catena-Poly[[tetrakis(μ-3,3-dimethylbutyrato-O:O′)dicopper(II)]-μ-3,3-di­methylbutyrato-O:O′-[bis(2,6-di­methylpyridine-N)copper(II)]-μ-3,3-di­methylbutyrato-O:O′] and tetrakis(μ-2,2-dimethylpropanoato-O:O′)bis[(2,6-dimethylpyridine-N)copper(II)]

The two title compounds, [Cu₃(C₆H₁₁O₂)₆(C₇H₉N)₂]_n, (I), and [Cu₂(C₅H₉O₂)₄(C₇H₉N)₂], (II), have chain and finite-molecular structures, respectively. In (I), binuclear cage units and mononuclear 2,6-di­methyl­pyridine complexes, both of which have inversion centres, are arranged alternately and are linked by the carboxyl­ate ions to form one-dimensional chains along the a axis. In (II), the binuclear cage unit has an inversion centre and the coordination geometry around the Cu atom is typical square pyramidal, with 2,6-di­methyl­pyridine at the apical position.

S1. Comment

Copper(II) carboxylates usually have a cage structure with square-pyramidal coordination geometry and a monodentate ligand bonded at the axial position. 2,6-Dimethylpyridine, 2,6-Me₂py, is a bulky ligand which may cause a deformation of this cage structure, as observed in the crystals of [Cu₂(PhMe₂CCOO)₂(2,6-Me₂py)₂], where the geometry about the Cu^II is deformed from square-pyramidal toward trigonal bipyramidal (TBP). Alternatively, only a mononuclear complex, [Cu(RCOO)₂(2,6-Me₂py)₂], will be produced, as for R = Ph₃C or Ph₂MeC (Fujita et al., 1993). In this context, the crystal structures of the two title compounds, (I) and (II), respectively, are presented here. \sch

In (I), a novel polymeric structure was observed. The mononuclear moiety [Cu(RCOO)₂(2,6-Me₂py)₂] acts as the axial ligand to the binuclear unit. The carboxylato bridge between the mononuclear and binuclear units has a syn-anti conformation. An analysis of the temperature dependence of the magnetic susceptibility indicated that the spin-exchange interaction between the mononuclear and binuclear units is negligible. The Cu···Cu distance in the binuclear unit is 2.652 (1) Å, which is similar to that of the 3,3-dimethylbutyric acid adduct [2.599 (1) Å; Goto et al., 2000].

In (II), the binuclear cage structure of the copper pivalate does not have a TBP distortion, which is consistent with the high magnetic −2 J value of 379 cm⁻¹ (H = −2JS₁·S₂; Muto et al., 1986). The acridine adduct of copper(II) pivalate also has a cage structure with square-pyramidal coordination, the Cu···Cu and Cu—N distances being 2.702 (1) and 2.371 (5) Å, respectively (Kirillova et al., 1980). Copper pivalate remains a discrete dimeric structure even after the removal of the axial solvent ligands (Muto et al., 1986; Kato & Muto, 1988). In polymeric copper(II) pivalate, prepared by sublimation, the dinuclear cage is deformed and the coordination geometry around the Cu has a TBP distortion (Il'ina et al., 1992).

S2. Experimental

For (I), 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 had been stirred for 1 h at room temperature, the green precipitate was collected and dissolved in acetonitrile and 2,6-dimethylpyridine (54 mg, 0.5 mmol) was added. Blue crystals of (I) were grown from the solution by slow evaporation. For (II), a solution of 2,2-dimethylpropionic acid (613 mg, 6.0 mmol) in 0.25 M sodium hydroxide (50 ml) was neutralized with 0.25 M nitric acid and an aqueous solution of Cu(NO₃)₂·3H₂O (725 mg, 3.0 mmol) was added. After the solution had been stirred for 15 min at room temperature, the green precipitate was collected and dissolved in acetonitrile and 2,6-dimethylpyridine (321 mg, 3.0 mmol) was added. Green crystals of (II) were grown from the solution by slow evaporation.

S3. Refinement

Initially, both of the structures were refined as usual. The anisotropy in the atom displacement parameters became abnormally large for the methyl C atoms of the tert-butyl groups, suggesting libration and/or rotational disorder. Therefore, a split-site model was investigated for the tert-butyl groups in both compounds; it was found to be applicable for (II), but not for (I). For (II), the six methyl-C atoms were initially refined isotropically. Two sets of half-occupancy methyl groups, offset from one another by ca 30°, could be modelled for both tert-butyl groups based on the difference synthesis. Their anisotropic displacement parameters were then refined with their positional parameters fixed to avoid unreasonable geometry. Compared to the un-split model, R(F) slightly decreased from 0.050 to 0.048 on inceasing the number of parameters from 208 to 226. The magnitude of the displacement ellipsoids of the methyl C atoms apparently decreased, but the abnormal anisotropy of the displacement parameters did not disappear. In this manuscript, the split-site model is reported for (II). The positional parameters of all the H atoms were calculated geometrically and fixed with U(H) = 1.2 U_eq(parent atom).

Computing details

For both compounds, data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1993); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1999); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: TEXSAN; software used to prepare material for publication: TEXSAN.

Figures

	Fig. 1. The linear chain structure of (I) with displacement ellipsoids at the 50% probability level. H atoms and the tert-butyl groups of the dimethylbutyrato ligands are omitted for clarity.
	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 radii. Only one orientation of the tert-butyl groups is shown.

(I)

Crystal data

[Cu3(C6H11O2)6(C7H9N)2]	Z = 1
Mr = 1095.86	Dx = 1.251 Mg m^−3
Triclinic, P1	Mo Kα radiation, λ = 0.71073 Å
a = 12.525 (2) Å	Cell parameters from 25 reflections
b = 12.736 (2) Å	θ = 10–15°
c = 10.033 (2) Å	µ = 1.14 mm^−1
α = 94.64 (1)°	T = 298 K
β = 102.51 (1)°	Prism, blue
γ = 109.32 (1)°	0.4 × 0.1 × 0.1 mm
V = 1454.1 (5) Å^3

Data collection

Rigaku AFC-7R diffractometer	Rint = 0.021
θ/2θ scans	θmax = 27.5°
Absorption correction: integration (Coppens et al., 1965)	h = 0→16
Tmin = 0.472, Tmax = 0.753	k = −17→17
6956 measured reflections	l = −13→13
6651 independent reflections	3 standard reflections every 150 reflections
4193 reflections with I > 2σ(I)	intensity decay: none

Refinement

Refinement on F^2	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.045	w = 1/{σ^2Fo^2 + [0.05(Fo^2 + 2Fc^2)/3]^2}
wR(F^2) = 0.115	(Δ/σ)max = 0.006
S = 1.08	Δρmax = 0.41 e Å^−3
6651 reflections	Δρmin = −0.61 e Å^−3
304 parameters

Special details

Refinement. Refinement using reflections with F² > 0.0 σ(F²). The weighted R-factor (wR) and goodness of fit (S) are based on F². R-factor (gt) are based on F. The threshold expression of F² > 2.0 σ(F²) is used only for calculating R-factor (gt).

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

	x	y	z	Uiso*/Ueq
Cu1	0.39771 (3)	−0.01312 (3)	0.02690 (4)	0.0366 (1)
Cu2	0	0	0	0.0373 (2)
O1	0.4572 (2)	0.1533 (2)	0.0615 (3)	0.0577 (8)
O2	0.6285 (2)	0.1745 (2)	0.0140 (3)	0.0549 (8)
O3	0.3478 (2)	−0.0095 (2)	−0.1720 (2)	0.0528 (7)
O4	0.5191 (2)	0.0105 (2)	−0.2182 (2)	0.0494 (7)
O5	0.2223 (2)	−0.0375 (2)	0.0512 (2)	0.0474 (7)
O6	0.0631 (2)	−0.0846 (2)	0.1269 (2)	0.0459 (7)
N1	0.0861 (2)	0.1482 (2)	0.1369 (3)	0.0476 (8)
C1	0.5562 (3)	0.2117 (3)	0.0473 (4)	0.0483 (10)
C2	0.5913 (4)	0.3390 (3)	0.0746 (5)	0.067 (1)
C3	0.6623 (4)	0.3959 (4)	0.2214 (5)	0.075 (1)
C4	0.6890 (6)	0.5217 (4)	0.2334 (7)	0.122 (2)
C5	0.7745 (6)	0.3749 (6)	0.2594 (8)	0.140 (3)
C6	0.5900 (7)	0.3501 (6)	0.3214 (7)	0.157 (3)
C7	0.4136 (3)	0.0026 (3)	−0.2518 (3)	0.0402 (8)
C8	0.3630 (3)	0.0112 (3)	−0.4003 (3)	0.0453 (9)
C9	0.3677 (3)	0.1309 (3)	−0.4251 (4)	0.049 (1)
C10	0.3247 (4)	0.1264 (4)	−0.5803 (4)	0.068 (1)
C11	0.2911 (5)	0.1686 (4)	−0.3509 (5)	0.087 (2)
C12	0.4938 (4)	0.2136 (4)	−0.3737 (5)	0.085 (2)
C13	0.1618 (3)	−0.0919 (3)	0.1225 (3)	0.0399 (9)
C14	0.2032 (3)	−0.1699 (3)	0.2079 (4)	0.0490 (10)
C15	0.1138 (3)	−0.2806 (3)	0.2240 (4)	0.060 (1)
C16	0.0335 (5)	−0.3444 (4)	0.0878 (7)	0.107 (2)
C17	0.0414 (5)	−0.2575 (5)	0.3207 (6)	0.098 (2)
C18	0.1813 (5)	−0.3517 (5)	0.2887 (7)	0.111 (2)
C19	0.1754 (3)	0.2305 (3)	0.1093 (4)	0.052 (1)
C20	0.2279 (4)	0.3344 (4)	0.1951 (5)	0.075 (1)
C21	0.1902 (5)	0.3547 (4)	0.3086 (5)	0.082 (2)
C22	0.1013 (5)	0.2720 (4)	0.3367 (5)	0.076 (2)
C23	0.0488 (3)	0.1677 (3)	0.2497 (4)	0.056 (1)
C24	0.2145 (3)	0.2074 (3)	−0.0151 (5)	0.062 (1)
C25	−0.0476 (4)	0.0746 (4)	0.2784 (4)	0.071 (1)
H1	0.6373	0.3698	0.0123	0.0800*
H2	0.5211	0.3564	0.0558	0.0800*
H3	0.7307	0.5576	0.3269	0.1458*
H4	0.7362	0.5516	0.1720	0.1458*
H5	0.6170	0.5357	0.2089	0.1458*
H6	0.7581	0.2951	0.2520	0.1679*
H7	0.8216	0.4049	0.1978	0.1679*
H8	0.8162	0.4109	0.3528	0.1679*
H9	0.6327	0.3875	0.4140	0.1881*
H10	0.5175	0.3633	0.2976	0.1881*
H11	0.5738	0.2705	0.3157	0.1881*
H12	0.4059	−0.0130	−0.4570	0.0543*
H13	0.2825	−0.0384	−0.4281	0.0543*
H14	0.3273	0.2000	−0.5984	0.0813*
H15	0.3741	0.1027	−0.6271	0.0813*
H16	0.2457	0.0738	−0.6131	0.0813*
H17	0.3189	0.1718	−0.2531	0.1046*
H18	0.2935	0.2420	−0.3694	0.1046*
H19	0.2120	0.1159	−0.3829	0.1046*
H20	0.5214	0.2160	−0.2760	0.1021*
H21	0.5424	0.1894	−0.4214	0.1021*
H22	0.4970	0.2874	−0.3912	0.1021*
H23	0.2582	−0.1893	0.1670	0.0588*
H24	0.2426	−0.1279	0.2993	0.0588*
H25	−0.0096	−0.3001	0.0467	0.1289*
H26	0.0785	−0.3599	0.0277	0.1289*
H27	−0.0201	−0.4141	0.1012	0.1289*
H28	0.0930	−0.2170	0.4087	0.1180*
H29	−0.0021	−0.2132	0.2805	0.1180*
H30	−0.0118	−0.3277	0.3333	0.1180*
H31	0.1273	−0.4214	0.3015	0.1329*
H32	0.2264	−0.3672	0.2287	0.1329*
H33	0.2329	−0.3112	0.3767	0.1329*
H34	0.2910	0.3923	0.1744	0.0897*
H35	0.2262	0.4267	0.3681	0.0989*
H36	0.0743	0.2853	0.4168	0.0914*
H37	0.2397	0.1442	−0.0088	0.0750*
H38	0.1507	0.1906	−0.0961	0.0750*
H39	0.2783	0.2725	−0.0212	0.0750*
H40	−0.0655	0.0994	0.3610	0.0851*
H41	−0.1159	0.0533	0.2019	0.0851*
H42	−0.0238	0.0109	0.2907	0.0851*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0316 (2)	0.0394 (2)	0.0408 (2)	0.0139 (2)	0.0093 (2)	0.0128 (2)
Cu2	0.0322 (3)	0.0418 (3)	0.0457 (3)	0.0181 (3)	0.0151 (3)	0.0147 (3)
O1	0.051 (1)	0.044 (1)	0.080 (2)	0.022 (1)	0.014 (1)	0.011 (1)
O2	0.058 (2)	0.040 (1)	0.067 (2)	0.015 (1)	0.023 (1)	0.007 (1)
O3	0.038 (1)	0.079 (2)	0.045 (1)	0.021 (1)	0.011 (1)	0.023 (1)
O4	0.043 (1)	0.066 (2)	0.045 (1)	0.026 (1)	0.011 (1)	0.017 (1)
O5	0.041 (1)	0.054 (1)	0.059 (1)	0.023 (1)	0.021 (1)	0.027 (1)
O6	0.038 (1)	0.050 (1)	0.059 (1)	0.020 (1)	0.019 (1)	0.022 (1)
N1	0.043 (1)	0.051 (2)	0.054 (2)	0.024 (1)	0.010 (1)	0.012 (1)
C1	0.053 (2)	0.036 (2)	0.048 (2)	0.013 (2)	0.002 (2)	0.010 (2)
C2	0.084 (3)	0.040 (2)	0.078 (3)	0.021 (2)	0.024 (2)	0.016 (2)
C3	0.082 (3)	0.046 (2)	0.080 (3)	0.003 (2)	0.020 (3)	−0.002 (2)
C4	0.147 (5)	0.048 (3)	0.137 (5)	0.007 (3)	0.027 (4)	−0.015 (3)
C5	0.104 (5)	0.108 (5)	0.157 (6)	0.027 (4)	−0.035 (4)	−0.025 (5)
C6	0.200 (8)	0.128 (6)	0.093 (5)	−0.019 (5)	0.074 (5)	−0.015 (4)
C7	0.040 (2)	0.038 (2)	0.041 (2)	0.015 (1)	0.006 (1)	0.008 (1)
C8	0.047 (2)	0.049 (2)	0.039 (2)	0.020 (2)	0.006 (1)	0.008 (1)
C9	0.056 (2)	0.051 (2)	0.043 (2)	0.023 (2)	0.011 (2)	0.013 (2)
C10	0.085 (3)	0.077 (3)	0.048 (2)	0.038 (3)	0.009 (2)	0.023 (2)
C11	0.136 (5)	0.087 (3)	0.089 (3)	0.078 (4)	0.061 (3)	0.039 (3)
C12	0.082 (3)	0.066 (3)	0.084 (3)	0.006 (2)	0.000 (3)	0.033 (3)
C13	0.037 (2)	0.040 (2)	0.044 (2)	0.015 (1)	0.011 (1)	0.010 (1)
C14	0.039 (2)	0.050 (2)	0.061 (2)	0.017 (2)	0.013 (2)	0.026 (2)
C15	0.051 (2)	0.047 (2)	0.080 (3)	0.014 (2)	0.011 (2)	0.028 (2)
C16	0.117 (4)	0.049 (3)	0.127 (5)	0.027 (3)	−0.016 (4)	−0.004 (3)
C17	0.086 (4)	0.110 (4)	0.118 (4)	0.033 (3)	0.054 (3)	0.062 (4)
C18	0.084 (3)	0.083 (4)	0.181 (6)	0.038 (3)	0.029 (4)	0.087 (4)
C19	0.044 (2)	0.046 (2)	0.068 (2)	0.020 (2)	0.008 (2)	0.019 (2)
C20	0.068 (3)	0.050 (3)	0.089 (3)	0.012 (2)	−0.003 (2)	0.018 (2)
C21	0.100 (4)	0.055 (3)	0.075 (3)	0.026 (3)	−0.003 (3)	−0.003 (2)
C22	0.092 (3)	0.077 (3)	0.063 (3)	0.043 (3)	0.012 (2)	0.000 (2)
C23	0.052 (2)	0.062 (2)	0.056 (2)	0.027 (2)	0.007 (2)	0.007 (2)
C24	0.045 (2)	0.053 (2)	0.097 (3)	0.017 (2)	0.027 (2)	0.031 (2)
C25	0.058 (2)	0.097 (4)	0.061 (3)	0.028 (2)	0.022 (2)	0.006 (2)

Geometric parameters (Å, º)

Cu1—Cu1^i	2.652 (1)	C9—C12	1.526 (6)
Cu1—O1	1.972 (3)	C10—H14	0.960
Cu1—O2^i	1.965 (2)	C10—H15	0.960
Cu1—O3	1.967 (2)	C10—H16	0.960
Cu1—O4^i	1.967 (2)	C11—H17	0.960
Cu1—O5	2.185 (2)	C11—H18	0.960
Cu2—O5	2.923 (2)	C11—H19	0.960
Cu2—O6	1.938 (2)	C12—H20	0.960
Cu2—O6^ii	1.938 (2)	C12—H21	0.960
Cu2—N1	2.050 (3)	C12—H22	0.960
Cu2—N1^ii	2.050 (3)	C13—C14	1.509 (4)
O1—C1	1.263 (4)	C14—C15	1.529 (5)
O2—C1	1.243 (4)	C14—H23	0.960
O3—C7	1.252 (4)	C14—H24	0.960
O4—C7	1.259 (4)	C15—C16	1.491 (7)
O5—C13	1.238 (4)	C15—C17	1.537 (6)
O6—C13	1.280 (3)	C15—C18	1.523 (6)
N1—C19	1.353 (4)	C16—H25	0.960
N1—C23	1.350 (4)	C16—H26	0.960
C1—C2	1.516 (5)	C16—H27	0.960
C2—C3	1.523 (6)	C17—H28	0.960
C2—H1	0.960	C17—H29	0.960
C2—H2	0.960	C17—H30	0.960
C3—C4	1.513 (7)	C18—H31	0.960
C3—C5	1.492 (8)	C18—H32	0.960
C3—C6	1.518 (7)	C18—H33	0.960
C4—H3	0.960	C19—C20	1.385 (6)
C4—H4	0.960	C19—C24	1.478 (6)
C4—H5	0.961	C20—C21	1.361 (7)
C5—H6	0.961	C20—H34	0.960
C5—H7	0.960	C21—C22	1.355 (7)
C5—H8	0.960	C21—H35	0.960
C6—H9	0.960	C22—C23	1.395 (6)
C6—H10	0.961	C22—H36	0.960
C6—H11	0.960	C23—C25	1.485 (6)
C7—C8	1.515 (4)	C24—H37	0.960
C8—C9	1.548 (5)	C24—H38	0.960
C8—H12	0.960	C24—H39	0.960
C8—H13	0.960	C25—H40	0.960
C9—C10	1.523 (5)	C25—H41	0.960
C9—C11	1.503 (5)	C25—H42	0.960
Cu1···Cu1^i	2.6515 (9)
Cu1^i—Cu1—O1	84.2 (1)	C9—C10—H14	109.5
Cu1^i—Cu1—O2^i	83.6 (1)	C9—C10—H15	109.5
Cu1^i—Cu1—O3	83.3 (1)	C9—C10—H16	109.5
Cu1^i—Cu1—O4^i	84.4 (1)	H14—C10—H15	109.5
Cu1^i—Cu1—O5	174.9 (1)	H14—C10—H16	109.5
O1—Cu1—O2^i	167.7 (1)	H15—C10—H16	109.5
O1—Cu1—O3	88.9 (1)	C9—C11—H17	109.5
O1—Cu1—O4^i	89.1 (1)	C9—C11—H18	109.5
O1—Cu1—O5	96.7 (1)	C9—C11—H19	109.5
O2^i—Cu1—O3	90.3 (1)	H17—C11—H18	109.5
O2^i—Cu1—O4^i	89.1 (1)	H17—C11—H19	109.4
O2^i—Cu1—O5	95.6 (1)	H18—C11—H19	109.5
O3—Cu1—O4^i	167.7 (1)	C9—C12—H20	109.5
O3—Cu1—O5	91.7 (1)	C9—C12—H21	109.5
O4^i—Cu1—O5	100.7 (1)	C9—C12—H22	109.5
O6—Cu2—O6^ii	180.0	H20—C12—H21	109.4
O6—Cu2—N1	92.2 (1)	H20—C12—H22	109.5
O6—Cu2—N1^ii	87.8 (1)	H21—C12—H22	109.5
O6^ii—Cu2—N1	87.8 (1)	O5—C13—O6	121.9 (3)
O6^ii—Cu2—N1^ii	92.2 (1)	O5—C13—C14	120.4 (3)
N1—Cu2—N1^ii	180.0	O6—C13—C14	117.7 (3)
Cu1—O1—C1	122.4 (2)	C13—C14—C15	119.4 (3)
Cu1^i—O2—C1	124.0 (2)	C13—C14—H23	106.9
Cu1—O3—C7	124.2 (2)	C13—C14—H24	106.9
Cu1^i—O4—C7	122.7 (2)	C15—C14—H23	106.9
Cu1—O5—C13	134.1 (2)	C15—C14—H24	106.9
Cu2—O6—C13	117.8 (2)	H23—C14—H24	109.5
Cu2—N1—C19	120.1 (2)	C14—C15—C16	111.6 (4)
Cu2—N1—C23	120.3 (2)	C14—C15—C17	110.3 (4)
C19—N1—C23	119.4 (3)	C14—C15—C18	107.6 (3)
O1—C1—O2	125.9 (3)	C16—C15—C17	109.4 (4)
O1—C1—C2	117.4 (3)	C16—C15—C18	109.1 (4)
O2—C1—C2	116.7 (3)	C17—C15—C18	108.7 (4)
C1—C2—C3	115.2 (3)	C15—C16—H25	109.5
C1—C2—H1	108.0	C15—C16—H26	109.5
C1—C2—H2	108.0	C15—C16—H27	109.5
C3—C2—H1	108.0	H25—C16—H26	109.5
C3—C2—H2	108.0	H25—C16—H27	109.5
H1—C2—H2	109.5	H26—C16—H27	109.5
C2—C3—C4	109.1 (4)	C15—C17—H28	109.5
C2—C3—C5	111.9 (4)	C15—C17—H29	109.5
C2—C3—C6	108.8 (4)	C15—C17—H30	109.5
C4—C3—C5	109.1 (5)	H28—C17—H29	109.5
C4—C3—C6	108.9 (5)	H28—C17—H30	109.5
C5—C3—C6	109.0 (6)	H29—C17—H30	109.5
C3—C4—H3	109.5	C15—C18—H31	109.5
C3—C4—H4	109.5	C15—C18—H32	109.5
C3—C4—H5	109.5	C15—C18—H33	109.5
H3—C4—H4	109.5	H31—C18—H32	109.4
H3—C4—H5	109.4	H31—C18—H33	109.5
H4—C4—H5	109.4	H32—C18—H33	109.4
C3—C5—H6	109.5	N1—C19—C20	120.6 (4)
C3—C5—H7	109.5	N1—C19—C24	118.5 (3)
C3—C5—H8	109.5	C20—C19—C24	120.9 (4)
H6—C5—H7	109.4	C19—C20—C21	120.2 (4)
H6—C5—H8	109.4	C19—C20—H34	119.9
H7—C5—H8	109.5	C21—C20—H34	119.9
C3—C6—H9	109.5	C20—C21—C22	119.2 (4)
C3—C6—H10	109.5	C20—C21—H35	120.4
C3—C6—H11	109.5	C22—C21—H35	120.4
H9—C6—H10	109.4	C21—C22—C23	120.3 (4)
H9—C6—H11	109.5	C21—C22—H36	119.9
H10—C6—H11	109.4	C23—C22—H36	119.9
O3—C7—O4	125.3 (3)	N1—C23—C22	120.3 (4)
O3—C7—C8	117.4 (3)	N1—C23—C25	117.9 (3)
O4—C7—C8	117.3 (3)	C22—C23—C25	121.8 (4)
C7—C8—C9	114.9 (3)	C19—C24—H37	109.5
C7—C8—H12	108.1	C19—C24—H38	109.5
C7—C8—H13	108.1	C19—C24—H39	109.5
C9—C8—H12	108.1	H37—C24—H38	109.5
C9—C8—H13	108.1	H37—C24—H39	109.5
H12—C8—H13	109.5	H38—C24—H39	109.5
C8—C9—C10	107.9 (3)	C23—C25—H40	109.5
C8—C9—C11	110.7 (3)	C23—C25—H41	109.5
C8—C9—C12	109.5 (3)	C23—C25—H42	109.5
C10—C9—C11	109.8 (3)	H40—C25—H41	109.5
C10—C9—C12	109.3 (3)	H40—C25—H42	109.5
C11—C9—C12	109.7 (4)	H41—C25—H42	109.5
Cu1—O5—C13—O6	173.8 (2)	Cu2—O6—C13—O5	7.7 (4)

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

(II)

Crystal data

[Cu2(C5H9O2)4(C7H9N)2]	Z = 1
Mr = 745.90	Dx = 1.254 Mg m^−3
Triclinic, P1	Mo Kα radiation, λ = 0.71073 Å
a = 10.986 (4) Å	Cell parameters from 25 reflections
b = 11.195 (5) Å	θ = 10–15°
c = 9.564 (4) Å	µ = 1.12 mm^−1
α = 107.66 (4)°	T = 298 K
β = 97.15 (4)°	Prism, green
γ = 61.82 (3)°	0.25 × 0.20 × 0.20 mm
V = 987.7 (8) Å^3

Data collection

Rigaku AFC-7R diffractometer	3449 reflections with I > 2σ(I)
θ/2θ scans	Rint = 0.047
Absorption correction: integration (Coppens et al., 1965)	θmax = 27.5°
Tmin = 0.803, Tmax = 0.844	h = 0→14
4761 measured reflections	k = −15→15
4524 independent reflections	l = −12→3

Refinement

Refinement on F^2	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.048	w = 1/{σ^2Fo^2 + [0.1(Fo^2 + 2Fc^2)/3]^2}
wR(F^2) = 0.152	(Δ/σ)max = 0.027
S = 1.05	Δρmax = 0.74 e Å^−3
4524 reflections	Δρmin = −0.36 e Å^−3
226 parameters

Special details

Refinement. Refinement using reflections with F² > 0.0 σ(F²). The weighted R-factor (wR) and goodness of fit (S) are based on F². R-factor (gt) are based on F. The threshold expression of F² > 2.0 σ(F²) is used only for calculating R-factor (gt).

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cu1	−0.01511 (4)	0.40360 (4)	0.04544 (4)	0.0439 (1)
O1	−0.1781 (3)	0.5732 (3)	0.1470 (3)	0.0629 (7)
O2	−0.1534 (3)	0.7324 (2)	0.0759 (3)	0.0632 (7)
O3	−0.1197 (3)	0.3867 (3)	−0.1353 (3)	0.0679 (8)
O4	−0.0968 (3)	0.5465 (3)	−0.2065 (3)	0.0684 (8)
N1	−0.0467 (3)	0.2424 (3)	0.1297 (3)	0.0603 (9)
C1	−0.2134 (3)	0.6970 (3)	0.1469 (3)	0.0523 (8)
C2	−0.3373 (4)	0.8138 (4)	0.2429 (5)	0.076 (1)
C3A	−0.415 (1)	0.937 (1)	0.176 (1)	0.109 (4)	0.50
C3B	−0.384 (1)	0.960 (1)	0.236 (1)	0.104 (4)	0.50
C4A	−0.269 (2)	0.873 (2)	0.387 (2)	0.149 (6)	0.50
C4B	−0.285 (2)	0.813 (2)	0.400 (2)	0.221 (10)	0.50
C5A	−0.413 (1)	0.767 (2)	0.312 (2)	0.156 (6)	0.50
C5B	−0.448 (1)	0.773 (1)	0.245 (2)	0.170 (6)	0.50
C6	−0.1404 (3)	0.4580 (4)	−0.2219 (4)	0.0582 (9)
C7	−0.2276 (5)	0.4388 (5)	−0.3566 (4)	0.083 (1)
C8A	−0.360 (2)	0.589 (2)	−0.339 (2)	0.131 (5)	0.50
C8B	−0.374 (2)	0.535 (2)	−0.304 (2)	0.180 (8)	0.50
C9A	−0.155 (1)	0.425 (1)	−0.491 (1)	0.095 (3)	0.50
C9B	−0.218 (2)	0.490 (2)	−0.475 (2)	0.164 (8)	0.50
C10A	−0.283 (2)	0.337 (2)	−0.363 (2)	0.129 (6)	0.50
C10B	−0.214 (1)	0.286 (1)	−0.407 (2)	0.121 (5)	0.50
C11	0.0619 (5)	0.1413 (4)	0.1795 (4)	0.074 (1)
C12	0.0482 (7)	0.0351 (5)	0.2150 (6)	0.103 (2)
C13	−0.0786 (9)	0.0358 (7)	0.1989 (7)	0.122 (3)
C14	−0.1861 (7)	0.1379 (6)	0.1553 (6)	0.107 (2)
C15	−0.1712 (5)	0.2421 (5)	0.1203 (4)	0.075 (1)
C16	0.1960 (5)	0.1425 (5)	0.1934 (6)	0.098 (2)
C17	−0.2912 (5)	0.3521 (6)	0.0704 (6)	0.098 (2)
H1A	−0.3501	0.9636	0.1514	0.1026*	0.50
H1B	−0.3072	0.9812	0.2555	0.0988*	0.50
H2A	−0.4590	0.9091	0.0877	0.1026*	0.50
H2B	−0.4177	0.9678	0.1397	0.0988*	0.50
H3A	−0.4826	1.0155	0.2445	0.1026*	0.50
H3B	−0.4560	1.0250	0.3077	0.0988*	0.50
H4A	−0.2113	0.7973	0.4304	0.1285*	0.50
H4B	−0.2536	0.7204	0.4106	0.1803*	0.50
H5A	−0.2134	0.9090	0.3620	0.1285*	0.50
H5B	−0.2110	0.8372	0.4166	0.1803*	0.50
H6A	−0.3400	0.9466	0.4567	0.1285*	0.50
H6B	−0.3596	0.8803	0.4686	0.1803*	0.50
H7A	−0.4792	0.8461	0.3823	0.1169*	0.50
H7B	−0.5152	0.8422	0.3189	0.1160*	0.50
H8A	−0.4634	0.7278	0.2361	0.1169*	0.50
H8B	−0.4924	0.7693	0.1496	0.1160*	0.50
H9A	−0.3509	0.6966	0.3565	0.1169*	0.50
H9B	−0.4085	0.6826	0.2607	0.1160*	0.50
H10A	−0.3314	0.6602	−0.3241	0.1236*	0.50
H10B	−0.3884	0.6304	−0.2716	0.1596*	0.50
H11A	−0.4143	0.5866	−0.4258	0.1236*	0.50
H11B	−0.4352	0.5252	−0.3826	0.1596*	0.50
H12A	−0.4153	0.6100	−0.2558	0.1236*	0.50
H12B	−0.3923	0.5101	−0.2239	0.1596*	0.50
H13A	−0.0716	0.3362	−0.5131	0.0953*	0.50
H13B	−0.1263	0.4342	−0.5183	0.1628*	0.50
H14A	−0.2146	0.4279	−0.5730	0.0953*	0.50
H14B	−0.2838	0.4821	−0.5484	0.1628*	0.50
H15A	−0.1314	0.5007	−0.4702	0.0953*	0.50
H15B	−0.2363	0.5866	−0.4369	0.1628*	0.50
H16A	−0.3330	0.3656	−0.2744	0.1302*	0.50
H16B	−0.2354	0.2656	−0.3251	0.1136*	0.50
H17A	−0.3418	0.3352	−0.4456	0.1302*	0.50
H17B	−0.2770	0.2800	−0.4843	0.1136*	0.50
H18A	−0.2064	0.2436	−0.3744	0.1302*	0.50
H18B	−0.1212	0.2191	−0.4412	0.1136*	0.50
H19	0.1256	−0.0362	0.2503	0.1211*
H20	−0.0878	−0.0381	0.2207	0.1419*
H21	−0.2735	0.1373	0.1465	0.1315*
H22	0.2627	0.0658	0.2301	0.1191*
H23	0.2270	0.1330	0.0992	0.1191*
H24	0.1865	0.2304	0.2605	0.1191*
H25	−0.3092	0.4429	0.1357	0.1168*
H26	−0.2731	0.3485	−0.0271	0.1168*
H27	−0.3706	0.3369	0.0691	0.1168*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0442 (2)	0.0466 (2)	0.0401 (2)	−0.0195 (2)	0.0011 (1)	0.0124 (1)
O1	0.056 (1)	0.060 (1)	0.069 (2)	−0.021 (1)	0.017 (1)	0.014 (1)
O2	0.058 (1)	0.053 (1)	0.069 (2)	−0.014 (1)	0.016 (1)	0.018 (1)
O3	0.071 (2)	0.091 (2)	0.055 (1)	−0.047 (1)	−0.015 (1)	0.025 (1)
O4	0.079 (2)	0.075 (2)	0.056 (1)	−0.039 (1)	−0.021 (1)	0.026 (1)
N1	0.077 (2)	0.054 (2)	0.051 (2)	−0.031 (1)	0.008 (1)	0.010 (1)
C1	0.044 (2)	0.056 (2)	0.049 (2)	−0.017 (1)	0.001 (1)	0.014 (1)
C2	0.061 (2)	0.060 (2)	0.084 (3)	−0.007 (2)	0.026 (2)	0.016 (2)
C3A	0.076 (6)	0.078 (7)	0.14 (1)	0.010 (5)	0.038 (7)	0.053 (7)
C3B	0.098 (8)	0.080 (7)	0.118 (9)	−0.024 (6)	0.041 (7)	0.017 (6)
C4A	0.13 (1)	0.16 (1)	0.085 (9)	−0.06 (1)	0.035 (9)	−0.058 (9)
C4B	0.12 (2)	0.27 (3)	0.13 (2)	−0.03 (2)	0.05 (1)	−0.05 (2)
C5A	0.12 (1)	0.10 (1)	0.21 (2)	−0.007 (8)	0.13 (1)	0.035 (10)
C5B	0.057 (6)	0.075 (8)	0.34 (2)	−0.023 (6)	0.08 (1)	−0.01 (1)
C6	0.049 (2)	0.069 (2)	0.044 (2)	−0.022 (2)	−0.005 (1)	0.009 (2)
C7	0.085 (3)	0.103 (3)	0.059 (2)	−0.049 (3)	−0.030 (2)	0.024 (2)
C8A	0.073 (8)	0.16 (1)	0.13 (1)	−0.039 (8)	−0.050 (8)	0.05 (1)
C8B	0.081 (10)	0.26 (2)	0.15 (1)	−0.06 (1)	−0.057 (9)	0.03 (2)
C9A	0.101 (7)	0.128 (9)	0.033 (4)	−0.044 (7)	−0.006 (4)	0.009 (4)
C9B	0.24 (2)	0.26 (2)	0.081 (9)	−0.17 (2)	−0.07 (1)	0.08 (1)
C10A	0.16 (1)	0.14 (1)	0.113 (9)	−0.10 (1)	−0.07 (1)	0.042 (9)
C10B	0.17 (1)	0.118 (9)	0.080 (7)	−0.087 (10)	−0.062 (8)	0.019 (7)
C11	0.102 (3)	0.055 (2)	0.059 (2)	−0.027 (2)	0.018 (2)	0.015 (2)
C12	0.150 (5)	0.063 (3)	0.091 (3)	−0.033 (3)	0.026 (3)	0.029 (2)
C13	0.188 (7)	0.091 (4)	0.125 (5)	−0.087 (5)	0.037 (5)	0.026 (3)
C14	0.157 (6)	0.094 (4)	0.104 (4)	−0.086 (4)	0.026 (4)	0.014 (3)
C15	0.100 (3)	0.080 (3)	0.062 (2)	−0.059 (3)	0.016 (2)	0.003 (2)
C16	0.088 (3)	0.089 (3)	0.115 (4)	−0.021 (3)	−0.009 (3)	0.064 (3)
C17	0.073 (3)	0.134 (4)	0.120 (4)	−0.067 (3)	−0.007 (3)	0.048 (3)

Geometric parameters (Å, º)

Cu1—Cu1^i	2.722 (1)	C7—C8B	1.494 (5)
Cu1—O1	1.964 (2)	C7—C9A	1.526 (5)
Cu1—O2^i	1.973 (2)	C7—C9B	1.450 (5)
Cu1—O3	1.964 (2)	C7—C10A	1.509 (5)
Cu1—O4^i	1.962 (3)	C7—C10B	1.566 (5)
Cu1—N1	2.360 (3)	C8A—H10A	0.955
O1—C1	1.250 (4)	C8A—H11A	0.959
O2—C1	1.256 (4)	C8A—H12A	0.964
O3—C6	1.248 (4)	C8B—H10B	0.953
O4—C6	1.255 (4)	C8B—H11B	0.961
N1—C11	1.357 (5)	C8B—H12B	0.966
N1—C15	1.360 (5)	C9A—H13A	0.962
C1—C2	1.519 (4)	C9A—H14A	0.959
C2—C3A	1.526 (4)	C9A—H15A	0.958
C2—C3B	1.490 (4)	C9B—H13B	0.963
C2—C4A	1.602 (5)	C9B—H14B	0.960
C2—C4B	1.541 (5)	C9B—H15B	0.957
C2—C5A	1.470 (4)	C10A—H16A	0.955
C2—C5B	1.491 (4)	C10A—H17A	0.960
C3A—H1A	0.963	C10A—H18A	0.963
C3A—H2A	0.963	C10B—H16B	0.961
C3A—H3A	0.956	C10B—H17B	0.958
C3B—H1B	0.956	C10B—H18B	0.962
C3B—H2B	0.961	C11—C12	1.407 (6)
C3B—H3B	0.959	C11—C16	1.468 (7)
C4A—H4A	0.964	C12—C13	1.378 (9)
C4A—H5A	0.957	C12—H19	0.961
C4A—H6A	0.961	C13—C14	1.329 (9)
C4B—H4B	0.959	C13—H20	0.963
C4B—H5B	0.952	C14—C15	1.390 (7)
C4B—H6B	0.962	C14—H21	0.957
C5A—H7A	0.955	C15—C17	1.466 (7)
C5A—H8A	0.982	C16—H22	0.960
C5A—H9A	0.946	C16—H23	0.961
C5B—H7B	0.953	C16—H24	0.963
C5B—H8B	0.976	C17—H25	0.958
C5B—H9B	0.947	C17—H26	0.962
C6—C7	1.530 (5)	C17—H27	0.961
C7—C8A	1.600 (5)
Cu1···Cu1^i	2.7223 (7)	C11···C14^ii	3.589 (7)
N1···C13^ii	3.544 (7)	C12···C15^ii	3.580 (6)
C11···C13^ii	3.540 (8)
Cu1^i—Cu1—O1	81.8 (1)	C6—C7—C8A	105.7 (3)
Cu1^i—Cu1—O2^i	83.7 (1)	C6—C7—C8B	105.0 (3)
Cu1^i—Cu1—O3	84.2 (1)	C6—C7—C9A	108.5 (3)
Cu1^i—Cu1—O4^i	81.1 (1)	C6—C7—C9B	116.6 (3)
Cu1^i—Cu1—N1	178.2 (1)	C6—C7—C10A	113.7 (3)
O1—Cu1—O2^i	165.5 (1)	C6—C7—C10B	111.3 (3)
O1—Cu1—O3	90.7 (1)	C8A—C7—C9A	101.6 (3)
O1—Cu1—O4^i	88.1 (1)	C8A—C7—C10A	105.8 (3)
O1—Cu1—N1	96.4 (1)	C8B—C7—C9B	102.0 (3)
O2^i—Cu1—O3	87.1 (1)	C8B—C7—C10B	105.8 (3)
O2^i—Cu1—O4^i	90.4 (1)	C9A—C7—C10A	120.0 (3)
O2^i—Cu1—N1	98.1 (1)	C9B—C7—C10B	114.5 (3)
O3—Cu1—O4^i	165.3 (1)	C7—C8A—H10A	109.5
O3—Cu1—N1	96.2 (1)	C7—C8A—H11A	109.5
O4^i—Cu1—N1	98.5 (1)	C7—C8A—H12A	109.1
Cu1—O1—C1	126.0 (2)	H10A—C8A—H11A	109.9
Cu1^i—O2—C1	123.2 (2)	H10A—C8A—H12A	109.6
Cu1—O3—C6	123.0 (2)	H11A—C8A—H12A	109.2
Cu1^i—O4—C6	126.6 (2)	C7—C8B—H10B	109.7
Cu1—N1—C11	120.4 (3)	C7—C8B—H11B	109.6
Cu1—N1—C15	121.1 (3)	C7—C8B—H12B	109.2
C11—N1—C15	118.4 (4)	H10B—C8B—H11B	109.9
O1—C1—O2	125.2 (3)	H10B—C8B—H12B	109.5
O1—C1—C2	117.2 (3)	H11B—C8B—H12B	108.9
O2—C1—C2	117.5 (3)	C7—C9A—H13A	109.5
C1—C2—C3A	110.7 (3)	C7—C9A—H14A	109.5
C1—C2—C3B	116.9 (3)	C7—C9A—H15A	109.3
C1—C2—C4A	103.3 (3)	H13A—C9A—H14A	109.4
C1—C2—C4B	103.2 (3)	H13A—C9A—H15A	109.5
C1—C2—C5A	115.8 (3)	H14A—C9A—H15A	109.7
C1—C2—C5B	112.8 (3)	C7—C9B—H13B	109.5
C3A—C2—C4A	104.9 (3)	C7—C9B—H14B	109.6
C3A—C2—C5A	120.7 (3)	C7—C9B—H15B	109.4
C3B—C2—C4B	105.4 (3)	H13B—C9B—H14B	109.2
C3B—C2—C5B	116.5 (3)	H13B—C9B—H15B	109.4
C4A—C2—C5A	98.2 (3)	H14B—C9B—H15B	109.7
C4B—C2—C5B	98.9 (2)	C7—C10A—H16A	109.4
C2—C3A—H1A	109.4	C7—C10A—H17A	109.3
C2—C3A—H2A	109.7	C7—C10A—H18A	109.3
C2—C3A—H3A	109.6	H16A—C10A—H17A	110.0
H1A—C3A—H2A	109.0	H16A—C10A—H18A	109.7
H1A—C3A—H3A	109.6	H17A—C10A—H18A	109.2
H2A—C3A—H3A	109.6	C7—C10B—H16B	109.4
C2—C3B—H1B	109.2	C7—C10B—H17B	109.7
C2—C3B—H2B	109.5	C7—C10B—H18B	109.6
C2—C3B—H3B	109.1	H16B—C10B—H17B	109.6
H1B—C3B—H2B	109.7	H16B—C10B—H18B	109.2
H1B—C3B—H3B	109.9	H17B—C10B—H18B	109.5
H2B—C3B—H3B	109.5	N1—C11—C12	121.1 (5)
C2—C4A—H4A	109.2	N1—C11—C16	118.9 (4)
C2—C4A—H5A	110.0	C12—C11—C16	120.0 (5)
C2—C4A—H6A	109.6	C11—C12—C13	118.6 (5)
H4A—C4A—H5A	109.4	C11—C12—H19	120.6
H4A—C4A—H6A	109.1	C13—C12—H19	120.7
H5A—C4A—H6A	109.6	C12—C13—C14	120.2 (5)
C2—C4B—H4B	108.9	C12—C13—H20	118.9
C2—C4B—H5B	109.5	C14—C13—H20	120.9
C2—C4B—H6B	108.9	C13—C14—C15	120.6 (6)
H4B—C4B—H5B	110.2	C13—C14—H21	118.8
H4B—C4B—H6B	109.4	C15—C14—H21	120.6
H5B—C4B—H6B	110.0	N1—C15—C14	121.0 (5)
C2—C5A—H7A	109.9	N1—C15—C17	119.7 (4)
C2—C5A—H8A	108.7	C14—C15—C17	119.3 (5)
C2—C5A—H9A	110.2	C11—C16—H22	109.9
H7A—C5A—H8A	108.1	C11—C16—H23	109.8
H7A—C5A—H9A	111.1	C11—C16—H24	109.4
H8A—C5A—H9A	108.8	H22—C16—H23	109.4
C2—C5B—H7B	109.4	H22—C16—H24	109.2
C2—C5B—H8B	108.6	H23—C16—H24	109.1
C2—C5B—H9B	109.6	C15—C17—H25	109.6
H7B—C5B—H8B	108.7	C15—C17—H26	109.6
H7B—C5B—H9B	111.2	C15—C17—H27	109.5
H8B—C5B—H9B	109.2	H25—C17—H26	109.4
O3—C6—O4	125.1 (3)	H25—C17—H27	109.5
O3—C6—C7	118.1 (4)	H26—C17—H27	109.2
O4—C6—C7	116.8 (3)

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