μ 1,2 Ethanediylbis(di­phenyl­phosphine) κ2P:P′ bis­­{acetato[1,2 ethanediylbis(di­phenyl­phosphine) κ2P,P′]copper(I)} di­ethyl ether disolvate

13 

(1)metal-organic papers Acta Crystallographica Section E. Structure Reports Online ISSN 1600-5368. Thorsten Morawitz,a Hans-Wolfram Lerner,a Miriam Bru Roigb and Michael Boltea* a. Institut fu¨r Anorganische Chemie, J. W. GoetheUniversita¨t Frankfurt, Marie-Curie-Strasse 11, 60439 Frankfurt/Main, Germany, and b Departament de Quı´mica Inorga`nica i Orga`nica, University Jaume I, Campus Riu Sec, Avenida Sos Baynat s/n, 12071 Castellon de la Plana, Spain Correspondence e-mail: bolte@chemie.uni-frankfurt.de. Key indicators Single-crystal X-ray study T = 173 K ˚ Mean (C–C) = 0.017 A R factor = 0.119 wR factor = 0.291 Data-to-parameter ratio = 15.7. l-1,2-Ethanediylbis(diphenylphosphine)-j2P:P0 bis{acetato[1,2-ethanediylbis(diphenylphosphine)j2P,P0 ]copper(I)} diethyl ether disolvate. The title compound, [Cu2(C2H3O2)2(C26H24P2)3]2C4H10O, crystallizes with one dicopper(I) unit located on a centre of inversion and two diethyl ether molecules in general positions. The Cu atoms exhibit slightly distorted tetrahedral coordination.. Received 23 September 2005 Accepted 29 September 2005 Online 5 October 2005. Comment Tris(1-pyrazolyl)borates (1) (‘scorpinates’) were introduced by Trofimenko (1993) more than 30 years ago and are today well established as ligands in coordination chemistry, but only a limited number of transition metal complexes with the ditopic heteroscorpionate ligand (2) (Bieller et al., 2004) have been structurally characterized. We have become interested in the reaction of ligand (2) with Cu+ ions. While CuI salts such as Cu(CH3CO2) are not soluble in organic solvents, we have prepared the dinuclear complex [Cu2(CH3CO2)2(Ph2PCH2CH2PPh2)3] as a starting material.. For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.. # 2005 International Union of Crystallography Printed in Great Britain – all rights reserved. Acta Cryst. (2005). E61, m2201–m2203. In the structure of the title compound, (3), each Cu atom is coordinated by one O atom of the acetate anion and three P atoms of two 1,2-bis(diphenylphosphino)ethane ligands within a slightly distorted tetrahedron. The asymmetric unit contains one Cu atom, one acetate ligand, one diethyl ether molecule and one and a half crystallographically independent 1,2-bis(diphenylphosphino)ethane ligands. One of the phosphorus ligands is located in a general position, whereas the other is doi:10.1107/S1600536805031089. Morawitz et al.. . [Cu2(C2H3O2)2(C26H24P2)3]2C4H10O. m2201.

(2) metal-organic papers Data collection 7379 independent reflections 6686 reflections with I > 2(I) Rint = 0.091 max = 25.4 h = 15 ! 15 k = 15 ! 15 l = 17 ! 17. Stoe IPDS-II two-circle diffractometer ! scans Absorption correction: multi-scan (MULABS; Spek, 2003; Blessing, 1995) Tmin = 0.714, Tmax = 0.750 42630 measured reflections. Refinement. Figure 1 Perspective view of the title compound with the atom numbering; displacement ellipsoids are drawn at the 50% probability level and solvent molecules and H atoms have been omitted for clarity. The labelled atoms indicate the asymmetric unit; the complete molecule is generated by a centre of inversion at (1  x, 1  y, 1  z).. located on a centre of inversion. This ligand connects two symmetry-related Cu atoms into the complete [Cu2(CH3CO2)2(Ph2PCH2CH2PPh2)3] unit (Fig. 1). Bond lengths and angles can be regarded as normal (Cambridge Structural Database, Version 1.6 plus three updates; MOGUL Version 1.0; Allen, 2002). The five-membered ring shows an envelope conformation, with atoms P2, Cu1, P1 and C1 in a plane (r.m.s. ˚ ) and atom C2 deviating by 0.71 (1) A ˚ deviation = 0.037 A from this plane. The central methylene bridge adopts an antiperiplanar conformation, but the bridge composed of atoms C1 and C2 is in an anticlinal conformation. Only one of the two acetate O atoms (O71) coordinates to the Cu atom. ˚ from Cu1. On the other The other (O72) is found 3.012 (7) A hand, two weak C—H  O contacts are found for O72 (Table 2). The diethyl ether molecules are not coordinated to the Cu atom and are located in holes in the structure.. Refinement on F 2 R[F 2 > 2(F 2)] = 0.119 wR(F 2) = 0.291 S = 1.13 7379 reflections 469 parameters H-atom parameters constrained. w = 1/[ 2(Fo2) + (0.067P)2 + 33.8808P] where P = (Fo2 + 2Fc2)/3 (/)max < 0.001 ˚ 3 max = 3.04 e A ˚ 3 min = 1.48 e A. Table 1 ˚ ,  ). Selected geometric parameters (A Cu1—O71 Cu1—P2 Cu1—P3. 2.015 (6) 2.275 (2) 2.289 (2). O71—Cu1—P2 O71—Cu1—P3 P2—Cu1—P3. Cu1—P1 C71—O71 C71—O72. 119.63 (18) 108.90 (18) 116.12 (8). P2—Cu1—P1—C1 P1—Cu1—P2—C2 Cu1—P1—C1—C2. O71—Cu1—P1 P2—Cu1—P1 P3—Cu1—P1. 4.7 (3) 19.6 (3) 35.3 (6). P1—C1—C2—P2 Cu1—P2—C2—C1. 2.343 (2) 1.233 (10) 1.281 (10) 110.51 (18) 90.30 (9) 109.61 (8) 55.8 (7) 46.7 (6). Table 2 ˚ ,  ). Hydrogen-bond geometry (A D—H  A C33—H33  O72 C62—H62  O72. i. D—H. H  A. D  A. D—H  A. 0.95 0.95. 2.43 2.47. 3.361 (12) 3.380 (10). 166 161. Symmetry code: (i) x; y þ 1; z þ 1.. Experimental The title compound was obtained from a solution of copper(I) acetate (1 mmol) and 1,2-bis(diphenylphosphino)ethane (1 mmol) in tetrahydrofuran (THF, 10 ml). X-ray quality crystals of the title compound were grown by slow diffusion of diethyl ether into this THF solution at ambient temperature. Crystal data [Cu2(C2H3O2)2(C26H24P2)3]2C4H10O Mr = 1588.58 Triclinic, P1 ˚ a = 12.6520 (9) A ˚ b = 12.8760 (9) A ˚ c = 14.2907 (11) A  = 85.069 (6)  = 83.287 (6)  = 61.629 (5) ˚3 V = 2033.2 (3) A. m2202. Morawitz et al.. Z=1 Dx = 1.297 Mg m3 Mo K radiation Cell parameters from 42635 reflections  = 3.6–25.6  = 0.69 mm1 T = 173 (2) K Block, colourless 0.52  0.48  0.44 mm. . [Cu2(C2H3O2)2(C26H24P2)3]2C4H10O. H atoms were refined with fixed individual displacement parameters [Uiso(H) = 1.2Ueq(C) or 1.5 Ueq(methyl C)] using a riding ˚ for aromatic, methyl and model, with C—H = 0.95, 0.98 and 0.99 A methylene H atoms, respectively. The highest peak in the final ˚ from Cu1 and the deepest hole is difference map is located 0.95 A ˚ located 0.77 A from Cu1. Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 1991); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2003).. MBR thanks MECD for personal financial support (FPU Program).. Acta Cryst. (2005). E61, m2201–m2203.

(3) metal-organic papers References Allen, F. H. (2002). Acta Cryst. B58, 380–388. Bieller, S., Zhang, F., Bolte, M., Bats, J. W., Lerner, H.-W. & Wagner, M. (2004). Organometallics, 23, 2107–2113. Blessing, R. H. (1995). Acta Cryst. A51, 33–38.. Acta Cryst. (2005). E61, m2201–m2203. Sheldrick, G. M. (1990). Acta Cryst. A46, 467–473. Sheldrick, G. M. (1991). SHELXTL-Plus. Release 4.1. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Sheldrick, G. M. (1997). SHELXL97. University of Go¨ttingen, Germany. Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Stoe & Cie (2001). X-AREA. Stoe & Cie, Darmstadt, Germany. Trofimenko, S. (1993). Chem. Rev. 93, 943–980.. Morawitz et al.. . [Cu2(C2H3O2)2(C26H24P2)3]2C4H10O. m2203.

(4) supporting information. supporting information Acta Cryst. (2005). E61, m2201–m2203. [https://doi.org/10.1107/S1600536805031089]. µ-1,2-Ethanediylbis(diphenylphosphine)-κ2P:P′-bis{acetato[1,2-ethanediylbis(diphenylphosphine)-κ2P,P′]copper(I)} diethyl ether disolvate Thorsten Morawitz, Hans-Wolfram Lerner, Miriam Bru Roig and Michael Bolte µ-1,2-Ethanediylbis(diphenylphosphine)-κ2P:P′-bis{acetato[1,2- ethanediylbis(diphenylphosphine)κ2P,P′]copper(I)} diethyl ether disolvate Crystal data [Cu2(C2H3O2)2(C26H24P2)3]·2C4H10O Mr = 1588.58 Triclinic, P1 a = 12.6520 (9) Å b = 12.8760 (9) Å c = 14.2907 (11) Å α = 85.069 (6)° β = 83.287 (6)° γ = 61.629 (5)° V = 2033.2 (3) Å3. Z=1 F(000) = 834 Dx = 1.297 Mg m−3 Mo Kα radiation, λ = 0.71073 Å Cell parameters from 42635 reflections θ = 3.6–25.6° µ = 0.69 mm−1 T = 173 K Block, colourless 0.52 × 0.48 × 0.44 mm. Data collection Stoe IPDS-II two-circle diffractometer Radiation source: fine-focus sealed tube Graphite monochromator ω scans Absorption correction: multi-scan (MULABS; Spek, 2003; Blessing, 1995) Tmin = 0.714, Tmax = 0.750. 42630 measured reflections 7379 independent reflections 6686 reflections with I > 2σ(I) Rint = 0.091 θmax = 25.4°, θmin = 3.6° h = −15→15 k = −15→15 l = −17→17. Refinement Refinement on F2 Least-squares matrix: full R[F2 > 2σ(F2)] = 0.119 wR(F2) = 0.291 S = 1.13 7379 reflections 469 parameters 0 restraints Primary atom site location: structure-invariant direct methods. Acta Cryst. (2005). E61, m2201–m2203. Secondary atom site location: difference Fourier map Hydrogen site location: inferred from neighbouring sites H-atom parameters constrained w = 1/[σ2(Fo2) + (0.067P)2 + 33.8808P] where P = (Fo2 + 2Fc2)/3 (Δ/σ)max < 0.001 Δρmax = 3.04 e Å−3 Δρmin = −1.48 e Å−3. sup-1.

(5) supporting information Special details 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. Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2). Cu1 P1 P2 P3 C1 H1A H1B C2 H2A H2B C3 H3A H3B C11 C12 H12 C13 H13 C14 H14 C15 H15 C16 H16 C21 C22 H22 C23 H23 C24 H24 C25 H25 C26 H26. x. y. z. Uiso*/Ueq. 0.42001 (9) 0.5964 (2) 0.3144 (2) 0.37349 (18) 0.5447 (8) 0.5981 0.5505 0.4138 (9) 0.3871 0.4088 0.4953 (7) 0.5724 0.4790 0.7298 (8) 0.8434 (9) 0.8558 0.9400 (9) 1.0177 0.9212 (9) 0.9860 0.8074 (9) 0.7949 0.7111 (8) 0.6342 0.6664 (9) 0.6445 (10) 0.5948 0.6950 (11) 0.6763 0.7747 (12) 0.8141 0.7945 (10) 0.8455 0.7396 (9) 0.7520. 0.33781 (8) 0.24905 (18) 0.31020 (18) 0.52948 (16) 0.2007 (8) 0.1928 0.1222 0.2887 (8) 0.2579 0.3652 0.5307 (7) 0.4889 0.6132 0.1079 (7) 0.0714 (8) 0.1213 −0.0388 (9) −0.0632 −0.1110 (7) −0.1859 −0.0751 (8) −0.1260 0.0362 (7) 0.0619 0.3361 (8) 0.3817 (9) 0.3649 0.4512 (10) 0.4854 0.4711 (11) 0.5136 0.4283 (9) 0.4439 0.3620 (8) 0.3345. 0.37325 (7) 0.27189 (16) 0.26825 (16) 0.39475 (15) 0.1762 (7) 0.1179 0.1938 0.1571 (6) 0.1087 0.1332 0.4508 (6) 0.4116 0.4568 0.3006 (6) 0.2531 (7) 0.2051 0.2756 (8) 0.2434 0.3443 (7) 0.3594 0.3922 (8) 0.4391 0.3713 (7) 0.4052 0.2100 (7) 0.1175 (7) 0.0832 0.0757 (8) 0.0143 0.1249 (8) 0.0948 0.2167 (8) 0.2505 0.2600 (7) 0.3236. 0.0229 (3) 0.0269 (5) 0.0260 (5) 0.0206 (4) 0.0330 (19) 0.040* 0.040* 0.036 (2) 0.043* 0.043* 0.0263 (17) 0.032* 0.032* 0.0277 (18) 0.038 (2) 0.046* 0.044 (2) 0.053* 0.039 (2) 0.047* 0.042 (2) 0.050* 0.034 (2) 0.041* 0.035 (2) 0.041 (2) 0.049* 0.050 (3) 0.060* 0.055 (3) 0.066* 0.045 (2) 0.054* 0.034 (2) 0.041*. Acta Cryst. (2005). E61, m2201–m2203. sup-2.

(6) supporting information C31 C32 H32 C33 H33 C34 H34 C35 H35 C36 H36 C41 C42 H42 C43 H43 C44 H44 C45 H45 C46 H46 C51 C52 H52 C53 H53 C54 H54 C55 H55 C56 H56 C61 C62 H62 C63 H63 C64 H64 C65 H65 C66 H66 C71 C72 H72A H72B. 0.1673 (8) 0.0871 (8) 0.1082 −0.0278 (8) −0.0849 −0.0538 (9) −0.1277 0.0246 (10) 0.0028 0.1365 (9) 0.1909 0.2961 (7) 0.2423 (10) 0.2122 0.2327 (11) 0.1993 0.2717 (10) 0.2611 0.3264 (9) 0.3568 0.3374 (9) 0.3726 0.3646 (8) 0.2614 (11) 0.1985 0.2478 (13) 0.1762 0.3369 (16) 0.3280 0.4421 (15) 0.5035 0.4583 (10) 0.5301 0.2401 (7) 0.1522 (7) 0.1619 0.0507 (8) −0.0079 0.0351 (8) −0.0347 0.1225 (7) 0.1130 0.2232 (7) 0.2816 0.3501 (7) 0.3601 (11) 0.2794 0.3973. Acta Cryst. (2005). E61, m2201–m2203. 0.4290 (7) 0.4873 (7) 0.4622 0.5857 (8) 0.6245 0.6227 (9) 0.6910 0.5633 (10) 0.5885 0.4656 (8) 0.4248 0.1762 (7) 0.1514 (8) 0.2052 0.0458 (9) 0.0270 −0.0295 (8) −0.0981 −0.0063 (8) −0.0609 0.0983 (8) 0.1155 0.6156 (7) 0.6557 (9) 0.6390 0.7200 (10) 0.7465 0.7450 (10) 0.7881 0.7064 (11) 0.7249 0.6409 (9) 0.6142 0.6367 (6) 0.6074 (7) 0.5302 0.6910 (8) 0.6702 0.8049 (8) 0.8618 0.8351 (7) 0.9120 0.7523 (6) 0.7736 0.2663 (6) 0.2284 (11) 0.2510 0.2675. 0.2387 (6) 0.3143 (7) 0.3770 0.2975 (8) 0.3488 0.2070 (8) 0.1957 0.1311 (8) 0.0686 0.1468 (7) 0.0950 0.2761 (6) 0.2074 (8) 0.1554 0.2152 (8) 0.1672 0.2924 (7) 0.2992 0.3603 (7) 0.4117 0.3534 (7) 0.4011 0.2844 (6) 0.2373 (7) 0.2640 0.1518 (8) 0.1212 0.1120 (8) 0.0535 0.1584 (9) 0.1311 0.2442 (8) 0.2745 0.4653 (6) 0.5098 (6) 0.5046 0.5615 (7) 0.5917 0.5689 (7) 0.6032 0.5258 (7) 0.5318 0.4742 (6) 0.4445 0.5492 (6) 0.6539 (8) 0.6852 0.6834. 0.0291 (19) 0.0313 (19) 0.038* 0.039 (2) 0.047* 0.045 (2) 0.054* 0.050 (3) 0.060* 0.040 (2) 0.047* 0.0271 (18) 0.044 (3) 0.053* 0.050 (3) 0.060* 0.043 (2) 0.051* 0.040 (2) 0.048* 0.036 (2) 0.043* 0.0284 (18) 0.044 (2) 0.053* 0.056 (3) 0.067* 0.075 (5) 0.091* 0.069 (4) 0.083* 0.046 (2) 0.055* 0.0230 (16) 0.0266 (17) 0.032* 0.038 (2) 0.045* 0.037 (2) 0.045* 0.0306 (19) 0.037* 0.0248 (17) 0.030* 0.0241 (17) 0.052 (3) 0.078* 0.078*. sup-3.

(7) supporting information H72C O71 O72 C81 H81A H81B H81C C82 H82A H82B O83 C84 H84A H84B C85 H85A H85B H85C. 0.4099 0.4425 (5) 0.2433 (6) 0.381 (3) 0.4541 0.3995 0.3494 0.2887 (15) 0.2712 0.3220 0.1805 (10) 0.0948 (19) 0.1313 0.0699 −0.0103 (19) −0.0698 −0.0466 0.0157. 0.1426 0.2507 (5) 0.3139 (5) 0.124 (3) 0.0706 0.1228 0.2040 0.0830 (16) 0.0829 0.0008 0.1540 (10) 0.1106 (16) 0.0257 0.1202 0.180 (2) 0.1514 0.2634 0.1707. 0.6599 0.4995 (4) 0.5225 (5) 0.9233 (16) 0.8857 0.9881 0.8958 0.9238 (13) 0.8581 0.9498 0.9772 (7) 0.9743 (12) 0.9934 0.9097 1.0402 (13) 1.0408 1.0199 1.1037. 0.078* 0.0321 (14) 0.0379 (15) 0.183 (15) 0.274* 0.274* 0.274* 0.097 (6) 0.117* 0.117* 0.086 (3) 0.093 (5) 0.112* 0.112* 0.131 (9) 0.196* 0.196* 0.196*. Atomic displacement parameters (Å2). Cu1 P1 P2 P3 C1 C2 C3 C11 C12 C13 C14 C15 C16 C21 C22 C23 C24 C25 C26 C31 C32 C33 C34 C35 C36 C41. U11. U22. U33. U12. U13. U23. 0.0236 (5) 0.0324 (12) 0.0310 (11) 0.0193 (10) 0.035 (5) 0.049 (6) 0.024 (4) 0.029 (4) 0.044 (6) 0.035 (5) 0.041 (5) 0.044 (6) 0.031 (5) 0.049 (6) 0.064 (7) 0.069 (8) 0.082 (9) 0.056 (7) 0.041 (5) 0.030 (4) 0.032 (5) 0.025 (5) 0.037 (5) 0.054 (7) 0.050 (6) 0.028 (4). 0.0131 (5) 0.0211 (10) 0.0199 (10) 0.0104 (9) 0.029 (4) 0.037 (5) 0.021 (4) 0.020 (4) 0.033 (5) 0.045 (6) 0.014 (4) 0.021 (4) 0.021 (4) 0.026 (4) 0.045 (6) 0.056 (7) 0.062 (7) 0.040 (6) 0.030 (5) 0.021 (4) 0.021 (4) 0.027 (5) 0.033 (5) 0.043 (6) 0.024 (4) 0.015 (4). 0.0353 (6) 0.0334 (12) 0.0346 (12) 0.0337 (11) 0.041 (5) 0.031 (5) 0.037 (5) 0.038 (5) 0.038 (5) 0.054 (6) 0.057 (6) 0.066 (7) 0.051 (6) 0.038 (5) 0.032 (5) 0.042 (6) 0.050 (6) 0.056 (6) 0.039 (5) 0.048 (5) 0.049 (5) 0.069 (7) 0.062 (7) 0.055 (7) 0.040 (5) 0.041 (5). −0.0105 (4) −0.0170 (9) −0.0169 (9) −0.0070 (7) −0.020 (4) −0.030 (5) −0.012 (3) −0.014 (3) −0.018 (4) −0.019 (5) −0.008 (4) −0.019 (4) −0.013 (4) −0.025 (4) −0.042 (5) −0.045 (6) −0.061 (7) −0.037 (5) −0.023 (4) −0.020 (4) −0.018 (4) −0.015 (4) −0.014 (4) −0.025 (5) −0.015 (4) −0.011 (3). −0.0074 (4) −0.0052 (9) −0.0084 (9) −0.0087 (8) 0.001 (4) 0.002 (4) −0.011 (3) −0.005 (4) −0.004 (4) 0.000 (5) −0.010 (5) −0.019 (5) −0.008 (4) −0.002 (4) −0.004 (4) −0.011 (5) −0.002 (6) −0.005 (5) 0.000 (4) −0.010 (4) −0.012 (4) −0.003 (4) −0.008 (5) −0.017 (5) −0.004 (4) −0.010 (4). 0.0007 (4) −0.0002 (8) 0.0002 (8) 0.0010 (7) −0.005 (4) −0.004 (4) 0.002 (3) 0.000 (3) 0.000 (4) −0.007 (5) −0.004 (4) 0.013 (4) 0.002 (4) −0.004 (4) 0.003 (4) 0.011 (5) 0.006 (5) −0.001 (5) −0.001 (4) 0.002 (4) 0.002 (4) −0.005 (4) 0.009 (5) 0.020 (5) 0.004 (4) 0.002 (3). Acta Cryst. (2005). E61, m2201–m2203. sup-4.

(8) supporting information C42 C43 C44 C45 C46 C51 C52 C53 C54 C55 C56 C61 C62 C63 C64 C65 C66 C71 C72 O71 O72 C81 C82 O83 C84 C85. 0.056 (6) 0.071 (8) 0.060 (7) 0.052 (6) 0.040 (5) 0.040 (5) 0.066 (7) 0.094 (10) 0.135 (14) 0.103 (11) 0.051 (6) 0.022 (4) 0.023 (4) 0.030 (5) 0.027 (5) 0.023 (4) 0.021 (4) 0.029 (4) 0.054 (7) 0.031 (3) 0.032 (3) 0.25 (3) 0.075 (11) 0.078 (7) 0.136 (17) 0.108 (16). 0.023 (5) 0.030 (5) 0.018 (4) 0.022 (4) 0.028 (5) 0.018 (4) 0.033 (5) 0.043 (6) 0.035 (6) 0.041 (6) 0.030 (5) 0.013 (3) 0.018 (4) 0.036 (5) 0.025 (4) 0.016 (4) 0.011 (3) 0.007 (3) 0.053 (7) 0.020 (3) 0.026 (3) 0.30 (4) 0.083 (11) 0.097 (8) 0.086 (12) 0.22 (3). 0.067 (7) 0.071 (7) 0.056 (6) 0.052 (6) 0.045 (5) 0.032 (4) 0.045 (6) 0.040 (6) 0.028 (6) 0.062 (8) 0.054 (6) 0.038 (5) 0.044 (5) 0.053 (6) 0.050 (6) 0.051 (5) 0.045 (5) 0.041 (5) 0.047 (6) 0.044 (4) 0.054 (4) 0.125 (19) 0.110 (14) 0.070 (6) 0.067 (10) 0.070 (12). −0.026 (5) −0.037 (5) −0.023 (4) −0.021 (4) −0.019 (4) −0.017 (4) −0.031 (5) −0.038 (7) −0.020 (8) −0.040 (7) −0.019 (5) −0.010 (3) −0.012 (3) −0.020 (4) −0.004 (4) −0.006 (3) −0.008 (3) −0.010 (3) −0.025 (6) −0.010 (3) −0.013 (3) −0.23 (3) −0.015 (9) −0.028 (6) −0.057 (12) −0.085 (18). −0.030 (5) −0.038 (6) −0.010 (5) −0.018 (5) −0.017 (4) −0.004 (4) −0.022 (5) −0.021 (6) 0.002 (7) 0.031 (8) −0.001 (5) −0.011 (3) −0.009 (3) −0.005 (4) −0.007 (4) −0.010 (4) −0.010 (3) −0.013 (4) −0.005 (5) −0.008 (3) −0.008 (3) 0.08 (2) 0.010 (10) −0.009 (5) −0.025 (10) −0.004 (11). 0.012 (4) 0.010 (5) 0.003 (4) 0.011 (4) 0.006 (4) 0.000 (3) 0.007 (4) 0.010 (5) 0.009 (5) 0.002 (6) 0.005 (4) 0.001 (3) −0.001 (3) 0.001 (4) −0.006 (4) −0.001 (4) 0.000 (3) 0.004 (3) 0.010 (5) 0.003 (3) 0.004 (3) −0.11 (2) −0.048 (10) −0.009 (6) 0.003 (8) 0.027 (14). Geometric parameters (Å, º) Cu1—O71 Cu1—P2 Cu1—P3 Cu1—P1 P1—C21 P1—C1 P1—C11 P2—C31 P2—C41 P2—C2 P3—C3 P3—C51 P3—C61 C1—C2 C1—H1A C1—H1B C2—H2A C2—H2B C3—C3i. Acta Cryst. (2005). E61, m2201–m2203. 2.015 (6) 2.275 (2) 2.289 (2) 2.343 (2) 1.847 (9) 1.851 (9) 1.855 (9) 1.830 (9) 1.839 (8) 1.859 (9) 1.825 (8) 1.831 (9) 1.844 (8) 1.539 (13) 0.9900 0.9900 0.9900 0.9900 1.541 (16). C41—C46 C41—C42 C42—C43 C42—H42 C43—C44 C43—H43 C44—C45 C44—H44 C45—C46 C45—H45 C46—H46 C51—C52 C51—C56 C52—C53 C52—H52 C53—C54 C53—H53 C54—C55 C54—H54. 1.395 (12) 1.396 (13) 1.414 (12) 0.9500 1.376 (14) 0.9500 1.383 (14) 0.9500 1.413 (12) 0.9500 0.9500 1.388 (13) 1.420 (13) 1.395 (14) 0.9500 1.36 (2) 0.9500 1.41 (2) 0.9500. sup-5.

(9) supporting information C3—H3A C3—H3B C11—C16 C11—C12 C12—C13 C12—H12 C13—C14 C13—H13 C14—C15 C14—H14 C15—C16 C15—H15 C16—H16 C21—C22 C21—C26 C22—C23 C22—H22 C23—C24 C23—H23 C24—C25 C24—H24 C25—C26 C25—H25 C26—H26 C31—C32 C31—C36 C32—C33 C32—H32 C33—C34 C33—H33 C34—C35 C34—H34 C35—C36 C35—H35 C36—H36. 0.9900 0.9900 1.385 (12) 1.390 (13) 1.406 (14) 0.9500 1.373 (14) 0.9500 1.395 (14) 0.9500 1.407 (12) 0.9500 0.9500 1.402 (13) 1.403 (13) 1.388 (13) 0.9500 1.421 (15) 0.9500 1.381 (15) 0.9500 1.403 (12) 0.9500 0.9500 1.386 (13) 1.392 (13) 1.433 (12) 0.9500 1.361 (15) 0.9500 1.384 (16) 0.9500 1.403 (15) 0.9500 0.9500. C55—C56 C55—H55 C56—H56 C61—C62 C61—C66 C62—C63 C62—H62 C63—C64 C63—H63 C64—C65 C64—H64 C65—C66 C65—H65 C66—H66 C71—O71 C71—O72 C71—C72 C72—H72A C72—H72B C72—H72C C81—C82 C81—H81A C81—H81B C81—H81C C82—O83 C82—H82A C82—H82B O83—C84 C84—C85 C84—H84A C84—H84B C85—H85A C85—H85B C85—H85C. 1.404 (16) 0.9500 0.9500 1.405 (11) 1.414 (10) 1.399 (13) 0.9500 1.395 (13) 0.9500 1.402 (13) 0.9500 1.388 (12) 0.9500 0.9500 1.233 (10) 1.281 (10) 1.533 (13) 0.9800 0.9800 0.9800 1.48 (3) 0.9800 0.9800 0.9800 1.407 (17) 0.9900 0.9900 1.44 (2) 1.47 (3) 0.9900 0.9900 0.9800 0.9800 0.9800. O71—Cu1—P2 O71—Cu1—P3 P2—Cu1—P3 O71—Cu1—P1 P2—Cu1—P1 P3—Cu1—P1 C21—P1—C1 C21—P1—C11 C1—P1—C11 C21—P1—Cu1 C1—P1—Cu1 C11—P1—Cu1. 119.63 (18) 108.90 (18) 116.12 (8) 110.51 (18) 90.30 (9) 109.61 (8) 104.1 (4) 102.2 (4) 99.7 (4) 121.3 (3) 101.9 (3) 123.7 (3). C31—C36—C35 C31—C36—H36 C35—C36—H36 C46—C41—C42 C46—C41—P2 C42—C41—P2 C41—C42—C43 C41—C42—H42 C43—C42—H42 C44—C43—C42 C44—C43—H43 C42—C43—H43. 119.6 (10) 120.2 120.2 119.8 (8) 118.4 (6) 121.8 (6) 119.8 (9) 120.1 120.1 120.0 (9) 120.0 120.0. Acta Cryst. (2005). E61, m2201–m2203. sup-6.

(10) supporting information C31—P2—C41 C31—P2—C2 C41—P2—C2 C31—P2—Cu1 C41—P2—Cu1 C2—P2—Cu1 C3—P3—C51 C3—P3—C61 C51—P3—C61 C3—P3—Cu1 C51—P3—Cu1 C61—P3—Cu1 C2—C1—P1 C2—C1—H1A P1—C1—H1A C2—C1—H1B P1—C1—H1B H1A—C1—H1B C1—C2—P2 C1—C2—H2A P2—C2—H2A C1—C2—H2B P2—C2—H2B H2A—C2—H2B C3i—C3—P3 C3i—C3—H3A P3—C3—H3A C3i—C3—H3B P3—C3—H3B H3A—C3—H3B C16—C11—C12 C16—C11—P1 C12—C11—P1 C11—C12—C13 C11—C12—H12 C13—C12—H12 C14—C13—C12 C14—C13—H13 C12—C13—H13 C13—C14—C15 C13—C14—H14 C15—C14—H14 C14—C15—C16 C14—C15—H15 C16—C15—H15 C11—C16—C15 C11—C16—H16 C15—C16—H16. Acta Cryst. (2005). E61, m2201–m2203. 104.4 (4) 104.4 (4) 101.8 (4) 120.7 (3) 120.6 (3) 102.0 (3) 104.4 (4) 101.2 (4) 100.7 (4) 108.9 (3) 113.6 (3) 125.8 (2) 111.8 (6) 109.3 109.3 109.3 109.3 107.9 109.4 (6) 109.8 109.8 109.8 109.8 108.2 109.4 (7) 109.8 109.8 109.8 109.8 108.2 120.2 (8) 116.7 (7) 123.1 (7) 120.4 (9) 119.8 119.8 119.5 (9) 120.2 120.2 120.4 (9) 119.8 119.8 120.3 (9) 119.9 119.9 119.2 (9) 120.4 120.4. C43—C44—C45 C43—C44—H44 C45—C44—H44 C44—C45—C46 C44—C45—H45 C46—C45—H45 C41—C46—C45 C41—C46—H46 C45—C46—H46 C52—C51—C56 C52—C51—P3 C56—C51—P3 C51—C52—C53 C51—C52—H52 C53—C52—H52 C54—C53—C52 C54—C53—H53 C52—C53—H53 C53—C54—C55 C53—C54—H54 C55—C54—H54 C56—C55—C54 C56—C55—H55 C54—C55—H55 C55—C56—C51 C55—C56—H56 C51—C56—H56 C62—C61—C66 C62—C61—P3 C66—C61—P3 C63—C62—C61 C63—C62—H62 C61—C62—H62 C64—C63—C62 C64—C63—H63 C62—C63—H63 C63—C64—C65 C63—C64—H64 C65—C64—H64 C66—C65—C64 C66—C65—H65 C64—C65—H65 C65—C66—C61 C65—C66—H66 C61—C66—H66 O71—C71—O72 O71—C71—C72 O72—C71—C72. 120.5 (8) 119.7 119.7 120.2 (9) 119.9 119.9 119.5 (8) 120.2 120.2 118.9 (9) 117.7 (7) 123.4 (7) 121.7 (11) 119.2 119.2 120.3 (12) 119.9 119.9 119.4 (10) 120.3 120.3 121.4 (12) 119.3 119.3 118.4 (11) 120.8 120.8 118.5 (7) 121.5 (6) 120.0 (6) 120.4 (7) 119.8 119.8 120.3 (8) 119.8 119.8 119.9 (8) 120.1 120.1 119.9 (8) 120.1 120.1 121.1 (8) 119.5 119.5 126.2 (8) 118.5 (8) 115.2 (8). sup-7.

(11) supporting information C22—C21—C26 C22—C21—P1 C26—C21—P1 C23—C22—C21 C23—C22—H22 C21—C22—H22 C22—C23—C24 C22—C23—H23 C24—C23—H23 C25—C24—C23 C25—C24—H24 C23—C24—H24 C24—C25—C26 C24—C25—H25 C26—C25—H25 C25—C26—C21 C25—C26—H26 C21—C26—H26 C32—C31—C36 C32—C31—P2 C36—C31—P2 C31—C32—C33 C31—C32—H32 C33—C32—H32 C34—C33—C32 C34—C33—H33 C32—C33—H33 C33—C34—C35 C33—C34—H34 C35—C34—H34 C34—C35—C36 C34—C35—H35 C36—C35—H35. 119.1 (8) 122.8 (7) 118.0 (7) 120.5 (9) 119.7 119.7 119.9 (10) 120.1 120.1 119.7 (9) 120.2 120.2 120.2 (9) 119.9 119.9 120.5 (9) 119.8 119.8 120.2 (8) 115.9 (7) 123.8 (7) 119.8 (9) 120.1 120.1 118.9 (9) 120.6 120.6 121.6 (10) 119.2 119.2 119.8 (10) 120.1 120.1. C71—C72—H72A C71—C72—H72B H72A—C72—H72B C71—C72—H72C H72A—C72—H72C H72B—C72—H72C C71—O71—Cu1 C82—C81—H81A C82—C81—H81B H81A—C81—H81B C82—C81—H81C H81A—C81—H81C H81B—C81—H81C O83—C82—C81 O83—C82—H82A C81—C82—H82A O83—C82—H82B C81—C82—H82B H82A—C82—H82B C82—O83—C84 O83—C84—C85 O83—C84—H84A C85—C84—H84A O83—C84—H84B C85—C84—H84B H84A—C84—H84B C84—C85—H85A C84—C85—H85B H85A—C85—H85B C84—C85—H85C H85A—C85—H85C H85B—C85—H85C. 109.5 109.5 109.5 109.5 109.5 109.5 116.6 (5) 109.5 109.5 109.5 109.5 109.5 109.5 113.1 (16) 109.0 109.0 109.0 109.0 107.8 110.3 (14) 107.4 (15) 110.2 110.2 110.2 110.2 108.5 109.5 109.5 109.5 109.5 109.5 109.5. O71—Cu1—P1—C21 P2—Cu1—P1—C21 P3—Cu1—P1—C21 O71—Cu1—P1—C1 P2—Cu1—P1—C1 P3—Cu1—P1—C1 O71—Cu1—P1—C11 P2—Cu1—P1—C11 P3—Cu1—P1—C11 O71—Cu1—P2—C31 P3—Cu1—P2—C31 P1—Cu1—P2—C31 O71—Cu1—P2—C41 P3—Cu1—P2—C41. −127.8 (4) 110.2 (4) −7.8 (4) 117.3 (3) −4.7 (3) −122.7 (3) 7.0 (4) −115.0 (3) 127.0 (3) 111.4 (4) −22.5 (4) −134.6 (3) −22.0 (4) −155.9 (3). P1—C21—C26—C25 C41—P2—C31—C32 C2—P2—C31—C32 Cu1—P2—C31—C32 C41—P2—C31—C36 C2—P2—C31—C36 Cu1—P2—C31—C36 C36—C31—C32—C33 P2—C31—C32—C33 C31—C32—C33—C34 C32—C33—C34—C35 C33—C34—C35—C36 C32—C31—C36—C35 P2—C31—C36—C35. −179.7 (8) 92.8 (6) −160.7 (6) −47.0 (7) −90.6 (8) 15.9 (8) 129.6 (7) −0.1 (12) 176.7 (6) −2.5 (12) 4.1 (15) −3.0 (16) 1.1 (13) −175.3 (7). Acta Cryst. (2005). E61, m2201–m2203. sup-8.

(12) supporting information P1—Cu1—P2—C41 O71—Cu1—P2—C2 P3—Cu1—P2—C2 P1—Cu1—P2—C2 O71—Cu1—P3—C3 P2—Cu1—P3—C3 P1—Cu1—P3—C3 O71—Cu1—P3—C51 P2—Cu1—P3—C51 P1—Cu1—P3—C51 O71—Cu1—P3—C61 P2—Cu1—P3—C61 P1—Cu1—P3—C61 C21—P1—C1—C2 C11—P1—C1—C2 Cu1—P1—C1—C2 P1—C1—C2—P2 C31—P2—C2—C1 C41—P2—C2—C1 Cu1—P2—C2—C1 C51—P3—C3—C3i C61—P3—C3—C3i Cu1—P3—C3—C3i C21—P1—C11—C16 C1—P1—C11—C16 Cu1—P1—C11—C16 C21—P1—C11—C12 C1—P1—C11—C12 Cu1—P1—C11—C12 C16—C11—C12—C13 P1—C11—C12—C13 C11—C12—C13—C14 C12—C13—C14—C15 C13—C14—C15—C16 C12—C11—C16—C15 P1—C11—C16—C15 C14—C15—C16—C11 C1—P1—C21—C22 C11—P1—C21—C22 Cu1—P1—C21—C22 C1—P1—C21—C26 C11—P1—C21—C26 Cu1—P1—C21—C26 C26—C21—C22—C23 P1—C21—C22—C23 C21—C22—C23—C24 C22—C23—C24—C25 C23—C24—C25—C26. Acta Cryst. (2005). E61, m2201–m2203. 92.0 (3) −133.6 (4) 92.5 (3) −19.6 (3) 58.7 (4) −162.7 (3) −62.3 (3) 174.5 (4) −46.9 (3) 53.5 (3) −61.2 (4) 77.4 (3) 177.8 (3) −91.6 (7) 163.0 (6) 35.3 (6) −55.8 (7) 173.2 (6) −78.5 (6) 46.7 (6) 175.3 (7) 71.1 (8) −63.2 (8) 160.9 (7) −92.2 (7) 19.2 (8) −21.0 (8) 85.9 (8) −162.7 (6) 0.6 (14) −177.4 (7) 0.7 (15) −0.6 (15) −0.8 (15) −1.9 (13) 176.2 (7) 2.1 (14) 18.0 (9) 121.5 (9) −95.7 (8) −165.2 (7) −61.8 (8) 81.1 (8) 0.3 (16) 177.0 (9) 3.5 (18) −4.7 (19) 2.2 (18). C34—C35—C36—C31 C31—P2—C41—C46 C2—P2—C41—C46 Cu1—P2—C41—C46 C31—P2—C41—C42 C2—P2—C41—C42 Cu1—P2—C41—C42 C46—C41—C42—C43 P2—C41—C42—C43 C41—C42—C43—C44 C42—C43—C44—C45 C43—C44—C45—C46 C42—C41—C46—C45 P2—C41—C46—C45 C44—C45—C46—C41 C3—P3—C51—C52 C61—P3—C51—C52 Cu1—P3—C51—C52 C3—P3—C51—C56 C61—P3—C51—C56 Cu1—P3—C51—C56 C56—C51—C52—C53 P3—C51—C52—C53 C51—C52—C53—C54 C52—C53—C54—C55 C53—C54—C55—C56 C54—C55—C56—C51 C52—C51—C56—C55 P3—C51—C56—C55 C3—P3—C61—C62 C51—P3—C61—C62 Cu1—P3—C61—C62 C3—P3—C61—C66 C51—P3—C61—C66 Cu1—P3—C61—C66 C66—C61—C62—C63 P3—C61—C62—C63 C61—C62—C63—C64 C62—C63—C64—C65 C63—C64—C65—C66 C64—C65—C66—C61 C62—C61—C66—C65 P3—C61—C66—C65 O72—C71—O71—Cu1 C72—C71—O71—Cu1 P2—Cu1—O71—C71 P3—Cu1—O71—C71 P1—Cu1—O71—C71. 0.3 (15) −133.3 (8) 118.3 (8) 6.6 (9) 46.7 (9) −61.8 (9) −173.5 (7) −1.6 (16) 178.5 (9) 2.7 (18) −3.5 (18) 3.2 (17) 1.2 (15) −178.8 (8) −2.0 (16) −164.1 (7) −59.5 (8) 77.5 (7) 17.2 (9) 121.8 (8) −101.2 (7) 0.0 (15) −178.7 (8) 0.1 (17) −0.6 (18) 1.0 (19) −0.9 (17) 0.4 (14) 179.0 (8) −125.6 (7) 127.2 (7) −2.4 (8) 55.6 (7) −51.6 (7) 178.8 (5) 0.0 (12) −178.8 (7) 0.5 (14) −1.2 (14) 1.3 (14) −0.8 (13) 0.2 (12) 179.0 (6) 13.9 (10) −164.9 (6) −57.8 (6) 79.1 (6) −160.5 (5). sup-9.

(13) supporting information C24—C25—C26—C21 C22—C21—C26—C25. 1.5 (16) −2.8 (15). C81—C82—O83—C84 C82—O83—C84—C85. 179.6 (19) 173.4 (15). Symmetry code: (i) −x+1, −y+1, −z+1.. Hydrogen-bond geometry (Å, º) D—H···A C33—H33···O72 C62—H62···O72. ii. D—H. H···A. D···A. D—H···A. 0.95 0.95. 2.43 2.47. 3.361 (12) 3.380 (10). 166 161. Symmetry code: (ii) −x, −y+1, −z+1.. Acta Cryst. (2005). E61, m2201–m2203. sup-10.

(14)

New documents

Modality is signaled in example 3 by the subjunctive mood in the verb German Konjunktiv II, by the modal adverb vielleicht ‘maybe’ and the modal auxiliary verb können again.. The

modal: yao, „need to‟ modality type: priority --> teleological prejacent: „in the following three years, the annual GDP growth of Shanghai needs to be around 10% to 11%‟ background:

The adverbials selected for this research meet the requirements of the scope of epistemic modality and evidentiality described above The list, which is not exhaustive in the present

It uses semantic clues organized in E_M semantic resources database that lead to the opening of new E_M segments; it also uses a syntactic parser to calculate the length of an E_M

Whereas in ii below, two modal values within the same information units will be compositional and the dominant value will prevail: ii GIL: // I think that it has to be these In ii there

For the triplet dataset, the model yields a main effect of verb type, and produces the lowest thematic fit for the metonymic condition corresponding to the longest reading times and eye

We included patients who received therapeutic hypothermia using overall surface or endovascular cooling devices and compared the neurological outcomes, efficacies and adverse events of

Although the amount of data obtained for each question is still relatively small the largest amount of answers given to a reasonably sized amount of questions was 6, the results on

information incorporate this information in ways that are not always efficient We used restricted cubic splines to assess how admission vital signs data predict mortality in patients

This requires representations of interpretation that explicitly link discourse entities with grounded symbols and track the heterogeneous prominence that these entities get in virtue of