The title two compounds, [Cu2(C5H9O2)4(C4H8O2)]n, (I), and [Cu2(C6H11O2)4(C4H8O2)]n, (II), are isomorphous. The binuclear CuII units have a cage structure and are linked by the dioxane molecules to form a zigzag chain along the c axis. The binuclear copper unit and the dioxane ligand each have a centre of symmetry.
Supporting information
CCDC references: 143321; 143322
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. 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, a green
precipitate was collected and dissolved in dioxane. From the solution, blue
crystals of (I) were grown by slow evaporation. 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, a green precipitate was
collected and dissolved in dioxane. From the solution, blue crystals of (II)
were grown by slow evaporation.
The positional parameters of all the H atoms were calculated geometrically and
fixed with U(H) = 1.2 Ueq(parent atom). The max/min ratio of the
atomic displacement parameters are abnormally large for the tert-butyl
moieties in (I) and (II), which may be due to vibrational and rotational
disorder.
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.
Crystal data top
[Cu2(C5H9O2)4(C4H8O2)] | Z = 1 |
Mr = 619.70 | F(000) = 326 |
Triclinic, P1 | Dx = 1.278 Mg m−3 |
a = 9.633 (2) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.665 (1) Å | Cell parameters from 25 reflections |
c = 9.030 (2) Å | θ = 10–15° |
α = 112.28 (1)° | µ = 1.36 mm−1 |
β = 110.19 (2)° | T = 297 K |
γ = 83.72 (1)° | Prism, blue |
V = 805.4 (3) Å3 | 0.5 × 0.1 × 0.1 mm |
Data collection top
Rigaku AFC-7R diffractometer | 2697 reflections with I > 2σ(I) |
Radiation source: Rigaku rotating anode | Rint = 0.091 |
Graphite monochromator | θmax = 30°, θmin = 2.5° |
θ–2θ scans | h = 0→14 |
Absorption correction: integration (Coppens et al., 1965) | k = −15→15 |
Tmin = 0.829, Tmax = 0.886 | l = −13→13 |
4955 measured reflections | 3 standard reflections every 150 reflections |
4697 independent reflections | intensity decay: 3.9% |
Refinement top
Refinement on F | 0 restraints |
Least-squares matrix: full | 0 constraints |
R[F2 > 2σ(F2)] = 0.051 | H-atom parameters not refined |
wR(F2) = 0.070 | w = 1/[σ2(Fo) + 0.00250|Fo|2] |
S = 1.08 | (Δ/σ)max = 0.008 |
2697 reflections | Δρmax = 0.58 e Å−3 |
163 parameters | Δρmin = −0.65 e Å−3 |
Crystal data top
[Cu2(C5H9O2)4(C4H8O2)] | γ = 83.72 (1)° |
Mr = 619.70 | V = 805.4 (3) Å3 |
Triclinic, P1 | Z = 1 |
a = 9.633 (2) Å | Mo Kα radiation |
b = 10.665 (1) Å | µ = 1.36 mm−1 |
c = 9.030 (2) Å | T = 297 K |
α = 112.28 (1)° | 0.5 × 0.1 × 0.1 mm |
β = 110.19 (2)° | |
Data collection top
Rigaku AFC-7R diffractometer | 2697 reflections with I > 2σ(I) |
Absorption correction: integration (Coppens et al., 1965) | Rint = 0.091 |
Tmin = 0.829, Tmax = 0.886 | 3 standard reflections every 150 reflections |
4955 measured reflections | intensity decay: 3.9% |
4697 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.051 | 0 restraints |
wR(F2) = 0.070 | H-atom parameters not refined |
S = 1.08 | Δρmax = 0.58 e Å−3 |
2697 reflections | Δρmin = −0.65 e Å−3 |
163 parameters | |
Special details top
Refinement. Refinement based on F against all reflections. The weighted
R-factor (wR) and goodness of fit (S) are based on
F, conventional R-factors (R) are calculated on F,
with F set to zero for negative F. The threshold expression of
F2 > σ(F2) is used only for calculating
R-factors(gt) etc. thus the refinement was done using all
reflections. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cu1 | 0.97163 (6) | 0.49209 (5) | 0.12465 (6) | 0.0428 (1) | |
O1 | 1.1625 (4) | 0.4033 (4) | 0.1703 (4) | 0.0621 (10) | |
O2 | 1.2094 (4) | 0.4159 (4) | −0.0478 (4) | 0.0631 (10) | |
O3 | 0.8783 (4) | 0.3185 (3) | −0.0383 (4) | 0.0648 (10) | |
O4 | 0.9248 (4) | 0.3317 (3) | −0.2561 (4) | 0.0623 (9) | |
O5 | 0.9105 (3) | 0.4752 (3) | 0.3303 (3) | 0.0568 (9) | |
C1 | 1.2413 (5) | 0.3810 (4) | 0.0786 (5) | 0.052 (1) | |
C2 | 1.3846 (6) | 0.3070 (7) | 0.1191 (8) | 0.078 (2) | |
C3 | 1.407 (1) | 0.270 (2) | 0.267 (2) | 0.290 (9) | |
C4 | 1.5108 (9) | 0.386 (1) | 0.139 (2) | 0.219 (7) | |
C5 | 1.372 (1) | 0.174 (1) | −0.028 (2) | 0.238 (6) | |
C6 | 0.8739 (5) | 0.2716 (4) | −0.1898 (5) | 0.053 (1) | |
C7 | 0.8008 (7) | 0.1305 (6) | −0.2994 (7) | 0.078 (2) | |
C8 | 0.898 (1) | 0.0314 (8) | −0.235 (2) | 0.195 (5) | |
C9 | 0.789 (1) | 0.0917 (8) | −0.4835 (9) | 0.144 (3) | |
C10 | 0.655 (1) | 0.131 (1) | −0.282 (2) | 0.261 (6) | |
C11 | 0.9621 (7) | 0.3684 (5) | 0.3917 (6) | 0.073 (2) | |
C12 | 1.1046 (6) | 0.4061 (6) | 0.5323 (6) | 0.074 (2) | |
H1 | 1.3234 | 0.2163 | 0.2464 | 0.3484* | |
H2 | 1.4951 | 0.2186 | 0.2859 | 0.3484* | |
H3 | 1.4161 | 0.3508 | 0.3656 | 0.3484* | |
H4 | 1.5998 | 0.3360 | 0.1618 | 0.2623* | |
H5 | 1.4942 | 0.4021 | 0.0368 | 0.2623* | |
H6 | 1.5205 | 0.4710 | 0.2319 | 0.2623* | |
H7 | 1.2884 | 0.1225 | −0.0445 | 0.2847* | |
H8 | 1.3575 | 0.1920 | −0.1287 | 0.2847* | |
H9 | 1.4602 | 0.1244 | −0.0039 | 0.2847* | |
H10 | 0.8541 | −0.0578 | −0.2982 | 0.2340* | |
H11 | 0.9930 | 0.0330 | −0.2465 | 0.2340* | |
H12 | 0.9100 | 0.0553 | −0.1170 | 0.2340* | |
H13 | 0.7468 | 0.0018 | −0.5477 | 0.1722* | |
H14 | 0.7267 | 0.1544 | −0.5286 | 0.1722* | |
H15 | 0.8856 | 0.0945 | −0.4907 | 0.1722* | |
H16 | 0.6662 | 0.1562 | −0.1649 | 0.3138* | |
H17 | 0.5941 | 0.1949 | −0.3257 | 0.3138* | |
H18 | 0.6102 | 0.0421 | −0.3452 | 0.3138* | |
H19 | 0.8900 | 0.3484 | 0.4317 | 0.0872* | |
H20 | 0.9752 | 0.2895 | 0.3009 | 0.0872* | |
H21 | 1.1775 | 0.4240 | 0.4919 | 0.0894* | |
H22 | 1.1357 | 0.3325 | 0.5719 | 0.0894* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu1 | 0.0521 (3) | 0.0552 (3) | 0.0294 (2) | −0.0001 (2) | 0.0177 (2) | 0.0199 (2) |
O1 | 0.064 (2) | 0.086 (2) | 0.053 (2) | 0.015 (2) | 0.028 (1) | 0.039 (2) |
O2 | 0.063 (2) | 0.089 (2) | 0.058 (2) | 0.016 (2) | 0.031 (2) | 0.042 (2) |
O3 | 0.087 (2) | 0.066 (2) | 0.045 (2) | −0.020 (2) | 0.026 (2) | 0.016 (1) |
O4 | 0.084 (2) | 0.063 (2) | 0.044 (1) | −0.013 (2) | 0.026 (2) | 0.015 (1) |
O5 | 0.070 (2) | 0.077 (2) | 0.036 (1) | 0.001 (2) | 0.025 (1) | 0.028 (1) |
C1 | 0.051 (2) | 0.060 (3) | 0.049 (2) | 0.004 (2) | 0.017 (2) | 0.024 (2) |
C2 | 0.064 (3) | 0.103 (4) | 0.084 (4) | 0.020 (3) | 0.032 (3) | 0.052 (3) |
C3 | 0.20 (1) | 0.58 (3) | 0.31 (2) | 0.26 (2) | 0.17 (1) | 0.38 (2) |
C4 | 0.057 (4) | 0.26 (1) | 0.38 (2) | −0.004 (6) | 0.016 (8) | 0.21 (2) |
C5 | 0.19 (1) | 0.16 (1) | 0.25 (2) | 0.113 (9) | 0.04 (1) | 0.02 (1) |
C6 | 0.055 (2) | 0.057 (3) | 0.046 (2) | −0.003 (2) | 0.016 (2) | 0.018 (2) |
C7 | 0.096 (4) | 0.064 (3) | 0.064 (3) | −0.021 (3) | 0.025 (3) | 0.008 (2) |
C8 | 0.27 (1) | 0.067 (5) | 0.19 (1) | −0.015 (7) | −0.01 (1) | 0.054 (6) |
C9 | 0.24 (1) | 0.093 (5) | 0.067 (4) | −0.055 (6) | 0.038 (6) | −0.009 (4) |
C10 | 0.19 (1) | 0.25 (1) | 0.25 (1) | −0.165 (10) | 0.15 (1) | −0.13 (1) |
C11 | 0.124 (5) | 0.063 (3) | 0.046 (2) | −0.007 (3) | 0.041 (3) | 0.022 (2) |
C12 | 0.099 (4) | 0.093 (4) | 0.061 (3) | 0.038 (3) | 0.051 (3) | 0.047 (3) |
Geometric parameters (Å, º) top
Cu1—Cu1i | 2.560 (1) | C5—H7 | 0.961 |
Cu1—O1 | 1.959 (3) | C5—H8 | 0.960 |
Cu1—O2i | 1.947 (3) | C5—H9 | 0.960 |
Cu1—O3 | 1.946 (3) | C6—C7 | 1.537 (6) |
Cu1—O4i | 1.959 (3) | C7—C8 | 1.49 (1) |
Cu1—O5 | 2.205 (2) | C7—C9 | 1.518 (9) |
O1—C1 | 1.251 (5) | C7—C10 | 1.46 (1) |
O2—C1 | 1.261 (5) | C8—H10 | 0.960 |
O3—C6 | 1.253 (5) | C8—H11 | 0.960 |
O4—C6 | 1.253 (5) | C8—H12 | 0.960 |
O5—C11 | 1.419 (6) | C9—H13 | 0.960 |
O5—C12ii | 1.434 (6) | C9—H14 | 0.960 |
C1—C2 | 1.515 (7) | C9—H15 | 0.960 |
C2—C3 | 1.48 (1) | C10—H16 | 0.959 |
C2—C4 | 1.47 (1) | C10—H17 | 0.961 |
C2—C5 | 1.51 (1) | C10—H18 | 0.960 |
C3—H1 | 0.960 | C11—C12 | 1.479 (8) |
C3—H2 | 0.960 | C11—H19 | 0.960 |
C3—H3 | 0.959 | C11—H20 | 0.960 |
C4—H4 | 0.960 | C12—H21 | 0.960 |
C4—H5 | 0.960 | C12—H22 | 0.960 |
C4—H6 | 0.961 | | |
| | | |
Cu1···Cu1i | 2.560 (1) | O4···C12iii | 3.320 (6) |
O2···C12iii | 3.534 (5) | O4···C11iii | 3.487 (5) |
| | | |
Cu1i—Cu1—O1 | 85.3 (1) | C2—C5—H8 | 109.5 |
Cu1i—Cu1—O2i | 84.7 (1) | C2—C5—H9 | 109.5 |
Cu1i—Cu1—O3 | 84.5 (1) | H7—C5—H8 | 109.4 |
Cu1i—Cu1—O4i | 85.4 (1) | H7—C5—H9 | 109.4 |
Cu1i—Cu1—O5 | 176.9 (1) | H8—C5—H9 | 109.5 |
O1—Cu1—O2i | 170.0 (1) | O3—C6—O4 | 124.5 (4) |
O1—Cu1—O3 | 89.4 (2) | O3—C6—C7 | 116.7 (4) |
O1—Cu1—O4i | 89.2 (1) | O4—C6—C7 | 118.8 (4) |
O1—Cu1—O5 | 96.9 (1) | C6—C7—C8 | 107.2 (6) |
O2i—Cu1—O3 | 90.2 (2) | C6—C7—C9 | 111.4 (5) |
O2i—Cu1—O4i | 89.5 (2) | C6—C7—C10 | 108.3 (6) |
O2i—Cu1—O5 | 93.1 (1) | C8—C7—C9 | 107.7 (7) |
O3—Cu1—O4i | 169.9 (1) | C8—C7—C10 | 110.8 (10) |
O3—Cu1—O5 | 93.4 (1) | C9—C7—C10 | 111.3 (8) |
O4i—Cu1—O5 | 96.7 (1) | C7—C8—H10 | 109.4 |
Cu1—O1—C1 | 122.3 (3) | C7—C8—H11 | 109.5 |
Cu1i—O2—C1 | 123.4 (3) | C7—C8—H12 | 109.5 |
Cu1—O3—C6 | 123.6 (3) | H10—C8—H11 | 109.5 |
Cu1i—O4—C6 | 121.9 (3) | H10—C8—H12 | 109.5 |
Cu1—O5—C11 | 121.6 (3) | H11—C8—H12 | 109.5 |
Cu1—O5—C12ii | 120.9 (3) | C7—C9—H13 | 109.5 |
C11—O5—C12ii | 108.7 (3) | C7—C9—H14 | 109.5 |
O1—C1—O2 | 124.2 (4) | C7—C9—H15 | 109.5 |
O1—C1—C2 | 118.9 (4) | H13—C9—H14 | 109.5 |
O2—C1—C2 | 116.9 (4) | H13—C9—H15 | 109.5 |
C1—C2—C3 | 111.2 (5) | H14—C9—H15 | 109.5 |
C1—C2—C4 | 111.0 (6) | C7—C10—H16 | 109.5 |
C1—C2—C5 | 107.9 (6) | C7—C10—H17 | 109.4 |
C3—C2—C4 | 112.7 (10) | C7—C10—H18 | 109.5 |
C3—C2—C5 | 105.6 (10) | H16—C10—H17 | 109.5 |
C4—C2—C5 | 108.2 (9) | H16—C10—H18 | 109.6 |
C2—C3—H1 | 109.4 | H17—C10—H18 | 109.4 |
C2—C3—H2 | 109.4 | O5—C11—C12 | 111.2 (4) |
C2—C3—H3 | 109.5 | O5—C11—H19 | 109.0 |
H1—C3—H2 | 109.5 | O5—C11—H20 | 109.0 |
H1—C3—H3 | 109.5 | C12—C11—H19 | 109.0 |
H2—C3—H3 | 109.5 | C12—C11—H20 | 109.0 |
C2—C4—H4 | 109.5 | H19—C11—H20 | 109.5 |
C2—C4—H5 | 109.5 | O5ii—C12—C11 | 110.6 (4) |
C2—C4—H6 | 109.4 | O5ii—C12—H21 | 109.2 |
H4—C4—H5 | 109.5 | O5ii—C12—H22 | 109.2 |
H4—C4—H6 | 109.5 | C11—C12—H21 | 109.2 |
H5—C4—H6 | 109.4 | C11—C12—H22 | 109.2 |
C2—C5—H7 | 109.5 | H21—C12—H22 | 109.5 |
Symmetry codes: (i) −x+2, −y+1, −z; (ii) −x+2, −y+1, −z+1; (iii) x, y, z−1. |
Crystal data top
[Cu2(C6H11O2)4(C4H8O2)] | Z = 1 |
Mr = 675.81 | Dx = 1.267 Mg m−3 |
Triclinic, P1 | Mo Kα radiation, λ = 0.71073 Å |
a = 10.080 (1) Å | Cell parameters from 25 reflections |
b = 11.308 (2) Å | θ = 10–15° |
c = 8.952 (1) Å | µ = 1.25 mm−1 |
α = 113.30 (1)° | T = 298 K |
β = 108.92 (1)° | Prism, blue |
γ = 84.64 (1)° | 0.4 × 0.4 × 0.4 mm |
V = 885.8 (2) Å3 | |
Data collection top
Rigaku AFC-7R diffractometer | Rint = 0.01 |
θ–2θ scans | θmax = 30° |
Absorption correction: integration (Coppens et al., 1965) | h = −14→14 |
Tmin = 0.559, Tmax = 0.665 | k = −16→0 |
5397 measured reflections | l = −13→13 |
5156 independent reflections | 3 standard reflections every 150 reflections |
3998 reflections with I > 2σ(I) | intensity decay: 2.4% |
Refinement top
Refinement on F | H-atom parameters not refined |
R[F2 > 2σ(F2)] = 0.041 | w = 1/[σ2(Fo) + 0.00250|Fo|2] |
wR(F2) = 0.075 | (Δ/σ)max = 0.048 |
S = 1.07 | Δρmax = 0.48 e Å−3 |
5155 reflections | Δρmin = −0.37 e Å−3 |
181 parameters | |
Crystal data top
[Cu2(C6H11O2)4(C4H8O2)] | γ = 84.64 (1)° |
Mr = 675.81 | V = 885.8 (2) Å3 |
Triclinic, P1 | Z = 1 |
a = 10.080 (1) Å | Mo Kα radiation |
b = 11.308 (2) Å | µ = 1.25 mm−1 |
c = 8.952 (1) Å | T = 298 K |
α = 113.30 (1)° | 0.4 × 0.4 × 0.4 mm |
β = 108.92 (1)° | |
Data collection top
Rigaku AFC-7R diffractometer | 3998 reflections with I > 2σ(I) |
Absorption correction: integration (Coppens et al., 1965) | Rint = 0.01 |
Tmin = 0.559, Tmax = 0.665 | 3 standard reflections every 150 reflections |
5397 measured reflections | intensity decay: 2.4% |
5156 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.041 | 181 parameters |
wR(F2) = 0.075 | H-atom parameters not refined |
S = 1.07 | Δρmax = 0.48 e Å−3 |
5155 reflections | Δρmin = −0.37 e Å−3 |
Special details top
Refinement. Refinement using reflections with F2 > -10.0 σ(F2). The
weighted R-factor (wR), goodness of fit (S) and
R-factor (gt) are based on F, with F set to zero for
negative 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 (Å2) top | x | y | z | Uiso*/Ueq | |
Cu1 | 0.47683 (3) | −0.00999 (3) | 0.12658 (3) | 0.04156 (9) | |
O1 | 0.5023 (2) | 0.1785 (2) | 0.2370 (2) | 0.0566 (5) | |
O2 | 0.5393 (3) | 0.1953 (2) | 0.0127 (3) | 0.0622 (6) | |
O3 | 0.2804 (2) | 0.0087 (2) | 0.0096 (3) | 0.0573 (6) | |
O4 | 0.3195 (2) | 0.0239 (2) | −0.2138 (3) | 0.0607 (6) | |
O5 | 0.4197 (2) | −0.0394 (2) | 0.3268 (2) | 0.0483 (5) | |
C1 | 0.5297 (3) | 0.2428 (2) | 0.1626 (3) | 0.0510 (6) | |
C2 | 0.5544 (3) | 0.3869 (3) | 0.2578 (4) | 0.0617 (8) | |
C3 | 0.7072 (4) | 0.4326 (3) | 0.3426 (6) | 0.078 (1) | |
C4 | 0.7652 (8) | 0.3744 (7) | 0.482 (1) | 0.197 (3) | |
C5 | 0.7172 (5) | 0.5773 (3) | 0.4375 (6) | 0.088 (1) | |
C6 | 0.7944 (7) | 0.3900 (6) | 0.232 (1) | 0.169 (3) | |
C7 | 0.2405 (3) | 0.0256 (3) | −0.1286 (3) | 0.0514 (6) | |
C8 | 0.0878 (3) | 0.0515 (3) | −0.1947 (4) | 0.0604 (8) | |
C9 | 0.0553 (3) | 0.1953 (3) | −0.1346 (5) | 0.0690 (10) | |
C10 | 0.1290 (6) | 0.2627 (6) | −0.203 (1) | 0.132 (3) | |
C11 | 0.1008 (5) | 0.2567 (5) | 0.0592 (7) | 0.115 (2) | |
C12 | −0.1034 (4) | 0.2051 (5) | −0.2042 (7) | 0.104 (2) | |
C13 | 0.3809 (3) | 0.0679 (3) | 0.4551 (3) | 0.0522 (7) | |
C14 | 0.5077 (3) | 0.1312 (2) | 0.6046 (3) | 0.0528 (7) | |
H1 | 0.5119 | 0.4268 | 0.1777 | 0.0741* | |
H2 | 0.5096 | 0.4142 | 0.3451 | 0.0741* | |
H3 | 0.7093 | 0.4009 | 0.5581 | 0.2361* | |
H4 | 0.7613 | 0.2821 | 0.4283 | 0.2361* | |
H5 | 0.8607 | 0.4046 | 0.5469 | 0.2361* | |
H6 | 0.8125 | 0.6043 | 0.5072 | 0.1052* | |
H7 | 0.6875 | 0.6179 | 0.3565 | 0.1052* | |
H8 | 0.6578 | 0.6018 | 0.5090 | 0.1052* | |
H9 | 0.7905 | 0.2975 | 0.1801 | 0.2036* | |
H10 | 0.7610 | 0.4237 | 0.1437 | 0.2036* | |
H11 | 0.8896 | 0.4204 | 0.2978 | 0.2036* | |
H12 | 0.0592 | 0.0155 | −0.3176 | 0.0725* | |
H13 | 0.0347 | 0.0099 | −0.1563 | 0.0725* | |
H14 | 0.2287 | 0.2564 | −0.1591 | 0.1587* | |
H15 | 0.0993 | 0.2230 | −0.3260 | 0.1587* | |
H16 | 0.1059 | 0.3519 | −0.1680 | 0.1587* | |
H17 | 0.2005 | 0.2515 | 0.1041 | 0.1379* | |
H18 | 0.0763 | 0.3456 | 0.0951 | 0.1379* | |
H19 | 0.0542 | 0.2123 | 0.1011 | 0.1379* | |
H20 | −0.1268 | 0.2941 | −0.1682 | 0.1251* | |
H21 | −0.1333 | 0.1658 | −0.3270 | 0.1251* | |
H22 | −0.1497 | 0.1615 | −0.1610 | 0.1251* | |
H23 | 0.3364 | 0.1293 | 0.4071 | 0.0627* | |
H24 | 0.3167 | 0.0384 | 0.4933 | 0.0627* | |
H25 | 0.4790 | 0.2000 | 0.6918 | 0.0634* | |
H26 | 0.5695 | 0.1653 | 0.5679 | 0.0634* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu1 | 0.0514 (2) | 0.0463 (2) | 0.0293 (1) | −0.0001 (1) | 0.0148 (1) | 0.0148 (1) |
O1 | 0.070 (1) | 0.0506 (10) | 0.0481 (9) | −0.0057 (9) | 0.0252 (9) | 0.0102 (8) |
O2 | 0.092 (2) | 0.049 (1) | 0.0478 (10) | −0.0005 (10) | 0.0259 (10) | 0.0164 (8) |
O3 | 0.054 (1) | 0.073 (1) | 0.053 (1) | −0.0003 (9) | 0.0155 (8) | 0.0324 (9) |
O4 | 0.057 (1) | 0.085 (1) | 0.0453 (9) | 0.0089 (10) | 0.0175 (8) | 0.0303 (10) |
O5 | 0.061 (1) | 0.0556 (10) | 0.0344 (7) | 0.0045 (8) | 0.0177 (7) | 0.0214 (7) |
C1 | 0.053 (1) | 0.046 (1) | 0.049 (1) | 0.002 (1) | 0.017 (1) | 0.0119 (10) |
C2 | 0.069 (2) | 0.045 (1) | 0.068 (2) | 0.005 (1) | 0.029 (1) | 0.012 (1) |
C3 | 0.067 (2) | 0.048 (2) | 0.107 (3) | −0.005 (1) | 0.031 (2) | 0.014 (2) |
C4 | 0.166 (6) | 0.114 (5) | 0.224 (8) | −0.041 (4) | −0.096 (6) | 0.091 (5) |
C5 | 0.111 (3) | 0.051 (2) | 0.095 (3) | −0.018 (2) | 0.044 (2) | 0.008 (2) |
C6 | 0.139 (5) | 0.107 (4) | 0.228 (8) | −0.045 (4) | 0.131 (6) | −0.040 (4) |
C7 | 0.051 (1) | 0.056 (1) | 0.044 (1) | −0.002 (1) | 0.0104 (10) | 0.018 (1) |
C8 | 0.046 (1) | 0.077 (2) | 0.056 (1) | −0.003 (1) | 0.009 (1) | 0.028 (1) |
C9 | 0.048 (2) | 0.075 (2) | 0.085 (2) | 0.009 (1) | 0.019 (1) | 0.036 (2) |
C10 | 0.099 (3) | 0.117 (4) | 0.242 (8) | 0.023 (3) | 0.070 (4) | 0.123 (5) |
C11 | 0.079 (3) | 0.116 (4) | 0.092 (3) | 0.032 (3) | 0.013 (2) | −0.001 (3) |
C12 | 0.056 (2) | 0.134 (4) | 0.125 (4) | 0.025 (2) | 0.017 (2) | 0.066 (3) |
C13 | 0.062 (1) | 0.061 (1) | 0.047 (1) | 0.017 (1) | 0.027 (1) | 0.028 (1) |
C14 | 0.075 (2) | 0.046 (1) | 0.043 (1) | 0.007 (1) | 0.024 (1) | 0.0205 (10) |
Geometric parameters (Å, º) top
Cu1—Cu1i | 2.553 (1) | C6—H9 | 0.960 |
Cu1—O1 | 1.964 (2) | C6—H10 | 0.959 |
Cu1—O2i | 1.959 (2) | C6—H11 | 0.961 |
Cu1—O3 | 1.953 (2) | C7—C8 | 1.505 (4) |
Cu1—O4i | 1.961 (2) | C8—C9 | 1.537 (5) |
Cu1—O5 | 2.198 (2) | C8—H12 | 0.960 |
O1—C1 | 1.260 (3) | C8—H13 | 0.960 |
O2—C1 | 1.266 (3) | C9—C10 | 1.511 (6) |
O3—C7 | 1.257 (3) | C9—C11 | 1.515 (6) |
O4—C7 | 1.263 (3) | C9—C12 | 1.528 (5) |
O5—C13 | 1.430 (3) | C10—H14 | 0.961 |
O5—C14ii | 1.435 (3) | C10—H15 | 0.959 |
C1—C2 | 1.510 (4) | C10—H16 | 0.961 |
C2—C3 | 1.515 (5) | C11—H17 | 0.960 |
C2—H1 | 0.960 | C11—H18 | 0.961 |
C2—H2 | 0.960 | C11—H19 | 0.959 |
C3—C4 | 1.564 (8) | C12—H20 | 0.960 |
C3—C5 | 1.512 (4) | C12—H21 | 0.960 |
C3—C6 | 1.450 (7) | C12—H22 | 0.961 |
C4—H3 | 0.961 | C13—C14 | 1.497 (4) |
C4—H4 | 0.960 | C13—H23 | 0.960 |
C4—H5 | 0.960 | C13—H24 | 0.960 |
C5—H6 | 0.960 | C14—H25 | 0.960 |
C5—H7 | 0.960 | C14—H26 | 0.960 |
C5—H8 | 0.960 | | |
| | | |
Cu1···Cu1i | 2.5526 (5) | O4···C13iii | 3.440 (3) |
O2···C14iii | 3.341 (3) | O5···C12iv | 3.479 (5) |
O4···C14iii | 3.421 (3) | | |
| | | |
Cu1i—Cu1—O1 | 86.3 (1) | C3—C6—H10 | 109.5 |
Cu1i—Cu1—O2i | 84.5 (1) | C3—C6—H11 | 109.4 |
Cu1i—Cu1—O3 | 84.8 (1) | H9—C6—H10 | 109.6 |
Cu1i—Cu1—O4i | 85.8 (1) | H9—C6—H11 | 109.4 |
Cu1i—Cu1—O5 | 174.6 (1) | H10—C6—H11 | 109.5 |
O1—Cu1—O2i | 170.7 (1) | O3—C7—O4 | 124.6 (3) |
O1—Cu1—O3 | 89.4 (1) | O3—C7—C8 | 117.2 (2) |
O1—Cu1—O4i | 89.3 (1) | O4—C7—C8 | 118.2 (2) |
O1—Cu1—O5 | 97.4 (1) | C7—C8—C9 | 114.1 (2) |
O2i—Cu1—O3 | 90.8 (1) | C7—C8—H12 | 108.3 |
O2i—Cu1—O4i | 89.1 (1) | C7—C8—H13 | 108.3 |
O2i—Cu1—O5 | 91.9 (1) | C9—C8—H12 | 108.3 |
O3—Cu1—O4i | 170.5 (1) | C9—C8—H13 | 108.3 |
O3—Cu1—O5 | 91.2 (1) | H12—C8—H13 | 109.5 |
O4i—Cu1—O5 | 98.3 (1) | C8—C9—C10 | 110.0 (4) |
Cu1—O1—C1 | 121.1 (2) | C8—C9—C11 | 110.1 (3) |
Cu1i—O2—C1 | 123.4 (2) | C8—C9—C12 | 107.7 (3) |
Cu1—O3—C7 | 123.1 (2) | C10—C9—C11 | 110.4 (4) |
Cu1i—O4—C7 | 121.5 (2) | C10—C9—C12 | 109.8 (4) |
Cu1—O5—C13 | 119.7 (1) | C11—C9—C12 | 108.9 (3) |
Cu1—O5—C14ii | 119.7 (1) | C9—C10—H14 | 109.4 |
C13—O5—C14ii | 111.1 (2) | C9—C10—H15 | 109.5 |
O1—C1—O2 | 124.7 (2) | C9—C10—H16 | 109.4 |
O1—C1—C2 | 118.4 (2) | H14—C10—H15 | 109.5 |
O2—C1—C2 | 116.9 (2) | H14—C10—H16 | 109.4 |
C1—C2—C3 | 115.0 (3) | H15—C10—H16 | 109.5 |
C1—C2—H1 | 108.1 | C9—C11—H17 | 109.5 |
C1—C2—H2 | 108.1 | C9—C11—H18 | 109.4 |
C3—C2—H1 | 108.1 | C9—C11—H19 | 109.5 |
C3—C2—H2 | 108.1 | H17—C11—H18 | 109.4 |
H1—C2—H2 | 109.5 | H17—C11—H19 | 109.6 |
C2—C3—C4 | 105.1 (4) | H18—C11—H19 | 109.5 |
C2—C3—C5 | 109.7 (3) | C9—C12—H20 | 109.5 |
C2—C3—C6 | 115.7 (4) | C9—C12—H21 | 109.5 |
C4—C3—C5 | 106.3 (4) | C9—C12—H22 | 109.4 |
C4—C3—C6 | 107.5 (6) | H20—C12—H21 | 109.5 |
C5—C3—C6 | 112.0 (4) | H20—C12—H22 | 109.4 |
C3—C4—H3 | 109.5 | H21—C12—H22 | 109.5 |
C3—C4—H4 | 109.6 | O5—C13—C14 | 110.6 (2) |
C3—C4—H5 | 109.6 | O5—C13—H23 | 109.2 |
H3—C4—H4 | 109.4 | O5—C13—H24 | 109.2 |
H3—C4—H5 | 109.3 | C14—C13—H23 | 109.2 |
H4—C4—H5 | 109.5 | C14—C13—H24 | 109.2 |
C3—C5—H6 | 109.5 | H23—C13—H24 | 109.5 |
C3—C5—H7 | 109.5 | O5ii—C14—C13 | 110.2 (2) |
C3—C5—H8 | 109.5 | O5ii—C14—H25 | 109.3 |
H6—C5—H7 | 109.4 | O5ii—C14—H26 | 109.3 |
H6—C5—H8 | 109.5 | C13—C14—H25 | 109.3 |
H7—C5—H8 | 109.4 | C13—C14—H26 | 109.3 |
C3—C6—H9 | 109.4 | H25—C14—H26 | 109.5 |
Symmetry codes: (i) −x+1, −y, −z; (ii) −x+1, −y, −z+1; (iii) x, y, z−1; (iv) −x, −y, −z. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | [Cu2(C5H9O2)4(C4H8O2)] | [Cu2(C6H11O2)4(C4H8O2)] |
Mr | 619.70 | 675.81 |
Crystal system, space group | Triclinic, P1 | Triclinic, P1 |
Temperature (K) | 297 | 298 |
a, b, c (Å) | 9.633 (2), 10.665 (1), 9.030 (2) | 10.080 (1), 11.308 (2), 8.952 (1) |
α, β, γ (°) | 112.28 (1), 110.19 (2), 83.72 (1) | 113.30 (1), 108.92 (1), 84.64 (1) |
V (Å3) | 805.4 (3) | 885.8 (2) |
Z | 1 | 1 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 1.36 | 1.25 |
Crystal size (mm) | 0.5 × 0.1 × 0.1 | 0.4 × 0.4 × 0.4 |
|
Data collection |
Diffractometer | Rigaku AFC-7R diffractometer | Rigaku AFC-7R diffractometer |
Absorption correction | Integration (Coppens et al., 1965) | Integration (Coppens et al., 1965) |
Tmin, Tmax | 0.829, 0.886 | 0.559, 0.665 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4955, 4697, 2697 | 5397, 5156, 3998 |
Rint | 0.091 | 0.01 |
(sin θ/λ)max (Å−1) | 0.703 | 0.703 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.051, 0.070, 1.08 | 0.041, 0.075, 1.07 |
No. of reflections | 2697 | 5155 |
No. of parameters | 163 | 181 |
No. of restraints | 0 | ? |
H-atom treatment | H-atom parameters not refined | H-atom parameters not refined |
Δρmax, Δρmin (e Å−3) | 0.58, −0.65 | 0.48, −0.37 |
Selected geometric parameters (Å, º) for (I) topCu1—Cu1i | 2.560 (1) | Cu1—O5 | 2.205 (2) |
Cu1—O1 | 1.959 (3) | O1—C1 | 1.251 (5) |
Cu1—O2i | 1.947 (3) | O2—C1 | 1.261 (5) |
Cu1—O3 | 1.946 (3) | O3—C6 | 1.253 (5) |
Cu1—O4i | 1.959 (3) | O4—C6 | 1.253 (5) |
| | | |
O1—Cu1—O2i | 170.0 (1) | O1—C1—O2 | 124.2 (4) |
O3—Cu1—O4i | 169.9 (1) | O3—C6—O4 | 124.5 (4) |
Symmetry code: (i) −x+2, −y+1, −z. |
Selected geometric parameters (Å, º) for (II) topCu1—Cu1i | 2.553 (1) | Cu1—O5 | 2.198 (2) |
Cu1—O1 | 1.964 (2) | O1—C1 | 1.260 (3) |
Cu1—O2i | 1.959 (2) | O2—C1 | 1.266 (3) |
Cu1—O3 | 1.953 (2) | O3—C7 | 1.257 (3) |
Cu1—O4i | 1.961 (2) | O4—C7 | 1.263 (3) |
| | | |
O1—Cu1—O2i | 170.7 (1) | O1—C1—O2 | 124.7 (2) |
O3—Cu1—O4i | 170.5 (1) | O3—C7—O4 | 124.6 (3) |
Symmetry code: (i) −x+1, −y, −z. |
The magnetic -2 J values of the binuclear Cu unit of (I) and (II) were determined to be 387 and 363 cm-1, respectively (H = -2JS1·S2). The spin-exchange interaction through the dioxane bridge is negligible. The -2 J values of [Cu2(Me3CCOO)4L2] (L = pyridine and 2-methylpyridine) were reported to be 366 and 371 cm-1, respectively (Muto et al., 1986). Structures of dimeric copper(II)–3,3-dimethylbutyrate adducts have been reported recently, the -2 J values of [Cu2(Me3CCH2COO)4L2] (L = pyridine, 2-methylpyridine, 3-methylpyridine and 4-methylpyridine) being in the range 348–363 cm-1 (Goto et al., 2000).