Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270105013594/hj1048sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270105013594/hj1048Isup2.hkl |
CCDC reference: 250665
For the preparation of the title compound, which was carried out under an inert atmosphere, Na2(acacen) (2.149 g, 8.01 mmol), prepared from the reaction of N,N'-ethylenebis(acetylacetoneimine) and NaH, was added slowly via a solid addition funnel to a stirring solution of GaCl3 (1.49 g, 8.00 mmol) in benzene. The reaction was then stirred overnight at room temperature. The yellow solution was filtered and the precipitant was washed with benzene to extract additional product. The solution was dried in vacuo and recrystallized via sublimation to yield yellow crystals suitable for X-ray crystallographic analysis.
A measure of disorder was observed for atoms C11 and C12 and their adjacent positions, with occupancies of approximately 60:40%. H atoms on disordered C atoms were placed in calculated positions and treated using a riding model (C—H = 0.97 Å). All other H atoms were freely refined [C—H = 0.88 (3)–1.05 (3) Å].
Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
[Ga(C12H18N2O2)Cl] | F(000) = 672 |
Mr = 327.45 | Dx = 1.584 Mg m−3 |
Monoclinic, P21/n | Melting point: 204 K |
Hall symbol: -P2yn | Mo Kα radiation, λ = 0.71073 Å |
a = 7.2163 (6) Å | Cell parameters from 2980 reflections |
b = 24.102 (2) Å | θ = 1.7–28.3° |
c = 8.0669 (7) Å | µ = 2.19 mm−1 |
β = 101.776 (1)° | T = 163 K |
V = 1373.5 (2) Å3 | Plate, light yellow |
Z = 4 | 0.33 × 0.20 × 0.12 mm |
Bruker SMART CCD diffractometer | 3298 independent reflections |
Radiation source: fine-focus sealed tube | 2992 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.024 |
ϕ and ω scans | θmax = 28.3°, θmin = 1.7° |
Absorption correction: empirical (using intensity measurements) (SADABS; Bruker, 1998) | h = −9→9 |
Tmin = 0.531, Tmax = 0.779 | k = −31→31 |
14190 measured reflections | l = −10→10 |
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)] = 0.020 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.051 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0217P)2 + 0.5951P] where P = (Fo2 + 2Fc2)/3 |
3298 reflections | (Δ/σ)max = 0.001 |
239 parameters | Δρmax = 0.32 e Å−3 |
0 restraints | Δρmin = −0.25 e Å−3 |
[Ga(C12H18N2O2)Cl] | V = 1373.5 (2) Å3 |
Mr = 327.45 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 7.2163 (6) Å | µ = 2.19 mm−1 |
b = 24.102 (2) Å | T = 163 K |
c = 8.0669 (7) Å | 0.33 × 0.20 × 0.12 mm |
β = 101.776 (1)° |
Bruker SMART CCD diffractometer | 3298 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Bruker, 1998) | 2992 reflections with I > 2σ(I) |
Tmin = 0.531, Tmax = 0.779 | Rint = 0.024 |
14190 measured reflections |
R[F2 > 2σ(F2)] = 0.020 | 0 restraints |
wR(F2) = 0.051 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.08 | Δρmax = 0.32 e Å−3 |
3298 reflections | Δρmin = −0.25 e Å−3 |
239 parameters |
Experimental. Elemental Analyses: Anal·(Chemisar Laboratories, Inc, Guelph, Ontario, Canada). Calc. (found) for C12H18ClGaN2O2: C, 44.01 (44.13); H, 5.54 (5.61)%. 1H(300 MHz, 298 K, C6D6): 1.30 [s, 6H, CH3], 1.89 [s, 6H, CH3], 2.48 [q, JCH = 7 Hz, 2H, = CH2], 3.02 [q, JCH = 7 Hz, 2H, CH2], 4.82 [s, 2H, CH] 13C(75 MHz, 298 K, = C6D6): 27.33, 31.70, 50.00, 103.08, 177.73, 185.43. MS m/z 328 (M + H)+ |
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) | |
Ga1 | 0.42884 (2) | 0.126226 (6) | 0.688556 (18) | 0.01465 (5) | |
Cl1 | 0.24796 (5) | 0.062662 (14) | 0.53377 (4) | 0.02138 (8) | |
O1 | 0.32351 (15) | 0.19524 (4) | 0.59564 (13) | 0.0209 (2) | |
O2 | 0.30059 (16) | 0.14324 (5) | 0.86696 (13) | 0.0238 (2) | |
N1 | 0.64611 (18) | 0.13472 (5) | 0.57333 (17) | 0.0235 (3) | |
N2 | 0.61844 (18) | 0.08040 (5) | 0.84724 (16) | 0.0215 (3) | |
C1 | 0.2578 (3) | 0.27584 (7) | 0.4278 (2) | 0.0308 (4) | |
C2 | 0.3839 (2) | 0.22712 (6) | 0.48766 (18) | 0.0215 (3) | |
C3 | 0.5470 (2) | 0.21946 (7) | 0.4289 (2) | 0.0258 (3) | |
C4 | 0.6761 (2) | 0.17499 (7) | 0.47261 (18) | 0.0229 (3) | |
C5 | 0.8530 (3) | 0.17561 (10) | 0.4006 (3) | 0.0418 (5) | |
C6 | 0.1966 (3) | 0.14418 (9) | 1.1242 (2) | 0.0310 (4) | |
C7 | 0.3351 (2) | 0.12432 (6) | 1.02110 (18) | 0.0214 (3) | |
C8 | 0.4815 (2) | 0.08999 (7) | 1.09081 (19) | 0.0240 (3) | |
C9 | 0.6210 (2) | 0.06896 (6) | 1.00652 (18) | 0.0206 (3) | |
C10 | 0.7733 (3) | 0.03274 (8) | 1.1081 (2) | 0.0316 (4) | |
C11 | 0.8083 (6) | 0.0970 (2) | 0.6444 (6) | 0.0271 (10) | 0.604 (12) |
H11A | 0.9107 | 0.1183 | 0.7118 | 0.033* | 0.604 (12) |
H11B | 0.8552 | 0.0795 | 0.5527 | 0.033* | 0.604 (12) |
C12 | 0.7417 (13) | 0.0530 (3) | 0.7538 (10) | 0.0273 (12) | 0.587 (19) |
H12A | 0.6741 | 0.0237 | 0.6836 | 0.033* | 0.587 (19) |
H12B | 0.8488 | 0.0367 | 0.8306 | 0.033* | 0.587 (19) |
C11B | 0.7474 (10) | 0.0809 (2) | 0.5804 (9) | 0.0211 (15) | 0.396 (12) |
H11C | 0.8636 | 0.0847 | 0.5385 | 0.025* | 0.396 (12) |
H11D | 0.6685 | 0.0528 | 0.5147 | 0.025* | 0.396 (12) |
C12B | 0.7890 (15) | 0.0666 (5) | 0.7690 (14) | 0.0237 (16) | 0.413 (19) |
H12C | 0.8985 | 0.0873 | 0.8266 | 0.028* | 0.413 (19) |
H12D | 0.8181 | 0.0273 | 0.7835 | 0.028* | 0.413 (19) |
H1A | 0.223 (4) | 0.2943 (10) | 0.519 (3) | 0.058 (7)* | |
H1B | 0.149 (4) | 0.2645 (11) | 0.361 (3) | 0.061 (7)* | |
H1C | 0.313 (4) | 0.3024 (11) | 0.368 (3) | 0.059 (7)* | |
H3 | 0.576 (3) | 0.2461 (8) | 0.357 (2) | 0.030 (5)* | |
H5A | 0.851 (3) | 0.2073 (11) | 0.336 (3) | 0.053 (7)* | |
H5B | 0.954 (4) | 0.1781 (10) | 0.482 (3) | 0.055 (7)* | |
H5C | 0.860 (4) | 0.1394 (11) | 0.329 (3) | 0.064 (8)* | |
H6A | 0.215 (3) | 0.1286 (9) | 1.230 (3) | 0.048 (7)* | |
H6B | 0.075 (3) | 0.1342 (8) | 1.063 (3) | 0.037 (6)* | |
H6C | 0.204 (4) | 0.1835 (11) | 1.133 (3) | 0.054 (7)* | |
H8 | 0.491 (3) | 0.0799 (8) | 1.200 (2) | 0.034 (5)* | |
H10A | 0.757 (3) | 0.0269 (9) | 1.224 (3) | 0.046 (6)* | |
H10B | 0.782 (3) | −0.0005 (10) | 1.056 (3) | 0.045 (6)* | |
H10C | 0.888 (3) | 0.0486 (9) | 1.116 (3) | 0.042 (6)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ga1 | 0.01474 (8) | 0.01490 (8) | 0.01408 (8) | 0.00243 (5) | 0.00237 (5) | 0.00118 (5) |
Cl1 | 0.02214 (17) | 0.01832 (16) | 0.02242 (16) | −0.00162 (13) | 0.00158 (13) | −0.00144 (13) |
O1 | 0.0231 (5) | 0.0175 (5) | 0.0226 (5) | 0.0047 (4) | 0.0057 (4) | 0.0048 (4) |
O2 | 0.0273 (6) | 0.0289 (6) | 0.0161 (5) | 0.0105 (5) | 0.0069 (4) | 0.0044 (4) |
N1 | 0.0191 (6) | 0.0235 (6) | 0.0297 (7) | 0.0033 (5) | 0.0093 (5) | 0.0033 (5) |
N2 | 0.0222 (6) | 0.0201 (6) | 0.0206 (6) | 0.0068 (5) | 0.0003 (5) | 0.0000 (5) |
C1 | 0.0397 (10) | 0.0211 (8) | 0.0289 (8) | 0.0059 (7) | 0.0005 (8) | 0.0076 (7) |
C2 | 0.0285 (8) | 0.0162 (6) | 0.0170 (6) | −0.0013 (6) | −0.0018 (6) | 0.0004 (5) |
C3 | 0.0312 (8) | 0.0255 (8) | 0.0203 (7) | −0.0048 (6) | 0.0044 (6) | 0.0065 (6) |
C4 | 0.0191 (7) | 0.0292 (8) | 0.0201 (7) | −0.0064 (6) | 0.0036 (5) | 0.0000 (6) |
C5 | 0.0264 (9) | 0.0566 (13) | 0.0457 (11) | −0.0035 (9) | 0.0150 (9) | 0.0169 (10) |
C6 | 0.0335 (9) | 0.0399 (10) | 0.0222 (8) | 0.0052 (8) | 0.0119 (7) | 0.0051 (7) |
C7 | 0.0244 (7) | 0.0224 (7) | 0.0177 (7) | −0.0035 (6) | 0.0053 (6) | 0.0008 (5) |
C8 | 0.0263 (8) | 0.0272 (8) | 0.0175 (7) | −0.0020 (6) | 0.0026 (6) | 0.0082 (6) |
C9 | 0.0212 (7) | 0.0155 (6) | 0.0220 (7) | −0.0018 (5) | −0.0034 (6) | 0.0029 (5) |
C10 | 0.0307 (9) | 0.0297 (9) | 0.0296 (9) | 0.0063 (7) | −0.0052 (7) | 0.0087 (7) |
C11 | 0.0189 (17) | 0.0374 (19) | 0.0250 (18) | 0.0087 (14) | 0.0043 (14) | −0.0039 (16) |
C12 | 0.026 (3) | 0.028 (3) | 0.028 (2) | 0.011 (2) | 0.005 (2) | 0.002 (2) |
C11B | 0.018 (2) | 0.023 (2) | 0.023 (3) | 0.0046 (18) | 0.006 (2) | 0.0000 (19) |
C12B | 0.018 (4) | 0.024 (4) | 0.028 (3) | 0.006 (2) | 0.001 (3) | −0.002 (3) |
Ga1—O2 | 1.9078 (10) | C1—H1A | 0.94 (2) |
Ga1—O1 | 1.9168 (10) | C1—H1B | 0.90 (3) |
Ga1—N1 | 1.9897 (13) | C1—H1C | 0.94 (3) |
Ga1—N2 | 2.0039 (12) | C3—H3 | 0.918 (19) |
Ga1—Cl1 | 2.2237 (4) | C5—H5A | 0.92 (3) |
O1—C2 | 1.3016 (18) | C5—H5B | 0.88 (3) |
O2—C7 | 1.2998 (17) | C5—H5C | 1.05 (3) |
N1—C4 | 1.312 (2) | C6—H6A | 0.92 (2) |
N1—C11B | 1.483 (4) | C6—H6B | 0.95 (2) |
N1—C11 | 1.500 (3) | C6—H6C | 0.95 (3) |
N2—C9 | 1.3106 (19) | C8—H8 | 0.903 (16) |
N2—C12 | 1.439 (8) | C10—H10A | 0.98 (2) |
N2—C12B | 1.531 (11) | C10—H10B | 0.91 (2) |
C1—C2 | 1.504 (2) | C10—H10C | 0.90 (2) |
C2—C3 | 1.368 (2) | C11—H11A | 0.9700 |
C3—C4 | 1.416 (2) | C11—H11B | 0.9700 |
C4—C5 | 1.507 (2) | C11B—H11D | 0.9700 |
C6—C7 | 1.503 (2) | C11B—H11C | 0.9700 |
C7—C8 | 1.370 (2) | C12—H12B | 0.9700 |
C8—C9 | 1.418 (2) | C12—H12A | 0.9700 |
C9—C10 | 1.508 (2) | C12B—H12C | 0.9700 |
C11—C12 | 1.520 (9) | C12B—H12D | 0.9700 |
C11B—C12B | 1.529 (13) | ||
O2—Ga1—O1 | 83.90 (4) | C2—C1—H1A | 111.1 (15) |
O2—Ga1—N1 | 151.66 (6) | C2—C1—H1B | 110.6 (17) |
O1—Ga1—N1 | 90.88 (5) | C2—C1—H1C | 113.9 (17) |
O2—Ga1—N2 | 90.56 (5) | H1A—C1—H1B | 106 (2) |
O1—Ga1—N2 | 153.22 (5) | H1A—C1—H1C | 107 (2) |
N1—Ga1—N2 | 81.65 (5) | H1B—C1—H1C | 108 (2) |
O2—Ga1—Cl1 | 104.61 (4) | C2—C3—H3 | 116.6 (13) |
O1—Ga1—Cl1 | 103.76 (3) | C4—C3—H3 | 117.6 (13) |
N1—Ga1—Cl1 | 103.70 (4) | C4—C5—H5A | 108.0 (14) |
N2—Ga1—Cl1 | 103.00 (4) | C4—C5—H5B | 110.6 (17) |
C2—O1—Ga1 | 127.85 (10) | C4—C5—H5C | 110.0 (16) |
C7—O2—Ga1 | 128.21 (10) | H5A—C5—H5B | 106 (2) |
C4—N1—C11B | 121.9 (2) | H5A—C5—H5C | 112 (2) |
C4—N1—C11 | 118.06 (18) | H5B—C5—H5C | 110 (2) |
C4—N1—Ga1 | 127.65 (11) | C7—C6—H6A | 113.5 (14) |
C11B—N1—Ga1 | 108.72 (19) | C7—C6—H6B | 106.3 (14) |
C11—N1—Ga1 | 112.76 (14) | C7—C6—H6C | 109.0 (17) |
C9—N2—C12 | 122.0 (3) | H6A—C6—H6B | 109 (2) |
C9—N2—C12B | 120.5 (4) | H6A—C6—H6C | 110 (2) |
C9—N2—Ga1 | 127.83 (11) | H6B—C6—H6C | 109 (2) |
C12—N2—Ga1 | 109.5 (3) | C7—C8—H8 | 117.5 (14) |
C12B—N2—Ga1 | 111.0 (4) | C9—C8—H8 | 116.8 (14) |
O1—C2—C3 | 125.57 (14) | C9—C10—H10A | 112.8 (13) |
O1—C2—C1 | 114.33 (14) | C9—C10—H10B | 111.7 (15) |
C3—C2—C1 | 120.10 (14) | C9—C10—H10C | 110.5 (14) |
C2—C3—C4 | 125.75 (14) | H10A—C10—H10B | 110 (2) |
N1—C4—C3 | 122.07 (14) | H10A—C10—H10C | 106 (2) |
N1—C4—C5 | 120.39 (15) | H10B—C10—H10C | 105 (2) |
C3—C4—C5 | 117.54 (15) | N1—C11—H11A | 109.82 |
O2—C7—C8 | 125.85 (14) | N1—C11—H11B | 109.82 |
O2—C7—C6 | 113.50 (14) | H11A—C11—H11B | 108.26 |
C8—C7—C6 | 120.64 (14) | N1—C11B—H11C | 111.08 |
C7—C8—C9 | 125.65 (14) | N1—C11B—H11D | 111.08 |
N2—C9—C8 | 121.70 (13) | H11C—C11B—H11D | 109.05 |
N2—C9—C10 | 121.15 (15) | N2—C12—H12A | 110.41 |
C8—C9—C10 | 117.14 (14) | N2—C12—H12B | 110.41 |
N1—C11—C12 | 109.3 (4) | H12A—C12—H12B | 108.62 |
N2—C12—C11 | 106.6 (5) | N2—C12B—H12C | 109.56 |
N1—C11B—C12B | 103.4 (6) | N2—C12B—H12D | 109.56 |
C11B—C12B—N2 | 110.5 (7) | H12C—C12B—H12D | 108.11 |
O2—Ga1—O1—C2 | 157.15 (12) | C1—C2—C3—C4 | −178.84 (15) |
N1—Ga1—O1—C2 | 5.08 (12) | C11B—N1—C4—C3 | 161.9 (4) |
N2—Ga1—O1—C2 | 78.11 (16) | C11—N1—C4—C3 | −166.1 (3) |
Cl1—Ga1—O1—C2 | −99.26 (12) | Ga1—N1—C4—C3 | −1.3 (2) |
O1—Ga1—O2—C7 | −158.61 (13) | C11B—N1—C4—C5 | −18.8 (5) |
N1—Ga1—O2—C7 | −78.14 (17) | C11—N1—C4—C5 | 13.2 (4) |
N2—Ga1—O2—C7 | −4.87 (13) | Ga1—N1—C4—C5 | 177.99 (14) |
Cl1—Ga1—O2—C7 | 98.72 (13) | C2—C3—C4—N1 | 2.2 (3) |
O2—Ga1—N1—C4 | −80.41 (18) | C2—C3—C4—C5 | −177.04 (17) |
O1—Ga1—N1—C4 | −1.67 (14) | Ga1—O2—C7—C8 | 4.3 (2) |
N2—Ga1—N1—C4 | −155.85 (15) | Ga1—O2—C7—C6 | −176.30 (12) |
Cl1—Ga1—N1—C4 | 102.72 (13) | O2—C7—C8—C9 | −0.2 (3) |
O2—Ga1—N1—C11B | 114.6 (4) | C6—C7—C8—C9 | −179.58 (16) |
O1—Ga1—N1—C11B | −166.7 (4) | C12—N2—C9—C8 | −170.7 (5) |
N2—Ga1—N1—C11B | 39.2 (4) | C12B—N2—C9—C8 | 168.4 (5) |
Cl1—Ga1—N1—C11B | −62.3 (4) | Ga1—N2—C9—C8 | −1.1 (2) |
O2—Ga1—N1—C11 | 85.1 (3) | C12—N2—C9—C10 | 9.4 (5) |
O1—Ga1—N1—C11 | 163.8 (3) | C12B—N2—C9—C10 | −11.5 (5) |
N2—Ga1—N1—C11 | 9.6 (3) | Ga1—N2—C9—C10 | 178.95 (12) |
Cl1—Ga1—N1—C11 | −91.8 (3) | C7—C8—C9—N2 | −1.4 (2) |
O2—Ga1—N2—C9 | 3.36 (13) | C7—C8—C9—C10 | 178.58 (16) |
O1—Ga1—N2—C9 | 80.85 (17) | C4—N1—C11—C12 | −178.8 (4) |
N1—Ga1—N2—C9 | 156.00 (14) | C11B—N1—C11—C12 | −73.0 (6) |
Cl1—Ga1—N2—C9 | −101.77 (13) | Ga1—N1—C11—C12 | 14.2 (6) |
O2—Ga1—N2—C12 | 174.0 (4) | C9—N2—C12—C11 | −139.9 (4) |
O1—Ga1—N2—C12 | −108.5 (4) | C12B—N2—C12—C11 | −49 (2) |
N1—Ga1—N2—C12 | −33.4 (4) | Ga1—N2—C12—C11 | 48.8 (6) |
Cl1—Ga1—N2—C12 | 68.9 (4) | N1—C11—C12—N2 | −40.3 (7) |
O2—Ga1—N2—C12B | −166.9 (5) | C4—N1—C11B—C12B | 140.6 (5) |
O1—Ga1—N2—C12B | −89.5 (5) | C11—N1—C11B—C12B | 50.1 (7) |
N1—Ga1—N2—C12B | −14.3 (5) | Ga1—N1—C11B—C12B | −53.4 (6) |
Cl1—Ga1—N2—C12B | 87.9 (5) | N1—C11B—C12B—N2 | 41.1 (9) |
Ga1—O1—C2—C3 | −5.8 (2) | C9—N2—C12B—C11B | 176.9 (5) |
Ga1—O1—C2—C1 | 174.47 (11) | C12—N2—C12B—C11B | 76 (2) |
O1—C2—C3—C4 | 1.4 (3) | Ga1—N2—C12B—C11B | −11.9 (9) |
Experimental details
Crystal data | |
Chemical formula | [Ga(C12H18N2O2)Cl] |
Mr | 327.45 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 163 |
a, b, c (Å) | 7.2163 (6), 24.102 (2), 8.0669 (7) |
β (°) | 101.776 (1) |
V (Å3) | 1373.5 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.19 |
Crystal size (mm) | 0.33 × 0.20 × 0.12 |
Data collection | |
Diffractometer | Bruker SMART CCD diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Bruker, 1998) |
Tmin, Tmax | 0.531, 0.779 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14190, 3298, 2992 |
Rint | 0.024 |
(sin θ/λ)max (Å−1) | 0.667 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.020, 0.051, 1.08 |
No. of reflections | 3298 |
No. of parameters | 239 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.32, −0.25 |
Computer programs: SMART (Bruker, 1998), SMART, SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL.
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There has been recent interest in the design of methodology en route toward metal oxynitrides, possessing intermediate properties between oxide and nitride phases (Kim et al., 2000; Pan et al., 1985; Erlat et al., 2004). Novel materials composed of group 13 oxynitrides have recently been used as supports for catalytic applications (Delsarte et al., 2003; Centeno et al., 2000) and high-temperature ceramics (Cao & Metselaar, 1991; Hwang & Chen, 1994; Ryabora & Savitskaya, 1968). The sputter deposition of aluminium oxynitride films onto polymer matrices has recently been found to impart superior water vapor permeation resistance (Delsarte et al., 2003).
We are focused on the design of single-source precursors for oxynitride films and nanostructural materials. Such suitable compounds must contain both M—O and M—N units; for certain applications, the backbone of the ligand should also contain small amounts of carbon. For oxide thin films, metal B-diketonate complexes have been widely used because of their low cost, stability, high volatility, low toxicity, and lack of M—C bonds (Barron, 1996). Furthermore, the volatility of these complexes has been found to change dramatically upon substitution of fluorine for hydrogen groups, allowing for fine tuning of the deposition conditions (Fahlman & Barron, 2000).
Compounds that contain the Schiff base ligand N,N'-ethylenebis(acetylacetoneimine) (acacen) may represent a suitable class of materials for oxynitride-based materials, because of the relatively low carbon content and the presence of direct M—O and M—N bonds. This ligand system has been well studied, as numerous transition metal (Baker et al., 1970; Larkworthy et al., 1984; Gambarotta et al., 1985) and rare earth complexes (Cai et al., 2001; Junk & Smith, 2003) have been isolated. Metal–acacen complexes are comparable to those containing the salen family of ligands, which are widely employed for catalytic applications (Atwood & Harvey, 2001). We have now synthesized the title complex, (I), and it represents the first use of this ligand on a group 13 metal, and only the second on a main-group metal (Ewings et al., 1976). The most common method used to synthesize metal–acacen complexes consists of exothermic reactions between the neutral acacenH2 moiety and a metal alkyl (Baker et al., 1970; Larkworthy et al., 1984; Gambarotta et al., 1985; Cai et al., 2001; Junk & Smith, 2003). However, this route was not successful with regard to the group 13 analogs, and we instead used the reaction of an Na2(acacen) salt with the correponding metal chloride.
A number of points regarding the structure and bonding in (I) (Fig. 1) are relevant. The compound contains a five-coordinate Ga atom in a distorted square-pyramidal geometry, with the ligand occupying the basal plane at a Ga—N2O2 plane distance of 0.47 Å. The Cl atom occupies the apical site at a distance of 2.2237 (4) Å. The average Ga—O and Ga—N bond distances are 1.91 and 2.00 Å, respectively, and are comparable to those of analogous salen derivatives (Atwood & Harvey). When comparing this structure with other complexes with GaN2O2Cl coordination environments, it is apparent that having a single N2O2 four-coordinate ligand lessens the level of distortion from the ideal square pyramidal geometry. Indeed, in systems where the ligands are allowed to rotate more freely, the geometry is much more distorted. Furthermore, when comparing this group 13 metal–acacen complex to one of the numerous five-coordinate transition metal complexes, the geometries are very similar (Clark et al., 1969; Sato et al., 1981). Thus far, our attempts to grow single crystals of the aluminium analogue have not been successful.