trans-Diacetonitrile­tetra­kis(1H-pyrazole-κN2)nickel(II) dinitrate

Chen, C.-H.; Hsieh, C.-C.; Lee, H.M.; Horng, Y.-C.

doi:10.1107/S1600536809049472

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 12| December 2009| Page m1680

doi:10.1107/S1600536809049472

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trans-Diacetonitriletetrakis(1H-pyrazole-κN²)nickel(II) dinitrate

Chien-Hong Chen,^a,^b Chang-Chih Hsieh,^c Hon Man Lee ^c and Yih-Chern Horng ^c ^*

^aSchool of Applied Chemistry, Chung Shan Medical University, Taichung City 40201, Taiwan, ^bDepartment of Medical Research, Chung Shan Medical University Hospital, Taichung City, Taiwan, and ^cDepartment of Chemistry, National Changhua University of Education, Changhua 50058, Taiwan
^*Correspondence e-mail: ychorng@cc.ncue.edu.tw

(Received 2 November 2009; accepted 19 November 2009; online 25 November 2009)

In the title complex, [Ni(CH₃CN)₂(C₃H₄N₂)₄](NO₃)₂, the cation lies on an inversion center and adopts an octahedral coordination geometry about the Ni atom. The two acetonitrile ligands are in a trans conformation. N—H⋯O hydrogen bonds between cations and anions link the complex molecules into one-dimensional chains running parallel to [100].

Related literature

For general background and the structures of other salts of this cation, see: Hsieh et al. (2009 ).

Experimental

Crystal data

[Ni(C₂H₃N)₂(C₃H₄N₂)₄](NO₃)₂
M_r = 537.17
Monoclinic, P 2₁ /c
a = 9.9815 (5) Å
b = 15.2831 (8) Å
c = 7.6845 (4) Å
β = 98.817 (2)°
V = 1158.40 (10) Å³
Z = 2
Mo Kα radiation
μ = 0.90 mm⁻¹
T = 150 K
0.32 × 0.23 × 0.15 mm

Data collection

Bruker APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.762, T_max = 0.877
13134 measured reflections
2992 independent reflections
2247 reflections with I > 2σ
R_int = 0.038

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.149
S = 1.09
2992 reflections
161 parameters
3 restraints
H-atom parameters constrained
Δρ_max = 1.13 e Å⁻³
Δρ_min = −0.49 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H8⋯O1ⁱ	0.88	1.94	2.797 (4)	164
N2—H4⋯O3	0.88	1.95	2.782 (3)	158
Symmetry code: (i) -x, -y+1, -z+2.

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXSL97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL; software used to prepare material for publication: DIAMOND (Brandenburg, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809049472/pv2232sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809049472/pv2232Isup2.hkl

checkCIF report

Comment top

In the title complex (Fig. 1), the Ni atom lies on an inversion center and adopts an octahedral coordination geometry. The two acetonitrile ligands are in a trans conformation. The classocal intermolecular hydrogen bonds of the type N—H···O between cations and anions link the complex into one-dimensional chains (Table 1). For general background and the structures of other salts of this cation, see: Hsieh et al. (2009).

Related literature top

For general background and the structures of other salts of this cation, see: Hsieh et al. (2009).

Experimental top

A solution of Ni(NO₃)₂. 6H₂O (0.29 g, 0.97 mmol) and pyrazole (0.30 g, 4.30 mmol) in MeCN (25 ml) was stirred at room temperature for 10 min. After the resultant bluesolution was filtered and concentrated to 5 ml under vacuum, the concentrated filtrate was layered with diethyl ether (5-fold portion) and then kept at room temperature for 3 days. The air-stable blue crystals of the title compound (0.39 g, 74%) obtained were suitable for X-ray crystallographic analysis.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: DIAMOND (Brandenburg, 1999).

Figures top

	Fig. 1. The structure of the title complex, showing 50% displacement ellipsoids; the H atoms are dipicted by circles of an arbitrary radius. Unlabeled atoms of the complex are related to labeled atoms by the symmetry operation: 1 - x, 1 - y, 2 - z.
	Fig. 2. A packing diagram of the title compound along the [001] direction showing the intermolecular hydrogen bonded network (dashed lines).

trans-Diacetonitriletetrakis(1H-pyrazole-κN</i<>²)nickel(II) dinitrate top

Crystal data top

[Ni(C₂H₃N)₂(C₃H₄N₂)₄](NO₃)₂	F(000) = 556
M_r = 537.17	D_x = 1.540 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3410 reflections
a = 9.9815 (5) Å	θ = 2.7–25.6°
b = 15.2831 (8) Å	µ = 0.90 mm⁻¹
c = 7.6845 (4) Å	T = 150 K
β = 98.817 (2)°	Block, blue
V = 1158.40 (10) Å³	0.32 × 0.23 × 0.15 mm
Z = 2

Data collection top

Bruker SMART APEXII diffractometer	2992 independent reflections
Radiation source: fine-focus sealed tube	2247 reflections with I > 2σ
Graphite monochromator	R_int = 0.038
ω scans	θ_max = 28.7°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −13→13
T_min = 0.762, T_max = 0.877	k = −17→20
13134 measured reflections	l = −10→10

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.149	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0852P)² + 0.4971P] where P = (F_o² + 2F_c²)/3
2992 reflections	(Δ/σ)_max < 0.001
161 parameters	Δρ_max = 1.13 e Å⁻³
3 restraints	Δρ_min = −0.49 e Å⁻³

Crystal data top

[Ni(C₂H₃N)₂(C₃H₄N₂)₄](NO₃)₂	V = 1158.40 (10) Å³
M_r = 537.17	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.9815 (5) Å	µ = 0.90 mm⁻¹
b = 15.2831 (8) Å	T = 150 K
c = 7.6845 (4) Å	0.32 × 0.23 × 0.15 mm
β = 98.817 (2)°

Data collection top

Bruker SMART APEXII diffractometer	2992 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2247 reflections with I > 2σ
T_min = 0.762, T_max = 0.877	R_int = 0.038
13134 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	3 restraints
wR(F²) = 0.149	H-atom parameters constrained
S = 1.09	Δρ_max = 1.13 e Å⁻³
2992 reflections	Δρ_min = −0.49 e Å⁻³
161 parameters

Special details top

Experimental. IR (KBr, n_max/cm^-1): 3120w (NH), 2283m (C≡ N), 2210m (C≡ N). Elem. Anal. Calcd (%) for C₁₆H₂₂N₁₂NiO₆: C 35.78; H 4.13; N 31.29. Found: C 35.32; H 4.01; N 31.03.

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
C1	0.5375 (3)	0.65817 (19)	0.7527 (4)	0.0381 (6)
H1	0.6327	0.6507	0.7595	0.046*
C2	0.4624 (3)	0.7228 (2)	0.6544 (4)	0.0459 (7)
H2	0.4948	0.7667	0.5837	0.055*
C3	0.3328 (3)	0.70974 (19)	0.6813 (4)	0.0418 (7)
H3	0.2559	0.7429	0.6316	0.050*
C4	0.3550 (4)	0.4130 (3)	0.6557 (5)	0.0562 (8)
H5	0.4194	0.4355	0.5882	0.067*
C5	0.2476 (4)	0.3580 (3)	0.5885 (5)	0.0596 (9)
H6	0.2260	0.3373	0.4710	0.072*
C6	0.1824 (3)	0.3406 (2)	0.7211 (5)	0.0540 (8)
H7	0.1043	0.3048	0.7182	0.065*
C7	0.7342 (3)	0.44589 (18)	0.7733 (4)	0.0370 (6)
C8	0.8414 (3)	0.4248 (2)	0.6709 (5)	0.0521 (8)
H9	0.8102	0.4377	0.5464	0.078*
H10	0.8641	0.3626	0.6846	0.078*
H11	0.9219	0.4600	0.7130	0.078*
N1	0.4583 (2)	0.60812 (14)	0.8361 (3)	0.0300 (5)
N2	0.3329 (2)	0.64146 (14)	0.7908 (3)	0.0344 (5)
H4	0.2601	0.6210	0.8284	0.041*
N3	0.3559 (2)	0.43008 (14)	0.8258 (3)	0.0321 (5)
N4	0.2488 (3)	0.38387 (18)	0.8626 (4)	0.0492 (6)
H8	0.2243	0.3820	0.9678	0.059*
N5	0.6507 (2)	0.46282 (15)	0.8523 (3)	0.0326 (5)
N6	0.0036 (2)	0.62767 (19)	0.8693 (4)	0.0478 (6)
Ni1	0.5000	0.5000	1.0000	0.02738 (16)
O1	−0.1214 (2)	0.61818 (17)	0.8375 (3)	0.0568 (6)
O2	0.0532 (3)	0.6921 (2)	0.9519 (5)	0.0830 (9)
O3	0.0787 (2)	0.57249 (18)	0.8160 (5)	0.0825 (10)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0336 (13)	0.0342 (14)	0.0469 (16)	−0.0011 (11)	0.0078 (11)	0.0069 (12)
C2	0.0505 (17)	0.0364 (16)	0.0508 (18)	−0.0010 (13)	0.0080 (14)	0.0127 (13)
C3	0.0444 (15)	0.0296 (14)	0.0482 (16)	0.0067 (12)	−0.0025 (12)	0.0060 (12)
C4	0.0565 (19)	0.065 (2)	0.0475 (15)	−0.0069 (17)	0.0077 (14)	−0.0042 (16)
C5	0.063 (2)	0.059 (2)	0.054 (2)	0.0008 (18)	0.0007 (17)	−0.0118 (17)
C6	0.0427 (17)	0.0406 (18)	0.078 (2)	−0.0024 (13)	0.0063 (16)	−0.0045 (16)
C7	0.0355 (13)	0.0302 (14)	0.0446 (15)	−0.0020 (11)	0.0038 (11)	−0.0021 (11)
C8	0.0481 (17)	0.0486 (19)	0.063 (2)	0.0019 (14)	0.0212 (16)	−0.0106 (16)
N1	0.0263 (10)	0.0244 (10)	0.0388 (12)	0.0008 (8)	0.0031 (8)	0.0021 (9)
N2	0.0280 (10)	0.0261 (11)	0.0472 (13)	0.0001 (8)	−0.0005 (9)	0.0031 (9)
N3	0.0334 (11)	0.0241 (11)	0.0384 (11)	0.0016 (8)	0.0040 (9)	0.0006 (9)
N4	0.0395 (13)	0.0452 (15)	0.0627 (16)	−0.0042 (11)	0.0069 (11)	−0.0050 (13)
N5	0.0299 (10)	0.0270 (11)	0.0414 (12)	0.0005 (9)	0.0072 (9)	−0.0003 (10)
N6	0.0319 (12)	0.0479 (15)	0.0629 (17)	−0.0029 (11)	0.0052 (11)	0.0070 (13)
Ni1	0.0254 (2)	0.0217 (2)	0.0352 (3)	0.00207 (16)	0.00500 (17)	0.00278 (18)
O1	0.0320 (10)	0.0643 (15)	0.0750 (16)	−0.0002 (10)	0.0110 (10)	0.0051 (13)
O2	0.0547 (16)	0.080 (2)	0.104 (2)	0.0142 (15)	−0.0210 (16)	−0.0326 (18)
O3	0.0345 (12)	0.0513 (16)	0.163 (3)	−0.0029 (11)	0.0188 (16)	−0.0222 (17)

Geometric parameters (Å, º) top

C1—N1	1.333 (3)	C8—H9	0.9800
C1—C2	1.391 (4)	C8—H10	0.9800
C1—H1	0.9500	C8—H11	0.9800
C2—C3	1.355 (4)	N1—N2	1.346 (3)
C2—H2	0.9500	N1—Ni1	2.081 (2)
C3—N2	1.340 (4)	N2—H4	0.8800
C3—H3	0.9500	N3—N4	1.347 (3)
C4—N3	1.332 (4)	N3—Ni1	2.100 (2)
C4—C5	1.398 (5)	N4—H8	0.8800
C4—H5	0.9500	N5—Ni1	2.097 (2)
C5—C6	1.318 (5)	N6—O2	1.234 (4)
C5—H6	0.9500	N6—O3	1.238 (4)
C6—N4	1.355 (5)	N6—O1	1.243 (3)
C6—H7	0.9500	Ni1—N1ⁱ	2.081 (2)
C7—N5	1.134 (3)	Ni1—N5ⁱ	2.097 (2)
C7—C8	1.458 (4)	Ni1—N3ⁱ	2.100 (2)

N1—C1—C2	111.0 (2)	C3—N2—N1	111.6 (2)
N1—C1—H1	124.5	C3—N2—H4	124.2
C2—C1—H1	124.5	N1—N2—H4	124.2
C3—C2—C1	105.1 (3)	C4—N3—N4	102.5 (3)
C3—C2—H2	127.5	C4—N3—Ni1	128.8 (2)
C1—C2—H2	127.5	N4—N3—Ni1	128.40 (19)
N2—C3—C2	107.6 (2)	N3—N4—C6	113.2 (3)
N2—C3—H3	126.2	N3—N4—H8	123.4
C2—C3—H3	126.2	C6—N4—H8	123.4
N3—C4—C5	111.7 (3)	C7—N5—Ni1	177.3 (2)
N3—C4—H5	124.1	O2—N6—O3	119.9 (3)
C5—C4—H5	124.1	O2—N6—O1	120.4 (3)
C6—C5—C4	106.1 (3)	O3—N6—O1	119.7 (3)
C6—C5—H6	126.9	N1—Ni1—N1ⁱ	180.000 (1)
C4—C5—H6	126.9	N1—Ni1—N5	88.92 (9)
C5—C6—N4	106.4 (3)	N1ⁱ—Ni1—N5	91.08 (9)
C5—C6—H7	126.8	N1—Ni1—N5ⁱ	91.08 (9)
N4—C6—H7	126.8	N1ⁱ—Ni1—N5ⁱ	88.92 (9)
N5—C7—C8	179.5 (3)	N5—Ni1—N5ⁱ	180.00 (12)
C7—C8—H9	109.5	N1—Ni1—N3ⁱ	92.05 (8)
C7—C8—H10	109.5	N1ⁱ—Ni1—N3ⁱ	87.95 (8)
H9—C8—H10	109.5	N5—Ni1—N3ⁱ	90.28 (9)
C7—C8—H11	109.5	N5ⁱ—Ni1—N3ⁱ	89.72 (8)
H9—C8—H11	109.5	N1—Ni1—N3	87.95 (8)
H10—C8—H11	109.5	N1ⁱ—Ni1—N3	92.05 (8)
C1—N1—N2	104.8 (2)	N5—Ni1—N3	89.72 (8)
C1—N1—Ni1	131.92 (18)	N5ⁱ—Ni1—N3	90.28 (9)
N2—N1—Ni1	123.30 (16)	N3ⁱ—Ni1—N3	180.0

N1—C1—C2—C3	−0.2 (4)	N2—N1—Ni1—N5	145.4 (2)
C1—C2—C3—N2	0.5 (4)	C1—N1—Ni1—N5ⁱ	146.4 (3)
N3—C4—C5—C6	−0.5 (5)	N2—N1—Ni1—N5ⁱ	−34.6 (2)
C4—C5—C6—N4	0.0 (4)	C1—N1—Ni1—N3ⁱ	56.7 (3)
C2—C1—N1—N2	−0.2 (3)	N2—N1—Ni1—N3ⁱ	−124.3 (2)
C2—C1—N1—Ni1	178.9 (2)	C1—N1—Ni1—N3	−123.3 (3)
C2—C3—N2—N1	−0.7 (3)	N2—N1—Ni1—N3	55.7 (2)
C1—N1—N2—C3	0.5 (3)	C4—N3—Ni1—N1	60.2 (3)
Ni1—N1—N2—C3	−178.69 (18)	N4—N3—Ni1—N1	−127.2 (2)
C5—C4—N3—N4	0.7 (4)	C4—N3—Ni1—N1ⁱ	−119.8 (3)
C5—C4—N3—Ni1	174.8 (2)	N4—N3—Ni1—N1ⁱ	52.8 (2)
C4—N3—N4—C6	−0.7 (3)	C4—N3—Ni1—N5	−28.7 (3)
Ni1—N3—N4—C6	−174.8 (2)	N4—N3—Ni1—N5	143.9 (2)
C5—C6—N4—N3	0.5 (4)	C4—N3—Ni1—N5ⁱ	151.3 (3)
C1—N1—Ni1—N5	−33.6 (3)	N4—N3—Ni1—N5ⁱ	−36.1 (2)

Symmetry code: (i) −x+1, −y+1, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H8···O1ⁱⁱ	0.88	1.94	2.797 (4)	164
N2—H4···O3	0.88	1.95	2.782 (3)	158

Symmetry code: (ii) −x, −y+1, −z+2.

Experimental details

Crystal data
Chemical formula	[Ni(C₂H₃N)₂(C₃H₄N₂)₄](NO₃)₂
M_r	537.17
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	150
a, b, c (Å)	9.9815 (5), 15.2831 (8), 7.6845 (4)
β (°)	98.817 (2)
V (Å³)	1158.40 (10)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.90
Crystal size (mm)	0.32 × 0.23 × 0.15

Data collection
Diffractometer	Bruker SMART APEXII diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.762, 0.877
No. of measured, independent and observed (I > 2σ) reflections	13134, 2992, 2247
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.675

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.149, 1.09
No. of reflections	2992
No. of parameters	161
No. of restraints	3
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.13, −0.49

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), DIAMOND (Brandenburg, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H8···O1ⁱ	0.88	1.94	2.797 (4)	164.3
N2—H4···O3	0.88	1.95	2.782 (3)	158.3

Symmetry code: (i) −x, −y+1, −z+2.

Acknowledgements

We are grateful to the National Science Council of Taiwan for financial support.

References

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Hsieh, C.-C., Lee, C.-J. & Horng, Y.-C. (2009). Organometallics, 28, 4923–4928. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
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