Synthesis and molecular structures of the Co3(μ-OOCPh) 4(μ,η2-OOCPh)2[OC(Ph)OHNEt 3]2 and Co(Hdmpz)2(OOCPh)2 complexes (Hdmpz = 3,5-dimethylpyrazole)

Article abstract of DOI:10.1134/S0036023610070119

The product of the thermal reaction between cobalt acetate hydrate and benzoic acid reacts with a triethylamine excess to form the trinuclear complex Co₃(μ-OOCPh)₄(μ,η₂-OOCPh) ₂[OC(Ph)OHNEt₃]₂, and its reaction with 3,5-dimethylpyrazole yields the mononuclear complex Co(Hdmpz) ₂(OOCPh)₂. The compound structures are discussed on the basis of X-ray crystallographic data. Pleiades Publishing, Ltd., 2010.

Full text of DOI:10.1134/S0036023610070119

ISSN 0036ꢀ0236, Russian Journal of Inorganic Chemistry, 2010, Vol. 55, No. 7, pp. 1057–1063. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © I.V. Anan’ev, M.A. Yakovleva, E.V. Perova, S.E. Nefedov, 2010, published in Zhurnal Neorganicheskoi Khimii, 2010, Vol. 55, No. 7, pp. 1127–1133.
COORDINATION COMPOUNDS
Synthesis and Molecular Structures of the Co3(
μ
ꢀOOCPh)4(
μ
,
2ꢀ
η
OOCPh)2[OC(Ph)OHNEt3]2 and Co(Hdmpz)2(OOCPh)2
Complexes (Hdmpz = 3,5ꢀDimethylpyrazole)
I. V. Anan’ev, M. A. Yakovleva, E. V. Perova, and S. E. Nefedov
Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences,
Leninskii pr. 31, Moscow, 119991 Russia
eꢀmail: snef@igic.ras.ru
Received November 15, 2009
Abstract—The product of the thermal reaction between cobalt acetate hydrate and benzoic acid reacts with
a triethylamine excess to form the trinuclear complex Co3( ꢀOOCPh)4(
2ꢀOOCPh)2[OC(Ph)OHNEt3]2
μ
μ,η
,
and its reaction with 3,5ꢀdimethylpyrazole yields the mononuclear complex Co(Hdmpz)2(OOCPh)2. The
compound structures are discussed on the basis of Xꢀray crystallographic data.
DOI: 10.1134/S0036023610070119
The deprotonation behavior of 3,5ꢀdimethylpyraꢀ
zole (Hdmpz) and the peculiarities of the structures of
the pyrazolateꢀbridged transition metal compounds
formed are determined by the nature of the transition
metal, the R substituent in the carboxylate anion, and
the reaction conditions.
EXPERIMENTAL
All procedures relating to the synthesis and isolaꢀ
tion of complexes were carried out in a pure argon
atmosphere with the use of dry solvents.
IR spectra were recorded as KBr pellets on a
NexusꢀNicolet spectrophotometer in the range of
400–4000 cm–1.
For example, we have previously shown that the
reactions
of
binuclear
pivalates
M2(μꢀ
Xꢀray diffraction studies were performed by the stanꢀ
dard procedure on an automated Bruker SMART Apex II
OOCMe)4(NEt3)2, containing donor tertꢀbutyl subꢀ
stituents in the carboxylate anion, with Hdmpz
depends on the transition metal nature and leads to
deprotonation of pyrazole at room temperature with
diffractometer with a CCD detector (λMo, graphite
monochromator, scan). The structures were solved
ω
with the use of the SHELXTL PLUS (PC version) and
refined with the SHELXTLꢀ97 program packages [13,
14]. Crystal data and refinement parameters are shown in
Table 1. Atomic coordinates and selected geometric
parameters are compiled in Tables 2–5.
formation of the pyrazolateꢀbridged dimers M2(
μꢀ
dmpz)2(Hdmpz)2(OOCBut)2 (M = Zn, Co), binuclear
complexes M2(
ꢀOOCBut)4(Hdmpz)2 (M = Cu, Ni),
μ
or the mononuclear complex Cu(Hdmpz)2(OOCBut)2
[1–6].
Synthesis
of
Co3(
μ
ꢀOOCPh)4(
μ
,
2ꢀ
η
OOCPh)2[OC(Ph)OHNEt3]2 (1). To 1 g (4.01 mmol)
of cobalt acetate tetrahydrate, 1.47 g (12.03 mmol) of
benzoic acid in 20 mL of оꢀxylene was added. The
mixture obtained was refluxed with stirring for 3 h.
The suspension formed was cooled to room temperaꢀ
ture, and a triethylamine excess (4 mL, 28.78 mmol)
was added. The resulting solution was concentrated to
Note that the complexes obtained can be used to
produce more complex polynuclear clusters and even
metalꢀcontaining polymers with unsaturated bridging
organic moieties and transition metal atoms [7–11].
In this work, reactions of cobalt benzoate, which
contains an acceptor phenyl substituent in the carboxꢀ
ylate anion, with triethylamine and Hdmpz are conꢀ
sidered in comparison with analogous reactions of
cobalt pivalate and acetate containing donor tertꢀbutyl
and methyl substituents. It is well known that the
strength of carboxylic acids changes as follows:
PhCOOH > MeCOOH > ButCOOH [12].
10 mL and kept at
⎯
15 С for a day. The violet crystals
°
formed were isolated by decantation, washed with cold
hexane, and dried in an argon flow. Yield, 2.11 g
(78.3%).
For Co3C68H72N2O16 anal. calcd (%): C, 60.22; H,
5.80. Found (%):C, 60.19; H, 5.77.
1057

1058
ANAN’EV et al.
Table 1. Crystal data and refinement details for structures 1 and 2
1
2
Chemical formula
FW
C68H72Co3N2O16
1350.07
C24H26CoN4O4
493.42
T
, K
120(2)
150(2)
Color
Violet
Violet
Crystal system
Space group
Monoclinic
Monoclinic
P
2(1)/
n
P2(1)/n
Unit cell parameters (Å, deg)
a
b
c
= 13.4012(15)
= 15.6336(17)
= 16.6327(18)
a
b
c
= 12.2366(5)
= 14.0892(6)
= 14.2885(6)
α
= 90
= 108.837(2)
= 90
α
= 90
= 95.461(1)
= 90
β
β
γ
γ
V
Z
, Å3
3298.1(6)
2
2452.21(18)
4
ρcalcd, g/cm3
, mm–1
1.359
0.814
1406
1.336
0.736
1028
μ
F(000)
Crystal dimensions, mm
θ scan range, deg
0.14
1.71–27.00
17, –19 19, –21
22296
×
0.12
×
0.10
0.16
2.03–29.00
16, –19 19, –17
21346
×
0.14
×
0.12
Reflection index range
Reflections measured
Independent reflections
GOOF
–17
≤
h
≤
≤
k
≤
≤
l
≤
19 –16
≤
h
≤
≤
k
≤
≤
l ≤ 19
7092 [R
(int) = 0.0337]
1.017
6453 [R
(int) = 0.0533]
1.001
R
[
I
> 2
σ
(
I
)]
R
1 = 0.0441, wR2 = 0.1089
1 = 0.0654, wR2 = 0.1227
0.755 and –0.687
R
1 = 0.0330, wR2 = 0.0818
1 = 0.0462, wR2 = 0.0854
0.393 and –0.293
R (for all reflections)
Residual electron density (max/min), e Å–3
)
R
R
R
(
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 55 No. 7 2010

SYNTHESIS AND MOLECULAR STRUCTURES
1059
Table 2. Atomic coordinates (×104) and equivalent isotropic
×
IR (cm–1): 3438 m, 3028 m, 2853 w, 2222 w, 1610 s,
1567 s, 1491 m, 1472 m, 1448 m, 1366 s, 1339 m,
1175 m, 1158 m, 1130 m, 1068 m, 1026 m, 937 w,
839 m, 819 w, 720 s, 676 s, 691 m, 554 w, 468 m, 442 w.
factors (Å2
Atom
103) for complex 1
x
y
z
Ueq
Co(1)
Co(2)
O(1)
5000
5000
0
35(1)
41(1)
46(1)
75(1)
54(1)
55(1)
51(1)
53(1)
65(1)
79(1)
49(1)
54(1)
70(1)
95(1)
Synthesis of Co(Hdmpz)2(OOCBut)2 (2). To a soluꢀ
3624(1)
4380(1)
4978(2)
5552(2)
4527(2)
6448(1)
7491(1)
2958(2)
2456(2)
4833(2)
5081(2)
5363(3)
5569(3)
5448(4)
5147(4)
4980(3)
5292(2)
5951(2)
5560(3)
6199(4)
7199(4)
7576(3)
6951(3)
7311(2)
8233(2)
9197(2)
10066(3)
9955(3)
8997(3)
8138(3)
2631(2)
2512(2)
2440(3)
2418(3)
2437(3)
2471(3)
2521(2)
1854(9)
2428(5)
263(7)
6095(1)
6301(1)
7282(2)
4837(1)
5468(1)
5535(1)
958(1)
103(1)
tion of 0.25 g (0.18 mmol) of complex
1 in 7 mL of
benzene, a solution of 0.106 g (1.11 mmol) of
3,5ꢀdimethylpyrazole in 5 mL of benzene was added.
The resulting solution was concentrated to 10 mL and
O(2)
1093(1)
1297(1)
1944(1)
127(1)
O(3)
O(4)
kept at +5 С for 2 days. The violet crystals formed
°
O(5)
were isolated by decantation, washed with cold hexꢀ
ane, and dried in an argon flow. Yield, 0.14 g (82.8%).
O(6)
4716(1) –354(1)
O(7)
6937(1)
7602(2)
7033(2)
1505(2)
266(1)
362(2)
For CoC24H26N4O4 anal. calcd (%): C, 58.42; H,
5.31. Found (%):C, 58.37; H, 5.37.
O(8)
C(1)
C(2)
7588(2) –270(2)
7259(2) –930(2)
7798(3) –1515(3)
IR (cm–1): 3189 m, 3138 m, 3105 m, 3064 m, 3030 m,
2972 m, 2927 m, 2862 m, 2738 m, 2677 m, 2491 w,
1975 w, 1922 w, 1605 s, 1566 s, 1545 s, 1491 m, 1475 m,
1449 m, 1397 s, 1292 s, 1171 m, 1152 m, 1069 m, 1045 m,
1024 m, 981 w, 943 w, 850 m, 840 m, 806 m, 784 w, 742 w,
723 s, 707 m, 571 w, 447 m, 422 m.
C(3)
C(4)
C(5)
8661(3) –1463(3) 103(2)
C(6)
9001(3) –824(4)
8467(2) –210(3)
106(2)
79(1)
45(1)
50(1)
64(1)
90(1)
101(2)
C(7)
C(8)
5007(2)
4651(2)
4638(2)
4342(3)
4052(3)
4063(3)
4354(3)
5353(2)
5923(2)
5757(2)
6267(3)
6939(3)
7112(3)
6607(2)
7592(2)
8393(2)
9179(2)
9921(2)
9888(3)
9124(3)
8363(2)
1932(2)
2773(2)
3453(2)
4232(2)
4334(3)
Reaction of Co2(
ꢀdmpz)2(Hdmpz)2(OOCBut)2
µ
C(9)
with PhCOOH. Benzoic acid (0.068 g, 0.56 mmol)
was added to a solution of 0.1 g (0.14 mmol) of Co2(μꢀ
C(10)
C(11)
C(12)
C(13)
C(14)
C(15)
C(16)
C(17)
C(18)
C(19)
C(20)
C(21)
C(22)
C(23)
C(24)
C(25)
C(26)
C(27)
C(28)
C(29)
C(30)
C(31)
C(32)
C(33)
C(34)
N(1)
dmpz)2(Hdmpz)2(OOCBut)2 in 15 mL of
о
ꢀxylene,
for 3 h. The soluꢀ
tion obtained was concentrated to 5 mL and kept at
+5 for several days. The violet crystals formed were
isolated by decantation, washed with cold hexane, and
dried in an argon flow. Yield of , 0.098 g (71%).
and the mixture was stirred at 140 С
°
3668(3) 103(2)
2886(2)
50(2)
77(1)
41(1)
46(1)
65(1)
79(1)
87(1)
96(1)
70(1)
53(1)
46(1)
66(1)
81(1)
84(1)
81(1)
59(1)
°С
462(2)
2
360(2)
For CoC24H26N4O4 anal. calcd (%): C, 58.42; H,
5.31; N, 11.35. Found (%):C, 58.99; H, 4.97; N,
11.03.
753(3)
1228(3)
1336(3)
950(2)
IR (cm–1): 3189 m, 3138 m, 3105 m, 3064 m, 3030 m,
2972 m, 2927 m, 2862 m, 2738 m, 2677 m, 2491 w,
1975 w, 1922 w, 1605 s, 1566 s, 1545 s, 1491 m, 1475 m,
1449 m, 1397 s, 1292 s, 1171 m, 1152 m, 1069 m, 1045 m,
1024 m, 981 w, 943 w, 850 m, 840 m, 806 m, 784 w, 742 w,
723 s, 707 m, 571 w, 447 m, 422 m.
1045(2)
1499(2)
1110(2)
1550(3)
2370(3)
2761(2)
2329(2)
RESULTS AND DISCUSSION
7543(7) –1905(4) 251(7)
8202(5) –1867(4) 153(3)
7788(6) –1640(5) 232(6)
8030(5) –1048(4) 132(2)
6394(3) –1374(3) 123(2)
It was found that the compound obtained by the
thermal reaction between cobalt acetate hydrate and
benzoic acid reacts with excess triethylamine to proꢀ
–264(4)
1141(5)
506(4)
duce
OOCPh)4(
violet
trinuclear
complex
Co3(μꢀ
(1)
μ,η
2ꢀOOCPh)2[OC(Ph)OHNEt3]2
5965(3) –2196(3)
7310(2) –1377(2)
112(2)
79(1)
containing axially coordinated adduct of carboxylic
acid and triethylamine:
1197(3)
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 55 No. 7 2010

1060
ANAN’EV et al.
Compound
of unknown
structure
PhCOOH excess
xylene
Co(OOCMe)2
⋅
4H2O
145°С
Et N,
3
xylene,
22
Ph
C
°С
Ph
C
O
O
Ph
C
Et3N
H
O
O
O
PhC
O
O
O
Co
O
Co
O
H
Co
O
C
Ph
NEt3
CPh
O
O
O
O
C
OH
Ph
1
C
Ph
Hdmpz,
benzene,
22°С
Me
N
Me
Me
But
C
Me
Me
Co
Ph
C
N
N N
N
O
O
H
O
Me
O
H
N
PhCOOH
xylene
145°С
Co
Co
H
H
O
N
Me
O
N N
C
Ph
O
O
N N
N
C
Me
But
Me
Me
Me
Me
2
According to the Xꢀray diffraction data, three bonding distance Co···Co of 3.2811(5) Å. The atoms
cobalt atoms of that lie on the same line are at a nonꢀ are connected in pairs by two ꢀО,О'ꢀbenzoate bridges
1
μ
Table 3. Selected bond lengths (d) and bond angles (ω) for complex 1
Bond
d, Å
Bond
d, Å
Co(1)O(3)
Co(1)O(5)
Co(1)O(1)
Co(2)O(4)
Co(2)O(7)
2.0580(18)
2.0607(17)
2.2249(17)
1.9586(19)
1.970(2)
Co(1)O(3)#1
Co(1)O(5)#1
Co(1)O(1)#1
Co(2)O(6)#1
Co(2)O(1)
2.0580(18)
2.0607(17)
2.2250(17)
1.9688(19)
2.0209(17)
Angle
ω
,
deg
Angle
ω
, deg
O(3)Co(1)O(3)#1
O(3)#1Co(1)O(5)
O(3)#1Co(1)O(5)#1
O(3)Co(1)O(1)
179.999(1)
93.73(8)
86.27(8)
92.84(7)
89.07(7)
87.16(7)
90.93(7)
180.0
101.34(9)
110.77(8)
128.54(8)
133.07(16)
139.38(18)
140.94(18)
112.36(19)
O(3)Co(1)O(5)
86.27(8)
93.73(8)
180.0
O(3)Co(1)O(5)#1
O(5)Co(1)O(5)#1
O(3)#1Co(1)O(1)
O(5)#1Co(1)O(1)
O(3)#1Co(1)O(1)#1
O(5)#1Co(1)O(1)#1
O(4)Co(2)O(6)#1
O(6)#1Co(2)O(7)
O(6)#1Co(2)O(1)
C(1)O(1)Co(2)
87.16(7)
90.93(7)
92.84(7)
89.07(7)
105.50(9)
106.48(9)
102.37(8)
101.20(16)
101.11(7)
123.99(18)
122.19(16)
O(5)Co(1)O(1)
O(3)Co(1)O(1)#1
O(5)Co(1)O(1)#1
O(1)Co(1)O(1)#1
O(4)Co(2)O(7)
O(4)Co(2)O(1)
O(7)Co(2)O(1)
C(1)O(1)Co(1)
C(8)O(3)Co(1)
C(15)O(5)Co(1)
C(22)O(7)Co(2)
Co(2)O(1)Co(1)
C(8)O(4)Co(2)
C(15)O(6)Co(2)#1
Symmetry codes: #1 –x + 1, –y + 1, –z.
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 55 No. 7 2010

SYNTHESIS AND MOLECULAR STRUCTURES
1061
C(12)
C(11)
C(5A)
C(4A)
C(30)
C(13)
C(6A)
C(31)
C(29)
C(10)
O(4)
C(32)
C(7A)
N(1)
C(14)
C(25A)
C(9)
C(24A)
H(1A)
C(3A)
C(2A)
C(34)
O(8A)
C(8)
C(33)
C(1A)
O(2A)
C(23A)
C(22A)
O(7A)
C(26A)
O(3)
C(19A)
C(20A)
O(1A)
C(17A)
Co(2)
Co(1)
C(27A)
Co(2A)
C(28A)
O(7)
C(15A)
O(6A)
O(5A)
C(15)
C(21)
O(5)
C(28)
O(6)
C(17)
C(27)
C(22)
C(16)
C(20)
O(1)
C(1)
C(18)
O(2)
C(19)
O(4A)
O(3A)
C(33A)
C(23)
C(34A)
C(8A)
C(9A)
O(8)
C(2)
C(26)
C(14A)
H(1AA)
C(3)
N(1A)
C(24)
C(32A)
C(7)
C(25)
C(10A)
C(13A)
C(29A)
C(31A)
C(4)
C(11A)
C(30A)
C(12A)
C(6)
C(5)
Fig. 1. Structure of complex 1.
C(22C)
C(22D)
C(23C)
C(21C)
C(23D)
C(21D)
C(8A)
C(7A)
C(6A)
C(24C)
C(10A)
C(14C)
C(12C)
C(20D)
C(4A)
C(9A)
C(24D)
C(20C)
C(19C)
C(3A)
N(3A) C(1A)
C(2A)
N(1A)
C(19D)
C(5A)
C(18C)
N(4A)
C(15C)
N(2A)
C(18D)
O(3C)
C(13C)
C(14D)
O(4D)
O(3D)
C(15D)
O(4C)
H(2AA)
O(2C)
H(4AA)
C(11C)
Co(1A)
C(16D)
O(1A)
C(17A)
C(16C)
C(17C)
O(2D)
C(11D)
C(12A)
Co(1C)
C(17D)
O(1D)
O(2A)
C(16A)
H(4AD)
O(1C)
H(2AC)
C(11A)
O(3A)
C(13A)
Co(1D)
H(4AC)
N(4C)
N(1D)
N(1C)
C(2C)
O(4A)
H(2AD)
N(4D)
C(15A)
C(18A)
N(2C)
C(4C)
C(5C)
C(20)
N(3D)
C(14A)
N(2D)
C(1C)
N(3C)
C(19A)
C(1D)
C(9C)
C(3C)
C(10C)
C(24A)
C(9D)
C(20A)
C(4D)
C(3D)
C(10D)
C(6C)
C(6D)
C(5D)
C(7C)
C(8C)
C(7D)
C(8D)
C(21A)
C(23A)
C(22A)
Fig. 2. A fragment of crystal packing of complex
2.
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 55 No. 7 2010

1062
ANAN’EV et al.
Table 4. Atomic coordinates (×104) and equivalent isotropic
×
(Co(1)–O(3), 2.055(2) Å; Co(1)–O(5), 2.061(2) Å;
Co(2)–O(4), 1.955(2) Å; Co(2)–O(6), 1.967(2) Å)
and one ꢀО bridging benzoate anion (Co(1)–O(1),
2.227(2) Å; Co(2)–O(1), 2.019(2) Å). The central
cobalt atom has a distorted octahedral environment,
and each of the peripheral atoms is in a tetragonalꢀ
pyramidal environment, which, in addition to oxygen
atoms of the bridging anions, is completed by contacts
factors (Å2
103) for complex 2
μ
Atom
x
y
z
Ueq
Co(1)
O(1)
2690(1)
472(1)
2133(1)
2183(1)
2697(1)
3314(1)
3195(1)
1625(1)
1309(1)
1109(1)
1273(1)
1382(1)
1614(1)
922(1)
24(1)
33(1)
35(1)
29(1)
29(1)
26(1)
27(1)
26(1)
27(1)
32(1)
44(1)
40(1)
32(1)
47(1)
30(1)
43(1)
33(1)
30(1)
41(1)
28(1)
29(1)
42(1)
53(1)
50(1)
41(1)
32(1)
23(1)
23(1)
31(1)
35(1)
34(1)
34(1)
28(1)
1519(1) –491(1)
with the O(2) atom of the
μꢀО bridging moiety
O(2)
924(1)
3502(1)
3028(1)
865(1)
892(1)
(Co(2)–O(2), 2.554(3) Å) and the oxygen atom of the
O(3)
adduct PhCOO···HNEt3 (Co(2)–O(7) 1.970(2)
Å)
(Fig. 1, Tables 2, 3).
O(4)
2418(1)
When complex
1 interacts with excess Hdmpz in
N(1)
N(2)
N(3)
N(4)
C(1)
3806(1) –417(1)
3550(1) –1310(1)
benzene, deprotonation of pyrazole does not occur, as
distinct from the cobalt complexes containing pivalate
or acetate anions, and the violet mononuclear comꢀ
plex Co(OOCPh)2(Hdmpz)2 (2) is formed. In this
2477(1)
2710(1)
1472(1)
2401(1)
complex, according to Xꢀray diffraction data, the
cobalt(II) atom has a distorted tetrahedral environꢀ
ment of two oxygen atoms of the two terminal benꢀ
zoate anions (Co(1)–O(1), 1.979(1) Å; Co(1)–O(3),
1.966(1) Å) and two nitrogen atoms of the coordinated
Hdmpz molecules (Co(1)–N(1), 2.038(1) Å; Co(1)–
N(3), 2.031(1) Å). In the crystal unit of the complex,
linear polymers are formed due to intermolecular
hydrogen bonds of the pyrazole NH fragments and oxyꢀ
gen atoms of the benzoate anions (N···O, 2.681(2) Å)
(Fig.2, Tables 4, 5).
4818(1) –253(1)
5368(2) 679(1)
C(2)
C(3)
5195(1) –1041(1)
4371(1) –1705(1)
4290(2) –2683(1)
C(4)
889(1)
C(5)
480(1)
C(6)
2188(1)
1849(2)
2243(1)
2578(1)
2790(2)
775(1)
1403(1)
186(1)
Complex
when we tried to replace the terminal pivalate anions
in Co2(
ꢀdmpz)2(Hdmpz)2(OOCBut)2 with more
2 was unexpectedly obtained in high yield
C(7)
472(1) –253(1)
2294(1) –227(1)
μ
basic benzoate anions. However, this reaction likely
proceeded through protonation of the bridging pyraꢀ
zolate anions due to the presence of strong benzoic
acid, as it occurred with the pyrazolateꢀbridged dimer
in the reaction with trifluoromethanesulfonic acid [1,
15], and pivalic acid was formed.
C(8)
C(9)
2918(1)
3961(1)
10(1)
482(1)
467(1)
C(10)
C(11)
C(12)
C(13)
C(14)
C(15)
C(16)
C(17)
C(18)
C(19)
C(20)
C(21)
C(22)
C(23)
C(24)
2519(1)
2692(1)
2988(1)
3150(2)
3030(1)
2737(1)
2563(1)
3643(1)
4620(1)
4962(1)
5855(1)
6411(1)
6076(1)
5183(1)
Thus, the studies performed have shown that the
structures of the products of the reactions of zinc, copꢀ
per, and cobalt carboxylates with triethylamine and
pyrazole are determined by the Lewis acidity of the
metal center, which depends on the donor ability of
the R substituent in the carboxylate anion. For less
basic benzoate and acetate anions, the adduct
[OC(R)O]–(HNEt3)+ (R = Ph, Me) is coordinated in
the zinc, copper, and cobalt complexes at an excess of
triethylamine in the presence of the corresponding
acids; whereas for the pivalate anion, complexes
–275(1) –476(1)
–1141(1) 44(1)
–2111(2) –418(2)
–2213(2) –1382(2)
–1354(1) –1901(1)
–388(1) –1449(1)
3457(1)
3990(1)
4130(1)
4634(1)
5018(1)
4889(1)
4370(1)
1735(1)
1897(1)
2819(1)
2977(1)
2221(1)
1305(1)
1142(1)
M2(
ꢀOOCBut)4(NEt3)2 were obtained under the same
μ
conditions. The reactions of zinc benzoate and acetate
with Hdmpz in the presence of triethylamine lead to
deprotonation of pyrazole and formation of binuclear
complexes containing intramolecular hydrogen bonds
of the pyrazole NH moieties with oxygen atoms of the
carboxylate anions [16–18]. Cobalt forms a trinuclear
complex with intermolecular hydrogen bonds in case
of acetate and a mononuclear complex in case of benꢀ
zoate [16, 17]. The interaction of {[Cu2(
μꢀ
OOCMe)4[μꢀOOCMe(HNEt3)]}n with 3,5ꢀdimethylꢀ
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 55 No. 7 2010

SYNTHESIS AND MOLECULAR STRUCTURES
1063
Table 5. Selected bond lengths (d) and bond angles (ω) for
complex 2
tific Schools of Russia; grant no. NShꢀ1733.2008.03),
and the Presidium and the Division of Chemistry and
Materials Science of the Russian Academy of Sciences
(programs “Theoretical and Experimental Investigaꢀ
tions of the Nature of the Chemical Bond and the
Mechanisms of Important Chemical Reactions and
Processes” and “Targeted Synthesis of Inorganic
Compounds and Design of Functional Materials”).
Bond
d, Å
Bond
d, Å
Co(1)O(3)
Co(1)N(3)
O(1)C(11)
O(3)C(18)
N(1)C(1)
N(2)C(4)
N(3)N(4)
1.9658(10) Co(1)O(1)
2.0309(12) Co(1)N(1)
1.2813(19) O(2)C(11)
1.2812(16) O(4)C(18)
1.9789(11)
2.0378(13)
1.2404(18)
1.2431(16)
1.3630(16)
1.3350(19)
1.3417(19)
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pyrazole does not lead to deprotonation of pyrazole,
and monoꢀ and binuclear complexes were isolated as
was observed for pivalates. However, the binuclear
complex with bridging acetate anions contains interꢀ
molecular hydrogen bonds, whereas the binuclear
complex with bridging pivalate anions contains
intramolecular hydrogen bonds between the NH fragꢀ
ments of the coordinated pyrazole and oxygen atoms
of the corresponding anion [18].
Note also that, in the absence of triethylamine,
deprotonation of pyrazole with zinc and cobalt acetate
hydrates occurs on heating to 150
mation of the complexes
°
С
and leads to forꢀ
M3(μꢀ
dmpz)4(Hdmpz)2(OOCMe)2, in which the character
of hydrogen bonds depends on the natures of the tranꢀ
sition metal and solvation molecules [16].
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ACKNOWLEDGMENTS
This work was supported by the Russian Foundaꢀ
tion for Basic Research (project nos. 08ꢀ03ꢀ01063, 08ꢀ
03ꢀ90455), the Council for Grants of the President of
the Russian Federation (for Support of Leading Scienꢀ
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 55 No. 7 2010