Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270110037595/gd3360sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270110037595/gd3360Isup2.hkl |
CCDC reference: 798589
Ytterbium acetate hydrate (Acros Organics, 99.90%) (1.0 g, 2.9 mmol) was mixed with 0.19 M sodium acetate solution (15.6 ml, 3.0 mmol). The mixture was placed in a Teflon liner inside a Parr acid-digestion vessel (Model 4744; 45 ml). The vessel was sealed and heated to a temperature of 443 K inside a conventional laboratory oven. After two weeks, the vessel was removed from the hot oven and allowed to cool to room temperature on the laboratory bench before opening. A white solid material was obtained that was submerged in liquid [Specify liquid?] and rinsed four times with deionised water in order to remove any water-soluble starting materials. Most of the product had formed crystals in the form of long needles. Small amounts of the product were stored in a scintillation vial with small quantities of deionised water until a single crystal was chosen for X-ray structural analysis.
The H atoms on water molecule O27 could not be located. All other H atoms were visible in difference maps. Hydroxide H atoms were idealized to yield three equal Yb—O—H angles and O—H distances of 1.00 Å, and were treated as riding. The H atoms of the acetate methyl groups were idealized with C—H distances of 0.98 Å based on electron density in the expected circles, and a torsional parameter was refined for each methyl group. Water H atoms were placed based on difference maps and treated as riding in the refinement, after adjusting the O—H distances to 0.84 Å. Uiso values were assigned as 1.2Ueq of the attached atom for OH groups and as 1.5Ueq of the attached atom for methyl groups and water molecules.
The largest difference peak is 0.72 Å from atom Yb6, and the top 30 peaks are within 1.08 Å of Yb positions. The deepest hole is 0.65 Å from atom Yb2. The deepest hole which is not near a Yb position is 1.18 Å from atom O4, with a depth of -2.96 e Å-3. This is about 10% of the magnitude of the electron density at the O4 site, 28.8 e Å-3. The r.m.s. deviation from the mean in the final difference map is 0.59 e Å-3.
Data collection: COLLECT (Nonius, 2000); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: CrystalMaker (Version 8.3.1 for Mac; Palmer, 2010); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
[Yb(C2H3O2)(OH)2]·0.5H2O | Z = 12 |
Mr = 275.11 | F(000) = 1488 |
Triclinic, P1 | Dx = 3.539 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.3235 (10) Å | Cell parameters from 13849 reflections |
b = 12.1765 (14) Å | θ = 2.5–35.6° |
c = 15.5502 (15) Å | µ = 18.03 mm−1 |
α = 109.796 (5)° | T = 90 K |
β = 92.666 (6)° | Lath, colourless |
γ = 108.745 (5)° | 0.15 × 0.10 × 0.07 mm |
V = 1548.9 (3) Å3 |
Nonius KappaCCD with Oxford Cryostream diffractometer | 14105 independent reflections |
Radiation source: fine-focus sealed tube | 11613 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.042 |
ω and ϕ scans | θmax = 35.6°, θmin = 2.6° |
Absorption correction: multi-scan (HKL SCALEPACK; Otwinowski & Minor 1997) | h = −15→15 |
Tmin = 0.173, Tmax = 0.365 | k = −19→19 |
56149 measured reflections | l = −25→25 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.044 | H-atom parameters constrained |
wR(F2) = 0.120 | w = 1/[σ2(Fo2) + (0.080P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max = 0.002 |
14105 reflections | Δρmax = 5.71 e Å−3 |
413 parameters | Δρmin = −5.73 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.00105 (9) |
[Yb(C2H3O2)(OH)2]·0.5H2O | γ = 108.745 (5)° |
Mr = 275.11 | V = 1548.9 (3) Å3 |
Triclinic, P1 | Z = 12 |
a = 9.3235 (10) Å | Mo Kα radiation |
b = 12.1765 (14) Å | µ = 18.03 mm−1 |
c = 15.5502 (15) Å | T = 90 K |
α = 109.796 (5)° | 0.15 × 0.10 × 0.07 mm |
β = 92.666 (6)° |
Nonius KappaCCD with Oxford Cryostream diffractometer | 14105 independent reflections |
Absorption correction: multi-scan (HKL SCALEPACK; Otwinowski & Minor 1997) | 11613 reflections with I > 2σ(I) |
Tmin = 0.173, Tmax = 0.365 | Rint = 0.042 |
56149 measured reflections |
R[F2 > 2σ(F2)] = 0.044 | 0 restraints |
wR(F2) = 0.120 | H-atom parameters constrained |
S = 1.01 | Δρmax = 5.71 e Å−3 |
14105 reflections | Δρmin = −5.73 e Å−3 |
413 parameters |
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. H atoms on water molecule O27 could not be located. The largest difference peak is 0.72 Å from Yb6, and the top 30 peaks are within 1.08 Å of Yb positions. The deepest hole is 0.65 Å from Yb2. The deepest hole which is not near a Yb position is 1.18 Å from O4, with a depth of -2.96 e Å-3. This is about 10% of the magnitude of the electron density at the O4 site, 28.8 e Å-3. The r.m.s. deviation from the mean in the final difference map is 0.59 e Å-3. |
x | y | z | Uiso*/Ueq | ||
Yb1 | 0.49629 (3) | 0.66955 (2) | 0.221061 (17) | 0.00577 (5) | |
Yb2 | 0.78616 (3) | 0.92281 (2) | 0.433478 (17) | 0.00506 (5) | |
Yb3 | 0.57975 (3) | 0.60690 (2) | 0.432760 (17) | 0.00505 (5) | |
Yb4 | 0.99763 (3) | 0.76052 (2) | 0.527080 (17) | 0.00515 (5) | |
Yb5 | 0.78609 (3) | 0.43045 (2) | 0.474671 (17) | 0.00524 (5) | |
Yb6 | 0.62550 (3) | 0.17451 (2) | 0.555417 (17) | 0.00491 (5) | |
O1 | 0.3519 (5) | 0.4564 (4) | 0.1714 (3) | 0.0100 (8) | |
O2 | 0.3642 (5) | 0.5147 (4) | 0.0521 (3) | 0.0112 (8) | |
O3 | 0.2685 (5) | 0.6943 (4) | 0.1948 (3) | 0.0090 (7) | |
O4 | 0.2070 (5) | 0.8096 (4) | 0.3231 (3) | 0.0089 (7) | |
O5 | 0.5618 (5) | 0.8118 (4) | 0.1534 (3) | 0.0109 (8) | |
O6 | 0.5164 (6) | 0.9833 (5) | 0.2364 (4) | 0.0144 (9) | |
O7 | 0.8945 (5) | 0.9595 (5) | 0.3128 (4) | 0.0132 (9) | |
O8 | 0.9864 (5) | 1.1546 (4) | 0.3174 (3) | 0.0100 (8) | |
O9 | 0.5511 (5) | 0.4219 (4) | 0.3195 (4) | 0.0123 (8) | |
O10 | 0.7087 (5) | 0.3183 (4) | 0.3199 (3) | 0.0107 (8) | |
O11 | 1.0490 (5) | 0.4746 (4) | 0.2721 (3) | 0.0109 (8) | |
O12 | 0.8695 (5) | 0.5471 (5) | 0.2417 (3) | 0.0125 (8) | |
O13 | 0.6967 (5) | 0.7100 (4) | 0.3340 (3) | 0.0071 (7) | |
H13 | 0.7806 | 0.6822 | 0.3078 | 0.009* | |
O14 | 0.5458 (5) | 0.8572 (4) | 0.3468 (3) | 0.0071 (7) | |
H14 | 0.5372 | 0.9231 | 0.3243 | 0.009* | |
O15 | 0.3974 (5) | 0.6328 (4) | 0.3448 (3) | 0.0073 (7) | |
H15 | 0.2974 | 0.5606 | 0.3254 | 0.009* | |
O16 | 0.7731 (5) | 0.7995 (4) | 0.5244 (3) | 0.0080 (7) | |
H16 | 0.7508 | 0.8377 | 0.5877 | 0.010* | |
O17 | 1.0272 (5) | 0.8961 (4) | 0.4520 (3) | 0.0072 (7) | |
H17 | 1.0642 | 0.8679 | 0.3919 | 0.009* | |
O18 | 0.6157 (5) | 0.9696 (4) | 0.5337 (3) | 0.0059 (7) | |
H18 | 0.6377 | 0.9597 | 0.5937 | 0.007* | |
O19 | 0.7492 (5) | 1.1080 (4) | 0.4293 (3) | 0.0071 (7) | |
H19 | 0.6977 | 1.0986 | 0.3680 | 0.009* | |
O20 | 0.8224 (5) | 0.5875 (4) | 0.4221 (3) | 0.0068 (7) | |
H20 | 0.8467 | 0.5671 | 0.3579 | 0.008* | |
O21 | 0.9950 (5) | 0.6010 (4) | 0.5750 (3) | 0.0077 (7) | |
H21 | 0.9934 | 0.6194 | 0.6426 | 0.009* | |
O22 | 0.6434 (5) | 0.5412 (4) | 0.5500 (3) | 0.0061 (7) | |
H22 | 0.7011 | 0.6115 | 0.6095 | 0.007* | |
O23 | 0.5555 (5) | 0.2835 (4) | 0.4718 (3) | 0.0075 (7) | |
H23 | 0.4966 | 0.2286 | 0.4079 | 0.009* | |
O24 | 0.8515 (5) | 0.3315 (4) | 0.5607 (3) | 0.0061 (7) | |
H24 | 0.9053 | 0.3888 | 0.6252 | 0.007* | |
O25 | 0.6682 (5) | 0.5906 (4) | 0.1399 (3) | 0.0123 (8) | |
H25A | 0.6325 | 0.5637 | 0.0831 | 0.018* | |
H25B | 0.7373 | 0.5717 | 0.1612 | 0.018* | |
O26 | 0.7653 (5) | 0.7131 (5) | 0.7411 (4) | 0.0141 (9) | |
H26A | 0.7252 | 0.6577 | 0.7625 | 0.021* | |
H26B | 0.7787 | 0.7890 | 0.7700 | 0.021* | |
O27 | 0.6610 (5) | 0.8794 (5) | 0.6952 (4) | 0.0136 (9) | |
C1 | 0.3228 (7) | 0.4288 (6) | 0.0847 (4) | 0.0109 (10) | |
C2 | 0.2448 (7) | 0.2948 (6) | 0.0213 (5) | 0.0137 (11) | |
H2A | 0.1734 | 0.2895 | −0.0295 | 0.021* | |
H2B | 0.1879 | 0.2468 | 0.0561 | 0.021* | |
H2C | 0.3222 | 0.2606 | −0.0043 | 0.021* | |
C3 | 0.1914 (7) | 0.7564 (6) | 0.2346 (4) | 0.0089 (10) | |
C4 | 0.0770 (8) | 0.7763 (7) | 0.1759 (5) | 0.0150 (12) | |
H4A | 0.1276 | 0.8519 | 0.1632 | 0.023* | |
H4B | −0.0077 | 0.7861 | 0.2090 | 0.023* | |
H4C | 0.0366 | 0.7041 | 0.1172 | 0.023* | |
C5 | 0.5133 (7) | 0.8994 (6) | 0.1606 (5) | 0.0124 (11) | |
C6 | 0.4453 (11) | 0.9005 (8) | 0.0711 (6) | 0.0271 (17) | |
H6A | 0.4077 | 0.9700 | 0.0848 | 0.041* | |
H6B | 0.3597 | 0.8214 | 0.0382 | 0.041* | |
H6C | 0.5243 | 0.9108 | 0.0321 | 0.041* | |
C7 | 0.9324 (6) | 1.0375 (6) | 0.2734 (4) | 0.0081 (9) | |
C8 | 0.9117 (8) | 0.9940 (6) | 0.1697 (4) | 0.0134 (11) | |
H8A | 0.8591 | 1.0404 | 0.1484 | 0.020* | |
H8B | 0.8500 | 0.9044 | 0.1423 | 0.020* | |
H8C | 1.0126 | 1.0086 | 0.1504 | 0.020* | |
C9 | 0.6108 (7) | 0.3434 (5) | 0.2781 (4) | 0.0083 (9) | |
C10 | 0.5659 (7) | 0.2777 (6) | 0.1743 (5) | 0.0132 (11) | |
H10A | 0.6330 | 0.2307 | 0.1511 | 0.020* | |
H10B | 0.5765 | 0.3395 | 0.1456 | 0.020* | |
H10C | 0.4588 | 0.2200 | 0.1587 | 0.020* | |
C11 | 0.9558 (6) | 0.4845 (6) | 0.2168 (5) | 0.0102 (10) | |
C12 | 0.9491 (7) | 0.4201 (7) | 0.1130 (5) | 0.0144 (11) | |
H12A | 0.8547 | 0.4149 | 0.0788 | 0.022* | |
H12B | 0.9498 | 0.3357 | 0.1000 | 0.022* | |
H12C | 1.0386 | 0.4684 | 0.0937 | 0.022* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Yb1 | 0.00629 (10) | 0.00545 (10) | 0.00607 (10) | 0.00274 (8) | 0.00109 (8) | 0.00215 (8) |
Yb2 | 0.00457 (10) | 0.00432 (10) | 0.00679 (10) | 0.00197 (7) | 0.00097 (7) | 0.00234 (8) |
Yb3 | 0.00482 (10) | 0.00466 (10) | 0.00673 (10) | 0.00237 (7) | 0.00146 (7) | 0.00271 (8) |
Yb4 | 0.00466 (10) | 0.00412 (10) | 0.00744 (11) | 0.00204 (8) | 0.00118 (8) | 0.00262 (8) |
Yb5 | 0.00474 (10) | 0.00436 (10) | 0.00760 (11) | 0.00221 (7) | 0.00129 (7) | 0.00284 (8) |
Yb6 | 0.00463 (10) | 0.00428 (10) | 0.00648 (10) | 0.00201 (7) | 0.00134 (7) | 0.00234 (8) |
O1 | 0.014 (2) | 0.0068 (18) | 0.0091 (19) | 0.0021 (15) | 0.0016 (15) | 0.0048 (15) |
O2 | 0.0101 (18) | 0.0101 (19) | 0.014 (2) | 0.0030 (16) | 0.0008 (16) | 0.0058 (17) |
O3 | 0.0091 (18) | 0.0097 (19) | 0.0096 (19) | 0.0065 (15) | 0.0029 (15) | 0.0023 (16) |
O4 | 0.0063 (17) | 0.0122 (19) | 0.0097 (19) | 0.0032 (15) | 0.0003 (14) | 0.0063 (16) |
O5 | 0.0135 (19) | 0.0101 (19) | 0.015 (2) | 0.0075 (16) | 0.0069 (17) | 0.0081 (17) |
O6 | 0.023 (2) | 0.010 (2) | 0.012 (2) | 0.0090 (18) | 0.0042 (18) | 0.0032 (17) |
O7 | 0.016 (2) | 0.016 (2) | 0.017 (2) | 0.0093 (18) | 0.0108 (18) | 0.0132 (19) |
O8 | 0.0127 (19) | 0.0057 (17) | 0.0078 (19) | 0.0022 (15) | −0.0003 (15) | −0.0007 (15) |
O9 | 0.0085 (18) | 0.0077 (19) | 0.016 (2) | 0.0029 (15) | 0.0043 (16) | −0.0010 (17) |
O10 | 0.0119 (19) | 0.012 (2) | 0.0083 (19) | 0.0052 (16) | 0.0000 (15) | 0.0028 (16) |
O11 | 0.0116 (19) | 0.017 (2) | 0.0064 (18) | 0.0074 (17) | 0.0005 (15) | 0.0059 (17) |
O12 | 0.0110 (19) | 0.018 (2) | 0.011 (2) | 0.0080 (17) | 0.0034 (16) | 0.0048 (18) |
O13 | 0.0065 (16) | 0.0081 (18) | 0.0098 (19) | 0.0048 (14) | 0.0022 (14) | 0.0047 (15) |
O14 | 0.0066 (16) | 0.0072 (17) | 0.0082 (18) | 0.0037 (14) | 0.0006 (14) | 0.0027 (15) |
O15 | 0.0094 (17) | 0.0063 (17) | 0.0061 (17) | 0.0029 (14) | 0.0014 (14) | 0.0022 (14) |
O16 | 0.0071 (17) | 0.0068 (17) | 0.0112 (19) | 0.0041 (14) | 0.0016 (14) | 0.0032 (15) |
O17 | 0.0059 (16) | 0.0043 (16) | 0.0120 (19) | 0.0017 (13) | 0.0018 (14) | 0.0039 (15) |
O18 | 0.0096 (17) | 0.0017 (15) | 0.0041 (16) | −0.0001 (13) | −0.0010 (13) | 0.0004 (13) |
O19 | 0.0066 (16) | 0.0057 (17) | 0.0096 (19) | 0.0042 (14) | 0.0023 (14) | 0.0015 (15) |
O20 | 0.0054 (16) | 0.0036 (16) | 0.0126 (19) | 0.0012 (13) | 0.0020 (14) | 0.0049 (15) |
O21 | 0.0089 (17) | 0.0064 (17) | 0.0112 (19) | 0.0034 (14) | 0.0029 (15) | 0.0064 (15) |
O22 | 0.0082 (17) | 0.0046 (16) | 0.0060 (17) | 0.0034 (14) | 0.0022 (14) | 0.0014 (14) |
O23 | 0.0093 (17) | 0.0080 (18) | 0.0065 (18) | 0.0051 (15) | −0.0005 (14) | 0.0029 (15) |
O24 | 0.0060 (16) | 0.0051 (16) | 0.0073 (18) | 0.0020 (13) | 0.0010 (14) | 0.0023 (14) |
O25 | 0.013 (2) | 0.016 (2) | 0.0075 (19) | 0.0100 (17) | 0.0002 (16) | 0.0003 (17) |
O26 | 0.016 (2) | 0.012 (2) | 0.018 (2) | 0.0044 (17) | 0.0041 (18) | 0.0098 (19) |
O27 | 0.017 (2) | 0.016 (2) | 0.013 (2) | 0.0104 (18) | 0.0040 (17) | 0.0064 (18) |
C1 | 0.010 (2) | 0.011 (3) | 0.008 (2) | 0.003 (2) | 0.0002 (19) | 0.000 (2) |
C2 | 0.016 (3) | 0.010 (3) | 0.011 (3) | 0.001 (2) | 0.000 (2) | 0.002 (2) |
C3 | 0.009 (2) | 0.010 (2) | 0.009 (2) | 0.0033 (19) | 0.0034 (19) | 0.004 (2) |
C4 | 0.018 (3) | 0.018 (3) | 0.011 (3) | 0.013 (2) | −0.002 (2) | 0.004 (2) |
C5 | 0.013 (3) | 0.010 (3) | 0.018 (3) | 0.005 (2) | 0.005 (2) | 0.008 (2) |
C6 | 0.048 (5) | 0.025 (4) | 0.016 (3) | 0.021 (4) | 0.002 (3) | 0.011 (3) |
C7 | 0.008 (2) | 0.010 (2) | 0.007 (2) | 0.0041 (19) | 0.0021 (18) | 0.0025 (19) |
C8 | 0.018 (3) | 0.010 (3) | 0.009 (3) | 0.002 (2) | 0.001 (2) | 0.001 (2) |
C9 | 0.009 (2) | 0.006 (2) | 0.010 (2) | 0.0013 (18) | 0.0025 (19) | 0.0039 (19) |
C10 | 0.012 (3) | 0.013 (3) | 0.010 (3) | 0.005 (2) | −0.001 (2) | 0.000 (2) |
C11 | 0.003 (2) | 0.015 (3) | 0.012 (3) | 0.0017 (19) | 0.0027 (18) | 0.005 (2) |
C12 | 0.014 (3) | 0.019 (3) | 0.009 (3) | 0.006 (2) | 0.004 (2) | 0.002 (2) |
Yb1—O5 | 2.257 (4) | O9—C9 | 1.263 (7) |
Yb1—O3 | 2.276 (4) | O10—C9 | 1.268 (7) |
Yb1—O15 | 2.288 (4) | O11—C11 | 1.256 (7) |
Yb1—O13 | 2.310 (4) | O12—C11 | 1.265 (7) |
Yb1—O25 | 2.333 (4) | O13—H13 | 1.0000 |
Yb1—O1 | 2.333 (4) | O14—Yb6ii | 2.289 (4) |
Yb1—O14 | 2.338 (4) | O14—H14 | 1.0000 |
Yb1—O2 | 2.613 (5) | O15—Yb6ii | 2.418 (4) |
Yb2—O7 | 2.279 (4) | O15—H15 | 1.0000 |
Yb2—O14 | 2.306 (4) | O16—H16 | 1.0000 |
Yb2—O18 | 2.343 (4) | O17—Yb2i | 2.377 (4) |
Yb2—O13 | 2.362 (4) | O17—H17 | 1.0000 |
Yb2—O16 | 2.367 (4) | O18—Yb6ii | 2.363 (4) |
Yb2—O17i | 2.377 (4) | O18—Yb6v | 2.373 (4) |
Yb2—O17 | 2.390 (4) | O18—H18 | 1.0000 |
Yb2—O19 | 2.409 (4) | O19—Yb4i | 2.298 (4) |
Yb3—O9 | 2.265 (5) | O19—Yb6v | 2.360 (4) |
Yb3—O15 | 2.298 (4) | O19—H19 | 1.0000 |
Yb3—O23ii | 2.342 (4) | O20—H20 | 1.0000 |
Yb3—O22 | 2.346 (4) | O21—Yb5iii | 2.314 (4) |
Yb3—O20 | 2.357 (4) | O21—H21 | 1.0000 |
Yb3—O16 | 2.358 (4) | O22—Yb3ii | 2.371 (4) |
Yb3—O22ii | 2.371 (4) | O22—H22 | 1.0000 |
Yb3—O13 | 2.388 (4) | O23—Yb3ii | 2.342 (4) |
Yb4—O20 | 2.232 (4) | O23—H23 | 1.0000 |
Yb4—O8i | 2.261 (5) | O24—Yb4iii | 2.292 (4) |
Yb4—O17 | 2.282 (4) | O24—H24 | 1.0000 |
Yb4—O16 | 2.291 (4) | O25—H25A | 0.8400 |
Yb4—O24iii | 2.292 (4) | O25—H25B | 0.8400 |
Yb4—O21 | 2.298 (4) | O26—H26A | 0.8402 |
Yb4—O19i | 2.298 (4) | O26—H26B | 0.8435 |
Yb5—O24 | 2.258 (4) | C1—C2 | 1.498 (9) |
Yb5—O20 | 2.260 (4) | C2—H2A | 0.9800 |
Yb5—O10 | 2.271 (5) | C2—H2B | 0.9800 |
Yb5—O22 | 2.278 (4) | C2—H2C | 0.9800 |
Yb5—O23 | 2.300 (4) | C3—C4 | 1.502 (9) |
Yb5—O21iii | 2.314 (4) | C4—H4A | 0.9800 |
Yb5—O21 | 2.338 (5) | C4—H4B | 0.9800 |
Yb6—O14ii | 2.289 (4) | C4—H4C | 0.9800 |
Yb6—O4ii | 2.308 (4) | C5—C6 | 1.508 (10) |
Yb6—O24 | 2.322 (4) | C6—H6A | 0.9800 |
Yb6—O23 | 2.350 (4) | C6—H6B | 0.9800 |
Yb6—O19iv | 2.360 (4) | C6—H6C | 0.9800 |
Yb6—O18ii | 2.363 (4) | C7—C8 | 1.499 (9) |
Yb6—O18iv | 2.373 (4) | C8—H8A | 0.9800 |
Yb6—O15ii | 2.418 (4) | C8—H8B | 0.9800 |
O1—C1 | 1.267 (8) | C8—H8C | 0.9800 |
O2—C1 | 1.272 (7) | C9—C10 | 1.505 (9) |
O3—C3 | 1.243 (7) | C10—H10A | 0.9800 |
O4—C3 | 1.285 (8) | C10—H10B | 0.9800 |
O4—Yb6ii | 2.308 (4) | C10—H10C | 0.9800 |
O5—C5 | 1.261 (7) | C11—C12 | 1.525 (9) |
O6—C5 | 1.264 (8) | C12—H12A | 0.9800 |
O7—C7 | 1.265 (7) | C12—H12B | 0.9800 |
O8—C7 | 1.265 (7) | C12—H12C | 0.9800 |
O8—Yb4i | 2.261 (5) | ||
O5—Yb1—O3 | 78.42 (16) | O4ii—Yb6—O15ii | 88.04 (15) |
O5—Yb1—O15 | 143.46 (16) | O24—Yb6—O15ii | 74.67 (14) |
O3—Yb1—O15 | 81.87 (15) | O23—Yb6—O15ii | 67.34 (15) |
O5—Yb1—O13 | 110.23 (16) | O19iv—Yb6—O15ii | 137.91 (14) |
O3—Yb1—O13 | 144.55 (16) | O18ii—Yb6—O15ii | 110.92 (14) |
O15—Yb1—O13 | 71.19 (15) | O18iv—Yb6—O15ii | 148.26 (14) |
O5—Yb1—O25 | 85.09 (16) | C1—O1—Yb1 | 100.5 (4) |
O3—Yb1—O25 | 140.34 (16) | C1—O2—Yb1 | 87.3 (4) |
O15—Yb1—O25 | 128.09 (16) | C3—O3—Yb1 | 140.3 (4) |
O13—Yb1—O25 | 75.06 (16) | C3—O4—Yb6ii | 132.4 (4) |
O5—Yb1—O1 | 135.62 (17) | C5—O5—Yb1 | 128.9 (4) |
O3—Yb1—O1 | 86.02 (16) | C7—O7—Yb2 | 143.8 (4) |
O15—Yb1—O1 | 72.37 (16) | C7—O8—Yb4i | 121.6 (4) |
O13—Yb1—O1 | 106.46 (15) | C9—O9—Yb3 | 148.3 (4) |
O25—Yb1—O1 | 81.02 (16) | C9—O10—Yb5 | 116.9 (4) |
O5—Yb1—O14 | 77.83 (16) | Yb1—O13—Yb2 | 109.94 (16) |
O3—Yb1—O14 | 81.96 (15) | Yb1—O13—Yb3 | 104.86 (16) |
O15—Yb1—O14 | 69.12 (15) | Yb2—O13—Yb3 | 102.42 (17) |
O13—Yb1—O14 | 67.33 (15) | Yb1—O13—H13 | 112.9 |
O25—Yb1—O14 | 129.42 (15) | Yb2—O13—H13 | 112.9 |
O1—Yb1—O14 | 140.86 (15) | Yb3—O13—H13 | 112.9 |
O5—Yb1—O2 | 83.34 (16) | Yb6ii—O14—Yb2 | 105.86 (17) |
O3—Yb1—O2 | 73.63 (15) | Yb6ii—O14—Yb1 | 109.38 (17) |
O15—Yb1—O2 | 119.94 (15) | Yb2—O14—Yb1 | 110.93 (16) |
O13—Yb1—O2 | 140.07 (14) | Yb6ii—O14—H14 | 110.2 |
O25—Yb1—O2 | 68.76 (15) | Yb2—O14—H14 | 110.2 |
O1—Yb1—O2 | 52.33 (15) | Yb1—O14—H14 | 110.2 |
O14—Yb1—O2 | 151.70 (14) | Yb1—O15—Yb3 | 108.59 (17) |
O7—Yb2—O14 | 89.42 (17) | Yb1—O15—Yb6ii | 106.69 (16) |
O7—Yb2—O18 | 143.95 (15) | Yb3—O15—Yb6ii | 103.69 (17) |
O14—Yb2—O18 | 71.08 (15) | Yb1—O15—H15 | 112.4 |
O7—Yb2—O13 | 85.21 (16) | Yb3—O15—H15 | 112.4 |
O14—Yb2—O13 | 66.98 (14) | Yb6ii—O15—H15 | 112.4 |
O18—Yb2—O13 | 112.51 (14) | Yb4—O16—Yb3 | 105.81 (17) |
O7—Yb2—O16 | 140.88 (15) | Yb4—O16—Yb2 | 107.38 (16) |
O14—Yb2—O16 | 108.25 (14) | Yb3—O16—Yb2 | 103.19 (17) |
O18—Yb2—O16 | 75.06 (14) | Yb4—O16—H16 | 113.2 |
O13—Yb2—O16 | 71.19 (15) | Yb3—O16—H16 | 113.2 |
O7—Yb2—O17i | 93.85 (17) | Yb2—O16—H16 | 113.2 |
O14—Yb2—O17i | 140.76 (14) | Yb4—O17—Yb2i | 99.23 (17) |
O18—Yb2—O17i | 84.11 (14) | Yb4—O17—Yb2 | 106.93 (16) |
O13—Yb2—O17i | 152.25 (14) | Yb2i—O17—Yb2 | 111.34 (17) |
O16—Yb2—O17i | 93.40 (15) | Yb4—O17—H17 | 112.8 |
O7—Yb2—O17 | 76.19 (16) | Yb2i—O17—H17 | 112.8 |
O14—Yb2—O17 | 148.94 (15) | Yb2—O17—H17 | 112.8 |
O18—Yb2—O17 | 134.30 (15) | Yb2—O18—Yb6ii | 102.35 (16) |
O13—Yb2—O17 | 84.28 (14) | Yb2—O18—Yb6v | 107.75 (15) |
O16—Yb2—O17 | 70.91 (14) | Yb6ii—O18—Yb6v | 108.55 (16) |
O17i—Yb2—O17 | 68.66 (17) | Yb2—O18—H18 | 112.5 |
O7—Yb2—O19 | 73.97 (15) | Yb6ii—O18—H18 | 112.5 |
O14—Yb2—O19 | 73.51 (14) | Yb6v—O18—H18 | 112.5 |
O18—Yb2—O19 | 71.56 (14) | Yb4i—O19—Yb6v | 106.54 (17) |
O13—Yb2—O19 | 135.24 (15) | Yb4i—O19—Yb2 | 97.84 (15) |
O16—Yb2—O19 | 143.86 (15) | Yb6v—O19—Yb2 | 106.01 (16) |
O17i—Yb2—O19 | 69.95 (14) | Yb4i—O19—H19 | 114.9 |
O17—Yb2—O19 | 126.27 (14) | Yb6v—O19—H19 | 114.9 |
O9—Yb3—O15 | 90.69 (16) | Yb2—O19—H19 | 114.9 |
O9—Yb3—O23ii | 143.01 (15) | Yb4—O20—Yb5 | 108.24 (18) |
O15—Yb3—O23ii | 69.45 (15) | Yb4—O20—Yb3 | 107.82 (17) |
O9—Yb3—O22 | 92.37 (16) | Yb5—O20—Yb3 | 98.48 (15) |
O15—Yb3—O22 | 149.26 (14) | Yb4—O20—H20 | 113.7 |
O23ii—Yb3—O22 | 90.49 (14) | Yb5—O20—H20 | 113.7 |
O9—Yb3—O20 | 70.83 (16) | Yb3—O20—H20 | 113.7 |
O15—Yb3—O20 | 137.84 (15) | Yb4—O21—Yb5iii | 99.82 (15) |
O23ii—Yb3—O20 | 143.75 (15) | Yb4—O21—Yb5 | 103.46 (17) |
O22—Yb3—O20 | 71.32 (14) | Yb5iii—O21—Yb5 | 106.32 (18) |
O9—Yb3—O16 | 140.41 (15) | Yb4—O21—H21 | 115.2 |
O15—Yb3—O16 | 111.82 (15) | Yb5iii—O21—H21 | 115.2 |
O23ii—Yb3—O16 | 76.56 (15) | Yb5—O21—H21 | 115.2 |
O22—Yb3—O16 | 84.26 (15) | Yb5—O22—Yb3 | 98.27 (16) |
O20—Yb3—O16 | 70.76 (15) | Yb5—O22—Yb3ii | 106.16 (16) |
O9—Yb3—O22ii | 74.37 (15) | Yb3—O22—Yb3ii | 109.55 (17) |
O15—Yb3—O22ii | 81.02 (14) | Yb5—O22—H22 | 113.9 |
O23ii—Yb3—O22ii | 71.96 (14) | Yb3—O22—H22 | 113.9 |
O22—Yb3—O22ii | 70.45 (17) | Yb3ii—O22—H22 | 113.9 |
O20—Yb3—O22ii | 126.14 (13) | Yb5—O23—Yb3ii | 106.37 (17) |
O16—Yb3—O22ii | 138.89 (15) | Yb5—O23—Yb6 | 103.61 (16) |
O9—Yb3—O13 | 88.63 (16) | Yb3ii—O23—Yb6 | 104.45 (16) |
O15—Yb3—O13 | 69.62 (14) | Yb5—O23—H23 | 113.8 |
O23ii—Yb3—O13 | 111.37 (14) | Yb3ii—O23—H23 | 113.8 |
O22—Yb3—O13 | 141.01 (14) | Yb6—O23—H23 | 113.8 |
O20—Yb3—O13 | 72.30 (14) | Yb5—O24—Yb4iii | 101.70 (16) |
O16—Yb3—O13 | 70.90 (15) | Yb5—O24—Yb6 | 105.88 (16) |
O22ii—Yb3—O13 | 145.87 (15) | Yb4iii—O24—Yb6 | 108.04 (17) |
O20—Yb4—O8i | 129.82 (16) | Yb5—O24—H24 | 113.4 |
O20—Yb4—O17 | 100.84 (15) | Yb4iii—O24—H24 | 113.4 |
O8i—Yb4—O17 | 115.41 (16) | Yb6—O24—H24 | 113.4 |
O20—Yb4—O16 | 74.23 (15) | Yb1—O25—H25A | 107.3 |
O8i—Yb4—O16 | 83.24 (16) | Yb1—O25—H25B | 126.9 |
O17—Yb4—O16 | 74.23 (15) | H25A—O25—H25B | 123.5 |
O20—Yb4—O24iii | 78.00 (15) | H26A—O26—H26B | 122.2 |
O8i—Yb4—O24iii | 131.21 (16) | O1—C1—O2 | 119.6 (6) |
O17—Yb4—O24iii | 91.12 (15) | O1—C1—C2 | 119.7 (6) |
O16—Yb4—O24iii | 145.22 (16) | O2—C1—C2 | 120.6 (6) |
O20—Yb4—O21 | 74.24 (16) | O1—C1—Yb1 | 53.6 (3) |
O8i—Yb4—O21 | 76.42 (16) | O2—C1—Yb1 | 66.2 (3) |
O17—Yb4—O21 | 166.26 (16) | C2—C1—Yb1 | 171.2 (5) |
O16—Yb4—O21 | 115.65 (15) | C1—C2—H2A | 109.5 |
O24iii—Yb4—O21 | 75.37 (15) | C1—C2—H2B | 109.5 |
O20—Yb4—O19i | 146.93 (15) | H2A—C2—H2B | 109.5 |
O8i—Yb4—O19i | 79.25 (16) | C1—C2—H2C | 109.5 |
O17—Yb4—O19i | 73.61 (15) | H2A—C2—H2C | 109.5 |
O16—Yb4—O19i | 131.77 (15) | H2B—C2—H2C | 109.5 |
O24iii—Yb4—O19i | 69.67 (15) | O3—C3—O4 | 124.5 (6) |
O21—Yb4—O19i | 103.29 (15) | O3—C3—C4 | 118.3 (6) |
O24—Yb5—O20 | 155.16 (15) | O4—C3—C4 | 117.2 (5) |
O24—Yb5—O10 | 116.35 (16) | C3—C4—H4A | 109.5 |
O20—Yb5—O10 | 79.96 (16) | C3—C4—H4B | 109.5 |
O24—Yb5—O22 | 109.70 (15) | H4A—C4—H4B | 109.5 |
O20—Yb5—O22 | 74.35 (15) | C3—C4—H4C | 109.5 |
O10—Yb5—O22 | 118.13 (16) | H4A—C4—H4C | 109.5 |
O24—Yb5—O23 | 76.28 (14) | H4B—C4—H4C | 109.5 |
O20—Yb5—O23 | 127.24 (14) | O5—C5—O6 | 124.6 (6) |
O10—Yb5—O23 | 78.72 (16) | O5—C5—C6 | 116.3 (6) |
O22—Yb5—O23 | 74.44 (15) | O6—C5—C6 | 119.0 (6) |
O24—Yb5—O21iii | 75.69 (14) | C5—C6—H6A | 109.5 |
O20—Yb5—O21iii | 91.52 (14) | C5—C6—H6B | 109.5 |
O10—Yb5—O21iii | 76.26 (16) | H6A—C6—H6B | 109.5 |
O22—Yb5—O21iii | 156.61 (15) | C5—C6—H6C | 109.5 |
O23—Yb5—O21iii | 128.38 (14) | H6A—C6—H6C | 109.5 |
O24—Yb5—O21 | 82.93 (14) | H6B—C6—H6C | 109.5 |
O20—Yb5—O21 | 72.97 (15) | O7—C7—O8 | 123.2 (6) |
O10—Yb5—O21 | 138.49 (16) | O7—C7—C8 | 120.6 (6) |
O22—Yb5—O21 | 84.25 (15) | O8—C7—C8 | 116.2 (5) |
O23—Yb5—O21 | 142.78 (15) | C7—C8—H8A | 109.5 |
O21iii—Yb5—O21 | 73.68 (18) | C7—C8—H8B | 109.5 |
O14ii—Yb6—O4ii | 81.56 (15) | H8A—C8—H8B | 109.5 |
O14ii—Yb6—O24 | 136.47 (15) | C7—C8—H8C | 109.5 |
O4ii—Yb6—O24 | 75.92 (15) | H8A—C8—H8C | 109.5 |
O14ii—Yb6—O23 | 108.99 (14) | H8B—C8—H8C | 109.5 |
O4ii—Yb6—O23 | 145.22 (15) | O9—C9—O10 | 122.9 (6) |
O24—Yb6—O23 | 74.12 (14) | O9—C9—C10 | 118.9 (6) |
O14ii—Yb6—O19iv | 153.93 (15) | O10—C9—C10 | 118.2 (5) |
O4ii—Yb6—O19iv | 100.99 (15) | C9—C10—H10A | 109.5 |
O24—Yb6—O19iv | 68.11 (14) | C9—C10—H10B | 109.5 |
O23—Yb6—O19iv | 83.83 (14) | H10A—C10—H10B | 109.5 |
O14ii—Yb6—O18ii | 71.02 (15) | C9—C10—H10C | 109.5 |
O4ii—Yb6—O18ii | 136.21 (14) | H10A—C10—H10C | 109.5 |
O24—Yb6—O18ii | 145.95 (14) | H10B—C10—H10C | 109.5 |
O23—Yb6—O18ii | 77.47 (14) | O11—C11—O12 | 124.2 (6) |
O19iv—Yb6—O18ii | 90.67 (14) | O11—C11—C12 | 118.0 (5) |
O14ii—Yb6—O18iv | 84.43 (14) | O12—C11—C12 | 117.8 (6) |
O4ii—Yb6—O18iv | 72.51 (15) | C11—C12—H12A | 109.5 |
O24—Yb6—O18iv | 122.07 (14) | C11—C12—H12B | 109.5 |
O23—Yb6—O18iv | 139.82 (15) | H12A—C12—H12B | 109.5 |
O19iv—Yb6—O18iv | 71.92 (14) | C11—C12—H12C | 109.5 |
O18ii—Yb6—O18iv | 71.45 (16) | H12A—C12—H12C | 109.5 |
O14ii—Yb6—O15ii | 67.72 (14) | H12B—C12—H12C | 109.5 |
Symmetry codes: (i) −x+2, −y+2, −z+1; (ii) −x+1, −y+1, −z+1; (iii) −x+2, −y+1, −z+1; (iv) x, y−1, z; (v) x, y+1, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O13—H13···O12 | 1.00 | 2.06 | 2.989 (6) | 153 |
O14—H14···O6 | 1.00 | 1.79 | 2.718 (6) | 154 |
O15—H15···O11vi | 1.00 | 2.20 | 3.115 (6) | 152 |
O16—H16···O27 | 1.00 | 1.89 | 2.873 (7) | 166 |
O17—H17···O4vii | 1.00 | 1.91 | 2.820 (6) | 150 |
O18—H18···O27 | 1.00 | 2.16 | 3.124 (6) | 163 |
O19—H19···O6 | 1.00 | 2.29 | 3.194 (7) | 151 |
O20—H20···O12 | 1.00 | 1.77 | 2.762 (6) | 170 |
O21—H21···O11iii | 1.00 | 2.00 | 2.829 (6) | 138 |
O22—H22···O26 | 1.00 | 1.94 | 2.906 (7) | 161 |
O23—H23···O27ii | 1.00 | 1.89 | 2.864 (7) | 164 |
O24—H24···O11iii | 1.00 | 1.78 | 2.722 (6) | 155 |
O25—H25A···O2viii | 0.84 | 2.00 | 2.779 (7) | 154 |
O25—H25A···O2 | 0.84 | 2.36 | 2.802 (6) | 113 |
O25—H25B···O12 | 0.84 | 1.88 | 2.691 (6) | 163 |
O26—H26A···O1ii | 0.84 | 1.97 | 2.810 (6) | 173 |
O26—H26B···O27 | 0.84 | 2.30 | 2.781 (6) | 116 |
Symmetry codes: (ii) −x+1, −y+1, −z+1; (iii) −x+2, −y+1, −z+1; (vi) x−1, y, z; (vii) x+1, y, z; (viii) −x+1, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | [Yb(C2H3O2)(OH)2]·0.5H2O |
Mr | 275.11 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 90 |
a, b, c (Å) | 9.3235 (10), 12.1765 (14), 15.5502 (15) |
α, β, γ (°) | 109.796 (5), 92.666 (6), 108.745 (5) |
V (Å3) | 1548.9 (3) |
Z | 12 |
Radiation type | Mo Kα |
µ (mm−1) | 18.03 |
Crystal size (mm) | 0.15 × 0.10 × 0.07 |
Data collection | |
Diffractometer | Nonius KappaCCD with Oxford Cryostream diffractometer |
Absorption correction | Multi-scan (HKL SCALEPACK; Otwinowski & Minor 1997) |
Tmin, Tmax | 0.173, 0.365 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 56149, 14105, 11613 |
Rint | 0.042 |
(sin θ/λ)max (Å−1) | 0.819 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.120, 1.01 |
No. of reflections | 14105 |
No. of parameters | 413 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 5.71, −5.73 |
Computer programs: COLLECT (Nonius, 2000), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), CrystalMaker (Version 8.3.1 for Mac; Palmer, 2010).
D—H···A | D—H | H···A | D···A | D—H···A |
O13—H13···O12 | 1.00 | 2.06 | 2.989 (6) | 152.8 |
O14—H14···O6 | 1.00 | 1.79 | 2.718 (6) | 153.6 |
O15—H15···O11i | 1.00 | 2.20 | 3.115 (6) | 152.0 |
O16—H16···O27 | 1.00 | 1.89 | 2.873 (7) | 166.1 |
O17—H17···O4ii | 1.00 | 1.91 | 2.820 (6) | 150.1 |
O18—H18···O27 | 1.00 | 2.16 | 3.124 (6) | 162.5 |
O19—H19···O6 | 1.00 | 2.29 | 3.194 (7) | 150.6 |
O20—H20···O12 | 1.00 | 1.77 | 2.762 (6) | 169.6 |
O21—H21···O11iii | 1.00 | 2.00 | 2.829 (6) | 138.2 |
O22—H22···O26 | 1.00 | 1.94 | 2.906 (7) | 161.3 |
O23—H23···O27iv | 1.00 | 1.89 | 2.864 (7) | 164.1 |
O24—H24···O11iii | 1.00 | 1.78 | 2.722 (6) | 154.9 |
O25—H25A···O2v | 0.84 | 2.00 | 2.779 (7) | 154.2 |
O25—H25A···O2 | 0.84 | 2.36 | 2.802 (6) | 113.3 |
O25—H25B···O12 | 0.84 | 1.88 | 2.691 (6) | 162.8 |
O26—H26A···O1iv | 0.84 | 1.97 | 2.810 (6) | 172.5 |
O26—H26B···O27 | 0.84 | 2.30 | 2.781 (6) | 116.4 |
Symmetry codes: (i) x−1, y, z; (ii) x+1, y, z; (iii) −x+2, −y+1, −z+1; (iv) −x+1, −y+1, −z+1; (v) −x+1, −y+1, −z. |
The creation of open frameworks has increased considerably over the last decade due to their widespread potential applications in electronic applications (Férey et al., 2007), drug delivery (Horcajada et al., 2008; Vallet-Regi et al., 2007), catalytic systems (Gándara et al., 2008; Mueller et al., 2008) etc. We recently discussed the structural trends within an extended series of lanthanide bis-hydroxychlorides [Ln(OH)2Cl; Zehnder et al., 2010], which represent purely inorganic three-dimensional open frameworks, as they may have potential implications for the long-term isolation and storage of radioactive waste materials. Other purely inorganic three-dimensional networks, assembling to various forms of zeolite structures, have become very useful as molecular sieves (Meier et al., 1996). In more recent years, these purely inorganic three-dimensional extended lattices have evolved into frameworks incorporating organic building units (Li et al., 2007). The replacement of inorganic entities with larger organic spacer entities has led to a large number of new materials with significantly larger pore sizes and unique properties. These new materials, mainly integrating organic ligand systems into three-dimensional coordination polymers, are known as metal organic frameworks (MOFs) (Bradshaw et al., 2005; Kawano et al., 2007).
We are currently extending our work from exclusively inorganic lanthanide mixed-ligand compounds to MOF materials, and therefore consider the acetate ligand as one of the possible organic entities. We were curious to see if we could construct the acetate analogues of the Ln(OH)2Cl compounds that we recently investigated. We were able to obtain single crystals of the title compound, (I), of sufficiently high quality for a single-crystal X-ray structural analysis. Compound (I) is an excellent candidate for demonstrating the feasibility of replacing inorganic ligand systems with organic entities in order to obtain hybrid frameworks. In such frameworks, inorganic ligands and organic entities are part of the resulting coordination environment. Moreover, (I) shows that organic entities with one major coordination site will rather lead to the creation of frameworks with limited dimensionality. As we illustrate here, (I) assembles as a two-dimensional layered framework, in which individual layers interact through hydrogen bonds.
To our knowledge, the single-crystal X-ray structural characterization of a lanthanide bis(hydroxide) acetate is unprecedented. However, a small number of related lanthanide compounds have been under investigation. Sakagami and co-workers discussed the structure of a heteronuclear CrIII–NdIII complex, which incorporates hydroxide and acetate groups in the coordination environment. These researchers point out that compounds such as [Cr2Nd3(µ-OOCCH3)6(µ-OH)6(H2O)9]Br3(NaBr)(H2O)8 may have unusual electronic and magnetic properties (Sakagami et al., 1997). Another research team reported the synthesis and structural characterization of CsLu(CH3COO)4 and Cs2[Lu3(CH3COO)10(OH)(H2O)], and the changes these compounds undergo during thermal decomposition. Cs2[Lu3(CH3COO)10(OH)(H2O)] assembles to form trimers of Lu centres that are linked by Cs+ cations (Lossin & Meyer, 1993). More recently, a group of investigators assessed the structural and magnetic properties of Tb4 spin clusters incorporating acetate anions and various organic ligands with hydroxyl groups that possess chelating as well as linking capacities. The coordination of the acetate entities in these Tb compounds seems to prevent the formation of a three-dimensional linked crystal structure. Therefore, the trimers integrating carboxylate O atoms and OH groups into the coordination environment remain as isolated individual clusters (Bircher et al., 2007).
In various other experiments, we extended the organic part of the ligand by exchanging acetate with phenyl acetate. We obtained a small number of lanthanide phenylacetates that have been discussed previously (Hasegawa, Ikeuchi et al., 1989; Hasegawa, Morita et al., 1989; Hasegawa et al., 1990). These compounds assemble in one-dimensional channels of lanthanide metal centres that are linked by carboxylate groups and stretch infinitely along the a axis. The bulky hydrophobic parts of the phenylacetate entities are oriented in all directions surrounding the metal–carboxylate channels. In order to obtain an extended structure that is linked via strong coordination bonds in three dimensions, it is essential to employ spacer units that contain two or more major coordination sites. This has been established by a number of researchers who have made use of organic entities, e.g. terephthalic acid (Daiguebonne et al., 2006, 2008; Haquin et al., 2009; Kerbellec et al., 2009; Long et al., 2001), phthalic acid (Li et al., 2009) and glutaric acid (Serpaggi & Férey, 1998). We recently obtained various MOF materials incorporating these types of organic ligands, which will be discussed elsewhere.
Here we present the synthesis and characterization of the title compound, (I), a lanthanide mixed-ligand complex comprised of inorganic and organic components. Compound (I) crystallizes in the triclinic crystal system, space group P1, and it assembles as a two-dimensional layered framework. Individual layers are composed of highly linked YbIII centres, hydroxy groups and acetate entities that stretch infinitely along the a and b axes. Each layer is segmented into an inner layer that accommodates a dense network of YbIII cations and hydroxy groups, while the outer layer also includes carboxylate groups and water molecules. The layers exhibit six crystallographically independent YbIII atoms as the centres of four eight- and two seven-coordinate Yb–O polyhedra. Three of the four YbO8 and the two YbO7 polyhedra contain YbIII centres that are narrowly interlinked within the inner layer of the ab plane. The other YbO8 polyhedra feature the terminal YbIII cations, which stick out from the surface of the outer layer on both sides, pointing towards adjacent layers in the c direction. The YbIII centres of the five coordination polyhedra in the inner layer comprise only hydroxide groups and one carboxylate O atom, respectively [Which is which?]. The Yb—O bond distances within these five polyhedra vary between 2.232 (4) and 2.418 (4) Å. The corresponding bond distances in the YbO8 polyhedra of the terminal YbIII cations are somewhat longer and range between 2.257 (4) and 2.613 (5) Å. The coordination polyhedra are interlinked via edge sharing, utilizing two hydroxy groups. Hydroxy groups bind in both µ3- and µ2-fashion, connecting to three and two Yb3+ cations, respectively.
The carboxylate O atoms bind in an exclusively µ1-fashion to the YbIII atoms. Fig. 1 emphasizes the arrangement of the six different coordination polyhedra, in a view along the a axis utilizing different shaded patterns. The acetate anions are arranged with their carboxylate groups oriented towards the YbIII atoms, while their CH3 groups point towards the adjacent layer in the c direction. Fig. 2 illustrates the layered system of (I) in a view along the b axis, demonstrating that the individual layers interact via hydrogen bonding between coordinating water molecules and carboxylate O atoms. One can also recognize two different kinds of interstitial water molecules.
Two groups of acetate anions coordinate in a monodentate fashion to two YbIII atoms of the inner layer, with bond distances of Yb4—O8 = 2.261 (5) and Yb2—O7 = 2.279 (4) Å for one, and Yb3—O9 = 2.265 (5) and Yb5—O10 = 2.271 (5) Å for the other. One group of acetate units does not coordinate to any metal centre whatsoever. In these cases, both carboxylate O atoms are held in place via hydrogen bonds originating from the hydroxy groups, with hydrogen-bond distances of 1.77 and 1.78 Å. The terminal YbIII atom is linked to one bidentate carboxylate group [Yb1—O1 = 2.333 (4) and Yb1—O2 = 2.613 (5) Å] and two different carboxylate groups, of which only one O atom coordinates to the terminal YbIII atom. One of these two carboxylate units possesses an O atom that remains uncoordinated which is the receiver of a hydrogen bond (2.285 Å) from one hydroxy group. The Yb1—O5 distance of the coordinated O atom is 2.257 (4) Å. The second O atom of the other carboxylate group coordinates to one of the YbIII atoms within the inner layer, with Yb6—O4 = 2.308 (4) Å. The coordination bond to the external YbIII atom is Yb1—O3 = 2.276 (4) Å.
Thus, the terminal YbIII atoms exhibit the most diverse coordination environments, as their YbO8 polyhedra also accommodate one water molecule. These are the only coordinating water O atoms, with Yb1—O25 = 2.333 (4) Å. One of the water H atoms connects via a hydrogen bond (2.00 Å) to one of the carboxylate groups within the adjacent layer that coordinate in bidentate fashion to the terminal YbIII atoms of that layer. Fig. 3 illustrates the ligand environment of the terminal YbIII atom, in the form of displacement ellipsoids for each atom at a probability level of 50%.