Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680702884X/ym2055sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680702884X/ym2055Isup2.hkl |
CCDC reference: 657621
Key indicators
- Single-crystal X-ray study
- T = 296 K
- Mean (C-C) = 0.004 Å
- R factor = 0.032
- wR factor = 0.081
- Data-to-parameter ratio = 18.1
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.98 PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT417_ALERT_2_C Short Inter D-H..H-D H11W .. H14W .. 2.11 Ang. PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) . 1.15 Ratio
Alert level G REFLT03_ALERT_1_G ALERT: Expected hkl max differ from CIF values From the CIF: _diffrn_reflns_theta_max 30.03 From the CIF: _reflns_number_total 6163 From the CIF: _diffrn_reflns_limit_ max hkl 15. 22. 15. From the CIF: _diffrn_reflns_limit_ min hkl -15. -22. -15. TEST1: Expected hkl limits for theta max Calculated maximum hkl 15. 24. 16. Calculated minimum hkl -15. -24. -16. PLAT794_ALERT_5_G Check Predicted Bond Valency for Sm1 (3) 3.40 PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 21
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 4 ALERT level C = Check and explain 3 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
For related literature, see: van Albada et al. (1999); Benelli & Gatteschi (2002); Brouca-Cabarrecq et al. (2002); Duan et al. (2004); Ghosh & Bharadwaj (2003).
The title compound was hydrothermally synthesized at 150°C for 72 h in a 40 ml Teflon-lined steel autoclave under autogenous pressure. The starting solution was prepared by mixing Na2MoO4.2H2O, Sm2O3, NaCl, pyridine-2,6-dicarboxylic acid, and deionized water with a molar ratio of 2:1:2:1:555 (total volume, 15 ml), and its pH value was adjusted to 3.05 by hydrochloric acid. After the hydrothermal reaction, the autoclave was slowly cooled to room temperature, and colorless crystals were produced.
The H atoms bonded to a C atom were positioned geometrically after each cycle in idealized locations and refined as riding on their parent C atoms with C—H = 0.93 Å and Uiso(H) = 1.2Uiso(C atom). All the hydrogen atoms bonded to an O atom of water molecules were located in a difference Fourier map, and isotropically refined with distance restraints of O—H = 0.85 Å and H—H = 0.93 Å, and with Uiso(H) = 1.5Uiso(O atom). The maximum and minimum electron-density peaks are located at 1.23 and 0.82 Å, respectively, from Sm1.
The use of rare earth elements for constructing metal-organic frameworks (MOFs) has been attracted much attention due to their variety of magnetic and optical properties (Benelli & Gatteschi, 2002). Since rare earth ions have a large radius and much affinity for oxygen atoms of ligands, pyridine-2,6-dicarboxylic acid (H2dipic) is widely studied for constructing MOFs containing rare earth elements (Brouca-Cabarrecq et al., 2002;. Duan et al., 2004; Ghosh & Bharadwaj, 2003). Hydrogen-bonding involving water molecules plays an important role in self-assembly processes for building MOF architectures. The structure of the title compound has already been reported (van Albada et al., 1999), but the role of water molecules was not fully understood. We here report the X-ray crystal structure analysis of the compound, and demonstrate a unique hydogen-bonding cluster of water molecules located in interlayer spaces.
A samarium(III) ion is coordinated by two dipic molecules and three water molecules, forming ninefolded coordination environment with four carboxylic oxygen atoms, two dipic nitrogen atoms, and three oxygen atoms of water molecules (Fig.1). All the bond distances for Sm—O and Na—O are comparable to those reported previously (van Albada et al., 1999). The asymmetric unit involves seven water molecules, which are classified into two groups; one is the molecules coordinating metal ions (O1W, O2W, O3W, and O5W) and the other the molecules isolated as a water of crystallization (O4W, O6W, and O7W) with relatively large thermal vibration ellipsoids. The structure can be described as a layered structure, which consists of metallic coordination polymer layers, separated by an interlamellar region populated by water molecules of crystallization. In the layer block, chains are constructed by the ninefolded samarium polyhedra and the sodium octahedra with edge-sharing fashion, running along the direction parallel to the c axis. Each chain is bridged by carboxylate groups of the embedded dipic molecules to adjacent chains, thus forming a two-dimensional network. The interlayer water molecules form unique octamer clusters by hydrogen-bonding, giving eight-membered rings (Fig.2). The atoms O4W, O5W, O6W, and O7W are related to those of the symmetrically equivalent opposite side by the center of symmetry. The rings are tightly fixed to the two-dimensional sheets at the atoms of O5W coordinationg to Na1. In the ring, O4W behaves as hydrogen acceptors while O5W behaves as hydrogen donors, in the hydrogen-bonding scheme. Both the atoms show tetracoordination. On the other hand, the atoms O6W and O7W behave both as hydogen donors and acceptors with tricoordination. The average O···O distance in the ring is 2.796 Å, somewhat longer than that of ice (2.76 Å). The two-dimensional structure of the compound is largely a consequence of hydrogen-bonding interactions among water molecules themselves and the MOF.
For related literature, see: van Albada et al. (1999); Benelli & Gatteschi (2002); Brouca-Cabarrecq et al. (2002); Duan et al. (2004); Ghosh & Bharadwaj (2003).
Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
[NaSm(C7H3NO4)2(H2O)4]·3H2O | F(000) = 1244 |
Mr = 629.66 | Dx = 1.9 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.7107 Å |
Hall symbol: -P 2ybc | Cell parameters from 19188 reflections |
a = 11.2065 (4) Å | θ = 2.2–30.0° |
b = 17.4485 (3) Å | µ = 2.77 mm−1 |
c = 11.3728 (4) Å | T = 296 K |
β = 98.163 (1)° | Plate, colourless |
V = 2201.27 (12) Å3 | 0.30 × 0.18 × 0.04 mm |
Z = 4 |
Rigaku R-AXIS-IV diffractometer | 5944 reflections with I > 2σ(I) |
Detector resolution: 10.00 pixels mm-1 | Rint = 0.046 |
ω scans | θmax = 30.0°, θmin = 1.8° |
Absorption correction: numerical (ABSCOR; Higashi, 1999) | h = −15→15 |
Tmin = 0.558, Tmax = 0.895 | k = −22→22 |
22103 measured reflections | l = −15→15 |
6163 independent reflections |
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)] = 0.032 | H-atom parameters constrained |
wR(F2) = 0.081 | w = 1/[σ2(Fo2) + (0.0403P)2 + 2.6934P] where P = (Fo2 + 2Fc2)/3 |
S = 1.17 | (Δ/σ)max < 0.001 |
6163 reflections | Δρmax = 0.97 e Å−3 |
341 parameters | Δρmin = −1.28 e Å−3 |
21 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.00064 (16) |
[NaSm(C7H3NO4)2(H2O)4]·3H2O | V = 2201.27 (12) Å3 |
Mr = 629.66 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 11.2065 (4) Å | µ = 2.77 mm−1 |
b = 17.4485 (3) Å | T = 296 K |
c = 11.3728 (4) Å | 0.30 × 0.18 × 0.04 mm |
β = 98.163 (1)° |
Rigaku R-AXIS-IV diffractometer | 6163 independent reflections |
Absorption correction: numerical (ABSCOR; Higashi, 1999) | 5944 reflections with I > 2σ(I) |
Tmin = 0.558, Tmax = 0.895 | Rint = 0.046 |
22103 measured reflections |
R[F2 > 2σ(F2)] = 0.032 | 21 restraints |
wR(F2) = 0.081 | H-atom parameters constrained |
S = 1.17 | Δρmax = 0.97 e Å−3 |
6163 reflections | Δρmin = −1.28 e Å−3 |
341 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 | ||
Sm1 | 0.102796 (11) | 0.181254 (7) | 0.774431 (10) | 0.01333 (6) | |
Na1 | 0.08028 (12) | 0.37858 (7) | 0.61494 (11) | 0.0256 (2) | |
N11 | 0.3268 (2) | 0.15540 (13) | 0.78946 (18) | 0.0169 (4) | |
O11 | 0.3317 (2) | 0.14824 (14) | 0.48054 (17) | 0.0274 (5) | |
O12 | 0.18328 (19) | 0.16788 (12) | 0.58886 (17) | 0.0198 (4) | |
O13 | 0.3800 (2) | 0.17141 (15) | 1.10109 (19) | 0.0303 (5) | |
O14 | 0.21058 (18) | 0.16585 (13) | 0.97242 (17) | 0.0210 (4) | |
C11 | 0.2934 (3) | 0.15591 (16) | 0.5767 (2) | 0.0185 (5) | |
C12 | 0.3796 (2) | 0.15293 (17) | 0.6910 (2) | 0.0197 (5) | |
C13 | 0.5037 (3) | 0.1523 (2) | 0.6958 (3) | 0.0342 (7) | |
H13 | 0.5387 | 0.1488 | 0.6267 | 0.041* | |
C14 | 0.5747 (3) | 0.1570 (3) | 0.8057 (3) | 0.0437 (9) | |
H14 | 0.6583 | 0.1569 | 0.8112 | 0.052* | |
C15 | 0.5201 (3) | 0.1618 (3) | 0.9069 (3) | 0.0360 (8) | |
H15 | 0.5661 | 0.1665 | 0.9813 | 0.043* | |
C16 | 0.3956 (3) | 0.15934 (18) | 0.8955 (2) | 0.0210 (5) | |
C17 | 0.3240 (3) | 0.16562 (17) | 0.9990 (2) | 0.0196 (5) | |
N21 | −0.0648 (2) | 0.11795 (13) | 0.63391 (19) | 0.0173 (4) | |
O21 | −0.03307 (18) | 0.26630 (11) | 0.64738 (17) | 0.0212 (4) | |
O22 | −0.2002 (2) | 0.28990 (13) | 0.5209 (2) | 0.0285 (5) | |
O23 | 0.10578 (18) | 0.04169 (13) | 0.76633 (17) | 0.0238 (4) | |
O24 | 0.0160 (2) | −0.07055 (12) | 0.7216 (2) | 0.0291 (5) | |
C21 | −0.1269 (2) | 0.24589 (16) | 0.5790 (2) | 0.0188 (5) | |
C22 | −0.1463 (2) | 0.16042 (17) | 0.5652 (2) | 0.0187 (5) | |
C23 | −0.2356 (3) | 0.12771 (19) | 0.4838 (3) | 0.0280 (6) | |
H23 | −0.2919 | 0.1581 | 0.4373 | 0.034* | |
C24 | −0.2390 (3) | 0.0490 (2) | 0.4735 (3) | 0.0345 (7) | |
H24 | −0.2972 | 0.0256 | 0.4187 | 0.041* | |
C25 | −0.1552 (3) | 0.00475 (18) | 0.5450 (3) | 0.0280 (6) | |
H25 | −0.1564 | −0.0484 | 0.5395 | 0.034* | |
C26 | −0.0693 (2) | 0.04196 (16) | 0.6252 (2) | 0.0190 (5) | |
C27 | 0.0243 (3) | −0.00019 (15) | 0.7095 (2) | 0.0195 (5) | |
O1W | −0.0451 (2) | 0.12687 (13) | 0.9033 (2) | 0.0277 (4) | |
H1W | −0.094 | 0.1591 | 0.927 | 0.042* | |
H2W | −0.084 | 0.0863 | 0.880 | 0.042* | |
O2W | 0.21951 (19) | 0.30604 (12) | 0.75680 (18) | 0.0214 (4) | |
H3W | 0.248 | 0.326 | 0.8231 | 0.032* | |
H4W | 0.272 | 0.308 | 0.710 | 0.032* | |
O3W | 0.03015 (19) | 0.28534 (12) | 0.89442 (16) | 0.0199 (4) | |
H5W | 0.006 | 0.3247 | 0.854 | 0.03* | |
H6W | 0.083 | 0.2981 | 0.952 | 0.03* | |
O4W | 0.2530 (3) | −0.05242 (17) | 0.9220 (2) | 0.0394 (6) | |
H7W | 0.231 | −0.0993 | 0.924 | 0.059* | |
H8W | 0.205 | −0.029 | 0.868 | 0.059* | |
O5W | 0.1904 (2) | 0.49655 (15) | 0.6342 (2) | 0.0356 (5) | |
H9W | 0.220 | 0.506 | 0.571 | 0.053* | |
H10W | 0.247 | 0.492 | 0.692 | 0.053* | |
O6W | 0.5694 (4) | 0.4115 (4) | 0.7266 (4) | 0.110 (2) | |
H11W | 0.517 | 0.387 | 0.680 | 0.165* | |
H12W | 0.619 | 0.432 | 0.686 | 0.165* | |
O7W | 0.3811 (4) | 0.4793 (2) | 0.8188 (3) | 0.0625 (9) | |
H13W | 0.390 | 0.450 | 0.879 | 0.094* | |
H14W | 0.438 | 0.471 | 0.778 | 0.094* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Sm1 | 0.01602 (8) | 0.01226 (9) | 0.01101 (7) | −0.00069 (4) | −0.00049 (5) | 0.00020 (3) |
Na1 | 0.0319 (6) | 0.0210 (6) | 0.0238 (6) | −0.0002 (5) | 0.0037 (5) | 0.0002 (4) |
N11 | 0.0193 (10) | 0.0185 (11) | 0.0118 (9) | 0.0019 (8) | −0.0016 (7) | 0.0002 (7) |
O11 | 0.0312 (11) | 0.0386 (13) | 0.0126 (8) | 0.0042 (9) | 0.0038 (8) | −0.0025 (8) |
O12 | 0.0197 (9) | 0.0253 (10) | 0.0138 (8) | −0.0002 (7) | 0.0004 (7) | −0.0016 (7) |
O13 | 0.0259 (11) | 0.0509 (15) | 0.0127 (9) | 0.0062 (9) | −0.0026 (8) | −0.0020 (8) |
O14 | 0.0193 (9) | 0.0286 (10) | 0.0147 (8) | 0.0002 (8) | 0.0015 (7) | 0.0014 (7) |
C11 | 0.0245 (13) | 0.0156 (13) | 0.0146 (11) | 0.0025 (9) | −0.0002 (9) | −0.0010 (8) |
C12 | 0.0210 (12) | 0.0242 (14) | 0.0140 (10) | 0.0012 (10) | 0.0031 (9) | −0.0004 (9) |
C13 | 0.0211 (14) | 0.060 (2) | 0.0218 (14) | 0.0070 (14) | 0.0054 (11) | 0.0024 (14) |
C14 | 0.0154 (14) | 0.088 (3) | 0.0279 (16) | 0.0085 (16) | 0.0023 (12) | −0.0003 (18) |
C15 | 0.0208 (14) | 0.065 (2) | 0.0206 (14) | 0.0042 (14) | −0.0029 (11) | −0.0033 (14) |
C16 | 0.0209 (12) | 0.0282 (14) | 0.0129 (11) | 0.0044 (10) | −0.0010 (9) | 0.0009 (9) |
C17 | 0.0236 (13) | 0.0201 (13) | 0.0143 (11) | 0.0043 (10) | 0.0000 (9) | 0.0007 (9) |
N21 | 0.0206 (10) | 0.0140 (11) | 0.0166 (9) | −0.0019 (8) | 0.0002 (8) | 0.0002 (7) |
O21 | 0.0221 (10) | 0.0172 (10) | 0.0221 (9) | −0.0009 (7) | −0.0038 (7) | 0.0009 (7) |
O22 | 0.0259 (11) | 0.0232 (12) | 0.0339 (11) | 0.0036 (8) | −0.0048 (9) | 0.0076 (8) |
O23 | 0.0278 (11) | 0.0148 (11) | 0.0264 (10) | 0.0013 (7) | −0.0044 (8) | −0.0002 (7) |
O24 | 0.0401 (13) | 0.0142 (10) | 0.0322 (11) | −0.0027 (8) | 0.0026 (9) | 0.0016 (7) |
C21 | 0.0206 (12) | 0.0170 (13) | 0.0179 (11) | 0.0002 (9) | −0.0003 (9) | 0.0017 (8) |
C22 | 0.0191 (12) | 0.0182 (13) | 0.0175 (11) | −0.0025 (9) | −0.0020 (9) | 0.0026 (9) |
C23 | 0.0269 (14) | 0.0286 (16) | 0.0249 (13) | −0.0031 (11) | −0.0082 (11) | 0.0030 (11) |
C24 | 0.0350 (17) | 0.0297 (18) | 0.0338 (16) | −0.0102 (13) | −0.0128 (13) | −0.0042 (12) |
C25 | 0.0348 (16) | 0.0182 (15) | 0.0287 (14) | −0.0070 (11) | −0.0030 (12) | −0.0040 (10) |
C26 | 0.0233 (12) | 0.0159 (12) | 0.0171 (11) | −0.0041 (9) | 0.0008 (9) | −0.0017 (8) |
C27 | 0.0283 (13) | 0.0134 (12) | 0.0174 (11) | 0.0006 (9) | 0.0051 (9) | 0.0007 (8) |
O1W | 0.0303 (11) | 0.0241 (11) | 0.0311 (11) | −0.0060 (8) | 0.0124 (9) | −0.0066 (8) |
O2W | 0.0251 (10) | 0.0217 (10) | 0.0175 (9) | −0.0034 (8) | 0.0031 (7) | −0.0020 (7) |
O3W | 0.0260 (10) | 0.0184 (10) | 0.0144 (8) | 0.0001 (7) | −0.0004 (7) | −0.0009 (6) |
O4W | 0.0395 (14) | 0.0407 (16) | 0.0358 (13) | 0.0055 (11) | −0.0021 (10) | 0.0070 (11) |
O5W | 0.0414 (14) | 0.0278 (13) | 0.0396 (13) | 0.0008 (10) | 0.0124 (11) | 0.0022 (10) |
O6W | 0.055 (2) | 0.204 (6) | 0.077 (3) | −0.058 (3) | 0.026 (2) | −0.071 (4) |
O7W | 0.071 (2) | 0.065 (2) | 0.054 (2) | −0.0094 (18) | 0.0177 (17) | 0.0094 (16) |
Sm1—O14 | 2.4144 (19) | C15—H15 | 0.93 |
Sm1—O12 | 2.4213 (19) | C16—C17 | 1.520 (4) |
Sm1—O23 | 2.437 (2) | N21—C26 | 1.330 (3) |
Sm1—O21 | 2.4460 (19) | N21—C22 | 1.338 (3) |
Sm1—O3W | 2.478 (2) | O21—C21 | 1.267 (3) |
Sm1—N11 | 2.533 (2) | O22—C21 | 1.243 (3) |
Sm1—N21 | 2.540 (2) | O23—C27 | 1.272 (3) |
Sm1—O1W | 2.547 (2) | O24—C27 | 1.240 (3) |
Sm1—O2W | 2.562 (2) | O24—Na1iv | 2.445 (3) |
Sm1—Na1 | 3.8831 (12) | C21—C22 | 1.512 (4) |
Sm1—Na1i | 4.0532 (12) | C22—C23 | 1.386 (4) |
Na1—O21 | 2.392 (2) | C23—C24 | 1.379 (5) |
Na1—O5W | 2.394 (3) | C23—H23 | 0.93 |
Na1—O2W | 2.434 (3) | C24—C25 | 1.387 (5) |
Na1—O24ii | 2.445 (3) | C24—H24 | 0.93 |
Na1—O14iii | 2.456 (2) | C25—C26 | 1.389 (4) |
Na1—O1Wiii | 2.610 (3) | C25—H25 | 0.93 |
Na1—Sm1iii | 4.0532 (12) | C26—C27 | 1.509 (4) |
Na1—H4W | 2.58 | O1W—Na1i | 2.610 (3) |
N11—C16 | 1.338 (3) | O1W—H1W | 0.851 |
N11—C12 | 1.339 (3) | O1W—H2W | 0.854 |
O11—C11 | 1.238 (3) | O2W—H3W | 0.848 |
O12—C11 | 1.278 (3) | O2W—H4W | 0.849 |
O13—C17 | 1.243 (3) | O3W—H5W | 0.851 |
O14—C17 | 1.264 (3) | O3W—H6W | 0.845 |
O14—Na1i | 2.456 (2) | O4W—H7W | 0.856 |
C11—C12 | 1.506 (4) | O4W—H8W | 0.855 |
C12—C13 | 1.384 (4) | O5W—H9W | 0.848 |
C13—C14 | 1.385 (5) | O5W—H10W | 0.852 |
C13—H13 | 0.93 | O6W—H11W | 0.854 |
C14—C15 | 1.380 (5) | O6W—H12W | 0.854 |
C14—H14 | 0.93 | O7W—H13W | 0.851 |
C15—C16 | 1.383 (4) | O7W—H14W | 0.852 |
O14—Sm1—O12 | 127.10 (7) | O2W—Na1—H4W | 19.2 |
O14—Sm1—O23 | 85.20 (7) | O24ii—Na1—H4W | 106.6 |
O12—Sm1—O23 | 82.06 (7) | O14iii—Na1—H4W | 65.6 |
O14—Sm1—O21 | 143.66 (7) | O1Wiii—Na1—H4W | 132.6 |
O12—Sm1—O21 | 79.70 (7) | Sm1—Na1—H4W | 52.0 |
O23—Sm1—O21 | 126.48 (6) | Sm1iii—Na1—H4W | 96.7 |
O14—Sm1—O3W | 74.21 (7) | C16—N11—C12 | 119.3 (2) |
O12—Sm1—O3W | 137.98 (7) | C16—N11—Sm1 | 119.38 (17) |
O23—Sm1—O3W | 139.51 (7) | C12—N11—Sm1 | 120.03 (17) |
O21—Sm1—O3W | 69.82 (7) | C11—O12—Sm1 | 126.48 (17) |
O14—Sm1—N11 | 63.73 (7) | C17—O14—Sm1 | 125.19 (17) |
O12—Sm1—N11 | 63.47 (7) | C17—O14—Na1i | 120.86 (17) |
O23—Sm1—N11 | 78.80 (7) | Sm1—O14—Na1i | 112.64 (9) |
O21—Sm1—N11 | 132.52 (7) | O11—C11—O12 | 125.1 (2) |
O3W—Sm1—N11 | 119.57 (7) | O11—C11—C12 | 119.9 (3) |
O14—Sm1—N21 | 139.98 (7) | O12—C11—C12 | 115.0 (2) |
O12—Sm1—N21 | 75.13 (7) | N11—C12—C13 | 121.8 (3) |
O23—Sm1—N21 | 63.55 (7) | N11—C12—C11 | 114.5 (2) |
O21—Sm1—N21 | 63.22 (7) | C13—C12—C11 | 123.5 (2) |
O3W—Sm1—N21 | 113.19 (7) | C12—C13—C14 | 118.8 (3) |
N11—Sm1—N21 | 127.06 (7) | C12—C13—H13 | 120.6 |
O14—Sm1—O1W | 72.65 (7) | C14—C13—H13 | 120.6 |
O12—Sm1—O1W | 145.01 (7) | C15—C14—C13 | 119.3 (3) |
O23—Sm1—O1W | 70.31 (7) | C15—C14—H14 | 120.4 |
O21—Sm1—O1W | 99.49 (8) | C13—C14—H14 | 120.4 |
O3W—Sm1—O1W | 70.40 (7) | C14—C15—C16 | 118.7 (3) |
N11—Sm1—O1W | 127.92 (8) | C14—C15—H15 | 120.6 |
N21—Sm1—O1W | 73.54 (7) | C16—C15—H15 | 120.6 |
O14—Sm1—O2W | 88.52 (7) | N11—C16—C15 | 122.0 (3) |
O12—Sm1—O2W | 75.89 (7) | N11—C16—C17 | 113.7 (2) |
O23—Sm1—O2W | 146.73 (7) | C15—C16—C17 | 124.2 (3) |
O21—Sm1—O2W | 73.75 (7) | O13—C17—O14 | 125.4 (3) |
O3W—Sm1—O2W | 68.38 (7) | O13—C17—C16 | 118.5 (3) |
N11—Sm1—O2W | 69.18 (7) | O14—C17—C16 | 116.0 (2) |
N21—Sm1—O2W | 131.34 (7) | C26—N21—C22 | 119.5 (2) |
O1W—Sm1—O2W | 137.96 (7) | C26—N21—Sm1 | 119.82 (18) |
O14—Sm1—Na1 | 121.67 (6) | C22—N21—Sm1 | 120.60 (18) |
O12—Sm1—Na1 | 71.69 (5) | C21—O21—Na1 | 123.25 (17) |
O23—Sm1—Na1 | 150.29 (5) | C21—O21—Sm1 | 125.80 (18) |
O21—Sm1—Na1 | 36.14 (5) | Na1—O21—Sm1 | 106.76 (8) |
O3W—Sm1—Na1 | 66.59 (5) | C27—O23—Sm1 | 125.49 (18) |
N11—Sm1—Na1 | 100.81 (6) | C27—O24—Na1iv | 119.5 (2) |
N21—Sm1—Na1 | 95.65 (5) | O22—C21—O21 | 125.5 (3) |
O1W—Sm1—Na1 | 126.50 (6) | O22—C21—C22 | 118.7 (2) |
O2W—Sm1—Na1 | 37.82 (5) | O21—C21—C22 | 115.8 (2) |
O14—Sm1—Na1i | 34.01 (5) | N21—C22—C23 | 122.0 (3) |
O12—Sm1—Na1i | 152.80 (5) | N21—C22—C21 | 114.2 (2) |
O23—Sm1—Na1i | 77.40 (5) | C23—C22—C21 | 123.7 (3) |
O21—Sm1—Na1i | 127.06 (5) | C24—C23—C22 | 118.4 (3) |
O3W—Sm1—Na1i | 65.96 (5) | C24—C23—H23 | 120.8 |
N11—Sm1—Na1i | 94.89 (5) | C22—C23—H23 | 120.8 |
N21—Sm1—Na1i | 110.38 (5) | C23—C24—C25 | 119.8 (3) |
O1W—Sm1—Na1i | 38.75 (6) | C23—C24—H24 | 120.1 |
O2W—Sm1—Na1i | 113.29 (5) | C25—C24—H24 | 120.1 |
Na1—Sm1—Na1i | 131.76 (2) | C24—C25—C26 | 118.3 (3) |
O21—Na1—O5W | 165.54 (10) | C24—C25—H25 | 120.9 |
O21—Na1—O2W | 77.07 (8) | C26—C25—H25 | 120.9 |
O5W—Na1—O2W | 96.48 (9) | N21—C26—C25 | 122.0 (3) |
O21—Na1—O24ii | 83.03 (8) | N21—C26—C27 | 115.0 (2) |
O5W—Na1—O24ii | 84.01 (9) | C25—C26—C27 | 122.9 (3) |
O2W—Na1—O24ii | 89.74 (8) | O24—C27—O23 | 124.9 (3) |
O21—Na1—O14iii | 102.81 (8) | O24—C27—C26 | 119.8 (3) |
O5W—Na1—O14iii | 89.13 (9) | O23—C27—C26 | 115.3 (2) |
O2W—Na1—O14iii | 83.57 (8) | Sm1—O1W—Na1i | 103.62 (8) |
O24ii—Na1—O14iii | 169.83 (10) | Sm1—O1W—H1W | 115 |
O21—Na1—O1Wiii | 83.36 (8) | Na1i—O1W—H1W | 91 |
O5W—Na1—O1Wiii | 108.58 (9) | Sm1—O1W—H2W | 118 |
O2W—Na1—O1Wiii | 143.37 (9) | Na1i—O1W—H2W | 116 |
O24ii—Na1—O1Wiii | 118.45 (9) | H1W—O1W—H2W | 108.8 |
O14iii—Na1—O1Wiii | 70.89 (7) | Na1—O2W—Sm1 | 101.97 (8) |
O21—Na1—Sm1 | 37.10 (5) | Na1—O2W—H3W | 120 |
O5W—Na1—Sm1 | 136.15 (8) | Sm1—O2W—H3W | 114 |
O2W—Na1—Sm1 | 40.21 (5) | Na1—O2W—H4W | 90 |
O24ii—Na1—Sm1 | 88.46 (6) | Sm1—O2W—H4W | 119 |
O14iii—Na1—Sm1 | 91.32 (6) | H3W—O2W—H4W | 109.6 |
O1Wiii—Na1—Sm1 | 112.90 (6) | Sm1—O3W—H5W | 113 |
O21—Na1—Sm1iii | 92.45 (6) | Sm1—O3W—H6W | 112 |
O5W—Na1—Sm1iii | 101.99 (7) | H5W—O3W—H6W | 110.0 |
O2W—Na1—Sm1iii | 112.23 (6) | H7W—O4W—H8W | 108.0 |
O24ii—Na1—Sm1iii | 156.07 (7) | Na1—O5W—H9W | 111 |
O14iii—Na1—Sm1iii | 33.35 (5) | Na1—O5W—H10W | 108 |
O1Wiii—Na1—Sm1iii | 37.64 (5) | H9W—O5W—H10W | 109.3 |
Sm1—Na1—Sm1iii | 102.07 (3) | H11W—O6W—H12W | 108.7 |
O21—Na1—H4W | 88.4 | H13W—O7W—H14W | 109.1 |
O5W—Na1—H4W | 89.1 |
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) −x, y+1/2, −z+3/2; (iii) x, −y+1/2, z−1/2; (iv) −x, y−1/2, −z+3/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1W···O22i | 0.85 | 1.93 | 2.753 (3) | 162 |
O1W—H2W···O5Wiv | 0.85 | 1.96 | 2.794 (3) | 165 |
O2W—H3W···O11i | 0.85 | 1.95 | 2.790 (3) | 169 |
O2W—H4W···O13iii | 0.85 | 1.88 | 2.725 (3) | 170 |
O3W—H5W···O24ii | 0.85 | 2.02 | 2.853 (3) | 166 |
O3W—H6W···O12i | 0.85 | 1.89 | 2.725 (3) | 173 |
O4W—H7W···O22iv | 0.86 | 2.08 | 2.907 (4) | 163 |
O4W—H8W···O23 | 0.86 | 1.94 | 2.779 (3) | 168 |
O5W—H9W···O4Wiii | 0.85 | 1.96 | 2.784 (4) | 163 |
O5W—H10W···O7W | 0.85 | 1.94 | 2.791 (5) | 177 |
O6W—H11W···O13iii | 0.85 | 1.95 | 2.789 (5) | 168 |
O6W—H12W···O4Wv | 0.85 | 2.03 | 2.858 (5) | 163 |
O7W—H13W···O11i | 0.85 | 2.22 | 2.989 (4) | 151 |
O7W—H14W···O6W | 0.85 | 1.96 | 2.754 (7) | 155 |
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) −x, y+1/2, −z+3/2; (iii) x, −y+1/2, z−1/2; (iv) −x, y−1/2, −z+3/2; (v) −x+1, y+1/2, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | [NaSm(C7H3NO4)2(H2O)4]·3H2O |
Mr | 629.66 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 296 |
a, b, c (Å) | 11.2065 (4), 17.4485 (3), 11.3728 (4) |
β (°) | 98.163 (1) |
V (Å3) | 2201.27 (12) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.77 |
Crystal size (mm) | 0.30 × 0.18 × 0.04 |
Data collection | |
Diffractometer | Rigaku R-AXIS-IV |
Absorption correction | Numerical (ABSCOR; Higashi, 1999) |
Tmin, Tmax | 0.558, 0.895 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 22103, 6163, 5944 |
Rint | 0.046 |
(sin θ/λ)max (Å−1) | 0.704 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.081, 1.17 |
No. of reflections | 6163 |
No. of parameters | 341 |
No. of restraints | 21 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.97, −1.28 |
Computer programs: PROCESS-AUTO (Rigaku, 1998), PROCESS-AUTO, CrystalStructure (Rigaku/MSC, 2004), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
Sm1—O14 | 2.4144 (19) | Sm1—O2W | 2.562 (2) |
Sm1—O12 | 2.4213 (19) | Na1—O21 | 2.392 (2) |
Sm1—O23 | 2.437 (2) | Na1—O5W | 2.394 (3) |
Sm1—O21 | 2.4460 (19) | Na1—O2W | 2.434 (3) |
Sm1—O3W | 2.478 (2) | Na1—O24i | 2.445 (3) |
Sm1—N11 | 2.533 (2) | Na1—O14ii | 2.456 (2) |
Sm1—N21 | 2.540 (2) | Na1—O1Wii | 2.610 (3) |
Sm1—O1W | 2.547 (2) |
Symmetry codes: (i) −x, y+1/2, −z+3/2; (ii) x, −y+1/2, z−1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1W···O22iii | 0.851 | 1.931 | 2.753 (3) | 162 |
O1W—H2W···O5Wiv | 0.854 | 1.961 | 2.794 (3) | 165 |
O2W—H3W···O11iii | 0.848 | 1.954 | 2.790 (3) | 169 |
O2W—H4W···O13ii | 0.849 | 1.884 | 2.725 (3) | 170 |
O3W—H5W···O24i | 0.851 | 2.019 | 2.853 (3) | 166 |
O3W—H6W···O12iii | 0.845 | 1.885 | 2.725 (3) | 173 |
O4W—H7W···O22iv | 0.856 | 2.077 | 2.907 (4) | 163 |
O4W—H8W···O23 | 0.855 | 1.938 | 2.779 (3) | 168 |
O5W—H9W···O4Wii | 0.848 | 1.961 | 2.784 (4) | 163 |
O5W—H10W···O7W | 0.852 | 1.939 | 2.791 (5) | 177 |
O6W—H11W···O13ii | 0.854 | 1.947 | 2.789 (5) | 168 |
O6W—H12W···O4Wv | 0.854 | 2.03 | 2.858 (5) | 163 |
O7W—H13W···O11iii | 0.851 | 2.22 | 2.989 (4) | 151 |
O7W—H14W···O6W | 0.852 | 1.96 | 2.754 (7) | 155 |
Symmetry codes: (i) −x, y+1/2, −z+3/2; (ii) x, −y+1/2, z−1/2; (iii) x, −y+1/2, z+1/2; (iv) −x, y−1/2, −z+3/2; (v) −x+1, y+1/2, −z+3/2. |
Subscribe to Acta Crystallographica Section E: Crystallographic Communications
The full text of this article is available to subscribers to the journal.
- Information on subscribing
- Sample issue
- If you have already subscribed, you may need to register
The use of rare earth elements for constructing metal-organic frameworks (MOFs) has been attracted much attention due to their variety of magnetic and optical properties (Benelli & Gatteschi, 2002). Since rare earth ions have a large radius and much affinity for oxygen atoms of ligands, pyridine-2,6-dicarboxylic acid (H2dipic) is widely studied for constructing MOFs containing rare earth elements (Brouca-Cabarrecq et al., 2002;. Duan et al., 2004; Ghosh & Bharadwaj, 2003). Hydrogen-bonding involving water molecules plays an important role in self-assembly processes for building MOF architectures. The structure of the title compound has already been reported (van Albada et al., 1999), but the role of water molecules was not fully understood. We here report the X-ray crystal structure analysis of the compound, and demonstrate a unique hydogen-bonding cluster of water molecules located in interlayer spaces.
A samarium(III) ion is coordinated by two dipic molecules and three water molecules, forming ninefolded coordination environment with four carboxylic oxygen atoms, two dipic nitrogen atoms, and three oxygen atoms of water molecules (Fig.1). All the bond distances for Sm—O and Na—O are comparable to those reported previously (van Albada et al., 1999). The asymmetric unit involves seven water molecules, which are classified into two groups; one is the molecules coordinating metal ions (O1W, O2W, O3W, and O5W) and the other the molecules isolated as a water of crystallization (O4W, O6W, and O7W) with relatively large thermal vibration ellipsoids. The structure can be described as a layered structure, which consists of metallic coordination polymer layers, separated by an interlamellar region populated by water molecules of crystallization. In the layer block, chains are constructed by the ninefolded samarium polyhedra and the sodium octahedra with edge-sharing fashion, running along the direction parallel to the c axis. Each chain is bridged by carboxylate groups of the embedded dipic molecules to adjacent chains, thus forming a two-dimensional network. The interlayer water molecules form unique octamer clusters by hydrogen-bonding, giving eight-membered rings (Fig.2). The atoms O4W, O5W, O6W, and O7W are related to those of the symmetrically equivalent opposite side by the center of symmetry. The rings are tightly fixed to the two-dimensional sheets at the atoms of O5W coordinationg to Na1. In the ring, O4W behaves as hydrogen acceptors while O5W behaves as hydrogen donors, in the hydrogen-bonding scheme. Both the atoms show tetracoordination. On the other hand, the atoms O6W and O7W behave both as hydogen donors and acceptors with tricoordination. The average O···O distance in the ring is 2.796 Å, somewhat longer than that of ice (2.76 Å). The two-dimensional structure of the compound is largely a consequence of hydrogen-bonding interactions among water molecules themselves and the MOF.