Bis{2-[(2-furylmeth­yl)imino­meth­yl]-5-meth­oxy­phenolato-κ2N,O}zinc(II)

Li, C.

doi:10.1107/S1600536811011536

metal-organic compounds

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Volume 67| Part 4| April 2011| Page m512

doi:10.1107/S1600536811011536

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Bis{2-[(2-furylmethyl)iminomethyl]-5-methoxyphenolato-κ²N,O}zinc(II)

Chunyan Li ^a ^*

^aCollege of Health Science, Wuhan Institute of Physical Education, Wuhan 430079, People's Republic of China
^*Correspondence e-mail: lichunyan2009@yahoo.com.cn

(Received 21 January 2011; accepted 28 March 2011; online 31 March 2011)

In the title complex, [Zn(C₁₃H₁₂NO₃)₂], the Zn^II ion is located on a twofold rotation axis and is coordinated by two bidentate Schiff base ligands in a distorted tetrahedral environment. The complex molecules are stacked in columns along the b axis through C—H⋯O hydrogen bonds.

Related literature

For the biological activity and applications of Zn(II) complexes, see: Csaszar et al. (1985 ); Greener et al. (1996 ); Gultneh et al. (1996 ); Aoki & Kimura (2004 ). For applications of furfurylamine derivatives, see: Camejo et al. (1992 ); Ledovskikh & Camejo (1993 ). For a related structure, see; Cai et al. (2010 ).

Experimental

Crystal data

[Zn(C₁₃H₁₂NO₃)₂]
M_r = 525.84
Monoclinic, C 2/c
a = 27.210 (4) Å
b = 5.2244 (7) Å
c = 19.007 (3) Å
β = 119.507 (2)°
V = 2351.5 (5) Å³
Z = 4
Mo Kα radiation
μ = 1.09 mm⁻¹
T = 298 K
0.32 × 0.20 × 0.13 mm

Data collection

Bruker SMART CCD area detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.722, T_max = 0.871
6855 measured reflections
2303 independent reflections
2062 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.049
wR(F²) = 0.128
S = 1.01
2303 reflections
160 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.64 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9A⋯O1ⁱ	0.97	2.32	3.292 (6)	177
Symmetry code: (i) $[-x, y-1, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); 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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811011536/is2670sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811011536/is2670Isup2.hkl

checkCIF report

Comment top

Zinc(II) complexes with the chelate ligands are extensively investigated as models for the active site of carbonic anhydrase and other hydrolytically active enzymes (Greener et al., 1996; Gultneh et al., 1996). Zinc(II) complexes are also studied on the role of zinc(II) structural properties in protein folding (Aoki & Kimura, 2004). Interestingly, zinc(II) complexes are becoming important in pharmaceutical, dye, plastic industries and for liquid crystal technology (Csaszar et al., 1985). In addition, the furfuryl amine and its derivatives are widely used as bioactive antibacterial agents and as steel corrosion inhibitors in recent research (Ledovskikh & Camejo, 1993; Camejo et al., 1992). By taking the biological importance of furfurylamine into account, we designed the title complex containing nitrogen-oxygen donor atoms coordinated with zinc(II).

The title complex reported here is the mononuclear zinc(II) complex of Schiff-base ligand, derived from the condensation of 4-methoxysalicylaldehyde and furfuryl amine (Fig. 1). The zinc(II) atom has a distorted tetrahedral coordination formed by two N atoms and two O atoms from two Schiff-base ligands. The bond distances of Zn—O and Zn—N are 1.925 (3) and 1.984 (3) Å, respectively. The dihedral angle between the coordination planes (N1/Zn1/O1 and N1A/Zn1A/O1A) is 87.24 (8)° (symmetry code A: - x, y, 1/2 - z), which is slightly larger than that of 84.43 (6)° between the corresponding coordination planes around zinc(II) atom observed in the similar Schiff base zinc(II) complex, bis(3,5-dibromo-N-benzylsalicylaldiminato-N,O)zinc(II) (Cai et al., 2010). The O1—Zn1—O1 angle is 109.27 (18)° and the N1—Zn1—N1 angle is 120.08 (18)°. The other angles subtended at the Zn(II) ion in (ZnN₂O₂) is in the range of 96.69 (11)–117.49 (12)°.

In the crystal structure, the molecules are linked via intermolecular C—H···O hydrogen bonds forming a column along the b axis (Fig. 2).

Related literature top

For the biological activity and applications of Zn(II) complexes, see: Csaszar et al. (1985); Greener et al. (1996); Gultneh et al. (1996); Aoki & Kimura (2004). For applications of furfurylamine derivatives, see: Camejo et al. (1992); Ledovskikh & Camejo (1993). For a related structure, see; Cai et al. (2010).

Experimental top

4-Methoxysalicylaldehyde (304 mg, 2 mmol) and furfurylamine (194 mg, 2 mmol) were dissolved in an aqueous methanol solution (25 mL).The mixture was stirred at room temperature for 1 h to give a clear yellow solution, which was added to a solutionof Zn(NO₃)₂.6H₂O (298 mg, 1 mmol) in methanol (10 mL). The mixture was stirred for 30 min at room temperature to give a yellow solution and then filtered. The yellow single crystals suitable for X-ray analysis were obtained by slowly evaporating the above filtrate at room temperature. The crystals were isolated and dried in a vacuum desiccator containing anhydrous CaCl₂, in about 71% yield. Anal. Calcd for C₂₆H₂₄ZnN₂O₆: C 59.38, H 4.60, N 5.33%. Found: C 59.20, H 4.73 N, 5.30%.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000; program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (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, with the atom labeling scheme. Displacement ellipsoids are drawn at the 30% probability level. The suffix A corresponds to symmetry code - x, y, 1/2 - z.
	Fig. 2. A packing diagram of the title compound, viewed along the b axis.

Bis{2-[(2-furylmethyl)iminomethyl]-5-methoxyphenolato- κ²N,O}zinc(II) top

Crystal data top

[Zn(C₁₃H₁₂NO₃)₂]	F(000) = 1088
M_r = 525.84	D_x = 1.485 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2246 reflections
a = 27.210 (4) Å	θ = 2.5–23.7°
b = 5.2244 (7) Å	µ = 1.09 mm⁻¹
c = 19.007 (3) Å	T = 298 K
β = 119.507 (2)°	Block, yellow
V = 2351.5 (5) Å³	0.32 × 0.20 × 0.13 mm
Z = 4

Data collection top

Bruker SMART CCD area detector diffractometer	2303 independent reflections
Radiation source: fine-focus sealed tube	2062 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
ϕ and ω scans	θ_max = 26.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −33→33
T_min = 0.722, T_max = 0.871	k = −6→6
6855 measured reflections	l = −23→20

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.128	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0784P)² + 2.4971P] where P = (F_o² + 2F_c²)/3
2303 reflections	(Δ/σ)_max < 0.001
160 parameters	Δρ_max = 0.64 e Å⁻³
1 restraint	Δρ_min = −0.31 e Å⁻³

Crystal data top

[Zn(C₁₃H₁₂NO₃)₂]	V = 2351.5 (5) Å³
M_r = 525.84	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 27.210 (4) Å	µ = 1.09 mm⁻¹
b = 5.2244 (7) Å	T = 298 K
c = 19.007 (3) Å	0.32 × 0.20 × 0.13 mm
β = 119.507 (2)°

Data collection top

Bruker SMART CCD area detector diffractometer	2303 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	2062 reflections with I > 2σ(I)
T_min = 0.722, T_max = 0.871	R_int = 0.026
6855 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	1 restraint
wR(F²) = 0.128	H-atom parameters constrained
S = 1.01	Δρ_max = 0.64 e Å⁻³
2303 reflections	Δρ_min = −0.31 e Å⁻³
160 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
Zn1	0.0000	0.78566 (12)	0.2500	0.0427 (3)
N1	0.02638 (12)	0.5960 (6)	0.18435 (18)	0.0394 (7)
O1	0.06578 (11)	0.9989 (6)	0.30670 (18)	0.0549 (7)
O2	0.24426 (12)	1.3537 (7)	0.3745 (2)	0.0665 (9)
O3	−0.03914 (17)	0.7542 (6)	0.0242 (2)	0.0729 (10)
C1	0.11535 (15)	0.8329 (7)	0.2413 (2)	0.0403 (8)
C2	0.10942 (14)	1.0010 (7)	0.2954 (2)	0.0402 (8)
C3	0.15270 (16)	1.1795 (8)	0.3399 (3)	0.0465 (9)
H3	0.1490	1.2918	0.3750	0.056*
C4	0.20061 (16)	1.1895 (8)	0.3319 (3)	0.0489 (9)
C5	0.20638 (16)	1.0283 (9)	0.2781 (3)	0.0550 (10)
H5	0.2382	1.0385	0.2720	0.066*
C6	0.16505 (16)	0.8560 (9)	0.2348 (3)	0.0505 (10)
H6	0.1694	0.7483	0.1993	0.061*
C7	0.2397 (2)	1.5304 (9)	0.4279 (3)	0.0675 (13)
H7A	0.2080	1.6411	0.3976	0.101*
H7B	0.2736	1.6309	0.4545	0.101*
H7C	0.2345	1.4386	0.4675	0.101*
C8	0.07515 (15)	0.6467 (7)	0.1911 (2)	0.0417 (8)
H8	0.0851	0.5491	0.1591	0.050*
C9	−0.00946 (17)	0.4112 (8)	0.1224 (2)	0.0508 (9)
H9A	−0.0260	0.2943	0.1446	0.061*
H9B	0.0134	0.3118	0.1061	0.061*
C10	−0.05497 (17)	0.5418 (8)	0.0510 (2)	0.0517 (10)
C11	−0.1095 (2)	0.4911 (15)	0.0025 (3)	0.0929 (17)
H11	−0.1303	0.3563	0.0065	0.111*
C12	−0.1294 (3)	0.6947 (16)	−0.0583 (4)	0.102 (2)
H12	−0.1661	0.7157	−0.1007	0.123*
C13	−0.0861 (3)	0.8419 (15)	−0.0423 (3)	0.103 (2)
H13	−0.0874	0.9855	−0.0721	0.123*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0333 (4)	0.0510 (4)	0.0525 (4)	0.000	0.0278 (3)	0.000
N1	0.0346 (15)	0.0452 (16)	0.0426 (16)	0.0013 (13)	0.0222 (13)	0.0020 (13)
O1	0.0396 (15)	0.0674 (18)	0.0709 (18)	−0.0102 (13)	0.0372 (14)	−0.0200 (15)
O2	0.0414 (16)	0.070 (2)	0.083 (2)	−0.0157 (14)	0.0268 (16)	−0.0085 (18)
O3	0.079 (2)	0.070 (2)	0.064 (2)	0.0066 (17)	0.0316 (19)	0.0094 (16)
C1	0.0326 (18)	0.047 (2)	0.045 (2)	0.0031 (15)	0.0226 (16)	0.0047 (16)
C2	0.0301 (17)	0.0457 (19)	0.047 (2)	0.0029 (14)	0.0205 (15)	0.0023 (16)
C3	0.038 (2)	0.047 (2)	0.054 (2)	−0.0002 (16)	0.0232 (18)	−0.0007 (17)
C4	0.0342 (19)	0.052 (2)	0.056 (2)	−0.0027 (16)	0.0188 (18)	0.0068 (18)
C5	0.0336 (19)	0.074 (3)	0.066 (3)	0.0003 (18)	0.0304 (19)	0.005 (2)
C6	0.037 (2)	0.065 (3)	0.057 (2)	0.0034 (18)	0.0289 (18)	−0.002 (2)
C7	0.059 (3)	0.060 (3)	0.068 (3)	−0.018 (2)	0.019 (2)	−0.003 (2)
C8	0.0398 (19)	0.047 (2)	0.044 (2)	0.0051 (15)	0.0252 (17)	0.0000 (16)
C9	0.052 (2)	0.045 (2)	0.060 (2)	−0.0084 (18)	0.031 (2)	−0.0046 (19)
C10	0.043 (2)	0.065 (3)	0.050 (2)	−0.0058 (18)	0.0245 (18)	−0.014 (2)
C11	0.050 (3)	0.155 (5)	0.079 (3)	−0.021 (3)	0.036 (3)	−0.049 (3)
C12	0.064 (4)	0.167 (7)	0.056 (3)	0.042 (4)	0.015 (3)	−0.015 (3)
C13	0.119 (6)	0.113 (5)	0.055 (3)	0.052 (5)	0.027 (4)	0.014 (3)

Geometric parameters (Å, º) top

Zn1—O1ⁱ	1.925 (3)	C4—C5	1.391 (6)
Zn1—O1	1.925 (3)	C5—C6	1.357 (6)
Zn1—N1	1.984 (3)	C5—H5	0.9300
Zn1—N1ⁱ	1.984 (3)	C6—H6	0.9300
N1—C8	1.296 (4)	C7—H7A	0.9600
N1—C9	1.463 (5)	C7—H7B	0.9600
O1—C2	1.306 (4)	C7—H7C	0.9600
O2—C4	1.362 (5)	C8—H8	0.9300
O2—C7	1.422 (6)	C9—C10	1.479 (6)
O3—C13	1.360 (7)	C9—H9A	0.9700
O3—C10	1.375 (5)	C9—H9B	0.9700
C1—C2	1.422 (5)	C10—C11	1.332 (6)
C1—C6	1.422 (5)	C11—C12	1.465 (10)
C1—C8	1.423 (5)	C11—H11	0.9300
C2—C3	1.411 (5)	C12—C13	1.311 (11)
C3—C4	1.386 (6)	C12—H12	0.9300
C3—H3	0.9300	C13—H13	0.9300

O1ⁱ—Zn1—O1	109.27 (18)	C1—C6—H6	118.6
O1ⁱ—Zn1—N1	117.49 (12)	O2—C7—H7A	109.5
O1—Zn1—N1	96.69 (11)	O2—C7—H7B	109.5
O1ⁱ—Zn1—N1ⁱ	96.69 (11)	H7A—C7—H7B	109.5
O1—Zn1—N1ⁱ	117.49 (12)	O2—C7—H7C	109.5
N1—Zn1—N1ⁱ	120.08 (18)	H7A—C7—H7C	109.5
C8—N1—C9	117.3 (3)	H7B—C7—H7C	109.5
C8—N1—Zn1	120.4 (3)	N1—C8—C1	128.1 (3)
C9—N1—Zn1	122.1 (2)	N1—C8—H8	115.9
C2—O1—Zn1	125.6 (2)	C1—C8—H8	115.9
C4—O2—C7	118.4 (3)	N1—C9—C10	111.1 (3)
C13—O3—C10	107.1 (5)	N1—C9—H9A	109.4
C2—C1—C6	117.5 (3)	C10—C9—H9A	109.4
C2—C1—C8	125.7 (3)	N1—C9—H9B	109.4
C6—C1—C8	116.7 (3)	C10—C9—H9B	109.4
O1—C2—C3	117.7 (3)	H9A—C9—H9B	108.0
O1—C2—C1	123.4 (3)	C11—C10—O3	110.5 (5)
C3—C2—C1	118.9 (3)	C11—C10—C9	133.4 (5)
C4—C3—C2	120.8 (4)	O3—C10—C9	116.0 (4)
C4—C3—H3	119.6	C10—C11—C12	104.7 (6)
C2—C3—H3	119.6	C10—C11—H11	127.6
O2—C4—C3	123.4 (4)	C12—C11—H11	127.6
O2—C4—C5	115.9 (4)	C13—C12—C11	107.5 (5)
C3—C4—C5	120.7 (4)	C13—C12—H12	126.2
C6—C5—C4	119.2 (3)	C11—C12—H12	126.2
C6—C5—H5	120.4	C12—C13—O3	110.1 (7)
C4—C5—H5	120.4	C12—C13—H13	124.9
C5—C6—C1	122.9 (4)	O3—C13—H13	124.9
C5—C6—H6	118.6

Symmetry code: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9A···O1ⁱⁱ	0.97	2.32	3.292 (6)	177

Symmetry code: (ii) −x, y−1, −z+1/2.

Experimental details

Crystal data
Chemical formula	[Zn(C₁₃H₁₂NO₃)₂]
M_r	525.84
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	298
a, b, c (Å)	27.210 (4), 5.2244 (7), 19.007 (3)
β (°)	119.507 (2)
V (Å³)	2351.5 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.09
Crystal size (mm)	0.32 × 0.20 × 0.13

Data collection
Diffractometer	Bruker SMART CCD area detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.722, 0.871
No. of measured, independent and observed [I > 2σ(I)] reflections	6855, 2303, 2062
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.128, 1.01
No. of reflections	2303
No. of parameters	160
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.64, −0.31

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SAINT (Bruker, 2000, SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9A···O1ⁱ	0.97	2.32	3.292 (6)	177

Symmetry code: (i) −x, y−1, −z+1/2.

Acknowledgements

This work was supported by the Education Office of Hubei Province (D20104104).

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