Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100002298/qb0180sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100002298/qb0180Isup2.hkl |
CCDC reference: 143323
The title compound was obtained from the reaction of hydrated Tb(ClO4)3 with antipyrine in a 1:3 molar ratio in MeOH–MeCN mixed medium (v/v 1:1). Vapour diffusion of diethyl ether into the dilute reaction mixture gave colorless crystals suitable for single-crystal X-ray structure determination.
Difference maps indicated that the methyl H atoms at C4 and C5 were possibly disordered and these H atoms were allowed for at C4 and C5 by placing six 0.5 occupancy, equally spaced riding H atoms at these sites.
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SHELXTL (Bruker, 1998); program(s) used to solve structure: SHELXTL; program(s) used to refine structure: SHELXTL; software used to prepare material for publication: SHELXTL.
C66H72N12O6Tb·3(ClO4) | Dx = 1.444 Mg m−3 |
Mr = 1586.63 | Mo Kα radiation, λ = 0.71073 Å |
Trigonal, R3 | Cell parameters from 980 reflections |
a = 13.9691 (10) Å | θ = 2.6–16.8° |
c = 32.390 (3) Å | µ = 1.15 mm−1 |
V = 5473.6 (8) Å3 | T = 293 K |
Z = 3 | Block, colorless |
F(000) = 2436 | 0.21 × 0.15 × 0.06 mm |
Bruker SMART 1K CCD area-detector diffractometer | 2800 independent reflections |
Radiation source: fine-focus sealed tube | 2688 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.054 |
ϕ and ω scans | θmax = 27.5°, θmin = 1.8° |
Absorption correction: multi-scan Multi-scan (Blessing, 1995) | h = −9→18 |
Tmin = 0.793, Tmax = 0.933 | k = −18→18 |
12276 measured reflections | l = −42→39 |
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)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.110 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0697P)2] where P = (Fo2 + 2Fc2)/3 |
2800 reflections | (Δ/σ)max = 0.017 |
160 parameters | Δρmax = 0.80 e Å−3 |
0 restraints | Δρmin = −0.50 e Å−3 |
C66H72N12O6Tb·3(ClO4) | Z = 3 |
Mr = 1586.63 | Mo Kα radiation |
Trigonal, R3 | µ = 1.15 mm−1 |
a = 13.9691 (10) Å | T = 293 K |
c = 32.390 (3) Å | 0.21 × 0.15 × 0.06 mm |
V = 5473.6 (8) Å3 |
Bruker SMART 1K CCD area-detector diffractometer | 2800 independent reflections |
Absorption correction: multi-scan Multi-scan (Blessing, 1995) | 2688 reflections with I > 2σ(I) |
Tmin = 0.793, Tmax = 0.933 | Rint = 0.054 |
12276 measured reflections |
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.110 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.80 e Å−3 |
2800 reflections | Δρmin = −0.50 e Å−3 |
160 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 | Occ. (<1) | |
Tb1 | 0.0000 | 0.0000 | 0.0000 | 0.03472 (15) | |
O1 | −0.11759 (18) | 0.02504 (19) | 0.04133 (7) | 0.0434 (5) | |
N1 | −0.2737 (2) | 0.0377 (2) | 0.05057 (9) | 0.0451 (6) | |
N2 | −0.3318 (3) | 0.0436 (3) | 0.08415 (11) | 0.0645 (9) | |
C1 | −0.1882 (3) | 0.0242 (3) | 0.06515 (10) | 0.0394 (7) | |
C2 | −0.1998 (3) | 0.0159 (3) | 0.10838 (11) | 0.0581 (9) | |
H2 | −0.1551 | 0.0050 | 0.1268 | 0.070* | |
C3 | −0.2884 (4) | 0.0268 (4) | 0.11809 (13) | 0.0698 (12) | |
C4 | −0.3377 (6) | 0.0192 (6) | 0.16031 (17) | 0.122 (3) | |
H4A | −0.3900 | 0.0446 | 0.1588 | 0.182* | 0.50 |
H4B | −0.2800 | 0.0644 | 0.1794 | 0.182* | 0.50 |
H4C | −0.3744 | −0.0562 | 0.1695 | 0.182* | 0.50 |
H4D | −0.3062 | −0.0094 | 0.1797 | 0.182* | 0.50 |
H4E | −0.4163 | −0.0292 | 0.1591 | 0.182* | 0.50 |
H4F | −0.3219 | 0.0914 | 0.1690 | 0.182* | 0.50 |
C5 | −0.4457 (4) | 0.0215 (5) | 0.07828 (19) | 0.0903 (17) | |
H5A | −0.4628 | 0.0141 | 0.0493 | 0.136* | 0.50 |
H5B | −0.4523 | 0.0816 | 0.0894 | 0.136* | 0.50 |
H5C | −0.4963 | −0.0458 | 0.0922 | 0.136* | 0.50 |
H5D | −0.4781 | 0.0192 | 0.1047 | 0.136* | 0.50 |
H5E | −0.4886 | −0.0483 | 0.0646 | 0.136* | 0.50 |
H5F | −0.4447 | 0.0791 | 0.0618 | 0.136* | 0.50 |
C6 | −0.2749 (2) | 0.0830 (3) | 0.01147 (11) | 0.0433 (7) | |
C7 | −0.2754 (3) | 0.0264 (3) | −0.02312 (11) | 0.0507 (8) | |
H7 | −0.2816 | −0.0429 | −0.0207 | 0.061* | |
C8 | −0.2666 (4) | 0.0724 (5) | −0.06146 (15) | 0.0815 (15) | |
H8 | −0.2654 | 0.0340 | −0.0847 | 0.098* | |
C9 | −0.2599 (4) | 0.1685 (7) | −0.0661 (2) | 0.104 (2) | |
H9 | −0.2549 | 0.1971 | −0.0925 | 0.124* | |
C10 | −0.2602 (4) | 0.2273 (5) | −0.0322 (3) | 0.103 (2) | |
H10 | −0.2556 | 0.2956 | −0.0357 | 0.123* | |
C11 | −0.2673 (3) | 0.1857 (4) | 0.00741 (19) | 0.0725 (13) | |
H11 | −0.2670 | 0.2254 | 0.0305 | 0.087* | |
Cl1 | 0.6667 | 0.3333 | 0.11996 (6) | 0.0738 (5) | |
O12 | 0.6667 | 0.3333 | 0.0778 (3) | 0.131 (3) | |
O11 | 0.5646 (6) | 0.2555 (7) | 0.1302 (3) | 0.241 (4) | |
Cl2 | −0.3333 | 0.3333 | −0.1667 | 0.0779 (8) | |
O22 | −0.3333 | 0.3333 | −0.1264 (6) | 0.152 (8) | 0.50 |
O21 | −0.2661 (15) | 0.4378 (11) | −0.1819 (4) | 0.187 (5) | 0.50 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Tb1 | 0.03412 (16) | 0.03412 (16) | 0.0359 (2) | 0.01706 (8) | 0.000 | 0.000 |
O1 | 0.0415 (12) | 0.0572 (14) | 0.0413 (12) | 0.0321 (11) | 0.0085 (9) | 0.0031 (10) |
N1 | 0.0380 (14) | 0.0593 (17) | 0.0432 (15) | 0.0282 (13) | 0.0071 (11) | −0.0071 (13) |
N2 | 0.0486 (18) | 0.089 (2) | 0.061 (2) | 0.0379 (18) | 0.0179 (15) | −0.0116 (18) |
C1 | 0.0376 (15) | 0.0398 (16) | 0.0395 (16) | 0.0185 (13) | 0.0007 (13) | −0.0017 (13) |
C2 | 0.061 (2) | 0.070 (2) | 0.0397 (18) | 0.030 (2) | 0.0048 (16) | 0.0015 (17) |
C3 | 0.070 (3) | 0.086 (3) | 0.043 (2) | 0.032 (2) | 0.0175 (19) | −0.007 (2) |
C4 | 0.143 (6) | 0.165 (7) | 0.061 (3) | 0.081 (5) | 0.049 (4) | −0.001 (4) |
C5 | 0.049 (2) | 0.120 (4) | 0.109 (4) | 0.048 (3) | 0.015 (2) | −0.023 (3) |
C6 | 0.0281 (14) | 0.0443 (17) | 0.060 (2) | 0.0199 (13) | −0.0019 (13) | −0.0021 (15) |
C7 | 0.0483 (19) | 0.059 (2) | 0.0468 (19) | 0.0284 (17) | −0.0064 (15) | −0.0051 (16) |
C8 | 0.065 (3) | 0.122 (5) | 0.053 (3) | 0.044 (3) | −0.012 (2) | 0.007 (3) |
C9 | 0.059 (3) | 0.131 (6) | 0.120 (5) | 0.048 (4) | 0.001 (3) | 0.061 (4) |
C10 | 0.060 (3) | 0.069 (3) | 0.191 (7) | 0.042 (3) | −0.001 (4) | 0.052 (4) |
C11 | 0.051 (2) | 0.056 (2) | 0.123 (4) | 0.036 (2) | −0.008 (2) | −0.008 (2) |
Cl1 | 0.0876 (8) | 0.0876 (8) | 0.0462 (9) | 0.0438 (4) | 0.000 | 0.000 |
O12 | 0.152 (5) | 0.152 (5) | 0.088 (5) | 0.076 (3) | 0.000 | 0.000 |
O11 | 0.179 (7) | 0.227 (9) | 0.250 (8) | 0.050 (6) | 0.121 (6) | 0.064 (7) |
Cl2 | 0.0907 (13) | 0.0907 (13) | 0.0521 (15) | 0.0454 (6) | 0.000 | 0.000 |
O22 | 0.191 (13) | 0.191 (13) | 0.073 (11) | 0.096 (7) | 0.000 | 0.000 |
O21 | 0.202 (15) | 0.155 (11) | 0.177 (15) | 0.070 (10) | 0.057 (12) | 0.064 (10) |
Tb1—O1i | 2.278 (2) | C6—C11 | 1.391 (5) |
Tb1—O1ii | 2.278 (2) | C7—C8 | 1.375 (6) |
Tb1—O1iii | 2.278 (2) | C7—H7 | 0.9300 |
Tb1—O1 | 2.278 (2) | C8—C9 | 1.307 (9) |
Tb1—O1iv | 2.278 (2) | C8—H8 | 0.9300 |
Tb1—O1v | 2.278 (2) | C9—C10 | 1.373 (9) |
O1—C1 | 1.248 (4) | C9—H9 | 0.9300 |
N1—C1 | 1.382 (4) | C10—C11 | 1.392 (9) |
N1—N2 | 1.384 (4) | C10—H10 | 0.9300 |
N1—C6 | 1.420 (5) | C11—H11 | 0.9300 |
N2—C3 | 1.332 (6) | Cl1—O11vi | 1.333 (6) |
N2—C5 | 1.474 (5) | Cl1—O11 | 1.333 (6) |
C1—C2 | 1.408 (5) | Cl1—O11vii | 1.333 (6) |
C2—C3 | 1.357 (6) | Cl1—O12 | 1.365 (8) |
C2—H2 | 0.9300 | Cl2—O22 | 1.303 (18) |
C3—C4 | 1.511 (6) | Cl2—O22viii | 1.303 (18) |
C4—H4A | 0.9600 | Cl2—O21ix | 1.373 (11) |
C4—H4B | 0.9600 | Cl2—O21x | 1.373 (11) |
C4—H4C | 0.9600 | Cl2—O21viii | 1.373 (11) |
C4—H4D | 0.9600 | Cl2—O21 | 1.373 (11) |
C4—H4E | 0.9600 | Cl2—O21xi | 1.373 (11) |
C4—H4F | 0.9600 | Cl2—O21xii | 1.373 (11) |
C5—H5A | 0.9600 | O22—O21ix | 1.516 (16) |
C5—H5B | 0.9600 | O22—O21viii | 1.516 (17) |
C5—H5C | 0.9600 | O22—O21xii | 1.516 (16) |
C5—H5D | 0.9600 | O21—O22viii | 1.516 (16) |
C5—H5E | 0.9600 | O21—O21ix | 1.618 (17) |
C5—H5F | 0.9600 | O21—O21xii | 1.618 (17) |
C6—C7 | 1.370 (5) | ||
O1i—Tb1—O1ii | 180 | H5B—C5—H5F | 56.3 |
O1i—Tb1—O1iii | 88.96 (8) | H5C—C5—H5F | 141.1 |
O1ii—Tb1—O1iii | 91.04 (8) | H5D—C5—H5F | 109.5 |
O1i—Tb1—O1 | 91.04 (8) | H5E—C5—H5F | 109.5 |
O1ii—Tb1—O1 | 88.96 (8) | C7—C6—C11 | 119.6 (4) |
O1iii—Tb1—O1 | 91.04 (8) | C7—C6—N1 | 118.0 (3) |
O1i—Tb1—O1iv | 91.04 (8) | C11—C6—N1 | 122.1 (4) |
O1ii—Tb1—O1iv | 88.96 (8) | C6—C7—C8 | 119.7 (4) |
O1iii—Tb1—O1iv | 180 | C6—C7—H7 | 120.2 |
O1—Tb1—O1iv | 88.96 (8) | C8—C7—H7 | 120.2 |
O1i—Tb1—O1v | 88.96 (8) | C9—C8—C7 | 121.9 (6) |
O1ii—Tb1—O1v | 91.04 (8) | C9—C8—H8 | 119.1 |
O1iii—Tb1—O1v | 88.96 (8) | C7—C8—H8 | 119.1 |
O1—Tb1—O1v | 180 | C8—C9—C10 | 120.2 (6) |
O1iv—Tb1—O1v | 91.04 (8) | C8—C9—H9 | 119.9 |
C1—O1—Tb1 | 171.7 (2) | C10—C9—H9 | 119.9 |
C1—N1—N2 | 108.2 (3) | C9—C10—C11 | 120.5 (5) |
C1—N1—C6 | 124.7 (3) | C9—C10—H10 | 119.7 |
N2—N1—C6 | 122.5 (3) | C11—C10—H10 | 119.7 |
C3—N2—N1 | 107.8 (3) | C6—C11—C10 | 118.1 (5) |
C3—N2—C5 | 127.5 (4) | C6—C11—H11 | 121.0 |
N1—N2—C5 | 119.3 (4) | C10—C11—H11 | 121.0 |
O1—C1—N1 | 121.4 (3) | O11vi—Cl1—O11 | 114.0 (3) |
O1—C1—C2 | 132.3 (3) | O11vi—Cl1—O11vii | 114.0 (3) |
N1—C1—C2 | 106.2 (3) | O11—Cl1—O11vii | 114.0 (3) |
C3—C2—C1 | 107.2 (4) | O11vi—Cl1—O12 | 104.5 (4) |
C3—C2—H2 | 126.4 | O11—Cl1—O12 | 104.5 (4) |
C1—C2—H2 | 126.4 | O11vii—Cl1—O12 | 104.5 (4) |
N2—C3—C2 | 110.5 (3) | O22—Cl2—O22viii | 180 |
N2—C3—C4 | 121.9 (5) | O22—Cl2—O21ix | 68.9 (6) |
C2—C3—C4 | 127.7 (5) | O22viii—Cl2—O21ix | 111.1 (6) |
C3—C4—H4A | 109.5 | O22—Cl2—O21x | 111.1 (6) |
C3—C4—H4B | 109.5 | O22viii—Cl2—O21x | 68.9 (6) |
H4A—C4—H4B | 109.5 | O21ix—Cl2—O21x | 179.998 (4) |
C3—C4—H4C | 109.5 | O22—Cl2—O21viii | 68.9 (6) |
H4A—C4—H4C | 109.5 | O22viii—Cl2—O21viii | 111.1 (6) |
H4B—C4—H4C | 109.5 | O21ix—Cl2—O21viii | 107.8 (7) |
C3—C4—H4D | 109.5 | O21x—Cl2—O21viii | 72.2 (7) |
H4A—C4—H4D | 141.1 | O22—Cl2—O21 | 111.1 (6) |
H4B—C4—H4D | 56.3 | O22viii—Cl2—O21 | 68.9 (6) |
H4C—C4—H4D | 56.3 | O21ix—Cl2—O21 | 72.2 (7) |
C3—C4—H4E | 109.5 | O21x—Cl2—O21 | 107.8 (7) |
H4A—C4—H4E | 56.3 | O21viii—Cl2—O21 | 180 |
H4B—C4—H4E | 141.1 | O22—Cl2—O21xi | 111.1 (6) |
H4C—C4—H4E | 56.3 | O22viii—Cl2—O21xi | 68.9 (6) |
H4D—C4—H4E | 109.5 | O21ix—Cl2—O21xi | 72.2 (7) |
C3—C4—H4F | 109.5 | O21x—Cl2—O21xi | 107.8 (7) |
H4A—C4—H4F | 56.3 | O21viii—Cl2—O21xi | 72.2 (7) |
H4B—C4—H4F | 56.3 | O21—Cl2—O21xi | 107.8 (7) |
H4C—C4—H4F | 141.1 | O22—Cl2—O21xii | 68.9 (6) |
H4D—C4—H4F | 109.5 | O22viii—Cl2—O21xii | 111.1 (6) |
H4E—C4—H4F | 109.5 | O21ix—Cl2—O21xii | 107.8 (7) |
N2—C5—H5A | 109.5 | O21x—Cl2—O21xii | 72.2 (7) |
N2—C5—H5B | 109.5 | O21viii—Cl2—O21xii | 107.8 (7) |
H5A—C5—H5B | 109.5 | O21—Cl2—O21xii | 72.2 (7) |
N2—C5—H5C | 109.5 | O21xi—Cl2—O21xii | 180 |
H5A—C5—H5C | 109.5 | Cl2—O22—O21ix | 57.7 (8) |
H5B—C5—H5C | 109.5 | Cl2—O22—O21viii | 57.7 (8) |
N2—C5—H5D | 109.5 | O21ix—O22—O21viii | 94.1 (10) |
H5A—C5—H5D | 141.1 | Cl2—O22—O21xii | 57.7 (8) |
H5B—C5—H5D | 56.3 | O21ix—O22—O21xii | 94.1 (10) |
H5C—C5—H5D | 56.3 | O21viii—O22—O21xii | 94.1 (10) |
N2—C5—H5E | 109.5 | Cl2—O21—O22viii | 53.4 (8) |
H5A—C5—H5E | 56.3 | Cl2—O21—O21ix | 53.9 (3) |
H5B—C5—H5E | 141.1 | O22viii—O21—O21ix | 89.5 (7) |
H5C—C5—H5E | 56.3 | Cl2—O21—O21xii | 53.9 (3) |
H5D—C5—H5E | 109.5 | O22viii—O21—O21xii | 89.5 (7) |
N2—C5—H5F | 109.5 | O21ix—O21—O21xii | 86.6 (13) |
H5A—C5—H5F | 56.3 |
Symmetry codes: (i) x−y, x, −z; (ii) −x+y, −x, z; (iii) y, −x+y, −z; (iv) −y, x−y, z; (v) −x, −y, −z; (vi) −y+1, x−y, z; (vii) −x+y+1, −x+1, z; (viii) −x−2/3, −y+2/3, −z−1/3; (ix) x−y+1/3, x+2/3, −z−1/3; (x) −x+y−1, −x, z; (xi) −y, x−y+1, z; (xii) y−2/3, −x+y−1/3, −z−1/3. |
Experimental details
Crystal data | |
Chemical formula | C66H72N12O6Tb·3(ClO4) |
Mr | 1586.63 |
Crystal system, space group | Trigonal, R3 |
Temperature (K) | 293 |
a, c (Å) | 13.9691 (10), 32.390 (3) |
V (Å3) | 5473.6 (8) |
Z | 3 |
Radiation type | Mo Kα |
µ (mm−1) | 1.15 |
Crystal size (mm) | 0.21 × 0.15 × 0.06 |
Data collection | |
Diffractometer | Bruker SMART 1K CCD area-detector diffractometer |
Absorption correction | Multi-scan Multi-scan (Blessing, 1995) |
Tmin, Tmax | 0.793, 0.933 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12276, 2800, 2688 |
Rint | 0.054 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.110, 1.04 |
No. of reflections | 2800 |
No. of parameters | 160 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.80, −0.50 |
Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXTL (Bruker, 1998), SHELXTL.
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As a bulky monodentate ligand with hard O atom as donor, antipyrine has long been known to form complexes with transition and alkaline-earth metals, as well as rare-earth metals. Its lanthanide complexes have drawn much attention primarily due to the interest in exploring their luminescent properties. The lanthanide nitrates or iodides react steadily with antipyrine to offer complexes involving three or six antipyrines (Baker & Jeffery, 1974), in which a brilliantly triboluminescent characteristic was found (Rheingold & King, 1989). Our interests in finding highly luminescent terbium(III) or europium(III) complexes led us to synthesize a series of lanthanide complexes incorporating aromatic heterocyclic ligands (Su et al., 1997, 1998, 1999). This paper reports the structure of a terbium(III) antipyrine complexe with perchlorate as counter-anion, (I), which servers as a complement for comparison with the nitrate and iodide complexes.
The X-ray structure estabilshes that (I) consists of a discrete monomeric [Tb(C11H12N2O)6]3+ cation and three perchlorate anions. The central terbium(III) ion is in an octahedral geometry, bonding to O atoms of six antipyrine ligands. The molecule possesses -3 symmetry, with the Tb atom residues at inversion centers. So the six antipyrines are S6 related with only one unique, and the six Tb—O bonds are identical with a distance of 2.278 (2) Å. The O—Tb—O angles of 88.96 (8), 91.04 (8) and 180° closely resemble the theoretical values, indicating that the coordination polyhedral of the terbium(III) ion is normal as predicted by ligand-field theories. The benzene ring and pyrazole ring are both planar with mean-plane equations 12.491X - 0.860Y + 1.516Z = -3.4899 and 1.745X + 11.099 + 2.329Z = 0.0795, and mean deviations of 0.0036 and 0.0133 Å, respectively.
One of the perchlorate anions possesses a threefold axis passing through one Cl—O bond, while another lies on a symmetry center with the O atoms S6 disordered, each set of ClO4- anion possessing half occupancy.