Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270113018064/ku3104sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270113018064/ku3104Isup2.hkl |
CCDC reference: 958928
In recent years, increasing attention has been paid to niobium oxyfluorides due to their specific structure-related properties, such as ferroelectricity, piezoelectricity and second-order nonlinear optical activity (Hagerman & Poeppelmeier, 1995). The [NbOF5]2- anion has been employed as a building block to construct niobium oxyfluorides with isolated cluster or linear chain structures. This fact stems not only from their unique architectures but also from their wide applications. Up to now, niobium oxyfluorides based on the [NbOF5]2- anion have been synthesized and reported, e.g. [H2N(C2H4)2NH2][NbOF5] (Feng et al., 2010), (HNC6H6OH)2[Cu(py)4(NbOF5)2] (py is pyridine; Welk et al., 2002), (pyH)2[Cu(py)4(NbOF5)2] (Halasyamani et al., 1996), Cd(py)4NbOF5 (Guillory et al., 2006), (4-apyH)2[Cu(4-apy)4(NbOF5)2] (4-apy is pyridin-4-amine; Izumi et al., 2005), and Cd(3-apy)4NbOF5 and Cu(3-apy)4NbOF5 (3-apy is pyridin-3-amine; Izumi et al., 2005). However, in comparison with such well characterized niobium oxyfluorides based on the [NbOF5]2- anion, investigations on the [NbOF4]- anion are relatively rare, examples being (Hphen)[NbOF4].H2O (Hphen is 1,10-phenanthrolinium; Zhao et al., 2009), and NH4NbOF4, Ag(pyz)NbOF4 (pyz is pyrazine) and Cu(bpy)NbOF4.2H2O (bpy = bipyridine) (Lin & Maggard, 2010). It is of particular interest that the incorporation of a second transition metal, copper, may lead to novel niobium oxyfluorides with unexpected structures and properties. Accordingly, our research group is paying special attention to synthesizing and exploring copper oxyfluorides based on the [NbOF4]- anion. As an extension of known materials with structure-related properties, we have successfully isolated the title novel niobium–copper oxyfluoride, [Cu2(obpy)2][NbOF4], (I) (obpy is 2,2'-bipyridin-6-olate), based on the linear [NbOF4]- anion, by the hydrothermal method and characterized it by elemental analysis, energy-dispersive X-ray spectroscopy (EDS), IR spectroscopy, X-ray photoelectron spectroscopy (XPS) and X-ray single-crystal diffraction.
All chemicals were of reagent grade quality obtained from commercial sources and were used without further purification. Compound (I) was obtained by a hydrothermal method. Nb2O5 (0.27 g, 1 mmol) was dissolved in HF (0.56 g, 40 wt.%, 11.2 mmol) and kept at 383 K for 12 h. The solution was then cooled, and CuO (0.20 g, 2.5 mmol), 2,2'-bipyridine (0.24 g, 1.5 mmol), KOH (0.12 g, 2 mmol) and H2O (10 ml, 556 mmol) were added. The mixture was stirred for 30 min, and then transferred into a Teflon-lined stainless steel autoclave (50 ml) and heated at 443 K for 8 d. After the mixture had been cooled slowly to room temperature, dark-red crystals were obtained. The product was filtered off, washed with deionized water, purified ultrasonically and dried in a vacuum desiccator at ambient temperature. (yield 62%, based on Nb2O5). It is noted that 0.12 g KOH provided an alkaline environment for the formation of the 2,2'-bipyridin-6-olate ligand according to the Gillard mechanism (Gillard, 1975). Elemental analysis of C, H and N was performed with a Perkin–Elmer 240 analyser. Analysis, calculated for (I): C 36.62, H 2.29, N 8.54%; found: C 36.39, H 2.43, N 8.72%.
Crystal data, data collection and structure refinement details are summarized in Table 1. All H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C). In addition, the Cu atom was split into two sites with different oxidation states (Cu1 and Cu1'), according to the XPS results. The Cu1 and Cu1' sites were freely refined with a site-occupancy factor ratio of 0.5:0.5 (1:1).
The structural unit of (I) consists of one C2-symmetric [NbOF4]- anion and one C2-symmetric coordinated [Cu2(obpy)2]+ cation (Fig. 1). In the coordinated [Cu2(obpy)2]+ cation, the oxidation state of each Cu atom is disordered [Cu1 is CuI and Cu1' is CuII]; such disordered Cu sites are similar to what was observed in [Cu2(obpy)2][CuCl2] (Guo et al., 2007). Besides the weak Cu···Cu interaction of 2.39 Å, the disordered Cu sites are also coordinated by two N atoms from one obpy ligand and by one O atom from the other obpy ligand, respectively. The whole structure of the [NbOF4]- anion can be viewed as an infinite linear chain in which the central NbF4 fragments are connected to each other through two µ2-O atoms. The NbV metal centre is five-coordinated by four F atoms and one O atom in the first coordination shell, forming a square-pyramidal coordination geometry. The Nb—F and Nb—O bond lengths are 1.9151 (16)–1.9158 (16) and 1.749 (3) Å, respectively, consistent with those reported for known niobium oxyfluorides (Heier et al., 1998). These square pyramids are further connected to each other via trans O atoms [Nb—O = 2.185 (3) Å], forming an infinite linear {[NbOF4]-}n polyanion (Fig. 2a).
In addition, besides the electrostatic interactions between the [NbOF4]- and [Cu2(obpy)2]+ units, there are π–π stacking interactions between pyridine rings along the b axis. These pyridine rings are parallel to each other, with a centroid-to-centroid distance of 3.610 (2) Å. Such π–π stacking interactions between aromatic groups are rather common in coordination polymers (Li et al., 2003). It is worth noting that the [NbOF4]- and [Cu2(obpy)2]+ units are linked via nonclassical C—H···F hydrogen-bonding interactions; each [NbOF4]- anion is linked to four surrounding [Cu2(obpy)2]+ coordinated cations (Fig. 2b), giving rise to the supramolecular architecture (Fig. 3a). Obviously, these electrostatic, π–π stacking and hydrogen-bonding interactions are responsible for the chemical stability of (I). To understand fully the structure of (I), the topological approach is applied to simplify the supramolecular architecture. By considering the coordination and hydrogen bonding between linear [NbOF4]- anions and [Cu2(obpy)2]+ cations (each [Cu2(obpy)2]+ cation is considered as a single node), the supramolecular structure can be simplified as a (4,6)-connected network with the Schläfli symbol (44.62)(44.610.8) (Fig. 3b).
The EDS results for the single crystal of (I) indicate the presence of the elements Nb, Cu, F, O, C and N. The EDS results and elemental analysis are in agreement with the single-crystal X-ray structural analysis.
In the IR spectrum of (I) (Fig. 4), there are three characteristic asymmetric vibrations resulting from the [NbOF4]- anion, namely, ν(Nb═O), ν(Nb—O) and ν(Nb—F) at 900, 779 and 567 cm-1, respectively (Zhao et al., 2009). Comparing the IR spectrum of (I) with that of (Hphen)[NbOF4].H2O (Zhao et al., 2009), the Nb═O stretch is shifted from 906 to 900 cm-1, and the Nb—O and Nb—F vibrations are shifted from 791 to 779 cm-1 and from 582 to 567 cm-1, respectively. This is probably due to the fact that the [NbOF4]- anion is affected by the surrounding metal-coordinated [Cu2(obpy)2]+ cations. The peak at 418 cm-1 can be ascribed to ν(Cu—O) (Alimaje et al., 2011). In addition, in the high-frequency region of the IR spectrum, weak absorption bands observed at 3110 and 3062 cm-1 can be attributed to the νC—H vibration of the obpy groups, while in the low-frequency region, a series of absorptions in the range of 1621–1102 cm-1 (1621, 1600, 1547, 1494, 1462, 1378, 1298, 1266, 1171, 1123 and 1102 cm-1) should be assigned to the obpy ligands (Wang et al., 2009). The vibrations of the OH group were not found in the IR spectrum of (I), indicating that atoms O1 are not protonated. These results further confirm that the coordinated [Cu2(obpy)2]+ cation contains disordered oxidation states CuI and CuII. Again, these results are in agreement with the single-crystal X-ray diffraction analysis.
In order to confirm the oxidation states of Cu further by means of an additional experimental technique, XPS measurement of (I) was performed. The spin-orbit components (2p3/2 and 2p1/2) of the Cu2p peak were deconvoluted into two curves at approximately 932.2 and 952.0 eV (Fig. 5), confirming the presence of CuI in (I) (Cheng et al., 2005; Brust et al., 1997). Meanwhile, the typical shake-up lines (935–945 eV) of CuII were also observed, revealing the presence of a bivalent oxidation state in (I) (Avgouropoulos & Loannides, 2003). These results futher indicate that (I) contains disordered oxidation states CuI and CuII.
In summary, the title copper–niobium oxyfluoride, [Cu2(obpy)2][NbOF4], has been obtained by the hydrothermal method. Compound (I) enriches the family of known niobium oxyfluorides and features the first copper–niobium oxyfluoride based on the linear {[NbOF4]-}n polyanion. The successful synthesis of (I) indicates that many copper–niobium oxyfluorides with unexpected structures and interesting physical properties may be accessible using a similar method.
For related literature, see: Alimaje et al. (2011); Avgouropoulos & Loannides (2003); Brust et al. (1997); Cheng et al. (2005); Feng et al. (2010); Gillard (1975); Guillory et al. (2006); Guo et al. (2007); Hagerman & Poeppelmeier (1995); Halasyamani et al. (1996); Heier et al. (1998); Izumi et al. (2005); Li et al. (2003); Lin & Maggard (2010); Wang et al. (2009); Welk et al. (2002); Zhao et al. (2009).
Data collection: SMART (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
[Cu(C10H7N2O)][NbF4O] | F(000) = 1284 |
Mr = 654.34 | Dx = 2.118 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C2yc | Cell parameters from 4143 reflections |
a = 18.2718 (12) Å | θ = 2.3–28.3° |
b = 3.9347 (3) Å | µ = 2.67 mm−1 |
c = 29.0066 (19) Å | T = 296 K |
β = 100.188 (1)° | Block, dark-red |
V = 2052.5 (2) Å3 | 0.25 × 0.22 × 0.18 mm |
Z = 4 |
Bruker APEXII CCD area-detector diffractometer | 1803 independent reflections |
Radiation source: fine-focus sealed tube | 1744 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.020 |
ϕ and ω scans | θmax = 25.0°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | h = −21→19 |
Tmin = 0.555, Tmax = 0.645 | k = −4→3 |
4803 measured reflections | l = −29→34 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.021 | H-atom parameters constrained |
wR(F2) = 0.058 | w = 1/[σ2(Fo2) + (0.0285P)2 + 3.5708P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max = 0.001 |
1803 reflections | Δρmax = 0.31 e Å−3 |
165 parameters | Δρmin = −0.46 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.00189 (14) |
[Cu(C10H7N2O)][NbF4O] | V = 2052.5 (2) Å3 |
Mr = 654.34 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 18.2718 (12) Å | µ = 2.67 mm−1 |
b = 3.9347 (3) Å | T = 296 K |
c = 29.0066 (19) Å | 0.25 × 0.22 × 0.18 mm |
β = 100.188 (1)° |
Bruker APEXII CCD area-detector diffractometer | 1803 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | 1744 reflections with I > 2σ(I) |
Tmin = 0.555, Tmax = 0.645 | Rint = 0.020 |
4803 measured reflections |
R[F2 > 2σ(F2)] = 0.021 | 0 restraints |
wR(F2) = 0.058 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.31 e Å−3 |
1803 reflections | Δρmin = −0.46 e Å−3 |
165 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' | 0.22824 (17) | 1.2301 (9) | 0.53642 (14) | 0.0252 (11) | 0.50 |
Cu1 | 0.2283 (2) | 1.2231 (11) | 0.53647 (16) | 0.0444 (16) | 0.50 |
Nb1 | 0.5000 | 0.17503 (7) | 0.7500 | 0.02394 (13) | |
C1 | 0.36714 (13) | 0.9089 (7) | 0.53007 (8) | 0.0348 (6) | |
C2 | 0.43305 (15) | 0.7326 (7) | 0.54958 (10) | 0.0411 (6) | |
H2 | 0.4691 | 0.6880 | 0.5315 | 0.049* | |
C3 | 0.44304 (15) | 0.6294 (7) | 0.59498 (10) | 0.0413 (6) | |
H3 | 0.4859 | 0.5105 | 0.6076 | 0.050* | |
C4 | 0.38995 (15) | 0.6991 (7) | 0.62298 (10) | 0.0373 (6) | |
H4 | 0.3971 | 0.6302 | 0.6541 | 0.045* | |
C5 | 0.32704 (13) | 0.8721 (6) | 0.60317 (8) | 0.0308 (5) | |
C6 | 0.26597 (13) | 0.9676 (6) | 0.62803 (8) | 0.0310 (5) | |
C7 | 0.26389 (15) | 0.8821 (7) | 0.67426 (9) | 0.0391 (6) | |
H7 | 0.3027 | 0.7612 | 0.6920 | 0.047* | |
C8 | 0.20307 (16) | 0.9801 (8) | 0.69326 (9) | 0.0444 (7) | |
H8 | 0.2002 | 0.9223 | 0.7240 | 0.053* | |
C9 | 0.14667 (16) | 1.1629 (7) | 0.66682 (10) | 0.0436 (7) | |
H9 | 0.1058 | 1.2318 | 0.6795 | 0.052* | |
C10 | 0.15164 (15) | 1.2424 (7) | 0.62124 (10) | 0.0397 (6) | |
H10 | 0.1136 | 1.3665 | 0.6032 | 0.048* | |
F1 | 0.51425 (10) | 0.2299 (4) | 0.68656 (5) | 0.0438 (4) | |
F2 | 0.39560 (9) | 0.2446 (5) | 0.72939 (6) | 0.0516 (5) | |
O2 | 0.5000 | −0.2695 (6) | 0.7500 | 0.0539 (8) | |
N1 | 0.31612 (11) | 0.9730 (5) | 0.55723 (6) | 0.0312 (5) | |
N2 | 0.21043 (12) | 1.1443 (6) | 0.60217 (7) | 0.0331 (5) | |
O1 | 0.14525 (10) | 1.4915 (6) | 0.51323 (6) | 0.0460 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1' | 0.0199 (17) | 0.0338 (16) | 0.021 (2) | 0.0082 (12) | 0.0007 (13) | 0.0010 (13) |
Cu1 | 0.045 (3) | 0.063 (3) | 0.025 (3) | 0.0097 (18) | 0.0095 (18) | 0.0014 (17) |
Nb1 | 0.03008 (19) | 0.01473 (17) | 0.02723 (18) | 0.000 | 0.00566 (12) | 0.000 |
C1 | 0.0333 (13) | 0.0404 (14) | 0.0305 (13) | 0.0051 (11) | 0.0051 (10) | −0.0019 (11) |
C2 | 0.0331 (14) | 0.0477 (16) | 0.0425 (16) | 0.0093 (11) | 0.0068 (12) | 0.0008 (12) |
C3 | 0.0340 (14) | 0.0412 (15) | 0.0459 (15) | 0.0070 (12) | −0.0009 (11) | 0.0047 (13) |
C4 | 0.0376 (14) | 0.0402 (15) | 0.0315 (13) | −0.0014 (11) | −0.0006 (10) | 0.0080 (11) |
C5 | 0.0323 (12) | 0.0294 (12) | 0.0290 (12) | −0.0057 (10) | 0.0011 (9) | −0.0002 (10) |
C6 | 0.0341 (13) | 0.0326 (13) | 0.0261 (12) | −0.0095 (10) | 0.0043 (10) | −0.0024 (10) |
C7 | 0.0460 (15) | 0.0385 (14) | 0.0317 (13) | −0.0128 (12) | 0.0036 (11) | 0.0010 (11) |
C8 | 0.0579 (17) | 0.0490 (17) | 0.0298 (13) | −0.0174 (14) | 0.0170 (12) | −0.0041 (12) |
C9 | 0.0488 (16) | 0.0435 (16) | 0.0448 (15) | −0.0144 (13) | 0.0252 (13) | −0.0104 (13) |
C10 | 0.0351 (14) | 0.0420 (15) | 0.0435 (15) | −0.0038 (11) | 0.0111 (12) | −0.0062 (12) |
F1 | 0.0567 (10) | 0.0464 (9) | 0.0302 (8) | 0.0028 (7) | 0.0129 (7) | 0.0028 (6) |
F2 | 0.0295 (8) | 0.0691 (12) | 0.0539 (10) | 0.0000 (7) | 0.0012 (7) | −0.0072 (8) |
O2 | 0.089 (2) | 0.0160 (12) | 0.0587 (19) | 0.000 | 0.0174 (17) | 0.000 |
N1 | 0.0301 (10) | 0.0377 (12) | 0.0249 (10) | 0.0026 (9) | 0.0029 (8) | −0.0003 (9) |
N2 | 0.0328 (11) | 0.0383 (12) | 0.0286 (10) | −0.0020 (9) | 0.0066 (8) | −0.0029 (9) |
O1 | 0.0418 (10) | 0.0704 (14) | 0.0267 (9) | 0.0222 (10) | 0.0086 (7) | 0.0059 (9) |
Cu1—O1 | 1.874 (4) | C3—C4 | 1.398 (4) |
Cu1—N1 | 1.888 (4) | C3—H3 | 0.9300 |
Cu1—N2 | 2.014 (5) | C4—C5 | 1.372 (4) |
Cu1'—O1 | 1.857 (4) | C4—H4 | 0.9300 |
Cu1'—N1 | 1.903 (4) | C5—N1 | 1.371 (3) |
Cu1'—N2 | 2.019 (5) | C5—C6 | 1.480 (3) |
Cu1'—Cu1'i | 2.391 (8) | C6—N2 | 1.344 (3) |
Cu1'—Cu1i | 2.3932 (10) | C6—C7 | 1.390 (3) |
Nb1—O2 | 1.749 (3) | C7—C8 | 1.380 (4) |
Nb1—F2ii | 1.9151 (16) | C7—H7 | 0.9300 |
Nb1—F2 | 1.9151 (16) | C8—C9 | 1.374 (4) |
Nb1—F1ii | 1.9158 (16) | C8—H8 | 0.9300 |
Nb1—F1 | 1.9158 (16) | C9—C10 | 1.377 (4) |
Nb1—O2iii | 2.185 (3) | C9—H9 | 0.9300 |
C1—O1i | 1.297 (3) | C10—N2 | 1.349 (3) |
C1—N1 | 1.346 (3) | C10—H10 | 0.9300 |
C1—C2 | 1.418 (4) | O2—Nb1iv | 2.185 (2) |
C2—C3 | 1.359 (4) | O1—C1i | 1.297 (3) |
C2—H2 | 0.9300 | ||
O1—Cu1'—N1 | 176.5 (3) | C3—C2—H2 | 120.3 |
O1—Cu1'—N2 | 100.20 (19) | C1—C2—H2 | 120.3 |
N1—Cu1'—N2 | 83.08 (16) | C2—C3—C4 | 121.1 (3) |
O1—Cu1'—Cu1'i | 91.2 (2) | C2—C3—H3 | 119.5 |
N1—Cu1'—Cu1'i | 85.49 (19) | C4—C3—H3 | 119.5 |
N2—Cu1'—Cu1'i | 168.6 (2) | C5—C4—C3 | 118.1 (2) |
O1—Cu1'—Cu1i | 90.83 (14) | C5—C4—H4 | 121.0 |
N1—Cu1'—Cu1i | 85.87 (14) | C3—C4—H4 | 121.0 |
N2—Cu1'—Cu1i | 168.92 (9) | N1—C5—C4 | 121.2 (2) |
Cu1'i—Cu1'—Cu1i | 0.65 (19) | N1—C5—C6 | 114.0 (2) |
O1—Cu1—N1 | 175.7 (3) | C4—C5—C6 | 124.8 (2) |
O1—Cu1—N2 | 99.8 (2) | N2—C6—C7 | 121.1 (2) |
N1—Cu1—N2 | 83.62 (19) | N2—C6—C5 | 114.8 (2) |
O1—Cu1—Cu1'i | 90.74 (16) | C7—C6—C5 | 124.1 (2) |
N1—Cu1—Cu1'i | 85.76 (16) | C8—C7—C6 | 118.6 (3) |
N2—Cu1—Cu1'i | 169.30 (15) | C8—C7—H7 | 120.7 |
O1—Cu1—Cu1i | 90.3 (3) | C6—C7—H7 | 120.7 |
N1—Cu1—Cu1i | 86.1 (2) | C9—C8—C7 | 120.1 (2) |
N2—Cu1—Cu1i | 169.6 (3) | C9—C8—H8 | 120.0 |
Cu1'i—Cu1—Cu1i | 0.65 (19) | C7—C8—H8 | 120.0 |
O2—Nb1—F2ii | 98.22 (5) | C8—C9—C10 | 119.0 (3) |
O2—Nb1—F2 | 98.22 (6) | C8—C9—H9 | 120.5 |
F2ii—Nb1—F2 | 163.56 (11) | C10—C9—H9 | 120.5 |
O2—Nb1—F1ii | 96.47 (5) | N2—C10—C9 | 121.4 (3) |
F2ii—Nb1—F1ii | 88.91 (8) | N2—C10—H10 | 119.3 |
F2—Nb1—F1ii | 89.24 (8) | C9—C10—H10 | 119.3 |
O2—Nb1—F1 | 96.47 (5) | Nb1—O2—Nb1iv | 180.0 |
F2ii—Nb1—F1 | 89.24 (8) | C1—N1—C5 | 121.2 (2) |
F2—Nb1—F1 | 88.91 (8) | C1—N1—Cu1 | 123.3 (2) |
F1ii—Nb1—F1 | 167.05 (10) | C5—N1—Cu1 | 115.5 (2) |
O2—Nb1—O2iii | 180.000 (2) | C1—N1—Cu1' | 123.1 (2) |
F2ii—Nb1—O2iii | 81.78 (5) | C5—N1—Cu1' | 115.6 (2) |
F2—Nb1—O2iii | 81.78 (6) | C6—N2—C10 | 119.8 (2) |
F1ii—Nb1—O2iii | 83.53 (5) | C6—N2—Cu1 | 112.0 (2) |
F1—Nb1—O2iii | 83.53 (5) | C10—N2—Cu1 | 128.2 (2) |
O1i—C1—N1 | 119.3 (2) | C6—N2—Cu1' | 112.44 (18) |
O1i—C1—C2 | 121.7 (2) | C10—N2—Cu1' | 127.8 (2) |
N1—C1—C2 | 119.0 (2) | C1i—O1—Cu1' | 120.6 (2) |
C3—C2—C1 | 119.5 (3) | C1i—O1—Cu1 | 120.7 (2) |
Symmetry codes: (i) −x+1/2, −y+5/2, −z+1; (ii) −x+1, y, −z+3/2; (iii) x, y+1, z; (iv) x, y−1, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···F1 | 0.93 | 2.51 | 3.162 (3) | 127 |
C8—H8···F2v | 0.93 | 2.49 | 3.252 (3) | 139 |
Symmetry code: (v) −x+1/2, y+1/2, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C10H7N2O)][NbF4O] |
Mr | 654.34 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 296 |
a, b, c (Å) | 18.2718 (12), 3.9347 (3), 29.0066 (19) |
β (°) | 100.188 (1) |
V (Å3) | 2052.5 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.67 |
Crystal size (mm) | 0.25 × 0.22 × 0.18 |
Data collection | |
Diffractometer | Bruker APEXII CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2008) |
Tmin, Tmax | 0.555, 0.645 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4803, 1803, 1744 |
Rint | 0.020 |
(sin θ/λ)max (Å−1) | 0.594 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.021, 0.058, 1.07 |
No. of reflections | 1803 |
No. of parameters | 165 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.31, −0.46 |
Computer programs: SMART (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
Cu1—O1 | 1.874 (4) | Cu1'—N2 | 2.019 (5) |
Cu1—N1 | 1.888 (4) | Nb1—O2 | 1.749 (3) |
Cu1—N2 | 2.014 (5) | Nb1—F2 | 1.9151 (16) |
Cu1'—O1 | 1.857 (4) | Nb1—F1 | 1.9158 (16) |
Cu1'—N1 | 1.903 (4) | Nb1—O2i | 2.185 (3) |
Symmetry code: (i) x, y+1, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···F1 | 0.93 | 2.51 | 3.162 (3) | 127.2 |
C8—H8···F2ii | 0.93 | 2.49 | 3.252 (3) | 138.7 |
Symmetry code: (ii) −x+1/2, y+1/2, −z+3/2. |
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