catena-Poly[[bis­(pyridine-κN)nickel(II)]-μ-oxalato-κ4O1,O2:O1′,O2′]

Xuan, Z.-Y.; Che, Y.; Huang, Y.-C.

doi:10.1107/S1600536808021703

metal-organic compounds

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Volume 64| Part 8| August 2008| Page m1040

doi:10.1107/S1600536808021703

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catena-Poly[[bis(pyridine-κN)nickel(II)]-μ-oxalato-κ⁴O¹,O²:O^1′,O^2′]

Zhen-Yu Xuan,^a ^* Yong Che ^a and Yong-Chun Huang ^a

^aDepartment of Laboratory and Equipment Management, Yanbian University, Yanbian 133002, People's Republic of China
^*Correspondence e-mail: [email protected]

(Received 6 July 2008; accepted 12 July 2008; online 19 July 2008)

The title compound, [Ni(C₂O₄)(C₅H₅N)₂]_n, was synthesized under hydro(solvo)thermal conditions. The Ni^II atom, lying on a twofold rotation axis, has an octahedral coordination geometry involving two N atoms from two pyridine ligands and four O atoms from two oxalate ligands. The Ni atoms are connected by the tetradentate bridging oxalate ligands into a one-dimensional zigzag chain.

Related literature

For related literature, see: Lu et al. (1999 ); Vaidhyanathan et al. (2002 ); Wang et al. (2007 ); Yao et al. (2007 ).

Experimental

Crystal data

[Ni(C₂O₄)(C₅H₅N)₂]
M_r = 304.93
Monoclinic, C 2/c
a = 14.357 (3) Å
b = 10.801 (2) Å
c = 8.6669 (17) Å
β = 91.52 (3)°
V = 1343.5 (5) Å³
Z = 4
Mo Kα radiation
μ = 1.45 mm⁻¹
T = 293 (2) K
0.26 × 0.24 × 0.22 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.640, T_max = 0.726
6433 measured reflections
1519 independent reflections
1297 reflections with I > 2σ(I)
R_int = 0.041

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.103
S = 1.04
1519 reflections
87 parameters
H-atom parameters constrained
Δρ_max = 0.73 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Ni1—O2ⁱ	2.046 (2)
Ni1—O1	2.0716 (18)
Ni1—N1	2.081 (2)

O2ⁱ—Ni1—O2ⁱⁱ	168.78 (10)
O2ⁱ—Ni1—O1	89.88 (7)
O2ⁱⁱ—Ni1—O1	81.96 (7)
O1—Ni1—O1ⁱⁱⁱ	86.81 (11)
O2ⁱ—Ni1—N1	94.02 (8)
O2ⁱⁱ—Ni1—N1	93.66 (9)
O1—Ni1—N1	89.92 (9)
O1ⁱⁱⁱ—Ni1—N1	174.81 (8)
N1—Ni1—N1ⁱⁱⁱ	93.61 (13)
Symmetry codes: (i) $[x, -y+1, z+{\script{1\over 2}}]$ ; (ii) -x+1, -y+1, -z; (iii) $[-x+1, y, -z+{\script{1\over 2}}]$ .

Data collection: PROCESS-AUTO (Rigaku, 1998 ); cell refinement: PROCESS-AUTO; data reduction: PROCESS-AUTO; 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 global, I. DOI: 10.1107/S1600536808021703/hy2144sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808021703/hy2144Isup2.hkl

checkCIF report

Comment top

Much research work has been done on metal–oxalate compounds, in the context of studies of molecular-based magnets and open framework structures (Lu et al., 1999; Yao et al., 2007). The geometrical coordination mode and strength of this ligand provide both rigidity and preferred coordination specificity for metal centers (Vaidhyanathan et al., 2002; Wang et al., 2007). In this paper, we report the hydro(solvo)thermal synthesis and structure of a new one-dimensional nickelous oxalate coordination polymer.

The title compound consists of one Ni^II atom lying on a twofold rotation axis, an oxalate ligand and two coordinated pyridine molecules (Fig. 1). The Ni^II atom exhibits a distorted octahedral geometry, defined by four O atoms of two oxalate ligands and two pyridine N atoms in a cis arrangement. The Ni—O distances are 2.046 (2) and 2.0716 (18) Å, while the O—Ni—O angles show distortions particularly as a result of chelation (Table 1). The tetradentate oxalate ligands link adjacent Ni atoms into a one-dimensional zigzag chain.

Related literature top

For related literature, see: Lu et al. (1999); Vaidhyanathan et al. (2002); Wang et al. (2007); Yao et al. (2007).

Experimental top

A mixture of K₂C₂O₄.H₂O (0.037 g, 0.2 mmol), H₃BO₃ (0.013 g, 0.2 mmol), NiCl₂.2H₂O (0.033 g, 0.2 mmol), KOH (0.012 g, 0.2 mmol), pyridine (4 ml) and water (8 ml) in a 25 ml Teflon-lined stainless steel reactor was heated from 298 to 393 K in 2 h and maintained at 393 K for 72 h. After the mixture was cooled to 298 K, blue crystals of the title compound were obtained.

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: PROCESS-AUTO (Rigaku, 1998); 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. Part of the polymeric structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry codes: (i) x, 1-y, 1/2+z; (ii) 1-x, 1-y, -z; (iii) 1-x, y, 1/2-z.]

catena-Poly[[bis(pyridine-κN)nickel(II)]- µ-oxalato-κ⁴O¹,O²:O^1',O^2'] top

Crystal data top

[Ni(C₂O₄)(C₅H₅N)₂]	F(000) = 624
M_r = 304.93	D_x = 1.508 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1532 reflections
a = 14.357 (3) Å	θ = 3.3–27.5°
b = 10.801 (2) Å	µ = 1.45 mm⁻¹
c = 8.6669 (17) Å	T = 293 K
β = 91.52 (3)°	Block, blue
V = 1343.5 (5) Å³	0.26 × 0.24 × 0.22 mm
Z = 4

Data collection top

Rigaku R-AXIS RAPID diffractometer	1519 independent reflections
Radiation source: rotating anode	1297 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.041
Detector resolution: 10.0 pixels mm^-1	θ_max = 27.5°, θ_min = 3.3°
ω scans	h = −18→18
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −13→13
T_min = 0.640, T_max = 0.726	l = −11→10
6433 measured reflections

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.103	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0487P)² + 1.5041P] where P = (F_o² + 2F_c²)/3
1519 reflections	(Δ/σ)_max < 0.001
87 parameters	Δρ_max = 0.73 e Å⁻³
0 restraints	Δρ_min = −0.30 e Å⁻³

Crystal data top

[Ni(C₂O₄)(C₅H₅N)₂]	V = 1343.5 (5) Å³
M_r = 304.93	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 14.357 (3) Å	µ = 1.45 mm⁻¹
b = 10.801 (2) Å	T = 293 K
c = 8.6669 (17) Å	0.26 × 0.24 × 0.22 mm
β = 91.52 (3)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	1519 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1297 reflections with I > 2σ(I)
T_min = 0.640, T_max = 0.726	R_int = 0.041
6433 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.103	H-atom parameters constrained
S = 1.04	Δρ_max = 0.73 e Å⁻³
1519 reflections	Δρ_min = −0.30 e Å⁻³
87 parameters

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

	x	y	z	U_iso*/U_eq
Ni1	0.5000	0.35667 (4)	0.2500	0.04167 (19)
O1	0.57949 (11)	0.49601 (17)	0.1553 (2)	0.0468 (4)
O2	0.57299 (12)	0.62481 (16)	−0.0453 (2)	0.0465 (4)
N1	0.59041 (14)	0.2248 (2)	0.1633 (3)	0.0491 (5)
C1	0.5679 (2)	0.1569 (3)	0.0391 (5)	0.0726 (10)
H1	0.5088	0.1664	−0.0059	0.090*
C2	0.6274 (3)	0.0743 (4)	−0.0251 (6)	0.0911 (13)
H2	0.6085	0.0290	−0.1116	0.090*
C3	0.7145 (3)	0.0584 (3)	0.0378 (5)	0.0790 (11)
H3	0.7558	0.0019	−0.0040	0.090*
C4	0.7395 (2)	0.1274 (4)	0.1630 (5)	0.0725 (10)
H4	0.7986	0.1190	0.2083	0.090*
C5	0.6764 (2)	0.2103 (3)	0.2231 (4)	0.0592 (8)
H5	0.6946	0.2577	0.3083	0.090*
C6	0.54390 (16)	0.5345 (2)	0.0324 (3)	0.0405 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0290 (2)	0.0460 (3)	0.0499 (3)	0.000	−0.00167 (18)	0.000
O1	0.0341 (9)	0.0554 (11)	0.0503 (11)	−0.0087 (7)	−0.0082 (8)	0.0032 (8)
O2	0.0358 (9)	0.0508 (10)	0.0527 (11)	−0.0083 (7)	−0.0047 (8)	0.0002 (8)
N1	0.0351 (11)	0.0486 (12)	0.0637 (15)	0.0030 (9)	0.0034 (10)	0.0006 (10)
C1	0.0480 (17)	0.074 (2)	0.096 (3)	0.0063 (15)	−0.0007 (17)	−0.0296 (19)
C2	0.067 (2)	0.089 (3)	0.118 (3)	0.007 (2)	0.011 (2)	−0.043 (3)
C3	0.060 (2)	0.068 (2)	0.110 (3)	0.0157 (17)	0.025 (2)	−0.009 (2)
C4	0.0438 (16)	0.086 (2)	0.088 (3)	0.0185 (15)	0.0097 (16)	0.021 (2)
C5	0.0401 (14)	0.070 (2)	0.067 (2)	0.0114 (13)	0.0028 (13)	0.0074 (15)
C6	0.0293 (11)	0.0451 (13)	0.0470 (14)	−0.0015 (10)	0.0014 (10)	−0.0054 (11)

Geometric parameters (Å, º) top

Ni1—O2ⁱ	2.046 (2)	C1—C2	1.364 (5)
Ni1—O2ⁱⁱ	2.046 (2)	C1—H1	0.9300
Ni1—O1	2.0716 (18)	C2—C3	1.362 (6)
Ni1—O1ⁱⁱⁱ	2.0716 (18)	C2—H2	0.9300
Ni1—N1	2.081 (2)	C3—C4	1.357 (6)
Ni1—N1ⁱⁱⁱ	2.081 (2)	C3—H3	0.9300
O1—C6	1.240 (3)	C4—C5	1.385 (5)
O2—C6	1.263 (3)	C4—H4	0.9300
O2—Ni1ⁱⁱ	2.046 (2)	C5—H5	0.9300
N1—C1	1.335 (4)	C6—C6ⁱⁱ	1.556 (4)
N1—C5	1.336 (3)

O2ⁱ—Ni1—O2ⁱⁱ	168.78 (10)	C5—N1—Ni1	121.3 (2)
O2ⁱ—Ni1—O1	89.88 (7)	N1—C1—C2	123.1 (3)
O2ⁱⁱ—Ni1—O1	81.96 (7)	N1—C1—H1	118.4
O2ⁱ—Ni1—O1ⁱⁱⁱ	81.96 (7)	C2—C1—H1	118.4
O2ⁱⁱ—Ni1—O1ⁱⁱⁱ	89.88 (7)	C3—C2—C1	119.9 (4)
O1—Ni1—O1ⁱⁱⁱ	86.81 (11)	C3—C2—H2	120.1
O2ⁱ—Ni1—N1	94.02 (8)	C1—C2—H2	120.1
O2ⁱⁱ—Ni1—N1	93.66 (9)	C4—C3—C2	118.1 (3)
O1—Ni1—N1	89.92 (9)	C4—C3—H3	121.0
O1ⁱⁱⁱ—Ni1—N1	174.81 (8)	C2—C3—H3	121.0
O2ⁱ—Ni1—N1ⁱⁱⁱ	93.66 (9)	C3—C4—C5	119.7 (3)
O2ⁱⁱ—Ni1—N1ⁱⁱⁱ	94.02 (8)	C3—C4—H4	120.2
O1—Ni1—N1ⁱⁱⁱ	174.81 (8)	C5—C4—H4	120.2
O1ⁱⁱⁱ—Ni1—N1ⁱⁱⁱ	89.92 (9)	N1—C5—C4	122.4 (3)
N1—Ni1—N1ⁱⁱⁱ	93.61 (13)	N1—C5—H5	118.8
C6—O1—Ni1	111.39 (15)	C4—C5—H5	118.8
C6—O2—Ni1ⁱⁱ	111.64 (15)	O1—C6—O2	125.6 (2)
C1—N1—C5	116.8 (3)	O1—C6—C6ⁱⁱ	117.5 (3)
C1—N1—Ni1	121.8 (2)	O2—C6—C6ⁱⁱ	116.9 (3)

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

Experimental details

Crystal data
Chemical formula	[Ni(C₂O₄)(C₅H₅N)₂]
M_r	304.93
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	14.357 (3), 10.801 (2), 8.6669 (17)
β (°)	91.52 (3)
V (Å³)	1343.5 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.45
Crystal size (mm)	0.26 × 0.24 × 0.22

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.640, 0.726
No. of measured, independent and observed [I > 2σ(I)] reflections	6433, 1519, 1297
R_int	0.041
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.103, 1.04
No. of reflections	1519
No. of parameters	87
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.73, −0.30

Computer programs: PROCESS-AUTO (Rigaku, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top

Ni1—O2ⁱ	2.046 (2)	Ni1—N1	2.081 (2)
Ni1—O1	2.0716 (18)

O2ⁱ—Ni1—O2ⁱⁱ	168.78 (10)	O2ⁱⁱ—Ni1—N1	93.66 (9)
O2ⁱ—Ni1—O1	89.88 (7)	O1—Ni1—N1	89.92 (9)
O2ⁱⁱ—Ni1—O1	81.96 (7)	O1ⁱⁱⁱ—Ni1—N1	174.81 (8)
O1—Ni1—O1ⁱⁱⁱ	86.81 (11)	N1—Ni1—N1ⁱⁱⁱ	93.61 (13)
O2ⁱ—Ni1—N1	94.02 (8)

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

Acknowledgements

The authors thank Yanbian University for supporting this work.

References

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