metal-organic compounds
catena-Poly[triethylammonium [[tetra-μ-acetato-κ8O:O′-dicuprate(II)]-μ-acetato-κ2O:O′] tetrahydrofuran monosolvate]
aInstitute of Inorganic Chemistry, University of Hamburg, Hamburg, Germany, and bInstitute for Physical Chemistry, TU Kaiserslautern, Kaiserslautern, Germany
*Correspondence e-mail: prosenc@chemie.uni-kl.de
In the title compound, {[(C2H5)3NH][Cu2(CH3COO)5]·C4H8O}n, the two different CuII atoms are coordinated in a pseudo-square-pyramidal environment by five O atoms from the acetate ligands. Neighbouring pairs of CuII atoms are linked by four basally coordinating bridging acetate ligands as in the of copper acetate monohydrate. The fifth, apically coordinating ligand links two of the dicopper tetraacetate paddlewheel-units together, thus building a linear coordination polymer which extends along [10-1]. Each apical acetate ligand is linked by an N—H⋯O hydrogen bond to a triethylammonium cation. Weak C—H⋯O hydrogen bonding interactions also occur.
Related literature
For the ); de Meester et al. (1973). For copper-based coordination polymers, see: Furukawa et al. (2008). The title compound was obtained as a minor byproduct in the synthesis of a copper–salene compound, see: Kleij et al. (2005).
of dicoppertetraacetate dihydrate, see: van Niekerk & Schoening (1953Experimental
Crystal data
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Refinement
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Data collection: APEX2 (Bruker, 2009); cell SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrik, 2008); program(s) used to refine structure: SHELXL97 (Sheldrik, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2.
Supporting information
10.1107/S1600536812033405/hp2044sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812033405/hp2044Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812033405/hp2044Isup3.mol
C-bound hydrogen atoms were placed in calculated positions with C—H distance of 0.99 - 1.00 Å and refined as riding with Uiso(H) = xUeq(C), where x = 1.5 for methyl and x = 1.2 for all other H-atoms. H atoms on N atoms were located in a difference Fourier map and refined isotropically.
Data collection: APEX2 (Bruker, 2009); cell
SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrik, 2008); program(s) used to refine structure: SHELXL97 (Sheldrik, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).Fig. 1. : Asymmertic unit of he title compound including the triethylammonium-cation and the co-crystallized THF-Molecule. Thermal ellipsoids are drawn at 50% probability. | |
Fig. 2. : Two units of dicoppertetraacetate linked by a bridging acetato-ligand. The three hydrogen-bonds between the triethylammonium-cation and the acetato-ligand as well as the short intramolecular contact between H6c and O1 are shown as red dashed lines. The THF-molecule has been omitted for clarity. | |
Fig. 3. : Packing of the polymeric chains. The solvate-molecule, the cation and the hydrogen-atoms have been omitted for clarity. No direct inter-chain contact could be observed. |
(C6H16N)[Cu2(C2H3O2)5]·C4H8O | F(000) = 1248 |
Mr = 596.60 | Dx = 1.541 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 9902 reflections |
a = 12.1520 (2) Å | θ = 2.4–34.0° |
b = 12.2726 (2) Å | µ = 1.71 mm−1 |
c = 18.7306 (3) Å | T = 100 K |
β = 112.956 (1)° | Block, clear dark blue |
V = 2572.19 (7) Å3 | 0.25 × 0.09 × 0.06 mm |
Z = 4 |
Bruker APEX II CCD area-detector diffractometer | 4713 independent reflections |
Radiation source: micro-focus | 4047 reflections with I > 2σ(I) |
Multi-layer optics monochromator | Rint = 0.040 |
Detector resolution: 8 pixels mm-1 | θmax = 25.4°, θmin = 1.8° |
ω and ϕ scans | h = −14→14 |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | k = −14→14 |
Tmin = 0.681, Tmax = 0.747 | l = −22→22 |
102874 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.023 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.062 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.13 | w = 1/[σ2(Fo2) + (0.0203P)2 + 2.3331P] where P = (Fo2 + 2Fc2)/3 |
4713 reflections | (Δ/σ)max = 0.004 |
319 parameters | Δρmax = 0.32 e Å−3 |
0 restraints | Δρmin = −0.36 e Å−3 |
(C6H16N)[Cu2(C2H3O2)5]·C4H8O | V = 2572.19 (7) Å3 |
Mr = 596.60 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 12.1520 (2) Å | µ = 1.71 mm−1 |
b = 12.2726 (2) Å | T = 100 K |
c = 18.7306 (3) Å | 0.25 × 0.09 × 0.06 mm |
β = 112.956 (1)° |
Bruker APEX II CCD area-detector diffractometer | 4713 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | 4047 reflections with I > 2σ(I) |
Tmin = 0.681, Tmax = 0.747 | Rint = 0.040 |
102874 measured reflections |
R[F2 > 2σ(F2)] = 0.023 | 0 restraints |
wR(F2) = 0.062 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.13 | Δρmax = 0.32 e Å−3 |
4713 reflections | Δρmin = −0.36 e Å−3 |
319 parameters |
Experimental. Absorption correction: SADABS-2008/1 (Bruker, 2009) was used for absorption correction. wR2(int) was 0.1027 before and 0.0524 after correction. The Ratio of minimum to maximum transmission is 0.9107. The λ/2 correction factor is 0.0000. |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
Cu1 | 0.58451 (2) | 0.505128 (19) | 0.570813 (12) | 0.01381 (7) | |
Cu2 | 0.937948 (19) | 0.502200 (18) | 0.923936 (12) | 0.01216 (7) | |
O1 | 0.45990 (12) | 0.43975 (12) | 0.59966 (8) | 0.0217 (3) | |
O2 | 0.51683 (14) | 0.65182 (12) | 0.57030 (8) | 0.0275 (4) | |
O3 | 0.31686 (13) | 0.43082 (15) | 0.48086 (8) | 0.0336 (4) | |
O4 | 0.62799 (13) | 0.35832 (13) | 0.54785 (9) | 0.0295 (4) | |
O5 | 0.72384 (12) | 0.52443 (11) | 0.68184 (7) | 0.0169 (3) | |
O6 | 0.85592 (12) | 0.52508 (11) | 0.80224 (7) | 0.0154 (3) | |
O7 | 0.80423 (12) | 0.54543 (12) | 0.95269 (8) | 0.0211 (3) | |
O8 | 0.90257 (13) | 0.34674 (11) | 0.93393 (8) | 0.0203 (3) | |
O9 | 1.09120 (12) | 0.45715 (12) | 0.91883 (8) | 0.0211 (3) | |
O10 | 0.99288 (13) | 0.65590 (11) | 0.93776 (8) | 0.0203 (3) | |
C1 | 0.35629 (17) | 0.41637 (16) | 0.55266 (11) | 0.0170 (4) | |
C2 | 0.27189 (19) | 0.36747 (18) | 0.58551 (12) | 0.0231 (5) | |
H2A | 0.3171 | 0.3447 | 0.6392 | 0.035* | |
H2B | 0.2317 | 0.3041 | 0.5544 | 0.035* | |
H2C | 0.2121 | 0.4219 | 0.5842 | 0.035* | |
C3 | 0.42955 (17) | 0.69004 (16) | 0.51461 (11) | 0.0177 (4) | |
C4 | 0.3902 (2) | 0.80429 (18) | 0.52395 (13) | 0.0259 (5) | |
H4A | 0.3487 | 0.8030 | 0.5595 | 0.039* | |
H4B | 0.3360 | 0.8320 | 0.4734 | 0.039* | |
H4C | 0.4603 | 0.8518 | 0.5450 | 0.039* | |
C5 | 0.75337 (16) | 0.49915 (14) | 0.75148 (10) | 0.0123 (4) | |
C6 | 0.66926 (17) | 0.43909 (17) | 0.77852 (11) | 0.0179 (4) | |
H6A | 0.6513 | 0.4842 | 0.8158 | 0.027* | |
H6B | 0.7064 | 0.3708 | 0.8034 | 0.027* | |
H6C | 0.5951 | 0.4230 | 0.7340 | 0.027* | |
C7 | 0.81493 (17) | 0.55813 (16) | 1.02184 (11) | 0.0158 (4) | |
C8 | 0.70571 (18) | 0.59690 (18) | 1.03438 (12) | 0.0210 (4) | |
H8A | 0.6998 | 0.6764 | 1.0293 | 0.032* | |
H8B | 0.7125 | 0.5759 | 1.0864 | 0.032* | |
H8C | 0.6340 | 0.5635 | 0.9956 | 0.032* | |
C9 | 0.94290 (17) | 0.30002 (16) | 0.99907 (11) | 0.0150 (4) | |
C10 | 0.91147 (18) | 0.18182 (16) | 1.00283 (12) | 0.0199 (4) | |
H10A | 0.8507 | 0.1762 | 1.0250 | 0.030* | |
H10B | 0.9832 | 0.1416 | 1.0355 | 0.030* | |
H10C | 0.8801 | 0.1508 | 0.9505 | 0.030* | |
N1 | 0.95203 (15) | 0.68314 (14) | 0.74095 (9) | 0.0157 (3) | |
C11 | 0.89976 (19) | 0.78890 (17) | 0.75415 (12) | 0.0216 (4) | |
H11A | 0.9146 | 0.8465 | 0.7220 | 0.026* | |
H11B | 0.9409 | 0.8104 | 0.8092 | 0.026* | |
C12 | 0.76660 (19) | 0.78157 (18) | 0.73454 (13) | 0.0250 (5) | |
H12A | 0.7520 | 0.7316 | 0.7708 | 0.037* | |
H12B | 0.7260 | 0.7543 | 0.6815 | 0.037* | |
H12C | 0.7357 | 0.8540 | 0.7387 | 0.037* | |
C13 | 0.92652 (18) | 0.66676 (16) | 0.65642 (11) | 0.0178 (4) | |
H13A | 0.9663 | 0.7252 | 0.6388 | 0.021* | |
H13B | 0.8394 | 0.6730 | 0.6262 | 0.021* | |
C14 | 0.96895 (19) | 0.55746 (17) | 0.64007 (12) | 0.0230 (5) | |
H14A | 0.9390 | 0.4997 | 0.6639 | 0.034* | |
H14B | 1.0565 | 0.5560 | 0.6618 | 0.034* | |
H14C | 0.9388 | 0.5458 | 0.5839 | 0.034* | |
C15 | 1.08264 (18) | 0.67378 (18) | 0.79283 (12) | 0.0208 (4) | |
H15A | 1.1132 | 0.6029 | 0.7832 | 0.025* | |
H15B | 1.0912 | 0.6749 | 0.8476 | 0.025* | |
C16 | 1.15768 (19) | 0.76417 (18) | 0.78030 (13) | 0.0259 (5) | |
H16A | 1.2415 | 0.7536 | 0.8151 | 0.039* | |
H16B | 1.1296 | 0.8345 | 0.7914 | 0.039* | |
H16C | 1.1506 | 0.7630 | 0.7264 | 0.039* | |
O11 | 0.68670 (15) | 0.43535 (14) | 0.26275 (10) | 0.0376 (4) | |
C17 | 0.6524 (2) | 0.36448 (19) | 0.31112 (13) | 0.0279 (5) | |
H17A | 0.6561 | 0.4038 | 0.3582 | 0.034* | |
H17B | 0.7072 | 0.3013 | 0.3274 | 0.034* | |
C18 | 0.52537 (19) | 0.32611 (18) | 0.26465 (13) | 0.0255 (5) | |
H18A | 0.4663 | 0.3716 | 0.2754 | 0.031* | |
H18B | 0.5146 | 0.2490 | 0.2759 | 0.031* | |
C19 | 0.5144 (2) | 0.34046 (19) | 0.18108 (13) | 0.0293 (5) | |
H19A | 0.5431 | 0.2750 | 0.1626 | 0.035* | |
H19B | 0.4308 | 0.3555 | 0.1458 | 0.035* | |
C20 | 0.5939 (2) | 0.4374 (2) | 0.18684 (15) | 0.0346 (6) | |
H20A | 0.6284 | 0.4327 | 0.1470 | 0.041* | |
H20B | 0.5476 | 0.5059 | 0.1788 | 0.041* | |
H1 | 0.918 (2) | 0.632 (2) | 0.7560 (13) | 0.021 (6)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.01246 (12) | 0.01771 (13) | 0.00901 (12) | −0.00095 (9) | 0.00175 (9) | 0.00001 (9) |
Cu2 | 0.01315 (12) | 0.01314 (12) | 0.00850 (12) | −0.00060 (9) | 0.00238 (9) | 0.00073 (9) |
O1 | 0.0174 (7) | 0.0319 (8) | 0.0128 (7) | −0.0052 (6) | 0.0027 (6) | 0.0026 (6) |
O2 | 0.0324 (9) | 0.0187 (8) | 0.0196 (8) | 0.0037 (7) | −0.0027 (7) | −0.0015 (6) |
O3 | 0.0194 (8) | 0.0648 (12) | 0.0126 (7) | −0.0166 (8) | 0.0020 (6) | 0.0037 (8) |
O4 | 0.0259 (8) | 0.0317 (9) | 0.0204 (8) | 0.0122 (7) | −0.0022 (6) | −0.0061 (7) |
O5 | 0.0154 (7) | 0.0231 (7) | 0.0085 (6) | −0.0025 (6) | 0.0007 (5) | 0.0013 (5) |
O6 | 0.0148 (7) | 0.0179 (7) | 0.0096 (6) | −0.0037 (5) | 0.0007 (5) | 0.0013 (5) |
O7 | 0.0167 (7) | 0.0308 (8) | 0.0147 (7) | 0.0024 (6) | 0.0050 (6) | −0.0011 (6) |
O8 | 0.0247 (7) | 0.0162 (7) | 0.0137 (7) | −0.0020 (6) | 0.0007 (6) | 0.0017 (6) |
O9 | 0.0178 (7) | 0.0307 (8) | 0.0139 (7) | 0.0050 (6) | 0.0051 (6) | 0.0018 (6) |
O10 | 0.0275 (8) | 0.0158 (7) | 0.0141 (7) | −0.0045 (6) | 0.0043 (6) | 0.0002 (6) |
C1 | 0.0183 (10) | 0.0164 (10) | 0.0170 (10) | 0.0010 (8) | 0.0076 (8) | −0.0008 (8) |
C2 | 0.0226 (11) | 0.0275 (12) | 0.0210 (11) | −0.0034 (9) | 0.0103 (9) | 0.0004 (9) |
C3 | 0.0181 (10) | 0.0191 (10) | 0.0185 (10) | −0.0008 (8) | 0.0101 (8) | 0.0024 (8) |
C4 | 0.0281 (12) | 0.0214 (11) | 0.0282 (12) | 0.0028 (9) | 0.0109 (10) | −0.0006 (9) |
C5 | 0.0139 (9) | 0.0083 (9) | 0.0140 (9) | 0.0010 (7) | 0.0046 (8) | −0.0016 (7) |
C6 | 0.0157 (10) | 0.0205 (10) | 0.0143 (9) | −0.0019 (8) | 0.0024 (8) | 0.0008 (8) |
C7 | 0.0188 (10) | 0.0113 (9) | 0.0176 (10) | −0.0024 (8) | 0.0074 (8) | 0.0002 (8) |
C8 | 0.0193 (10) | 0.0240 (11) | 0.0212 (10) | 0.0010 (8) | 0.0094 (9) | 0.0000 (9) |
C9 | 0.0136 (9) | 0.0157 (10) | 0.0156 (10) | 0.0020 (8) | 0.0057 (8) | 0.0009 (8) |
C10 | 0.0218 (10) | 0.0161 (10) | 0.0189 (10) | −0.0013 (8) | 0.0047 (8) | 0.0015 (8) |
N1 | 0.0184 (8) | 0.0137 (8) | 0.0157 (8) | −0.0030 (7) | 0.0073 (7) | −0.0003 (7) |
C11 | 0.0292 (11) | 0.0154 (10) | 0.0214 (11) | −0.0020 (8) | 0.0111 (9) | −0.0018 (8) |
C12 | 0.0281 (12) | 0.0214 (11) | 0.0290 (12) | 0.0048 (9) | 0.0149 (10) | 0.0011 (9) |
C13 | 0.0208 (10) | 0.0182 (10) | 0.0132 (9) | −0.0015 (8) | 0.0053 (8) | 0.0002 (8) |
C14 | 0.0260 (11) | 0.0220 (11) | 0.0224 (11) | −0.0005 (9) | 0.0110 (9) | −0.0035 (9) |
C15 | 0.0193 (10) | 0.0253 (11) | 0.0159 (10) | −0.0025 (9) | 0.0047 (8) | 0.0016 (9) |
C16 | 0.0238 (11) | 0.0251 (12) | 0.0305 (12) | −0.0058 (9) | 0.0124 (10) | −0.0032 (10) |
O11 | 0.0344 (9) | 0.0347 (10) | 0.0437 (10) | −0.0099 (8) | 0.0151 (8) | −0.0029 (8) |
C17 | 0.0300 (12) | 0.0254 (12) | 0.0281 (12) | 0.0035 (9) | 0.0110 (10) | −0.0050 (10) |
C18 | 0.0254 (12) | 0.0222 (11) | 0.0295 (12) | 0.0057 (9) | 0.0114 (10) | 0.0024 (9) |
C19 | 0.0284 (12) | 0.0298 (12) | 0.0281 (12) | 0.0012 (10) | 0.0091 (10) | 0.0000 (10) |
C20 | 0.0373 (14) | 0.0307 (13) | 0.0414 (14) | 0.0035 (11) | 0.0216 (12) | 0.0080 (11) |
Cu1—O1 | 1.9664 (14) | C9—O10ii | 1.258 (2) |
Cu1—O4 | 1.9717 (15) | C9—C10 | 1.509 (3) |
Cu1—O3i | 1.9738 (15) | C10—H10A | 0.9800 |
Cu1—O2 | 1.9777 (15) | C10—H10B | 0.9800 |
Cu1—O5 | 2.1216 (13) | C10—H10C | 0.9800 |
Cu1—Cu1i | 2.6498 (4) | N1—C13 | 1.504 (2) |
Cu2—O7 | 1.9735 (14) | N1—C11 | 1.507 (3) |
Cu2—O9 | 1.9804 (14) | N1—C15 | 1.508 (3) |
Cu2—O8 | 1.9806 (14) | N1—H1 | 0.85 (2) |
Cu2—O10 | 1.9839 (14) | C11—C12 | 1.516 (3) |
Cu2—O6 | 2.1204 (13) | C11—H11A | 0.9900 |
Cu2—Cu2ii | 2.6542 (4) | C11—H11B | 0.9900 |
O1—C1 | 1.256 (2) | C12—H12A | 0.9800 |
O2—C3 | 1.253 (2) | C12—H12B | 0.9800 |
O3—C1 | 1.252 (2) | C12—H12C | 0.9800 |
O3—Cu1i | 1.9739 (15) | C13—C14 | 1.511 (3) |
O4—C3i | 1.254 (2) | C13—H13A | 0.9900 |
O5—C5 | 1.250 (2) | C13—H13B | 0.9900 |
O6—C5 | 1.278 (2) | C14—H14A | 0.9800 |
O7—C7 | 1.260 (2) | C14—H14B | 0.9800 |
O8—C9 | 1.261 (2) | C14—H14C | 0.9800 |
O9—C7ii | 1.258 (2) | C15—C16 | 1.511 (3) |
O10—C9ii | 1.258 (2) | C15—H15A | 0.9900 |
C1—C2 | 1.511 (3) | C15—H15B | 0.9900 |
C2—H2A | 0.9800 | C16—H16A | 0.9800 |
C2—H2B | 0.9800 | C16—H16B | 0.9800 |
C2—H2C | 0.9800 | C16—H16C | 0.9800 |
C3—O4i | 1.254 (2) | O11—C20 | 1.429 (3) |
C3—C4 | 1.513 (3) | O11—C17 | 1.430 (3) |
C4—H4A | 0.9800 | C17—C18 | 1.521 (3) |
C4—H4B | 0.9800 | C17—H17A | 0.9900 |
C4—H4C | 0.9800 | C17—H17B | 0.9900 |
C5—C6 | 1.499 (3) | C18—C19 | 1.529 (3) |
C6—H6A | 0.9800 | C18—H18A | 0.9900 |
C6—H6B | 0.9800 | C18—H18B | 0.9900 |
C6—H6C | 0.9800 | C19—C20 | 1.510 (3) |
C7—O9ii | 1.258 (2) | C19—H19A | 0.9900 |
C7—C8 | 1.512 (3) | C19—H19B | 0.9900 |
C8—H8A | 0.9800 | C20—H20A | 0.9900 |
C8—H8B | 0.9800 | C20—H20B | 0.9900 |
C8—H8C | 0.9800 | ||
O1—Cu1—O4 | 89.30 (7) | O10ii—C9—O8 | 125.38 (18) |
O1—Cu1—O3i | 167.73 (6) | O10ii—C9—C10 | 116.43 (17) |
O4—Cu1—O3i | 89.50 (8) | O8—C9—C10 | 118.18 (17) |
O1—Cu1—O2 | 90.54 (7) | C9—C10—H10A | 109.5 |
O4—Cu1—O2 | 167.71 (6) | C9—C10—H10B | 109.5 |
O3i—Cu1—O2 | 88.05 (8) | H10A—C10—H10B | 109.5 |
O1—Cu1—O5 | 100.48 (5) | C9—C10—H10C | 109.5 |
O4—Cu1—O5 | 97.85 (6) | H10A—C10—H10C | 109.5 |
O3i—Cu1—O5 | 91.78 (6) | H10B—C10—H10C | 109.5 |
O2—Cu1—O5 | 94.27 (6) | C13—N1—C11 | 111.15 (15) |
O1—Cu1—Cu1i | 82.90 (4) | C13—N1—C15 | 113.66 (15) |
O4—Cu1—Cu1i | 84.68 (4) | C11—N1—C15 | 111.40 (16) |
O3i—Cu1—Cu1i | 84.83 (4) | C13—N1—H1 | 108.7 (15) |
O2—Cu1—Cu1i | 83.10 (4) | C11—N1—H1 | 106.9 (16) |
O5—Cu1—Cu1i | 175.77 (4) | C15—N1—H1 | 104.5 (15) |
O7—Cu2—O9 | 167.99 (6) | N1—C11—C12 | 112.80 (17) |
O7—Cu2—O8 | 90.06 (6) | N1—C11—H11A | 109.0 |
O9—Cu2—O8 | 88.77 (6) | C12—C11—H11A | 109.0 |
O7—Cu2—O10 | 88.84 (6) | N1—C11—H11B | 109.0 |
O9—Cu2—O10 | 89.82 (6) | C12—C11—H11B | 109.0 |
O8—Cu2—O10 | 167.95 (6) | H11A—C11—H11B | 107.8 |
O7—Cu2—O6 | 99.55 (5) | C11—C12—H12A | 109.5 |
O9—Cu2—O6 | 92.39 (5) | C11—C12—H12B | 109.5 |
O8—Cu2—O6 | 101.58 (5) | H12A—C12—H12B | 109.5 |
O10—Cu2—O6 | 90.44 (5) | C11—C12—H12C | 109.5 |
O7—Cu2—Cu2ii | 84.03 (4) | H12A—C12—H12C | 109.5 |
O9—Cu2—Cu2ii | 83.96 (4) | H12B—C12—H12C | 109.5 |
O8—Cu2—Cu2ii | 86.12 (4) | N1—C13—C14 | 112.69 (16) |
O10—Cu2—Cu2ii | 81.83 (4) | N1—C13—H13A | 109.1 |
O6—Cu2—Cu2ii | 171.44 (4) | C14—C13—H13A | 109.1 |
C1—O1—Cu1 | 124.71 (13) | N1—C13—H13B | 109.1 |
C3—O2—Cu1 | 124.07 (13) | C14—C13—H13B | 109.1 |
C1—O3—Cu1i | 122.14 (13) | H13A—C13—H13B | 107.8 |
C3i—O4—Cu1 | 122.47 (13) | C13—C14—H14A | 109.5 |
C5—O5—Cu1 | 142.18 (12) | C13—C14—H14B | 109.5 |
C5—O6—Cu2 | 132.82 (12) | H14A—C14—H14B | 109.5 |
C7—O7—Cu2 | 123.23 (13) | C13—C14—H14C | 109.5 |
C9—O8—Cu2 | 120.83 (13) | H14A—C14—H14C | 109.5 |
C7ii—O9—Cu2 | 123.01 (13) | H14B—C14—H14C | 109.5 |
C9ii—O10—Cu2 | 125.84 (13) | N1—C15—C16 | 113.03 (17) |
O3—C1—O1 | 125.42 (18) | N1—C15—H15A | 109.0 |
O3—C1—C2 | 117.23 (18) | C16—C15—H15A | 109.0 |
O1—C1—C2 | 117.35 (17) | N1—C15—H15B | 109.0 |
C1—C2—H2A | 109.5 | C16—C15—H15B | 109.0 |
C1—C2—H2B | 109.5 | H15A—C15—H15B | 107.8 |
H2A—C2—H2B | 109.5 | C15—C16—H16A | 109.5 |
C1—C2—H2C | 109.5 | C15—C16—H16B | 109.5 |
H2A—C2—H2C | 109.5 | H16A—C16—H16B | 109.5 |
H2B—C2—H2C | 109.5 | C15—C16—H16C | 109.5 |
O2—C3—O4i | 125.63 (19) | H16A—C16—H16C | 109.5 |
O2—C3—C4 | 116.98 (18) | H16B—C16—H16C | 109.5 |
O4i—C3—C4 | 117.39 (18) | C20—O11—C17 | 109.24 (17) |
C3—C4—H4A | 109.5 | O11—C17—C18 | 107.89 (18) |
C3—C4—H4B | 109.5 | O11—C17—H17A | 110.1 |
H4A—C4—H4B | 109.5 | C18—C17—H17A | 110.1 |
C3—C4—H4C | 109.5 | O11—C17—H17B | 110.1 |
H4A—C4—H4C | 109.5 | C18—C17—H17B | 110.1 |
H4B—C4—H4C | 109.5 | H17A—C17—H17B | 108.4 |
O5—C5—O6 | 120.95 (17) | C17—C18—C19 | 102.34 (18) |
O5—C5—C6 | 121.24 (16) | C17—C18—H18A | 111.3 |
O6—C5—C6 | 117.81 (16) | C19—C18—H18A | 111.3 |
C5—C6—H6A | 109.5 | C17—C18—H18B | 111.3 |
C5—C6—H6B | 109.5 | C19—C18—H18B | 111.3 |
H6A—C6—H6B | 109.5 | H18A—C18—H18B | 109.2 |
C5—C6—H6C | 109.5 | C20—C19—C18 | 102.71 (19) |
H6A—C6—H6C | 109.5 | C20—C19—H19A | 111.2 |
H6B—C6—H6C | 109.5 | C18—C19—H19A | 111.2 |
O9ii—C7—O7 | 125.74 (18) | C20—C19—H19B | 111.2 |
O9ii—C7—C8 | 117.27 (17) | C18—C19—H19B | 111.2 |
O7—C7—C8 | 116.98 (17) | H19A—C19—H19B | 109.1 |
C7—C8—H8A | 109.5 | O11—C20—C19 | 106.94 (19) |
C7—C8—H8B | 109.5 | O11—C20—H20A | 110.3 |
H8A—C8—H8B | 109.5 | C19—C20—H20A | 110.3 |
C7—C8—H8C | 109.5 | O11—C20—H20B | 110.3 |
H8A—C8—H8C | 109.5 | C19—C20—H20B | 110.3 |
H8B—C8—H8C | 109.5 | H20A—C20—H20B | 108.6 |
O4—Cu1—O1—C1 | −84.84 (17) | O8—Cu2—O9—C7ii | −85.90 (16) |
O3i—Cu1—O1—C1 | −0.4 (4) | O10—Cu2—O9—C7ii | 82.13 (16) |
O2—Cu1—O1—C1 | 82.87 (17) | O6—Cu2—O9—C7ii | 172.55 (16) |
O5—Cu1—O1—C1 | 177.31 (16) | Cu2ii—Cu2—O9—C7ii | 0.33 (15) |
Cu1i—Cu1—O1—C1 | −0.12 (16) | O7—Cu2—O10—C9ii | 83.93 (16) |
O1—Cu1—O2—C3 | −81.93 (17) | O9—Cu2—O10—C9ii | −84.13 (16) |
O4—Cu1—O2—C3 | 7.2 (4) | O8—Cu2—O10—C9ii | −0.9 (4) |
O3i—Cu1—O2—C3 | 85.87 (17) | O6—Cu2—O10—C9ii | −176.52 (16) |
O5—Cu1—O2—C3 | 177.52 (17) | Cu2ii—Cu2—O10—C9ii | −0.21 (15) |
Cu1i—Cu1—O2—C3 | 0.85 (16) | Cu1i—O3—C1—O1 | 0.0 (3) |
O1—Cu1—O4—C3i | 80.50 (17) | Cu1i—O3—C1—C2 | 179.53 (14) |
O3i—Cu1—O4—C3i | −87.28 (17) | Cu1—O1—C1—O3 | 0.1 (3) |
O2—Cu1—O4—C3i | −8.8 (4) | Cu1—O1—C1—C2 | −179.43 (14) |
O5—Cu1—O4—C3i | −179.01 (16) | Cu1—O2—C3—O4i | 0.8 (3) |
Cu1i—Cu1—O4—C3i | −2.43 (16) | Cu1—O2—C3—C4 | −179.51 (14) |
O1—Cu1—O5—C5 | 10.1 (2) | Cu1—O5—C5—O6 | 175.75 (13) |
O4—Cu1—O5—C5 | −80.6 (2) | Cu1—O5—C5—C6 | −5.2 (3) |
O3i—Cu1—O5—C5 | −170.3 (2) | Cu2—O6—C5—O5 | 178.19 (12) |
O2—Cu1—O5—C5 | 101.5 (2) | Cu2—O6—C5—C6 | −0.9 (3) |
Cu1i—Cu1—O5—C5 | 153.0 (5) | Cu2—O7—C7—O9ii | −1.9 (3) |
O7—Cu2—O6—C5 | −45.10 (17) | Cu2—O7—C7—C8 | 177.02 (13) |
O9—Cu2—O6—C5 | 136.17 (16) | Cu2—O8—C9—O10ii | 0.0 (3) |
O8—Cu2—O6—C5 | 46.94 (17) | Cu2—O8—C9—C10 | 179.31 (13) |
O10—Cu2—O6—C5 | −133.99 (16) | C13—N1—C11—C12 | 78.9 (2) |
Cu2ii—Cu2—O6—C5 | −159.3 (2) | C15—N1—C11—C12 | −153.20 (17) |
O9—Cu2—O7—C7 | 3.0 (4) | C11—N1—C13—C14 | −175.42 (17) |
O8—Cu2—O7—C7 | 87.31 (16) | C15—N1—C13—C14 | 57.9 (2) |
O10—Cu2—O7—C7 | −80.69 (16) | C13—N1—C15—C16 | 66.7 (2) |
O6—Cu2—O7—C7 | −170.94 (15) | C11—N1—C15—C16 | −59.8 (2) |
Cu2ii—Cu2—O7—C7 | 1.21 (15) | C20—O11—C17—C18 | −4.7 (2) |
O7—Cu2—O8—C9 | −83.88 (15) | O11—C17—C18—C19 | 23.3 (2) |
O9—Cu2—O8—C9 | 84.17 (15) | C17—C18—C19—C20 | −31.8 (2) |
O10—Cu2—O8—C9 | 0.8 (4) | C17—O11—C20—C19 | −16.4 (2) |
O6—Cu2—O8—C9 | 176.36 (14) | C18—C19—C20—O11 | 30.4 (2) |
Cu2ii—Cu2—O8—C9 | 0.14 (14) | O1—Cu1—Cu2—O7 | −39.67 (7) |
O7—Cu2—O9—C7ii | −1.4 (4) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+2, −y+1, −z+2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O5 | 0.85 (2) | 2.59 (2) | 3.212 (2) | 130.7 (19) |
N1—H1···O6 | 0.85 (2) | 1.89 (2) | 2.737 (2) | 173 (2) |
C6—H6C···O1 | 0.98 | 2.42 | 3.3238 (18) | 153 |
C13—H13B···O3i | 0.99 | 2.51 | 3.2956 (19) | 137 |
C15—H15B···O10 | 0.99 | 2.43 | 3.3041 (19) | 147 |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | (C6H16N)[Cu2(C2H3O2)5]·C4H8O |
Mr | 596.60 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 100 |
a, b, c (Å) | 12.1520 (2), 12.2726 (2), 18.7306 (3) |
β (°) | 112.956 (1) |
V (Å3) | 2572.19 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.71 |
Crystal size (mm) | 0.25 × 0.09 × 0.06 |
Data collection | |
Diffractometer | Bruker APEX II CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2009) |
Tmin, Tmax | 0.681, 0.747 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 102874, 4713, 4047 |
Rint | 0.040 |
(sin θ/λ)max (Å−1) | 0.603 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.023, 0.062, 1.13 |
No. of reflections | 4713 |
No. of parameters | 319 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.32, −0.36 |
Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrik, 2008), SHELXL97 (Sheldrik, 2008), OLEX2 (Dolomanov et al., 2009).
Cu1—O1 | 1.9664 (14) | Cu2—O7 | 1.9735 (14) |
Cu1—O4 | 1.9717 (15) | Cu2—O9 | 1.9804 (14) |
Cu1—O3i | 1.9738 (15) | Cu2—O8 | 1.9806 (14) |
Cu1—O2 | 1.9777 (15) | Cu2—O10 | 1.9839 (14) |
Cu1—O5 | 2.1216 (13) | Cu2—O6 | 2.1204 (13) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O5 | 0.85 (2) | 2.59 (2) | 3.212 (2) | 130.7 (19) |
N1—H1···O6 | 0.85 (2) | 1.89 (2) | 2.737 (2) | 173 (2) |
C6—H6C···O1 | 0.98 | 2.42 | 3.3238 (18) | 153 |
C13—H13B···O3i | 0.99 | 2.51 | 3.2956 (19) | 137 |
C15—H15B···O10 | 0.99 | 2.43 | 3.3041 (19) | 147 |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Acknowledgements
The DFG is gratefiully acknowledged for financial support (SFB 668 - TP A4).
References
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The title compound, catena-poly[[triethylammonium [[tetra-µ-acetato-κ8O:O'-dicuprate(II)]-m-acetato-κ2O:O'] tetrahydrofuran monosolvate], was obtained as a minor byproduct in the synthesis of a copper-salene compound (Kleij et al., 2005). The crystal structure consists of dicoppertetraacetate-paddlewheel-units with copper in a pseudo square-pyramidal coordination environment (Fig. 2). These monomeric units are interconnected by bridging, apically coordinating acetato-ligands, thus forming infinite zigzag chains along the [1 0 - 1] plane with an angle of about 165.4 ° with respect to the Cu—Cu bond-vectors (Fig. 3). Additionally, the monomers are skewed in respect to each other as indicated by the torsion-angle O1—Cu1—Cu2—O7 = -39.67 (7)° (see Fig.3, Table 1). One triethylammonium cation per dicoppertetraacetate monomer is present in the crystal structure. A hydrogen-bond between this cation and an oxygen-atom of the bridging acetato-ligand (O6) can be observed (d(N1—H1···O6) = 2.737 (2) Å, Table 2, Fig. 2). Two additional contacts are present between the coordination-chain and the alkyle-residues of the triethylammonium-cations (d(C15—H15B···O10) = 3.3041 (19) Å and d(C13—H13B···O3) = 3.2956 (19) Å, table 2). One short intra-chain contact is found between the methyl group of the bridging acetato-ligand (C6) and oxygen atom O1 of the monomeric unit with a distance of d(C6—H6C···O1) = 3.3238 (18) Å. However, no direct inter-chain contact could be observed. Furthermore, one molecule of tetrahydrofuran per dicoppertetraacetate-unit is present in the crystal structure. In spite of hydrogen-bonds being detected around this solvate-molecule, its orientation could be modeled unequivocally. The Cu—Cu distances in the monomers are d(Cu1—Cu1') = 2.6498 (4) Å and d(Cu2—Cu2') = 2.6542 (4) Å, respectively. This is significantly longer than the distance of 2.616 (1) Å found in dicoppertetraacetate-dihydrate (de Meester et al., 1973). To the contrary, the apical Cu—O bonds in the title-compound are shorter (d(Cu1—O5) = 2.1216 (13) Å and d(Cu2—O6) = 2.1204 (13) Å) than the bond between copper and the aqua-ligand in dicoppertetraacetate-dihydrate (d(Cu—O(H2)) = 2.156 (4) Å). Finally it is to mention that, indicated by the slight differences in the Cu—Cu distances and the Cu—O bond-lengths and the Cu—Cu—O difference of the bond angles to the apically coordinating acetato-ligands mentioned in table 1, two neighbouring monomers exhibit a minor asymmetry. The aforementioned skewing and the position of the triethylammonoium-cation, especially the N—H···O hydrogen bond, are further indicators of this.