Bis[4-methyl-2-(4-methyl­phenyldiazen­yl)phenolato-κ2N,O]nickel(II)

Guan, D.; Sun, H.

doi:10.1107/S1600536809013920

metal-organic compounds

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Volume 65| Part 5| May 2009| Page m566

doi:10.1107/S1600536809013920

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Bis[4-methyl-2-(4-methylphenyldiazenyl)phenolato-κ²N,O]nickel(II)

Dexin Guan ^a and Hongjian Sun ^a ^*

^aSchool of Chemistry and Chemical Engineering, Shandong University, Jinan 250100, People's Republic of China
^*Correspondence e-mail: hjsun@sdu.edu.cn

(Received 3 April 2009; accepted 14 April 2009; online 25 April 2009)

In the crystal structure of the title compound, [Ni(C₁₄H₁₃N₂O)₂], the Ni^II ion is located on an inversion center and is coordinated by two 4-methyl-2-(4-methylphenyldiazenyl)phenolate anions in a slightly distorted square-planar geometry. Within the anion, the two benzene rings are twisted from each other with a dihedral angle of 45.97 (12)°. No hydrogen bonding is found in the crystal structure.

Related literature

For general background, see: Frey (2005 ).

Experimental

Crystal data

[Ni(C₁₄H₁₃N₂O)₂]
M_r = 509.24
Monoclinic, P 2₁ /c
a = 9.5211 (10) Å
b = 10.8162 (11) Å
c = 12.2647 (13) Å
β = 105.367 (2)°
V = 1217.9 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.83 mm⁻¹
T = 293 K
0.15 × 0.15 × 0.10 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.885, T_max = 0.920
7063 measured reflections
2775 independent reflections
1890 reflections with I > 2σ(I)
R_int = 0.032

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.099
S = 1.02
2775 reflections
212 parameters
All H-atom parameters refined
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Selected bond lengths (Å)

Ni—O	1.8118 (16)
Ni—N1	1.8988 (18)

Data collection: APEX2 (Bruker, 2008 ); cell refinement: SAINT (Bruker, 2008); 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, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809013920/xu2508sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809013920/xu2508Isup2.hkl

checkCIF report

Comment top

Nickel hydride complexes are one of the most valuable catalysts and intermediates. Frey (2005) has successfully synthesized a new type of nickel hydride Ni(H)(ortho-S—C₆H₄PPh₂)(PMe₃)₂. In the previous work in our lab, we have reported similar reactions between nickel or cobalt hydrides and phenol derivates. So the reaction between Ni(H)(ortho-S—C₆H₄PPh₂)(PMe₃)₂ and phenol derivates was carried out to explore the acidity of the hydrogen ligand. The title compound, as an unexpected compound, was synthesized.

The molecular structure is shown in Fig. 1. The Ni^II ion is located in an inversion center and coordinated by two 2-(4'-methylphenylazo)-4-methylphenol anions in a square-planar geometry (Table 1). No hydrogen bonding is found in the crystal structure.

Related literature top

For general background, see: Frey (2005).

Experimental top

Ni(H)(ortho-S-C₆H₄PPh₂)(PMe₃)₂ (1.19 g, 2.35 mmol) and 2-(4'-methylphenylazo)-4-methylphenol (0.54 g, 2.38 mmol) was mixed in -80 °C. The mixture was stirred between -20 °C to 0 °C for 18 h and a red solution was formed. Green residue was filtered off, Then the solvent was removed in vacuum. The residue was extracted with pentane, and then diethyl ether. The extractions were kept in -20°C. The title compound was obtained from the pentane extractions as green crystals for X-ray diffraction.

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); 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, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

Fig. 1. View of the title compound, showing 25% displacement ellipsoids. H atoms were omitted. Symmetry code: (A) 2 - x, 2 - y, -z.

Bis[4-methyl-2-(4-methylphenyldiazenyl)phenolato- κ²N,O]nickel(II) top

Crystal data top

[Ni(C₁₄H₁₃N₂O)₂]	F(000) = 532
M_r = 509.24	D_x = 1.389 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1666 reflections
a = 9.5211 (10) Å	θ = 2.6–23.4°
b = 10.8162 (11) Å	µ = 0.83 mm⁻¹
c = 12.2647 (13) Å	T = 293 K
β = 105.367 (2)°	Block, green
V = 1217.9 (2) Å³	0.15 × 0.15 × 0.10 mm
Z = 2

Data collection top

Bruker SMART APEX diffractometer	2775 independent reflections
Radiation source: fine-focus sealed tube	1890 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
ω scans	θ_max = 27.6°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→11
T_min = 0.885, T_max = 0.920	k = −13→13
7063 measured reflections	l = −9→15

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.099	All H-atom parameters refined
S = 1.02	w = 1/[σ²(F_o²) + (0.0451P)² + 0.1292P] where P = (F_o² + 2F_c²)/3
2775 reflections	(Δ/σ)_max < 0.001
212 parameters	Δρ_max = 0.24 e Å⁻³
0 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

[Ni(C₁₄H₁₃N₂O)₂]	V = 1217.9 (2) Å³
M_r = 509.24	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.5211 (10) Å	µ = 0.83 mm⁻¹
b = 10.8162 (11) Å	T = 293 K
c = 12.2647 (13) Å	0.15 × 0.15 × 0.10 mm
β = 105.367 (2)°

Data collection top

Bruker SMART APEX diffractometer	2775 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1890 reflections with I > 2σ(I)
T_min = 0.885, T_max = 0.920	R_int = 0.032
7063 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.099	All H-atom parameters refined
S = 1.02	Δρ_max = 0.24 e Å⁻³
2775 reflections	Δρ_min = −0.19 e Å⁻³
212 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
Ni	1.0000	1.0000	0.0000	0.04172 (15)
N1	0.96662 (19)	0.83618 (16)	0.04286 (15)	0.0412 (4)
N2	1.02859 (19)	0.77982 (17)	0.13462 (15)	0.0448 (5)
O	1.0688 (2)	1.04670 (16)	0.14634 (14)	0.0552 (5)
C7	1.1204 (2)	0.8429 (2)	0.22272 (18)	0.0428 (5)
C1	0.8685 (2)	0.75494 (19)	−0.03615 (18)	0.0402 (5)
C6	0.9169 (3)	0.6442 (2)	−0.0673 (2)	0.0440 (5)
C4	0.6804 (3)	0.6040 (2)	−0.1919 (2)	0.0474 (6)
C5	0.8231 (3)	0.5700 (2)	−0.1455 (2)	0.0480 (6)
C2	0.7255 (3)	0.7908 (2)	−0.0813 (2)	0.0527 (6)
C12	1.1914 (3)	0.7700 (3)	0.3162 (2)	0.0524 (6)
C8	1.1345 (3)	0.9729 (2)	0.2279 (2)	0.0462 (6)
C3	0.6333 (3)	0.7146 (2)	−0.1575 (2)	0.0559 (7)
C9	1.2225 (3)	1.0238 (3)	0.3292 (2)	0.0571 (7)
C11	1.2798 (3)	0.8206 (3)	0.4119 (2)	0.0560 (7)
C10	1.2937 (3)	0.9492 (3)	0.4156 (2)	0.0595 (7)
C13	0.5765 (5)	0.5215 (4)	−0.2756 (4)	0.0741 (10)
C14	1.3546 (5)	0.7421 (5)	0.5127 (3)	0.0827 (11)
H10	1.347 (3)	0.987 (2)	0.479 (2)	0.050 (7)*
H5	0.862 (3)	0.494 (2)	−0.165 (2)	0.048 (7)*
H6	1.014 (2)	0.624 (2)	−0.0350 (18)	0.047 (6)*
H12	1.173 (3)	0.686 (2)	0.311 (2)	0.061 (8)*
H3	0.541 (3)	0.737 (2)	−0.185 (2)	0.066 (8)*
H9	1.232 (3)	1.111 (3)	0.333 (2)	0.066 (8)*
H13B	0.594 (4)	0.440 (4)	−0.253 (3)	0.127 (16)*
H13A	0.603 (5)	0.522 (4)	−0.338 (4)	0.127 (19)*
H2	0.689 (3)	0.867 (3)	−0.057 (2)	0.076 (8)*
H13C	0.491 (5)	0.541 (3)	−0.290 (3)	0.106 (15)*
H14C	1.454 (4)	0.752 (4)	0.527 (3)	0.111 (13)*
H14A	1.318 (4)	0.761 (4)	0.576 (3)	0.119 (14)*
H14B	1.341 (5)	0.663 (5)	0.504 (4)	0.16 (2)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni	0.0496 (3)	0.0325 (2)	0.0400 (2)	−0.00195 (18)	0.00673 (18)	−0.00217 (18)
N1	0.0429 (10)	0.0346 (10)	0.0423 (10)	−0.0008 (8)	0.0046 (8)	−0.0015 (8)
N2	0.0455 (11)	0.0419 (11)	0.0439 (11)	0.0006 (8)	0.0062 (9)	0.0001 (9)
O	0.0800 (13)	0.0372 (8)	0.0422 (9)	−0.0034 (8)	0.0052 (9)	−0.0025 (8)
C7	0.0422 (12)	0.0466 (13)	0.0379 (12)	0.0001 (10)	0.0076 (10)	−0.0020 (10)
C1	0.0418 (13)	0.0339 (11)	0.0414 (12)	−0.0036 (9)	0.0047 (10)	0.0028 (9)
C6	0.0388 (13)	0.0380 (12)	0.0513 (14)	0.0008 (10)	0.0050 (10)	0.0000 (11)
C4	0.0496 (14)	0.0398 (13)	0.0466 (13)	−0.0069 (10)	0.0020 (11)	0.0021 (11)
C5	0.0507 (14)	0.0354 (13)	0.0547 (15)	0.0018 (11)	0.0085 (12)	−0.0051 (11)
C2	0.0449 (14)	0.0416 (14)	0.0648 (16)	0.0060 (11)	0.0029 (12)	−0.0021 (12)
C12	0.0568 (16)	0.0512 (16)	0.0472 (14)	0.0059 (13)	0.0103 (12)	0.0003 (12)
C8	0.0476 (14)	0.0508 (15)	0.0414 (13)	−0.0060 (10)	0.0142 (11)	−0.0070 (10)
C3	0.0388 (14)	0.0512 (15)	0.0672 (17)	0.0062 (12)	−0.0045 (12)	0.0028 (13)
C9	0.0657 (17)	0.0606 (18)	0.0435 (14)	−0.0125 (13)	0.0119 (13)	−0.0114 (12)
C11	0.0481 (14)	0.0743 (19)	0.0431 (14)	0.0056 (13)	0.0077 (11)	−0.0004 (13)
C10	0.0530 (16)	0.083 (2)	0.0392 (14)	−0.0108 (15)	0.0070 (12)	−0.0122 (14)
C13	0.067 (2)	0.061 (2)	0.075 (2)	−0.0100 (17)	−0.0148 (19)	−0.0089 (17)
C14	0.074 (3)	0.112 (4)	0.0518 (19)	0.013 (2)	−0.0005 (17)	0.013 (2)

Geometric parameters (Å, º) top

Ni—Oⁱ	1.8118 (16)	C2—C3	1.374 (3)
Ni—O	1.8118 (16)	C2—H2	0.98 (3)
Ni—N1	1.8988 (18)	C12—C11	1.364 (3)
Ni—N1ⁱ	1.8988 (18)	C12—H12	0.92 (2)
N1—N2	1.278 (2)	C8—C9	1.413 (3)
N1—C1	1.451 (3)	C3—H3	0.89 (2)
N2—C7	1.377 (3)	C9—C10	1.361 (4)
O—C8	1.303 (3)	C9—H9	0.95 (3)
C7—C12	1.408 (3)	C11—C10	1.397 (4)
C7—C8	1.412 (3)	C11—C14	1.513 (4)
C1—C6	1.373 (3)	C10—H10	0.91 (3)
C1—C2	1.382 (3)	C13—H13B	0.92 (4)
C6—C5	1.381 (3)	C13—H13A	0.87 (5)
C6—H6	0.93 (2)	C13—H13C	0.81 (4)
C4—C5	1.377 (3)	C14—H14C	0.92 (4)
C4—C3	1.382 (3)	C14—H14A	0.95 (4)
C4—C13	1.514 (4)	C14—H14B	0.86 (5)
C5—H5	0.95 (2)

Oⁱ—Ni—O	180.000 (1)	C11—C12—H12	121.2 (16)
Oⁱ—Ni—N1	88.33 (8)	C7—C12—H12	116.8 (16)
O—Ni—N1	91.67 (8)	O—C8—C7	123.7 (2)
Oⁱ—Ni—N1ⁱ	91.67 (8)	O—C8—C9	119.2 (2)
O—Ni—N1ⁱ	88.33 (8)	C7—C8—C9	117.0 (2)
N1—Ni—N1ⁱ	180.0	C2—C3—C4	121.8 (2)
N2—N1—C1	111.38 (17)	C2—C3—H3	119.1 (17)
N2—N1—Ni	128.07 (14)	C4—C3—H3	119.2 (17)
C1—N1—Ni	120.38 (13)	C10—C9—C8	120.7 (3)
N1—N2—C7	120.24 (19)	C10—C9—H9	122.2 (16)
C8—O—Ni	124.29 (15)	C8—C9—H9	117.0 (16)
N2—C7—C12	115.5 (2)	C12—C11—C10	117.3 (2)
N2—C7—C8	124.1 (2)	C12—C11—C14	121.8 (3)
C12—C7—C8	120.1 (2)	C10—C11—C14	120.8 (3)
C6—C1—C2	120.0 (2)	C9—C10—C11	122.8 (3)
C6—C1—N1	120.67 (19)	C9—C10—H10	117.0 (15)
C2—C1—N1	119.3 (2)	C11—C10—H10	120.2 (14)
C1—C6—C5	119.8 (2)	C4—C13—H13B	109 (2)
C1—C6—H6	117.3 (15)	C4—C13—H13A	108 (3)
C5—C6—H6	122.9 (15)	H13B—C13—H13A	101 (3)
C5—C4—C3	118.0 (2)	C4—C13—H13C	115 (3)
C5—C4—C13	121.3 (3)	H13B—C13—H13C	114 (3)
C3—C4—C13	120.8 (3)	H13A—C13—H13C	108 (4)
C4—C5—C6	121.2 (2)	C11—C14—H14C	109 (2)
C4—C5—H5	121.9 (15)	C11—C14—H14A	111 (2)
C6—C5—H5	116.9 (15)	H14C—C14—H14A	113 (3)
C3—C2—C1	119.2 (2)	C11—C14—H14B	115 (3)
C3—C2—H2	120.0 (15)	H14C—C14—H14B	104 (4)
C1—C2—H2	120.8 (15)	H14A—C14—H14B	104 (4)
C11—C12—C7	122.0 (3)

Symmetry code: (i) −x+2, −y+2, −z.

Experimental details

Crystal data
Chemical formula	[Ni(C₁₄H₁₃N₂O)₂]
M_r	509.24
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	9.5211 (10), 10.8162 (11), 12.2647 (13)
β (°)	105.367 (2)
V (Å³)	1217.9 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.83
Crystal size (mm)	0.15 × 0.15 × 0.10

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.885, 0.920
No. of measured, independent and observed [I > 2σ(I)] reflections	7063, 2775, 1890
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.652

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.099, 1.02
No. of reflections	2775
No. of parameters	212
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.19

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Selected bond lengths (Å) top

Ni—O

1.8118 (16)

Ni—N1

1.8988 (18)

Acknowledgements

Financial support from the Natural Science Foundation of China (grant Nos. 20872080 and 20772072) is gratefully acknowledged.

References

Bruker (2008). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Frey, M. (2005). PhD thesis, Darmstadt University of Technology, Germany. Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar