Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807055043/zl2080sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807055043/zl2080Isup2.hkl |
CCDC reference: 642146
Key indicators
- Single-crystal X-ray study
- T = 296 K
- Mean (C-C) = 0.005 Å
- R factor = 0.022
- wR factor = 0.046
- Data-to-parameter ratio = 14.1
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for Tb1 PLAT369_ALERT_2_C Long C(sp2)-C(sp2) Bond C1 - C1_b ... 1.53 Ang. PLAT369_ALERT_2_C Long C(sp2)-C(sp2) Bond C3 - C3_a ... 1.53 Ang. PLAT417_ALERT_2_C Short Inter D-H..H-D H1W .. H5W .. 2.10 Ang. PLAT417_ALERT_2_C Short Inter D-H..H-D H4W .. H7 .. 2.13 Ang. PLAT480_ALERT_4_C Long H...A H-Bond Reported H5W .. O3 .. 2.63 Ang. PLAT480_ALERT_4_C Long H...A H-Bond Reported H3W .. O5 .. 2.64 Ang. PLAT731_ALERT_1_C Bond Calc 0.82(3), Rep 0.825(10) ...... 3.00 su-Ra O2W -H3W 1.555 1.555 PLAT735_ALERT_1_C D-H Calc 0.82(3), Rep 0.825(10) ...... 3.00 su-Ra O2W -H3W 1.555 1.555 PLAT735_ALERT_1_C D-H Calc 0.82(3), Rep 0.825(10) ...... 3.00 su-Ra O2W -H3W 1.555 1.555 PLAT736_ALERT_1_C H...A Calc 1.88(3), Rep 1.876(11) ...... 2.73 su-Ra H2W -O2 1.555 4.565 PLAT736_ALERT_1_C H...A Calc 2.10(3), Rep 2.102(13) ...... 2.31 su-Ra H3W -O6 1.555 4.556 PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) . 1.16 Ratio
Alert level G PLAT794_ALERT_5_G Check Predicted Bond Valency for Tb1 (3) 3.31 PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 9
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 13 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 5 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 5 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 3 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
For related literature, see: Brandenburg & Putz, (2006); Moulton & Zaworotko (2001); Zeng et al., (2007).
A mixture of Tb4O7 (0.189 g; 0.25 mmol), oxalic acid (0.135 g; 1.5 mmol), water and methanol (3 ml: 7 mL mixture) and HClO4 (0.385 mmol) was stirred vigorously for 20 min and then sealed in a Teflon-lined stainless-steel autoclave (20 ml, capacity). The autoclave was heated to and maintained at 433 K for 7 days, and then cooled to room temperature at 5 K h-1 to obtain the crystals.
Water H atoms were tentatively located in difference Fourier maps and were refined with distance restraints of O–H = 0.82 Å and H···H = 1.29 Å, each within a standard deviation of 0.01 Å; with Uiso(H) = 1.5 Ueq(O,). H atoms on the methanol molecule were placed at calculated positions and were treated as riding on the parent C atoms with C—H = 0.96 Å, and O—H = 0.82 Å, with Uiso(H) = 1.5 Ueq(O,C).
Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2004); Diamond (Brandenburg & Putz, 2006); software used to prepare material for publication: SHELXTL (Bruker, 2004).
[Tb(C2O4)1.5(H2O)3]·CH4O | F(000) = 716 |
Mr = 377.04 | Dx = 2.609 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -p 2ybc | Cell parameters from 2200 reflections |
a = 10.8284 (2) Å | θ = 2.1–27.5° |
b = 9.8002 (2) Å | µ = 7.41 mm−1 |
c = 9.8846 (1) Å | T = 296 K |
β = 113.774 (1)° | Blocky, colorless |
V = 959.95 (3) Å3 | 0.21 × 0.18 × 0.16 mm |
Z = 4 |
Bruker APEX-II area-detector diffractometer | 2196 independent reflections |
Radiation source: fine-focus sealed tube | 1901 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.030 |
ϕ and ω scan | θmax = 27.5°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −13→14 |
Tmin = 0.231, Tmax = 0.308 | k = −12→10 |
9378 measured reflections | l = −12→12 |
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)] = 0.022 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.046 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0203P)2 + 0.2004P] where P = (Fo2 + 2Fc2)/3 |
2196 reflections | (Δ/σ)max < 0.001 |
156 parameters | Δρmax = 0.60 e Å−3 |
9 restraints | Δρmin = −0.81 e Å−3 |
[Tb(C2O4)1.5(H2O)3]·CH4O | V = 959.95 (3) Å3 |
Mr = 377.04 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.8284 (2) Å | µ = 7.41 mm−1 |
b = 9.8002 (2) Å | T = 296 K |
c = 9.8846 (1) Å | 0.21 × 0.18 × 0.16 mm |
β = 113.774 (1)° |
Bruker APEX-II area-detector diffractometer | 2196 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1901 reflections with I > 2σ(I) |
Tmin = 0.231, Tmax = 0.308 | Rint = 0.030 |
9378 measured reflections |
R[F2 > 2σ(F2)] = 0.022 | 9 restraints |
wR(F2) = 0.046 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | Δρmax = 0.60 e Å−3 |
2196 reflections | Δρmin = −0.81 e Å−3 |
156 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. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.0535 (4) | 0.0300 (4) | 0.5707 (4) | 0.0192 (8) | |
C2 | 0.4991 (4) | 0.0507 (3) | 0.5581 (4) | 0.0164 (8) | |
C3 | 0.0337 (4) | −0.0697 (4) | 0.0043 (4) | 0.0175 (8) | |
C4 | 0.4073 (6) | 0.5977 (6) | 0.3276 (6) | 0.0630 (16) | |
H4A | 0.4698 | 0.6234 | 0.4249 | 0.094* | |
H4B | 0.4240 | 0.5050 | 0.3085 | 0.094* | |
H4C | 0.3167 | 0.6058 | 0.3211 | 0.094* | |
O1 | 0.1573 (3) | 0.0771 (3) | 0.5630 (3) | 0.0253 (6) | |
O2 | 0.0265 (3) | 0.0275 (3) | 0.6839 (3) | 0.0234 (6) | |
O3 | 0.3887 (2) | 0.1093 (3) | 0.5326 (3) | 0.0235 (6) | |
O4 | 0.6077 (3) | 0.0669 (3) | 0.6689 (3) | 0.0219 (6) | |
O5 | 0.1274 (3) | −0.1003 (3) | 0.1245 (3) | 0.0247 (6) | |
O6 | −0.0103 (2) | −0.1420 (3) | −0.1111 (2) | 0.0227 (6) | |
H5W | 0.270 (3) | 0.2601 (15) | 0.180 (4) | 0.034* | |
H2W | 0.131 (4) | 0.345 (2) | 0.325 (3) | 0.034* | |
H1W | 0.200 (4) | 0.307 (3) | 0.4602 (15) | 0.034* | |
H3W | 0.150 (2) | −0.219 (4) | 0.438 (4) | 0.034* | |
H6W | 0.3747 (11) | 0.182 (3) | 0.223 (4) | 0.034* | |
H4W | 0.270 (2) | −0.184 (4) | 0.5270 (19) | 0.034* | |
O7 | 0.4246 (3) | 0.6869 (3) | 0.2191 (3) | 0.0414 (8) | |
H7 | 0.4062 | 0.7655 | 0.2326 | 0.062* | |
O1W | 0.1664 (3) | 0.2778 (3) | 0.3756 (3) | 0.0340 (7) | |
O2W | 0.2145 (3) | −0.1722 (3) | 0.4416 (3) | 0.0316 (7) | |
O3W | 0.2913 (3) | 0.1790 (3) | 0.1933 (3) | 0.0282 (7) | |
Tb1 | 0.189510 (16) | 0.046207 (17) | 0.329650 (15) | 0.01138 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.019 (2) | 0.016 (2) | 0.0237 (18) | −0.0033 (17) | 0.0098 (17) | −0.0037 (15) |
C2 | 0.014 (2) | 0.015 (2) | 0.0195 (17) | 0.0010 (17) | 0.0060 (15) | 0.0049 (14) |
C3 | 0.014 (2) | 0.020 (2) | 0.0195 (17) | 0.0011 (17) | 0.0078 (15) | 0.0015 (15) |
C4 | 0.083 (5) | 0.055 (4) | 0.056 (3) | −0.004 (3) | 0.033 (3) | −0.012 (3) |
O1 | 0.0203 (16) | 0.0317 (17) | 0.0262 (13) | −0.0102 (13) | 0.0117 (12) | −0.0084 (12) |
O2 | 0.0227 (16) | 0.0303 (18) | 0.0177 (12) | −0.0068 (13) | 0.0087 (12) | −0.0037 (11) |
O3 | 0.0173 (15) | 0.0262 (16) | 0.0238 (12) | 0.0025 (13) | 0.0051 (11) | −0.0064 (12) |
O4 | 0.0143 (14) | 0.0256 (17) | 0.0209 (12) | 0.0038 (12) | 0.0021 (11) | −0.0023 (11) |
O5 | 0.0224 (16) | 0.0263 (16) | 0.0178 (12) | 0.0075 (13) | 0.0004 (11) | −0.0007 (11) |
O6 | 0.0264 (16) | 0.0205 (15) | 0.0180 (12) | −0.0005 (13) | 0.0056 (11) | −0.0048 (11) |
O7 | 0.044 (2) | 0.037 (2) | 0.0373 (16) | 0.0060 (17) | 0.0095 (15) | −0.0110 (15) |
O1W | 0.049 (2) | 0.0232 (17) | 0.0186 (12) | 0.0133 (15) | 0.0021 (13) | 0.0009 (12) |
O2W | 0.0266 (17) | 0.035 (2) | 0.0298 (14) | −0.0039 (15) | 0.0079 (13) | 0.0091 (13) |
O3W | 0.0255 (16) | 0.0258 (17) | 0.0341 (15) | 0.0032 (13) | 0.0129 (14) | 0.0088 (13) |
Tb1 | 0.00966 (10) | 0.01277 (11) | 0.01034 (8) | −0.00022 (8) | 0.00259 (7) | −0.00001 (6) |
C1—O1 | 1.246 (4) | O4—Tb1ii | 2.455 (3) |
C1—O2 | 1.266 (4) | O5—Tb1 | 2.351 (2) |
C1—C1i | 1.529 (7) | O6—Tb1iii | 2.436 (2) |
C2—O4 | 1.252 (4) | O7—H7 | 0.8200 |
C2—O3 | 1.257 (4) | O1W—Tb1 | 2.348 (3) |
C2—C2ii | 1.526 (7) | O1W—H2W | 0.821 (10) |
C3—O5 | 1.249 (4) | O1W—H1W | 0.818 (10) |
C3—O6 | 1.262 (4) | O2W—Tb1 | 2.374 (3) |
C3—C3iii | 1.535 (7) | O2W—H3W | 0.825 (10) |
C4—O7 | 1.453 (6) | O2W—H4W | 0.825 (10) |
C4—H4A | 0.9600 | O3W—Tb1 | 2.434 (3) |
C4—H4B | 0.9600 | O3W—H5W | 0.824 (10) |
C4—H4C | 0.9600 | O3W—H6W | 0.830 (10) |
O1—Tb1 | 2.486 (2) | Tb1—O2i | 2.400 (3) |
O2—Tb1i | 2.400 (3) | Tb1—O6iii | 2.436 (2) |
O3—Tb1 | 2.360 (2) | Tb1—O4ii | 2.455 (3) |
O1—C1—O2 | 126.7 (3) | O1W—Tb1—O2W | 141.49 (10) |
O1—C1—C1i | 117.2 (4) | O5—Tb1—O2W | 77.91 (9) |
O2—C1—C1i | 116.1 (4) | O3—Tb1—O2W | 86.94 (10) |
O4—C2—O3 | 126.8 (3) | O1W—Tb1—O2i | 97.15 (10) |
O4—C2—C2ii | 116.6 (4) | O5—Tb1—O2i | 80.49 (9) |
O3—C2—C2ii | 116.5 (4) | O3—Tb1—O2i | 131.49 (8) |
O5—C3—O6 | 126.2 (3) | O2W—Tb1—O2i | 71.34 (9) |
O5—C3—C3iii | 116.9 (4) | O1W—Tb1—O3W | 72.39 (10) |
O6—C3—C3iii | 116.8 (4) | O5—Tb1—O3W | 83.37 (9) |
O7—C4—H4A | 109.5 | O3—Tb1—O3W | 82.42 (9) |
O7—C4—H4B | 109.5 | O2W—Tb1—O3W | 138.43 (10) |
H4A—C4—H4B | 109.5 | O2i—Tb1—O3W | 141.16 (9) |
O7—C4—H4C | 109.5 | O1W—Tb1—O6iii | 71.95 (8) |
H4A—C4—H4C | 109.5 | O5—Tb1—O6iii | 67.79 (8) |
H4B—C4—H4C | 109.5 | O3—Tb1—O6iii | 141.38 (9) |
C1—O1—Tb1 | 118.6 (2) | O2W—Tb1—O6iii | 131.37 (9) |
C1—O2—Tb1i | 121.6 (2) | O2i—Tb1—O6iii | 69.88 (8) |
C2—O3—Tb1 | 121.4 (2) | O3W—Tb1—O6iii | 71.32 (9) |
C2—O4—Tb1ii | 118.0 (2) | O1W—Tb1—O4ii | 126.88 (10) |
C3—O5—Tb1 | 120.9 (2) | O5—Tb1—O4ii | 70.92 (8) |
C3—O6—Tb1iii | 117.4 (2) | O3—Tb1—O4ii | 66.71 (8) |
C4—O7—H7 | 109.5 | O2W—Tb1—O4ii | 69.91 (9) |
Tb1—O1W—H2W | 136 (2) | O2i—Tb1—O4ii | 135.56 (9) |
Tb1—O1W—H1W | 120 (2) | O3W—Tb1—O4ii | 68.96 (9) |
H2W—O1W—H1W | 104.0 (16) | O6iii—Tb1—O4ii | 124.77 (8) |
Tb1—O2W—H3W | 123 (3) | O1W—Tb1—O1 | 68.74 (9) |
Tb1—O2W—H4W | 120 (3) | O5—Tb1—O1 | 140.93 (9) |
H3W—O2W—H4W | 103.0 (16) | O3—Tb1—O1 | 66.50 (8) |
Tb1—O3W—H5W | 116 (3) | O2W—Tb1—O1 | 73.13 (9) |
Tb1—O3W—H6W | 120 (3) | O2i—Tb1—O1 | 65.82 (8) |
H5W—O3W—H6W | 102.2 (16) | O3W—Tb1—O1 | 135.47 (9) |
O1W—Tb1—O5 | 137.87 (9) | O6iii—Tb1—O1 | 114.59 (8) |
O1W—Tb1—O3 | 73.41 (10) | O4ii—Tb1—O1 | 120.61 (8) |
O5—Tb1—O3 | 137.62 (9) |
Symmetry codes: (i) −x, −y, −z+1; (ii) −x+1, −y, −z+1; (iii) −x, −y, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O3W—H5W···O1iv | 0.82 (1) | 2.06 (2) | 2.823 (4) | 155 (4) |
O3W—H5W···O3iv | 0.82 (1) | 2.63 (3) | 3.048 (4) | 113 (3) |
O1W—H2W···O2iv | 0.82 (1) | 1.88 (1) | 2.685 (4) | 168 (4) |
O2W—H3W···O6v | 0.83 (1) | 2.10 (1) | 2.913 (4) | 168 (4) |
O2W—H3W···O5v | 0.83 (1) | 2.64 (3) | 3.240 (4) | 131 (3) |
O3W—H6W···O7vi | 0.83 (1) | 2.01 (1) | 2.841 (4) | 176 (4) |
O2W—H4W···O7vii | 0.83 (1) | 1.96 (1) | 2.774 (4) | 168 (3) |
O1W—H1W···O3Wvii | 0.82 (1) | 2.11 (1) | 2.906 (4) | 163 (3) |
O7—H7···O4viii | 0.82 | 1.95 | 2.735 (4) | 161 |
Symmetry codes: (iv) x, −y+1/2, z−1/2; (v) x, −y−1/2, z+1/2; (vi) −x+1, y−1/2, −z+1/2; (vii) x, −y+1/2, z+1/2; (viii) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Tb(C2O4)1.5(H2O)3]·CH4O |
Mr | 377.04 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 296 |
a, b, c (Å) | 10.8284 (2), 9.8002 (2), 9.8846 (1) |
β (°) | 113.774 (1) |
V (Å3) | 959.95 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 7.41 |
Crystal size (mm) | 0.21 × 0.18 × 0.16 |
Data collection | |
Diffractometer | Bruker APEX-II area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.231, 0.308 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9378, 2196, 1901 |
Rint | 0.030 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.022, 0.046, 1.06 |
No. of reflections | 2196 |
No. of parameters | 156 |
No. of restraints | 9 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.60, −0.81 |
Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2004); Diamond (Brandenburg & Putz, 2006), SHELXTL (Bruker, 2004).
D—H···A | D—H | H···A | D···A | D—H···A |
O3W—H5W···O1i | 0.824 (10) | 2.056 (18) | 2.823 (4) | 155 (4) |
O3W—H5W···O3i | 0.824 (10) | 2.63 (3) | 3.048 (4) | 113 (3) |
O1W—H2W···O2i | 0.821 (10) | 1.876 (11) | 2.685 (4) | 168 (4) |
O2W—H3W···O6ii | 0.825 (10) | 2.102 (13) | 2.913 (4) | 168 (4) |
O2W—H3W···O5ii | 0.825 (10) | 2.64 (3) | 3.240 (4) | 131 (3) |
O3W—H6W···O7iii | 0.830 (10) | 2.011 (11) | 2.841 (4) | 176 (4) |
O2W—H4W···O7iv | 0.825 (10) | 1.960 (11) | 2.774 (4) | 168 (3) |
O1W—H1W···O3Wiv | 0.818 (10) | 2.114 (12) | 2.906 (4) | 163 (3) |
O7—H7···O4v | 0.82 | 1.95 | 2.735 (4) | 161.3 |
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) x, −y−1/2, z+1/2; (iii) −x+1, y−1/2, −z+1/2; (iv) x, −y+1/2, z+1/2; (v) −x+1, −y+1, −z+1. |
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Molecular self-assembly of supramolecular architectures has received much attention during recent decades (Zeng et al., 2007; Moulton & Zaworotko, 2001). The structures and properties of such systems depend on the coordination and geometric preferences of both the central metal ions and the bridging building blocks, as well as the influence of weaker non-covalent interactions, such as hydrogen bonds and π-π stacking interactions. Recently, we obtained the title coordination polymer, which was synthesized under hydrothermal conditions.
As illustrated in Fig. 1, in the structure of the title compound each TbIII centre is in a tri-capped-trigonal prismatic geometry, defined by six carboxyl O atoms from three oxalate ligands and three water molecules. The oxalate ligands link the TbIII ions to form a smooth layer perpendicular to the c axis in which the shortest Tb···Tb separation is 6.210 (3) Å. These layers are connected through O—H···O hydrogen bonding (Table 1) involving the coordinating water and the methanol molecules as donors and acceptors, forming a three-dimensional supramolecular network (Fig. 2). The individual layers formed by the oxalate and metal ions form a motif which, via topological analysis, can be described as a 3-connected (63) sheet (Fig. 3).