Diaqua­bis(benzyl­oxyacetato)copper(II)

Abstract

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,

• a = 11.8847 (4) Å

• b = 7.1509 (2) Å

• c = 11.6564 (5) Å

• β = 110.283 (3)°

• V = 929.21 (6) ų

• 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[F ² > 2σ(F ²)] = 0.034

• wR(F ²) = 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

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.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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) ; (ii) .

supplementary crystallographic information

Comment

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.

Experimental

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%.

Refinement

The C-bound H atoms were placed in calculated positions, with C—H = 0.93 or 0.97 Å, and were refined in the riding-model approximation, with U_iso(H) = 1.2U_eq(C). The H atoms of the water molecule were located in a difference Fourier map and refined with bond restrint O—H = 0.84 (2) Å in the riding-model approximation, with U_iso(H) = 1.5U_eq(O).

Figures

Fig. 1.

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

Crystal data

[Cu(C9H9O3)2(H2O)2]	F000 = 446
Mr = 429.91	Dx = 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 = 1.8–27.6º
b = 7.1509 (2) Å	µ = 1.22 mm−1
c = 11.6564 (5) Å	T = 296 (2) K
β = 110.283 (3)º	Prism, blue
V = 929.21 (6) Å3	0.32 × 0.24 × 0.18 mm
Z = 2

Data collection

Bruker P4 diffractometer	2144 independent reflections
Radiation source: fine-focus sealed tube	1606 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.035
Detector resolution: 10.000 pixels mm-1	θmax = 27.6º
T = 296(2) K	θmin = 1.8º
ω scans	h = −15→15
Absorption correction: multi-scan(SADABS; Sheldrick, 1996)	k = −9→8
Tmin = 0.711, Tmax = 0.803	l = −15→10
7991 measured reflections

Refinement

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.034	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.082	w = 1/[σ2(Fo2) + (0.0429P)2] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max < 0.001
2144 reflections	Δρmax = 0.40 e Å−3
130 parameters	Δρmin = −0.57 e Å−3
3 restraints	Extinction correction: none
Primary atom site location: structure-invariant direct methods

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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 codes: (i) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W1···O2ii	0.839 (9)	1.978 (12)	2.796 (2)	165 (2)
O1W—H1W2···O2iii	0.83 (2)	1.964 (10)	2.788 (2)	173 (2)

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