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Acta Cryst. (2007). E63, m1467-m1468    [ doi:10.1107/S1600536807019551 ]

catena-Poly[[[diaquadinitratocopper(II)]-[mu]-4,4'-bipyridine] hemihydrate]

X.-C. Lin, H. Yin and Y. Lin

Abstract top

The title compound, {[Cu(C10H8N2)(NO3)2(H2O)2]·0.5H2O}n, has a linear polymeric structure, with the bridging ligand 4,4'-bipyridine (bipy) connecting the CuII ions. Each ion lies on an inversion center and has a distorted octahedral environment, being coordinated by two bipy ligands, two nitrate anions and two water molecules [Cu-N = 2.010 (3) Å and Cu-O = 1.981 (3) and 2.414 (3) Å]. In the crystal structure, the linear polymeric chains, propagating in two directions, are linked by intermolecular O-H...O hydrogen bonds, resulting in a three-dimensional supramolecular network, which has channels parallel to the c axis containing the water molecules of crystallization. The water molecule is equally disordered over two positions.

Comment top

Supramolecular architectures based on –M-bipy-M– have been receiving increasing attention, which are often extended through weaker interactions including hydrogen bonding and πi-πi stacking (Woodward et al., 2006; Lu et al., 2006; Ghosh et al., 2005). In this work, we chose 4,4'-bipyridine as a spacer ligand to react with a copper salt, resulting in the novel one-dimensional title compound, {[Cu(C10H8N2)(NO3)2(H2O)2].0.5(H2O)}n (I), which are linked into three-dimensional architecture by intermolecular hydrogen bonds.

Part of the chain structure of (I) is shown in Fig. 1. Each Cu (II) center is situated on an inversion center, coordinated by two N atoms of two bridging bipy ligands, two water molecules and two nitrato anions in a distorted octahedral environment. The bipy ligand bridges the adjacent Cu(II) centers, leading to the formation of linear –Cu-bipy-Cu- chains in which the distance of two neighboring Cu(II) centers is 11.043 (4) Å, and the nearest Cu···Cu (x + 1/2, -y + 1, -z - 1/2) interchain separation is 7.058 (3) Å.

In the packing diagram, the linear chains are arranged in a cross-like fashion and linked by numerous intermolecular hydrogen bonds O—H···O between the coordinated water molecules and nitrato anions (Table 2) (Fig. 2), resulting in a three-dimensional supramolecular array. The rhombic channels running along

the c axis (Fig. 2) are filled with the disordered crystalline water molecules.

Related literature top

For related literature, see: Ghosh et al. (2005); Lu et al. (2006); Woodward et al. (2006).

Experimental top

An ethanol solution of 4,4'-bipyridine(0.1 mmol) was added to one side of a H-tube, and an ethanol solution of Cu(NO3)2(0.1 mmol) was added to another side of the H-tube. The tube stood at room temperature for about one and a half month, and well shaped crystals of (I) were obtained.

Refinement top

Atom O1W of the crystalline water molecule is disordered between two positions, A and B, respectively. The final occupancy factors for the atoms O1WA and O1WB were assigned to 0.25 each. The H atoms attached to O1WA and O1WB were not positioned. H atoms of the coordinated water molecule were located from difference maps and refined with the O—H distances restrained to 0.82 (1) Å. All other H atoms were positioned geometrically and treated as riding [C—H=0.93Å and Uiso(H)=1.2Ueq(C)].

Computing details top

Data collection: TEXRAY (Molecular Structure Corporation, 1999); cell refinement: TEXRAY; data reduction: TEXSAN (Molecular Structure Corporation, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEX (McArdle,1995); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. Part of the polymeric chain structure of (I), showing the atom-numbering scheme and displacement ellipsoids drawn at the 50% probability level. All H atoms have been omitted for clarity. [Symmetry codes: (A) -x + 1/2, -y + 1.5, z; (B) -x, -y + 1, -z; (C) x - 1/2, y - 1/2, -z; (D) -x - 1/2, -y + 1/2, z.]
[Figure 2] Fig. 2. Packing of (I) viewed down the c axis, showing the intermolecular hydrogen bonds as dotted lines. H atoms not-involved in hydrogen bonding have been omitted.
catena-Poly[[[diaquadinitratocopper(II)]-µ-4,4'-bipyridine] hemihydrate] top
Crystal data top
[Cu(C10H8N2)(NO3)2(H2O)2]·0.5H2OF(000) = 788
Mr = 387.78Dx = 1.561 Mg m−3
Orthorhombic, PccnMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ab 2acCell parameters from 9004 reflections
a = 12.014 (7) Åθ = 3.4–27.6°
b = 18.533 (8) ŵ = 1.37 mm−1
c = 7.411 (3) ÅT = 293 K
V = 1650.1 (14) Å3Block, blue
Z = 40.23 × 0.20 × 0.18 mm
Data collection top
Rigaku Weissenberg IP
diffractometer		1892 independent reflections
Radiation source: rotor target1281 reflections with I > 2σ(I)
graphiteRint = 0.054
ω scansθmax = 27.5°, θmin = 3.4°
Absorption correction: multi-scan
(TEXRAY; Molecular Structure Corporation, 1999)		h = −15→15
Tmin = 0.737, Tmax = 0.803k = −24→24
14611 measured reflectionsl = −9→9
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)] = 0.049Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.157H atoms treated by a mixture of independent and constrained refinement
S = 1.12 w = 1/[σ2(Fo2) + (0.0874P)2 + 0.4871P]
where P = (Fo2 + 2Fc2)/3
1892 reflections(Δ/σ)max < 0.001
118 parametersΔρmax = 0.87 e Å−3
2 restraintsΔρmin = −0.35 e Å−3
Crystal data top
[Cu(C10H8N2)(NO3)2(H2O)2]·0.5H2OV = 1650.1 (14) Å3
Mr = 387.78Z = 4
Orthorhombic, PccnMo Kα radiation
a = 12.014 (7) ŵ = 1.37 mm−1
b = 18.533 (8) ÅT = 293 K
c = 7.411 (3) Å0.23 × 0.20 × 0.18 mm
Data collection top
Rigaku Weissenberg IP
diffractometer		1281 reflections with I > 2σ(I)
Absorption correction: multi-scan
(TEXRAY; Molecular Structure Corporation, 1999)		Rint = 0.054
Tmin = 0.737, Tmax = 0.803θmax = 27.5°
14611 measured reflectionsStandard reflections: none
1892 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.049H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.157Δρmax = 0.87 e Å−3
S = 1.12Δρmin = −0.35 e Å−3
1892 reflectionsAbsolute structure: ?
118 parametersFlack parameter: ?
2 restraintsRogers parameter: ?
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*/UeqOcc. (<1)
Cu10.00000.50000.00000.0295 (2)
O1−0.1229 (2)0.54296 (15)0.1421 (3)0.0432 (6)
H01A−0.126 (4)0.543 (2)0.251 (3)0.056 (12)*
H01B−0.184 (2)0.546 (2)0.095 (6)0.064 (14)*
O20.1102 (2)0.44599 (15)0.2366 (3)0.0539 (7)
O3−0.0023 (3)0.4179 (3)0.4510 (7)0.0966 (16)
O40.1711 (3)0.43196 (19)0.5051 (3)0.0585 (8)
N10.0885 (2)0.59087 (14)0.0366 (4)0.0336 (6)
N20.0904 (3)0.43241 (17)0.3962 (4)0.0439 (7)
C10.0439 (3)0.65525 (19)0.0012 (5)0.0394 (8)
H1A−0.03100.6574−0.02990.047*
C20.1038 (3)0.71886 (17)0.0087 (5)0.0402 (8)
H2A0.06930.7626−0.01730.048*
C30.2153 (3)0.71715 (15)0.0551 (5)0.0323 (7)
C40.2612 (3)0.64983 (16)0.0930 (5)0.0394 (8)
H4A0.33590.64600.12410.047*
C50.1958 (3)0.58901 (17)0.0842 (5)0.0394 (8)
H5A0.22760.54470.11260.047*
O1WB0.75000.75000.352 (6)0.190 (16)*0.25
O1WA0.75000.75000.155 (5)0.162 (13)*0.25
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0220 (3)0.0297 (3)0.0369 (4)−0.00525 (18)−0.0001 (2)−0.0010 (2)
O10.0279 (14)0.0664 (16)0.0353 (14)0.0009 (11)−0.0004 (10)−0.0099 (13)
O20.0491 (17)0.0749 (18)0.0377 (13)0.0021 (13)−0.0044 (11)0.0083 (13)
O30.042 (2)0.157 (5)0.091 (2)−0.038 (2)0.0125 (18)0.002 (3)
O40.0395 (16)0.097 (2)0.0391 (14)−0.0062 (15)−0.0082 (11)−0.0008 (13)
N10.0235 (14)0.0323 (13)0.0450 (14)−0.0042 (11)−0.0034 (11)−0.0006 (12)
N20.0322 (17)0.0560 (17)0.0436 (16)−0.0112 (13)0.0000 (13)0.0010 (14)
C10.0242 (17)0.0363 (17)0.058 (2)−0.0018 (14)−0.0050 (14)0.0036 (14)
C20.0237 (17)0.0309 (16)0.066 (2)0.0008 (12)−0.0041 (15)0.0045 (14)
C30.0241 (16)0.0288 (14)0.0441 (16)−0.0034 (12)−0.0008 (13)0.0003 (13)
C40.0246 (16)0.0333 (14)0.060 (2)−0.0012 (13)−0.0104 (15)−0.0006 (16)
C50.0282 (17)0.0314 (14)0.059 (2)0.0002 (13)−0.0109 (15)0.0019 (15)
Geometric parameters (Å, °) top
Cu1—O1i1.981 (3)N1—C51.336 (4)
Cu1—O11.981 (3)C1—C21.382 (5)
Cu1—N1i2.010 (3)C1—H1A0.9300
Cu1—N12.010 (3)C2—C31.383 (5)
Cu1—O22.414 (3)C2—H2A0.9300
Cu1—O2i2.414 (3)C3—C41.393 (4)
O1—H01A0.805 (19)C3—C3ii1.477 (6)
O1—H01B0.812 (19)C4—C51.376 (4)
O2—N21.232 (4)C4—H4A0.9300
O3—N21.216 (4)C5—H5A0.9300
O4—N21.261 (4)O1WB—O1WA1.46 (6)
N1—C11.334 (4)
O1i—Cu1—O1180.0C1—N1—Cu1120.7 (2)
O1i—Cu1—N1i89.21 (12)C5—N1—Cu1121.6 (2)
O1—Cu1—N1i90.79 (12)O3—N2—O2122.8 (4)
O1i—Cu1—N190.79 (12)O3—N2—O4119.3 (4)
O1—Cu1—N189.21 (12)O2—N2—O4117.9 (3)
N1i—Cu1—N1180.00 (8)N1—C1—C2123.1 (3)
O1i—Cu1—O279.09 (10)N1—C1—H1A118.5
O1—Cu1—O2100.91 (10)C2—C1—H1A118.5
N1i—Cu1—O292.33 (10)C1—C2—C3119.6 (3)
N1—Cu1—O287.67 (10)C1—C2—H2A120.2
O1i—Cu1—O2i100.91 (10)C3—C2—H2A120.2
O1—Cu1—O2i79.09 (10)C2—C3—C4117.0 (3)
N1i—Cu1—O2i87.67 (10)C2—C3—C3ii121.9 (3)
N1—Cu1—O2i92.33 (10)C4—C3—C3ii121.0 (4)
O2—Cu1—O2i180.0C5—C4—C3119.9 (3)
Cu1—O1—H01A125 (3)C5—C4—H4A120.1
Cu1—O1—H01B118 (3)C3—C4—H4A120.1
H01A—O1—H01B113 (5)N1—C5—C4122.8 (3)
N2—O2—Cu1132.5 (2)N1—C5—H5A118.6
C1—N1—C5117.5 (3)C4—C5—H5A118.6
O1i—Cu1—O2—N2−165.3 (3)O2i—Cu1—N1—C5−146.5 (3)
O1—Cu1—O2—N214.7 (3)Cu1—O2—N2—O330.3 (6)
N1i—Cu1—O2—N2−76.6 (3)Cu1—O2—N2—O4−151.6 (3)
N1—Cu1—O2—N2103.4 (3)C5—N1—C1—C21.1 (5)
O2i—Cu1—O2—N2113 (74)Cu1—N1—C1—C2−174.1 (3)
O1i—Cu1—N1—C1129.5 (3)N1—C1—C2—C3−0.1 (5)
O1—Cu1—N1—C1−50.5 (3)C1—C2—C3—C4−0.3 (5)
N1i—Cu1—N1—C143.7 (6)C1—C2—C3—C3ii176.4 (3)
O2—Cu1—N1—C1−151.4 (3)C2—C3—C4—C5−0.3 (5)
O2i—Cu1—N1—C128.6 (3)C3ii—C3—C4—C5−177.1 (3)
O1i—Cu1—N1—C5−45.6 (3)C1—N1—C5—C4−1.8 (5)
O1—Cu1—N1—C5134.4 (3)Cu1—N1—C5—C4173.5 (3)
N1i—Cu1—N1—C5−131.4 (3)C3—C4—C5—N11.4 (6)
O2—Cu1—N1—C533.5 (3)
Symmetry codes: (i) −x, −y+1, −z; (ii) −x+1/2, −y+3/2, z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H01B···O4iii0.81 (2)1.94 (2)2.744 (4)171 (5)
O1—H01A···O4iv0.81 (2)1.94 (2)2.718 (4)161 (4)
Symmetry codes: (iii) x−1/2, −y+1, −z+1/2; (iv) −x, −y+1, −z+1.
Table 1
Selected geometric parameters (Å, °) top
Cu1—O11.981 (3)O2—N21.232 (4)
Cu1—N12.010 (3)O3—N21.216 (4)
Cu1—O22.414 (3)O4—N21.261 (4)
O1—Cu1—N1i90.79 (12)O1—Cu1—O2100.91 (10)
O1—Cu1—N189.21 (12)N1i—Cu1—O292.33 (10)
O1i—Cu1—O279.09 (10)N1—Cu1—O287.67 (10)
Symmetry codes: (i) −x, −y+1, −z.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H01B···O4ii0.81 (2)1.94 (2)2.744 (4)171 (5)
O1—H01A···O4iii0.81 (2)1.94 (2)2.718 (4)161 (4)
Symmetry codes: (ii) x−1/2, −y+1, −z+1/2; (iii) −x, −y+1, −z+1.
Acknowledgements top

We gratefully acknowledge financial support from the Science and Technology Project of Fujian Province, China (grant No. 2001BA804A26–09) and the Foundation of Fuzhou University (grant No. 2006-XY-3).

references
References top

Ghosh, S. K., Ribas, J. & Bharadwaj, P. K. (2005). Cryst. Growth Des. 5, 623–629.

Lu, W.-J., Zhu, Y.-M. & Zhong, K.-L. (2006). Acta Cryst. E62, m3036–m3038.

McArdle, P. (1995). J. Appl. Cryst. 28, 65–?.

Molecular Structure Corporation (1999). TEXRAY and TEXSAN. Versions 1.10. MSC, The Woodlands, Texas, USA.

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

Woodward, J. D., Backov, R. V., Abboud, K. A. & Talham, D. R. (2006). Polyhedron, 25, 2605–2615.