catena-Poly[[[diaqua­dinitratocopper(II)]-μ-4,4′-bipyridine] hemihydrate]

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 Cu^II 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.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.005 Å
• H-atom completeness 93%
• Disorder in solvent or counterion
• R factor = 0.049
• wR factor = 0.157
• Data-to-parameter ratio = 16.0

checkCIF/PLATON results

No syntax errors found



Alert level C
CHEMW01_ALERT_1_C  The difference between the given and expected weight for
            compound is greater 1 mass unit. Check that all hydrogen
            atoms have been taken into account.
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............       0.50 Ratio
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.97
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.47
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         O2
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         N2
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.01
PLAT302_ALERT_4_C Anion/Solvent Disorder .........................      25.00 Perc.
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #          5
            O2  -CU1 -O2  -N2     11.00  0.00   5.565   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #          8
            N1  -CU1 -N1  -C1     43.70  0.60   5.565   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         13
            N1  -CU1 -N1  -C5   -131.40  0.30   5.565   1.555   1.555   1.555
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........          4

Alert level G
FORMU01_ALERT_2_G  There is a discrepancy between the atom counts in the
            _chemical_formula_sum and the formula from the _atom_site* data.
            Atom count from _chemical_formula_sum:C10 H13 Cu1 N4 O8.5
            Atom count from the _atom_site data:  C10 H12 Cu1 N4 O8.5
CELLZ01_ALERT_1_G Difference between formula and atom_site contents detected.
CELLZ01_ALERT_1_G WARNING: H atoms missing from atom site list. Is this intentional?
           From the CIF: _cell_formula_units_Z    4
           From the CIF: _chemical_formula_sum  C10 H13 Cu N4 O8.5
           TEST: Compare cell contents of formula and atom_site data

           atom    Z*formula  cif sites diff
           C         40.00     40.00    0.00
           H         52.00     48.00    4.00
           Cu         4.00      4.00    0.00
           N         16.00     16.00    0.00
           O         34.00     34.00    0.00
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
  14 ALERT level C = Check and explain
   5 ALERT level G = General alerts; check

   8 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   5 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   6 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

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

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

S2. Experimental

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.

S3. Refinement

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 U_iso(H)=1.2Ueq(C)].

Computing details

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

	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.]
	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]

Crystal data

[Cu(C10H8N2)(NO3)2(H2O)2]·0.5H2O	F(000) = 788
Mr = 387.78	Dx = 1.561 Mg m^−3
Orthorhombic, Pccn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ab 2ac	Cell parameters from 9004 reflections
a = 12.014 (7) Å	θ = 3.4–27.6°
b = 18.533 (8) Å	µ = 1.37 mm^−1
c = 7.411 (3) Å	T = 293 K
V = 1650.1 (14) Å^3	Block, blue
Z = 4	0.23 × 0.20 × 0.18 mm

Data collection

Rigaku Weissenberg IP diffractometer	1892 independent reflections
Radiation source: rotor target	1281 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.054
ω scans	θmax = 27.5°, θmin = 3.4°
Absorption correction: multi-scan (TEXRAY; Molecular Structure Corporation, 1999)	h = −15→15
Tmin = 0.737, Tmax = 0.803	k = −24→24
14611 measured reflections	l = −9→9

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.157	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	w = 1/[σ^2(Fo^2) + (0.0874P)^2 + 0.4871P] where P = (Fo^2 + 2Fc^2)/3
1892 reflections	(Δ/σ)max < 0.001
118 parameters	Δρmax = 0.87 e Å^−3
2 restraints	Δρmin = −0.35 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cu1	0.0000	0.5000	0.0000	0.0295 (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)*
O2	0.1102 (2)	0.44599 (15)	0.2366 (3)	0.0539 (7)
O3	−0.0023 (3)	0.4179 (3)	0.4510 (7)	0.0966 (16)
O4	0.1711 (3)	0.43196 (19)	0.5051 (3)	0.0585 (8)
N1	0.0885 (2)	0.59087 (14)	0.0366 (4)	0.0336 (6)
N2	0.0904 (3)	0.43241 (17)	0.3962 (4)	0.0439 (7)
C1	0.0439 (3)	0.65525 (19)	0.0012 (5)	0.0394 (8)
H1A	−0.0310	0.6574	−0.0299	0.047*
C2	0.1038 (3)	0.71886 (17)	0.0087 (5)	0.0402 (8)
H2A	0.0693	0.7626	−0.0173	0.048*
C3	0.2153 (3)	0.71715 (15)	0.0551 (5)	0.0323 (7)
C4	0.2612 (3)	0.64983 (16)	0.0930 (5)	0.0394 (8)
H4A	0.3359	0.6460	0.1241	0.047*
C5	0.1958 (3)	0.58901 (17)	0.0842 (5)	0.0394 (8)
H5A	0.2276	0.5447	0.1126	0.047*
O1WB	0.7500	0.7500	0.352 (6)	0.190 (16)*	0.25
O1WA	0.7500	0.7500	0.155 (5)	0.162 (13)*	0.25

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0220 (3)	0.0297 (3)	0.0369 (4)	−0.00525 (18)	−0.0001 (2)	−0.0010 (2)
O1	0.0279 (14)	0.0664 (16)	0.0353 (14)	0.0009 (11)	−0.0004 (10)	−0.0099 (13)
O2	0.0491 (17)	0.0749 (18)	0.0377 (13)	0.0021 (13)	−0.0044 (11)	0.0083 (13)
O3	0.042 (2)	0.157 (5)	0.091 (2)	−0.038 (2)	0.0125 (18)	0.002 (3)
O4	0.0395 (16)	0.097 (2)	0.0391 (14)	−0.0062 (15)	−0.0082 (11)	−0.0008 (13)
N1	0.0235 (14)	0.0323 (13)	0.0450 (14)	−0.0042 (11)	−0.0034 (11)	−0.0006 (12)
N2	0.0322 (17)	0.0560 (17)	0.0436 (16)	−0.0112 (13)	0.0000 (13)	0.0010 (14)
C1	0.0242 (17)	0.0363 (17)	0.058 (2)	−0.0018 (14)	−0.0050 (14)	0.0036 (14)
C2	0.0237 (17)	0.0309 (16)	0.066 (2)	0.0008 (12)	−0.0041 (15)	0.0045 (14)
C3	0.0241 (16)	0.0288 (14)	0.0441 (16)	−0.0034 (12)	−0.0008 (13)	0.0003 (13)
C4	0.0246 (16)	0.0333 (14)	0.060 (2)	−0.0012 (13)	−0.0104 (15)	−0.0006 (16)
C5	0.0282 (17)	0.0314 (14)	0.059 (2)	0.0002 (13)	−0.0109 (15)	0.0019 (15)

Geometric parameters (Å, º)

Cu1—O1^i	1.981 (3)	N1—C5	1.336 (4)
Cu1—O1	1.981 (3)	C1—C2	1.382 (5)
Cu1—N1^i	2.010 (3)	C1—H1A	0.9300
Cu1—N1	2.010 (3)	C2—C3	1.383 (5)
Cu1—O2	2.414 (3)	C2—H2A	0.9300
Cu1—O2^i	2.414 (3)	C3—C4	1.393 (4)
O1—H01A	0.805 (19)	C3—C3^ii	1.477 (6)
O1—H01B	0.812 (19)	C4—C5	1.376 (4)
O2—N2	1.232 (4)	C4—H4A	0.9300
O3—N2	1.216 (4)	C5—H5A	0.9300
O4—N2	1.261 (4)	O1WB—O1WA	1.46 (6)
N1—C1	1.334 (4)
O1^i—Cu1—O1	180.0	C1—N1—Cu1	120.7 (2)
O1^i—Cu1—N1^i	89.21 (12)	C5—N1—Cu1	121.6 (2)
O1—Cu1—N1^i	90.79 (12)	O3—N2—O2	122.8 (4)
O1^i—Cu1—N1	90.79 (12)	O3—N2—O4	119.3 (4)
O1—Cu1—N1	89.21 (12)	O2—N2—O4	117.9 (3)
N1^i—Cu1—N1	180.00 (8)	N1—C1—C2	123.1 (3)
O1^i—Cu1—O2	79.09 (10)	N1—C1—H1A	118.5
O1—Cu1—O2	100.91 (10)	C2—C1—H1A	118.5
N1^i—Cu1—O2	92.33 (10)	C1—C2—C3	119.6 (3)
N1—Cu1—O2	87.67 (10)	C1—C2—H2A	120.2
O1^i—Cu1—O2^i	100.91 (10)	C3—C2—H2A	120.2
O1—Cu1—O2^i	79.09 (10)	C2—C3—C4	117.0 (3)
N1^i—Cu1—O2^i	87.67 (10)	C2—C3—C3^ii	121.9 (3)
N1—Cu1—O2^i	92.33 (10)	C4—C3—C3^ii	121.0 (4)
O2—Cu1—O2^i	180.0	C5—C4—C3	119.9 (3)
Cu1—O1—H01A	125 (3)	C5—C4—H4A	120.1
Cu1—O1—H01B	118 (3)	C3—C4—H4A	120.1
H01A—O1—H01B	113 (5)	N1—C5—C4	122.8 (3)
N2—O2—Cu1	132.5 (2)	N1—C5—H5A	118.6
C1—N1—C5	117.5 (3)	C4—C5—H5A	118.6
O1^i—Cu1—O2—N2	−165.3 (3)	O2^i—Cu1—N1—C5	−146.5 (3)
O1—Cu1—O2—N2	14.7 (3)	Cu1—O2—N2—O3	30.3 (6)
N1^i—Cu1—O2—N2	−76.6 (3)	Cu1—O2—N2—O4	−151.6 (3)
N1—Cu1—O2—N2	103.4 (3)	C5—N1—C1—C2	1.1 (5)
O2^i—Cu1—O2—N2	113 (74)	Cu1—N1—C1—C2	−174.1 (3)
O1^i—Cu1—N1—C1	129.5 (3)	N1—C1—C2—C3	−0.1 (5)
O1—Cu1—N1—C1	−50.5 (3)	C1—C2—C3—C4	−0.3 (5)
N1^i—Cu1—N1—C1	43.7 (6)	C1—C2—C3—C3^ii	176.4 (3)
O2—Cu1—N1—C1	−151.4 (3)	C2—C3—C4—C5	−0.3 (5)
O2^i—Cu1—N1—C1	28.6 (3)	C3^ii—C3—C4—C5	−177.1 (3)
O1^i—Cu1—N1—C5	−45.6 (3)	C1—N1—C5—C4	−1.8 (5)
O1—Cu1—N1—C5	134.4 (3)	Cu1—N1—C5—C4	173.5 (3)
N1^i—Cu1—N1—C5	−131.4 (3)	C3—C4—C5—N1	1.4 (6)
O2—Cu1—N1—C5	33.5 (3)

Symmetry codes: (i) −x, −y+1, −z; (ii) −x+1/2, −y+3/2, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H01B···O4^iii	0.81 (2)	1.94 (2)	2.744 (4)	171 (5)
O1—H01A···O4^iv	0.81 (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.