Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100003401/qb0193sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100003401/qb0193trisup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100003401/qb0193monosup3.hkl |
CCDC references: 144690; 144691
Both types of crystals were obtained by the following procedure: 50 mg of pyridoin was dissolved in 15 ml of methanol by gentle heating followed by the addition of an excess of tetramethylammonium hydroxide. A 5 ml me thanolic solution of Ni(NO3)2.6H2O (45 mg) was then added. Crystals were grown directly from this solution.
Given that the Ni atom in the triclinic crystal is situated on a centre of symmetry the decision to opt for the non-centrosymmetric space group P21 over P21/m for the monoclinic form was made after careful examination of the data, the Patterson map and the refined structure. Furthermore the absence of a mirror plane normal to the b axis as required for the space group P21/m is apparent. The Flack test result is ambiguous indicating that the absolute configuration could not be reliably determined. It was not possible to unambiguously identify H atoms of the hydroxyl group in either structure, presumably because of disorder and as a consequence they were not included in the models.
For both compounds, data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: PROCESS_DATA (Gable et al., 1993); program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997).
[Ni(C12H9N2O3)2] | Z = 1 |
Mr = 517.13 | F(000) = 266 |
Triclinic, P1 | Dx = 1.625 Mg m−3 |
a = 7.6800 (11) Å | Cu Kα radiation, λ = 1.54180 Å |
b = 8.576 (2) Å | Cell parameters from 24 reflections |
c = 8.889 (2) Å | θ = 10.6–34.6° |
α = 88.29 (2)° | µ = 1.79 mm−1 |
β = 78.46 (2)° | T = 293 K |
γ = 67.29 (2)° | Parallelepiped, pale purple |
V = 528.40 (18) Å3 | 0.17 × 0.11 × 0.08 mm |
Enraf-Nonius CAD-4 diffractometer | 1844 reflections with I > 2α(I) |
Radiation source: fine-focus sealed tube | Rint = 0.015 |
None monochromator | θmax = 74.7°, θmin = 5.1° |
ω–2θ scans | h = −9→9 |
Absorption correction: numerical (SHELX76; Sheldrick, 1976) | k = −10→10 |
Tmin = 0.755, Tmax = 0.875 | l = −11→1 |
2619 measured reflections | 3 standard reflections every 120 min |
2168 independent reflections | intensity decay: none |
Refinement on F2 | Primary atom site location: heavy-atom method |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.131 | Only H-atom displacement parameters refined |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0796P)2 + 0.164P] where P = (Fo2 + 2Fc2)/3 |
2168 reflections | (Δ/σ)max < 0.001 |
162 parameters | Δρmax = 0.55 e Å−3 |
0 restraints | Δρmin = −0.67 e Å−3 |
[Ni(C12H9N2O3)2] | γ = 67.29 (2)° |
Mr = 517.13 | V = 528.40 (18) Å3 |
Triclinic, P1 | Z = 1 |
a = 7.6800 (11) Å | Cu Kα radiation |
b = 8.576 (2) Å | µ = 1.79 mm−1 |
c = 8.889 (2) Å | T = 293 K |
α = 88.29 (2)° | 0.17 × 0.11 × 0.08 mm |
β = 78.46 (2)° |
Enraf-Nonius CAD-4 diffractometer | 1844 reflections with I > 2α(I) |
Absorption correction: numerical (SHELX76; Sheldrick, 1976) | Rint = 0.015 |
Tmin = 0.755, Tmax = 0.875 | 3 standard reflections every 120 min |
2619 measured reflections | intensity decay: none |
2168 independent reflections |
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.131 | Only H-atom displacement parameters refined |
S = 1.07 | Δρmax = 0.55 e Å−3 |
2168 reflections | Δρmin = −0.67 e Å−3 |
162 parameters |
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 | ||
Ni1 | 0.0000 | 0.0000 | 0.0000 | 0.0314 (2) | |
O1 | −0.0221 (3) | −0.2040 (2) | −0.0952 (2) | 0.0400 (4) | |
O2 | 0.1073 (3) | −0.4212 (3) | −0.2695 (2) | 0.0498 (5) | |
O3 | 0.4065 (3) | −0.3631 (2) | −0.3861 (2) | 0.0469 (5) | |
N1 | 0.0930 (3) | 0.0573 (3) | −0.2229 (2) | 0.0348 (5) | |
N2 | 0.2883 (3) | −0.1512 (3) | −0.0110 (2) | 0.0365 (5) | |
C1 | 0.2133 (4) | −0.0690 (3) | −0.3247 (3) | 0.0340 (5) | |
C2 | 0.2731 (5) | −0.0396 (4) | −0.4765 (3) | 0.0471 (7) | |
H2 | 0.3555 | −0.1289 | −0.5458 | 0.062 (5)* | |
C3 | 0.2083 (5) | 0.1244 (4) | −0.5234 (4) | 0.0559 (8) | |
H3 | 0.2458 | 0.1468 | −0.6251 | 0.062 (5)* | |
C4 | 0.0875 (6) | 0.2547 (4) | −0.4180 (4) | 0.0559 (8) | |
H4 | 0.0433 | 0.3662 | −0.4468 | 0.062 (5)* | |
C5 | 0.0343 (5) | 0.2161 (3) | −0.2697 (3) | 0.0459 (7) | |
H5 | −0.0462 | 0.3040 | −0.1983 | 0.062 (5)* | |
C6 | 0.2825 (4) | −0.2471 (3) | −0.2653 (3) | 0.0352 (5) | |
C7 | 0.3888 (4) | −0.2537 (3) | −0.1356 (3) | 0.0338 (5) | |
C8 | 0.5820 (4) | −0.3594 (3) | −0.1480 (3) | 0.0422 (6) | |
H8 | 0.6502 | −0.4291 | −0.2360 | 0.063 (5)* | |
C9 | 0.6704 (4) | −0.3588 (4) | −0.0271 (4) | 0.0486 (7) | |
H9 | 0.7991 | −0.4290 | −0.0325 | 0.063 (5)* | |
C10 | 0.5663 (5) | −0.2534 (4) | 0.1015 (4) | 0.0521 (7) | |
H10 | 0.6233 | −0.2512 | 0.1840 | 0.063 (5)* | |
C11 | 0.3776 (4) | −0.1522 (4) | 0.1050 (3) | 0.0465 (7) | |
H11 | 0.3076 | −0.0807 | 0.1916 | 0.063 (5)* | |
C12 | 0.1057 (4) | −0.2956 (3) | −0.2042 (3) | 0.0357 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.0354 (3) | 0.0288 (3) | 0.0270 (3) | −0.0083 (2) | −0.0072 (2) | −0.0048 (2) |
O1 | 0.0441 (10) | 0.0377 (9) | 0.0385 (10) | −0.0179 (8) | −0.0035 (8) | −0.0086 (8) |
O2 | 0.0652 (13) | 0.0377 (10) | 0.0497 (12) | −0.0220 (9) | −0.0127 (10) | −0.0120 (9) |
O3 | 0.0550 (11) | 0.0384 (10) | 0.0337 (10) | −0.0069 (9) | 0.0005 (8) | −0.0133 (8) |
N1 | 0.0428 (11) | 0.0283 (10) | 0.0305 (10) | −0.0098 (9) | −0.0088 (9) | −0.0028 (8) |
N2 | 0.0365 (11) | 0.0364 (11) | 0.0323 (11) | −0.0080 (9) | −0.0091 (8) | −0.0051 (8) |
C1 | 0.0402 (12) | 0.0325 (12) | 0.0289 (12) | −0.0128 (10) | −0.0085 (10) | −0.0034 (9) |
C2 | 0.0629 (18) | 0.0461 (15) | 0.0305 (13) | −0.0210 (14) | −0.0052 (12) | −0.0024 (11) |
C3 | 0.085 (2) | 0.0531 (17) | 0.0346 (15) | −0.0333 (17) | −0.0120 (15) | 0.0090 (13) |
C4 | 0.091 (2) | 0.0361 (15) | 0.0474 (17) | −0.0274 (16) | −0.0261 (17) | 0.0090 (13) |
C5 | 0.0654 (18) | 0.0303 (12) | 0.0399 (15) | −0.0137 (12) | −0.0159 (13) | −0.0001 (11) |
C6 | 0.0411 (13) | 0.0296 (11) | 0.0286 (12) | −0.0077 (10) | −0.0039 (10) | −0.0075 (9) |
C7 | 0.0376 (12) | 0.0299 (11) | 0.0311 (12) | −0.0107 (9) | −0.0054 (10) | −0.0003 (9) |
C8 | 0.0392 (13) | 0.0343 (13) | 0.0462 (15) | −0.0091 (11) | −0.0037 (11) | 0.0001 (11) |
C9 | 0.0345 (13) | 0.0475 (16) | 0.0636 (19) | −0.0135 (12) | −0.0157 (13) | 0.0067 (14) |
C10 | 0.0484 (16) | 0.0564 (18) | 0.0567 (18) | −0.0188 (14) | −0.0259 (14) | 0.0031 (14) |
C11 | 0.0460 (15) | 0.0518 (16) | 0.0385 (15) | −0.0114 (13) | −0.0155 (12) | −0.0079 (12) |
C12 | 0.0454 (13) | 0.0280 (11) | 0.0329 (12) | −0.0109 (10) | −0.0121 (10) | −0.0039 (9) |
Ni1—O1 | 2.0445 (18) | N2—C11 | 1.346 (3) |
Ni1—O1i | 2.0445 (18) | C1—C2 | 1.384 (4) |
Ni1—N2 | 2.073 (2) | C1—C6 | 1.527 (3) |
Ni1—N2i | 2.073 (2) | C2—C3 | 1.381 (4) |
Ni1—N1 | 2.079 (2) | C3—C4 | 1.379 (5) |
Ni1—N1i | 2.079 (2) | C4—C5 | 1.370 (4) |
O1—C12 | 1.261 (3) | C6—C7 | 1.529 (4) |
O2—C12 | 1.233 (3) | C6—C12 | 1.561 (4) |
O3—C6 | 1.404 (3) | C7—C8 | 1.392 (4) |
N1—C1 | 1.340 (3) | C8—C9 | 1.383 (4) |
N1—C5 | 1.341 (3) | C9—C10 | 1.379 (5) |
N2—C7 | 1.337 (3) | C10—C11 | 1.367 (4) |
O1—Ni1—O1i | 180.0 | N1—C1—C6 | 116.9 (2) |
O1—Ni1—N2 | 86.87 (8) | C2—C1—C6 | 121.4 (2) |
O1i—Ni1—N2 | 93.13 (8) | C3—C2—C1 | 119.0 (3) |
O1—Ni1—N2i | 93.13 (8) | C4—C3—C2 | 119.4 (3) |
O1i—Ni1—N2i | 86.87 (8) | C5—C4—C3 | 118.4 (3) |
N2—Ni1—N2i | 180.0 | N1—C5—C4 | 123.0 (3) |
O1—Ni1—N1 | 87.04 (8) | O3—C6—C1 | 109.4 (2) |
O1i—Ni1—N1 | 92.96 (8) | O3—C6—C7 | 109.8 (2) |
N2—Ni1—N1 | 84.90 (9) | C1—C6—C7 | 109.8 (2) |
N2i—Ni1—N1 | 95.10 (9) | O3—C6—C12 | 108.7 (2) |
O1—Ni1—N1i | 92.96 (8) | C1—C6—C12 | 109.6 (2) |
O1i—Ni1—N1i | 87.04 (8) | C7—C6—C12 | 109.6 (2) |
N2—Ni1—N1i | 95.10 (9) | N2—C7—C8 | 121.7 (2) |
N2i—Ni1—N1i | 84.90 (9) | N2—C7—C6 | 116.8 (2) |
N1—Ni1—N1i | 180.00 (11) | C8—C7—C6 | 121.4 (2) |
C12—O1—Ni1 | 121.67 (17) | C9—C8—C7 | 118.7 (3) |
C1—N1—C5 | 118.6 (2) | C10—C9—C8 | 119.5 (3) |
C1—N1—Ni1 | 119.03 (17) | C11—C10—C9 | 118.5 (3) |
C5—N1—Ni1 | 122.39 (19) | N2—C11—C10 | 123.0 (3) |
C7—N2—C11 | 118.6 (2) | O2—C12—O1 | 127.1 (3) |
C7—N2—Ni1 | 119.36 (17) | O2—C12—C6 | 115.4 (2) |
C11—N2—Ni1 | 122.06 (18) | O1—C12—C6 | 117.5 (2) |
N1—C1—C2 | 121.7 (2) |
Symmetry code: (i) −x, −y, −z. |
[Ni(C12H9N2O3)2] | F(000) = 532 |
Mr = 517.13 | Dx = 1.598 Mg m−3 |
Monoclinic, P21 | Cu Kα radiation, λ = 1.54180 Å |
a = 7.7763 (8) Å | Cell parameters from 25 reflections |
b = 15.736 (2) Å | θ = 11.7–37.6° |
c = 8.8390 (14) Å | µ = 1.76 mm−1 |
β = 96.560 (11)° | T = 293 K |
V = 1074.5 (2) Å3 | Parallelepiped, pale purple |
Z = 2 | 0.11 × 0.10 × 0.07 mm |
Enraf-Nonius CAD-4 diffractometer | 2102 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.034 |
None monochromator | θmax = 74.6°, θmin = 5.0° |
ω–2θ scans | h = −9→9 |
Absorption correction: numerical (SHELX76; Sheldrick, 1976) | k = −19→1 |
Tmin = 0.776, Tmax = 0.905 | l = −1→11 |
2922 measured reflections | 3 standard reflections every 120 min |
2445 independent reflections | intensity decay: none |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.044 | Only H-atom displacement parameters refined |
wR(F2) = 0.116 | w = 1/[σ2(Fo2) + (0.0605P)2 + 0.3968P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max < 0.001 |
2445 reflections | Δρmax = 0.43 e Å−3 |
321 parameters | Δρmin = −0.56 e Å−3 |
1 restraint | Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881 |
Primary atom site location: heavy-atom method | Absolute structure parameter: 0.48 (10) |
[Ni(C12H9N2O3)2] | V = 1074.5 (2) Å3 |
Mr = 517.13 | Z = 2 |
Monoclinic, P21 | Cu Kα radiation |
a = 7.7763 (8) Å | µ = 1.76 mm−1 |
b = 15.736 (2) Å | T = 293 K |
c = 8.8390 (14) Å | 0.11 × 0.10 × 0.07 mm |
β = 96.560 (11)° |
Enraf-Nonius CAD-4 diffractometer | 2102 reflections with I > 2σ(I) |
Absorption correction: numerical (SHELX76; Sheldrick, 1976) | Rint = 0.034 |
Tmin = 0.776, Tmax = 0.905 | 3 standard reflections every 120 min |
2922 measured reflections | intensity decay: none |
2445 independent reflections |
R[F2 > 2σ(F2)] = 0.044 | Only H-atom displacement parameters refined |
wR(F2) = 0.116 | Δρmax = 0.43 e Å−3 |
S = 1.05 | Δρmin = −0.56 e Å−3 |
2445 reflections | Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881 |
321 parameters | Absolute structure parameter: 0.48 (10) |
1 restraint |
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 | ||
Ni1 | 0.06566 (10) | 0.00000 (11) | 0.19905 (9) | 0.0315 (2) | |
O1 | −0.0175 (5) | 0.1067 (3) | 0.3003 (4) | 0.0398 (9) | |
O2 | 0.0463 (6) | 0.2131 (3) | 0.4645 (6) | 0.0601 (13) | |
O3 | 0.3513 (6) | 0.1652 (3) | 0.5556 (4) | 0.0474 (10) | |
O4 | 0.1582 (5) | −0.1062 (3) | 0.1043 (4) | 0.0414 (9) | |
O5 | 0.1193 (7) | −0.2071 (3) | −0.0720 (5) | 0.0579 (12) | |
O6 | −0.1919 (6) | −0.1676 (4) | −0.1711 (5) | 0.0587 (12) | |
N1 | 0.1676 (5) | −0.0359 (3) | 0.4172 (5) | 0.0332 (10) | |
N2 | 0.2985 (5) | 0.0616 (3) | 0.1862 (5) | 0.0346 (10) | |
N3 | −0.0344 (6) | 0.0363 (3) | −0.0190 (5) | 0.0348 (10) | |
N4 | −0.1660 (6) | −0.0663 (3) | 0.1997 (5) | 0.0383 (10) | |
C1 | 0.2567 (6) | 0.0216 (3) | 0.5067 (6) | 0.0319 (12) | |
C2 | 0.3369 (7) | 0.0010 (6) | 0.6494 (6) | 0.0459 (12) | |
H2 | 0.3995 | 0.0416 | 0.7091 | 0.042 (9)* | |
C3 | 0.3222 (8) | −0.0816 (5) | 0.7017 (7) | 0.0512 (16) | |
H3 | 0.3751 | −0.0967 | 0.7976 | 0.042 (9)* | |
C4 | 0.2300 (8) | −0.1407 (4) | 0.6127 (7) | 0.0465 (15) | |
H4 | 0.2174 | −0.1959 | 0.6472 | 0.042 (9)* | |
C5 | 0.1556 (8) | −0.1157 (4) | 0.4685 (6) | 0.0382 (12) | |
H5 | 0.0955 | −0.1557 | 0.4057 | 0.042 (9)* | |
C6 | 0.2673 (7) | 0.1113 (4) | 0.4439 (6) | 0.0362 (12) | |
C7 | 0.3641 (7) | 0.1107 (4) | 0.3028 (6) | 0.0356 (11) | |
C8 | 0.5144 (8) | 0.1577 (4) | 0.2978 (8) | 0.0458 (14) | |
H8 | 0.5576 | 0.1913 | 0.3799 | 0.054 (10)* | |
C9 | 0.5993 (9) | 0.1535 (5) | 0.1675 (8) | 0.0479 (15) | |
H9 | 0.6998 | 0.1845 | 0.1602 | 0.054 (10)* | |
C10 | 0.5305 (8) | 0.1023 (5) | 0.0503 (7) | 0.0516 (16) | |
H10 | 0.5851 | 0.0977 | −0.0376 | 0.054 (10)* | |
C11 | 0.3820 (7) | 0.0579 (4) | 0.0630 (6) | 0.0423 (13) | |
H11 | 0.3373 | 0.0237 | −0.0179 | 0.054 (10)* | |
C12 | 0.0788 (8) | 0.1475 (4) | 0.3971 (6) | 0.0389 (13) | |
C13 | −0.1087 (7) | −0.0226 (4) | −0.1154 (6) | 0.0385 (14) | |
C14 | −0.1757 (8) | −0.0009 (6) | −0.2625 (6) | 0.0513 (14) | |
H14 | −0.2260 | −0.0423 | −0.3284 | 0.082 (14)* | |
C15 | −0.1679 (10) | 0.0814 (5) | −0.3103 (8) | 0.0614 (19) | |
H15 | −0.2122 | 0.0964 | −0.4089 | 0.082 (14)* | |
C16 | −0.0947 (9) | 0.1410 (5) | −0.2124 (7) | 0.0549 (17) | |
H16 | −0.0899 | 0.1975 | −0.2423 | 0.082 (14)* | |
C17 | −0.0267 (9) | 0.1162 (4) | −0.0659 (7) | 0.0439 (14) | |
H17 | 0.0254 | 0.1568 | 0.0007 | 0.082 (14)* | |
C18 | −0.1147 (7) | −0.1134 (4) | −0.0546 (6) | 0.0386 (13) | |
C19 | −0.2224 (7) | −0.1158 (4) | 0.0824 (6) | 0.0377 (12) | |
C20 | −0.3670 (8) | −0.1676 (5) | 0.0800 (8) | 0.0511 (15) | |
H20 | −0.4017 | −0.2023 | −0.0030 | 0.064 (11)* | |
C21 | −0.4569 (8) | −0.1656 (6) | 0.2047 (9) | 0.057 (2) | |
H21 | −0.5554 | −0.1989 | 0.2066 | 0.064 (11)* | |
C22 | −0.4018 (8) | −0.1147 (5) | 0.3267 (8) | 0.0572 (18) | |
H22 | −0.4609 | −0.1142 | 0.4125 | 0.064 (11)* | |
C23 | −0.2584 (8) | −0.0646 (5) | 0.3206 (7) | 0.0461 (14) | |
H23 | −0.2238 | −0.0284 | 0.4017 | 0.064 (11)* | |
C24 | 0.0711 (8) | −0.1459 (4) | −0.0035 (6) | 0.0388 (12) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.0312 (3) | 0.0352 (4) | 0.0281 (3) | −0.0017 (4) | 0.0039 (3) | −0.0009 (4) |
O1 | 0.039 (2) | 0.041 (2) | 0.039 (2) | 0.0071 (17) | 0.0049 (16) | 0.0006 (19) |
O2 | 0.071 (3) | 0.042 (3) | 0.067 (3) | 0.014 (2) | 0.005 (2) | −0.018 (2) |
O3 | 0.062 (3) | 0.044 (2) | 0.034 (2) | −0.013 (2) | −0.0027 (18) | −0.0121 (18) |
O4 | 0.0359 (18) | 0.042 (2) | 0.046 (2) | 0.0019 (17) | 0.0041 (16) | −0.006 (2) |
O5 | 0.079 (3) | 0.041 (2) | 0.056 (3) | 0.004 (2) | 0.020 (2) | −0.008 (2) |
O6 | 0.071 (3) | 0.061 (3) | 0.043 (2) | −0.021 (3) | −0.001 (2) | −0.017 (2) |
N1 | 0.038 (2) | 0.031 (2) | 0.030 (2) | 0.0031 (19) | 0.0026 (18) | 0.0011 (19) |
N2 | 0.036 (2) | 0.036 (2) | 0.033 (2) | −0.007 (2) | 0.0080 (17) | −0.001 (2) |
N3 | 0.036 (2) | 0.041 (2) | 0.028 (2) | −0.004 (2) | 0.0053 (18) | 0.001 (2) |
N4 | 0.036 (2) | 0.042 (3) | 0.038 (2) | −0.003 (2) | 0.0078 (18) | −0.001 (2) |
C1 | 0.033 (2) | 0.035 (3) | 0.028 (2) | −0.0012 (19) | 0.0028 (19) | −0.001 (2) |
C2 | 0.049 (3) | 0.054 (3) | 0.034 (2) | −0.004 (4) | −0.001 (2) | −0.001 (4) |
C3 | 0.056 (3) | 0.062 (4) | 0.034 (3) | −0.002 (3) | −0.001 (3) | 0.010 (3) |
C4 | 0.051 (3) | 0.043 (3) | 0.048 (3) | 0.015 (3) | 0.015 (3) | 0.018 (3) |
C5 | 0.046 (3) | 0.030 (3) | 0.039 (3) | 0.001 (3) | 0.005 (2) | 0.004 (2) |
C6 | 0.043 (3) | 0.035 (3) | 0.031 (3) | −0.006 (2) | 0.002 (2) | −0.007 (2) |
C7 | 0.036 (2) | 0.038 (3) | 0.033 (3) | −0.004 (2) | 0.004 (2) | −0.001 (2) |
C8 | 0.042 (3) | 0.043 (3) | 0.051 (3) | −0.008 (3) | 0.000 (3) | 0.001 (3) |
C9 | 0.037 (3) | 0.047 (4) | 0.060 (4) | −0.008 (3) | 0.008 (3) | 0.008 (3) |
C10 | 0.047 (3) | 0.062 (4) | 0.048 (3) | −0.002 (3) | 0.016 (3) | 0.009 (3) |
C11 | 0.038 (3) | 0.051 (4) | 0.040 (3) | −0.009 (3) | 0.011 (2) | −0.008 (3) |
C12 | 0.047 (3) | 0.036 (3) | 0.035 (3) | 0.002 (3) | 0.006 (2) | 0.003 (2) |
C13 | 0.043 (3) | 0.046 (4) | 0.026 (2) | 0.000 (2) | 0.005 (2) | 0.000 (2) |
C14 | 0.062 (3) | 0.061 (4) | 0.030 (2) | −0.009 (5) | −0.002 (2) | −0.003 (4) |
C15 | 0.076 (4) | 0.069 (5) | 0.037 (3) | −0.004 (4) | −0.005 (3) | 0.014 (3) |
C16 | 0.071 (5) | 0.051 (4) | 0.043 (3) | 0.002 (4) | 0.004 (3) | 0.010 (3) |
C17 | 0.050 (3) | 0.041 (3) | 0.041 (3) | 0.001 (3) | 0.008 (3) | 0.005 (3) |
C18 | 0.044 (3) | 0.042 (3) | 0.030 (3) | −0.009 (3) | 0.001 (2) | −0.007 (2) |
C19 | 0.037 (3) | 0.032 (3) | 0.044 (3) | −0.006 (2) | 0.001 (2) | 0.002 (2) |
C20 | 0.045 (3) | 0.050 (4) | 0.056 (4) | −0.014 (3) | 0.000 (3) | 0.007 (3) |
C21 | 0.029 (3) | 0.065 (5) | 0.078 (5) | −0.007 (3) | 0.007 (3) | 0.019 (4) |
C22 | 0.040 (3) | 0.073 (5) | 0.063 (4) | 0.000 (3) | 0.025 (3) | 0.010 (4) |
C23 | 0.044 (3) | 0.056 (4) | 0.040 (3) | 0.000 (3) | 0.014 (2) | 0.004 (3) |
C24 | 0.052 (3) | 0.026 (3) | 0.039 (3) | −0.002 (2) | 0.013 (3) | −0.001 (2) |
Ni1—O4 | 2.037 (4) | C1—C6 | 1.523 (8) |
Ni1—O1 | 2.042 (4) | C2—C3 | 1.389 (11) |
Ni1—N2 | 2.069 (4) | C3—C4 | 1.367 (9) |
Ni1—N3 | 2.075 (4) | C4—C5 | 1.395 (8) |
Ni1—N1 | 2.077 (4) | C6—C7 | 1.529 (7) |
Ni1—N4 | 2.082 (5) | C6—C12 | 1.583 (8) |
O1—C12 | 1.249 (7) | C7—C8 | 1.388 (8) |
O2—C12 | 1.232 (7) | C8—C9 | 1.392 (9) |
O3—C6 | 1.405 (6) | C9—C10 | 1.372 (10) |
O4—C24 | 1.269 (7) | C10—C11 | 1.365 (8) |
O5—C24 | 1.218 (7) | C13—C14 | 1.387 (7) |
O6—C18 | 1.416 (7) | C13—C18 | 1.530 (8) |
N1—C1 | 1.341 (6) | C14—C15 | 1.366 (12) |
N1—C5 | 1.342 (7) | C15—C16 | 1.356 (10) |
N2—C11 | 1.331 (7) | C16—C17 | 1.398 (8) |
N2—C7 | 1.341 (7) | C18—C19 | 1.549 (8) |
N3—C17 | 1.327 (8) | C18—C24 | 1.551 (8) |
N3—C13 | 1.343 (7) | C19—C20 | 1.388 (8) |
N4—C19 | 1.331 (7) | C20—C21 | 1.371 (9) |
N4—C23 | 1.355 (7) | C21—C22 | 1.372 (11) |
C1—C2 | 1.380 (7) | C22—C23 | 1.372 (9) |
O4—Ni1—O1 | 177.53 (17) | C1—C6—C7 | 110.1 (5) |
O4—Ni1—N2 | 90.52 (17) | O3—C6—C12 | 108.0 (5) |
O1—Ni1—N2 | 87.83 (19) | C1—C6—C12 | 110.0 (5) |
O4—Ni1—N3 | 87.50 (18) | C7—C6—C12 | 108.4 (4) |
O1—Ni1—N3 | 94.42 (18) | N2—C7—C8 | 122.0 (5) |
N2—Ni1—N3 | 93.30 (18) | N2—C7—C6 | 116.9 (5) |
O4—Ni1—N1 | 92.50 (18) | C8—C7—C6 | 121.2 (5) |
O1—Ni1—N1 | 85.56 (17) | C7—C8—C9 | 118.8 (6) |
N2—Ni1—N1 | 86.27 (18) | C10—C9—C8 | 118.1 (6) |
N3—Ni1—N1 | 179.6 (2) | C11—C10—C9 | 119.9 (6) |
O4—Ni1—N4 | 86.37 (19) | N2—C11—C10 | 122.8 (6) |
O1—Ni1—N4 | 95.33 (18) | O2—C12—O1 | 128.5 (6) |
N2—Ni1—N4 | 176.4 (2) | O2—C12—C6 | 114.2 (5) |
N3—Ni1—N4 | 84.70 (18) | O1—C12—C6 | 117.3 (5) |
N1—Ni1—N4 | 95.73 (19) | N3—C13—C14 | 120.9 (6) |
C12—O1—Ni1 | 121.9 (4) | N3—C13—C18 | 116.7 (4) |
C24—O4—Ni1 | 122.0 (4) | C14—C13—C18 | 122.4 (6) |
C1—N1—C5 | 118.8 (5) | C15—C14—C13 | 119.9 (7) |
C1—N1—Ni1 | 118.8 (4) | C16—C15—C14 | 119.2 (6) |
C5—N1—Ni1 | 122.3 (4) | C15—C16—C17 | 119.0 (7) |
C11—N2—C7 | 118.4 (5) | N3—C17—C16 | 121.9 (6) |
C11—N2—Ni1 | 122.4 (4) | O6—C18—C13 | 109.5 (5) |
C7—N2—Ni1 | 119.1 (3) | O6—C18—C19 | 109.4 (5) |
C17—N3—C13 | 119.1 (5) | C13—C18—C19 | 109.7 (5) |
C17—N3—Ni1 | 121.7 (4) | O6—C18—C24 | 108.4 (5) |
C13—N3—Ni1 | 119.2 (4) | C13—C18—C24 | 110.2 (5) |
C19—N4—C23 | 118.0 (5) | C19—C18—C24 | 109.5 (4) |
C19—N4—Ni1 | 119.9 (4) | N4—C19—C20 | 123.4 (6) |
C23—N4—Ni1 | 122.0 (4) | N4—C19—C18 | 115.8 (5) |
N1—C1—C2 | 122.1 (6) | C20—C19—C18 | 120.8 (5) |
N1—C1—C6 | 117.1 (4) | C21—C20—C19 | 117.5 (7) |
C2—C1—C6 | 120.8 (5) | C20—C21—C22 | 120.2 (6) |
C1—C2—C3 | 118.5 (6) | C23—C22—C21 | 119.1 (6) |
C4—C3—C2 | 120.2 (5) | N4—C23—C22 | 121.8 (6) |
C3—C4—C5 | 118.0 (6) | O5—C24—O4 | 126.5 (6) |
N1—C5—C4 | 122.4 (6) | O5—C24—C18 | 116.4 (5) |
O3—C6—C1 | 110.1 (4) | O4—C24—C18 | 117.1 (5) |
O3—C6—C7 | 110.2 (5) |
Experimental details
(tri) | (mono) | |
Crystal data | ||
Chemical formula | [Ni(C12H9N2O3)2] | [Ni(C12H9N2O3)2] |
Mr | 517.13 | 517.13 |
Crystal system, space group | Triclinic, P1 | Monoclinic, P21 |
Temperature (K) | 293 | 293 |
a, b, c (Å) | 7.6800 (11), 8.576 (2), 8.889 (2) | 7.7763 (8), 15.736 (2), 8.8390 (14) |
α, β, γ (°) | 88.29 (2), 78.46 (2), 67.29 (2) | 90, 96.560 (11), 90 |
V (Å3) | 528.40 (18) | 1074.5 (2) |
Z | 1 | 2 |
Radiation type | Cu Kα | Cu Kα |
µ (mm−1) | 1.79 | 1.76 |
Crystal size (mm) | 0.17 × 0.11 × 0.08 | 0.11 × 0.10 × 0.07 |
Data collection | ||
Diffractometer | Enraf-Nonius CAD-4 diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | Numerical (SHELX76; Sheldrick, 1976) | Numerical (SHELX76; Sheldrick, 1976) |
Tmin, Tmax | 0.755, 0.875 | 0.776, 0.905 |
No. of measured, independent and observed reflections | 2619, 2168, 1844 [I > 2α(I)] | 2922, 2445, 2102 [I > 2σ(I)] |
Rint | 0.015 | 0.034 |
(sin θ/λ)max (Å−1) | 0.626 | 0.625 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.131, 1.07 | 0.044, 0.116, 1.05 |
No. of reflections | 2168 | 2445 |
No. of parameters | 162 | 321 |
No. of restraints | 0 | 1 |
H-atom treatment | Only H-atom displacement parameters refined | Only H-atom displacement parameters refined |
Δρmax, Δρmin (e Å−3) | 0.55, −0.67 | 0.43, −0.56 |
Absolute structure | ? | Flack H D (1983), Acta Cryst. A39, 876-881 |
Absolute structure parameter | ? | 0.48 (10) |
Computer programs: CAD-4 Software (Enraf-Nonius, 1989), CAD-4 Software, PROCESS_DATA (Gable et al., 1993), SHELXS86 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997).
Ni1—O1 | 2.0445 (18) | O1—C12 | 1.261 (3) |
Ni1—N2 | 2.073 (2) | O2—C12 | 1.233 (3) |
Ni1—N1 | 2.079 (2) | O3—C6 | 1.404 (3) |
O1—Ni1—N2 | 86.87 (8) | C12—O1—Ni1 | 121.67 (17) |
O1—Ni1—N2i | 93.13 (8) | C1—N1—Ni1 | 119.03 (17) |
O1—Ni1—N1 | 87.04 (8) | C5—N1—Ni1 | 122.39 (19) |
N2—Ni1—N1 | 84.90 (9) | C7—N2—Ni1 | 119.36 (17) |
O1—Ni1—N1i | 92.96 (8) | C11—N2—Ni1 | 122.06 (18) |
N2—Ni1—N1i | 95.10 (9) | O2—C12—O1 | 127.1 (3) |
Symmetry code: (i) −x, −y, −z. |
Ni1—O4 | 2.037 (4) | O1—C12 | 1.249 (7) |
Ni1—O1 | 2.042 (4) | O2—C12 | 1.232 (7) |
Ni1—N2 | 2.069 (4) | O3—C6 | 1.405 (6) |
Ni1—N3 | 2.075 (4) | O4—C24 | 1.269 (7) |
Ni1—N1 | 2.077 (4) | O5—C24 | 1.218 (7) |
Ni1—N4 | 2.082 (5) | O6—C18 | 1.416 (7) |
O4—Ni1—O1 | 177.53 (17) | N1—Ni1—N4 | 95.73 (19) |
O4—Ni1—N2 | 90.52 (17) | C12—O1—Ni1 | 121.9 (4) |
O1—Ni1—N2 | 87.83 (19) | C24—O4—Ni1 | 122.0 (4) |
O4—Ni1—N3 | 87.50 (18) | C1—N1—Ni1 | 118.8 (4) |
O1—Ni1—N3 | 94.42 (18) | C5—N1—Ni1 | 122.3 (4) |
N2—Ni1—N3 | 93.30 (18) | C11—N2—Ni1 | 122.4 (4) |
O4—Ni1—N1 | 92.50 (18) | C7—N2—Ni1 | 119.1 (3) |
O1—Ni1—N1 | 85.56 (17) | C17—N3—Ni1 | 121.7 (4) |
N2—Ni1—N1 | 86.27 (18) | C13—N3—Ni1 | 119.2 (4) |
N3—Ni1—N1 | 179.6 (2) | C19—N4—Ni1 | 119.9 (4) |
O4—Ni1—N4 | 86.37 (19) | C23—N4—Ni1 | 122.0 (4) |
O1—Ni1—N4 | 95.33 (18) | O2—C12—O1 | 128.5 (6) |
N2—Ni1—N4 | 176.4 (2) | O5—C24—O4 | 126.5 (6) |
N3—Ni1—N4 | 84.70 (18) |
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As part of a broad study to examine relatively simple chelating ligands which have the potential to bridge metal centres, the reaction between 2,2'-pyridoin, (I), and nickel nitrate in the presence of base was investigated. From the initial reaction mixture pale-mauve triclinic centrosymmetric crystals of bis(pyridilate)nickel(II), (II), were obtained. This complex, which has been reported previously (Black, 1967; Black & Srivastare, 1969) but was not crystallographically characterized, can be obtained by the metal-promoted rearrangement of 2,2'-pyridil, (III), in basic solution. The reaction is analogous to the benzilic acid rearrangement which applies broadly to aromatic α-diketones (Selman & Eastham, 1960). We propose that oxidation of (I) to (III) occurs in our mixture and this is followed by the rearrangement reported by Black.
Analysis of the geometry of the bonds in the complex suggests very little strain. From a consideration of bond angles at donor atoms, it appears that non-bonded electron pairs are oriented directly towards the octahedral nickel centre. The complementary relationship between the geometry of the tridentate ligand and the octahedral metal centre suggests that this monoanion and substituted derivatives have potential as blocking ligands when three vacant facial sites on an octahedral metal centre are required.
Further attempts at the above reaction yielded monoclinic crystals with systematic absences consistent with the space groups P21 and P21/m. Despite a thorough investigation, a solution could only be obtained in the space group P21. The monoclinic form shows the absence of crystallographic symmetry within the complex leading to an asymmetric unit twice the size of the triclinic form.