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Acta Cryst. (2007). E63, m2282    [ doi:10.1107/S1600536807037804 ]

[mu]-4,4'-Bipyridine-[kappa]2N:N'-bis[aqua(nitrato-[kappa]O)(1,10-phenanthroline-[kappa]2N,N')copper(II)] dinitrate

Z.-X. Du and J.-X. Li

Abstract top

The title compound, [Cu2(NO3)2(C10H8N2)(C12H8N2)2(H2O)2](NO3)2, comprises a binuclear copper complex cation and two nitrate anions. In the doubly-charged bridged dicopper cation, each Cu atom is five-coordinated in a distorted square-pyramidal geometry, formed by one O atom of the coordinated water molecule, one O atom of a coordinated nitrate anion, two N atoms from the bidentate 1,10-phenanthroline (phen) ligand and another N atom from the 4,4'-bipyridine (bipy) ligand. The bipy ligand bridges the Cu atoms to give a centrosymmetric binuclear structure. The complex is stabilized by hydrogen bonds and aromatic ring-stacking interactions [average interplanar distance 3.3139 (2) Å and ring-centroid separation 3.7971 (9) Å.

Comment top

In the previous literatures, binuclear copper complexes containing (phen-Cu-bipy-Cu-phen) subunit (Blake et al., 1998; Wu et al., 2002; Lin et al., 2005) have been reported. In our paper, we describe another new compound containing (phen-Cu-bipy-Cu-phen) subunit, (I), (Fig.1).

Compound (I) is comprised of a binuclear copper complex cation and two nitrate anions. In the doubly charged bridged dicopper cation, each Cu center has distorted square-pyramidal geometry, formed by one O atom of the coordinated water molecule, one O atom of coordinated nitrate anion, two N atoms from bidentate 1,10-phenanthroline (phen) ligand and another N atom from 4,4'-bipyridine (bipy) (Table 1). The plane N1/N2/O1/N3 defines the base of the pyramid while water O7 occupies the apex. The distance from Cu1 to the least-squares plane N1/N2/O1/N3 is 0.1924 (4)Å towards O7. The bipy ligand bridge the Cu atoms to give this binuclear structure.

The water molecules and coordinated nitrate O atoms take part in intermolecular hydrogen bonds interactions and they join complex cations into a one-dimensional chain structure along a axis (Fig. 2 and Table 2). The chains are further expanded into two-dimensional network via the π-π stacking between 1,10-phenanthroline rings of adjacent chains of (I) (Fig. 3). The dihedral angle of aromatics involved in stacking is 0.0002 (3)°. Interplanar average distance and ring-centroid separation distance are 3.3139 (2) Å, 3.7971 (9) Å, respectively.

Related literature top

For related literature, see: Blake et al. (1998); Wu et al. (2002); Lin et al. (2005).

Experimental top

A 10 ml water solution of Cu(NO)3·3H2O (0.242 g,1 mmol) was dropped into 10 ml me thanol solution of 4,4'-bipyridine (0.078 g, 0.5 mmol) and 1,10-phenanthroline (0.18 g,1 mmol) to be stirred for 4 h at 333 K. The filtrate stayed in air for about one week to obtain blue block-shaped crystals. Analysis, found (%): C 43.85, H 3.05, N 15.16. C34H28Cu2N10O14 requires (%): C 43.98, H 3.02, N 15.09.

Refinement top

H atoms were positioned geometrically with C—H = 0.93 Å, O—H = 0.82 Å, and treated as riding atoms, with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(O).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2; data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2004); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing the atom-numbering scheme. Atoms with the suffix A are are at the symmetry position (−x + 1, −y + 2, −z + 1).
[Figure 2] Fig. 2. Packing diagram, showing the one-dimensional chain structure of (I), linked via hydrogen bonds (dashed lines). H atoms on C atoms and uncoordinated nitrate anions have been omitted for clarity.
[Figure 3] Fig. 3. The π–π stacking diagram between 1,10-phenanthroline rings of adjacent chains of (I). H atoms on C atoms and uncoordinated nitrate anions have been omitted.
µ-4,4'-Bipyridine-κ2N:N'-bis[aqua(nitrato-κO)(1,10- phenanthroline-κ2N,N')copper(II)] dinitrate top
Crystal data top
[Cu2(NO3)2(C10H8N2)(C12H8N2)2(H2O)2](NO3)2Z = 1
Mr = 927.76F000 = 472
Triclinic, P1Dx = 1.723 Mg m−3
Hall symbol: -P 1Mo Kα radiation
λ = 0.71073 Å
a = 7.3754 (18) ÅCell parameters from 3225 reflections
b = 8.925 (2) Åθ = 2.7–27.0º
c = 13.812 (3) ŵ = 1.28 mm−1
α = 92.347 (2)ºT = 291 (2) K
β = 97.596 (2)ºBlock, blue
γ = 96.311 (3)º0.37 × 0.27 × 0.21 mm
V = 894.3 (4) Å3
Data collection top
Bruker APEXII CCD area-detector
diffractometer		3200 independent reflections
Radiation source: fine-focus sealed tube2909 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.021
T = 291(2) Kθmax = 25.5º
φ and ω scansθmin = 2.7º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −8→8
Tmin = 0.647, Tmax = 0.776k = −10→10
6155 measured reflectionsl = −16→16
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.050H-atom parameters constrained
wR(F2) = 0.227  w = 1/[σ2(Fo2) + (0.183P)2 + 1.6705P]
where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max < 0.001
3200 reflectionsΔρmax = 0.89 e Å−3
271 parametersΔρmin = −0.76 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Cu2(NO3)2(C10H8N2)(C12H8N2)2(H2O)2](NO3)2γ = 96.311 (3)º
Mr = 927.76V = 894.3 (4) Å3
Triclinic, P1Z = 1
a = 7.3754 (18) ÅMo Kα
b = 8.925 (2) ŵ = 1.28 mm−1
c = 13.812 (3) ÅT = 291 (2) K
α = 92.347 (2)º0.37 × 0.27 × 0.21 mm
β = 97.596 (2)º
Data collection top
Bruker APEXII CCD area-detector
diffractometer		3200 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2909 reflections with I > 2σ(I)
Tmin = 0.647, Tmax = 0.776Rint = 0.021
6155 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.050271 parameters
wR(F2) = 0.227H-atom parameters constrained
S = 1.02Δρmax = 0.89 e Å−3
3200 reflectionsΔρmin = −0.76 e Å−3
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 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cu10.69132 (8)0.51338 (6)0.71023 (4)0.0247 (3)
O10.8055 (5)0.4093 (5)0.6066 (3)0.0350 (9)
O21.0496 (6)0.5437 (6)0.6817 (3)0.0462 (11)
O31.0720 (6)0.3763 (6)0.5659 (3)0.0506 (12)
O40.4104 (7)0.0751 (6)0.7586 (4)0.0540 (12)
O50.1351 (9)0.0598 (9)0.6823 (5)0.082 (2)
O60.1944 (10)−0.0793 (7)0.8020 (5)0.0754 (18)
O70.4292 (6)0.3593 (5)0.6762 (4)0.0452 (11)
H1W0.44310.27740.69930.068*
H2W0.33030.35870.64040.068*
N10.6613 (6)0.6354 (5)0.8332 (3)0.0260 (9)
N20.7736 (6)0.3662 (5)0.8101 (3)0.0255 (9)
N30.6235 (7)0.6792 (5)0.6252 (3)0.0321 (10)
N40.9803 (6)0.4446 (5)0.6181 (3)0.0322 (10)
N50.2454 (8)0.0181 (6)0.7465 (4)0.0423 (12)
C10.8307 (8)0.2313 (6)0.7951 (4)0.0328 (12)
H10.83630.19600.73140.039*
C20.8818 (8)0.1423 (7)0.8717 (5)0.0381 (13)
H2A0.92070.04870.85890.046*
C30.8750 (8)0.1918 (7)0.9661 (5)0.0397 (14)
H3A0.90840.13181.01740.048*
C40.8170 (7)0.3343 (6)0.9852 (4)0.0293 (11)
C50.8056 (8)0.3986 (7)1.0814 (4)0.0358 (13)
H5A0.83740.34481.13610.043*
C60.7489 (8)0.5364 (7)1.0925 (4)0.0370 (13)
H6A0.74350.57611.15520.044*
C70.6971 (7)0.6229 (6)1.0106 (4)0.0314 (12)
C80.6355 (8)0.7680 (7)1.0179 (4)0.0371 (13)
H80.62650.81321.07860.044*
C90.5897 (8)0.8397 (6)0.9341 (5)0.0379 (13)
H90.54960.93470.93790.045*
C100.6025 (8)0.7715 (6)0.8425 (4)0.0323 (12)
H100.56930.82210.78650.039*
C110.7076 (7)0.5630 (6)0.9160 (4)0.0244 (10)
C120.7669 (7)0.4173 (6)0.9032 (4)0.0249 (10)
C130.4474 (9)0.6993 (7)0.5978 (5)0.0449 (15)
H130.35610.62660.61220.054*
C140.3950 (9)0.8222 (7)0.5495 (5)0.0401 (14)
H140.27060.83140.53250.048*
C150.5268 (8)0.9328 (6)0.5258 (4)0.0295 (11)
C160.7091 (10)0.9111 (8)0.5549 (6)0.0521 (18)
H160.80290.98180.54070.063*
C170.7528 (9)0.7864 (8)0.6044 (5)0.0480 (17)
H170.87610.77600.62410.058*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0303 (4)0.0238 (4)0.0218 (4)0.0077 (3)0.0047 (3)0.0055 (3)
O10.029 (2)0.047 (2)0.0290 (19)0.0074 (17)0.0032 (15)−0.0030 (16)
O20.040 (2)0.055 (3)0.043 (2)0.001 (2)0.0053 (19)0.000 (2)
O30.047 (3)0.072 (3)0.041 (2)0.033 (2)0.015 (2)0.009 (2)
O40.050 (3)0.050 (3)0.060 (3)0.002 (2)0.001 (2)0.008 (2)
O50.059 (3)0.100 (5)0.083 (4)0.008 (3)−0.011 (3)0.036 (4)
O60.085 (4)0.057 (3)0.090 (4)0.010 (3)0.027 (3)0.039 (3)
O70.033 (2)0.035 (2)0.064 (3)0.0007 (18)−0.007 (2)0.014 (2)
N10.028 (2)0.024 (2)0.027 (2)0.0036 (17)0.0069 (17)0.0044 (16)
N20.025 (2)0.022 (2)0.030 (2)0.0051 (17)0.0061 (17)0.0044 (17)
N30.041 (3)0.031 (2)0.027 (2)0.009 (2)0.0051 (19)0.0078 (18)
N40.033 (2)0.040 (3)0.026 (2)0.010 (2)0.0070 (18)0.0111 (19)
N50.054 (3)0.031 (3)0.045 (3)0.010 (2)0.014 (2)0.004 (2)
C10.032 (3)0.026 (3)0.042 (3)0.004 (2)0.006 (2)0.007 (2)
C20.038 (3)0.025 (3)0.053 (4)0.008 (2)0.003 (3)0.008 (2)
C30.033 (3)0.037 (3)0.050 (4)0.006 (3)0.002 (2)0.023 (3)
C40.023 (2)0.032 (3)0.032 (3)0.000 (2)0.002 (2)0.011 (2)
C50.032 (3)0.047 (3)0.025 (3)−0.003 (3)−0.003 (2)0.014 (2)
C60.032 (3)0.053 (4)0.024 (3)−0.006 (3)0.003 (2)−0.002 (2)
C70.025 (3)0.037 (3)0.032 (3)−0.003 (2)0.008 (2)−0.001 (2)
C80.037 (3)0.038 (3)0.035 (3)−0.002 (2)0.009 (2)−0.011 (2)
C90.038 (3)0.027 (3)0.051 (4)0.004 (2)0.015 (3)−0.005 (2)
C100.038 (3)0.023 (3)0.037 (3)0.007 (2)0.007 (2)0.002 (2)
C110.020 (2)0.027 (3)0.026 (2)−0.0016 (19)0.0067 (18)0.0010 (19)
C120.020 (2)0.028 (3)0.028 (2)0.004 (2)0.0020 (18)0.0089 (19)
C130.037 (3)0.032 (3)0.061 (4)−0.005 (3)−0.009 (3)0.016 (3)
C140.035 (3)0.034 (3)0.047 (3)−0.001 (2)−0.010 (2)0.014 (2)
C150.042 (3)0.027 (3)0.021 (2)0.008 (2)0.004 (2)0.003 (2)
C160.040 (4)0.054 (4)0.073 (5)0.016 (3)0.026 (3)0.038 (4)
C170.038 (3)0.052 (4)0.063 (4)0.020 (3)0.019 (3)0.028 (3)
Geometric parameters (Å, °) top
Cu1—N31.992 (5)C3—H3A0.9300
Cu1—O12.000 (4)C4—C121.410 (7)
Cu1—N22.025 (4)C4—C51.441 (8)
Cu1—N12.030 (4)C5—C61.351 (9)
Cu1—O72.230 (4)C5—H5A0.9300
O1—N41.280 (6)C6—C71.430 (8)
O2—N41.239 (7)C6—H6A0.9300
O3—N41.238 (6)C7—C111.406 (7)
O4—N51.253 (8)C7—C81.423 (8)
O5—N51.220 (8)C8—C91.367 (9)
O6—N51.243 (8)C8—H80.9300
O7—H1W0.8200C9—C101.400 (8)
O7—H2W0.8251C9—H90.9300
N1—C101.341 (7)C10—H100.9300
N1—C111.359 (7)C11—C121.429 (7)
N2—C11.336 (7)C13—C141.372 (8)
N2—C121.355 (7)C13—H130.9300
N3—C131.338 (8)C14—C151.387 (9)
N3—C171.343 (9)C14—H140.9300
C1—C21.386 (8)C15—C161.388 (9)
C1—H10.9300C15—C15i1.485 (10)
C2—C31.368 (10)C16—C171.376 (9)
C2—H2A0.9300C16—H160.9300
C3—C41.412 (8)C17—H170.9300
N3—Cu1—O193.23 (18)C3—C4—C5124.7 (5)
N3—Cu1—N2172.57 (18)C6—C5—C4120.5 (5)
O1—Cu1—N291.76 (17)C6—C5—H5A119.8
N3—Cu1—N192.10 (18)C4—C5—H5A119.8
O1—Cu1—N1161.67 (18)C5—C6—C7121.9 (5)
N2—Cu1—N181.49 (17)C5—C6—H6A119.1
N3—Cu1—O798.37 (19)C7—C6—H6A119.1
O1—Cu1—O792.06 (18)C11—C7—C8116.8 (5)
N2—Cu1—O786.94 (17)C11—C7—C6118.8 (5)
N1—Cu1—O7104.49 (18)C8—C7—C6124.3 (5)
N4—O1—Cu1111.1 (3)C9—C8—C7118.9 (5)
Cu1—O7—H1W109.5C9—C8—H8120.5
Cu1—O7—H2W136.7C7—C8—H8120.5
H1W—O7—H2W113.0C8—C9—C10120.6 (5)
C10—N1—C11118.0 (5)C8—C9—H9119.7
C10—N1—Cu1129.5 (4)C10—C9—H9119.7
C11—N1—Cu1112.5 (3)N1—C10—C9121.9 (5)
C1—N2—C12118.7 (5)N1—C10—H10119.0
C1—N2—Cu1128.6 (4)C9—C10—H10119.0
C12—N2—Cu1112.6 (3)N1—C11—C7123.7 (5)
C13—N3—C17117.3 (5)N1—C11—C12116.5 (4)
C13—N3—Cu1121.4 (4)C7—C11—C12119.9 (5)
C17—N3—Cu1120.7 (4)N2—C12—C4123.0 (5)
O3—N4—O2123.2 (5)N2—C12—C11116.9 (4)
O3—N4—O1118.3 (5)C4—C12—C11120.1 (5)
O2—N4—O1118.5 (4)N3—C13—C14123.2 (6)
O5—N5—O6120.3 (7)N3—C13—H13118.4
O5—N5—O4120.5 (6)C14—C13—H13118.4
O6—N5—O4119.2 (6)C13—C14—C15120.3 (6)
N2—C1—C2122.0 (5)C13—C14—H14119.8
N2—C1—H1119.0C15—C14—H14119.8
C2—C1—H1119.0C14—C15—C16116.1 (5)
C3—C2—C1120.1 (5)C14—C15—C15i121.2 (7)
C3—C2—H2A119.9C16—C15—C15i122.7 (7)
C1—C2—H2A119.9C17—C16—C15120.8 (6)
C2—C3—C4119.8 (5)C17—C16—H16119.6
C2—C3—H3A120.1C15—C16—H16119.6
C4—C3—H3A120.1N3—C17—C16122.3 (6)
C12—C4—C3116.5 (5)N3—C17—H17118.9
C12—C4—C5118.8 (5)C16—C17—H17118.9
N3—Cu1—O1—N497.0 (4)C5—C6—C7—C11−0.7 (8)
N2—Cu1—O1—N4−77.5 (4)C5—C6—C7—C8179.6 (5)
N1—Cu1—O1—N4−9.7 (7)C11—C7—C8—C90.3 (8)
O7—Cu1—O1—N4−164.5 (4)C6—C7—C8—C9−180.0 (5)
N3—Cu1—N1—C104.4 (5)C7—C8—C9—C100.2 (9)
O1—Cu1—N1—C10111.3 (6)C11—N1—C10—C90.6 (8)
N2—Cu1—N1—C10−179.4 (5)Cu1—N1—C10—C9179.8 (4)
O7—Cu1—N1—C10−94.8 (5)C8—C9—C10—N1−0.7 (9)
N3—Cu1—N1—C11−176.3 (4)C10—N1—C11—C70.1 (8)
O1—Cu1—N1—C11−69.4 (7)Cu1—N1—C11—C7−179.3 (4)
N2—Cu1—N1—C11−0.1 (3)C10—N1—C11—C12179.1 (4)
O7—Cu1—N1—C1184.5 (4)Cu1—N1—C11—C12−0.3 (6)
N3—Cu1—N2—C1−148.8 (13)C8—C7—C11—N1−0.5 (8)
O1—Cu1—N2—C1−16.6 (5)C6—C7—C11—N1179.8 (5)
N1—Cu1—N2—C1−179.5 (5)C8—C7—C11—C12−179.5 (5)
O7—Cu1—N2—C175.4 (5)C6—C7—C11—C120.8 (8)
N3—Cu1—N2—C1231.2 (15)C1—N2—C12—C4−0.3 (8)
O1—Cu1—N2—C12163.4 (4)Cu1—N2—C12—C4179.8 (4)
N1—Cu1—N2—C120.5 (3)C1—N2—C12—C11179.1 (5)
O7—Cu1—N2—C12−104.6 (4)Cu1—N2—C12—C11−0.9 (6)
O1—Cu1—N3—C13115.9 (5)C3—C4—C12—N2−0.3 (8)
N2—Cu1—N3—C13−112.0 (14)C5—C4—C12—N2179.9 (5)
N1—Cu1—N3—C13−81.6 (5)C3—C4—C12—C11−179.7 (5)
O7—Cu1—N3—C1323.4 (5)C5—C4—C12—C110.5 (8)
O1—Cu1—N3—C17−73.1 (5)N1—C11—C12—N20.8 (7)
N2—Cu1—N3—C1759.0 (15)C7—C11—C12—N2179.9 (4)
N1—Cu1—N3—C1789.3 (5)N1—C11—C12—C4−179.8 (4)
O7—Cu1—N3—C17−165.7 (5)C7—C11—C12—C4−0.7 (8)
Cu1—O1—N4—O3172.2 (4)C17—N3—C13—C140.6 (10)
Cu1—O1—N4—O2−6.7 (6)Cu1—N3—C13—C14171.9 (5)
C12—N2—C1—C20.5 (8)N3—C13—C14—C150.5 (11)
Cu1—N2—C1—C2−179.5 (4)C13—C14—C15—C16−0.7 (9)
N2—C1—C2—C3−0.1 (9)C13—C14—C15—C15i−179.6 (7)
C1—C2—C3—C4−0.5 (9)C14—C15—C16—C17−0.1 (10)
C2—C3—C4—C120.6 (8)C15i—C15—C16—C17178.7 (7)
C2—C3—C4—C5−179.5 (5)C13—N3—C17—C16−1.5 (11)
C12—C4—C5—C6−0.4 (8)Cu1—N3—C17—C16−172.8 (6)
C3—C4—C5—C6179.8 (6)C15—C16—C17—N31.3 (12)
C4—C5—C6—C70.5 (9)
Symmetry codes: (i) −x+1, −y+2, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O7—H2W···O3ii0.832.072.886 (6)172
Symmetry codes: (ii) x−1, y, z.
Table 1
Selected geometric parameters (Å, °) top
Cu1—N31.992 (5)Cu1—N12.030 (4)
Cu1—O12.000 (4)Cu1—O72.230 (4)
Cu1—N22.025 (4)
N3—Cu1—O193.23 (18)N2—Cu1—N181.49 (17)
O1—Cu1—N291.76 (17)O1—Cu1—O792.06 (18)
N3—Cu1—N192.10 (18)N1—Cu1—O7104.49 (18)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O7—H2W···O3i0.832.072.886 (6)172
Symmetry codes: (i) x−1, y, z.
Acknowledgements top

This work was supported by the National Natural Science Foundation of China (grant No. 20471026) and the Natural Science Foundation of Henan province (grant No. 0311021200).

references
References top

Blake, A. J., Hill, S. J., Hubberstey, P. & Wan-Sheung, L. (1998). J. Chem. Soc. Dalton Trans. pp. 909–915.

Bruker (2004). APEX2, SAINT and SHELXTL. Bruker AXS Inc., Madison, Wisconsin, USA.

Lin, X.-J., Shen, Z., Li, Y.-Z., Uno, H., Song, Y., Xu, H.-J. & You, X.-Z. (2005). J. Coord. Chem. 58, 1139–1144.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.

Wu, C.-D., Zhan, X.-P., Lu, C.-Z. & Zhuang, H.-H. (2002). Chin. J. Struct. Chem. 21, 525–529.