The two isomorphous lanthanide coordination polymers, {[Ln
2(C
6H
4NO
2)
2(C
8H
4O
4)(OH)
2(H
2O)]·H
2O}
n (Ln = Er and Tm), contain two crystallographically independent Ln ions which are both eight-coordinated by O atoms, but with quite different coordination environments. In both crystal structures, adjacent Ln atoms are bridged by μ
3-OH groups and carboxylate groups of isonicotinate and benzene-1,2-dicarboxylate ligands, forming infinite chains in which the Er
Er and Tm
Tm distances are in the ranges 3.622 (3)–3.894 (4) and 3.599 (7)–3.873 (1) Å, respectively. Adjacent chains are further connected through hydrogen bonds and π–π interactions into a three-dimensional supramolecular framework.
Supporting information
CCDC references: 669167; 669168
The title compounds were synthesized under hydrothermal conditions. Typically, a mixture of Ln2O3 (0.5 mmol; Er 0.192 g, Tm 0.193 g), HIN (2.00 mmol, 0.247 g), H2BDC (1.00 mmol, 0.167 g) and water (10 ml), in the ratio of 1:4:2:1112, was sealed in a 25 ml Teflon-lined steel autoclave and heated under autogenous pressure at 443 K for 6 d. The prism-like crystals obtained were recovered by filtration, washed with distilled water and dried in air.
H atoms bound to C atoms were positioned geometrically, with C—H distances of 0.93 Å, and constrained to ride on their parent atoms [Uiso(H) = 1.2Ueq(C)]. H atoms bound to O atoms were located in a difference Fourier map and refined as riding in the as-found positions [Uiso(H) = 1.2Ueq(O)].
For both compounds, data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1999); software used to prepare material for publication: SHELXTL (Bruker, 1999).
(I) Poly[aqua(µ
3-benzene-1,2-dicarboxylato-
κ4O,
O':
O':
O'')bis(µ
3– hydroxido)bis(µ
2-isonicotinato-
κ2O:
O')dierbium(III) monohydrate
top
Crystal data top
[Er2(C6H4NO2)2(C8H4O4)(OH)2(H2O)]·H2O | F(000) = 1536 |
Mr = 812.88 | Dx = 2.329 Mg m−3 |
Monoclinic, p21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 18413 reflections |
a = 7.2706 (5) Å | θ = 1.8–26.5° |
b = 24.2780 (4) Å | µ = 7.26 mm−1 |
c = 13.3668 (2) Å | T = 295 K |
β = 100.708 (4)° | Prism, red |
V = 2318.36 (17) Å3 | 0.45 × 0.10 × 0.09 mm |
Z = 4 | |
Data collection top
Siemems SMART CCD diffractometer | 4769 independent reflections |
Radiation source: fine-focus sealed tube | 4563 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.036 |
ϕ and ω scans | θmax = 26.5°, θmin = 1.8° |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | h = −9→9 |
Tmin = 0.399, Tmax = 0.511 | k = −30→29 |
18413 measured reflections | l = −16→16 |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.029 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.067 | H-atom parameters constrained |
S = 1.19 | w = 1/[σ2(Fo2) + (0.0263P)2 + 4.9192P] where P = (Fo2 + 2Fc2)/3 |
4769 reflections | (Δ/σ)max = 0.001 |
325 parameters | Δρmax = 1.76 e Å−3 |
0 restraints | Δρmin = −1.41 e Å−3 |
Crystal data top
[Er2(C6H4NO2)2(C8H4O4)(OH)2(H2O)]·H2O | V = 2318.36 (17) Å3 |
Mr = 812.88 | Z = 4 |
Monoclinic, p21/c | Mo Kα radiation |
a = 7.2706 (5) Å | µ = 7.26 mm−1 |
b = 24.2780 (4) Å | T = 295 K |
c = 13.3668 (2) Å | 0.45 × 0.10 × 0.09 mm |
β = 100.708 (4)° | |
Data collection top
Siemems SMART CCD diffractometer | 4769 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 4563 reflections with I > 2σ(I) |
Tmin = 0.399, Tmax = 0.511 | Rint = 0.036 |
18413 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.029 | 0 restraints |
wR(F2) = 0.067 | H-atom parameters constrained |
S = 1.19 | Δρmax = 1.76 e Å−3 |
4769 reflections | Δρmin = −1.41 e Å−3 |
325 parameters | |
Special details top
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) top | x | y | z | Uiso*/Ueq | |
Er1 | 0.58951 (3) | 0.454643 (8) | 0.398835 (15) | 0.01102 (7) | |
Er2 | 0.91911 (3) | 0.492512 (8) | 0.626252 (15) | 0.01118 (7) | |
O1 | 0.1068 (5) | 0.52598 (16) | 0.1930 (3) | 0.0240 (8) | |
O1W | 0.9014 (7) | 0.8486 (2) | 1.0199 (4) | 0.0569 (14) | |
H1W | 0.9439 | 0.8167 | 0.9936 | 0.068* | |
H2W | 0.7788 | 0.8481 | 1.0053 | 0.068* | |
O2 | 0.3687 (5) | 0.51179 (15) | 0.3019 (3) | 0.0182 (7) | |
O3 | 0.6819 (6) | 0.60570 (17) | 0.3285 (4) | 0.0423 (11) | |
O4 | 0.7641 (5) | 0.51853 (14) | 0.3102 (3) | 0.0187 (7) | |
O5 | 0.6621 (4) | 0.52711 (13) | 0.5156 (2) | 0.0120 (6) | |
H5 | 0.6796 | 0.5575 | 0.4866 | 0.014* | |
O6 | 0.9148 (4) | 0.45157 (13) | 0.4673 (2) | 0.0128 (7) | |
H6 | 0.9509 | 0.4176 | 0.4651 | 0.015* | |
O7 | 0.7093 (5) | 0.39610 (15) | 0.2890 (3) | 0.0236 (8) | |
H7W | 0.6623 | 0.3652 | 0.2646 | 0.028* | |
H8W | 0.8241 | 0.4002 | 0.2809 | 0.028* | |
O8 | 0.6144 (5) | 0.38738 (16) | 0.5195 (3) | 0.0280 (9) | |
O9 | 0.8535 (6) | 0.39941 (15) | 0.6491 (3) | 0.0289 (9) | |
O10 | 0.9275 (5) | 0.57681 (14) | 0.7090 (3) | 0.0195 (7) | |
O11 | 0.6344 (5) | 0.60890 (16) | 0.6763 (3) | 0.0288 (9) | |
C1 | 0.4039 (9) | 0.5679 (3) | −0.0365 (4) | 0.0430 (17) | |
H1A | 0.3466 | 0.5686 | −0.1048 | 0.052* | |
C2 | 0.5869 (10) | 0.5846 (3) | −0.0078 (5) | 0.0460 (19) | |
H2A | 0.6521 | 0.5974 | −0.0568 | 0.055* | |
C3 | 0.6754 (8) | 0.5825 (3) | 0.0935 (5) | 0.0375 (15) | |
H3A | 0.8000 | 0.5931 | 0.1117 | 0.045* | |
C4 | 0.5786 (7) | 0.5645 (2) | 0.1678 (4) | 0.0197 (11) | |
C5 | 0.3910 (7) | 0.5478 (2) | 0.1389 (4) | 0.0218 (11) | |
C6 | 0.3056 (9) | 0.5502 (3) | 0.0364 (4) | 0.0327 (14) | |
H6A | 0.1810 | 0.5398 | 0.0171 | 0.039* | |
C7 | 0.6792 (7) | 0.5645 (2) | 0.2771 (4) | 0.0217 (11) | |
C8 | 0.2808 (7) | 0.5273 (2) | 0.2121 (4) | 0.0192 (10) | |
C9 | 1.0018 (11) | 0.6974 (4) | 0.9441 (6) | 0.056 (2) | |
H9A | 1.0722 | 0.6917 | 1.0088 | 0.067* | |
C10 | 0.8399 (11) | 0.7548 (3) | 0.8268 (7) | 0.055 (2) | |
H10A | 0.7988 | 0.7902 | 0.8075 | 0.066* | |
C11 | 0.7928 (9) | 0.7123 (3) | 0.7569 (6) | 0.0406 (16) | |
H11A | 0.7191 | 0.7188 | 0.6934 | 0.049* | |
C12 | 0.9677 (9) | 0.6535 (3) | 0.8794 (5) | 0.0414 (16) | |
H12A | 1.0178 | 0.6191 | 0.8993 | 0.050* | |
C13 | 0.8585 (7) | 0.6607 (2) | 0.7846 (4) | 0.0247 (12) | |
C14 | 0.8022 (7) | 0.6119 (2) | 0.7169 (4) | 0.0185 (10) | |
C15 | 0.7356 (10) | 0.2478 (3) | 0.7691 (6) | 0.0495 (19) | |
H15A | 0.7844 | 0.2385 | 0.8363 | 0.059* | |
C16 | 0.5696 (10) | 0.2249 (3) | 0.6147 (6) | 0.0439 (17) | |
H16A | 0.5030 | 0.1987 | 0.5719 | 0.053* | |
C17 | 0.7622 (10) | 0.3012 (3) | 0.7372 (5) | 0.0412 (16) | |
H17A | 0.8299 | 0.3265 | 0.7816 | 0.049* | |
C18 | 0.5846 (9) | 0.2772 (2) | 0.5766 (5) | 0.0362 (15) | |
H18A | 0.5272 | 0.2861 | 0.5104 | 0.043* | |
C19 | 0.6869 (7) | 0.3159 (2) | 0.6391 (4) | 0.0228 (11) | |
C20 | 0.7213 (8) | 0.3727 (2) | 0.6000 (4) | 0.0229 (11) | |
N1 | 0.9394 (9) | 0.7477 (3) | 0.9189 (5) | 0.0581 (19) | |
N2 | 0.6447 (8) | 0.2097 (2) | 0.7091 (5) | 0.0459 (15) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Er1 | 0.01092 (12) | 0.00925 (12) | 0.01294 (11) | −0.00006 (7) | 0.00237 (8) | −0.00124 (7) |
Er2 | 0.01085 (12) | 0.01073 (12) | 0.01217 (11) | −0.00049 (7) | 0.00269 (8) | −0.00025 (7) |
O1 | 0.0152 (19) | 0.035 (2) | 0.0209 (18) | 0.0006 (16) | 0.0021 (14) | 0.0040 (16) |
O1W | 0.060 (3) | 0.037 (3) | 0.075 (4) | −0.011 (2) | 0.015 (3) | −0.028 (3) |
O2 | 0.0149 (18) | 0.025 (2) | 0.0147 (17) | 0.0036 (14) | 0.0030 (13) | 0.0065 (14) |
O3 | 0.045 (3) | 0.020 (2) | 0.058 (3) | 0.0010 (19) | −0.001 (2) | −0.011 (2) |
O4 | 0.0152 (18) | 0.0196 (19) | 0.0219 (18) | 0.0026 (14) | 0.0054 (14) | 0.0051 (14) |
O5 | 0.0137 (16) | 0.0081 (16) | 0.0144 (16) | −0.0006 (12) | 0.0028 (12) | 0.0015 (13) |
O6 | 0.0161 (17) | 0.0069 (16) | 0.0158 (16) | 0.0015 (12) | 0.0044 (13) | −0.0004 (12) |
O7 | 0.0198 (19) | 0.020 (2) | 0.034 (2) | −0.0063 (15) | 0.0114 (15) | −0.0151 (16) |
O8 | 0.025 (2) | 0.022 (2) | 0.037 (2) | 0.0040 (16) | 0.0066 (17) | 0.0152 (17) |
O9 | 0.044 (2) | 0.017 (2) | 0.027 (2) | −0.0068 (17) | 0.0099 (18) | 0.0035 (16) |
O10 | 0.0165 (18) | 0.0178 (19) | 0.0257 (19) | −0.0010 (14) | 0.0077 (14) | −0.0047 (15) |
O11 | 0.0165 (19) | 0.023 (2) | 0.046 (2) | −0.0027 (15) | 0.0025 (17) | −0.0163 (18) |
C1 | 0.046 (4) | 0.068 (5) | 0.017 (3) | 0.014 (3) | 0.012 (3) | 0.017 (3) |
C2 | 0.047 (4) | 0.059 (5) | 0.038 (4) | 0.019 (3) | 0.026 (3) | 0.033 (3) |
C3 | 0.025 (3) | 0.046 (4) | 0.045 (4) | 0.005 (3) | 0.015 (3) | 0.021 (3) |
C4 | 0.020 (3) | 0.019 (3) | 0.022 (3) | 0.007 (2) | 0.009 (2) | 0.008 (2) |
C5 | 0.019 (3) | 0.028 (3) | 0.018 (3) | 0.005 (2) | 0.003 (2) | 0.007 (2) |
C6 | 0.029 (3) | 0.049 (4) | 0.019 (3) | 0.010 (3) | 0.002 (2) | 0.008 (3) |
C7 | 0.017 (3) | 0.017 (3) | 0.032 (3) | −0.003 (2) | 0.007 (2) | 0.006 (2) |
C8 | 0.023 (3) | 0.016 (3) | 0.019 (3) | 0.000 (2) | 0.005 (2) | 0.003 (2) |
C9 | 0.056 (5) | 0.062 (6) | 0.049 (5) | −0.009 (4) | 0.006 (4) | −0.034 (4) |
C10 | 0.056 (5) | 0.022 (4) | 0.092 (6) | −0.009 (3) | 0.023 (4) | −0.024 (4) |
C11 | 0.035 (4) | 0.029 (4) | 0.058 (4) | −0.001 (3) | 0.007 (3) | −0.014 (3) |
C12 | 0.033 (4) | 0.048 (4) | 0.041 (4) | −0.006 (3) | 0.002 (3) | −0.019 (3) |
C13 | 0.014 (3) | 0.026 (3) | 0.037 (3) | −0.007 (2) | 0.011 (2) | −0.016 (2) |
C14 | 0.014 (2) | 0.018 (3) | 0.024 (3) | −0.0064 (19) | 0.0079 (19) | −0.006 (2) |
C15 | 0.057 (5) | 0.036 (4) | 0.056 (5) | 0.009 (3) | 0.012 (4) | 0.030 (3) |
C16 | 0.042 (4) | 0.023 (3) | 0.066 (5) | −0.007 (3) | 0.008 (3) | 0.005 (3) |
C17 | 0.054 (4) | 0.028 (4) | 0.040 (4) | −0.008 (3) | 0.004 (3) | 0.012 (3) |
C18 | 0.034 (3) | 0.022 (3) | 0.050 (4) | −0.001 (3) | 0.000 (3) | 0.009 (3) |
C19 | 0.024 (3) | 0.013 (3) | 0.032 (3) | 0.003 (2) | 0.007 (2) | 0.009 (2) |
C20 | 0.033 (3) | 0.012 (3) | 0.027 (3) | 0.003 (2) | 0.014 (2) | 0.004 (2) |
N1 | 0.047 (4) | 0.060 (5) | 0.069 (5) | −0.018 (3) | 0.014 (3) | −0.044 (4) |
N2 | 0.041 (3) | 0.022 (3) | 0.079 (4) | 0.006 (2) | 0.023 (3) | 0.025 (3) |
Geometric parameters (Å, º) top
Er1—O8 | 2.278 (4) | C1—C2 | 1.376 (10) |
Er1—O2 | 2.325 (3) | C1—C6 | 1.380 (8) |
Er1—O7 | 2.326 (3) | C1—H1A | 0.9300 |
Er1—O11i | 2.331 (4) | C2—C3 | 1.388 (9) |
Er1—O5 | 2.346 (3) | C2—H2A | 0.9300 |
Er1—O5i | 2.372 (3) | C3—C4 | 1.390 (7) |
Er1—O6 | 2.373 (3) | C3—H3A | 0.9300 |
Er1—O4 | 2.445 (3) | C4—C5 | 1.406 (7) |
Er1—Er2 | 3.6224 (3) | C4—C7 | 1.507 (7) |
Er1—Er2ii | 3.8688 (4) | C5—C6 | 1.396 (7) |
Er1—Er2i | 3.8694 (4) | C5—C8 | 1.463 (7) |
Er1—Er1i | 3.8944 (4) | C6—H6A | 0.9300 |
Er2—O5 | 2.315 (3) | C9—N1 | 1.325 (11) |
Er2—O4ii | 2.318 (3) | C9—C12 | 1.365 (9) |
Er2—O10 | 2.322 (3) | C9—H9A | 0.9300 |
Er2—O6ii | 2.329 (3) | C10—N1 | 1.318 (11) |
Er2—O6 | 2.341 (3) | C10—C11 | 1.391 (9) |
Er2—O9 | 2.342 (4) | C10—H10A | 0.9300 |
Er2—O2i | 2.461 (3) | C11—C13 | 1.367 (9) |
Er2—O1i | 2.499 (4) | C11—H11A | 0.9300 |
Er2—Er2ii | 3.7924 (4) | C12—C13 | 1.376 (8) |
O1—C8 | 1.244 (6) | C12—H12A | 0.9300 |
O1W—H1W | 0.9268 | C13—C14 | 1.501 (7) |
O1W—H2W | 0.8767 | C15—N2 | 1.318 (10) |
O2—C8 | 1.306 (6) | C15—C17 | 1.389 (9) |
O3—C7 | 1.211 (7) | C15—H15A | 0.9300 |
O4—C7 | 1.312 (6) | C16—N2 | 1.330 (9) |
O5—H5 | 0.8539 | C16—C18 | 1.380 (8) |
O6—H6 | 0.8675 | C16—H16A | 0.9300 |
O7—H7W | 0.8627 | C17—C19 | 1.371 (8) |
O7—H8W | 0.8669 | C17—H17A | 0.9300 |
O8—C20 | 1.256 (6) | C18—C19 | 1.380 (8) |
O9—C20 | 1.241 (7) | C18—H18A | 0.9300 |
O10—C14 | 1.267 (6) | C19—C20 | 1.513 (7) |
O11—C14 | 1.241 (6) | | |
| | | |
O8—Er1—O2 | 141.05 (12) | C2—C1—H1A | 120.1 |
O8—Er1—O7 | 91.10 (14) | C6—C1—H1A | 120.1 |
O2—Er1—O7 | 108.27 (13) | C1—C2—C3 | 120.7 (5) |
O8—Er1—O11i | 77.76 (15) | C1—C2—H2A | 119.7 |
O2—Er1—O11i | 78.47 (13) | C3—C2—H2A | 119.7 |
O7—Er1—O11i | 68.72 (12) | C2—C3—C4 | 120.3 (6) |
O8—Er1—O5 | 95.05 (13) | C2—C3—H3A | 119.9 |
O2—Er1—O5 | 88.28 (11) | C4—C3—H3A | 119.9 |
O7—Er1—O5 | 144.47 (11) | C3—C4—C5 | 119.2 (5) |
O11i—Er1—O5 | 146.72 (12) | C3—C4—C7 | 118.3 (5) |
O8—Er1—O5i | 76.09 (12) | C5—C4—C7 | 122.5 (4) |
O2—Er1—O5i | 69.07 (11) | C6—C5—C4 | 119.3 (5) |
O7—Er1—O5i | 146.22 (12) | C6—C5—C8 | 118.1 (5) |
O11i—Er1—O5i | 77.99 (12) | C4—C5—C8 | 122.6 (5) |
O5—Er1—O5i | 68.76 (12) | C1—C6—C5 | 120.8 (6) |
O8—Er1—O6 | 76.26 (12) | C1—C6—H6A | 119.6 |
O2—Er1—O6 | 140.25 (11) | C5—C6—H6A | 119.6 |
O7—Er1—O6 | 76.16 (12) | O3—C7—O4 | 123.6 (5) |
O11i—Er1—O6 | 135.37 (12) | O3—C7—C4 | 120.2 (5) |
O5—Er1—O6 | 71.47 (11) | O4—C7—C4 | 116.1 (5) |
O5i—Er1—O6 | 128.51 (11) | O1—C8—O2 | 119.1 (4) |
O8—Er1—O4 | 144.83 (12) | O1—C8—C5 | 122.3 (4) |
O2—Er1—O4 | 73.65 (11) | O2—C8—C5 | 118.5 (4) |
O7—Er1—O4 | 78.03 (12) | O1—C8—Er2i | 60.7 (3) |
O11i—Er1—O4 | 126.51 (13) | O2—C8—Er2i | 59.2 (2) |
O5—Er1—O4 | 76.93 (11) | C5—C8—Er2i | 168.9 (4) |
O5i—Er1—O4 | 129.15 (11) | N1—C9—C12 | 123.1 (8) |
O6—Er1—O4 | 68.70 (11) | N1—C9—H9A | 118.5 |
O5—Er2—O4ii | 154.89 (12) | C12—C9—H9A | 118.5 |
O5—Er2—O10 | 86.05 (12) | N1—C10—C11 | 123.6 (7) |
O4ii—Er2—O10 | 89.48 (12) | N1—C10—H10A | 118.2 |
O5—Er2—O6ii | 83.29 (11) | C11—C10—H10A | 118.2 |
O4ii—Er2—O6ii | 71.64 (12) | C13—C11—C10 | 117.9 (7) |
O10—Er2—O6ii | 76.79 (11) | C13—C11—H11A | 121.0 |
O5—Er2—O6 | 72.60 (11) | C10—C11—H11A | 121.0 |
O4ii—Er2—O6 | 97.38 (12) | C9—C12—C13 | 119.3 (7) |
O10—Er2—O6 | 143.26 (12) | C9—C12—H12A | 120.3 |
O6ii—Er2—O6 | 71.40 (12) | C13—C12—H12A | 120.3 |
O5—Er2—O9 | 105.88 (13) | C11—C13—C12 | 118.6 (6) |
O4ii—Er2—O9 | 93.06 (13) | C11—C13—C14 | 121.2 (5) |
O10—Er2—O9 | 140.96 (13) | C12—C13—C14 | 120.1 (5) |
O6ii—Er2—O9 | 140.45 (12) | O11—C14—O10 | 126.0 (5) |
O6—Er2—O9 | 74.92 (12) | O11—C14—C13 | 116.5 (4) |
O5—Er2—O2i | 67.71 (11) | O10—C14—C13 | 117.5 (4) |
O4ii—Er2—O2i | 135.33 (11) | N2—C15—C17 | 123.4 (7) |
O10—Er2—O2i | 78.50 (12) | N2—C15—H15A | 118.3 |
O6ii—Er2—O2i | 142.87 (11) | C17—C15—H15A | 118.3 |
O6—Er2—O2i | 117.85 (11) | N2—C16—C18 | 124.0 (7) |
O9—Er2—O2i | 72.52 (13) | N2—C16—H16A | 118.0 |
O5—Er2—O1i | 119.08 (11) | C18—C16—H16A | 118.0 |
O4ii—Er2—O1i | 82.71 (11) | C19—C17—C15 | 118.9 (7) |
O10—Er2—O1i | 72.41 (13) | C19—C17—H17A | 120.6 |
O6ii—Er2—O1i | 139.76 (12) | C15—C17—H17A | 120.6 |
O6—Er2—O1i | 144.17 (12) | C19—C18—C16 | 118.2 (6) |
O9—Er2—O1i | 69.32 (13) | C19—C18—H18A | 120.9 |
O2i—Er2—O1i | 52.62 (11) | C16—C18—H18A | 120.9 |
O1W—O1W—H2W | 107.5 | C17—C19—C18 | 118.5 (5) |
Er2ii—O6—H6 | 110.2 | C17—C19—C20 | 120.3 (5) |
Er2—O6—H6 | 118.7 | C18—C19—C20 | 121.1 (5) |
Er1—O6—H6 | 107.7 | O9—C20—O8 | 126.9 (5) |
Er1—O7—H7W | 126.9 | O9—C20—C19 | 117.1 (5) |
Er1—O7—H8W | 119.4 | O8—C20—C19 | 116.0 (5) |
H7W—O7—H8W | 112.1 | C10—N1—C9 | 117.4 (6) |
C2—C1—C6 | 119.7 (6) | C15—N2—C16 | 117.0 (6) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+2, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1W···N1 | 0.93 | 1.95 | 2.834 (8) | 160 |
O5—H5···O3 | 0.85 | 2.42 | 3.170 (6) | 147 |
O6—H6···O1Wiii | 0.87 | 1.98 | 2.826 (6) | 164 |
O7—H7W···N2iv | 0.86 | 1.96 | 2.788 (6) | 161 |
O7—H8W···O10ii | 0.87 | 1.87 | 2.716 (5) | 165 |
Symmetry codes: (ii) −x+2, −y+1, −z+1; (iii) −x+2, y−1/2, −z+3/2; (iv) x, −y+1/2, z−1/2. |
(II) Poly[aqua(µ
3-benzene-1,2-dicarboxylato-
κ4O,
O':
O':
O'')bis(µ
3-hydroxido)bis(µ
2-isonicotinato-
κ2O:
O')thulium(III) monohydrate
top
Crystal data top
[Tm2(C6H4NO2)2(C8H4O4)(OH)2(H2O)]·H2O | F(000) = 1544 |
Mr = 816.22 | Dx = 2.354 Mg m−3 |
Monoclinic, p21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 18502 reflections |
a = 7.2434 (2) Å | θ = 1.7–26.5° |
b = 24.2180 (6) Å | µ = 7.72 mm−1 |
c = 13.3606 (4) Å | T = 295 K |
β = 100.700 (3)° | Prism, brown |
V = 2302.97 (11) Å3 | 0.35 × 0.09 × 0.07 mm |
Z = 4 | |
Data collection top
Siemems SMART CCD diffractometer | 4754 independent reflections |
Radiation source: fine-focus sealed tube | 4602 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.026 |
ϕ and ω scans | θmax = 26.5°, θmin = 1.7° |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | h = −9→9 |
Tmin = 0.373, Tmax = 0.577 | k = −29→30 |
18502 measured reflections | l = −16→16 |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.025 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.060 | H-atom parameters constrained |
S = 1.17 | w = 1/[σ2(Fo2) + (0.0276P)2 + 4.1831P] where P = (Fo2 + 2Fc2)/3 |
4754 reflections | (Δ/σ)max = 0.002 |
325 parameters | Δρmax = 1.11 e Å−3 |
0 restraints | Δρmin = −1.31 e Å−3 |
Crystal data top
[Tm2(C6H4NO2)2(C8H4O4)(OH)2(H2O)]·H2O | V = 2302.97 (11) Å3 |
Mr = 816.22 | Z = 4 |
Monoclinic, p21/c | Mo Kα radiation |
a = 7.2434 (2) Å | µ = 7.72 mm−1 |
b = 24.2180 (6) Å | T = 295 K |
c = 13.3606 (4) Å | 0.35 × 0.09 × 0.07 mm |
β = 100.700 (3)° | |
Data collection top
Siemems SMART CCD diffractometer | 4754 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 4602 reflections with I > 2σ(I) |
Tmin = 0.373, Tmax = 0.577 | Rint = 0.026 |
18502 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.025 | 0 restraints |
wR(F2) = 0.060 | H-atom parameters constrained |
S = 1.17 | Δρmax = 1.11 e Å−3 |
4754 reflections | Δρmin = −1.31 e Å−3 |
325 parameters | |
Special details top
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) top | x | y | z | Uiso*/Ueq | |
Tm1 | 0.59003 (2) | 0.454897 (7) | 0.399404 (13) | 0.01278 (6) | |
Tm2 | 0.91843 (2) | 0.492537 (7) | 0.625664 (13) | 0.01309 (6) | |
O1 | 0.1057 (4) | 0.52578 (15) | 0.1945 (2) | 0.0257 (7) | |
O1W | 0.9011 (7) | 0.84841 (18) | 1.0193 (4) | 0.0605 (13) | |
H1W | 0.9435 | 0.8165 | 0.9930 | 0.073* | |
H2W | 0.7784 | 0.8479 | 1.0047 | 0.073* | |
O2 | 0.3689 (4) | 0.51172 (13) | 0.3029 (2) | 0.0212 (7) | |
O3 | 0.6818 (5) | 0.60627 (16) | 0.3283 (3) | 0.0442 (10) | |
O4 | 0.7650 (4) | 0.51876 (13) | 0.3111 (2) | 0.0193 (6) | |
O5 | 0.6622 (4) | 0.52721 (12) | 0.5154 (2) | 0.0138 (6) | |
H5 | 0.6798 | 0.5576 | 0.4863 | 0.017* | |
O6 | 0.9153 (4) | 0.45201 (11) | 0.4675 (2) | 0.0145 (6) | |
H6 | 0.9514 | 0.4181 | 0.4653 | 0.017* | |
O7 | 0.7094 (4) | 0.39701 (14) | 0.2895 (2) | 0.0258 (7) | |
H7W | 0.6624 | 0.3661 | 0.2651 | 0.031* | |
H8W | 0.8242 | 0.4011 | 0.2814 | 0.031* | |
O8 | 0.6154 (5) | 0.38747 (14) | 0.5187 (3) | 0.0315 (8) | |
O9 | 0.8544 (5) | 0.39973 (14) | 0.6484 (3) | 0.0309 (8) | |
O10 | 0.9274 (4) | 0.57651 (13) | 0.7080 (2) | 0.0222 (7) | |
O11 | 0.6328 (4) | 0.60859 (14) | 0.6750 (3) | 0.0309 (8) | |
C1 | 0.4036 (9) | 0.5674 (3) | −0.0361 (4) | 0.0476 (16) | |
H1A | 0.3465 | 0.5677 | −0.1045 | 0.057* | |
C2 | 0.5870 (9) | 0.5844 (3) | −0.0072 (5) | 0.0515 (18) | |
H2A | 0.6525 | 0.5970 | −0.0564 | 0.062* | |
C3 | 0.6752 (8) | 0.5829 (2) | 0.0935 (4) | 0.0410 (14) | |
H3A | 0.7996 | 0.5942 | 0.1117 | 0.049* | |
C4 | 0.5787 (6) | 0.5645 (2) | 0.1685 (4) | 0.0256 (10) | |
C5 | 0.3912 (6) | 0.5475 (2) | 0.1394 (4) | 0.0247 (10) | |
C6 | 0.3051 (8) | 0.5500 (2) | 0.0368 (4) | 0.0364 (13) | |
H6A | 0.1798 | 0.5398 | 0.0176 | 0.044* | |
C7 | 0.6795 (6) | 0.5645 (2) | 0.2774 (4) | 0.0245 (10) | |
C8 | 0.2815 (6) | 0.52723 (19) | 0.2139 (3) | 0.0223 (9) | |
C9 | 1.0001 (10) | 0.6968 (3) | 0.9434 (6) | 0.061 (2) | |
H9A | 1.0706 | 0.6908 | 1.0081 | 0.073* | |
C10 | 0.8386 (10) | 0.7551 (3) | 0.8267 (7) | 0.060 (2) | |
H10A | 0.7982 | 0.7906 | 0.8075 | 0.072* | |
C11 | 0.7917 (8) | 0.7124 (2) | 0.7563 (5) | 0.0439 (14) | |
H11A | 0.7183 | 0.7189 | 0.6926 | 0.053* | |
C12 | 0.9665 (8) | 0.6529 (3) | 0.8785 (5) | 0.0438 (14) | |
H12A | 1.0172 | 0.6184 | 0.8980 | 0.053* | |
C13 | 0.8573 (6) | 0.6603 (2) | 0.7844 (4) | 0.0287 (11) | |
C14 | 0.8011 (6) | 0.61155 (19) | 0.7157 (3) | 0.0226 (10) | |
C15 | 0.7365 (9) | 0.2477 (3) | 0.7692 (5) | 0.0526 (17) | |
H15A | 0.7858 | 0.2383 | 0.8364 | 0.063* | |
C16 | 0.5699 (9) | 0.2247 (2) | 0.6158 (5) | 0.0482 (16) | |
H16A | 0.5015 | 0.1985 | 0.5734 | 0.058* | |
C17 | 0.7636 (9) | 0.3011 (2) | 0.7375 (5) | 0.0441 (14) | |
H17A | 0.8314 | 0.3265 | 0.7821 | 0.053* | |
C18 | 0.5864 (8) | 0.2770 (2) | 0.5766 (5) | 0.0381 (13) | |
H18A | 0.5304 | 0.2857 | 0.5101 | 0.046* | |
C19 | 0.6887 (6) | 0.31574 (19) | 0.6394 (4) | 0.0252 (10) | |
C20 | 0.7218 (7) | 0.37263 (19) | 0.5994 (4) | 0.0248 (10) | |
N1 | 0.9381 (8) | 0.7474 (3) | 0.9196 (5) | 0.0615 (17) | |
N2 | 0.6451 (7) | 0.2096 (2) | 0.7099 (5) | 0.0486 (14) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Tm1 | 0.01099 (10) | 0.01237 (10) | 0.01469 (10) | −0.00007 (6) | 0.00161 (7) | −0.00139 (6) |
Tm2 | 0.01116 (10) | 0.01405 (10) | 0.01391 (10) | −0.00044 (6) | 0.00196 (7) | −0.00029 (6) |
O1 | 0.0159 (16) | 0.038 (2) | 0.0219 (16) | −0.0004 (14) | 0.0010 (13) | 0.0046 (15) |
O1W | 0.068 (3) | 0.042 (3) | 0.075 (3) | −0.013 (2) | 0.020 (3) | −0.030 (2) |
O2 | 0.0161 (15) | 0.0304 (18) | 0.0172 (15) | 0.0029 (12) | 0.0032 (12) | 0.0065 (13) |
O3 | 0.042 (2) | 0.027 (2) | 0.059 (3) | 0.0000 (17) | −0.0015 (19) | −0.0091 (19) |
O4 | 0.0138 (14) | 0.0223 (17) | 0.0215 (16) | 0.0019 (12) | 0.0029 (12) | 0.0066 (13) |
O5 | 0.0146 (14) | 0.0115 (14) | 0.0145 (14) | 0.0000 (11) | 0.0011 (11) | 0.0006 (11) |
O6 | 0.0170 (14) | 0.0094 (14) | 0.0171 (15) | 0.0014 (10) | 0.0032 (12) | 0.0000 (11) |
O7 | 0.0171 (16) | 0.0253 (18) | 0.0371 (19) | −0.0067 (13) | 0.0101 (14) | −0.0159 (15) |
O8 | 0.0260 (18) | 0.029 (2) | 0.040 (2) | 0.0027 (14) | 0.0076 (15) | 0.0163 (16) |
O9 | 0.044 (2) | 0.0177 (17) | 0.0327 (19) | −0.0050 (15) | 0.0101 (16) | 0.0017 (14) |
O10 | 0.0177 (15) | 0.0207 (17) | 0.0295 (17) | −0.0028 (12) | 0.0077 (13) | −0.0065 (13) |
O11 | 0.0167 (16) | 0.0253 (18) | 0.050 (2) | −0.0033 (13) | 0.0043 (15) | −0.0151 (16) |
C1 | 0.049 (4) | 0.071 (4) | 0.024 (3) | 0.016 (3) | 0.011 (3) | 0.019 (3) |
C2 | 0.054 (4) | 0.071 (5) | 0.038 (3) | 0.018 (3) | 0.028 (3) | 0.033 (3) |
C3 | 0.028 (3) | 0.050 (4) | 0.048 (3) | 0.005 (2) | 0.014 (2) | 0.024 (3) |
C4 | 0.023 (2) | 0.026 (3) | 0.028 (2) | 0.0057 (19) | 0.0071 (19) | 0.011 (2) |
C5 | 0.022 (2) | 0.031 (3) | 0.022 (2) | 0.0074 (18) | 0.0055 (19) | 0.0078 (19) |
C6 | 0.034 (3) | 0.052 (4) | 0.021 (3) | 0.011 (2) | 0.002 (2) | 0.007 (2) |
C7 | 0.016 (2) | 0.023 (3) | 0.034 (3) | −0.0018 (17) | 0.0048 (19) | 0.008 (2) |
C8 | 0.021 (2) | 0.021 (2) | 0.025 (2) | 0.0023 (18) | 0.0050 (18) | 0.0020 (19) |
C9 | 0.051 (4) | 0.070 (5) | 0.057 (4) | −0.010 (4) | 0.000 (3) | −0.035 (4) |
C10 | 0.056 (4) | 0.028 (3) | 0.100 (6) | −0.006 (3) | 0.025 (4) | −0.025 (4) |
C11 | 0.039 (3) | 0.035 (3) | 0.058 (4) | −0.004 (2) | 0.009 (3) | −0.014 (3) |
C12 | 0.036 (3) | 0.049 (4) | 0.044 (3) | −0.003 (3) | 0.003 (3) | −0.018 (3) |
C13 | 0.018 (2) | 0.031 (3) | 0.040 (3) | −0.0063 (19) | 0.011 (2) | −0.018 (2) |
C14 | 0.019 (2) | 0.023 (2) | 0.028 (2) | −0.0069 (18) | 0.0089 (18) | −0.0061 (19) |
C15 | 0.058 (4) | 0.045 (4) | 0.055 (4) | 0.001 (3) | 0.011 (3) | 0.032 (3) |
C16 | 0.043 (3) | 0.029 (3) | 0.071 (5) | −0.006 (2) | 0.007 (3) | 0.004 (3) |
C17 | 0.058 (4) | 0.030 (3) | 0.041 (3) | −0.007 (3) | 0.001 (3) | 0.012 (3) |
C18 | 0.034 (3) | 0.026 (3) | 0.052 (3) | 0.001 (2) | 0.001 (3) | 0.009 (2) |
C19 | 0.023 (2) | 0.016 (2) | 0.037 (3) | 0.0021 (18) | 0.009 (2) | 0.008 (2) |
C20 | 0.032 (3) | 0.019 (2) | 0.028 (2) | 0.0080 (19) | 0.016 (2) | 0.0050 (19) |
N1 | 0.051 (3) | 0.062 (4) | 0.074 (4) | −0.017 (3) | 0.018 (3) | −0.043 (3) |
N2 | 0.039 (3) | 0.028 (3) | 0.082 (4) | 0.004 (2) | 0.019 (3) | 0.023 (3) |
Geometric parameters (Å, º) top
Tm1—O8 | 2.266 (3) | C1—C2 | 1.376 (9) |
Tm1—O7 | 2.311 (3) | C1—C6 | 1.376 (8) |
Tm1—O2 | 2.314 (3) | C1—H1A | 0.9300 |
Tm1—O11i | 2.315 (3) | C2—C3 | 1.379 (8) |
Tm1—O5 | 2.332 (3) | C2—H2A | 0.9300 |
Tm1—O6 | 2.364 (3) | C3—C4 | 1.396 (7) |
Tm1—O5i | 2.366 (3) | C3—H3A | 0.9300 |
Tm1—O4 | 2.439 (3) | C4—C5 | 1.404 (7) |
Tm1—Tm2 | 3.5997 (3) | C4—C7 | 1.503 (7) |
Tm1—Tm2i | 3.8521 (2) | C5—C6 | 1.398 (7) |
Tm1—Tm2ii | 3.8539 (3) | C5—C8 | 1.469 (6) |
Tm1—Tm1i | 3.8731 (4) | C6—H6A | 0.9300 |
Tm2—O5 | 2.303 (3) | C9—N1 | 1.324 (10) |
Tm2—O10 | 2.308 (3) | C9—C12 | 1.366 (8) |
Tm2—O4ii | 2.308 (3) | C9—H9A | 0.9300 |
Tm2—O6ii | 2.315 (3) | C10—N1 | 1.327 (10) |
Tm2—O9 | 2.326 (3) | C10—C11 | 1.397 (9) |
Tm2—O6 | 2.327 (3) | C10—H10A | 0.9300 |
Tm2—O2i | 2.447 (3) | C11—C13 | 1.376 (8) |
Tm2—O1i | 2.482 (3) | C11—H11A | 0.9300 |
Tm2—Tm2ii | 3.7783 (4) | C12—C13 | 1.367 (8) |
O1—C8 | 1.252 (5) | C12—H12A | 0.9300 |
O1W—H1W | 0.9247 | C13—C14 | 1.503 (6) |
O1W—H2W | 0.8735 | C15—N2 | 1.313 (9) |
O2—C8 | 1.295 (5) | C15—C17 | 1.387 (8) |
O3—C7 | 1.217 (6) | C15—H15A | 0.9300 |
O4—C7 | 1.307 (5) | C16—N2 | 1.326 (8) |
O5—H5 | 0.8521 | C16—C18 | 1.384 (8) |
O6—H6 | 0.8652 | C16—H16A | 0.9300 |
O7—H7W | 0.8606 | C17—C19 | 1.370 (7) |
O7—H8W | 0.8638 | C17—H17A | 0.9300 |
O8—C20 | 1.255 (6) | C18—C19 | 1.379 (7) |
O9—C20 | 1.245 (6) | C18—H18A | 0.9300 |
O10—C14 | 1.266 (5) | C19—C20 | 1.513 (6) |
O11—C14 | 1.241 (5) | | |
| | | |
O8—Tm1—O7 | 91.08 (13) | Tm1—O7—H8W | 119.5 |
O8—Tm1—O2 | 141.07 (11) | H7W—O7—H8W | 112.0 |
O7—Tm1—O2 | 107.98 (11) | C2—C1—C6 | 119.5 (5) |
O8—Tm1—O11i | 77.43 (13) | C2—C1—H1A | 120.2 |
O7—Tm1—O11i | 68.76 (11) | C6—C1—H1A | 120.2 |
O2—Tm1—O11i | 78.50 (12) | C1—C2—C3 | 120.9 (5) |
O8—Tm1—O5 | 95.45 (12) | C1—C2—H2A | 119.5 |
O7—Tm1—O5 | 144.43 (10) | C3—C2—H2A | 119.5 |
O2—Tm1—O5 | 88.29 (10) | C2—C3—C4 | 120.4 (5) |
O11i—Tm1—O5 | 146.74 (11) | C2—C3—H3A | 119.8 |
O8—Tm1—O6 | 76.29 (11) | C4—C3—H3A | 119.8 |
O7—Tm1—O6 | 76.28 (10) | C3—C4—C5 | 118.9 (5) |
O2—Tm1—O6 | 140.30 (10) | C3—C4—C7 | 118.5 (5) |
O11i—Tm1—O6 | 135.33 (10) | C5—C4—C7 | 122.6 (4) |
O5—Tm1—O6 | 71.46 (9) | C6—C5—C4 | 119.4 (5) |
O8—Tm1—O5i | 76.26 (11) | C6—C5—C8 | 118.7 (4) |
O7—Tm1—O5i | 146.15 (10) | C4—C5—C8 | 121.9 (4) |
O2—Tm1—O5i | 69.05 (10) | C1—C6—C5 | 120.8 (5) |
O11i—Tm1—O5i | 77.82 (11) | C1—C6—H6A | 119.6 |
O5—Tm1—O5i | 68.94 (11) | C5—C6—H6A | 119.6 |
O6—Tm1—O5i | 128.61 (9) | O3—C7—O4 | 123.8 (5) |
O8—Tm1—O4 | 144.69 (11) | O3—C7—C4 | 119.7 (4) |
O7—Tm1—O4 | 77.75 (11) | O4—C7—C4 | 116.6 (4) |
O2—Tm1—O4 | 73.84 (10) | O1—C8—O2 | 119.2 (4) |
O11i—Tm1—O4 | 126.66 (12) | O1—C8—C5 | 121.7 (4) |
O5—Tm1—O4 | 76.86 (10) | O2—C8—C5 | 119.0 (4) |
O6—Tm1—O4 | 68.55 (10) | N1—C9—C12 | 123.7 (7) |
O5i—Tm1—O4 | 129.35 (10) | N1—C9—H9A | 118.1 |
O5—Tm2—O10 | 86.09 (10) | C12—C9—H9A | 118.1 |
O5—Tm2—O4ii | 154.84 (10) | N1—C10—C11 | 123.2 (7) |
O10—Tm2—O4ii | 89.53 (11) | N1—C10—H10A | 118.4 |
O5—Tm2—O6ii | 83.25 (10) | C11—C10—H10A | 118.4 |
O10—Tm2—O6ii | 76.93 (10) | C13—C11—C10 | 117.9 (6) |
O4ii—Tm2—O6ii | 71.64 (10) | C13—C11—H11A | 121.1 |
O5—Tm2—O9 | 106.22 (11) | C10—C11—H11A | 121.1 |
O10—Tm2—O9 | 141.05 (12) | C9—C12—C13 | 119.1 (6) |
O4ii—Tm2—O9 | 92.65 (12) | C9—C12—H12A | 120.4 |
O6ii—Tm2—O9 | 140.08 (11) | C13—C12—H12A | 120.4 |
O5—Tm2—O6 | 72.64 (10) | C12—C13—C11 | 118.8 (5) |
O10—Tm2—O6 | 143.11 (11) | C12—C13—C14 | 120.2 (5) |
O4ii—Tm2—O6 | 97.13 (10) | C11—C13—C14 | 120.8 (5) |
O6ii—Tm2—O6 | 71.02 (11) | O11—C14—O10 | 126.3 (4) |
O9—Tm2—O6 | 75.09 (11) | O11—C14—C13 | 116.5 (4) |
O5—Tm2—O2i | 67.81 (10) | O10—C14—C13 | 117.2 (4) |
O10—Tm2—O2i | 78.57 (11) | N2—C15—C17 | 123.8 (6) |
O4ii—Tm2—O2i | 135.33 (10) | N2—C15—H15A | 118.1 |
O6ii—Tm2—O2i | 143.03 (10) | C17—C15—H15A | 118.1 |
O9—Tm2—O2i | 72.77 (12) | N2—C16—C18 | 124.3 (6) |
O6—Tm2—O2i | 118.08 (10) | N2—C16—H16A | 117.9 |
O5—Tm2—O1i | 119.44 (10) | C18—C16—H16A | 117.9 |
O10—Tm2—O1i | 72.33 (11) | C19—C17—C15 | 118.7 (6) |
O4ii—Tm2—O1i | 82.42 (10) | C19—C17—H17A | 120.6 |
O6ii—Tm2—O1i | 139.60 (10) | C15—C17—H17A | 120.6 |
O9—Tm2—O1i | 69.45 (12) | C19—C18—C16 | 117.8 (5) |
O6—Tm2—O1i | 144.46 (11) | C19—C18—H18A | 121.1 |
O2i—Tm2—O1i | 52.92 (10) | C16—C18—H18A | 121.1 |
H1W—O1W—H2W | 107.5 | C17—C19—C18 | 118.6 (5) |
Tm2—O5—H5 | 115.8 | C17—C19—C20 | 120.9 (5) |
Tm1—O5—H5 | 112.3 | C18—C19—C20 | 120.5 (5) |
Tm1i—O5—H5 | 104.7 | O9—C20—O8 | 126.3 (4) |
Tm2ii—O6—H6 | 110.0 | O9—C20—C19 | 116.8 (4) |
Tm2—O6—H6 | 118.6 | O8—C20—C19 | 116.9 (4) |
Tm1—O6—H6 | 107.5 | C9—N1—C10 | 117.1 (6) |
Tm1—O7—H7W | 126.8 | C15—N2—C16 | 116.8 (5) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+2, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1W···N1 | 0.92 | 1.94 | 2.822 (7) | 160 |
O5—H5···O3 | 0.85 | 2.42 | 3.172 (5) | 148 |
O6—H6···O1Wiii | 0.87 | 1.99 | 2.830 (5) | 165 |
O7—H7W···N2iv | 0.86 | 1.97 | 2.798 (6) | 161 |
O7—H8W···O10ii | 0.86 | 1.86 | 2.702 (4) | 165 |
Symmetry codes: (ii) −x+2, −y+1, −z+1; (iii) −x+2, y−1/2, −z+3/2; (iv) x, −y+1/2, z−1/2. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | [Er2(C6H4NO2)2(C8H4O4)(OH)2(H2O)]·H2O | [Tm2(C6H4NO2)2(C8H4O4)(OH)2(H2O)]·H2O |
Mr | 812.88 | 816.22 |
Crystal system, space group | Monoclinic, p21/c | Monoclinic, p21/c |
Temperature (K) | 295 | 295 |
a, b, c (Å) | 7.2706 (5), 24.2780 (4), 13.3668 (2) | 7.2434 (2), 24.2180 (6), 13.3606 (4) |
β (°) | 100.708 (4) | 100.700 (3) |
V (Å3) | 2318.36 (17) | 2302.97 (11) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 7.26 | 7.72 |
Crystal size (mm) | 0.45 × 0.10 × 0.09 | 0.35 × 0.09 × 0.07 |
|
Data collection |
Diffractometer | Siemems SMART CCD diffractometer | Siemems SMART CCD diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.399, 0.511 | 0.373, 0.577 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 18413, 4769, 4563 | 18502, 4754, 4602 |
Rint | 0.036 | 0.026 |
(sin θ/λ)max (Å−1) | 0.628 | 0.628 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.029, 0.067, 1.19 | 0.025, 0.060, 1.17 |
No. of reflections | 4769 | 4754 |
No. of parameters | 325 | 325 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.76, −1.41 | 1.11, −1.31 |
Selected bond lengths (Å) for (I) topEr1—O8 | 2.278 (4) | Er2—O5 | 2.315 (3) |
Er1—O2 | 2.325 (3) | Er2—O4ii | 2.318 (3) |
Er1—O7 | 2.326 (3) | Er2—O10 | 2.322 (3) |
Er1—O11i | 2.331 (4) | Er2—O6ii | 2.329 (3) |
Er1—O5 | 2.346 (3) | Er2—O6 | 2.341 (3) |
Er1—O5i | 2.372 (3) | Er2—O9 | 2.342 (4) |
Er1—O6 | 2.373 (3) | Er2—O2i | 2.461 (3) |
Er1—O4 | 2.445 (3) | Er2—O1i | 2.499 (4) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+2, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1W···N1 | 0.93 | 1.95 | 2.834 (8) | 159.8 |
O5—H5···O3 | 0.85 | 2.42 | 3.170 (6) | 147.2 |
O6—H6···O1Wiii | 0.87 | 1.98 | 2.826 (6) | 164.4 |
O7—H7W···N2iv | 0.86 | 1.96 | 2.788 (6) | 160.7 |
O7—H8W···O10ii | 0.87 | 1.87 | 2.716 (5) | 164.6 |
Symmetry codes: (ii) −x+2, −y+1, −z+1; (iii) −x+2, y−1/2, −z+3/2; (iv) x, −y+1/2, z−1/2. |
Selected bond lengths (Å) for (II) topTm1—O8 | 2.266 (3) | Tm2—O5 | 2.303 (3) |
Tm1—O7 | 2.311 (3) | Tm2—O10 | 2.308 (3) |
Tm1—O2 | 2.314 (3) | Tm2—O4ii | 2.308 (3) |
Tm1—O11i | 2.315 (3) | Tm2—O6ii | 2.315 (3) |
Tm1—O5 | 2.332 (3) | Tm2—O9 | 2.326 (3) |
Tm1—O6 | 2.364 (3) | Tm2—O6 | 2.327 (3) |
Tm1—O5i | 2.366 (3) | Tm2—O2i | 2.447 (3) |
Tm1—O4 | 2.439 (3) | Tm2—O1i | 2.482 (3) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+2, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1W···N1 | 0.92 | 1.94 | 2.822 (7) | 159.7 |
O5—H5···O3 | 0.85 | 2.42 | 3.172 (5) | 147.5 |
O6—H6···O1Wiii | 0.87 | 1.99 | 2.830 (5) | 164.5 |
O7—H7W···N2iv | 0.86 | 1.97 | 2.798 (6) | 160.6 |
O7—H8W···O10ii | 0.86 | 1.86 | 2.702 (4) | 164.7 |
Symmetry codes: (ii) −x+2, −y+1, −z+1; (iii) −x+2, y−1/2, −z+3/2; (iv) x, −y+1/2, z−1/2. |
In recent years, the rational design and construction of metal coordination polymers has aroused great interest owing to their intriguing topological architectures and the potential application as functional materials (Meares & Wensel, 1984; Scott & Horrocks, 1992; Reineke et al., 1999; Eddaoudi et al., 2001). In constructing coordination polymers, multifunctional connectors such as a variety of carboxylate ligands are usually utilized as bridging groups, forming one-, two- and three-dimensional networks (Choi & Suh, 1998; MacGillivray et al., 1998; Evans et al., 1999; Chen et al., 2001; Suresh et al., 2001; Kumagai et al., 2002; Lu & Babb, 2003; Song et al., 2003; Zhang et al., 2004). So far, numerous architectures have been assembled from the particular combination of appropriate metal centers and versatile ligands. Our interest in the area is to explore the possible construction of coordination polymers involving two types of different ligands simultaneously in a system, and to understand the cooperativity of both ligands. To the best of our knowledge, this area still remains underdeveloped (Cheng et al., 2006). Selecting the acids HIN and H2BDC as mixed ligands [where IN is the isonicotinate anion (C6H4NO2) and BDC is the benzene-1,2-dicarboxylate anion (C8H4O4)] and adopting the hydrothermal technique, we obtained the title compounds, (I) and (II), which display novel one-dimensional chain-like coordination features.
As shown in Fig. 1, the asymmetric unit contains two unique erbium(III) [or thulium(III)] atoms, two –OH− ions, one BDC and two IN ligands, and one aqua ligand, as well as one uncoordinated water molecule. All the LnIII ions are eight-coordinate, but with markedly different coordination enviroments. Atom Er1 (or Tm1) is surrounded by three –OH groups, two carboxylate O atoms from two IN ligands, two carboxylate O atoms from a BDC ligand and an aqua ligand. Atom Er2 (or Tm2), on the other hand, is coordinated by three –OH groups, two carboxylate O atoms from two IN ligands and three carboxylate O atoms from two BDC ligands. The Er—O and Tm—O distances span the ranges 2.278 (4)–2.499 (4) Å and 2.266 (3)–2.482 (3) Å, respectively.
The LnIII centers are bridged by hydroxido and oxo groups to form an infinite wave-like chain with Er···Er distances in the range 3.622 (3)–3.894 (4) Å [Tm···Tm = 3.599 (7)–3.873 (1) Å]. The BDC and IN ligands, coordinating the metal centers through the carboxylate O atoms, protrude outside of the above chain (Fig. 2). Despite the abundant and versatile coordination modes often found in IN and BDC ligands, only a single bidentate (for IN) and a unique pentadentate bridging (for BDC) modes are adopted in the crystal structures of the title compounds (Fig. 3). This suggests a high cooperativity between the IN and BDC ligands in the formation of (I) and (II). Adjacent chains are further connected into a three-dimensional supramolecular framework through hydrogen bonds and π–π stacking interactions. The former, described in Tables 2 and 4, exhibit O/N···O distances in the ranges 2.716 (5)–3.170 (6) Å for (I) and 2.702 (4)–3.1723 (5) Å for (II); the latter, in turn, lead to interplanar distances between neighbouring IN ligands of 3.546 (1) Å for (I) and 3.540 (2) Å for (II) (Fig. 4).