In the crystals of the five title compounds, tetrakis-(μ-3,3-dimethylbutyrato-
O:
O′)bis(ethanol-
O)dicopper(II)–ethanol (1/2), [Cu
2(C
6H
11O
2)
4(C
2H
6O)
2]·2C
2H
6O, (I), tetrakis(μ-3,3-dimethylbutyrato-
O:
O′)bis(2-methylpyridine-
N)dicopper(II), [Cu
2(C
6H
11O
2)
4(C
6H
7N)
2], (II), tetrakis-(μ-3,3-dimethylbutyrato-
O:
O′)bis(3-methylpyridine-
N)di-copper(II), [Cu
2(C
6H
11O
2)
4(C
6H
7N)
2], (III), tetrakis-(μ-3,3-dimethylbutyrato-
O:
O′)bis(4-methylpyridine-
N)di-copper(II), [Cu
2(C
6H
11O
2)
4(C
6H
7N)
2], (IV), and tetrakis-(μ-3,3-dimethylbutyrato-
O:
O′)bis(3,3-dimethylbutyric acid-
O)dicopper(II), [Cu
2(C
6H
11O
2)
4(C
6H
12O
2)
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.
Supporting information
CCDC references: 140911; 140912; 140913; 140914; 140915
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) Å3, 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).
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, Uiso(H) = 0.3 Å2 for (I), 0.2 Å2 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).
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.
(I) tetrakis(µ-3,3-dimethylbutyrato-
O:
O')di(ethanol-O)dicopper(II) diethanol solvate
top
Crystal data top
[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) Å3 | 0.5 × 0.4 × 0.3 mm |
Data collection top
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 top
Refinement on F | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.076 | w = 1/[σ2(F) + 0.000225F2] |
wR(F2) = 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 | |
Crystal data top
[Cu2(C6H11O2)4(C2H6O)2]·2C2H6O | γ = 88.43 (1)° |
Mr = 771.98 | V = 1065.8 (3) Å3 |
Triclinic, P1 | Z = 1 |
a = 10.765 (2) Å | Mo Kα radiation |
b = 10.923 (2) Å | µ = 1.05 mm−1 |
c = 9.820 (1) Å | T = 299 K |
α = 105.43 (1)° | 0.5 × 0.4 × 0.3 mm |
β = 106.50 (1)° | |
Data collection top
Rigaku AFC-5 diffractometer | 3646 reflections with |Fo| > 3σ(|Fo|) |
Absorption correction: integration (Coppens et al., 1965) | Rint = 0.012 |
Tmin = 0.569, Tmax = 0.822 | 3 standard reflections every 100 reflections |
5151 measured reflections | intensity decay: none |
4888 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.076 | 182 parameters |
wR(F2) = 0.077 | H-atom parameters constrained |
S = 1.44 | Δρmax = 1.23 e Å−3 |
3646 reflections | Δρmin = −0.91 e Å−3 |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | 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 (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
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) top
Cu1—Cu1i | 2.602 (3) | C10—H10B | 0.960 |
Cu1—O2 | 1.971 (3) | C12—H12A | 0.960 |
Cu1—O3i | 1.968 (3) | C12—H12B | 0.960 |
Cu1—O4 | 1.952 (3) | C12—H12C | 0.960 |
Cu1—O5i | 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—O3i | 168.9 (1) | H12A—C12—H12B | 109.3 |
O2—Cu1—O4 | 89.7 (2) | H12A—C12—H12C | 109.3 |
O2—Cu1—O5i | 90.1 (2) | H12B—C12—H12C | 109.0 |
O2—Cu1—O6 | 97.3 (1) | C11—C13—H13A | 106.6 |
O3i—Cu1—O4 | 89.8 (2) | C11—C13—H13B | 112.0 |
O3i—Cu1—O5i | 88.2 (2) | C11—C13—H13C | 108.7 |
O3i—Cu1—O6 | 93.7 (1) | H13A—C13—H13B | 110.3 |
O4—Cu1—O5i | 168.8 (2) | H13A—C13—H13C | 110.3 |
O4—Cu1—O6 | 96.6 (2) | H13B—C13—H13C | 109.0 |
O5i—Cu1—O6 | 94.5 (2) | C11—C14—H14A | 113.3 |
Cu1—O2—C9 | 126.6 (3) | C11—C14—H14B | 109.0 |
Cu1i—O3—C9 | 120.5 (3) | C11—C14—H14C | 107.7 |
Cu1—O4—C15 | 121.6 (3) | H14A—C14—H14B | 108.9 |
Cu1i—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)
top
Crystal data top
[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) Å3 | Prism, green |
Z = 2 | 0.5 × 0.2 × 0.2 mm |
Data collection top
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 top
Refinement on F | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.050 | w = 1/[σ2(F) + 0.000225F2] |
wR(F2) = 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 | |
Crystal data top
[Cu2(C6H11O2)4(C6H7N)2] | V = 2040.3 (4) Å3 |
Mr = 773.96 | Z = 2 |
Monoclinic, P21/a | Mo Kα radiation |
a = 10.040 (2) Å | µ = 1.09 mm−1 |
b = 18.468 (1) Å | T = 299 K |
c = 11.649 (1) Å | 0.5 × 0.2 × 0.2 mm |
β = 109.16 (1)° | |
Data collection top
Rigaku AFC-5 diffractometer | 3226 reflections with |Fo| > 3σ(|Fo|) |
Absorption correction: integration (Coppens et al., 1965) | Rint = 0.014 |
Tmin = 0.794, Tmax = 0.830 | 3 standard reflections every 100 reflections |
5080 measured reflections | intensity decay: none |
4678 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.050 | 217 parameters |
wR(F2) = 0.044 | H-atom parameters constrained |
S = 1.24 | Δρmax = 0.39 e Å−3 |
3226 reflections | Δρmin = −0.48 e Å−3 |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | 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 (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
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) top
Cu1—Cu1i | 2.666 (3) | C8—H8B | 0.959 |
Cu1—O2 | 1.969 (2) | C10—H10A | 0.961 |
Cu1—O3i | 1.982 (2) | C10—H10B | 0.960 |
Cu1—O4 | 1.969 (2) | C10—H10C | 0.960 |
Cu1—O5i | 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—O3i | 167.2 (1) | H10A—C10—H10B | 109.5 |
O2—Cu1—O4 | 89.6 (1) | H10A—C10—H10C | 109.5 |
O2—Cu1—O5i | 89.0 (1) | H10B—C10—H10C | 109.0 |
O2—Cu1—N6 | 100.7 (1) | C9—C11—H11A | 109.2 |
O3i—Cu1—O4 | 88.9 (1) | C9—C11—H11B | 110.2 |
O3i—Cu1—O5i | 89.7 (1) | C9—C11—H11C | 108.7 |
O3i—Cu1—N6 | 92.1 (1) | H11A—C11—H11B | 109.9 |
O4—Cu1—O5i | 167.3 (1) | H11A—C11—H11C | 109.8 |
O4—Cu1—N6 | 93.8 (1) | H11B—C11—H11C | 109.0 |
O5i—Cu1—N6 | 98.9 (1) | C9—C12—H12A | 108.4 |
Cu1—O2—C7 | 123.6 (2) | C9—C12—H12B | 109.7 |
Cu1i—O3—C7 | 123.6 (2) | C9—C12—H12C | 110.1 |
Cu1—O4—C13 | 124.4 (2) | H12A—C12—H12B | 109.8 |
Cu1i—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)
top
Crystal data top
[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) Å3 | 0.6 × 0.4 × 0.4 mm |
Data collection top
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 top
Refinement on F | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.046 | w = 1/[σ2(F) + 0.000225F2] |
wR(F2) = 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 | |
Crystal data top
[Cu2(C6H11O2)4(C6H7N)2] | γ = 63.11 (1)° |
Mr = 773.96 | V = 1046.7 (3) Å3 |
Triclinic, P1 | Z = 1 |
a = 10.603 (2) Å | Mo Kα radiation |
b = 11.216 (2) Å | µ = 1.06 mm−1 |
c = 10.289 (1) Å | T = 299 K |
α = 105.80 (1)° | 0.6 × 0.4 × 0.4 mm |
β = 101.01 (1)° | |
Data collection top
Rigaku AFC-5 diffractometer | 4058 reflections with |Fo| > 3σ(|Fo|) |
Absorption correction: integration (Coppens et al., 1965) | Rint = 0.011 |
Tmin = 0.965, Tmax = 0.973 | 3 standard reflections every 100 reflections |
5071 measured reflections | intensity decay: none |
4810 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.046 | 217 parameters |
wR(F2) = 0.048 | H-atom parameters constrained |
S = 1.19 | Δρmax = 0.40 e Å−3 |
4058 reflections | Δρmin = −0.72 e Å−3 |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | 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 (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
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) top
Cu1—Cu1i | 2.640 (2) | C8—H8B | 0.960 |
Cu1—O2 | 1.975 (2) | C10—H10A | 0.960 |
Cu1—O3i | 1.968 (2) | C10—H10B | 0.960 |
Cu1—O4 | 1.976 (2) | C10—H10C | 0.960 |
Cu1—O5i | 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—O3i | 168.1 (1) | H10A—C10—H10B | 110.2 |
O2—Cu1—O4 | 89.3 (1) | H10A—C10—H10C | 110.1 |
O2—Cu1—O5i | 89.3 (1) | H10B—C10—H10C | 109.0 |
O2—Cu1—N6 | 94.1 (1) | C9—C11—H11A | 111.8 |
O3i—Cu1—O4 | 91.0 (1) | C9—C11—H11B | 109.0 |
O3i—Cu1—O5i | 87.8 (1) | C9—C11—H11C | 108.7 |
O3i—Cu1—N6 | 97.7 (1) | H11A—C11—H11B | 109.2 |
O4—Cu1—O5i | 167.7 (1) | H11A—C11—H11C | 109.2 |
O4—Cu1—N6 | 92.2 (1) | H11B—C11—H11C | 109.0 |
O5i—Cu1—N6 | 100.1 (1) | C9—C12—H12A | 110.1 |
Cu1—O2—C7 | 122.6 (1) | C9—C12—H12B | 109.1 |
Cu1i—O3—C7 | 123.4 (2) | C9—C12—H12C | 109.6 |
Cu1—O4—C13 | 126.4 (1) | H12A—C12—H12B | 109.5 |
Cu1i—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)
top
Crystal data top
[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) Å3 | 0.5 × 0.4 × 0.2 mm |
Data collection top
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 top
Refinement on F | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.067 | w = 1/[σ2(F) + 0.000225F2] |
wR(F2) = 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 | |
Crystal data top
[Cu2(C6H11O2)4(C6H7N)2] | γ = 74.80 (1)° |
Mr = 773.96 | V = 2113.2 (6) Å3 |
Triclinic, P1 | Z = 2 |
a = 11.346 (2) Å | Mo Kα radiation |
b = 18.584 (3) Å | µ = 1.05 mm−1 |
c = 10.606 (2) Å | T = 297 K |
α = 90.44 (1)° | 0.5 × 0.4 × 0.2 mm |
β = 101.40 (1)° | |
Data collection top
Rigaku AFC-5 diffractometer | 5211 reflections with |Fo| > 3σ(|Fo|) |
Absorption correction: integration (Coppens et al., 1965) | Rint = 0.017 |
Tmin = 0.967, Tmax = 0.984 | 3 standard reflections every 100 reflections |
10177 measured reflections | intensity decay: none |
9683 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.067 | 433 parameters |
wR(F2) = 0.052 | H-atom parameters constrained |
S = 1.32 | Δρmax = 0.66 e Å−3 |
5211 reflections | Δρmin = −0.66 e Å−3 |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | 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 (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
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) top
Cu1—Cu1i | 2.638 (4) | C16—H16A | 0.960 |
Cu1—O3 | 1.967 (3) | C16—H16B | 0.960 |
Cu1—O4i | 1.966 (3) | C16—H16C | 0.960 |
Cu1—O5 | 1.960 (4) | C17—H17A | 0.960 |
Cu1—O6i | 1.961 (4) | C17—H17B | 0.959 |
Cu1—N11 | 2.175 (4) | C17—H17C | 0.961 |
Cu2—Cu2ii | 2.641 (4) | C18—H18A | 0.960 |
Cu2—O7 | 1.967 (3) | C18—H18B | 0.960 |
Cu2—O8ii | 1.985 (4) | C18—H18C | 0.960 |
Cu2—O9 | 1.974 (4) | C20—H20A | 0.960 |
Cu2—O10ii | 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—O4i | 168.1 (2) | H17B—C17—H17C | 109.0 |
O3—Cu1—O5 | 88.7 (2) | C15—C18—H18A | 112.7 |
O3—Cu1—O6i | 89.6 (2) | C15—C18—H18B | 108.8 |
O3—Cu1—N11 | 98.0 (2) | C15—C18—H18C | 108.2 |
O4i—Cu1—O5 | 88.5 (2) | H18A—C18—H18B | 109.0 |
O4i—Cu1—O6i | 90.7 (2) | H18A—C18—H18C | 109.1 |
O4i—Cu1—N11 | 93.9 (2) | H18B—C18—H18C | 109.1 |
O5—Cu1—O6i | 168.0 (2) | C19—C20—H20A | 108.3 |
O5—Cu1—N11 | 99.5 (2) | C19—C20—H20B | 108.5 |
O6i—Cu1—N11 | 92.5 (2) | C21—C20—H20A | 108.1 |
O7—Cu2—O8ii | 168.1 (2) | C21—C20—H20B | 108.6 |
O7—Cu2—O9 | 89.1 (2) | H20A—C20—H20B | 109.0 |
O7—Cu2—O10ii | 89.3 (2) | C21—C22—H22A | 107.0 |
O7—Cu2—N12 | 95.6 (2) | C21—C22—H22B | 109.0 |
O8ii—Cu2—O9 | 89.5 (2) | C21—C22—H22C | 110.8 |
O8ii—Cu2—O10ii | 89.6 (2) | H22A—C22—H22B | 110.5 |
O8ii—Cu2—N12 | 96.3 (2) | H22A—C22—H22C | 110.5 |
O9—Cu2—O10ii | 168.0 (2) | H22B—C22—H22C | 109.0 |
O9—Cu2—N12 | 99.0 (2) | C21—C23—H23A | 109.5 |
O10ii—Cu2—N12 | 93.0 (2) | C21—C23—H23B | 109.3 |
Cu1—O3—C13 | 121.3 (3) | C21—C23—H23C | 109.2 |
Cu1i—O4—C13 | 125.6 (3) | H23A—C23—H23B | 109.9 |
Cu1—O5—C19 | 121.4 (3) | H23A—C23—H23C | 110.0 |
Cu1i—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 |
Cu2ii—O8—C31 | 122.7 (3) | H24A—C24—H24B | 109.4 |
Cu2—O9—C37 | 120.3 (4) | H24A—C24—H24C | 109.3 |
Cu2ii—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)
top
Crystal data top
[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) Å3 | Prism, green |
Z = 2 | 0.3 × 0.3 × 0.25 mm |
Data collection top
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 top
Refinement on F | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.070 | w = 1/[σ2(F) + 0.000225F2] |
wR(F2) = 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 | |
Crystal data top
[Cu2(C6H11O2)4(C6H12O2)2] | V = 2268.2 (5) Å3 |
Mr = 820.02 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.890 (2) Å | µ = 0.99 mm−1 |
b = 18.211 (2) Å | T = 297 K |
c = 11.787 (1) Å | 0.3 × 0.3 × 0.25 mm |
β = 103.98 (1)° | |
Data collection top
Rigaku AFC-5 diffractometer | 2610 reflections with |Fo| > 3σ(|Fo|) |
Absorption correction: integration (Coppens et al., 1965) | Rint = 0.016 |
Tmin = 0.792, Tmax = 0.793 | 3 standard reflections every 100 reflections |
5475 measured reflections | intensity decay: none |
5214 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.070 | 226 parameters |
wR(F2) = 0.054 | H-atom parameters constrained |
S = 1.33 | Δρmax = 0.93 e Å−3 |
2610 reflections | Δρmin = −0.74 e Å−3 |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | 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 (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
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) top
Cu1—Cu1i | 2.599 (1) | C11—H11B | 0.960 |
Cu1—O2 | 2.005 (4) | C11—H11C | 0.960 |
Cu1—O3i | 1.955 (4) | C12—H12A | 0.960 |
Cu1—O4 | 1.950 (4) | C12—H12B | 0.960 |
Cu1—O5i | 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—O3i | 169.3 (2) | C10—C12—H12B | 108.8 |
O2—Cu1—O4 | 88.8 (2) | C10—C12—H12C | 109.3 |
O2—Cu1—O5i | 89.2 (2) | H12A—C12—H12B | 109.4 |
O2—Cu1—O6 | 90.7 (2) | H12A—C12—H12C | 109.4 |
O3i—Cu1—O4 | 89.9 (2) | H12B—C12—H12C | 109.0 |
O3i—Cu1—O5i | 89.9 (2) | C10—C13—H13A | 105.6 |
O3i—Cu1—O6 | 100.0 (2) | C10—C13—H13B | 111.2 |
O4—Cu1—O5i | 169.0 (2) | C10—C13—H13C | 109.6 |
O4—Cu1—O6 | 91.0 (2) | H13A—C13—H13B | 110.7 |
O5i—Cu1—O6 | 99.8 (2) | H13A—C13—H13C | 110.7 |
Cu1—O2—C8 | 125.0 (4) | H13B—C13—H13C | 109.0 |
Cu1i—O3—C8 | 121.9 (4) | C14—C15—H15A | 107.9 |
Cu1—O4—C14 | 125.0 (4) | C14—C15—H15B | 109.4 |
Cu1i—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) top
D—H···A | D—H | H···A | D···A | D—H···A |
O7—H7···O2 | 0.96 | 1.72 | 2.617 (5) | 154 |
Experimental details
| (I) | (II) | (III) | (IV) |
Crystal data |
Chemical formula | [Cu2(C6H11O2)4(C2H6O)2]·2C2H6O | [Cu2(C6H11O2)4(C6H7N)2] | [Cu2(C6H11O2)4(C6H7N)2] | [Cu2(C6H11O2)4(C6H7N)2] |
Mr | 771.98 | 773.96 | 773.96 | 773.96 |
Crystal system, space group | Triclinic, P1 | Monoclinic, P21/a | Triclinic, P1 | Triclinic, P1 |
Temperature (K) | 299 | 299 | 299 | 297 |
a, b, c (Å) | 10.765 (2), 10.923 (2), 9.820 (1) | 10.040 (2), 18.468 (1), 11.649 (1) | 10.603 (2), 11.216 (2), 10.289 (1) | 11.346 (2), 18.584 (3), 10.606 (2) |
α, β, γ (°) | 105.43 (1), 106.50 (1), 88.43 (1) | 90, 109.16 (1), 90 | 105.80 (1), 101.01 (1), 63.11 (1) | 90.44 (1), 101.40 (1), 74.80 (1) |
V (Å3) | 1065.8 (3) | 2040.3 (4) | 1046.7 (3) | 2113.2 (6) |
Z | 1 | 2 | 1 | 2 |
Radiation type | Mo Kα | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 1.05 | 1.09 | 1.06 | 1.05 |
Crystal size (mm) | 0.5 × 0.4 × 0.3 | 0.5 × 0.2 × 0.2 | 0.6 × 0.4 × 0.4 | 0.5 × 0.4 × 0.2 |
|
Data collection |
Diffractometer | Rigaku AFC-5 diffractometer | Rigaku AFC-5 diffractometer | Rigaku AFC-5 diffractometer | Rigaku AFC-5 diffractometer |
Absorption correction | Integration (Coppens et al., 1965) | Integration (Coppens et al., 1965) | Integration (Coppens et al., 1965) | Integration (Coppens et al., 1965) |
Tmin, Tmax | 0.569, 0.822 | 0.794, 0.830 | 0.965, 0.973 | 0.967, 0.984 |
No. of measured, independent and observed [|Fo| > 3σ(|Fo|)] reflections | 5151, 4888, 3646 | 5080, 4678, 3226 | 5071, 4810, 4058 | 10177, 9683, 5211 |
Rint | 0.012 | 0.014 | 0.011 | 0.017 |
(sin θ/λ)max (Å−1) | 0.650 | 0.650 | 0.650 | 0.650 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.076, 0.077, 1.44 | 0.050, 0.044, 1.24 | 0.046, 0.048, 1.19 | 0.067, 0.052, 1.32 |
No. of reflections | 3646 | 3226 | 4058 | 5211 |
No. of parameters | 182 | 217 | 217 | 433 |
No. of restraints | ? | ? | ? | ? |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.23, −0.91 | 0.39, −0.48 | 0.40, −0.72 | 0.66, −0.66 |
| (V) |
Crystal data |
Chemical formula | [Cu2(C6H11O2)4(C6H12O2)2] |
Mr | 820.02 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 297 |
a, b, c (Å) | 10.890 (2), 18.211 (2), 11.787 (1) |
α, β, γ (°) | 90, 103.98 (1), 90 |
V (Å3) | 2268.2 (5) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.99 |
Crystal size (mm) | 0.3 × 0.3 × 0.25 |
|
Data collection |
Diffractometer | Rigaku AFC-5 diffractometer |
Absorption correction | Integration (Coppens et al., 1965) |
Tmin, Tmax | 0.792, 0.793 |
No. of measured, independent and observed [|Fo| > 3σ(|Fo|)] reflections | 5475, 5214, 2610 |
Rint | 0.016 |
(sin θ/λ)max (Å−1) | 0.650 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.070, 0.054, 1.33 |
No. of reflections | 2610 |
No. of parameters | 226 |
No. of restraints | ? |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.93, −0.74 |
Selected geometric parameters (Å, º) for (I) topCu1—Cu1i | 2.602 (3) | Cu1—O6 | 2.164 (3) |
Cu1—O2 | 1.971 (3) | O2—C9 | 1.250 (4) |
Cu1—O3i | 1.968 (3) | O3—C9 | 1.268 (5) |
Cu1—O4 | 1.952 (3) | O4—C15 | 1.243 (5) |
Cu1—O5i | 1.958 (3) | O5—C15 | 1.250 (5) |
| | | |
O2—Cu1—O3i | 168.9 (1) | O2—C9—O3 | 123.9 (4) |
O4—Cu1—O5i | 168.8 (2) | O4—C15—O5 | 126.2 (4) |
Symmetry code: (i) −x, −y, −z. |
Selected geometric parameters (Å, º) for (II) topCu1—Cu1i | 2.666 (3) | Cu1—N6 | 2.238 (3) |
Cu1—O2 | 1.969 (2) | O2—C7 | 1.251 (4) |
Cu1—O3i | 1.982 (2) | O3—C7 | 1.249 (4) |
Cu1—O4 | 1.969 (2) | O4—C13 | 1.258 (4) |
Cu1—O5i | 1.967 (2) | O5—C13 | 1.254 (4) |
| | | |
O2—Cu1—O3i | 167.2 (1) | O2—C7—O3 | 125.7 (3) |
O4—Cu1—O5i | 167.3 (1) | O4—C13—O5 | 125.2 (3) |
Symmetry code: (i) −x+1, −y, −z+1. |
Selected geometric parameters (Å, º) for (III) topCu1—Cu1i | 2.640 (2) | Cu1—N6 | 2.163 (2) |
Cu1—O2 | 1.975 (2) | O2—C7 | 1.260 (2) |
Cu1—O3i | 1.968 (2) | O3—C7 | 1.257 (2) |
Cu1—O4 | 1.976 (2) | O4—C13 | 1.245 (2) |
Cu1—O5i | 1.973 (2) | O5—C13 | 1.251 (2) |
| | | |
O2—Cu1—O3i | 168.1 (1) | O2—C7—O3 | 125.6 (2) |
O4—Cu1—O5i | 167.7 (1) | O4—C13—O5 | 125.3 (2) |
Symmetry code: (i) −x, −y+1, −z+2. |
Selected geometric parameters (Å, º) for (IV) topCu1—Cu1i | 2.638 (4) | Cu2—O10ii | 1.960 (4) |
Cu1—O3 | 1.967 (3) | Cu2—N12 | 2.167 (4) |
Cu1—O4i | 1.966 (3) | O3—C13 | 1.258 (6) |
Cu1—O5 | 1.960 (4) | O4—C13 | 1.266 (6) |
Cu1—O6i | 1.961 (4) | O5—C19 | 1.272 (6) |
Cu1—N11 | 2.175 (4) | O6—C19 | 1.240 (6) |
Cu2—Cu2ii | 2.641 (4) | O7—C31 | 1.228 (7) |
Cu2—O7 | 1.967 (3) | O8—C31 | 1.278 (6) |
Cu2—O8ii | 1.985 (4) | O9—C37 | 1.259 (7) |
Cu2—O9 | 1.974 (4) | O10—C37 | 1.249 (7) |
| | | |
O3—Cu1—O4i | 168.1 (2) | O3—C13—O4 | 124.7 (5) |
O5—Cu1—O6i | 168.0 (2) | O5—C19—O6 | 124.9 (5) |
O7—Cu2—O8ii | 168.1 (2) | O7—C31—O8 | 125.7 (5) |
O9—Cu2—O10ii | 168.0 (2) | O9—C37—O10 | 125.5 (5) |
Symmetry codes: (i) −x, −y, −z+1; (ii) −x, −y+1, −z. |
Selected geometric parameters (Å, º) for (V) topCu1—Cu1i | 2.599 (1) | Cu1—O6 | 2.186 (5) |
Cu1—O2 | 2.005 (4) | O2—C8 | 1.285 (8) |
Cu1—O3i | 1.955 (4) | O3—C8 | 1.243 (8) |
Cu1—O4 | 1.950 (4) | O4—C14 | 1.255 (8) |
Cu1—O5i | 1.946 (4) | O5—C14 | 1.262 (8) |
| | | |
O2—Cu1—O3i | 169.3 (2) | O2—C8—O3 | 123.6 (6) |
O4—Cu1—O5i | 169.0 (2) | O4—C14—O5 | 124.4 (6) |
Symmetry code: (i) −x+1, −y+2, −z+1. |
Hydrogen-bond geometry (Å, º) for (V) top
D—H···A | D—H | H···A | D···A | D—H···A |
O7—H7···O2 | 0.960 | 1.720 | 2.617 (5) | 154.1 |
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.