O6—H62···N2ii | 0.88 | 1.91 | 2.792 (5) | 178 |
O7—H71···N6iv | 0.88 | 2.07 | 2.890 (5) | 154 |
O7—H72···N5i | 0.88 | 1.96 | 2.762 (5) | 152 |
O8—H81···N3v | 0.88 | 1.96 | 2.792 (6) | 157 |
O8—H82···N4vi | 0.88 | 2.02 | 2.855 (6) | 159 |
O9—H91···N2ii | 0.88 | 2.47 | 3.294 (6) | 156 |
O9—H92···O8iii | 0.88 | 2.12 | 2.945 (5) | 155 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+1, −y, −z; (iii) −x+1, −y+1, −z; (iv) x+1, y, z; (v) x, y+1, z; (vi) x+1, y+1, z. |
Experimental details
Crystal data | |
Chemical formula | [CrDy(C4H7NO)4(CN)6(H2O)3]·2H2O |
Mr | 801.12 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 9.1442 (18), 12.448 (3), 14.518 (3) |
α, β, γ (°) | 90.19 (3), 92.40 (3), 91.10 (3) |
V (Å3) | 1650.8 (6) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 2.64 |
Crystal size (mm) | 0.20 × 0.10 × 0.08 |
Data collection | |
Diffractometer | Nonius KappaCCD area-detector diffractometer |
Absorption correction | Empirical (using intensity measurements) (Blessing, 1995, 1997) |
Tmin, Tmax | 0.625, 0.812 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9078, 5798, 5457 |
Rint | 0.046 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.029, 0.074, 1.13 |
No. of reflections | 5798 |
No. of parameters | 389 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 2.25, −0.95 |
Computer programs: COLLECT (Nonius, 1998), HKL SCALEPACK (Otwinowski & Minor, 1997), HKL DENZO (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2002), SHELXL97.
Dy—O1 | 2.326 (3) | Dy—N1 | 2.458 (4) |
Dy—O3 | 2.337 (3) | Cr—C3 | 2.061 (4) |
Dy—O4 | 2.354 (3) | Cr—C5 | 2.064 (4) |
Dy—O2 | 2.373 (3) | Cr—C4 | 2.066 (4) |
Dy—O7 | 2.374 (3) | Cr—C2 | 2.081 (4) |
Dy—O6 | 2.383 (3) | Cr—C1 | 2.088 (4) |
Dy—O5 | 2.394 (3) | Cr—C6 | 2.088 (4) |
O1—Dy—O3 | 136.65 (12) | O7—Dy—O6 | 67.39 (10) |
O1—Dy—O4 | 88.05 (14) | O1—Dy—O5 | 68.44 (11) |
O3—Dy—O4 | 77.80 (14) | O3—Dy—O5 | 69.05 (11) |
O1—Dy—O2 | 76.31 (11) | O4—Dy—O5 | 81.61 (12) |
O3—Dy—O2 | 135.47 (12) | O2—Dy—O5 | 137.63 (11) |
O4—Dy—O2 | 74.29 (11) | O7—Dy—O5 | 123.17 (12) |
O1—Dy—O7 | 79.61 (13) | O6—Dy—O5 | 76.14 (11) |
O3—Dy—O7 | 132.63 (13) | O1—Dy—N1 | 149.59 (12) |
O4—Dy—O7 | 144.12 (11) | O3—Dy—N1 | 72.28 (12) |
O2—Dy—O7 | 70.10 (10) | O4—Dy—N1 | 90.87 (13) |
O1—Dy—O6 | 103.88 (13) | O2—Dy—N1 | 74.17 (12) |
O3—Dy—O6 | 73.53 (13) | O7—Dy—N1 | 83.68 (13) |
O4—Dy—O6 | 148.46 (11) | O6—Dy—N1 | 92.71 (13) |
O2—Dy—O6 | 136.60 (10) | O5—Dy—N1 | 141.33 (11) |
D—H···A | D—H | H···A | D···A | D—H···A |
N7—H7···O2 | 0.86 | 2.46 | 3.075 (6) | 129 |
N7—H7···N5i | 0.86 | 2.46 | 3.183 (7) | 142 |
N8—H8···O4 | 0.86 | 2.44 | 3.028 (6) | 126 |
N9—H9···N2ii | 0.86 | 2.51 | 3.290 (7) | 152 |
N10—H10···O5 | 0.86 | 2.38 | 3.096 (6) | 141 |
N10—H10···O9iii | 0.86 | 2.55 | 3.147 (6) | 127 |
O5—H51···O8 | 0.88 | 1.85 | 2.724 (4) | 170 |
O5—H52···O9 | 0.88 | 1.88 | 2.754 (5) | 169 |
O6—H61···N6iv | 0.88 | 2.01 | 2.861 (5) | 162 |
O6—H62···N2ii | 0.88 | 1.91 | 2.792 (5) | 178 |
O7—H71···N6iv | 0.88 | 2.07 | 2.890 (5) | 154 |
O7—H72···N5i | 0.88 | 1.96 | 2.762 (5) | 152 |
O8—H81···N3v | 0.88 | 1.96 | 2.792 (6) | 157 |
O8—H82···N4vi | 0.88 | 2.02 | 2.855 (6) | 159 |
O9—H91···N2ii | 0.88 | 2.47 | 3.294 (6) | 156 |
O9—H92···O8iii | 0.88 | 2.12 | 2.945 (5) | 155. |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+1, −y, −z; (iii) −x+1, −y+1, −z; (iv) x+1, y, z; (v) x, y+1, z; (vi) x+1, y+1, z. |
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Recently, there has been considerable interest in lanthanide(III) hexacyanoferrates, and the analogous cobalt(III) and chromium(III) complexes, because of their potential as catalytic, semiconductor and magnetic materials (Hulliger et al., 1976). Also, some of these cyanides can form semipermeable membranes, which are very important in connection with the desalination of sea water. In particular, a series of three-dimensional cyano-bridged 4f-3 d complexes, Ln[M(CN)6].nH2O (M is CrIII or FeIII), exhibit magnetic ordering (Hulliger et al., 1976). Incorporation of organic ligands into these three-dimensional 4f-3 d adducts may reduce the dimensionality of the parent complexes and give various molecular structures. Along this line, we have employed the simple ligand dimethylformamide (dmf) to prepare cyano-bridged 4f-3 d dimers, [Ln(dmf)4(H2O)4Fe(CN)6]·H2O (Kou et al., 1998; Kautz et al., 2000) and [Pr(dmf)4(H2O)3Cr(CN)6]·H2O (Combs et al., 2000), a one-dimensional zigzag chain, [Sm(dmf)4(H2O)2Cr(CN)6]·H2O (Kou, Gao & Jin, 2001), and two-dimensional brick-wall-like complexes, [Ln(dmf)2(H2O)3Cr(CN)6]·H2O (Ln is Sm or Gd; Kou, Gao & Jin, 2001; Kou, Gao, Sun & Zhang, 2001). In the present study, we used 2-pyrrolidone (pyr) to synthesize the cyano-bridged bimetallic complex [Dy(pyr)4(H2O)3Cr(CN)6]·2H2O, (I).
A perspective view of (I) is shown in Fig. 1, and selected bond distances and angles are listed in Table 1. The crystal structure of (I) consists of a neutral cyano-bridged bimetallic fragment. The lanthanide ion is eight-coordinate and the coordination polyhedron can be described as a distorted square antiprism. Seven O atoms of three water molecules and four pyr molecules, and one N atom of the bridging CN ligand, coordinate to DyIII. The bridging cyanide coordinates to the DyIII ion in a bent fashion, with a bond angle of 162.4 (3)° for C1—N1—Dy. The Cr···Dy metal–metal distance is 5.592 (2) Å.
The N1—Dy—O(H2O) angles range from 83.68 (13) to 141.33 (11)°, generally larger than the average value for N1—Dy—O(pyr) [96.36 (6)°]. This reflects the fact that small water molecules are more polar than bulky 2-pyrrolidone ligands, and the electrostatic repulsion force may be significant.
The Cr—C—N bond angles are nearly linear and range from 174.2 (4) to 179.5 (5)°, indicative of directional bonding involving the π orbitals of the metal centre. The Cr—C bond distances are in the range 2.061 (4)–2.088 (4) Å, consistent with the corresponding literature values (Combs et al., 2000; Kou, Gao & Jin, 2001; Kou, Gao, Sun & Zhang, 2001).
The coordinated and uncoordinated water molecules are hydrogen bonded to the non-bridging cyanide N atom and to water molecules to produce a hydrogen-bonded three-dimensional network; details are available in Table 2.