Synthesis and structure of Co(III) coordination compounds [Co(DH) 2(Anil)2][BF4] and [Co(DH)2(Py) 2][BF4]

Article abstract of DOI:10.1023/A:1015521317602

The complex compounds [Co(DH)₂(Anil)₂][BF ₄] and [Co(DH)₂(Py)₂][BF₄] were synthesized from Co(BF₄)₂·6H₂O-DH ₂-A-alcohol-water systems (DH₂ is dimethylglyoxim and A is pyridine (Py) or aniline (Anil)), and their crystal structures were determined using X-ray diffraction analysis. In octahedral Co(III) complexes, two dimethylglyoxime radicals lie in the equatorial plane and are joined via the intramolecular hydrogen bond O-H...O. The complexes with pyridine and aniline have similar configurations but different crystal structures.

Full text of DOI:10.1023/A:1015521317602

Russian Journal of Coordination Chemistry, Vol. 28, No. 5, 2002, pp. 346–351. Translated from Koordinatsionnaya Khimiya, Vol. 28, No. 5, 2002, pp. 370–376.
Original Russian Text Copyright © 2002 by Malinovskii, Coropchanu, Bologa, Bel’skii.
Synthesis and Structure of Co(III) Coordination Compounds
[Co(DH)2(Anil)2][BF4] and [Co(DH)2(Py)2][BF4]
S. T. Malinovskii*, E. B. Coropchanu*, A. O. Bologa*, and V. K. Bel’skii**
*Institute of Chemistry, Academy of Sciences of Moldova, ul. Academiei 3, Chisinau, MD 2028 Moldova
**Karpov Institute of Physical Chemistry, ul Vorontsovo pole 10, Moscow, 103064 Russia
Received March 11, 2001
Abstract—The complex compounds [Co(DH)2(Anil)2][BF4] and [Co(DH)2(Py)2][BF4] were synthesized from
Co(BF4)2 · 6H2O–DH2–A–alcohol–water systems (DH2 is dimethylglyoxim and A is pyridine (Py) or aniline
(Anil)), and their crystal structures were determined using X-ray diffraction analysis. In octahedral Co(III)
complexes, two dimethylglyoxime radicals lie in the equatorial plane and are joined via the intramolecular
hydrogen bond O–H···O. The complexes with pyridine and aniline have similar configurations but different
crystal structures.
Co(III) is known to form stable complexes with
chelating α-dioxime ligands. These complexes can be out using a similar procedure (yield, 45%).
applied as industrial catalysts [1, 2], stimulators of
hemogenesis [3], antihypoxic medicines [4], and as a For C18H24CoF4N6O4B
model of vitamin B12 [5, 6].
Synthesis of [Co(DH)2(Py)2][BF4] (II) was carried
anal. calcd. (%): Co, 11.03; C, 40.47; H, 4.53; N, 15.73.
Found (%): Co, 10.86; C, 40.20; H, 5.75; N, 15.63.
Coordination compounds of Co(III) with α-
dioximes have different structures depending on their
synthesis conditions (pH of solutions), composition,
and nature of the coordinated ligands.
UV spectra of solutions I and II were recorded on
a Specord M-40 spectrometer in the 200–400 nm range
using a methanol/water mixture as a solvent; the solu-
tion concentration was 10–4 mol/l.
In this work, the results of synthesis and X-ray dif-
fraction analysis of two Co(III) coordination com-
X-ray diffraction analysis. The single crystals of
compound I were obtained in the form of dark brown
needles (0.54 × 0.12 × 0.10 mm). Their diffraction pat-
terns were taken on a CAD-4 diffractometer (MoKα
radiation, graphite monochromator, θ/2θ scan mode).
pounds—[Co(DH)2(Anil)2][BF4]
(I)
and
[Co(DH)2(Py)2][BF4] (II), where DH is dimethylgly-
1
oxime radical , Anil is aniline, and Py is pyridine—are
reported.
Compound II crystallized in the form of dark brown
prisms (0.42 × 0.22 × 0.18 mm); their diffraction pat-
terns were taken on a SYNTEX P1 diffractometer
(CuKα radiation, graphite monochromator, θ/2θ scan
mode).
EXPERIMENTAL
Synthesis of [Co(DH)2(Anil)2][BF4] (I). A solution
of 0.23 g (0.002 mol) of dimethylglyoxime in 30 ml of
methanol and 0.23 ml (0.0025 mol) of aniline were
added to a solution of 0.34 g (0.001 mol) of Co(BF4)2 ·
6H2O in 30 ml of water. The reaction mixture was
placed into a graphite crucible and heated on a water
bath at 50°ë. Crystalline needles precipitated from a
dark brown solution upon slow cooling (yield, 40%).
Compound I is soluble in alcohol and slightly soluble
in water.
Crystals I are orthorhombic: a = 23.828(3) Å, b =
17.035(3) Å, c = 12.623 Å, space group Pbca, Z = 8,
ρ(calcd) = 1.455 g/cm3.
Crystals II are monoclinic: a = 12.034(2) Å, b =
7.549(2) Å, c = 13.506(3) Å, β = 104.74(3)°, space group
Pn, Z = 2, ρ(calcd) = 1.495 g/cm3.
Structures I and II were solved by direct methods
(SHELX86 program [7]) and refined using 2320 (for I)
and 1356 (for II) independent reflections with I > 3σ.
For C20H28CoF4N6O4B
anal. calcd. (%): Co, 10.48; C, 42.73; H, 5.02; N, 14.95.
Non-hydrogen atoms were refined in the full-matrix
anisotropic approximation on F2; hydrogen atoms were
isotropically refined. The hydrogen atoms were refined
using the rigid group model. The calculations were per-
formed using the SHELX93 program [8].
Found (%):
Co, 10.24; C, 41.86; H, 5.50; N, 14.55.
1
H3C C C CH3
HON NO–
1070-3284/02/2805-0346$27.00 © 2002 åÄIä “Nauka /Interperiodica”

SYNTHESIS AND STRUCTURE OF Co(III) COORDINATION COMPOUNDS
347
Table 1. Coordinates of non-hydrogen atoms (×104) and their isotropic thermal parameters Ueq (×103) in structures I and II
I
II
Atom
x
y
z
Ueq, Å2
x
y
z
Ueq, Å2
Co
6344(1)
6355(2)
5701(2)
6965(2)
6351(2)
6124(2)
5803(2)
6876(2)
6567(2)
5786(2)
6920(2)
6393(3)
6225(3)
6574(2)
5976(2)
6842(2)
5726(2)
5533(2)
5495(5)
5066(3)
7158(2)
6964(2)
7614(4)
7202(6)
5242(2)
5162(3)
4636(5)
4206(4)
4283(3)
4801(3)
7506(2)
7743(3)
8296(3)
8600(3)
8360(3)
7808(3)
7412(1)
8775(2)
7206(2)
7627(2)
6098(2)
8408(3)
7664(3)
7160(2)
6427(2)
6906(4)
7912(3)
9983(4)
9556(4)
9516(3)
10437(3)
10405(3)
8758(3)
8316(3)
9533(6)
8585(5)
6517(3)
6080(3)
6250(6)
5314(6)
6680(4)
5951(4)
5748(7)
6268(9)
6976(8)
7200(5)
7813(3)
8291(3)
8168(5)
7575(5)
7095(4)
7220(3)
6201(1)
7556(3)
4316(3)
8085(3)
4785(3)
6709(3)
5143(3)
7259(3)
5681(3)
7171(4)
5262(4)
3834(7)
3018(6)
4630(6)
4180(4)
3519(4)
6212(5)
5288(4)
6527(9)
4586(6)
7127(4)
6181(5)
7816(7)
5835(8)
6774(4)
6339(6)
5961(6)
6043(7)
6475(7)
6856(5)
5525(4)
6283(5)
6552(5)
7575(5)
7095(4)
7220(3)
30(1)
51(1)
41(1)
40(1)
46(1)
35(1)
33(1)
31(1)
32(1)
36(1)
35(1)
60(2)
196(4)
159(3)
110(2)
102(2)
44(1)
39(1)
73(3)
58(2)
36(1)
38(1)
56(2)
66(2)
43(2)
58(2)
86(3)
103(4)
93(3)
62(2)
33(1)
44(1)
59(2)
61(2)
53(2)
41(1)
6418
7505(3)
4842(13)
10955(12)
10162(12)
4049(11)
6490(15)
9435(13)
8496(12)
5602(13)
6515(15)
8436(15)
6331
41(1)
71(3)
57(3)
54(3)
63(3)
54(4)
43(3)
43(3)
52(3)
39(3)
50(3)
78(5)
123(5)
92(3)
86(3)
121(5)
40(4)
47(4)
61(4)
57(4)
60(5)
59(5)
85(7)
79(6)
80(8)
84(6)
76(5)
70(5)
54(4)
57(4)
64(5)
75(5)
72(5)
53(5)
O(1)
O(2)
O(3)
O(4)
N(1)
N(2)
N(3)
N(4)
N(5)
N(6)
B
5129(11)
5711(9)
5024(10)
6746(9)
7653(8)
5916(8)
5402(10)
6224(9)
7245(10)
6423(11)
7459(8)
5164(10)
7726(10)
7197(11)
5129(11)
5373(12)
7714(10)
7466(12)
5870(10)
6948(11)
5602(18)
6547(15)
4688(10)
5732(10)
5551(15)
4182(14)
4413(14)
3478(13)
3132(13)
8514(15)
8607(13)
9800(20)
9440(19)
5820(20)
5470(20)
5066(19)
5098(16)
5531(14)
7344(16)
7680(16)
7655(17)
7357(17)
6997(14)
1130(30) 10708(18)
2023(19) 11322(13)
2168(14) 10725(13)
F(1)
F(2)
F(3)
861(13)
9800(8)
F(4)
–455(13) 11215(9)
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
C(8)
C(9)
C(10)
C(11)
C(12)
C(13)
C(14)
C(15)
C(16)
C(17)
C(18)
C(19)
C(20)
7471(14)
9247(18)
10600(20)
6750(20)
5822(18)
7570(20)
8140(30)
4470(20)
7550(16)
6840(20)
5160(30)
4060(20)
4816(19)
10110(18)
10850(20)
9910(30)
8100(30)
7503(18)
5131(10)
5630(12)
5476(13)
4454(12)
7001(14)
7466(14)
8144(14)
7189(16)
8301(16)
9076(15)
9056(16)
8201(16)
7474(12)
5211(13)
4355(13)
3545(15)
3529(13)
4309(13)
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 28 No. 5 2002

348
MALINOVSKII et al.
C(11)
C(12)
C(13)
C(10)
C(8)
C(9)
N(5)
O(4)
C(14)
C(6)
N(4)
O(2)
N(2)
C(4)
C(3)
C(2)
C(5)
C(7)
N(3)
O(3)
Co
C(1)
C(20)
N(1)
O(1)
C(19)
N(6)
C(15)
F(1)
C(16)
C(18)
F(2)
C(17)
B
F(3)
F(4)
Fig. 1. The structure of the molecule of complex I.
The final R-factor was equal 0.023 for I and 0.084
for II.
z
Coordinates and thermal parameters of the basis
atoms in structures I and II are presented in Table 1.
y
0
Co(d)
F(2)
F(4)
B
C(11)
Co(c)
C(3)
C(12)
F(3)
F(1)
C(10)
C(13)
O(2)
C(2)
C(4)
C(9)
N(2)
C(1)
N(1)
N(5)
F(1a)
F(2a)
F(3a)
F(4a)
O(1)
Co(a)
Co
O(3)
N(3)
C(6)
N(6)
O(4)
N(4)
Co(b)
C(18)
C(17)
C(5)
C(8)
C(14)
C(7)
C(15)
x
C(16)
Fig. 3. A fragment of the crystal structure of complex I.
Fig. 2. The structure of the molecule of complex II.
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 28 No. 5 2002

SYNTHESIS AND STRUCTURE OF Co(III) COORDINATION COMPOUNDS
349
RESULTS AND DISCUSSION
joined together via intramolecular hydrogen bonds O–
H…O (for I, O(1)···O(3) 2.528, O(1)–H(1) 0.84, and
O(3)···H(1) 1.7 Å; the O(1)–H(1)···O(3) angle is 171°;
for II, O(1)···O(4) 2.514 and O(2)···O(3) 2.481 Å). The
hydrogen bond parameters are close to those of other
Co(III) complexes with α-dioximes [11–13]. Location
of the hydrogen atoms in structure II was a failure
because of insufficient experimental data and the poor
quality of the single crystal.
The UV spectra of complexes I and II show two
absorption bands. The band at 246 nm is typical of
Co(III) dioximines with two dimethylglyoxime radi-
cals in the equatorial plane and is due to the intraligand
(DH) π–π transition [9]. The other band at ~370 nm is
produced by pyridine or aniline in compounds I and II,
respectively, and is due to charge transfer from the axial
ligands to the cobalt ion [10].
The average Co–N distance in the coordination
polyhedron of the cobalt atom in compounds I and II is
equal to 1.889 Å. The interatomic distances and bond
angles of I and II given in Table 2 are in good agree-
ment with the literature data [11–15] and correspond to
the atomic hybridization.
The structures of molecules I and II with different
complex
cations
[Co(DH)2(Anil)2]+
and
[Co(DH)2(Py)2]+ are shown in Figs. 1 and 2, respec-
tively. The [BF4]– anions in both structures are in the
outer sphere.
The cobalt atom in complex cations of I and II
exhibits a similar trans-octahedral coordination (6N).
The Co(III) coordination polyhedron, apart from four N
atoms of two bidentate-chelate ligands DH, includes
two nitrogen atoms of aniline (in the case of I) or of
pyridine (in the case of II). In both cases, two dimeth-
The metal rings of dimethylglyoximes are planar
to within 0.02 Å. The shifts of atoms from selected
planar fragments of the structures are illustrated in
Table 3.
In I, the dihedral angles formed by the equatorial
ylglyoxime radicals lie in the equatorial plane and are plane of the central atom of the complex cation (N(1),
Table 2. Interatomic distances and bond angles in structures I and II
I
II
Bond
Co–N(4)
d, Å
Bond
B–F(2)
d, Å
Bond
d, Å
Bond
B–F(1)
d, Å
1.879(4)
1.888(4)
1.893(5)
1.906(4)
2.005(5)
2.006(5)
1.355(6)
1.325(5)
1.330(5)
1.364(5)
1.285(7)
1.297(6)
1.296(6)
1.283(6)
1.444(7)
1.447(8)
1.323(9)
1.332(8)
1.351(9)
1.352(9)
1.462(8)
1.484(9)
1.496(8)
1.466(9)
1.481(7)
1.490(9)
1.371(8)
1.379(9)
1.39(1)
Co–N(4)
1.89(1)
1.89(1)
1.88(1)
1.91(1)
1.96(1)
1.97(1)
1.34(2)
1.35(1)
1.37(1)
1.35(1)
1.33(2)
1.24(2)
1.25(2)
1.31(2)
1.35(2)
1.39(3)
1.35(2)
1.37(2)
1.40(3)
1.29(2)
1.39(2)
1.35(2)
1.49(2)
1.46(2)
1.50(2)
1.45(2)
1.48(3)
1.56(2)
1.33(4)
1.36(3)
1.43(3)
1.35(2)
1.43(2)
1.30(3)
1.41(3)
1.32(2)
Co–N(1)
Co–N(3)
Co–N(2)
Co–N(5)
Co–N(6)
O(1)–N(1)
O(2)–N(2)
O(3)–N(3)
O(4)–N(4)
N(1)–C(1)
N(2)–C(2)
N(3)–C(5)
N(4)–C(6)
N(5)–C(9)
N(6)–C(15)
B–F(1)
C(1)–C(2)
Co–N(1)
B–F(3)
C(1)–C(3)
Co–N(3)
B–F(4)
C(2)–C(4)
Co–N(2)
B–F(2)
C(5)–C(7)
Co–N(5)
C(1)–C(2)
C(1)–C(4)
C(2)–C(3)
C(5)–C(6)
C(5)–C(8)
C(6)–C(7)
C(9)–C(10)
C(10)–C(11)
C(11)–C(12)
C(12)–C(13)
C(14)–C(15)
C(15)–C(16)
C(16)–C(17)
C(17)–C(18)
C(5)–C(6)
Co–N(6)
C(6)–C(8)
O(1)–N(1)
O(2)–N(2)
O(3)–N(3)
O(4)–N(4)
N(1)–C(1)
N(2)–C(2)
N(3)–C(6)
N(4)–C(5)
N(5)–C(13)
N(5)–C(9)
N(6)–C(14)
N(6)–C(18)
C(9)–C(10)
C(9)–C(14)
C(10)–C(11)
C(11)–C(12)
C(12)–C(13)
C(13)–C(14)
C(15)–C(16)
C(15)–C(20)
C(16)–C(17)
C(17)–C(18)
C(18)–C(19)
C(19)–C(20)
1.36(1)
1.34(1)
1.38(1)
1.376(7)
1.378(7)
1.379(8)
1.374(9)
1.364(9)
1.387(8)
B–F(3)
B–F(4)
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 28 No. 5 2002

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MALINOVSKII et al.
Table 2. (Contd.)
I
II
Angle
ω, deg
Angle
ω, deg
Angle
ω, deg
Angle
ω, deg
N(4)CoN(1)
N(4)CoN(3)
N(1)CoN(3)
N(4)CoN(2)
N(1)CoN(2)
N(3)CoN(2)
N(4)CoN(5)
N(1)CoN(5)
N(3)CoN(5)
N(2)CoN(5)
N(4)CoN(6)
N(1)CoN(6)
N(3)CoN(6)
N(2)CoN(6)
N(5)CoN(6)
C(1)N(1)O(1)
C(1)N(1)Co
O(1)N(1)Co
C(2)N(2)O(2)
C(2)N(2)Co
O(2)N(2)Co
C(5)N(3)O(3)
C(5)N(3)Co
O(3)N(3)Co
C(6)N(4)O(4)
C(6)N(4)Co
O(4)N(4)Co
C(9)N(5)Co
C(15)N(6)Co
F(1)BF(3)
179.3(2) F(1)BF(2)
110.5(7) N(3)CoN(1)
109.6(7) N(3)CoN(4)
106.1(7) N(1)CoN(4)
112.6(5) N(3)CoN(2)
123.8(6) N(1)CoN(2)
123.7(6) N(4)CoN(2)
113.4(5) N(3)CoN(5)
123.2(5) N(1)CoN(5)
123.3(5) N(4)CoN(5)
124.8(6) N(2)CoN(5)
111.5(5) N(3)CoN(6)
123.7(6) N(1)CoN(6)
113.3(5) N(4)CoN(6)
122.8(6) N(2)CoN(6)
123.9(6) N(5)CoN(6)
120.3(7) C(1)N(1)O(1)
120.4(6) C(1)N(1)Co
119.2(6) O(1)N(1)Co
119.4(8) C(2)N(2)O(2)
179.1(7) F(3)BF(4)
80.3(5) F(1)BF(2)
112(2)
105(2)
114(2)
111(2)
121(1)
116(1)
119(1)
125.7(9)
121(1)
109(1)
130(1)
124(1)
116(1)
120(2)
109(2)
126(1)
125(2)
116(2)
126(2)
118(2)
120(1)
123(2)
81.5(2) F(3)BF(2)
98.7(2) F(4)BF(2)
99.0(5) F(3)BF(2)
98.5(2) N(1)C(1)C(2)
81.3(2) N(1)C(1)C(3)
179.6(2) C(2)C(1)C(3)
91.0(2) N(2)C(2)C(1)
89.7(2) N(2)C(2)C(4)
85.2(2) C(1)C(2)C(4)
94.3(2) N(3)C(5)C(7)
88.7(2) N(3)C(5)C(6)
90.6(2) C(7)C(5)C(6)
93.0(2) N(4)C(6)C(5)
87.4(2) N(4)C(6)C(8)
178.2(2) C(5)C(6)C(8)
118.2(5) C(10)C(9)C(14)
117.1(4) C(10)C(9)N(5)
124.7(4) C(14)C(9)N(5)
121.6(4) C(9)C(10)C(11)
99.6(5) F(4)BF(2)
81.1(6) C(9)N(5)Co
179.2(7) C(14)N(6)C(18)
91.6(5) C(14)N(6)Co
88.8(6) C(18)N(6)Co
90.6(5) N(1)C(1)C(4)
90.2(5) N(1)C(1)C(2)
90.0(5) C(4)C(1)C(2)
89.5(5) N(2)C(2)C(3)
88.7(6) N(2)C(2)C(1)
90.5(5) C(3)C(2)C(1)
178.1(6) N(4)C(5)C(6)
120(1)
N(4)C(5)C(8)
117.2(9) C(6)C(5)C(8)
123(1)
123(1)
N(3)C(6)C(5)
N(3)C(6)C(7)
115.4(4) C(12)C(11)C(10) 119.6(9) C(2)N(2)Co
123.0(3) C(13)C(12)C(11) 121.0(9) O(2)N(2)Co
121.6(5) C(12)C(13)C(14) 121.0(1) C(6)N(3)O(3)
116.8(9) C(5)C(6)C(7)
120(1)
120(1)
117(1)
C(10)C(9)N(5)
C(11)C(10)C(9)
116.8(4) C(13)C(14)C(9)
118.7(9) C(6)N(3)Co
C(10)C(11)C(12) 118(2)
121.6(3) C(16)C(15)C(20) 121.4(6) O(3)N(3)Co
123.4(9) C(13)C(12)C(11) 116(2)
119.8(5) C(16)C(15)N(6)
116.7(4) C(20)C(15)N(6)
119.1(5) C(5)N(4)O(4)
119.4(5) C(5)N(4)Co
119(1)
N(5)C(13)C(12)
126(2)
120(2)
117.7(9) N(6)C(14)C(15)
123.4(3) C(15)C(16)C(17) 118.3(6) O(4)N(4)Co
120.0(4) C(18)C(17)C(16) 120.8(6) C(13)N(5)C(9)
118.6(4) C(19)C(18)C(17) 120.6(6) C(13)N(5)Co
110.4(7) C(18)C(19)C(20) 119.5(6) F(1)BF(3)
107.7(8) C(15)C(20)C(19) 119.3(6) F(1)BF(4)
112.4(6)
124(1)
116(1)
C(16)C(15)C(14) 121(2)
C(15)C(16)C(17) 120(2)
122.6(9) C(18)C(17)C(16) 117(2)
111(2)
105(2)
C(17)C(18)N(6)
126(1)
F(1)BF(4)
F(3)BF(4)
Table 3. The deviations of atoms (Å) from selected mean-square planes in structures I and II
I
II
N(1) (0.009), N(2) (–0.009), N(3) (–0.009), N(4) (0.009),
Co* (–0.002)
N(1) (0.011), N(2) (–0.012), N(3) (0.012), N(4) (–0.011),
Co* (–0.023)
Co (–0.023), N(1) (0.0224), N(2) (0.027), C(1) (–0.011),
C(2) (–0.017), O(1)* (0.090), O(2)* (0.090)
Co (0.012), N(1) (–0.019), N(2) (0.008), C(1) (0.017),
C(2) (0.002), O(1)* (0.037), O(2)* (0.011)
Co (0.025), N(3) (–0.030), N(4) (–0.025), C(5) (0.019),
C(6) (0.010)
Co (0.005), N(3) (0), N(4) (–0.013), C(5) (0.014),
C(6) (–0.007), O(3)* (0.010), O(4)* (0.046)
C(9) (–0.006), C(10) (0.006), C(11) (–0.003), C(12) (0),
C(13) (0), C(14) (0.003), N(5)* (0)
N(6) (–0.018), C(14) (0.007), C(15) (0.001), C(16) (0),
C(17) (–0.001), C(18) (0.020)
C(15) (–0.001), C(16) (0.008), C(17) (–0.005), C(18) (–0.004),
C(19) (0.011), C(20) (–0.008), N(6)* (0.061)
N(5) (0.003), C(9) (0.026), C(10) (–0.048), C(11) (0.040),
C(12) (–0.012), C(13) (–0.009)
* The atoms that were not used in the calculation of the mean-square planes are marked by an asterisk.
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 28 No. 5 2002

SYNTHESIS AND STRUCTURE OF Co(III) COORDINATION COMPOUNDS
351
z
y
0
Co(c)
Co(d)
Co(a)
Co(b)
x
Fig. 4. A fragment of the crystal structure of complex II.
3. Bowman, K., Gaughan, A.P., and Dori, Z., J. Am. Chem.
Soc., 1972, vol. 94, no. 3, p. 727.
N(2), N(3), N(4)) and the mean-square planes of the
aniline molecules (C(9), C(10), C(11), C(12), C(13),
C(14) and C(15), C(16), C(17), C(18), C(19), C(20))
are equal to 145.0° and 151.4°, respectively. In II, the
analogous angles formed by the plane of N(1)–N(9)
atoms and pyridine molecules (N(5), C(9), C(10),
C(11), C(12), C(13) and N(6), C(14), C(15), C(16),
C(17), C(18)) are equal to 89.0° and 91.1°.
4. Matkovskii, K.L., Izv. Akad. Nauk Mold. SSR, Biol.
Khim. Nauki, 1971, no. 5, p. 88.
5. Schrauzer, G.N. and Windgassen, R.I., J. Am. Chem.
Soc., 1967, vol. 89, no. 9, p. 1999.
6. Weber, J.H. and Schrauzer, G.N., J. Am. Chem. Soc.,
1970, vol. 92, no. 3, p. 726.
The N–H···F hydrogen bond is of crucial impor-
tance in the formation of the crystal structure of com-
pound I (Fig. 3): F(2)···N(6) 2.96, F(2)···H(6) 2.29, and
N(6)···H(6) 0.73 Å; the angle at the hydrogen atom is
equal to 156°.
7. Sheldrick, G.M., Acta Crystallogr., Sect. A: Found.
Crystallogr., 1990, vol. 46, no. 5, p. 467.
8. Sheldrick, G.M., SHELX93: Program for the Refinement
of Crystal Structure, Göttingen: Univ. of Göttingen,
1993.
In complex II, the complex cation and anions are
bound via electrostatic interactions F(3)···C(12),
F(3)···C(10) (0.5 + x, –1 – y, 0.5 – z), F(2)···C(5) (–0.5 +
x; 1 – y; 0.5 + z), and F(2)···C(6) (–0.5 + x; 1 – y, 0.5 + z)
(Fig. 4); the corresponding interatomic distances are
equal to 3.16, 3.18, 2.92, and 2.97 Å. Short F(2)···C(5)
and F(2)···C(6) contacts can be interpreted as the inter-
action of the fluorine electron cloud with the π cloud of
the metal ring.
9. Roos, B., Acta Chem. Scand., 1965, vol. 19, no. 7,
p. 1715.
10. Matsumoto, C., Masuda, I., and Shinra, K., Nippon
Kagaku Zasshi, 1967, vol. 88, no. 1, p. 46.
11. Botoshanskii, M.M., Dvorkin, A.A., Simonov, Yu.A.,
and Malinovskii, T.I., Kristallicheskie struktury neor-
ganicheskikh soedinenii (Crystal Structures of Inorganic
Compounds), Malinovskii, T.I., Ed., Chisinau: Shtiintsa,
1974, p. 26.
Other intermolecular contacts shorter than the sum
of the van der Waals radii of the respective atoms were
not observed in structures I and II.
12. Bresciani-Pahor, N., Forcolin, M., Marzilli, L.G., et al.,
Coord. Chem. Rev., 1985, vol. 63, no. 1, p. 1.
13. Simonov, Yu.A., Zavodnik, V.E., Shkurpelo, A.A., et al.,
Zh. Strukt. Khim., 1985, vol. 26, no. 2, p. 99.
REFERENCES
1. Panov, V.B., Khidekel’, M.L., and Shchepinov, S.A., Izv.
Akad. Nauk SSSR, Ser. Khim., 1968, no. 10, p. 2397.
14. Rusanovskii, M.E., Samus’, I.D., and Proskina, N.N.,
Izv. Akad. Nauk Mold. SSR, Ser. Fiz.-Tekh. Mat. Nauk,
1984, no. 2, p. 55.
2. Rogachev, B.G. and Khidekel’, M.L., Izv. Akad. Nauk 15. Simonov, Yu.A., Kravtsov, V.Kh., Gerbeleu, N.V., et al.,
SSSR, Ser. Khim., 1969, no. 1, p. 141. Zh. Neorg. Khim., 1999, vol. 44, no. 9, p. 1468.
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 28 No. 5 2002