52
S. Latreche, F. Schaper / Inorganica Chimica Acta 365 (2011) 49–53
Table 3
Details of X-ray diffraction studies.
2
4
5
6
7
Formula
C
34H58Cl2Cr2N4ꢁC4H10
O
C34H58CrN4
574.84; 1.17
150; 1256
monoclinic
C2/c
C22H42CrN4
414.60; 1.17
120; 452
monoclinic
P21/n
C26H50CrN4
470.70; 1.10
150; 258
C42H50CrN4
662.86; 1.23
150; 708
monoclinic
P21
Mw (g/mol); Dcalc (g/cm3)
T (K); F (0 0 0)
Crystal system
Space group
Unit cell
771.86; 1.27
150; 414
triclinic
triclinic
ꢀ
ꢀ
P1
P1
a (Å)
b (Å)
c (Å)
7.8609(6)
10.3257(9)
13.8494(11)
70.534(4)
89.745(4)
74.072(4)
1014.5(1); 1
3.4–67.6; 0.99
17 901; 0.047
3633 (0.083)
5.87
15.5202(10)
10.5337(6)
20.4759(12)
90
102.460(3)
90
3268.7(3); 4
5.1–67.7; 0.99
28 655; 0.020
2936 (0.053)
3.07
9.1356(10)
10.6954(12)
12.7505(14)
90
108.926(4)
90
1178.5(2); 2
5.2–67.9; 1.00
20 649; 0.024
2125 (0.066)
4.07
7.8129(5)
9.6859(6)
10.7842(6)
108.941(3)
111.229(3)
91.208(4)
710.6(1); 1
4.7–67.4; 0.99
10 990; 0.031
2515 (0.043)
3.43
9.9141(3)
18.4773(6)
10.2334(3)
90
106.902(1)
90
1793.6(1); 2
4.5–67.8; 1.00
28 484; 0.030
5738 (0.050)
2.88
0.030; 0.082
1.048; 0.025(3)
0.25, ꢀ0.23
a
(°)
b (°)
c
(°)
V (Å3); Z
h Range (°); completeness
Reflections collected; R
r
Independent reflections (Rint
)
l
(mmꢀ1
)
R1(F); wR(F2)a
0.086; 0.245
1.086
1.3, ꢀ1.1
0.031; 0.089
1.056
0.38, ꢀ0.37
0.034; 0.096
1.058
0.34, ꢀ0.58
0.035; 0.098
1.081
0.27, ꢀ0.22
Goodness-of-fit (GOF) (F2)a; Flack-x
Residual electron density
a
R1(F) based on observed reflections with I > 2r
(I), wR(F2) and GOF(F2) based on all data.
4.1. {nacnacBnCr(
l-Cl)}2, 1
4.4. nacnacn2PrCr, 5
CrCl2(THF)x (0.150 g, 0.56 mmol for x = 2) was dissolved in tolu-
Following the protocol for 4, CrCl2(THF)x (0.20 g, 0.75 mmol for
x = 2) in THF (30 mL), nacnacnPrLi(THF) (0.45 g, 1.7 mmol) in THF
(20 mL) gave after extraction with diethyl ether (40 mL) and crys-
ene (30 mL). A solution of nacnacBnLi(THF) (0.400 g, 1.12 mmol) in
toluene (20 mL) was added at room temperature, on which the col-
or of the solution changed to red. After stirring overnight at room
temperature, the obtained mixture was filtered to remove LiCl, the
solvent was removed under vacuum and the remaining residue
was washed several times with hexane. After drying under vacuum
0.300 g (65%) of 1 were obtained as a red powder. Anal. Calc. for
tallization red crystals of
5 (140 mg, 45%). Anal. calcd. for
C22H42N4Cr: C, 63.73; H, 10.21; N, 13.51. Found: C, 59.24; H,
9.94; N, 11.58%.
C
38H42Cl2Cr2N4: C, 62.55; H, 5.80; N, 7.68. Found: C, 65.78; H,
4.5. nacnaci2BuCr, 6
6.35; N, 7.52%. UV–Vis (Tol; kmax, nm (
577 (360, shoulder). Mp.: 125 °C.
e
, Mꢀ1 cmꢀ1)): 378 (2680),
Following the protocol for 4, CrCl2(THF)x (0.55 g, 2.3 mmol for
x = 2) in THF (30 mL), nacnaciBuLi(THF) (1.34 g, 4.6 mmol) in THF
(20 mL) gave after extraction with diethyl ether (80 mL) and crys-
tallization red crystals of
6 (0.87 g, 87%). Anal. calcd. for
4.2. {nacnacCyCr(
l-Cl)}2, 2
C26H50N4Cr: C, 66.34; H, 10.71; N, 11.90. Found: C, 65.70; H,
10.24; N, 11.81%. Mp.: 80 °C.
CrCl2(THF)x (0.17 g, 0.75 mmol for x = 2) was dissolved in tolu-
ene (20 mL). A solution of nacnacCyLi(THF) (0.25 g, 0.75 mmol) in
toluene (20 mL) was added and the reaction mixture was stirred
overnight at room temperature. The solvent was removed under
vacuum and the residue was extracted with diethyl ether
(80 mL). The extract was filtered to remove LiCl, concentrated,
and kept at –30 °C. Brown crystals of 3 (24% yield) separated after
several days. Anal. Calc. for C38H42N4Cr: C, 75.22; H, 6.98; N, 9.23.
4.6. S–nacnacC2HðMeÞPhCr, 7
Following the protocol for 4, CrCl2(THF)x (0.40 g, 1.7 mmol for
x = 2) in THF (20 mL) and nacnacCH(Me)PhLi(THF) (1.3 g, 3.4 mmol)
in THF (20 mL) gave after extraction with diethyl ether (100 mL)
and crystallization red crystals of 7 (0.98 g, 86%). Anal. Calc. for
Found: C, 73.66; H, 7.14; N, 8.96%. UV–Vis (Tol; kmax, nm (
e,
Mꢀ1 cmꢀ1)): 376 (2580). Mp.: 152–155 °C.
C42H50N4Cr: C, 76.10; H, 7.60; N, 8.45. Found: C, 75.73; H, 7.67;
N, 8.49%. UV–Vis (Tol; kmax, nm (
(65, shoulder). Mp: 180 °C.
e
, Mꢀ1 cmꢀ1)): 371 (2210), 496
4.3. nacnacC2yCr, 4
4.7. X-ray diffraction studies
CrCl2(THF)x (0.30 g, 1.28 mmol for x = 2) was dissolved in THF
(20 mL) and a solution of nacnacCyLi(THF) (0.90 g, 2.6 mmol) in
toluene (15 mL) was added. The reaction mixture was stirred over-
night at room temperature. The solvent was removed under vac-
uum and the residue was extracted with diethyl ether (150 mL).
The extract was filtered to remove LiCl, concentrated, and kept at
ꢀ30 °C. Red crystals of 4 (0.63 g, 86%) separated after several days.
Anal. Calc. for C34H58N4Cr: C, 71.04; H, 10.17; N, 9.75. Found: C,
Diffraction data were collected on a Bruker Microstar–Proteum
with Helios optics equipped with a rotating anode source for Cu
Ka radiation (Table 3). Cell refinement and data reduction were
done using APEX2 [28]. Absorption corrections were applied using
SADABS [29]. Structures were solved by direct methods using SHELXS97
and refined on F2 by full-matrix least squares using SHELXL97 [30]. All
non-hydrogen atoms were refined anisotropically. Hydrogen atoms
were refined isotropic on calculated positions. A disordered diethyl
ether molecule in 2 was refined using appropriate restraints.
70.11; H, 10.15; N, 9.42%. UV–Vis (Tol; kmax, nm (
365 (6440), 487 (240, shoulder). Mp.: 180 °C
e
, Mꢀ1 cmꢀ1)):