Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270108005349/sf3070sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270108005349/sf3070Isup2.hkl |
CCDC reference: 686419
An aqueous solution (1 ml) of Cu(NO3)2 (188 mg, 1 mmol) was added to a solution of Dy(C4H5O2)3(H2O)6 (81.7 mg, 0.16 mmol) in water (3 ml) with stirring. An ethanol solution (1 ml) of phenanthroline (15.1 mg, 0.076 mmol) was added to the mixture. The resulting solution was filtered and the filtrate was allowed to stand at room temperature. After two weeks, blue needle crystals of (I) suitable for X-ray crystallographic study were obtained.
Temperature-dependent magnetic susceptibilities were collected from the pure crystal sample in the 5–300 K range using a Quantum Design PPMS-9 magnetometer in an applied field of 20 kOe (1 Oe = 79.58 A m-1). An effective magnetic moment of 3.589 µB was observed at 300 K. With decreasing temperature, the µeff(T) functions increase and reach 3.859 µB at 18 K, and then decrease rapidly to 3.54 µB at 5 K. Such behaviour is characteristic of predominantly ferromagnetic exchange coupling in CuII3 systems (Haase & Gehring, 1985). The observed susceptibility data are well fitted to the Curie–Weiss law [χm = C/(T - θ)], with Weiss constant θ = 3.52 K. IR: ν(OH) 3650–2900, ν(C═C) 1645, ν(COO)as 1541, ν(COO)s 1426, ν(NO3) 1384 cm-1.
The H atoms of the hydrocarbon groups were placed in calculated positions, with C—H = 0.96 Å for the methyl group or 0.93 Å for the terminal CH2 group, and they were included in the final cycles of refinement in a riding model, with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C). H atoms from water molecules were located in a difference Fourier map, and their coordinates and displacement parameters were fixed during structure refinement, using a riding model, with Uiso(H) = 1.2 Ueq(O).
Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: CrystalStructure (Rigaku/MSC & Rigaku, 2002); data reduction: CrystalStructure (Rigaku/MSC & Rigaku, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
[Cu3(C4H5O2)2(OH)2(C12H8N2)2(H2O)2](NO3)2·2H2O | Z = 1 |
Mr = 951.29 | F(000) = 485 |
Triclinic, P1 | Dx = 1.712 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71069 Å |
a = 7.3779 (5) Å | Cell parameters from 6352 reflections |
b = 11.1570 (9) Å | θ = 3.0–27.4° |
c = 12.5830 (9) Å | µ = 1.80 mm−1 |
α = 71.081 (2)° | T = 293 K |
β = 81.596 (2)° | Needle, blue |
γ = 70.529 (2)° | 0.35 × 0.08 × 0.02 mm |
V = 922.94 (12) Å3 |
Rigaku R-AXIS RAPID diffractometer | 4172 independent reflections |
Radiation source: fine-focus sealed tube | 3356 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.029 |
Detector resolution: 10.0 pixels mm-1 | θmax = 27.4°, θmin = 3.0° |
ω scans | h = −8→9 |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | k = −14→14 |
Tmin = 0.572, Tmax = 0.965 | l = −16→16 |
8975 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)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.120 | H-atom parameters constrained |
S = 1.13 | w = 1/[σ2(Fo2) + (0.0675P)2 + 0.1148P] where P = (Fo2 + 2Fc2)/3 |
4172 reflections | (Δ/σ)max = 0.002 |
271 parameters | Δρmax = 0.53 e Å−3 |
0 restraints | Δρmin = −0.53 e Å−3 |
[Cu3(C4H5O2)2(OH)2(C12H8N2)2(H2O)2](NO3)2·2H2O | γ = 70.529 (2)° |
Mr = 951.29 | V = 922.94 (12) Å3 |
Triclinic, P1 | Z = 1 |
a = 7.3779 (5) Å | Mo Kα radiation |
b = 11.1570 (9) Å | µ = 1.80 mm−1 |
c = 12.5830 (9) Å | T = 293 K |
α = 71.081 (2)° | 0.35 × 0.08 × 0.02 mm |
β = 81.596 (2)° |
Rigaku R-AXIS RAPID diffractometer | 4172 independent reflections |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 3356 reflections with I > 2σ(I) |
Tmin = 0.572, Tmax = 0.965 | Rint = 0.029 |
8975 measured reflections |
R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
wR(F2) = 0.120 | H-atom parameters constrained |
S = 1.13 | Δρmax = 0.53 e Å−3 |
4172 reflections | Δρmin = −0.53 e Å−3 |
271 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 | ||
Cu1 | 0.5000 | 0.0000 | 0.0000 | 0.02985 (14) | |
Cu2 | 0.57035 (5) | −0.03202 (3) | −0.23383 (3) | 0.03213 (13) | |
O1 | 0.3649 (3) | 0.01196 (19) | −0.12575 (16) | 0.0323 (4) | |
O2 | 0.6478 (4) | −0.2161 (2) | −0.14337 (19) | 0.0486 (6) | |
O3 | 0.6092 (3) | −0.1945 (2) | 0.03045 (18) | 0.0408 (5) | |
O4 | 0.1068 (3) | −0.1396 (3) | −0.0591 (2) | 0.0497 (6) | |
O5 | 0.7678 (3) | 0.0296 (2) | −0.1518 (2) | 0.0456 (5) | |
N3 | 0.1086 (4) | −0.3237 (3) | 0.2507 (2) | 0.0457 (6) | |
O6 | 0.2592 (4) | −0.3094 (3) | 0.2669 (3) | 0.0919 (11) | |
O7 | 0.0654 (5) | −0.4231 (3) | 0.3049 (3) | 0.0816 (10) | |
O8 | −0.0003 (4) | −0.2339 (3) | 0.1781 (2) | 0.0663 (8) | |
N1 | 0.5011 (3) | 0.1456 (2) | −0.3527 (2) | 0.0350 (5) | |
N2 | 0.7326 (3) | −0.0881 (3) | −0.3643 (2) | 0.0398 (6) | |
C1 | 0.3902 (5) | 0.2629 (3) | −0.3434 (3) | 0.0488 (8) | |
H1 | 0.3363 | 0.2695 | −0.2732 | 0.059* | |
C2 | 0.5825 (4) | 0.1392 (3) | −0.4559 (2) | 0.0386 (7) | |
C3 | 0.7076 (4) | 0.0115 (4) | −0.4616 (3) | 0.0417 (7) | |
C4 | 0.8479 (5) | −0.2074 (4) | −0.3662 (4) | 0.0569 (9) | |
H4 | 0.8666 | −0.2773 | −0.2999 | 0.068* | |
C5 | 0.3514 (6) | 0.3769 (4) | −0.4355 (4) | 0.0647 (11) | |
H5 | 0.2723 | 0.4575 | −0.4259 | 0.078* | |
C6 | 0.4281 (6) | 0.3709 (4) | −0.5388 (4) | 0.0710 (13) | |
H6 | 0.4016 | 0.4470 | −0.6003 | 0.085* | |
C7 | 0.5486 (5) | 0.2484 (4) | −0.5521 (3) | 0.0570 (10) | |
C8 | 0.6394 (7) | 0.2266 (6) | −0.6575 (3) | 0.0798 (16) | |
H8 | 0.6136 | 0.2970 | −0.7234 | 0.096* | |
C9 | 0.7585 (7) | 0.1086 (7) | −0.6625 (3) | 0.0774 (15) | |
H9 | 0.8173 | 0.0996 | −0.7314 | 0.093* | |
C10 | 0.7979 (5) | −0.0036 (5) | −0.5657 (3) | 0.0586 (11) | |
C11 | 0.9204 (6) | −0.1309 (6) | −0.5639 (4) | 0.0724 (14) | |
H11 | 0.9857 | −0.1462 | −0.6296 | 0.087* | |
C12 | 0.9435 (6) | −0.2309 (5) | −0.4672 (5) | 0.0748 (14) | |
H12 | 1.0224 | −0.3158 | −0.4665 | 0.090* | |
C31 | 0.6521 (4) | −0.2627 (3) | −0.0375 (2) | 0.0353 (6) | |
C32 | 0.7148 (5) | −0.4106 (3) | 0.0115 (3) | 0.0451 (7) | |
C33 | 0.7374 (7) | −0.4870 (4) | −0.0560 (4) | 0.0749 (13) | |
H33A | 0.7736 | −0.5791 | −0.0263 | 0.090* | |
H33B | 0.7169 | −0.4476 | −0.1324 | 0.090* | |
C34 | 0.7444 (7) | −0.4644 (4) | 0.1339 (3) | 0.0701 (12) | |
H34A | 0.7215 | −0.3923 | 0.1649 | 0.105* | |
H34B | 0.8742 | −0.5216 | 0.1467 | 0.105* | |
H34C | 0.6566 | −0.5142 | 0.1694 | 0.105* | |
H101 | 0.2523 | 0.0843 | −0.1435 | 0.039* | |
H401 | 0.0815 | −0.1654 | 0.0183 | 0.060* | |
H402 | 0.2111 | −0.1153 | −0.0748 | 0.060* | |
H501 | 0.8906 | −0.0176 | −0.1295 | 0.055* | |
H502 | 0.7712 | 0.1197 | −0.1819 | 0.055* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0354 (3) | 0.0272 (2) | 0.0258 (2) | −0.00682 (19) | −0.00484 (18) | −0.00762 (18) |
Cu2 | 0.0365 (2) | 0.0313 (2) | 0.0262 (2) | −0.00690 (15) | −0.00155 (13) | −0.00885 (14) |
O1 | 0.0308 (9) | 0.0351 (10) | 0.0288 (10) | −0.0063 (8) | −0.0027 (7) | −0.0098 (8) |
O2 | 0.0700 (16) | 0.0313 (11) | 0.0370 (12) | −0.0051 (10) | −0.0045 (11) | −0.0099 (9) |
O3 | 0.0563 (13) | 0.0285 (10) | 0.0346 (11) | −0.0087 (9) | −0.0084 (9) | −0.0069 (9) |
O4 | 0.0498 (13) | 0.0625 (15) | 0.0404 (12) | −0.0247 (11) | −0.0043 (10) | −0.0111 (11) |
O5 | 0.0424 (12) | 0.0473 (13) | 0.0479 (13) | −0.0181 (10) | −0.0097 (10) | −0.0079 (11) |
N3 | 0.0432 (15) | 0.0442 (15) | 0.0459 (16) | −0.0101 (12) | −0.0027 (12) | −0.0110 (13) |
O6 | 0.0605 (18) | 0.075 (2) | 0.135 (3) | −0.0251 (15) | −0.0338 (19) | −0.008 (2) |
O7 | 0.080 (2) | 0.0606 (18) | 0.088 (2) | −0.0295 (16) | −0.0158 (17) | 0.0135 (17) |
O8 | 0.0517 (15) | 0.0621 (17) | 0.0552 (16) | 0.0008 (13) | −0.0044 (12) | 0.0042 (13) |
N1 | 0.0345 (12) | 0.0355 (12) | 0.0321 (12) | −0.0116 (10) | −0.0040 (9) | −0.0042 (10) |
N2 | 0.0337 (13) | 0.0510 (15) | 0.0418 (14) | −0.0125 (11) | 0.0018 (10) | −0.0249 (13) |
C1 | 0.0439 (17) | 0.0383 (17) | 0.060 (2) | −0.0129 (14) | −0.0046 (15) | −0.0072 (16) |
C2 | 0.0372 (15) | 0.0538 (18) | 0.0283 (14) | −0.0236 (14) | −0.0051 (11) | −0.0049 (13) |
C3 | 0.0344 (15) | 0.067 (2) | 0.0357 (16) | −0.0253 (14) | 0.0029 (12) | −0.0221 (15) |
C4 | 0.0449 (19) | 0.060 (2) | 0.071 (3) | −0.0074 (16) | 0.0002 (17) | −0.036 (2) |
C5 | 0.056 (2) | 0.0388 (19) | 0.086 (3) | −0.0116 (16) | −0.013 (2) | 0.0006 (19) |
C6 | 0.063 (2) | 0.064 (3) | 0.068 (3) | −0.031 (2) | −0.027 (2) | 0.027 (2) |
C7 | 0.053 (2) | 0.078 (3) | 0.0394 (18) | −0.0393 (19) | −0.0147 (15) | 0.0094 (17) |
C8 | 0.082 (3) | 0.135 (5) | 0.0292 (19) | −0.072 (3) | −0.0093 (19) | 0.009 (2) |
C9 | 0.071 (3) | 0.152 (5) | 0.034 (2) | −0.068 (3) | 0.0116 (18) | −0.032 (3) |
C10 | 0.049 (2) | 0.113 (3) | 0.0416 (19) | −0.050 (2) | 0.0131 (15) | −0.039 (2) |
C11 | 0.051 (2) | 0.122 (4) | 0.078 (3) | −0.041 (3) | 0.028 (2) | −0.074 (3) |
C12 | 0.048 (2) | 0.095 (4) | 0.106 (4) | −0.017 (2) | 0.014 (2) | −0.074 (3) |
C31 | 0.0396 (15) | 0.0266 (13) | 0.0387 (16) | −0.0095 (11) | −0.0045 (12) | −0.0077 (12) |
C32 | 0.0504 (18) | 0.0294 (15) | 0.0510 (19) | −0.0092 (13) | 0.0002 (14) | −0.0100 (14) |
C33 | 0.108 (4) | 0.0334 (19) | 0.077 (3) | −0.011 (2) | −0.007 (3) | −0.0188 (19) |
C34 | 0.099 (3) | 0.0317 (18) | 0.058 (2) | −0.0074 (19) | −0.005 (2) | 0.0023 (17) |
Cu1—O1i | 1.9369 (19) | C2—C7 | 1.393 (5) |
Cu1—O1 | 1.9369 (19) | C2—C3 | 1.433 (5) |
Cu1—O3 | 1.973 (2) | C3—C10 | 1.415 (4) |
Cu1—O3i | 1.973 (2) | C4—C12 | 1.418 (6) |
Cu1—Cu2i | 3.0275 (4) | C4—H4 | 0.9300 |
Cu1—Cu2 | 3.0275 (4) | C5—C6 | 1.352 (6) |
Cu2—O1 | 1.9295 (19) | C5—H5 | 0.9300 |
Cu2—O2 | 1.932 (2) | C6—C7 | 1.408 (6) |
Cu2—N1 | 2.012 (2) | C6—H6 | 0.9300 |
Cu2—N2 | 2.028 (2) | C7—C8 | 1.452 (6) |
Cu2—O5 | 2.286 (2) | C8—C9 | 1.333 (7) |
O1—H101 | 0.939 | C8—H8 | 0.9300 |
O2—C31 | 1.265 (4) | C9—C10 | 1.417 (7) |
O3—C31 | 1.262 (3) | C9—H9 | 0.9300 |
O4—H401 | 0.931 | C10—C11 | 1.401 (7) |
O4—H402 | 0.874 | C11—C12 | 1.344 (7) |
O5—H501 | 0.915 | C11—H11 | 0.9300 |
O5—H502 | 0.960 | C12—H12 | 0.9300 |
N3—O7 | 1.216 (4) | C31—C32 | 1.494 (4) |
N3—O6 | 1.228 (4) | C32—C33 | 1.344 (5) |
N3—O8 | 1.252 (4) | C32—C34 | 1.480 (5) |
N1—C1 | 1.324 (4) | C33—H33A | 0.9300 |
N1—C2 | 1.363 (4) | C33—H33B | 0.9300 |
N2—C4 | 1.325 (4) | C34—H34A | 0.9600 |
N2—C3 | 1.347 (4) | C34—H34B | 0.9600 |
C1—C5 | 1.392 (5) | C34—H34C | 0.9600 |
C1—H1 | 0.9300 | ||
O1i—Cu1—O1 | 180.00 (11) | C5—C1—H1 | 118.9 |
O1i—Cu1—O3 | 89.19 (8) | N1—C2—C7 | 123.2 (3) |
O1—Cu1—O3 | 90.81 (8) | N1—C2—C3 | 116.2 (3) |
O1i—Cu1—O3i | 90.81 (8) | C7—C2—C3 | 120.6 (3) |
O1—Cu1—O3i | 89.19 (8) | N2—C3—C10 | 123.8 (3) |
O3—Cu1—O3i | 180.00 (15) | N2—C3—C2 | 116.5 (3) |
O1i—Cu1—Cu2i | 38.37 (5) | C10—C3—C2 | 119.7 (3) |
O1—Cu1—Cu2i | 141.63 (5) | N2—C4—C12 | 121.5 (4) |
O3—Cu1—Cu2i | 102.61 (6) | N2—C4—H4 | 119.2 |
O3i—Cu1—Cu2i | 77.39 (6) | C12—C4—H4 | 119.2 |
O1i—Cu1—Cu2 | 141.63 (5) | C6—C5—C1 | 120.4 (4) |
O1—Cu1—Cu2 | 38.37 (5) | C6—C5—H5 | 119.8 |
O3—Cu1—Cu2 | 77.39 (6) | C1—C5—H5 | 119.8 |
O3i—Cu1—Cu2 | 102.61 (6) | C5—C6—C7 | 119.2 (3) |
Cu2i—Cu1—Cu2 | 180.000 (17) | C5—C6—H6 | 120.4 |
O1—Cu2—O2 | 90.89 (9) | C7—C6—H6 | 120.4 |
O1—Cu2—N1 | 97.49 (9) | C2—C7—C6 | 117.0 (4) |
O2—Cu2—N1 | 169.20 (10) | C2—C7—C8 | 117.5 (4) |
O1—Cu2—N2 | 164.93 (9) | C6—C7—C8 | 125.4 (4) |
O2—Cu2—N2 | 88.74 (10) | C9—C8—C7 | 121.9 (4) |
N1—Cu2—N2 | 81.41 (11) | C9—C8—H8 | 119.1 |
O1—Cu2—O5 | 90.64 (8) | C7—C8—H8 | 119.1 |
O2—Cu2—O5 | 94.88 (10) | C8—C9—C10 | 121.7 (4) |
N1—Cu2—O5 | 91.82 (9) | C8—C9—H9 | 119.2 |
N2—Cu2—O5 | 104.40 (9) | C10—C9—H9 | 119.2 |
O1—Cu2—Cu1 | 38.55 (6) | C11—C10—C9 | 125.2 (4) |
O2—Cu2—Cu1 | 79.42 (6) | C11—C10—C3 | 116.3 (4) |
N1—Cu2—Cu1 | 111.36 (7) | C9—C10—C3 | 118.5 (4) |
N2—Cu2—Cu1 | 155.17 (7) | C12—C11—C10 | 120.0 (3) |
O5—Cu2—Cu1 | 55.67 (6) | C12—C11—H11 | 120.0 |
Cu2—O1—Cu1 | 103.08 (9) | C10—C11—H11 | 120.0 |
Cu2—O1—H101 | 124.01 | C11—C12—C4 | 120.2 (4) |
Cu1—O1—H101 | 115.55 | C11—C12—H12 | 119.9 |
C31—O2—Cu2 | 128.47 (19) | C4—C12—H12 | 119.9 |
C31—O3—Cu1 | 129.10 (19) | O3—C31—O2 | 125.3 (3) |
H401—O4—H402 | 110.6 | O3—C31—C32 | 117.1 (3) |
Cu2—O5—H501 | 127.89 | O2—C31—C32 | 117.5 (3) |
Cu2—O5—H502 | 117.26 | C33—C32—C34 | 123.7 (3) |
H501—O5—H502 | 103.5 | C33—C32—C31 | 119.1 (3) |
O7—N3—O6 | 120.5 (3) | C34—C32—C31 | 117.1 (3) |
O7—N3—O8 | 120.6 (3) | C32—C33—H33A | 120.0 |
O6—N3—O8 | 119.0 (3) | C32—C33—H33B | 120.0 |
C1—N1—C2 | 117.8 (3) | H33A—C33—H33B | 120.0 |
C1—N1—Cu2 | 129.2 (2) | C32—C34—H34A | 109.5 |
C2—N1—Cu2 | 112.9 (2) | C32—C34—H34B | 109.5 |
C4—N2—C3 | 118.1 (3) | H34A—C34—H34B | 109.5 |
C4—N2—Cu2 | 128.9 (3) | C32—C34—H34C | 109.5 |
C3—N2—Cu2 | 112.9 (2) | H34A—C34—H34C | 109.5 |
N1—C1—C5 | 122.2 (4) | H34B—C34—H34C | 109.5 |
N1—C1—H1 | 118.9 |
Symmetry code: (i) −x+1, −y, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H101···O8ii | 0.94 | 2.03 | 2.970 (4) | 177 |
O4—H401···O8 | 0.93 | 1.99 | 2.910 (3) | 171 |
O4—H402···O1 | 0.87 | 2.00 | 2.819 (4) | 156 |
O5—H501···O4iii | 0.92 | 1.84 | 2.731 (4) | 166 |
O5—H502···O6i | 0.96 | 1.99 | 2.936 (4) | 168 |
Symmetry codes: (i) −x+1, −y, −z; (ii) −x, −y, −z; (iii) x+1, y, z. |
Experimental details
Crystal data | |
Chemical formula | [Cu3(C4H5O2)2(OH)2(C12H8N2)2(H2O)2](NO3)2·2H2O |
Mr | 951.29 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 7.3779 (5), 11.1570 (9), 12.5830 (9) |
α, β, γ (°) | 71.081 (2), 81.596 (2), 70.529 (2) |
V (Å3) | 922.94 (12) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 1.80 |
Crystal size (mm) | 0.35 × 0.08 × 0.02 |
Data collection | |
Diffractometer | Rigaku R-AXIS RAPID diffractometer |
Absorption correction | Multi-scan (ABSCOR; Higashi, 1995) |
Tmin, Tmax | 0.572, 0.965 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8975, 4172, 3356 |
Rint | 0.029 |
(sin θ/λ)max (Å−1) | 0.648 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.120, 1.13 |
No. of reflections | 4172 |
No. of parameters | 271 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.53, −0.53 |
Computer programs: PROCESS-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC & Rigaku, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
Cu1—O1 | 1.9369 (19) | Cu2—N1 | 2.012 (2) |
Cu1—O3 | 1.973 (2) | Cu2—N2 | 2.028 (2) |
Cu1—Cu2 | 3.0275 (4) | Cu2—O5 | 2.286 (2) |
Cu2—O1 | 1.9295 (19) | O2—C31 | 1.265 (4) |
Cu2—O2 | 1.932 (2) | O3—C31 | 1.262 (3) |
O1i—Cu1—O3 | 89.19 (8) | O2—Cu2—N2 | 88.74 (10) |
O1—Cu1—O3 | 90.81 (8) | N1—Cu2—N2 | 81.41 (11) |
O1—Cu2—O2 | 90.89 (9) | O1—Cu2—O5 | 90.64 (8) |
O1—Cu2—N1 | 97.49 (9) | O2—Cu2—O5 | 94.88 (10) |
O2—Cu2—N1 | 169.20 (10) | N1—Cu2—O5 | 91.82 (9) |
O1—Cu2—N2 | 164.93 (9) | N2—Cu2—O5 | 104.40 (9) |
Symmetry code: (i) −x+1, −y, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H101···O8ii | 0.94 | 2.03 | 2.970 (4) | 177 |
O4—H401···O8 | 0.93 | 1.99 | 2.910 (3) | 171 |
O4—H402···O1 | 0.87 | 2.00 | 2.819 (4) | 156 |
O5—H501···O4iii | 0.92 | 1.84 | 2.731 (4) | 166 |
O5—H502···O6i | 0.96 | 1.99 | 2.936 (4) | 168 |
Symmetry codes: (i) −x+1, −y, −z; (ii) −x, −y, −z; (iii) x+1, y, z. |
Molecular magnetic compounds have recently attracted attention and have been developed to a large extent (Miller & Drillon, 2001a,b, 2002; Bruda et al., 2006; Narasimha et al., 2006). In particular, ferromagnetic exchange coupling in the mixed bridged unit CuII–RO/RCO2–CuII leads to a quartet ground state for the trinuclear system (Haase & Gehring, 1985). Because various ligands show different abilities for mediating electronic effects between copper ions, these coordination compounds display rich magnetic behaviour over various temperature ranges (Rao et al., 2004; Setifi et al., 2006; Chen et al., 2006; Das et al., 2006; Tao et al., 2006). Efforts to obtain new compounds in which rare earth ions are coupled magnetically to transition metal ions and/or organic radicals are increasing rapidly (Mishra et al., 2005; Mori et al., 2005, 2006; Costes, Dahan & Wernsdorfer, 2006; Costes, Auchel et al., 2006; Murugesu et al., 2006; Yeung et al., 2006). However, it is difficult to clarify what contributes most to the magnetic interaction between rare earth and transition metal ions, because a change in magnetic properties depends on many factors.
In recent years, we have pursued a research project investigating the structures and properties of heteronuclear complexes of rare earth and transition metals bridged by carboxyl groups (Wu et al., 2002a,b, 2003, 2004; Zhu et al., 2005). The title complex, (I), was obtained during the preparation of a dysprosium–copper carboxyl compound. Its structure and magnetic properties are promising for the elucidation of the magnetic interaction between different 4f and 3d metallic ions in heteroneuclear complexes.
The molecular structure and intramolecular arrangement of (I) are shown in Fig. 1. The symmetric centre of the molecule is situated at atom Cu1. The coordination environments that surround the CuII ions can be divided into two types. Atom Cu2 is in a CuN2O3 environment formed by two N atoms of a bidentate phenanthroline ligand and three O atoms from a water molecule, an α-methylacrylate group and a hydroxyl group, composing a distorted square-pyramidal geometry. Atoms O1, O2, N1 and N2 are in the equatorial plane and atom O5 occupies the vertex of the square-pyramid. Atom Cu1 is coordinated by atoms O1, O1iii, O3 and O3iii, which constitute a square plane [symmetry code: (iii) 1 - x, -y, -z]. It is noted that atoms O5 and O5iii of the water molecules occupy the axial sites of an octahedral polyhedron if atom Cu1 is considered as six-coordinated (dashed lines in Fig. 1). The Cu1—O5 distance is 2.567 Å. Three CuII ions in the molecule are in a linear arrangement linked by α-methylacrylate and hydroxyl groups to give two mixed bridged Cu2–OH/RCOO–Cu1 units with a Cu2···Cu1 distance of 3.0275 Å. As Table 1 shows, the Cu—O bond lengths in the square planes are similar, with an average bond length of 1.9468 Å. The axial Cu—O distance is 2.287 (2) Å, which is obviously longer than those in the square planes. The two Cu—N distances are nearly the same, with an average value of 2.021 Å. All bond lengths are in agreement with those in other reports (Gehring et al., 1993; Setifi et al., 2006; Tao et al., 2006). Electronic delocalization in the OCO fragment is complete, with two almost equivalent CO bond lengths [1.265 (4) Å for C31—O2 and 1.262 (3) Å for C31—O3]. The phenanthroline ligand adopts a bidentate coordination mode and possesses local C2v symmetry.
A packing diagram for complex (I) is shown in Fig. 2. The copper complex cations are associated with their identical neighbours through stacking of the phenanthroline aromatic rings in an `offset' manner. There is no evidence, however, of strong π–π stacking interactions. The aryl rings of neighbouring phenanthroline ligands are approximately parallel, with a dihedral angle of 0.82° and an approximate perpendicular distance of 3.687 Å.
Hydrogen bonds play an important role in the stability of the crystal structure of (I). As Fig. 3 shows, there are also many intermolecular hydrogen bonds between O atoms of the water molecules and O atoms of the nitrate ions or hydroxyl groups. Atoms O1, O4, O5i, O6ii, N3ii and O8ii are interlinked by hydrogen bonds to form a six-ring cycle [symmetry codes: (i) -1 + x, y, z; (ii) -x, -y, -z]. Atoms O1ii, O4ii, O5iii, O6, N3 and O8 are also joined together by hydrogen bonds to form another six-ring cycle. Meanwhile, there are two cycles linked by hydrogen bonds between atoms O4 and O8, and O4ii and O8ii. These hydrogen bonds form a one-dimensional structure along the a axis, which is advantageous for decreasing the energy. The hydrogen-bond distances are in the range 2.731–2.968 Å, with an average of 2.873 Å, which is in good agreement with typical values for O—H···O interactions [Reference?].