Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803008778/dn6068sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803008778/dn6068Isup2.hkl |
CCDC reference: 214583
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.007 Å
- R factor = 0.058
- wR factor = 0.142
- Data-to-parameter ratio = 12.4
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
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%.
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.
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.
[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) Å3 | 0.46 × 0.34 × 0.26 mm |
Z = 4 |
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 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)] = 0.058 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.142 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0464P)2 + 12.8239P] where P = (Fo2 + 2Fc2)/3 |
2637 reflections | (Δ/σ)max = 0.001 |
213 parameters | Δρmax = 0.40 e Å−3 |
0 restraints | Δρmin = −0.37 e Å−3 |
[Ni(C10H8N2)3](ClO4)2 | V = 3034.8 (6) Å3 |
Mr = 726.16 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 17.502 (2) Å | µ = 0.88 mm−1 |
b = 10.777 (1) Å | T = 293 K |
c = 16.092 (2) Å | 0.46 × 0.34 × 0.26 mm |
β = 90.959 (2)° |
Siemens SMART CCD diffractometer | 2637 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2026 reflections with I > 2σ(I) |
Tmin = 0.621, Tmax = 0.796 | Rint = 0.033 |
4475 measured reflections |
R[F2 > 2σ(F2)] = 0.058 | 0 restraints |
wR(F2) = 0.142 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0464P)2 + 12.8239P] where P = (Fo2 + 2Fc2)/3 |
2637 reflections | Δρmax = 0.40 e Å−3 |
213 parameters | Δρmin = −0.37 e Å−3 |
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. |
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) |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
Ni—N3 | 2.071 (3) | C6—N2 | 1.345 (5) |
Ni—N3i | 2.071 (3) | C6—C7 | 1.380 (6) |
Ni—N2 | 2.085 (3) | C7—C8 | 1.368 (7) |
Ni—N2i | 2.085 (3) | C7—H7 | 0.9300 |
Ni—N1 | 2.090 (3) | C8—C9 | 1.360 (7) |
Ni—N1i | 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—C11i | 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—N3i | 79.11 (19) | C6—C7—H7 | 120.3 |
N3—Ni—N2 | 172.13 (14) | C9—C8—C7 | 119.8 (5) |
N3i—Ni—N2 | 97.08 (13) | C9—C8—H8 | 120.1 |
N2—Ni—N2i | 87.50 (19) | C7—C8—H8 | 120.1 |
N3—Ni—N1 | 94.71 (14) | C8—C9—C10 | 118.7 (5) |
N3i—Ni—N1 | 92.96 (14) | C8—C9—H9 | 120.7 |
N2—Ni—N1 | 78.53 (14) | C10—C9—H9 | 120.7 |
N2i—Ni—N1 | 94.22 (14) | N2—C10—C9 | 122.7 (4) |
N1—Ni—N1i | 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—C11i | 115.1 (2) |
O4—Cl—O2 | 108.3 (4) | C12—C11—C11i | 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. |
Experimental details
Crystal data | |
Chemical formula | [Ni(C10H8N2)3](ClO4)2 |
Mr | 726.16 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 293 |
a, b, c (Å) | 17.502 (2), 10.777 (1), 16.092 (2) |
β (°) | 90.959 (2) |
V (Å3) | 3034.8 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.88 |
Crystal size (mm) | 0.46 × 0.34 × 0.26 |
Data collection | |
Diffractometer | Siemens SMART CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.621, 0.796 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4475, 2637, 2026 |
Rint | 0.033 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.058, 0.142, 1.08 |
No. of reflections | 2637 |
No. of parameters | 213 |
H-atom treatment | H-atom parameters constrained |
w = 1/[σ2(Fo2) + (0.0464P)2 + 12.8239P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 0.40, −0.37 |
Computer programs: SMART (Siemens, 1996), SMART, SAINT (Siemens, 1994), SHELXTL (Siemens, 1994), SHELXL97 (Sheldrick, 1997), PLUTON (Spek, 2003) and ORTEP-3 (Farrugia, 1997), SHELXL97.
Ni—N3 | 2.071 (3) | C1—N1 | 1.342 (6) |
Ni—N2 | 2.085 (3) | C5—N1 | 1.348 (5) |
Ni—N1 | 2.090 (3) | C6—N2 | 1.345 (5) |
Cl—O4 | 1.373 (4) | C10—N2 | 1.343 (6) |
Cl—O1 | 1.381 (5) | C11—N3 | 1.347 (5) |
Cl—O3 | 1.417 (4) | C15—N3 | 1.350 (6) |
Cl—O2 | 1.429 (5) | ||
N3—Ni—N3i | 79.11 (19) | N3i—Ni—N1 | 92.96 (14) |
N3—Ni—N2 | 172.13 (14) | N2—Ni—N1 | 78.53 (14) |
N3i—Ni—N2 | 97.08 (13) | N2i—Ni—N1 | 94.22 (14) |
N2—Ni—N2i | 87.50 (19) | N1—Ni—N1i | 170.06 (19) |
N3—Ni—N1 | 94.71 (14) |
Symmetry code: (i) −x+1, y, −z+1/2. |
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 ZnII 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 ZnII 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 ZnII 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 ZnII 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).