Manganese(II) carboxylates containing coordinated 3,5-dimethylpyrazole

Article abstract of DOI:10.1134/S0036023615080215

Reactions of manganese(II) pivalate, benzoate, and cymantrenecarboxylate with 3,5-dimethylpirazole (Hdmpz) have been found to result in mononuclear complexes (Hdmpz)₄Mn(OOCR) where R = Bu^t and Ph, respectively, and binuclear complex {Mn(μ-OOCC₅H₄Mn(CO)₃)(OOCC₅H₄Mn(CO)₃) (Hdmpz)₂(OH₂)}₂ which contains a pyrazole solvate molecule. The obtained complexes have been isolated in high yields as single crystals and have been characterized by chemical analysis, IR spectroscopy, and X-ray diffraction.

Full text of DOI:10.1134/S0036023615080215

ISSN 0036ꢀ0236, Russian Journal of Inorganic Chemistry, 2015, Vol. 60, No. 8, pp. 934–941. © Pleiades Publishing, Ltd., 2015.
Original Russian Text © M.A. Uvarova, A.A. Ageshina, M.A. Golubnichaya, S.E. Nefedov, 2015, published in Zhurnal Neorganicheskoi Khimii, 2015, Vol. 60, No. 8, pp. 1032–
1039.
COORDINATION
COMPOUNDS
Manganese(II) Carboxylates Containing Coordinated
3,5ꢀDimethylpyrazole
M. A. Uvarova, A. A. Ageshina, M. A. Golubnichaya, and S. E. Nefedov
Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Science,
Leninskii pr. 31, Moscow, 119991 Russia
eꢀmail: snef@igic.ras.ru
Received February 20, 2015
Abstract—Reactions of manganese(II) pivalate, benzoate, and cymantrenecarboxylate with 3,5ꢀdimethylpiꢀ
razole (Hdmpz) have been found to result in mononuclear complexes (Hdmpz)4Mn(OOCR) where R = But
and Ph, respectively, and binuclear complex {Mn(μꢀOOCC5H4Mn(CO)3)(OOCC5H4Mn(CO)3)
(Hdmpz)2(OH2)}2 which contains a pyrazole solvate molecule. The obtained complexes have been isolated
in high yields as single crystals and have been characterized by chemical analysis, IR spectroscopy, and Xꢀray
diffraction.
DOI: 10.1134/S0036023615080215
The ability of heterocyclic 3,5ꢀdimetylpyrazole to
IR spectra were recorded on a Specord Mꢀ80 and a
be deprotonated in the course of reactions with carꢀ NexusꢀNicolet spectrophotometers in KBr pellets in
boxylates of transitional metals is due to the nature of the range of frequencies from 400 to 4000 cm–1.
the transitional metal and that of substituent R in the
Xꢀray diffraction studies were performed according
carboxylate anion.
to the standard procedure on a Bruker SMART Apex II
In particular, for M2(
ꢀOOCBut)4(NEt3)2 binuꢀ
μ
automated diffractometer equipped with a CCD
detector ( Mo, graphite monochromator, ꢀscanꢀ
λ
ω
clear pivalates that contain a donor tertꢀbutyl substitꢀ
uent in the carboxylate anion, it was found that
depending on the nature of the transitional metal at
room temperature in benzene there is the deprotonaꢀ
tion of pyrazole to form pyrazolateꢀbridged dimers
ning). The calculations of the structures were carried
out using the SHELXTL PLUS program package (PC
version). The refinement of the structures was perꢀ
formed using the SHELXTLꢀ97 program [12, 13].
M2(
ꢀdmpz)2(Hdmpz)2(OOCBut)2 (M = Zn, Co),
μ
Crystallographic data and refinement details are
presented in Table 1; coordinates of atoms and the
main geometrical parameters of the studied complexes
are listed in Tables 2–7. Full tables of atomic coordiꢀ
nates, bond lengths, and valence angles are deposited
in the Cambridge Structural Database (CCDC
1063752–1063754).
binuclear lantern dimer M2(μꢀ(OOCBut)4(Hdmpz)2
(M = Cu, Ni) containing Hdmpz in the axial positions,
or mononuclear complexes MX(Hdmpz)2(OOCBut)2
(M = Ni, X = H2O; M = Cu, X = O) [1–11].
)
Replacement of the bridged pivalate anion in comꢀ
plexes of the same type containing coordinated trimethyꢀ
lamine by the less donor acetate or benzoate anions in
similar reactions leads to formation of pyrazolateꢀbridged
Synthesis of Complexes
Mn(Hdmpz)4(OOCBut)2 (1)
. Solid Hdmpz (0.08 g,
0.8 mmol) was added to a solution of complex
Mn2(OOCBut)4 (Et3NHOOBut)2 (0.1 g, 0.1 mmol) in
methylene chloride, and the solution was mixed at
room temperature for 1 h. After addition of hexane
(5 mL), the obtained solution was allowed to stand for
dimers Zn2(μꢀdmpz)2(Hdmpz)2(OOCR)2 (R = Me,
Ph), trinuclear Co3(
and mononuclear Co(OOCPh)2(Hdmpz)2 complexes
[1–11].
μ
ꢀdmpz)4(Hdmpz)2(OOCMe)2
,
In the present work, structural features of products
of reactions of manganese(II) carboxylates containing
anions of pivalic, benzoic, and cymantrenecarboxylic
acids with 3,5ꢀdimethylpyrazole are considered.
24 h at a temperature of +5°С. The formed colorless
large crystals were separated from the mother solution
by decantation, washed with hexane, and dried in an
argon stream. The yield was 91% (0.11 mg).
EXPERIMENTAL
For MnC30H50O4N8 anal. calcd. (%): C, 56.16; H,
7.81; N, 17.47.
All the operations on synthesis and isolation of
complexes were carried out in the atmosphere of pure
argon using absolutized solvents.
Found (%): C, 56.30; H, 7.66; N, 17.07.
934

MANGANESE(II) CARBOXYLATES CONTAINING COORDINATED
935
Table 1. Crystallographic parameters and refinement details for structures 1–3
1
2
3
Molecular formula
FW
C30H50MnN8O4
641.72
C34H42MnN8O4
681.70
C66H68Mn6N12O22
1710.96
T
, K
150(2)
150(2)
150(2)
Color
Colorless
Triclinic
Colorless
Triclinic
Colorless
Triclinic
Singony
Space group
P
1
P
1
P1
Unit cell parameters, Å, deg
a
b
c
= 9.0774(13)
= 9.2949(14)
= 11.8125(17)
= 106.761(3)
= 99.251(3)
= 109.274(3)
864.0(2)
a
b
c
= 9.1379(14)
= 9.2097(14)
= 11.0026(17)
= 102.767(2)
= 93.783(2)
= 102.716(2)
874.5(2)
a
b
c
= 12.151(3)
= 13.033(4)
= 14.182(6)
= 107.668(6)
= 97.688(6)
= 116.251(4)
α
β
γ
α
β
γ
α
β
γ
V
Z
, Å3
1822.5(11)
1
1
1
ρcalc, mg/m3
, mm–1
(000)
Crystal size, mm
range, deg
1.233
1.294
1.559
1.051
716
μ
0.426
0.426
F
343
359
0.20
×
0.18
×
0.16
0.10
×
0.08
×
0.06
0.18
×
0.16 × 0.14
θ
1.88–29.98
2.30–29.00
2.11–28.00
Reflection index ranges
–12
–13
–16
≤
≤
≤
h
k
l
≤
≤
12,
12,
–12
–12
–15
≤
≤
≤
h
k
l
≤
12,
12,
15
–16
–17
–18
≤
≤
≤
h
k
l
≤
15,
17,
18
≤
≤
≤16
≤
≤
Number of reflections
Number of unique reflections
GOOF
10171
9563
18443
4912 [
R
(int) = 0.0386]
0.935
4611 [
R
(int) = 0.0323]
1.017
8702 [
R
(int) = 0.0703]
1.043
R
[I
> 2σ(I
)]
R
1 = 0.0627,
R
1 = 0.0511,
R
1 = 0.0769,
wR2 = 0.1532
wR2 = 0.1290
wR2 = 0.1861
R
(on all the reflections)
R
1 = 0.0776,
R
1 = 0.0729,
R1 = 0.1370,
wR2 = 0.2216
wR2 = 0.1648
wR2 = 0.1422
max/min electron density peaks,
e Å–3
2.274 and –0.613
0.730 and –0.572
2.121 and –0.735
IR (cm–1): 3430 br w, 3184 w, 3100 w, 2984 w, 2956 m, solution was mixed for 15 min. The obtained clear
1584 w, 1548 s, 1476 s, 1412 s, 1384 s, 1360 m, 1308 s, solution was concentrated to 10 mL; after addition of
1224 s, 1192 w, 1147 w, 1056 m, 812 w, 792 m, 744 w, benzene (5 mL) it was allowed to stand for 24 h at a
620 w, 542 w.
temperature of +5°С. The formed colorless large crysꢀ
tals were separated from the mother solution by
decantation, washed with hexane, and dried in an
argon stream. The yield was 65% (0.17 g).
Mn(Hdmpz)4(OOCPh)2 (2). Benzoic acid (0.15 g,
1.2 mmol) was added to a suspension of aqueous manꢀ
ganese acetate (0.1 g, 0.4 mmol) in acetonitrile, the
obtained solution was mixed for 2 h at a temperature of
For MnC34H42O4N8 anal. calcd. (%): C, 59.91; H,
80°С; 3,5ꢀdimethylpyrazole was then added, and the 6.16; N, 16.44.
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 60 No. 8 2015

936
UVAROVA et al.
Table 2. Atomic coordinates (
104) and equivalent isotroꢀ
×
×
103) in complex
1
Found (%): C, 59.60; H, 6.32; N, 16.13.
pic factors (Å2
Atom
IR (cm–1): 3138 br w, 3110 w, 2491 w, 1605 s, 1566 s,
1544 s, 1473 m, 1449 m, 1396 s, 1363 s, 1291 s, 1171 m,
1068 w, 1044 m, 1024 m, 943 w, 849 s, 806 w, 723 s, 706 m,
678 m, 570 w, 446 m.
x
y
z
Ueq
Mn(1)
O(1)
O(2)
N(1)
N(2)
N(3)
N(4)
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)
10000
5000
0
22(1)
26(1)
31(1)
24(1)
26(1)
23(1)
25(1)
25(1)
28(1)
37(1)
41(1)
43(1)
26(1)
31(1)
30(1)
29(1)
42(1)
26(1)
34(1)
30(1)
28(1)
36(1)
11220(2) 7376(2) 1548(1)
9565(2)
8902(2)
8049(2) 2605(1)
3857(2) 1319(1)
4804(2) 2331(1)
{Mn(μꢀOOCC5H4Mn(CO)3)(OOCC5H4Mn(CO)3)ꢀ
(Hdmpz)2(OH2)}2
·
Hdmpz (3) Cymantrenecarboxyꢀ
.
lic acid (0.2 g, 0.8 mmol) was added to a suspension of
aqueous manganese acetate (0.1 g, 0.4 mmol) in aceꢀ
tonitrile; the mixture was mixed for 1 h until complete
dissolution of the solid. 3,5ꢀDymethylpyrazole (0.07 g,
0.8 mmol) was added to the obtained solution, and the
reaction mixture was mixed for 15 min. The obtained
clear solution was concentrated to 5 mL, after addition
of benzene (2 mL) it was allowed to stand for 3 days at
8645(2)
12126(2)
12641(2)
4286(2)
581(1)
3431(2) –306(2)
10948(2) 8323(2) 2412(2)
12360(2) 9909(2) 3332(2)
13957(2) 10115(3) 3002(2)
11942(3) 11366(3) 3300(2)
12517(3) 9825(3) 4621(2)
a temperature of +5°С. The formed lightꢀyellow crysꢀ
tals were separated from the mother solution by
decantation, washed with hexane, and dried in an
argon stream. The yield was 75% (0.2 g).
8621(2)
8801(3)
8184(2)
8230(2)
7906(3)
13121(2)
2419(2) 1457(2)
1037(2) 547(2)
2452(2) 2554(2)
4001(3) 3088(2)
4800(3) 4264(2)
4547(2) 1651(2)
For Mn6C46H32O20N4 anal. calcd. (%): C, 42.79;
H, 2.48; N, 4.34.
Found (%): C, 43.11; H, 2.84; N, 4.02.
12954(3) 5433(3) 2869(2)
14256(2) 3850(2) 1441(2)
IR (cm–1): 3447 w, 3107 br w, 2927 w, 2017 s, 1932 s,
1553 s, 1472 m, 1393 w, 1356 s, 1292 w, 1193 m, 1162 w,
1027 m, 930 w, 792 m, 737 m, 661 s, 651 m, 621 s, 537 s,
445 m, 406 w.
13910(2)
3145(2)
181(2)
14678(3) 2224(3) –606(2)
Table 3. Selected bond lengths (
d
) and bond angles (
, Å
ω
) in complex
1
Bond
d
Bond
d, Å
Mn(1)–O(1)
2.2029(12)
2.3027(15)
2.3056(14)
Mn(1)–O(1)#1
Mn(1)–N(1)
Mn(1)–N(3)
2.2029(12)
2.3027(15)
2.3056(14)
Mn(1)–N(1)#1
Mn(1)–N(3)#1
Angle
ω
, deg
Angle
ω
, deg
O(1)Mn(1)O(1)#1
O(1)#1Mn(1)N(1)#1
O(1)#1Mn(1)N(1)
O(1)Mn(1)N(3)#1
N(1)#1Mn(1)N(3)#1
O(1)Mn(1)N(3)
180.0
O(1)Mn(1)N(1)#1
O(1)Mn(1)N(1)
N(1)#1Mn(1)N(1)
O(1)#1Mn(1)N(3)#1
N(1)Mn(1)N(3)#1
O(1)#1Mn(1)N(3)
N(1)Mn(1)N(3)
C(1)O(1)Mn(1)
91.10(5)
88.90(5)
88.90(5)
91.10(5)
89.82(5)
85.20(5)
90.18(5)
94.80(5)
180.0
180.00(4)
90.18(5)
94.80(5)
89.82(5)
N(1)#1Mn(1)N(3)
N(3)#1Mn(1)N(3)
C(6)N(1)N(2)
85.20(5)
141.57(12)
133.97(12)
111.96(16)
135.46(12)
105.00(14)
120.26(11)
105.06(14)
119.43(11)
C(6)N(1)Mn(1)
C(9)N(2)N(1)
N(2)N(1)Mn(1)
C(11)N(3)N(4)
C(11)N(3)Mn(1)
N(4)N(3)Mn(1)
Symmetrical transformations used to generate equivalent atoms: #1 –x + 2, –y + 1, –z.
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 60 No. 8 2015

MANGANESE(II) CARBOXYLATES CONTAINING COORDINATED
104) and equivalent isotroꢀ
937
Table 4. Atomic coordinates (
×
RESULTS AND DISCUSSION
3
pic factors (Å2
Atom
×
10 ) in complex 2
It was found that the reaction of the earlier prepared
μ
x
y
z
Ueq
binuclear complex Mn2(
ꢀOOCBut)4(Et3NHOOBut)2
with 8 mols of 3,5ꢀdimethylpyrazole in methylene chloꢀ
ride at room temperature results in the formation of colꢀ
orless mononuclear complex Mn(Hdmpz)4(OOCBut)2
Mn(1)
0
0
0
22(1)
30(1)
32(1)
27(1)
28(1)
27(1)
28(1)
31(1)
43(1)
35(1)
30(1)
42(1)
33(1)
48(1)
41(1)
33(1)
47(1)
27(1)
27(1)
34(1)
43(1)
48(1)
47(1)
37(1)
O(1)
O(2)
N(1)
N(2)
N(3)
N(4)
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)
1949(2)
911(2)
1452(1)
2593(1)
2400(2) –710(2)
(1)
with a yield of 91%.
1401(2)
686(2)
953(2) –1451(2)
1292(2) –2442(2)
According to Xꢀray diffraction analysis data (Tables 1–
3, Fig. 1), one manganese(II) atom in the complex has
an octahedral environment formed by four nitrogen
atoms belonging to four coordinated Hdmpz moleꢀ
cules (Mn–N 2.3027(15)–2.3056(14) Å) and the two
oxygen atoms of pivalate anions located in the axial
position (Mn–O 2.2029(12) Å).
819(2) –2179(2) –610(2)
1522(2) –2728(2) 257(2)
2837(2)
4001(3)
3024(3)
1625(3)
1070(3)
1121(3) –1679(2)
815(3) –824(2)
1561(3) –2804(2)
1646(2) –3274(2)
2037(3) –4444(2)
It should be noted that hydrogen atoms of the pyrꢀ
role fragment of the coordinated heterocycles are
linked in pairs by hydrogen bonds with the terminal
731(3) –3219(3) –1697(2)
66(3) –3019(3) –2907(2)
1377(3) –4406(3) –1500(2)
1877(3) –4051(3) –242(2)
oxygen atoms of the carboxylate anions (
N O
⋅⋅⋅
2.748(3), 2.755(3) Å).
A similar reaction between manganese(II) benꢀ
zoate obtained by reacting aqueous manganese(II)
acetate with benzoic acid in boiling benzene and
Hdmpz also affords colorless mononuclear complex
2675(3) –4849(3)
533(3)
2305(2)
3047(2)
4013(2)
4713(2)
4453(3)
3498(3)
2796(2)
2698(2)
4034(2)
4866(3)
6102(3)
6507(3)
5705(3)
4460(3)
570(2)
1769(2)
1436(3)
2522(3)
3940(3)
4281(3)
3194(3)
Mn(Hdmpz)4(OOCPh)2 (
trosymmetric complex (Tables 1, 4, 5; Fig. 2), as well
, four equatorially located pyrazole
N 2.2737(17)–2.3130(16) Å) and two
2) in 65% yield. In cenꢀ
2
as in complex
molecules (Mn
1
⎯
oxygen atoms lying in the axial positions of the benꢀ
zoate anions (Mn–O 2.1911(14) Å) of the octahedral
environment of the central metal atom are bonded
with the manganese(II) atom.
Table 5. Selected bond lengths (
d
) and bond angles (
, Å
ω
) in complex 2
Bond
d
Bond
d, Å
Mn(1)–O(1)
Mn(1)–N(3)
Mn(1)–N(1)#1
2.1911(14)
2.2737(17)
2.3130(16)
Mn(1)–O(1)#1
Mn(1)–N(3)#1
Mn(1)–N(1)
2.1911(14)
2.2737(17)
2.3130(16)
Angle
ω
, deg
Angle
ω
, deg
O(1)Mn(1)O(1)#1
O(1)#1Mn(1)N(3)
O(1)#1Mn(1)N(3)#1
O(1)Mn(1)N(1)#1
N(3)Mn(1)N(1)#1
O(1)Mn(1)N(1)
180.0
O(1)Mn(1)N(3)
89.34(6)
90.66(6)
180.0
90.66(6)
89.34(6)
89.17(6)
92.69(6)
90.84(6)
87.31(6)
180.00(7)
104.78(16)
119.68(12)
O(1)Mn(1)N(3)#1
N(3)Mn(1)N(3)#1
O(1)#1Mn(1)N(1)#1
N(3)#1Mn(1)N(1)#1
O(1)#1Mn(1)N(1)
N(3)#1Mn(1)N(1)
C(11)O(1)Mn(1)
C(1)N(1)Mn(1)
90.84(6)
87.31(6)
89.16(6)
92.69(6)
143.00(14)
135.00(14)
N(3)Mn(1)N(1)
N(1)#1Mn(1)N(1)
C(1)N(1)N(2)
N(2)N(1)Mn(1)
Symmetrical transformations used to generate equivalent atoms: #1 –
x, –y, –z.
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 60 No. 8 2015

938
UVAROVA et al.
104) and equivalent isotroꢀ
Table 6. Atomic coordinates (
×
103) in complex
3
pic factors (Å2
Atom
×
C(5A)
C(3A)
C(2A)
C(4A)
x
y
z
Ueq
C(10A)
Mn(1)
Mn(2)
Mn(3) –900(1)
1631(1)
3081(1)
4242(1)
2552(1)
3499(1)
5299(4)
4839(3)
3655(4)
3628(7)
4142(6)
6102(5)
3036(6)
4912(1)
1013(1)
1028(1)
6261(3)
4014(3)
3607(3)
4047(4)
–66(5)
22(1)
29(1)
32(1)
31(1)
25(1)
33(1)
84(2)
84(2)
61(1)
90(2)
58(1)
49(1)
54(1)
37(1)
26(1)
28(1)
27(1)
27(1)
27(1)
38(1)
30(1)
28(1)
44(2)
29(1)
39(1)
31(1)
29(1)
39(1)
25(1)
27(1)
33(1)
42(2)
37(1)
31(1)
54(2)
40(2)
54(2)
35(1)
32(1)
36(1)
41(2)
41(2)
35(1)
39(1)
37(1)
38(1)
56(2)
44(2)
93(2)
83(3)
103(3)
134(5)
132(5)
O(2A)
C(15)
C(1A)
H(2A)
N(2A)
C(9A)
C(8A)
O(1)
O(2)
O(3)
O(4)
O(5)
O(6)
O(7)
O(8)
O(9)
O(10)
O(11)
N(1)
N(2)
N(3)
N(4)
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
C(8)
C(9)
1336(4)
590(3)
H(4)
N(4)
C(7)
C(14)
O(1A)
C(12A)
C(11A)
2316(4)
4120(5)
–2549(6)
1272(5)
249(7)
C(13)
C(6A)
Mn(1)
N(1A)
N(3A)
N(3)
C(6)
2152(4)
–639(5)
C(11)
N(1)
1854(5)
757(4)
1527(5) –1249(3)
C(7A)
C(13A)
C(12)
669(4)
1082(4)
6018(4)
3516(4)
3315(4)
2515(4)
2642(4)
3138(5)
3193(6)
2700(5)
2836(5)
2565(6)
1316(5)
810(5)
1243(4)
739(4)
4379(5)
3456(4)
2464(4)
3437(4)
–280(4)
–1201(4)
2186(5)
1154(6)
2988(5)
3781(5)
4846(6)
–610(5)
175(6)
O(1)
C(1)
C(8)
C(14A)
5459(3)
5916(3)
5730(3)
4520(3)
4909(3)
6668(4)
7114(5)
6950(4)
6342(4)
6283(5)
4289(4)
3830(5)
4553(4)
4956(4)
5353(5)
3479(4)
2439(4)
1726(4)
840(5)
N(4A)
H(4A)
H(2)
C(3)
N(2)
C(15A)
C(9)
O(2)
C(2)
C(10)
C(4)
C(5)
Fig. 1. Structure of complex
1 (shown as 30% probability
ellipsoids).
–1720(5)
–2069(5)
718(5)
In spite of the change in the basicity of the carboxꢀ
ylate anion due to the introduction of the acceptor
phenyl substituent in comparison with the donor tertꢀ
butyl substituent, the values of bond lengths in monoꢀ
1596(5)
1509(6)
4352(5)
3288(5)
2746(5)
1764(6)
1688(5)
2631(5)
3926(7)
5079(6)
3229(7)
3720(6)
3959(5)
4158(5)
4377(6)
4334(5)
4062(5)
1910(6)
1405(6)
1642(6)
C(10) –3155(5)
C(11) –578(5)
C(12) –1112(5)
C(13) –2348(5)
C(14) –2499(6)
C(15) –1379(6)
nuclear complexes
mer , in complex
ments of pyrazole form hydrogen bonds with the oxygen
1
and
2 are almost equal. As in monoꢀ
1
2 the hydrogen atoms of the NH fragꢀ
1000(4)
1989(4)
356(6)
1710(5)
9(5)
atoms of the carboxylate anions (O⋅⋅⋅N 2.738(2),
C(16)
C(17) –1856(7)
–508(6)
2.769(3) Å).
Finally, a similar reaction between manganese(II)
cymantrene prepared by reacting aqueous mangaꢀ
nese(II) acetate with cymantrenecarboxylic acid in
boiling benzene and pyrazole unexpectedly leads to
C(18)
C(19)
C(20)
C(21)
C(22)
C(23)
C(24)
C(25)
C(26)
C(27)
C(28)
412(7)
–203(8)
3345(5)
3671(5)
2951(6)
3616(6)
4746(6)
4773(6)
2321(6)
1672(6)
3849(6)
3470(4)
2552(4)
1811(5)
1091(5)
1358(5)
2269(4)
–366(5)
1154(5)
839(5)
6955(5)
7689(5)
6944(6)
7524(8)
the formation of colorless binuclear complex {Mn(
OOCC5H4Mn(CO)3)(OOCC5H4Mn(CO)3) (Hdmpz)2
(OH2)}2 (
μ
ꢀ
⋅
3)
containing a solvate molecule of pyrazole
Hdmpz with a yield of 75%.
In centrosymmetric complex
3
(Tables 1, 6, 7; Fig. 3),
the two manganese atoms are located at the nonbondꢀ
ing metal–metal distance of 5.1553(6) Å and are conꢀ
nected by two bridged cymantrenecarboxylate anions
(Mn–O 2.169 (4), 2.206(3) Å). Each manganese atom
in the dimer has the distorted octahedral environment
formed by two nitrogen atoms belonging to two pyraꢀ
zole molecules (Mn–N 2.244(4), 2.287(4) Å), the
hydrogen atoms of whose pyrrole fragments form short
hydrogen bonds with the oxygen atoms of the bridged
(N(4)–O(2) 2.857(6) Å) and terminal carboxylate
N(1S) –5349(6) –1410(6)
C(3S) –3944(6) 679(6)
N(2S) –4171(8) –1049(8)
C(4S) –5306(9)
C(1S) –3354(12)
C(5S) –6261(13)
C(2S) –1976(13)
–243(9)
71(11) 7321(9)
–9(12) 7837(10)
532(13) 7290(10)
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 60 No. 8 2015

MANGANESE(II) CARBOXYLATES CONTAINING COORDINATED
939
Table 7. Selected bond distances (
d
) and bond angles (
, Å
ω
) in complex 3
Bond
d
Bond
d, Å
Mn(1)–O(1)
Mn(1)–O(3)
Mn(1)–N(3)
Mn(2)–C(27)
Mn(2)–C(26)
Mn(2)–C(25)
Mn(2)–C(24)
Mn(3)–C(17)
Mn(3)–C(19)
Mn(3)–C(12)
Mn(3)–C(16)
2.169(4)
2.195(4)
2.244(4)
1.792(7)
1.794(6)
2.142(6)
2.149(6)
1.779(7)
1.792(7)
2.135(5)
2.146(6)
Mn(1)–O(11)
Mn(1)–O(2)
Mn(1)–N(1)
Mn(2)–C(28)
Mn(2)–C(23)
Mn(2)–C(22)
Mn(2)–C(21)
Mn(3)–C(18)
Mn(3)–C(14)
Mn(3)–C(13)
Mn(3)–C(15)
2.188(4)
2.206(3)
2.287(4)
1.789(7)
2.133(6)
2.142(6)
2.151(5)
1.786(7)
2.137(7)
2.137(6)
2.152(6)
Angle
ω
, deg
Angle
ω
, deg
O(1)Mn(1)O(11)
O(11)Mn(1)O(3)
O(11)Mn(1)O(2)
O(1)Mn(1)N(3)
O(3)Mn(1)N(3)
O(1)Mn(1)N(1)
O(3)Mn(1)N(1)
N(3)Mn(1)N(1)
C(11)O(2)Mn(1)
C(1)N(1)N(2)
81.57(15)
84.26(15)
92.86(14)
91.96(15)
102.26(15)
89.35(15)
95.60(15)
86.05(16)
134.5(3)
O(1)Mn(1)O(3)
O(1)Mn(1)O(2)
O(3)Mn(1)O(2)
O(11)Mn(1)N(3)
O(2)Mn(1)N(3)
O(11)Mn(1)N(1)
O(2)Mn(1)N(1)
C(11)#1O(1)Mn(1)
C(20)O(3)Mn(1)
C(1)N(1)Mn(1)
C(4)N(2)N(1)
165.21(15)
86.11(14)
90.40(14)
173.46(15)
87.62(15)
92.89(16)
172.07(14)
142.0(4)
138.1(4)
105.1(4)
135.4(3)
N(2)N(1)Mn(1)
C(6)N(3)N(4)
119.4(3)
112.7(4)
105.0(4)
C(6)N(3)Mn(1)
131.7(3)
N(4)N(3)Mn(1)
118.7(3)
Symmetrical transformations used to generate equivalent atoms: #1 –x, –y + 1, –z + 1.
anion (Mn–O 2.195 (4) Å, N⋅⋅⋅O 2.716(5) Å). In the
coordination sphere of each metal atom, there is a
coordinated water molecule (Mn–O 2.188 (4) Å), the
appearance of which is obviously due to the weak
basicity of both pyrazole and cymantrenecarboxylic
acid.
Thus, it has been found that, unlike zinc and cobalt
carboxylates, in the case of a more electronꢀdeficient
manganese(II) atom there is no deprotonation of
3,5ꢀdimethylpyrazole depending on the nature of R
substituents in the carboxylate anion.
Similar results were recently received in reactions
of 3,5ꢀdiisopropylpyrazole with anions of pꢀnitrobenꢀ
In addition, in the crystal cell of complex 3 there is
zoic and
pꢀfluorobenzoic acids [14].
a distorted solvate molecule of pyrazole, one of the
nitrogen atoms of which is bonded by a hydrogen bond
with the hydrogen atom of the coordinated water molꢀ
ACKNOWLEDGMENTS
ecule (N⋅⋅⋅O 2.898(5) Å) and the hydrogen atom of the
NH fragment is bonded by a rather weak hydrogen
bond with oxygen atom O(4) of the terminal carboxyꢀ
This work was supported using equipment of the
Shared Facilities Center of the Kurnakov Institute by the
Federal Agency for Research Organizations and Russian
Foundation for Basic Research (project nos. 13ꢀ03ꢀ90420
late anion (N⋅⋅⋅O 3.128(6) Å).
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 60 No. 8 2015

940
UVAROVA et al.
C(14A)
C(15A)
C(13A)
C(16A)
C(12A)
O(2A)
C(5)
C(10A)
C(17A)
H(2D)
N(2)
H(4AA)
C(11A)
C(4)
C(7)
O(1A)
C(9A)
C(3)
N(4A)
N(1)
N(3A)
C(8A)
C(2A)
Mn(1)
C(6)
C(1)
C(6A)
C(1A)
C(2)
N(3)
N(1A)
N(2A)
C(8)
C(7A)
N(4)
O(1)
C(9)
C(3A)
C(4A)
C(11)
H(4A)
H(2DA)
C(17)
C(10)
O(2)
C(16)
C(15)
C(5A)
C(12)
C(13)
C(14)
Fig. 2. Molecular structure of complex
2
(shown as 30% probability ellipsoids).
O(8)
O(7)
C(23)
O(5)
C(24)
O(6)
C(19)
C(28)
Mn(3)
C(17)
C(2A)
C(3A)
C(22)
C(21)
Mn(2)
C(10A)
C(25)
C(27)
O(9)
O(10)
C(1A)
C(8A) C(9A)
C(14)
C(15)
C(4A)
C(5A)
C(13)
N(4A)
C(11)
C(20)
O(3)
N(1A)
C(7A)
C(16)
O(11)
C(12)
O(2)
N(3A)
N(2A)
O(4)
O(1A)
Mn(1A)
Mn(1)
N(3)
C(7)
O(1)
O(11A)
N(2)
O(4A)
O(9A)
O(3A)
O(2A)
C(12A)
C(6)
N(1)
N(4)
C(11A)
C(13A)
C(5)
C(20A)
C(16A)
C(8)
C(9)
C(14A)
C(27A)
C(21A)
C(4)
C(25A)
Mn(3A)
C(1)
C(10)
O(6A)
C(15A)
C(3)
C(2)
C(22A)
Mn(2A)
O(10A) C(28A)
C(23A)
C(17A)
C(24A)
C(19A)
O(7A)
C(26A)
O(8A)
O(5A)
Fig. 3. Structure of binuclear complex
3 (shown as 30% probability ellipsoids).
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 60 No. 8 2015

MANGANESE(II) CARBOXYLATES CONTAINING COORDINATED
941
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Translated by V. Avdeeva
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 60 No. 8 2015