metal-organic compounds
The title complex, [Tb(C11H12N2O)6]I3, has essentially the same structure at 160 K as at room temperature, and is clearly centrosymmetric without any disorder, contrary to some proposals regarding the possible mechanism of triboluminescence. Terbium has an octahedral coordination and lies in a position of symmetry, with all six antipyrine ligands crystallographically equivalent. One iodide anion lies in a special position of site symmetry , and another is on a threefold rotation axis, to give three iodide anions per terbium-centred complex cation.
Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802005093/na6149sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802005093/na6149Isup2.hkl |
CCDC reference: 183769
Key indicators
- Single-crystal X-ray study
- T = 160 K
- Mean (C-C) = 0.004 Å
- R factor = 0.019
- wR factor = 0.047
- Data-to-parameter ratio = 21.5
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level B:
SYMMS_02 Alert B The unit-cell lengths a and c should be equal for a rhombohedral cell Cell 13.7474 13.7474 31.9658 Angles 90.0000 90.0000 120.0000 SYMMS_02 Alert B Cell angles alpha and gamma should be equal for a rhombohedral cell Cell 13.7474 13.7474 31.9658 Angles 90.0000 90.0000 120.0000 SYMMS_02 Alert B All angles should not be 90 for a rhombohedral cell Cell 13.7474 13.7474 31.9658 Angles 90.0000 90.0000 120.0000
Alert Level C:
PLAT_030 Alert C Refined Extinction parameter within range .... 3.00 Sigma General Notes
ABSTM_02 When printed, the submitted absorption T values will be replaced by the scaled T values. Since the ratio of scaled T's is identical to the ratio of reported T values, the scaling does not imply a change to the absorption corrections used in the study. Ratio of Tmax expected/reported 0.878 Tmax scaled 0.432 Tmin scaled 0.340
0 Alert Level A = Potentially serious problem
3 Alert Level B = Potential problem
1 Alert Level C = Please check
Computing details top
Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997b); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and local programs.
(I) top
Crystal data top
[Tb(C11H12N2O)6]I3 | F(000) = 2472 |
Mr = 1668.98 | Dx = 1.589 Mg m−3 |
Rhombohedral, R3 | Mo Kα radiation, λ = 0.71073 Å |
a = 13.7474 (3) Å | Cell parameters from 12573 reflections |
c = 31.9658 (14) Å | θ = 3.0–28.9° |
α = 90° | µ = 2.40 mm−1 |
γ = 120° | T = 160 K |
V = 5231.9 (3) Å3 | Block, colourless |
Z = 3 | 0.50 × 0.40 × 0.35 mm |
Data collection top
Bruker SMART 1K CCD diffractometer | 2945 independent reflections |
Radiation source: sealed tube | 2692 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.020 |
Detector resolution: 8.192 pixels mm-1 | θmax = 28.9°, θmin = 1.8° |
ω rotation with narrow frames scans | h = −17→17 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1997a) | k = −18→18 |
Tmin = 0.387, Tmax = 0.492 | l = −43→43 |
15672 measured reflections |
Refinement top
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)] = 0.019 | H-atom parameters constrained |
wR(F2) = 0.047 | w = 1/[σ2(Fo2) + (0.0204P)2 + 8.1659P] where P = (Fo2 + 2Fc2)/3 |
S = 1.10 | (Δ/σ)max < 0.001 |
2945 reflections | Δρmax = 0.35 e Å−3 |
137 parameters | Δρmin = −0.77 e Å−3 |
0 restraints | Extinction correction: SHELXTL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.00009 (3) |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
x | y | z | Uiso*/Ueq | ||
Tb | 0.0000 | 0.0000 | 0.0000 | 0.01863 (6) | |
O1 | −0.11349 (10) | 0.02865 (10) | 0.04196 (4) | 0.0281 (3) | |
N1 | −0.33249 (14) | 0.04546 (16) | 0.08622 (5) | 0.0415 (4) | |
N2 | −0.27309 (12) | 0.04007 (13) | 0.05215 (5) | 0.0298 (3) | |
C1 | −0.18594 (14) | 0.02658 (14) | 0.06669 (5) | 0.0253 (3) | |
C2 | −0.19706 (17) | 0.01697 (17) | 0.11044 (6) | 0.0363 (4) | |
H2 | −0.1500 | 0.0058 | 0.1293 | 0.044* | |
C3 | −0.28844 (19) | 0.0268 (2) | 0.12084 (6) | 0.0447 (5) | |
C4 | −0.3408 (3) | 0.0167 (3) | 0.16288 (8) | 0.0754 (9) | |
H4A | −0.3537 | 0.0800 | 0.1671 | 0.113* | |
H4B | −0.2903 | 0.0176 | 0.1847 | 0.113* | |
H4C | −0.4125 | −0.0539 | 0.1644 | 0.113* | |
C5 | −0.44747 (18) | 0.0240 (2) | 0.08044 (9) | 0.0561 (6) | |
H5A | −0.5010 | −0.0523 | 0.0898 | 0.084* | |
H5B | −0.4602 | 0.0320 | 0.0508 | 0.084* | |
H5C | −0.4580 | 0.0782 | 0.0969 | 0.084* | |
C6 | −0.27165 (14) | 0.09003 (15) | 0.01298 (6) | 0.0286 (3) | |
C7 | −0.26096 (18) | 0.19576 (18) | 0.01085 (9) | 0.0513 (6) | |
H7 | −0.2608 | 0.2346 | 0.0354 | 0.062* | |
C8 | −0.2505 (2) | 0.2430 (2) | −0.02876 (13) | 0.0748 (10) | |
H8 | −0.2436 | 0.3151 | −0.0310 | 0.090* | |
C9 | −0.2498 (2) | 0.1883 (3) | −0.06428 (11) | 0.0733 (10) | |
H9 | −0.2429 | 0.2220 | −0.0909 | 0.088* | |
C10 | −0.25923 (18) | 0.0851 (2) | −0.06136 (7) | 0.0544 (6) | |
H10 | −0.2576 | 0.0474 | −0.0860 | 0.065* | |
C11 | −0.27111 (15) | 0.03450 (17) | −0.02277 (6) | 0.0337 (4) | |
H11 | −0.2788 | −0.0380 | −0.0210 | 0.040* | |
I1 | −0.3333 | 0.3333 | 0.124103 (7) | 0.04370 (8) | |
I2 | −0.3333 | 0.3333 | −0.1667 | 0.05569 (11) |
Atomic displacement parameters (Å2) top
U11 | U22 | U33 | U12 | U13 | U23 | |
Tb | 0.01812 (7) | 0.01812 (7) | 0.01965 (9) | 0.00906 (3) | 0.000 | 0.000 |
O1 | 0.0272 (6) | 0.0347 (6) | 0.0280 (6) | 0.0197 (5) | 0.0042 (5) | 0.0027 (5) |
N1 | 0.0325 (8) | 0.0607 (11) | 0.0376 (9) | 0.0280 (8) | 0.0087 (7) | −0.0089 (8) |
N2 | 0.0265 (7) | 0.0415 (8) | 0.0271 (7) | 0.0214 (7) | 0.0020 (6) | −0.0050 (6) |
C1 | 0.0235 (8) | 0.0262 (8) | 0.0260 (8) | 0.0123 (6) | 0.0005 (6) | −0.0011 (6) |
C2 | 0.0382 (10) | 0.0435 (11) | 0.0251 (9) | 0.0187 (9) | 0.0009 (7) | −0.0009 (8) |
C3 | 0.0459 (12) | 0.0555 (13) | 0.0308 (10) | 0.0239 (10) | 0.0105 (9) | −0.0046 (9) |
C4 | 0.084 (2) | 0.110 (3) | 0.0389 (13) | 0.053 (2) | 0.0273 (13) | 0.0004 (14) |
C5 | 0.0311 (11) | 0.0680 (16) | 0.0738 (17) | 0.0282 (11) | 0.0072 (10) | −0.0171 (13) |
C6 | 0.0212 (7) | 0.0289 (8) | 0.0379 (9) | 0.0142 (7) | −0.0026 (7) | −0.0009 (7) |
C7 | 0.0363 (11) | 0.0365 (11) | 0.0894 (18) | 0.0243 (9) | −0.0062 (11) | −0.0031 (11) |
C8 | 0.0402 (13) | 0.0511 (15) | 0.140 (3) | 0.0280 (12) | 0.0030 (16) | 0.0432 (18) |
C9 | 0.0369 (12) | 0.097 (2) | 0.084 (2) | 0.0323 (14) | 0.0048 (13) | 0.0540 (19) |
C10 | 0.0342 (11) | 0.0852 (18) | 0.0357 (11) | 0.0237 (12) | −0.0052 (9) | 0.0129 (11) |
C11 | 0.0277 (9) | 0.0391 (10) | 0.0323 (9) | 0.0152 (8) | −0.0052 (7) | −0.0014 (8) |
I1 | 0.04874 (10) | 0.04874 (10) | 0.03362 (12) | 0.02437 (5) | 0.000 | 0.000 |
I2 | 0.06590 (16) | 0.06590 (16) | 0.03527 (18) | 0.03295 (8) | 0.000 | 0.000 |
Geometric parameters (Å, º) top
Tb—O1 | 2.2367 (11) | C4—H4B | 0.980 |
Tb—O1i | 2.2367 (11) | C4—H4C | 0.980 |
Tb—O1ii | 2.2367 (11) | C5—H5A | 0.980 |
Tb—O1iii | 2.2367 (11) | C5—H5B | 0.980 |
Tb—O1iv | 2.2367 (11) | C5—H5C | 0.980 |
Tb—O1v | 2.2367 (11) | C6—C7 | 1.388 (3) |
O1—C1 | 1.261 (2) | C6—C11 | 1.376 (3) |
N1—N2 | 1.385 (2) | C7—H7 | 0.950 |
N1—C3 | 1.347 (3) | C7—C8 | 1.397 (4) |
N1—C5 | 1.468 (3) | C8—H8 | 0.950 |
N2—C1 | 1.381 (2) | C8—C9 | 1.364 (5) |
N2—C6 | 1.423 (2) | C9—H9 | 0.950 |
C1—C2 | 1.406 (2) | C9—C10 | 1.363 (4) |
C2—H2 | 0.950 | C10—H10 | 0.950 |
C2—C3 | 1.370 (3) | C10—C11 | 1.385 (3) |
C3—C4 | 1.498 (3) | C11—H11 | 0.950 |
C4—H4A | 0.980 | ||
O1i—Tb—O1ii | 180.0 | C3—C4—H4A | 109.5 |
O1i—Tb—O1iii | 87.75 (4) | C3—C4—H4B | 109.5 |
O1ii—Tb—O1iii | 92.25 (4) | C3—C4—H4C | 109.5 |
O1—Tb—O1i | 92.25 (4) | H4A—C4—H4B | 109.5 |
O1—Tb—O1ii | 87.75 (4) | H4A—C4—H4C | 109.5 |
O1—Tb—O1iii | 92.25 (4) | H4B—C4—H4C | 109.5 |
O1i—Tb—O1iv | 92.25 (4) | N1—C5—H5A | 109.5 |
O1ii—Tb—O1iv | 87.75 (4) | N1—C5—H5B | 109.5 |
O1iii—Tb—O1iv | 180.0 | N1—C5—H5C | 109.5 |
O1—Tb—O1iv | 87.75 (4) | H5A—C5—H5B | 109.5 |
O1i—Tb—O1v | 87.75 (4) | H5A—C5—H5C | 109.5 |
O1ii—Tb—O1v | 92.25 (4) | H5B—C5—H5C | 109.5 |
O1iii—Tb—O1v | 87.75 (4) | N2—C6—C7 | 121.15 (19) |
O1—Tb—O1v | 180.0 | N2—C6—C11 | 117.73 (16) |
O1iv—Tb—O1v | 92.25 (4) | C7—C6—C11 | 120.9 (2) |
Tb—O1—C1 | 170.00 (12) | C6—C7—H7 | 121.2 |
N2—N1—C3 | 107.60 (15) | C6—C7—C8 | 117.6 (3) |
N2—N1—C5 | 119.66 (17) | H7—C7—C8 | 121.2 |
C3—N1—C5 | 127.39 (19) | C7—C8—H8 | 119.1 |
N1—N2—C1 | 108.47 (14) | C7—C8—C9 | 121.8 (2) |
N1—N2—C6 | 122.15 (15) | H8—C8—C9 | 119.1 |
C1—N2—C6 | 123.85 (14) | C8—C9—H9 | 120.2 |
O1—C1—N2 | 120.96 (15) | C8—C9—C10 | 119.6 (2) |
O1—C1—C2 | 132.34 (17) | H9—C9—C10 | 120.2 |
N2—C1—C2 | 106.65 (15) | C9—C10—H10 | 119.7 |
C1—C2—H2 | 126.4 | C9—C10—C11 | 120.6 (3) |
C1—C2—C3 | 107.11 (18) | H10—C10—C11 | 119.7 |
H2—C2—C3 | 126.4 | C6—C11—C10 | 119.5 (2) |
N1—C3—C2 | 109.97 (17) | C6—C11—H11 | 120.2 |
N1—C3—C4 | 120.9 (2) | C10—C11—H11 | 120.2 |
C2—C3—C4 | 129.1 (2) |
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. |