catena-Poly[[tetra­aqua­[trans-1,2-bis­(4-pyrid­yl)ethene-κ² N:N′]nickel(II)] dinitrate]

Abstract

In the title compound, {[Ni(C₁₂H₁₀N₂)(H₂O)₄](NO₃)₂}_n, the Ni^II ion, lying on a crystallographic inversion center, has a distorted octa­hedral coordination sphere comprising four water ligands and two N-atom donors from the trans-related 1,2-bis­(4-pyrid­yl)ethene ligands, which also have crystallographic inversion symmetry. These ligands bridge the Ni^II complex units, forming chains extending along the [110] and [10] directions. The nitrate counter-anions stabilize the crystal structure through water–nitrate O—H⋯O hydrogen bonds.

Related literature

For inter­actions of metal ions with amino acids, see: Daniele et al. (2008 ▶); Parkin (2004 ▶); Tshuva & Lippard (2004 ▶). For related complexes,see: Lee et al. (2008 ▶); Yu et al. (2008 ▶); Park et al. (2008 ▶); Shin et al. (2009 ▶); Yu et al. (2009 ▶, 2010 ▶); Kim et al. (2011 ▶).

Experimental

Crystal data

• [Ni(C₁₂H₁₀N₂)(H₂O)₄](NO₃)₂

• M _r = 436.99

• Monoclinic,

• a = 7.415 (3) Å

• b = 11.426 (4) Å

• c = 10.950 (4) Å

• β = 97.307 (7)°

• V = 920.1 (6) ų

• Z = 2

• Mo Kα radiation

• μ = 1.11 mm⁻¹

• T = 293 K

• 0.15 × 0.08 × 0.08 mm

Data collection

• Bruker SMART CCD area-detector diffractometer

• 4954 measured reflections

• 1799 independent reflections

• 1116 reflections with I > 2σ(I)

• R _int = 0.173

Refinement

• R[F ² > 2σ(F ²)] = 0.068

• wR(F ²) = 0.238

• S = 1.14

• 1799 reflections

• 136 parameters

• 4 restraints

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 1.08 e Å⁻³

• Δρ_min = −1.86 e Å⁻³

Data collection: SMART (Bruker, 1997 ▶); cell refinement: SAINT (Bruker, 1997 ▶); 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. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2B⋯O3i	0.93 (7)	2.28 (8)	3.176 (9)	162 (8)
O2—H2A⋯O5ii	0.93 (6)	2.14 (7)	3.068 (8)	176 (7)
O1—H1B⋯O3iii	0.93 (4)	2.29 (2)	3.212 (9)	170 (8)
O1—H1A⋯O4iv	0.93 (6)	2.37 (3)	3.252 (8)	158 (7)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .

supplementary crystallographic information

Comment

The interaction of transition metal ions with biologically active molecules such as amino acids and various acids is very important in biological systems (Daniele et al., 2008; Parkin, 2004; Tshuva & Lippard, 2004). In attempting to model the interaction, we have extensively studied the interaction of the transition metal carboxylates e.g. copper(II), cadmium(II), and zinc(II) benzoates with a variety of spacers such as quinoxaline, 6-methylquinoline, 3-methylquinoline, trans-1-(2-pyridyl)-2-(4-pyridyl)ethylene, and di-2-pyridyl ketone (Lee et al., 2008; Yu et al., 2008; Park et al., 2008; Shin et al., 2009; Yu et al., 2009; Yu et al., 2010; Kim et al., 2011). However, nickel as a metal ion source has rarely been used. In this work, we have employed nickel(II) trimethylacetate as a building block and trans-1,2-bis(4-pyridyl)ethene as a ligand. We report here on the structure of a new complex poly[tetraqua[trans-1,2-bis(4-pyridyl)ethene]nickel(II) dinitrate].

In the crystal structure of the title compound, [Ni(C₁₂H₁₀N₂)(H₂O)₄] . 2(NO₃)]_n, the Ni^II ion lies on a crystallographic inversion center with the distorted octahedral coordination sphere comprising four water ligands and two N donors from the trans-related 1,2-bis(4-pyridyl)ethene ligands, which also have crystallographic inversion symmetry (Fig. 1). These ligands bridge the Ni^II complex units to form a one-dimensional chain structure. The nitrate counter-anions stabilize the crystal structure through water O—H···O_nitrate hydrogen bonds (Table 1).

Experimental

36.4 mg (0.125 mmol) of Ni(NO₃)₂^.6H₂O and 29.0 mg (0.25 mmol) of (CH₃)₃CCOOH and 29.5 mg (0. 25 mmol) of NH₄OH were dissolved in 4 ml of methanol and carefully layered with 4 ml of a chloroform solution of trans-1,2-bis(4-pyridyl)ethene (47.0 mg, 0.25 mmol). Crystals of the title compound suitable for X-ray analysis were obtained within a month.

Refinement

H atoms were placed in calculated positions with C—H distances of 0.93 Å (pyridyl) and included in the refinement with a riding-motion approximation with U_iso(H) = 1.2U_eq(C). The water H atoms were located in a difference Fourier, and refined isotropically with O—H restraints (0.93 Å).

Figures

Fig. 1.

A fragment of one-dimensional chain structure of the title compound showing the atom numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Inter-species hydrogen bonds are shown as dashed lines. For symmetry codes: (i) (-x + 1, -y + 1, -z); (ii) -x, -y + 2, -z). For other codes, see Table 1.

Crystal data

[Ni(C12H10N2)(H2O)4](NO3)2	F(000) = 452
Mr = 436.99	Dx = 1.577 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1268 reflections
a = 7.415 (3) Å	θ = 2.6–23.4°
b = 11.426 (4) Å	µ = 1.11 mm−1
c = 10.950 (4) Å	T = 293 K
β = 97.307 (7)°	Block, brown
V = 920.1 (6) Å3	0.15 × 0.08 × 0.08 mm
Z = 2

Data collection

Bruker SMART CCD area-detector diffractometer	1116 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.173
graphite	θmax = 26.0°, θmin = 2.6°
φ and ω scans	h = −8→9
4954 measured reflections	k = −11→14
1799 independent reflections	l = −11→13

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)] = 0.068	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.238	H atoms treated by a mixture of independent and constrained refinement
S = 1.14	w = 1/[σ2(Fo2) + (0.1257P)2] where P = (Fo2 + 2Fc2)/3
1799 reflections	(Δ/σ)max < 0.001
136 parameters	Δρmax = 1.08 e Å−3
4 restraints	Δρmin = −1.86 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.0496 (8)	0.7389 (5)	−0.0578 (7)	0.0346 (15)
H1	−0.0705	0.7450	−0.0939	0.042*
C2	0.1365 (8)	0.6328 (5)	−0.0637 (7)	0.0414 (18)
H2	0.0758	0.5697	−0.1038	0.050*
C3	0.3181 (8)	0.6207 (5)	−0.0086 (7)	0.0364 (16)
C4	0.3954 (8)	0.7169 (5)	0.0524 (7)	0.0374 (16)
H4	0.5137	0.7129	0.0923	0.045*
C5	0.2991 (7)	0.8183 (5)	0.0544 (7)	0.0350 (16)
H5	0.3542	0.8814	0.0981	0.042*
C6	0.4117 (9)	0.5087 (5)	−0.0174 (8)	0.0431 (19)
H6	0.3429	0.4452	−0.0495	0.052*
N1	0.1284 (6)	0.8326 (4)	−0.0032 (5)	0.0271 (11)
Ni1	0.0000	1.0000	0.0000	0.0287 (4)
O1	0.0809 (9)	1.0135 (4)	0.1951 (7)	0.0630 (17)
H1A	0.098 (12)	0.946 (4)	0.242 (7)	0.076*
H1B	0.200 (4)	1.036 (7)	0.189 (9)	0.076*
O2	0.2381 (6)	1.0811 (4)	−0.0466 (7)	0.0666 (18)
H2A	0.226 (11)	1.148 (5)	−0.095 (7)	0.080*
H2B	0.306 (10)	1.024 (6)	−0.080 (9)	0.080*
N2	0.4686 (7)	0.8286 (5)	0.7660 (6)	0.0481 (16)
O3	0.4935 (7)	0.9318 (4)	0.8009 (6)	0.0684 (17)
O4	0.5938 (8)	0.7571 (5)	0.7875 (7)	0.0699 (18)
O5	0.3209 (7)	0.7990 (5)	0.7106 (7)	0.083 (2)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
C1	0.031 (3)	0.026 (3)	0.046 (4)	0.005 (2)	0.000 (3)	−0.002 (3)
C2	0.030 (3)	0.023 (3)	0.069 (5)	0.003 (2)	−0.005 (3)	−0.010 (3)
C3	0.030 (3)	0.018 (3)	0.060 (5)	0.009 (2)	−0.001 (3)	0.004 (3)
C4	0.028 (3)	0.018 (3)	0.064 (5)	0.004 (2)	−0.005 (3)	0.000 (3)
C5	0.024 (3)	0.020 (3)	0.060 (5)	0.001 (2)	0.001 (3)	−0.001 (3)
C6	0.037 (3)	0.014 (3)	0.076 (6)	0.009 (2)	0.000 (3)	−0.003 (3)
N1	0.027 (2)	0.022 (2)	0.033 (3)	0.0061 (19)	0.005 (2)	−0.001 (2)
Ni1	0.0214 (6)	0.0136 (6)	0.0485 (8)	0.0038 (4)	−0.0049 (5)	−0.0014 (4)
O1	0.066 (4)	0.051 (3)	0.066 (4)	0.000 (3)	−0.013 (3)	0.000 (3)
O2	0.044 (3)	0.035 (3)	0.121 (6)	0.003 (2)	0.010 (3)	0.012 (3)
N2	0.040 (3)	0.036 (3)	0.064 (5)	−0.003 (2)	−0.012 (3)	−0.010 (3)
O3	0.064 (3)	0.035 (3)	0.098 (5)	−0.008 (2)	−0.018 (3)	−0.016 (3)
O4	0.059 (3)	0.059 (3)	0.091 (5)	0.017 (3)	0.006 (3)	−0.008 (3)
O5	0.055 (3)	0.074 (4)	0.110 (6)	−0.017 (3)	−0.030 (4)	−0.016 (4)

Geometric parameters (Å, °)

C1—N1	1.326 (7)	N1—Ni1	2.138 (4)
C1—C2	1.378 (8)	Ni1—O2	2.113 (5)
C1—H1	0.9300	Ni1—O2ii	2.113 (5)
C2—C3	1.411 (8)	Ni1—N1ii	2.138 (4)
C2—H2	0.9300	Ni1—O1ii	2.149 (7)
C3—C4	1.373 (8)	Ni1—O1	2.149 (7)
C3—C6	1.465 (8)	O1—H1A	0.93 (6)
C4—C5	1.362 (7)	O1—H1B	0.93 (4)
C4—H4	0.9300	O2—H2A	0.93 (6)
C5—N1	1.350 (7)	O2—H2B	0.93 (7)
C5—H5	0.9300	N2—O5	1.231 (6)
C6—C6i	1.331 (13)	N2—O4	1.236 (7)
C6—H6	0.9300	N2—O3	1.245 (7)
N1—C1—C2	123.4 (5)	O2ii—Ni1—N1ii	90.05 (18)
N1—C1—H1	118.3	O2—Ni1—N1	90.05 (18)
C2—C1—H1	118.3	O2ii—Ni1—N1	89.95 (18)
C1—C2—C3	119.5 (5)	N1ii—Ni1—N1	180.0
C1—C2—H2	120.3	O2—Ni1—O1ii	85.9 (3)
C3—C2—H2	120.3	O2ii—Ni1—O1ii	94.1 (3)
C4—C3—C2	116.5 (5)	N1ii—Ni1—O1ii	90.7 (2)
C4—C3—C6	124.0 (5)	N1—Ni1—O1ii	89.3 (2)
C2—C3—C6	119.5 (5)	O2—Ni1—O1	94.1 (3)
C5—C4—C3	120.1 (5)	O2ii—Ni1—O1	85.9 (3)
C5—C4—H4	119.9	N1ii—Ni1—O1	89.3 (2)
C3—C4—H4	119.9	N1—Ni1—O1	90.7 (2)
N1—C5—C4	123.9 (6)	O1ii—Ni1—O1	179.999 (2)
N1—C5—H5	118.1	Ni1—O1—H1A	119 (6)
C4—C5—H5	118.1	Ni1—O1—H1B	96 (6)
C6i—C6—C3	124.7 (7)	H1A—O1—H1B	102 (8)
C6i—C6—H6	117.7	Ni1—O2—H2A	118 (5)
C3—C6—H6	117.7	Ni1—O2—H2B	108 (5)
C1—N1—C5	116.5 (5)	H2A—O2—H2B	112 (9)
C1—N1—Ni1	123.9 (4)	O5—N2—O4	120.8 (6)
C5—N1—Ni1	119.6 (4)	O5—N2—O3	120.0 (6)
O2—Ni1—O2ii	180.0	O4—N2—O3	119.3 (5)
O2—Ni1—N1ii	89.95 (18)
N1—C1—C2—C3	0.7 (12)	C4—C5—N1—C1	4.3 (10)
C1—C2—C3—C4	2.2 (11)	C4—C5—N1—Ni1	−176.6 (6)
C1—C2—C3—C6	−178.6 (7)	C1—N1—Ni1—O2	−134.3 (5)
C2—C3—C4—C5	−1.8 (11)	C5—N1—Ni1—O2	46.7 (5)
C6—C3—C4—C5	179.1 (7)	C1—N1—Ni1—O2ii	45.7 (5)
C3—C4—C5—N1	−1.5 (11)	C5—N1—Ni1—O2ii	−133.3 (5)
C4—C3—C6—C6i	−9.6 (17)	C1—N1—Ni1—O1ii	−48.4 (5)
C2—C3—C6—C6i	171.3 (11)	C5—N1—Ni1—O1ii	132.5 (5)
C2—C1—N1—C5	−3.8 (10)	C1—N1—Ni1—O1	131.6 (5)
C2—C1—N1—Ni1	177.1 (6)	C5—N1—Ni1—O1	−47.5 (5)

Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x, −y+2, −z.

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2B···O3iii	0.93 (7)	2.28 (8)	3.176 (9)	162 (8)
O2—H2A···O5iv	0.93 (6)	2.14 (7)	3.068 (8)	176 (7)
O1—H1B···O3v	0.93 (4)	2.29 (2)	3.212 (9)	170 (8)
O1—H1A···O4vi	0.93 (6)	2.37 (3)	3.252 (8)	158 (7)

Symmetry codes: (iii) x, y, z−1; (iv) −x+1/2, y+1/2, −z+1/2; (v) −x+1, −y+2, −z+1; (vi) x−1/2, −y+3/2, z−1/2.