{2-(4-Hy­droxy­phen­yl)-2-[(3-meth­oxy-2-oxidobenzyl­idene)amino-κ2O2,N]propanoato-κO}(1,10-phenanthroline-κ2N,N′)copper(II) dihydrate

Pu, X.; Li, L.; Dong, J.; Jing, B.

doi:10.1107/S1600536811009627

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 4| April 2011| Pages m465-m466

doi:10.1107/S1600536811009627

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{2-(4-Hydroxyphenyl)-2-[(3-methoxy-2-oxidobenzylidene)amino-κ²O²,N]propanoato-κO}(1,10-phenanthroline-κ²N,N′)copper(II) dihydrate

Xuewei Pu,^a Lianzhi Li,^a ^* Jianfang Dong ^b and Buqin Jing ^a

^aSchool of Chemistry and Chemical Engineering, Liaocheng University, Shandong 252059, People's Republic of China, and ^bDepartment of Material Science, Shandong Polytechnic Technician College, Shandong 252027, People's Republic of China
^*Correspondence e-mail: lilianzhi1963@yahoo.com.cn

(Received 14 January 2011; accepted 14 March 2011; online 19 March 2011)

In the title complex, [Cu(C₁₇H₁₅NO₅)(C₁₂H₈N₂)]·2H₂O, the central Cu^II ion is five-coordinate, bound to one N atom and two O atoms from the Schiff base ligand and by two N atoms from a 1,10-phenanthroline ligand in a distorted square-pyramidal configuration. In the crystal, intermolecular O—H⋯O and C—H⋯O hydrogen bonds form a two-dimensional network parallel to (001).

Related literature

For background to Schiff bases and the applications of Schiff base–copper complexes, see: Chohan et al. (1998 ); Nath et al. (2001 ); Raso et al. (1999 ); Yamada (1966 ). For the structure of a similar complex with a five-coordinate Cu^II ion, see: Qiu et al. (2008 ).

Experimental

Crystal data

[Cu(C₁₇H₁₅NO₅)(C₁₂H₈N₂)]·2H₂O
M_r = 593.08
Monoclinic, C 2
a = 11.755 (3) Å
b = 20.653 (5) Å
c = 13.202 (3) Å
β = 96.935 (4)°
V = 3181.6 (14) Å³
Z = 4
Mo Kα radiation
μ = 0.73 mm⁻¹
T = 298 K
0.48 × 0.42 × 0.38 mm

Data collection

Bruker SMART 1000 CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.720, T_max = 0.769
8117 measured reflections
3778 independent reflections
2811 reflections with I > 2σ(I)
R_int = 0.040

Refinement

R[F² > 2σ(F²)] = 0.071
wR(F²) = 0.202
S = 1.04
3778 reflections
363 parameters
15 restraints
H-atom parameters constrained
Δρ_max = 1.19 e Å⁻³
Δρ_min = −0.32 e Å⁻³
Absolute structure: Flack (1983 ), 956 Friedel pairs
Flack parameter: −0.02 (3)

Table 1
Selected bond lengths (Å)

Cu1—N1	1.926 (10)
Cu1—O4	1.935 (5)
Cu1—O1	1.989 (5)
Cu1—N3	2.029 (9)
Cu1—N2	2.325 (8)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O6—H31⋯O2	0.85	1.93	2.684 (9)	148
O3—H3⋯O6ⁱ	0.82	2.53	2.843 (11)	104
O6—H30⋯O6ⁱⁱ	0.85	2.44	2.888 (11)	114
O7—H33⋯O2ⁱⁱⁱ	0.85	2.15	2.721 (13)	125
C18—H18⋯O5^iv	0.93	2.46	3.268 (13)	145
Symmetry codes: (i) $[x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ ; (ii) -x, y, -z; (iii) x, y, z+1; (iv) -x+1, y, -z+1.

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); 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) and DIAMOND (Brandenburg, 1999 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811009627/rn2083sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811009627/rn2083Isup2.hkl

checkCIF report

Comment top

Schiff bases still play an important role as ligands in metal coordination chemistry even after almost a century since their discovery (Yamada, 1966). It has been reported that amino acid Schiff bases and their first row transition metal complexes exhibit fungicidal, bactericidal, antiviral, and antitubercular activity (Chohan et al., 1998; Nath et al., 2001). Considerable efforts have been devoted to copper(II) complexes of tridentate N-alkylidene or N-arylidene alkanato Schiff base ligands, due to their structural diversity, electrochemical properties as well as a potential model for a number of important biological systems (Raso et al., 1999). Herein, we report the synthesis and crystal structure of a new copper(II) complex with a tridentate Schiff base ligand derived from the condensation of L-tyrosine and o-vanillin, with a 1,10-phenanthroline coligand.

As shown in Fig 1, the central Cu^II ion is five coordinate, bound to two O atoms and one N atom of the Schiff base ligand and two N atoms of the 1,10-phenanthroline ligand, forming a distorted square-pyramidal geometry. The O1, O4, N1, and N2 atoms are in the equatorial plane, and N3 is in the axial position. The Cu^II ion lies 0.5068 (39)Å above the equatorial plane towards N3. The Cu1—N3 bond is significantly longer [2.325 (8) Å] (Table 1) as seen previously [2.231 (3) Å] (Qiu et al., 2008).

In the crystal, the combination of intramolecular and intermolecular hydrogen bonds (Table 2) leads to a two-dimensional network (Fig. 2).

Related literature top

For background to Schiff bases and the applications of Schiff base–copper complexes, see: Chohan et al. (1998); Nath et al. (2001); Raso et al. (1999); Yamada (1966). For the structure of a similar five-coordinate copper(II) complex, see: Qiu et al. (2008).

Experimental top

L-Tyrosine(1 mmol, 146.2 mg) and potassium hydroxide (1 mmol, 56.1 mg) were dissolved in hot methanol (10 ml) and added successively to a methanol solution of o-vanillin (1 mmol, 152.2 mg). The mixture was then stirred at 323 K for 2 h. Subsequently, an aqueous solution(2 ml) of cupric acetate monohydrate (1 mmol, 199.7 mg) was added dropwise and stirred for 2 h. A methanol solution (5 ml) of 1,10-phenanthroline (1 mmol, 198.2 mg) was added dropwise and stirred for 4 h. The solution was held at room temperature for ten days, whereupon green block-shaped crystals suitable for X-ray diffraction were obtained.

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The structure of the title compound, drawn with 30% probability displacement ellipsoids.
	Fig. 2. The two-dimensional network of the title complex linked by hydrogen bonds.

{2-(4-Hydroxyphenyl)-2-[(3-methoxy-2-oxidobenzylidene)amino- κ²O²,N]propanoato-κO}(1,10-phenanthroline- κ²N,N')copper(II) dihydrate top

Crystal data top

[Cu(C₁₇H₁₅NO₅)(C₁₂H₈N₂)]·2H₂O	F(000) = 1228
M_r = 593.08	D_x = 1.238 Mg m⁻³
Monoclinic, C2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C 2y	Cell parameters from 2405 reflections
a = 11.755 (3) Å	θ = 2.4–22.2°
b = 20.653 (5) Å	µ = 0.73 mm⁻¹
c = 13.202 (3) Å	T = 298 K
β = 96.935 (4)°	Block, blue
V = 3181.6 (14) Å³	0.48 × 0.42 × 0.38 mm
Z = 4

Data collection top

Bruker SMART 1000 CCD area-detector diffractometer	3778 independent reflections
Radiation source: fine-focus sealed tube	2811 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.040
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −13→13
T_min = 0.720, T_max = 0.769	k = −10→24
8117 measured reflections	l = −15→15

Refinement top

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)] = 0.071	H-atom parameters constrained
wR(F²) = 0.202	w = 1/[σ²(F_o²) + (0.1348P)²] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
3778 reflections	Δρ_max = 1.19 e Å⁻³
363 parameters	Δρ_min = −0.32 e Å⁻³
15 restraints	Absolute structure: Flack (1983), 957 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.02 (3)

Crystal data top

[Cu(C₁₇H₁₅NO₅)(C₁₂H₈N₂)]·2H₂O	V = 3181.6 (14) Å³
M_r = 593.08	Z = 4
Monoclinic, C2	Mo Kα radiation
a = 11.755 (3) Å	µ = 0.73 mm⁻¹
b = 20.653 (5) Å	T = 298 K
c = 13.202 (3) Å	0.48 × 0.42 × 0.38 mm
β = 96.935 (4)°

Data collection top

Bruker SMART 1000 CCD area-detector diffractometer	3778 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2811 reflections with I > 2σ(I)
T_min = 0.720, T_max = 0.769	R_int = 0.040
8117 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.071	H-atom parameters constrained
wR(F²) = 0.202	Δρ_max = 1.19 e Å⁻³
S = 1.04	Δρ_min = −0.32 e Å⁻³
3778 reflections	Absolute structure: Flack (1983), 957 Friedel pairs
363 parameters	Absolute structure parameter: −0.02 (3)
15 restraints

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

	x	y	z	U_iso*/U_eq
Cu1	0.47884 (7)	0.39140 (5)	0.30240 (6)	0.0528 (3)
O1	0.3247 (4)	0.3954 (4)	0.2218 (4)	0.0629 (13)
O2	0.1982 (6)	0.4622 (4)	0.1409 (6)	0.086 (2)
O3	0.6863 (7)	0.7563 (4)	0.1644 (6)	0.093 (2)
H3	0.6884	0.7738	0.1089	0.139*
O4	0.6105 (4)	0.3954 (4)	0.4054 (4)	0.0615 (13)
O5	0.7833 (6)	0.3774 (4)	0.5400 (5)	0.085 (2)
O6	0.0460 (5)	0.3655 (3)	0.1065 (5)	0.091 (2)
H30	0.0785	0.3555	0.0545	0.110*
H31	0.0698	0.4039	0.1183	0.110*
O7	0.1122 (9)	0.5336 (6)	0.9760 (9)	0.140 (4)
H33	0.1504	0.5389	1.0343	0.169*
H32	0.1276	0.4940	0.9671	0.169*
N1	0.4673 (6)	0.4843 (5)	0.2928 (5)	0.048 (2)
N3	0.4572 (7)	0.2951 (4)	0.3234 (6)	0.057 (2)
N2	0.5696 (6)	0.3454 (4)	0.1729 (5)	0.064 (2)
C1	0.2914 (8)	0.4502 (5)	0.1928 (7)	0.064 (2)
C2	0.3727 (7)	0.5070 (4)	0.2167 (6)	0.0523 (19)
H2	0.3323	0.5430	0.2447	0.063*
C3	0.4188 (7)	0.5280 (5)	0.1168 (6)	0.058 (2)
H3A	0.4647	0.4932	0.0938	0.070*
H3B	0.3544	0.5350	0.0647	0.070*
C4	0.4896 (7)	0.5882 (4)	0.1279 (5)	0.0502 (18)
C5	0.4378 (8)	0.6477 (5)	0.1252 (8)	0.072 (3)
H5	0.3583	0.6500	0.1152	0.086*
C6	0.5015 (8)	0.7054 (5)	0.1372 (7)	0.070 (2)
H6	0.4648	0.7453	0.1353	0.084*
C7	0.6210 (9)	0.7016 (5)	0.1519 (6)	0.067 (2)
C8	0.6746 (8)	0.6425 (6)	0.1572 (7)	0.070 (3)
H8	0.7542	0.6405	0.1691	0.084*
C9	0.6109 (8)	0.5849 (5)	0.1449 (6)	0.059 (2)
H9	0.6479	0.5451	0.1479	0.071*
C10	0.5227 (7)	0.5261 (5)	0.3509 (6)	0.055 (2)
H10	0.5003	0.5692	0.3433	0.065*
C11	0.6173 (7)	0.5113 (5)	0.4271 (6)	0.055 (2)
C12	0.6726 (9)	0.5654 (5)	0.4794 (7)	0.075 (3)
H12	0.6470	0.6075	0.4654	0.090*
C13	0.7641 (9)	0.5534 (7)	0.5505 (8)	0.089 (3)
H13	0.8008	0.5880	0.5857	0.107*
C14	0.8038 (10)	0.4923 (6)	0.5719 (7)	0.079 (3)
H14	0.8680	0.4864	0.6194	0.095*
C15	0.7517 (8)	0.4403 (6)	0.5254 (6)	0.061 (2)
C16	0.6550 (7)	0.4463 (5)	0.4466 (6)	0.056 (2)
C17	0.8766 (10)	0.3668 (7)	0.6178 (10)	0.106 (4)
H17A	0.9476	0.3727	0.5899	0.158*
H17B	0.8728	0.3235	0.6435	0.158*
H17C	0.8722	0.3971	0.6723	0.158*
C18	0.4013 (8)	0.2711 (5)	0.3963 (7)	0.068 (2)
H18	0.3718	0.2998	0.4408	0.081*
C19	0.3855 (10)	0.2077 (6)	0.4090 (9)	0.084 (3)
H19	0.3461	0.1933	0.4617	0.101*
C20	0.4272 (10)	0.1631 (6)	0.3443 (10)	0.085 (3)
H20	0.4154	0.1189	0.3515	0.101*
C21	0.4880 (8)	0.1874 (5)	0.2676 (8)	0.067 (2)
C22	0.5018 (7)	0.2544 (5)	0.2576 (7)	0.059 (2)
C23	0.5601 (7)	0.2798 (5)	0.1781 (6)	0.054 (2)
C24	0.6054 (9)	0.2391 (6)	0.1102 (8)	0.073 (3)
C25	0.6605 (8)	0.2653 (7)	0.0366 (8)	0.088 (3)
H25	0.6918	0.2384	−0.0093	0.106*
C26	0.6710 (10)	0.3290 (8)	0.0287 (9)	0.092 (3)
H26	0.7081	0.3465	−0.0233	0.110*
C27	0.6258 (8)	0.3701 (6)	0.0993 (7)	0.080 (3)
H27	0.6350	0.4147	0.0948	0.096*
C28	0.5357 (9)	0.1457 (6)	0.1986 (10)	0.085 (3)
H28	0.5291	0.1010	0.2037	0.103*
C29	0.5923 (12)	0.1733 (7)	0.1232 (10)	0.092 (4)
H29	0.6236	0.1457	0.0783	0.110*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0548 (5)	0.0557 (6)	0.0464 (5)	−0.0062 (6)	−0.0006 (3)	0.0017 (5)
O1	0.062 (3)	0.053 (3)	0.070 (3)	−0.016 (4)	−0.005 (2)	0.000 (4)
O2	0.070 (4)	0.092 (5)	0.089 (5)	−0.018 (4)	−0.025 (4)	0.032 (4)
O3	0.096 (5)	0.082 (5)	0.102 (5)	−0.038 (4)	0.023 (4)	−0.002 (4)
O4	0.066 (3)	0.059 (3)	0.055 (3)	−0.004 (4)	−0.009 (2)	−0.001 (4)
O5	0.086 (4)	0.090 (7)	0.072 (4)	0.003 (4)	−0.021 (3)	0.009 (4)
O6	0.108 (5)	0.077 (5)	0.084 (5)	−0.032 (4)	−0.008 (4)	0.007 (4)
O7	0.127 (7)	0.129 (9)	0.162 (9)	0.001 (7)	0.002 (6)	0.026 (8)
N1	0.052 (4)	0.054 (5)	0.037 (3)	−0.001 (3)	0.003 (3)	0.003 (3)
N3	0.057 (4)	0.056 (5)	0.057 (4)	−0.004 (4)	0.001 (3)	−0.005 (4)
N2	0.053 (4)	0.084 (6)	0.052 (4)	−0.003 (4)	−0.006 (3)	−0.002 (4)
C1	0.055 (5)	0.063 (6)	0.071 (5)	−0.014 (4)	−0.004 (4)	0.009 (5)
C2	0.056 (4)	0.056 (5)	0.044 (4)	0.000 (4)	0.001 (3)	0.007 (4)
C3	0.055 (4)	0.073 (6)	0.046 (4)	−0.013 (4)	0.002 (3)	0.005 (4)
C4	0.060 (5)	0.051 (5)	0.039 (4)	−0.008 (4)	0.004 (3)	0.006 (3)
C5	0.053 (5)	0.073 (7)	0.092 (7)	0.009 (5)	0.019 (4)	0.020 (6)
C6	0.074 (6)	0.057 (6)	0.082 (6)	−0.003 (5)	0.020 (5)	0.006 (5)
C7	0.089 (6)	0.062 (6)	0.054 (5)	−0.014 (5)	0.021 (4)	0.000 (4)
C8	0.051 (5)	0.083 (7)	0.071 (6)	−0.021 (5)	−0.012 (4)	0.007 (5)
C9	0.067 (5)	0.064 (6)	0.047 (5)	−0.004 (5)	0.005 (4)	0.001 (4)
C10	0.062 (5)	0.054 (5)	0.044 (4)	−0.014 (4)	−0.005 (4)	0.001 (4)
C11	0.056 (4)	0.062 (6)	0.047 (4)	−0.009 (4)	0.008 (3)	−0.002 (4)
C12	0.097 (7)	0.066 (6)	0.058 (5)	−0.014 (6)	−0.005 (5)	−0.010 (5)
C13	0.086 (7)	0.099 (9)	0.076 (7)	−0.021 (6)	−0.016 (5)	−0.018 (6)
C14	0.088 (7)	0.094 (8)	0.051 (5)	−0.015 (6)	−0.006 (5)	0.000 (5)
C15	0.057 (5)	0.081 (7)	0.043 (4)	−0.005 (5)	0.000 (3)	0.011 (5)
C16	0.053 (4)	0.075 (6)	0.039 (4)	−0.006 (4)	0.001 (3)	−0.002 (4)
C17	0.088 (7)	0.126 (12)	0.090 (7)	0.011 (7)	−0.037 (6)	−0.001 (7)
C18	0.069 (5)	0.076 (7)	0.059 (5)	−0.006 (5)	0.014 (4)	0.005 (5)
C19	0.088 (7)	0.083 (8)	0.083 (7)	−0.026 (6)	0.018 (5)	0.003 (6)
C20	0.088 (7)	0.061 (6)	0.101 (8)	−0.016 (6)	−0.004 (6)	−0.007 (6)
C21	0.067 (5)	0.050 (5)	0.077 (6)	−0.006 (5)	−0.016 (4)	−0.005 (5)
C22	0.053 (4)	0.063 (6)	0.054 (5)	−0.008 (4)	−0.017 (4)	−0.003 (4)
C23	0.049 (4)	0.062 (6)	0.047 (4)	0.001 (4)	−0.003 (3)	−0.008 (4)
C24	0.067 (6)	0.085 (7)	0.063 (5)	0.005 (5)	−0.007 (4)	−0.016 (5)
C25	0.066 (6)	0.121 (8)	0.075 (6)	0.022 (7)	0.001 (5)	−0.012 (7)
C26	0.081 (7)	0.132 (9)	0.066 (6)	0.025 (7)	0.022 (5)	0.015 (7)
C27	0.076 (5)	0.105 (10)	0.060 (5)	0.001 (6)	0.013 (4)	0.015 (6)
C28	0.083 (7)	0.061 (7)	0.108 (9)	−0.005 (5)	−0.006 (6)	−0.005 (6)
C29	0.092 (8)	0.092 (8)	0.088 (8)	0.012 (7)	−0.001 (6)	−0.041 (7)

Geometric parameters (Å, º) top

Cu1—N1	1.926 (10)	C8—H8	0.9300
Cu1—O4	1.935 (5)	C9—H9	0.9300
Cu1—O1	1.989 (5)	C10—C11	1.439 (11)
Cu1—N3	2.029 (9)	C10—H10	0.9300
Cu1—N2	2.325 (8)	C11—C12	1.429 (13)
O1—C1	1.243 (12)	C11—C16	1.428 (13)
O2—C1	1.245 (11)	C12—C13	1.363 (15)
O3—C7	1.365 (12)	C12—H12	0.9300
O3—H3	0.8200	C13—C14	1.363 (17)
O4—C16	1.267 (12)	C13—H13	0.9300
O5—C15	1.357 (14)	C14—C15	1.347 (15)
O5—C17	1.425 (12)	C14—H14	0.9300
O6—H30	0.8500	C15—C16	1.450 (12)
O6—H31	0.8500	C17—H17A	0.9600
O7—H33	0.8500	C17—H17B	0.9600
O7—H32	0.8501	C17—H17C	0.9600
N1—C10	1.280 (11)	C18—C19	1.337 (16)
N1—C2	1.482 (10)	C18—H18	0.9300
N3—C18	1.325 (13)	C19—C20	1.384 (17)
N3—C22	1.358 (13)	C19—H19	0.9300
N2—C27	1.339 (12)	C20—C21	1.400 (17)
N2—C23	1.361 (12)	C20—H20	0.9300
C1—C2	1.521 (12)	C21—C22	1.402 (14)
C2—C3	1.547 (11)	C21—C28	1.418 (16)
C2—H2	0.9800	C22—C23	1.422 (13)
C3—C4	1.493 (12)	C23—C24	1.382 (14)
C3—H3A	0.9700	C24—C25	1.346 (16)
C3—H3B	0.9700	C24—C29	1.379 (18)
C4—C5	1.370 (13)	C25—C26	1.327 (19)
C4—C9	1.418 (13)	C25—H25	0.9300
C5—C6	1.405 (14)	C26—C27	1.412 (17)
C5—H5	0.9300	C26—H26	0.9300
C6—C7	1.396 (14)	C27—H27	0.9300
C6—H6	0.9300	C28—C29	1.39 (2)
C7—C8	1.373 (15)	C28—H28	0.9300
C8—C9	1.404 (14)	C29—H29	0.9300

N1—Cu1—O4	92.8 (3)	C12—C11—C16	122.4 (8)
N1—Cu1—O1	82.6 (3)	C12—C11—C10	116.1 (9)
O4—Cu1—O1	166.9 (3)	C16—C11—C10	121.5 (8)
N1—Cu1—N3	167.6 (3)	C13—C12—C11	117.7 (10)
O4—Cu1—N3	92.8 (3)	C13—C12—H12	121.1
O1—Cu1—N3	89.6 (3)	C11—C12—H12	121.1
N1—Cu1—N2	113.2 (3)	C14—C13—C12	122.3 (11)
O4—Cu1—N2	97.8 (2)	C14—C13—H13	118.9
O1—Cu1—N2	95.3 (2)	C12—C13—H13	118.9
N3—Cu1—N2	77.1 (3)	C15—C14—C13	121.2 (10)
C1—O1—Cu1	115.8 (6)	C15—C14—H14	119.4
C7—O3—H3	109.5	C13—C14—H14	119.4
C16—O4—Cu1	126.2 (7)	C14—C15—O5	126.5 (8)
C15—O5—C17	115.1 (9)	C14—C15—C16	122.2 (10)
H30—O6—H31	101.8	O5—C15—C16	111.2 (9)
H33—O7—H32	98.7	O4—C16—C11	126.9 (7)
C10—N1—C2	118.6 (9)	O4—C16—C15	118.9 (9)
C10—N1—Cu1	127.3 (6)	C11—C16—C15	114.2 (8)
C2—N1—Cu1	113.6 (6)	O5—C17—H17A	109.5
C18—N3—C22	119.8 (9)	O5—C17—H17B	109.5
C18—N3—Cu1	123.1 (8)	H17A—C17—H17B	109.5
C22—N3—Cu1	117.1 (7)	O5—C17—H17C	109.5
C27—N2—C23	117.8 (9)	H17A—C17—H17C	109.5
C27—N2—Cu1	133.5 (7)	H17B—C17—H17C	109.5
C23—N2—Cu1	108.7 (6)	N3—C18—C19	123.1 (10)
O1—C1—O2	125.1 (9)	N3—C18—H18	118.5
O1—C1—C2	118.1 (7)	C19—C18—H18	118.5
O2—C1—C2	116.7 (9)	C18—C19—C20	120.6 (10)
N1—C2—C1	107.4 (7)	C18—C19—H19	119.7
N1—C2—C3	110.8 (6)	C20—C19—H19	119.7
C1—C2—C3	108.4 (7)	C19—C20—C21	117.3 (10)
N1—C2—H2	110.1	C19—C20—H20	121.4
C1—C2—H2	110.1	C21—C20—H20	121.4
C3—C2—H2	110.1	C22—C21—C20	119.8 (10)
C4—C3—C2	113.5 (7)	C22—C21—C28	118.6 (10)
C4—C3—H3A	108.9	C20—C21—C28	121.6 (10)
C2—C3—H3A	108.9	N3—C22—C21	119.5 (9)
C4—C3—H3B	108.9	N3—C22—C23	120.1 (9)
C2—C3—H3B	108.9	C21—C22—C23	120.4 (9)
H3A—C3—H3B	107.7	N2—C23—C24	122.2 (9)
C5—C4—C9	118.8 (8)	N2—C23—C22	117.1 (8)
C5—C4—C3	120.2 (8)	C24—C23—C22	120.7 (10)
C9—C4—C3	121.0 (8)	C25—C24—C23	118.7 (12)
C4—C5—C6	121.9 (8)	C25—C24—C29	123.8 (12)
C4—C5—H5	119.1	C23—C24—C29	117.5 (11)
C6—C5—H5	119.1	C26—C25—C24	120.9 (12)
C7—C6—C5	118.8 (9)	C26—C25—H25	119.5
C7—C6—H6	120.6	C24—C25—H25	119.5
C5—C6—H6	120.6	C25—C26—C27	119.9 (11)
O3—C7—C8	118.8 (9)	C25—C26—H26	120.1
O3—C7—C6	120.9 (10)	C27—C26—H26	120.1
C8—C7—C6	120.3 (9)	N2—C27—C26	120.6 (12)
C7—C8—C9	120.8 (9)	N2—C27—H27	119.7
C7—C8—H8	119.6	C26—C27—H27	119.7
C9—C8—H8	119.6	C29—C28—C21	118.2 (11)
C8—C9—C4	119.4 (10)	C29—C28—H28	120.9
C8—C9—H9	120.3	C21—C28—H28	120.9
C4—C9—H9	120.3	C24—C29—C28	124.4 (12)
N1—C10—C11	124.7 (9)	C24—C29—H29	117.8
N1—C10—H10	117.6	C28—C29—H29	117.8
C11—C10—H10	117.6

C1—C2—C3—C4	173.6 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O6—H31···O2	0.85	1.93	2.684 (9)	148
O3—H3···O6ⁱ	0.82	2.53	2.843 (11)	104
O6—H30···O6ⁱⁱ	0.85	2.44	2.888 (11)	114
O7—H33···O2ⁱⁱⁱ	0.85	2.15	2.721 (13)	125
C18—H18···O5^iv	0.93	2.46	3.268 (13)	145

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

Experimental details

Crystal data
Chemical formula	[Cu(C₁₇H₁₅NO₅)(C₁₂H₈N₂)]·2H₂O
M_r	593.08
Crystal system, space group	Monoclinic, C2
Temperature (K)	298
a, b, c (Å)	11.755 (3), 20.653 (5), 13.202 (3)
β (°)	96.935 (4)
V (Å³)	3181.6 (14)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.73
Crystal size (mm)	0.48 × 0.42 × 0.38

Data collection
Diffractometer	Bruker SMART 1000 CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.720, 0.769
No. of measured, independent and observed [I > 2σ(I)] reflections	8117, 3778, 2811
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.071, 0.202, 1.04
No. of reflections	3778
No. of parameters	363
No. of restraints	15
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.19, −0.32
Absolute structure	Flack (1983), 957 Friedel pairs
Absolute structure parameter	−0.02 (3)

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Cu1—N1	1.926 (10)	Cu1—N3	2.029 (9)
Cu1—O4	1.935 (5)	Cu1—N2	2.325 (8)
Cu1—O1	1.989 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O6—H31···O2	0.85	1.93	2.684 (9)	148
O3—H3···O6ⁱ	0.82	2.53	2.843 (11)	104
O6—H30···O6ⁱⁱ	0.85	2.44	2.888 (11)	114
O7—H33···O2ⁱⁱⁱ	0.85	2.15	2.721 (13)	125
C18—H18···O5^iv	0.93	2.46	3.268 (13)	145

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

Acknowledgements

The authors thank the Natural Science Foundation of Shandong Province (No. Y2004B02) for a research grant.

References

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