Diaqua­bis(benzyl­oxyacetato)copper(II)

Sun, S.-L.; Chen, C.-L.; Gu, C.-S.; Song, W.-D.; Hao, X.-M.

doi:10.1107/S1600536808010593

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 5| May 2008| Page m691

doi:10.1107/S1600536808010593

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Diaquabis(benzyloxyacetato)copper(II)

Sheng-Li Sun,^a Chun-Liang Chen,^a Chang-Sheng Gu,^b ^* Weng-Dong Song ^b and Xiao-Min Hao ^b

^aMonitoring Center of Marine Resources and the Environment, Guangdong Ocean University, Zhanjiang 524088, People's Republic of China, and ^bDepartment of Applied Chemistry, Guangdong Ocean University, Zhanjiang 524088, People's Republic of China
^*Correspondence e-mail: liujiwei0706@163.com

(Received 7 April 2008; accepted 17 April 2008; online 23 April 2008)

In the title mononuclear complex, [Cu(C₉H₉O₃)₂(H₂O)₂], the Cu^II ion, located on an inversion center, is hexacoordinated by four O atoms from two benzyloxyacetate ligands [Cu—O = 1.9420 (14) and 2.2922 (14) Å] and two water molecules [Cu—O = 2.0157 (15) Å] in a distorted octahedral geometry. In the crystal structure, intermolecular O—H⋯O hydrogen bonds link the molecules into layers parallel to the bc plane.

Related literature

For general background, see: Eddaoudi et al. (2005 ).

Experimental

Crystal data

[Cu(C₉H₉O₃)₂(H₂O)₂]
M_r = 429.91
Monoclinic, P 2₁ /c
a = 11.8847 (4) Å
b = 7.1509 (2) Å
c = 11.6564 (5) Å
β = 110.283 (3)°
V = 929.21 (6) Å³
Z = 2
Mo Kα radiation
μ = 1.22 mm⁻¹
T = 296 (2) K
0.32 × 0.24 × 0.18 mm

Data collection

Bruker P4/APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.711, T_max = 0.803
7991 measured reflections
2144 independent reflections
1606 reflections with I > 2σ(I)
R_int = 0.035

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.082
S = 1.03
2144 reflections
130 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.57 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1W1⋯O2ⁱ	0.839 (9)	1.978 (12)	2.796 (2)	165 (2)
O1W—H1W2⋯O2ⁱⁱ	0.83 (2)	1.964 (10)	2.788 (2)	173 (2)
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; 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: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808010593/cv2398sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808010593/cv2398Isup2.hkl

checkCIF report

Comment top

Current interests in supramolecular chemistry are rapidly expanding for their intriguing architectures and potential applications (Eddaoudi et al., 2005). The organic aromatic carboxylate ligand, benzyloxyacetate, has various coordination modes and can link metal centres through carboxylate groups or/and benzyloxy group into different extended architectures. Therefore, benzyloxyacetate can be considered as a good candidate to construct various metal-organic complexes. Herein we report the crystal structure of the title mononuclear complex of benzyloxyacetate, [Cu(C₉H₉O₃)₂(H₂O)₂], (I).

As illustrated in Fig. 1, the Cu^II ion lies on an inversion center and displays an octahedral geometry defined by four carboxylate O atoms from two different benzyloxyacetate ligands and two water molecules. The Cu—O and Cu—Ow bond lengths are 1.942 (1), 2.292 (1) and 2.016 (2) Å, respectively. The characteristic C—O(carboxylate) bond lengths suggest electron localization of the carboxylate groups of the anionic ligands. In the crystal structure, intermolecular hydrogen bonds (Table 1) give rise to a supramolecular structure.

Related literature top

For general background, see: Eddaoudi et al. (2005).

Experimental top

The ligand, benzyloxyacetic acid was commercially available and used without further purification. The title complex was prepared by the addition of Cu(Ac)₂.H₂O (4.00 g, 20 mmol) to a hot aqueous solution of benzyloxyacetic acid (1.66 g, 10 mmol); the pH was adjusted to 6 with 0.1M sodium hydroxide. The solution was allowed to evaporate at room temperature. Blue prismatic crystals were separated from the filtered solution after several days. C&H analysis. Calc. for C₁₈H₂₂CuO₈: C 50.28, H 5.16%. Found: C 50.26, H 5.17%.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (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: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of (I) showing the atomic numbering and 30% probability displacement ellipsoids [symmetry code: (i) -x+1, -y, -z+1].

Diaquabis(benzyloxyacetato)copper(II) top

Crystal data top

[Cu(C₉H₉O₃)₂(H₂O)₂]	F(000) = 446
M_r = 429.91	D_x = 1.536 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 7991 reflections
a = 11.8847 (4) Å	θ = 1.8–27.6°
b = 7.1509 (2) Å	µ = 1.22 mm⁻¹
c = 11.6564 (5) Å	T = 296 K
β = 110.283 (3)°	Prism, blue
V = 929.21 (6) Å³	0.32 × 0.24 × 0.18 mm
Z = 2

Data collection top

Bruker P4 diffractometer	2144 independent reflections
Radiation source: fine-focus sealed tube	1606 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.035
Detector resolution: 10.000 pixels mm^-1	θ_max = 27.6°, θ_min = 1.8°
ω scans	h = −15→15
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −9→8
T_min = 0.711, T_max = 0.803	l = −15→10
7991 measured reflections

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.082	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0429P)²] where P = (F_o² + 2F_c²)/3
2144 reflections	(Δ/σ)_max < 0.001
130 parameters	Δρ_max = 0.40 e Å⁻³
3 restraints	Δρ_min = −0.57 e Å⁻³

Crystal data top

[Cu(C₉H₉O₃)₂(H₂O)₂]	V = 929.21 (6) Å³
M_r = 429.91	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.8847 (4) Å	µ = 1.22 mm⁻¹
b = 7.1509 (2) Å	T = 296 K
c = 11.6564 (5) Å	0.32 × 0.24 × 0.18 mm
β = 110.283 (3)°

Data collection top

Bruker P4 diffractometer	2144 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1606 reflections with I > 2σ(I)
T_min = 0.711, T_max = 0.803	R_int = 0.035
7991 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	3 restraints
wR(F²) = 0.082	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.40 e Å⁻³
2144 reflections	Δρ_min = −0.57 e Å⁻³
130 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cu1	0.5000	0.0000	0.5000	0.02860 (13)
O1	0.47417 (14)	0.2249 (2)	0.58090 (13)	0.0345 (4)
O2	0.53762 (17)	0.4957 (2)	0.67150 (14)	0.0417 (4)
O3	0.66880 (13)	0.1742 (2)	0.52517 (14)	0.0407 (4)
O1W	0.42562 (15)	0.1187 (2)	0.33393 (14)	0.0374 (4)
C1	0.5503 (2)	0.3554 (3)	0.61482 (17)	0.0325 (5)
C2	0.6644 (2)	0.3444 (3)	0.5852 (2)	0.0376 (5)
C3	0.7506 (2)	0.1723 (4)	0.4603 (2)	0.0442 (6)
C4	0.8798 (2)	0.1745 (3)	0.54208 (19)	0.0341 (5)
C5	0.9166 (2)	0.0908 (4)	0.6556 (2)	0.0427 (6)
C6	1.0355 (3)	0.0908 (4)	0.7283 (2)	0.0510 (7)
C7	1.1196 (2)	0.1751 (4)	0.6891 (2)	0.0513 (7)
C8	1.0844 (2)	0.2568 (4)	0.5758 (3)	0.0507 (7)
C9	0.9650 (2)	0.2583 (4)	0.5025 (2)	0.0430 (6)
H1W1	0.425 (2)	0.2360 (13)	0.335 (2)	0.056*
H1W2	0.457 (2)	0.075 (3)	0.286 (2)	0.056*
H2A	0.6675	0.4486	0.5331	0.045*
H2B	0.7333	0.3530	0.6601	0.045*
H3A	0.7352	0.2803	0.4067	0.053*
H3B	0.7361	0.0612	0.4094	0.053*
H5A	0.8604	0.0339	0.6833	0.051*
H6A	1.0593	0.0333	0.8045	0.061*
H7A	1.1998	0.1768	0.7392	0.062*
H8A	1.1414	0.3115	0.5482	0.061*
H9A	0.9416	0.3157	0.4262	0.052*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0348 (2)	0.0229 (2)	0.03073 (19)	−0.00185 (16)	0.01464 (16)	−0.00319 (15)
O1	0.0435 (9)	0.0261 (8)	0.0393 (8)	−0.0028 (7)	0.0212 (7)	−0.0052 (7)
O2	0.0643 (11)	0.0267 (9)	0.0400 (8)	−0.0002 (8)	0.0254 (8)	−0.0066 (7)
O1W	0.0465 (10)	0.0316 (9)	0.0357 (8)	0.0020 (8)	0.0160 (7)	0.0004 (7)
C1	0.0444 (13)	0.0287 (12)	0.0245 (9)	0.0028 (10)	0.0122 (10)	0.0021 (9)
C2	0.0400 (13)	0.0300 (13)	0.0423 (12)	−0.0057 (10)	0.0136 (11)	−0.0086 (10)
O3	0.0369 (9)	0.0375 (9)	0.0537 (9)	−0.0061 (7)	0.0234 (8)	−0.0147 (8)
C3	0.0414 (14)	0.0559 (17)	0.0389 (12)	−0.0013 (12)	0.0188 (11)	−0.0086 (11)
C4	0.0382 (12)	0.0335 (12)	0.0347 (11)	0.0017 (10)	0.0178 (10)	−0.0028 (9)
C5	0.0493 (16)	0.0419 (14)	0.0427 (12)	0.0061 (12)	0.0233 (12)	0.0054 (11)
C6	0.0590 (18)	0.0537 (17)	0.0393 (13)	0.0205 (14)	0.0158 (13)	0.0053 (12)
C7	0.0400 (14)	0.0482 (17)	0.0584 (15)	0.0070 (13)	0.0077 (13)	−0.0118 (13)
C8	0.0413 (15)	0.0456 (16)	0.0726 (18)	−0.0036 (12)	0.0289 (14)	−0.0005 (14)
C9	0.0453 (14)	0.0432 (15)	0.0459 (13)	0.0038 (11)	0.0225 (12)	0.0055 (11)

Geometric parameters (Å, º) top

Cu1—O1	1.9420 (14)	C3—C4	1.500 (3)
Cu1—O3	2.2922 (14)	C3—H3A	0.9700
Cu1—O1W	2.0157 (15)	C3—H3B	0.9700
O1—C1	1.264 (3)	C4—C5	1.379 (3)
O2—C1	1.239 (2)	C4—C9	1.386 (3)
Cu1—O1ⁱ	1.9420 (14)	C5—C6	1.372 (4)
Cu1—O3ⁱ	2.2922 (14)	C5—H5A	0.9300
Cu1—O1Wⁱ	2.0157 (15)	C6—C7	1.374 (4)
O3—C3	1.424 (2)	C6—H6A	0.9300
O1W—H1W1	0.839 (9)	C7—C8	1.370 (4)
O1W—H1W2	0.83 (2)	C7—H7A	0.9300
C1—C2	1.512 (3)	C8—C9	1.380 (4)
C2—O3	1.414 (2)	C8—H8A	0.9300
C2—H2A	0.9700	C9—H9A	0.9300
C2—H2B	0.9700

O1ⁱ—Cu1—O1	180.00 (7)	C1—C2—H2B	109.6
O1ⁱ—Cu1—O3	103.51 (6)	C2—O3—C3	114.88 (17)
O1—Cu1—O3	76.49 (6)	C2—O3—Cu1	110.48 (12)
O1ⁱ—Cu1—O1W	88.45 (6)	C3—O3—Cu1	130.94 (13)
O1—Cu1—O1W	91.55 (6)	C4—C3—H3A	108.9
O3—Cu1—O3ⁱ	180.0	C4—C3—H3B	108.9
O1W—Cu1—O3	88.11 (6)	C4—C5—H5A	119.7
O1Wⁱ—Cu1—O3	91.89 (6)	C4—C9—H9A	119.9
O1W—Cu1—O1Wⁱ	180.0	C5—C4—C9	118.8 (2)
Cu1—O1W—H1W1	114.0 (18)	C5—C4—C3	121.3 (2)
Cu1—O1W—H1W2	109.5 (18)	C5—C6—C7	120.4 (2)
O1ⁱ—Cu1—O3ⁱ	76.49 (6)	C5—C6—H6A	119.8
O1—Cu1—O3ⁱ	103.51 (6)	C6—C5—C4	120.6 (2)
O1ⁱ—Cu1—O1Wⁱ	91.55 (6)	C6—C5—H5A	119.7
O1—Cu1—O1Wⁱ	88.45 (6)	C6—C7—H7A	120.2
O1—C1—C2	119.44 (18)	C7—C6—H6A	119.8
O2—C1—O1	123.9 (2)	C7—C8—C9	120.3 (2)
O2—C1—C2	116.6 (2)	C7—C8—H8A	119.9
O3—C2—C1	110.35 (18)	C8—C7—C6	119.6 (2)
O3—C2—H2A	109.6	C8—C7—H7A	120.2
O3—C2—H2B	109.6	C8—C9—C4	120.3 (2)
O3—C3—C4	113.51 (18)	C8—C9—H9A	119.9
O3—C3—H3A	108.9	C9—C8—H8A	119.9
O3—C3—H3B	108.9	C9—C4—C3	119.9 (2)
O1W—Cu1—O3ⁱ	91.89 (6)	H1W1—O1W—H1W2	113.6 (15)
O1Wⁱ—Cu1—O3ⁱ	88.11 (6)	H2A—C2—H2B	108.1
C1—O1—Cu1	123.14 (13)	H3A—C3—H3B	107.7
C1—C2—H2A	109.6

Cu1—O1—C1—O2	−176.53 (15)	O1W—Cu1—O3—C2	92.76 (14)
Cu1—O1—C1—C2	3.9 (3)	O1Wⁱ—Cu1—O3—C2	−87.24 (14)
Cu1—O3—C3—C4	−134.22 (17)	O1W—Cu1—O3—C3	−63.95 (19)
O1ⁱ—Cu1—O3—C2	−179.29 (13)	O1Wⁱ—Cu1—O3—C3	116.05 (19)
O1—Cu1—O3—C2	0.71 (13)	C1—C2—O3—C3	161.48 (18)
O1ⁱ—Cu1—O3—C3	24.0 (2)	C1—C2—O3—Cu1	0.7 (2)
O1—Cu1—O3—C3	−156.0 (2)	C2—O3—C3—C4	69.9 (3)
O1—C1—C2—O3	−2.8 (3)	C3—C4—C5—C6	178.6 (2)
O2—C1—C2—O3	177.60 (17)	C3—C4—C9—C8	−178.3 (2)
O3—Cu1—O1—C1	−2.51 (15)	C4—C5—C6—C7	0.3 (4)
O3ⁱ—Cu1—O1—C1	177.49 (15)	C5—C4—C9—C8	0.2 (3)
O3—C3—C4—C5	31.9 (3)	C5—C6—C7—C8	−1.2 (4)
O3—C3—C4—C9	−149.7 (2)	C6—C7—C8—C9	1.5 (4)
O1W—Cu1—O1—C1	−90.19 (16)	C7—C8—C9—C4	−1.0 (4)
O1Wⁱ—Cu1—O1—C1	89.81 (16)	C9—C4—C5—C6	0.1 (3)

Symmetry code: (i) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W1···O2ⁱⁱ	0.84 (1)	1.98 (1)	2.796 (2)	165 (2)
O1W—H1W2···O2ⁱⁱⁱ	0.83 (2)	1.96 (1)	2.788 (2)	173 (2)

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

Experimental details

Crystal data
Chemical formula	[Cu(C₉H₉O₃)₂(H₂O)₂]
M_r	429.91
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	11.8847 (4), 7.1509 (2), 11.6564 (5)
β (°)	110.283 (3)
V (Å³)	929.21 (6)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.22
Crystal size (mm)	0.32 × 0.24 × 0.18

Data collection
Diffractometer	Bruker P4 diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.711, 0.803
No. of measured, independent and observed [I > 2σ(I)] reflections	7991, 2144, 1606
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.653

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.082, 1.03
No. of reflections	2144
No. of parameters	130
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.40, −0.57

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W1···O2ⁱ	0.839 (9)	1.978 (12)	2.796 (2)	165 (2)
O1W—H1W2···O2ⁱⁱ	0.83 (2)	1.964 (10)	2.788 (2)	173 (2)

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

Acknowledgements

This work was supported by Guangdong Ocean University (Project Nos. 0612178 and 0612179) and Zhanjiang City Technology Tender (Project No. 0810014).

References

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