Tetra­aqua­bis­(pyridine-κN)nickel(II) dinitrate

Wriedt, M.; Jess, I.; Näther, C.

doi:10.1107/S1600536810021653

metal-organic compounds

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Volume 66| Part 7| July 2010| Page m780

doi:10.1107/S1600536810021653

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Tetraaquabis(pyridine-κN)nickel(II) dinitrate

Mario Wriedt,^a ^* Inke Jess ^a and Christian Näther ^a

^aInstitut für Anorganische Chemie, Christian-Albrechts-Universität Kiel, Max-Eyth-Strasse 2, 24098 Kiel, Germany
^*Correspondence e-mail: mwriedt@ac.uni-kiel.de

(Received 25 May 2010; accepted 7 June 2010; online 16 June 2010)

In the title compound, [Ni(C₅H₅N)₂(H₂O)₄](NO₃)₂, the Ni^II ion is coordinated by two N-bonded pyridine ligands and four water molecules in an octahedral coordination mode. The asymmetric unit consists of one Ni^II ion located on an inversion center, as well as one pyridine ligand, one nitrate anion and two water molecules in general positions. In the crystal structure, the discrete complex cations and nitrate anions are connected by O—H⋯O and C—H⋯O hydrogen bonds.

Related literature

For general background to thermal decomposition reactions as an alternative tool for the discovery and preparation of new ligand-deficient coordination polymers with defined magnetic properties, see: Wriedt & Näther (2009a ,b ); Wriedt et al. (2009a ,b ). For a related structure, see: Halut-Desportes (1981 ).

Experimental

Crystal data

[Ni(C₅H₅N)₂(H₂O)₄](NO₃)₂
M_r = 412.99
Monoclinic, P 2₁ /n
a = 7.3245 (4) Å
b = 11.3179 (6) Å
c = 10.9347 (5) Å
β = 96.436 (4)°
V = 900.75 (8) Å³
Z = 2
Mo Kα radiation
μ = 1.13 mm⁻¹
T = 293 K
0.28 × 0.16 × 0.07 mm

Data collection

Stoe IPDS-2 diffractometer
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2002 ) T_min = 0.801, T_max = 0.927
12828 measured reflections
2427 independent reflections
2087 reflections with I > 2σ(I)
R_int = 0.040

Refinement

R[F² > 2σ(F²)] = 0.049
wR(F²) = 0.129
S = 1.15
2427 reflections
115 parameters
H-atom parameters constrained
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.47 e Å⁻³

Table 1
Selected bond lengths (Å)

Ni1—O4	2.113 (2)
Ni1—O5	2.128 (2)
Ni1—N1	2.140 (2)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H1O4⋯O2ⁱ	0.82	2.39	3.209 (4)	174
O4—H2O4⋯O1ⁱⁱ	0.82	2.26	3.077 (4)	179
O4—H3O4⋯O1	0.82	2.32	3.087 (3)	157
O5—H1O5⋯O3ⁱⁱⁱ	0.82	2.28	3.091 (4)	169
O5—H2O5⋯O1	0.82	2.43	3.191 (4)	155
C2—H2⋯O1^iv	0.93	2.50	3.310 (4)	145
C4—H4⋯O2^v	0.93	2.54	3.461 (4)	170
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (ii) -x+2, -y+1, -z+1; (iii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iv) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (v) $[-x+{\script{5\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-AREA; 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/S1600536810021653/hy2315sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810021653/hy2315Isup2.hkl

checkCIF report

Comment top

Recently, we have shown that thermal decomposition reactions are an elegant route for the discovery and preparation of new ligand-deficient coordination polymers with defined magnetic properties (Wriedt & Näther, 2009a,b; Wriedt et al., 2009a,b). In our ongoing investigation on the synthesis, structures and properties of such compounds based on paramagnetic transition metal pseudo-halides and N-donor ligands, we have reacted nickel(II) dinitrate hexahydrate, sodium dicyanamide and pyridine. In this reaction single crystals of the title compound were grown.

The title compound (Fig. 1) represents a discrete complex cation, in which the Ni^II atom, lying on an inversion center, is coordinated by two pyridine ligands and four water molecules in an octahedral coordination mode. The nitrate anions are not coordinated to the metal atoms (Fig. 2). The NiN₂O₄ octahedron is slightly distorted with Ni—N_pyridine distances of 2.140 (2) Å and Ni—O_water distances of 2.113 (2) and 2.128 (2) Å (Table 1). The angles arround the metal atoms range between 85.71 (10) to 94.29 (10) and 180°. A similar coordination is found in a related structure (Halut-Desportes, 1981). The opposite pyridyl rings are coplanar due to symmetry. The shortest intermolecular Ni···Ni distance amounts to 7.3245 (4) Å.

Related literature top

For general background to thermal decomposition reactions as an elegant route for the discovery and preparation of new ligand-deficient coordination polymers with defined magnetic properties, see: Wriedt & Näther (2009a,b); Wriedt et al. (2009a,b). For a related structure, see: Halut-Desportes (1981).

Experimental top

Ni(NO₃)₂.6H₂O (72.7 mg, 0.25 mmol), sodium dicyanamide (44.5 mg, 0.5 mmol) and pyridine (0.5 ml) obtained from Alfa Aesar were reacted in a closed test-tube at 120°C for 3 d. On cooling light green block-shaped single crystals of the title compound were grown in a mixture with unknown phases.

Computing details top

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA (Stoe & Cie, 2002); data reduction: X-AREA (Stoe & Cie, 2002); 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 compound with displacement ellipsoids drawn at the 30% probability level. Disordering of the H atoms is shown with full and open bonds. [Symmetry code: (i) -x+1, -y+1, -z+1.]
	Fig. 2. Packing arrangement of the title compound with view along the a axis.

Tetraaquabis(pyridine-κN)nickel(II) dinitrate top

Crystal data top

[Ni(C₅H₅N)₂(H₂O)₄](NO₃)₂	F(000) = 428
M_r = 412.99	D_x = 1.523 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 12828 reflections
a = 7.3245 (4) Å	θ = 2.6–29.2°
b = 11.3179 (6) Å	µ = 1.13 mm⁻¹
c = 10.9347 (5) Å	T = 293 K
β = 96.436 (4)°	Block, light green
V = 900.75 (8) Å³	0.28 × 0.16 × 0.07 mm
Z = 2

Data collection top

Stoe IPDS-2 diffractometer	2427 independent reflections
Radiation source: fine-focus sealed tube	2087 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.040
ω scans	θ_max = 29.2°, θ_min = 2.6°
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2002)	h = −10→9
T_min = 0.801, T_max = 0.927	k = −15→15
12828 measured reflections	l = −15→14

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.129	H-atom parameters constrained
S = 1.15	w = 1/[σ²(F_o²) + (0.0554P)² + 0.6589P] where P = (F_o² + 2F_c²)/3
2427 reflections	(Δ/σ)_max < 0.001
115 parameters	Δρ_max = 0.32 e Å⁻³
0 restraints	Δρ_min = −0.47 e Å⁻³

Crystal data top

[Ni(C₅H₅N)₂(H₂O)₄](NO₃)₂	V = 900.75 (8) Å³
M_r = 412.99	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.3245 (4) Å	µ = 1.13 mm⁻¹
b = 11.3179 (6) Å	T = 293 K
c = 10.9347 (5) Å	0.28 × 0.16 × 0.07 mm
β = 96.436 (4)°

Data collection top

Stoe IPDS-2 diffractometer	2427 independent reflections
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2002)	2087 reflections with I > 2σ(I)
T_min = 0.801, T_max = 0.927	R_int = 0.040
12828 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	0 restraints
wR(F²) = 0.129	H-atom parameters constrained
S = 1.15	Δρ_max = 0.32 e Å⁻³
2427 reflections	Δρ_min = −0.47 e Å⁻³
115 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Ni1	0.5000	0.5000	0.5000	0.03618 (15)
N1	0.6201 (3)	0.32862 (19)	0.4879 (2)	0.0421 (5)
C1	0.5276 (4)	0.2407 (3)	0.4281 (3)	0.0526 (7)
H1	0.4095	0.2555	0.3908	0.063*
C2	0.5994 (6)	0.1285 (3)	0.4191 (4)	0.0678 (9)
H2	0.5305	0.0693	0.3770	0.081*
C3	0.7731 (6)	0.1062 (3)	0.4729 (4)	0.0735 (10)
H3	0.8250	0.0317	0.4676	0.088*
C4	0.8695 (4)	0.1951 (3)	0.5348 (4)	0.0629 (8)
H4	0.9881	0.1819	0.5722	0.076*
C5	0.7896 (4)	0.3040 (3)	0.5412 (3)	0.0486 (6)
H5	0.8560	0.3636	0.5844	0.058*
N2	1.0498 (3)	0.6620 (2)	0.7423 (2)	0.0501 (5)
O1	1.0070 (3)	0.5655 (2)	0.6942 (2)	0.0635 (6)
O2	1.1995 (4)	0.6760 (3)	0.8009 (3)	0.0956 (10)
O3	0.9347 (5)	0.7424 (3)	0.7281 (3)	0.0905 (9)
O4	0.7425 (3)	0.5820 (2)	0.4544 (2)	0.0624 (6)
H1O4	0.7224	0.6435	0.4154	0.094*	0.667
H2O4	0.8088	0.5431	0.4141	0.094*	0.667
H3O4	0.8104	0.5993	0.5166	0.094*	0.667
O5	0.5815 (4)	0.5041 (2)	0.6930 (2)	0.0670 (6)
H1O5	0.5830	0.4380	0.7239	0.101*	0.667
H2O5	0.6849	0.5295	0.7147	0.101*	0.667
H3O5	0.5148	0.5457	0.7304	0.101*	0.667

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0330 (2)	0.0335 (2)	0.0415 (2)	−0.00085 (16)	0.00174 (15)	−0.00095 (18)
N1	0.0411 (10)	0.0356 (10)	0.0498 (11)	0.0028 (8)	0.0065 (9)	−0.0007 (9)
C1	0.0526 (15)	0.0430 (14)	0.0613 (17)	−0.0008 (12)	0.0017 (13)	−0.0071 (12)
C2	0.083 (2)	0.0423 (16)	0.079 (2)	−0.0013 (15)	0.0110 (18)	−0.0126 (15)
C3	0.080 (2)	0.0451 (17)	0.099 (3)	0.0188 (16)	0.025 (2)	0.0026 (18)
C4	0.0477 (16)	0.0579 (18)	0.085 (2)	0.0131 (14)	0.0137 (15)	0.0159 (17)
C5	0.0403 (13)	0.0465 (14)	0.0595 (16)	0.0008 (11)	0.0069 (11)	0.0062 (12)
N2	0.0541 (13)	0.0526 (14)	0.0443 (11)	−0.0080 (11)	0.0088 (10)	−0.0055 (10)
O1	0.0690 (14)	0.0510 (13)	0.0687 (14)	−0.0078 (10)	−0.0002 (11)	−0.0095 (11)
O2	0.0725 (18)	0.123 (3)	0.0858 (19)	−0.0316 (17)	−0.0137 (15)	−0.0169 (18)
O3	0.104 (2)	0.0689 (17)	0.102 (2)	0.0254 (16)	0.0278 (18)	−0.0123 (15)
O4	0.0518 (12)	0.0568 (13)	0.0788 (15)	−0.0035 (10)	0.0088 (10)	0.0059 (11)
O5	0.0763 (16)	0.0655 (15)	0.0575 (13)	−0.0031 (11)	0.0000 (11)	−0.0016 (11)

Geometric parameters (Å, º) top

Ni1—O4	2.113 (2)	C4—H4	0.9300
Ni1—O5	2.128 (2)	C5—H5	0.9300
Ni1—N1	2.140 (2)	N2—O2	1.216 (4)
N1—C1	1.333 (4)	N2—O1	1.238 (3)
N1—C5	1.340 (3)	N2—O3	1.238 (4)
C1—C2	1.381 (4)	O4—H1O4	0.8200
C1—H1	0.9300	O4—H2O4	0.8200
C2—C3	1.365 (5)	O4—H3O4	0.8200
C2—H2	0.9300	O5—H1O5	0.8200
C3—C4	1.364 (5)	O5—H2O5	0.8200
C3—H3	0.9300	O5—H3O5	0.8200
C4—C5	1.369 (4)

O4—Ni1—O4ⁱ	180.00 (11)	C4—C3—C2	118.9 (3)
O4—Ni1—O5ⁱ	85.71 (10)	C4—C3—H3	120.6
O4ⁱ—Ni1—O5ⁱ	94.29 (10)	C2—C3—H3	120.6
O4—Ni1—O5	94.29 (10)	C3—C4—C5	119.3 (3)
O4ⁱ—Ni1—O5	85.71 (10)	C3—C4—H4	120.4
O5ⁱ—Ni1—O5	180.000 (1)	C5—C4—H4	120.4
O4—Ni1—N1	91.23 (9)	N1—C5—C4	123.1 (3)
O4ⁱ—Ni1—N1	88.77 (9)	N1—C5—H5	118.5
O5ⁱ—Ni1—N1	89.46 (9)	C4—C5—H5	118.5
O5—Ni1—N1	90.54 (9)	O2—N2—O1	120.5 (3)
O4—Ni1—N1ⁱ	88.77 (9)	O2—N2—O3	122.1 (3)
O4ⁱ—Ni1—N1ⁱ	91.23 (9)	O1—N2—O3	117.3 (3)
O5ⁱ—Ni1—N1ⁱ	90.54 (9)	Ni1—O4—H1O4	112.9
O5—Ni1—N1ⁱ	89.46 (9)	Ni1—O4—H2O4	117.0
N1—Ni1—N1ⁱ	180.000 (1)	H1O4—O4—H2O4	105.0
C1—N1—C5	116.9 (2)	Ni1—O4—H3O4	110.9
C1—N1—Ni1	121.15 (19)	H1O4—O4—H3O4	106.6
C5—N1—Ni1	121.94 (19)	H2O4—O4—H3O4	103.5
N1—C1—C2	123.0 (3)	Ni1—O5—H1O5	112.2
N1—C1—H1	118.5	Ni1—O5—H2O5	116.2
C2—C1—H1	118.5	H1O5—O5—H2O5	103.3
C3—C2—C1	118.9 (3)	Ni1—O5—H3O5	113.0
C3—C2—H2	120.6	H1O5—O5—H3O5	107.4
C1—C2—H2	120.6	H2O5—O5—H3O5	103.7

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H1O4···O2ⁱⁱ	0.82	2.39	3.209 (4)	174
O4—H2O4···O1ⁱⁱⁱ	0.82	2.26	3.077 (4)	179
O4—H3O4···O1	0.82	2.32	3.087 (3)	157
O5—H1O5···O3^iv	0.82	2.28	3.091 (4)	169
O5—H2O5···O1	0.82	2.43	3.191 (4)	155
C2—H2···O1^v	0.93	2.50	3.310 (4)	145
C4—H4···O2^vi	0.93	2.54	3.461 (4)	170

Symmetry codes: (ii) x−1/2, −y+3/2, z−1/2; (iii) −x+2, −y+1, −z+1; (iv) −x+3/2, y−1/2, −z+3/2; (v) x−1/2, −y+1/2, z−1/2; (vi) −x+5/2, y−1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	[Ni(C₅H₅N)₂(H₂O)₄](NO₃)₂
M_r	412.99
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	7.3245 (4), 11.3179 (6), 10.9347 (5)
β (°)	96.436 (4)
V (Å³)	900.75 (8)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.13
Crystal size (mm)	0.28 × 0.16 × 0.07

Data collection
Diffractometer	Stoe IPDS2 diffractometer
Absorption correction	Numerical (X-SHAPE and X-RED32; Stoe & Cie, 2002)
T_min, T_max	0.801, 0.927
No. of measured, independent and observed [I > 2σ(I)] reflections	12828, 2427, 2087
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.687

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.129, 1.15
No. of reflections	2427
No. of parameters	115
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.47

Computer programs: X-AREA (Stoe & Cie, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Ni1—O4	2.113 (2)	Ni1—N1	2.140 (2)
Ni1—O5	2.128 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H1O4···O2ⁱ	0.82	2.39	3.209 (4)	174
O4—H2O4···O1ⁱⁱ	0.82	2.26	3.077 (4)	179
O4—H3O4···O1	0.82	2.32	3.087 (3)	157
O5—H1O5···O3ⁱⁱⁱ	0.82	2.28	3.091 (4)	169
O5—H2O5···O1	0.82	2.43	3.191 (4)	155
C2—H2···O1^iv	0.93	2.50	3.310 (4)	145
C4—H4···O2^v	0.93	2.54	3.461 (4)	170

Symmetry codes: (i) x−1/2, −y+3/2, z−1/2; (ii) −x+2, −y+1, −z+1; (iii) −x+3/2, y−1/2, −z+3/2; (iv) x−1/2, −y+1/2, z−1/2; (v) −x+5/2, y−1/2, −z+3/2.

Acknowledgements

MW thanks the Stiftung Stipendien-Fonds des Verbandes der Chemischen Industrie and the Studienstiftung des deutschen Volkes for a PhD scholarship. We gratefully acknowledge financial support by the State of Schleswig-Holstein and the Deutsche Forschungsgemeinschaft (Project 720/3-1). We thank Professor Dr Wolfgang Bensch for the opportunity to use his experimental facilities.

References

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