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

Abstract

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 SO₄ ²⁻ 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,

• a = 7.5293 (15) Å

• b = 10.734 (2) Å

• c = 17.740 (4) Å

• β = 99.73 (3)°

• V = 1413.2 (5) ų

• 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[F ² > 2σ(F ²)] = 0.045

• wR(F ²) = 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.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

All H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93–0.97 Å and U_iso(H) = 1.2 times U_eq(C).

Figures

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.

Crystal data

[Cu2(SO4)2(C11H16N4)2]	F(000) = 748
Mr = 727.76	Dx = 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

Rigaku Mercury diffractometer	2580 independent reflections
Radiation source: fine-focus sealed tube	2253 reflections with I > 2σ(I)
graphite	Rint = 0.039
Detector resolution: 14.6306 pixels mm-1	θmax = 25.4°, θmin = 3.0°
ω scans	h = −9→9
Absorption correction: multi-scan (Jacobson, 1998)	k = −12→12
Tmin = 0.704, Tmax = 0.737	l = −21→21
13344 measured reflections

Refinement

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(Fo2) + (0.054P)2 + 2.0475P] where P = (Fo2 + 2Fc2)/3
2580 reflections	(Δ/σ)max < 0.001
194 parameters	Δρmax = 0.46 e Å−3
0 restraints	Δρmin = −0.42 e Å−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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 codes: (i) −x, −y+1, −z.