Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803012704/ya6163sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803012704/ya6163Isup2.hkl |
CCDC reference: 177954
The compound was synthesized hydrothermally from nickel nitrate hexahydrate (0.29 g, 1 mmol), terephthalic acid (0.17 g, 1 mmol), 4,4'-bipyridine dihydrochloride (0.23 g, 1 mmol) and sodium hydroxide (0.16 g, 4 mmol) in water (18 ml). The mixture was placed in a 20 ml Teflon-lined stainless-steel vessel, which was heated at 493 K for 100 h. The vessel was cooled to room temperature at a rate of 6 K h−1. The product was isolated in 25% yield.
The aromatic portion of one of the terephthalate groups (at the Wyckoff 2 d site of 2/m symmetry), made up of atoms C5, C6 and C7, showed large displacement parameters for atoms C6 and C7. However, the free refinement of these two atoms by imposing a PART −1 command in SHELXL97 (Sheldrick, 1997) was unstable. H atoms were generated geometrically (C—H = 0.93 Å) and included in the subsequent refinement in the riding motion approximation with Uiso(H) = 1.2Ueq(C).
Data collection: CAD-4 Software (Enraf-Nonius, 1988); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.
[Ni(C8H4O4)(C10H8N2)] | F(000) = 776 |
Mr = 379.01 | Dx = 1.512 Mg m−3 |
Monoclinic, C2/m | Mo Kα radiation, λ = 0.71073 Å |
a = 16.610 (3) Å | Cell parameters from 25 reflections |
b = 10.222 (2) Å | θ = 14.0–16.0° |
c = 11.237 (2) Å | µ = 1.19 mm−1 |
β = 119.22 (3)° | T = 298 K |
V = 1665.1 (5) Å3 | Block, green |
Z = 4 | 0.18 × 0.18 × 0.11 mm |
Enraf-Nonius CAD-4 diffractometer | 1312 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.038 |
Graphite monochromator | θmax = 26.0°, θmin = 2.1° |
ω scans | h = 0→20 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→12 |
Tmin = 0.696, Tmax = 0.877 | l = −13→12 |
1790 measured reflections | 3 standard reflections every 60 min |
1728 independent reflections | intensity decay: none |
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)] = 0.055 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.135 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0649P)2 + 1.5719P] where P = (Fo2 + 2Fc2)/3 |
1728 reflections | (Δ/σ)max = 0.001 |
128 parameters | Δρmax = 0.67 e Å−3 |
0 restraints | Δρmin = −0.73 e Å−3 |
[Ni(C8H4O4)(C10H8N2)] | V = 1665.1 (5) Å3 |
Mr = 379.01 | Z = 4 |
Monoclinic, C2/m | Mo Kα radiation |
a = 16.610 (3) Å | µ = 1.19 mm−1 |
b = 10.222 (2) Å | T = 298 K |
c = 11.237 (2) Å | 0.18 × 0.18 × 0.11 mm |
β = 119.22 (3)° |
Enraf-Nonius CAD-4 diffractometer | 1312 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.038 |
Tmin = 0.696, Tmax = 0.877 | 3 standard reflections every 60 min |
1790 measured reflections | intensity decay: none |
1728 independent reflections |
R[F2 > 2σ(F2)] = 0.055 | 0 restraints |
wR(F2) = 0.135 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.67 e Å−3 |
1728 reflections | Δρmin = −0.73 e Å−3 |
128 parameters |
x | y | z | Uiso*/Ueq | ||
Ni1 | 0.63763 (5) | 0.5000 | 0.15968 (7) | 0.0204 (2) | |
O1 | 0.5599 (2) | 0.3384 (3) | 0.1060 (3) | 0.030 (1) | |
O2 | 0.7648 (2) | 0.6073 (3) | 0.2635 (3) | 0.034 (1) | |
N1 | 0.6494 (4) | 0.5000 | −0.0159 (5) | 0.029 (1) | |
N2 | 0.6350 (4) | 0.5000 | −0.6569 (5) | 0.028 (1) | |
C1 | 0.5000 | 0.2834 (6) | 0.0000 | 0.023 (1) | |
C2 | 0.5000 | 0.1366 (6) | 0.0000 | 0.026 (1) | |
C3 | 0.5728 (3) | 0.0668 (4) | 0.1012 (5) | 0.037 (1) | |
C4 | 0.8056 (4) | 0.5000 | 0.3015 (6) | 0.031 (2) | |
C5 | 0.9073 (4) | 0.5000 | 0.4034 (7) | 0.032 (2) | |
C6 | 0.9709 (6) | 0.5000 | 0.3714 (9) | 0.17 (1) | |
C7 | 1.0645 (7) | 0.5000 | 0.468 (1) | 0.20 (1) | |
C8 | 0.6533 (3) | 0.3893 (5) | −0.0760 (5) | 0.036 (1) | |
C9 | 0.6551 (4) | 0.3842 (5) | −0.1963 (5) | 0.040 (1) | |
C10 | 0.6537 (5) | 0.5000 | −0.2622 (6) | 0.032 (2) | |
C11 | 0.6482 (5) | 0.5000 | −0.3981 (6) | 0.032 (2) | |
C12 | 0.6469 (6) | 0.3881 (5) | −0.4644 (6) | 0.080 (3) | |
C13 | 0.6392 (5) | 0.3915 (6) | −0.5913 (6) | 0.071 (2) | |
H3 | 0.6224 | 0.1116 | 0.1702 | 0.044* | |
H6 | 0.9544 | 0.5000 | 0.2795 | 0.207* | |
H7 | 1.1078 | 0.5000 | 0.4386 | 0.245* | |
H8 | 0.6548 | 0.3107 | −0.0334 | 0.044* | |
H9 | 0.6573 | 0.3040 | −0.2336 | 0.048* | |
H12 | 0.6514 | 0.3078 | −0.4227 | 0.096* | |
H13 | 0.6368 | 0.3123 | −0.6337 | 0.085* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.0262 (4) | 0.0165 (4) | 0.0159 (4) | 0.000 | 0.0082 (3) | 0.000 |
O1 | 0.041 (2) | 0.016 (2) | 0.025 (2) | −0.006 (1) | 0.010 (1) | −0.002 (1) |
O2 | 0.031 (2) | 0.026 (2) | 0.036 (2) | −0.001 (1) | 0.008 (1) | 0.002 (1) |
N1 | 0.036 (3) | 0.029 (3) | 0.023 (3) | 0.000 | 0.015 (2) | 0.000 |
N2 | 0.041 (3) | 0.018 (3) | 0.027 (3) | 0.000 | 0.018 (3) | 0.000 |
C1 | 0.029 (3) | 0.014 (3) | 0.026 (3) | 0.000 | 0.014 (3) | 0.000 |
C2 | 0.032 (3) | 0.010 (3) | 0.034 (3) | 0.000 | 0.015 (3) | 0.000 |
C3 | 0.034 (3) | 0.018 (2) | 0.036 (2) | 0.001 (2) | −0.001 (2) | −0.002 (2) |
C4 | 0.033 (4) | 0.029 (4) | 0.028 (3) | 0.000 | 0.013 (3) | 0.000 |
C5 | 0.026 (3) | 0.031 (4) | 0.030 (3) | 0.000 | 0.007 (3) | 0.000 |
C6 | 0.026 (5) | 0.46 (3) | 0.033 (5) | 0.000 | 0.011 (4) | 0.000 |
C7 | 0.027 (5) | 0.53 (4) | 0.047 (6) | 0.000 | 0.014 (5) | 0.000 |
C8 | 0.060 (3) | 0.024 (3) | 0.035 (2) | 0.005 (2) | 0.032 (2) | 0.003 (2) |
C9 | 0.070 (4) | 0.026 (3) | 0.036 (3) | 0.006 (2) | 0.035 (3) | 0.000 (2) |
C10 | 0.047 (4) | 0.024 (3) | 0.025 (3) | 0.000 | 0.017 (3) | 0.000 |
C11 | 0.049 (4) | 0.023 (4) | 0.031 (3) | 0.000 | 0.024 (3) | 0.000 |
C12 | 0.198 (8) | 0.020 (3) | 0.052 (4) | 0.002 (4) | 0.083 (5) | 0.006 (3) |
C13 | 0.153 (7) | 0.029 (3) | 0.048 (3) | 0.001 (4) | 0.062 (4) | −0.002 (3) |
Ni1—O1 | 1.999 (3) | C5—C6 | 1.27 (1) |
Ni1—O1i | 1.999 (3) | C5—C7v | 1.28 (1) |
Ni1—O2 | 2.149 (3) | C6—C7 | 1.40 (1) |
Ni1—O2i | 2.149 (3) | C7—C5v | 1.28 (1) |
Ni1—N1 | 2.076 (5) | C8—C9 | 1.367 (6) |
Ni1—N2ii | 2.084 (5) | C9—C10 | 1.391 (6) |
O1—C1 | 1.252 (4) | C10—C9i | 1.391 (6) |
O2—C4 | 1.250 (4) | C10—C11 | 1.484 (8) |
N1—C8 | 1.335 (5) | C11—C12i | 1.360 (6) |
N1—C8i | 1.335 (5) | C11—C12 | 1.360 (6) |
N2—C13i | 1.314 (6) | C12—C13 | 1.369 (7) |
N2—C13 | 1.314 (6) | C3—H3 | 0.93 |
C1—O1iii | 1.252 (4) | C6—H6 | 0.93 |
C1—C2 | 1.501 (8) | C7—H7 | 0.93 |
C2—C3iii | 1.387 (5) | C8—H8 | 0.93 |
C2—C3 | 1.387 (5) | C9—H9 | 0.93 |
C3—C3iv | 1.365 (9) | C12—H12 | 0.93 |
C4—O2i | 1.250 (4) | C13—H13 | 0.93 |
C4—C5 | 1.508 (9) | ||
O1—Ni1—O1i | 111.4 (2) | O2i—C4—C5 | 118.6 (3) |
O1—Ni1—O2 | 154.7 (1) | O2—C4—C5 | 118.6 (3) |
O1—Ni1—O2i | 93.5 (1) | C6—C5—C7v | 114.9 (8) |
O1—Ni1—N1 | 93.4 (1) | C6—C5—C4 | 124.2 (7) |
O1—Ni1—N2ii | 88.6 (1) | C7v—C5—C4 | 120.9 (7) |
O1i—Ni1—O2 | 93.5 (1) | C5—C6—C7 | 122.8 (9) |
O1i—Ni1—O2i | 154.7 (1) | C5v—C7—C6 | 122 (1) |
O1i—Ni1—N1 | 93.4 (1) | N1—C8—C9 | 124.2 (4) |
O1i—Ni1—N2ii | 88.6 (1) | C8—C9—C10 | 119.4 (5) |
O2—Ni1—O2i | 61.3 (2) | C9i—C10—C9 | 116.7 (6) |
O2—Ni1—N1 | 89.5 (2) | C9i—C10—C11 | 121.7 (3) |
O2—Ni1—N2ii | 87.3 (2) | C9—C10—C11 | 121.7 (3) |
O2i—Ni1—N1 | 89.5 (2) | C12i—C11—C12 | 114.5 (6) |
O2i—Ni1—N2ii | 87.3 (2) | C12i—C11—C10 | 122.7 (3) |
N1—Ni1—N2ii | 176.3 (2) | C12—C11—C10 | 122.7 (3) |
C1—O1—Ni1 | 138.9 (3) | C11—C12—C13 | 121.3 (5) |
C4—O2—Ni1 | 87.9 (3) | N2—C13—C12 | 123.9 (5) |
C8—N1—C8i | 115.8 (5) | C3iv—C3—H3 | 119.5 |
C8—N1—Ni1 | 122.1 (3) | C2—C3—H3 | 119.5 |
C8i—N1—Ni1 | 122.1 (3) | C5—C6—H6 | 118.6 |
C13i—N2—C13 | 115.1 (6) | C7—C6—H6 | 118.6 |
C13i—N2—Ni1vi | 122.2 (3) | C5v—C7—H7 | 118.8 |
C13—N2—Ni1vi | 122.2 (3) | C6—C7—H7 | 118.8 |
O1—C1—O1iii | 126.7 (5) | N1—C8—H8 | 117.9 |
O1—C1—C2 | 116.7 (3) | C9—C8—H8 | 117.9 |
O1iii—C1—C2 | 116.7 (3) | C8—C9—H9 | 120.3 |
C3iii—C2—C3 | 118.0 (6) | C10—C9—H9 | 120.3 |
C3iii—C2—C1 | 121.0 (3) | C11—C12—H12 | 119.4 |
C3—C2—C1 | 121.0 (3) | C13—C12—H12 | 119.4 |
C3iv—C3—C2 | 121.0 (3) | N2—C13—H13 | 118.1 |
O2i—C4—O2 | 122.6 (6) | C12—C13—H13 | 118.1 |
O1i—Ni1—O1—C1 | 62.0 (5) | C3iii—C2—C3—C3iv | 0.0 |
N1—Ni1—O1—C1 | −33.1 (4) | C1—C2—C3—C3iv | 180.0 |
N2ii—Ni1—O1—C1 | 150.0 (4) | Ni1—O2—C4—O2i | 4.4 (7) |
O2—Ni1—O1—C1 | −129.3 (4) | Ni1—O2—C4—C5 | −172.2 (6) |
O2i—Ni1—O1—C1 | −122.8 (4) | O2i—C4—C5—C6 | 91.6 (6) |
O1—Ni1—O2—C4 | 4.9 (5) | O2—C4—C5—C6 | −91.6 (6) |
O1i—Ni1—O2—C4 | 174.4 (4) | O2i—C4—C5—C7v | −88.4 (6) |
N1—Ni1—O2—C4 | −92.2 (4) | O2—C4—C5—C7v | 88.4 (6) |
N2ii—Ni1—O2—C4 | 86.0 (4) | C7v—C5—C6—C7 | 0.000 (3) |
O2i—Ni1—O2—C4 | −2.5 (4) | C4—C5—C6—C7 | 180.000 (2) |
O1—Ni1—N1—C8 | −34.0 (5) | C5—C6—C7—C5v | 0.000 (2) |
O1i—Ni1—N1—C8 | −145.7 (5) | C8i—N1—C8—C9 | −4 (1) |
N2ii—Ni1—N1—C8 | 90.2 (5) | Ni1—N1—C8—C9 | 175.6 (4) |
O2—Ni1—N1—C8 | 120.8 (5) | N1—C8—C9—C10 | 0.5 (9) |
O2i—Ni1—N1—C8 | 59.5 (5) | C8—C9—C10—C9i | 3 (1) |
O1—Ni1—N1—C8i | 145.7 (5) | C8—C9—C10—C11 | −175.1 (6) |
O1i—Ni1—N1—C8i | 34.0 (5) | C9i—C10—C11—C12i | 2 (1) |
N2ii—Ni1—N1—C8i | −90.2 (5) | C9—C10—C11—C12i | −179.8 (7) |
O2—Ni1—N1—C8i | −59.5 (5) | C9i—C10—C11—C12 | 179.8 (7) |
O2i—Ni1—N1—C8i | −120.8 (5) | C9—C10—C11—C12 | −2 (1) |
Ni1—O1—C1—O1iii | −33.8 (3) | C12i—C11—C12—C13 | −4 (2) |
Ni1—O1—C1—C2 | 146.2 (3) | C10—C11—C12—C13 | 178.2 (7) |
O1—C1—C2—C3iii | 168.3 (3) | C13i—N2—C13—C12 | 0 (1) |
O1iii—C1—C2—C3iii | −11.7 (3) | Ni1vi—N2—C13—C12 | 173.2 (6) |
O1—C1—C2—C3 | −11.7 (3) | C11—C12—C13—N2 | 2 (1) |
O1iii—C1—C2—C3 | 168.3 (3) |
Symmetry codes: (i) x, −y+1, z; (ii) x, y, z+1; (iii) −x+1, y, −z; (iv) x, −y, z; (v) −x+2, −y+1, −z+1; (vi) x, y, z−1. |
Experimental details
Crystal data | |
Chemical formula | [Ni(C8H4O4)(C10H8N2)] |
Mr | 379.01 |
Crystal system, space group | Monoclinic, C2/m |
Temperature (K) | 298 |
a, b, c (Å) | 16.610 (3), 10.222 (2), 11.237 (2) |
β (°) | 119.22 (3) |
V (Å3) | 1665.1 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.19 |
Crystal size (mm) | 0.18 × 0.18 × 0.11 |
Data collection | |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.696, 0.877 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1790, 1728, 1312 |
Rint | 0.038 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.055, 0.135, 1.03 |
No. of reflections | 1728 |
No. of parameters | 128 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.67, −0.73 |
Computer programs: CAD-4 Software (Enraf-Nonius, 1988), CAD-4 Software, XCAD4 (Harms, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976), SHELXL97.
Ni1—O1 | 1.999 (3) | Ni1—N1 | 2.076 (5) |
Ni1—O2 | 2.149 (3) | ||
O1—Ni1—O1i | 111.4 (2) | O2—Ni1—O2i | 61.3 (2) |
O1—Ni1—O2 | 154.7 (1) | O2—Ni1—N1 | 89.5 (2) |
O1—Ni1—O2i | 93.5 (1) | O2—Ni1—N2ii | 87.3 (2) |
O1—Ni1—N1 | 93.4 (1) | N1—Ni1—N2ii | 176.3 (2) |
O1—Ni1—N2ii | 88.6 (1) |
Symmetry codes: (i) x, −y+1, z; (ii) x, y, z+1. |
4,4'-Bipyridine(terephthalato)nickel(II), [Ni(C8H4O4)(C10H8N2)], exists as poly[µ2-terephthalato-µ4-terephthalato-bis[(µ2-4,4'- bipyridine)nickel(II)]]. Two independent terephthalato groups both occupy positions of 2/m symmetry; one of these groups acts as a µ4 bridge and coordinates four different Ni atoms with each of its O atoms. The other one acts as a µ2-bridge and serves as a bidentate chelate for two neighboring metal atoms (Fig. 1). Consequently, the terephthalate–nickel framework forms infinite two-dimensional layers parallel to the ab plane of the crystal. The layers are linked into a three-dimensional network through the µ2-bridging 4,4'-bipyridine ligands occupying a special position across the mirror plane. The compound is isostructural with the published cobalt analog, whose detailed description (Tao et al., 2000) also applies to the title compound.