Dimeric copper(II) 3,3-dimethyl­butyrate adducts with ethanol, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine and 3,3-dimethylbutyric acid

In the crystals of the five title compounds, tetrakis-(μ-3,3-dimethylbutyrato-O:O′)bis(ethanol-O)dicopper(II)–ethanol (1/2), [Cu₂(C₆H₁₁O₂)₄(C₂H₆O)₂]·2C₂H₆O, (I), tetrakis(μ-3,3-dimethylbutyrato-O:O′)bis(2-methylpyridine-N)di­copper(II), [Cu₂(C₆H₁₁O₂)₄(C₆H₇N)₂], (II), tetrakis-(μ-3,3-dimethylbutyrato-O:O′)bis(3-methylpyridine-N)di-copper(II), [Cu₂(C₆H₁₁O₂)₄(C₆H₇N)₂], (III), tetrakis-(μ-3,3-dimethylbutyrato-O:O′)bis(4-methylpyridine-N)di-copper(II), [Cu₂(C₆H₁₁O₂)₄(C₆H₇N)₂], (IV), and tetrakis-(μ-3,3-dimethylbutyrato-O:O′)bis(3,3-dimethylbutyric acid-O)dicopper(II), [Cu₂(C₆H₁₁O₂)₄(C₆H₁₂O₂)₂], (V), the di­nuclear Cu^II complexes all have centrosymmetric cage structures and (IV) has two independent molecules. The Cu...Cu separations are: (I) 2.602 (3) Å, (II) 2.666 (3) Å, (III) 2.640 (2) Å, (IV) 2.638 (4) Å and (V) 2.599 (1) Å.

S1. Comment

Structures and magnetic properties of the dimeric copper(II) carboxylates have been investigated revealing that the electronic structure of the OCO bridge reflects the strength of the antiferromagnetic interaction (Yamanaka et al., 1991; Harada et al., 1997). The organosilane group directly bonded to the OCO bridge greatly enhances the antiferromagnetic interaction due to the σ-electron donation character. For example, the complex [Cu₂(PhMe₂SiCOO)₄(H₂O)₂] shows the −2 J value of 1000 ±150 cm⁻¹ (Steward et al., 1986). Recently, the −2 J values of the trimethylsilylacetate copper(II) complexes, [Cu₂(Me₃SiCH₂COO)₄L₂] (L = pyridine, 2-methylpyridine, 3-methylpyridine and quinoline) were determined to be 328 cm⁻¹ on average (Nakagawa et al., 1999). In this paper, the corresponding carbon carboxylate copper(II) complexes, [Cu₂(Me₃CCH₂COO)₄L₂] [L = 2-methylpyridine, (II), 3-methylpyridine, (III), and 4-methylpyridine, (IV)] were examined. The magnetic −2 J value of the pyridine adduct, [Cu₂(Me₃CCH₂COO)₄(py)₂] was determined to be 348 cm⁻¹, and those of 2-, 3-, and 4-methylpyridine adducts were determined to be (II) 363, (III) 355 and (IV) 354 cm⁻¹ (H = −2JS₁·S₂). This indicates that the Si atom bonded to the α-carbon of the carboxylato bridge slightly reduces the antiferromagnetic interaction.

The −2 J of non-adduct, [Cu₂(Me₃CCH₂COO)₄], obtained from (V) by removing axial acid ligands in a vacuum is 364 cm⁻¹, which is nearly in the range of 348–363 cm⁻¹ for the pyridine and methylpyridine adducts. This suggests that the non-adduct created from (V) has a discrete dimer structure, with the apical position free from coordination.

The binuclear copper complexes, (I)-(V) have a centre of symmetry, and the geometry around the Cu atoms is a typical square-pyramidal coordination. The Cu···Cu distances are 2.602 (3) in (I) and 2.599 (1) Å in (V) for O donor axial ligands, and 2.638 (4)–2.666 (3) Å in (II)-(IV) for N donor axial ligands. This is the result of larger deviation of the Cu atom from the O₄ basal plane to the N atom than that to the O atom at the apical position. In (V), the Cu1—O2 bond length of 2.005 (4) Å is 0.05 Å longer than those of the other Cu—O bonds in the cage due to the intramolecular O7—H7···O2 hydrogen bond.

S2. Experimental

3,3-Dimethylbutyric acid (116 mg, 1.0 mmol) and CuCO₃·Cu(OH)₂·H₂O (60 mg, 0.25 mmol) were suspended in a mixture of water and methanol (3:1, 20 ml). After the solution was stirred for 1 h at room temperature a green precipitate was collected and dissolved in ethanol. From the solution, green crystals of (I) were grown by slow evaporation. When 2-, 3-, or 4-methylpyridine (46.5 mg, 0.50 mmol) was added to the solution, the colour changed from green to blue, and green crystals of (II), (III) or (IV) were obtained.

Crystals of the pyridine adduct were prepared in a similar way: [Cu₂(C₆H₁₁O₂)₄(C₅H₅N)₂], monoclinic, P2₁/c, a = 9.956 (2), b = 18.445 (2), c = 21.703 (2) Å, β = 98.11 (1)°, V = 3946 (1) ų, Z = 4, Cu···Cu = 2.634 (3) Å, −2 J = 348 cm⁻¹. Crystals of the acid adduct, (V), were grown from an acetonitrile solution of (I) with the addition 3,3-dimethylbutyric acid (58 mg, 0.50 mmol).

S3. Refinement

The crystal specimen of (I) was sealed in a capillary with mother liquor, and that of (II) was coated with adhesive to avoid efflorescence. In (I), there is a positional disorder of the O atom in the ethanol for crystallization. The O and C atoms of the disordered ethanol were refined isotropically and the occupation factors of the ethanol O7 and O8 positions were assumed to be 30 and 70%, respectively, based on the displacement parameters. There are hydrogen bonds including these O atoms: O6—H6···O8 (x − 1, y, z − 1), O6···O8 = 2.718 (5) Å; O3—H···O7 (1 − x, −y, 1 − z), O3···O7 = 3.040 (10) Å; O3—H···O8 (x − 1, y, z), O3···O8 = 2.884 (5) Å. Non-H atoms of the ligating ethanol in (I) were also refined isotropically to avoid unusual displacement parameters.

The max/min ratio of the atom displacement parameters are abnormally large for the methyl C atoms of the tert-butyl groups, which may be due to the vibrational and rotational disorder. The positions of all the H atoms were calculated geometrically except ethanol for crystallization in (I), and a riding model was used in their refinement [C—H 0.96 Å, U_iso(H) = 0.3 Ų for (I), 0.2 Ų for (I)-(IV)].

The magnetic susceptibilities over the temperature range 80–300 K were determined by the Faraday method at Saga University. The procedure for determining the −2 J value from cryomagnetic data based on the Bleaney-Bowers equation is described elsewhere (Harada et al., 1997).

Computing details

For all compounds, data collection: MSC/AFC Diffractometer Control System (Molecular Structure Corporation, 1993); cell refinement: MSC/AFC Diffractometer Control System; data reduction: local programs; program(s) used to solve structure: CRYSTAN-GM (Edwards et al., 1996); program(s) used to refine structure: CRYSTAN-GM; molecular graphics: CRYSTAN-GM; software used to prepare material for publication: CRYSTAN-GM.

Figures

	Fig. 1. The molecular structure of (I). Displacement ellipsoids are plotted at the 50% probability level and H atoms are shown as spheres of arbitrary radius.
	Fig. 2. The molecular structure of (II). Displacement ellipsoids are plotted at the 50% probability level and H atoms are shown as spheres of arbitrary radius.
	Fig. 3. The molecular structure of (III). Displacement ellipsoids are plotted at the 50% probability level and H atoms are shown as spheres of arbitrary radius.
	Fig. 4. The molecular structure of (IV): (a) and (b) show the two independent molecules. Displacement ellipsoids are plotted at the 50% probability level and H atoms are shown as spheres of arbitrary radius.
	Fig. 5. The molecular structure of (V). Displacement ellipsoids are plotted at the 50% probability level and H atoms are shown as spheres of arbitrary radius.

(I) tetrakis(µ-3,3-dimethylbutyrato-O:O')di(ethanol-O)dicopper(II) diethanol solvate

Crystal data

[Cu2(C6H11O2)4(C2H6O)2]·2C2H6O	Z = 1
Mr = 771.98	F(000) = 414
Triclinic, P1	Dx = 1.203 Mg m^−3
a = 10.765 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.923 (2) Å	Cell parameters from 25 reflections
c = 9.820 (1) Å	θ = 10–15°
α = 105.43 (1)°	µ = 1.05 mm^−1
β = 106.50 (1)°	T = 299 K
γ = 88.43 (1)°	Prism, green
V = 1065.8 (3) Å^3	0.5 × 0.4 × 0.3 mm

Data collection

Rigaku AFC-5 diffractometer	Rint = 0.012
θ–2θ scans	θmax = 27.5°
Absorption correction: integration (Coppens et al., 1965)	h = 0→14
Tmin = 0.569, Tmax = 0.822	k = −14→14
5151 measured reflections	l = −13→13
4888 independent reflections	3 standard reflections every 100 reflections
3646 reflections with |Fo| > 3σ(|Fo|)	intensity decay: none

Refinement

Refinement on F	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.076	w = 1/[σ^2(F) + 0.000225F^2]
wR(F^2) = 0.077	(Δ/σ)max = 0.03
S = 1.44	Δρmax = 1.23 e Å^−3
3646 reflections	Δρmin = −0.91 e Å^−3
182 parameters

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cu1	0.02105 (4)	0.06067 (4)	−0.08944 (4)	0.0488 (2)
O2	0.0647 (3)	0.2026 (2)	0.0917 (2)	0.069 (1)
O3	0.0303 (3)	0.0997 (2)	0.2458 (2)	0.068 (1)
O4	0.1980 (2)	0.0055 (2)	−0.0346 (3)	0.068 (1)
O5	0.1632 (2)	−0.0944 (3)	0.1221 (3)	0.069 (1)
O6	0.0498 (3)	0.1655 (3)	−0.2376 (3)	0.0756 (8)*
O7	0.8388 (9)	−0.056 (1)	0.454 (1)	0.092 (3)*	0.300
O8	0.9068 (4)	0.1333 (4)	0.4773 (5)	0.094 (1)*	0.700
C9	0.0642 (3)	0.1982 (3)	0.2174 (4)	0.059 (2)
C10	0.1042 (4)	0.3205 (4)	0.3434 (4)	0.078 (2)
C11	0.2511 (4)	0.3557 (4)	0.3911 (4)	0.083 (2)
C12	0.2858 (6)	0.3980 (7)	0.2717 (6)	0.158 (4)
C13	0.2804 (6)	0.4691 (5)	0.5302 (6)	0.142 (3)
C14	0.3327 (6)	0.2444 (7)	0.4243 (9)	0.186 (5)
C15	0.2332 (3)	−0.0563 (3)	0.0581 (4)	0.063 (2)
C16	0.3759 (4)	−0.0935 (4)	0.0957 (5)	0.082 (2)
C17	0.3975 (4)	−0.2353 (4)	0.0360 (5)	0.083 (2)
C18	0.5459 (5)	−0.2505 (5)	0.0677 (8)	0.142 (4)
C19	0.3464 (7)	−0.3136 (6)	0.116 (1)	0.193 (6)
C20	0.3314 (9)	−0.2814 (8)	−0.1239 (7)	0.267 (6)
C21	0.0953 (7)	0.3153 (7)	−0.1819 (8)	0.170 (3)*
C22	−0.006 (1)	0.405 (1)	−0.180 (1)	0.410 (8)*
C23	0.7810 (7)	0.0587 (7)	0.4208 (8)	0.156 (2)*
C24	0.6912 (8)	0.1071 (8)	0.4862 (9)	0.194 (3)*
H6	−0.03180	0.15845	−0.31197	0.30*
H10A	0.07951	0.30996	0.42632	0.30*
H10B	0.05871	0.38926	0.31132	0.30*
H12A	0.37751	0.41772	0.30070	0.30*
H12B	0.24021	0.47162	0.25400	0.30*
H12C	0.26271	0.33002	0.18250	0.30*
H13A	0.37209	0.48879	0.55921	0.30*
H13B	0.25559	0.44959	0.60891	0.30*
H13C	0.23339	0.53989	0.50551	0.30*
H14A	0.42442	0.26406	0.45326	0.30*
H14B	0.31102	0.17326	0.33816	0.30*
H14C	0.31082	0.22166	0.50286	0.30*
H16A	0.41088	−0.07132	0.20107	0.30*
H16B	0.42248	−0.04462	0.05637	0.30*
H18A	0.55850	−0.33891	0.02931	0.30*
H18B	0.58830	−0.22341	0.17181	0.30*
H18C	0.58090	−0.20011	0.01941	0.30*
H19A	0.35895	−0.40206	0.07733	0.30*
H19B	0.25525	−0.30056	0.09913	0.30*
H19C	0.38875	−0.28756	0.21983	0.30*
H20A	0.34393	−0.36976	−0.16223	0.30*
H20B	0.36733	−0.23186	−0.17243	0.30*
H20C	0.24033	−0.26816	−0.14193	0.30*
H21A	0.14494	0.33432	−0.24168	0.30*
H21B	0.14944	0.33172	−0.08198	0.30*
H22A	0.03074	0.49018	−0.14843	0.30*
H22B	−0.05370	0.38900	−0.11620	0.30*
H22C	−0.06460	0.38880	−0.27840	0.30*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0601 (3)	0.0467 (2)	0.0412 (2)	−0.0018 (2)	0.0177 (2)	0.0113 (2)
O2	0.100 (2)	0.054 (2)	0.048 (1)	−0.012 (1)	0.023 (1)	0.006 (1)
O3	0.092 (2)	0.062 (2)	0.047 (1)	−0.015 (1)	0.026 (1)	0.005 (1)
O4	0.062 (2)	0.074 (2)	0.077 (2)	0.009 (1)	0.026 (1)	0.030 (2)
O5	0.060 (2)	0.084 (2)	0.070 (2)	0.012 (1)	0.021 (1)	0.029 (1)
C9	0.063 (2)	0.055 (2)	0.053 (2)	0.000 (2)	0.018 (2)	0.006 (2)
C10	0.094 (3)	0.063 (3)	0.064 (2)	−0.015 (2)	0.028 (2)	−0.010 (2)
C11	0.088 (3)	0.080 (3)	0.062 (2)	−0.025 (3)	0.008 (2)	−0.002 (2)
C12	0.124 (5)	0.231 (8)	0.108 (4)	−0.095 (5)	0.028 (4)	0.023 (5)
C13	0.176 (6)	0.115 (5)	0.091 (4)	−0.070 (4)	0.025 (4)	−0.035 (3)
C14	0.115 (5)	0.136 (6)	0.240 (8)	0.010 (4)	−0.044 (5)	0.036 (6)
C15	0.060 (2)	0.054 (2)	0.061 (2)	−0.003 (2)	0.013 (2)	−0.002 (2)
C16	0.054 (2)	0.074 (3)	0.106 (3)	0.007 (2)	0.015 (2)	0.013 (2)
C17	0.070 (3)	0.074 (3)	0.101 (3)	0.018 (2)	0.028 (2)	0.015 (3)
C18	0.096 (4)	0.120 (5)	0.225 (7)	0.052 (3)	0.066 (4)	0.056 (5)
C19	0.192 (7)	0.113 (5)	0.368 (12)	0.073 (5)	0.173 (8)	0.132 (7)
C20	0.29 (1)	0.25 (1)	0.11 (1)	0.14 (1)	−0.02 (1)	−0.09 (1)

Geometric parameters (Å, º)

Cu1—Cu1^i	2.602 (3)	C10—H10B	0.960
Cu1—O2	1.971 (3)	C12—H12A	0.960
Cu1—O3^i	1.968 (3)	C12—H12B	0.960
Cu1—O4	1.952 (3)	C12—H12C	0.960
Cu1—O5^i	1.958 (3)	C13—H13A	0.960
Cu1—O6	2.164 (3)	C13—H13B	0.960
O2—C9	1.250 (4)	C13—H13C	0.960
O3—C9	1.268 (5)	C14—H14A	0.960
O4—C15	1.243 (5)	C14—H14B	0.960
O5—C15	1.250 (5)	C14—H14C	0.960
O6—C21	1.623 (8)	C16—H16A	0.960
O7—C23	1.461 (13)	C16—H16B	0.959
O8—C23	1.483 (9)	C18—H18A	0.960
C9—C10	1.533 (6)	C18—H18B	0.960
C10—C11	1.544 (7)	C18—H18C	0.960
C11—C12	1.509 (8)	C19—H19A	0.961
C11—C13	1.541 (7)	C19—H19B	0.960
C11—C14	1.531 (9)	C19—H19C	0.960
C15—C16	1.544 (6)	C20—H20A	0.959
C16—C17	1.539 (7)	C20—H20B	0.960
C17—C18	1.552 (7)	C20—H20C	0.960
C17—C19	1.508 (9)	C21—H21A	0.960
C17—C20	1.480 (9)	C21—H21B	0.960
C21—C22	1.448 (14)	C22—H22A	0.960
C23—C24	1.331 (12)	C22—H22B	0.964
O6—H6	0.960	C22—H22C	0.962
C10—H10A	0.960
O2—Cu1—O3^i	168.9 (1)	H12A—C12—H12B	109.3
O2—Cu1—O4	89.7 (2)	H12A—C12—H12C	109.3
O2—Cu1—O5^i	90.1 (2)	H12B—C12—H12C	109.0
O2—Cu1—O6	97.3 (1)	C11—C13—H13A	106.6
O3^i—Cu1—O4	89.8 (2)	C11—C13—H13B	112.0
O3^i—Cu1—O5^i	88.2 (2)	C11—C13—H13C	108.7
O3^i—Cu1—O6	93.7 (1)	H13A—C13—H13B	110.3
O4—Cu1—O5^i	168.8 (2)	H13A—C13—H13C	110.3
O4—Cu1—O6	96.6 (2)	H13B—C13—H13C	109.0
O5^i—Cu1—O6	94.5 (2)	C11—C14—H14A	113.3
Cu1—O2—C9	126.6 (3)	C11—C14—H14B	109.0
Cu1^i—O3—C9	120.5 (3)	C11—C14—H14C	107.7
Cu1—O4—C15	121.6 (3)	H14A—C14—H14B	108.9
Cu1^i—O5—C15	123.3 (3)	H14A—C14—H14C	108.8
Cu1—O6—C21	122.4 (3)	H14B—C14—H14C	109.0
O2—C9—O3	123.9 (4)	C15—C16—H16A	108.3
O2—C9—C10	117.6 (4)	C15—C16—H16B	107.7
O3—C9—C10	118.4 (3)	C17—C16—H16A	107.7
C9—C10—C11	113.1 (4)	C17—C16—H16B	108.5
C10—C11—C12	109.6 (4)	H16A—C16—H16B	109.0
C10—C11—C13	107.7 (4)	C17—C18—H18A	107.2
C10—C11—C14	112.0 (4)	C17—C18—H18B	110.7
C12—C11—C13	107.9 (5)	C17—C18—H18C	109.6
C12—C11—C14	109.7 (5)	H18A—C18—H18B	110.2
C13—C11—C14	109.9 (5)	H18A—C18—H18C	110.2
O4—C15—O5	126.2 (4)	H18B—C18—H18C	109.0
O4—C15—C16	117.6 (4)	C17—C19—H19A	110.0
O5—C15—C16	116.2 (4)	C17—C19—H19B	107.6
C15—C16—C17	115.5 (4)	C17—C19—H19C	111.2
C16—C17—C18	107.7 (4)	H19A—C19—H19B	109.5
C16—C17—C19	110.2 (5)	H19A—C19—H19C	109.5
C16—C17—C20	111.1 (5)	H19B—C19—H19C	109.0
C18—C17—C19	108.1 (5)	C17—C20—H20A	111.9
C18—C17—C20	110.7 (6)	C17—C20—H20B	107.3
C19—C17—C20	108.9 (6)	C17—C20—H20C	109.6
O6—C21—C22	116.6 (7)	H20A—C20—H20B	109.5
O7—C23—O8	93.8 (6)	H20A—C20—H20C	109.5
O7—C23—C24	116.5 (8)	H20B—C20—H20C	109.0
O8—C23—C24	115.1 (7)	O6—C21—H21A	109.9
Cu1—O6—H6	105.9	O6—C21—H21B	107.3
C21—O6—H6	106.0	C22—C21—H21A	107.4
C9—C10—H10A	108.7	C22—C21—H21B	106.3
C9—C10—H10B	108.6	H21A—C21—H21B	109.0
C11—C10—H10A	109.3	C21—C22—H22A	109.9
C11—C10—H10B	108.1	C21—C22—H22B	107.8
H10A—C10—H10B	109.0	C21—C22—H22C	108.5
C11—C12—H12A	109.3	H22A—C22—H22B	112.3
C11—C12—H12B	111.1	H22A—C22—H22C	109.8
C11—C12—H12C	108.8	H22B—C22—H22C	108.5

Symmetry code: (i) −x, −y, −z.

(II) tetrakis(µ-3,3-dimethylbutyrato-O:O')-di(2-methylpyridine-N)dicopper(II)

Crystal data

[Cu2(C6H11O2)4(C6H7N)2]	F(000) = 820
Mr = 773.96	Dx = 1.260 Mg m^−3
Monoclinic, P21/a	Mo Kα radiation, λ = 0.71073 Å
a = 10.040 (2) Å	Cell parameters from 25 reflections
b = 18.468 (1) Å	θ = 10–15°
c = 11.649 (1) Å	µ = 1.09 mm^−1
β = 109.16 (1)°	T = 299 K
V = 2040.3 (4) Å^3	Prism, green
Z = 2	0.5 × 0.2 × 0.2 mm

Data collection

Rigaku AFC-5 diffractometer	Rint = 0.014
θ–2θ scans	θmax = 27.5°
Absorption correction: integration (Coppens et al., 1965)	h = 0→13
Tmin = 0.794, Tmax = 0.830	k = 0→24
5080 measured reflections	l = −15→15
4678 independent reflections	3 standard reflections every 100 reflections
3226 reflections with |Fo| > 3σ(|Fo|)	intensity decay: none

Refinement

Refinement on F	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.050	w = 1/[σ^2(F) + 0.000225F^2]
wR(F^2) = 0.044	(Δ/σ)max = 0.03
S = 1.24	Δρmax = 0.39 e Å^−3
3226 reflections	Δρmin = −0.48 e Å^−3
217 parameters

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

	x	y	z	Uiso*/Ueq
Cu1	0.41299 (3)	0.04924 (2)	0.43088 (3)	0.0435 (1)
O2	0.3671 (2)	−0.0284 (1)	0.3083 (2)	0.0592 (8)
O3	0.5119 (2)	−0.1109 (1)	0.4229 (2)	0.0633 (9)
O4	0.2787 (2)	0.0071 (1)	0.5031 (2)	0.0586 (8)
O5	0.4241 (2)	−0.0752 (1)	0.6191 (2)	0.0568 (8)
N6	0.2633 (2)	0.1357 (1)	0.3313 (2)	0.0493 (9)
C7	0.4225 (3)	−0.0898 (2)	0.3263 (3)	0.055 (1)
C8	0.3791 (3)	−0.1425 (2)	0.2199 (3)	0.072 (1)
C9	0.2374 (3)	−0.1792 (2)	0.2001 (3)	0.067 (1)
C10	0.1199 (4)	−0.1247 (3)	0.1574 (5)	0.169 (3)
C11	0.2397 (8)	−0.2145 (3)	0.3171 (5)	0.225 (4)
C12	0.2148 (4)	−0.2374 (2)	0.1029 (3)	0.099 (2)
C13	0.3083 (3)	−0.0426 (2)	0.5814 (2)	0.053 (1)
C14	0.1947 (3)	−0.0636 (2)	0.6353 (3)	0.063 (1)
C15	0.2024 (3)	−0.0211 (2)	0.7514 (3)	0.065 (1)
C16	0.0774 (4)	−0.0454 (2)	0.7904 (3)	0.106 (2)
C17	0.3401 (4)	−0.0359 (3)	0.8531 (3)	0.110 (2)
C18	0.1880 (4)	0.0605 (2)	0.7253 (4)	0.116 (2)
C19	0.2110 (3)	0.1752 (2)	0.4049 (3)	0.077 (1)
C20	0.1213 (4)	0.2332 (2)	0.3645 (4)	0.092 (2)
C21	0.0843 (4)	0.2515 (2)	0.2446 (4)	0.086 (2)
C22	0.1343 (3)	0.2114 (2)	0.1673 (3)	0.068 (2)
C23	0.2234 (3)	0.1527 (2)	0.2135 (3)	0.051 (1)
C24	0.2737 (4)	0.1062 (2)	0.1315 (3)	0.072 (1)
H8A	0.45017	−0.17934	0.23356	0.20*
H8B	0.37397	−0.11634	0.14746	0.20*
H10A	0.03050	−0.14750	0.14612	0.20*
H10B	0.12060	−0.10430	0.08182	0.20*
H10C	0.13440	−0.08670	0.21652	0.20*
H11A	0.15035	−0.23727	0.30580	0.20*
H11B	0.25825	−0.17907	0.38070	0.20*
H11C	0.31345	−0.25017	0.33900	0.20*
H12A	0.12539	−0.26024	0.09161	0.20*
H12B	0.28889	−0.27274	0.12851	0.20*
H12C	0.21529	−0.21614	0.02781	0.20*
H14A	0.20433	−0.11426	0.65464	0.20*
H14B	0.10403	−0.05516	0.57564	0.20*
H16A	0.08373	−0.01855	0.86263	0.20*
H16B	0.08283	−0.09645	0.80693	0.20*
H16C	−0.00987	−0.03505	0.72743	0.20*
H17A	0.34641	−0.00906	0.92526	0.20*
H17B	0.41731	−0.02256	0.82596	0.20*
H17C	0.34611	−0.08666	0.87146	0.20*
H18A	0.19434	0.08728	0.79749	0.20*
H18B	0.09844	0.06968	0.66449	0.20*
H18C	0.26164	0.07588	0.69509	0.20*
H19	0.23824	0.16195	0.48915	0.20*
H20	0.08542	0.25957	0.41899	0.20*
H21	0.02402	0.29248	0.21458	0.20*
H22	0.10788	0.22415	0.08289	0.20*
H24A	0.24058	0.12491	0.05013	0.20*
H24B	0.24137	0.05790	0.13793	0.20*
H24C	0.37487	0.10680	0.16223	0.20*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0414 (2)	0.0359 (2)	0.0424 (2)	0.0023 (2)	0.0101 (1)	−0.0010 (2)
O2	0.066 (1)	0.046 (1)	0.046 (1)	−0.002 (1)	0.009 (1)	−0.008 (1)
O3	0.054 (1)	0.052 (1)	0.058 (1)	0.006 (1)	0.003 (1)	−0.017 (1)
O4	0.050 (1)	0.060 (1)	0.059 (1)	0.003 (1)	0.021 (1)	0.009 (1)
O5	0.051 (1)	0.045 (1)	0.069 (1)	0.002 (1)	0.024 (1)	0.011 (1)
N6	0.048 (1)	0.042 (1)	0.048 (1)	0.005 (1)	0.006 (1)	0.002 (1)
C7	0.042 (2)	0.051 (2)	0.050 (2)	−0.008 (1)	0.017 (1)	−0.013 (1)
C8	0.054 (2)	0.067 (2)	0.061 (2)	0.000 (2)	0.015 (2)	−0.027 (2)
C9	0.064 (2)	0.059 (2)	0.053 (2)	−0.011 (2)	0.014 (2)	−0.017 (2)
C10	0.054 (3)	0.131 (4)	0.220 (6)	0.016 (3)	−0.002 (3)	−0.096 (4)
C11	0.319 (8)	0.206 (6)	0.082 (3)	−0.199 (6)	0.060 (4)	−0.028 (4)
C12	0.094 (3)	0.070 (2)	0.084 (3)	0.001 (2)	−0.005 (2)	−0.035 (2)
C13	0.048 (2)	0.043 (2)	0.049 (2)	−0.009 (2)	0.017 (1)	−0.011 (2)
C14	0.052 (2)	0.057 (2)	0.064 (2)	−0.010 (1)	0.026 (2)	−0.004 (2)
C15	0.051 (2)	0.064 (2)	0.064 (2)	−0.004 (2)	0.027 (2)	−0.002 (2)
C16	0.084 (3)	0.095 (3)	0.114 (3)	−0.013 (2)	0.067 (2)	−0.002 (3)
C17	0.073 (3)	0.164 (4)	0.062 (2)	0.016 (3)	0.017 (2)	−0.017 (3)
C18	0.120 (3)	0.060 (2)	0.125 (3)	−0.008 (2)	0.079 (3)	−0.016 (2)
C19	0.071 (2)	0.069 (2)	0.066 (2)	0.021 (2)	0.013 (2)	−0.013 (2)
C20	0.086 (3)	0.071 (2)	0.089 (3)	0.033 (2)	0.014 (2)	−0.012 (2)
C21	0.081 (3)	0.061 (2)	0.104 (3)	0.024 (2)	0.011 (2)	0.013 (2)
C22	0.062 (2)	0.063 (2)	0.077 (2)	0.007 (2)	0.008 (2)	0.021 (2)
C23	0.043 (2)	0.046 (2)	0.059 (2)	−0.006 (1)	0.009 (1)	0.010 (1)
C24	0.080 (2)	0.072 (2)	0.055 (2)	0.009 (2)	0.025 (2)	0.010 (2)

Geometric parameters (Å, º)

Cu1—Cu1^i	2.666 (3)	C8—H8B	0.959
Cu1—O2	1.969 (2)	C10—H10A	0.961
Cu1—O3^i	1.982 (2)	C10—H10B	0.960
Cu1—O4	1.969 (2)	C10—H10C	0.960
Cu1—O5^i	1.967 (2)	C11—H11A	0.961
Cu1—N6	2.238 (3)	C11—H11B	0.959
O2—C7	1.251 (4)	C11—H11C	0.961
O3—C7	1.249 (4)	C12—H12A	0.961
O4—C13	1.258 (4)	C12—H12B	0.960
O5—C13	1.254 (4)	C12—H12C	0.961
N6—C19	1.356 (4)	C14—H14A	0.960
N6—C23	1.335 (4)	C14—H14B	0.960
C7—C8	1.523 (5)	C16—H16A	0.960
C8—C9	1.523 (5)	C16—H16B	0.961
C9—C10	1.505 (6)	C16—H16C	0.960
C9—C11	1.503 (7)	C17—H17A	0.960
C9—C12	1.524 (5)	C17—H17B	0.960
C13—C14	1.522 (4)	C17—H17C	0.960
C14—C15	1.542 (5)	C18—H18A	0.960
C15—C16	1.535 (5)	C18—H18B	0.960
C15—C17	1.521 (5)	C18—H18C	0.960
C15—C18	1.535 (5)	C19—H19	0.960
C19—C20	1.378 (6)	C20—H20	0.960
C20—C21	1.365 (6)	C21—H21	0.961
C21—C22	1.380 (6)	C22—H22	0.960
C22—C23	1.396 (5)	C24—H24A	0.960
C23—C24	1.491 (5)	C24—H24B	0.960
C8—H8A	0.960	C24—H24C	0.960
O2—Cu1—O3^i	167.2 (1)	H10A—C10—H10B	109.5
O2—Cu1—O4	89.6 (1)	H10A—C10—H10C	109.5
O2—Cu1—O5^i	89.0 (1)	H10B—C10—H10C	109.0
O2—Cu1—N6	100.7 (1)	C9—C11—H11A	109.2
O3^i—Cu1—O4	88.9 (1)	C9—C11—H11B	110.2
O3^i—Cu1—O5^i	89.7 (1)	C9—C11—H11C	108.7
O3^i—Cu1—N6	92.1 (1)	H11A—C11—H11B	109.9
O4—Cu1—O5^i	167.3 (1)	H11A—C11—H11C	109.8
O4—Cu1—N6	93.8 (1)	H11B—C11—H11C	109.0
O5^i—Cu1—N6	98.9 (1)	C9—C12—H12A	108.4
Cu1—O2—C7	123.6 (2)	C9—C12—H12B	109.7
Cu1^i—O3—C7	123.6 (2)	C9—C12—H12C	110.1
Cu1—O4—C13	124.4 (2)	H12A—C12—H12B	109.8
Cu1^i—O5—C13	122.9 (2)	H12A—C12—H12C	109.8
Cu1—N6—C19	112.9 (2)	H12B—C12—H12C	109.0
Cu1—N6—C23	128.7 (2)	C13—C14—H14A	108.3
C19—N6—C23	118.4 (3)	C13—C14—H14B	108.7
O2—C7—O3	125.7 (3)	C15—C14—H14A	108.5
O2—C7—C8	116.8 (3)	C15—C14—H14B	108.4
O3—C7—C8	117.5 (3)	H14A—C14—H14B	109.0
C7—C8—C9	114.2 (3)	C15—C16—H16A	106.5
C8—C9—C10	110.2 (3)	C15—C16—H16B	110.3
C8—C9—C11	108.6 (4)	C15—C16—H16C	110.2
C8—C9—C12	109.2 (3)	H16A—C16—H16B	110.4
C10—C9—C11	111.5 (4)	H16A—C16—H16C	110.4
C10—C9—C12	108.5 (4)	H16B—C16—H16C	109.0
C11—C9—C12	108.8 (4)	C15—C17—H17A	111.8
O4—C13—O5	125.2 (3)	C15—C17—H17B	108.9
O4—C13—C14	117.0 (3)	C15—C17—H17C	108.9
O5—C13—C14	117.8 (3)	H17A—C17—H17B	109.2
C13—C14—C15	113.8 (3)	H17A—C17—H17C	109.1
C14—C15—C16	107.5 (3)	H17B—C17—H17C	109.0
C14—C15—C17	111.3 (3)	C15—C18—H18A	111.0
C14—C15—C18	110.5 (3)	C15—C18—H18B	108.9
C16—C15—C17	109.9 (3)	C15—C18—H18C	109.3
C16—C15—C18	108.2 (3)	H18A—C18—H18B	109.4
C17—C15—C18	109.4 (4)	H18A—C18—H18C	109.3
N6—C19—C20	123.1 (4)	H18B—C18—H18C	109.0
C19—C20—C21	118.0 (4)	N6—C19—H19	118.0
C20—C21—C22	120.0 (4)	C20—C19—H19	118.9
C21—C22—C23	119.2 (4)	C19—C20—H20	120.9
N6—C23—C22	121.2 (3)	C21—C20—H20	121.1
N6—C23—C24	118.2 (3)	C20—C21—H21	119.7
C22—C23—C24	120.6 (3)	C22—C21—H21	120.4
C7—C8—H8A	108.6	C21—C22—H22	120.0
C7—C8—H8B	108.2	C23—C22—H22	120.8
C9—C8—H8A	108.5	C23—C24—H24A	110.2
C9—C8—H8B	108.3	C23—C24—H24B	107.0
H8A—C8—H8B	109.0	C23—C24—H24C	107.1
C9—C10—H10A	110.4	H24A—C24—H24B	113.2
C9—C10—H10B	109.0	H24A—C24—H24C	110.2
C9—C10—H10C	109.5	H24B—C24—H24C	109.0

Symmetry code: (i) −x+1, −y, −z+1.

(III) tetrakis(µ-3,3-dimethylbutyrato-O:O')di(3-methylpyridine-N)dicopper(II)

Crystal data

[Cu2(C6H11O2)4(C6H7N)2]	Z = 1
Mr = 773.96	F(000) = 410
Triclinic, P1	Dx = 1.228 Mg m^−3
a = 10.603 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.216 (2) Å	Cell parameters from 25 reflections
c = 10.289 (1) Å	θ = 10–15°
α = 105.80 (1)°	µ = 1.06 mm^−1
β = 101.01 (1)°	T = 299 K
γ = 63.11 (1)°	Prism, green
V = 1046.7 (3) Å^3	0.6 × 0.4 × 0.4 mm

Data collection

Rigaku AFC-5 diffractometer	Rint = 0.011
θ–2θ scans	θmax = 27.5°
Absorption correction: integration (Coppens et al., 1965)	h = 0→14
Tmin = 0.965, Tmax = 0.973	k = −15→15
5071 measured reflections	l = −13→13
4810 independent reflections	3 standard reflections every 100 reflections
4058 reflections with |Fo| > 3σ(|Fo|)	intensity decay: none

Refinement

Refinement on F	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.046	w = 1/[σ^2(F) + 0.000225F^2]
wR(F^2) = 0.048	(Δ/σ)max = 0.03
S = 1.19	Δρmax = 0.40 e Å^−3
4058 reflections	Δρmin = −0.72 e Å^−3
217 parameters

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

	x	y	z	Uiso*/Ueq
Cu1	0.10838 (2)	0.50339 (2)	0.95836 (2)	0.0434 (1)
O2	0.2232 (1)	0.3808 (1)	1.0842 (1)	0.0593 (6)
O3	0.0395 (1)	0.3697 (1)	1.1488 (1)	0.0645 (6)
O4	0.0997 (1)	0.3443 (1)	0.8216 (1)	0.0547 (6)
O5	−0.0825 (1)	0.3376 (1)	0.8900 (1)	0.0570 (6)
N6	0.2907 (1)	0.4857 (1)	0.8761 (1)	0.0490 (6)
C7	0.1695 (2)	0.3380 (2)	1.1502 (2)	0.0530 (8)
C8	0.2724 (2)	0.2377 (2)	1.2370 (2)	0.0762 (9)
C9	0.2596 (2)	0.2855 (2)	1.3888 (2)	0.0662 (9)
C10	0.3805 (3)	0.1812 (3)	1.4596 (2)	0.125 (2)
C11	0.1232 (3)	0.3002 (4)	1.4268 (3)	0.145 (2)
C12	0.2630 (4)	0.4245 (3)	1.4352 (3)	0.148 (2)
C13	0.0170 (2)	0.2917 (2)	0.8157 (2)	0.0486 (7)
C14	0.0405 (2)	0.1602 (2)	0.7108 (2)	0.0586 (8)
C15	0.1481 (2)	0.0296 (2)	0.7596 (2)	0.0627 (9)
C16	0.0940 (3)	0.0136 (2)	0.8780 (3)	0.106 (1)
C17	0.1642 (3)	−0.0920 (2)	0.6420 (2)	0.101 (1)
C18	0.2918 (2)	0.0354 (2)	0.8065 (3)	0.110 (1)
C19	0.3032 (2)	0.5926 (2)	0.8556 (2)	0.068 (1)
C20	0.4270 (2)	0.5787 (2)	0.8172 (2)	0.088 (1)
C21	0.5408 (2)	0.4534 (3)	0.7971 (2)	0.077 (1)
C22	0.5287 (2)	0.3420 (2)	0.8134 (2)	0.0645 (9)
C23	0.4013 (2)	0.3642 (2)	0.8540 (2)	0.0594 (9)
C24	0.6493 (2)	0.2006 (3)	0.7932 (3)	0.107 (1)
H8A	0.36717	0.21578	1.22001	0.20*
H8B	0.25667	0.15618	1.20851	0.20*
H10A	0.37175	0.21304	1.55539	0.20*
H10B	0.46955	0.17094	1.43819	0.20*
H10C	0.37525	0.09454	1.42979	0.20*
H11A	0.11448	0.33200	1.52257	0.20*
H11B	0.11898	0.21310	1.39867	0.20*
H11C	0.04588	0.36430	1.38027	0.20*
H12A	0.25434	0.45631	1.53101	0.20*
H12B	0.18584	0.48811	1.38821	0.20*
H12C	0.35084	0.41781	1.41451	0.20*
H14A	0.07326	0.16413	0.63191	0.20*
H14B	−0.04884	0.15423	0.68651	0.20*
H16A	0.16151	−0.06729	0.90924	0.20*
H16B	0.00521	0.00721	0.84954	0.20*
H16C	0.07981	0.09231	0.95044	0.20*
H17A	0.23174	−0.17290	0.67318	0.20*
H17B	0.19794	−0.08270	0.56668	0.20*
H17C	0.07484	−0.09720	0.61398	0.20*
H18A	0.35929	−0.04552	0.83773	0.20*
H18B	0.27969	0.11388	0.87873	0.20*
H18C	0.32729	0.04368	0.73193	0.20*
H19	0.22381	0.68072	0.86829	0.20*
H20	0.43381	0.65694	0.80366	0.20*
H21	0.62816	0.44351	0.77190	0.20*
H23	0.39242	0.28697	0.86737	0.20*
H24A	0.61996	0.13552	0.80617	0.20*
H24B	0.72737	0.20722	0.85470	0.20*
H24C	0.67397	0.17882	0.70190	0.20*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0390 (1)	0.0477 (1)	0.0450 (1)	−0.0177 (1)	0.0049 (1)	0.0154 (1)
O2	0.0443 (6)	0.0680 (8)	0.0564 (7)	−0.0132 (6)	0.0023 (5)	0.0267 (6)
O3	0.0557 (7)	0.0680 (8)	0.0678 (8)	−0.0190 (6)	0.0026 (6)	0.0363 (6)
O4	0.0625 (7)	0.0592 (7)	0.0528 (7)	−0.0345 (6)	0.0117 (5)	0.0052 (5)
O5	0.0558 (7)	0.0559 (7)	0.0638 (7)	−0.0291 (6)	0.0109 (6)	0.0032 (6)
N6	0.0477 (8)	0.0577 (8)	0.0490 (8)	−0.0287 (7)	0.0049 (6)	0.0131 (6)
C7	0.053 (1)	0.047 (1)	0.042 (1)	−0.008 (1)	0.002 (1)	0.012 (1)
C8	0.072 (1)	0.071 (1)	0.050 (1)	0.005 (1)	0.004 (1)	0.028 (1)
C9	0.072 (1)	0.069 (1)	0.047 (1)	−0.019 (1)	0.001 (1)	0.024 (1)
C10	0.120 (2)	0.128 (2)	0.065 (1)	0.001 (2)	−0.008 (1)	0.050 (1)
C11	0.120 (2)	0.221 (3)	0.100 (2)	−0.053 (2)	0.024 (2)	0.087 (2)
C12	0.222 (4)	0.137 (3)	0.083 (2)	−0.098 (3)	−0.030 (2)	0.024 (2)
C13	0.0502 (9)	0.0495 (9)	0.0431 (9)	−0.0206 (8)	−0.0021 (7)	0.0158 (7)
C14	0.073 (1)	0.057 (1)	0.047 (1)	−0.032 (1)	0.004 (1)	0.005 (1)
C15	0.072 (1)	0.051 (1)	0.060 (1)	−0.022 (1)	0.011 (1)	0.006 (1)
C16	0.147 (2)	0.071 (1)	0.101 (2)	−0.027 (1)	0.035 (2)	0.036 (1)
C17	0.137 (2)	0.058 (1)	0.088 (2)	−0.032 (1)	0.011 (1)	−0.006 (1)
C18	0.070 (1)	0.082 (2)	0.137 (2)	−0.012 (1)	−0.001 (1)	0.010 (2)
C19	0.068 (1)	0.070 (1)	0.079 (1)	−0.037 (1)	0.007 (1)	0.026 (1)
C20	0.089 (2)	0.093 (2)	0.111 (2)	−0.056 (1)	0.010 (1)	0.040 (1)
C21	0.061 (1)	0.112 (2)	0.075 (1)	−0.050 (1)	0.005 (1)	0.027 (1)
C22	0.049 (1)	0.081 (1)	0.065 (1)	−0.032 (1)	0.009 (1)	0.006 (1)
C23	0.052 (1)	0.059 (1)	0.070 (1)	−0.025 (1)	0.010 (1)	0.011 (1)
C24	0.058 (1)	0.092 (2)	0.154 (2)	−0.012 (1)	0.032 (1)	0.010 (2)

Geometric parameters (Å, º)

Cu1—Cu1^i	2.640 (2)	C8—H8B	0.960
Cu1—O2	1.975 (2)	C10—H10A	0.960
Cu1—O3^i	1.968 (2)	C10—H10B	0.960
Cu1—O4	1.976 (2)	C10—H10C	0.960
Cu1—O5^i	1.973 (2)	C11—H11A	0.960
Cu1—N6	2.163 (2)	C11—H11B	0.959
O2—C7	1.260 (2)	C11—H11C	0.960
O3—C7	1.257 (2)	C12—H12A	0.960
O4—C13	1.245 (2)	C12—H12B	0.960
O5—C13	1.251 (2)	C12—H12C	0.960
N6—C19	1.339 (3)	C14—H14A	0.961
N6—C23	1.331 (3)	C14—H14B	0.960
C7—C8	1.522 (3)	C16—H16A	0.960
C8—C9	1.518 (3)	C16—H16B	0.960
C9—C10	1.514 (4)	C16—H16C	0.960
C9—C11	1.495 (4)	C17—H17A	0.960
C9—C12	1.517 (4)	C17—H17B	0.960
C13—C14	1.518 (3)	C17—H17C	0.960
C14—C15	1.539 (3)	C18—H18A	0.960
C15—C16	1.525 (3)	C18—H18B	0.960
C15—C17	1.524 (3)	C18—H18C	0.959
C15—C18	1.533 (3)	C19—H19	0.960
C19—C20	1.372 (3)	C20—H20	0.960
C20—C21	1.370 (4)	C21—H21	0.960
C21—C22	1.369 (3)	C23—H23	0.960
C22—C23	1.384 (3)	C24—H24A	0.960
C22—C24	1.510 (4)	C24—H24B	0.960
C8—H8A	0.960	C24—H24C	0.960
O2—Cu1—O3^i	168.1 (1)	H10A—C10—H10B	110.2
O2—Cu1—O4	89.3 (1)	H10A—C10—H10C	110.1
O2—Cu1—O5^i	89.3 (1)	H10B—C10—H10C	109.0
O2—Cu1—N6	94.1 (1)	C9—C11—H11A	111.8
O3^i—Cu1—O4	91.0 (1)	C9—C11—H11B	109.0
O3^i—Cu1—O5^i	87.8 (1)	C9—C11—H11C	108.7
O3^i—Cu1—N6	97.7 (1)	H11A—C11—H11B	109.2
O4—Cu1—O5^i	167.7 (1)	H11A—C11—H11C	109.2
O4—Cu1—N6	92.2 (1)	H11B—C11—H11C	109.0
O5^i—Cu1—N6	100.1 (1)	C9—C12—H12A	110.1
Cu1—O2—C7	122.6 (1)	C9—C12—H12B	109.1
Cu1^i—O3—C7	123.4 (2)	C9—C12—H12C	109.6
Cu1—O4—C13	126.4 (1)	H12A—C12—H12B	109.5
Cu1^i—O5—C13	120.4 (1)	H12A—C12—H12C	109.5
Cu1—N6—C19	123.5 (2)	H12B—C12—H12C	109.0
Cu1—N6—C23	118.7 (2)	C13—C14—H14A	108.7
C19—N6—C23	117.6 (2)	C13—C14—H14B	108.1
O2—C7—O3	125.6 (2)	C15—C14—H14A	108.5
O2—C7—C8	116.6 (2)	C15—C14—H14B	108.1
O3—C7—C8	117.8 (2)	H14A—C14—H14B	109.0
C7—C8—C9	116.3 (2)	C15—C16—H16A	110.2
C8—C9—C10	109.0 (2)	C15—C16—H16B	109.4
C8—C9—C11	111.9 (2)	C15—C16—H16C	109.1
C8—C9—C12	109.2 (2)	H16A—C16—H16B	109.5
C10—C9—C11	108.2 (2)	H16A—C16—H16C	109.5
C10—C9—C12	111.0 (2)	H16B—C16—H16C	109.0
C11—C9—C12	107.6 (3)	C15—C17—H17A	107.3
O4—C13—O5	125.3 (2)	C15—C17—H17B	109.9
O4—C13—C14	117.1 (2)	C15—C17—H17C	110.4
O5—C13—C14	117.7 (2)	H17A—C17—H17B	110.1
C13—C14—C15	114.2 (2)	H17A—C17—H17C	110.1
C14—C15—C16	110.1 (2)	H17B—C17—H17C	109.0
C14—C15—C17	107.9 (2)	C15—C18—H18A	111.4
C14—C15—C18	110.9 (2)	C15—C18—H18B	109.5
C16—C15—C17	109.3 (2)	C15—C18—H18C	108.8
C16—C15—C18	108.4 (2)	H18A—C18—H18B	109.1
C17—C15—C18	110.3 (2)	H18A—C18—H18C	109.1
N6—C19—C20	121.4 (2)	H18B—C18—H18C	108.9
C19—C20—C21	120.2 (3)	N6—C19—H19	119.1
C20—C21—C22	119.3 (2)	C20—C19—H19	119.5
C21—C22—C23	117.2 (2)	C19—C20—H20	119.9
C21—C22—C24	122.4 (2)	C21—C20—H20	119.8
C23—C22—C24	120.4 (2)	C20—C21—H21	120.5
N6—C23—C22	124.2 (2)	C22—C21—H21	120.2
C7—C8—H8A	108.1	N6—C23—H23	118.0
C7—C8—H8B	107.5	C22—C23—H23	117.8
C9—C8—H8A	108.3	C22—C24—H24A	110.4
C9—C8—H8B	107.4	C22—C24—H24B	106.6
H8A—C8—H8B	109.1	C22—C24—H24C	106.4
C9—C10—H10A	108.1	H24A—C24—H24B	113.7
C9—C10—H10B	109.9	H24A—C24—H24C	110.4
C9—C10—H10C	109.5	H24B—C24—H24C	109.0

Symmetry code: (i) −x, −y+1, −z+2.

(IV) tetrakis(µ-3,3-dimethylbutyrato-O:O')di(4-methylpyridine-N)dicopper(II)

Crystal data

[Cu2(C6H11O2)4(C6H7N)2]	Z = 2
Mr = 773.96	F(000) = 820
Triclinic, P1	Dx = 1.216 Mg m^−3
a = 11.346 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 18.584 (3) Å	Cell parameters from 25 reflections
c = 10.606 (2) Å	θ = 10–15°
α = 90.44 (1)°	µ = 1.05 mm^−1
β = 101.40 (1)°	T = 297 K
γ = 74.80 (1)°	Prism, green
V = 2113.2 (6) Å^3	0.5 × 0.4 × 0.2 mm

Data collection

Rigaku AFC-5 diffractometer	Rint = 0.017
θ–2θ scans	θmax = 27.5°
Absorption correction: integration (Coppens et al., 1965)	h = 0→15
Tmin = 0.967, Tmax = 0.984	k = −24→24
10177 measured reflections	l = −14→14
9683 independent reflections	3 standard reflections every 100 reflections
5211 reflections with |Fo| > 3σ(|Fo|)	intensity decay: none

Refinement

Refinement on F	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.067	w = 1/[σ^2(F) + 0.000225F^2]
wR(F^2) = 0.052	(Δ/σ)max = 0.03
S = 1.32	Δρmax = 0.66 e Å^−3
5211 reflections	Δρmin = −0.66 e Å^−3
433 parameters

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

	x	y	z	Uiso*/Ueq
Cu1	0.06668 (5)	0.03941 (3)	0.45775 (5)	0.0572 (2)
Cu2	0.06231 (5)	0.43734 (3)	−0.04235 (5)	0.0649 (3)
O3	0.1940 (3)	0.0002 (2)	0.6135 (3)	0.071 (1)
O4	0.0824 (3)	−0.0691 (2)	0.6808 (3)	0.075 (2)
O5	−0.0137 (3)	0.1194 (2)	0.5587 (3)	0.077 (1)
O6	−0.1278 (3)	0.0530 (2)	0.6276 (3)	0.078 (1)
O7	0.2008 (3)	0.4847 (2)	−0.0166 (3)	0.080 (2)
O8	0.0960 (3)	0.5912 (2)	0.0533 (3)	0.083 (2)
O9	0.1133 (3)	0.4012 (2)	0.1399 (3)	0.082 (2)
O10	0.0061 (3)	0.5073 (2)	0.2087 (3)	0.080 (2)
N11	0.1727 (3)	0.0985 (2)	0.3677 (3)	0.060 (2)
N12	0.1581 (3)	0.3389 (2)	−0.1287 (3)	0.069 (2)
C13	0.1777 (4)	−0.0444 (3)	0.6930 (4)	0.067 (2)
C14	0.2808 (4)	−0.0719 (3)	0.8117 (4)	0.080 (2)
C15	0.2481 (5)	−0.0424 (3)	0.9391 (5)	0.082 (2)
C16	0.1486 (6)	−0.0750 (4)	0.9734 (5)	0.139 (4)
C17	0.3654 (6)	−0.0686 (4)	1.0454 (5)	0.140 (4)
C18	0.2022 (7)	0.0411 (4)	0.9322 (6)	0.147 (4)
C19	−0.0960 (4)	0.1114 (3)	0.6193 (4)	0.059 (2)
C20	−0.1620 (4)	0.1792 (3)	0.6831 (4)	0.073 (2)
C21	−0.2795 (4)	0.2288 (3)	0.5958 (5)	0.079 (2)
C22	−0.3361 (5)	0.2936 (3)	0.6736 (6)	0.134 (3)
C23	−0.3725 (5)	0.1818 (4)	0.5526 (7)	0.155 (4)
C24	−0.2508 (7)	0.2587 (4)	0.4805 (7)	0.182 (4)
C25	0.2930 (4)	0.0682 (2)	0.3681 (4)	0.070 (2)
C26	0.3620 (4)	0.1028 (3)	0.3078 (5)	0.077 (2)
C27	0.3068 (5)	0.1711 (3)	0.2446 (4)	0.076 (2)
C28	0.1823 (5)	0.2024 (3)	0.2445 (5)	0.081 (2)
C29	0.1197 (4)	0.1643 (3)	0.3070 (5)	0.078 (2)
C30	0.3790 (5)	0.2110 (3)	0.1764 (6)	0.118 (3)
C31	0.1922 (4)	0.5481 (3)	0.0210 (4)	0.064 (2)
C32	0.3025 (4)	0.5818 (3)	0.0282 (5)	0.076 (2)
C33	0.2980 (5)	0.6259 (3)	−0.0944 (5)	0.084 (3)
C34	0.1838 (6)	0.6895 (4)	−0.1233 (8)	0.161 (5)
C35	0.3036 (7)	0.5731 (4)	−0.2036 (6)	0.170 (5)
C36	0.4125 (5)	0.6562 (3)	−0.0761 (6)	0.135 (4)
C37	0.0793 (5)	0.4435 (3)	0.2268 (5)	0.077 (3)
C38	0.1334 (5)	0.4141 (3)	0.3666 (5)	0.092 (3)
C39	0.2465 (5)	0.4408 (3)	0.4304 (5)	0.090 (3)
C40	0.2153 (7)	0.5244 (4)	0.4329 (6)	0.140 (4)
C41	0.3516 (6)	0.4139 (5)	0.3561 (6)	0.171 (5)
C42	0.2904 (6)	0.4081 (3)	0.5674 (6)	0.134 (4)
C43	0.2797 (4)	0.3208 (3)	−0.1258 (4)	0.070 (2)
C44	0.3411 (4)	0.2613 (3)	−0.1846 (4)	0.075 (2)
C45	0.2785 (4)	0.2160 (3)	−0.2545 (4)	0.072 (2)
C46	0.1533 (5)	0.2355 (3)	−0.2603 (7)	0.135 (3)
C47	0.0974 (5)	0.2949 (3)	−0.1977 (6)	0.136 (3)
C48	0.3397 (5)	0.1518 (3)	−0.3252 (5)	0.114 (3)
H14A	0.35406	−0.05823	0.80021	0.20*
H14B	0.29876	−0.12533	0.81801	0.20*
H16A	0.12666	−0.05544	1.05211	0.20*
H16B	0.18066	−0.12834	0.98321	0.20*
H16C	0.07626	−0.06284	0.90491	0.20*
H17A	0.34354	−0.04902	1.12411	0.20*
H17B	0.43134	−0.05022	1.02521	0.20*
H17C	0.39164	−0.12222	1.05181	0.20*
H18A	0.18028	0.06075	1.01091	0.20*
H18B	0.13028	0.05615	0.86361	0.20*
H18C	0.26698	0.06115	0.91341	0.20*
H20A	−0.10482	0.20896	0.70967	0.20*
H20B	−0.18522	0.16246	0.75777	0.20*
H22A	−0.40937	0.32383	0.61789	0.20*
H22B	−0.27657	0.32193	0.70019	0.20*
H22C	−0.35707	0.27563	0.74859	0.20*
H23A	−0.44589	0.21204	0.49700	0.20*
H23B	−0.39439	0.16384	0.62700	0.20*
H23C	−0.33399	0.13994	0.50770	0.20*
H24A	−0.32421	0.28886	0.42488	0.20*
H24B	−0.21061	0.21836	0.43358	0.20*
H24C	−0.19431	0.28856	0.50978	0.20*
H25	0.33255	0.02083	0.41354	0.20*
H26	0.44844	0.07913	0.30944	0.20*
H28	0.14018	0.24985	0.20074	0.20*
H29	0.03318	0.18623	0.30749	0.20*
H30A	0.32728	0.25791	0.13667	0.20*
H30B	0.41141	0.17791	0.11414	0.20*
H30C	0.44731	0.21761	0.24084	0.20*
H32A	0.37806	0.54207	0.04426	0.20*
H32B	0.30346	0.61448	0.09856	0.20*
H34A	0.17973	0.71708	−0.20089	0.20*
H34B	0.18683	0.72168	−0.05219	0.20*
H34C	0.11083	0.67148	−0.13149	0.20*
H35A	0.29943	0.60070	−0.28120	0.20*
H35B	0.23513	0.55080	−0.21370	0.20*
H35C	0.38043	0.53440	−0.18400	0.20*
H36A	0.40838	0.68376	−0.15368	0.20*
H36B	0.48718	0.61576	−0.05928	0.20*
H36C	0.41308	0.68826	−0.00478	0.20*
H38A	0.15693	0.36051	0.36925	0.20*
H38B	0.06943	0.43101	0.41545	0.20*
H40A	0.28659	0.54163	0.47041	0.20*
H40B	0.15189	0.54063	0.48271	0.20*
H40C	0.18349	0.54553	0.34661	0.20*
H41A	0.42287	0.43112	0.39363	0.20*
H41B	0.32317	0.43192	0.26783	0.20*
H41C	0.37467	0.36032	0.35943	0.20*
H42A	0.36169	0.42528	0.60494	0.20*
H42B	0.31239	0.35458	0.56694	0.20*
H42C	0.22509	0.42448	0.61484	0.20*
H43	0.32705	0.35196	−0.07917	0.20*
H44	0.42983	0.25094	−0.17610	0.20*
H46	0.10313	0.20754	−0.31190	0.20*
H47	0.00931	0.30558	−0.20133	0.20*
H48A	0.28108	0.12657	−0.36991	0.20*
H48B	0.40255	0.11970	−0.26093	0.20*
H48C	0.37935	0.17200	−0.38303	0.20*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0519 (4)	0.0633 (4)	0.0572 (4)	−0.0244 (3)	0.0135 (3)	0.0001 (3)
Cu2	0.0620 (4)	0.0575 (4)	0.0725 (4)	−0.0234 (3)	0.0124 (3)	−0.0033 (3)
O3	0.052 (2)	0.092 (2)	0.072 (2)	−0.027 (2)	0.005 (2)	0.010 (2)
O4	0.067 (2)	0.103 (3)	0.068 (2)	−0.037 (2)	−0.001 (2)	0.021 (2)
O5	0.066 (2)	0.068 (2)	0.088 (2)	−0.026 (2)	0.022 (2)	−0.015 (2)
O6	0.085 (2)	0.067 (2)	0.079 (2)	−0.032 (2)	0.033 (2)	−0.009 (2)
O7	0.069 (2)	0.061 (2)	0.108 (3)	−0.033 (2)	0.015 (2)	−0.011 (2)
O8	0.076 (2)	0.081 (2)	0.091 (3)	−0.047 (2)	0.025 (2)	−0.020 (2)
O9	0.100 (3)	0.064 (2)	0.077 (3)	−0.023 (2)	0.002 (2)	0.008 (2)
O10	0.078 (2)	0.078 (2)	0.078 (2)	−0.015 (2)	0.016 (2)	0.009 (2)
N11	0.060 (3)	0.061 (2)	0.060 (2)	−0.025 (2)	0.018 (2)	0.004 (2)
N12	0.057 (3)	0.060 (2)	0.082 (3)	−0.023 (2)	0.014 (2)	−0.011 (2)
C13	0.062 (3)	0.070 (3)	0.052 (3)	−0.004 (3)	0.009 (3)	−0.010 (3)
C14	0.053 (3)	0.117 (4)	0.055 (3)	−0.006 (3)	0.000 (2)	0.001 (3)
C15	0.077 (4)	0.102 (4)	0.055 (3)	−0.014 (3)	0.002 (3)	0.000 (3)
C16	0.135 (6)	0.200 (7)	0.081 (4)	−0.045 (5)	0.041 (4)	0.016 (4)
C17	0.112 (5)	0.221 (8)	0.070 (4)	−0.025 (5)	−0.022 (4)	0.004 (4)
C18	0.201 (7)	0.112 (5)	0.096 (5)	−0.029 (5)	0.014 (5)	−0.031 (4)
C19	0.054 (3)	0.072 (3)	0.045 (3)	−0.014 (3)	0.000 (2)	−0.004 (2)
C20	0.072 (3)	0.073 (3)	0.064 (3)	−0.018 (3)	0.015 (3)	−0.012 (3)
C21	0.070 (4)	0.074 (3)	0.080 (4)	−0.009 (3)	0.024 (3)	−0.005 (3)
C22	0.104 (5)	0.117 (5)	0.135 (6)	0.004 (4)	0.041 (4)	−0.037 (4)
C23	0.069 (4)	0.166 (6)	0.196 (7)	−0.024 (4)	−0.007 (4)	−0.044 (6)
C24	0.224 (8)	0.130 (6)	0.139 (6)	0.068 (5)	0.097 (6)	0.064 (5)
C25	0.063 (3)	0.065 (3)	0.078 (3)	−0.015 (3)	0.023 (3)	0.004 (3)
C26	0.070 (3)	0.075 (3)	0.082 (4)	−0.018 (3)	0.034 (3)	0.003 (3)
C27	0.083 (4)	0.075 (3)	0.066 (3)	−0.029 (3)	0.030 (3)	−0.006 (3)
C28	0.078 (4)	0.070 (3)	0.097 (4)	−0.019 (3)	0.021 (3)	0.019 (3)
C29	0.066 (3)	0.072 (3)	0.096 (4)	−0.016 (3)	0.020 (3)	0.019 (3)
C30	0.118 (5)	0.115 (5)	0.131 (5)	−0.048 (4)	0.063 (4)	0.022 (4)
C31	0.068 (3)	0.078 (4)	0.049 (3)	−0.033 (3)	0.004 (2)	0.002 (3)
C32	0.064 (3)	0.086 (3)	0.083 (4)	−0.042 (3)	0.007 (3)	−0.005 (3)
C33	0.083 (4)	0.097 (4)	0.079 (4)	−0.054 (3)	0.014 (3)	−0.005 (3)
C34	0.089 (5)	0.152 (6)	0.265 (9)	−0.012 (5)	0.029 (5)	0.117 (6)
C35	0.223 (8)	0.221 (8)	0.090 (5)	−0.150 (7)	0.057 (5)	−0.039 (5)
C36	0.115 (5)	0.152 (6)	0.152 (6)	−0.092 (4)	0.047 (4)	−0.020 (5)
C37	0.078 (4)	0.077 (4)	0.083 (4)	−0.043 (3)	0.011 (3)	0.003 (3)
C38	0.114 (5)	0.098 (4)	0.069 (4)	−0.032 (4)	0.005 (3)	0.021 (3)
C39	0.093 (4)	0.101 (4)	0.066 (4)	−0.014 (4)	−0.004 (3)	0.007 (3)
C40	0.201 (7)	0.115 (5)	0.102 (5)	−0.060 (5)	−0.033 (5)	0.007 (4)
C41	0.094 (5)	0.291 (10)	0.106 (5)	−0.037 (6)	0.004 (4)	−0.011 (6)
C42	0.170 (6)	0.137 (6)	0.077 (4)	−0.016 (5)	−0.014 (4)	0.020 (4)
C43	0.061 (3)	0.080 (3)	0.069 (3)	−0.029 (3)	0.000 (3)	−0.003 (3)
C44	0.058 (3)	0.084 (4)	0.072 (3)	−0.021 (3)	0.015 (3)	−0.020 (3)
C45	0.064 (3)	0.077 (3)	0.069 (3)	−0.027 (3)	0.017 (3)	−0.011 (3)
C46	0.063 (4)	0.111 (5)	0.195 (7)	−0.039 (3)	0.028 (4)	−0.077 (5)
C47	0.062 (4)	0.113 (5)	0.197 (7)	−0.043 (3)	0.035 (4)	−0.086 (5)
C48	0.095 (4)	0.106 (4)	0.114 (5)	−0.032 (3)	0.033 (3)	−0.051 (4)

Geometric parameters (Å, º)

Cu1—Cu1^i	2.638 (4)	C16—H16A	0.960
Cu1—O3	1.967 (3)	C16—H16B	0.960
Cu1—O4^i	1.966 (3)	C16—H16C	0.960
Cu1—O5	1.960 (4)	C17—H17A	0.960
Cu1—O6^i	1.961 (4)	C17—H17B	0.959
Cu1—N11	2.175 (4)	C17—H17C	0.961
Cu2—Cu2^ii	2.641 (4)	C18—H18A	0.960
Cu2—O7	1.967 (3)	C18—H18B	0.960
Cu2—O8^ii	1.985 (4)	C18—H18C	0.960
Cu2—O9	1.974 (4)	C20—H20A	0.960
Cu2—O10^ii	1.960 (4)	C20—H20B	0.960
Cu2—N12	2.167 (4)	C22—H22A	0.960
O3—C13	1.258 (6)	C22—H22B	0.959
O4—C13	1.266 (6)	C22—H22C	0.960
O5—C19	1.272 (6)	C23—H23A	0.960
O6—C19	1.240 (6)	C23—H23B	0.960
O7—C31	1.228 (7)	C23—H23C	0.960
O8—C31	1.278 (6)	C24—H24A	0.960
O9—C37	1.259 (7)	C24—H24B	0.960
O10—C37	1.249 (7)	C24—H24C	0.960
N11—C25	1.332 (6)	C25—H25	0.961
N11—C29	1.322 (6)	C26—H26	0.960
N12—C43	1.326 (6)	C28—H28	0.960
N12—C47	1.329 (7)	C29—H29	0.960
C13—C14	1.526 (7)	C30—H30A	0.960
C14—C15	1.531 (7)	C30—H30B	0.960
C15—C16	1.517 (9)	C30—H30C	0.960
C15—C17	1.535 (8)	C32—H32A	0.960
C15—C18	1.500 (9)	C32—H32B	0.959
C19—C20	1.515 (7)	C34—H34A	0.960
C20—C21	1.537 (7)	C34—H34B	0.960
C21—C22	1.528 (8)	C34—H34C	0.960
C21—C23	1.539 (8)	C35—H35A	0.960
C21—C24	1.474 (9)	C35—H35B	0.961
C25—C26	1.380 (7)	C35—H35C	0.960
C26—C27	1.373 (7)	C36—H36A	0.960
C27—C28	1.379 (8)	C36—H36B	0.960
C27—C30	1.518 (8)	C36—H36C	0.960
C28—C29	1.378 (7)	C38—H38A	0.960
C31—C32	1.528 (7)	C38—H38B	0.959
C32—C33	1.528 (7)	C40—H40A	0.960
C33—C34	1.488 (9)	C40—H40B	0.960
C33—C35	1.513 (9)	C40—H40C	0.960
C33—C36	1.524 (8)	C41—H41A	0.960
C37—C38	1.533 (8)	C41—H41B	0.960
C38—C39	1.528 (8)	C41—H41C	0.960
C39—C40	1.502 (9)	C42—H42A	0.960
C39—C41	1.531 (9)	C42—H42B	0.960
C39—C42	1.516 (8)	C42—H42C	0.960
C43—C44	1.361 (7)	C43—H43	0.960
C44—C45	1.364 (7)	C44—H44	0.960
C45—C46	1.359 (8)	C46—H46	0.960
C45—C48	1.492 (8)	C47—H47	0.960
C46—C47	1.359 (9)	C48—H48A	0.960
C14—H14A	0.961	C48—H48B	0.960
C14—H14B	0.959	C48—H48C	0.960
O3—Cu1—O4^i	168.1 (2)	H17B—C17—H17C	109.0
O3—Cu1—O5	88.7 (2)	C15—C18—H18A	112.7
O3—Cu1—O6^i	89.6 (2)	C15—C18—H18B	108.8
O3—Cu1—N11	98.0 (2)	C15—C18—H18C	108.2
O4^i—Cu1—O5	88.5 (2)	H18A—C18—H18B	109.0
O4^i—Cu1—O6^i	90.7 (2)	H18A—C18—H18C	109.1
O4^i—Cu1—N11	93.9 (2)	H18B—C18—H18C	109.1
O5—Cu1—O6^i	168.0 (2)	C19—C20—H20A	108.3
O5—Cu1—N11	99.5 (2)	C19—C20—H20B	108.5
O6^i—Cu1—N11	92.5 (2)	C21—C20—H20A	108.1
O7—Cu2—O8^ii	168.1 (2)	C21—C20—H20B	108.6
O7—Cu2—O9	89.1 (2)	H20A—C20—H20B	109.0
O7—Cu2—O10^ii	89.3 (2)	C21—C22—H22A	107.0
O7—Cu2—N12	95.6 (2)	C21—C22—H22B	109.0
O8^ii—Cu2—O9	89.5 (2)	C21—C22—H22C	110.8
O8^ii—Cu2—O10^ii	89.6 (2)	H22A—C22—H22B	110.5
O8^ii—Cu2—N12	96.3 (2)	H22A—C22—H22C	110.5
O9—Cu2—O10^ii	168.0 (2)	H22B—C22—H22C	109.0
O9—Cu2—N12	99.0 (2)	C21—C23—H23A	109.5
O10^ii—Cu2—N12	93.0 (2)	C21—C23—H23B	109.3
Cu1—O3—C13	121.3 (3)	C21—C23—H23C	109.2
Cu1^i—O4—C13	125.6 (3)	H23A—C23—H23B	109.9
Cu1—O5—C19	121.4 (3)	H23A—C23—H23C	110.0
Cu1^i—O6—C19	125.6 (3)	H23B—C23—H23C	109.0
Cu1—N11—C25	120.9 (3)	C21—C24—H24A	112.1
Cu1—N11—C29	121.5 (3)	C21—C24—H24B	109.9
Cu2—O7—C31	123.5 (3)	C21—C24—H24C	107.1
Cu2^ii—O8—C31	122.7 (3)	H24A—C24—H24B	109.4
Cu2—O9—C37	120.3 (4)	H24A—C24—H24C	109.3
Cu2^ii—O10—C37	126.0 (4)	H24B—C24—H24C	108.9
Cu2—N12—C43	123.2 (3)	N11—C25—H25	118.0
Cu2—N12—C47	122.1 (4)	C26—C25—H25	119.5
C25—N11—C29	117.6 (4)	C25—C26—H26	120.2
C43—N12—C47	114.5 (4)	C27—C26—H26	119.9
O3—C13—O4	124.7 (5)	C27—C28—H28	119.9
O3—C13—C14	118.1 (4)	C29—C28—H28	120.8
O4—C13—C14	117.2 (4)	N11—C29—H29	117.4
C13—C14—C15	114.9 (4)	C28—C29—H29	119.2
C14—C15—C16	110.3 (5)	C27—C30—H30A	111.5
C14—C15—C17	108.1 (5)	C27—C30—H30B	106.9
C14—C15—C18	111.4 (5)	C27—C30—H30C	106.2
C16—C15—C17	107.6 (5)	H30A—C30—H30B	111.6
C16—C15—C18	109.0 (5)	H30A—C30—H30C	111.5
C17—C15—C18	110.4 (5)	H30B—C30—H30C	109.0
O5—C19—O6	124.9 (5)	C31—C32—H32A	108.6
O5—C19—C20	117.2 (4)	C31—C32—H32B	108.4
O6—C19—C20	117.8 (4)	C33—C32—H32A	108.4
C19—C20—C21	114.3 (4)	C33—C32—H32B	108.5
C20—C21—C22	108.1 (5)	H32A—C32—H32B	109.0
C20—C21—C23	108.7 (5)	C33—C34—H34A	111.6
C20—C21—C24	111.9 (5)	C33—C34—H34B	107.5
C22—C21—C23	110.3 (5)	C33—C34—H34C	110.0
C22—C21—C24	109.2 (5)	H34A—C34—H34B	109.3
C23—C21—C24	108.7 (5)	H34A—C34—H34C	109.4
N11—C25—C26	122.5 (5)	H34B—C34—H34C	109.0
C25—C26—C27	119.9 (5)	C33—C35—H35A	108.7
C26—C27—C28	117.4 (5)	C33—C35—H35B	109.8
C26—C27—C30	121.6 (5)	C33—C35—H35C	109.2
C28—C27—C30	120.9 (5)	H35A—C35—H35B	110.1
C27—C28—C29	119.3 (5)	H35A—C35—H35C	110.1
N11—C29—C28	123.3 (5)	H35B—C35—H35C	108.9
O7—C31—O8	125.7 (5)	C33—C36—H36A	108.0
O7—C31—C32	119.2 (5)	C33—C36—H36B	110.2
O8—C31—C32	115.0 (5)	C33—C36—H36C	109.8
C31—C32—C33	113.7 (4)	H36A—C36—H36B	109.9
C32—C33—C34	111.1 (5)	H36A—C36—H36C	109.9
C32—C33—C35	108.3 (5)	H36B—C36—H36C	109.0
C32—C33—C36	108.9 (5)	C37—C38—H38A	109.0
C34—C33—C35	111.3 (6)	C37—C38—H38B	107.9
C34—C33—C36	109.0 (5)	C39—C38—H38A	108.7
C35—C33—C36	108.1 (5)	C39—C38—H38B	108.0
O9—C37—O10	125.5 (5)	H38A—C38—H38B	109.0
O9—C37—C38	117.1 (5)	C39—C40—H40A	112.0
O10—C37—C38	117.4 (5)	C39—C40—H40B	108.2
C37—C38—C39	114.1 (5)	C39—C40—H40C	109.3
C38—C39—C40	111.6 (5)	H40A—C40—H40B	109.1
C38—C39—C41	109.5 (5)	H40A—C40—H40C	109.1
C38—C39—C42	108.7 (5)	H40B—C40—H40C	109.0
C40—C39—C41	108.8 (6)	C39—C41—H41A	110.8
C40—C39—C42	109.0 (5)	C39—C41—H41B	110.0
C41—C39—C42	109.2 (6)	C39—C41—H41C	108.4
N12—C43—C44	124.3 (5)	H41A—C41—H41B	109.4
C43—C44—C45	120.9 (5)	H41A—C41—H41C	109.3
C44—C45—C46	114.9 (5)	H41B—C41—H41C	109.0
C44—C45—C48	123.5 (5)	C39—C42—H42A	107.0
C46—C45—C48	121.6 (5)	C39—C42—H42B	109.7
C45—C46—C47	121.5 (6)	C39—C42—H42C	109.9
N12—C47—C46	123.8 (5)	H42A—C42—H42B	110.6
C13—C14—H14A	108.8	H42A—C42—H42C	110.6
C13—C14—H14B	107.6	H42B—C42—H42C	109.0
C15—C14—H14A	108.7	N12—C43—H43	117.4
C15—C14—H14B	107.6	C44—C43—H43	118.3
H14A—C14—H14B	109.1	C43—C44—H44	119.5
C15—C16—H16A	110.2	C45—C44—H44	119.6
C15—C16—H16B	108.5	C45—C46—H46	119.1
C15—C16—H16C	109.3	C47—C46—H46	119.4
H16A—C16—H16B	109.9	N12—C47—H47	117.2
H16A—C16—H16C	109.9	C46—C47—H47	119.0
H16B—C16—H16C	109.0	C45—C48—H48A	112.0
C15—C17—H17A	106.9	C45—C48—H48B	105.3
C15—C17—H17B	109.7	C45—C48—H48C	106.2
C15—C17—H17C	109.7	H48A—C48—H48B	112.0
H17A—C17—H17B	110.8	H48A—C48—H48C	111.9
H17A—C17—H17C	110.7	H48B—C48—H48C	109.0

Symmetry codes: (i) −x, −y, −z+1; (ii) −x, −y+1, −z.

(V) tetrakis(µ-3,3-dimethylbutyrato-O:O')di(3,3-dimethylbutyric acid-O)dicopper(II)

Crystal data

[Cu2(C6H11O2)4(C6H12O2)2]	F(000) = 876
Mr = 820.02	Dx = 1.201 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 10.890 (2) Å	Cell parameters from 25 reflections
b = 18.211 (2) Å	θ = 10–15°
c = 11.787 (1) Å	µ = 0.99 mm^−1
β = 103.98 (1)°	T = 297 K
V = 2268.2 (5) Å^3	Prism, green
Z = 2	0.3 × 0.3 × 0.25 mm

Data collection

Rigaku AFC-5 diffractometer	Rint = 0.016
θ–2θ scans	θmax = 27.5°
Absorption correction: integration (Coppens et al., 1965)	h = 0→14
Tmin = 0.792, Tmax = 0.793	k = 0→23
5475 measured reflections	l = −15→15
5214 independent reflections	3 standard reflections every 100 reflections
2610 reflections with |Fo| > 3σ(|Fo|)	intensity decay: none

Refinement

Refinement on F	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.070	w = 1/[σ^2(F) + 0.000225F^2]
wR(F^2) = 0.054	(Δ/σ)max = 0.008
S = 1.33	Δρmax = 0.93 e Å^−3
2610 reflections	Δρmin = −0.74 e Å^−3
226 parameters

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

	x	y	z	Uiso*/Ueq
Cu1	0.43461 (7)	0.94487 (4)	0.44711 (6)	0.0543 (3)
O2	0.6014 (4)	0.9193 (2)	0.4134 (3)	0.065 (2)
O3	0.7109 (3)	1.0144 (3)	0.5046 (3)	0.071 (2)
O4	0.4025 (4)	1.0115 (2)	0.3136 (3)	0.063 (2)
O5	0.5134 (4)	1.1063 (2)	0.4040 (3)	0.063 (2)
O6	0.3429 (4)	0.8546 (2)	0.3362 (3)	0.072 (2)
O7	0.4990 (5)	0.8185 (3)	0.2616 (5)	0.109 (2)
C8	0.7023 (6)	0.9583 (3)	0.4432 (5)	0.055 (3)
C9	0.8148 (6)	0.9329 (3)	0.4013 (6)	0.077 (3)
C10	0.8267 (6)	0.9709 (4)	0.2867 (6)	0.087 (3)
C11	0.8465 (7)	1.0533 (5)	0.3060 (6)	0.117 (4)
C12	0.7094 (8)	0.9579 (5)	0.1901 (6)	0.125 (4)
C13	0.9428 (8)	0.9377 (5)	0.2535 (8)	0.154 (5)
C14	0.4419 (6)	1.0763 (4)	0.3159 (5)	0.061 (3)
C15	0.3996 (6)	1.1215 (3)	0.2058 (5)	0.062 (3)
C16	0.2634 (6)	1.1506 (4)	0.1849 (6)	0.070 (3)
C17	0.2396 (7)	1.2011 (4)	0.0768 (6)	0.090 (3)
C18	0.1673 (7)	1.0885 (4)	0.1622 (8)	0.115 (4)
C19	0.2494 (8)	1.1962 (5)	0.2899 (7)	0.123 (4)
C20	0.3804 (7)	0.8173 (3)	0.2675 (6)	0.063 (3)
C21	0.2974 (6)	0.7668 (3)	0.1797 (5)	0.076 (3)
C22	0.2444 (7)	0.8030 (4)	0.0617 (6)	0.082 (3)
C23	0.1556 (7)	0.7466 (5)	−0.0128 (6)	0.119 (4)
C24	0.1768 (9)	0.8727 (5)	0.0728 (7)	0.156 (5)
C25	0.3534 (9)	0.8182 (5)	0.0033 (7)	0.145 (5)
H7	0.55865	0.84962	0.31324	0.20*
H13A	0.94881	0.96236	0.18309	0.20*
H13B	0.93311	0.88566	0.24069	0.20*
H13C	1.01701	0.94656	0.31499	0.20*
H11A	0.85249	1.07799	0.23562	0.20*
H11B	0.92319	1.06109	0.36512	0.20*
H11C	0.77679	1.07329	0.33262	0.20*
H12A	0.71543	0.98263	0.11967	0.20*
H12B	0.63733	0.97613	0.21477	0.20*
H12C	0.69903	0.90613	0.17527	0.20*
H24A	0.14405	0.89711	−0.00038	0.20*
H24B	0.23475	0.90511	0.12352	0.20*
H24C	0.10775	0.86191	0.10762	0.20*
H23A	0.12290	0.77101	−0.08599	0.20*
H23B	0.08870	0.73321	0.02331	0.20*
H23C	0.20190	0.70331	−0.02309	0.20*
H17A	0.15468	1.21925	0.06495	0.20*
H17B	0.24928	1.17445	0.00915	0.20*
H17C	0.29898	1.24095	0.09135	0.20*
H19A	0.16452	1.21436	0.27814	0.20*
H19B	0.30742	1.23666	0.29974	0.20*
H19C	0.26962	1.16616	0.35894	0.20*
H18A	0.08244	1.10668	0.15037	0.20*
H18B	0.18554	1.05598	0.22827	0.20*
H18C	0.17554	1.06198	0.09397	0.20*
H21A	0.22837	0.74987	0.21031	0.20*
H21B	0.34727	0.72537	0.16771	0.20*
H15A	0.40421	1.09095	0.14061	0.20*
H15B	0.45571	1.16255	0.20891	0.20*
H9A	0.80643	0.88111	0.38664	0.20*
H9B	0.89063	0.94181	0.46094	0.20*
H25A	0.32070	0.84257	−0.06991	0.20*
H25B	0.39180	0.77247	−0.00961	0.20*
H25C	0.41580	0.84847	0.05339	0.20*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0579 (4)	0.0576 (4)	0.0417 (3)	−0.0144 (5)	0.0082 (3)	0.0009 (5)
O2	0.056 (3)	0.065 (3)	0.066 (3)	−0.005 (2)	0.012 (2)	−0.001 (2)
O3	0.055 (3)	0.083 (3)	0.061 (3)	−0.016 (2)	0.014 (2)	−0.013 (2)
O4	0.076 (3)	0.063 (3)	0.046 (2)	−0.006 (3)	0.009 (2)	0.007 (2)
O5	0.073 (3)	0.066 (3)	0.049 (3)	−0.015 (2)	0.006 (2)	0.012 (2)
O6	0.082 (3)	0.065 (3)	0.056 (3)	−0.028 (3)	0.018 (2)	−0.010 (2)
O7	0.065 (3)	0.097 (4)	0.129 (4)	0.004 (3)	0.009 (3)	−0.050 (3)
C8	0.057 (4)	0.064 (5)	0.046 (3)	−0.001 (4)	0.010 (3)	0.019 (4)
C9	0.061 (4)	0.075 (5)	0.090 (5)	0.008 (4)	0.029 (4)	0.008 (4)
C10	0.078 (5)	0.087 (6)	0.080 (5)	−0.010 (4)	0.036 (4)	−0.012 (4)
C11	0.138 (7)	0.098 (6)	0.106 (6)	−0.026 (6)	0.057 (5)	0.012 (6)
C12	0.129 (7)	0.166 (9)	0.067 (5)	−0.038 (7)	0.033 (5)	−0.001 (5)
C13	0.131 (7)	0.133 (7)	0.180 (9)	0.005 (7)	0.110 (7)	−0.001 (7)
C14	0.052 (4)	0.078 (6)	0.051 (4)	−0.004 (4)	0.018 (3)	0.009 (4)
C15	0.067 (4)	0.073 (5)	0.048 (4)	−0.002 (4)	0.013 (3)	0.015 (3)
C16	0.069 (5)	0.069 (5)	0.071 (5)	−0.003 (4)	0.004 (4)	0.015 (4)
C17	0.112 (6)	0.081 (5)	0.080 (5)	0.003 (5)	−0.008 (4)	0.027 (4)
C18	0.072 (5)	0.102 (6)	0.177 (9)	−0.018 (5)	−0.009 (5)	0.043 (6)
C19	0.124 (7)	0.131 (8)	0.106 (6)	0.049 (6)	0.035 (6)	0.015 (6)
C20	0.067 (5)	0.052 (5)	0.063 (5)	−0.003 (4)	0.009 (4)	0.004 (4)
C21	0.082 (5)	0.064 (5)	0.063 (4)	−0.015 (4)	−0.005 (4)	−0.017 (4)
C22	0.077 (5)	0.094 (6)	0.057 (4)	0.019 (4)	0.005 (4)	−0.021 (4)
C23	0.083 (5)	0.153 (8)	0.086 (5)	0.015 (5)	−0.007 (4)	−0.050 (5)
C24	0.18 (1)	0.14 (1)	0.11 (1)	0.10 (1)	−0.04 (1)	−0.03 (1)
C25	0.167 (9)	0.160 (9)	0.083 (6)	−0.024 (7)	0.034 (6)	−0.020 (6)

Geometric parameters (Å, º)

Cu1—Cu1^i	2.599 (1)	C11—H11B	0.960
Cu1—O2	2.005 (4)	C11—H11C	0.960
Cu1—O3^i	1.955 (4)	C12—H12A	0.960
Cu1—O4	1.950 (4)	C12—H12B	0.960
Cu1—O5^i	1.946 (4)	C12—H12C	0.961
Cu1—O6	2.186 (5)	C13—H13A	0.960
O2—C8	1.285 (8)	C13—H13B	0.961
O3—C8	1.243 (8)	C13—H13C	0.960
O4—C14	1.255 (8)	C15—H15A	0.960
O5—C14	1.262 (8)	C15—H15B	0.960
O6—C20	1.201 (8)	C17—H17A	0.960
O7—C20	1.310 (9)	C17—H17B	0.960
C8—C9	1.500 (9)	C17—H17C	0.960
C9—C10	1.550 (10)	C18—H18A	0.960
C10—C11	1.526 (11)	C18—H18B	0.960
C10—C12	1.510 (11)	C18—H18C	0.960
C10—C13	1.535 (11)	C19—H19A	0.960
C14—C15	1.512 (9)	C19—H19B	0.960
C15—C16	1.538 (10)	C19—H19C	0.960
C16—C17	1.542 (10)	C21—H21A	0.959
C16—C18	1.519 (11)	C21—H21B	0.960
C16—C19	1.528 (11)	C23—H23A	0.959
C20—C21	1.511 (10)	C23—H23B	0.960
C21—C22	1.522 (10)	C23—H23C	0.959
C22—C23	1.532 (11)	C24—H24A	0.959
C22—C24	1.490 (12)	C24—H24B	0.960
C22—C25	1.534 (12)	C24—H24C	0.959
O7—H7	0.960	C25—H25A	0.959
C9—H9A	0.959	C25—H25B	0.960
C9—H9B	0.960	C25—H25C	0.960
C11—H11A	0.960
O2—Cu1—O3^i	169.3 (2)	C10—C12—H12B	108.8
O2—Cu1—O4	88.8 (2)	C10—C12—H12C	109.3
O2—Cu1—O5^i	89.2 (2)	H12A—C12—H12B	109.4
O2—Cu1—O6	90.7 (2)	H12A—C12—H12C	109.4
O3^i—Cu1—O4	89.9 (2)	H12B—C12—H12C	109.0
O3^i—Cu1—O5^i	89.9 (2)	C10—C13—H13A	105.6
O3^i—Cu1—O6	100.0 (2)	C10—C13—H13B	111.2
O4—Cu1—O5^i	169.0 (2)	C10—C13—H13C	109.6
O4—Cu1—O6	91.0 (2)	H13A—C13—H13B	110.7
O5^i—Cu1—O6	99.8 (2)	H13A—C13—H13C	110.7
Cu1—O2—C8	125.0 (4)	H13B—C13—H13C	109.0
Cu1^i—O3—C8	121.9 (4)	C14—C15—H15A	107.9
Cu1—O4—C14	125.0 (4)	C14—C15—H15B	109.4
Cu1^i—O5—C14	121.5 (4)	C16—C15—H15A	107.8
Cu1—O6—C20	130.3 (5)	C16—C15—H15B	108.6
O2—C8—O3	123.6 (6)	H15A—C15—H15B	109.0
O2—C8—C9	116.9 (6)	C16—C17—H17A	106.8
O3—C8—C9	119.5 (6)	C16—C17—H17B	110.8
C8—C9—C10	113.3 (6)	C16—C17—H17C	109.4
C9—C10—C11	110.3 (6)	H17A—C17—H17B	110.4
C9—C10—C12	110.8 (6)	H17A—C17—H17C	110.4
C9—C10—C13	107.1 (6)	H17B—C17—H17C	109.0
C11—C10—C12	109.2 (7)	C16—C18—H18A	111.5
C11—C10—C13	109.3 (7)	C16—C18—H18B	108.5
C12—C10—C13	110.2 (7)	C16—C18—H18C	108.8
O4—C14—O5	124.4 (6)	H18A—C18—H18B	109.5
O4—C14—C15	117.5 (6)	H18A—C18—H18C	109.5
O5—C14—C15	118.1 (6)	H18B—C18—H18C	109.1
C14—C15—C16	114.0 (5)	C16—C19—H19A	110.5
C15—C16—C17	107.5 (6)	C16—C19—H19B	108.9
C15—C16—C18	111.6 (6)	C16—C19—H19C	109.3
C15—C16—C19	109.7 (6)	H19A—C19—H19B	109.6
C17—C16—C18	109.1 (6)	H19A—C19—H19C	109.6
C17—C16—C19	108.4 (6)	H19B—C19—H19C	109.0
C18—C16—C19	110.4 (7)	C20—C21—H21A	109.4
O6—C20—O7	121.8 (7)	C20—C21—H21B	108.3
O6—C20—C21	124.1 (7)	C22—C21—H21A	108.9
O7—C20—C21	114.1 (6)	C22—C21—H21B	108.0
C20—C21—C22	113.2 (6)	H21A—C21—H21B	109.0
C21—C22—C23	106.3 (6)	C22—C23—H23A	104.5
C21—C22—C24	112.0 (6)	C22—C23—H23B	111.0
C21—C22—C25	109.0 (6)	C22—C23—H23C	110.2
C23—C22—C24	111.4 (7)	H23A—C23—H23B	111.1
C23—C22—C25	108.3 (6)	H23A—C23—H23C	111.0
C24—C22—C25	109.8 (7)	H23B—C23—H23C	109.0
C20—O7—H7	120.1	C22—C24—H24A	113.5
C8—C9—H9A	108.2	C22—C24—H24B	108.3
C8—C9—H9B	109.5	C22—C24—H24C	108.5
C10—C9—H9A	107.8	H24A—C24—H24B	108.7
C10—C9—H9B	108.9	H24A—C24—H24C	108.7
H9A—C9—H9B	109.0	H24B—C24—H24C	109.0
C10—C11—H11A	111.6	C22—C25—H25A	109.1
C10—C11—H11B	108.7	C22—C25—H25B	109.2
C10—C11—H11C	109.1	C22—C25—H25C	109.7
H11A—C11—H11B	109.2	H25A—C25—H25B	109.9
H11A—C11—H11C	109.2	H25A—C25—H25C	109.9
H11B—C11—H11C	108.9	H25B—C25—H25C	109.0
C10—C12—H12A	110.9

Symmetry code: (i) −x+1, −y+2, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7···O2	0.96	1.72	2.617 (5)	154