T.A. Bazhenova et al.
Inorganica Chimica Acta 522 (2021) 120358
of a homogeneous green–brown solution occurred. The addition of
excess of NH4PF6 to the cooled, filtered solution followed by slow
evaporation over 2 weeks gave light brown crystals of 2. (90 mg, yield
45%). The complex was identified by X-ray diffraction analysis.
[Cr(HL)(H2O)Cl]ClO4⋅0.25H2O (3). To a mixture of H2L (184 mg,
0.45 mmol) and LiClO4 (190 mg ,1.78 mmol) in 17 ml of C2H5OH under
Ar atmosphere solid CrCl2 4H2O (90 mg, 0.46 mmol) was added while
stirring. The green–brown mixture was stirred at 60 ◦C for 1 h, then
cooled to r.t. and filtered. Light brown block crystals 3 suitable for
single-crystal X-ray diffraction were obtained by slow evaporation of the
filtrate after several days. Yield: 40% (112 mg). Anal. Calc. for
CrC23H26N5O7Cl2 (M.W.: 607 g molꢀ 1) C, 45.48; H, 4.31; N, 11.53%.
Found: C, 45.91; H, 4.05; N, 11.75%. FT-IR (solid) νmax/cmꢀ 1: 697 s,
712vs, 811 m, 1051vs, 1099vs, 1132 s, 1169 s, 1273 m, 1300 s, 1392vs,
1425 m, 1500 s, 1526 s, 1572 m, 1600 m, 3256w, 3615w.
NaN3 in absolute methanol (360 mg, 5.5 mmol of NaN3 in 20 ml of
CH3OH) a portion of solid 1a (60 mg, or 0.1 mmol) was added while
stirring and the reaction mixture was stirred at 40 ◦C for 15 min. The
formation of a homogeneous green–brown solution was observed. The
reaction solution was cooled to r. t., filtered through a fritted glass filter
and left for crystallization at room temperature. After a few hours, the
formation of plate-shaped golden-brown crystals occurred. After this,
the solvent was decanted, and the crystalline precipitate was washed
with diethyl ether (2x3 ml) and dried in air. Upon drying, crystals of 10
easily lose crystallization alcohol. To carry out X-ray diffraction, the
crystal was quickly removed from the mother liquor and immediately
placed at a low temperature (200–250 K nitrogen stream, see Crystal
structure determination section). Elemental analysis corresponds to a
complex 10 without 2 CH3OH solvate molecules. Yield: 67% (45 mg).
Anal. Calc. for CrNaC27H31N11O6 (M.W.: 680 g molꢀ 1) C, 47.65; H, 4.59;
[Cr(HLOCH3)(H2O)2](NO3)2⋅H2O⋅C2H5OH (4). Complex
4
was
N, 22.64%. Found: C, 47.41; H, 4.13; N, 22.84%. FT-IR (solid) νmax/
prepared from CrIII nitrate according to the literature method [25].
Yield: 45%. Anal. Calc. for CrC27H36N7O14 (M.W.: 734 g molꢀ 1) C,
44.14; H, 4.94; N, 13.35%. Found: 44.51; H, 5.25; N, 13.75%. FT-IR
(solid) νmax/cmꢀ 1: 2958vs, 2904 s, 2867 s, 1606vs, 1557vs, 1529vs,
1494vs, 1386vs, 1315vs, 1269 s, 1190 m, 1166 m, 848 m, 682 m.
[Cr(LOCH3)(CH3OH)(OCH3)]⋅CH3OH (5). Complex 1a (350 mg,
0.57 mmol) was added to 22 ml of CH3OH. To this suspension the so-
lution of NaOCH3 in CH3OH (0.44 M, 3.9 ml, 92 mg, 1.7 mmol) was
added. The mixture was stirred for 10 min. The green–brown solid
dissolved during this time and the color of the resulting solution turned
red-brown. The reaction mixture was filtered and the filtrate was
allowed to crystallize at r. t. After 10 days the red-brown crystalline solid
(suitable for X-ray diffraction analysis) was separated from the mother
liquor, washed with CH3OH (5 ml), Et2O (5 ml) and dried in vacuum to
give 5. Yield: 61% (210 mg). Anal. Calc. for C28H34N5O7Cr (M.W.: 604.6
g molꢀ 1) C, 55.62; H, 5.67; N, 11.58%. Found: C, 55.31; H, 5.81; N,
cmꢀ 1: 765 s, 804 m, 849 s, 906 m, 1023vs, 1051 s, 1006 m, 1138 m,
1167vs, 1175vs, 1254vs, 1376vs, 1407 m, 1505 s, 1585 m, 1607 m,
2072vs, 2090vs, 2837 m, 3075 m, 3307w.
[Cr(LOCH3)(CN)2][Na(H2O)(C2H5OH)] (11). A sample of complex
1a (60 mg, or 0.1 mmol) was added to 15 ml of absolute methanol, and a
solid sample of NaCN⋅2H2O salt (40 mg, 0.47 mmol) was added to this
suspension with stirring using a magnetic stirrer. The reaction mixture
was stirred at 60 ◦C for 2 h. During this time, a complete dissolution of
the complex observed followed the formation of a homogeneous red-
brown color solution. The reaction mixture was cooled to room tem-
perature, concentrated to about 5 ml by pumping out the solvent in
vacuo. After this, a fine-crystalline orange precipitate developed. The
precipitate was dissolved in ethanol, filtered through a glass filter and
left at r. t. for slow evaporation. After some days, the formation of
rhombus-shaped bright red crystals of 11 occurred. The mother liquor
was decanted from the crystals; the precipitate was washed with diethyl
ether (2x3 ml) and dried in air. Yield: 40% (26 mg). Anal. Calc. for
CrNaC29H31N7O6 (M.W.: 648 g molꢀ 1) C, 50.91; H, 4.60; N, 11.42%.
Found: C, 53.45; H, 4.93; N, 14.85%. FT-IR (solid) νmax/cmꢀ 1: 755 s,
840 m, 1055 s, 1173vs, 1244 s, 1369vs, 1505 s, 1591 m, 1604 s, 2137 m,
2943 m, 3230 m, 3406w.
11.62%. FT-IR (solid sample)
ν
, cmꢀ 1: 2930 m, 1607 m, 1583 m, 1505 s,
1379vs, 1307 m, 1256 s, 1170 s, 1029vs, 994 m, 908 m, 842 s, 814 m,
761 s.
[Cr(HLOCH3)(NCS)2]⋅1.5H2O (6). Complex 1a (150 mg, 0.24 mmol)
was added to 20 ml of CH3OH. The mixture was stirred for 10 min.,
followed by the addition of the ethanol solution of NH4NCS (90 mg, ~ 1
mmol in 8 ml EtOH). The resulting solution continued to stir at 50 ◦C for
1 h. The precipitate of 6 developed during the first 10 min. The green-
–brown mixture was cooled to r.t., and filtrated. The crystalline solid
obtained was washed with Et2O (2x5 ml) and dried in vacuum. Yield:
71% (111 mg). Anal. Calc. for CrC27H25N7O5S2 (M.W.: 652 g molꢀ 1) C,
49.69; H, 3.91; N, 15.03; S, 9.82%. Found: C, 51.04; H, 4.35; N, 14.84; S,
9.35%. FT-IR (solid) νmax/cmꢀ 1: 761 s, 805 m, 844 s, 1024 m, 1051 m,
1171vs, 1255vs, 1301 m, 1383vs, 1493 s, 1561 m, 1603vs, 2064vs,
3075w, 3509w. Single crystals of 6 suitable for X-ray diffraction analysis
were obtained by slow evaporation of mother liquor.
2.2. Crystal structure determination
X-ray diffraction data were collected on an APEX II DUO CCD
diffractometer (for 1) and on an Oxford Diffraction Gemini-R CCD
diffractometer (for 2–11) [λ(MoKα) = 0.71073 Å, graphite mono-
chromator, ω-scans]. Crystals 7–9 were found in the same dried batch;
other single crystals were taken from mother liquid using a nylon loop
with paratone oil and immediately transferred into cold (200–250 K)
nitrogen stream of the diffractometer. All the transfer process took no
more than 5–7 s to prevent solvent loss and to preserve diffraction
quality of the crystals. Then crystals were cooled down to 120–150 K to
collect the full set of data. Data reduction with empirical absorption
correction of experimental intensities (Scale3AbsPack program) was
made with the CrysAlisPro software [45]. The structures were solved by
a direct method using SHELXS [46] or by a charge-flipping algorithm
using Superflip [47] and refined by a full-matrix least squares method
using SHELX-2016 program. All non-hydrogen atoms were refined
anysotropically. The positions of H atoms were calculated geometrically
and refined in a riding model with isotropic displacement parameters
depending on Ueq of connected atom. Torsion angles for methyl and
hydroxyl groups were refined using HFIX 137 and HFIX 147, respec-
[Cr(HLOCH3)(N3)2]⋅xH2O (7, x ¼ 0.2, 8, x ¼ 0, 9, x ¼ 0). To a
methanol solution of NaN3 (56 mg, 0.86 mmol in 16 ml) was added solid
complex 1a (50 mg, 0.082 mmol). The mixture was stirred at 60 ◦C for
approximately 10 min. Then the hot cloudy mixture was filtered and left
for crystallization under slow evaporation. After storing overnight at the
room temperature, black crystals appeared, the color of the solution
became pale yellow. The crystalline black solid was separated from so-
lution by decantation, washed with CH3OH (1.5 ml) and Et2O (2 ml),
dried under weak stream of Ar for 5 min. Yield: 67% (33 mg). Anal. Calc.
for C25H24N11O4Cr (M.W.: 604 g molꢀ 1) C, 50.51; H, 4.07; N, 25.92%.
Found: C, 49.95; H, 4.36; N, 25.51%. FT-IR (solid sample)
ν
, cmꢀ 1: 761 s,
–
844 m, 1024 s, 1168vs, 1252vs, 1308 m, 1338 m, 1381vs, 1508 m, 1559
m, 1607 s, 2059vs. In this reaction under an excess of NaN3 from 2.5 to
10, three phases, (7, 8, 9) of the complex [Cr(HLOCH3)(N3)2]⋅xH2O (7, x
= 0.2, 8, x = 0, 9, x = 0) are formed in the same batch, which were
identified by single crystal X-ray diffraction analysis (see crystal struc-
ture determination).
tively. N H bonds were refined without restraints (except for DFIX in 2
and 7). H atoms in water were found from difference Fourier map and
refined with bond length restraints (SADI or DFIX). For disordered sol-
vate water molecules with occupancy of 0.5 or less (in 3, 6, 7) hydrogen
atoms were not localized but included into compound formula.
In all the structures 1–11 the Cr complex is in a general position, i.e.
its molecular geometry is not restricted by the crystal symmetry.
[Cr(LOCH3)(N3)2][Na(CH3OH)2]⋅2CH3OH (10). To a solution of
3