Synthesis and characterization of gallium complexes bearing 4-alkyl-2,6-bis(aryliminomethylene)-phenol ligands; crystal structure of dimethyl[4-methyl-2,6-bis-(p-methylphenyliminomethylene)-phenolato]gallium

Article abstract of DOI:10.1016/j.ica.2005.11.048

Eight new dimethylgallium complexes bearing 4-alkyl-2,6- bis(aryliminomethylene)-phenol ligands of type Me₂GaL [L = 4-methyl-2,6-bis-(phenyliminomethylene)-phenolato (3); L = 4-methyl-2,6-bis-(p- methylphenyliminomethylene)-phenolato (4); L = 4

Full text of DOI:10.1016/j.ica.2005.11.048

Inorganica Chimica Acta 359 (2006) 1339–1343
www.elsevier.com/locate/ica
Synthesis and characterization of gallium complexes bearing
4-alkyl-2,6-bis(aryliminomethylene)-phenol ligands; crystal structure
of dimethyl[4-methyl-2,6-bis-(p-methylphenyliminomethylene)-
phenolato]gallium
c
d
a,
a
Weijin Gu a,b, Yingzhong Shen , Yizhi Li , Yi Pan *, Chengjian Zhu
a
Department of Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, PR China
b
Department of Chemistry, Nanjing Normal University, Nanjing 210097, PR China
School of Material Science and Engineering, Nanjing University of Aeronautics and Astronautics, Nanjing, 210016, PR China
Coordination Chemistry Institute, State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing 210093, PR China
c
d
Received 29 October 2004; accepted 7 November 2005
Available online 20 February 2006
Abstract
Eight new dimethylgallium complexes bearing 4-alkyl-2,6-bis(aryliminomethylene)-phenol ligands of type Me2GaL [L = 4-methyl-2,
6-bis-(phenyliminomethylene)-phenolato (3); L = 4-methyl-2,6-bis-(p-methylphenyliminomethylene)-phenolato (4); L = 4-methyl-2,6-
bis-(1-naphthyliminomethylene)-phenolato (5); L = 4-methyl-2,6-bis-(2-chlorophenyliminomethylene)-phenolato (6); 4-tert-butyl-2,6-bis-
(phenyliminomethylene)-phenolato (7); L = 4-tert-butyl-2,6-bis-(p-methylphenyliminomethylene)-phenolato (8); L = 4-tert-butyl-2,6-
bis-(1-naphthyliminomethylene)-phenolato (9); and L = 4-tert-butyl-2,6-bis-(2-chlorophenyliminomethylene)-phenolato] (3) have been syn-
thesized by the reaction of trimethylgallium with appropriate phenol. The complexes obtained have been characterized by elemental
analysis, 1H NMR, IR and mass spectroscopy, respectively. The solid-state structures of dimethyl[4-methyl-2,6-bis-(p-methylphenylimi-
nomethylene)-phenolato]gallium (4) have been determined by X-ray single crystal analysis. In the structure, Ga atom is coordinated by
one nitrogen atom and the other nitrogen atom remains constant. The distorted tetrahedron geometry around gallium is presented.
ꢀ 2006 Elsevier B.V. All rights reserved.
Keywords: Trimethylgallium; 4-Alkyl-2,6-bis(aryliminomethylene)-phenol; X-ray crystallography
1. Introduction
lic complexes and search for the new electroluminescent
materials, we report herein the synthesis and characteriza-
tion of gallium complexes bearing 4-alkyl-2,6-bis(arylimi-
nomethylene)-phenol. A crystal structure of 4 has been
determined by X-ray analysis.
The chemistry of group 13 elements has been under
investigation for the last few decades owing to their rich
structural information [1–4] and wide application in mate-
rial science [5,6], organic reactions [7] and asymmetric syn-
thesis [8–11]. Recently, we have reported some
organogallium complexes and their application in the elec-
troluminescence materials [12–14]. In order to get a deeper
insight into the structural aspect of group 13 organometal-
2. Experimental
2.1. General procedure
All reactions were performed in a glove box under nitro-
gen. The solvents were refluxed with sodium benzophenone
and distilled under nitrogen prior to use. The Schiff-base
ligands were prepared by condensation of 2-hydroxy-5-
*
Corresponding author. Tel.: +86 25 83593153; fax: +86 25 83317761.
E-mail address: yipan@netra.nju.edu.cn (Y. Pan).
0020-1693/$ - see front matter ꢀ 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2005.11.048

1340
W. Gu et al. / Inorganica Chimica Acta 359 (2006) 1339–1343
alkyl-benzene-1,3-dicarbaldehyde [15] with 2 equiv. of ani-
line, 4-methylaniline, 1-naphthaniline and 2-chloroaniline,
respectively. Trimethylgallium were provided by the
National 863 Program Advanced Material MO Precursors
R&D Center of China. 1H NMR spectra were recorded on
a Bruker ARX-300 spectrometer with TMS as internal
standard. Infrared spectra were collected on a Shimadzu
IR 408 instrument in KBr pellets. Mass spectra were mea-
sured on a VG-ZAB-HS spectrometer (electron impact ion-
ization). Elemental analyses were performed on Foss
Heraeus CHN-O-Rapid elemental analyzer. Melting points
were observed in an electrothermal melting point apparatus
in sealed capillaries and were uncorrected.
2.4. Preparation of dimethyl[4-methyl-2,6-bis-(1-
naphthyliminomethylene)-phenolato] gallium (5)
Prepared in the same manner as described for 3 from 4-
methyl-2,6-bis-(1-naphthyliminomethylene)-phenol
(1.026 g, 2 mmol) and trimethylgallium (1) (0.2 mL,
2 mmol). The orange powder residue was recrystallized
from cyclohexane–benzene solution, giving the orange
crystal. Yield: 0.62 g (61% based on 1).
(2c)
M.p.: 184–186 ꢁC. Anal. Calc. for C31H27N2OGa
(513.29): C, 72.54; H, 5.30; N, 5.46. Found: C, 72.53; H,
5.40; N, 5.42%. IR data m (cmꢀ1): 3047, 1623, 1592, 1567,
1
1508, 1459, 1390, 1225, 988, 780, 771, 636. H NMR data
(CDCl3): 9.23 (s, 1H, ACH@N), 8.45 (s, 1H, ACH@N),
8.21 (s, 1H, ArH), 7.0–7.9 (m, 15H, ArH), 2.40 (s, 3H,
ArCH3), ꢀ0.24 (s, 6H, Ga(CH3)2). MS data: 512 (M+,
12.99%), 499 (65.13%), 497 (100.00%), 272 (9.15%), 248
(15.53%), 71 (12.9%), 69 (20.04%).
2.2. Preparation of dimethyl[4-methyl-2,6-bis-
(phenyliminomethylene)-phenolato] gallium (3)
Trimethylgallium (1) (0.2 mL, 2 mmol), dissolved in
15 mL of benzene, was added dropwise in 10 min with stir-
ring to 4-methyl-2,6-bis-(phenyliminomethylene)-phenol
(2a) (0.629 g, 2 mmol), dissolved in 4 mL of benzene, at
room temperature. After stirring the reaction mixture for
an additional 30 min at this temperature, all volatiles were
removed in oil-pump vacuum and the yellow powder resi-
due was recrystallized from cyclohexane–benzene solution,
giving the orange crystal. Yield: 0.58 g (70 % base on 1).
M.p.: 172–173 ꢁC. Anal. Calc. for C23H23N2OGa
(413.17): C, 66.86; H, 5.61; N, 6.78. Found: C, 66.60; H,
5.82; N, 6.98%. IR data m (cmꢀ1): 2920, 1620, 1585, 1544,
2.5. Preparation of dimethyl[4-methyl-2,6-bis-(2-
chlorophenyliminomethylene)-phenolato] gallium (6)
Prepared in the same manner as described for 3 from 4-
methyl-2,6-bis-(2-chlorophenyliminomethylene)-phenol (2d)
(0.964 g, 2 mmol) and trimethylgallium (1) (0.2 mL,
2 mmol). The yellow powder residue was recrystallized
from cyclohexane–benzene solution, giving the yellow crys-
tal. Yield: 0.72 g (75% based on 1).
M.p.: 113–115 ꢁC. Anal. Calc. for C23H21N2OCl2Ga
(482.06): C, 57.31; H, 4.39; N, 5.81. Found: C, 57.39; H,
4.60; N, 5.63%. IR data m (cmꢀ1): 2963, 1619, 1578, 1542,
1472, 1441, 1364, 1204, 986, 817, 760. 1H NMR data
(CDCl3): 9.00 (s, 1H, ACH@N), 8.28 (s, 1H, ACH@N),
8.11 (s, 1H, ArH), 7.10–7.56 (m, 9H, ArH), 2.34 (s, 3H,
ArCH3), ꢀ0.23 (s, 6H, Ga(CH3)2). MS data: 480 (M+,
1.09%), 469 (43.85%), 467 (100.00%), 465 (74.07%), 347
(2.57%), 256 (2.57%), 233 (10.02%), 77 (4.57%), 71
(13.80%), 69 (20.29%).
1
1483, 1443, 1365, 1200, 986, 871, 817, 762. H NMR data
(CDCl3): 9.08 (s, 1H, ACH@N), 8.23 (s, 1H, ACH@N),
8.20 (s, 1H, ArH), 7.18–7.50 (m, 9H, ArH), 2.36 (s, 3H,
ArCH3), ꢀ0.20 (s, 6H, Ga(CH3)2). MS data: 412 (M+,
4.46%), 400 (23.25%), 399 (95.78%), 397 (100.00%), 313
(8.29%), 305 (7.12%), 297 (5.60%), 199 (10.09%), 77.0
(15.02%), 71 (18.57), 69 (17.5%).
2.3. Preparation of dimethyl[4-methyl-2,6-bis-(p-
methylphenyliminomethylene)-phenolato] gallium (4)
2.6. Preparation of dimethyl[4-tert-butyl-2,6-bis-
(phenyliminomethylene)-phenolato]gallium (7)
Prepared in the same manner as described for 3 from
4-methyl-2,6-bis-(p-methylphenyliminomethylene)-phenol-
(2b) (0.882 g, 2 mmol) and trimethylgallium (1) (0.2 mL,
2 mmol). The orange powder residue was recrystallized
from cyclohexane–benzene solution, giving the orange
crystal. Yield: 0.57 g (65% based on 1).
Prepared in the same manner as described for 3 from 4-
tert-butyl-2,6-bis-(phenyliminomethylene)-phenol
(0.910 g, 2 mmol) and trimethylgallium (1) (0.2 mL,
2 mmol). The yellow powder residue was recrystallized
from cyclohexane–benzene solution containing 7, giving
the yellow crystal. Yield: 0.69 g (76% based on 1).
(2e)
M.p.: 192–194 ꢁC. Anal. Calc. for C25H27N2OGa
(441.22): C, 68.05; H, 6.17; N, 6.35. Found: C, 68.26; H,
5.92; N, 6.38%. IR data m (cmꢀ1): 2918, 1621, 1587, 1547,
M.p.: 190–192 ꢁC. Anal. Calc. for C26H29N2OGa
(455.25): C, 69.58; H, 6.88; N, 5.80. Found: C, 69.55; H,
6.72; N, 5.99%. IR data m (cmꢀ1): 2960, 1620, 1586, 1541,
1
1506, 1444, 1364, 1200, 982, 871, 818, 770. H NMR data
(CDCl3): 9.09 (s, 1H, ACH@N), 8.21 (s, 1H, ACH@N),
8.18 (s, 1H, ArH), 7.10–7.39 (m, 9H, ArH), 2.42 (s, 3H,
ArCH3), 2.39 (s, 3H, ArCH3), 2.33 (s, 3H, ArCH3),
ꢀ0.21 (s, 6H, Ga(CH3)2). MS data: 440 (M+, 2.27%), 427
(35.96%), 425 (52.2%), 338 (67.09%), 336 (100.00%), 293
(7.41%), 251 (8.20%), 225 (29.63%), 99 (4.55%), 91
(22.40%), 71 (21.90%), 69 (33.03%).
1
1486, 1448, 1371, 1193, 835, 759. H NMR data (CDCl3):
9.09 (s, 1H, ACH@N), 8.44 (s, 1H, ACH@N), 8.30 (s,
1H, ArH), 7.23–7.52 (m, 11H, ArH), 1.39 (s, 9H, CMe3),
ꢀ0.20 (s, 6H, Ga(CH3)2). MS data: 454 (M+, 7.08%), 441
(100.00%), 409 (14.08%), 339 (7.81%), 219 (6.05%), 104
(5.23%), 99 (4.64%), 77 (7.70%), 69 (27.06%).

W. Gu et al. / Inorganica Chimica Acta 359 (2006) 1339–1343
1341
2.7. Preparation of dimethyl[4-tert-butyl-2,6-bis-(p-
methylphenyliminomethylene)-phenolato]gallium (8)
(1.95%), 313 (3.78%), 254 (6.11%), 77 (2.05%), 71
(11.9%), 69 (18.89%).
Prepared in the same manner as described for 3 from 4-
tert-butyl-2,6-bis-(p-methylphenyliminomethylene)-phenol
(2f) (0.966 g, 2 mmol) and trimethylgallium (1) (0.2 mL,
2 mmol). The yellow powder residue was recrystallized
from cyclohexane–benzene solution containing 8, giving
the yellow crystal. Yield: 0.70 g (72% based on 1).
2.10. Determination of the crystal structures of 4
Single crystal of complexes 4 was obtained by recrystal-
lization from cyclohexane–benzene solution. X-ray struc-
ture measurement was performed on a Bruker SMART
Apex CCD detector equipped with graphite monochroma-
tor. Crystal data of 4 and the data collection as well as
refinement details are given in Table 2.
The unit cell was determined with the program SMART
[16]. For data integration and refinement of the unit cell,
the program SAINT [16] was used. The space group was
determined using the program ABSEN [17]. All data were
corrected for absorption using SADABS [18]. The structure
was solved using direct methods (SHELX-97 [19]), refined
using least-square methods (SHELX-97 [19]) and drawn using
ZORTEP [20]. All non-hydrogen atoms were fully refined in
their located positions; the hydrogen atoms were taken
from the electron density difference map and refined freely.
M.p.: 168–169 ꢁC. Anal. Calc. for C28H33N2OGa
(483.30): C, 69.59; H, 6.88; N, 5.80. Found: C, 69.55; H,
6.48; N, 6.06%. IR data m (cmꢀ1): 2961, 1620, 1587, 1542,
1
1503, 1441, 1363, 1193, 817, 773. H NMR data (CDCl3):
9.09 (s, 1H, ACH@N), 8.42 (s, 1H, ACH@N), 8.28 (s,
1H, ArH), 7.15–7.34 (m, 9H, ArH), 2.43 (s, 3H, ArCH3),
2.40 (s, 3H, ArCH3), 1.37 (s, 9H, CMe3), ꢀ0.20 (s, 6H,
Ga(CH3)2). MS data: 482 (M+, 4.12 %), 469 (67.15%),
467 (100.00%), 437 (5.44%), 367 (3.18%), 233 (6.74%), 71
(7.81%), 69 (10.34%).
2.8. Preparation of dimethyl[4-tert-butyl-2,6-bis-(1-
naphthyliminomethylene)-phenolato]gallium (9)
3. Results and discussion
Prepared in the same manner as described for 3 from 4-
tert-butyl-2,6-bis-(1-naphthyliminomethylene)-phenol (2g)
(1.11 g, 2 mmol) and trimethylgallium (1) (0.2 mL,
2 mmol). The yellow powder residue was recrystallized
from cyclohexane–benzene solution, giving the yellow pow-
der. Yield: 0.66 g (59% based on 1).
3.1. Synthesis and characterization
The reaction of trimethylgallium (1) with 4-alkyl-2,6-
bis(aryliminomethylene)-phenol (2a–h), which were
obtained by the condensation of 2-hydroxy-5-methyl(or
tert-butyl)benzene-1,3-dicarbaldehyde [15] with 2 equiv.
of aniline, 4-methylaniline, 1-naphthaniline and 2-chloro-
aniline, respectively, proceeded smoothly at room tempera-
ture in benzene. By the removal of methane, complexes
3–10 are formed in high yield (see Scheme 1 and Table 1).
Although trimethylgallium is extremely moisture and
oxygen sensitive, the complexes obtained are fairly stable
on exposure to air. Compounds 3–10 could be left at ambi-
ent atmosphere for months without obvious decomposi-
tion. The complexes are nearly insoluble in cold saturated
hydrocarbons such as hexane or petroleum and very solu-
ble in unsaturated hydrocarbons such as benzene or tolu-
ene. All the products obtained gave satisfactory elemental
M.p.: 145–147 ꢁC. Anal. Calc. for C34H33N2OGa
(555.37): C, 73.53; H, 5.99; N, 5.04. Found: C, 73.65; H,
6.28; N, 5.26%. IR data m (cmꢀ1): 2962, 1619, 1542, 1448,
1
1393, 1364, 1248, 845, 801, 777, 745, 690. H NMR data
(CDCl3): 9.25 (s, 1H, ACH@N), 8.70(s, 1 H, ACH@N),
8.28 (s, 1H, ArH), 7.2–8.0 (m, 15H, ArH), 1.43 (s, 9H,
CMe3), ꢀ0.27 (s, 6H, Ga(CH3)2). MS data: 554 (M+,
11.45%), 541 (70.47%), 539 (100.00%), 456 (4.51%), 314
(15.22%), 269 (16.09%), 101 (36.07%), 99 (55.45%), 71
(23.19%), 69 (32.15%).
2.9. Preparation of dimethyl[4-tert-butyl-2,6-bis-(2-
chlorophenyliminomethylene)-phenolato]gallium (10)
1
analysis results and were characterized by IR, H NMR
Prepared in the same manner as described for 3 from
4-tert-butyl-2,6-bis-(2-chlorophenyliminomethylene)-phenol
(2h) (1.048 g, 2 mmol) and trimethylgallium (1) (0.2 mL,
2 mmol). The yellow powder residue was recrystallized
from cyclohexane–benzene solution containing 10, giving
the yellow crystal. Yield: 0.75 g (72% based on 1).
M.p.: 73–75 ꢁC. Anal. Calc. for C26H27N2OCl2Ga
(524.14): C, 59.58; H, 5.19; N, 5.34. Found: C, 59.50; H,
5.18; N, 5.31%. IR data m (cmꢀ1): 2964, 1619, 1595, 1579,
1390, 1365, 1248, 836, 756, 733, 692. 1H NMR data
(CDCl3): 9.03 (s, 1H, ACH@N), 8.54 (s, 1H, ACH@N),
8.17 (s, 1H, ArH), 7.20–7.60 (m, 9H, ArH), 1.39 (s, 9H,
CMe3), ꢀ0.19 (s, 6H, Ga(CH3)2). MS data: 524 (M+,
1.24%), 511 (45.93%), 509 (100.00%), 507 (81.12%), 443
and mass spectrometry, respectively.
In the IR spectra of 3–10, the absence of O–H stretch
vibration absorption verifies the reaction of the active
hydrogen atom of the ligands with trimethylgallium by
the removal of 1 equiv. of methane. The C–H stretch vibra-
tions of the gallium-bonded methyl groups are visible in the
region of 2900 and 2950 cmꢀ1
.
In the 1H NMR spectra of the complexes, Chemical
shifts of the metal-bonded carbon protons in gallium com-
plexes (3–10) (ꢀ0.20 to ꢀ0.24 ppm) move upfield com-
pared with the related metallic alkylide (TMGa:
ꢀ0.10 ppm), indicating that the gallium atoms are coordi-
nated by nitrogen atoms. It is very interesting to note that
the two kinds of chemical shifts of the methine protons for

1342
W. Gu et al. / Inorganica Chimica Acta 359 (2006) 1339–1343
R
R
C6H6
Ga(CH3)3
+
HC
N
CH
N
HC
N
CH
N
-CH4
OH
O
1
Ar
Ar
Ar
Ar
Ga
H C
CH
2a - h
3
3
3 - 10
Scheme 1. Synthesis of complexes 3–10.
Table 1
Synthesis of complexes 3–10
plexes, indicating that it is very easy to eliminate one
methyl group. The relative intensity of the peaks for the
metal containing species agrees well with the isotopic distri-
bution of the metals (69Ga (ca. 60%), 71Ga (ca. 40%)).
Compound
R
Ar
3
4
methyl
methyl
methyl
methyl
tert-butyl
tert-butyl
tert-butyl
tert-butyl
phenyl
4-methylphenyl
1-naphthyl
2-chlorophenyl
phenyl
4-methylphenyl
1-naphthyl
5
3.2. Solid-state structures of 4
6
7
Single crystals of 4 could be obtained by recrystallization
of a saturated benzene solution containing 4 at ꢀ20 ꢁC. The
result of the X-ray structure analysis of 4 is depicted in Fig. 1.
Important crystal data, collection and refinement parame-
ters are summarized in Table 2 and selected interatomic dis-
8
9
10
2-chlorophenyl
the gallium complexes are present. One appeared in the
range of 9.08–9.25 ppm, which are similar to those of the
free ligands. The others, however, appeared in the range
of 8.21–8.70 ppm, which are upfield shifted compared with
those of the free ligands. This illustrates that only one
nitrogen atom in the molecule coordinates to the gallium
atom and the other nitrogen atom remains constant. This
could also be confirmed by the X-ray crystal structure
determination (see below).
˚
tances (A) and bond angles (ꢁ) are given in Table 3. Complex
ꢀ
4 crystallizes in the triclinic space group P1. Although a few
dimethylgallium complexes were found to be dimeric
[21–23], compound 4 exists as a monomer in the solid state.
Gallium atom is in a distorted tetrahedron geometry. This
may be due to the relatively more crowded environment
around gallium bounded O and N atoms. The angle of
O1–Ga1–N2 reduces to 91.99(9)ꢁ, which is much less than
the value of ideal tetrahedron geometry (109.5ꢁ). This should
be caused by the strain in the ring Ga1O1C1C6C7N2. The
angle of C24–Ga1–C25 increases to 126.91(19)ꢁ, this is
because the methyl group is bigger than N or O atoms. The
The molecule ion peaks (M+) of complexes 3–10 were all
visible in their mass spectra, although the abundances are
low for some of them. There is no peak beyond the M+ sig-
nal in the spectra, which illustrates the monomeric status of
the complexes in the solid state. Fairly strong intensity
peaks of (M+ ꢀ 15) are observed in almost all the com-
˚
Ga1–O1 bond length (1.894(2) A) is slightly longer than
those of N,N-ethylene(salicylideneiminato) bis[dimethylgal-
Fig. 1. Molecular structure of 4, showing 50% probability displacement ellipsoids.

W. Gu et al. / Inorganica Chimica Acta 359 (2006) 1339–1343
1343
Table 2
Crystal data, collection parameters, and refinements for 4
4. Supplementary material
Formula
C25H27GaN2O
411.21
orange
0.3 · 0.2 · 0.20
triclinic
Crystallographic data (comprising hydrogen atom coor-
dinates, thermal parameters and full tables of bond lengths
and bond angles) for the structural analysis have been
deposited with the Cambridge Crystallographic Data Cen-
ter (Deposition No. CCDC 252078) Copies of this informa-
tion may be obtained free of charge from The Director,
CCDC, 12 Union Road, Cambridge, CB2 1EZ, UK (fax:
+44 1223 336 033; e-mail: deposit@ccdc.cam.ac.uk or
www: http://www.ccdc.cam.ac.uk).
Formula weight
Crystal colour
Crystal dimensions (mm)
Crystal system
Space group
ꢀ
P1
˚
a (A)
9.8450(1)
10.3650(1)
11.251(2)
77.840(1)
88.120(1)
86.640(1)
1120.2(3)
2
˚
b (A)
˚
c (A)
a (ꢁ)
b (ꢁ)
c (ꢁ)
3
˚
V (A )
Acknowledgments
Z value
Dcalc (g cmꢀ3
)
1.308
We gratefully acknowledge the National Natural Sci-
ence Foundation of China, Science Foundation of Jiangsu
Province and the 863 High Technology Program for their
financial support. The research funds for Y. Pan from
Qing-Lan Program of Jiangsu Province and Kua-Shi-Ji
Program of Education Ministry of China are also
acknowledged.
Index ranges
ꢀ11 6 h6 11; ꢀ5 6 k 6 12;
ꢀ13 6 l 6 13
F(000)
l(Mo Ka) (mmꢀ1
Diffractometer
460
1.246
)
Bruker Smart Apex; CCD
area detector
Mo Ka (k = 0.71073 A)
˚
Radiation
Temperature (K)
H range (ꢁ)
Number of reflections measured
Independent reflections observed
(I) > 2.00(r(I))
293
2.0–25.0
3877
References
3133
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Number of parameters
Correction
267
Lorentz-polarization
0.0431/0.0521
0.1017/ 0.1036
1.13
R1 [I > 2r(I)]a
wR2 [I > 2r(I)]b
Goodness-of-fit [F2]c
ꢀ3
˚
Dqmax (e Aꢀ3
)
0.496
˚
Dqmin (e A
)
ꢀ0.503
(D/r)max
0.00
P
P
a
R1 = |Fobs ꢀ Fcalc|/ Fcalc
.
P
P
2
2
b
c
Rw ¼ ½ wðF 2obs ꢀ F 2calcÞꢁ =½ wðF 2obsÞꢁ .
P
S ¼ ½ wðF 2obs ꢀ F 2calcÞꢁ=ðn ꢀ pÞ1=2, n is the number of reflections and
p is the parameters used.
[11] C.J. Zhu, F. Yuan, W.J. Gu, Y. Pan, Chem. Commun. (2003) 692.
[12] C.X. Xu, Y.P. Cui, Y.Z. Shen, H.W. Gu, Y. Pan, Y.K. Li, Appl.
Phys. Lett. 75 (1999) 1827.
[13] Y.Z. Shen, H.W. Gu, Y. Pan, G. Dong, T. Wu, X.P. Jin, X.Y.
Huang, H.W. Hu, J. Organomet. Chem. 605 (2000) 234.
[14] Y.Z. Shen, H.W. Gu, W.J. Gu, F. Yuan, Y. Zhu, Y. Pan, J.
Organomet. Chem. 681 (2003) 51.
Table 3
˚
Selected interatomic bond distances (A) and bond angles (ꢁ) for 4
Bond distances
Ga(1)–O(1)
Ga(1)–C(24)
C(1)–C(6)
N(2)–C(7)
N(1)–C(8)
1.894(2)
1.941(3)
1.425(4)
1.297(4)
1.265(4)
Ga(1)–N(2)
O(1)–C(1)
C(6)–C(7)
N(2)–C(17)
N(1)–C(10)
2.031(2)
1.320(4)
1.434(5)
1.433(4)
1.425(4)
[15] L.Y. Wang, W.H. Sun, L.Q. Han, Z.L. Li, Y.L. Hu, C. He, C.H.
Yan, J. Organomet. Chem. 650 (2002) 59.
[16] Bruker AXS, Inc., Madison, WI, USA, 1998.
[17] P. McArdle, J. Appl. Crystallogr. 29 (1996) 306.
[18] G.M. Sheldrick, SADABS V 2.01, Program for Empirical Absorption
Correction of Area Detector Data, University of Go¨ttingen, Ger-
many, 2000.
[19] G.M. Sheldrick, SHELX-97, Programs for Crystal Structure Analysis
(Release 97-2), University of Go¨ttingen, Germany, 1997.
[20] L. Zsolnai, G. Huttner, ZORTEP, University of Heidelberg, Germany,
1994.
Bond angles
O(1)–Ga(1)–N(2)
O(1)–Ga(1)–C(25)
N(2)–Ga(1)–C(25)
Ga(1)–N(2)–C(7)
Ga(1)–O(1)–C(1)
C(1)–C(6)–C(7)
91.99(9)
110.10(2)
105.11(2)
119.4(2)
124.26(2)
123.0(3)
O(1)–Ga(1)–C(2)
N(2)–Ga(1)–C(2)
C(24)–Ga(1)–C(3)
Ga(1)–N(2)–C(3)
O(1)–C(1)–C(6)
N(2)–C(7)–C(6)
106.98(1)
110.20(1)
126.91(2)
122.54(2)
122.9(3)
126.7(3)
[21] D.G. Hendershot, M. Barber, R. Kumar, J.P. Oliver, Organometal-
lics 10 (1991) 3320.
[22] K.H. Thiele, E. Hecht, T. Gelbrich, U. Dumichen, J. Dumichen, J.
Organomet. Chem. 89 (1997) 540.
[23] H. Schumann, M. Frick, B. Heymer, F. Girgsdies, J. Organomet.
Chem. 9 (1987) 326.
[24] K.S. Chong, S.J. Rettig, A. Storr, J. Trotter, Can. J. Chem. 55 (1977)
2540.
˚
lium] (1.869(2)–1.874(2) A) [24]. The Ga1–N2 bond length
˚
(2.031(2) A) is comparable to the reported values of N,N-
ethylene(salicylideneiminato)bis[dimethylgallium] (2.026(3)–
2.035(3) A [24]. The O–Ga distance is shorter than that of
N–Ga by about 0.142 A, indicating that the nitrogen atom
˚
˚
is datively bounded to the gallium atom.