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The crystal structure of the title compound, poly­[bis-[copper(I)-μ-(4,4′-bipyridyl)-N:N′]-μ-dimolybdato-O:O′],[Cu2(C10H8N2)2{Mo2O7}]n, consists of {Mo2O7}2− units (with the central O atom lying on twofold symmetry axes) and [Cu(4,4′-bipy)]nn+ chains (bipy = bipyridyl); the chains are generated by a c-glide-plane operation. The {Mo2O7}2− units are covalently bridged to two [Cu(4,4′-bipy)]nn+ chains, forming a complex with a bridged double-chain structure. The Cu—O and Cu—N distances are 2.191 (3) and 1.933 (3) Å, respectively.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270199015036/na1440sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270199015036/na1440Isup2.hkl
Contains datablock I

CCDC reference: 143221

Comment top

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.

Experimental top

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.

Refinement top

All H atoms were refined and C—H distances are in the range 0.87 (5)–0.98 (5) Å.

Computing details top

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.

Figures top
[Figure 1] Fig. 1. A view of (I) showing 50% probability displacement ellipsoids and the atom-numbering scheme. H atoms are omitted for clarity.
poly[bis[copper(I)-µ-(4,4'-bipyridyl)-N:N']-µ-dimolybdato-O:O'] top
Crystal data top
[Cu2Mo2O7(C10H8N2)2]Dx = 2.148 Mg m3
Mr = 743.33Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, PbcnCell parameters from 33 reflections
a = 11.839 (2) Åθ = 4.9–11.5°
b = 9.108 (2) ŵ = 2.94 mm1
c = 21.319 (4) ÅT = 293 K
V = 2298.8 (8) Å3Block, orange
Z = 40.50 × 0.42 × 0.38 mm
F(000) = 1448
Data collection top
Siemens P4
diffractometer
1549 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.019
Graphite monochromatorθmax = 25°, θmin = 2.6°
2θ/ω scansh = 114
Absorption correction: empirical (using intensity measurements)
(North et al., 1968)
k = 110
Tmin = 0.229, Tmax = 0.325l = 251
2750 measured reflections3 standard reflections every 97 reflections
2016 independent reflections intensity decay: none
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.028Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.069All H-atom parameters refined
S = 0.90Calculated w = 1/[σ2(Fo2) + (0.0414P)2]
where P = (Fo2 + 2Fc2)/3
2016 reflections(Δ/σ)max = 0.001
191 parametersΔρmax = 0.51 e Å3
0 restraintsΔρmin = 0.90 e Å3
Crystal data top
[Cu2Mo2O7(C10H8N2)2]V = 2298.8 (8) Å3
Mr = 743.33Z = 4
Orthorhombic, PbcnMo Kα radiation
a = 11.839 (2) ŵ = 2.94 mm1
b = 9.108 (2) ÅT = 293 K
c = 21.319 (4) Å0.50 × 0.42 × 0.38 mm
Data collection top
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 = 0.3253 standard reflections every 97 reflections
2750 measured reflections intensity decay: none
2016 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0280 restraints
wR(F2) = 0.069All H-atom parameters refined
S = 0.90Δρmax = 0.51 e Å3
2016 reflectionsΔρmin = 0.90 e Å3
191 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Mo0.45340 (3)0.03341 (3)0.333146 (15)0.02855 (12)
Cu0.34433 (5)0.36438 (6)0.34565 (2)0.0364 (2)
O10.3773 (3)0.1279 (3)0.34115 (12)0.0429 (8)
O20.3712 (3)0.1814 (3)0.35402 (14)0.0463 (8)
O31/20.0568 (6)1/40.092 (2)
O40.5694 (4)0.0268 (4)0.3807 (3)0.0877 (15)
N10.3575 (3)0.4170 (3)0.25812 (13)0.0269 (7)
N20.3547 (3)0.5925 (4)0.06575 (14)0.0289 (7)
C10.3589 (4)0.5573 (5)0.2387 (2)0.0316 (9)
H10.358 (3)0.630 (4)0.2675 (16)0.018 (9)*
C20.3635 (4)0.5968 (4)0.1764 (2)0.0288 (9)
H20.360 (4)0.702 (5)0.1667 (16)0.032 (11)*
C30.3641 (3)0.4890 (4)0.1301 (2)0.0240 (8)
C40.3644 (4)0.3437 (4)0.1500 (2)0.0299 (9)
H40.368 (4)0.267 (5)0.1203 (18)0.037 (12)*
C50.3624 (4)0.3130 (4)0.2135 (2)0.0295 (9)
H50.359 (3)0.211 (4)0.2282 (16)0.024 (10)*
C60.3616 (3)0.5267 (4)0.0621 (2)0.0262 (8)
C70.3044 (4)0.4378 (5)0.0201 (2)0.0409 (12)
H70.272 (4)0.359 (5)0.034 (2)0.043 (13)*
C80.3038 (4)0.4733 (6)0.0430 (2)0.0413 (11)
H80.263 (4)0.415 (5)0.067 (2)0.052 (14)*
C90.4095 (4)0.6791 (4)0.0252 (2)0.0292 (9)
H90.446 (3)0.765 (4)0.0411 (15)0.019 (9)*
C100.4153 (4)0.6494 (4)0.0386 (2)0.0276 (9)
H100.460 (4)0.710 (5)0.065 (2)0.041 (12)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mo0.0334 (2)0.0242 (2)0.0281 (2)0.0017 (2)0.0090 (2)0.00278 (14)
Cu0.0501 (3)0.0466 (3)0.0123 (2)0.0046 (3)0.0002 (2)0.0005 (2)
O10.057 (2)0.035 (2)0.037 (2)0.014 (2)0.012 (2)0.0057 (13)
O20.055 (2)0.035 (2)0.049 (2)0.009 (2)0.015 (2)0.0029 (14)
O30.160 (6)0.061 (4)0.054 (3)00.074 (4)0
O40.059 (3)0.071 (3)0.133 (4)0.008 (2)0.051 (3)0.021 (3)
N10.031 (2)0.035 (2)0.0150 (14)0.000 (2)0.0029 (14)0.0011 (12)
N20.031 (2)0.038 (2)0.0181 (14)0.002 (2)0.0024 (14)0.0029 (13)
C10.039 (2)0.033 (2)0.022 (2)0.001 (2)0.001 (2)0.006 (2)
C20.037 (2)0.029 (2)0.020 (2)0.003 (2)0.002 (2)0.0030 (15)
C30.021 (2)0.034 (2)0.017 (2)0.001 (2)0.0009 (15)0.0026 (15)
C40.041 (2)0.032 (2)0.017 (2)0.000 (2)0.002 (2)0.002 (2)
C50.039 (3)0.030 (2)0.019 (2)0.002 (2)0.002 (2)0.003 (2)
C60.026 (2)0.037 (2)0.015 (2)0.004 (2)0.001 (2)0.0034 (15)
C70.050 (3)0.048 (3)0.025 (2)0.021 (2)0.010 (2)0.008 (2)
C80.045 (3)0.054 (3)0.024 (2)0.014 (3)0.010 (2)0.004 (2)
C90.039 (2)0.028 (2)0.021 (2)0.004 (2)0.003 (2)0.001 (2)
C100.037 (2)0.027 (2)0.018 (2)0.001 (2)0.001 (2)0.002 (2)
Geometric parameters (Å, º) top
Mo—O41.709 (4)C3—C41.390 (5)
Mo—O21.721 (3)C3—C61.489 (5)
Mo—O11.732 (3)C4—C51.382 (5)
Mo—O31.8687 (8)C6—C71.385 (6)
Cu—N11.933 (3)C6—C101.381 (5)
Cu—N2i1.933 (3)C7—C81.384 (5)
Cu—O12.191 (3)C9—C101.388 (5)
O3—Moii1.869 (1)C1—H10.905
N1—C11.343 (5)C2—H20.976
N1—C51.344 (5)C4—H40.944
N2—C81.332 (5)C5—H50.979
N2—C91.339 (5)C7—H70.869
N2—Cuiii1.933 (3)C8—H80.879
C1—C21.378 (5)C9—H90.955
C2—C31.392 (5)C10—H100.953
O4—Mo—O2109.2 (2)C9—N2—Cuiii122.8 (3)
O4—Mo—O1109.3 (2)N1—C1—C2123.1 (3)
O2—Mo—O1110.2 (2)C1—C2—C3120.0 (4)
O4—Mo—O3109.3 (2)C4—C3—C2117.1 (3)
O2—Mo—O3108.8 (2)C4—C3—C6121.1 (3)
O1—Mo—O3110.1 (2)C2—C3—C6121.8 (3)
N1—Cu—N2i152.59 (14)C3—C4—C5119.5 (4)
N1—Cu—O1100.8 (1)N1—C5—C4123.4 (4)
N2i—Cu—O1103.37 (12)C7—C6—C10117.6 (3)
Mo—O1—Cu158.6 (2)C7—C6—C3120.3 (4)
Moii—O3—Mo166.9 (3)C10—C6—C3122.1 (3)
C1—N1—C5116.9 (3)C6—C7—C8119.7 (4)
C1—N1—Cu122.3 (2)N2—C8—C7122.8 (4)
C5—N1—Cu120.8 (3)N2—C9—C10122.8 (4)
C8—N2—C9117.7 (3)C6—C10—C9119.4 (4)
C8—N2—Cuiii119.5 (3)
Symmetry codes: (i) x, y1, z+1/2; (ii) x+1, y, z+1/2; (iii) x, y1, z1/2.

Experimental details

Crystal data
Chemical formula[Cu2Mo2O7(C10H8N2)2]
Mr743.33
Crystal system, space groupOrthorhombic, Pbcn
Temperature (K)293
a, b, c (Å)11.839 (2), 9.108 (2), 21.319 (4)
V3)2298.8 (8)
Z4
Radiation typeMo Kα
µ (mm1)2.94
Crystal size (mm)0.50 × 0.42 × 0.38
Data collection
DiffractometerSiemens P4
diffractometer
Absorption correctionEmpirical (using intensity measurements)
(North et al., 1968)
Tmin, Tmax0.229, 0.325
No. of measured, independent and
observed [I > 2σ(I)] reflections
2750, 2016, 1549
Rint0.019
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.028, 0.069, 0.90
No. of reflections2016
No. of parameters191
H-atom treatmentAll H-atom parameters refined
Δρmax, Δρmin (e Å3)0.51, 0.90

Computer programs: XSCANS (Siemens, 1994a), XSCANS, SHELXTL (Siemens, 1994b), SHELXS86 (Sheldrick, 1990), SHELXL93 (Sheldrick, 1993), SHELXTL.

Selected geometric parameters (Å, º) top
Mo—O41.709 (4)Cu—O12.191 (3)
Mo—O21.721 (3)N1—C11.343 (5)
Mo—O11.732 (3)N1—C51.344 (5)
Mo—O31.8687 (8)N2—C81.332 (5)
Cu—N11.933 (3)N2—C91.339 (5)
Cu—N2i1.933 (3)C3—C61.489 (5)
O4—Mo—O2109.2 (2)O2—Mo—O3108.8 (2)
O4—Mo—O1109.3 (2)O1—Mo—O3110.1 (2)
O2—Mo—O1110.2 (2)N1—Cu—O1100.8 (1)
O4—Mo—O3109.3 (2)
Symmetry code: (i) x, y1, z+1/2.
 

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