Synthesis and structure of trinuclear pyrazolate-bridged acetates M 3(μ-dmpz)4(Hdmpz)2(OOCMe)2 (M = Zn or Co; Hdmpz = 3,5-dimethylpyrazole)

ISSN 0036-0236, Russian Journal of Inorganic Chemistry, 2009, Vol. 54, No. 11, pp. 1713–1729. © Pleiades Publishing, Inc., 2009.

Original Russian Text © S.E. Nefedov, I.V. Pruss, E.V. Perova, G.L. Kamalov, 2009, published in Zhurnal Neorganicheskoi Khimii, 2009, Vol. 54, No. 11, pp. 1792–1807.

COORDINATION COMPOUNDS

Synthesis and Structure of Trinuclear Pyrazolate-Bridged

Acetates M₃(m-dmpz)₄(Hdmpz)₂(OOCMe)₂(M = Zn or Co;

Hdmpz = 3,5-Dimethylpyrazole)

S. E. Nefedov^a, I. V. Pruss^a, E. V. Perova^a, and G. L. Kamalov^b

^aKurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences,

Leninskii pr. 31, Moscow, 119991 Russia

E-mail: snef@igic.ras.ru

^bPhysicochemical Institute, National Academy of Sciences of Ukraine, Kiev, Ukraine

Received April 27, 2008

Abstract—We discovered that reactions of hydrous cobalt and zinc acetates with 3,5-dimethylpyrazole

(Hdmpz) in boiling xylene or toluene or upon the thermolysis of solid precursors (150°C) yield trinuclear pyra-

zolate-bridged complexes M₃(μ-dmpz)₄(Hdmpz)₂(OOCMe)₂(M = Zn or Co). Depending on the crystallization

conditions, these complexes contain various solvating molecules (benzene, toluene, or Hdmpz), which inﬂu-

ences the character of intramolecular and intermolecular hydrogen bonding, as shown by X-ray crystallography.

DOI: 10.1134/S0036023609110060

Transition-metal carboxylates (acetates) are con- vating molecules on intramolecular and intermolecular

ventionally used in advanced coordination chemistry as hydrogen bonding in the complexes synthesized.

precursors for complexes with coordinated organic

ligands. In many cases, the formation of new com-

pounds in such reactions is accompanied by proton

EXPERIMENTAL

All operations in the synthesis and recovery of com-

plexes were carried out in a pure argon atmosphere

using absolute solvents.

IR spectra were recorded as KBr discs on a Specord

M-80 spectrophotometer over the frequency range

392–4000 cm^–1.

transfer from an organic molecule with the appearance

of the corresponding anion and recovery of carboxylic

acid. Depending on the reaction parameters, deprotona-

tion of pyrazole or its analogues in the presence of tran-

sition-metal carboxylates (acetates) yields di-, tri-, or

polynuclear complexes and pyrazolate-bridged poly-

mers [1–6].

X-ray crystallography experiments were performed

For example, possible intermediates of the reactions using a routine procedure on a Bruker Smart Apex II

yielding acetate-pyrazolate- and pyrazolate-bridged automated diffractometer equipped with a CCD detec-

polymers [Zn(μ-OOCMe)(μ-pz)]_nand [Zn(μ-pz)₂]_nwere tor (λMo, graphite monochromator, ω scans). Struc-

tures were solved using the SHELXTL PLUS program

package (a PC version). Structure reﬁnement was per-

formed using the SHELXTL-97 program package

[11, 12].

Crystal data and the details of structure reﬁnement are

listed in Table 1.Atomic coordinates and selected geomet-

ric parameters of the complexes are in Tables 2–11.

recovered as a result of a comprehensive study of the

reaction between hydrous zinc acetate and pyrazole in

alcohol or water at room temperature [1].

It was found, however, that the reactions of dinuclear

pivalates M₂(μ-OOCBu^t)₄(NEt₃)₂(M = Zn or Co) with

3,5-dimethylpyrazole (Hdmpz) at room temperature result

in pyrazole deprotonation and the formation of pyrazolate-

bridged dimers M₂(μ-dmpz)₂(Hdmpz)₂(OOCBu^t)₂[7–10].

Syntheses

Continuing on our studies of the speciﬁcs of

3,5-dimethylpyrazole deprotonation as a function of

Co₃(m-dmpz)₄(Hdmpz)₂(OOCMe)₂(1). To 3,5-dime-

the nature of the transition metal and carboxylate anion, thylpyrazole (0.044 g, 0.46 mmol) in xylene (20 mL),

here we discuss the structures of products of the reac- hydrous cobalt acetate (0.1 g, 0.23 mmol) was added.

tion of hydrous cobalt and zinc acetates with 3,5-dime- This suspension was heated for 30 min with stirring at

thylpyrazole in a boiling organic solvent (toluene or 145°ë until complete dissolution. The resulting violet

xylene) and thermolysis at 150°ë. We also consider the solution was reduced in volume to 10 mL and allowed

inﬂuence of the nature of the transition metal and sol- at stand for 24 h at –5°ë. Violet crystals were separated

1713

1714

Table 1. Crystallographic parameters and details of structure refinement for 1–5

2 (1 × 0.5C₆H₅Me) 3 (1 × 0.5C₆H₆)

C₃₄H₅₀Co₃N₁₂O₄C_37.5H_53.5Co₃N₁₂O₄C₃₇H₅₃Co₃N₁₂O₄C₄₀H₅₆N₁₂O₄Zn₃C₃₉H₅₈Co₃N₁₄O₄

NEFEDOV et al.

1

4 × C₆H₆

5 (1 × Hdmpz)

Bulk formula

FW

867.65

120(2)

913.21

120(2)

906.70

120(2)

965.08

120(2)

963.78

120(2)

T, K

Color

Violet

Water color

Triclinic

P-1

Violet

Crystals system

Monoclinic

P2(1)/c

Monoclinic

P2(1)/c

Monoclinic

P2(1)/c

Triclinic

P2(1)/c

Space group

Unit cell parameters

a, Å

13.3691(16)

14.6453(18)

21.143(3)

90

13.2196(6)

17.1872(7)

19.3268(8)

90

13.285(7)

17.389(10)

19.794(11)

90

8.381(2)

16.389(4)

19.272(5)

113.144(4)

101.980(4)

90.897(4)

2367.2(11)

2

18.2553(16)

14.3583(13)

19.3896(19)

90

b, Å

c, Å

α, deg

β, deg

γ, deg

V, Å³

Z

93.162(2)

90

97.9150(10)

90

96.772(10)

90

112.018(2)

90

4133.4(9)

4

4349.4(3)

4

4541(4)

4

4711.6(8)

4

ρ

_calc, mg/m³

1.394

1.395

1.326

1.354

1.359

M, mm^–1

1.240

1.183

1.132

1.558

1.097

F(000)

1804

1902

1888

1004

2012

Crystal size, mm

θ scan range, deg

Reflection index ranges

0.14 × 0.12 × 0.10 0.14 × 0.12 × 0.10 0.14 × 0.12 × 0.10 0.12 × 0.10 × 0.08 0.12 × 0.10 × 0.08

1.69–25.00

2.37–29.00

1.94–27.00

2.13–25.00

1.82–25.00

–15 ≤ h ≤ 15,

–17 ≤ k ≤ 17,

–20 ≤ l ≤ 25

–18 ≤ h ≤ 18,

–23 ≤ k ≤ 20,

–26 ≤ l ≤ 26

–16 ≤ h ≤ 16,

–22 ≤ k ≤ 22,

–25 ≤ l ≤ 25

–9 ≤ h ≤ 9,

–19 ≤ k ≤ 19,

–22 ≤ l ≤ 22

–21 ≤ h ≤ 11,

–16 ≤ k ≤ 16,

–5 ≤ l ≤ 23

Reflections

24698

32532

41900

15307

11253

Independent reflections

7171

11404

9700

7676

7182

[R(int) = 0.1010] [R(int) = 0.0601] [R(int) = 0.1533] [R(int) = 0.1186] [R(int) = 0.0640]

GOOF

0.898

0.993

0.871

0.977

0.818

R (I > 2σ(I))

R1 = 0.0476,

wR2 = 0.0663

R1 = 0.0312,

wR2 = 0.0578

R1 = 0.0484,

wR2 = 0.0840

R1 = 0.0793,

wR2 = 0.0820

R1 = 0.0447,

wR2 = 0.0638

R ( on all reflections)

R1 = 0.1236,

wR2 = 0.0778

R1 = 0.0477,

wR2 = 0.0604

R1 = 0.1367,

wR2 = 0.0996

R1 = 0.1954,

wR2 = 0.1069

R1 = 0.1074,

wR2 = 0.0743

Electron density peaks

(min/max), e Å^–3

1.045, –0.378

0.492, –0.320

1.028, –0.668

0.596, –0.860

0.406, –0.315

RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 54 No. 11 2009

SYNTHESIS AND STRUCTURE

1715

Table 2. Coordinates of atoms (×10⁴) and their equivalent isotropic factors (Å²× 10³) for complex 1

Atom

x

y

z

U_eq

47(1)

Co(1)

Co(2)

Co(3)

O(1)

O(2)

O(3)

O(4)

N(1)

N(2)

N(3)

N(4)

N(5)

N(6)

N(7)

N(8)

N(9)

N(10)

N(11)

N(12)

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)

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)

–8732(1)

–6169(1)

–11208(1)

–5596(3)

–4627(3)

–11678(3)

–12819(3)

–8287(3)

–7323(3)

–7682(2)

–6715(2)

–9961(2)

–10865(3)

–9014(3)

–9954(3)

–5228(3)

–4262(3)

–12139(3)

–13080(3)

–8846(4)

–9937(3)

–8261(4)

–7302(4)

–6376(4)

–7798(3)

–8747(3)

–6907(4)

–6256(3)

–5186(3)

–9988(4)

–9128(4)

–10930(4)

–11438(4)

–12484(3)

–8354(4)

–7242(3)

–8848(4)

–9869(4)

–10735(4)

–11960(4)

–10991(4)

–12774(5)

–13491(4)

–14542(4)

–5429(4)

–6453(4)

–4577(4)

–3846(4)

–2770(4)

–4947(5)

–4533(4)

–12352(5)

–12542(4)

7915(1)

7463(1)

1351(1)

1000(1)

54(1)

55(1)

96(1)

132(2)

85(1)

165(2)

55(1)

46(1)

48(1)

52(1)

56(1)

54(1)

69(1)

62(1)

72(1)

71(2)

104(2)

89(2)

71(2)

106(2)

48(1)

66(1)

62(1)

52(1)

85(2)

57(1)

81(2)

69(2)

65(1)

99(2)

73(2)

115(2)

85(2)

69(1)

102(2)

74(2)

122(3)

88(2)

80(2)

120(2)

66(1)

101(2)

82(2)

77(2)

116(2)

96(1)

109(2)

100(2)

8022(1)

6659(3)

7764(3)

6770(2)

7016(3)

6803(2)

6672(2)

8861(2)

8709(2)

8332(2)

8514(2)

7888(2)

7951(2)

7527(2)

7265(2)

8932(3)

8719(3)

6096(3)

6044(3)

5513(3)

5874(3)

5499(4)

9754(3)

10142(3)

10195(3)

9529(3)

9633(3)

8627(3)

8524(3)

9003(3)

8929(3)

9229(3)

7868(3)

7815(4)

7901(4)

7949(3)

7995(4)

9741(4)

10216(3)

10023(4)

9367(4)

9279(4)

7735(3)

8072(4)

7628(4)

7321(3)

7097(4)

7035(5)

6573(4)

6474(5)

5494(3)

1933(1)

1662(2)

1826(2)

1995(2)

1298(3)

911(2)

731(2)

1281(2)

1108(2)

852(2)

1110(2)

2260(2)

2496(2)

286(2)

328(2)

2310(2)

2464(2)

690(3)

800(3)

366(3)

396(3)

135(3)

1387(2)

1607(2)

1280(2)

1107(2)

952(2)

249(3)

–155(2)

106(3)

648(3)

750(3)

2756(3)

2676(2)

3306(3)

3133(3)

3526(2)

2579(3)

2519(3)

2890(3)

2799(3)

3027(3)

–309(3)

–542(2)

–657(3)

–236(3)

–329(3)

1995(3)

2583(2)

1636(4)

1634(3)

RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 54 No. 11 2009

1716

NEFEDOV et al.

Table 3. Bond lengths (d) and bond angles (ω) for complex 1

Bond

d, Å

Bond

d, Å

Bond

d, Å

Bond

d, Å

Co(1)–N(7)

Co(1)–N(1)

Co(2)–O(1)

Co(2)–N(2)

Co(3)–O(3)

Co(3)–N(8)

O(1)–C(31)

O(3)–C(33)

N(1)–C(1)

N(2)–C(4)

N(3)–N(4)

N(5)–C(11)

N(6)–C(14)

N(7)–N(8)

N(9)–C(26)

N(10)–C(29)

1.980(4) N(11)–N(12)

1.984(3) C(1)–C(3)

1.953(4) C(3)–C(4)

1.986(4) C(6)–C(8)

1.944(3) C(8)–C(9)

2.005(4) C(11)–C(13)

1.218(6) C(13)–C(14)

1.226(7) C(16)–C(18)

1.344(5) C(18)–C(19)

1.369(5) C(21)–C(23)

1.381(4) C(23)–C(24)

1.345(5) C(24)–C(25)

1.351(5) C(26)–C(27)

1.381(4) C(29)–C(30)

1.308(5) C(33)–C(34)

1.353(4) Co(1)–N(5)

1.368(6) Co(2)–N(4)

1.385(6) Co(2)–N(9)

1.385(5) Co(3)–N(6)

1.371(6) Co(3)–N(11)

1.392(6) O(2)–C(31)

1.369(6) O(4)–C(33)

1.371(6) N(1)–N(2)

1.396(6) N(3)–C(6)

1.365(6) N(4)–C(9)

1.363(6) N(5)–N(6)

1.516(6) N(7)–C(16)

1.513(6) N(8)–C(19)

1.499(7) N(9)–N(10)

1.458(7) N(11)–C(21)

1.999(3)

1.984(3)

2.021(3)

1.960(4)

2.018(4)

1.211(6)

1.215(7)

1.377(4)

1.337(5)

1.349(5)

1.379(4)

1.332(5)

1.346(5)

1.344(4)

1.331(5)

1.322(5)

C(1)–C(2)

1.492(6)

1.488(6)

1.488(5)

1.494(6)

1.476(6)

1.493(6)

1.507(6)

1.462(6)

1.481(6)

0.9300

C(4)–C(5)

C(6)–C(7)

C(9)–C(10)

C(11)–C(12)

C(14)–C(15)

C(16)–C(17)

C(19)–C(20)

C(21)–C(22)

C(23)–H(23A)

C(26)–C(28)

C(28)–C(29)

C(31)–C(32)

1.397(6)

1.361(7)

1.496(7)

1.345(6)

N(12)–C(24)

Co(1)–N(3)

Angle

1.984(3)

Angle

ω, deg

Angle

ω, deg

Angle

ω, deg

N(7)Co(1)N(3) 105.03(14) N(10)N(9)Co(2) 124.9(3)

N(3)Co(1)N(1) 107.86(15) C(21)N(11)N(12) 104.4(4)

C(33)O(3)Co(3)

C(1)N(1)Co(1)

C(4)N(2)N(1)

121.4(5)

128.2(3)

107.9(4)

C(14)C(13)C(11) 105.7(5)

N(6)C(14)C(15)

N(7)C(16)C(18)

121.7(5)

109.8(5)

N(12)N(11)Co(3) 123.1(3)

N(7)Co(1)N(1) 121.14(15)

N(7)Co(1)N(5) 108.93(16) N(1)C(1)C(3)

N(3)Co(1)N(5) 108.15(14) C(3)C(1)C(2)

O(1)Co(2)N(4) 127.20(15) N(2)C(4)C(3)

N(4)Co(2)N(2) 106.52(15) C(3)C(4)C(5)

N(4)Co(2)N(9) 106.94(14) N(3)C(6)C(7)

O(3)Co(3)N(6) 119.92(15) C(9)C(8)C(6)

N(6)Co(3)N(8) 108.53(15) N(4)C(9)C(10)

109.4(4)

129.5(5)

107.8(4)

128.9(5)

122.3(4)

106.0(4)

122.2(4)

N(1)N(2)Co(2)

C(6)N(3)Co(1)

C(9)N(4)N(3)

N(3)N(4)Co(2)

C(11)N(5)Co(1)

C(14)N(6)N(5)

N(5)N(6)Co(3)

C(16)N(7)Co(1)

C(19)N(8)N(7)

124.4(3)

125.6(3)

106.9(3)

122.3(3)

125.3(3)

106.0(4)

122.2(3)

127.7(3)

109.5(4)

C(18)C(16)C(17) 128.4(5)

N(8)C(19)C(18) 106.8(4)

C(18)C(19)C(20) 130.3(5)

N(11)C(21)C(22) 121.2(5)

C(23)C(21)C(22) 128.6(5)

N(12)C(24)C(23) 105.7(5)

C(23)C(24)C(25) 132.3(6)

N(6)Co(3)N(11) 106.73(15) N(5)C(11)C(13) 108.0(4)

C(13)C(11)C(12) 129.7(5)

N(9)C(26)C(27)

121.6(5)

C(29)C(28)C(26) 105.6(5)

N(10)C(29)C(30) 123.4(6)

C(31)O(1)Co(2) 112.3(4)

C(1)N(1)N(2)

N(2)N(1)Co(1)

C(4)N(2)Co(2)

C(6)N(3)N(4)

N(4)N(3)Co(1)

C(9)N(4)Co(2)

C(11)N(5)N(6)

N(6)N(5)Co(1)

108.0(4) N(6)C(14)C(13) 110.7(4)

123.6(3) C(13)C(14)C(15) 127.5(5)

127.5(3) N(7)C(16)C(17) 121.9(5)

108.7(3) C(16)C(18)C(19) 106.8(5)

125.8(3) N(8)C(19)C(20) 122.9(5)

130.4(3) N(11)C(21)C(23) 110.2(5)

N(7)N(8)Co(3)

C(26)N(9)Co(2)

N(9)N(10)C(29)

122.5(3)

128.8(3)

111.5(4)

O(2)C(31)O(1)

O(1)C(31)C(32)

O(4)C(33)C(34)

118.7(7)

119.6(6)

123.9(7)

C(21)N(11)Co(3) 131.1(3)

C(24)N(12)N(11) 112.6(4)

C(24)C(23)C(21) 107.0(5)

N(12)C(24)C(25) 121.9(6)

N(1)C(1)C(2)

121.0(4)

106.9(4)

123.3(5)

108.7(4)

128.9(5)

109.7(4)

128.1(4)

122.2(4)

109.6(4) N(1)Co(1)N(5)

124.2(3) O(1)Co(2)N(2)

105.23(14) C(1)C(3)C(4)

96.98(15) N(2)C(4)C(5)

109.13(16) N(3)C(6)C(8)

108.60(15) C(8)C(6)C(7)

99.98(15) N(4)C(9)C(8)

N(9)C(26)C(28)

110.4(5)

C(28)C(26)C(27) 127.9(5)

N(10)C(29)C(28) 106.4(5)

C(28)C(29)C(30) 130.2(6)

C(14)N(6)Co(3) 130.9(3) O(1)Co(2)N(9)

C(16)N(7)N(8)

N(8)N(7)Co(1)

107.1(4) N(2)Co(2)N(9)

125.1(3) O(3)Co(3)N(8)

O(2)C(31)C(32)

O(4)C(33)O(3)

O(3)C(33)C(34)

121.6(6)

117.9(7)

118.2(7)

C(19)N(8)Co(3) 128.0(3) O(3)Co(3)N(11) 112.77(15) C(8)C(9)C(10)

C(26)N(9)N(10) 106.0(4) N(8)Co(3)N(11) 108.25(16) N(5)C(11)C(12)

RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 54 No. 11 2009

SYNTHESIS AND STRUCTURE

1717

Table 4. Coordinates of atoms (×10⁴) and their equivalent isotropic factors (Å²× 10³) for 1 × 0.5C₆H₅Me (2)

Atom

x

y

z

U_eq

Co(1)

Co(2)

Co(3)

O(1)

O(2)

O(3)

O(4)

N(1)

N(2)

N(3)

N(4)

N(5)

N(6)

N(7)

N(8)

N(9)

N(10)

N(11)

N(12)

C(1)

3904(1)

6408(1)

1359(1)

6841(1)

8075(1)

289(1)

–684(1)

4139(1)

5088(1)

5197(1)

6128(1)

3414(1)

2536(1)

2855(1)

1878(1)

7391(1)

8321(1)

538(1)

–401(1)

3434(1)

2312(1)

3913(1)

4953(1)

5829(1)

5278(1)

4387(1)

6257(1)

6767(1)

7844(1)

3974(1)

4994(1)

3454(1)

2561(1)

1703(1)

2929(1)

3908(1)

2002(1)

1364(1)

271(1)

8131(1)

7966(1)

7846(1)

6883(1)

7245(1)

7508(1)

6931(1)

8002(1)

7938(1)

8501(1)

8549(1)

7191(1)

7149(1)

8970(1)

8852(1)

8618(1)

8380(1)

7997(1)

7671(1)

7942(1)

7980(1)

7841(1)

7837(1)

7716(1)

8876(1)

8940(1)

9170(1)

8955(1)

9135(1)

6551(1)

6432(1)

6083(1)

6477(1)

6249(1)

9712(1)

10020(1)

10088(1)

9528(1)

9599(1)

9337(1)

9775(1)

9563(1)

8940(1)

8825(1)

8332(1)

8744(1)

8224(1)

7810(1)

7540(1)

6736(1)

5908(1)

6931(1)

6240(1)

5709(2)

5339(2)

4607(2)

4243(3)

1766(1)

1228(1)

2244(1)

1197(1)

2013(1)

1532(1)

664(1)

15(1)

16(1)

23(1)

31(1)

25(1)

24(1)

16(1)

18(1)

17(1)

16(1)

17(1)

18(1)

20(1)

31(1)

22(1)

19(1)

28(1)

20(1)

27(1)

22(1)

19(1)

23(1)

21(1)

31(1)

23(1)

19(1)

27(1)

20(1)

27(1)

23(1)

20(1)

29(1)

18(1)

24(1)

21(1)

20(1)

28(1)

22(1)

29(1)

25(1)

22(1)

32(1)

21(1)

36(1)

21(1)

38(1)

54(1)

55(1)

52(1)

43(1)

777(1)

565(1)

2322(1)

2075(1)

2220(1)

2526(1)

1784(1)

1939(1)

753(1)

610(1)

3041(1)

3040(1)

208(1)

C(2)

C(3)

C(4)

C(5)

C(6)

C(7)

C(8)

C(9)

267(1)

–381(1)

–133(1)

–536(1)

2936(1)

3339(1)

3098(1)

2546(1)

2440(1)

2402(1)

2165(1)

2822(1)

2888(1)

3283(1)

1588(1)

1380(1)

1605(1)

1824(1)

1944(1)

500(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)

C(25)

C(26)

C(27)

C(28)

C(29)

C(30)

C(31)

C(32)

C(33)

C(34)

C(35)

C(36)

C(37)

C(38)

7264(1)

6298(1)

8119(1)

8777(1)

9815(1)

774(1)

550(1)

196(1)

277(1)

69(1)

3667(1)

3854(1)

4061(1)

3649(1)

3772(1)

1634(1)

1661(1)

1115(1)

1187(1)

307(1)

1773(1)

–21(1)

–760(1)

–1799(1)

7636(1)

8006(2)

73(1)

786(2)

5169(2)

5959(2)

5816(2)

6569(3)

72(1)

–244(1)

–508(2)

RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 54 No. 11 2009

1718

NEFEDOV et al.

Table 5. Bond lengths (d) and bond angles (ω) for 1 × 0.5C₆H₅Me (2)

Bond

d, Å

Bond

d, Å

Bond

d, Å

Bond

d, Å

Co(1)–N(5)

Co(1)–N(3)

Co(2)–O(1)

Co(2)–N(2)

Co(3)–O(3)

Co(3)–N(6)

O(1)–C(31)

O(3)–C(33)

N(1)–C(1)

1.9893(13) C(1)–C(3)

1.9935(13) C(3)–C(4)

1.9506(12) C(6)–C(8)

2.0183(13) C(8)–C(9)

1.9219(12) C(11)–C(13)

1.9798(13) C(13)–C(14)

1.2796(19) C(16)–C(18)

1.387(2)

1.392(2)

1.385(2)

1.390(2)

1.382(2)

1.390(2)

1.383(2)

1.399(2)

1.375(2)

1.393(2)

1.372(2)

1.504(3)

1.354(3)

1.400(3)

Co(1)–N(7)

Co(2)–N(4)

Co(2)–N(9)

Co(3)–N(8)

Co(3)–N(11)

O(2)–C(31)

O(4)–C(33)

N(1)–N(2)

N(3)–C(6)

2.0032(13) C(4)–C(5)

1.9956(13) C(6)–C(7)

2.0278(13) C(9)–C(10)

1.9794(13) C(11)–C(12)

2.0199(12) C(14)–C(15)

1.496(2)

1.504(2)

1.498(2)

1.497(2)

1.503(2)

1.502(2)

1.500(2)

1.497(2)

1.495(2)

1.498(2)

1.510(2)

1.401(3)

1.335(5)

1.234(2)

C(16)–C(17)

1.2342(19) C(19)–C(20)

1.3765(16) C(21)–C(22)

1.286(2)

1.344(2)

1.348(2)

C(18)–C(19)

C(21)–C(23)

C(23)–C(24)

1.341(2)

1.348(2)

C(24)–C(25)

C(26)–C(27)

N(2)–C(4)

N(4)–C(9)

N(3)–N(4)

N(5)–C(11)

N(6)–C(14)

N(7)–N(8)

N(9)–C(21)

N(10)–C(24)

N(11)–N(12)

1.3833(16) C(26)–C(28)

N(5)–N(6)

N(7)–C(16)

N(8)–C(19)

N(9)–N(10)

N(11)–C(26)

N(12)–C(29)

C(1)–C(2)

1.3765(16) C(29)–C(30)

1.345(2)

1.349(2)

C(28)–C(29)

C(31)–C(32)

1.339(2)

1.349(2)

C(33)–C(34)

C(35)–C(37)#1

1.3801(16) C(35)–C(36)

1.3605(16) C(37)–C(38)

1.338(2)

1.332(2)

1.346(2)

1.3618(17)

C(36)–C(37)

C(37)–C(35)#1 1.401(3)

1.3493(19)

1.504(2)

Co(1)–N(1)

Angle

1.9916(13)

Angle

ω, deg

Angle

ω, deg

Angle

ω, deg

N(5)Co(1)N(1) 115.81(6) N(12)N(11)Co(3) 122.14(10) N(1)N(2)Co(2) 123.63(10) C(18)C(16)C(17) 129.58(16)

N(1)Co(1)N(3) 108.54(5) N(1)C(1)C(3)

N(1)Co(1)N(7) 107.27(5) C(3)C(1)C(2)

O(1)Co(2)N(4) 126.30(5) N(2)C(4)C(3)

N(4)Co(2)N(2) 106.92(5) C(3)C(4)C(5)

N(4)Co(2)N(9) 107.26(5) N(3)C(6)C(7)

O(3)Co(3)N(8) 107.59(5) C(6)C(8)C(9)

109.71(13) C(6)N(3)Co(1) 126.03(10) C(19)C(18)C(16) 105.14(15)

129.35(15) C(9)N(4)N(3) 107.58(12) N(8)C(19)C(20) 121.20(15)

109.35(13) N(3)N(4)Co(2) 121.87(10) N(9)C(21)C(23) 110.07(14)

128.39(15) C(11)N(5)Co(1) 125.40(10) C(23)C(21)C(22) 129.36(16)

121.40(15) C(14)N(6)N(5) 107.77(12) N(10)C(24)C(23) 107.05(13)

105.38(15) N(5)N(6)Co(3) 121.81(10) C(23)C(24)C(25) 131.50(16)

N(8)Co(3)N(6) 108.62(5) N(4)C(9)C(10) 122.25(14) C(16)N(7)Co(1) 127.07(10) N(11)C(26)C(27) 120.69(14)

N(8)Co(3)N(11) 111.10(5) N(5)C(11)C(13) 109.19(14) C(19)N(8)N(7) 107.66(13) C(29)C(28)C(26) 106.40(15)

C(31)O(1)Co(2) 112.72(11) C(13)C(11)C(12) 129.61(16) N(7)N(8)Co(3) 124.43(10) N(12)C(29)C(30) 121.52(16)

C(1)N(1)N(2)

107.99(12) N(6)C(14)C(13) 109.46(13) C(21)N(9)Co(2) 128.51(10) O(2)C(31)O(1)

121.90(17)

N(2)N(1)Co(1) 124.24(10) C(13)C(14)C(15) 129.29(16) C(24)N(10)N(9) 111.06(13) O(1)C(31)C(32) 116.36(16)

C(4)N(2)Co(2) 128.46(10) N(7)C(16)C(17) 120.73(14 C(26)N(11)Co(3) 131.43(11) O(4)C(33)C(34) 120.03(16)

C(6)N(3)N(4)

108.09(13) N(5)Co(1)N(3) 109.19(5) C(29)N(12)N(11) 110.85(14) N(8)C(19)C(18) 109.58(14)

N(4)N(3)Co(1) 124.78(10) N(5)Co(1)N(7) 107.98(5)

C(9)N(4)Co(2) 130.07(10) N(3)Co(1)N(7) 107.77(5)

C(11)N(5)N(6) 108.11(13) O(1)Co(2)N(2) 100.88(5)

N(6)N(5)Co(1) 125.24(10) O(1)Co(2)N(9) 107.70(5)

C(14)N(6)Co(3) 128.63(10) N(2)Co(2)N(9) 106.17(5)

C(16)N(7)N(8) 107.94(12) O(3)Co(3)N(6) 119.15(5)

N(1)C(1)C(2)

C(1)C(3)C(4)

N(2)C(4)C(5)

N(3)C(6)C(8)

C(8)C(6)C(7)

N(4)C(9)C(8)

120.94(14) C(18)C(19)C(20) 129.22(16)

105.06(14) N(9)C(21)C(22) 120.55(14)

122.23(14) C(24)C(23)C(21) 105.80(15)

109.57(13) N(10)C(24)C(25) 121.45(16)

129.02(15) N(11)C(26)C(28) 109.71(15)

109.38(14) C(28)C(26)C(27) 129.60(16)

N(8)N(7)Co(1) 124.69(10) O(3)Co(3)N(11) 99.47(5) C(8)C(9)C(10) 128.36(15) N(12)C(29)C(28) 106.89(14)

C(19)N(8)Co(3) 127.88(10) N(6)Co(3)N(11) 110.60(5) N(5)C(11)C(12) 121.20(15) C(28)C(29)C(30) 131.58(15)

C(21)N(9)N(10) 106.02(12) C(33)O(3)Co(3) 139.48(11) C(14)C(13)C(11) 105.47(15) O(2)C(31)C(32) 121.74(17)

N(10)N(9)Co(2) 125.44(10) C(1)N(1)Co(1) 127.75(10) N(6)C(14)C(15) 121.25(14) O(4)C(33)O(3) 122.11(16)

C(26)N(11)N(12) 106.13(12) C(4)N(2)N(1) 107.89(12) N(7)C(16)C(18) 109.67(14) O(3)C(33)C(34) 117.86(15)

RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 54 No. 11 2009

SYNTHESIS AND STRUCTURE

1719

Table 6. Coordinates of atoms (×10⁴) and their equivalent isotropic factors (Å²× 10³) for complex 1 × 0.5C₆H₆(3)

Atom

x

y

z

U_eq

Co(1)

Co(2)

Co(3)

O(1)

O(2)

O(3)

O(4)

N(1)

N(2)

N(3)

N(4)

N(5)

N(6)

N(7)

N(8)

N(9)

N(10)

N(11)

N(12)

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)

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)

C(35)

C(36)

C(37)

C(38)

C(39)

C(40)

3784(1)

6289(1)

1241(1)

6704(2)

7957(2)

207(2)

–777(3)

5056(2)

5973(2)

4043(2)

4992(2)

2726(2)

1754(2)

3317(2)

2421(2)

7290(2)

8215(2)

407(2)

–538(2)

5126(3)

4247(3)

6077(3)

6601(3)

7674(3)

3360(3)

2246(3)

3851(3)

4869(3)

5746(3)

2789(3)

3757(3)

1864(3)

1249(3)

137(3)

3890(3)

4915(3)

3390(3)

2488(3)

1646(3)

7189(3)

6252(3)

8058(3)

8690(3)

9725(3)

649(3)

8140(1)

8006(1)

7829(1)

6933(2)

7300(2)

7510(2)

6966(2)

8514(2)

8582(2)

8009(2)

7954(2)

8963(2)

8828(2)

7219(2)

7166(2)

8640(2)

8399(2)

7976(2)

7673(2)

8869(2)

8891(3)

9161(3)

8978(2)

9161(3)

7939(2)

7960(3)

7837(2)

7834(2)

7724(3)

9687(3)

10008(3)

10039(3)

9492(3)

9541(3)

6616(3)

6509(3)

6171(3)

6531(3)

6292(3)

9346(3)

9805(3)

9552(3)

8938(3)

8803(3)

8288(3)

8692(3)

8168(3)

7782(3)

7515(3)

6784(3)

5956(3)

6929(5)

6236(4)

5657(6)

5874(4)

5404(8)

4716(7)

4499(4)

4970(8)

1739(1)

1205(1)

2207(1)

1232(2)

1963(2)

1489(2)

689(2)

2272(2)

2028(2)

774(2)

41(1)

46(1)

47(1)

63(1)

85(1)

79(1)

94(1)

48(1)

47(1)

44(1)

46(1)

43(1)

44(1)

45(1)

46(1)

49(1)

52(1)

48(1)

53(1)

52(1)

81(2)

59(1)

50(1)

69(1)

47(1)

78(2)

54(1)

51(1)

79(2)

50(1)

74(1)

62(1)

52(1)

87(2)

59(1)

90(2)

67(1)

53(1)

81(2)

51(1)

70(1)

59(1)

51(1)

79(2)

59(1)

81(2)

69(1)

58(1)

85(2)

57(1)

111(2)

141(2)

164(8)

101(5)

121(5)

109(5)

119(5)

120(4)

567(2)

1763(2)

1913(2)

2202(2)

2492(2)

741(2)

608(2)

2988(2)

2990(2)

2879(2)

3285(2)

3025(2)

2491(2)

2395(3)

224(2)

275(2)

–333(2)

–109(2)

–503(2)

1568(2)

1367(3)

1580(2)

1803(2)

1929(3)

2410(2)

2181(3)

2844(2)

2887(2)

3288(3)

493(2)

538(2)

206(2)

287(2)

76(3)

3601(2)

3790(2)

3987(2)

3586(2)

3706(3)

1658(3)

1763(3)

1179(5)

1337(4)

820(4)

1614(3)

–134(3)

–891(3)

–1915(3)

7462(3)

7727(4)

–76(5)

407(5)

2510(10)

3406(10)

3831(7)

3362(10)

2466(10)

2041(6)

573(6)

115(5)

–96(4)

150(6)

608(6)

RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 54 No. 11 2009

1720

NEFEDOV et al.

Table 7. Bond lengths (d) and bond angles (ω) for 1 × 0.5C₆H₆

Bond

d, Å

Bond

d, Å

Bond

d, Å

Bond

d, Å

Co(1)–N(7)

Co(1)–N(3)

Co(2)–O(1)

Co(2)–N(4)

Co(3)–O(3)

Co(3)–N(6)

O(1)–C(31)

O(3)–C(33)

N(1)–C(1)

N(2)–C(4)

N(3)–N(4)

N(5)–C(11)

N(6)–C(14)

N(7)–N(8)

N(9)–C(21)

1.980(3)

1.995(3)

1.945(3)

2.014(3)

1.938(3)

1.980(3)

1.261(5)

1.218(7)

1.346(5)

1.352(5)

1.374(4)

1.323(5)

1.340(5)

1.385(4)

1.323(5)

N(10)–C(24)

N(11)–N(12)

C(1)–C(3)

1.332(5)

1.362(4)

1.361(5)

1.372(6)

1.356(5)

1.373(5)

1.376(5)

1.361(5)

1.383(5)

1.364(5)

1.393(5)

1.356(5)

1.377(5)

1.381(6)

1.492(7)

Co(1)–N(1)

Co(1)–N(5)

Co(2)–N(2)

Co(2)–N(9)

Co(3)–N(8)

Co(3)–N(11)

O(2)–C(31)

O(4)–C(33)

N(1)–N(2)

N(3)–C(6)

N(4)–C(9)

N(5)–N(6)

N(7)–C(16)

N(8)–C(19)

N(9)–N(10)

1.992(3)

2.010(3)

1.998(3)

2.028(3)

1.974(3)

2.020(3)

1.229(5)

1.266(8)

1.367(4)

1.338(4)

1.344(5)

1.379(4)

1.332(5)

1.349(5)

1.353(4)

N(11)–C(26)

N(12)–C(29)

C(1)–C(2)

1.335(5)

1.332(5)

1.495(5)

1.489(5)

1.497(5)

1.529(5)

1.496(5)

1.504(5)

1.490(5)

1.501(5)

1.472(6)

1.483(5)

1.383(8)

C(3)–C(4)

C(4)–C(5)

C(6)–C(8)

C(6)–C(7)

C(8)–C(9)

C(9)–C(10)

C(11)–C(12)

C(14)–C(15)

C(16)–C(17)

C(19)–C(20)

C(21)–C(22)

C(24)–C(25)

C(26)–C(27)

C(29)–C(30)

C(33)–C(34)

C(11)–C(13)

C(13)–C(14)

C(16)–C(18)

C(18)–C(19)

C(21)–C(23)

C(23)–C(24)

C(26)–C(28)

C(28)–C(29)

C(31)–C(32)

Angle

ω, deg

Angle

ω, deg

Angle

ω, deg

Angle

ω, deg

N(7)Co(1)N(1) 108.16(13) N(10)N(9)Co(2)

125.4(3)

C(33)O(3)Co(3) 139.1(5)

C(14)C(13)C(11)

N(6)C(14)C(15)

105.4(4)

119.8(4)

N(1)Co(1)N(3) 108.20(13) C(26)N(11)N(12) 106.0(3)

N(7)Co(1)N(3) 116.76(13) N(12)N(11)Co(3) 122.9(3)

C(1)N(1)Co(1)

C(4)N(2)N(1)

126.0(3)

108.0(3)

N(7)C(16)C(18) 109.5(4)

N(7)Co(1)N(5) 107.89(13) N(1)C(1)C(3)

N(1)Co(1)N(5) 107.90(13) C(3)C(1)C(2)

O(1)Co(2)N(2) 122.99(13) N(2)C(4)C(3)

N(2)Co(2)N(4) 106.69(13) C(3)C(4)C(5)

N(2)Co(2)N(9) 108.01(14) N(3)C(6)C(7)

O(3)Co(3)N(8) 120.87(14) C(6)C(8)C(9)

N(8)Co(3)N(6) 107.86(13) N(4)C(9)C(10)

N(8)Co(3)N(11) 110.10(13) N(5)C(11)C(13)

109.0(4)

129.8(4)

108.2(3)

128.8(4)

121.6(3)

106.7(4)

122.0(4)

109.3(4)

N(1)N(2)Co(2) 121.7(2) C(18)C(16)C(17) 129.8(4)

C(6)N(3)Co(1)

C(9)N(4)N(3)

N(3)N(4)Co(2)

127.8(2)

107.4(3)

123.9(2)

N(8)C(19)C(18)

C(18)C(19)C(20)

N(9)C(21)C(22)

C(23)C(21)C(22)

N(10)C(24)C(23)

C(23)C(24)C(25)

N(11)C(26)C(27)

C(26)C(28)C(29)

N(12)C(29)C(30)

O(2)C(31)O(1)

109.8(4)

128.3(4)

121.6(4)

128.7(4)

106.7(3)

131.7(4)

122.3(4)

107.5(4)

121.5(4)

121.2(5)

116.6(5)

120.1(7)

106.4(4)

121.6(4)

109.1(4)

128.6(5)

105.6(4)

132.8(4)

122.2(5)

119.9(7)

C(11)N(5)Co(1) 127.1(3)

C(14)N(6)N(5)

N(5)N(6)Co(3)

106.4(3)

125.2(2)

C(16)N(7)Co(1) 125.5(3)

C(31)O(1)Co(2) 114.6(3)

C(1)N(1)N(2) 107.8(3)

N(2)N(1)Co(1) 125.3(3)

C(4)N(2)Co(2) 129.4(3)

C(6)N(3)N(4) 108.1(3)

N(4)N(3)Co(1) 124.1(2)

C(9)N(4)Co(2) 128.7(2)

C(11)N(5)N(6) 108.5(3)

N(6)N(5)Co(1) 124.0(2)

C(14)N(6)Co(3) 128.3(3)

C(16)N(7)N(8) 107.9(3)

N(8)N(7)Co(1) 125.3(2)

C(19)N(8)Co(3) 129.7(3)

C(21)N(9)N(10) 105.6(3)

C(13)C(11)C(12) 129.5(4)

N(6)C(14)C(13) 110.2(4)

C(13)C(14)C(15) 130.0(4)

N(7)C(16)C(17) 120.8(4)

C(19)C(18)C(16) 105.8(4)

C(19)N(8)N(7)

N(7)N(8)Co(3)

107.1(3)

122.4(2)

C(21)N(9)Co(2) 128.9(3)

C(24)N(10)N(9) 111.6(3)

C(26)N(11)Co(3) 130.7(3)

C(29)N(12)N(11) 111.7(3)

O(1)C(31)C(32)

O(3)C(33)C(34)

C(24)C(23)C(21)

N(10)C(24)C(25)

N(11)C(26)C(28)

C(28)C(26)C(27)

N(12)C(29)C(28)

C(28)C(29)C(30)

O(2)C(31)C(32)

O(3)C(33)O(4)

N(8)C(19)C(20)

N(9)C(21)C(23)

N(3)Co(1)N(5)

O(1)Co(2)N(4)

O(1)Co(2)N(9)

N(4)Co(2)N(9)

O(3)Co(3)N(6)

O(3)Co(3)N(11)

N(6)Co(3)N(11)

122.0(4)

109.7(4)

N(1)C(1)C(2)

121.1(4)

107.0(4)

122.9(4)

109.1(3)

129.2(4)

108.7(3)

129.3(4)

107.64(12) C(1)C(3)C(4)

101.10(13) N(2)C(4)C(5)

109.55(13) N(3)C(6)C(8)

107.38(13) C(8)C(6)C(7)

105.91(14) N(4)C(9)C(8)

101.09(14) C(8)C(9)C(10)

110.70(13) N(5)C(11)C(12) 121.1(4)

O(4)C(33)C(34)

RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 54 No. 11 2009

SYNTHESIS AND STRUCTURE

1721

Table 8. Coordinates of atoms (×10⁴) and their equivalent isotropic factors (Å²× 10³) for complex 4 × C₆H₆

Atom

x

y

z

U_eq

Zn(1)

Zn(2)

Zn(3)

O(1)

O(2)

O(3)

O(4)

N(1)

N(2)

N(3)

N(4)

N(5)

N(6)

N(7)

N(8)

N(9)

N(10)

N(11)

N(12)

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)

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)

C(35)

C(36)

C(37)

C(38)

C(39)

C(40)

38(1)

24(1)

7516(1)

8284(1)

6812(1)

9452(3)

9690(5)

5975(3)

5974(5)

8205(4)

8454(4)

7123(4)

7405(4)

8190(4)

7947(4)

6410(4)

6166(4)

7922(5)

8455(4)

6890(4)

6574(4)

8448(5)

8267(5)

8871(5)

8882(5)

9254(5)

6518(5)

6086(5)

6430(5)

6991(5)

7166(5)

8964(5)

9408(5)

9184(5)

8545(5)

8486(6)

5777(5)

5850(5)

5119(5)

5356(5)

4883(5)

7320(5)

6582(6)

7470(6)

8198(6)

8678(6)

7064(6)

7429(6)

6854(6)

6536(6)

6188(6)

9893(7)

10754(5)

5717(7)

5002(5)

8718(8)

9008(4)

8406(9)

7516(8)

7227(5)

7828(10)

4854(1)

6893(1)

2779(1)

7276(3)

8362(3)

2114(3)

954(3)

46(1)

55(1)

80(1)

125(3)

80(2)

109(2)

49(2)

54(2)

51(2)

47(2)

46(2)

48(2)

44(2)

54(2)

66(2)

69(2)

61(2)

65(2)

51(2)

71(2)

58(2)

53(2)

78(3)

56(2)

72(2)

59(2)

52(2)

74(2)

55(2)

69(2)

71(2)

57(2)

88(3)

50(2)

64(2)

68(2)

66(2)

106(3)

60(2)

95(3)

73(3)

75(3)

111(4)

75(3)

114(4)

84(3)

76(3)

116(4)

80(1)

103(3)

80(2)

112(4)

139(5)

162(6)

170(6)

125(4)

142(5)

157(7)

–439(1)

–791(6)

–1438(7)

–2442(5)

–2989(6)

1940(6)

1952(6)

–1692(6)

–1691(6)

–929(6)

–1095(6)

809(5)

5732(3)

6500(3)

5269(3)

6040(3)

4245(3)

3454(3)

4146(3)

3373(3)

7794(3)

8512(3)

2031(3)

1256(3)

5670(4)

4897(4)

6405(4)

6917(4)

7787(4)

4844(4)

3976(3)

5351(4)

6088(4)

6851(4)

4516(4)

5363(4)

3909(4)

3267(4)

2451(4)

4357(4)

5178(4)

3719(4)

3115(4)

2266(4)

7906(4)

7247(4)

8685(4)

9066(4)

9904(4)

2087(5)

2881(4)

1344(5)

826(5)

708(6)

705(6)

518(7)

909(8)

179(7)

3429(9)

3780(7)

4393(8)

3480(9)

3900(8)

–3031(9)

–3378(8)

–3893(8)

–3054(9)

–3452(8)

–1665(7)

–1704(8)

–2314(8)

–1935(8)

–2311(8)

1473(7)

1710(7)

1789(8)

1308(8)

1346(10)

1644(8)

2134(9)

1999(8)

1288(9)

1271(10)

2496(10)

3689(9)

2752(11)

1276(11)

783(10)

–1336(10)

–1993(9)

–3226(10)

–4660(9)

–3406(8)

–3697(9)

–3782(9)

–3576(9)

–3284(8)

–3199(7)

–37(4)

7832(5)

7861(5)

1435(5)

1210(4)

–592(7)

148(7)

488(3)

89(7)

–650(7)

–991(3)

RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 54 No. 11 2009

1722

NEFEDOV et al.

Table 9. Bond lengths (d) and bond angles (ω) for 4 × C₆H₆

Bond

d, Å

Bond

d, Å

Bond

d, Å

Bond

d, Å

Zn(1)–N(5)

Zn(1)–N(3)

Zn(2)–O(1)

Zn(2)–N(4)

Zn(3)–N(6)

Zn(3)–O(3)

O(1)–C(31)

O(3)–C(33)

N(1)–C(1)

N(2)–C(4)

N(3)–N(4)

N(5)–C(11)

N(6)–C(14)

N(7)–N(8)

N(9)–C(21)

1.977(5)

2.003(6)

1.953(5)

1.984(5)

1.970(5)

1.999(5)

1.217(8)

1.233(8)

1.347(7)

1.371(7)

1.371(6)

1.379(7)

1.334(8)

1.365(6)

1.327(9)

N(10)–C(24)

N(11)–N(12)

C(1)–C(3)

1.344(9)

1.369(6)

1.370(8)

1.362(9)

1.378(9)

1.377(8)

1.367(10)

1.372(8)

1.359(8)

1.354(10)

1.387(9)

1.354(9)

1.400(9)

1.362(9)

1.508(12)

Zn(1)–N(1)

Zn(1)–N(7)

Zn(2)–N(2)

Zn(2)–N(9)

Zn(3)–N(8)

Zn(3)–N(11)

O(2)–C(31)

O(4)–C(33)

N(1)–N(2)

N(3)–C(6)

N(4)–C(9)

N(5)–N(6)

N(7)–C(16)

N(8)–C(19)

N(9)–N(10)

2.000(5)

2.006(5)

1.980(6)

2.027(6)

1.972(6)

2.045(6)

N(11)–C(26)

N(12)–C(29)

C(1)–C(2)

1.329(8)

1.346(8)

1.492(8)

1.501(8)

1.497(8)

1.492(8)

1.512(8)

1.502(9)

1.509(8)

1.518(8)

1.506(8)

1.496(9)

1.525(9)

1.492(9)

1.531(11)

C(3)–C(4)

C(4)–C(5)

C(6)–C(8)

C(6)–C(7)

C(8)–C(9)

C(9)–C(10)

C(11)–C(13)

C(13)–C(14)

C(16)–C(18)

C(18)–C(19)

C(21)–C(23)

C(23)–C(24)

C(26)–C(28)

C(28)–C(29)

C(31)–C(32)

1.209(11) C(11)–C(12)

1.207(10) C(14)–C(15)

1.370(6)

1.363(7)

1.358(7)

1.391(6)

1.345(8)

1.367(8)

1.358(6)

C(16)–C(17)

C(19)–C(20)

C(21)–C(22)

C(24)–C(25)

C(26)–C(27)

C(29)–C(30)

C(33)–C(34)

Angle

ω, deg

Angle

ω, deg

Angle

ω, deg

Angle

ω, deg

N(5)Zn(1)N(1) 113.6(2)

N(1)Zn(1)N(3) 109.4(2)

N(5)Zn(1)N(3) 109.5(2)

N(5)Zn(1)N(7) 108.7(2)

N(10)N(9)Zn(2)

120.7(5)

C(33)O(3)Zn(3)

C(1)N(1)Zn(1)

N(1)N(2)C(4)

136.4(6) C(11)C(13)C(14) 106.0(7)

126.3(5) N(6)C(14)C(15) 121.2(7)

107.0(5) N(7)C(16)C(18) 108.1(6)

128.4(5) C(18)C(16)C(17) 130.4(7)

126.4(5) C(18)C(19)N(8) 109.0(6)

107.6(5) N(8)C(19)C(20) 119.9(8)

123.9(4) N(9)C(21)C(22) 122.1(7)

126.3(5) C(23)C(21)C(22) 128.2(8)

107.3(5) N(10)C(24)C(23) 104.8(7)

122.4(4) C(23)C(24)C(25) 132.1(8)

125.0(4) N(11)C(26)C(27) 119.8(7)

106.3(6) C(29)C(28)C(26) 107.9(7)

129.6(5) N(12)C(29)C(30) 121.9(8)

C(26)N(11)N(12) 105.7(6)

N(12)N(11)Zn(3) 118.9(5)

N(1)C(1)C(3)

107.6(6)

131.1(7)

108.0(6)

120.7(7)

121.4(7)

107.1(7)

121.6(6)

109.1(6)

120.3(7)

110.8(7)

C(4)N(2)Zn(2)

C(6)N(3)Zn(1)

C(9)N(4)N(3)

N(1)Zn(1)N(7) 108.23(19) C(3)C(1)C(2)

O(1)Zn(2)N(2) 105.6(2)

N(2)Zn(2)N(4) 110.3(2)

N(2)Zn(2)N(9) 110.5(2)

N(6)Zn(3)N(8) 112.2(2)

N(8)Zn(3)O(3) 103.1(2)

N(8)Zn(3)N(11) 109.2(2)

C(31)O(1)Zn(2) 136.2(6)

C(3)C(4)N(2)

N(2)C(4)C(5)

N(3)C(6)C(7)

C(9)C(8)C(6)

N(4)C(9)C(10)

C(13)C(11)N(5)

N(5)C(11)C(12)

N(6)C(14)C(13)

N(3)N(4)Zn(2)

C(11)N(5)Zn(1)

C(14)N(6)N(5)

N(5)N(6)Zn(3)

C(16)N(7)Zn(1)

N(7)N(8)C(19)

C(19)N(8)Zn(3)

C(21)N(9)Zn(2)

C(24)N(10)N(9)

C(1)N(1)N(2)

109.2(5)

N(2)N(1)Zn(1) 124.4(4)

N(1)N(2)Zn(2) 124.5(4)

C(13)C(14)C(15) 128.0(8)

N(7)C(16)C(17) 121.4(6)

133.2(5) O(2)C(31)O(1)

125.6(10)

112.9(6) O(1)C(31)C(32) 118.2(10)

C(6)N(3)N(4)

108.6(5)

C(19)C(18)C(16) 107.5(7)

C(18)C(19)C(20) 131.1(7)

C(26)N(11)Zn(3) 134.5(5) O(4)C(33)C(34) 118.7(8)

C(29)N(12)N(11) 111.9(7) C(24)C(23)C(21) 108.0(8)

N(4)N(3)Zn(1) 125.0(4)

C(9)N(4)Zn(2) 128.5(5)

C(11)N(5)N(6) 106.8(6)

N(6)N(5)Zn(1) 126.8(4)

C(14)N(6)Zn(3) 129.7(5)

C(16)N(7)N(8) 109.1(5)

N(8)N(7)Zn(1) 125.9(4)

N(7)N(8)Zn(3) 123.4(4)

C(21)N(9)N(10) 104.7(6)

N(9)C(21)C(23)

N(3)Zn(1)N(7)

O(1)Zn(2)N(4)

O(1)Zn(2)N(9)

N(4)Zn(2)N(9)

N(6)Zn(3)O(3)

N(6)Zn(3)N(11)

O(3)Zn(3)N(11)

109.7(6)

107.2(2)

109.9(2)

108.2(2)

112.0(2)

109.5(2)

116.1(2)

105.8(2)

N(1)C(1)C(2)

C(4)C(3)C(1)

C(3)C(4)C(5)

N(3)C(6)C(8)

C(8)C(6)C(7)

N(4)C(9)C(8)

C(8)C(9)C(10)

121.3(6) N(10)C(24)C(25) 123.1(8)

108.2(7) N(11)C(26)C(28) 109.0(7)

131.2(7) C(28)C(26)C(27) 131.2(8)

107.9(6) N(12)C(29)C(28) 105.5(8)

130.7(7) C(28)C(29)C(30) 132.6(8)

108.8(6) O(2)C(31)C(32) 116.3(9)

129.6(7) O(4)C(33)O(3)

127.2(9)

C(13)C(11)C(12) 130.6(7) O(3)C(33)C(34) 114.1(9)

RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 54 No. 11 2009

SYNTHESIS AND STRUCTURE

1723

Table 10. Coordinates of atoms (×10⁴) and their equivalent isotropic factors (Å²× 10³) for adduct 1 × Hdmpz (5)

Atom

x

y

z

U_eq

Co(1)

Co(2)

Co(3)

O(1)

2187(1)

366(1)

3934(1)

304(2)

–755(2)

3808(2)

5004(2)

1171(2)

472(2)

1653(1)

1589(1)

2551(1)

2609(2)

2412(3)

3370(3)

3609(3)

2128(2)

2129(3)

705(3)

3540(1)

1949(1)

5021(1)

1280(2)

257(2)

5761(2)

6596(2)

3556(2)

2924(2)

2731(2)

2079(2)

4526(2)

5069(2)

3404(2)

4002(2)

1577(2)

890(2)

5197(2)

5773(2)

–1070(3)

–1044(3)

4102(3)

4874(2)

3857(3)

3112(3)

2553(3)

2622(3)

3214(3)

1914(3)

1600(3)

835(2)

41(1)

48(1)

51(1)

72(1)

81(1)

75(1)

99(2)

45(1)

47(1)

45(1)

46(1)

45(1)

43(1)

49(1)

52(1)

61(1)

64(1)

94(2)

87(2)

53(1)

83(2)

63(2)

54(1)

77(2)

44(1)

68(2)

56(2)

51(2)

77(2)

89(2)

59(2)

71(2)

58(2)

98(2)

61(2)

97(2)

63(2)

52(2)

88(2)

54(2)

77(2)

62(2)

60(2)

92(2)

76(2)

150(4)

88(2)

67(2)

105(2)

54(2)

73(2)

75(1)

115(3)

83(2)

141(3)

99(2)

88(2)

107(2)

O(2)

O(3)

O(4)

N(1)

N(2)

N(3)

1944(2)

1283(2)

2743(2)

3408(2)

2876(2)

3431(2)

–609(2)

–1196(2)

5084(2)

5673(3)

–2697(4)

–2128(3)

1006(3)

1614(3)

214(3)

N(4)

777(3)

N(5)

1020(3)

1363(3)

2633(3)

3083(3)

791(3)

N(6)

N(7)

N(8)

N(9)

N(10)

N(11)

N(12)

N(13)

N(14)

C(1)

897(3)

2335(3)

2737(3)

2250(4)

2869(5)

2505(4)

2623(4)

2758(4)

2529(4)

2662(4)

37(3)

C(2)

C(3)

C(4)

–97(3)

C(5)

–917(3)

2413(3)

3184(3)

2054(3)

1359(3)

757(3)

C(6)

C(7)

–219(3)

–320(3)

161(4)

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)

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)

C(35)

C(36)

C(37)

C(38)

C(39)

72(3)

1790(3)

2512(3)

3041(3)

3583(3)

4290(3)

3734(3)

4387(3)

3383(3)

2857(3)

2324(3)

–847(3)

–337(3)

–1564(3)

–1775(3)

–2476(3)

5429(3)

4956(3)

6231(3)

6368(3)

7123(3)

–170(3)

57(3)

–279(4)

258(4)

4331(3)

4786(3)

5502(3)

5658(3)

6360(2)

3744(3)

4265(3)

2980(3)

2793(3)

2019(2)

1878(3)

2646(3)

1395(3)

773(3)

87(4)

783(4)

986(4)

3803(4)

4423(4)

3821(4)

3095(4)

2802(4)

74(4)

–247(3)

–257(4)

273(4)

235(4)

55(3)

1921(4)

1409(5)

2065(4)

2586(4)

2943(4)

2837(4)

3728(3)

3681(4)

4136(4)

2535(6)

1959(5)

3320(6)

3520(5)

4286(5)

4788(3)

4103(3)

5102(3)

5711(3)

6286(3)

632(3)

340(3)

4304(4)

3938(3)

–3313(4)

–4059(4)

–3153(5)

–2374(5)

–1843(3)

6390(3)

6867(3)

–1649(4)

–1845(4)

–1971(3)

–1571(4)

–1635(3)

RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 54 No. 11 2009

1724

NEFEDOV et al.

Table 11. Bond lengths (d) and bond angles (ω) for 1 × Hdmpz (5)

Bond

d, Å

Bond

d, Å

Bond

d, Å

Bond

d, Å

Co(1)–N(7)

Co(1)–N(3)

Co(2)–O(1)

Co(2)–N(2)

Co(3)–O(3)

Co(3)–N(8)

O(1)–C(31)

O(3)–C(33)

N(1)–C(1)

1.971(4)

1.997(4)

1.932(3)

1.984(4)

1.934(3)

1.994(4)

1.273(5)

1.296(5)

1.320(5)

1.352(5)

1.386(4)

1.337(6)

1.351(5)

1.381(4)

1.334(6)

1.338(5)

1.355(4)

N(13)–C(35)

N(14)–C(38)

C(1)–C(2)

C(4)–C(5)

C(6)–C(7)

C(9)–C(10)

C(12)–C(13)

C(14)–C(15)

C(16)–C(18)

C(19)–C(20)

C(21)–C(23)

C(24)–C(25)

C(26)–C(27)

C(29)–C(30)

C(33)–C(34)

C(35)–C(36)

C(38)–C(39)

1.321(7)

1.333(7)

1.502(5)

1.496(5)

1.491(5)

1.484(6)

1.384(6)

1.513(6)

1.376(6)

1.511(6)

1.378(6)

1.497(6)

1.479(6)

1.501(6)

1.481(7)

1.516(8)

1.502(8)

Co(1)–N(1)

Co(1)–N(5)

Co(2)–N(4)

Co(2)–N(9)

Co(3)–N(6)

Co(3)–N(11)

O(2)–C(31)

O(4)–C(33)

N(1)–N(2)

N(3)–C(6)

1.986(4) N(13)–N(14)

2.013(4) C(1)–C(3)

1.978(4) C(3)–C(4)

2.010(4) C(6)–C(8)

1.976(4) C(8)–C(9)

2.020(4) C(11)–C(12)

1.207(5) C(13)–C(14)

1.191(6) C(16)–C(17)

1.399(4) C(18)–C(19)

1.355(5) C(21)–C(22)

1.327(5) C(23)–C(24)

1.367(4) C(26)–C(28)

1.346(5) C(28)–C(29)

1.354(6) C(31)–C(32)

1.369(4) C(35)–C(37)

1.325(6) C(37)–C(38)

1.337(6)

1.355(6)

1.391(6)

1.379(6)

1.371(6)

1.496(6)

1.359(6)

1.527(6)

1.370(6)

1.503(6)

1.354(6)

1.374(6)

1.340(7)

1.518(6)

1.372(8)

1.370(8)

N(2)–C(4)

N(3)–N(4)

N(5)–C(12)

N(6)–C(14)

N(7)–N(8)

N(9)–C(21)

N(10)–C(24)

N(11)–N(12)

N(4)–C(9)

N(5)–N(6)

N(7)–C(19)

N(8)–C(16)

N(9)–N(10)

N(11)–C(26)

N(12)–C(29)

Angle

ω, deg

Angle

ω, deg

Angle

ω, deg

Angle

ω, deg

N(7)Co(1)N(1)

N(1)Co(1)N(3)

N(1)Co(1)N(5)

O(1)Co(2)N(4)

N(4)Co(2)N(2)

N(4)Co(2)N(9)

O(3)Co(3)N(6)

N(6)Co(3)N(8)

113.84(15) C(3)C(1)C(2)

108.22(16) N(2)C(4)C(3)

106.37(15) C(3)C(4)C(5)

111.45(16) N(3)C(6)C(7)

109.47(16) C(9)C(8)C(6)

107.66(16) N(4)C(9)C(10)

126.6(5)

109.2(4)

129.4(5)

121.5(4)

105.6(5)

121.7(5)

C(16)N(8)N(7)

N(7)N(8)Co(3)

C(21)N(9)Co(2) 132.3(4) O(4)C(33)C(34)

C(24)N(10)N(9) 111.7(4) N(13)C(35)C(37) 112.5(7)

C(26)N(11)Co(3) 131.7(4) C(37)C(35)C(36) 131.2(8)

C(29)N(12)N(11) 110.1(5) N(14)C(38)C(37) 105.5(7)

C(38)N(14)N(13) 113.4(6) C(37)C(38)C(39) 132.2(8)

108.7(4) O(2)C(31)O(1)

125.0(3) O(1)C(31)C(32)

125.8(5)

113.9(5)

120.5(6)

107.18(15) N(5)C(12)C(13) 108.9(5)

108.99(16) C(13)C(12)C(11) 129.0(6)

N(1)C(1)C(2)

110.21(15) C(4)C(3)C(1)

109.25(15) N(2)C(4)C(5)

108.78(16) N(3)C(6)C(8)

107.71(15) C(8)C(6)C(7)

111.69(15) N(4)C(9)C(8)

108.82(16) C(8)C(9)C(10)

122.7(5) N(6)C(14)C(15)

105.2(5) N(8)C(16)C(18)

119.6(5)

108.7(5)

N(6)Co(3)N(11) 110.60(16) N(7)Co(1)N(3)

C(31)O(1)Co(2) 134.9(3)

N(7)Co(1)N(5)

N(3)Co(1)N(5)

O(1)Co(2)N(2)

O(1)Co(2)N(9)

N(2)Co(2)N(9)

O(3)Co(3)N(8)

121.4(5) C(18)C(16)C(17) 129.4(5)

109.1(4) N(7)C(19)C(18) 111.0(4)

129.3(5) C(18)C(19)C(20) 127.0(5)

110.3(4) N(9)C(21)C(22) 119.2(5)

128.0(5) C(24)C(23)C(21) 106.9(5)

C(1)N(1)N(2)

N(2)N(1)Co(1)

C(4)N(2)Co(2)

C(6)N(3)N(4)

N(4)N(3)Co(1)

C(9)N(4)Co(2)

C(12)N(5)N(6)

N(6)N(5)Co(1)

C(14)N(6)Co(3) 127.3(4)

C(19)N(7)N(8)

N(8)N(7)Co(1)

C(16)N(8)Co(3) 123.9(3)

C(21)N(9)N(10) 104.3(4)

N(10)N(9)Co(2) 123.4(3)

C(26)N(11)N(12) 106.0(4)

N(12)N(11)Co(3) 121.8(4)

C(35)N(13)N(14) 103.0(6)

107.2(4)

122.4(3)

127.8(3)

107.1(4)

121.8(3)

127.5(3)

108.6(4)

123.6(3)

111.31(15) N(5)C(12)C(11) 122.1(5) N(10)C(24)C(25) 121.8(5)

O(3)Co(3)N(11) 111.92(16) C(14)C(13)C(12) 105.5(5) N(11)C(26)C(28) 109.6(5)

N(8)Co(3)N(11) 106.82(17) N(6)C(14)C(13) 110.2(4) C(28)C(26)C(27) 129.7(6)

C(33)O(3)Co(3) 132.2(4)

C(13)C(14)C(15) 130.2(5) N(12)C(29)C(28) 107.5(5)

N(8)C(16)C(17) 121.8(5) C(28)C(29)C(30) 131.4(6)

C(19)C(18)C(16) 105.5(5) O(2)C(31)C(32)

N(7)C(19)C(20) 122.0(5) O(4)C(33)O(3)

N(9)C(21)C(23) 110.6(4) O(3)C(33)C(34)

C(23)C(21)C(22) 130.2(5) N(13)C(35)C(36) 116.2(8)

N(10)C(24)C(23) 106.5(5) C(38)C(37)C(35) 105.5(7)

C(23)C(24)C(25) 131.7(5) N(14)C(38)C(39) 122.2(8)

N(11)C(26)C(27) 120.7(5)

C(1)N(1)Co(1)

C(4)N(2)N(1)

N(1)N(2)Co(2)

C(6)N(3)Co(1)

C(9)N(4)N(3)

N(3)N(4)Co(2)

130.4(3)

107.7(4)

124.5(3)

129.7(3)

107.8(4)

124.4(3)

106.0(4)

121.7(3)

120.3(5)

124.6(6)

114.9(5)

C(12)N(5)Co(1) 127.6(4)

C(14)N(6)N(5)

N(5)N(6)Co(3)

106.8(4)

125.7(3)

C(29)C(28)C(26) 106.8(6)

N(1)C(1)C(3)

110.7(4)

C(19)N(7)Co(1) 131.5(3)

N(12)C(29)C(30) 121.0(6)

RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 54 No. 11 2009

SYNTHESIS AND STRUCTURE

1725

from the mother solution by decantation, washed with 1480 w, 1416 m, 1332 w, 1300 w, 1136 w, 1040 m,

hexane, and dried in ﬂowing argon. Yield: 0.063 g

(90%).

772 w, 744 w, 680 m, 624 w, 484 w, 428 w, 400 w, 356 m.

Zn₃(m-dmpz)₄(Hdmpz)₂(OOCMe)₂¥ ë₆ç₆(4). A

mixture of zinc acetate hydrate (0.2 g, 0.9 mmol) and

Hdmpz (0.173 g, 1.8 mmol) was kept for 2 h at 150°ë.

The resulting colorless solid product was washed with

heptane (10 mL × 3) to remove unreacted Hdmpz and

dissolved in hot benzene (20 mL). The resulting violet

solution was reduced in volume to 5 mL and kept at

+5°ë for 24 h. Colorless crystals were separated from

the mother solution by decantation, washed with cold

hexane, and dried in ﬂowing argon. Yield: 0.13 g (45%).

For C₃₄H₅₀Co₃N₁₂O₄anal. calcd., %: C, 47.07; H,

5.81; N, 19.37.

Found, %: C, 47.11; H, 5.78; N, 19.41.

IR spectrum (KBr), ν, cm^–1: 3588 w, 3428 m br,

2932 w, 2872 w, 1684 w, 1664 w, 1564 s, 1416 s,

1336 m, 1172 w, 1132 w, 1040 m, 936 w, 756 w, 676 m,

616 w, 428 w, 376 w, 316 w.

Co₃(m-dmpz)₄(Hdmpz)₂(OOCMe)₂(1 × 0.5ë₆ç₅Me)

(2). To 3,5-dimethylpyrazole (0.044 g, 0.46 mmol) in

toluene (20 mL), cobalt acetate hydrate (0.1 g,

0.23 mmol) was added. The reaction mixture was

boiled with stirring for 3 h at 110°ë to complete disso-

lution. The resulting violet solution was reduced in vol-

ume to 10 mL and kept for 24 h at +5°ë. Violet crystals

were separated from the mother solution by decanta-

tion, washed with hexane, and dried in ﬂowing argon.

Yield: 0.062 g (85%).

For C₄₀H₅₆N₁₂O₄Zn₃anal. calcd.,%: C, 49.78; H,

5.85; N, 17.42.

Found, %: C, 49.74; H, 5.88; N, 17.46.

IR spectrum (KBr), ν, cm^–1: 3124 w, 2928 w,

2856 w, 1696 w, 1604 m, 1564 m, 1524 m, 1472 w,

1428 s, 1336 s, 1304 m, 1188 m, 1152 m, 1092 w,

1048 s, 1016 m, 900 m, 804 w, 772 s, 756 m, 744 m,

660 s, 592 w, 512 w, 428 m, 336 m.

For C_37.5H_53.5Co₃N₁₂O₄anal. calcd.,%: C, 49.28; H,

5.92; N, 18.41.

Found, %: C, 49.32; H, 5.88; N, 18.44.

Co₃(m-dmpz)₄(Hdmpz)₂(OOCMe)₂(1 × Hdmpz)

(5). A mixture of cobalt acetate hydrate (0.2 g,

0.46 mmol) and 3,5-dimethylpyrazole (0.097 g,

1 mmol) was kept for 2 h at 150°ë. The mixture gradu-

ally changed from pink to violet. The solid product was

extracted by CH₂Cl₂(15 mL), hexane (10 mL) was

added, reduced in volume to 10 mL, and kept at 0°ë for

24 h. Violet crystals were separated from the mother

solution by decantation, washed with cold hexane, and

dried in ﬂowing argon. Yield: 0.059 g (40%).

IR spectrum (KBr), ν, cm^–1: 3454 s, 3118 w, 2922 w,

2859 w, 1619 s, 1564 s, 1526 s, 1414 s, 1333 m,

1297 m, 1169 w, 1131 w, 1086 w, 1041 s, 937 w, 773 m,

738 m, 657 m, 613 w, 494 w, 468 w, 427 w.

Co₃(m-dmpz)₄(Hdmpz)₂(OOCMe)₂(1 × 0.5ë₆ç₆) (3).

(a) Cobalt acetate hydrate (0.1 g, 0.23 mmol) and

Hdmpz (0.044 g, 0.46 mmol) were boiled in benzene

(20 mL) for 3 h. The resulting violet solution was

cooled to room temperature on an oil bath, separated by

decantation from a pink jelly precipitate, reduced in

volume to 5 mL, and kept at +5°ë for 24 h. Violet crys-

tals were separated from the mother solution by decan-

tation, washed with cold hexane, and dried in ﬂowing

argon. Yield: 0.006 g (8%).

For C₃₉H₅₈Co₃N₁₄O₄anal. calcd.,%: C, 48.60; H,

6.07; N, 20.35.

Found, %: C, 48.56; H, 6.11; N, 20.39.

(b) A mixture of cobalt acetate hydrate (0.2 g,

0.46 mmol) and 3,5-dimethylpyrazole (0.088 g,

0.92 mmol) was kept for 2 h at 150°ë. The mixture

gradually changed from pink to violet. The solid prod-

uct was washed with heptane (10 mL × 3) to remove

unreacted Hdmpz and dissolved in hot benzene

(20 mL). The resulting violet solution was reduced in

volume to 5 mL and kept at +5°ë for 24 h. Violet crys-

tals were separated from the mother solution by decan-

tation, washed with cold hexane, and dried in ﬂowing

argon. Yield: 0.049 g (35%).

IR spectrum (KBr), ν, cm^–1: 3425 w, 3236 m,

3124 w, 2924 w, 1660 w, 1564 s, 1524 s, 1460 w,

1408 s, 1324 s, 1296 s, 1184 m, 1132 m, 1088 w,

1040 s, 1016 m, 980 w, 932 w, 784 m, 756 m, 660 s,

588 w, 516 w, 448 w, 428 m, 360 m.

RESULTS AND DISCUSSION

We found that the reaction of hydrous cobalt ace-

tates with 2 mol of 3,5-dimethylpyrazole in boiling

xylene or toluene yields, in near-quantitative yield,

violet trinuclear pyrazolate-bridged complex

Co₃(μ-dmpz)₆(Hdmpz)₂(OOCMe)₂(complex 1) and

its toluene solvate 1 × 0.5C₆H₅Me (2), respectively:

For C₃₇H₅₃Co₃N₁₂O₄anal. calcd.,%: C, 49.01; H,

5.89; N, 18.54.

Found, %: C, 48.98; H, 5.93; N, 18.57.

IR spectrum (KBr), ν, cm^–1: 3676 w, 3472 m br,

2924 w, 2852 w, 1716 w, 1660 w, 1564 m, 1528 m,

RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 54 No. 11 2009

1726

NEFEDOV et al.

Me

C

N

H

N N

O

2Hdmpz

Boiling xylene

or toluene

Co

Co(OOCMe)₂· 4H₂O

Co

H

N

O

C

N

Me

When a mixture of crystalline cobalt or zinc acetate

In complex 1 acetate anions form a staggered con-

hydrate with Hdmpz in the ratio 1 : 2 is heated at 150°ë formation (with the angle of 21.6° formed by

for 2 h with subsequent elimination of unreacted pyra- C(31A)C(32A) and C(31B)C(32B) lines), whereas in

zole by hexane and recrystallization from benzene, the formally looser unit cells containing solvating toluene

products are solvates of complex 1 with 0.5 C₆H₆mol- or benzene molecules, the acetate ions are parallel and

directed to one side.

ecules and Zn₃(μ-dmpz)₄(Hdmpz)₂(OOCMe)₂× C₆H₆

(4), respectively. In the presence of excess Hdmpz,

adduct 1 × Hdmpz (5) is formed; it was obtained by

recrystallization from CH₂Cl₂/hexane.

We should mention that structure has recently been

solved at room temperature for complex 1, which was

prepared in high yield by the thermolysis of cobalt ace-

tate and 3,5-dimethylpyrazole at 130°ë for 24 h fol-

lowed by extraction with CH₂Cl₂[6], and the geometry

of this complex, including the character of intermolec-

ular hydrogen bonds, completely matches the geometry

of complex 1, which was structurally studied at 120 K.

X-ray crystallography shows that in complex 1

(Fig. 1; Tables 2, 3), the three cobalt atoms lying at non-

bonded Co···Co distances (3.5976(9) and 3.6073(9) Å)

and pyrazolate bridged with equalized Co–N distances

(1.960(4)–2.005(4) Å), form a virtually linear metal

core Co₃(angle Co₂/Co₂168.7°). The central cobalt

atom is surrounded by a tetrahedral array of four nitro-

gen atoms from the bridging pyrazolate anions; the tet-

rahedral surrounding of the peripheral cobalt atoms is

supplemented by the oxygen atoms of the terminal ace-

tate anion (Co–O, 1.944(3), 2.005(4) Å) and the nitro-

gen atom of the terminal pyrazole molecule (Co–N,

1.944(3), 1.953(4) Å).

Unlike in complexes 1–3, in zinc complex 4 (Fig. 4;

Tables 8, 9), which has a similar geometry despite the

presence of solvating benzene molecules, only short

intramolecular hydrogen bonds were found (N···O

2.625, 2.693 Å, ç···é 1.796 1.81 Å). In the trinuclear

complex 4 with the Zn₃metal core (Zn···Zn 3.622(1),

3.635(1) Å, Zn₂/Zn₂173.2°), the central zinc atom is sur-

rounded by a tetrahedral array of nitrogen atoms from

four bridging pyrazolate anions (Zn–N, 1.977(5)–

2.006(5) Å); the two peripheral zinc atoms have a tetra-

hedral surrounding, which includes, in addition to the

nitrogen atoms of the bridging pyrazolate anions, the

oxygen atom of the terminal acetate anion (Zn–O,

1.953(5), 1.999(5) Å) and the nitrogen atoms of the termi-

nal pyrazole molecules (Zn–N, 2.027(6), 2.045(6) Å).

The appearance of solvating toluene molecules in

crystals of complex 2 (Tables 3, 4) or benzene sol-

vating molecules in complex 3 (Tables 5, 6) only

insigniﬁcantly inﬂuences the geometry of a

Co₃(μ-dmpz)₆(Hdmpz)₂(OOCMe)₂molecule (Co···Co

3.6153(4), 3.6421(4) Å, Co–μ-N, 1.989(1)–2.018(1) Å;

Co–O, 1.922(1), 1.951(1) Å; Co–N, 2.012(1), 2.028(1) Å;

angle Co2/Co2 167.6° in complex 2; and Co···Co

3.6170(9), 3.6481(9) Å, Co–μ-N, 1.980(3)–2.014(3) Å;

Co–O, 1.938(3), 1.945(3) Å; Co–N, 2.020(3), 2.028(3) Å;

angle Co₂/Co₂173.8° in complex 3).

Finally, the substitution of the electron-deﬁcient

cobalt(II) atom for the electron-saturated zinc(II)

atom practically does not affect the geometry of

M₃(μ-dmpz)₄(Hdmpz)₂(OOCMe)₂trinuclear com-

plexes (possibly, except for the character of intermo-

lecular hydrogen bonds), which was also shown by

the comparison of geometries of dinuclear pyra-

zolate-bridged zinc and cobalt pivalates M₂(μ-

In crystals of complexes 1–3, the oxygen atoms of

acetate anions and the hydrogen atoms of NH moieties

in a molecule of complex 1 are linked by intermolecular

hydrogen bonds to form 1-D polymers (N···O 2.763–

2.908 Å); the character of these bonds, although having

virtually identical geometry with close Co(2A)···Co(2B)

distances (6.864, 6.572, 6.650 Å, respectively), in com-

plex 1 (Fig. 2) differs from that in complexes 2 and 3

(Fig. 3), the last two complexes having solvating sol-

vent molecules.

dmpz)₂(Hdmpz)₂(OOCBu^t)₂[7–10].

Possibly, the existence of intramolecular hydrogen

bonds in trinuclear Zn₃(μ-dmpz)₆(Hdmpz)₂(OOCMe)₂is

responsible for the inhibited formation of [Zn(dmpz)₂]_n

polymer [1], in contrast to [Zn(pz)₂]_npolymer. The latter

RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 54 No. 11 2009

SYNTHESIS AND STRUCTURE

1727

O(4)

C(8)

C(7)

C(6)

C(10)

C(9)

N(4)

C(33)

C(34)

O(3)

C(15)

N(3)

C(12)

C(22)

C(23)

C(13)

C(21)

N(9)

C(14)

C(11)

C(24)

H(12A)

C(25)

Co(3)

N(6)

N(5)

N(7)

N(10)

C(31)

H(10A)

N(12)

Co(2)

Co(1)

C(16)

O(1)

C(17)

N(8)

C(30)

N(11)

N(2)

N(1)

C(32)

C(29)

C(19)

C(1)

C(18)

C(20)

O(2)

C(26)

C(4)

C(28)

C(5)

C(27)

C(2)

C(3)

Fig. 1. Structure of complex 1.

C(32B)

O(2B)

C(31B)

O(1B)

N(7B)

N(3B)

N(8B)

N(11B)

H(10B)

N(10B)

Co(2B)

N(4B)

N(2B)

N(12B)

Co(1B)

Co(3B)

H(12B)

C(32A)

N(9B)

O(3B)

N(6B)

C(33B)

N(1B)

N(5B)

C(34B)

O(4B)

C(31A)

O(1A)

O(2A)

N(7A)

N(8A)

N(6A)

Co(2A)

H(10A)

N(10A)

Co(3A)

N(4A)

N(12A)

H(12A)

Co(1A)

N(3A)

N(11A)

O(3A)

C(33A)

N(9A)

N(2A)

N(1A)

N(5A)

C(34A)

O(4A)

Fig. 2. Intermolecular hydrogen bonds in complex 1.

is formed upon the thermolysis (220°C) of binuclear atom of the coordinated pyrazole molecule (N···O 2.763 Å;

Zn₂(μ-pz)₂(Hpz)₂(OOCMe)₂, where X-ray crystallogra-

phy detected intermolecular hydrogen bonds like those

observed in complexes 1–3 [1].

O···H 1.96 Å; Co–O, 1.932(3) Å; Co–N, 2.010(4) Å).

The geometry of the Co₃molecule is another than in com-

plex 1: with close values of Co(1)···Co(2) (3.5901(9) Å)

and Co(1)···Co(3) (3.6356(9) Å) nonbonded distances

and the Co–μ-N (1.971(4)–2.013(4) Å) and Co(2,3)–N

(2.010(4), 2.020(4) Å) bond lengths, the angle Co₂/Co₂

decreases to 160.7° and the oxygen atom of the terminal

acetate anion and the hydrogen of the NH moiety of

pyrazole, both coordinated to the Co(3) atom, form a

short intramolecular hydrogen bond (O···N 2.658 Å;

Intramolecular hydrogen bonds are also observed in

adduct 1 × Hdmpz (5). X-ray crystallography shows

that in adduct 5 (Fig. 5; Tables 10, 11), the hydrogen

atom of the NH moiety of the solvating Hdmpz mole-

cule is hydrogen-bonded to the oxygen atom of the ter-

minal acetate anion (N···O 2.886 Å; O···H 2.08 Å)

belonging to trinuclear complex 1, which is also linked

via intramolecular hydrogen bond with the hydrogen O···H 1.85 Å).

RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 54 No. 11 2009

1728

NEFEDOV et al.

C(28B)

C(27B)

C(30B)

C(26B)

N(11B)

C(29B)

N(12B)

H(12B)

N(6B)

N(3A)

Co(3B)

N(5B)

N(4A)

O(2A)

Co(1B)

Co(1A)

O(3B)

C(23A)

N(8B)

Co(2A)

C(31A)

N(7B)

O(1A)

C(34B)

C(33B)

H(10A)

N(10A)

N(9A)

N(1A)

N(2A)

O(4B)

C(21A)

C(22A)

C(24A)

C(23A)

C(25A)

Fig. 3. Intermolecular hydrogen bonds in complexes 2 and 3 (only coordination cores for the Co(2) and Co(3) and basal nitrogen

atoms of bridging pyrazolate anions are shown).

C(13)

C(125)

C(12)

C(15)

C(26)

C(11)

C(14)

N(6)

C(23)

C(24)

C(21)

N(5)

C(10)

C(8)

N(9)

C(27)

C(25)

C(6)

C(9)

C(7)

C(29)

C(30)

C(22)

N(10)

H(10A)

N(11)

N(3)

N(4)

N(12)

Zn(1)

Zn(3)

Zn(2)

H(12A)

N(2)

C(4)

N(1)

C(5)

O(3)

C(33)

C(34)

C(1)

O(4)

N(7)

N(8)

C(2)

O(1)

C(3)

C(3S)

O(2)

C(31)

C(4S)

C(2S)

C(1S)

C(16)

C(19)

C(17)

C(20)

C(5S)

C(18)

C(6S)

C(32)

Fig. 4. Structure of complex 4 × ë ç .

6

To summarize, we discovered that, unlike zinc nuclear pyrazolate-bridged complexes M₃(μ-

and cobalt pivalates which react with Hdmpz under

mild conditions to yield pyrazolate-bridged dimers

M₂(μ-dmpz)₂(Hdmpz)₂(OOCBu^t)₂, aqueous acetates

dmpz)₄(Hdmpz)₂(OOCMe)₂, where the character of

hydrogen bonding is dictated by the nature of the

transition metal and the nature of solvating mole-

in similar reactions upon heating to 150°ë yield tri- cules.

RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 54 No. 11 2009

SYNTHESIS AND STRUCTURE

1729

C(39)

C(38)

C(3)

C(5)

C(2)

O(3)

C(4)

C(1)

O(4)

H(2)

C(17)

C(35)

N(14)

C(33)

C(31)

C(16)

C(34)

N(13)

C(37)

C(36)

C(18)

N(1)

C(19)

N(2)

N(8)

O(1)

Co(3)

O(2)

N(12)

N(11)

H(3)

C(32)

N(7)

C(30)

N(6)

H(1)

N(10)

C(20)

Co(2)

C(29)

Co(1)

N(5)

C(12)

N(9)

C(21)

C(13)

C(24)

C(26)

C(25)

C(28)

C(22)

N(4)

C(9)

N(3)

C(6)

C(23)

C(11)

C(27)

C(10)

C(7)

C(8)

Fig. 5. Structure of adduct 1 × Hdmpz (5).

4. A. Cingolani, S. Galli, N. Masciocchi, et al., J. Am.

ACKNOWLEDGMENTS

Chem. Soc. 127, 6144 (2005).

This work was supported by the Russian Foundation

for Basic Research (project nos. 08-03-01063, 08-03-

90455), the Presidential Foundation (Program for Sup-

port of Leading Scientiﬁc Schools of Russia; grant no.

NSh-1733.2008.03), and the Presidium of the Division

of Chemistry and Materials Science of the Russian

Academy of Sciences (programs “Theoretical and

Experimental Investigations of the Nature of Chemical

Bonds and the Mechanisms of the Most Important

Chemical Reactions and Processes” and “Targeted

Synthesis of Inorganic Compounds and Design of

Functional Materials”).

5. N. Masciocchi, G. A. Ardizzoia, S. Brenna, et al., Inorg.

Chem. 41, 6080 (2002).

6. H. N. Miras, H. Zhao, R. Herchel, et al., Eur. J. Inorg.

Chem. 30, 4745 (2008).

7. S. E. Nefedov, Russ. J. Inorg. Chem. 51 (Suppl. 1), 49

(2006).

8. T. O. Denisova, E. V. Amel’chenkova, I. V. Pruss, et al.,

Zh. Neorg. Khim. 51 (7), 1098 (2006) [Russ. J. Inorg.

Chem. 51 (7), (2006)].

9. E. V. Amel’chenkova, T. O. Denisova, and S. E. Nefedov,

Zh. Neorg. Khim. 51 (8), 1304 (2006) [Russ. J. Inorg.

Chem. 51 (8), 1218 (2006)].

10. E. V. Amel’chenkova, T. O. Denisova, and S. E. Nefedov,

Zh. Neorg. Khim. 51 (11), 1763 (2006) [Russ. J. Inorg.

Chem. 51 (11), 1763 (2006)].

11. SMART (Control) and SAINT (Integration) Software,

Version 5.0, Bruker AXS Inc. (Madison, WI, 1997).

12. G. M. Sheldrick, SADABS. Program for Scaling and

Correction of Area Detector Data (Univ. of Göttingen,

Göttingen, 1997).

REFERENCES

1. A. Cingolani, S. Galli, N. Masciocchi, et al., J. Chem.

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RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 54 No. 11 2009

Article Doi

Synthesis and structure of trinuclear pyrazolate-bridged acetates M 3(μ-dmpz)4(Hdmpz)2(OOCMe)2 (M = Zn or Co; Hdmpz = 3,5-dimethylpyrazole)

DOI: 10.1134/S0036023609110060

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Article abstract of DOI:10.1134/S0036023609110060

Full text of DOI:10.1134/S0036023609110060

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