Bis[2,4-dichloro-6-(ethyl­imino­meth­yl)phenolato-κ2N,O]nickel(II)

Huang, Q.P.; Zhang, S.H.; Guo, J.J.; Feng, C.; Tang, F.S.

doi:10.1107/S160053681104325X

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 11| November 2011| Page m1611

doi:10.1107/S160053681104325X

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Bis[2,4-dichloro-6-(ethyliminomethyl)phenolato-κ²N,O]nickel(II)

Qiu Ping Huang,^a Shu Hua Zhang,^a ^* Jing Jing Guo,^a Chao Feng ^a and Fu Shun Tang ^a ^*

^aKey Laboratory of Non-ferrous Metal Materials and Processing Technology, Ministry of Education, College of Chemistry and Bioengineering, Guilin University of Technology, Guilin 541004, People's Republic of China
^*Correspondence e-mail: zsh720108@163.com, 387810573@qq.com

(Received 10 October 2011; accepted 19 October 2011; online 29 October 2011)

In the title compound, [Ni(C₉H₈Cl₂NO)₂], the Ni^II ion lies on an inversion centre and is coordinated in a slightly distorted square-planar geometry by an N and an O atom from two symmetry-related bidentate 2,4-dichloro-6-(ethyliminomethyl)phenolate ligands. In the crystal structure, there are short Cl⋯Cl distances of 3.506 (1) and 3.350 (1) Å.

Related literature

For halogen–halogen interactions in supramolecular chemistry and crystal engineering, see: Cohen et al. (1964 ); Desiraju (1989 ); Xiao & Zhang (2008 ); Aakeröy et al. (2011 ).

Experimental

Crystal data

[Ni(C₉H₈Cl₂NO)₂]
M_r = 492.84
Monoclinic, P 2₁ /c
a = 7.5004 (6) Å
b = 9.3155 (7) Å
c = 14.1498 (12) Å
β = 103.841 (1)°
V = 959.94 (13) Å³
Z = 2
Mo Kα radiation
μ = 1.58 mm⁻¹
T = 293 K
0.32 × 0.28 × 0.26 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ) T_min = 0.612, T_max = 0.667
4890 measured reflections
1685 independent reflections
1267 reflections with I > 2σ(I)
R_int = 0.060

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.055
S = 0.97
1685 reflections
124 parameters
H-atom parameters constrained
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); 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 I, global. DOI: 10.1107/S160053681104325X/lh5353sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681104325X/lh5353Isup2.hkl

checkCIF report

Comment top

Halogens have a ubiquitous presence in both inorganic and organic chemistry. Schiff bases of chloro substituents on aromatic systems have aroused interest in recent years because these halogenated compounds are an attractive target for use in supramolecular chemistry and crystal engineering wherein the halogen atoms are directly involved in forming intermolecular interactions (Cohen et al., 1964; Desiraju, 1989; Xiao & Zhang, 2008; Aakeröy et al. 2011). The title compound, (I), contains a deprotonated 2,4-dichloro-2-ethyliminomethyl-phenol ligand, with two Cl atoms accesible for Cl···Cl interactions.

In (I), the Ni^II ion lies on an inversion center and is coordinated by two O and two N atoms from two symmetry related bidentate 2,4-diChloro-N-ethylsalicylaldimino ligands, forming a slightly distorted square-planar geometry (Fig. 1). In the crystal, there are short Cl···Cl contacts (Cl1···Cl2ⁱ 3.506 (1) Å, Cl2···Cl2ⁱⁱ 3.350 (1) Å symmetry code:(i) 1 - x, 1/2 + y, 1/2 - z, (ii) -x, -y, -z) (Fig. 2).

Related literature top

For halogen–halogen interactions in supramolecular chemistry and crystal engineering, see: Cohen et al. (1964); Desiraju (1989); Xiao & Zhang (2008); Aakeröy et al. (2011).

Experimental top

A solution of (0.191 g, 1.0 mmol) 3,5-dichloro-2-hydroxy-benzaldehyde and (0.044 g, 1 mmol) ethylamine and (0.040 g, 1 mmol) sodium hydroxide in 20 ml absolute methanol was added slowly a solution of nickel nitrate hexahydrate (0.145 g, 0.5 mmol) in methanol. The mixture was stirred for 3 h at room temperature to give a green solution which was filtered and the filtrate was left to stand at room temperature. Green block-shaped crystals suitable for X-ray diffraction were obtained by slow evaporation. yield: 78.2% (Based on Nickel). Elemental analysis calculated: C 43.83, H 3.75, N 5.68%; Found: C 43.79, H,3.78, N 5.71%.

Computing details top

Data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); 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 (I), showing 30% probability displacement ellipsoids. H atoms are omitted.
	Fig. 2. Part of the crystal structure showing short Cl···Cl contacts as dashed lines.

Bis[2,4-dichloro-6-(ethyliminomethyl)phenolato-κ²N,O]nickel(II) top

Crystal data top

[Ni(C₉H₈Cl₂NO)₂]	F(000) = 500
M_r = 492.84	D_x = 1.705 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1685 reflections
a = 7.5004 (6) Å	θ = 2.6–25.0°
b = 9.3155 (7) Å	µ = 1.58 mm⁻¹
c = 14.1498 (12) Å	T = 293 K
β = 103.841 (1)°	Block, green
V = 959.94 (13) Å³	0.32 × 0.28 × 0.26 mm
Z = 2

Data collection top

Bruker SMART CCD diffractometer	1685 independent reflections
Radiation source: fine-focus sealed tube	1267 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.060
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −8→7
T_min = 0.612, T_max = 0.667	k = −11→8
4890 measured reflections	l = −16→16

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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.055	H-atom parameters constrained
S = 0.97	w = 1/[σ²(F_o²) + (0.0012P)²] where P = (F_o² + 2F_c²)/3
1685 reflections	(Δ/σ)_max < 0.001
124 parameters	Δρ_max = 0.28 e Å⁻³
0 restraints	Δρ_min = −0.35 e Å⁻³

Crystal data top

[Ni(C₉H₈Cl₂NO)₂]	V = 959.94 (13) Å³
M_r = 492.84	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.5004 (6) Å	µ = 1.58 mm⁻¹
b = 9.3155 (7) Å	T = 293 K
c = 14.1498 (12) Å	0.32 × 0.28 × 0.26 mm
β = 103.841 (1)°

Data collection top

Bruker SMART CCD diffractometer	1685 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2004)	1267 reflections with I > 2σ(I)
T_min = 0.612, T_max = 0.667	R_int = 0.060
4890 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	0 restraints
wR(F²) = 0.055	H-atom parameters constrained
S = 0.97	Δρ_max = 0.28 e Å⁻³
1685 reflections	Δρ_min = −0.35 e Å⁻³
124 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
C1	0.6897 (3)	0.3911 (3)	0.06190 (18)	0.0321 (6)
C2	0.5743 (3)	0.3976 (3)	0.12798 (17)	0.0344 (7)
C3	0.4233 (3)	0.3110 (3)	0.11860 (18)	0.0383 (7)
H3A	0.3502	0.3176	0.1631	0.046*
C4	0.3801 (3)	0.2139 (3)	0.0429 (2)	0.0384 (7)
C5	0.4853 (3)	0.2045 (3)	−0.02361 (18)	0.0393 (7)
H5A	0.4546	0.1393	−0.0747	0.047*
C6	0.6402 (3)	0.2937 (3)	−0.01460 (18)	0.0324 (6)
Cl1	0.62781 (9)	0.51726 (8)	0.22421 (4)	0.0454 (2)
Cl2	0.18645 (10)	0.10465 (8)	0.03097 (5)	0.0538 (2)
Ni1	1.0000	0.5000	0.0000	0.03205 (15)
O1	0.8324 (2)	0.47509 (19)	0.07451 (12)	0.0393 (5)
C7	0.7422 (3)	0.2847 (3)	−0.08801 (18)	0.0374 (7)
H7A	0.7023	0.2171	−0.1369	0.045*
C8	0.9509 (4)	0.3268 (3)	−0.18214 (19)	0.0465 (8)
H8A	0.9135	0.2303	−0.2040	0.056*
H8B	1.0840	0.3302	−0.1659	0.056*
C9	0.8770 (4)	0.4311 (4)	−0.26300 (19)	0.0654 (10)
H9A	0.9229	0.4067	−0.3187	0.098*
H9B	0.9155	0.5265	−0.2419	0.098*
H9C	0.7453	0.4266	−0.2800	0.098*
N1	0.8836 (3)	0.3602 (2)	−0.09375 (14)	0.0337 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0305 (15)	0.0322 (17)	0.0333 (15)	0.0026 (13)	0.0070 (13)	0.0053 (13)
C2	0.0343 (16)	0.0373 (17)	0.0315 (15)	0.0041 (13)	0.0078 (13)	0.0053 (13)
C3	0.0341 (16)	0.0456 (19)	0.0376 (16)	0.0033 (14)	0.0132 (14)	0.0094 (15)
C4	0.0303 (16)	0.0388 (17)	0.0449 (17)	−0.0045 (14)	0.0068 (14)	0.0099 (15)
C5	0.0387 (16)	0.0399 (18)	0.0376 (17)	−0.0064 (14)	0.0055 (15)	−0.0018 (13)
C6	0.0329 (15)	0.0315 (16)	0.0332 (15)	−0.0005 (13)	0.0084 (13)	0.0012 (13)
Cl1	0.0483 (4)	0.0536 (5)	0.0372 (4)	−0.0018 (4)	0.0162 (4)	−0.0060 (4)
Cl2	0.0394 (4)	0.0634 (6)	0.0583 (5)	−0.0150 (4)	0.0110 (4)	0.0083 (4)
Ni1	0.0334 (3)	0.0326 (3)	0.0319 (3)	−0.0019 (2)	0.0112 (2)	−0.0032 (2)
O1	0.0403 (11)	0.0445 (13)	0.0372 (10)	−0.0116 (10)	0.0173 (9)	−0.0094 (9)
C7	0.0427 (17)	0.0348 (17)	0.0341 (16)	−0.0010 (14)	0.0077 (14)	−0.0038 (13)
C8	0.0481 (18)	0.051 (2)	0.0465 (18)	−0.0117 (15)	0.0238 (15)	−0.0196 (16)
C9	0.055 (2)	0.105 (3)	0.0394 (18)	−0.013 (2)	0.0178 (17)	0.002 (2)
N1	0.0374 (13)	0.0342 (13)	0.0326 (12)	−0.0020 (11)	0.0143 (11)	−0.0027 (11)

Geometric parameters (Å, º) top

C1—O1	1.303 (3)	Ni1—O1ⁱ	1.8382 (16)
C1—C6	1.393 (3)	Ni1—N1ⁱ	1.914 (2)
C1—C2	1.419 (3)	Ni1—N1	1.914 (2)
C2—C3	1.372 (3)	C7—N1	1.291 (3)
C2—Cl1	1.731 (3)	C7—H7A	0.9300
C3—C4	1.380 (3)	C8—N1	1.489 (3)
C3—H3A	0.9300	C8—C9	1.502 (4)
C4—C5	1.368 (3)	C8—H8A	0.9700
C4—Cl2	1.749 (3)	C8—H8B	0.9700
C5—C6	1.410 (3)	C9—H9A	0.9600
C5—H5A	0.9300	C9—H9B	0.9600
C6—C7	1.432 (3)	C9—H9C	0.9600
Ni1—O1	1.8382 (16)

O1—C1—C6	123.7 (2)	O1ⁱ—Ni1—N1	87.10 (8)
O1—C1—C2	119.6 (2)	N1ⁱ—Ni1—N1	180.0
C6—C1—C2	116.7 (2)	C1—O1—Ni1	130.49 (17)
C3—C2—C1	122.1 (3)	N1—C7—C6	127.1 (3)
C3—C2—Cl1	119.1 (2)	N1—C7—H7A	116.5
C1—C2—Cl1	118.9 (2)	C6—C7—H7A	116.5
C2—C3—C4	119.7 (3)	N1—C8—C9	111.6 (2)
C2—C3—H3A	120.1	N1—C8—H8A	109.3
C4—C3—H3A	120.1	C9—C8—H8A	109.3
C5—C4—C3	120.6 (2)	N1—C8—H8B	109.3
C5—C4—Cl2	119.9 (2)	C9—C8—H8B	109.3
C3—C4—Cl2	119.4 (2)	H8A—C8—H8B	108.0
C4—C5—C6	119.9 (3)	C8—C9—H9A	109.5
C4—C5—H5A	120.1	C8—C9—H9B	109.5
C6—C5—H5A	120.1	H9A—C9—H9B	109.5
C1—C6—C5	121.0 (2)	C8—C9—H9C	109.5
C1—C6—C7	120.8 (2)	H9A—C9—H9C	109.5
C5—C6—C7	118.2 (2)	H9B—C9—H9C	109.5
O1—Ni1—O1ⁱ	180.00 (13)	C7—N1—C8	112.8 (2)
O1—Ni1—N1ⁱ	87.10 (8)	C7—N1—Ni1	124.90 (19)
O1ⁱ—Ni1—N1ⁱ	92.90 (8)	C8—N1—Ni1	122.30 (17)
O1—Ni1—N1	92.90 (8)

Symmetry code: (i) −x+2, −y+1, −z.

Experimental details

Crystal data
Chemical formula	[Ni(C₉H₈Cl₂NO)₂]
M_r	492.84
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	7.5004 (6), 9.3155 (7), 14.1498 (12)
β (°)	103.841 (1)
V (Å³)	959.94 (13)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.58
Crystal size (mm)	0.32 × 0.28 × 0.26

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2004)
T_min, T_max	0.612, 0.667
No. of measured, independent and observed [I > 2σ(I)] reflections	4890, 1685, 1267
R_int	0.060
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.055, 0.97
No. of reflections	1685
No. of parameters	124
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.35

Computer programs: SMART (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (grant No. 21161006) and by the Startup Foundation of Guilin University of Technology (to SHZ).

References

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