Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104021456/ta1453sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104021456/ta1453Isup2.hkl |
CCDC reference: 254919
To prepare (I), H2dmg (0.058 g, 0.5 mmol) and Cu(ClO4)26H2O (0.270 g, 0.75 mmol) were dissolved in methanol (10 ml) and a 0.5M NaOH aqueous solution (1 ml) was added in order to deprotonate the oximate groups. The resulting mixture was stirred for 1 h at room temperature and then filtered and evaporated at room temperature. After 4 d, dark-red crystals of the complex suitable for X-ray single-crystal analysis were obtained. These were collected by filter suction and air-dried. All chemicals used in this experiment were purchased commercially and used without further purification. Yield: 60%. Analysis found: C 25.56, H 3.77, N 14.10%; calcualted: C 24.43, H 3.90, N 14.25%. IR (cm−1): ν 1589 (s, C=N), 1201 (s, N—O), 1090 (s, Cl=O). The room-temperature value of CMT for (I) (CM, the molar magnetic susceptibility for a one-dimensional copper chain; ca 0.454 cm3 K mol−1) is higher than the expected value for a one-dimensional chain of copper(II) ions (ca 0.374 cm3 K mol−1), so the CMT value of (I) reveals a ferromagnetic coupling between the copper(II) ions.
Table 2. Intra-chain hydrogen-bonding geometry of (I).
The O atoms of the perchlorate ion occupy two positions. They were refined freely but with a parameter constraining their populations to 1.0. Consequently, the Ueq(max)/Ueq(min) ratio for the perchlorate group is larger than usual. Hydroxy H atoms were positioned geometrically (O—H = 0.82 Å), and the coordinates of water H atoms were calculated using HYDROGEN (Nardelli, 1999) (O—H = 0.8498 and 0.8501 Å). All of these H atoms were allowed to ride on their parent atoms in the final refinement. H atoms attached to C atoms were placed in calculated positions (C—H = 0.93 Å) and allowed to ride on the parent atoms. For all H atoms, Uiso(H) values were constrained to 1.5Ueq of the parent atom??.
Data collection: SMART (Bruker, 2000); cell refinement: SMART; data reduction: SMART and SAINT? (Bruker, 1999); program(s) used to solve structure: SHELXTL (Bruker, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL and ORTEPII? (Johnson, 1976); software used to prepare material for publication: SHELXTL.
[Cu4(C2H6N2O2)2(C2H7N2O2)2(C2H8N2O2)2](ClO4)2·2H2O | Z = 1 |
Mr = 1179.78 | F(000) = 600 |
Triclinic, P1 | Dx = 1.817 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.458 (3) Å | Cell parameters from 1006 reflections |
b = 10.381 (3) Å | θ = 2.5–26.4° |
c = 12.838 (3) Å | µ = 2.16 mm−1 |
α = 88.402 (5)° | T = 293 K |
β = 74.831 (4)° | Prism, red |
γ = 63.064 (4)° | 0.12 × 0.10 × 0.06 mm |
V = 1078.5 (5) Å3 |
Bruker SMART CCD area-detector diffractometer | 4356 independent reflections |
Radiation source: fine-focus sealed tube | 3341 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.024 |
ϕ and ω scans | θmax = 26.4°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Bruker, 1999) | h = −11→11 |
Tmin = 0.762, Tmax = 0.878 | k = −9→12 |
6254 measured reflections | l = −14→16 |
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)] = 0.044 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.093 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.005P)2 + 2.5P] where P = (Fo2 + 2Fc2)/3 |
4356 reflections | (Δ/σ)max = 0.001 |
305 parameters | Δρmax = 0.66 e Å−3 |
20 restraints | Δρmin = −0.66 e Å−3 |
[Cu4(C2H6N2O2)2(C2H7N2O2)2(C2H8N2O2)2](ClO4)2·2H2O | γ = 63.064 (4)° |
Mr = 1179.78 | V = 1078.5 (5) Å3 |
Triclinic, P1 | Z = 1 |
a = 9.458 (3) Å | Mo Kα radiation |
b = 10.381 (3) Å | µ = 2.16 mm−1 |
c = 12.838 (3) Å | T = 293 K |
α = 88.402 (5)° | 0.12 × 0.10 × 0.06 mm |
β = 74.831 (4)° |
Bruker SMART CCD area-detector diffractometer | 4356 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1999) | 3341 reflections with I > 2σ(I) |
Tmin = 0.762, Tmax = 0.878 | Rint = 0.024 |
6254 measured reflections |
R[F2 > 2σ(F2)] = 0.044 | 20 restraints |
wR(F2) = 0.093 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.66 e Å−3 |
4356 reflections | Δρmin = −0.66 e Å−3 |
305 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 | Occ. (<1) | |
Cu1 | 0.21477 (6) | 0.84447 (5) | 0.40438 (4) | 0.03069 (15) | |
Cu2 | 0.57969 (6) | 0.50808 (5) | 0.36959 (4) | 0.03108 (15) | |
O1 | 0.3943 (3) | 0.5293 (3) | 0.3196 (2) | 0.0353 (7) | |
O2 | 0.0076 (4) | 1.0770 (3) | 0.2912 (3) | 0.0487 (9) | |
H2 | 0.0014 | 1.1212 | 0.3455 | 0.073* | |
O3 | 0.4705 (3) | 0.6399 (3) | 0.5042 (2) | 0.0318 (7) | |
O4 | 0.0220 (4) | 1.1577 (3) | 0.4702 (2) | 0.0395 (7) | |
O5 | 0.7110 (4) | 0.3426 (4) | 0.1435 (3) | 0.0559 (10) | |
H5 | 0.6170 | 0.3515 | 0.1616 | 0.084* | |
O6 | 0.8202 (4) | 0.5035 (4) | 0.4873 (2) | 0.0442 (8) | |
H6 | 0.7391 | 0.5204 | 0.5385 | 0.066* | |
N1 | 0.2934 (4) | 0.6683 (3) | 0.3046 (3) | 0.0289 (8) | |
N2 | 0.1065 (4) | 0.9319 (4) | 0.2908 (3) | 0.0338 (8) | |
N3 | 0.3637 (4) | 0.7798 (4) | 0.4987 (3) | 0.0289 (8) | |
N4 | 0.1493 (4) | 1.0321 (4) | 0.4820 (3) | 0.0331 (8) | |
N5 | 0.7439 (4) | 0.3853 (4) | 0.2313 (3) | 0.0370 (9) | |
N6 | 0.7962 (4) | 0.4657 (4) | 0.3937 (3) | 0.0333 (8) | |
C1 | 0.2949 (7) | 0.5778 (5) | 0.1285 (4) | 0.0510 (13) | |
H1A | 0.3726 | 0.5860 | 0.0669 | 0.077* | |
H1B | 0.1988 | 0.5908 | 0.1083 | 0.077* | |
H1C | 0.3447 | 0.4834 | 0.1528 | 0.077* | |
C2 | 0.2464 (5) | 0.6907 (4) | 0.2170 (3) | 0.0305 (9) | |
C3 | 0.1379 (5) | 0.8461 (5) | 0.2085 (3) | 0.0342 (10) | |
C4 | 0.0714 (7) | 0.8958 (6) | 0.1127 (4) | 0.0624 (16) | |
H4A | 0.0058 | 0.9995 | 0.1227 | 0.094* | |
H4B | 0.0043 | 0.8511 | 0.1062 | 0.094* | |
H4C | 0.1616 | 0.8685 | 0.0480 | 0.094* | |
C5 | 0.4545 (6) | 0.8564 (5) | 0.6385 (4) | 0.0492 (13) | |
H5A | 0.3837 | 0.8753 | 0.7111 | 0.074* | |
H5B | 0.5042 | 0.9202 | 0.6288 | 0.074* | |
H5C | 0.5394 | 0.7574 | 0.6262 | 0.074* | |
C6 | 0.3553 (5) | 0.8820 (5) | 0.5596 (3) | 0.0302 (9) | |
C7 | 0.2315 (5) | 1.0298 (4) | 0.5488 (3) | 0.0331 (10) | |
C8 | 0.2034 (6) | 1.1613 (5) | 0.6113 (4) | 0.0491 (13) | |
H8A | 0.1124 | 1.2448 | 0.5972 | 0.074* | |
H8B | 0.3010 | 1.1741 | 0.5898 | 0.074* | |
H8C | 0.1785 | 1.1502 | 0.6874 | 0.074* | |
C9 | 1.0227 (7) | 0.3097 (7) | 0.1085 (4) | 0.0620 (16) | |
H9A | 0.9991 | 0.2510 | 0.0662 | 0.093* | |
H9B | 1.1279 | 0.2518 | 0.1217 | 0.093* | |
H9C | 1.0253 | 0.3893 | 0.0695 | 0.093* | |
C10 | 0.8916 (6) | 0.3673 (5) | 0.2141 (3) | 0.0384 (11) | |
C11 | 0.9252 (5) | 0.4105 (5) | 0.3118 (3) | 0.0348 (10) | |
C12 | 1.0920 (6) | 0.3852 (6) | 0.3141 (4) | 0.0553 (14) | |
H12A | 1.1037 | 0.4713 | 0.2976 | 0.083* | |
H12B | 1.1746 | 0.3058 | 0.2612 | 0.083* | |
H12C | 1.1056 | 0.3623 | 0.3849 | 0.083* | |
Cl1 | 0.6308 (3) | 0.7722 (2) | 0.16147 (12) | 0.0894 (6) | |
O7 | 0.549 (2) | 0.764 (4) | 0.2676 (10) | 0.083 (4) | 0.596 (7) |
O8 | 0.583 (3) | 0.705 (4) | 0.0945 (19) | 0.115 (6) | 0.596 (7) |
O9 | 0.620 (2) | 0.9028 (11) | 0.1315 (13) | 0.157 (6) | 0.596 (7) |
O10 | 0.8153 (9) | 0.6862 (10) | 0.1513 (6) | 0.101 (3) | 0.596 (7) |
O7' | 0.597 (4) | 0.738 (5) | 0.2688 (16) | 0.083 (4) | 0.404 (7) |
O8' | 0.638 (5) | 0.685 (5) | 0.077 (3) | 0.115 (6) | 0.404 (7) |
O9' | 0.4807 (16) | 0.9083 (12) | 0.1730 (17) | 0.157 (6) | 0.404 (7) |
O10' | 0.702 (2) | 0.8646 (18) | 0.1335 (12) | 0.101 (3) | 0.404 (7) |
O11 | 0.5060 (7) | 0.2079 (5) | 0.1070 (4) | 0.0998 (16) | |
H11A | 0.5060 | 0.2152 | 0.0409 | 0.150* | |
H11B | 0.5444 | 0.1193 | 0.1194 | 0.150* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0351 (3) | 0.0231 (3) | 0.0298 (3) | −0.0056 (2) | −0.0170 (2) | 0.0006 (2) |
Cu2 | 0.0280 (3) | 0.0297 (3) | 0.0269 (3) | −0.0055 (2) | −0.0083 (2) | −0.0005 (2) |
O1 | 0.0357 (16) | 0.0261 (15) | 0.0397 (17) | −0.0056 (13) | −0.0194 (13) | 0.0002 (13) |
O2 | 0.061 (2) | 0.0290 (17) | 0.0393 (19) | −0.0021 (16) | −0.0225 (17) | 0.0032 (14) |
O3 | 0.0294 (15) | 0.0278 (15) | 0.0264 (15) | −0.0029 (12) | −0.0089 (12) | 0.0024 (12) |
O4 | 0.0420 (17) | 0.0227 (15) | 0.0431 (18) | −0.0040 (13) | −0.0155 (14) | 0.0026 (13) |
O5 | 0.052 (2) | 0.081 (3) | 0.0385 (19) | −0.031 (2) | −0.0166 (16) | −0.0048 (18) |
O6 | 0.0436 (19) | 0.056 (2) | 0.0332 (17) | −0.0228 (17) | −0.0096 (14) | −0.0054 (16) |
N1 | 0.0269 (17) | 0.0259 (18) | 0.0295 (18) | −0.0070 (15) | −0.0108 (14) | 0.0041 (14) |
N2 | 0.0352 (19) | 0.0254 (18) | 0.0308 (19) | −0.0032 (15) | −0.0139 (15) | 0.0047 (15) |
N3 | 0.0282 (18) | 0.0258 (18) | 0.0270 (18) | −0.0072 (15) | −0.0084 (14) | 0.0021 (14) |
N4 | 0.037 (2) | 0.0258 (18) | 0.0318 (19) | −0.0096 (16) | −0.0103 (16) | 0.0018 (15) |
N5 | 0.036 (2) | 0.040 (2) | 0.0284 (19) | −0.0109 (17) | −0.0109 (16) | −0.0001 (16) |
N6 | 0.0338 (19) | 0.034 (2) | 0.0301 (19) | −0.0132 (16) | −0.0097 (16) | 0.0008 (15) |
C1 | 0.066 (3) | 0.043 (3) | 0.036 (3) | −0.015 (3) | −0.020 (2) | −0.003 (2) |
C2 | 0.031 (2) | 0.032 (2) | 0.026 (2) | −0.0124 (18) | −0.0090 (17) | 0.0003 (17) |
C3 | 0.036 (2) | 0.037 (2) | 0.027 (2) | −0.0125 (19) | −0.0126 (18) | 0.0054 (18) |
C4 | 0.082 (4) | 0.050 (3) | 0.043 (3) | −0.008 (3) | −0.039 (3) | 0.006 (2) |
C5 | 0.051 (3) | 0.044 (3) | 0.053 (3) | −0.015 (2) | −0.027 (3) | −0.003 (2) |
C6 | 0.030 (2) | 0.034 (2) | 0.024 (2) | −0.0136 (18) | −0.0062 (17) | −0.0034 (17) |
C7 | 0.035 (2) | 0.029 (2) | 0.031 (2) | −0.0135 (19) | −0.0043 (18) | −0.0037 (17) |
C8 | 0.055 (3) | 0.037 (3) | 0.055 (3) | −0.018 (2) | −0.019 (3) | −0.008 (2) |
C9 | 0.053 (3) | 0.088 (4) | 0.039 (3) | −0.034 (3) | 0.003 (2) | −0.011 (3) |
C10 | 0.041 (3) | 0.037 (2) | 0.030 (2) | −0.015 (2) | −0.007 (2) | 0.0032 (19) |
C11 | 0.034 (2) | 0.034 (2) | 0.036 (2) | −0.017 (2) | −0.0074 (19) | 0.0061 (19) |
C12 | 0.037 (3) | 0.079 (4) | 0.051 (3) | −0.030 (3) | −0.007 (2) | 0.000 (3) |
Cl1 | 0.1526 (19) | 0.1262 (16) | 0.0440 (9) | −0.1128 (16) | −0.0227 (10) | 0.0113 (9) |
O7 | 0.078 (12) | 0.150 (12) | 0.052 (3) | −0.076 (11) | −0.020 (4) | 0.010 (3) |
O8 | 0.185 (19) | 0.172 (10) | 0.055 (8) | −0.137 (13) | −0.034 (10) | 0.005 (5) |
O9 | 0.213 (17) | 0.109 (7) | 0.215 (13) | −0.118 (11) | −0.082 (13) | 0.043 (8) |
O10 | 0.096 (6) | 0.162 (8) | 0.065 (4) | −0.088 (6) | 0.002 (4) | −0.001 (5) |
O7' | 0.078 (12) | 0.150 (12) | 0.052 (3) | −0.076 (11) | −0.020 (4) | 0.010 (3) |
O8' | 0.185 (19) | 0.172 (10) | 0.055 (8) | −0.137 (13) | −0.034 (10) | 0.005 (5) |
O9' | 0.213 (17) | 0.109 (7) | 0.215 (13) | −0.118 (11) | −0.082 (13) | 0.043 (8) |
O10' | 0.096 (6) | 0.162 (8) | 0.065 (4) | −0.088 (6) | 0.002 (4) | −0.001 (5) |
O11 | 0.145 (5) | 0.072 (3) | 0.094 (4) | −0.046 (3) | −0.059 (3) | 0.017 (3) |
Cu1—N4 | 1.965 (3) | C3—C4 | 1.499 (6) |
Cu1—N2 | 1.966 (3) | C4—H4A | 0.9600 |
Cu1—N3 | 1.973 (3) | C4—H4B | 0.9600 |
Cu1—N1 | 1.984 (3) | C4—H4C | 0.9600 |
Cu1—O4i | 2.400 (3) | C5—C6 | 1.494 (6) |
Cu2—O1 | 1.941 (3) | C5—H5A | 0.9600 |
Cu2—O3 | 1.961 (3) | C5—H5B | 0.9600 |
Cu2—N6 | 1.997 (4) | C5—H5C | 0.9600 |
Cu2—N5 | 2.019 (4) | C6—C7 | 1.480 (6) |
Cu2—O3ii | 2.308 (3) | C7—C8 | 1.483 (6) |
O1—N1 | 1.365 (4) | C8—H8A | 0.9600 |
O2—N2 | 1.366 (4) | C8—H8B | 0.9600 |
O2—H2 | 0.8200 | C8—H8C | 0.9600 |
O3—N3 | 1.355 (4) | C9—C10 | 1.493 (6) |
O3—Cu2ii | 2.308 (3) | C9—H9A | 0.9600 |
O4—N4 | 1.355 (4) | C9—H9B | 0.9600 |
O4—Cu1i | 2.400 (3) | C9—H9C | 0.9600 |
O5—N5 | 1.379 (5) | C10—C11 | 1.498 (6) |
O5—H5 | 0.8200 | C11—C12 | 1.486 (6) |
O6—N6 | 1.379 (4) | C12—H12A | 0.9600 |
O6—H6 | 0.8200 | C12—H12B | 0.9600 |
N1—C2 | 1.292 (5) | C12—H12C | 0.9600 |
N2—C3 | 1.283 (5) | Cl1—O9 | 1.363 (8) |
N3—C6 | 1.296 (5) | Cl1—O10' | 1.397 (9) |
N4—C7 | 1.292 (5) | Cl1—O8 | 1.401 (8) |
N5—C10 | 1.281 (6) | Cl1—O8' | 1.401 (10) |
N6—C11 | 1.284 (5) | Cl1—O7' | 1.402 (9) |
C1—C2 | 1.481 (6) | Cl1—O7 | 1.404 (8) |
C1—H1A | 0.9600 | Cl1—O9' | 1.455 (9) |
C1—H1B | 0.9600 | Cl1—O10 | 1.528 (7) |
C1—H1C | 0.9600 | O11—H11A | 0.85 |
C2—C3 | 1.488 (6) | O11—H11B | 0.85 |
N4—Cu1—N2 | 94.38 (14) | C2—C3—C4 | 122.7 (4) |
N4—Cu1—N3 | 79.96 (14) | C3—C4—H4A | 109.5 |
N2—Cu1—N3 | 164.17 (15) | C3—C4—H4B | 109.5 |
N4—Cu1—N1 | 170.67 (14) | H4A—C4—H4B | 109.5 |
N2—Cu1—N1 | 79.64 (14) | C3—C4—H4C | 109.5 |
N3—Cu1—N1 | 103.92 (13) | H4A—C4—H4C | 109.5 |
N4—Cu1—O4i | 87.32 (13) | H4B—C4—H4C | 109.5 |
N2—Cu1—O4i | 96.35 (13) | C6—C5—H5A | 109.5 |
N3—Cu1—O4i | 98.12 (12) | C6—C5—H5B | 109.5 |
N1—Cu1—O4i | 100.38 (12) | H5A—C5—H5B | 109.5 |
O1—Cu2—O3 | 102.47 (12) | C6—C5—H5C | 109.5 |
O1—Cu2—N6 | 169.22 (13) | H5A—C5—H5C | 109.5 |
O3—Cu2—N6 | 88.16 (13) | H5B—C5—H5C | 109.5 |
O1—Cu2—N5 | 91.93 (14) | N3—C6—C7 | 114.2 (4) |
O3—Cu2—N5 | 163.92 (14) | N3—C6—C5 | 124.3 (4) |
N6—Cu2—N5 | 77.30 (14) | C7—C6—C5 | 121.4 (4) |
O1—Cu2—O3ii | 89.98 (12) | N4—C7—C6 | 113.6 (4) |
N6—Cu2—O3ii | 94.10 (13) | N4—C7—C8 | 123.9 (4) |
N5—Cu2—O3ii | 109.59 (13) | C6—C7—C8 | 122.5 (4) |
N1—O1—Cu2 | 114.4 (2) | C7—C8—H8A | 109.5 |
N2—O2—H2 | 109.5 | C7—C8—H8B | 109.5 |
N3—O3—Cu2 | 117.6 (2) | H8A—C8—H8B | 109.5 |
N3—O3—Cu2ii | 125.7 (2) | C7—C8—H8C | 109.5 |
Cu2—O3—Cu2ii | 102.07 (12) | H8A—C8—H8C | 109.5 |
N4—O4—Cu1i | 103.4 (2) | H8B—C8—H8C | 109.5 |
N5—O5—H5 | 109.5 | C10—C9—H9A | 109.5 |
N6—O6—H6 | 109.5 | C10—C9—H9B | 109.5 |
C2—N1—O1 | 118.5 (3) | H9A—C9—H9B | 109.5 |
C2—N1—Cu1 | 115.6 (3) | C10—C9—H9C | 109.5 |
O1—N1—Cu1 | 125.8 (2) | H9A—C9—H9C | 109.5 |
C3—N2—O2 | 118.3 (3) | H9B—C9—H9C | 109.5 |
C3—N2—Cu1 | 116.9 (3) | N5—C10—C9 | 125.2 (4) |
O2—N2—Cu1 | 124.7 (3) | N5—C10—C11 | 113.7 (4) |
C6—N3—O3 | 119.0 (3) | C9—C10—C11 | 121.1 (4) |
C6—N3—Cu1 | 115.7 (3) | N6—C11—C12 | 124.2 (4) |
O3—N3—Cu1 | 125.3 (2) | N6—C11—C10 | 112.7 (4) |
C7—N4—O4 | 120.7 (3) | C12—C11—C10 | 123.1 (4) |
C7—N4—Cu1 | 116.4 (3) | C11—C12—H12A | 109.5 |
O4—N4—Cu1 | 122.8 (3) | C11—C12—H12B | 109.5 |
C10—N5—O5 | 114.9 (4) | H12A—C12—H12B | 109.5 |
C10—N5—Cu2 | 116.1 (3) | C11—C12—H12C | 109.5 |
O5—N5—Cu2 | 127.6 (3) | H12A—C12—H12C | 109.5 |
C11—N6—O6 | 115.5 (4) | H12B—C12—H12C | 109.5 |
C11—N6—Cu2 | 117.7 (3) | O9—Cl1—O8 | 113.8 (16) |
O6—N6—Cu2 | 126.4 (3) | O10'—Cl1—O8' | 117 (2) |
C2—C1—H1A | 109.5 | O10'—Cl1—O7' | 120 (2) |
C2—C1—H1B | 109.5 | O8'—Cl1—O7' | 120 (3) |
H1A—C1—H1B | 109.5 | O9—Cl1—O7 | 119.5 (15) |
C2—C1—H1C | 109.5 | O8—Cl1—O7 | 104.8 (14) |
H1A—C1—H1C | 109.5 | O10'—Cl1—O9' | 81.3 (9) |
H1B—C1—H1C | 109.5 | O8'—Cl1—O9' | 106 (2) |
N1—C2—C1 | 125.6 (4) | O7'—Cl1—O9' | 98.1 (18) |
N1—C2—C3 | 114.1 (4) | O9—Cl1—O10 | 101.0 (8) |
C1—C2—C3 | 120.3 (4) | O8—Cl1—O10 | 111.3 (12) |
N2—C3—C2 | 113.6 (3) | O7—Cl1—O10 | 106.1 (8) |
N2—C3—C4 | 123.8 (4) | H11A—O11—H11B | 110.3 |
Symmetry codes: (i) −x, −y+2, −z+1; (ii) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O4 | 0.82 | 1.73 | 2.525 (5) | 161 |
O5—H5···O1 | 0.82 | 2.53 | 3.046 (4) | 122 |
O5—H5···O11 | 0.82 | 2.38 | 2.984 (9) | 131 |
O6—H6···O3 | 0.82 | 2.43 | 2.897 (4) | 117 |
O6—H6···O1ii | 0.82 | 2.12 | 2.885 (4) | 154 |
O11—H11A···O8iii | 0.85 | 2.11 | 2.92 (3) | 159 |
O11—H11B···O9iv | 0.85 | 2.04 | 2.885 (12) | 171 |
Symmetry codes: (ii) −x+1, −y+1, −z+1; (iii) −x+1, −y+1, −z; (iv) x, y−1, z. |
Experimental details
Crystal data | |
Chemical formula | [Cu4(C2H6N2O2)2(C2H7N2O2)2(C2H8N2O2)2](ClO4)2·2H2O |
Mr | 1179.78 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 9.458 (3), 10.381 (3), 12.838 (3) |
α, β, γ (°) | 88.402 (5), 74.831 (4), 63.064 (4) |
V (Å3) | 1078.5 (5) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 2.16 |
Crystal size (mm) | 0.12 × 0.10 × 0.06 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 1999) |
Tmin, Tmax | 0.762, 0.878 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6254, 4356, 3341 |
Rint | 0.024 |
(sin θ/λ)max (Å−1) | 0.626 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.093, 1.07 |
No. of reflections | 4356 |
No. of parameters | 305 |
No. of restraints | 20 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.66, −0.66 |
Computer programs: SMART (Bruker, 2000), SMART and SAINT? (Bruker, 1999), SHELXTL (Bruker, 1997), SHELXTL and ORTEPII? (Johnson, 1976).
Cu1—N4 | 1.965 (3) | Cu2—O1 | 1.941 (3) |
Cu1—N2 | 1.966 (3) | Cu2—O3 | 1.961 (3) |
Cu1—N3 | 1.973 (3) | Cu2—N6 | 1.997 (4) |
Cu1—N1 | 1.984 (3) | Cu2—N5 | 2.019 (4) |
Cu1—O4i | 2.400 (3) | Cu2—O3ii | 2.308 (3) |
N4—Cu1—N2 | 94.38 (14) | O1—Cu2—O3 | 102.47 (12) |
N4—Cu1—N3 | 79.96 (14) | O1—Cu2—N6 | 169.22 (13) |
N2—Cu1—N3 | 164.17 (15) | O3—Cu2—N6 | 88.16 (13) |
N4—Cu1—N1 | 170.67 (14) | O1—Cu2—N5 | 91.93 (14) |
N2—Cu1—N1 | 79.64 (14) | O3—Cu2—N5 | 163.92 (14) |
N3—Cu1—N1 | 103.92 (13) | N6—Cu2—N5 | 77.30 (14) |
N4—Cu1—O4i | 87.32 (13) | O1—Cu2—O3ii | 89.98 (12) |
N2—Cu1—O4i | 96.35 (13) | N6—Cu2—O3ii | 94.10 (13) |
N3—Cu1—O4i | 98.12 (12) | N5—Cu2—O3ii | 109.59 (13) |
N1—Cu1—O4i | 100.38 (12) |
Symmetry codes: (i) −x, −y+2, −z+1; (ii) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O4 | 0.82 | 1.73 | 2.525 (5) | 161 |
O5—H5···O1 | 0.82 | 2.53 | 3.046 (4) | 122 |
O5—H5···O11 | 0.82 | 2.38 | 2.984 (9) | 131 |
O6—H6···O3 | 0.82 | 2.43 | 2.897 (4) | 117 |
O6—H6···O1ii | 0.82 | 2.12 | 2.885 (4) | 154 |
O11—H11A···O8iii | 0.85 | 2.11 | 2.92 (3) | 159 |
O11—H11B···O9iv | 0.85 | 2.04 | 2.885 (12) | 171 |
Symmetry codes: (ii) −x+1, −y+1, −z+1; (iii) −x+1, −y+1, −z; (iv) x, y−1, z. |
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Self-assembly processes involving metal ions have attracted much attention in the past few years because a metal ion together with its ligand contains a variety of structural information to guide the self-assembly reaction (Lehn, 1995). Recent attention has particularly been focused on the construction of various supramolecular structures. In these structures, the very simple topological types of coordination arrays are one-dimensional architectures, such as one-dimensional zigzag chains (Mimura et al., 1998; Colacio et al., 1999) and a one-dimensional helix (Ranford et al., 1999). The most commonly used strategy to obtain these extended structures is to employ appropriate bridging ligands, which are capable of linking to several metal centers through direct bond formation.
It is well known that the oximate group (=N—O–) can function as a bridging ligand to link two metal ions through the imine N atom and the deprotonated O atom, and this group can coordinate with metal ions in versatile ways. Dimethylglyoxime (H2dmg) has four potential donor sites. Framework molecular models show that it is more likely to act as a bridging ligand between two metal ions than as a terminal ligand (Cervera et al., 1997; Ruiz et al., 1997). Recently, several groups, including our own, have reported the syntheses, X-ray crystal structure analyses and SQUID (superconducting quantum interference device) measurements of complicated complexes of transition metals using this bridging ligand (Chen et al., 2003; Li et al., 2002; Liu et al., 2002; Zhang et al., 2003). In this present contribution, we have extended our work using this ligand to form one-dimensional zigzag chains containing multidentate dimethylglyoxime. In this paper, we report the synthesis, structure and spectroscopic properties of the title compound, {[Cu4(dmg)2(Hdmg)2(H2dmg)2](ClO4)2·2H2O}∞, (I).
The principal feature of the structure of (I) is polymeric chains extending along [110]. The translationally repeating unit of these chains is a centrosymmetric sequence of four square-pyramidally coordinated CuII ions (Fig. 1). Cu1 and Cu1i [symmetry code: (i) −x, 2 − y, 1 − z] are at the 1,4-positions of a centrosymmetric six-membered ring that is in a chair conformation. The two unique Cu atoms (Cu1 and Cu2) are also bridged in a six-membered ring but in the half-chair conformation. This tetranuclear unit is repeated by lattice translation, incorporating another centre of symmetry, this time involving an oxo bridge (O3) between atoms Cu2 and Cu2ii [symmetry code: (ii) 1 − x, 1 − y, 1 − z] giving a four-membered ring. This linking style forms an interesting Cu2O2 quadrangular junction. To our knowledge, it is rare for metal coordination polymers to be connected through double bridges in a quadrangular junction.
A remarkable feature of this coordination environment is that all ligands are either H2dmg or one of its ions, and there are no coordinated water molecules; in this respect, compound (I) differs from all previously reported complexes containing dimethylglyoxime ligands. Among the six ligands in each tetranuclear moiety, two (H2dmg) are bidentate terminal ligands, two (Hdmg−) are tridentate bridging ligands within the moiety, and the other two (dmg2−) are tetradentate but are bound to five different Cu atoms because atom O3 bridges two Cu atoms.
As can be seen from Fig. 2, the entire polymer is a one-dimensional zigzag chain, which is built from Cu4 moieties. In order to form double Cu—O—Cu bonding bridges, the symmetrical dinuclear CuII unit in the Cu4 moiety adopts a chair form. The zigzag chain is further stabilized by intrachain hydrogen bonding by all three OH groups (Fig. 1 and Table 2). Both bonds of the bifurcated O6—H hydrogen bonds are intrachain, as is the O5—H hydrogen bond. The other component of the latter is to the uncoordinated water molecule (O11).
There are weak and ill-defined interactions between O atoms of the disordered perchlorate ion and both Cu atoms near the sixth (vacant) octahedral coordination site of the Cu atoms. The uncoordinated water molecule is located in the interchain region.
The crystal structure of (I) exhibits some characteristics that differ from those of previously reported structures, viz. all coordination sites are occupied by dimethylglyoxime ligands and double Cu—O—Cu bridges are connected in a quadrangular form. This polymeric structure shows the amazing bridging ability and the fantastic coordinating versatility of the dimethylglyoxime ligand, which can play an important role in the direct assembly of coordination polymers. Further investigation is in progress.