Bis[2-(pyridin-2-yl)ethanol-κ² N,O]bis­(thio­cyanato-κN)nickel(II)

Abstract

In the title complex, [Ni(NCS)₂(C₇H₉NO)₂], the Ni^II atom is in a distorted octa­hedral coordination environment defined by two N atoms of the two thio­cyanate ions and by the N and O atoms of the two chelating 2-(pyridin-2-yl)ethanol ligands. The complex mol­ecule is located around a crystallographic inversion center. In the crystal, mol­ecules are connected into a two-dimensional polymeric structure parallel to (100) by O—H⋯S hydrogen bonds.

Related literature

For related structures, see: Pan et al. (2007 ▶); Yu et al. (2010 ▶).

Experimental

Crystal data

• [Ni(NCS)₂(C₇H₉NO)₂]

• M _r = 421.17

• Monoclinic,

• a = 8.7197 (9) Å

• b = 13.8634 (15) Å

• c = 7.8655 (7) Å

• β = 105.496 (2)°

• V = 916.26 (16) ų

• Z = 2

• Mo Kα radiation

• μ = 1.30 mm⁻¹

• T = 298 K

• 0.42 × 0.41 × 0.40 mm

Data collection

• Bruker SMART 1000 CCD diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.611, T _max = 0.624

• 4493 measured reflections

• 1616 independent reflections

• 1408 reflections with I > 2σ(I)

• R _int = 0.020

Refinement

• R[F ² > 2σ(F ²)] = 0.027

• wR(F ²) = 0.076

• S = 1.07

• 1616 reflections

• 115 parameters

• 5 restraints

• H-atom parameters constrained

• Δρ_max = 0.41 e Å⁻³

• Δρ_min = −0.55 e Å⁻³

Data collection: SMART (Siemens, 1996 ▶); cell refinement: SAINT (Siemens, 1996 ▶); 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.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Selected bond lengths (Å).

Ni1—N2	2.052 (2)
Ni1—N1	2.1011 (19)
Ni1—O1	2.1030 (15)

Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯S1i	0.93	2.66	3.2183 (19)	119

Symmetry code: (i) .

supplementary crystallographic information

Comment

Molecular materials with porous coordination frameworks have recently drawn considerable interest because of their attractive properties. The importance of the work in this area is the construction of porous materials from metal ions and organic ligands as building blocks. As a flexible ligand, 2-(hydroxyethyl)pyridine (hepH) can adopt a variety of possible binding modes. As a contribution to this field, we report here the synthesis and structure of the title compound.

In the title complex molecule, [Ni(SCN)₂(C₇H₉NO)₂], the nickel(II) atom displays a distorted octahedral coordination geometry, provided by two N atoms of two thiocyanate ions and by the N and O atoms of two 2-(hydroxyethyl)pyridine ligands. Bond lengths and angles involving the metal centre are typical and comparable with those observed in related Co^(II) complexes (Pan et al., 2007; Yu et al., 2010). In the crystal structure, molecules are linked through intermolecular O—H···S hydrogen bonds (Table 1).

Experimental

To a stirred methanol (10 ml) and acetonitrile (10 ml) solution of NiCl₂.6H₂O (1 mmol, 238 mg) was added 2-(pyridyn-2-yl)ethanol (2 mmol, 246 mg) in 5 ml me thanol and tetramethylammonium hydroxide(0.4 mmol, 165 mg, 25% solution in water). After 30 min to the above solution was added KSCN (2 mmol, 194 mg) and the solution was stirred for additional 6 h. The resulting red solution was filtered and was allowed to stand at room temperature for about one week, whereupon blue block crystal, suitable for X-ray diffraction analysis, was obtained.

Refinement

All H atoms were placed in geometrically idealized positions (O–H= 0.93, C—H = 0.93-0.97 Å) and treated as riding on their parent atoms, with U_iso(H) = 1.2U_eq(C). A rigid bond restraints were applied to the Uij values of Ni1, N2, S1 and C8 atoms via DELU instruction of SHELXL97 (Sheldrick, 2008).

Figures

Fig. 1.

The molecular structure of the title compound, with atom labels and 30% probability displacement ellipsoids. Atoms labelled with the suffix A are generated by the symmetry operation -x + 2,-y,-z.

Crystal data

[Ni(NCS)2(C7H9NO)2]	F(000) = 436
Mr = 421.17	Dx = 1.527 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2904 reflections
a = 8.7197 (9) Å	θ = 2.4–28.0°
b = 13.8634 (15) Å	µ = 1.30 mm−1
c = 7.8655 (7) Å	T = 298 K
β = 105.496 (2)°	Block, blue
V = 916.26 (16) Å3	0.42 × 0.41 × 0.40 mm
Z = 2

Data collection

Bruker SMART 1000 CCD diffractometer	1616 independent reflections
Radiation source: fine-focus sealed tube	1408 reflections with I > 2σ(I)
graphite	Rint = 0.020
phi and ω scans	θmax = 25.0°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→8
Tmin = 0.611, Tmax = 0.624	k = −16→15
4493 measured reflections	l = −7→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)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.076	H-atom parameters constrained
S = 1.07	w = 1/[σ2(Fo2) + (0.0356P)2 + 0.5792P] where P = (Fo2 + 2Fc2)/3
1616 reflections	(Δ/σ)max = 0.001
115 parameters	Δρmax = 0.41 e Å−3
5 restraints	Δρmin = −0.55 e Å−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Ni1	1.0000	0.5000	0.0000	0.03039 (15)
S1	1.22010 (9)	0.69823 (5)	0.50929 (9)	0.0528 (2)
N1	0.7906 (2)	0.54485 (14)	0.0607 (2)	0.0341 (4)
N2	1.1214 (2)	0.57961 (15)	0.2136 (3)	0.0409 (5)
O1	0.9851 (2)	0.62603 (12)	−0.1523 (2)	0.0415 (4)
H1	1.0793	0.6489	−0.1717	0.050*
C1	0.8438 (3)	0.6798 (2)	−0.2289 (4)	0.0498 (7)
H1A	0.8409	0.6968	−0.3493	0.060*
H1B	0.8448	0.7391	−0.1630	0.060*
C2	0.6971 (3)	0.62185 (19)	−0.2278 (3)	0.0452 (6)
H2A	0.6039	0.6570	−0.2936	0.054*
H2B	0.7005	0.5613	−0.2886	0.054*
C3	0.6788 (3)	0.60033 (17)	−0.0472 (3)	0.0373 (5)
C4	0.5510 (3)	0.6363 (2)	0.0063 (4)	0.0484 (6)
H4	0.4762	0.6754	−0.0692	0.058*
C5	0.5344 (3)	0.6142 (2)	0.1710 (4)	0.0535 (7)
H5	0.4484	0.6374	0.2077	0.064*
C6	0.6478 (3)	0.5570 (2)	0.2799 (4)	0.0499 (7)
H6	0.6397	0.5409	0.3920	0.060*
C7	0.7733 (3)	0.52394 (19)	0.2214 (3)	0.0415 (6)
H7	0.8496	0.4854	0.2963	0.050*
C8	1.1618 (3)	0.62905 (16)	0.3352 (3)	0.0320 (5)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Ni1	0.0355 (2)	0.0261 (2)	0.0306 (2)	0.00073 (16)	0.01065 (17)	−0.00126 (16)
S1	0.0696 (5)	0.0394 (4)	0.0428 (4)	−0.0032 (3)	0.0034 (3)	−0.0099 (3)
N1	0.0367 (10)	0.0311 (10)	0.0352 (10)	0.0005 (8)	0.0107 (8)	−0.0025 (8)
N2	0.0445 (11)	0.0363 (11)	0.0409 (10)	−0.0004 (9)	0.0100 (9)	−0.0065 (8)
O1	0.0447 (9)	0.0338 (9)	0.0486 (10)	0.0025 (7)	0.0170 (8)	0.0102 (7)
C1	0.0591 (17)	0.0436 (15)	0.0482 (15)	0.0122 (12)	0.0168 (13)	0.0162 (12)
C2	0.0467 (15)	0.0452 (15)	0.0402 (13)	0.0105 (12)	0.0057 (11)	0.0042 (11)
C3	0.0365 (12)	0.0326 (12)	0.0409 (13)	−0.0014 (10)	0.0070 (10)	−0.0048 (10)
C4	0.0398 (13)	0.0425 (15)	0.0630 (17)	0.0045 (12)	0.0137 (12)	−0.0034 (12)
C5	0.0480 (15)	0.0498 (16)	0.0713 (19)	−0.0007 (13)	0.0310 (14)	−0.0105 (14)
C6	0.0558 (16)	0.0530 (16)	0.0485 (15)	−0.0084 (13)	0.0271 (13)	−0.0068 (13)
C7	0.0453 (14)	0.0429 (14)	0.0393 (13)	−0.0025 (11)	0.0163 (11)	0.0006 (11)
C8	0.0324 (12)	0.0273 (11)	0.0361 (11)	0.0002 (9)	0.0087 (9)	0.0011 (7)

Geometric parameters (Å, °)

Ni1—N2	2.052 (2)	C2—C3	1.501 (3)
Ni1—N1	2.1011 (19)	C2—H2A	0.9700
Ni1—O1	2.1030 (15)	C2—H2B	0.9700
S1—C8	1.637 (2)	C3—C4	1.386 (4)
N1—C7	1.344 (3)	C4—C5	1.375 (4)
N1—C3	1.349 (3)	C4—H4	0.9300
N2—C8	1.153 (3)	C5—C6	1.374 (4)
O1—C1	1.428 (3)	C5—H5	0.9300
O1—H1	0.9300	C6—C7	1.375 (4)
C1—C2	1.513 (4)	C6—H6	0.9300
C1—H1A	0.9700	C7—H7	0.9300
C1—H1B	0.9700
N2i—Ni1—N2	180.00 (9)	O1—C1—H1B	109.5
N2i—Ni1—N1i	86.82 (8)	C2—C1—H1B	109.5
N2—Ni1—N1i	93.18 (8)	H1A—C1—H1B	108.1
N2i—Ni1—N1	93.18 (8)	C3—C2—C1	114.5 (2)
N2—Ni1—N1	86.82 (8)	C3—C2—H2A	108.6
N1i—Ni1—N1	180.0	C1—C2—H2A	108.6
N2i—Ni1—O1	92.32 (7)	C3—C2—H2B	108.6
N2—Ni1—O1	87.68 (7)	C1—C2—H2B	108.6
N1i—Ni1—O1	92.38 (7)	H2A—C2—H2B	107.6
N1—Ni1—O1	87.62 (7)	N1—C3—C4	121.2 (2)
N2i—Ni1—O1i	87.68 (7)	N1—C3—C2	117.8 (2)
N2—Ni1—O1i	92.32 (7)	C4—C3—C2	120.9 (2)
N1i—Ni1—O1i	87.62 (7)	C5—C4—C3	120.1 (3)
N1—Ni1—O1i	92.38 (7)	C5—C4—H4	119.9
O1—Ni1—O1i	180.00 (5)	C3—C4—H4	119.9
C7—N1—C3	118.1 (2)	C6—C5—C4	118.5 (3)
C7—N1—Ni1	118.18 (16)	C6—C5—H5	120.8
C3—N1—Ni1	123.47 (16)	C4—C5—H5	120.8
C8—N2—Ni1	167.28 (19)	C5—C6—C7	119.2 (3)
C1—O1—Ni1	126.06 (15)	C5—C6—H6	120.4
C1—O1—H1	117.0	C7—C6—H6	120.4
Ni1—O1—H1	117.0	N1—C7—C6	122.8 (3)
O1—C1—C2	110.9 (2)	N1—C7—H7	118.6
O1—C1—H1A	109.5	C6—C7—H7	118.6
C2—C1—H1A	109.5	N2—C8—S1	179.3 (2)
N2i—Ni1—N1—C7	121.90 (18)	N1—Ni1—O1—C1	−23.9 (2)
N2—Ni1—N1—C7	−58.10 (18)	O1—C1—C2—C3	65.5 (3)
O1—Ni1—N1—C7	−145.91 (18)	C7—N1—C3—C4	1.0 (3)
O1i—Ni1—N1—C7	34.09 (18)	Ni1—N1—C3—C4	−173.23 (18)
N2i—Ni1—N1—C3	−63.84 (19)	C7—N1—C3—C2	−178.9 (2)
N2—Ni1—N1—C3	116.16 (19)	Ni1—N1—C3—C2	6.9 (3)
O1—Ni1—N1—C3	28.35 (18)	C1—C2—C3—N1	−63.6 (3)
O1i—Ni1—N1—C3	−151.65 (18)	C1—C2—C3—C4	116.5 (3)
N1i—Ni1—N2—C8	176.2 (9)	N1—C3—C4—C5	−1.2 (4)
N1—Ni1—N2—C8	−3.8 (9)	C2—C3—C4—C5	178.7 (2)
O1—Ni1—N2—C8	84.0 (9)	C3—C4—C5—C6	0.7 (4)
O1i—Ni1—N2—C8	−96.0 (9)	C4—C5—C6—C7	0.0 (4)
N2i—Ni1—O1—C1	69.2 (2)	C3—N1—C7—C6	−0.4 (4)
N2—Ni1—O1—C1	−110.8 (2)	Ni1—N1—C7—C6	174.2 (2)
N1i—Ni1—O1—C1	156.1 (2)	C5—C6—C7—N1	−0.1 (4)

Symmetry codes: (i) −x+2, −y+1, −z.

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···S1ii	0.93	2.66	3.2183 (19)	119

Symmetry codes: (ii) x, −y+3/2, z−1/2.