metal-organic compounds
Diaquabis(4-hydroxy-5-nitropyridine-2-carboxylato-κ2N1,O2)copper(II)
aLaboratory of Catalysis Chemistry and Nanoscience, Department of Chemistry and Chemical Engineering, College of Environmental and Energy Engineering, Beijing University of Technology, Beijing 100124, People's Republic of China
*Correspondence e-mail: hxdai@bjut.edu.cn
In the title compound, [Cu(C6H3N2O5)2(H2O)2], the CuII ion, lying on an inversion center, is coordinated by two pyridine N atoms and two carboxylate O atoms from symmetry-related two 4-hydroxy-5-nitropyridine-2-carboxylate ligands, and two water molecules, forming a distorted octahedral geometry. In the crystal, O—H⋯O hydrogen bonds link the complex molecules. One of the H atoms of the water molecule is disordered over two sites of equal occupancy.
Related literature
For complexes based on the 4-hydroxylpyridine-2,6-dicarboxylic acid ligand, see: Zhao et al. (2006, 2009, 2011). For a similar reaction to the formation of the ligand, see: Xu et al. (2011).
Experimental
Crystal data
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Refinement
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Data collection: CrystalClear (Rigaku, 2005); cell CrystalClear; data reduction: CrystalClear; 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.
Supporting information
A mixture of 4-hydroxyl-pyridine-2,6-dicarboxylic acid (366 mg, 2.0 mmol), copper nitrate trihydrate (242 mg, 1.0 mmol), lanthanide nitrate hexahydrate (Ln = Eu, Sm, Pr, Tb) (1.0 mmol) and deionized water (10 ml) was placed in a 25 ml Teflon-lined steel autoclave, which was kept at 433 K for 3 days. The resuling blue prismatic crystals suitable for X-ray diffraction experiment were collected after washing with deionized water and diethyl ether (yield: 43% based on the mass of copper nitrate trihydrate).
H atoms bound to C atoms were positioned geometrically and refined as riding atoms, with C—H = 0.95 Å and with Uiso(H) = 1.2Ueq(C). H atoms bound to O atoms were located from a difference Fourier map and refined isotropically. One of H atoms of the water molecule is disordered over two sites with equal occupancy factors.
Data collection: CrystalClear (Rigaku, 2005); cell
CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); 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(C6H3N2O5)2(H2O)2] | F(000) = 470 |
Mr = 465.79 | Dx = 2.023 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 3085 reflections |
a = 6.5327 (7) Å | θ = 2.1–27.9° |
b = 9.7963 (10) Å | µ = 1.52 mm−1 |
c = 12.2562 (12) Å | T = 113 K |
β = 102.86 (2)° | Prism, colorless |
V = 764.68 (15) Å3 | 0.20 × 0.18 × 0.10 mm |
Z = 2 |
Rigaku Saturn 724 CCD diffractometer | 1829 independent reflections |
Radiation source: rotating anode | 1466 reflections with I > 2σ(I) |
Multilayer monochromator | Rint = 0.053 |
Detector resolution: 14.22 pixels mm-1 | θmax = 27.9°, θmin = 2.7° |
ω scans | h = −8→7 |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | k = −12→12 |
Tmin = 0.752, Tmax = 0.863 | l = −15→16 |
9563 measured reflections |
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)] = 0.029 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.077 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | w = 1/[σ2(Fo2) + (0.036P)2] where P = (Fo2 + 2Fc2)/3 |
1829 reflections | (Δ/σ)max < 0.001 |
149 parameters | Δρmax = 0.39 e Å−3 |
6 restraints | Δρmin = −0.49 e Å−3 |
[Cu(C6H3N2O5)2(H2O)2] | V = 764.68 (15) Å3 |
Mr = 465.79 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 6.5327 (7) Å | µ = 1.52 mm−1 |
b = 9.7963 (10) Å | T = 113 K |
c = 12.2562 (12) Å | 0.20 × 0.18 × 0.10 mm |
β = 102.86 (2)° |
Rigaku Saturn 724 CCD diffractometer | 1829 independent reflections |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | 1466 reflections with I > 2σ(I) |
Tmin = 0.752, Tmax = 0.863 | Rint = 0.053 |
9563 measured reflections |
R[F2 > 2σ(F2)] = 0.029 | 6 restraints |
wR(F2) = 0.077 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.39 e Å−3 |
1829 reflections | Δρmin = −0.49 e Å−3 |
149 parameters |
Experimental. Rigaku CrystalClear-SM Expert 2.0 r2 |
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 | 0.5000 | 0.01573 (13) | |
O1 | 0.0540 (2) | 0.53885 (14) | 0.66132 (12) | 0.0145 (3) | |
O2 | 0.1475 (2) | 0.70789 (14) | 0.78407 (11) | 0.0150 (3) | |
O3 | 0.3093 (2) | 1.08681 (14) | 0.52856 (13) | 0.0144 (3) | |
H3 | 0.331 (5) | 1.107 (3) | 0.592 (2) | 0.058 (11)* | |
O4 | 0.2830 (3) | 1.07679 (17) | 0.31323 (14) | 0.0291 (4) | |
O5 | 0.0819 (3) | 0.9216 (2) | 0.22215 (13) | 0.0408 (5) | |
O6 | 0.3578 (3) | 0.40247 (18) | 0.52615 (15) | 0.0253 (4) | |
H6A | 0.371 (5) | 0.381 (3) | 0.5936 (10) | 0.060 (11)* | |
H6B | 0.454 (7) | 0.455 (5) | 0.516 (3) | 0.06 (2)* | 0.50 |
H6C | 0.348 (10) | 0.332 (3) | 0.484 (3) | 0.09 (3)* | 0.50 |
N1 | 0.1030 (3) | 0.68775 (16) | 0.49202 (13) | 0.0113 (4) | |
C1 | 0.1142 (3) | 0.6591 (2) | 0.68823 (16) | 0.0121 (4) | |
C2 | 0.1493 (3) | 0.7498 (2) | 0.59364 (16) | 0.0108 (4) | |
C3 | 0.2222 (3) | 0.8799 (2) | 0.61022 (16) | 0.0109 (4) | |
H3A | 0.2576 | 0.9169 | 0.6837 | 0.013* | |
C4 | 0.2450 (3) | 0.9596 (2) | 0.51800 (17) | 0.0106 (4) | |
C5 | 0.1881 (3) | 0.8957 (2) | 0.41301 (16) | 0.0114 (4) | |
C6 | 0.1219 (3) | 0.7610 (2) | 0.40323 (16) | 0.0119 (4) | |
H6 | 0.0891 | 0.7197 | 0.3313 | 0.014* | |
N2 | 0.1874 (3) | 0.97025 (17) | 0.30795 (15) | 0.0150 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0276 (2) | 0.00876 (18) | 0.0110 (2) | −0.00692 (15) | 0.00460 (15) | −0.00212 (14) |
O1 | 0.0212 (8) | 0.0095 (7) | 0.0123 (8) | −0.0040 (6) | 0.0028 (6) | 0.0002 (5) |
O2 | 0.0251 (8) | 0.0103 (7) | 0.0088 (7) | −0.0004 (6) | 0.0021 (6) | −0.0006 (6) |
O3 | 0.0201 (8) | 0.0090 (7) | 0.0146 (8) | −0.0040 (6) | 0.0052 (7) | −0.0001 (6) |
O4 | 0.0442 (11) | 0.0199 (9) | 0.0253 (9) | −0.0091 (8) | 0.0124 (8) | 0.0029 (7) |
O5 | 0.0523 (13) | 0.0497 (12) | 0.0151 (9) | −0.0240 (10) | −0.0036 (9) | 0.0070 (8) |
O6 | 0.0271 (10) | 0.0238 (9) | 0.0234 (10) | −0.0057 (8) | 0.0019 (8) | 0.0029 (8) |
N1 | 0.0125 (9) | 0.0104 (8) | 0.0100 (8) | −0.0010 (7) | 0.0004 (7) | −0.0013 (6) |
C1 | 0.0107 (10) | 0.0107 (10) | 0.0149 (11) | 0.0005 (8) | 0.0027 (8) | 0.0031 (8) |
C2 | 0.0123 (10) | 0.0102 (9) | 0.0091 (10) | 0.0006 (8) | 0.0006 (8) | 0.0012 (7) |
C3 | 0.0109 (10) | 0.0116 (10) | 0.0093 (10) | 0.0000 (8) | 0.0007 (8) | −0.0011 (7) |
C4 | 0.0077 (9) | 0.0100 (9) | 0.0145 (10) | 0.0007 (7) | 0.0030 (8) | −0.0003 (7) |
C5 | 0.0104 (10) | 0.0139 (10) | 0.0105 (10) | −0.0004 (8) | 0.0034 (8) | 0.0030 (8) |
C6 | 0.0117 (11) | 0.0149 (10) | 0.0099 (10) | −0.0002 (8) | 0.0036 (8) | −0.0028 (8) |
N2 | 0.0150 (9) | 0.0165 (9) | 0.0136 (9) | −0.0015 (7) | 0.0033 (8) | 0.0011 (7) |
Cu1—N1 | 1.9685 (16) | O6—H6C | 0.85 (1) |
Cu1—O1 | 1.9667 (15) | N1—C6 | 1.332 (2) |
Cu1—O6 | 2.479 (2) | N1—C2 | 1.358 (2) |
O1—C1 | 1.263 (2) | C1—C2 | 1.518 (3) |
O2—C1 | 1.242 (2) | C2—C3 | 1.360 (3) |
O3—C4 | 1.312 (2) | C3—C4 | 1.409 (3) |
O3—H3 | 0.79 (3) | C3—H3A | 0.9500 |
O4—N2 | 1.211 (2) | C4—C5 | 1.405 (3) |
O5—N2 | 1.219 (2) | C5—C6 | 1.385 (3) |
O6—H6A | 0.84 (1) | C5—N2 | 1.480 (2) |
O6—H6B | 0.85 (1) | C6—H6 | 0.9500 |
O1—Cu1—O1i | 180.0 | O2—C1—C2 | 118.24 (17) |
O1—Cu1—N1 | 83.24 (6) | O1—C1—C2 | 115.97 (17) |
O1i—Cu1—N1 | 96.76 (6) | N1—C2—C3 | 123.75 (18) |
O1—Cu1—N1i | 96.76 (6) | N1—C2—C1 | 113.45 (17) |
O1i—Cu1—N1i | 83.24 (6) | C3—C2—C1 | 122.80 (18) |
N1—Cu1—N1i | 180.0 | C2—C3—C4 | 119.73 (18) |
O1—Cu1—O6 | 89.52 (6) | C2—C3—H3A | 120.1 |
O1—Cu1—O6i | 90.48 (6) | C4—C3—H3A | 120.1 |
N1—Cu1—O6i | 87.50 (7) | O3—C4—C5 | 121.85 (18) |
O6—Cu1—N1 | 92.50 (7) | O3—C4—C3 | 122.42 (18) |
O6—Cu1—O6i | 180.00 | C5—C4—C3 | 115.70 (18) |
C1—O1—Cu1 | 114.76 (13) | C6—C5—C4 | 121.20 (18) |
C4—O3—H3 | 109 (2) | C6—C5—N2 | 117.04 (17) |
H6A—O6—H6B | 112.7 (17) | C4—C5—N2 | 121.71 (17) |
H6A—O6—H6C | 111.5 (17) | N1—C6—C5 | 121.74 (18) |
H6B—O6—H6C | 111.2 (17) | N1—C6—H6 | 119.1 |
C6—N1—C2 | 117.79 (17) | C5—C6—H6 | 119.1 |
C6—N1—Cu1 | 129.69 (14) | O4—N2—O5 | 124.71 (18) |
C2—N1—Cu1 | 112.42 (13) | O4—N2—C5 | 118.54 (17) |
O2—C1—O1 | 125.79 (19) | O5—N2—C5 | 116.68 (17) |
N1—Cu1—O1—C1 | 3.72 (14) | N1—C2—C3—C4 | 2.6 (3) |
N1i—Cu1—O1—C1 | −176.28 (14) | C1—C2—C3—C4 | −178.09 (18) |
O1—Cu1—N1—C6 | −178.60 (18) | C2—C3—C4—O3 | 178.19 (18) |
O1i—Cu1—N1—C6 | 1.40 (18) | C2—C3—C4—C5 | 0.1 (3) |
O1—Cu1—N1—C2 | −2.41 (13) | O3—C4—C5—C6 | 179.52 (18) |
O1i—Cu1—N1—C2 | 177.59 (13) | C3—C4—C5—C6 | −2.4 (3) |
Cu1—O1—C1—O2 | 176.32 (16) | O3—C4—C5—N2 | −3.1 (3) |
Cu1—O1—C1—C2 | −4.1 (2) | C3—C4—C5—N2 | 175.00 (17) |
C6—N1—C2—C3 | −3.0 (3) | C2—N1—C6—C5 | 0.5 (3) |
Cu1—N1—C2—C3 | −179.66 (16) | Cu1—N1—C6—C5 | 176.56 (14) |
C6—N1—C2—C1 | 177.69 (16) | C4—C5—C6—N1 | 2.1 (3) |
Cu1—N1—C2—C1 | 1.0 (2) | N2—C5—C6—N1 | −175.38 (17) |
O2—C1—C2—N1 | −178.33 (17) | C6—C5—N2—O4 | −165.03 (19) |
O1—C1—C2—N1 | 2.1 (3) | C4—C5—N2—O4 | 17.5 (3) |
O2—C1—C2—C3 | 2.3 (3) | C6—C5—N2—O5 | 18.0 (3) |
O1—C1—C2—C3 | −177.27 (18) | C4—C5—N2—O5 | −159.5 (2) |
Symmetry code: (i) −x, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O2ii | 0.79 (3) | 1.79 (3) | 2.544 (2) | 160 (3) |
O6—H6A···O2iii | 0.84 (1) | 2.28 (2) | 3.014 (2) | 146 (3) |
O6—H6B···O6iv | 0.85 (1) | 2.00 (1) | 2.836 (3) | 170 (5) |
O6—H6C···O3v | 0.85 (1) | 2.49 (3) | 3.109 (2) | 130 (3) |
Symmetry codes: (ii) −x+1/2, y+1/2, −z+3/2; (iii) −x+1/2, y−1/2, −z+3/2; (iv) −x+1, −y+1, −z+1; (v) x, y−1, z. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C6H3N2O5)2(H2O)2] |
Mr | 465.79 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 113 |
a, b, c (Å) | 6.5327 (7), 9.7963 (10), 12.2562 (12) |
β (°) | 102.86 (2) |
V (Å3) | 764.68 (15) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.52 |
Crystal size (mm) | 0.20 × 0.18 × 0.10 |
Data collection | |
Diffractometer | Rigaku Saturn 724 CCD diffractometer |
Absorption correction | Multi-scan (CrystalClear; Rigaku, 2005) |
Tmin, Tmax | 0.752, 0.863 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9563, 1829, 1466 |
Rint | 0.053 |
(sin θ/λ)max (Å−1) | 0.658 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.029, 0.077, 1.04 |
No. of reflections | 1829 |
No. of parameters | 149 |
No. of restraints | 6 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.39, −0.49 |
Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O2i | 0.79 (3) | 1.79 (3) | 2.544 (2) | 160 (3) |
O6—H6A···O2ii | 0.84 (1) | 2.28 (2) | 3.014 (2) | 146 (3) |
O6—H6B···O6iii | 0.85 (1) | 2.00 (1) | 2.836 (3) | 170 (5) |
O6—H6C···O3iv | 0.85 (1) | 2.49 (3) | 3.109 (2) | 130 (3) |
Symmetry codes: (i) −x+1/2, y+1/2, −z+3/2; (ii) −x+1/2, y−1/2, −z+3/2; (iii) −x+1, −y+1, −z+1; (iv) x, y−1, z. |
Acknowledgements
This work was supported by the National High Technology Research and Development (863) Key Program of the Ministry of Science and Technology of China (No. 2009AA063201).
References
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Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Xu, J., Su, W.-P. & Hong, M.-C. (2011). CrystEngComm, 13, 3998–4004. Web of Science CSD CrossRef CAS Google Scholar
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Carboxylate ligands play an important role in constructing novel metal-organic frameworks (MOFs) in coordination chemistry. Especially, a large number of MOFs based on pyridyl dicarboxylic acid ligands containing N- and O-donors with multi-connecting ability have been constructed. 4-Hydroxyl-pyridine-2,6-dicarboxylic acid has been widely used in the construction of high-dimensional structures with large pores. It usually adopts diverse coordination binding modes such as chelating to one metal center, bridging bidentate in syn–syn or syn–anti configuration to two or three metal centers. A systematic study of 3d–4f, 4d–4f and 3d–4d–4f complexes based on 4-hydroxyl-pyridine-2,6-dicarboxylic acid ligand has been undertaken (Zhao et al., 2006, 2009, 2011). However, to the best of our knowledge, no reports on the synthesis of the title compound have been seen in literature. In this paper, we report the synthesis and crystal structure of the title compound using a hydrothermal method with 4-hydroxyl-pyridine-2,6-dicarboxylic acid as ligand.
The title compound features a 3-nitro-4-hydroxyl-pyridine-6-carboxylate ligand, which was in situ generated by decarboxylation and nitration of 4-hydroxyl-pyridine-2,6-dicarboxylic acid under the hydrothermal conditions. A similar reaction has been reported (Xu et al., 2011). Structure analysis shows that the CuII ion is centrosymmetrically coordinated by two N atoms [Cu—N = 1.9685 (16) Å] and two carboxylate O atoms [Cu—O = 1.9667 (15) Å] from two 3-nitro-4-hydroxyl-pyridine-6-carboxylate ligands and two water molecules [Cu—O = 2.479 (2) Å], forming a distorted octahedral geometry, as shown in Fig. 1. O—H···O hydrogen bonds link the complex molecules (Table 1).