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Acta Cryst. (2009). E65, m1208    [ doi:10.1107/S160053680903582X ]

Bis(2-methoxyphenolato-[kappa]2O,O')copper(II)

G.-Z. Mao, X.-L. Nong and S. H. Zhang

Abstract top

In the title compound, [Cu(C7H7O2)2], the asymmetric unit contains one and a half molecules with the central Cu(II) atoms situated on a general position and on a centre of inversion, respectively. Both Cu(II) atoms show a similar slightly distorted square-planar coordination, resulting from four O atoms of two 2-methoxyphenolate anions.

Comment top

2-Methoxy-phenol ligand can act as either mondentate ligand (Campello, et al., 1997), or didentate ligand (Sobota, et al., 2001), or mu2-o ligand or mu3:eta1:eta2-O ligand (Schumann, et al. 1996) or mu4:eta1:eta3-O ligand (Floriani, et al. 1988). However, copper compound with 2-Methoxy-phenol have not been reported till today (http://www.ccdc.cam.ac.uk/). The title compound, (I), is a new CuII complex prepared by reaction of 2-Methoxy-phenol and Copper(II) nitrate using solvothermal technique.

There are one CuÎI^ atom and two L- ligand in the asymetric unit. The CuII atom has a slightly distorted square-planar environment, formed by four O atoms from two different L- ligands. The L- ligand binds to copper in a didentate mode, through two O atoms. In the title complex, the two copper lied in the different position that the Cu2 is at the center of symmetry (010) plane and the Cu1 is at a general position (Fig. 2). The complex further constructed a 3-D network through very weak C–H···O hydrogen bond (C21–H21···O1i, 3.426 (1) Å, symmetry code: (i) 1 - y,2 - y,1 - z) and C–H···p hydrogen bond (C16···Pii, 3.652 (1) Å, symmetry code: (ii) 1 + x, y, z).

Related literature top

For 2-methoxy-phenol compounds, see: Campello et al. (1997); Floriani et al. (1988); Minhas et al. (1993); Kuo et al. (1999); Schumann et al. (1996); Sobota et al. (2001).

Experimental top

A solution of (0.124 g, 1 mmol) 2-Methoxy-phenol and (0.056 g, 1 mmol) potassium hydroxide in 8 ml absolute methanol was added ((0.125 g, 0.5 mmol) Copper nitrate tetrahydrate. The solution was placed in a 15-ml Tetlon-lined stainless steel parr bomb. The bomd was heated at 363 k for 96 h. The cooled mixture yielded blue block-shaped crystal of (1) in about 71% yield. The crystals were washed with methanol and then dried in air.

Refinement top

H atoms were positioned geometrically and refined with a riding model, with distances 0.96 Å(CH3) or 0.93 Å(aromatic ring). and with Uiso(H) = 1.2 Ueq(aromatic ring) or Uiso(H) = 1.5 Ueq((CH3).

Computing details top

Data collection: XSCANS (Bruker, 1997); cell refinement: XSCANS (Bruker, 1997); data reduction: SHELXTL (Sheldrick, 2008); 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
[Figure 1] Fig. 1. The molecular structure of (I), showing 30% probability displacement ellipsoids. Symmetry codes: (A) -x + 1, -y + 2, -z + 1.
[Figure 2] Fig. 2. Packing diagram of title complex,hydrogen atoms were omitted.
Bis(2-methoxyphenolato-κ2O,O')copper(II) top
Crystal data top
[Cu(C7H7O2)2]Z = 3
Mr = 333.82F(000) = 513
Triclinic, P1Dx = 1.425 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 9.5190 (19) ÅCell parameters from 4216 reflections
b = 11.540 (2) Åθ = 3.1–25.3°
c = 12.488 (3) ŵ = 1.42 mm−1
α = 102.83 (3)°T = 293 K
β = 103.93 (3)°Block, blue
γ = 111.20 (3)°0.23 × 0.12 × 0.08 mm
V = 1166.7 (6) Å3
Data collection top
Bruker P4
diffractometer		4164 independent reflections
Radiation source: fine-focus sealed tube3466 reflections with I > 2σ(I)
graphiteRint = 0.037
ω scansθmax = 25.3°, θmin = 3.1°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −11→11
Tmin = 0.656, Tmax = 0.857k = −13→13
6930 measured reflectionsl = −14→12
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.051Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.129H-atom parameters constrained
S = 0.93 w = 1/[σ2(Fo2) + (0.0653P)2 + 1.5P]
where P = (Fo2 + 2Fc2)/3
4164 reflections(Δ/σ)max = 0.001
289 parametersΔρmax = 0.70 e Å−3
4 restraintsΔρmin = −0.63 e Å−3
Crystal data top
[Cu(C7H7O2)2]γ = 111.20 (3)°
Mr = 333.82V = 1166.7 (6) Å3
Triclinic, P1Z = 3
a = 9.5190 (19) ÅMo Kα radiation
b = 11.540 (2) ŵ = 1.42 mm−1
c = 12.488 (3) ÅT = 293 K
α = 102.83 (3)°0.23 × 0.12 × 0.08 mm
β = 103.93 (3)°
Data collection top
Bruker P4
diffractometer		3466 reflections with I > 2σ(I)
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		Rint = 0.037
Tmin = 0.656, Tmax = 0.857θmax = 25.3°
6930 measured reflectionsStandard reflections: ?
4164 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.051H-atom parameters constrained
wR(F2) = 0.129Δρmax = 0.70 e Å−3
S = 0.93Δρmin = −0.63 e Å−3
4164 reflectionsAbsolute structure: ?
289 parametersFlack parameter: ?
4 restraintsRogers parameter: ?
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
xyzUiso*/Ueq
Cu10.52201 (5)0.70662 (4)0.76824 (4)0.03605 (16)
Cu20.50001.00000.50000.03477 (19)
C10.1962 (4)0.5274 (4)0.7391 (3)0.0393 (9)
C20.0931 (5)0.4117 (4)0.7551 (4)0.0544 (11)
H20.13880.36650.79340.065*
C3−0.0719 (6)0.3655 (5)0.7154 (5)0.0700 (14)
H3−0.13550.29010.72730.084*
C4−0.1437 (6)0.4304 (6)0.6579 (5)0.0746 (15)
H4−0.25520.39790.62980.090*
C5−0.0486 (5)0.5435 (5)0.6426 (4)0.0628 (13)
H5−0.09820.58670.60460.075*
C60.1233 (4)0.5970 (4)0.6827 (3)0.0418 (9)
C70.2162 (4)0.7193 (4)0.6650 (3)0.0419 (9)
C80.1304 (5)0.7895 (5)0.6067 (4)0.0573 (12)
H8A0.20860.86940.60530.086*
H8B0.06720.81070.65020.086*
H8C0.06130.73280.52780.086*
C90.8449 (4)0.8867 (4)0.7933 (4)0.0414 (9)
C100.9435 (5)1.0056 (4)0.7786 (4)0.0559 (11)
H100.89511.04500.73420.067*
C111.1084 (6)1.0620 (5)0.8293 (5)0.0699 (14)
H111.16991.13860.81800.084*
C121.1844 (5)1.0075 (5)0.8966 (5)0.0727 (15)
H121.29601.04770.93150.087*
C131.0938 (5)0.8930 (5)0.9118 (4)0.0605 (12)
H131.14640.85630.95650.073*
C140.9226 (4)0.8284 (4)0.8617 (3)0.0410 (9)
C150.8344 (4)0.7091 (4)0.8844 (3)0.0425 (9)
C160.9244 (6)0.6458 (5)0.9492 (5)0.0648 (13)
H16A0.84850.56570.95200.097*
H16B0.99020.70581.02770.097*
H16C0.99150.62590.90890.097*
C170.4664 (4)0.8676 (4)0.2612 (3)0.0362 (8)
C180.4051 (5)0.8508 (4)0.1408 (3)0.0453 (9)
H180.36340.90740.11970.054*
C190.4051 (5)0.7535 (4)0.0537 (4)0.0472 (10)
H190.36190.7437−0.02470.057*
C200.4707 (5)0.6694 (4)0.0840 (4)0.0465 (10)
H200.47240.60420.02590.056*
C210.5329 (4)0.6839 (4)0.2007 (4)0.0423 (9)
H210.57760.62830.21970.051*
C220.5311 (4)0.7810 (3)0.2934 (3)0.0336 (8)
C230.5920 (4)0.7872 (4)0.4156 (3)0.0378 (8)
C240.6642 (7)0.6950 (5)0.4440 (4)0.0690 (14)
H24A0.69450.70980.52670.104*
H24B0.75760.71210.42180.104*
H24C0.58610.60490.40130.104*
O10.3522 (3)0.5619 (2)0.7790 (2)0.0421 (6)
O20.3737 (4)0.7706 (3)0.6987 (3)0.0619 (8)
O30.6876 (3)0.8377 (3)0.7402 (3)0.0506 (7)
O40.6767 (4)0.6530 (3)0.8491 (3)0.0633 (9)
O50.4601 (4)0.9650 (3)0.3363 (2)0.0488 (7)
O60.5830 (4)0.8684 (3)0.5029 (3)0.0571 (8)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0312 (3)0.0370 (3)0.0406 (3)0.0157 (2)0.0112 (2)0.0147 (2)
Cu20.0444 (4)0.0352 (3)0.0314 (4)0.0241 (3)0.0137 (3)0.0117 (3)
C10.038 (2)0.039 (2)0.039 (2)0.0164 (16)0.0172 (17)0.0062 (17)
C20.051 (2)0.046 (2)0.066 (3)0.017 (2)0.027 (2)0.020 (2)
C30.049 (3)0.062 (3)0.087 (4)0.007 (2)0.034 (3)0.021 (3)
C40.034 (2)0.080 (4)0.093 (4)0.011 (2)0.020 (2)0.026 (3)
C50.038 (2)0.078 (3)0.064 (3)0.023 (2)0.012 (2)0.021 (3)
C60.0350 (19)0.048 (2)0.039 (2)0.0179 (17)0.0128 (17)0.0089 (18)
C70.0368 (18)0.053 (2)0.037 (2)0.0237 (18)0.0122 (16)0.0116 (19)
C80.052 (2)0.070 (3)0.061 (3)0.037 (2)0.016 (2)0.027 (3)
C90.036 (2)0.043 (2)0.043 (2)0.0142 (17)0.0169 (17)0.0146 (19)
C100.052 (3)0.050 (3)0.066 (3)0.017 (2)0.023 (2)0.027 (2)
C110.056 (3)0.056 (3)0.079 (4)0.003 (2)0.029 (3)0.022 (3)
C120.035 (2)0.073 (3)0.084 (4)0.003 (2)0.016 (2)0.020 (3)
C130.037 (2)0.078 (3)0.057 (3)0.021 (2)0.008 (2)0.023 (3)
C140.0334 (19)0.047 (2)0.038 (2)0.0156 (17)0.0107 (16)0.0122 (18)
C150.037 (2)0.055 (2)0.037 (2)0.0239 (18)0.0115 (17)0.0163 (19)
C160.057 (3)0.081 (3)0.066 (3)0.038 (3)0.014 (2)0.040 (3)
C170.0349 (18)0.0349 (19)0.035 (2)0.0156 (16)0.0097 (16)0.0073 (17)
C180.048 (2)0.050 (2)0.038 (2)0.0260 (19)0.0090 (18)0.0129 (19)
C190.052 (2)0.049 (2)0.031 (2)0.0178 (19)0.0122 (18)0.0062 (19)
C200.054 (2)0.039 (2)0.041 (2)0.0181 (18)0.0202 (19)0.0031 (18)
C210.043 (2)0.034 (2)0.052 (3)0.0194 (17)0.0206 (19)0.0093 (18)
C220.0306 (17)0.0305 (18)0.039 (2)0.0132 (14)0.0133 (15)0.0089 (16)
C230.0389 (19)0.0342 (19)0.046 (2)0.0214 (16)0.0170 (17)0.0123 (17)
C240.100 (4)0.081 (3)0.055 (3)0.071 (3)0.024 (3)0.023 (3)
O10.0376 (14)0.0390 (14)0.0541 (17)0.0187 (11)0.0173 (12)0.0189 (13)
O20.0529 (17)0.065 (2)0.074 (2)0.0300 (15)0.0214 (16)0.0286 (18)
O30.0351 (14)0.0563 (17)0.065 (2)0.0183 (13)0.0134 (13)0.0364 (16)
O40.0519 (18)0.065 (2)0.079 (2)0.0271 (16)0.0203 (16)0.0362 (18)
O50.079 (2)0.0494 (16)0.0350 (15)0.0463 (15)0.0201 (14)0.0154 (13)
O60.0668 (19)0.0625 (19)0.0566 (19)0.0401 (16)0.0235 (16)0.0246 (16)
Geometric parameters (Å, °) top
Cu1—O11.916 (3)C11—C121.378 (7)
Cu1—O31.916 (3)C11—H110.9300
Cu1—O21.934 (3)C12—C131.375 (7)
Cu1—O41.947 (3)C12—H120.9300
Cu2—O5i1.906 (3)C13—C141.423 (5)
Cu2—O51.906 (3)C13—H130.9300
Cu2—O6i1.952 (3)C14—C151.460 (6)
Cu2—O61.952 (3)C15—O41.311 (5)
C1—O11.319 (4)C15—C161.518 (5)
C1—C61.430 (5)C16—H16A0.9600
C1—C21.432 (6)C16—H16B0.9600
C2—C31.379 (6)C16—H16C0.9600
C2—H20.9300C17—O51.325 (4)
C3—C41.384 (7)C17—C181.417 (5)
C3—H30.9300C17—C221.429 (5)
C4—C51.378 (7)C18—C191.380 (6)
C4—H40.9300C18—H180.9300
C5—C61.431 (5)C19—C201.401 (6)
C5—H50.9300C19—H190.9300
C6—C71.467 (6)C20—C211.380 (6)
C7—O21.311 (5)C20—H200.9300
C7—C81.519 (5)C21—C221.430 (5)
C8—H8A0.9600C21—H210.9300
C8—H8B0.9600C22—C231.471 (5)
C8—H8C0.9600C23—O61.313 (5)
C9—O31.321 (4)C23—C241.520 (5)
C9—C141.428 (5)C24—H24A0.9600
C9—C101.436 (6)C24—H24B0.9600
C10—C111.374 (7)C24—H24C0.9600
C10—H100.9300
O1—Cu1—O3173.38 (12)C13—C12—H12120.3
O1—Cu1—O291.92 (12)C12—C13—C14122.6 (4)
O3—Cu1—O288.35 (12)C12—C13—H13118.7
O1—Cu1—O489.17 (12)C14—C13—H13118.7
O3—Cu1—O491.05 (12)C13—C14—C9117.6 (4)
O2—Cu1—O4175.72 (15)C13—C14—C15119.4 (4)
O5i—Cu2—O5180.000 (1)C9—C14—C15123.0 (3)
O5i—Cu2—O6i92.29 (12)O4—C15—C14121.6 (3)
O5—Cu2—O6i87.71 (12)O4—C15—C16118.1 (4)
O5i—Cu2—O687.71 (12)C14—C15—C16120.3 (3)
O5—Cu2—O692.29 (12)C15—C16—H16A109.5
O6i—Cu2—O6180.000 (1)C15—C16—H16B109.5
O1—C1—C6125.1 (3)H16A—C16—H16B109.5
O1—C1—C2116.9 (4)C15—C16—H16C109.5
C6—C1—C2118.0 (3)H16A—C16—H16C109.5
C3—C2—C1121.9 (4)H16B—C16—H16C109.5
C3—C2—H2119.1O5—C17—C18116.4 (3)
C1—C2—H2119.1O5—C17—C22124.8 (3)
C2—C3—C4120.5 (5)C18—C17—C22118.8 (3)
C2—C3—H3119.8C19—C18—C17122.2 (4)
C4—C3—H3119.8C19—C18—H18118.9
C3—C4—C5119.5 (4)C17—C18—H18118.9
C3—C4—H4120.3C18—C19—C20119.6 (4)
C5—C4—H4120.3C18—C19—H19120.2
C4—C5—C6122.7 (5)C20—C19—H19120.2
C4—C5—H5118.7C21—C20—C19119.7 (4)
C6—C5—H5118.7C21—C20—H20120.2
C1—C6—C5117.5 (4)C19—C20—H20120.2
C1—C6—C7123.1 (3)C20—C21—C22122.5 (4)
C5—C6—C7119.4 (4)C20—C21—H21118.7
O2—C7—C6121.4 (3)C22—C21—H21118.7
O2—C7—C8118.5 (4)C17—C22—C21117.2 (3)
C6—C7—C8120.1 (3)C17—C22—C23122.9 (3)
C7—C8—H8A109.5C21—C22—C23119.9 (3)
C7—C8—H8B109.5O6—C23—C22122.3 (3)
H8A—C8—H8B109.5O6—C23—C24117.6 (4)
C7—C8—H8C109.5C22—C23—C24120.1 (3)
H8A—C8—H8C109.5C23—C24—H24A109.5
H8B—C8—H8C109.5C23—C24—H24B109.5
O3—C9—C14124.7 (3)H24A—C24—H24B109.5
O3—C9—C10117.0 (4)C23—C24—H24C109.5
C14—C9—C10118.3 (4)H24A—C24—H24C109.5
C11—C10—C9120.8 (4)H24B—C24—H24C109.5
C11—C10—H10119.6C1—O1—Cu1127.9 (2)
C9—C10—H10119.6C7—O2—Cu1130.4 (3)
C10—C11—C12121.3 (4)C9—O3—Cu1127.4 (2)
C10—C11—H11119.3C15—O4—Cu1130.0 (3)
C12—C11—H11119.3C17—O5—Cu2127.9 (2)
C11—C12—C13119.4 (4)C23—O6—Cu2129.0 (3)
C11—C12—H12120.3
Symmetry codes: (i) −x+1, −y+2, −z+1.
Acknowledgements top

We acknowledge financial support by Guangxi Key Laboratory for Advanced Materials and New Preparation Technology (No. 0842003–25) and the Young Science Foundation of Guangxi Province (No. 0832085).

references
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