Aqua­bis­­(methacrylato-κO)bis­(pyridine-κN)copper(II)

In the crystal structure of the title complex, [Cu(C₄H₅O₂)₂(C₅H₅N)₂(H₂O)], the Cu^II cation is located on a twofold rotation axis and coordinated by two methyl­acrylate anions, two pyridine ligands and one water mol­ecule in a distorted square-pyramidal geometry. The coordinated water mol­ecule is also located on the twofold axis. In the crystal structure O—H⋯O hydrogen bonds link the mol­ecules, forming chains along the c axis.

Related literature

For general background to copper complexes, see: Du et al. (2004); Hu et al. (2004); Zhu et al. (2007). For a related structure, see: Wu & Wang (2004).

Experimental

Crystal data

• [Cu(C₄H₅O₂)₂(C₅H₅N)₂(H₂O)]

• M_r = 409.92

• Orthorhombic, F d d 2

• a = 15.619 (3) Å

• b = 40.200 (8) Å

• c = 6.0576 (12) Å

• V = 3803.4 (13) ų

• Z = 8

• Mo Kα radiation

• μ = 1.18 mm⁻¹

• T = 293 K

• 0.50 × 0.36 × 0.08 mm

Data collection

• Rigaku R-AXIS RAPID IP diffractometer

• Absorption correction: multi-scan ABSCOR (Higashi, 1995) T_min = 0.612, T_max = 0.913

• 7925 measured reflections

• 1808 independent reflections

• 1740 reflections with I > 2σ(I)

• R_int = 0.027

Refinement

• R[F² > 2σ(F²)] = 0.021

• wR(F²) = 0.055

• S = 1.09

• 1808 reflections

• 124 parameters

• 1 restraint

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.15 e Å⁻³

• Δρ_min = −0.19 e Å⁻³

• Absolute structure: Flack (1983), 797 Friedel pairs

• Flack parameter: 0.006 (13)

Table 1
Selected bond lengths (Å)

Cu—O1	2.281 (2)
Cu—O2	1.9389 (12)
Cu—N1	2.0254 (14)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O3^i	0.83 (3)	1.96 (3)	2.783 (2)	178 (2)
Symmetry code: (i) x, y, z+1.

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008; program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Supporting information

S1. Comment

Copper complexes with organic acids and other donor ligands exist extensively in living things, playing an important role in a vast range of chemical and biochemical catalytic systems. A series of copper-carboxylate complexes has been reported (Du et al., 2004; Hu et al., 2004; Zhu et al., 2007).

The molecular structure is shown in Fig. 1. The Cu atom is located on a twofold axis and coordinated with two methylacrylate, two pyridine ligands and one coordinated water molecule in a distorted square-pyramidal geometry (Table 1).

The compound is an infinite one-dimensional network structure connected by hydrogen bonds. It forms hydrogen bonds between coordination waters and carboxy group (Table 2).

The corresponding complex with one pyridine ligand has binuclear cage structural unit, two Cu atoms are bridged by four µ₂–O,O'α-methacrylate groups, forming a cage structure (Wu et al., 2004).

Related literature

For general background to copper complexes, see: Du et al. (2004); Hu et al. (2004); Zhu et al. (2007). For a related structure, see: Wu et al. (2004).

S2. Experimental

HL, CH₂C(CH₃)COOH, (0.5 ml, 6.0 mmol) and Cu(NO₃)₂.3H₂O (240 mg, 1.0 mmol) were dissolved in 60 ml H₂O, and the pH adjusted to 4.0 using 0.5 M NaOH. Two mililiters of 1.0 M pyridine solution were added into the mixed solution with stirring. After filtration, the filtrate was allowed to stand at room temperature and single crystals were obtained after one week.

S3. Refinement

Methyl H atoms were constrained to an ideal geometry with C—H distances of 0.96 Å and U_iso(H) = 1.5U_eq(C), but each group was allowed to rotate freely about its C—C bond. The methylene H atoms and aromatic H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms with C—H distances of 0.93 Å and U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008; program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

Fig. 1. The molecular structure of the title molecule showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level for non-H atoms.

Aquabis(methacrylato-κO)bis(pyridine-κN)copper(II)

Crystal data

[Cu(C4H5O2)2(C5H5N)2(H2O)]	F(000) = 1704
Mr = 409.92	Dx = 1.432 Mg m^−3
Orthorhombic, Fdd2	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: F 2 -2d	Cell parameters from 8692 reflections
a = 15.619 (3) Å	θ = 3.0–27.5°
b = 40.200 (8) Å	µ = 1.18 mm^−1
c = 6.0576 (12) Å	T = 293 K
V = 3803.4 (13) Å^3	Platelet, blue
Z = 8	0.50 × 0.36 × 0.08 mm

Data collection

Rigaku R-AXIS RAPID IP diffractometer	1808 independent reflections
Radiation source: fine-focus sealed tube	1740 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.027
Detector resolution: 10.00 pixels mm^-1	θmax = 25.8°, θmin = 3.3°
ω scans	h = −18→18
Absorption correction: multi-scan ABSCOR (Higashi, 1995)	k = −48→48
Tmin = 0.612, Tmax = 0.913	l = −7→7
7925 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.021	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.055	w = 1/[σ^2(Fo^2) + (0.0325P)^2 + 0.6515P] where P = (Fo^2 + 2Fc^2)/3
S = 1.09	(Δ/σ)max < 0.001
1808 reflections	Δρmax = 0.15 e Å^−3
124 parameters	Δρmin = −0.19 e Å^−3
1 restraint	Absolute structure: Flack (1983), 797 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.006 (13)

Special details

Experimental. Analysis: calculated C 52.74, H 5.41, N 6.83%; found C 52.61, H 5.22, N 6.69%. Spectroscopic analysis: IR (KBr, ν cm^-1): 700, 832, 936, 1036, 1214, 1243, 1368, 1417, 1599, 1642.

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
Cu	1.0000	0.0000	0.11357 (7)	0.03375 (10)
O1	1.0000	0.0000	0.4901 (4)	0.0450 (5)
O2	1.05574 (8)	0.04310 (3)	0.1163 (3)	0.0442 (3)
O3	1.03022 (11)	0.05452 (4)	−0.2378 (3)	0.0529 (4)
N1	0.88531 (9)	0.02292 (3)	0.0789 (3)	0.0361 (3)
C1	1.05091 (11)	0.06268 (5)	−0.0494 (3)	0.0371 (4)
C2	1.07255 (14)	0.09857 (5)	−0.0019 (4)	0.0460 (5)
C3	1.0791 (3)	0.10857 (7)	0.2115 (5)	0.0967 (13)
H3A	1.0922	0.1306	0.2439	0.116*
H3B	1.0705	0.0934	0.3252	0.116*
C4	1.0850 (2)	0.12071 (5)	−0.1829 (5)	0.0694 (7)
H4A	1.1000	0.1423	−0.1281	0.104*
H4B	1.0331	0.1222	−0.2672	0.104*
H4C	1.1302	0.1125	−0.2752	0.104*
C5	0.83858 (12)	0.01819 (5)	−0.1017 (3)	0.0431 (5)
H5	0.8607	0.0050	−0.2143	0.052*
C6	0.75841 (12)	0.03207 (5)	−0.1284 (8)	0.0485 (4)
H6	0.7275	0.0286	−0.2576	0.058*
C7	0.72506 (13)	0.05110 (5)	0.0387 (4)	0.0493 (5)
H7	0.6705	0.0602	0.0262	0.059*
C8	0.77349 (15)	0.05649 (5)	0.2250 (5)	0.0523 (6)
H8	0.7525	0.0695	0.3397	0.063*
C9	0.85367 (14)	0.04220 (4)	0.2390 (4)	0.0443 (4)
H9	0.8868	0.0461	0.3640	0.053*
H1	1.0098 (15)	0.0163 (6)	0.569 (6)	0.052 (8)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu	0.02640 (14)	0.04033 (15)	0.03451 (15)	0.00130 (13)	0.000	0.000
O1	0.0619 (14)	0.0422 (12)	0.0309 (11)	−0.0041 (9)	0.000	0.000
O2	0.0355 (6)	0.0454 (6)	0.0516 (8)	−0.0031 (5)	−0.0055 (7)	0.0079 (7)
O3	0.0684 (10)	0.0493 (7)	0.0410 (8)	−0.0091 (7)	0.0044 (8)	−0.0081 (7)
N1	0.0290 (7)	0.0405 (7)	0.0389 (9)	0.0003 (6)	0.0015 (7)	0.0002 (7)
C1	0.0287 (9)	0.0394 (9)	0.0432 (10)	0.0040 (7)	0.0049 (8)	−0.0027 (8)
C2	0.0534 (12)	0.0379 (9)	0.0468 (11)	0.0101 (8)	−0.0090 (10)	−0.0030 (9)
C3	0.185 (4)	0.0516 (14)	0.0534 (16)	0.0172 (18)	−0.027 (2)	−0.0070 (12)
C4	0.109 (2)	0.0436 (10)	0.0552 (16)	−0.0013 (12)	−0.0059 (15)	0.0058 (11)
C5	0.0357 (9)	0.0541 (10)	0.0394 (12)	0.0002 (8)	−0.0002 (8)	−0.0046 (8)
C6	0.0362 (9)	0.0556 (10)	0.0538 (11)	−0.0010 (8)	−0.0128 (11)	0.0031 (17)
C7	0.0319 (9)	0.0450 (10)	0.0711 (15)	0.0064 (8)	−0.0002 (10)	0.0046 (10)
C8	0.0475 (12)	0.0461 (11)	0.0634 (14)	0.0101 (9)	0.0061 (11)	−0.0088 (11)
C9	0.0419 (11)	0.0457 (9)	0.0453 (11)	0.0022 (8)	−0.0027 (9)	−0.0038 (9)

Geometric parameters (Å, º)

Cu—O1	2.281 (2)	C3—H3B	0.9300
Cu—O2	1.9389 (12)	C4—H4A	0.9600
Cu—O2^i	1.9391 (12)	C4—H4B	0.9600
Cu—N1	2.0254 (14)	C4—H4C	0.9600
Cu—N1^i	2.0254 (14)	C5—C6	1.380 (3)
O1—H1	0.82 (3)	C5—H5	0.9300
O2—C1	1.278 (2)	C6—C7	1.371 (5)
O3—C1	1.230 (3)	C6—H6	0.9300
N1—C5	1.329 (3)	C7—C8	1.376 (4)
N1—C9	1.336 (3)	C7—H7	0.9300
C1—C2	1.510 (3)	C8—C9	1.380 (3)
C2—C3	1.357 (4)	C8—H8	0.9300
C2—C4	1.425 (3)	C9—H9	0.9300
C3—H3A	0.9300
O2—Cu—O2^i	179.03 (10)	H3A—C3—H3B	120.0
O2—Cu—N1	89.51 (5)	C2—C4—H4A	109.5
O2^i—Cu—N1	90.59 (5)	C2—C4—H4B	109.5
O2—Cu—N1^i	90.59 (5)	H4A—C4—H4B	109.5
O2^i—Cu—N1^i	89.51 (5)	C2—C4—H4C	109.5
N1—Cu—N1^i	168.08 (10)	H4A—C4—H4C	109.5
O2—Cu—O1	89.51 (5)	H4B—C4—H4C	109.5
O2^i—Cu—O1	89.51 (5)	N1—C5—C6	122.5 (3)
N1—Cu—O1	95.96 (5)	N1—C5—H5	118.8
N1^i—Cu—O1	95.96 (5)	C6—C5—H5	118.8
Cu—O1—H1	126 (2)	C7—C6—C5	118.9 (3)
C1—O2—Cu	121.15 (13)	C7—C6—H6	120.5
C5—N1—C9	118.52 (16)	C5—C6—H6	120.5
C5—N1—Cu	120.41 (13)	C6—C7—C8	119.0 (2)
C9—N1—Cu	121.03 (14)	C6—C7—H7	120.5
O3—C1—O2	125.43 (17)	C8—C7—H7	120.5
O3—C1—C2	119.36 (18)	C7—C8—C9	118.9 (2)
O2—C1—C2	115.21 (18)	C7—C8—H8	120.5
C3—C2—C4	122.5 (2)	C9—C8—H8	120.5
C3—C2—C1	118.8 (2)	N1—C9—C8	122.1 (2)
C4—C2—C1	118.7 (2)	N1—C9—H9	118.9
C2—C3—H3A	120.0	C8—C9—H9	118.9
C2—C3—H3B	120.0

Symmetry code: (i) −x+2, −y, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O3^ii	0.83 (3)	1.96 (3)	2.783 (2)	178 (2)

Symmetry code: (ii) x, y, z+1.