Aqua­(6,6′-oxydipicolinato-κ2O,N,N′,O′)copper(II)

Sun, J.; Tong, X.

doi:10.1107/S160053680905346X

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 1| January 2010| Page m70

doi:10.1107/S160053680905346X

Open

access

Aqua(6,6′-oxydipicolinato-κ²O,N,N′,O′)copper(II)

Jingya Sun ^a ^* and Xiangdi Tong ^a

^aCollege of Marine Sciences, Zhejiang Ocean University, Zhoushan 316000, People's Republic of China
^*Correspondence e-mail: jingyasun2009@163.com

(Received 30 November 2009; accepted 11 December 2009; online 16 December 2009)

In the title complex, [Cu(C₁₂H₆N₂O₅)(H₂O)], the Cu^II ion is in a slightly distorted square-pyramidal coordination environment with two N and two O atoms from a 6,6′-oxydipicolinate ligand occupying the basal plane and a water ligand in the apical site. The dihedral angle between the two pyridine rings is 5.51 (6)°. In the crystal structure, intermolecular O—H⋯O hydrogen bonds link molecules into a two-dimensional network. In addition, weak intermolecular C—H⋯O and C=O(lone pair)⋯π(ring) interactions, with O⋯ring-centroid distances of 3.697 (4) and 3.094 (4) Å, provide additional stabilization.

Related literature

For intermolecular interactions, see: Choudhury et al. (2008 ). For the applications of picolinic acid compounds, see: Mann et al. (1992 ).

Experimental

Crystal data

[Cu(C₁₂H₆N₂O₅)(H₂O)]
M_r = 339.74
Monoclinic, P 2₁ /n
a = 7.2487 (16) Å
b = 21.055 (4) Å
c = 8.2269 (17) Å
β = 110.201 (9)°
V = 1178.4 (4) Å³
Z = 4
Mo Kα radiation
μ = 1.89 mm⁻¹
T = 296 K
0.40 × 0.35 × 0.30 mm

Data collection

Siemens SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.519, T_max = 0.602
6790 measured reflections
2074 independent reflections
1806 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.110
S = 1.18
2074 reflections
190 parameters
H-atom parameters constrained
Δρ_max = 0.48 e Å⁻³
Δρ_min = −0.37 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8⋯O4ⁱ	0.93	2.31	3.229 (4)	171
C9—H9⋯O2ⁱⁱ	0.93	2.42	3.331 (4)	165
C4—H4⋯O6ⁱⁱⁱ	0.93	2.54	3.303 (4)	140
O6—H6B⋯O4^iv	0.85	1.97	2.772 (3)	157
O6—H6A⋯O2^v	0.85	2.01	2.807 (3)	156
Symmetry codes: (i) x, y, z-1; (ii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iv) -x, -y, -z+2; (v) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: SMART (Siemens, 1996 ); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009 ) and SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680905346X/lh2964sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680905346X/lh2964Isup2.hkl

checkCIF report

Comment top

Picolinic acid compounds play an vital role in the development of coordination chemistry related to catalysis, magnetism and molecular architectures (Mann et al., 1992). As part of our studies on the synthesis and characterization of these types of compounds, we report here the synthesis and crystal structure of the title compound (I).

The molecular structure of the title compound (I) is shown in Fig. 1. The Cu^II ion is in a slightly distorted square-pyramidal coordination environment with two N and two O atoms from a 6,6'-oxydipicolinato ligand occupying the basal plane and one water ligand in the apical site. The dihedral angle between the two pyridine rings is 5.51 (6)°. The delocalization of electrons within the carboxylate groups is reflected in the C═O lengths. In the crystal structure, there are intermolecular O—H···O hydrogen bonds involving the carboxyl oxygen atoms and coordinated water molecules (Fig. 2) forming a two-dimensional network (see Table 1 for hydrogen bond geometries). In addition to weak intermolecular C-H···O interactions, further stabilization appears to be provided by weak C=O(lone pair)···π(ring) stacking interactions (Choudhury et al., 2008). The relevant distances are C12—O4···Cg1ⁱ = 3.697 (4) Å, Cg1 is the centroid of the ring defined by the atoms N1/C7-C11 [symmetry code: (i) -x, -y, 2-z] and the angle C12—O4···Cg1ⁱ is 98.95 (34)°; C1—O2···Cg2ⁱⁱ = 3.094 (4) Å, Cg2 is the centroid of the ring defined by the atoms N2/C2-C6 [symmetry code: (ii) 0.5+x, 0.5-y, 0.5+z] and the angle C1—O2···Cg2ⁱⁱ is 115.48 (4)° (see Fig. 3).

Related literature top

For information on similar types of intermolecular interactions as found in the title compound, see: Choudhury et al. (2008). For the applications of picolinic acid compounds, see: Mann et al. (1992).

Experimental top

All reagents were available commercially and were used without further purification. 6,6'-Oxydipicolinic acid (260 mg) was added to 1 mmol (132 mg) of CuCl₂ in 10 ml of water. The suspension was stirred for 4 h and filtered. After leaving the filtrate in air for one week, blue block-shaped crystals of (I) were formed. The crystals were isolated, washed with water three times and dried in a vacuum desicator using silica gel (Yield 75%). Elemental analysis: found C, 42.05; H, 2.96; N, 8.18%; calc. for C₁₂H₈CuN₂O₆; C, 42.17; H, 2.95; N, 8.20%.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009) and SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I) showing 50% proability displacement ellipsoids and the atom-numbering scheme.
	Fig. 2. Part of the crystal structure of (I) showing hydrogen bonds as dashed lines.
	Fig. 3. Part of the crystal structure of (I) showing C=O(lone pair)···π(ring) stacking interactions as dashed lines.

Aqua(6,6'-oxydipicolinato-κ²O,N,N',O')copper(II) top

Crystal data top

[Cu(C₁₂H₆N₂O₅)(H₂O)]	F(000) = 684
M_r = 339.74	D_x = 1.915 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2501 reflections
a = 7.2487 (16) Å	θ = 2.8–27.5°
b = 21.055 (4) Å	µ = 1.89 mm⁻¹
c = 8.2269 (17) Å	T = 296 K
β = 110.201 (9)°	Block, blue
V = 1178.4 (4) Å³	0.40 × 0.35 × 0.30 mm
Z = 4

Data collection top

Siemens SMART CCD diffractometer	2074 independent reflections
Radiation source: fine-focus sealed tube	1806 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
ϕ and ω scans	θ_max = 25.0°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→8
T_min = 0.519, T_max = 0.602	k = −24→24
6790 measured reflections	l = −9→8

Refinement top

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.110	H-atom parameters constrained
S = 1.18	w = 1/[σ²(F_o²) + (0.0671P)² + 0.1209P] where P = (F_o² + 2F_c²)/3
2074 reflections	(Δ/σ)_max < 0.001
190 parameters	Δρ_max = 0.48 e Å⁻³
0 restraints	Δρ_min = −0.37 e Å⁻³

Crystal data top

[Cu(C₁₂H₆N₂O₅)(H₂O)]	V = 1178.4 (4) Å³
M_r = 339.74	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.2487 (16) Å	µ = 1.89 mm⁻¹
b = 21.055 (4) Å	T = 296 K
c = 8.2269 (17) Å	0.40 × 0.35 × 0.30 mm
β = 110.201 (9)°

Data collection top

Siemens SMART CCD diffractometer	2074 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1806 reflections with I > 2σ(I)
T_min = 0.519, T_max = 0.602	R_int = 0.027
6790 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.110	H-atom parameters constrained
S = 1.18	Δρ_max = 0.48 e Å⁻³
2074 reflections	Δρ_min = −0.37 e Å⁻³
190 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	0.33165 (5)	0.109980 (17)	0.96148 (4)	0.02725 (18)
O3	0.2907 (3)	0.05841 (10)	1.1417 (3)	0.0327 (5)
N2	0.4163 (4)	0.14875 (12)	0.7848 (3)	0.0265 (6)
O1	0.4318 (3)	0.18774 (11)	1.0899 (3)	0.0336 (5)
O5	0.3272 (4)	0.06644 (11)	0.5777 (3)	0.0368 (6)
N1	0.2837 (4)	0.03042 (12)	0.8315 (3)	0.0254 (6)
O4	0.2158 (4)	−0.04040 (11)	1.1935 (3)	0.0409 (6)
O2	0.5275 (4)	0.28511 (11)	1.0481 (3)	0.0410 (6)
C12	0.2463 (4)	0.00062 (15)	1.1003 (4)	0.0268 (7)
C1	0.4833 (5)	0.23022 (15)	1.0031 (4)	0.0297 (7)
O6	0.0171 (3)	0.14739 (11)	0.8390 (3)	0.0382 (6)
H6A	−0.0120	0.1623	0.7373	0.046*
H6B	−0.0521	0.1144	0.8010	0.046*
C2	0.4850 (5)	0.20891 (14)	0.8261 (4)	0.0284 (7)
C5	0.4587 (5)	0.15934 (17)	0.5117 (4)	0.0342 (8)
H5	0.4473	0.1419	0.4048	0.041*
C11	0.2346 (4)	−0.01770 (15)	0.9187 (4)	0.0258 (7)
C10	0.1814 (5)	−0.07640 (16)	0.8462 (4)	0.0348 (8)
H10	0.1481	−0.1089	0.9075	0.042*
C6	0.4036 (5)	0.12555 (15)	0.6311 (4)	0.0298 (7)
C8	0.2272 (5)	−0.03744 (16)	0.5894 (4)	0.0358 (8)
H8	0.2241	−0.0430	0.4763	0.043*
C7	0.2808 (5)	0.02011 (15)	0.6721 (4)	0.0280 (7)
C9	0.1787 (5)	−0.08608 (16)	0.6763 (4)	0.0374 (8)
H9	0.1441	−0.1255	0.6235	0.045*
C3	0.5440 (5)	0.24521 (16)	0.7162 (4)	0.0366 (8)
H3	0.5919	0.2861	0.7470	0.044*
C4	0.5311 (5)	0.21967 (17)	0.5561 (5)	0.0407 (9)
H4	0.5715	0.2435	0.4793	0.049*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0409 (3)	0.0226 (3)	0.0216 (3)	−0.00293 (15)	0.01511 (19)	−0.00212 (14)
O3	0.0481 (14)	0.0300 (13)	0.0229 (11)	−0.0044 (10)	0.0161 (10)	−0.0017 (9)
N2	0.0309 (14)	0.0253 (14)	0.0242 (13)	0.0005 (11)	0.0105 (10)	0.0002 (11)
O1	0.0470 (14)	0.0288 (12)	0.0267 (11)	−0.0051 (10)	0.0150 (10)	−0.0053 (9)
O5	0.0589 (16)	0.0326 (13)	0.0237 (11)	−0.0090 (11)	0.0203 (11)	−0.0052 (10)
N1	0.0327 (14)	0.0225 (13)	0.0220 (12)	−0.0009 (11)	0.0108 (10)	−0.0010 (10)
O4	0.0594 (16)	0.0381 (14)	0.0303 (12)	−0.0093 (12)	0.0219 (11)	0.0034 (11)
O2	0.0495 (15)	0.0263 (13)	0.0471 (15)	−0.0071 (10)	0.0166 (12)	−0.0104 (11)
C12	0.0283 (16)	0.0302 (18)	0.0215 (15)	0.0000 (13)	0.0082 (13)	0.0033 (13)
C1	0.0275 (16)	0.0285 (19)	0.0323 (16)	0.0031 (13)	0.0094 (13)	−0.0018 (14)
O6	0.0378 (13)	0.0339 (13)	0.0400 (13)	0.0015 (10)	0.0098 (11)	0.0019 (11)
C2	0.0286 (16)	0.0233 (16)	0.0310 (16)	−0.0001 (13)	0.0075 (13)	0.0014 (13)
C5	0.0361 (18)	0.040 (2)	0.0298 (17)	0.0017 (14)	0.0164 (14)	0.0037 (14)
C11	0.0289 (16)	0.0250 (16)	0.0234 (15)	0.0026 (12)	0.0087 (12)	0.0014 (12)
C10	0.048 (2)	0.0268 (18)	0.0324 (18)	−0.0054 (14)	0.0167 (15)	−0.0001 (14)
C6	0.0361 (18)	0.0305 (18)	0.0246 (16)	0.0025 (14)	0.0130 (13)	0.0022 (13)
C8	0.046 (2)	0.036 (2)	0.0277 (16)	−0.0008 (15)	0.0161 (15)	−0.0095 (15)
C7	0.0348 (17)	0.0279 (17)	0.0227 (15)	0.0012 (13)	0.0117 (13)	−0.0001 (13)
C9	0.050 (2)	0.0285 (18)	0.0346 (18)	−0.0074 (16)	0.0160 (16)	−0.0114 (15)
C3	0.0374 (19)	0.0310 (18)	0.042 (2)	−0.0050 (15)	0.0142 (15)	0.0034 (16)
C4	0.043 (2)	0.042 (2)	0.042 (2)	−0.0028 (16)	0.0217 (16)	0.0123 (17)

Geometric parameters (Å, º) top

Cu1—O3	1.942 (2)	O6—H6A	0.8500
Cu1—N2	1.942 (3)	O6—H6B	0.8501
Cu1—O1	1.948 (2)	C2—C3	1.361 (5)
Cu1—N1	1.953 (2)	C5—C4	1.375 (5)
Cu1—O6	2.290 (2)	C5—C6	1.379 (4)
O3—C12	1.275 (4)	C5—H5	0.9300
N2—C6	1.328 (4)	C11—C10	1.368 (5)
N2—C2	1.361 (4)	C10—C9	1.406 (5)
O1—C1	1.278 (4)	C10—H10	0.9300
O5—C7	1.359 (4)	C8—C9	1.363 (5)
O5—C6	1.371 (4)	C8—C7	1.378 (5)
N1—C7	1.323 (4)	C8—H8	0.9300
N1—C11	1.358 (4)	C9—H9	0.9300
O4—C12	1.225 (4)	C3—C4	1.395 (5)
O2—C1	1.222 (4)	C3—H3	0.9300
C12—C11	1.517 (4)	C4—H4	0.9300
C1—C2	1.528 (4)

O3—Cu1—N2	167.91 (10)	N2—C2—C1	112.9 (3)
O3—Cu1—O1	100.51 (9)	C3—C2—C1	125.2 (3)
N2—Cu1—O1	84.13 (10)	C4—C5—C6	117.7 (3)
O3—Cu1—N1	83.87 (9)	C4—C5—H5	121.1
N2—Cu1—N1	89.62 (10)	C6—C5—H5	121.1
O1—Cu1—N1	168.68 (10)	N1—C11—C10	122.0 (3)
O3—Cu1—O6	97.86 (10)	N1—C11—C12	113.2 (3)
N2—Cu1—O6	92.86 (10)	C10—C11—C12	124.8 (3)
O1—Cu1—O6	94.45 (9)	C11—C10—C9	118.0 (3)
N1—Cu1—O6	95.29 (10)	C11—C10—H10	121.0
C12—O3—Cu1	114.87 (19)	C9—C10—H10	121.0
C6—N2—C2	118.7 (3)	N2—C6—O5	121.8 (3)
C6—N2—Cu1	128.4 (2)	N2—C6—C5	123.1 (3)
C2—N2—Cu1	112.8 (2)	O5—C6—C5	115.1 (3)
C1—O1—Cu1	114.29 (19)	C9—C8—C7	118.8 (3)
C7—O5—C6	128.3 (2)	C9—C8—H8	120.6
C7—N1—C11	118.9 (3)	C7—C8—H8	120.6
C7—N1—Cu1	128.5 (2)	N1—C7—O5	121.8 (3)
C11—N1—Cu1	112.4 (2)	N1—C7—C8	122.6 (3)
O4—C12—O3	126.1 (3)	O5—C7—C8	115.6 (3)
O4—C12—C11	118.5 (3)	C8—C9—C10	119.7 (3)
O3—C12—C11	115.4 (3)	C8—C9—H9	120.2
O2—C1—O1	126.1 (3)	C10—C9—H9	120.2
O2—C1—C2	118.6 (3)	C2—C3—C4	118.5 (3)
O1—C1—C2	115.3 (3)	C2—C3—H3	120.8
Cu1—O6—H6A	115.6	C4—C3—H3	120.8
Cu1—O6—H6B	104.6	C5—C4—C3	120.1 (3)
H6A—O6—H6B	91.5	C5—C4—H4	119.9
N2—C2—C3	121.9 (3)	C3—C4—H4	119.9

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8···O4ⁱ	0.93	2.31	3.229 (4)	171
C9—H9···O2ⁱⁱ	0.93	2.42	3.331 (4)	165
C4—H4···O6ⁱⁱⁱ	0.93	2.54	3.303 (4)	140
O6—H6B···O4^iv	0.85	1.97	2.772 (3)	157
O6—H6A···O2^v	0.85	2.01	2.807 (3)	156

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

Experimental details

Crystal data
Chemical formula	[Cu(C₁₂H₆N₂O₅)(H₂O)]
M_r	339.74
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	7.2487 (16), 21.055 (4), 8.2269 (17)
β (°)	110.201 (9)
V (Å³)	1178.4 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.89
Crystal size (mm)	0.40 × 0.35 × 0.30

Data collection
Diffractometer	Siemens SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.519, 0.602
No. of measured, independent and observed [I > 2σ(I)] reflections	6790, 2074, 1806
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.110, 1.18
No. of reflections	2074
No. of parameters	190
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.48, −0.37

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009) and SHELXTL (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8···O4ⁱ	0.93	2.31	3.229 (4)	171.4
C9—H9···O2ⁱⁱ	0.93	2.42	3.331 (4)	165.2
C4—H4···O6ⁱⁱⁱ	0.93	2.54	3.303 (4)	139.5
O6—H6B···O4^iv	0.85	1.97	2.772 (3)	157.2
O6—H6A···O2^v	0.85	2.01	2.807 (3)	156.0

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

References

Choudhury, S. R., Gamez, P., Robertazzi, A., Chen, C. Y., Lee, H. M. & Mukhopadhyay, S. (2008). Cryst. Growth Des. 8, 3773–3784. Web of Science CSD CrossRef CAS Google Scholar
Mann, Y., Chiment, F., Balasco, A., Cenicola, M. L., Amico, M. D., Parrilo, C., Rossi, F. & Marmo, E. (1992). Eur. J. Med. Chem. 27, 633–639. Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 1| January 2010| Page m70

doi:10.1107/S160053680905346X

Open

access