{6,6′-Dieth­oxy-2,2′-[ethane-1,2-diylbis(nitrilo­methyl­idyne)]diphenolato}zinc(II) monohydrate

Abstract

The mol­ecule of the title compound, [Zn(C₂₀H₂₂N₂O₄)]·H₂O, deviates from planarity with a dihedral angle between the two benzene rings is 18.3 (1)°. The four-coordinate Zn^II ion has a distorted square-planar coordination and is N₂O₂-chelated by the Schiff base ligand. The Zn^II ion and solvent water mol­ecule are located on a twofold rotation axis. The structure displays inter­molecular O—H⋯O hydrogen bonding.

Related literature

For the chemical properties of Schiff bases, see: Lindoy et al. (1976 ▶). For N,N′-disalicylideneethyl­enediamine complexes, see: Correia et al. (2005 ▶); Cunningham et al. (2000 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

• [Zn(C₂₀H₂₂N₂O₄)]·H₂O

• M _r = 437.78

• Orthorhombic,

• a = 12.6512 (16) Å

• b = 19.986 (3) Å

• c = 7.8708 (10) Å

• V = 1990.1 (4) ų

• Z = 4

• Mo Kα radiation

• μ = 1.27 mm⁻¹

• T = 273 K

• 0.25 × 0.21 × 0.17 mm

Data collection

• Bruker APEXII CCD area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ▶) T _min = 0.742, T _max = 0.813

• 9492 measured reflections

• 1855 independent reflections

• 1423 reflections with I > 2σ(I)

• R _int = 0.031

Refinement

• R[F ² > 2σ(F ²)] = 0.034

• wR(F ²) = 0.101

• S = 1.04

• 1855 reflections

• 133 parameters

• 1 restraint

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.24 e Å⁻³

• Δρ_min = −0.46 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT-Plus (Bruker, 2001 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP in SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: XP in SHELXTL.

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
O3—H3A⋯O1i	0.807 (10)	2.91 (5)	3.071 (4)	94 (3)

Symmetry code: (i) .

supplementary crystallographic information

Comment

The schiff bases have been extensively studied as effective ligands for metal ions and used in the mechanism of many biochemical processes (Lindoy et al., 1976). N,N-disalicylideneethylenediamine type schiff bases ligands present versatile steric, electronic and lipophilic properties (Correia et al. 2005; Cunningham et al. 2000). We report here the synthesis and crystal structure of the title compound. The molecular structure is shown in Fig.1. The values of the geometric parameters in the structure are normal (Allen et al., 1987). The interplanar angles beween the the two phenyl group is 18.3 (1)°. The four-coordinate Zn gives plane coordination.

Experimental

A mixture of 6,6'-Diethoxy-2,2'-(ethane-1,2-diyldiiminodimethylene)diphenol (0.1 mmol) and zinc acetate (0.1 mmol) in absolute methanol (20 ml) was heated at 50 centidegree and stirred for 30 min, then filtered. The resulting clear orange solution was moved to a tube, some ethyl ether was added, and then after 14 days, block-shaped crystals of the title complex suitable for X-ray diffraction analysis were obtained(yield: about 40%).

Refinement

The H atoms were fixed geometrically and were treated as riding on their parent C atoms, with C–H distances in the range of 0.93–0.97Å and with U_iso(H) = 1.2U_eq(parent atom), or U_iso(H) = 1.5U_eq(C_methyl). The coordinates of the water H atom were found in a difference Fourier map and refined with U_iso(H) = 1.2_Ueq(O).

Figures

Fig. 1.

The independent molecules of the title compound, showing 30% probability displacement ellipsoids and the atom-numbering scheme.

Crystal data

[Zn(C20H22N2O4)]·H2O	F(000) = 912
Mr = 437.78	Dx = 1.461 Mg m−3
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 2488 reflections
a = 12.6512 (16) Å	θ = 3.3–24.0°
b = 19.986 (3) Å	µ = 1.27 mm−1
c = 7.8708 (10) Å	T = 273 K
V = 1990.1 (4) Å3	Needle, colourless
Z = 4	0.25 × 0.21 × 0.17 mm

Data collection

Bruker APEXII CCD area-detector diffractometer	1855 independent reflections
Radiation source: fine-focus sealed tube	1423 reflections with I > 2σ(I)
graphite	Rint = 0.031
φ and ω scans	θmax = 25.5°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −15→13
Tmin = 0.742, Tmax = 0.813	k = −24→23
9492 measured reflections	l = −9→9

Refinement

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.101	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ2(Fo2) + (0.0592P)2 + 0.4077P] where P = (Fo2 + 2Fc2)/3
1855 reflections	(Δ/σ)max = 0.034
133 parameters	Δρmax = 0.24 e Å−3
1 restraint	Δρmin = −0.46 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Zn1	0.5000	0.475277 (19)	0.2500	0.04314 (18)
O1	0.40642 (12)	0.40659 (8)	0.1698 (2)	0.0441 (4)
O2	0.31927 (13)	0.29902 (8)	0.0342 (2)	0.0491 (4)
O3	0.5000	0.26838 (19)	0.2500	0.0940 (13)
N1	0.40920 (19)	0.54832 (10)	0.1725 (3)	0.0519 (6)
C1	0.2641 (2)	0.47896 (14)	0.0770 (3)	0.0530 (7)
C2	0.31464 (18)	0.41541 (12)	0.0957 (3)	0.0422 (6)
C3	0.26222 (19)	0.35776 (13)	0.0260 (3)	0.0468 (6)
C4	0.1632 (2)	0.36235 (17)	−0.0434 (4)	0.0619 (8)
H4	0.1294	0.3244	−0.0849	0.074*
C5	0.1133 (2)	0.4253 (2)	−0.0514 (4)	0.0800 (10)
H5	0.0453	0.4284	−0.0957	0.096*
C6	0.1628 (3)	0.48188 (19)	0.0045 (4)	0.0740 (10)
H6	0.1289	0.5230	−0.0055	0.089*
C7	0.3159 (2)	0.54153 (14)	0.1154 (4)	0.0588 (8)
H7	0.2774	0.5805	0.0967	0.071*
C8	0.2840 (2)	0.24216 (14)	−0.0638 (4)	0.0590 (8)
H8A	0.2683	0.2559	−0.1792	0.071*
H8B	0.2201	0.2238	−0.0142	0.071*
C9	0.3688 (3)	0.19045 (15)	−0.0647 (4)	0.0726 (9)
H9A	0.4320	0.2090	−0.1130	0.109*
H9B	0.3463	0.1528	−0.1312	0.109*
H9C	0.3827	0.1762	0.0496	0.109*
C10	0.4568 (3)	0.61556 (13)	0.1843 (4)	0.0651 (8)
H10A	0.4030	0.6479	0.2152	0.078*
H10B	0.4857	0.6283	0.0748	0.078*
H3A	0.487 (4)	0.2934 (18)	0.172 (4)	0.126 (18)*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Zn1	0.0450 (3)	0.0357 (3)	0.0487 (3)	0.000	0.00991 (18)	0.000
O1	0.0357 (9)	0.0407 (9)	0.0558 (11)	0.0034 (7)	−0.0043 (8)	0.0012 (8)
O2	0.0455 (10)	0.0505 (10)	0.0513 (10)	−0.0085 (8)	−0.0114 (8)	0.0028 (8)
O3	0.096 (3)	0.054 (2)	0.132 (4)	0.000	−0.064 (3)	0.000
N1	0.0604 (15)	0.0394 (11)	0.0558 (14)	0.0128 (11)	0.0222 (12)	0.0062 (11)
C1	0.0456 (15)	0.0639 (18)	0.0496 (16)	0.0188 (12)	0.0072 (13)	0.0064 (13)
C2	0.0342 (12)	0.0563 (15)	0.0361 (13)	0.0052 (11)	0.0062 (10)	0.0073 (11)
C3	0.0378 (14)	0.0650 (17)	0.0376 (13)	0.0001 (12)	0.0031 (10)	0.0109 (12)
C4	0.0378 (15)	0.095 (2)	0.0526 (17)	−0.0027 (15)	−0.0049 (12)	0.0055 (16)
C5	0.0401 (17)	0.126 (3)	0.074 (2)	0.0183 (19)	−0.0085 (15)	0.012 (2)
C6	0.054 (2)	0.091 (2)	0.077 (2)	0.0321 (17)	−0.0010 (15)	0.011 (2)
C7	0.0645 (19)	0.0545 (17)	0.0575 (17)	0.0282 (15)	0.0164 (15)	0.0095 (14)
C8	0.0666 (18)	0.0623 (18)	0.0481 (15)	−0.0252 (15)	−0.0096 (14)	0.0051 (13)
C9	0.092 (2)	0.0575 (18)	0.068 (2)	−0.0142 (17)	−0.0122 (18)	−0.0091 (15)
C10	0.090 (2)	0.0338 (14)	0.071 (2)	0.0088 (13)	0.0375 (16)	0.0048 (13)

Geometric parameters (Å, °)

Zn1—O1	1.9195 (16)	C4—C5	1.410 (5)
Zn1—O1i	1.9195 (16)	C4—H4	0.9300
Zn1—N1i	1.955 (2)	C5—C6	1.365 (5)
Zn1—N1	1.955 (2)	C5—H5	0.9300
O1—C2	1.311 (3)	C6—H6	0.9300
O2—C3	1.380 (3)	C7—H7	0.9300
O2—C8	1.444 (3)	C8—C9	1.489 (4)
O3—H3A	0.807 (10)	C8—H8A	0.9700
N1—C7	1.270 (4)	C8—H8B	0.9700
N1—C10	1.476 (3)	C9—H9A	0.9600
C1—C6	1.404 (4)	C9—H9B	0.9600
C1—C2	1.429 (3)	C9—H9C	0.9600
C1—C7	1.444 (4)	C10—C10i	1.505 (7)
C2—C3	1.438 (3)	C10—H10A	0.9700
C3—C4	1.369 (4)	C10—H10B	0.9700
O1—Zn1—O1i	88.69 (9)	C4—C5—H5	119.4
O1—Zn1—N1i	177.35 (8)	C5—C6—C1	121.0 (3)
O1i—Zn1—N1i	93.95 (9)	C5—C6—H6	119.5
O1—Zn1—N1	93.95 (9)	C1—C6—H6	119.5
O1i—Zn1—N1	177.35 (8)	N1—C7—C1	126.1 (2)
N1i—Zn1—N1	83.40 (15)	N1—C7—H7	117.0
C2—O1—Zn1	126.60 (15)	C1—C7—H7	117.0
C3—O2—C8	118.9 (2)	O2—C8—C9	109.0 (2)
C7—N1—C10	119.9 (2)	O2—C8—H8A	109.9
C7—N1—Zn1	125.21 (19)	C9—C8—H8A	109.9
C10—N1—Zn1	114.9 (2)	O2—C8—H8B	109.9
C6—C1—C2	119.1 (3)	C9—C8—H8B	109.9
C6—C1—C7	117.6 (3)	H8A—C8—H8B	108.3
C2—C1—C7	123.0 (3)	C8—C9—H9A	109.5
O1—C2—C1	124.1 (2)	C8—C9—H9B	109.5
O1—C2—C3	118.0 (2)	H9A—C9—H9B	109.5
C1—C2—C3	117.8 (2)	C8—C9—H9C	109.5
C4—C3—O2	123.6 (3)	H9A—C9—H9C	109.5
C4—C3—C2	121.3 (2)	H9B—C9—H9C	109.5
O2—C3—C2	115.0 (2)	N1—C10—C10i	109.85 (18)
C3—C4—C5	119.2 (3)	N1—C10—H10A	109.7
C3—C4—H4	120.4	C10i—C10—H10A	109.7
C5—C4—H4	120.4	N1—C10—H10B	109.7
C6—C5—C4	121.3 (3)	C10i—C10—H10B	109.7
C6—C5—H5	119.4	H10A—C10—H10B	108.2

Symmetry codes: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···O1i	0.81 (1)	2.91 (5)	3.071 (4)	94 (3)

Symmetry codes: (i) −x+1, y, −z+1/2.