[N-(3-Meth­oxy-2-oxidobenzyl­idene-κO2)threoninato-κ2O1,N](1,10-phenanthroline-κ2N,N′)copper(II) hemihydrate

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

doi:10.1107/S1600536811012049

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 5| May 2011| Page m536

doi:10.1107/S1600536811012049

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[N-(3-Methoxy-2-oxidobenzylidene-κO²)threoninato-κ²O¹,N](1,10-phenanthroline-κ²N,N′)copper(II) hemihydrate

Buqin Jing,^a,^b Lianzhi Li,^b ^* Jianfang Dong ^c and Jinghong Li ^b

^aCollege of Chemistry and Chemical Engineering, Shanxi Datong University, Datong, Shanxi 037009, People's Republic of China, ^bSchool of Chemistry and Chemical Engineering, Liaocheng University, Shandong 252059, People's Republic of China, and ^cDepartment of Materials Science, Shandong Polytechnic Technician College, Shandong 252027, People's Republic of China
^*Correspondence e-mail: lilianzhi1963@yahoo.com.cn

(Received 20 March 2011; accepted 31 March 2011; online 7 April 2011)

In the title complex, [Cu(C₁₂H₁₃NO₅)(C₁₂H₈N₂)]·0.5H₂O, the Cu^II ion is five-coordinated by one N atom and two O atoms from a tridentate Schiff base ligand, derived from the condensation of L-threonine and o-vanillin, and two N atoms from a 1,10-phenanthroline ligand in a distorted square-pyramidal geometry. In the crystal, intermolecular O—H⋯O hydrogen bonds form a one-dimensional left-handed helical structureextending parallel to [001]. The water molecule of crystallization shows half-occupancy.

Related literature

For general background to Schiff bases and their metal complexes, see: Chohan et al. (1998 ); Nath et al. (2001 ); Yamada (1966 ). For structures of related complexes with five-coordinate copper(II) derived from amino acid Schiff base ligands, see: Huang et al. (2010 ); Qiu et al. (2008 ).

Experimental

Crystal data

[Cu(C₁₂H₁₃NO₅)(C₁₂H₈N₂)]·0.5H₂O
M_r = 503.99
Tetragonal, I 4
a = 22.527 (6) Å
c = 10.290 (4) Å
V = 5222 (3) Å³
Z = 8
Mo Kα radiation
μ = 0.87 mm⁻¹
T = 293 K
0.50 × 0.15 × 0.11 mm

Data collection

Bruker SMART 1000 CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.669, T_max = 0.910
13788 measured reflections
4560 independent reflections
2419 reflections with I > 2σ(I)
R_int = 0.084

Refinement

R[F² > 2σ(F²)] = 0.076
wR(F²) = 0.267
S = 0.90
4560 reflections
307 parameters
511 restraints
H-atom parameters constrained
Δρ_max = 0.83 e Å⁻³
Δρ_min = −0.40 e Å⁻³
Absolute structure: Flack (1983 ), 2126 Friedel pairs
Flack parameter: −0.13 (5)

Table 1
Selected bond lengths (Å)

Cu1—N1	1.940 (8)
Cu1—N2	2.263 (9)
Cu1—N3	2.004 (8)
Cu1—O1	1.966 (6)
Cu1—O4	1.924 (7)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯O2ⁱ	0.82	2.10	2.767 (11)	138
Symmetry code: (i) $[-y+{\script{3\over 2}}, x-{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

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); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811012049/hy2419sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811012049/hy2419Isup2.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 et al., 1966). It has been reported that amino acid Schiff bases and their first row transition metal complexes exhibit fungicidal, bactericidal, antiviral and antitubercular activities (Chohan et al., 1998; Nath et al., 2001). 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-threonine and o-vanillin, and a 1,10-phenanthroline coligand.

The title complex has a mononuclear structure with an amino acid Schiff base ligand and a 1,10-phenanthroline ligand. As shown in Fig. 1, the Cu^II ion is five-coordinated by one N atom and two O atoms from the Schiff base ligand and by two N atoms from the 1,10-phenanthroline ligand, forming a seriously distorted square-pyramidal geometry. O1, O4, N1 and N3 atoms are located in the basal plane and N2 atom in the apical position. The Cu^II ion lies 0.1651 (4) Å above the basal plane towards N2. The Cu1—N2 bond is significantly longer [2.263 (9) Å] (Table 1) as seen previously [2.298 (4) Å] (Huang et al., 2010) and [2.231 (3) Å] (Qiu et al., 2008). In the crystal, intermolecular O3—H3···O2ⁱ (symmetry code: 3/2-y, -1/2+x, -1/2+z) hydrogen bonds (Table 2) form a one-dimensional left-handed helical structure (Fig. 2).

Related literature top

For general background to Schiff bases and their metal complexes, see: Chohan et al. (1998); Nath et al. (2001); Yamada (1966). For related structures of five-coordinate copper(II) complexes with amino acid Schiff base ligands, see: Huang et al. (2010); Qiu et al. (2008).

Experimental top

L-Threonine (1 mmol, 119 mg) and potassium hydroxide (1 mmol, 56 mg) were dissolved in hot methanol (10 ml) and added successively to a methanol solution of o-vanillin (1 mmol, 152 mg). The mixture was then stirred at 323 K for 2 h. Subsequently, an aqueous solution (2 ml) of cupric acetate hydrate (1 mmol, 200 mg) was added dropwise and stirred for 2 h. A methanol solution (5 ml) of phenanthroline (1 mmol, 198 mg) was added dropwise and stirred for 4 h. The solution was held at room temperature for two weeks, 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); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, drawn with 30% probability displacement ellipsoids.
	Fig. 2. The one-dimensional structure of the title compound, linked by O—H···O hydrogen bonds.

[N-(3-Methoxy-2-oxidobenzylidene-κO²)threoninato- κ²O¹,N](1,10-phenanthroline- κ²N,N')copper(II) hemihydrate top

Crystal data top

[Cu(C₁₂H₁₃NO₅)(C₁₂H₈N₂)]·0.5H₂O	D_x = 1.282 Mg m⁻³
M_r = 503.99	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I4	Cell parameters from 1876 reflections
Hall symbol: I 4	θ = 2.2–18.4°
a = 22.527 (6) Å	µ = 0.87 mm⁻¹
c = 10.290 (4) Å	T = 293 K
V = 5222 (3) Å³	Block, green
Z = 8	0.50 × 0.15 × 0.11 mm
F(000) = 2080

Data collection top

Bruker SMART 1000 CCD diffractometer	4560 independent reflections
Radiation source: fine-focus sealed tube	2419 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.084
ϕ and ω scans	θ_max = 25.0°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −26→20
T_min = 0.669, T_max = 0.910	k = −26→26
13788 measured reflections	l = −12→12

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)] = 0.076	H-atom parameters constrained
wR(F²) = 0.267	w = 1/[σ²(F_o²) + (0.182P)²] where P = (F_o² + 2F_c²)/3
S = 0.90	(Δ/σ)_max < 0.001
4560 reflections	Δρ_max = 0.83 e Å⁻³
307 parameters	Δρ_min = −0.40 e Å⁻³
511 restraints	Absolute structure: Flack (1983), 2126 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.13 (5)

Crystal data top

[Cu(C₁₂H₁₃NO₅)(C₁₂H₈N₂)]·0.5H₂O	Z = 8
M_r = 503.99	Mo Kα radiation
Tetragonal, I4	µ = 0.87 mm⁻¹
a = 22.527 (6) Å	T = 293 K
c = 10.290 (4) Å	0.50 × 0.15 × 0.11 mm
V = 5222 (3) Å³

Data collection top

Bruker SMART 1000 CCD diffractometer	4560 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2419 reflections with I > 2σ(I)
T_min = 0.669, T_max = 0.910	R_int = 0.084
13788 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.076	H-atom parameters constrained
wR(F²) = 0.267	Δρ_max = 0.83 e Å⁻³
S = 0.90	Δρ_min = −0.40 e Å⁻³
4560 reflections	Absolute structure: Flack (1983), 2126 Friedel pairs
307 parameters	Absolute structure parameter: −0.13 (5)
511 restraints

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cu1	0.87663 (4)	0.35499 (4)	0.6986 (2)	0.0480 (4)
N1	0.9319 (3)	0.3654 (4)	0.5559 (8)	0.0497 (19)
N2	0.7903 (4)	0.3312 (4)	0.5991 (9)	0.061 (2)
N3	0.8201 (4)	0.3524 (4)	0.8489 (8)	0.055 (2)
O1	0.8764 (3)	0.4423 (3)	0.7022 (10)	0.0605 (15)
O2	0.9201 (4)	0.5211 (3)	0.6114 (8)	0.082 (2)
O3	0.8996 (3)	0.3845 (3)	0.3014 (7)	0.0669 (19)
H3	0.9057	0.3985	0.2291	0.100*
O4	0.8993 (3)	0.2736 (3)	0.7261 (7)	0.061 (2)
O5	0.9025 (4)	0.1616 (3)	0.7772 (10)	0.089 (3)
O6	0.0168 (13)	0.2227 (13)	0.067 (3)	0.177 (12)	0.50
H25	0.0133	0.2266	−0.0149	0.265*	0.50
H26	0.0155	0.1854	0.0797	0.265*	0.50
C1	0.9087 (5)	0.4666 (5)	0.6146 (11)	0.063 (2)
C2	0.9336 (5)	0.4259 (5)	0.5068 (10)	0.063 (2)
H2	0.9739	0.4376	0.4815	0.075*
C3	0.8892 (5)	0.4301 (5)	0.3891 (10)	0.065 (2)
H3A	0.8493	0.4239	0.4244	0.077*
C4	0.8898 (6)	0.4907 (5)	0.3298 (12)	0.079 (3)
H4A	0.8622	0.4920	0.2588	0.118*
H4B	0.9290	0.4995	0.2984	0.118*
H4C	0.8786	0.5195	0.3940	0.118*
C5	0.9646 (5)	0.3267 (5)	0.5069 (11)	0.058 (2)
H5	0.9904	0.3385	0.4414	0.069*
C6	0.9653 (4)	0.2659 (5)	0.5439 (9)	0.059 (2)
C7	0.9331 (5)	0.2421 (4)	0.6499 (10)	0.063 (2)
C8	0.9367 (5)	0.1805 (4)	0.6756 (13)	0.070 (2)
C9	0.9703 (5)	0.1430 (5)	0.5961 (12)	0.076 (3)
H9	0.9695	0.1022	0.6104	0.091*
C10	1.0053 (5)	0.1662 (4)	0.4943 (11)	0.081 (3)
H10	1.0306	0.1420	0.4465	0.097*
C11	1.0007 (4)	0.2271 (4)	0.4679 (12)	0.070 (3)
H11	1.0216	0.2427	0.3979	0.084*
C12	0.9017 (6)	0.1000 (5)	0.8092 (16)	0.091 (3)
H12A	0.8767	0.0938	0.8835	0.137*
H12B	0.9413	0.0870	0.8288	0.137*
H12C	0.8866	0.0778	0.7368	0.137*
C13	0.7756 (5)	0.3181 (5)	0.4748 (11)	0.067 (3)
H13	0.8050	0.3210	0.4116	0.081*
C14	0.7194 (4)	0.3008 (5)	0.4365 (13)	0.078 (3)
H14	0.7113	0.2919	0.3500	0.093*
C15	0.6757 (5)	0.2969 (6)	0.5295 (13)	0.075 (3)
H15	0.6369	0.2877	0.5055	0.091*
C16	0.6892 (4)	0.3066 (5)	0.6563 (11)	0.067 (2)
C17	0.7462 (4)	0.3256 (4)	0.6924 (11)	0.0588 (18)
C18	0.7628 (5)	0.3374 (5)	0.8214 (8)	0.061 (2)
C19	0.7194 (5)	0.3332 (5)	0.9200 (8)	0.070 (2)
C20	0.7350 (5)	0.3438 (5)	1.0495 (10)	0.074 (3)
H20	0.7076	0.3398	1.1166	0.089*
C21	0.7923 (5)	0.3605 (6)	1.0725 (11)	0.079 (3)
H21	0.8035	0.3704	1.1567	0.095*
C22	0.8342 (5)	0.3630 (5)	0.9741 (10)	0.068 (3)
H22	0.8733	0.3722	0.9951	0.082*
C23	0.6463 (6)	0.3046 (6)	0.7582 (11)	0.081 (3)
H23	0.6072	0.2952	0.7375	0.097*
C24	0.6605 (5)	0.3161 (6)	0.8868 (11)	0.081 (3)
H24	0.6317	0.3127	0.9512	0.098*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0526 (6)	0.0562 (7)	0.0354 (5)	−0.0025 (5)	0.0009 (7)	0.0008 (7)
N1	0.052 (5)	0.059 (5)	0.038 (4)	0.007 (4)	−0.007 (4)	0.001 (4)
N2	0.069 (5)	0.069 (6)	0.046 (5)	0.002 (4)	0.000 (4)	0.009 (4)
N3	0.060 (5)	0.063 (5)	0.041 (5)	−0.003 (4)	0.002 (3)	0.006 (4)
O1	0.071 (4)	0.067 (4)	0.044 (3)	−0.002 (3)	0.004 (5)	0.002 (5)
O2	0.123 (7)	0.055 (4)	0.068 (5)	−0.028 (4)	0.019 (5)	−0.005 (4)
O3	0.093 (5)	0.071 (5)	0.036 (4)	−0.008 (4)	−0.004 (4)	0.000 (3)
O4	0.071 (4)	0.056 (4)	0.055 (6)	−0.002 (3)	0.007 (4)	−0.001 (3)
O5	0.107 (7)	0.051 (4)	0.109 (7)	−0.011 (4)	0.007 (5)	−0.002 (4)
O6	0.155 (13)	0.187 (14)	0.188 (15)	−0.014 (9)	0.013 (9)	−0.002 (9)
C1	0.073 (5)	0.067 (5)	0.050 (5)	−0.002 (5)	−0.005 (5)	0.009 (5)
C2	0.075 (5)	0.069 (5)	0.044 (5)	−0.006 (5)	−0.001 (4)	0.004 (4)
C3	0.075 (5)	0.077 (5)	0.042 (5)	−0.004 (5)	−0.001 (4)	0.010 (5)
C4	0.100 (5)	0.083 (5)	0.054 (5)	−0.001 (5)	0.003 (5)	0.010 (4)
C5	0.053 (5)	0.074 (5)	0.046 (5)	−0.005 (4)	−0.004 (4)	−0.007 (4)
C6	0.053 (5)	0.066 (5)	0.059 (5)	0.004 (4)	−0.010 (4)	−0.006 (4)
C7	0.061 (5)	0.060 (5)	0.068 (5)	0.004 (4)	−0.009 (4)	−0.003 (4)
C8	0.066 (5)	0.065 (5)	0.077 (6)	−0.001 (4)	−0.008 (4)	−0.007 (5)
C9	0.079 (5)	0.062 (5)	0.086 (6)	0.012 (4)	−0.002 (5)	−0.011 (5)
C10	0.080 (6)	0.075 (5)	0.086 (7)	0.007 (5)	−0.006 (5)	−0.014 (5)
C11	0.056 (5)	0.081 (5)	0.073 (6)	0.008 (5)	0.003 (5)	−0.011 (5)
C12	0.099 (5)	0.072 (5)	0.102 (6)	0.001 (5)	−0.002 (5)	0.003 (5)
C13	0.072 (6)	0.076 (6)	0.053 (6)	−0.001 (5)	−0.006 (5)	0.000 (5)
C14	0.085 (6)	0.082 (6)	0.065 (6)	0.000 (5)	−0.026 (5)	0.011 (5)
C15	0.072 (6)	0.081 (6)	0.073 (6)	−0.017 (5)	−0.021 (5)	0.005 (5)
C16	0.058 (4)	0.076 (5)	0.066 (5)	−0.009 (4)	−0.005 (4)	0.001 (4)
C17	0.058 (4)	0.066 (4)	0.052 (4)	−0.008 (3)	−0.002 (4)	0.005 (5)
C18	0.066 (4)	0.070 (5)	0.048 (4)	−0.007 (4)	0.004 (4)	0.010 (4)
C19	0.070 (5)	0.088 (5)	0.052 (5)	−0.001 (5)	0.013 (5)	0.005 (5)
C20	0.080 (6)	0.086 (6)	0.055 (5)	−0.004 (5)	0.016 (5)	0.007 (5)
C21	0.092 (6)	0.096 (6)	0.049 (6)	0.003 (6)	0.002 (5)	0.004 (5)
C22	0.077 (6)	0.071 (6)	0.056 (6)	−0.004 (5)	−0.004 (5)	0.007 (5)
C23	0.067 (5)	0.095 (6)	0.081 (6)	−0.009 (5)	−0.005 (4)	0.010 (5)
C24	0.073 (5)	0.098 (6)	0.073 (6)	−0.006 (5)	0.019 (5)	0.012 (5)

Geometric parameters (Å, º) top

Cu1—N1	1.940 (8)	C6—C11	1.417 (8)
Cu1—N2	2.263 (9)	C7—C8	1.417 (8)
Cu1—N3	2.004 (8)	C8—C9	1.397 (16)
Cu1—O1	1.966 (6)	C9—C10	1.413 (9)
Cu1—O4	1.924 (7)	C9—H9	0.9300
N1—C5	1.246 (13)	C10—C11	1.403 (8)
N1—C2	1.456 (12)	C10—H10	0.9300
N2—C17	1.387 (13)	C11—H11	0.9300
N2—C13	1.354 (14)	C12—H12A	0.9600
N3—C22	1.348 (13)	C12—H12B	0.9600
N3—C18	1.364 (13)	C12—H12C	0.9600
O1—C1	1.282 (13)	C13—C14	1.383 (10)
O2—C1	1.255 (12)	C13—H13	0.9300
O3—C3	1.388 (13)	C14—C15	1.376 (11)
O3—H3	0.8200	C14—H14	0.9300
O4—C7	1.302 (12)	C15—C16	1.358 (17)
O5—C8	1.367 (15)	C15—H15	0.9300
O5—C12	1.426 (13)	C16—C17	1.403 (8)
O6—H25	0.8500	C16—C23	1.427 (16)
O6—H26	0.8501	C17—C18	1.404 (8)
C1—C2	1.544 (15)	C18—C19	1.412 (8)
C2—C3	1.573 (14)	C19—C20	1.398 (8)
C2—H2	0.9800	C19—C24	1.424 (15)
C3—C4	1.494 (15)	C20—C21	1.365 (15)
C3—H3A	0.9800	C20—H20	0.9300
C4—H4A	0.9600	C21—C22	1.386 (10)
C4—H4B	0.9600	C21—H21	0.9300
C4—H4C	0.9600	C22—H22	0.9300
C5—C6	1.422 (15)	C23—C24	1.386 (9)
C5—H5	0.9300	C23—H23	0.9300
C6—C7	1.414 (8)	C24—H24	0.9300

N1—Cu1—O4	93.2 (3)	C9—C8—O5	124.4 (9)
N1—Cu1—O1	84.0 (3)	C9—C8—C7	121.0 (11)
O4—Cu1—O1	161.9 (3)	O5—C8—C7	114.5 (10)
N1—Cu1—N3	174.7 (3)	C8—C9—C10	120.8 (11)
O4—Cu1—N3	91.6 (3)	C8—C9—H9	119.6
O1—Cu1—N3	90.8 (3)	C10—C9—H9	119.6
N1—Cu1—N2	103.8 (3)	C11—C10—C9	117.7 (11)
O4—Cu1—N2	94.0 (3)	C11—C10—H10	121.2
O1—Cu1—N2	104.1 (3)	C9—C10—H10	121.2
N3—Cu1—N2	78.2 (4)	C10—C11—C6	122.5 (10)
C5—N1—C2	119.9 (9)	C10—C11—H11	118.8
C5—N1—Cu1	126.9 (8)	C6—C11—H11	118.8
C2—N1—Cu1	113.1 (6)	O5—C12—H12A	109.5
C17—N2—C13	117.4 (9)	O5—C12—H12B	109.5
C17—N2—Cu1	108.9 (6)	H12A—C12—H12B	109.5
C13—N2—Cu1	133.5 (7)	O5—C12—H12C	109.5
C22—N3—C18	117.7 (9)	H12A—C12—H12C	109.5
C22—N3—Cu1	125.6 (7)	H12B—C12—H12C	109.5
C18—N3—Cu1	116.6 (6)	N2—C13—C14	123.6 (11)
C1—O1—Cu1	114.4 (7)	N2—C13—H13	118.2
C3—O3—H3	109.5	C14—C13—H13	118.2
C7—O4—Cu1	125.9 (6)	C15—C14—C13	118.4 (12)
C8—O5—C12	119.1 (10)	C15—C14—H14	120.8
H25—O6—H26	104.6	C13—C14—H14	120.8
O1—C1—O2	123.5 (11)	C14—C15—C16	119.8 (11)
O1—C1—C2	117.2 (9)	C14—C15—H15	120.1
O2—C1—C2	119.2 (10)	C16—C15—H15	120.1
N1—C2—C1	107.3 (8)	C15—C16—C17	120.6 (11)
N1—C2—C3	107.9 (8)	C15—C16—C23	123.3 (9)
C1—C2—C3	106.7 (9)	C17—C16—C23	115.8 (10)
N1—C2—H2	111.6	N2—C17—C16	119.9 (10)
C1—C2—H2	111.6	N2—C17—C18	116.5 (7)
C3—C2—H2	111.6	C16—C17—C18	123.5 (10)
O3—C3—C4	114.2 (9)	N3—C18—C17	119.7 (7)
O3—C3—C2	110.4 (9)	N3—C18—C19	121.4 (9)
C4—C3—C2	111.3 (9)	C17—C18—C19	118.9 (10)
O3—C3—H3A	106.8	C20—C19—C24	120.6 (9)
C4—C3—H3A	106.8	C20—C19—C18	120.0 (10)
C2—C3—H3A	106.8	C24—C19—C18	119.4 (10)
C3—C4—H4A	109.5	C19—C20—C21	116.7 (11)
C3—C4—H4B	109.5	C19—C20—H20	121.6
H4A—C4—H4B	109.5	C21—C20—H20	121.6
C3—C4—H4C	109.5	C22—C21—C20	121.9 (11)
H4A—C4—H4C	109.5	C22—C21—H21	119.1
H4B—C4—H4C	109.5	C20—C21—H21	119.1
N1—C5—C6	124.9 (10)	N3—C22—C21	122.0 (11)
N1—C5—H5	117.6	N3—C22—H22	119.0
C6—C5—H5	117.6	C21—C22—H22	119.0
C7—C6—C11	118.8 (9)	C24—C23—C16	122.6 (11)
C7—C6—C5	124.4 (8)	C24—C23—H23	118.7
C11—C6—C5	116.9 (9)	C16—C23—H23	118.7
O4—C7—C6	123.9 (8)	C23—C24—C19	119.7 (11)
O4—C7—C8	117.1 (9)	C23—C24—H24	120.1
C6—C7—C8	119.0 (10)	C19—C24—H24	120.1

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O2ⁱ	0.82	2.10	2.767 (11)	138

Symmetry code: (i) −y+3/2, x−1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	[Cu(C₁₂H₁₃NO₅)(C₁₂H₈N₂)]·0.5H₂O
M_r	503.99
Crystal system, space group	Tetragonal, I4
Temperature (K)	293
a, c (Å)	22.527 (6), 10.290 (4)
V (Å³)	5222 (3)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.87
Crystal size (mm)	0.50 × 0.15 × 0.11

Data collection
Diffractometer	Bruker SMART 1000 CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.669, 0.910
No. of measured, independent and observed [I > 2σ(I)] reflections	13788, 4560, 2419
R_int	0.084
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.076, 0.267, 0.90
No. of reflections	4560
No. of parameters	307
No. of restraints	511
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.83, −0.40
Absolute structure	Flack (1983), 2126 Friedel pairs
Absolute structure parameter	−0.13 (5)

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

Selected bond lengths (Å) top

Cu1—N1	1.940 (8)	Cu1—O1	1.966 (6)
Cu1—N2	2.263 (9)	Cu1—O4	1.924 (7)
Cu1—N3	2.004 (8)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O2ⁱ	0.82	2.10	2.767 (11)	138

Symmetry code: (i) −y+3/2, x−1/2, z−1/2.

Acknowledgements

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

References

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