Di-μ-sulfato-bis­{[bis­(3,5-dimethyl­pyrazol-1-yl)methane]copper(II)}

Wu, Y.L.; Wang, X.C.; You, X.L.

doi:10.1107/S1600536808027840

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 10| October 2008| Page m1242

doi:10.1107/S1600536808027840

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Di-μ-sulfato-bis{[bis(3,5-dimethylpyrazol-1-yl)methane]copper(II)}

YanLi Wu,^a XingCong Wang ^a and XiuLi You ^a ^*

^aJiangxi Key Laboratory of Organic Chemistry, Jiangxi Science and Technology Normal University, Nanchang 330013, People's Republic of China
^*Correspondence e-mail: jxstnu116@yahoo.cn

(Received 29 June 2008; accepted 30 August 2008; online 6 September 2008)

The molecule of the title compound, [Cu₂(SO₄)₂(C₁₁H₁₆N₄)₂], sits on a center of symmetry. The Cu^II atom has a distorted trigonal–bipyramidal coordination geometry comprising three O atoms of the two symmetry-related SO₄²⁻ anions and two N atoms from one bis(3,5-dimethylpyrazol-1-yl)methane ligand.

Related literature

For related literature, see: Arnold et al. (2001 ); Dhar et al. (2004 ); Endres et al. (1984 ); Hatzidimitriou et al. (2006 ); He & Han (2006 ); Springsteen et al. (2006 ); Tamasi & Cini (2003 ); Thompson et al. (1998 ).

Experimental

Crystal data

[Cu₂(SO₄)₂(C₁₁H₁₆N₄)₂]
M_r = 727.76
Monoclinic, P 2₁ /n
a = 7.5293 (15) Å
b = 10.734 (2) Å
c = 17.740 (4) Å
β = 99.73 (3)°
V = 1413.2 (5) Å³
Z = 2
Mo Kα radiation
μ = 1.71 mm⁻¹
T = 291 (2) K
0.22 × 0.19 × 0.19 mm

Data collection

Rigaku Mercury diffractometer
Absorption correction: multi-scan (Jacobson, 1998 ) T_min = 0.704, T_max = 0.737
13344 measured reflections
2580 independent reflections
2253 reflections with I > 2σ(I)
R_int = 0.039

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.112
S = 1.07
2580 reflections
194 parameters
H-atom parameters constrained
Δρ_max = 0.46 e Å⁻³
Δρ_min = −0.42 e Å⁻³

Data collection: CrystalClear (Rigaku/MSC, 2001 ); cell refinement: CrystalClear; data reduction: CrystalStructure (Rigaku/MSC, 2004 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808027840/cs2085sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808027840/cs2085Isup2.hkl

checkCIF report

Comment top

SO₄^2- anion-bridged dimeric complexes of Cu(II) are reported extensively (Tamasi & Cini, 2003). In most of these structures the SO₄^2- anion acts as a bidentate bridge (Springsteen et al., 2006; He & Han, 2006; Arnold et al., 2001; Thompson et al., 1998; Endres et al., 1984). However, there are only two known examples of the tridentate bridge form (Hatzidimitriou et al., 2006; Dhar et al., 2004). The crystal structure of the title compound, [Cu(bdmpm)(SO₄)]₂ (bdmpm = bis(1,1-bis(3,5-dimethylpyrazol-1-yl)methane), shows a perfect centrosymmetric dimer, as two {Cu(bdmpm)}²⁺ units are bridged by two sulfate anions in the complex (Fig. 1). The Cu···Cu distance is 3.769 (11) Å and the copper atom has a trigonal bipyramidal CuN₂O₃ coordination geometry with the sulfate O(2) atom and the N(1) atom as axial ligand atoms.

Related literature top

For related literature, see: Arnold et al. (2001); Dhar et al. (2004); Endres et al. (1984); Hatzidimitriou et al. (2006); He & Han (2006); Springsteen et al. (2006); Tamasi & Cini (2003); Thompson et al. (1998).

Experimental top

The reaction of CuSO₄.5H₂O (25 mg, 0.1 mmol) with bdmpm (22 mg, 0.11 mmol) in MeOH (10 ml) was carried out at ambient temperature for 10 minutes, the mixture was filtered and the filtrate was then left for crystallization.

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2001); cell refinement: CrystalClear (Rigaku/MSC, 2001); data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure with displacement ellipsoids drawn at the 50% probability level. Atoms labeled with the suffix A are related by the (-x, 1 - y, - z) symmetry operator.

Di-µ-sulfato-bis{[bis(3,5-dimethylpyrazol-1-yl)methane]copper(II)} top

Crystal data top

[Cu₂(SO₄)₂(C₁₁H₁₆N₄)₂]	F(000) = 748
M_r = 727.76	D_x = 1.710 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 4573 reflections
a = 7.5293 (15) Å	θ = 3.0–25.4°
b = 10.734 (2) Å	µ = 1.71 mm⁻¹
c = 17.740 (4) Å	T = 291 K
β = 99.73 (3)°	Block, green
V = 1413.2 (5) Å³	0.22 × 0.19 × 0.19 mm
Z = 2

Data collection top

Rigaku Mercury diffractometer	2580 independent reflections
Radiation source: fine-focus sealed tube	2253 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.039
Detector resolution: 14.6306 pixels mm^-1	θ_max = 25.4°, θ_min = 3.0°
ω scans	h = −9→9
Absorption correction: multi-scan (Jacobson, 1998)	k = −12→12
T_min = 0.704, T_max = 0.737	l = −21→21
13344 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.112	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.054P)² + 2.0475P] where P = (F_o² + 2F_c²)/3
2580 reflections	(Δ/σ)_max < 0.001
194 parameters	Δρ_max = 0.46 e Å⁻³
0 restraints	Δρ_min = −0.42 e Å⁻³

Crystal data top

[Cu₂(SO₄)₂(C₁₁H₁₆N₄)₂]	V = 1413.2 (5) Å³
M_r = 727.76	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.5293 (15) Å	µ = 1.71 mm⁻¹
b = 10.734 (2) Å	T = 291 K
c = 17.740 (4) Å	0.22 × 0.19 × 0.19 mm
β = 99.73 (3)°

Data collection top

Rigaku Mercury diffractometer	2580 independent reflections
Absorption correction: multi-scan (Jacobson, 1998)	2253 reflections with I > 2σ(I)
T_min = 0.704, T_max = 0.737	R_int = 0.039
13344 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.112	H-atom parameters constrained
S = 1.07	Δρ_max = 0.46 e Å⁻³
2580 reflections	Δρ_min = −0.42 e Å⁻³
194 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cu1	−0.00166 (6)	0.33244 (4)	0.03099 (2)	0.03196 (18)
S1	−0.08737 (12)	0.41689 (8)	−0.10738 (5)	0.0301 (2)
O1	−0.2040 (4)	0.3437 (3)	−0.06474 (16)	0.0422 (7)
O2	0.0920 (3)	0.4113 (3)	−0.05419 (15)	0.0431 (7)
O3	−0.0756 (4)	0.3645 (3)	−0.18102 (15)	0.0461 (7)
O4	−0.1457 (4)	0.5477 (3)	−0.11429 (16)	0.0444 (7)
N1	−0.1409 (4)	0.2717 (3)	0.10764 (17)	0.0316 (7)
N2	−0.0581 (4)	0.1991 (3)	0.16697 (17)	0.0330 (7)
N3	0.1848 (4)	0.1141 (3)	0.11191 (17)	0.0316 (7)
N4	0.1593 (4)	0.1722 (3)	0.04242 (17)	0.0315 (7)
C1	−0.3116 (5)	0.2839 (4)	0.1176 (2)	0.0343 (9)
C2	−0.3360 (6)	0.2205 (4)	0.1837 (2)	0.0411 (10)
H2	−0.4423	0.2152	0.2036	0.049*
C3	−0.1745 (6)	0.1674 (4)	0.2137 (2)	0.0365 (9)
C4	−0.1213 (7)	0.0889 (5)	0.2836 (3)	0.0557 (13)
H4A	−0.0814	0.0089	0.2691	0.084*
H4B	−0.2230	0.0785	0.3092	0.084*
H4C	−0.0253	0.1291	0.3175	0.084*
C5	−0.4425 (5)	0.3586 (4)	0.0638 (2)	0.0433 (10)
H5A	−0.3832	0.4307	0.0478	0.065*
H5B	−0.5399	0.3843	0.0888	0.065*
H5C	−0.4889	0.3089	0.0198	0.065*
C6	0.1344 (5)	0.1810 (4)	0.1760 (2)	0.0331 (8)
H6A	0.1751	0.1348	0.2228	0.040*
H6B	0.1939	0.2615	0.1807	0.040*
C7	0.2597 (5)	−0.0001 (4)	0.1088 (2)	0.0360 (9)
C8	0.2818 (6)	−0.0156 (4)	0.0345 (2)	0.0418 (10)
H8	0.3300	−0.0851	0.0140	0.050*
C9	0.2187 (5)	0.0921 (4)	−0.0045 (2)	0.0340 (9)
C10	0.3072 (7)	−0.0825 (4)	0.1768 (3)	0.0509 (11)
H10A	0.4025	−0.0449	0.2123	0.076*
H10B	0.3462	−0.1619	0.1609	0.076*
H10C	0.2034	−0.0936	0.2009	0.076*
C11	0.2141 (6)	0.1216 (5)	−0.0874 (2)	0.0495 (11)
H11A	0.0912	0.1305	−0.1123	0.074*
H11B	0.2701	0.0552	−0.1111	0.074*
H11C	0.2779	0.1979	−0.0920	0.074*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0298 (3)	0.0404 (3)	0.0263 (3)	0.00246 (19)	0.0063 (2)	0.00527 (19)
S1	0.0345 (5)	0.0300 (5)	0.0251 (5)	−0.0015 (4)	0.0034 (4)	−0.0014 (4)
O1	0.0415 (16)	0.0482 (17)	0.0366 (15)	−0.0127 (13)	0.0059 (13)	0.0060 (13)
O2	0.0328 (15)	0.064 (2)	0.0313 (14)	−0.0037 (13)	0.0025 (12)	0.0067 (14)
O3	0.063 (2)	0.0462 (17)	0.0285 (14)	0.0050 (14)	0.0053 (14)	−0.0078 (13)
O4	0.0621 (19)	0.0333 (15)	0.0372 (15)	0.0054 (14)	0.0068 (14)	0.0024 (12)
N1	0.0287 (16)	0.0381 (18)	0.0286 (16)	0.0030 (14)	0.0066 (13)	0.0039 (14)
N2	0.0355 (18)	0.0353 (17)	0.0287 (16)	0.0059 (14)	0.0069 (14)	0.0051 (14)
N3	0.0357 (17)	0.0299 (16)	0.0297 (16)	0.0044 (14)	0.0068 (14)	−0.0006 (14)
N4	0.0336 (17)	0.0320 (17)	0.0293 (16)	0.0045 (13)	0.0062 (14)	0.0010 (13)
C1	0.033 (2)	0.034 (2)	0.038 (2)	0.0010 (16)	0.0112 (17)	−0.0067 (17)
C2	0.041 (2)	0.044 (2)	0.043 (2)	−0.0049 (19)	0.0210 (19)	0.0026 (19)
C3	0.044 (2)	0.034 (2)	0.035 (2)	−0.0025 (17)	0.0155 (19)	0.0045 (17)
C4	0.068 (3)	0.059 (3)	0.044 (3)	0.004 (2)	0.023 (2)	0.023 (2)
C5	0.028 (2)	0.057 (3)	0.045 (2)	0.0065 (19)	0.0064 (19)	0.002 (2)
C6	0.039 (2)	0.035 (2)	0.0249 (18)	0.0016 (17)	0.0035 (16)	0.0009 (16)
C7	0.034 (2)	0.029 (2)	0.043 (2)	0.0028 (16)	0.0017 (17)	0.0007 (17)
C8	0.046 (2)	0.035 (2)	0.044 (2)	0.0067 (18)	0.0077 (19)	−0.0071 (19)
C9	0.031 (2)	0.034 (2)	0.037 (2)	0.0013 (16)	0.0057 (17)	−0.0069 (17)
C10	0.069 (3)	0.035 (2)	0.047 (3)	0.011 (2)	0.003 (2)	0.005 (2)
C11	0.057 (3)	0.059 (3)	0.034 (2)	0.010 (2)	0.011 (2)	−0.008 (2)

Geometric parameters (Å, º) top

Cu1—N1	1.963 (3)	C2—H2	0.9300
Cu1—O2	1.964 (3)	C3—C4	1.497 (6)
Cu1—O1	2.085 (3)	C4—H4A	0.9600
Cu1—N4	2.094 (3)	C4—H4B	0.9600
Cu1—O4ⁱ	2.125 (3)	C4—H4C	0.9600
Cu1—S1	2.5939 (11)	C5—H5A	0.9600
S1—O3	1.439 (3)	C5—H5B	0.9600
S1—O4	1.470 (3)	C5—H5C	0.9600
S1—O1	1.479 (3)	C6—H6A	0.9700
S1—O2	1.513 (3)	C6—H6B	0.9700
O4—Cu1ⁱ	2.125 (3)	C7—C8	1.365 (5)
N1—C1	1.333 (5)	C7—C10	1.489 (6)
N1—N2	1.372 (4)	C8—C9	1.390 (6)
N2—C3	1.348 (5)	C8—H8	0.9300
N2—C6	1.444 (5)	C9—C11	1.499 (5)
N3—C7	1.354 (5)	C10—H10A	0.9600
N3—N4	1.366 (4)	C10—H10B	0.9600
N3—C6	1.449 (5)	C10—H10C	0.9600
N4—C9	1.326 (5)	C11—H11A	0.9600
C1—C2	1.394 (5)	C11—H11B	0.9600
C1—C5	1.486 (6)	C11—H11C	0.9600
C2—C3	1.367 (6)

N1—Cu1—O2	168.29 (12)	C3—C2—H2	126.4
N1—Cu1—O1	100.44 (11)	C1—C2—H2	126.4
O2—Cu1—O1	69.90 (11)	N2—C3—C2	106.4 (3)
N1—Cu1—N4	91.60 (12)	N2—C3—C4	122.8 (4)
O2—Cu1—N4	98.70 (12)	C2—C3—C4	130.8 (4)
O1—Cu1—N4	117.24 (12)	C3—C4—H4A	109.5
N1—Cu1—O4ⁱ	89.80 (12)	C3—C4—H4B	109.5
O2—Cu1—O4ⁱ	93.50 (11)	H4A—C4—H4B	109.5
O1—Cu1—O4ⁱ	139.06 (11)	C3—C4—H4C	109.5
N4—Cu1—O4ⁱ	101.80 (12)	H4A—C4—H4C	109.5
N1—Cu1—S1	134.03 (9)	H4B—C4—H4C	109.5
O2—Cu1—S1	35.47 (8)	C1—C5—H5A	109.5
O1—Cu1—S1	34.73 (8)	C1—C5—H5B	109.5
N4—Cu1—S1	115.22 (9)	H5A—C5—H5B	109.5
O4ⁱ—Cu1—S1	117.63 (8)	C1—C5—H5C	109.5
O3—S1—O4	111.17 (17)	H5A—C5—H5C	109.5
O3—S1—O1	112.93 (18)	H5B—C5—H5C	109.5
O4—S1—O1	110.82 (18)	N2—C6—N3	111.7 (3)
O3—S1—O2	111.43 (17)	N2—C6—H6A	109.3
O4—S1—O2	108.23 (17)	N3—C6—H6A	109.3
O1—S1—O2	101.81 (16)	N2—C6—H6B	109.3
O3—S1—Cu1	132.76 (13)	N3—C6—H6B	109.3
O4—S1—Cu1	115.83 (12)	H6A—C6—H6B	107.9
O1—S1—Cu1	53.44 (11)	N3—C7—C8	105.6 (3)
O2—S1—Cu1	48.89 (11)	N3—C7—C10	123.2 (4)
S1—O1—Cu1	91.83 (14)	C8—C7—C10	131.1 (4)
S1—O2—Cu1	95.64 (14)	C7—C8—C9	107.0 (4)
S1—O4—Cu1ⁱ	114.00 (17)	C7—C8—H8	126.5
C1—N1—N2	106.1 (3)	C9—C8—H8	126.5
C1—N1—Cu1	134.3 (3)	N4—C9—C8	110.4 (3)
N2—N1—Cu1	119.6 (2)	N4—C9—C11	121.7 (4)
C3—N2—N1	110.9 (3)	C8—C9—C11	127.9 (4)
C3—N2—C6	129.9 (3)	C7—C10—H10A	109.5
N1—N2—C6	118.6 (3)	C7—C10—H10B	109.5
C7—N3—N4	111.8 (3)	H10A—C10—H10B	109.5
C7—N3—C6	130.3 (3)	C7—C10—H10C	109.5
N4—N3—C6	117.8 (3)	H10A—C10—H10C	109.5
C9—N4—N3	105.1 (3)	H10B—C10—H10C	109.5
C9—N4—Cu1	136.3 (3)	C9—C11—H11A	109.5
N3—N4—Cu1	117.0 (2)	C9—C11—H11B	109.5
N1—C1—C2	109.3 (3)	H11A—C11—H11B	109.5
N1—C1—C5	121.1 (3)	C9—C11—H11C	109.5
C2—C1—C5	129.6 (4)	H11A—C11—H11C	109.5
C3—C2—C1	107.3 (3)	H11B—C11—H11C	109.5

Symmetry code: (i) −x, −y+1, −z.

Experimental details

Crystal data
Chemical formula	[Cu₂(SO₄)₂(C₁₁H₁₆N₄)₂]
M_r	727.76
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	291
a, b, c (Å)	7.5293 (15), 10.734 (2), 17.740 (4)
β (°)	99.73 (3)
V (Å³)	1413.2 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.71
Crystal size (mm)	0.22 × 0.19 × 0.19

Data collection
Diffractometer	Rigaku Mercury diffractometer
Absorption correction	Multi-scan (Jacobson, 1998)
T_min, T_max	0.704, 0.737
No. of measured, independent and observed [I > 2σ(I)] reflections	13344, 2580, 2253
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.112, 1.07
No. of reflections	2580
No. of parameters	194
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.46, −0.42

Computer programs: CrystalClear (Rigaku/MSC, 2001), CrystalStructure (Rigaku/MSC, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

The authors acknowledge Jiangxi Science and Technology Normal University for funding.

References

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