The two title compounds, [Cu3(C6H11O2)6(C7H9N)2]n, (I), and [Cu2(C5H9O2)4(C7H9N)2], (II), have chain and finite-molecular structures, respectively. In (I), binuclear cage units and mononuclear 2,6-dimethylpyridine complexes, both of which have inversion centres, are arranged alternately and are linked by the carboxylate ions to form one-dimensional chains along the a axis. In (II), the binuclear cage unit has an inversion centre and the coordination geometry around the Cu atom is typical square pyramidal, with 2,6-dimethylpyridine at the apical position.
Supporting information
CCDC references: 150306; 150307
For (I), 3,3-dimethylbutyric acid (116 mg, 1.0 mmol) and CuCO3·Cu(OH)2·H2O (60 mg, 0.25 mmol) were suspended in a mixture of water and methanol (3:1, 20 ml). After the solution had been stirred for 1 h at room temperature, the green precipitate was collected and dissolved in acetonitrile and 2,6-dimethylpyridine (54 mg, 0.5 mmol) was added. Blue crystals of (I) were grown from the solution by slow evaporation. For (II), a solution of 2,2-dimethylpropionic acid (613 mg, 6.0 mmol) in 0.25 M sodium hydroxide (50 ml) was neutralized with 0.25 M nitric acid and an aqueous solution of Cu(NO3)2·3H2O (725 mg, 3.0 mmol) was added. After the solution had been stirred for 15 min at room temperature, the green precipitate was collected and dissolved in acetonitrile and 2,6-dimethylpyridine (321 mg, 3.0 mmol) was added. Green crystals of (II) were grown from the solution by slow evaporation.
Initially, both of the structures were refined as usual. The anisotropy in the atom displacement parameters became abnormally large for the methyl C atoms of the tert-butyl groups, suggesting libration and/or rotational disorder. Therefore, a split-site model was investigated for the tert-butyl groups in both compounds; it was found to be applicable for (II), but not for (I). For (II), the six methyl-C atoms were initially refined isotropically. Two sets of half-occupancy methyl groups, offset from one another by ca 30°, could be modelled for both tert-butyl groups based on the difference synthesis. Their anisotropic displacement parameters were then refined with their positional parameters fixed to avoid unreasonable geometry. Compared to the un-split model, R(F) slightly decreased from 0.050 to 0.048 on inceasing the number of parameters from 208 to 226. The magnitude of the displacement ellipsoids of the methyl C atoms apparently decreased, but the abnormal anisotropy of the displacement parameters did not disappear. In this manuscript, the split-site model is reported for (II). The positional parameters of all the H atoms were calculated geometrically and fixed with U(H) = 1.2 Ueq(parent atom).
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
[Cu3(C6H11O2)6(C7H9N)2] | Z = 1 |
Mr = 1095.86 | Dx = 1.251 Mg m−3 |
Triclinic, P1 | Mo Kα radiation, λ = 0.71073 Å |
a = 12.525 (2) Å | Cell parameters from 25 reflections |
b = 12.736 (2) Å | θ = 10–15° |
c = 10.033 (2) Å | µ = 1.14 mm−1 |
α = 94.64 (1)° | T = 298 K |
β = 102.51 (1)° | Prism, blue |
γ = 109.32 (1)° | 0.4 × 0.1 × 0.1 mm |
V = 1454.1 (5) Å3 | |
Data collection top
Rigaku AFC-7R diffractometer | Rint = 0.021 |
θ/2θ scans | θmax = 27.5° |
Absorption correction: integration (Coppens et al., 1965) | h = 0→16 |
Tmin = 0.472, Tmax = 0.753 | k = −17→17 |
6956 measured reflections | l = −13→13 |
6651 independent reflections | 3 standard reflections every 150 reflections |
4193 reflections with I > 2σ(I) | intensity decay: none |
Refinement top
Refinement on F2 | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.045 | w = 1/{σ2Fo2 + [0.05(Fo2 + 2Fc2)/3]2} |
wR(F2) = 0.115 | (Δ/σ)max = 0.006 |
S = 1.08 | Δρmax = 0.41 e Å−3 |
6651 reflections | Δρmin = −0.61 e Å−3 |
304 parameters | |
Crystal data top
[Cu3(C6H11O2)6(C7H9N)2] | γ = 109.32 (1)° |
Mr = 1095.86 | V = 1454.1 (5) Å3 |
Triclinic, P1 | Z = 1 |
a = 12.525 (2) Å | Mo Kα radiation |
b = 12.736 (2) Å | µ = 1.14 mm−1 |
c = 10.033 (2) Å | T = 298 K |
α = 94.64 (1)° | 0.4 × 0.1 × 0.1 mm |
β = 102.51 (1)° | |
Data collection top
Rigaku AFC-7R diffractometer | 4193 reflections with I > 2σ(I) |
Absorption correction: integration (Coppens et al., 1965) | Rint = 0.021 |
Tmin = 0.472, Tmax = 0.753 | 3 standard reflections every 150 reflections |
6956 measured reflections | intensity decay: none |
6651 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.045 | 304 parameters |
wR(F2) = 0.115 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.41 e Å−3 |
6651 reflections | Δρmin = −0.61 e Å−3 |
Special details top
Refinement. Refinement using reflections with F2 > 0.0 σ(F2). The weighted R-factor (wR) and goodness of fit (S) are based on F2. R-factor (gt) are based on F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt). |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cu1 | 0.39771 (3) | −0.01312 (3) | 0.02690 (4) | 0.0366 (1) | |
Cu2 | 0 | 0 | 0 | 0.0373 (2) | |
O1 | 0.4572 (2) | 0.1533 (2) | 0.0615 (3) | 0.0577 (8) | |
O2 | 0.6285 (2) | 0.1745 (2) | 0.0140 (3) | 0.0549 (8) | |
O3 | 0.3478 (2) | −0.0095 (2) | −0.1720 (2) | 0.0528 (7) | |
O4 | 0.5191 (2) | 0.0105 (2) | −0.2182 (2) | 0.0494 (7) | |
O5 | 0.2223 (2) | −0.0375 (2) | 0.0512 (2) | 0.0474 (7) | |
O6 | 0.0631 (2) | −0.0846 (2) | 0.1269 (2) | 0.0459 (7) | |
N1 | 0.0861 (2) | 0.1482 (2) | 0.1369 (3) | 0.0476 (8) | |
C1 | 0.5562 (3) | 0.2117 (3) | 0.0473 (4) | 0.0483 (10) | |
C2 | 0.5913 (4) | 0.3390 (3) | 0.0746 (5) | 0.067 (1) | |
C3 | 0.6623 (4) | 0.3959 (4) | 0.2214 (5) | 0.075 (1) | |
C4 | 0.6890 (6) | 0.5217 (4) | 0.2334 (7) | 0.122 (2) | |
C5 | 0.7745 (6) | 0.3749 (6) | 0.2594 (8) | 0.140 (3) | |
C6 | 0.5900 (7) | 0.3501 (6) | 0.3214 (7) | 0.157 (3) | |
C7 | 0.4136 (3) | 0.0026 (3) | −0.2518 (3) | 0.0402 (8) | |
C8 | 0.3630 (3) | 0.0112 (3) | −0.4003 (3) | 0.0453 (9) | |
C9 | 0.3677 (3) | 0.1309 (3) | −0.4251 (4) | 0.049 (1) | |
C10 | 0.3247 (4) | 0.1264 (4) | −0.5803 (4) | 0.068 (1) | |
C11 | 0.2911 (5) | 0.1686 (4) | −0.3509 (5) | 0.087 (2) | |
C12 | 0.4938 (4) | 0.2136 (4) | −0.3737 (5) | 0.085 (2) | |
C13 | 0.1618 (3) | −0.0919 (3) | 0.1225 (3) | 0.0399 (9) | |
C14 | 0.2032 (3) | −0.1699 (3) | 0.2079 (4) | 0.0490 (10) | |
C15 | 0.1138 (3) | −0.2806 (3) | 0.2240 (4) | 0.060 (1) | |
C16 | 0.0335 (5) | −0.3444 (4) | 0.0878 (7) | 0.107 (2) | |
C17 | 0.0414 (5) | −0.2575 (5) | 0.3207 (6) | 0.098 (2) | |
C18 | 0.1813 (5) | −0.3517 (5) | 0.2887 (7) | 0.111 (2) | |
C19 | 0.1754 (3) | 0.2305 (3) | 0.1093 (4) | 0.052 (1) | |
C20 | 0.2279 (4) | 0.3344 (4) | 0.1951 (5) | 0.075 (1) | |
C21 | 0.1902 (5) | 0.3547 (4) | 0.3086 (5) | 0.082 (2) | |
C22 | 0.1013 (5) | 0.2720 (4) | 0.3367 (5) | 0.076 (2) | |
C23 | 0.0488 (3) | 0.1677 (3) | 0.2497 (4) | 0.056 (1) | |
C24 | 0.2145 (3) | 0.2074 (3) | −0.0151 (5) | 0.062 (1) | |
C25 | −0.0476 (4) | 0.0746 (4) | 0.2784 (4) | 0.071 (1) | |
H1 | 0.6373 | 0.3698 | 0.0123 | 0.0800* | |
H2 | 0.5211 | 0.3564 | 0.0558 | 0.0800* | |
H3 | 0.7307 | 0.5576 | 0.3269 | 0.1458* | |
H4 | 0.7362 | 0.5516 | 0.1720 | 0.1458* | |
H5 | 0.6170 | 0.5357 | 0.2089 | 0.1458* | |
H6 | 0.7581 | 0.2951 | 0.2520 | 0.1679* | |
H7 | 0.8216 | 0.4049 | 0.1978 | 0.1679* | |
H8 | 0.8162 | 0.4109 | 0.3528 | 0.1679* | |
H9 | 0.6327 | 0.3875 | 0.4140 | 0.1881* | |
H10 | 0.5175 | 0.3633 | 0.2976 | 0.1881* | |
H11 | 0.5738 | 0.2705 | 0.3157 | 0.1881* | |
H12 | 0.4059 | −0.0130 | −0.4570 | 0.0543* | |
H13 | 0.2825 | −0.0384 | −0.4281 | 0.0543* | |
H14 | 0.3273 | 0.2000 | −0.5984 | 0.0813* | |
H15 | 0.3741 | 0.1027 | −0.6271 | 0.0813* | |
H16 | 0.2457 | 0.0738 | −0.6131 | 0.0813* | |
H17 | 0.3189 | 0.1718 | −0.2531 | 0.1046* | |
H18 | 0.2935 | 0.2420 | −0.3694 | 0.1046* | |
H19 | 0.2120 | 0.1159 | −0.3829 | 0.1046* | |
H20 | 0.5214 | 0.2160 | −0.2760 | 0.1021* | |
H21 | 0.5424 | 0.1894 | −0.4214 | 0.1021* | |
H22 | 0.4970 | 0.2874 | −0.3912 | 0.1021* | |
H23 | 0.2582 | −0.1893 | 0.1670 | 0.0588* | |
H24 | 0.2426 | −0.1279 | 0.2993 | 0.0588* | |
H25 | −0.0096 | −0.3001 | 0.0467 | 0.1289* | |
H26 | 0.0785 | −0.3599 | 0.0277 | 0.1289* | |
H27 | −0.0201 | −0.4141 | 0.1012 | 0.1289* | |
H28 | 0.0930 | −0.2170 | 0.4087 | 0.1180* | |
H29 | −0.0021 | −0.2132 | 0.2805 | 0.1180* | |
H30 | −0.0118 | −0.3277 | 0.3333 | 0.1180* | |
H31 | 0.1273 | −0.4214 | 0.3015 | 0.1329* | |
H32 | 0.2264 | −0.3672 | 0.2287 | 0.1329* | |
H33 | 0.2329 | −0.3112 | 0.3767 | 0.1329* | |
H34 | 0.2910 | 0.3923 | 0.1744 | 0.0897* | |
H35 | 0.2262 | 0.4267 | 0.3681 | 0.0989* | |
H36 | 0.0743 | 0.2853 | 0.4168 | 0.0914* | |
H37 | 0.2397 | 0.1442 | −0.0088 | 0.0750* | |
H38 | 0.1507 | 0.1906 | −0.0961 | 0.0750* | |
H39 | 0.2783 | 0.2725 | −0.0212 | 0.0750* | |
H40 | −0.0655 | 0.0994 | 0.3610 | 0.0851* | |
H41 | −0.1159 | 0.0533 | 0.2019 | 0.0851* | |
H42 | −0.0238 | 0.0109 | 0.2907 | 0.0851* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu1 | 0.0316 (2) | 0.0394 (2) | 0.0408 (2) | 0.0139 (2) | 0.0093 (2) | 0.0128 (2) |
Cu2 | 0.0322 (3) | 0.0418 (3) | 0.0457 (3) | 0.0181 (3) | 0.0151 (3) | 0.0147 (3) |
O1 | 0.051 (1) | 0.044 (1) | 0.080 (2) | 0.022 (1) | 0.014 (1) | 0.011 (1) |
O2 | 0.058 (2) | 0.040 (1) | 0.067 (2) | 0.015 (1) | 0.023 (1) | 0.007 (1) |
O3 | 0.038 (1) | 0.079 (2) | 0.045 (1) | 0.021 (1) | 0.011 (1) | 0.023 (1) |
O4 | 0.043 (1) | 0.066 (2) | 0.045 (1) | 0.026 (1) | 0.011 (1) | 0.017 (1) |
O5 | 0.041 (1) | 0.054 (1) | 0.059 (1) | 0.023 (1) | 0.021 (1) | 0.027 (1) |
O6 | 0.038 (1) | 0.050 (1) | 0.059 (1) | 0.020 (1) | 0.019 (1) | 0.022 (1) |
N1 | 0.043 (1) | 0.051 (2) | 0.054 (2) | 0.024 (1) | 0.010 (1) | 0.012 (1) |
C1 | 0.053 (2) | 0.036 (2) | 0.048 (2) | 0.013 (2) | 0.002 (2) | 0.010 (2) |
C2 | 0.084 (3) | 0.040 (2) | 0.078 (3) | 0.021 (2) | 0.024 (2) | 0.016 (2) |
C3 | 0.082 (3) | 0.046 (2) | 0.080 (3) | 0.003 (2) | 0.020 (3) | −0.002 (2) |
C4 | 0.147 (5) | 0.048 (3) | 0.137 (5) | 0.007 (3) | 0.027 (4) | −0.015 (3) |
C5 | 0.104 (5) | 0.108 (5) | 0.157 (6) | 0.027 (4) | −0.035 (4) | −0.025 (5) |
C6 | 0.200 (8) | 0.128 (6) | 0.093 (5) | −0.019 (5) | 0.074 (5) | −0.015 (4) |
C7 | 0.040 (2) | 0.038 (2) | 0.041 (2) | 0.015 (1) | 0.006 (1) | 0.008 (1) |
C8 | 0.047 (2) | 0.049 (2) | 0.039 (2) | 0.020 (2) | 0.006 (1) | 0.008 (1) |
C9 | 0.056 (2) | 0.051 (2) | 0.043 (2) | 0.023 (2) | 0.011 (2) | 0.013 (2) |
C10 | 0.085 (3) | 0.077 (3) | 0.048 (2) | 0.038 (3) | 0.009 (2) | 0.023 (2) |
C11 | 0.136 (5) | 0.087 (3) | 0.089 (3) | 0.078 (4) | 0.061 (3) | 0.039 (3) |
C12 | 0.082 (3) | 0.066 (3) | 0.084 (3) | 0.006 (2) | 0.000 (3) | 0.033 (3) |
C13 | 0.037 (2) | 0.040 (2) | 0.044 (2) | 0.015 (1) | 0.011 (1) | 0.010 (1) |
C14 | 0.039 (2) | 0.050 (2) | 0.061 (2) | 0.017 (2) | 0.013 (2) | 0.026 (2) |
C15 | 0.051 (2) | 0.047 (2) | 0.080 (3) | 0.014 (2) | 0.011 (2) | 0.028 (2) |
C16 | 0.117 (4) | 0.049 (3) | 0.127 (5) | 0.027 (3) | −0.016 (4) | −0.004 (3) |
C17 | 0.086 (4) | 0.110 (4) | 0.118 (4) | 0.033 (3) | 0.054 (3) | 0.062 (4) |
C18 | 0.084 (3) | 0.083 (4) | 0.181 (6) | 0.038 (3) | 0.029 (4) | 0.087 (4) |
C19 | 0.044 (2) | 0.046 (2) | 0.068 (2) | 0.020 (2) | 0.008 (2) | 0.019 (2) |
C20 | 0.068 (3) | 0.050 (3) | 0.089 (3) | 0.012 (2) | −0.003 (2) | 0.018 (2) |
C21 | 0.100 (4) | 0.055 (3) | 0.075 (3) | 0.026 (3) | −0.003 (3) | −0.003 (2) |
C22 | 0.092 (3) | 0.077 (3) | 0.063 (3) | 0.043 (3) | 0.012 (2) | 0.000 (2) |
C23 | 0.052 (2) | 0.062 (2) | 0.056 (2) | 0.027 (2) | 0.007 (2) | 0.007 (2) |
C24 | 0.045 (2) | 0.053 (2) | 0.097 (3) | 0.017 (2) | 0.027 (2) | 0.031 (2) |
C25 | 0.058 (2) | 0.097 (4) | 0.061 (3) | 0.028 (2) | 0.022 (2) | 0.006 (2) |
Geometric parameters (Å, º) top
Cu1—Cu1i | 2.652 (1) | C9—C12 | 1.526 (6) |
Cu1—O1 | 1.972 (3) | C10—H14 | 0.960 |
Cu1—O2i | 1.965 (2) | C10—H15 | 0.960 |
Cu1—O3 | 1.967 (2) | C10—H16 | 0.960 |
Cu1—O4i | 1.967 (2) | C11—H17 | 0.960 |
Cu1—O5 | 2.185 (2) | C11—H18 | 0.960 |
Cu2—O5 | 2.923 (2) | C11—H19 | 0.960 |
Cu2—O6 | 1.938 (2) | C12—H20 | 0.960 |
Cu2—O6ii | 1.938 (2) | C12—H21 | 0.960 |
Cu2—N1 | 2.050 (3) | C12—H22 | 0.960 |
Cu2—N1ii | 2.050 (3) | C13—C14 | 1.509 (4) |
O1—C1 | 1.263 (4) | C14—C15 | 1.529 (5) |
O2—C1 | 1.243 (4) | C14—H23 | 0.960 |
O3—C7 | 1.252 (4) | C14—H24 | 0.960 |
O4—C7 | 1.259 (4) | C15—C16 | 1.491 (7) |
O5—C13 | 1.238 (4) | C15—C17 | 1.537 (6) |
O6—C13 | 1.280 (3) | C15—C18 | 1.523 (6) |
N1—C19 | 1.353 (4) | C16—H25 | 0.960 |
N1—C23 | 1.350 (4) | C16—H26 | 0.960 |
C1—C2 | 1.516 (5) | C16—H27 | 0.960 |
C2—C3 | 1.523 (6) | C17—H28 | 0.960 |
C2—H1 | 0.960 | C17—H29 | 0.960 |
C2—H2 | 0.960 | C17—H30 | 0.960 |
C3—C4 | 1.513 (7) | C18—H31 | 0.960 |
C3—C5 | 1.492 (8) | C18—H32 | 0.960 |
C3—C6 | 1.518 (7) | C18—H33 | 0.960 |
C4—H3 | 0.960 | C19—C20 | 1.385 (6) |
C4—H4 | 0.960 | C19—C24 | 1.478 (6) |
C4—H5 | 0.961 | C20—C21 | 1.361 (7) |
C5—H6 | 0.961 | C20—H34 | 0.960 |
C5—H7 | 0.960 | C21—C22 | 1.355 (7) |
C5—H8 | 0.960 | C21—H35 | 0.960 |
C6—H9 | 0.960 | C22—C23 | 1.395 (6) |
C6—H10 | 0.961 | C22—H36 | 0.960 |
C6—H11 | 0.960 | C23—C25 | 1.485 (6) |
C7—C8 | 1.515 (4) | C24—H37 | 0.960 |
C8—C9 | 1.548 (5) | C24—H38 | 0.960 |
C8—H12 | 0.960 | C24—H39 | 0.960 |
C8—H13 | 0.960 | C25—H40 | 0.960 |
C9—C10 | 1.523 (5) | C25—H41 | 0.960 |
C9—C11 | 1.503 (5) | C25—H42 | 0.960 |
| | | |
Cu1···Cu1i | 2.6515 (9) | | |
| | | |
Cu1i—Cu1—O1 | 84.2 (1) | C9—C10—H14 | 109.5 |
Cu1i—Cu1—O2i | 83.6 (1) | C9—C10—H15 | 109.5 |
Cu1i—Cu1—O3 | 83.3 (1) | C9—C10—H16 | 109.5 |
Cu1i—Cu1—O4i | 84.4 (1) | H14—C10—H15 | 109.5 |
Cu1i—Cu1—O5 | 174.9 (1) | H14—C10—H16 | 109.5 |
O1—Cu1—O2i | 167.7 (1) | H15—C10—H16 | 109.5 |
O1—Cu1—O3 | 88.9 (1) | C9—C11—H17 | 109.5 |
O1—Cu1—O4i | 89.1 (1) | C9—C11—H18 | 109.5 |
O1—Cu1—O5 | 96.7 (1) | C9—C11—H19 | 109.5 |
O2i—Cu1—O3 | 90.3 (1) | H17—C11—H18 | 109.5 |
O2i—Cu1—O4i | 89.1 (1) | H17—C11—H19 | 109.4 |
O2i—Cu1—O5 | 95.6 (1) | H18—C11—H19 | 109.5 |
O3—Cu1—O4i | 167.7 (1) | C9—C12—H20 | 109.5 |
O3—Cu1—O5 | 91.7 (1) | C9—C12—H21 | 109.5 |
O4i—Cu1—O5 | 100.7 (1) | C9—C12—H22 | 109.5 |
O6—Cu2—O6ii | 180.0 | H20—C12—H21 | 109.4 |
O6—Cu2—N1 | 92.2 (1) | H20—C12—H22 | 109.5 |
O6—Cu2—N1ii | 87.8 (1) | H21—C12—H22 | 109.5 |
O6ii—Cu2—N1 | 87.8 (1) | O5—C13—O6 | 121.9 (3) |
O6ii—Cu2—N1ii | 92.2 (1) | O5—C13—C14 | 120.4 (3) |
N1—Cu2—N1ii | 180.0 | O6—C13—C14 | 117.7 (3) |
Cu1—O1—C1 | 122.4 (2) | C13—C14—C15 | 119.4 (3) |
Cu1i—O2—C1 | 124.0 (2) | C13—C14—H23 | 106.9 |
Cu1—O3—C7 | 124.2 (2) | C13—C14—H24 | 106.9 |
Cu1i—O4—C7 | 122.7 (2) | C15—C14—H23 | 106.9 |
Cu1—O5—C13 | 134.1 (2) | C15—C14—H24 | 106.9 |
Cu2—O6—C13 | 117.8 (2) | H23—C14—H24 | 109.5 |
Cu2—N1—C19 | 120.1 (2) | C14—C15—C16 | 111.6 (4) |
Cu2—N1—C23 | 120.3 (2) | C14—C15—C17 | 110.3 (4) |
C19—N1—C23 | 119.4 (3) | C14—C15—C18 | 107.6 (3) |
O1—C1—O2 | 125.9 (3) | C16—C15—C17 | 109.4 (4) |
O1—C1—C2 | 117.4 (3) | C16—C15—C18 | 109.1 (4) |
O2—C1—C2 | 116.7 (3) | C17—C15—C18 | 108.7 (4) |
C1—C2—C3 | 115.2 (3) | C15—C16—H25 | 109.5 |
C1—C2—H1 | 108.0 | C15—C16—H26 | 109.5 |
C1—C2—H2 | 108.0 | C15—C16—H27 | 109.5 |
C3—C2—H1 | 108.0 | H25—C16—H26 | 109.5 |
C3—C2—H2 | 108.0 | H25—C16—H27 | 109.5 |
H1—C2—H2 | 109.5 | H26—C16—H27 | 109.5 |
C2—C3—C4 | 109.1 (4) | C15—C17—H28 | 109.5 |
C2—C3—C5 | 111.9 (4) | C15—C17—H29 | 109.5 |
C2—C3—C6 | 108.8 (4) | C15—C17—H30 | 109.5 |
C4—C3—C5 | 109.1 (5) | H28—C17—H29 | 109.5 |
C4—C3—C6 | 108.9 (5) | H28—C17—H30 | 109.5 |
C5—C3—C6 | 109.0 (6) | H29—C17—H30 | 109.5 |
C3—C4—H3 | 109.5 | C15—C18—H31 | 109.5 |
C3—C4—H4 | 109.5 | C15—C18—H32 | 109.5 |
C3—C4—H5 | 109.5 | C15—C18—H33 | 109.5 |
H3—C4—H4 | 109.5 | H31—C18—H32 | 109.4 |
H3—C4—H5 | 109.4 | H31—C18—H33 | 109.5 |
H4—C4—H5 | 109.4 | H32—C18—H33 | 109.4 |
C3—C5—H6 | 109.5 | N1—C19—C20 | 120.6 (4) |
C3—C5—H7 | 109.5 | N1—C19—C24 | 118.5 (3) |
C3—C5—H8 | 109.5 | C20—C19—C24 | 120.9 (4) |
H6—C5—H7 | 109.4 | C19—C20—C21 | 120.2 (4) |
H6—C5—H8 | 109.4 | C19—C20—H34 | 119.9 |
H7—C5—H8 | 109.5 | C21—C20—H34 | 119.9 |
C3—C6—H9 | 109.5 | C20—C21—C22 | 119.2 (4) |
C3—C6—H10 | 109.5 | C20—C21—H35 | 120.4 |
C3—C6—H11 | 109.5 | C22—C21—H35 | 120.4 |
H9—C6—H10 | 109.4 | C21—C22—C23 | 120.3 (4) |
H9—C6—H11 | 109.5 | C21—C22—H36 | 119.9 |
H10—C6—H11 | 109.4 | C23—C22—H36 | 119.9 |
O3—C7—O4 | 125.3 (3) | N1—C23—C22 | 120.3 (4) |
O3—C7—C8 | 117.4 (3) | N1—C23—C25 | 117.9 (3) |
O4—C7—C8 | 117.3 (3) | C22—C23—C25 | 121.8 (4) |
C7—C8—C9 | 114.9 (3) | C19—C24—H37 | 109.5 |
C7—C8—H12 | 108.1 | C19—C24—H38 | 109.5 |
C7—C8—H13 | 108.1 | C19—C24—H39 | 109.5 |
C9—C8—H12 | 108.1 | H37—C24—H38 | 109.5 |
C9—C8—H13 | 108.1 | H37—C24—H39 | 109.5 |
H12—C8—H13 | 109.5 | H38—C24—H39 | 109.5 |
C8—C9—C10 | 107.9 (3) | C23—C25—H40 | 109.5 |
C8—C9—C11 | 110.7 (3) | C23—C25—H41 | 109.5 |
C8—C9—C12 | 109.5 (3) | C23—C25—H42 | 109.5 |
C10—C9—C11 | 109.8 (3) | H40—C25—H41 | 109.5 |
C10—C9—C12 | 109.3 (3) | H40—C25—H42 | 109.5 |
C11—C9—C12 | 109.7 (4) | H41—C25—H42 | 109.5 |
| | | |
Cu1—O5—C13—O6 | 173.8 (2) | Cu2—O6—C13—O5 | 7.7 (4) |
Symmetry codes: (i) −x+1, −y, −z; (ii) −x, −y, −z. |
Crystal data top
[Cu2(C5H9O2)4(C7H9N)2] | Z = 1 |
Mr = 745.90 | Dx = 1.254 Mg m−3 |
Triclinic, P1 | Mo Kα radiation, λ = 0.71073 Å |
a = 10.986 (4) Å | Cell parameters from 25 reflections |
b = 11.195 (5) Å | θ = 10–15° |
c = 9.564 (4) Å | µ = 1.12 mm−1 |
α = 107.66 (4)° | T = 298 K |
β = 97.15 (4)° | Prism, green |
γ = 61.82 (3)° | 0.25 × 0.20 × 0.20 mm |
V = 987.7 (8) Å3 | |
Data collection top
Rigaku AFC-7R diffractometer | 3449 reflections with I > 2σ(I) |
θ/2θ scans | Rint = 0.047 |
Absorption correction: integration (Coppens et al., 1965) | θmax = 27.5° |
Tmin = 0.803, Tmax = 0.844 | h = 0→14 |
4761 measured reflections | k = −15→15 |
4524 independent reflections | l = −12→3 |
Refinement top
Refinement on F2 | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.048 | w = 1/{σ2Fo2 + [0.1(Fo2 + 2Fc2)/3]2} |
wR(F2) = 0.152 | (Δ/σ)max = 0.027 |
S = 1.05 | Δρmax = 0.74 e Å−3 |
4524 reflections | Δρmin = −0.36 e Å−3 |
226 parameters | |
Crystal data top
[Cu2(C5H9O2)4(C7H9N)2] | γ = 61.82 (3)° |
Mr = 745.90 | V = 987.7 (8) Å3 |
Triclinic, P1 | Z = 1 |
a = 10.986 (4) Å | Mo Kα radiation |
b = 11.195 (5) Å | µ = 1.12 mm−1 |
c = 9.564 (4) Å | T = 298 K |
α = 107.66 (4)° | 0.25 × 0.20 × 0.20 mm |
β = 97.15 (4)° | |
Data collection top
Rigaku AFC-7R diffractometer | 4524 independent reflections |
Absorption correction: integration (Coppens et al., 1965) | 3449 reflections with I > 2σ(I) |
Tmin = 0.803, Tmax = 0.844 | Rint = 0.047 |
4761 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.048 | 226 parameters |
wR(F2) = 0.152 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.74 e Å−3 |
4524 reflections | Δρmin = −0.36 e Å−3 |
Special details top
Refinement. Refinement using reflections with F2 > 0.0 σ(F2). The weighted R-factor (wR) and goodness of fit (S) are based on F2. R-factor (gt) are based on F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt). |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Cu1 | −0.01511 (4) | 0.40360 (4) | 0.04544 (4) | 0.0439 (1) | |
O1 | −0.1781 (3) | 0.5732 (3) | 0.1470 (3) | 0.0629 (7) | |
O2 | −0.1534 (3) | 0.7324 (2) | 0.0759 (3) | 0.0632 (7) | |
O3 | −0.1197 (3) | 0.3867 (3) | −0.1353 (3) | 0.0679 (8) | |
O4 | −0.0968 (3) | 0.5465 (3) | −0.2065 (3) | 0.0684 (8) | |
N1 | −0.0467 (3) | 0.2424 (3) | 0.1297 (3) | 0.0603 (9) | |
C1 | −0.2134 (3) | 0.6970 (3) | 0.1469 (3) | 0.0523 (8) | |
C2 | −0.3373 (4) | 0.8138 (4) | 0.2429 (5) | 0.076 (1) | |
C3A | −0.415 (1) | 0.937 (1) | 0.176 (1) | 0.109 (4) | 0.50 |
C3B | −0.384 (1) | 0.960 (1) | 0.236 (1) | 0.104 (4) | 0.50 |
C4A | −0.269 (2) | 0.873 (2) | 0.387 (2) | 0.149 (6) | 0.50 |
C4B | −0.285 (2) | 0.813 (2) | 0.400 (2) | 0.221 (10) | 0.50 |
C5A | −0.413 (1) | 0.767 (2) | 0.312 (2) | 0.156 (6) | 0.50 |
C5B | −0.448 (1) | 0.773 (1) | 0.245 (2) | 0.170 (6) | 0.50 |
C6 | −0.1404 (3) | 0.4580 (4) | −0.2219 (4) | 0.0582 (9) | |
C7 | −0.2276 (5) | 0.4388 (5) | −0.3566 (4) | 0.083 (1) | |
C8A | −0.360 (2) | 0.589 (2) | −0.339 (2) | 0.131 (5) | 0.50 |
C8B | −0.374 (2) | 0.535 (2) | −0.304 (2) | 0.180 (8) | 0.50 |
C9A | −0.155 (1) | 0.425 (1) | −0.491 (1) | 0.095 (3) | 0.50 |
C9B | −0.218 (2) | 0.490 (2) | −0.475 (2) | 0.164 (8) | 0.50 |
C10A | −0.283 (2) | 0.337 (2) | −0.363 (2) | 0.129 (6) | 0.50 |
C10B | −0.214 (1) | 0.286 (1) | −0.407 (2) | 0.121 (5) | 0.50 |
C11 | 0.0619 (5) | 0.1413 (4) | 0.1795 (4) | 0.074 (1) | |
C12 | 0.0482 (7) | 0.0351 (5) | 0.2150 (6) | 0.103 (2) | |
C13 | −0.0786 (9) | 0.0358 (7) | 0.1989 (7) | 0.122 (3) | |
C14 | −0.1861 (7) | 0.1379 (6) | 0.1553 (6) | 0.107 (2) | |
C15 | −0.1712 (5) | 0.2421 (5) | 0.1203 (4) | 0.075 (1) | |
C16 | 0.1960 (5) | 0.1425 (5) | 0.1934 (6) | 0.098 (2) | |
C17 | −0.2912 (5) | 0.3521 (6) | 0.0704 (6) | 0.098 (2) | |
H1A | −0.3501 | 0.9636 | 0.1514 | 0.1026* | 0.50 |
H1B | −0.3072 | 0.9812 | 0.2555 | 0.0988* | 0.50 |
H2A | −0.4590 | 0.9091 | 0.0877 | 0.1026* | 0.50 |
H2B | −0.4177 | 0.9678 | 0.1397 | 0.0988* | 0.50 |
H3A | −0.4826 | 1.0155 | 0.2445 | 0.1026* | 0.50 |
H3B | −0.4560 | 1.0250 | 0.3077 | 0.0988* | 0.50 |
H4A | −0.2113 | 0.7973 | 0.4304 | 0.1285* | 0.50 |
H4B | −0.2536 | 0.7204 | 0.4106 | 0.1803* | 0.50 |
H5A | −0.2134 | 0.9090 | 0.3620 | 0.1285* | 0.50 |
H5B | −0.2110 | 0.8372 | 0.4166 | 0.1803* | 0.50 |
H6A | −0.3400 | 0.9466 | 0.4567 | 0.1285* | 0.50 |
H6B | −0.3596 | 0.8803 | 0.4686 | 0.1803* | 0.50 |
H7A | −0.4792 | 0.8461 | 0.3823 | 0.1169* | 0.50 |
H7B | −0.5152 | 0.8422 | 0.3189 | 0.1160* | 0.50 |
H8A | −0.4634 | 0.7278 | 0.2361 | 0.1169* | 0.50 |
H8B | −0.4924 | 0.7693 | 0.1496 | 0.1160* | 0.50 |
H9A | −0.3509 | 0.6966 | 0.3565 | 0.1169* | 0.50 |
H9B | −0.4085 | 0.6826 | 0.2607 | 0.1160* | 0.50 |
H10A | −0.3314 | 0.6602 | −0.3241 | 0.1236* | 0.50 |
H10B | −0.3884 | 0.6304 | −0.2716 | 0.1596* | 0.50 |
H11A | −0.4143 | 0.5866 | −0.4258 | 0.1236* | 0.50 |
H11B | −0.4352 | 0.5252 | −0.3826 | 0.1596* | 0.50 |
H12A | −0.4153 | 0.6100 | −0.2558 | 0.1236* | 0.50 |
H12B | −0.3923 | 0.5101 | −0.2239 | 0.1596* | 0.50 |
H13A | −0.0716 | 0.3362 | −0.5131 | 0.0953* | 0.50 |
H13B | −0.1263 | 0.4342 | −0.5183 | 0.1628* | 0.50 |
H14A | −0.2146 | 0.4279 | −0.5730 | 0.0953* | 0.50 |
H14B | −0.2838 | 0.4821 | −0.5484 | 0.1628* | 0.50 |
H15A | −0.1314 | 0.5007 | −0.4702 | 0.0953* | 0.50 |
H15B | −0.2363 | 0.5866 | −0.4369 | 0.1628* | 0.50 |
H16A | −0.3330 | 0.3656 | −0.2744 | 0.1302* | 0.50 |
H16B | −0.2354 | 0.2656 | −0.3251 | 0.1136* | 0.50 |
H17A | −0.3418 | 0.3352 | −0.4456 | 0.1302* | 0.50 |
H17B | −0.2770 | 0.2800 | −0.4843 | 0.1136* | 0.50 |
H18A | −0.2064 | 0.2436 | −0.3744 | 0.1302* | 0.50 |
H18B | −0.1212 | 0.2191 | −0.4412 | 0.1136* | 0.50 |
H19 | 0.1256 | −0.0362 | 0.2503 | 0.1211* | |
H20 | −0.0878 | −0.0381 | 0.2207 | 0.1419* | |
H21 | −0.2735 | 0.1373 | 0.1465 | 0.1315* | |
H22 | 0.2627 | 0.0658 | 0.2301 | 0.1191* | |
H23 | 0.2270 | 0.1330 | 0.0992 | 0.1191* | |
H24 | 0.1865 | 0.2304 | 0.2605 | 0.1191* | |
H25 | −0.3092 | 0.4429 | 0.1357 | 0.1168* | |
H26 | −0.2731 | 0.3485 | −0.0271 | 0.1168* | |
H27 | −0.3706 | 0.3369 | 0.0691 | 0.1168* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu1 | 0.0442 (2) | 0.0466 (2) | 0.0401 (2) | −0.0195 (2) | 0.0011 (1) | 0.0124 (1) |
O1 | 0.056 (1) | 0.060 (1) | 0.069 (2) | −0.021 (1) | 0.017 (1) | 0.014 (1) |
O2 | 0.058 (1) | 0.053 (1) | 0.069 (2) | −0.014 (1) | 0.016 (1) | 0.018 (1) |
O3 | 0.071 (2) | 0.091 (2) | 0.055 (1) | −0.047 (1) | −0.015 (1) | 0.025 (1) |
O4 | 0.079 (2) | 0.075 (2) | 0.056 (1) | −0.039 (1) | −0.021 (1) | 0.026 (1) |
N1 | 0.077 (2) | 0.054 (2) | 0.051 (2) | −0.031 (1) | 0.008 (1) | 0.010 (1) |
C1 | 0.044 (2) | 0.056 (2) | 0.049 (2) | −0.017 (1) | 0.001 (1) | 0.014 (1) |
C2 | 0.061 (2) | 0.060 (2) | 0.084 (3) | −0.007 (2) | 0.026 (2) | 0.016 (2) |
C3A | 0.076 (6) | 0.078 (7) | 0.14 (1) | 0.010 (5) | 0.038 (7) | 0.053 (7) |
C3B | 0.098 (8) | 0.080 (7) | 0.118 (9) | −0.024 (6) | 0.041 (7) | 0.017 (6) |
C4A | 0.13 (1) | 0.16 (1) | 0.085 (9) | −0.06 (1) | 0.035 (9) | −0.058 (9) |
C4B | 0.12 (2) | 0.27 (3) | 0.13 (2) | −0.03 (2) | 0.05 (1) | −0.05 (2) |
C5A | 0.12 (1) | 0.10 (1) | 0.21 (2) | −0.007 (8) | 0.13 (1) | 0.035 (10) |
C5B | 0.057 (6) | 0.075 (8) | 0.34 (2) | −0.023 (6) | 0.08 (1) | −0.01 (1) |
C6 | 0.049 (2) | 0.069 (2) | 0.044 (2) | −0.022 (2) | −0.005 (1) | 0.009 (2) |
C7 | 0.085 (3) | 0.103 (3) | 0.059 (2) | −0.049 (3) | −0.030 (2) | 0.024 (2) |
C8A | 0.073 (8) | 0.16 (1) | 0.13 (1) | −0.039 (8) | −0.050 (8) | 0.05 (1) |
C8B | 0.081 (10) | 0.26 (2) | 0.15 (1) | −0.06 (1) | −0.057 (9) | 0.03 (2) |
C9A | 0.101 (7) | 0.128 (9) | 0.033 (4) | −0.044 (7) | −0.006 (4) | 0.009 (4) |
C9B | 0.24 (2) | 0.26 (2) | 0.081 (9) | −0.17 (2) | −0.07 (1) | 0.08 (1) |
C10A | 0.16 (1) | 0.14 (1) | 0.113 (9) | −0.10 (1) | −0.07 (1) | 0.042 (9) |
C10B | 0.17 (1) | 0.118 (9) | 0.080 (7) | −0.087 (10) | −0.062 (8) | 0.019 (7) |
C11 | 0.102 (3) | 0.055 (2) | 0.059 (2) | −0.027 (2) | 0.018 (2) | 0.015 (2) |
C12 | 0.150 (5) | 0.063 (3) | 0.091 (3) | −0.033 (3) | 0.026 (3) | 0.029 (2) |
C13 | 0.188 (7) | 0.091 (4) | 0.125 (5) | −0.087 (5) | 0.037 (5) | 0.026 (3) |
C14 | 0.157 (6) | 0.094 (4) | 0.104 (4) | −0.086 (4) | 0.026 (4) | 0.014 (3) |
C15 | 0.100 (3) | 0.080 (3) | 0.062 (2) | −0.059 (3) | 0.016 (2) | 0.003 (2) |
C16 | 0.088 (3) | 0.089 (3) | 0.115 (4) | −0.021 (3) | −0.009 (3) | 0.064 (3) |
C17 | 0.073 (3) | 0.134 (4) | 0.120 (4) | −0.067 (3) | −0.007 (3) | 0.048 (3) |
Geometric parameters (Å, º) top
Cu1—Cu1i | 2.722 (1) | C7—C8B | 1.494 (5) |
Cu1—O1 | 1.964 (2) | C7—C9A | 1.526 (5) |
Cu1—O2i | 1.973 (2) | C7—C9B | 1.450 (5) |
Cu1—O3 | 1.964 (2) | C7—C10A | 1.509 (5) |
Cu1—O4i | 1.962 (3) | C7—C10B | 1.566 (5) |
Cu1—N1 | 2.360 (3) | C8A—H10A | 0.955 |
O1—C1 | 1.250 (4) | C8A—H11A | 0.959 |
O2—C1 | 1.256 (4) | C8A—H12A | 0.964 |
O3—C6 | 1.248 (4) | C8B—H10B | 0.953 |
O4—C6 | 1.255 (4) | C8B—H11B | 0.961 |
N1—C11 | 1.357 (5) | C8B—H12B | 0.966 |
N1—C15 | 1.360 (5) | C9A—H13A | 0.962 |
C1—C2 | 1.519 (4) | C9A—H14A | 0.959 |
C2—C3A | 1.526 (4) | C9A—H15A | 0.958 |
C2—C3B | 1.490 (4) | C9B—H13B | 0.963 |
C2—C4A | 1.602 (5) | C9B—H14B | 0.960 |
C2—C4B | 1.541 (5) | C9B—H15B | 0.957 |
C2—C5A | 1.470 (4) | C10A—H16A | 0.955 |
C2—C5B | 1.491 (4) | C10A—H17A | 0.960 |
C3A—H1A | 0.963 | C10A—H18A | 0.963 |
C3A—H2A | 0.963 | C10B—H16B | 0.961 |
C3A—H3A | 0.956 | C10B—H17B | 0.958 |
C3B—H1B | 0.956 | C10B—H18B | 0.962 |
C3B—H2B | 0.961 | C11—C12 | 1.407 (6) |
C3B—H3B | 0.959 | C11—C16 | 1.468 (7) |
C4A—H4A | 0.964 | C12—C13 | 1.378 (9) |
C4A—H5A | 0.957 | C12—H19 | 0.961 |
C4A—H6A | 0.961 | C13—C14 | 1.329 (9) |
C4B—H4B | 0.959 | C13—H20 | 0.963 |
C4B—H5B | 0.952 | C14—C15 | 1.390 (7) |
C4B—H6B | 0.962 | C14—H21 | 0.957 |
C5A—H7A | 0.955 | C15—C17 | 1.466 (7) |
C5A—H8A | 0.982 | C16—H22 | 0.960 |
C5A—H9A | 0.946 | C16—H23 | 0.961 |
C5B—H7B | 0.953 | C16—H24 | 0.963 |
C5B—H8B | 0.976 | C17—H25 | 0.958 |
C5B—H9B | 0.947 | C17—H26 | 0.962 |
C6—C7 | 1.530 (5) | C17—H27 | 0.961 |
C7—C8A | 1.600 (5) | | |
| | | |
Cu1···Cu1i | 2.7223 (7) | C11···C14ii | 3.589 (7) |
N1···C13ii | 3.544 (7) | C12···C15ii | 3.580 (6) |
C11···C13ii | 3.540 (8) | | |
| | | |
Cu1i—Cu1—O1 | 81.8 (1) | C6—C7—C8A | 105.7 (3) |
Cu1i—Cu1—O2i | 83.7 (1) | C6—C7—C8B | 105.0 (3) |
Cu1i—Cu1—O3 | 84.2 (1) | C6—C7—C9A | 108.5 (3) |
Cu1i—Cu1—O4i | 81.1 (1) | C6—C7—C9B | 116.6 (3) |
Cu1i—Cu1—N1 | 178.2 (1) | C6—C7—C10A | 113.7 (3) |
O1—Cu1—O2i | 165.5 (1) | C6—C7—C10B | 111.3 (3) |
O1—Cu1—O3 | 90.7 (1) | C8A—C7—C9A | 101.6 (3) |
O1—Cu1—O4i | 88.1 (1) | C8A—C7—C10A | 105.8 (3) |
O1—Cu1—N1 | 96.4 (1) | C8B—C7—C9B | 102.0 (3) |
O2i—Cu1—O3 | 87.1 (1) | C8B—C7—C10B | 105.8 (3) |
O2i—Cu1—O4i | 90.4 (1) | C9A—C7—C10A | 120.0 (3) |
O2i—Cu1—N1 | 98.1 (1) | C9B—C7—C10B | 114.5 (3) |
O3—Cu1—O4i | 165.3 (1) | C7—C8A—H10A | 109.5 |
O3—Cu1—N1 | 96.2 (1) | C7—C8A—H11A | 109.5 |
O4i—Cu1—N1 | 98.5 (1) | C7—C8A—H12A | 109.1 |
Cu1—O1—C1 | 126.0 (2) | H10A—C8A—H11A | 109.9 |
Cu1i—O2—C1 | 123.2 (2) | H10A—C8A—H12A | 109.6 |
Cu1—O3—C6 | 123.0 (2) | H11A—C8A—H12A | 109.2 |
Cu1i—O4—C6 | 126.6 (2) | C7—C8B—H10B | 109.7 |
Cu1—N1—C11 | 120.4 (3) | C7—C8B—H11B | 109.6 |
Cu1—N1—C15 | 121.1 (3) | C7—C8B—H12B | 109.2 |
C11—N1—C15 | 118.4 (4) | H10B—C8B—H11B | 109.9 |
O1—C1—O2 | 125.2 (3) | H10B—C8B—H12B | 109.5 |
O1—C1—C2 | 117.2 (3) | H11B—C8B—H12B | 108.9 |
O2—C1—C2 | 117.5 (3) | C7—C9A—H13A | 109.5 |
C1—C2—C3A | 110.7 (3) | C7—C9A—H14A | 109.5 |
C1—C2—C3B | 116.9 (3) | C7—C9A—H15A | 109.3 |
C1—C2—C4A | 103.3 (3) | H13A—C9A—H14A | 109.4 |
C1—C2—C4B | 103.2 (3) | H13A—C9A—H15A | 109.5 |
C1—C2—C5A | 115.8 (3) | H14A—C9A—H15A | 109.7 |
C1—C2—C5B | 112.8 (3) | C7—C9B—H13B | 109.5 |
C3A—C2—C4A | 104.9 (3) | C7—C9B—H14B | 109.6 |
C3A—C2—C5A | 120.7 (3) | C7—C9B—H15B | 109.4 |
C3B—C2—C4B | 105.4 (3) | H13B—C9B—H14B | 109.2 |
C3B—C2—C5B | 116.5 (3) | H13B—C9B—H15B | 109.4 |
C4A—C2—C5A | 98.2 (3) | H14B—C9B—H15B | 109.7 |
C4B—C2—C5B | 98.9 (2) | C7—C10A—H16A | 109.4 |
C2—C3A—H1A | 109.4 | C7—C10A—H17A | 109.3 |
C2—C3A—H2A | 109.7 | C7—C10A—H18A | 109.3 |
C2—C3A—H3A | 109.6 | H16A—C10A—H17A | 110.0 |
H1A—C3A—H2A | 109.0 | H16A—C10A—H18A | 109.7 |
H1A—C3A—H3A | 109.6 | H17A—C10A—H18A | 109.2 |
H2A—C3A—H3A | 109.6 | C7—C10B—H16B | 109.4 |
C2—C3B—H1B | 109.2 | C7—C10B—H17B | 109.7 |
C2—C3B—H2B | 109.5 | C7—C10B—H18B | 109.6 |
C2—C3B—H3B | 109.1 | H16B—C10B—H17B | 109.6 |
H1B—C3B—H2B | 109.7 | H16B—C10B—H18B | 109.2 |
H1B—C3B—H3B | 109.9 | H17B—C10B—H18B | 109.5 |
H2B—C3B—H3B | 109.5 | N1—C11—C12 | 121.1 (5) |
C2—C4A—H4A | 109.2 | N1—C11—C16 | 118.9 (4) |
C2—C4A—H5A | 110.0 | C12—C11—C16 | 120.0 (5) |
C2—C4A—H6A | 109.6 | C11—C12—C13 | 118.6 (5) |
H4A—C4A—H5A | 109.4 | C11—C12—H19 | 120.6 |
H4A—C4A—H6A | 109.1 | C13—C12—H19 | 120.7 |
H5A—C4A—H6A | 109.6 | C12—C13—C14 | 120.2 (5) |
C2—C4B—H4B | 108.9 | C12—C13—H20 | 118.9 |
C2—C4B—H5B | 109.5 | C14—C13—H20 | 120.9 |
C2—C4B—H6B | 108.9 | C13—C14—C15 | 120.6 (6) |
H4B—C4B—H5B | 110.2 | C13—C14—H21 | 118.8 |
H4B—C4B—H6B | 109.4 | C15—C14—H21 | 120.6 |
H5B—C4B—H6B | 110.0 | N1—C15—C14 | 121.0 (5) |
C2—C5A—H7A | 109.9 | N1—C15—C17 | 119.7 (4) |
C2—C5A—H8A | 108.7 | C14—C15—C17 | 119.3 (5) |
C2—C5A—H9A | 110.2 | C11—C16—H22 | 109.9 |
H7A—C5A—H8A | 108.1 | C11—C16—H23 | 109.8 |
H7A—C5A—H9A | 111.1 | C11—C16—H24 | 109.4 |
H8A—C5A—H9A | 108.8 | H22—C16—H23 | 109.4 |
C2—C5B—H7B | 109.4 | H22—C16—H24 | 109.2 |
C2—C5B—H8B | 108.6 | H23—C16—H24 | 109.1 |
C2—C5B—H9B | 109.6 | C15—C17—H25 | 109.6 |
H7B—C5B—H8B | 108.7 | C15—C17—H26 | 109.6 |
H7B—C5B—H9B | 111.2 | C15—C17—H27 | 109.5 |
H8B—C5B—H9B | 109.2 | H25—C17—H26 | 109.4 |
O3—C6—O4 | 125.1 (3) | H25—C17—H27 | 109.5 |
O3—C6—C7 | 118.1 (4) | H26—C17—H27 | 109.2 |
O4—C6—C7 | 116.8 (3) | | |
Symmetry codes: (i) −x, −y+1, −z; (ii) −x, −y, −z. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | [Cu3(C6H11O2)6(C7H9N)2] | [Cu2(C5H9O2)4(C7H9N)2] |
Mr | 1095.86 | 745.90 |
Crystal system, space group | Triclinic, P1 | Triclinic, P1 |
Temperature (K) | 298 | 298 |
a, b, c (Å) | 12.525 (2), 12.736 (2), 10.033 (2) | 10.986 (4), 11.195 (5), 9.564 (4) |
α, β, γ (°) | 94.64 (1), 102.51 (1), 109.32 (1) | 107.66 (4), 97.15 (4), 61.82 (3) |
V (Å3) | 1454.1 (5) | 987.7 (8) |
Z | 1 | 1 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 1.14 | 1.12 |
Crystal size (mm) | 0.4 × 0.1 × 0.1 | 0.25 × 0.20 × 0.20 |
|
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 | 0.472, 0.753 | 0.803, 0.844 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6956, 6651, 4193 | 4761, 4524, 3449 |
Rint | 0.021 | 0.047 |
(sin θ/λ)max (Å−1) | 0.650 | 0.650 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.115, 1.08 | 0.048, 0.152, 1.05 |
No. of reflections | 6651 | 4524 |
No. of parameters | 304 | 226 |
No. of restraints | ? | ? |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.41, −0.61 | 0.74, −0.36 |
Selected geometric parameters (Å, º) for (I) topCu1—Cu1i | 2.652 (1) | Cu1—O5 | 2.185 (2) |
Cu1—O1 | 1.972 (3) | Cu2—O5 | 2.923 (2) |
Cu1—O2i | 1.965 (2) | Cu2—O6 | 1.938 (2) |
Cu1—O3 | 1.967 (2) | Cu2—N1 | 2.050 (3) |
Cu1—O4i | 1.967 (2) | | |
| | | |
O1—Cu1—O2i | 167.7 (1) | O1—C1—O2 | 125.9 (3) |
O3—Cu1—O4i | 167.7 (1) | O3—C7—O4 | 125.3 (3) |
O6—Cu2—N1 | 92.2 (1) | O5—C13—O6 | 121.9 (3) |
Cu1—O5—C13 | 134.1 (2) | | |
| | | |
Cu1—O5—C13—O6 | 173.8 (2) | Cu2—O6—C13—O5 | 7.7 (4) |
Symmetry code: (i) −x+1, −y, −z. |
Selected geometric parameters (Å, º) for (II) topCu1—Cu1i | 2.722 (1) | Cu1—O3 | 1.964 (2) |
Cu1—O1 | 1.964 (2) | Cu1—O4i | 1.962 (3) |
Cu1—O2i | 1.973 (2) | Cu1—N1 | 2.360 (3) |
| | | |
O1—Cu1—O2i | 165.5 (1) | O1—C1—O2 | 125.2 (3) |
O3—Cu1—O4i | 165.3 (1) | O3—C6—O4 | 125.1 (3) |
Symmetry code: (i) −x, −y+1, −z. |
Copper(II) carboxylates usually have a cage structure with square-pyramidal coordination geometry and a monodentate ligand bonded at the axial position. 2,6-Dimethylpyridine, 2,6-Me2py, is a bulky ligand which may cause a deformation of this cage structure, as observed in the crystals of [Cu2(PhMe2CCOO)2(2,6-Me2py)2], where the geometry about the CuII is deformed from square-pyramidal toward trigonal bipyramidal (TBP). Alternatively, only a mononuclear complex, [Cu(RCOO)2(2,6-Me2py)2], will be produced, as for R = Ph3C or Ph2MeC (Fujita et al., 1993). In this context, the crystal structures of the two title compounds, (I) and (II), respectively, are presented here. \sch
In (I), a novel polymeric structure was observed. The mononuclear moiety [Cu(RCOO)2(2,6-Me2py)2] acts as the axial ligand to the binuclear unit. The carboxylato bridge between the mononuclear and binuclear units has a syn-anti conformation. An analysis of the temperature dependence of the magnetic susceptibility indicated that the spin-exchange interaction between the mononuclear and binuclear units is negligible. The Cu···Cu distance in the binuclear unit is 2.652 (1) Å, which is similar to that of the 3,3-dimethylbutyric acid adduct [2.599 (1) Å; Goto et al., 2000].
In (II), the binuclear cage structure of the copper pivalate does not have a TBP distortion, which is consistent with the high magnetic −2 J value of 379 cm−1 (H = −2JS1·S2; Muto et al., 1986). The acridine adduct of copper(II) pivalate also has a cage structure with square-pyramidal coordination, the Cu···Cu and Cu—N distances being 2.702 (1) and 2.371 (5) Å, respectively (Kirillova et al., 1980). Copper pivalate remains a discrete dimeric structure even after the removal of the axial solvent ligands (Muto et al., 1986; Kato & Muto, 1988). In polymeric copper(II) pivalate, prepared by sublimation, the dinuclear cage is deformed and the coordination geometry around the Cu has a TBP distortion (Il'ina et al., 1992).