catena-Poly[[[triaqua­copper(II)]-μ-pyridine-2,3-dicarboxyl­ato-κ3N,O2:O3] monohydrate]

Hao, L.; Mu, C.; Kong, B.

doi:10.1107/S1600536808025439

metal-organic compounds

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Volume 64| Part 10| October 2008| Page m1229

doi:10.1107/S1600536808025439

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catena-Poly[[[triaquacopper(II)]-μ-pyridine-2,3-dicarboxylato-κ³N,O²:O³] monohydrate]

Lujiang Hao,^a ^* Chunhua Mu ^b and Binbin Kong ^a

^aCollege of Food and Biological Engineering, Shandong Institute of Light Industry, Jinan 250353, People's Republic of China, and ^bMaize Research Insitute, Shandong Academy of Agricultural Science, Jinan 250100, People's Republic of China
^*Correspondence e-mail: lujianghao001@yahoo.com.cn

(Received 15 June 2008; accepted 7 August 2008; online 6 September 2008)

In the title compound, {[Cu(C₇H₃NO₄)(H₂O)₃]·H₂O}_n, the Cu^II ion is bonded to three water molecules, one N,O-bidentate pyridine-2,3-dicarboxylate dianion and one O-bonded symmetry-generated dianion, resulting in a distorted CuNO₅ octahedral geometry. The bridging ligand results in an infinite chain. A network of O—H⋯O hydrogen bonds helps to establish the crystal structure.

Related literature

For background, see: Serre et al. (2005 ).

Experimental

Crystal data

[Cu(C₇H₃NO₄)(H₂O)₃]·H₂O
M_r = 300.71
Monoclinic, C c
a = 8.513 (3) Å
b = 17.983 (3) Å
c = 7.493 (3) Å
β = 114.486 (10)°
V = 1043.9 (6) Å³
Z = 4
Mo Kα radiation
μ = 2.13 mm⁻¹
T = 296 (2) K
0.40 × 0.28 × 0.22 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ) T_min = 0.484, T_max = 0.652
2686 measured reflections
1322 independent reflections
1310 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.089
S = 1.00
1322 reflections
180 parameters
14 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.61 e Å⁻³
Δρ_min = −0.60 e Å⁻³
Absolute structure: Flack (1983 ), 290 Friedel pairs
Flack parameter: 0.05 (3)

Table 1
Selected bond lengths (Å)

Cu1—O7	2.061 (3)
Cu1—O6	2.068 (3)
Cu1—O3	2.071 (3)
Cu1—O1	2.119 (4)
Cu1—O5	2.178 (5)
Cu1—N1	2.187 (4)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H3W⋯O4ⁱ	0.82 (9)	1.93 (8)	2.735 (6)	167 (8)
O5—H4W⋯O6ⁱⁱ	0.82 (2)	2.35 (8)	2.966 (5)	132 (10)
O6—H5W⋯O5ⁱⁱⁱ	0.82 (7)	2.29 (7)	2.966 (5)	140 (9)
O7—H7W⋯O2^iv	0.83 (8)	1.90 (9)	2.720 (5)	169 (8)
O7—H8W⋯O2ⁱⁱ	0.83 (8)	2.03 (4)	2.825 (5)	162 (11)
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[x, -y, z+{\script{1\over 2}}]$ ; (iii) $[x, -y, z-{\script{1\over 2}}]$ ; (iv) x, y, z+1.

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT-Plus (Bruker, 2004); data reduction: SAINT-Plus; 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

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808025439/hb2747sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808025439/hb2747Isup2.hkl

checkCIF report

Comment top

In recent years, carboxylic acids have been widely used as polydentate ligands, which can coordinate to transition or rare earth ions yielding complexes with interesting properties in biological systems (e.g. Serre et al., 2005). Herein, we report the synthesis and structure of the title compound, (I).

As shown in Fig. 1, the Cu^II ion in (I) is hexacoordinated with five oxygen atoms and one nitrogen atom, exhibiting a slightly distorted octahedral geometry (Table 1). The pyridine-2,3-dicarboxyalto ligand affords the pyridine N and one carboxylato oxygen atom in chelating coordination mode and a symmetry-generated ligand bonds from its carboxylate O-atom. The bridging ligand links neighboring copper(II) ions into a chain (Fig. 2). Extensive hydrogen bonding (Table 2) via hydrogen bonds between carboxylate oxygen atoms of pyridine-2,3-dicarboxyalte and the uncoordinated water molecules or coordinated aqua ligands, giving rise to a three-dimensional network.

Related literature top

For background, see: Serre et al. (2005).

Experimental top

A mixture of copper(II) chloride (0.5 mmol), pyridine-2,3-dicarboxylic acid (1 mmol), sodium hydroxide (1 mmol), H₂O (8 ml), and ethanol (8 ml) in a 25 ml Teflon-lined stainless steel autoclave was kept at 423 K for three days. Blue blocks of (I) were obtained after cooling to room temperature with a yield of 16%. Anal calc. for C₇H₁₁CuNO₈: C 27.93, H 2.99, N 4.66%; found: C 27.89, H 2.92, N 4.63%.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT-Plus (Bruker, 2004); data reduction: SAINT-Plus (Bruker, 2004; 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).

Figures top

	Fig. 1. The molecular structure of (I), drawn with 30% probability displacement ellipsoids for the non-hydrogen atoms. Atoms labeled with i are at the symmetry position (x - 1/2,-y + 1/2,z - 1/2).
	Fig. 2. Part of a polymeric chain in (I).

catena-Poly[[[triaquacopper(II)]-µ-pyridine-2,3-dicarboxylato- κ³N,O²:O³] monohydrate] top

Crystal data top

[Cu(C₇H₃NO₄)(H₂O)₃]·H₂O	F(000) = 612
M_r = 300.71	D_x = 1.913 Mg m⁻³
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2yc	Cell parameters from 2692 reflections
a = 8.513 (3) Å	θ = 2.9–28.1°
b = 17.983 (3) Å	µ = 2.13 mm⁻¹
c = 7.493 (3) Å	T = 296 K
β = 114.486 (10)°	Block, blue
V = 1043.9 (6) Å³	0.40 × 0.28 × 0.22 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	1322 independent reflections
Radiation source: fine-focus sealed tube	1310 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
ω scans	θ_max = 26.0°, θ_min = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −10→10
T_min = 0.484, T_max = 0.652	k = −22→22
2686 measured reflections	l = −4→9

Refinement top

Refinement on F²	Hydrogen site location: difmap and geom
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.030	w = 1/[σ²(F_o²) + (0.079P)² + 0.0702P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.089	(Δ/σ)_max < 0.001
S = 1.00	Δρ_max = 0.61 e Å⁻³
1322 reflections	Δρ_min = −0.60 e Å⁻³
180 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
14 restraints	Extinction coefficient: 0.018 (2)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 290 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.05 (3)

Crystal data top

[Cu(C₇H₃NO₄)(H₂O)₃]·H₂O	V = 1043.9 (6) Å³
M_r = 300.71	Z = 4
Monoclinic, Cc	Mo Kα radiation
a = 8.513 (3) Å	µ = 2.13 mm⁻¹
b = 17.983 (3) Å	T = 296 K
c = 7.493 (3) Å	0.40 × 0.28 × 0.22 mm
β = 114.486 (10)°

Data collection top

Bruker APEXII CCD diffractometer	1322 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2004)	1310 reflections with I > 2σ(I)
T_min = 0.484, T_max = 0.652	R_int = 0.028
2686 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.089	Δρ_max = 0.61 e Å⁻³
S = 1.00	Δρ_min = −0.60 e Å⁻³
1322 reflections	Absolute structure: Flack (1983), 290 Friedel pairs
180 parameters	Absolute structure parameter: 0.05 (3)
14 restraints

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

	x	y	z	U_iso*/U_eq
Cu1	0.00453 (5)	0.118674 (19)	0.25189 (5)	0.0226 (2)
C1	−0.1893 (6)	0.1125 (2)	−0.2173 (8)	0.0257 (10)
C2	0.0162 (7)	0.2776 (2)	0.2417 (8)	0.0261 (9)
C3	0.1909 (5)	0.2542 (2)	0.2398 (6)	0.0220 (8)
C4	0.3188 (5)	0.3044 (2)	0.2468 (6)	0.0224 (8)
C5	0.4612 (5)	0.2816 (2)	0.2256 (6)	0.0222 (9)
H5	0.5443	0.3154	0.2266	0.027*
C6	0.4781 (6)	0.2094 (3)	0.2034 (7)	0.0325 (10)
H6	0.5747	0.1922	0.1878	0.039*
C7	0.3554 (7)	0.1592 (3)	0.2028 (8)	0.0350 (10)
H7	0.3719	0.1088	0.1890	0.042*
N1	0.2118 (5)	0.18178 (19)	0.2218 (6)	0.0262 (7)
O1	−0.1400 (5)	0.0911 (2)	−0.0470 (5)	0.0356 (8)
O2	−0.2392 (5)	0.07157 (19)	−0.3667 (5)	0.0363 (7)
O3	−0.0834 (4)	0.22671 (17)	0.2399 (6)	0.0323 (7)
O4	−0.0130 (6)	0.34452 (16)	0.2387 (9)	0.0401 (8)
O5	0.1420 (5)	0.12328 (17)	0.5699 (7)	0.0311 (9)
O6	0.1266 (5)	0.01799 (18)	0.2664 (7)	0.0427 (9)
O7	−0.2021 (4)	0.07356 (18)	0.2898 (5)	0.0309 (7)
O8	0.4601 (7)	−0.0181 (3)	0.4257 (10)	0.0777 (18)
H1W	0.553 (6)	−0.004 (6)	0.515 (11)	0.093*
H2W	0.377 (7)	−0.006 (6)	0.451 (14)	0.093*
H4W	0.105 (10)	0.080 (2)	0.551 (16)	0.093*
H5W	0.092 (12)	−0.008 (5)	0.167 (10)	0.093*
H6W	0.229 (5)	0.011 (5)	0.340 (12)	0.093*
H7W	−0.214 (15)	0.067 (5)	0.393 (9)	0.093*
H8W	−0.195 (16)	0.034 (3)	0.238 (13)	0.093*
H3W	0.248 (3)	0.126 (4)	0.620 (19)	0.093*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0221 (3)	0.0153 (3)	0.0307 (3)	−0.0014 (2)	0.0111 (2)	0.0008 (2)
C1	0.024 (2)	0.021 (2)	0.033 (3)	0.0026 (14)	0.013 (2)	0.0011 (15)
C2	0.0229 (19)	0.0210 (17)	0.0315 (18)	0.0045 (18)	0.0084 (15)	−0.0004 (19)
C3	0.0223 (19)	0.0198 (18)	0.0229 (18)	0.0031 (15)	0.0083 (15)	0.0014 (14)
C4	0.0208 (18)	0.0218 (19)	0.0220 (17)	0.0000 (14)	0.0064 (15)	0.0016 (15)
C5	0.026 (2)	0.0141 (17)	0.032 (2)	0.0009 (13)	0.017 (2)	0.0013 (15)
C6	0.034 (3)	0.027 (2)	0.042 (3)	0.0042 (18)	0.022 (2)	0.0008 (16)
C7	0.045 (3)	0.0219 (18)	0.044 (2)	0.0067 (19)	0.025 (2)	0.0011 (18)
N1	0.0284 (18)	0.0215 (16)	0.0293 (17)	0.0018 (14)	0.0125 (15)	−0.0001 (14)
O1	0.0475 (19)	0.0275 (18)	0.0292 (16)	−0.0008 (15)	0.0133 (15)	0.0000 (14)
O2	0.055 (2)	0.0236 (14)	0.0343 (16)	−0.0049 (14)	0.0230 (16)	−0.0069 (13)
O3	0.0226 (17)	0.0253 (16)	0.0519 (19)	0.0004 (12)	0.0185 (14)	0.0011 (14)
O4	0.0274 (17)	0.0214 (15)	0.073 (2)	0.0041 (14)	0.0220 (17)	−0.0029 (19)
O5	0.0266 (16)	0.0281 (19)	0.033 (2)	−0.0011 (11)	0.0062 (16)	−0.0014 (12)
O6	0.0362 (17)	0.0247 (16)	0.056 (2)	0.0078 (15)	0.0077 (15)	−0.0088 (16)
O7	0.0313 (16)	0.0262 (15)	0.0355 (16)	−0.0074 (13)	0.0142 (14)	−0.0040 (14)
O8	0.035 (2)	0.054 (3)	0.108 (4)	0.0047 (18)	−0.006 (3)	−0.023 (3)

Geometric parameters (Å, º) top

Cu1—O7	2.061 (3)	C4—C1ⁱⁱ	1.525 (5)
Cu1—O6	2.068 (3)	C5—C6	1.325 (6)
Cu1—O3	2.071 (3)	C5—H5	0.9300
Cu1—O1	2.119 (4)	C6—C7	1.379 (7)
Cu1—O5	2.178 (5)	C6—H6	0.9300
Cu1—N1	2.187 (4)	C7—N1	1.350 (6)
C1—O1	1.228 (7)	C7—H7	0.9300
C1—O2	1.258 (6)	O5—H4W	0.82 (2)
C1—C4ⁱ	1.525 (5)	O5—H3W	0.82 (9)
C2—O4	1.227 (5)	O6—H5W	0.82 (7)
C2—O3	1.244 (6)	O6—H6W	0.83 (7)
C2—C3	1.552 (6)	O7—H7W	0.83 (8)
C3—N1	1.328 (5)	O7—H8W	0.83 (8)
C3—C4	1.399 (6)	O8—H1W	0.84 (8)
C4—C5	1.349 (6)	O8—H2W	0.83 (8)

O7—Cu1—O6	95.00 (16)	C3—C4—C1ⁱⁱ	123.2 (4)
O7—Cu1—O3	93.52 (13)	C6—C5—C4	117.5 (4)
O6—Cu1—O3	171.34 (14)	C6—C5—H5	121.2
O7—Cu1—O1	84.19 (14)	C4—C5—H5	121.2
O6—Cu1—O1	84.83 (16)	C5—C6—C7	121.3 (5)
O3—Cu1—O1	97.60 (15)	C5—C6—H6	119.3
O7—Cu1—O5	88.09 (15)	C7—C6—H6	119.3
O6—Cu1—O5	86.87 (16)	N1—C7—C6	121.4 (4)
O3—Cu1—O5	91.87 (14)	N1—C7—H7	119.3
O1—Cu1—O5	168.12 (14)	C6—C7—H7	119.3
O7—Cu1—N1	171.80 (13)	C3—N1—C7	118.0 (4)
O6—Cu1—N1	92.89 (17)	C3—N1—Cu1	110.5 (3)
O3—Cu1—N1	78.54 (13)	C7—N1—Cu1	131.3 (3)
O1—Cu1—N1	98.75 (15)	C1—O1—Cu1	145.4 (3)
O5—Cu1—N1	90.13 (15)	C2—O3—Cu1	117.2 (3)
O1—C1—O2	125.8 (4)	Cu1—O5—H4W	77 (8)
O1—C1—C4ⁱ	118.0 (4)	Cu1—O5—H3W	119 (10)
O2—C1—C4ⁱ	116.1 (4)	H4W—O5—H3W	114 (4)
O4—C2—O3	126.1 (5)	Cu1—O6—H5W	118 (7)
O4—C2—C3	117.0 (5)	Cu1—O6—H6W	122 (7)
O3—C2—C3	116.8 (4)	H5W—O6—H6W	114 (9)
N1—C3—C4	120.1 (4)	Cu1—O7—H7W	129 (8)
N1—C3—C2	115.9 (4)	Cu1—O7—H8W	92 (8)
C4—C3—C2	123.9 (4)	H7W—O7—H8W	112 (9)
C5—C4—C3	121.5 (4)	H1W—O8—H2W	111 (4)
C5—C4—C1ⁱⁱ	115.3 (4)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H3W···O4ⁱⁱ	0.82 (9)	1.93 (8)	2.735 (6)	167 (8)
O5—H4W···O6ⁱⁱⁱ	0.82 (2)	2.35 (8)	2.966 (5)	132 (10)
O6—H5W···O5^iv	0.82 (7)	2.29 (7)	2.966 (5)	140 (9)
O7—H7W···O2^v	0.83 (8)	1.90 (9)	2.720 (5)	169 (8)
O7—H8W···O2ⁱⁱⁱ	0.83 (8)	2.03 (4)	2.825 (5)	162 (11)

Symmetry codes: (ii) x+1/2, −y+1/2, z+1/2; (iii) x, −y, z+1/2; (iv) x, −y, z−1/2; (v) x, y, z+1.

Experimental details

Crystal data
Chemical formula	[Cu(C₇H₃NO₄)(H₂O)₃]·H₂O
M_r	300.71
Crystal system, space group	Monoclinic, Cc
Temperature (K)	296
a, b, c (Å)	8.513 (3), 17.983 (3), 7.493 (3)
β (°)	114.486 (10)
V (Å³)	1043.9 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.13
Crystal size (mm)	0.40 × 0.28 × 0.22

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2004)
T_min, T_max	0.484, 0.652
No. of measured, independent and observed [I > 2σ(I)] reflections	2686, 1322, 1310
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.089, 1.00
No. of reflections	1322
No. of parameters	180
No. of restraints	14
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.61, −0.60
Absolute structure	Flack (1983), 290 Friedel pairs
Absolute structure parameter	0.05 (3)

Computer programs: APEX2 (Bruker, 2004), SAINT-Plus (Bruker, 2004), SAINT-Plus (Bruker, 2004, SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Cu1—O7	2.061 (3)	Cu1—O1	2.119 (4)
Cu1—O6	2.068 (3)	Cu1—O5	2.178 (5)
Cu1—O3	2.071 (3)	Cu1—N1	2.187 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H3W···O4ⁱ	0.82 (9)	1.93 (8)	2.735 (6)	167 (8)
O5—H4W···O6ⁱⁱ	0.82 (2)	2.35 (8)	2.966 (5)	132 (10)
O6—H5W···O5ⁱⁱⁱ	0.82 (7)	2.29 (7)	2.966 (5)	140 (9)
O7—H7W···O2^iv	0.83 (8)	1.90 (9)	2.720 (5)	169 (8)
O7—H8W···O2ⁱⁱ	0.83 (8)	2.03 (4)	2.825 (5)	162 (11)

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

Acknowledgements

This work is supported by the Natural Science Foundation of Shandong Province (grant Nos. Y2007D39).

References

Bruker (2004). APEX2, SAINT-Plus and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Serre, C., Marrot, J. & Ferey, G. (2005). Inorg. Chem. 44, 654–658. Web of Science CSD CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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