Bis(acetato-κ2O,O′)bis­(2-amino­pyridine-κN)nickel(II)

Wang, Q.; Wang, D.-Q.

doi:10.1107/S1600536807066226

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 1| January 2008| Page m194

https://doi.org/10.1107/S1600536807066226

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Bis(acetato-κ²O,O′)bis(2-aminopyridine-κN)nickel(II)

Qiang Wang ^a and Da-Qi Wang ^a ^*

^aCollege of Chemistry and Chemical Engineering, Liaocheng University, Shandong 252059, People's Republic of China
^*Correspondence e-mail: wdq4899@163.com

(Received 13 November 2007; accepted 8 December 2007; online 18 December 2007)

The title complex, [Ni(C₂H₃O₂)₂(C₅H₆N₂)₂], has a distorted octahedral geometry around the Ni atom. Intermolecular and intramolecular N—H⋯O hydrogen bonds exist in the crystal structure.

Related literature

For general background, see: Roman et al. (1995 ).

Experimental

Crystal data

[Ni(C₂H₃O₂)₂(C₅H₆N₂)₂]
M_r = 365.01
Orthorhombic, P b c a
a = 14.281 (4) Å
b = 14.989 (5) Å
c = 15.241 (5) Å
V = 3262.5 (18) Å³
Z = 8
Mo Kα radiation
μ = 1.21 mm⁻¹
T = 298 (2) K
0.48 × 0.36 × 0.30 mm

Data collection

Siemens SMART CCD area–detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.593, T_max = 0.712
15953 measured reflections
2875 independent reflections
2173 reflections with I > 2σ(I)
R_int = 0.039

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.093
S = 0.95
2875 reflections
202 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2B⋯O2ⁱ	0.86	2.13	2.988 (3)	179
N2—H2A⋯O1	0.86	2.20	2.967 (3)	149
N4—H4A⋯O4	0.86	2.03	2.848 (4)	158
Symmetry code: (i) $[x+{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Siemens, 1996 ); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536807066226/rk2064sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807066226/rk2064Isup2.hkl

checkCIF report

Comment top

A lot of work has been devoted to the study of mixed–ligand complexes because of their key role in biological progress and their properties in areas such as analytical chemistry, catalysis and magnetochemistry (Roman et al., 1995). In this paper, we report the synthesis and crystal structure of the new title nickel complex.

The molecular structure of the title complex, (I), is shown on Fig.1. The Ni atom is in a distorted octahedral geometry [Ni—N = 2.069 (2)–2.079 (2) Å, Ni—O = 2.092 (2)–2.164 (2) Å], coordinated by two N atoms from two 2–aminopyridine ligands and four O atoms from two acetate groups. The intermolecular and intramolecular N—H···O hydrogen bonds are exist in the crystal structure.

Related literature top

For general background, see: Roman et al. (1995).

Experimental top

Nickel acetate tetrahydrate (2 mmol, 497.7 mg) in absolute ethanol (20 ml) was added dropwise to a absolute ethanol solution (20 ml) of 2–aminopyridine (4 mmol, 376.5 mg). The mixture was heated under reflux with stirring for 4 h. The solution was kept at room temperature for 20 days, after which large green block–shaped crystals of the title complex suitable for X–ray diffraction analysis were obtained.

Structure description top

For general background, see: Roman et al. (1995).

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL (Sheldrick, 1997b).

Figures top

Fig. 1. The molecular structure of the title complex with the atom numbering scheme. Displacement ellipsoids are shown at 30% probability level. H atoms are presented as a spheres of arbitrary radius.

Bis(acetato-κ²O,O')bis(2-aminopyridine-κN)nickel(II) top

Crystal data top

[Ni(C₂H₃O₂)₂(C₅H₆N₂)₂]	F(000) = 1520
M_r = 365.01	D_x = 1.486 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 4718 reflections
a = 14.281 (4) Å	θ = 2.4–27.7°
b = 14.989 (5) Å	µ = 1.21 mm⁻¹
c = 15.241 (5) Å	T = 298 K
V = 3262.5 (18) Å³	Block, green
Z = 8	0.48 × 0.36 × 0.30 mm

Data collection top

Siemens SMART CCD area–detector diffractometer	2875 independent reflections
Radiation source: fine–focus sealed tube	2173 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.039
φ– and ω–scans	θ_max = 25.0°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −16→16
T_min = 0.593, T_max = 0.712	k = −17→17
15953 measured reflections	l = −14→18

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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.093	H-atom parameters constrained
S = 0.95	w = 1/[σ²(F_o²) + (0.039P)² + 4.6901P] where P = (F_o² + 2F_c²)/3
2875 reflections	(Δ/σ)_max = 0.001
202 parameters	Δρ_max = 0.38 e Å⁻³
1 restraint	Δρ_min = −0.25 e Å⁻³

Crystal data top

[Ni(C₂H₃O₂)₂(C₅H₆N₂)₂]	V = 3262.5 (18) Å³
M_r = 365.01	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 14.281 (4) Å	µ = 1.21 mm⁻¹
b = 14.989 (5) Å	T = 298 K
c = 15.241 (5) Å	0.48 × 0.36 × 0.30 mm

Data collection top

Siemens SMART CCD area–detector diffractometer	2875 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2173 reflections with I > 2σ(I)
T_min = 0.593, T_max = 0.712	R_int = 0.039
15953 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	1 restraint
wR(F²) = 0.093	H-atom parameters constrained
S = 0.95	Δρ_max = 0.38 e Å⁻³
2875 reflections	Δρ_min = −0.25 e Å⁻³
202 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	0.65501 (2)	0.18431 (2)	0.30692 (2)	0.03492 (14)
N1	0.74523 (16)	0.17626 (15)	0.41287 (15)	0.0353 (6)
N2	0.88178 (18)	0.17679 (18)	0.33118 (18)	0.0475 (7)
H2A	0.8485	0.1789	0.2842	0.057*
H2B	0.9419	0.1759	0.3277	0.057*
N3	0.58868 (17)	0.06682 (16)	0.34427 (17)	0.0405 (6)
N4	0.44625 (19)	0.1315 (2)	0.3738 (2)	0.0654 (9)
H4A	0.4703	0.1828	0.3626	0.079*
H4B	0.3884	0.1274	0.3889	0.079*
O1	0.73266 (14)	0.12566 (15)	0.20530 (14)	0.0469 (5)
O2	0.59071 (15)	0.17241 (14)	0.17892 (14)	0.0470 (5)
O3	0.68659 (16)	0.32137 (14)	0.28166 (15)	0.0484 (6)
O4	0.56826 (15)	0.28132 (14)	0.36282 (15)	0.0472 (5)
C1	0.6643 (2)	0.1341 (2)	0.1533 (2)	0.0470 (5)
C2	0.6716 (3)	0.0967 (3)	0.0625 (3)	0.0723 (12)
H2C	0.6547	0.0348	0.0632	0.108*
H2D	0.7348	0.1029	0.0418	0.108*
H2E	0.6301	0.1286	0.0241	0.108*
C3	0.6159 (2)	0.3419 (2)	0.3261 (2)	0.0445 (8)
C4	0.5880 (3)	0.4383 (2)	0.3375 (3)	0.0667 (11)
H4C	0.6084	0.4591	0.3939	0.100*
H4D	0.5212	0.4435	0.3334	0.100*
H4E	0.6167	0.4736	0.2924	0.100*
C5	0.83976 (19)	0.17483 (18)	0.4102 (2)	0.0364 (7)
C6	0.8921 (2)	0.1720 (2)	0.4878 (2)	0.0500 (8)
H6	0.9572	0.1724	0.4854	0.060*
C7	0.8480 (3)	0.1687 (2)	0.5667 (2)	0.0541 (9)
H7	0.8826	0.1663	0.6184	0.065*
C8	0.7511 (3)	0.1690 (2)	0.5695 (2)	0.0526 (9)
H8	0.7193	0.1665	0.6227	0.063*
C9	0.7040 (2)	0.1731 (2)	0.4926 (2)	0.0458 (8)
H9	0.6389	0.1738	0.4947	0.055*
C10	0.4988 (2)	0.0580 (2)	0.3679 (2)	0.0416 (7)
C11	0.4604 (3)	−0.0261 (2)	0.3863 (3)	0.0609 (10)
H11	0.3981	−0.0312	0.4033	0.073*
C12	0.5143 (3)	−0.0994 (3)	0.3793 (3)	0.0698 (11)
H12	0.4891	−0.1553	0.3910	0.084*
C13	0.6068 (3)	−0.0916 (3)	0.3546 (3)	0.0719 (12)
H13	0.6451	−0.1415	0.3497	0.086*
C14	0.6401 (2)	−0.0087 (2)	0.3377 (3)	0.0608 (10)
H14	0.7023	−0.0034	0.3206	0.073*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0245 (2)	0.0418 (2)	0.0384 (2)	−0.00038 (16)	0.00112 (16)	−0.00062 (17)
N1	0.0281 (12)	0.0422 (14)	0.0355 (13)	−0.0029 (10)	0.0029 (10)	−0.0001 (11)
N2	0.0247 (13)	0.0668 (19)	0.0508 (17)	−0.0029 (12)	0.0040 (12)	−0.0038 (14)
N3	0.0295 (13)	0.0412 (14)	0.0508 (15)	−0.0025 (11)	0.0000 (12)	0.0003 (12)
N4	0.0373 (16)	0.0581 (18)	0.101 (3)	0.0006 (14)	0.0157 (17)	0.0063 (18)
O1	0.0317 (11)	0.0616 (14)	0.0475 (13)	0.0035 (10)	−0.0040 (10)	−0.0073 (11)
O2	0.0348 (10)	0.0558 (11)	0.0503 (11)	0.0000 (8)	−0.0056 (8)	−0.0050 (9)
O3	0.0461 (13)	0.0532 (13)	0.0457 (13)	−0.0089 (11)	0.0034 (11)	0.0038 (10)
O4	0.0402 (12)	0.0437 (12)	0.0577 (14)	0.0018 (10)	0.0092 (11)	0.0022 (11)
C1	0.0348 (10)	0.0558 (11)	0.0503 (11)	0.0000 (8)	−0.0056 (8)	−0.0050 (9)
C2	0.078 (3)	0.086 (3)	0.053 (2)	0.013 (2)	−0.012 (2)	−0.023 (2)
C3	0.0465 (19)	0.0452 (18)	0.0419 (18)	0.0012 (15)	−0.0081 (16)	0.0012 (15)
C4	0.091 (3)	0.0416 (19)	0.067 (2)	0.008 (2)	−0.005 (2)	0.0021 (18)
C5	0.0308 (15)	0.0315 (15)	0.0468 (18)	−0.0041 (12)	0.0014 (14)	−0.0025 (13)
C6	0.0346 (18)	0.056 (2)	0.059 (2)	−0.0048 (15)	−0.0110 (16)	−0.0002 (17)
C7	0.059 (2)	0.056 (2)	0.047 (2)	−0.0094 (17)	−0.0172 (18)	0.0030 (16)
C8	0.061 (2)	0.059 (2)	0.0378 (18)	−0.0087 (17)	0.0031 (17)	0.0000 (16)
C9	0.0367 (17)	0.059 (2)	0.0412 (18)	−0.0040 (15)	0.0053 (15)	−0.0003 (15)
C10	0.0330 (16)	0.0505 (18)	0.0414 (17)	−0.0034 (14)	0.0036 (14)	−0.0015 (15)
C11	0.045 (2)	0.063 (2)	0.075 (3)	−0.0148 (18)	0.0148 (19)	0.003 (2)
C12	0.076 (3)	0.048 (2)	0.085 (3)	−0.014 (2)	0.014 (2)	0.005 (2)
C13	0.071 (3)	0.044 (2)	0.101 (3)	0.0033 (19)	0.013 (2)	0.008 (2)
C14	0.043 (2)	0.048 (2)	0.092 (3)	0.0030 (16)	0.0131 (19)	0.011 (2)

Geometric parameters (Å, º) top

Ni1—N1	2.069 (2)	C2—H2D	0.9600
Ni1—N3	2.079 (2)	C2—H2E	0.9600
Ni1—O4	2.092 (2)	C3—C4	1.509 (5)
Ni1—O1	2.098 (2)	C4—H4C	0.9600
Ni1—O3	2.138 (2)	C4—H4D	0.9600
Ni1—O2	2.164 (2)	C4—H4E	0.9600
N1—C9	1.351 (4)	C5—C6	1.400 (4)
N1—C5	1.351 (4)	C6—C7	1.358 (5)
N2—C5	1.346 (4)	C6—H6	0.9300
N2—H2A	0.8600	C7—C8	1.384 (5)
N2—H2B	0.8600	C7—H7	0.9300
N3—C10	1.339 (4)	C8—C9	1.354 (5)
N3—C14	1.353 (4)	C8—H8	0.9300
N4—C10	1.336 (4)	C9—H9	0.9300
N4—H4A	0.8600	C10—C11	1.403 (5)
N4—H4B	0.8600	C11—C12	1.345 (5)
O1—C1	1.264 (4)	C11—H11	0.9300
O2—C1	1.259 (4)	C12—C13	1.379 (6)
O3—C3	1.254 (4)	C12—H12	0.9300
O4—C3	1.264 (4)	C13—C14	1.354 (5)
C1—C2	1.497 (5)	C13—H13	0.9300
C2—H2C	0.9600	C14—H14	0.9300

N1—Ni1—N3	91.18 (10)	O3—C3—O4	119.7 (3)
N1—Ni1—O4	95.25 (9)	O3—C3—C4	120.6 (3)
N3—Ni1—O4	101.98 (9)	O4—C3—C4	119.7 (3)
N1—Ni1—O1	102.86 (9)	C3—C4—H4C	109.5
N3—Ni1—O1	95.05 (10)	C3—C4—H4D	109.5
O4—Ni1—O1	154.83 (9)	H4C—C4—H4D	109.5
N1—Ni1—O3	93.74 (9)	C3—C4—H4E	109.5
N3—Ni1—O3	163.58 (9)	H4C—C4—H4E	109.5
O4—Ni1—O3	61.99 (9)	H4D—C4—H4E	109.5
O1—Ni1—O3	99.10 (9)	N2—C5—N1	118.2 (3)
N1—Ni1—O2	164.38 (9)	N2—C5—C6	121.3 (3)
N3—Ni1—O2	89.06 (9)	N1—C5—C6	120.6 (3)
O4—Ni1—O2	99.98 (9)	C7—C6—C5	120.1 (3)
O1—Ni1—O2	61.58 (8)	C7—C6—H6	119.9
O3—Ni1—O2	90.37 (8)	C5—C6—H6	119.9
C9—N1—C5	117.5 (3)	C6—C7—C8	119.4 (3)
C9—N1—Ni1	115.6 (2)	C6—C7—H7	120.3
C5—N1—Ni1	126.8 (2)	C8—C7—H7	120.3
C5—N2—H2A	120.0	C9—C8—C7	118.1 (3)
C5—N2—H2B	120.0	C9—C8—H8	121.0
H2A—N2—H2B	120.0	C7—C8—H8	121.0
C10—N3—C14	117.2 (3)	N1—C9—C8	124.3 (3)
C10—N3—Ni1	126.4 (2)	N1—C9—H9	117.8
C14—N3—Ni1	116.2 (2)	C8—C9—H9	117.8
C10—N4—H4A	120.0	N4—C10—N3	118.4 (3)
C10—N4—H4B	120.0	N4—C10—C11	120.5 (3)
H4A—N4—H4B	120.0	N3—C10—C11	121.1 (3)
C1—O1—Ni1	90.71 (19)	C12—C11—C10	119.6 (3)
C1—O2—Ni1	87.88 (19)	C12—C11—H11	120.2
C3—O3—Ni1	88.18 (19)	C10—C11—H11	120.2
C3—O4—Ni1	90.01 (19)	C11—C12—C13	120.0 (4)
O2—C1—O1	119.7 (3)	C11—C12—H12	120.0
O2—C1—C2	121.1 (3)	C13—C12—H12	120.0
O1—C1—C2	119.2 (3)	C14—C13—C12	117.8 (4)
C1—C2—H2C	109.5	C14—C13—H13	121.1
C1—C2—H2D	109.5	C12—C13—H13	121.1
H2C—C2—H2D	109.5	C13—C14—N3	124.3 (3)
C1—C2—H2E	109.5	C13—C14—H14	117.9
H2C—C2—H2E	109.5	N3—C14—H14	117.9
H2D—C2—H2E	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···O2ⁱ	0.86	2.13	2.988 (3)	179
N2—H2A···O1	0.86	2.20	2.967 (3)	149
N4—H4A···O4	0.86	2.03	2.848 (4)	158

Symmetry code: (i) x+1/2, y, −z+1/2.

Experimental details

Crystal data
Chemical formula	[Ni(C₂H₃O₂)₂(C₅H₆N₂)₂]
M_r	365.01
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	298
a, b, c (Å)	14.281 (4), 14.989 (5), 15.241 (5)
V (Å³)	3262.5 (18)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	1.21
Crystal size (mm)	0.48 × 0.36 × 0.30

Data collection
Diffractometer	Siemens SMART CCD area–detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.593, 0.712
No. of measured, independent and observed [I > 2σ(I)] reflections	15953, 2875, 2173
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.093, 0.95
No. of reflections	2875
No. of parameters	202
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.25

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···O2ⁱ	0.86	2.13	2.988 (3)	179.0
N2—H2A···O1	0.86	2.20	2.967 (3)	149.2
N4—H4A···O4	0.86	2.03	2.848 (4)	157.5

Symmetry code: (i) x+1/2, y, −z+1/2.

Acknowledgements

The authors acknowledge the financial support of the Shandong Province Science Foundation and the State Key Laboratory of Crystalline Materials, Shandong University, People's Republic of China.

References

Roman, P., Luque, A., Guzman-Miralles, C. & Beitia, J. I. (1995). Polyhedron, 14, 2863–2869. CSD CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (1997a). SHELXL97 and SHELXS97. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (1997b). SHELXTL. Version 5.1. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Siemens (1996). SMART and SAINT. Siemens Analytical X–ray Instruments Inc., Madison, Wisconsin, USA. Google Scholar