Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270199015036/na1440sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270199015036/na1440Isup2.hkl |
CCDC reference: 143221
The synthesis of (I) was carried out by the hydrothermal reaction of Na2MoO4·2H2O, CuSO4·5H2O, 4,4'-bipy, As2O3 and H2O (molar ratio of 1:1:1:0.5:500) in 30 ml Teflon-lined stainless steel autoclave for 5 d at 443 K. The resulting rectangular parallelepiped orange crystals were separated from the green paste by washing in water after cooling down to room temperature.
Data collection: XSCANS (Siemens, 1994a); cell refinement: XSCANS; data reduction: SHELXTL (Siemens, 1994b); program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL93 (Sheldrick, 1993); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Fig. 1. A view of (I) showing 50% probability displacement ellipsoids and the atom-numbering scheme. H atoms are omitted for clarity. |
[Cu2Mo2O7(C10H8N2)2] | Dx = 2.148 Mg m−3 |
Mr = 743.33 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pbcn | Cell parameters from 33 reflections |
a = 11.839 (2) Å | θ = 4.9–11.5° |
b = 9.108 (2) Å | µ = 2.94 mm−1 |
c = 21.319 (4) Å | T = 293 K |
V = 2298.8 (8) Å3 | Block, orange |
Z = 4 | 0.50 × 0.42 × 0.38 mm |
F(000) = 1448 |
Siemens P4 diffractometer | 1549 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.019 |
Graphite monochromator | θmax = 25°, θmin = 2.6° |
2θ/ω scans | h = −1→14 |
Absorption correction: empirical (using intensity measurements) (North et al., 1968) | k = −1→10 |
Tmin = 0.229, Tmax = 0.325 | l = −25→1 |
2750 measured reflections | 3 standard reflections every 97 reflections |
2016 independent reflections | intensity decay: none |
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) = 0.069 | All H-atom parameters refined |
S = 0.90 | Calculated w = 1/[σ2(Fo2) + (0.0414P)2] where P = (Fo2 + 2Fc2)/3 |
2016 reflections | (Δ/σ)max = −0.001 |
191 parameters | Δρmax = 0.51 e Å−3 |
0 restraints | Δρmin = −0.90 e Å−3 |
[Cu2Mo2O7(C10H8N2)2] | V = 2298.8 (8) Å3 |
Mr = 743.33 | Z = 4 |
Orthorhombic, Pbcn | Mo Kα radiation |
a = 11.839 (2) Å | µ = 2.94 mm−1 |
b = 9.108 (2) Å | T = 293 K |
c = 21.319 (4) Å | 0.50 × 0.42 × 0.38 mm |
Siemens P4 diffractometer | 1549 reflections with I > 2σ(I) |
Absorption correction: empirical (using intensity measurements) (North et al., 1968) | Rint = 0.019 |
Tmin = 0.229, Tmax = 0.325 | 3 standard reflections every 97 reflections |
2750 measured reflections | intensity decay: none |
2016 independent reflections |
R[F2 > 2σ(F2)] = 0.028 | 0 restraints |
wR(F2) = 0.069 | All H-atom parameters refined |
S = 0.90 | Δρmax = 0.51 e Å−3 |
2016 reflections | Δρmin = −0.90 e Å−3 |
191 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 on F2 for ALL reflections except for 0 with very negative F2 or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating _R_factor_obs 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 | ||
Mo | 0.45340 (3) | 0.03341 (3) | 0.333146 (15) | 0.02855 (12) | |
Cu | 0.34433 (5) | −0.36438 (6) | 0.34565 (2) | 0.0364 (2) | |
O1 | 0.3773 (3) | −0.1279 (3) | 0.34115 (12) | 0.0429 (8) | |
O2 | 0.3712 (3) | 0.1814 (3) | 0.35402 (14) | 0.0463 (8) | |
O3 | 1/2 | 0.0568 (6) | 1/4 | 0.092 (2) | |
O4 | 0.5694 (4) | 0.0268 (4) | 0.3807 (3) | 0.0877 (15) | |
N1 | 0.3575 (3) | −0.4170 (3) | 0.25812 (13) | 0.0269 (7) | |
N2 | 0.3547 (3) | −0.5925 (4) | −0.06575 (14) | 0.0289 (7) | |
C1 | 0.3589 (4) | −0.5573 (5) | 0.2387 (2) | 0.0316 (9) | |
H1 | 0.358 (3) | −0.630 (4) | 0.2675 (16) | 0.018 (9)* | |
C2 | 0.3635 (4) | −0.5968 (4) | 0.1764 (2) | 0.0288 (9) | |
H2 | 0.360 (4) | −0.702 (5) | 0.1667 (16) | 0.032 (11)* | |
C3 | 0.3641 (3) | −0.4890 (4) | 0.1301 (2) | 0.0240 (8) | |
C4 | 0.3644 (4) | −0.3437 (4) | 0.1500 (2) | 0.0299 (9) | |
H4 | 0.368 (4) | −0.267 (5) | 0.1203 (18) | 0.037 (12)* | |
C5 | 0.3624 (4) | −0.3130 (4) | 0.2135 (2) | 0.0295 (9) | |
H5 | 0.359 (3) | −0.211 (4) | 0.2282 (16) | 0.024 (10)* | |
C6 | 0.3616 (3) | −0.5267 (4) | 0.0621 (2) | 0.0262 (8) | |
C7 | 0.3044 (4) | −0.4378 (5) | 0.0201 (2) | 0.0409 (12) | |
H7 | 0.272 (4) | −0.359 (5) | 0.034 (2) | 0.043 (13)* | |
C8 | 0.3038 (4) | −0.4733 (6) | −0.0430 (2) | 0.0413 (11) | |
H8 | 0.263 (4) | −0.415 (5) | −0.067 (2) | 0.052 (14)* | |
C9 | 0.4095 (4) | −0.6791 (4) | −0.0252 (2) | 0.0292 (9) | |
H9 | 0.446 (3) | −0.765 (4) | −0.0411 (15) | 0.019 (9)* | |
C10 | 0.4153 (4) | −0.6494 (4) | 0.0386 (2) | 0.0276 (9) | |
H10 | 0.460 (4) | −0.710 (5) | 0.065 (2) | 0.041 (12)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mo | 0.0334 (2) | 0.0242 (2) | 0.0281 (2) | −0.0017 (2) | 0.0090 (2) | −0.00278 (14) |
Cu | 0.0501 (3) | 0.0466 (3) | 0.0123 (2) | −0.0046 (3) | −0.0002 (2) | 0.0005 (2) |
O1 | 0.057 (2) | 0.035 (2) | 0.037 (2) | −0.014 (2) | 0.012 (2) | −0.0057 (13) |
O2 | 0.055 (2) | 0.035 (2) | 0.049 (2) | 0.009 (2) | 0.015 (2) | −0.0029 (14) |
O3 | 0.160 (6) | 0.061 (4) | 0.054 (3) | 0 | 0.074 (4) | 0 |
O4 | 0.059 (3) | 0.071 (3) | 0.133 (4) | 0.008 (2) | −0.051 (3) | −0.021 (3) |
N1 | 0.031 (2) | 0.035 (2) | 0.0150 (14) | 0.000 (2) | −0.0029 (14) | 0.0011 (12) |
N2 | 0.031 (2) | 0.038 (2) | 0.0181 (14) | −0.002 (2) | −0.0024 (14) | −0.0029 (13) |
C1 | 0.039 (2) | 0.033 (2) | 0.022 (2) | −0.001 (2) | 0.001 (2) | 0.006 (2) |
C2 | 0.037 (2) | 0.029 (2) | 0.020 (2) | −0.003 (2) | 0.002 (2) | −0.0030 (15) |
C3 | 0.021 (2) | 0.034 (2) | 0.017 (2) | 0.001 (2) | −0.0009 (15) | −0.0026 (15) |
C4 | 0.041 (2) | 0.032 (2) | 0.017 (2) | 0.000 (2) | −0.002 (2) | 0.002 (2) |
C5 | 0.039 (3) | 0.030 (2) | 0.019 (2) | −0.002 (2) | −0.002 (2) | −0.003 (2) |
C6 | 0.026 (2) | 0.037 (2) | 0.015 (2) | −0.004 (2) | −0.001 (2) | −0.0034 (15) |
C7 | 0.050 (3) | 0.048 (3) | 0.025 (2) | 0.021 (2) | −0.010 (2) | −0.008 (2) |
C8 | 0.045 (3) | 0.054 (3) | 0.024 (2) | 0.014 (3) | −0.010 (2) | −0.004 (2) |
C9 | 0.039 (2) | 0.028 (2) | 0.021 (2) | 0.004 (2) | 0.003 (2) | −0.001 (2) |
C10 | 0.037 (2) | 0.027 (2) | 0.018 (2) | 0.001 (2) | −0.001 (2) | 0.002 (2) |
Mo—O4 | 1.709 (4) | C3—C4 | 1.390 (5) |
Mo—O2 | 1.721 (3) | C3—C6 | 1.489 (5) |
Mo—O1 | 1.732 (3) | C4—C5 | 1.382 (5) |
Mo—O3 | 1.8687 (8) | C6—C7 | 1.385 (6) |
Cu—N1 | 1.933 (3) | C6—C10 | 1.381 (5) |
Cu—N2i | 1.933 (3) | C7—C8 | 1.384 (5) |
Cu—O1 | 2.191 (3) | C9—C10 | 1.388 (5) |
O3—Moii | 1.869 (1) | C1—H1 | 0.905 |
N1—C1 | 1.343 (5) | C2—H2 | 0.976 |
N1—C5 | 1.344 (5) | C4—H4 | 0.944 |
N2—C8 | 1.332 (5) | C5—H5 | 0.979 |
N2—C9 | 1.339 (5) | C7—H7 | 0.869 |
N2—Cuiii | 1.933 (3) | C8—H8 | 0.879 |
C1—C2 | 1.378 (5) | C9—H9 | 0.955 |
C2—C3 | 1.392 (5) | C10—H10 | 0.953 |
O4—Mo—O2 | 109.2 (2) | C9—N2—Cuiii | 122.8 (3) |
O4—Mo—O1 | 109.3 (2) | N1—C1—C2 | 123.1 (3) |
O2—Mo—O1 | 110.2 (2) | C1—C2—C3 | 120.0 (4) |
O4—Mo—O3 | 109.3 (2) | C4—C3—C2 | 117.1 (3) |
O2—Mo—O3 | 108.8 (2) | C4—C3—C6 | 121.1 (3) |
O1—Mo—O3 | 110.1 (2) | C2—C3—C6 | 121.8 (3) |
N1—Cu—N2i | 152.59 (14) | C3—C4—C5 | 119.5 (4) |
N1—Cu—O1 | 100.8 (1) | N1—C5—C4 | 123.4 (4) |
N2i—Cu—O1 | 103.37 (12) | C7—C6—C10 | 117.6 (3) |
Mo—O1—Cu | 158.6 (2) | C7—C6—C3 | 120.3 (4) |
Moii—O3—Mo | 166.9 (3) | C10—C6—C3 | 122.1 (3) |
C1—N1—C5 | 116.9 (3) | C6—C7—C8 | 119.7 (4) |
C1—N1—Cu | 122.3 (2) | N2—C8—C7 | 122.8 (4) |
C5—N1—Cu | 120.8 (3) | N2—C9—C10 | 122.8 (4) |
C8—N2—C9 | 117.7 (3) | C6—C10—C9 | 119.4 (4) |
C8—N2—Cuiii | 119.5 (3) |
Symmetry codes: (i) x, −y−1, z+1/2; (ii) −x+1, y, −z+1/2; (iii) x, −y−1, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | [Cu2Mo2O7(C10H8N2)2] |
Mr | 743.33 |
Crystal system, space group | Orthorhombic, Pbcn |
Temperature (K) | 293 |
a, b, c (Å) | 11.839 (2), 9.108 (2), 21.319 (4) |
V (Å3) | 2298.8 (8) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.94 |
Crystal size (mm) | 0.50 × 0.42 × 0.38 |
Data collection | |
Diffractometer | Siemens P4 diffractometer |
Absorption correction | Empirical (using intensity measurements) (North et al., 1968) |
Tmin, Tmax | 0.229, 0.325 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2750, 2016, 1549 |
Rint | 0.019 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.028, 0.069, 0.90 |
No. of reflections | 2016 |
No. of parameters | 191 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.51, −0.90 |
Computer programs: XSCANS (Siemens, 1994a), XSCANS, SHELXTL (Siemens, 1994b), SHELXS86 (Sheldrick, 1990), SHELXL93 (Sheldrick, 1993), SHELXTL.
Mo—O4 | 1.709 (4) | Cu—O1 | 2.191 (3) |
Mo—O2 | 1.721 (3) | N1—C1 | 1.343 (5) |
Mo—O1 | 1.732 (3) | N1—C5 | 1.344 (5) |
Mo—O3 | 1.8687 (8) | N2—C8 | 1.332 (5) |
Cu—N1 | 1.933 (3) | N2—C9 | 1.339 (5) |
Cu—N2i | 1.933 (3) | C3—C6 | 1.489 (5) |
O4—Mo—O2 | 109.2 (2) | O2—Mo—O3 | 108.8 (2) |
O4—Mo—O1 | 109.3 (2) | O1—Mo—O3 | 110.1 (2) |
O2—Mo—O1 | 110.2 (2) | N1—Cu—O1 | 100.8 (1) |
O4—Mo—O3 | 109.3 (2) |
Symmetry code: (i) x, −y−1, z+1/2. |
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While bidendate bipyridyl complexes with copper(I) are known, those with 4,4'-bipy are uncommon (Hathaway, 1987). In recent years, however, some groups have reported a few 4,4'-bipy complexes with an open framework structure, such as [Cu(4,4'-bipy)Cl]n (Yaghi & Li, 1995a), which was synthesized in non-aqueous solvents, [Cu(4,4'-bipy)1.5NO3(H2O)1.25] (Yaghi & Li, 1995b), and [Cu(4,4'-bipy)Mo8O26] and [{Cu(4,4'-bipy)}4Mo15O47](Hagrman et al., 1997), which were synthesized under hydrothermal conditions. We report here the structure of a new compound, (I), which is the first example of a polyoxoanion-bridged copper(I) complex. \scheme
The structure of (I) consists of a covalently bridged framework built up from Mo2O72- units and [Cu(4,4'-bipy)]nn+ chains (Fig.1). The dimolybdate units are structurally related to the discrete dimolybdate anions which were isolated as the tetrabutylammonium salt by Day et al. (1977). The unit possesses crystallographic C2 symmetry and is built up from two distorted MoO4 tetrahedra by sharing a vertex. The Mo···Mo distance is 3.713 (1) Å. The Mo2O72- unit has three kinds of Mo—O bonds: 1.709 (4) and 1.721 (3) for Mo—Oterminal, 1.869 (1) for Mo—Obridge and 1.732 (3) Å for Mo—OCu. The Mo–O–Mo angle is 166.9 (3)°, which is greater than that of the discrete Mo2O72- anion (153.6°).
Copper(I) ions and 4,4'-bipy ligands are linked by means of a coordination bond, forming [Cu(4,4'-bipy)]nn+ chains. Two [Cu(4,4'-bipy)]nn+ chains are covalently linked through Mo2O72- units to form [Cu2(4,4'-bipy)2Mo2O7]n with a bridged double chain structure. The distance of the two chains is 3.376 (7) Å (based on the C1—C1A distance). It is interesting that Mo2O72- units are positioned on both sides of the two chains alternately.
The title complex possesses the distorted trigonal planar geometry of the copper(I) centre. The N1–Cu–N2i, N1–Cu–O1 and N2i–Cu–O1 angles are 152.59 (14), 100.78 (12) and 103.37 (12)°, respectively [symmetry code: (i) x, -1 - y, 1/2 + z]. N1, N2i, O1 and Cu are nearly in the same plane. The two pyridine rings of the bipyridyl molecule are not coplanar: the bipyridyl dihedral angle is 34.2 (6)°. As the calculated valence sum of Mo is 6.06 (Brown & Altermatt, 1985), the valence sum of Cu is deduced to be 1.