metal-organic compounds
Aquatris[1-(2,4-dioxo-2H-1-benzopyran-3-ylidene)ethan-1-olato]ethanolgadolinium(III) ethanol monosolvate
aFacultad de Química, Universidad Nacional Autónoma de México, Ciudad Universitaria, 04510 México D.F., Mexico, and bInstituto de Física, Benemérita Universidad Autónoma de Puebla, Av. San Claudio y 18 Sur, 72570 Puebla, Pue., Mexico
*Correspondence e-mail: sylvain_bernes@hotmail.com
The title compound, [Gd(C11H7O4)3(C2H5OH)(H2O)]·C2H5OH, was crystallized from ethanol, affording a solvate. The main ligand in the complex results from deprotonation of the hydroxy group in 3-acetyl-4-hydroxycoumarin (C11H8O4) and the resulting anionic ligands chelate the GdIII centre. Three anions, one ethanol and one water molecule are bonded to the lanthanide, giving an eight-coordinate metal centre with a slightly distorted trigonal–prismatic square-face-bicapped coordination geometry. All water and ethanol molecules participate in an intricate three-dimensional framework of hydrogen bonds. The complex is isostructural to the Tb and Dy compounds reported previously [Guzmán-Méndez et al. (2018). Inorg. Chem. 57, 908–911].
Keywords: crystal structure; lanthanide; gadolinium; solvate.
CCDC reference: 1909306
Structure description
We are currently probing the possibility of using a coumarin derivative, 3-acetyl-4-hydroxycoumarin, as an efficient luminescence sensitizer for lanthanide ions (Guzmán-Méndez et al., 2018). Although the molecular structure of this coumarin derivative is very simple, with an essentially planar conformation (Traven et al., 2000; Lyssenko & Antipin, 2001), weak intermolecular contacts in the solid state are known to promote (Ghouili et al., 2015). Such behaviour was previously studied in detail for a closely related system, 3-acetylcoumarin (Munshi et al., 2004; Munshi & Guru Row, 2006). For our part, we determined that the coordination ability of 3-acetyl-4-hydroxycoumarin towards lanthanides is related to the chelating character of the acetyl and hydroxyl groups, once the hydroxyl group has been deprotonated. The same behaviour has been reported for this ligand with a transition metal (CoII; Bejaoui et al., 2018) and a main-group element (B; Manaev et al., 2006). In the case of lanthanides, for which the is generally unpredictable, it is sometimes difficult to set up well-reproducible synthetic methods, especially when small coordinating molecules, such as water and may be included in the coordination sphere. However, isotypic or partially isotypic series may be obtained along the lanthanide group. For example, compounds with reproducible formulae {[LnL3(H2O)(EtOH)]·EtOH}, where L is the anion obtained from 3-acetyl-4-hydroxycoumarin, can be crystallized in the P21/c at least with Ln = Gd, Tb, Dy, Ho and Tm. The present report deals with the compound corresponding to Ln = Gd.
The complex crystallizes with one uncoordinated ethanol molecule (O57) per complex, with no disordered parts (Fig. 1). The neutral complex [GdL3(H2O)(EtOH)] is built up of an eight-coordinate GdIII ion, which is a common for this metal. Three coumarin ligands chelate the metal, with Gd—O bond lengths in the range 2.330 (2)–2.401 (2) Å, the coordination sphere being completed with one water molecule [Gd1—O53: 2.379 (3) Å] and one ethanol molecule [Gd—O54: 2.417 (3) Å]. The set of eight O atoms around the lanthanide is arranged to form a trigonal–prismatic square-face-bicapped polyhedron, corresponding to the TPRS-8 in the IUPAC nomenclature (IUPAC, 2005). The chelating fragment, O3—C4—C3—C11—O4 (and equivalent groups in other L ligands) displays geometric parameters consistent with a negative charge fully delocalized over the chelate, giving a strongly stabilizing six-membered metallacycle. Two ligands L are almost coplanar, forming a dihedral angle of 9.87 (8)°, while the third ligand bisects this plane, with dihedral angles of 80.05 (6) and 82.60 (5)° (mean planes are calculated using 15 non-H atoms for each ligand L; see Fig. 1, inset). This arrangement is similar to that observed for the eight-coordinate [LnL3(H2O)(EtOH)] and [LnL3(H2O)(MeOH)] complexes previously reported (Guzmán-Méndez et al., 2018).
Water and ethanol molecules participate in the building of a complex supramolecular structure based on O—H⋯O hydrogen bonds. The main feature is the formation of a one-dimensional frame along the [010] direction, in which molecules are connected using the non-coordinating carbonyl groups of two α-pyrone rings as acceptor to form bonds with coordinated water and ethanol molecules (Table 1, entries 1 and 2). The lattice ethanol molecule forms a third bond, with the coordinated water molecule (Table 1, entry 3). The resulting arrangement allows weak π–π interactions between coumarin ligands related by inversion, with a separation of 3.32 Å between the planes of these rings (Fig. 2).
Synthesis and crystallization
The synthesis was carried out using the methodology described in a previous publication (Guzmán-Méndez et al., 2018). The title complex was synthesized by dissolving 0.75 mmol HL in 40 ml EtOH with 0.75 mmol of sodium methoxide. To this mixture, an ethanolic solution of 0.25 mmol of Gd(NO3)3·6H2O was added dropwise. This mixture was allowed to react for 5 h at 333 K with vigorous stirring. After this time, the solvent was evaporated to 5 ml and water was added to precipitate the complex, which was then filtered and dried (yield: 89%). Colourless plate-shaped crystals were obtained from the slow evaporation of an ethanolic solution of the solid.
Refinement
Crystal data, data collection and structure .
details are summarized in Table 2Structural data
CCDC reference: 1909306
https://doi.org/10.1107/S2414314619004930/im4004sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314619004930/im4004Isup2.hkl
Data collection: X-AREA (Stoe & Cie, 2018); cell
X-AREA (Stoe & Cie, 2018); data reduction: X-AREA (Stoe & Cie, 2018); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 2008) and Mercury (Macrae et al., 2008); software used to prepare material for publication: publCIF (Westrip, 2010).[Gd(C11H7O4)3(C2H6O)(H2O)]·C2H6O | F(000) = 1764 |
Mr = 876.90 | Dx = 1.605 Mg m−3 |
Monoclinic, P21/c | Ag Kα radiation, λ = 0.56083 Å |
a = 11.5029 (3) Å | Cell parameters from 36640 reflections |
b = 31.8022 (9) Å | θ = 2.2–22.7° |
c = 10.8445 (3) Å | µ = 1.02 mm−1 |
β = 113.840 (2)° | T = 250 K |
V = 3628.62 (18) Å3 | Plate, colourless |
Z = 4 | 0.50 × 0.30 × 0.06 mm |
Stoe Stadivari diffractometer | 7317 independent reflections |
Radiation source: Sealed X-ray tube, Axo Astix-f Microfocus source | 5494 reflections with I > 2σ(I) |
Graded multilayer mirror monochromator | Rint = 0.051 |
Detector resolution: 5.81 pixels mm-1 | θmax = 20.5°, θmin = 2.2° |
ω scans | h = −14→14 |
Absorption correction: multi-scan (X-AREA; Stoe & Cie, 2018) | k = −39→39 |
Tmin = 0.583, Tmax = 1.000 | l = −13→13 |
45823 measured reflections |
Refinement on F2 | Primary atom site location: dual |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.034 | Hydrogen site location: mixed |
wR(F2) = 0.078 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0397P)2] where P = (Fo2 + 2Fc2)/3 |
7317 reflections | (Δ/σ)max = 0.002 |
495 parameters | Δρmax = 0.62 e Å−3 |
6 restraints | Δρmin = −0.65 e Å−3 |
0 constraints |
Refinement. H atoms bonded to C atoms were placed in idealized positions and refined as riding to their parent atoms, while remaining H atoms, for water and ethanol molecules, were placed using difference maps and refined with free coordinates. All O—H bond lengths were restrained to a distance target of 0.85 (2) Å, while H—O53—H angle for the water molecule was restrained with a target H···H = 1.34 (4) Å. Isotropic displacement parameters were calculated for all H atoms, as Uiso = xUeq(carrier atom) where x = 1.2 or x = 1.5. |
x | y | z | Uiso*/Ueq | ||
Gd1 | 0.32396 (2) | 0.38332 (2) | 0.65440 (2) | 0.03530 (7) | |
O1 | −0.2286 (2) | 0.36089 (11) | 0.5373 (3) | 0.0632 (8) | |
O2 | −0.1432 (3) | 0.34226 (12) | 0.7479 (3) | 0.0754 (10) | |
O3 | 0.1096 (2) | 0.40002 (9) | 0.5385 (2) | 0.0458 (6) | |
O4 | 0.2153 (2) | 0.38175 (9) | 0.8025 (2) | 0.0425 (6) | |
C2 | −0.1229 (4) | 0.35819 (15) | 0.6576 (4) | 0.0510 (10) | |
C3 | −0.0025 (3) | 0.37320 (12) | 0.6643 (4) | 0.0382 (9) | |
C4 | 0.0079 (3) | 0.38814 (12) | 0.5459 (4) | 0.0380 (8) | |
C5 | −0.1081 (4) | 0.39009 (13) | 0.4215 (4) | 0.0463 (10) | |
C6 | −0.1080 (4) | 0.40423 (16) | 0.3008 (4) | 0.0605 (12) | |
H6 | −0.031918 | 0.413900 | 0.297964 | 0.073* | |
C7 | −0.2187 (6) | 0.4043 (2) | 0.1843 (5) | 0.0825 (16) | |
H7 | −0.218139 | 0.414098 | 0.102814 | 0.099* | |
C8 | −0.3302 (6) | 0.38977 (19) | 0.1892 (6) | 0.0872 (18) | |
H8 | −0.405035 | 0.389533 | 0.109828 | 0.105* | |
C9 | −0.3339 (4) | 0.37599 (18) | 0.3048 (6) | 0.0756 (16) | |
H9 | −0.410644 | 0.366535 | 0.306605 | 0.091* | |
C10 | −0.2212 (4) | 0.37593 (14) | 0.4230 (5) | 0.0543 (11) | |
C11 | 0.1068 (3) | 0.37340 (12) | 0.7928 (4) | 0.0386 (9) | |
C12 | 0.0962 (4) | 0.36405 (16) | 0.9238 (4) | 0.0558 (11) | |
H12A | 0.026852 | 0.380229 | 0.929070 | 0.084* | |
H12B | 0.174997 | 0.371584 | 0.998382 | 0.084* | |
H12C | 0.079830 | 0.334292 | 0.928425 | 0.084* | |
O21 | 0.3255 (3) | 0.19355 (9) | 0.6550 (3) | 0.0593 (8) | |
O22 | 0.4516 (3) | 0.20264 (11) | 0.5523 (4) | 0.0754 (10) | |
O23 | 0.2292 (2) | 0.31735 (8) | 0.6307 (3) | 0.0427 (6) | |
O24 | 0.4223 (2) | 0.33318 (10) | 0.5646 (3) | 0.0505 (7) | |
C22 | 0.3833 (4) | 0.22069 (15) | 0.5968 (4) | 0.0528 (11) | |
C23 | 0.3607 (3) | 0.26510 (13) | 0.5977 (4) | 0.0397 (9) | |
C24 | 0.2634 (3) | 0.27989 (12) | 0.6364 (3) | 0.0366 (8) | |
C25 | 0.1987 (3) | 0.24889 (12) | 0.6863 (4) | 0.0397 (9) | |
C26 | 0.1059 (4) | 0.26070 (14) | 0.7297 (4) | 0.0517 (10) | |
H26 | 0.078409 | 0.288814 | 0.720969 | 0.062* | |
C27 | 0.0533 (4) | 0.23141 (16) | 0.7858 (5) | 0.0635 (12) | |
H27 | −0.009484 | 0.239634 | 0.815633 | 0.076* | |
C28 | 0.0922 (4) | 0.19063 (16) | 0.7982 (4) | 0.0635 (13) | |
H28 | 0.055881 | 0.170878 | 0.836663 | 0.076* | |
C29 | 0.1837 (4) | 0.17797 (15) | 0.7553 (4) | 0.0624 (12) | |
H29 | 0.210647 | 0.149802 | 0.764178 | 0.075* | |
C30 | 0.2355 (4) | 0.20766 (13) | 0.6984 (4) | 0.0467 (9) | |
C31 | 0.4325 (3) | 0.29467 (15) | 0.5552 (4) | 0.0461 (10) | |
C32 | 0.5275 (4) | 0.28046 (17) | 0.4999 (5) | 0.0718 (14) | |
H32A | 0.484305 | 0.264046 | 0.418714 | 0.108* | |
H32B | 0.592455 | 0.263356 | 0.566673 | 0.108* | |
H32C | 0.566722 | 0.304861 | 0.478848 | 0.108* | |
O41 | 0.6855 (2) | 0.47924 (9) | 0.4682 (3) | 0.0523 (7) | |
O42 | 0.5149 (3) | 0.48143 (10) | 0.2835 (3) | 0.0562 (7) | |
O43 | 0.5179 (2) | 0.41424 (9) | 0.6765 (2) | 0.0425 (6) | |
O44 | 0.3049 (2) | 0.41309 (9) | 0.4466 (2) | 0.0431 (6) | |
C42 | 0.5606 (3) | 0.46792 (13) | 0.3981 (4) | 0.0440 (9) | |
C43 | 0.4987 (3) | 0.44347 (12) | 0.4673 (4) | 0.0379 (8) | |
C44 | 0.5643 (3) | 0.43375 (12) | 0.6066 (4) | 0.0390 (9) | |
C45 | 0.6956 (3) | 0.44855 (13) | 0.6745 (4) | 0.0427 (9) | |
C46 | 0.7656 (4) | 0.44179 (15) | 0.8114 (4) | 0.0522 (11) | |
H46 | 0.729631 | 0.426631 | 0.861698 | 0.063* | |
C47 | 0.8878 (4) | 0.45728 (17) | 0.8737 (5) | 0.0654 (13) | |
H47 | 0.935060 | 0.452972 | 0.966420 | 0.079* | |
C48 | 0.9401 (4) | 0.47921 (18) | 0.7982 (5) | 0.0711 (15) | |
H48 | 1.023669 | 0.489430 | 0.840589 | 0.085* | |
C49 | 0.8725 (4) | 0.48642 (16) | 0.6625 (5) | 0.0660 (14) | |
H49 | 0.908613 | 0.501611 | 0.612360 | 0.079* | |
C50 | 0.7510 (3) | 0.47080 (13) | 0.6023 (4) | 0.0471 (10) | |
C51 | 0.3681 (3) | 0.43018 (12) | 0.3907 (4) | 0.0386 (8) | |
C52 | 0.3027 (4) | 0.43506 (15) | 0.2412 (4) | 0.0551 (11) | |
H52A | 0.351072 | 0.420692 | 0.198569 | 0.083* | |
H52B | 0.296218 | 0.464690 | 0.218116 | 0.083* | |
H52C | 0.218156 | 0.422977 | 0.209851 | 0.083* | |
O53 | 0.4721 (2) | 0.35409 (11) | 0.8598 (3) | 0.0536 (8) | |
H53A | 0.455 (4) | 0.3378 (13) | 0.911 (4) | 0.080* | |
H53B | 0.546 (2) | 0.3478 (16) | 0.871 (4) | 0.080* | |
O54 | 0.3384 (3) | 0.45345 (9) | 0.7454 (3) | 0.0535 (7) | |
H54 | 0.396 (4) | 0.4704 (13) | 0.748 (5) | 0.080* | |
C55 | 0.2554 (4) | 0.47760 (16) | 0.7856 (5) | 0.0677 (13) | |
H55A | 0.174962 | 0.462504 | 0.761659 | 0.081* | |
H55B | 0.237102 | 0.504482 | 0.737301 | 0.081* | |
C56 | 0.3133 (6) | 0.4856 (2) | 0.9332 (5) | 0.111 (2) | |
H56A | 0.254230 | 0.501409 | 0.958542 | 0.167* | |
H56B | 0.391127 | 0.501553 | 0.956454 | 0.167* | |
H56C | 0.332276 | 0.458980 | 0.981096 | 0.167* | |
O57 | 0.6984 (4) | 0.33100 (18) | 0.8778 (5) | 0.124 (2) | |
H57 | 0.714 (6) | 0.333 (2) | 0.808 (4) | 0.187* | |
C58 | 0.7719 (6) | 0.2997 (3) | 0.9692 (7) | 0.109 (2) | |
H58A | 0.740236 | 0.296023 | 1.039971 | 0.131* | |
H58B | 0.860265 | 0.309275 | 1.012364 | 0.131* | |
C59 | 0.7684 (7) | 0.2592 (3) | 0.9043 (9) | 0.140 (3) | |
H59A | 0.810851 | 0.238156 | 0.972477 | 0.210* | |
H59B | 0.811209 | 0.261618 | 0.843785 | 0.210* | |
H59C | 0.680693 | 0.250905 | 0.853506 | 0.210* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Gd1 | 0.03853 (10) | 0.03460 (12) | 0.03740 (11) | −0.00399 (9) | 0.02013 (8) | 0.00337 (9) |
O1 | 0.0395 (15) | 0.079 (3) | 0.069 (2) | −0.0063 (15) | 0.0202 (15) | −0.0025 (18) |
O2 | 0.0566 (17) | 0.105 (3) | 0.076 (2) | −0.0144 (18) | 0.0388 (16) | 0.020 (2) |
O3 | 0.0389 (13) | 0.0559 (18) | 0.0441 (15) | 0.0055 (12) | 0.0184 (12) | 0.0157 (13) |
O4 | 0.0419 (13) | 0.0498 (18) | 0.0401 (14) | −0.0059 (12) | 0.0210 (11) | −0.0001 (12) |
C2 | 0.043 (2) | 0.057 (3) | 0.056 (3) | 0.004 (2) | 0.024 (2) | 0.003 (2) |
C3 | 0.0394 (19) | 0.034 (2) | 0.045 (2) | 0.0002 (15) | 0.0215 (17) | 0.0014 (17) |
C4 | 0.0397 (19) | 0.034 (2) | 0.042 (2) | 0.0045 (16) | 0.0173 (16) | 0.0016 (17) |
C5 | 0.050 (2) | 0.043 (3) | 0.042 (2) | 0.0073 (18) | 0.0147 (18) | −0.0044 (18) |
C6 | 0.064 (3) | 0.066 (3) | 0.043 (2) | 0.009 (2) | 0.013 (2) | 0.003 (2) |
C7 | 0.091 (4) | 0.093 (5) | 0.045 (3) | 0.012 (3) | 0.008 (3) | 0.003 (3) |
C8 | 0.081 (4) | 0.085 (5) | 0.061 (3) | 0.010 (3) | −0.008 (3) | −0.013 (3) |
C9 | 0.053 (3) | 0.079 (4) | 0.075 (4) | 0.005 (3) | 0.005 (3) | −0.022 (3) |
C10 | 0.047 (2) | 0.049 (3) | 0.060 (3) | 0.0019 (19) | 0.014 (2) | −0.004 (2) |
C11 | 0.048 (2) | 0.032 (2) | 0.043 (2) | 0.0011 (16) | 0.0259 (18) | 0.0041 (16) |
C12 | 0.061 (2) | 0.072 (3) | 0.044 (2) | −0.002 (2) | 0.032 (2) | 0.005 (2) |
O21 | 0.0678 (18) | 0.0345 (17) | 0.072 (2) | 0.0106 (15) | 0.0253 (16) | −0.0012 (15) |
O22 | 0.078 (2) | 0.059 (2) | 0.098 (2) | 0.0106 (17) | 0.0451 (19) | −0.0266 (19) |
O23 | 0.0464 (14) | 0.0250 (15) | 0.0651 (17) | 0.0008 (11) | 0.0313 (13) | 0.0029 (13) |
O24 | 0.0552 (16) | 0.049 (2) | 0.0597 (17) | −0.0022 (14) | 0.0361 (14) | −0.0020 (15) |
C22 | 0.049 (2) | 0.052 (3) | 0.052 (2) | 0.005 (2) | 0.014 (2) | −0.011 (2) |
C23 | 0.0400 (19) | 0.038 (2) | 0.039 (2) | 0.0050 (17) | 0.0143 (16) | −0.0045 (18) |
C24 | 0.0380 (19) | 0.033 (2) | 0.036 (2) | −0.0010 (16) | 0.0121 (15) | −0.0030 (17) |
C25 | 0.044 (2) | 0.034 (2) | 0.037 (2) | −0.0042 (17) | 0.0114 (16) | 0.0013 (17) |
C26 | 0.057 (2) | 0.039 (3) | 0.066 (3) | −0.003 (2) | 0.032 (2) | 0.002 (2) |
C27 | 0.072 (3) | 0.059 (3) | 0.071 (3) | −0.014 (2) | 0.042 (3) | 0.000 (3) |
C28 | 0.080 (3) | 0.055 (3) | 0.051 (3) | −0.024 (3) | 0.022 (2) | 0.006 (2) |
C29 | 0.082 (3) | 0.041 (3) | 0.051 (3) | −0.009 (2) | 0.013 (2) | 0.002 (2) |
C30 | 0.054 (2) | 0.037 (3) | 0.042 (2) | −0.0026 (19) | 0.0122 (19) | −0.0013 (19) |
C31 | 0.046 (2) | 0.055 (3) | 0.040 (2) | 0.005 (2) | 0.0202 (17) | −0.002 (2) |
C32 | 0.070 (3) | 0.077 (4) | 0.090 (4) | 0.010 (3) | 0.055 (3) | −0.007 (3) |
O41 | 0.0537 (16) | 0.056 (2) | 0.0558 (17) | −0.0166 (14) | 0.0316 (14) | −0.0005 (14) |
O42 | 0.0722 (18) | 0.054 (2) | 0.0529 (17) | −0.0137 (15) | 0.0360 (15) | 0.0057 (15) |
O43 | 0.0412 (13) | 0.0496 (18) | 0.0381 (13) | −0.0098 (12) | 0.0174 (11) | 0.0044 (12) |
O44 | 0.0465 (14) | 0.0486 (18) | 0.0377 (13) | −0.0094 (12) | 0.0204 (11) | 0.0069 (12) |
C42 | 0.050 (2) | 0.040 (2) | 0.048 (2) | −0.0084 (18) | 0.0268 (19) | −0.0050 (19) |
C43 | 0.048 (2) | 0.034 (2) | 0.040 (2) | −0.0084 (17) | 0.0252 (17) | −0.0029 (17) |
C44 | 0.0405 (19) | 0.037 (2) | 0.044 (2) | −0.0041 (16) | 0.0218 (17) | −0.0056 (18) |
C45 | 0.041 (2) | 0.041 (2) | 0.048 (2) | −0.0049 (17) | 0.0204 (18) | −0.0072 (18) |
C46 | 0.046 (2) | 0.057 (3) | 0.051 (2) | −0.005 (2) | 0.0170 (19) | −0.010 (2) |
C47 | 0.052 (3) | 0.070 (4) | 0.068 (3) | −0.004 (2) | 0.018 (2) | −0.015 (3) |
C48 | 0.044 (2) | 0.082 (4) | 0.086 (4) | −0.018 (2) | 0.024 (3) | −0.032 (3) |
C49 | 0.053 (3) | 0.073 (4) | 0.081 (4) | −0.022 (2) | 0.036 (3) | −0.021 (3) |
C50 | 0.044 (2) | 0.046 (3) | 0.057 (3) | −0.0099 (19) | 0.026 (2) | −0.012 (2) |
C51 | 0.051 (2) | 0.030 (2) | 0.040 (2) | −0.0043 (17) | 0.0236 (17) | 0.0020 (17) |
C52 | 0.066 (3) | 0.061 (3) | 0.039 (2) | −0.017 (2) | 0.0212 (19) | 0.002 (2) |
O53 | 0.0438 (14) | 0.072 (2) | 0.0475 (16) | 0.0016 (15) | 0.0204 (13) | 0.0185 (15) |
O54 | 0.0657 (18) | 0.0407 (18) | 0.0727 (19) | −0.0148 (14) | 0.0471 (16) | −0.0094 (15) |
C55 | 0.077 (3) | 0.058 (3) | 0.084 (3) | −0.006 (3) | 0.049 (3) | −0.006 (3) |
C56 | 0.106 (4) | 0.171 (8) | 0.068 (4) | 0.024 (4) | 0.047 (3) | −0.016 (4) |
O57 | 0.082 (2) | 0.199 (6) | 0.125 (3) | 0.064 (3) | 0.074 (2) | 0.100 (4) |
C58 | 0.069 (4) | 0.154 (8) | 0.101 (5) | 0.013 (4) | 0.030 (3) | 0.055 (5) |
C59 | 0.129 (6) | 0.151 (9) | 0.183 (9) | 0.016 (6) | 0.108 (6) | 0.051 (7) |
Gd1—O23 | 2.330 (2) | C29—C30 | 1.387 (6) |
Gd1—O3 | 2.331 (2) | C29—H29 | 0.9400 |
Gd1—O43 | 2.360 (2) | C31—C32 | 1.513 (5) |
Gd1—O44 | 2.372 (2) | C32—H32A | 0.9700 |
Gd1—O53 | 2.379 (3) | C32—H32B | 0.9700 |
Gd1—O24 | 2.380 (3) | C32—H32C | 0.9700 |
Gd1—O4 | 2.401 (2) | O41—C50 | 1.367 (5) |
Gd1—O54 | 2.417 (3) | O41—C42 | 1.374 (4) |
O1—C10 | 1.363 (5) | O42—C42 | 1.215 (4) |
O1—C2 | 1.381 (5) | O43—C44 | 1.254 (4) |
O2—C2 | 1.206 (5) | O44—C51 | 1.244 (4) |
O3—C4 | 1.262 (4) | C42—C43 | 1.451 (5) |
O4—C11 | 1.238 (4) | C43—C44 | 1.423 (5) |
C2—C3 | 1.438 (5) | C43—C51 | 1.455 (5) |
C3—C4 | 1.419 (5) | C44—C45 | 1.465 (5) |
C3—C11 | 1.451 (5) | C45—C50 | 1.387 (5) |
C4—C5 | 1.466 (5) | C45—C46 | 1.390 (5) |
C5—C10 | 1.383 (6) | C46—C47 | 1.382 (6) |
C5—C6 | 1.384 (6) | C46—H46 | 0.9400 |
C6—C7 | 1.385 (6) | C47—C48 | 1.384 (7) |
C6—H6 | 0.9400 | C47—H47 | 0.9400 |
C7—C8 | 1.384 (8) | C48—C49 | 1.378 (7) |
C7—H7 | 0.9400 | C48—H48 | 0.9400 |
C8—C9 | 1.345 (8) | C49—C50 | 1.375 (6) |
C8—H8 | 0.9400 | C49—H49 | 0.9400 |
C9—C10 | 1.407 (6) | C51—C52 | 1.494 (5) |
C9—H9 | 0.9400 | C52—H52A | 0.9700 |
C11—C12 | 1.504 (5) | C52—H52B | 0.9700 |
C12—H12A | 0.9700 | C52—H52C | 0.9700 |
C12—H12B | 0.9700 | O53—H53A | 0.840 (19) |
C12—H12C | 0.9700 | O53—H53B | 0.835 (19) |
O21—C30 | 1.375 (5) | O54—C55 | 1.424 (5) |
O21—C22 | 1.388 (5) | O54—H54 | 0.847 (19) |
O22—C22 | 1.219 (5) | C55—C56 | 1.486 (7) |
O23—C24 | 1.248 (4) | C55—H55A | 0.9800 |
O24—C31 | 1.238 (5) | C55—H55B | 0.9800 |
C22—C23 | 1.437 (6) | C56—H56A | 0.9700 |
C23—C24 | 1.426 (5) | C56—H56B | 0.9700 |
C23—C31 | 1.444 (5) | C56—H56C | 0.9700 |
C24—C25 | 1.464 (5) | O57—C58 | 1.419 (7) |
C25—C30 | 1.368 (5) | O57—H57 | 0.84 (2) |
C25—C26 | 1.382 (5) | C58—C59 | 1.461 (10) |
C26—C27 | 1.378 (6) | C58—H58A | 0.9800 |
C26—H26 | 0.9400 | C58—H58B | 0.9800 |
C27—C28 | 1.361 (7) | C59—H59A | 0.9700 |
C27—H27 | 0.9400 | C59—H59B | 0.9700 |
C28—C29 | 1.372 (7) | C59—H59C | 0.9700 |
C28—H28 | 0.9400 | ||
O23—Gd1—O3 | 78.45 (9) | C27—C28—C29 | 120.8 (4) |
O23—Gd1—O43 | 140.12 (9) | C27—C28—H28 | 119.6 |
O3—Gd1—O43 | 135.25 (9) | C29—C28—H28 | 119.6 |
O23—Gd1—O44 | 113.27 (9) | C28—C29—C30 | 118.5 (5) |
O3—Gd1—O44 | 74.08 (8) | C28—C29—H29 | 120.7 |
O43—Gd1—O44 | 69.55 (8) | C30—C29—H29 | 120.7 |
O23—Gd1—O53 | 82.98 (10) | C25—C30—O21 | 121.8 (4) |
O3—Gd1—O53 | 142.64 (8) | C25—C30—C29 | 121.6 (4) |
O43—Gd1—O53 | 77.15 (9) | O21—C30—C29 | 116.6 (4) |
O44—Gd1—O53 | 143.28 (8) | O24—C31—C23 | 122.2 (3) |
O23—Gd1—O24 | 68.30 (8) | O24—C31—C32 | 115.8 (4) |
O3—Gd1—O24 | 120.42 (10) | C23—C31—C32 | 122.0 (4) |
O43—Gd1—O24 | 74.59 (9) | C31—C32—H32A | 109.5 |
O44—Gd1—O24 | 75.82 (9) | C31—C32—H32B | 109.5 |
O53—Gd1—O24 | 80.92 (10) | H32A—C32—H32B | 109.5 |
O23—Gd1—O4 | 73.04 (9) | C31—C32—H32C | 109.5 |
O3—Gd1—O4 | 69.03 (8) | H32A—C32—H32C | 109.5 |
O43—Gd1—O4 | 131.84 (8) | H32B—C32—H32C | 109.5 |
O44—Gd1—O4 | 140.41 (9) | C50—O41—C42 | 122.7 (3) |
O53—Gd1—O4 | 74.66 (8) | C44—O43—Gd1 | 139.5 (2) |
O24—Gd1—O4 | 136.22 (9) | C51—O44—Gd1 | 142.2 (2) |
O23—Gd1—O54 | 145.86 (8) | O42—C42—O41 | 113.4 (3) |
O3—Gd1—O54 | 83.85 (10) | O42—C42—C43 | 128.2 (3) |
O43—Gd1—O54 | 70.61 (9) | O41—C42—C43 | 118.4 (3) |
O44—Gd1—O54 | 89.10 (9) | C44—C43—C42 | 120.3 (3) |
O53—Gd1—O54 | 94.21 (11) | C44—C43—C51 | 121.7 (3) |
O24—Gd1—O54 | 145.06 (8) | C42—C43—C51 | 118.0 (3) |
O4—Gd1—O54 | 73.42 (9) | O43—C44—C43 | 125.2 (3) |
C10—O1—C2 | 121.8 (3) | O43—C44—C45 | 117.3 (3) |
C4—O3—Gd1 | 134.7 (2) | C43—C44—C45 | 117.4 (3) |
C11—O4—Gd1 | 136.6 (2) | C50—C45—C46 | 118.8 (3) |
O2—C2—O1 | 114.1 (3) | C50—C45—C44 | 119.7 (3) |
O2—C2—C3 | 126.6 (4) | C46—C45—C44 | 121.4 (3) |
O1—C2—C3 | 119.3 (3) | C47—C46—C45 | 120.2 (4) |
C4—C3—C2 | 119.8 (3) | C47—C46—H46 | 119.9 |
C4—C3—C11 | 120.6 (3) | C45—C46—H46 | 119.9 |
C2—C3—C11 | 119.5 (3) | C46—C47—C48 | 119.4 (4) |
O3—C4—C3 | 125.2 (3) | C46—C47—H47 | 120.3 |
O3—C4—C5 | 116.8 (3) | C48—C47—H47 | 120.3 |
C3—C4—C5 | 117.9 (3) | C49—C48—C47 | 121.5 (4) |
C10—C5—C6 | 118.5 (4) | C49—C48—H48 | 119.2 |
C10—C5—C4 | 119.1 (4) | C47—C48—H48 | 119.2 |
C6—C5—C4 | 122.4 (4) | C50—C49—C48 | 118.3 (4) |
C5—C6—C7 | 120.7 (5) | C50—C49—H49 | 120.9 |
C5—C6—H6 | 119.6 | C48—C49—H49 | 120.9 |
C7—C6—H6 | 119.6 | O41—C50—C49 | 116.9 (4) |
C8—C7—C6 | 119.3 (5) | O41—C50—C45 | 121.3 (3) |
C8—C7—H7 | 120.4 | C49—C50—C45 | 121.8 (4) |
C6—C7—H7 | 120.4 | O44—C51—C43 | 121.4 (3) |
C9—C8—C7 | 121.6 (5) | O44—C51—C52 | 115.9 (3) |
C9—C8—H8 | 119.2 | C43—C51—C52 | 122.7 (3) |
C7—C8—H8 | 119.2 | C51—C52—H52A | 109.5 |
C8—C9—C10 | 119.0 (5) | C51—C52—H52B | 109.5 |
C8—C9—H9 | 120.5 | H52A—C52—H52B | 109.5 |
C10—C9—H9 | 120.5 | C51—C52—H52C | 109.5 |
O1—C10—C5 | 122.0 (4) | H52A—C52—H52C | 109.5 |
O1—C10—C9 | 117.1 (4) | H52B—C52—H52C | 109.5 |
C5—C10—C9 | 120.9 (5) | Gd1—O53—H53A | 126 (3) |
O4—C11—C3 | 122.3 (3) | Gd1—O53—H53B | 122 (3) |
O4—C11—C12 | 115.2 (3) | H53A—O53—H53B | 104 (3) |
C3—C11—C12 | 122.4 (3) | C55—O54—Gd1 | 132.7 (2) |
C11—C12—H12A | 109.5 | C55—O54—H54 | 105 (3) |
C11—C12—H12B | 109.5 | Gd1—O54—H54 | 122 (3) |
H12A—C12—H12B | 109.5 | O54—C55—C56 | 111.0 (4) |
C11—C12—H12C | 109.5 | O54—C55—H55A | 109.4 |
H12A—C12—H12C | 109.5 | C56—C55—H55A | 109.4 |
H12B—C12—H12C | 109.5 | O54—C55—H55B | 109.4 |
C30—O21—C22 | 121.2 (3) | C56—C55—H55B | 109.4 |
C24—O23—Gd1 | 136.9 (2) | H55A—C55—H55B | 108.0 |
C31—O24—Gd1 | 140.6 (2) | C55—C56—H56A | 109.5 |
O22—C22—O21 | 113.0 (4) | C55—C56—H56B | 109.5 |
O22—C22—C23 | 127.8 (4) | H56A—C56—H56B | 109.5 |
O21—C22—C23 | 119.2 (3) | C55—C56—H56C | 109.5 |
C24—C23—C22 | 119.5 (3) | H56A—C56—H56C | 109.5 |
C24—C23—C31 | 119.8 (3) | H56B—C56—H56C | 109.5 |
C22—C23—C31 | 120.6 (3) | C58—O57—H57 | 113 (4) |
O23—C24—C23 | 124.7 (3) | O57—C58—C59 | 112.9 (7) |
O23—C24—C25 | 117.6 (3) | O57—C58—H58A | 109.0 |
C23—C24—C25 | 117.6 (3) | C59—C58—H58A | 109.0 |
C30—C25—C26 | 118.7 (4) | O57—C58—H58B | 109.0 |
C30—C25—C24 | 119.8 (3) | C59—C58—H58B | 109.0 |
C26—C25—C24 | 121.4 (4) | H58A—C58—H58B | 107.8 |
C27—C26—C25 | 120.2 (4) | C58—C59—H59A | 109.5 |
C27—C26—H26 | 119.9 | C58—C59—H59B | 109.5 |
C25—C26—H26 | 119.9 | H59A—C59—H59B | 109.5 |
C28—C27—C26 | 120.2 (4) | C58—C59—H59C | 109.5 |
C28—C27—H27 | 119.9 | H59A—C59—H59C | 109.5 |
C26—C27—H27 | 119.9 | H59B—C59—H59C | 109.5 |
C10—O1—C2—O2 | −176.4 (4) | C25—C26—C27—C28 | −0.3 (7) |
C10—O1—C2—C3 | 2.6 (6) | C26—C27—C28—C29 | −0.1 (7) |
O2—C2—C3—C4 | 174.9 (4) | C27—C28—C29—C30 | −0.2 (7) |
O1—C2—C3—C4 | −3.9 (6) | C26—C25—C30—O21 | 178.7 (4) |
O2—C2—C3—C11 | −5.9 (7) | C24—C25—C30—O21 | −5.2 (6) |
O1—C2—C3—C11 | 175.3 (4) | C26—C25—C30—C29 | −1.3 (6) |
Gd1—O3—C4—C3 | 28.2 (6) | C24—C25—C30—C29 | 174.8 (4) |
Gd1—O3—C4—C5 | −151.8 (3) | C22—O21—C30—C25 | 0.0 (5) |
C2—C3—C4—O3 | −176.2 (4) | C22—O21—C30—C29 | −179.9 (4) |
C11—C3—C4—O3 | 4.5 (6) | C28—C29—C30—C25 | 0.9 (6) |
C2—C3—C4—C5 | 3.8 (5) | C28—C29—C30—O21 | −179.1 (4) |
C11—C3—C4—C5 | −175.4 (3) | Gd1—O24—C31—C23 | 6.9 (7) |
O3—C4—C5—C10 | 177.6 (4) | Gd1—O24—C31—C32 | −171.6 (3) |
C3—C4—C5—C10 | −2.5 (5) | C24—C23—C31—O24 | 7.9 (6) |
O3—C4—C5—C6 | −0.1 (6) | C22—C23—C31—O24 | −174.3 (4) |
C3—C4—C5—C6 | 179.9 (4) | C24—C23—C31—C32 | −173.8 (4) |
C10—C5—C6—C7 | 0.2 (7) | C22—C23—C31—C32 | 4.0 (6) |
C4—C5—C6—C7 | 177.8 (5) | C50—O41—C42—O42 | 173.5 (4) |
C5—C6—C7—C8 | −0.4 (8) | C50—O41—C42—C43 | −4.4 (5) |
C6—C7—C8—C9 | 0.7 (9) | O42—C42—C43—C44 | −173.9 (4) |
C7—C8—C9—C10 | −0.8 (9) | O41—C42—C43—C44 | 3.6 (5) |
C2—O1—C10—C5 | −1.3 (6) | O42—C42—C43—C51 | 4.9 (6) |
C2—O1—C10—C9 | 177.9 (4) | O41—C42—C43—C51 | −177.5 (3) |
C6—C5—C10—O1 | 178.9 (4) | Gd1—O43—C44—C43 | −1.5 (6) |
C4—C5—C10—O1 | 1.2 (6) | Gd1—O43—C44—C45 | 177.1 (3) |
C6—C5—C10—C9 | −0.2 (6) | C42—C43—C44—O43 | 177.3 (4) |
C4—C5—C10—C9 | −177.9 (4) | C51—C43—C44—O43 | −1.5 (6) |
C8—C9—C10—O1 | −178.6 (5) | C42—C43—C44—C45 | −1.3 (5) |
C8—C9—C10—C5 | 0.5 (7) | C51—C43—C44—C45 | 179.9 (3) |
Gd1—O4—C11—C3 | −19.3 (6) | O43—C44—C45—C50 | −179.1 (4) |
Gd1—O4—C11—C12 | 161.5 (3) | C43—C44—C45—C50 | −0.5 (5) |
C4—C3—C11—O4 | −8.5 (6) | O43—C44—C45—C46 | −0.9 (6) |
C2—C3—C11—O4 | 172.3 (4) | C43—C44—C45—C46 | 177.8 (4) |
C4—C3—C11—C12 | 170.7 (4) | C50—C45—C46—C47 | 0.4 (6) |
C2—C3—C11—C12 | −8.6 (6) | C44—C45—C46—C47 | −177.9 (4) |
C30—O21—C22—O22 | −173.4 (4) | C45—C46—C47—C48 | −0.6 (7) |
C30—O21—C22—C23 | 8.0 (5) | C46—C47—C48—C49 | 0.8 (8) |
O22—C22—C23—C24 | 170.9 (4) | C47—C48—C49—C50 | −0.7 (8) |
O21—C22—C23—C24 | −10.8 (5) | C42—O41—C50—C49 | −175.6 (4) |
O22—C22—C23—C31 | −6.9 (6) | C42—O41—C50—C45 | 2.7 (6) |
O21—C22—C23—C31 | 171.4 (3) | C48—C49—C50—O41 | 178.6 (4) |
Gd1—O23—C24—C23 | −32.4 (6) | C48—C49—C50—C45 | 0.4 (7) |
Gd1—O23—C24—C25 | 147.7 (3) | C46—C45—C50—O41 | −178.4 (4) |
C22—C23—C24—O23 | −174.1 (3) | C44—C45—C50—O41 | −0.1 (6) |
C31—C23—C24—O23 | 3.7 (6) | C46—C45—C50—C49 | −0.3 (6) |
C22—C23—C24—C25 | 5.8 (5) | C44—C45—C50—C49 | 178.0 (4) |
C31—C23—C24—C25 | −176.4 (3) | Gd1—O44—C51—C43 | −10.3 (6) |
O23—C24—C25—C30 | −178.0 (3) | Gd1—O44—C51—C52 | 168.2 (3) |
C23—C24—C25—C30 | 2.1 (5) | C44—C43—C51—O44 | 6.5 (6) |
O23—C24—C25—C26 | −2.0 (5) | C42—C43—C51—O44 | −172.3 (3) |
C23—C24—C25—C26 | 178.1 (4) | C44—C43—C51—C52 | −171.9 (4) |
C30—C25—C26—C27 | 1.0 (6) | C42—C43—C51—C52 | 9.3 (5) |
C24—C25—C26—C27 | −175.0 (4) | Gd1—O54—C55—C56 | 114.2 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
O53—H53A···O22i | 0.84 (2) | 2.01 (2) | 2.840 (4) | 169 (4) |
O54—H54···O42ii | 0.85 (2) | 1.95 (2) | 2.768 (4) | 163 (5) |
O53—H53B···O57 | 0.84 (2) | 1.80 (2) | 2.634 (4) | 173 (5) |
O57—H57···O2iii | 0.84 (2) | 2.02 (5) | 2.740 (4) | 143 (7) |
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) −x+1, −y+1, −z+1; (iii) x+1, y, z. |
Funding information
Funding for this research was provided by: Dirección General de Asuntos del Personal Académico, Universidad Nacional Autónoma de México (grant No. IN 222615 to LG); Consejo Nacional de Ciencia y Tecnología (grant No. 268178).
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