Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807019551/cv2233sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807019551/cv2233Isup2.hkl |
CCDC reference: 648065
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (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
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.
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)].
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.
For related literature, see: Ghosh et al. (2005); Lu et al. (2006); Woodward et al. (2006).
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.
[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) Å3 | Block, blue |
Z = 4 | 0.23 × 0.20 × 0.18 mm |
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 on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.049 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.157 | H 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 parameters | Δρmax = 0.87 e Å−3 |
2 restraints | Δρmin = −0.35 e Å−3 |
[Cu(C10H8N2)(NO3)2(H2O)2]·0.5H2O | V = 1650.1 (14) Å3 |
Mr = 387.78 | Z = 4 |
Orthorhombic, Pccn | Mo Kα radiation |
a = 12.014 (7) Å | µ = 1.37 mm−1 |
b = 18.533 (8) Å | T = 293 K |
c = 7.411 (3) Å | 0.23 × 0.20 × 0.18 mm |
Rigaku Weissenberg IP diffractometer | 1892 independent reflections |
Absorption correction: multi-scan (TEXRAY; Molecular Structure Corporation, 1999) | 1281 reflections with I > 2σ(I) |
Tmin = 0.737, Tmax = 0.803 | Rint = 0.054 |
14611 measured reflections |
R[F2 > 2σ(F2)] = 0.049 | 2 restraints |
wR(F2) = 0.157 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.12 | Δρmax = 0.87 e Å−3 |
1892 reflections | Δρmin = −0.35 e Å−3 |
118 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 | 0.0000 | 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 |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
Cu1—O1i | 1.981 (3) | N1—C5 | 1.336 (4) |
Cu1—O1 | 1.981 (3) | C1—C2 | 1.382 (5) |
Cu1—N1i | 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—O2i | 2.414 (3) | C3—C4 | 1.393 (4) |
O1—H01A | 0.805 (19) | C3—C3ii | 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) | ||
O1i—Cu1—O1 | 180.0 | C1—N1—Cu1 | 120.7 (2) |
O1i—Cu1—N1i | 89.21 (12) | C5—N1—Cu1 | 121.6 (2) |
O1—Cu1—N1i | 90.79 (12) | O3—N2—O2 | 122.8 (4) |
O1i—Cu1—N1 | 90.79 (12) | O3—N2—O4 | 119.3 (4) |
O1—Cu1—N1 | 89.21 (12) | O2—N2—O4 | 117.9 (3) |
N1i—Cu1—N1 | 180.00 (8) | N1—C1—C2 | 123.1 (3) |
O1i—Cu1—O2 | 79.09 (10) | N1—C1—H1A | 118.5 |
O1—Cu1—O2 | 100.91 (10) | C2—C1—H1A | 118.5 |
N1i—Cu1—O2 | 92.33 (10) | C1—C2—C3 | 119.6 (3) |
N1—Cu1—O2 | 87.67 (10) | C1—C2—H2A | 120.2 |
O1i—Cu1—O2i | 100.91 (10) | C3—C2—H2A | 120.2 |
O1—Cu1—O2i | 79.09 (10) | C2—C3—C4 | 117.0 (3) |
N1i—Cu1—O2i | 87.67 (10) | C2—C3—C3ii | 121.9 (3) |
N1—Cu1—O2i | 92.33 (10) | C4—C3—C3ii | 121.0 (4) |
O2—Cu1—O2i | 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 |
O1i—Cu1—O2—N2 | −165.3 (3) | O2i—Cu1—N1—C5 | −146.5 (3) |
O1—Cu1—O2—N2 | 14.7 (3) | Cu1—O2—N2—O3 | 30.3 (6) |
N1i—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) |
O2i—Cu1—O2—N2 | 113 (74) | Cu1—N1—C1—C2 | −174.1 (3) |
O1i—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) |
N1i—Cu1—N1—C1 | 43.7 (6) | C1—C2—C3—C3ii | 176.4 (3) |
O2—Cu1—N1—C1 | −151.4 (3) | C2—C3—C4—C5 | −0.3 (5) |
O2i—Cu1—N1—C1 | 28.6 (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—C5 | 134.4 (3) | Cu1—N1—C5—C4 | 173.5 (3) |
N1i—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. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H01B···O4iii | 0.81 (2) | 1.94 (2) | 2.744 (4) | 171 (5) |
O1—H01A···O4iv | 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. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C10H8N2)(NO3)2(H2O)2]·0.5H2O |
Mr | 387.78 |
Crystal system, space group | Orthorhombic, Pccn |
Temperature (K) | 293 |
a, b, c (Å) | 12.014 (7), 18.533 (8), 7.411 (3) |
V (Å3) | 1650.1 (14) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.37 |
Crystal size (mm) | 0.23 × 0.20 × 0.18 |
Data collection | |
Diffractometer | Rigaku Weissenberg IP |
Absorption correction | Multi-scan (TEXRAY; Molecular Structure Corporation, 1999) |
Tmin, Tmax | 0.737, 0.803 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14611, 1892, 1281 |
Rint | 0.054 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.157, 1.12 |
No. of reflections | 1892 |
No. of parameters | 118 |
No. of restraints | 2 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.87, −0.35 |
Computer programs: TEXRAY (Molecular Structure Corporation, 1999), TEXRAY, TEXSAN (Molecular Structure Corporation, 1999), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEX (McArdle,1995), SHELXL97.
Cu1—O1 | 1.981 (3) | O2—N2 | 1.232 (4) |
Cu1—N1 | 2.010 (3) | O3—N2 | 1.216 (4) |
Cu1—O2 | 2.414 (3) | O4—N2 | 1.261 (4) |
O1—Cu1—N1i | 90.79 (12) | O1—Cu1—O2 | 100.91 (10) |
O1—Cu1—N1 | 89.21 (12) | N1i—Cu1—O2 | 92.33 (10) |
O1i—Cu1—O2 | 79.09 (10) | N1—Cu1—O2 | 87.67 (10) |
Symmetry code: (i) −x, −y+1, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H01B···O4ii | 0.812 (19) | 1.94 (2) | 2.744 (4) | 171 (5) |
O1—H01A···O4iii | 0.805 (19) | 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. |
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.