Tris(2,2'-bi­pyridine)­nickel(II) di­perchlorate

The title compound, [Ni(C₁₀H₈N₂)₃](ClO₄)₂, is built up of monomeric [Ni(bpy)₃]²⁺ cations (bpy = 2,2'-bi­pyridine) and two perchlorate anions. The asymmetric unit is one half cation and one anion, a twofold rotation axis passing through the Ni atom and bisecting one bpy ligand. The Ni^II ion is coordinated by six N atoms from three chelating bpy ligands in a highly distorted octahedral geometry, with Ni-N bond lengths ranging from 2.071 (4) to 2.091 (4) Å.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.007 Å
• R factor = 0.058
• wR factor = 0.142
• Data-to-parameter ratio = 12.4

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S1. Comment

When trying to prepare the nickel(II) complex containing 2,2'-bipyridine and 1,3,5-benzenetricarboxylate ligands through hydrothermal reaction, we could not obtain the expected compound but instead red prismatic crystals of tris(2,2'-bipyridine)nickel(II) bis(perchlorate), (I), were grown from the above solution by slow evaporation. The new complex has been characterized by elemental analysis and single-crystal diffraction analysis.

The title compound crystallizes in C2/c space group and consists of monomeric [Ni(bpy)₃]²⁺ cations and two perchlorate anions, being isostructural with the zinc(II) complex (Chen et al., 1995a,b). The nickel(II) ion is coordinated by six N atoms from three chleating bpy ligands in a highly distorted octahedral geometry (Fig. 1), with Ni—N bond lengths ranging from 2.071 (4) to 2.091 (4) Å, which is shorter than those [2.135 (2)–2.172 (3) Å] of the Zn^II isomorphous compound. this may be attributed to the shorter ionic radius of the Ni²⁺ cation. It is notable that one chelating bpy is bisected by the twofold axis. Comparing with the Zn^II isomorph, each pair of pyridine rings in the three bpy ligands are also non-coplanar, with a dihedral angle between each pair ranging from 7.2 to 18.3°, which is larger than those of the Zn^II isomorph. The distorted N—Mn—N angles resulting from the chelating bpy ligands range from 78.6 (1) to 79.1 (2)°, which is larger than those of the Zn^II isomorph [75.8 (1)–77.2 (1)°]. The crystal structure of the title compound is constructed by two-dimensional layers parallel to the ab plane. The molecular packing reveals the occurrence of pillars of cations and anions projected down the c axis (Fig. 2).

S2. Experimental

The hydrothermal reaction of nickel perchlorate (0.06 g, ca 0.20 mmol), 2,2'-bipyridine (0.05 g, 0.32 mmol) and 1,3,5-benzenetricarboxylic acid (0.05 g, 0.24 mmol) in the molar ratio of ca 2:3:2 at 433 K for 4 d gave, after cooling to room temperature at 5 K h⁻¹, a pale green solution. Red prismatic crystals of [Ni(bpy)₃](ClO₄)₂ were grown from the above solution by slow evaporation for about four days and isolated in 54% yield (base on Ni). Elemental analysis calculated for C₃₀H₂₄Cl₂N₆NiO₈: C 49.62, H 3.33, N 11.57%; found: C 49.51, H 3.10, N 11.39%.

S3. Refinement

The structure was solved by direct methods. Semi-empirical absorption correction was applied by using the SADABS (Sheldrick, 1996) program. All H atoms were located in a difference Fourier map but were introduced in idealized positions and treated as riding models.

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SMART; data reduction: SAINT (Siemens, 1994); program(s) used to solve structure: SHELXTL (Siemens, 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLUTON (Spek, 2003) and ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. View of the cation and anion of the title complex, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. Packing structure of the title complex along the c axis. H atoms have been omitted for clarity.

Tris(2,2'-bipyridine)nickel(II) bis(perchlorate)

Crystal data

[Ni(C10H8N2)3](ClO4)2	F(000) = 1488
Mr = 726.16	Dx = 1.589 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2134 reflections
a = 17.502 (2) Å	θ = 2.2–25.0°
b = 10.777 (1) Å	µ = 0.88 mm^−1
c = 16.092 (2) Å	T = 293 K
β = 90.959 (2)°	Prism, red
V = 3034.8 (6) Å^3	0.46 × 0.34 × 0.26 mm
Z = 4

Data collection

Siemens SMART CCD diffractometer	2637 independent reflections
Radiation source: fine-focus sealed tube	2026 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
ω scans	θmax = 25.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −20→12
Tmin = 0.621, Tmax = 0.796	k = −12→8
4475 measured reflections	l = −19→19

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.142	H-atom parameters constrained
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0464P)^2 + 12.8239P] where P = (Fo^2 + 2Fc^2)/3
2637 reflections	(Δ/σ)max = 0.001
213 parameters	Δρmax = 0.40 e Å^−3
0 restraints	Δρmin = −0.37 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
Ni	0.5000	0.47618 (7)	0.2500	0.0366 (2)
Cl	0.82564 (7)	0.50703 (13)	0.36477 (7)	0.0582 (4)
C1	0.6161 (3)	0.4270 (5)	0.1119 (3)	0.0508 (12)
H1	0.5871	0.3569	0.0991	0.061*
C2	0.6747 (3)	0.4588 (5)	0.0607 (3)	0.0556 (13)
H2	0.6848	0.4117	0.0138	0.067*
C3	0.7178 (3)	0.5602 (5)	0.0796 (3)	0.0564 (13)
H3	0.7572	0.5843	0.0450	0.068*
C4	0.7027 (3)	0.6264 (5)	0.1500 (3)	0.0517 (12)
H4	0.7325	0.6949	0.1642	0.062*
C5	0.6431 (2)	0.5911 (4)	0.2000 (3)	0.0384 (10)
C6	0.6225 (2)	0.6562 (4)	0.2776 (3)	0.0403 (10)
C7	0.6653 (3)	0.7517 (5)	0.3115 (3)	0.0583 (13)
H7	0.7092	0.7789	0.2853	0.070*
C8	0.6425 (3)	0.8059 (5)	0.3838 (4)	0.0650 (15)
H8	0.6715	0.8692	0.4077	0.078*
C9	0.5774 (3)	0.7669 (5)	0.4206 (3)	0.0561 (13)
H9	0.5607	0.8039	0.4692	0.067*
C10	0.5368 (3)	0.6718 (4)	0.3845 (3)	0.0481 (11)
H10	0.4924	0.6448	0.4098	0.058*
C11	0.4796 (2)	0.2157 (4)	0.2094 (3)	0.0383 (10)
C12	0.4680 (3)	0.1100 (4)	0.1620 (3)	0.0526 (12)
H12	0.4850	0.0332	0.1811	0.063*
C13	0.4310 (3)	0.1199 (5)	0.0865 (3)	0.0557 (13)
H13	0.4239	0.0500	0.0534	0.067*
C14	0.4044 (3)	0.2335 (5)	0.0599 (3)	0.0525 (12)
H14	0.3780	0.2412	0.0096	0.063*
C15	0.4178 (3)	0.3350 (5)	0.1092 (3)	0.0490 (12)
H15	0.3995	0.4118	0.0916	0.059*
N1	0.5988 (2)	0.4930 (3)	0.1797 (2)	0.0402 (9)
N2	0.5585 (2)	0.6160 (3)	0.3142 (2)	0.0387 (8)
N3	0.45655 (19)	0.3280 (3)	0.1823 (2)	0.0387 (8)
O1	0.8323 (4)	0.5843 (7)	0.4330 (3)	0.145 (2)
O2	0.8836 (3)	0.4142 (5)	0.3722 (4)	0.131 (2)
O3	0.7522 (3)	0.4515 (5)	0.3633 (4)	0.1109 (17)
O4	0.8371 (3)	0.5721 (6)	0.2927 (3)	0.125 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni	0.0358 (4)	0.0364 (4)	0.0376 (4)	0.000	−0.0010 (3)	0.000
Cl	0.0569 (8)	0.0751 (9)	0.0425 (7)	−0.0079 (6)	−0.0004 (5)	0.0024 (6)
C1	0.045 (3)	0.054 (3)	0.053 (3)	−0.001 (2)	0.002 (2)	−0.015 (2)
C2	0.045 (3)	0.075 (4)	0.047 (3)	0.006 (3)	0.006 (2)	−0.010 (3)
C3	0.037 (3)	0.075 (4)	0.058 (3)	0.001 (3)	0.009 (2)	0.002 (3)
C4	0.042 (3)	0.049 (3)	0.065 (3)	−0.007 (2)	0.005 (2)	−0.002 (2)
C5	0.035 (2)	0.037 (2)	0.043 (2)	0.0018 (19)	−0.0015 (18)	0.0041 (19)
C6	0.038 (2)	0.036 (2)	0.047 (3)	−0.0022 (19)	−0.002 (2)	0.003 (2)
C7	0.052 (3)	0.051 (3)	0.073 (4)	−0.016 (2)	0.008 (3)	−0.009 (3)
C8	0.061 (3)	0.060 (3)	0.074 (4)	−0.015 (3)	−0.004 (3)	−0.024 (3)
C9	0.063 (3)	0.053 (3)	0.052 (3)	−0.003 (3)	0.001 (2)	−0.013 (2)
C10	0.048 (3)	0.048 (3)	0.049 (3)	−0.004 (2)	0.007 (2)	−0.003 (2)
C11	0.030 (2)	0.035 (2)	0.050 (3)	−0.0021 (18)	0.0010 (18)	−0.0027 (19)
C12	0.056 (3)	0.041 (3)	0.062 (3)	−0.001 (2)	−0.002 (2)	−0.002 (2)
C13	0.063 (3)	0.048 (3)	0.056 (3)	−0.011 (2)	−0.001 (3)	−0.011 (2)
C14	0.050 (3)	0.061 (3)	0.046 (3)	−0.011 (2)	−0.010 (2)	−0.007 (2)
C15	0.045 (3)	0.049 (3)	0.053 (3)	−0.002 (2)	−0.009 (2)	0.002 (2)
N1	0.039 (2)	0.042 (2)	0.040 (2)	0.0018 (16)	0.0025 (16)	−0.0006 (16)
N2	0.042 (2)	0.0343 (19)	0.040 (2)	0.0001 (16)	−0.0007 (16)	0.0001 (16)
N3	0.0333 (19)	0.040 (2)	0.042 (2)	−0.0026 (16)	−0.0037 (15)	0.0003 (16)
O1	0.169 (6)	0.175 (6)	0.093 (4)	−0.052 (5)	0.011 (4)	−0.063 (4)
O2	0.090 (4)	0.109 (4)	0.193 (6)	0.010 (3)	−0.028 (4)	0.027 (4)
O3	0.068 (3)	0.123 (4)	0.142 (5)	−0.032 (3)	0.011 (3)	−0.010 (4)
O4	0.092 (3)	0.198 (6)	0.085 (3)	−0.004 (4)	0.008 (3)	0.073 (4)

Geometric parameters (Å, º)

Ni—N3	2.071 (3)	C6—N2	1.345 (5)
Ni—N3^i	2.071 (3)	C6—C7	1.380 (6)
Ni—N2	2.085 (3)	C7—C8	1.368 (7)
Ni—N2^i	2.085 (3)	C7—H7	0.9300
Ni—N1	2.090 (3)	C8—C9	1.360 (7)
Ni—N1^i	2.090 (3)	C8—H8	0.9300
Cl—O4	1.373 (4)	C9—C10	1.370 (6)
Cl—O1	1.381 (5)	C9—H9	0.9300
Cl—O3	1.417 (4)	C10—N2	1.343 (6)
Cl—O2	1.429 (5)	C10—H10	0.9300
C1—N1	1.342 (6)	C11—N3	1.347 (5)
C1—C2	1.369 (6)	C11—C12	1.384 (6)
C1—H1	0.9300	C11—C11^i	1.479 (8)
C2—C3	1.359 (7)	C12—C13	1.371 (7)
C2—H2	0.9300	C12—H12	0.9300
C3—C4	1.368 (7)	C13—C14	1.375 (7)
C3—H3	0.9300	C13—H13	0.9300
C4—C5	1.382 (6)	C14—C15	1.369 (6)
C4—H4	0.9300	C14—H14	0.9300
C5—N1	1.348 (5)	C15—N3	1.350 (6)
C5—C6	1.482 (6)	C15—H15	0.9300
N3—Ni—N3^i	79.11 (19)	C6—C7—H7	120.3
N3—Ni—N2	172.13 (14)	C9—C8—C7	119.8 (5)
N3^i—Ni—N2	97.08 (13)	C9—C8—H8	120.1
N2—Ni—N2^i	87.50 (19)	C7—C8—H8	120.1
N3—Ni—N1	94.71 (14)	C8—C9—C10	118.7 (5)
N3^i—Ni—N1	92.96 (14)	C8—C9—H9	120.7
N2—Ni—N1	78.53 (14)	C10—C9—H9	120.7
N2^i—Ni—N1	94.22 (14)	N2—C10—C9	122.7 (4)
N1—Ni—N1^i	170.06 (19)	N2—C10—H10	118.7
O4—Cl—O1	110.6 (4)	C9—C10—H10	118.7
O4—Cl—O3	110.3 (3)	N3—C11—C12	121.4 (4)
O1—Cl—O3	109.4 (4)	N3—C11—C11^i	115.1 (2)
O4—Cl—O2	108.3 (4)	C12—C11—C11^i	123.5 (3)
O1—Cl—O2	107.8 (4)	C13—C12—C11	119.2 (5)
O3—Cl—O2	110.4 (3)	C13—C12—H12	120.4
N1—C1—C2	122.5 (5)	C11—C12—H12	120.4
N1—C1—H1	118.8	C12—C13—C14	119.8 (5)
C2—C1—H1	118.8	C12—C13—H13	120.1
C3—C2—C1	119.1 (5)	C14—C13—H13	120.1
C3—C2—H2	120.4	C15—C14—C13	118.5 (4)
C1—C2—H2	120.4	C15—C14—H14	120.7
C2—C3—C4	119.3 (5)	C13—C14—H14	120.7
C2—C3—H3	120.3	N3—C15—C14	122.6 (4)
C4—C3—H3	120.3	N3—C15—H15	118.7
C3—C4—C5	119.8 (5)	C14—C15—H15	118.7
C3—C4—H4	120.1	C1—N1—C5	118.5 (4)
C5—C4—H4	120.1	C1—N1—Ni	126.4 (3)
N1—C5—C4	120.8 (4)	C5—N1—Ni	114.5 (3)
N1—C5—C6	115.3 (4)	C10—N2—C6	118.3 (4)
C4—C5—C6	123.9 (4)	C10—N2—Ni	126.7 (3)
N2—C6—C7	121.3 (4)	C6—N2—Ni	115.0 (3)
N2—C6—C5	115.6 (4)	C11—N3—C15	118.4 (4)
C7—C6—C5	123.1 (4)	C11—N3—Ni	114.7 (3)
C8—C7—C6	119.4 (5)	C15—N3—Ni	126.2 (3)
C8—C7—H7	120.3

Symmetry code: (i) −x+1, y, −z+1/2.