Bis(dicyanamido-κN1)bis­[2-(2-hydroxy­ethyl)pyridine-κ2N,O]nickel(II)

Kong, L.-Q.; Ju, X.-P.; Li, D.-C.

doi:10.1107/S1600536809043359

metal-organic compounds

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Volume 65| Part 12| December 2009| Page m1518

doi:10.1107/S1600536809043359

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Bis(dicyanamido-κN¹)bis[2-(2-hydroxyethyl)pyridine-κ²N,O]nickel(II)

Ling-Qian Kong,^a,^b Xiu-Ping Ju ^a and Da-Cheng Li ^b ^*

^aDongchang College of Liaocheng University, Shandong 252059, People's Republic of China, and ^bCollege of Chemistry and Chemical Engineering, Liaocheng University, Shandong 252059, People's Republic of China
^*Correspondence e-mail: lidacheng@lcu.edu.cn

(Received 12 September 2009; accepted 21 October 2009; online 7 November 2009)

In the title complex, [Ni{N(CN)₂}₂(C₇H₉NO)₂], the Ni^II ion (site symmetry $[\overline{1}]$ ) adopts a distorted trans-NiO₂N₄ octahedral geometry. In the crystal, intermolecular O—H⋯N hydrogen bonds link the molecules, forming a chain along the c axis.

Related literature

For related structures, see: Boskovic et al. (2002 ); Sanudo et al. (2003 ).

Experimental

Crystal data

[Ni(C₂N₃)₂(C₇H₉NO)₂]
M_r = 437.11
Triclinic, $[P \overline 1]$
a = 8.1498 (1) Å
b = 8.76020 (11) Å
c = 8.9201 (12) Å
α = 100.841 (1)°
β = 110.588 (2)°
γ = 115.359 (2)°
V = 493.66 (7) Å³
Z = 1
Mo Kα radiation
μ = 1.02 mm⁻¹
T = 298 K
0.28 × 0.20 × 0.15 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2003 ) T_min = 0.764, T_max = 0.863
2566 measured reflections
1718 independent reflections
1579 reflections with I > 2σ(I)
R_int = 0.016

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.095
S = 1.00
1718 reflections
133 parameters
H-atom parameters constrained
Δρ_max = 0.53 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Table 1
Selected bond lengths (Å)

Ni1—N2	2.065 (2)
Ni1—O1	2.0748 (16)
Ni1—N1	2.095 (2)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N4ⁱ	0.82	1.89	2.711 (3)	175
Symmetry code: (i) -x, -y, -z.

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); 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/S1600536809043359/hb5097sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809043359/hb5097Isup2.hkl

checkCIF report

Comment top

In recent years there has been considerable interest in metal complexes supported by hydroxyethyl-pyridine,the ligand due to its versatile coordination activities and bridging function. (Sanudo et al., 2003; Boskovic et al., 2002). As an extension of this work, we have synthesized the title compound, (I), and report herein its crystal structure.

The complex (Fig. 1) consists of two L2-(L = (hydroxyethyl)(pyridine)) ligands, one Ni^II ion and two dicyanmiden ligands. The coordination geometry around the Ni center is octahedral with a NiN₄O₂ ligand set (Table 1). Two atoms N1 of hydroxyethylpyridine ligand occpy the axial sites. In the crystal structure, intermolecular O—H···N hydrogen bonds link molecules to form a one-dimensional chain along to the c axis (Table 2).

Related literature top

For related structures, see: Boskovic et al. (2002); Sanudo et al. (2003).

Experimental top

2-Hydroxyethylpyridine (0.123 g, 1 mmol) was deprotonated by Et₄NOH (25%) in the prensence of nickel nitrate hexahydrate (0.5 mmol, 0.127 g) in a mixture of methanol and acetonitrile (V/V = 1:1) after the solution was stirred at room temperature for 0.5 h. Sodium dicyanmiden (5 mmol 0.486 g) was added to the above solution and then further stirred for 1 h. The resulting clear solution was filtered and left to stand at room temperature. Green blocks of (I) were obtained by slow evaporation of the solvents within 2 weeks. MP = 518-520 K (decomp).

Computing details top

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); 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 structure of the title complex, showing 30% probability displacement ellipsoids. Atoms labelled with the suffix A are generated by the symmetry operation (-x + 1,-y,-z + 1). H atoms have been omitted for clarity.
	Fig. 2. The crystal packing of (I), viewed approximately along the c axis.

Bis(dicyanamido-κN¹)bis[2-(2-hydroxyethyl)pyridine- κ²N,O]nickel(II) top

Crystal data top

[Ni(C₂N₃)₂(C₇H₉NO)₂]	Z = 1
M_r = 437.11	F(000) = 226
Triclinic, P1	D_x = 1.47 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.1498 (1) Å	Cell parameters from 1464 reflections
b = 8.76020 (11) Å	θ = 2.7–26.3°
c = 8.9201 (12) Å	µ = 1.02 mm⁻¹
α = 100.841 (1)°	T = 298 K
β = 110.588 (2)°	Block, green
γ = 115.359 (2)°	0.28 × 0.20 × 0.15 mm
V = 493.66 (7) Å³

Data collection top

Bruker SMART CCD diffractometer	1718 independent reflections
Radiation source: fine-focus sealed tube	1579 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.016
ω scans	θ_max = 25.0°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −9→9
T_min = 0.764, T_max = 0.863	k = −7→10
2566 measured reflections	l = −10→8

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.095	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0648P)² + 0.0746P] where P = (F_o² + 2F_c²)/3
1718 reflections	(Δ/σ)_max < 0.001
133 parameters	Δρ_max = 0.53 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

[Ni(C₂N₃)₂(C₇H₉NO)₂]	γ = 115.359 (2)°
M_r = 437.11	V = 493.66 (7) Å³
Triclinic, P1	Z = 1
a = 8.1498 (1) Å	Mo Kα radiation
b = 8.76020 (11) Å	µ = 1.02 mm⁻¹
c = 8.9201 (12) Å	T = 298 K
α = 100.841 (1)°	0.28 × 0.20 × 0.15 mm
β = 110.588 (2)°

Data collection top

Bruker SMART CCD diffractometer	1718 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2003)	1579 reflections with I > 2σ(I)
T_min = 0.764, T_max = 0.863	R_int = 0.016
2566 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.095	H-atom parameters constrained
S = 1.00	Δρ_max = 0.53 e Å⁻³
1718 reflections	Δρ_min = −0.22 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
Ni1	0.5000	0.0000	0.5000	0.03081 (18)
N1	0.7472 (3)	0.2759 (3)	0.6426 (3)	0.0341 (5)
N2	0.4639 (3)	0.0453 (3)	0.2748 (3)	0.0415 (5)
N3	0.3758 (4)	0.1688 (4)	0.0579 (4)	0.0700 (9)
N4	0.0438 (5)	0.0438 (4)	−0.1949 (4)	0.0731 (9)
O1	0.2970 (3)	0.0824 (2)	0.5031 (2)	0.0411 (4)
H1	0.1971	0.0414	0.4067	0.062*
C1	0.3611 (5)	0.2644 (4)	0.6012 (4)	0.0548 (8)
H1A	0.2523	0.2612	0.6245	0.066*
H1B	0.3849	0.3390	0.5343	0.066*
C2	0.5577 (5)	0.3491 (4)	0.7713 (4)	0.0537 (8)
H2A	0.5771	0.4562	0.8495	0.064*
H2B	0.5422	0.2608	0.8249	0.064*
C3	0.7468 (4)	0.4061 (4)	0.7512 (3)	0.0418 (6)
C4	0.9168 (5)	0.5852 (4)	0.8400 (4)	0.0614 (9)
H4	0.9143	0.6738	0.9136	0.074*
C5	1.0883 (5)	0.6328 (4)	0.8202 (5)	0.0653 (9)
H5	1.2039	0.7528	0.8817	0.078*
C6	1.0887 (5)	0.5030 (4)	0.7096 (4)	0.0559 (8)
H6	1.2034	0.5326	0.6932	0.067*
C7	0.9155 (4)	0.3274 (4)	0.6227 (4)	0.0428 (6)
H7	0.9151	0.2392	0.5456	0.051*
C8	0.4109 (4)	0.0950 (4)	0.1684 (3)	0.0375 (6)
C9	0.1941 (5)	0.0937 (4)	−0.0759 (4)	0.0489 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0250 (3)	0.0319 (3)	0.0300 (3)	0.0149 (2)	0.00897 (19)	0.01179 (19)
N1	0.0305 (11)	0.0347 (11)	0.0322 (10)	0.0171 (9)	0.0116 (9)	0.0121 (9)
N2	0.0354 (12)	0.0455 (13)	0.0324 (11)	0.0182 (11)	0.0097 (10)	0.0168 (10)
N3	0.0383 (14)	0.0750 (19)	0.0627 (17)	0.0120 (13)	0.0049 (13)	0.0479 (16)
N4	0.0540 (17)	0.096 (2)	0.0586 (17)	0.0432 (17)	0.0088 (15)	0.0389 (17)
O1	0.0317 (9)	0.0441 (10)	0.0426 (10)	0.0243 (8)	0.0104 (8)	0.0135 (8)
C1	0.0432 (16)	0.0479 (17)	0.079 (2)	0.0307 (14)	0.0288 (16)	0.0222 (16)
C2	0.0537 (18)	0.0443 (16)	0.0553 (18)	0.0233 (15)	0.0298 (15)	0.0066 (14)
C3	0.0383 (14)	0.0379 (14)	0.0383 (14)	0.0186 (12)	0.0138 (12)	0.0090 (12)
C4	0.055 (2)	0.0382 (16)	0.065 (2)	0.0180 (15)	0.0240 (17)	0.0000 (15)
C5	0.0440 (18)	0.0349 (16)	0.084 (2)	0.0086 (14)	0.0234 (17)	0.0074 (16)
C6	0.0350 (15)	0.0443 (16)	0.072 (2)	0.0136 (13)	0.0231 (15)	0.0168 (15)
C7	0.0343 (14)	0.0380 (14)	0.0502 (16)	0.0177 (12)	0.0188 (13)	0.0140 (13)
C8	0.0251 (12)	0.0406 (14)	0.0343 (13)	0.0117 (11)	0.0108 (11)	0.0133 (12)
C9	0.0486 (17)	0.0551 (17)	0.0520 (17)	0.0306 (15)	0.0239 (15)	0.0326 (15)

Geometric parameters (Å, º) top

Ni1—N2ⁱ	2.065 (2)	C1—C2	1.506 (4)
Ni1—N2	2.065 (2)	C1—H1A	0.9700
Ni1—O1	2.0748 (16)	C1—H1B	0.9700
Ni1—O1ⁱ	2.0748 (16)	C2—C3	1.491 (4)
Ni1—N1	2.095 (2)	C2—H2A	0.9700
Ni1—N1ⁱ	2.095 (2)	C2—H2B	0.9700
N1—C7	1.337 (3)	C3—C4	1.381 (4)
N1—C3	1.353 (3)	C4—C5	1.365 (5)
N2—C8	1.142 (3)	C4—H4	0.9300
N3—C8	1.293 (3)	C5—C6	1.360 (5)
N3—C9	1.296 (4)	C5—H5	0.9300
N4—C9	1.127 (4)	C6—C7	1.372 (4)
O1—C1	1.422 (3)	C6—H6	0.9300
O1—H1	0.8200	C7—H7	0.9300

N2ⁱ—Ni1—N2	180.0	O1—C1—H1B	109.6
N2ⁱ—Ni1—O1	92.61 (8)	C2—C1—H1B	109.6
N2—Ni1—O1	87.39 (8)	H1A—C1—H1B	108.1
N2ⁱ—Ni1—O1ⁱ	87.39 (8)	C3—C2—C1	113.5 (3)
N2—Ni1—O1ⁱ	92.61 (8)	C3—C2—H2A	108.9
O1—Ni1—O1ⁱ	180.0	C1—C2—H2A	108.9
N2ⁱ—Ni1—N1	91.92 (8)	C3—C2—H2B	108.9
N2—Ni1—N1	88.08 (8)	C1—C2—H2B	108.9
O1—Ni1—N1	89.07 (7)	H2A—C2—H2B	107.7
O1ⁱ—Ni1—N1	90.93 (7)	N1—C3—C4	120.6 (3)
N2ⁱ—Ni1—N1ⁱ	88.08 (8)	N1—C3—C2	117.7 (2)
N2—Ni1—N1ⁱ	91.92 (8)	C4—C3—C2	121.7 (3)
O1—Ni1—N1ⁱ	90.93 (7)	C5—C4—C3	120.3 (3)
O1ⁱ—Ni1—N1ⁱ	89.07 (7)	C5—C4—H4	119.8
N1—Ni1—N1ⁱ	180.0	C3—C4—H4	119.8
C7—N1—C3	117.8 (2)	C6—C5—C4	119.4 (3)
C7—N1—Ni1	117.74 (17)	C6—C5—H5	120.3
C3—N1—Ni1	124.45 (18)	C4—C5—H5	120.3
C8—N2—Ni1	156.7 (2)	C5—C6—C7	118.3 (3)
C8—N3—C9	122.3 (3)	C5—C6—H6	120.8
C1—O1—Ni1	124.15 (16)	C7—C6—H6	120.8
C1—O1—H1	109.5	N1—C7—C6	123.6 (3)
Ni1—O1—H1	113.9	N1—C7—H7	118.2
O1—C1—C2	110.2 (2)	C6—C7—H7	118.2
O1—C1—H1A	109.6	N2—C8—N3	172.5 (3)
C2—C1—H1A	109.6	N4—C9—N3	173.2 (3)

N2ⁱ—Ni1—N1—C7	115.4 (2)	O1—C1—C2—C3	74.7 (3)
N2—Ni1—N1—C7	−64.6 (2)	C7—N1—C3—C4	−1.0 (4)
O1—Ni1—N1—C7	−152.00 (19)	Ni1—N1—C3—C4	−179.8 (2)
O1ⁱ—Ni1—N1—C7	28.00 (19)	C7—N1—C3—C2	179.1 (3)
N2ⁱ—Ni1—N1—C3	−65.8 (2)	Ni1—N1—C3—C2	0.3 (3)
N2—Ni1—N1—C3	114.2 (2)	C1—C2—C3—N1	−56.9 (4)
O1—Ni1—N1—C3	26.8 (2)	C1—C2—C3—C4	123.2 (3)
O1ⁱ—Ni1—N1—C3	−153.2 (2)	N1—C3—C4—C5	−0.5 (5)
O1—Ni1—N2—C8	9.2 (5)	C2—C3—C4—C5	179.4 (3)
O1ⁱ—Ni1—N2—C8	−170.8 (5)	C3—C4—C5—C6	1.3 (6)
N1—Ni1—N2—C8	−80.0 (5)	C4—C5—C6—C7	−0.6 (5)
N1ⁱ—Ni1—N2—C8	100.0 (5)	C3—N1—C7—C6	1.8 (4)
N2ⁱ—Ni1—O1—C1	84.2 (2)	Ni1—N1—C7—C6	−179.3 (2)
N2—Ni1—O1—C1	−95.8 (2)	C5—C6—C7—N1	−1.0 (5)
N1—Ni1—O1—C1	−7.7 (2)	Ni1—N2—C8—N3	104 (2)
N1ⁱ—Ni1—O1—C1	172.3 (2)	C9—N3—C8—N2	177 (2)
Ni1—O1—C1—C2	−34.9 (3)	C8—N3—C9—N4	172 (3)

Symmetry code: (i) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N4ⁱⁱ	0.82	1.89	2.711 (3)	175

Symmetry code: (ii) −x, −y, −z.

Experimental details

Crystal data
Chemical formula	[Ni(C₂N₃)₂(C₇H₉NO)₂]
M_r	437.11
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	8.1498 (1), 8.76020 (11), 8.9201 (12)
α, β, γ (°)	100.841 (1), 110.588 (2), 115.359 (2)
V (Å³)	493.66 (7)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	1.02
Crystal size (mm)	0.28 × 0.20 × 0.15

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2003)
T_min, T_max	0.764, 0.863
No. of measured, independent and observed [I > 2σ(I)] reflections	2566, 1718, 1579
R_int	0.016
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.095, 1.00
No. of reflections	1718
No. of parameters	133
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.53, −0.22

Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Ni1—N2	2.065 (2)	Ni1—N1	2.095 (2)
Ni1—O1	2.0748 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N4ⁱ	0.82	1.89	2.711 (3)	175

Symmetry code: (i) −x, −y, −z.

References

Boskovic, C., Brechin, E. K. & Christou, G. (2002). J. Am. Chem. Soc. 124, 3725–3736. Web of Science CSD CrossRef PubMed CAS Google Scholar
Bruker (2003). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sanudo, E. C., Wernsdorfer, W. & Christou, G. (2003). Polyhedron, 22, 2267–2271. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar