WEO2: Contrasting the Computed Equilibrium Geometries for ScL3, [TiL3]+, CoL3, [ZnL3]-, GaL3 and [GeL3]+ (L = mda) with the Known Crystal Structures for Sc(acac)3, [Ti(acac)3]ClO4, Co(acac)3, Zn3(acac)6, Ga(acac)3 and [Ge(acac)3]ClO4


D3 Equilibrium Geometry for ScL3
Λ Isomer

Sc-O: 2.105 Å, C=O: 1.270 Å, C=C: 1.400 Å
dA-A = 2.754 Å, lA-A = 3.016 Å, dA-A / lA-A = 0.913
Normalized bite = dA-A / Sc-O = 1.308
Bite Angle = 81.73o
D3 Equilibrium Geometry for [TiL3]+
Λ Isomer

Ti-O: 1.958 Å, C=O: 1.283 Å, C=C: 1.394 Å
dA-A = 2.605 Å, lA-A = 2.773 Å, dA-A / lA-A = 0.940
Normalized bite = dA-A / Ti-L = 1.33
Bite Angle = 83.41o
D3 Equilibrium Geometry for CoL3
Λ Isomer

Co-O: 1.902 Å, C=O: 1.268 Å, C=C: 1.398 Å
dA-A = 2.834 Å, lA-A = 2.635 Å, dA-A / lA-A = 1.076
Normalized bite = dA-A / Co-L = 1.49
Bite Angle = 96.31o

D3 Equilibrium Geometry for [ZnL3]-
Λ Isomer

Zn-O: 2.115 Å, C=O: 1.258 Å, C=C: 1.406 Å
dA-A = 2.948 Å, lA-A = 2.995 Å, dA-A / lA-A = 0.984
Normalized bite = dA-A / Zn-O = 1.394
Bite Angle = 88.34o
D3 Equilibrium Geometry for GaL3
Λ Isomer

Ga-O: 1.978 Å, C=O: 1.271 Å, C=C: 1.399 Å
dA-A = 2.832 Å, lA-A = 2.768 Å, dA-A / lA-A = 1.023
Normalized bite = dA-A / Ga-O = 1.432
Bite Angle = 91.42o
D3 Equilibrium Geometry for [GeL3]+
Λ Isomer

Ge-O: 1.891 Å, C=O: 1.288 Å, C=C: 1.391 Å
dA-A = 2.752 Å, lA-A = 2.626 Å, dA-A / lA-A = 1.048
Normalized bite = dA-A / Ge-L = 1.46
Bite Angle = 93.38o
Known Structure for Sc(acac)3
≈ D3 Symmetry, R= 5.0%, Δ Isomer


Sc-O: 2.060 - 2.087 Å Ave = 2.070 Å
C=O: 1.239 - 1.261 Å, Ave = 1.253 Å
C=C: 1.374 - 1.390 Å, Ave = 1.381 Å
Ave dA-A = 2.715 Å, Ave lA-A* = 2.922 Å
dA-A / lA-A = 0.929, Ave Bite Angle = 81.97o
Normalized bite = dA-A / Sc-O = 1.311

Ref: T.J. Anderson, M.A. Neuman, G.A. Melson,
Inorg. Chem., Vol 12, 1973, p. 927.
CSD ID: ACACSc, Ave σ (C-C): 0.011-0.030 Å

Known Structure for [Ti(acac)3]+
≈ D3 Symmetry, R= 6.8%, Λ Isomer


Ti-O: 1.922 - 1.956 Å Ave = 1.940 Å
C=O: 1.285 - 1.294 Å, Ave = 1.290 Å
C=C: 1.372 - 1.392 Å, Ave = 1.384 Å
Ave dA-A = 2.604 Å, Ave lA-A* = 2.706 Å
dA-A / lA-A = 0.992, Ave Bite Angle = 84.28o
Normalized bite = dA-A / Sc-O = 1.342

Ref: U. Thewalt, T. Adam
Z. Naturforsch., B: Chem. Sci., Vol 33, 1978, p. 142.
CSD ID: TIACPC, Ave σ (C-C): 0.001-0.005 Å

Known Structure for Co(acac)3
≈ D3 Symmetry, R = 3.8%,
Λ Isomer


Co-O: 1.878 - 1.891 Å Ave = 1.885 Å
C=O: 1.262 - 1.276 Å, Ave = 1.269 Å
C=C: 1.377 - 1.386 Å, Ave = 1.382 Å
Ave dA-A = 2.814 Å, Ave lA-A = 2.600 Å
dA-A / lA-A = 1.082, Ave Bite Angle = 96.55o
Normalized bite = dA-A / Co-O = 1.492

Ref: G.J. Kriger, E. C. Reynhardt
Acta Crystallogr., Sect. B. Struct. Crystallogr.
Cryst. Chem.
, Vol 30, 1974, p. 822.
CSD ID: CoACAC03, Ave σ (C-C): 0.006-0.010 Å

Known Structure for Zn3(acac)6
with 3 Zn-Zn single bonds, R = 2.6%


Distances for terminal (non-bridging) acacs
Zn-O: 1.972 - 2.001 Å Ave = 1.986 Å
C=O: 1.262 - 1.276 Å, Ave = 1.269 Å
C=C: 1.378 - 1.382 Å, Ave = 1.380 Å
dA-A = 2.828 Å, lA-A = NA
dA-A / lA-A = NA, Bite Angle = 90.76o
Normalized bite = dA-A / Zn-O = 1.424

Ref: M.J. Bennett, F.A. Cotton, R. Eiss
Acta Crystallogr., Sect. B. Struct. Crystallogr.
Cryst. Chem.
, Vol 24, 1968, p. 904.
CDS ID: ZNACAT10, Ave σ (C-C): 0.006-0.010 Å
Known Structure for Ga(acac)3
≈ D3 Symmetry, R = 6.0%, Λ Isomer


Ga-O: 1.943 - 1.973 Å Ave = 1.948 Å
C=O: 1.238 - 1.270 Å, Ave = 1.264 Å
C=C: 1.381 - 1.420 Å, Ave = 1.392 Å
Ave dA-A = 2.808 Å, Ave lA-A = 2.726 Å
dA-A / lA-A = 1.030, Ave Bite Angle = 91.74o
Normalized bite = dA-A / Ga-O = 1.441
Ref: K. Dymock, G.J. Palenik
Acta Crystallogr., Sect. B. Struct. Crystallogr.
Cryst. Chem.
, Vol 30, 1974, p. 1364.
CDS ID: ACACGA, Ave σ (C-C): 0.011-0.030 Å
Known Structure for [Ge(acac)3]+
≈ D3 Symmetry, R= 4.14%, Δ Isomer


Ge-O: 1.860 - 1.875 Å Ave = 1.870 Å
C=O: 1.276 - 1.294 Å, Ave = 1.286 Å
C=C: 1.356 - 1.410 Å, Ave = 1.377 Å
Ave dA-A = 2.723 Å, Ave lA-A* = 2.569 Å
dA-A / lA-A = 1.060, Ave Bite Angle = 93.46o
Normalized bite = dA-A / Ge-O = 1.456

Ref: T. Ito, K. Toriumi, F.B. Ueno, K. Saito
Acta Crystallogr., Sect. B. Struct. Crystallogr.,
Vol 36, 1980, p. 2998
CSD ID: ACACGE, Ave σ (C-C): 0.011-0.030 Å

*The Average lA-A was taken as the average for the shortest interligand contact from each oxygen atom in the structure.