[N-(3-Meth­oxy-2-oxidobenzyl­idene-κO 2)leucinato-κ2 N,O](1,10-phenanthroline-κ2 N,N′)copper(II) monohydrate

Lei Huang; Jianfang Dong; Buqin Jing; Lianzhi Li; Daqi Wang

doi:10.1107/S160053681004554X

. 2010 Nov 13;66(Pt 12):m1553. doi: 10.1107/S160053681004554X

[N-(3-Methoxy-2-oxidobenzylidene-κO ²)leucinato-κ² N,O](1,10-phenanthroline-κ² N,N′)copper(II) monohydrate

Lei Huang ^a, Jianfang Dong ^a, Buqin Jing ^a, Lianzhi Li ^a,^*, Daqi Wang ^a

PMCID: PMC3011713 PMID: 21589245

Abstract

The asymmetric unit of the title complex, [Cu(C₁₄H₁₇NO₄)(C₁₂H₈N₂)]·H₂O, contains two independent Cu^II complex molecules and two uncoordinated water molecules. In each complex molecule, the Cu atom is O,N,O′-chelated by the tridentate Schiff base ligand and N,N′-chelated by the 1,10-phenanthroline ligand in a distorted square-pyramidal geometry. The Cu—N bond distances in the apical directions are 2.298 (4) and 2.268 (4) Å. In the crystal, intermolecular O—H⋯O and C—H⋯O hydrogen bonds together with C—H⋯π interactions result in a three-dimensional supramolecular structure.

Related literature

For related structures, see: Elena et al. (1995 ▶); Qiu et al. (2008 ▶).

Experimental

Crystal data

[Cu(C₁₄H₁₇NO₄)(C₁₂H₈N₂)]·H₂O
M _r = 525.05
Monoclinic,
a = 11.1981 (12) Å
b = 10.4190 (11) Å
c = 21.298 (2) Å
β = 98.5520 (10)°
V = 2457.3 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.93 mm⁻¹
T = 293 K
0.45 × 0.43 × 0.41 mm

Data collection

Bruker SMART 1000 CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.680, T _max = 0.702
12981 measured reflections
7382 independent reflections
5544 reflections with I > 2σ(I)
R _int = 0.027

Refinement

R[F ² > 2σ(F ²)] = 0.038
wR(F ²) = 0.101
S = 1.01
7382 reflections
637 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.30 e Å⁻³
Absolute structure: Flack (1983 ▶), 2779 Friedel pairs
Flack parameter: −0.010 (12)

Data collection: SMART (Siemens, 1996 ▶); cell refinement: SAINT (Siemens, 1996 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681004554X/xu5077sup1.cif

e-66-m1553-sup1.cif^{(33.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053681004554X/xu5077Isup2.hkl

e-66-m1553-Isup2.hkl^{(361.2KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Cu1—N1	1.919 (4)
Cu1—N2	2.010 (4)
Cu1—N3	2.298 (4)
Cu1—O1	1.960 (3)
Cu1—O3	1.929 (3)
Cu2—N4	1.934 (4)
Cu2—N5	2.268 (4)
Cu2—N6	2.039 (4)
Cu2—O5	1.953 (4)
Cu2—O7	1.945 (3)

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Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O9—H9A⋯O2	0.85	2.22	2.715 (7)	117
O9—H9B⋯O2	0.85	2.20	2.715 (7)	119
O10—H10A⋯O6	0.85	2.27	2.805 (8)	121
O10—H10B⋯O6	0.85	2.27	2.805 (8)	121
C24—H24⋯O10ⁱ	0.93	2.58	3.476 (8)	162
C40—H40A⋯O2ⁱⁱ	0.96	2.53	3.486 (7)	176
C43—H43⋯O8ⁱⁱⁱ	0.93	2.48	3.172 (6)	131
C50—H50⋯O9^iv	0.93	2.35	3.268 (7)	168
C25—H25⋯Cg1^v	0.93	2.51	3.426 (6)	168

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) .

Acknowledgments

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

supplementary crystallographic information

Comment

Schiff bases still play an important role as ligands in metal coordination chemistry even after almost a century since their discovery. Considerable efforts have been devotedd to copper(II) complexes of tridentate Schiff base ligands of N-alkylidene or N-arylidene alkanato type, due to their structural richness, electrochemical properties as well as a potential model for a number of important biological systems. 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 o-vanillin and L-leucine, and with 1,10-phenanthroline.

There are two independent structurses in the crystallographic asymmetric unit except the solvent water moleculars (Fig.1). In either of the two main molecular structures, the central Cu^II atom is five-coordinated by one N atom and two O atoms from the tridentate Schiff base ligand and two N atoms from 1,10-phenanthroline ligand, forming a seriously distorted square-pyramidal geomety. The O1, O3, N1, and N2 atoms (or O5, O7, N4, and N6) locate in equatorial plane, and N3 (or N5) in the apital position. The Cu1^II atom and Cu2^II atom lie 0.1552 (21)Å and 0.0859 (22)Å above theirs equatorial plane, respectively. Similar to that repoted previously (Elena et al., 1995; Qiu et al., 2008), the apital atoms (N3, N5) are much longer from their copper atoms, with the bond distances of Cu1—N3 = 2.298 (4)Å and Cu2—N5 = 2.268 (4)Å (Table 1). The tridentate Schiff base ligands coordinated to copper atoms form two penta-chelated rings(Cu1/O1/C1—C2/N1 and Cu2/O5/C27—C28/N4) and two hexa-chelated rings (Cu1/N1/C7—C9/O3 and Cu2/N4/C33—C35/O7). In each molecular, the penta-chelated ring and hexa-chelated ring have formed their individual dihedral angle 12.64 (22)° and 17.39 (21)°, respectively. The phenanthroline ligands are almost perpendicular to their individual equatorial plane (dihedral angle 89.03 (13)° and 86.24 (14)°).

In the crystal structure, there exist C—H···O and O—H···O hydrogen bonds (Table 2) which link the molecules into a three-dimensional network structure (Fig. 2). Additionally, the intermolecular C—H···π interaction [H25···Cgⁱ= 2.513 Å, C25···Cgⁱ= 3.426 Å, and C25—H25···Cgⁱ= 167.55°; symmetry code: (i) -x, y - 1/2, 1 - z; Cg is the centroid of the C8—C13 ring] also stablizes the crystal packing, along with the van der Waals forces.

Experimental

L-Leucine (1 mmol, 113.2 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-vanilline (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. An methanol solution (5 ml) of 1,10-phenanthroline monohydrate (1 mmol, 198.2 mg) was added dropwise and stirred for 4 h. The resultant solution was held at room temperature for 10 d, single crystals suitable for X-ray diffraction were obtained.