{2,2′-[(1,2-Di­cyano­ethene-1,2-di­yl)bis­(nitrilo­methanylyl­idyne)]diphenolato-κ4O,N,N′,O′}(methanol-κO)zinc

Wang, Z.-C.; Chu, J.; Zhan, S.-Z.

doi:10.1107/S1600536813016863

metal-organic compounds

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Volume 69| Part 7| July 2013| Page m419

https://doi.org/10.1107/S1600536813016863

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{2,2′-[(1,2-Dicyanoethene-1,2-diyl)bis(nitrilomethanylylidyne)]diphenolato-κ⁴O,N,N′,O′}(methanol-κO)zinc

Zhi-Chun Wang,^a Jing Chu ^a and Shu-Zhong Zhan ^a ^*

^aCollege of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510640, People's Republic of China
^*Correspondence e-mail: shzhzhan@scut.edu.cn

(Received 7 May 2013; accepted 18 June 2013; online 29 June 2013)

In the title complex, [Zn(C₁₈H₁₀N₄O₂)(CH₄O)], the Zn²⁺ cation is located on a mirror plane and is coordinated by a tetradentate Schiff base ligand anion (L²⁻) and a methanol molecule. The Zn²⁺ cation is surrounded by two N atoms and two O atoms from L²⁻, in a nearly planar configuration, and one methanol O atom, forming a slightly distorted square-pyramidal geometry. The methanol molecule is disordered over two sets of sites in a 0.5:0.5 ratio. In the crystal, O—H⋯O hydrogen bonds link the molecules into chains parallel to [001].

Related literature

For background to tetradentate Schiff-base complexes of transition metal ions, see: Bottcher et al. (1997 ); Mukherjee et al. (2008 ).

Experimental

Crystal data

[Zn(C₁₈H₁₀N₄O₂)(CH₄O)]
M_r = 411.71
Orthorhombic, P n m a
a = 18.052 (2) Å
b = 19.846 (2) Å
c = 5.0388 (6) Å
V = 1805.2 (4) Å³
Z = 4
Mo Kα radiation
μ = 1.39 mm⁻¹
T = 293 K
0.20 × 0.15 × 0.10 mm

Data collection

Bruker APEXII diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1999 ) T_min = 0.769, T_max = 0.874
5185 measured reflections
1608 independent reflections
1090 reflections with I > 2σ(I)
R_int = 0.044

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.104
S = 1.02
1608 reflections
133 parameters
12 restraints
H-atom parameters constrained
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O1ⁱ	0.93	1.85	2.776 (5)	178
Symmetry code: (i) $[x, -y+{\script{3\over 2}}, z+1]$ .

Data collection: APEX2 (Bruker, 2009 ); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536813016863/jj2167sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536813016863/jj2167Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536813016863/jj2167Isup3.cdx

checkCIF report

Comment top

The title complex is an example of a tetradentate Schiff-base group coordinated to a transition metal ion (Bottcher et al., 1997; Mukherjee et al., 2008). It consists of a Zn²⁺ ion, coordinated to a Schiff-base ligand ion (L^2-), and a CH₃OH molecule (Fig. 1). The zinc ion, located on an inversion center is surrounded by two nitrogen atoms and two oxygen atoms from L^2-, and one oxygen atom from CH₃OH molecule which upon symmetry expansion forms a slightly distorted quadrangular pyramid configuration. In the crystal, O—H···O hydrogen bonds (Table 1) link the molecules into one-dimensional chains (Fig. 2).

Related literature top

For background to tetradentate Schiff-base complexes of transition metal ions, see: Bottcher et al. (1997); Mukherjee et al. (2008)

Experimental top

To a solution, containing 2,3-bis(2-hydroxybenzylideneimino)-2,3-butenedinitrile (H₂L)(0.948 g, 3 mmol) andtriethylamine (0.600 g, 6 mmol) in methanol (30 ml), Zn(CH₃CO₂).2H₂O(0.659 g, 3 mmol) was added andthe mixture was stirred for 15 min. The solution was allowed to slowly evaporate,affording brown crystals, which were collected and dried in vacuo (0.786 g, 68%). Calcd for C₁₉H₁₄ZnN₄O₃:C, 55.38; H, 3.40; N, 13.60. Found: C, 56.19; H, 3.55; N, 13.81.

Structure description top

For background to tetradentate Schiff-base complexes of transition metal ions, see: Bottcher et al. (1997); Mukherjee et al. (2008)

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. Ortep view of the title compound, at the 30% probability level.
	Fig. 2. Packing diagram of the title compound viewed along the b axis. Dashed lines indicate O2—H2···O1 hydrogen bonds.

{2,2'-[(1,2-Dicyanoethene-1,2-diyl)bis(nitrilomethanylylidyne)]diphenolato-κ⁴O,N,N',O'}(methanol-κO)zinc top

Crystal data top

[Zn(C₁₈H₁₀N₄O₂)(CH₄O)]	F(000) = 840
M_r = 411.71	D_x = 1.515 Mg m⁻³
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 5185 reflections
a = 18.052 (2) Å	θ = 2.1–25°
b = 19.846 (2) Å	µ = 1.39 mm⁻¹
c = 5.0388 (6) Å	T = 293 K
V = 1805.2 (4) Å³	Block, orange
Z = 4	0.2 × 0.15 × 0.1 mm

Data collection top

Bruker APEXII diffractometer	1608 independent reflections
Radiation source: fine-focus sealed tube	1090 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.044
Detector resolution: 0.8409 pixels mm^-1	θ_max = 25.0°, θ_min = 2.1°
ω scan	h = −19→21
Absorption correction: multi-scan (SADABS; Bruker, 1999)	k = −20→23
T_min = 0.769, T_max = 0.874	l = −3→5
5185 measured reflections

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.104	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0537P)²] where P = (F_o² + 2F_c²)/3
1608 reflections	(Δ/σ)_max < 0.001
133 parameters	Δρ_max = 0.39 e Å⁻³
12 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

[Zn(C₁₈H₁₀N₄O₂)(CH₄O)]	V = 1805.2 (4) Å³
M_r = 411.71	Z = 4
Orthorhombic, Pnma	Mo Kα radiation
a = 18.052 (2) Å	µ = 1.39 mm⁻¹
b = 19.846 (2) Å	T = 293 K
c = 5.0388 (6) Å	0.2 × 0.15 × 0.1 mm

Data collection top

Bruker APEXII diffractometer	1608 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1999)	1090 reflections with I > 2σ(I)
T_min = 0.769, T_max = 0.874	R_int = 0.044
5185 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	12 restraints
wR(F²) = 0.104	H-atom parameters constrained
S = 1.02	Δρ_max = 0.39 e Å⁻³
1608 reflections	Δρ_min = −0.24 e Å⁻³
133 parameters

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	Occ. (<1)
Zn1	0.36935 (3)	0.7500	0.52857 (11)	0.0500 (2)
O1	0.34404 (15)	0.67853 (13)	0.2792 (5)	0.0617 (7)
O2	0.2889 (2)	0.7701 (2)	0.8065 (9)	0.0519 (16)	0.50
H2	0.3085	0.7877	0.9624	0.062*	0.50
N1	0.44377 (14)	0.68348 (14)	0.7145 (5)	0.0450 (7)
N2	0.5754 (2)	0.64994 (18)	1.2118 (8)	0.0825 (11)
C1	0.3527 (2)	0.61308 (19)	0.3065 (7)	0.0520 (9)
C2	0.3159 (2)	0.5695 (2)	0.1276 (8)	0.0611 (11)
H2A	0.2857	0.5879	−0.0032	0.073*
C3	0.3233 (2)	0.5009 (2)	0.1413 (8)	0.0634 (11)
H3	0.2987	0.4739	0.0188	0.076*
C4	0.3672 (2)	0.4708 (2)	0.3366 (8)	0.0603 (10)
H4	0.3712	0.4242	0.3466	0.072*
C5	0.4036 (2)	0.51024 (18)	0.5092 (8)	0.0552 (9)
H5	0.4330	0.4901	0.6382	0.066*
C6	0.39885 (19)	0.58166 (19)	0.5023 (7)	0.0489 (9)
C7	0.44203 (19)	0.61794 (19)	0.6914 (7)	0.0509 (9)
H7	0.4712	0.5930	0.8074	0.061*
C8	0.49009 (18)	0.71569 (16)	0.8927 (6)	0.0439 (8)
C9	0.5382 (2)	0.67901 (18)	1.0708 (8)	0.0528 (9)
C10	0.2165 (4)	0.7640 (8)	0.8168 (19)	0.090 (4)	0.50
H10A	0.2010	0.7610	0.9987	0.135*	0.50
H10B	0.2017	0.7240	0.7239	0.135*	0.50
H10C	0.1939	0.8026	0.7354	0.135*	0.50

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0500 (4)	0.0662 (4)	0.0338 (3)	0.000	−0.0057 (3)	0.000
O1	0.0808 (18)	0.0637 (17)	0.0407 (15)	−0.0081 (13)	−0.0153 (13)	0.0054 (13)
O2	0.047 (2)	0.069 (5)	0.040 (2)	−0.006 (2)	−0.003 (2)	−0.005 (2)
N1	0.0451 (16)	0.0554 (18)	0.0346 (16)	−0.0042 (13)	−0.0033 (13)	−0.0055 (14)
N2	0.086 (3)	0.081 (2)	0.080 (3)	0.000 (2)	−0.034 (2)	0.016 (2)
C1	0.053 (2)	0.066 (2)	0.037 (2)	−0.0128 (17)	0.0024 (17)	−0.0018 (19)
C2	0.066 (3)	0.072 (3)	0.045 (2)	−0.016 (2)	−0.005 (2)	0.000 (2)
C3	0.068 (3)	0.071 (3)	0.052 (2)	−0.022 (2)	0.001 (2)	−0.010 (2)
C4	0.056 (2)	0.060 (2)	0.064 (3)	−0.005 (2)	0.005 (2)	−0.009 (2)
C5	0.0480 (19)	0.062 (2)	0.056 (2)	−0.0038 (17)	−0.0036 (19)	−0.002 (2)
C6	0.0430 (17)	0.062 (2)	0.042 (2)	−0.0059 (16)	0.0011 (17)	−0.0050 (19)
C7	0.045 (2)	0.065 (2)	0.043 (2)	−0.0025 (17)	0.0014 (18)	0.0003 (19)
C8	0.0398 (18)	0.0580 (18)	0.0338 (18)	0.0036 (15)	−0.0024 (16)	−0.0016 (16)
C9	0.053 (2)	0.058 (2)	0.048 (2)	−0.0058 (18)	−0.0068 (19)	−0.0028 (19)
C10	0.064 (4)	0.095 (10)	0.111 (6)	0.017 (5)	0.001 (4)	−0.004 (6)

Geometric parameters (Å, º) top

Zn1—O1	1.949 (2)	C2—H2A	0.9300
Zn1—O1ⁱ	1.949 (2)	C3—C4	1.398 (5)
Zn1—O2	2.057 (4)	C3—H3	0.9300
Zn1—O2ⁱ	2.057 (4)	C4—C5	1.341 (5)
Zn1—N1ⁱ	2.104 (3)	C4—H4	0.9300
Zn1—N1	2.104 (3)	C5—C6	1.420 (5)
O1—C1	1.315 (4)	C5—H5	0.9300
O2—C10	1.313 (8)	C6—C7	1.426 (5)
O2—H2	0.9300	C7—H7	0.9300
N1—C7	1.306 (4)	C8—C8ⁱ	1.362 (6)
N1—C8	1.383 (4)	C8—C9	1.445 (5)
N2—C9	1.135 (5)	C10—H10A	0.9600
C1—C2	1.416 (5)	C10—H10B	0.9600
C1—C6	1.434 (5)	C10—H10C	0.9600
C2—C3	1.369 (5)

O1—Zn1—O1ⁱ	93.38 (15)	C1—C2—H2A	119.0
O1—Zn1—O2	114.48 (14)	C2—C3—C4	121.1 (4)
O1ⁱ—Zn1—O2	97.60 (14)	C2—C3—H3	119.5
O1—Zn1—O2ⁱ	97.60 (14)	C4—C3—H3	119.5
O1ⁱ—Zn1—O2ⁱ	114.48 (14)	C5—C4—C3	119.0 (4)
O2—Zn1—O2ⁱ	22.4 (2)	C5—C4—H4	120.5
O1—Zn1—N1ⁱ	153.31 (12)	C3—C4—H4	120.5
O1ⁱ—Zn1—N1ⁱ	88.86 (10)	C4—C5—C6	122.5 (4)
O2—Zn1—N1ⁱ	91.51 (14)	C4—C5—H5	118.8
O2ⁱ—Zn1—N1ⁱ	105.64 (14)	C6—C5—H5	118.8
O1—Zn1—N1	88.86 (10)	C5—C6—C7	117.0 (3)
O1ⁱ—Zn1—N1	153.31 (12)	C5—C6—C1	119.1 (3)
O2—Zn1—N1	105.64 (14)	C7—C6—C1	123.9 (3)
O2ⁱ—Zn1—N1	91.51 (14)	N1—C7—C6	125.1 (3)
N1ⁱ—Zn1—N1	77.74 (15)	N1—C7—H7	117.4
C1—O1—Zn1	128.6 (2)	C6—C7—H7	117.4
C10—O2—Zn1	135.4 (6)	C8ⁱ—C8—N1	117.52 (18)
C10—O2—H2	112.3	C8ⁱ—C8—C9	120.23 (18)
Zn1—O2—H2	112.3	N1—C8—C9	122.2 (3)
C7—N1—C8	122.2 (3)	N2—C9—C8	179.3 (4)
C7—N1—Zn1	124.7 (2)	O2—C10—H10A	109.5
C8—N1—Zn1	112.6 (2)	O2—C10—H10B	109.5
O1—C1—C2	118.8 (3)	H10A—C10—H10B	109.5
O1—C1—C6	124.8 (3)	O2—C10—H10C	109.5
C2—C1—C6	116.4 (4)	H10A—C10—H10C	109.5
C3—C2—C1	122.0 (4)	H10B—C10—H10C	109.5
C3—C2—H2A	119.0

O1ⁱ—Zn1—O1—C1	174.4 (2)	O1—C1—C2—C3	178.9 (4)
O2—Zn1—O1—C1	−85.6 (3)	C6—C1—C2—C3	0.5 (6)
O2ⁱ—Zn1—O1—C1	−70.3 (3)	C1—C2—C3—C4	0.9 (6)
N1ⁱ—Zn1—O1—C1	80.2 (4)	C2—C3—C4—C5	−1.3 (6)
N1—Zn1—O1—C1	21.1 (3)	C3—C4—C5—C6	0.3 (6)
O1—Zn1—O2—C10	−27.0 (11)	C4—C5—C6—C7	−178.1 (3)
O1ⁱ—Zn1—O2—C10	70.3 (10)	C4—C5—C6—C1	1.0 (5)
O2ⁱ—Zn1—O2—C10	−70.5 (10)	O1—C1—C6—C5	−179.7 (3)
N1ⁱ—Zn1—O2—C10	159.3 (10)	C2—C1—C6—C5	−1.4 (5)
N1—Zn1—O2—C10	−123.0 (10)	O1—C1—C6—C7	−0.7 (6)
O1—Zn1—N1—C7	−19.1 (3)	C2—C1—C6—C7	177.6 (3)
O1ⁱ—Zn1—N1—C7	−114.4 (3)	C8—N1—C7—C6	−176.3 (3)
O2—Zn1—N1—C7	96.0 (3)	Zn1—N1—C7—C6	11.9 (5)
O2ⁱ—Zn1—N1—C7	78.5 (3)	C5—C6—C7—N1	−179.3 (3)
N1ⁱ—Zn1—N1—C7	−175.9 (2)	C1—C6—C7—N1	1.7 (5)
O1—Zn1—N1—C8	168.4 (2)	C7—N1—C8—C8ⁱ	177.1 (2)
O1ⁱ—Zn1—N1—C8	73.1 (3)	Zn1—N1—C8—C8ⁱ	−10.2 (2)
O2—Zn1—N1—C8	−76.4 (2)	C7—N1—C8—C9	−1.8 (5)
O2ⁱ—Zn1—N1—C8	−94.0 (2)	Zn1—N1—C8—C9	170.9 (3)
N1ⁱ—Zn1—N1—C8	11.7 (2)	C8ⁱ—C8—C9—N2	119 (38)
Zn1—O1—C1—C2	166.1 (3)	N1—C8—C9—N2	−62 (38)
Zn1—O1—C1—C6	−15.6 (5)

Symmetry code: (i) x, −y+3/2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1ⁱⁱ	0.93	1.85	2.776 (5)	178

Symmetry code: (ii) x, −y+3/2, z+1.

Experimental details

Crystal data
Chemical formula	[Zn(C₁₈H₁₀N₄O₂)(CH₄O)]
M_r	411.71
Crystal system, space group	Orthorhombic, Pnma
Temperature (K)	293
a, b, c (Å)	18.052 (2), 19.846 (2), 5.0388 (6)
V (Å³)	1805.2 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.39
Crystal size (mm)	0.2 × 0.15 × 0.1

Data collection
Diffractometer	Bruker APEXII
Absorption correction	Multi-scan (SADABS; Bruker, 1999)
T_min, T_max	0.769, 0.874
No. of measured, independent and observed [I > 2σ(I)] reflections	5185, 1608, 1090
R_int	0.044
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.104, 1.02
No. of reflections	1608
No. of parameters	133
No. of restraints	12
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.39, −0.24

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1ⁱ	0.93	1.85	2.776 (5)	177.7

Symmetry code: (i) x, −y+3/2, z+1.

References

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