Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107028235/dn3047sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107028235/dn3047Isup2.hkl |
CCDC reference: 661788
A mixture of BaCl2·2H2O (0.244 g, 1.0 mmol), Na2Sasa (0.366 g, 1.0 mmol) and Bpy (0.156 g, 1.0 mmol) in water (10 ml) was sealed in a 25 ml Teflon-lined stainless steel reactor and heated at 383 K for 2 d under autogenous pressure. After slow cooling of the reaction mixture to room temperature at a speed of 2 K h-1, red block crystals suitable for X-ray diffraction analysis were obtained in high yield. Analysis calculated for C36H36Ba2N6O18S2: C 36.65, H 3.08, N 7.12%; found: C 36.57, H 3.03, N 7.03%. IR (KBr, cm-1): 3499 (s), 1625 (s), 1595 (s), 1481 (m), 1463 (m), 1216 (s), 1174 (s), 1123 (s), 1034 (s), 1008 (s), 846 (m), 804 (m), 686 (m), 622 (m). Thermogravimetric analysis showed a continuous weight loss between 368 and 443 K, corresponding to the loss of all coordinated water molecules (found: 9.31%; calculated: 9.16%). The 12.93% weight loss between 453 and 628 K may be due to the volatilization of Bpy; the organic ligand then decomposes gradually until 878 K, and finally, the sample was converted to a mixture of BaO and BaSO4.
H atoms attached to C and hydroxyl O atoms were positioned geometrically and treated as riding, with C—H distances of 0.95 Å and O—H of 0.82 Å, and with Uiso(H) value sof 1.2Ueq(C) or 1.5Ueq(O). H atoms of water molecule were located in difference Fourier maps and included in the subsequent refinement using restraints [O—H= 0.85 (1) Å and H···H= 1.39 (2) Å, with Uiso(H) = 1.5Ueq(O)].
Data collection: CrystalClear (Rigaku/MSC, 2000); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXL97.
[Ba2(C13H8N2O6S)2(H2O)6]·C10H8N2 | F(000) = 1164 |
Mr = 1179.5 | Dx = 1.865 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -p 2ybc | Cell parameters from 4975 reflections |
a = 8.2706 (16) Å | θ = 2.0–27.5° |
b = 8.3878 (16) Å | µ = 2.05 mm−1 |
c = 30.342 (6) Å | T = 293 K |
β = 93.542 (2)° | Prism, red |
V = 2100.8 (7) Å3 | 0.38 × 0.27 × 0.18 mm |
Z = 2 |
Rigaku? Model? CCD area-detector diffractometer | 4594 independent reflections |
Radiation source: fine-focus sealed tube | 4420 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.019 |
ω scans | θmax = 27.5°, θmin = 2.7° |
Absorption correction: multi-scan (Blessing, 1995) | h = −6→10 |
Tmin = 0.736, Tmax = 1.000 | k = −9→10 |
13373 measured reflections | l = −39→39 |
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) = 0.061 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0211P)2 + 4.0851P] where P = (Fo2 + 2Fc2)/3 |
4594 reflections | (Δ/σ)max < 0.001 |
290 parameters | Δρmax = 0.83 e Å−3 |
6 restraints | Δρmin = −0.61 e Å−3 |
[Ba2(C13H8N2O6S)2(H2O)6]·C10H8N2 | V = 2100.8 (7) Å3 |
Mr = 1179.5 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.2706 (16) Å | µ = 2.05 mm−1 |
b = 8.3878 (16) Å | T = 293 K |
c = 30.342 (6) Å | 0.38 × 0.27 × 0.18 mm |
β = 93.542 (2)° |
Rigaku? Model? CCD area-detector diffractometer | 4594 independent reflections |
Absorption correction: multi-scan (Blessing, 1995) | 4420 reflections with I > 2σ(I) |
Tmin = 0.736, Tmax = 1.000 | Rint = 0.019 |
13373 measured reflections |
R[F2 > 2σ(F2)] = 0.025 | 6 restraints |
wR(F2) = 0.061 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.83 e Å−3 |
4594 reflections | Δρmin = −0.61 e Å−3 |
290 parameters |
Experimental. Elemental analyses were determined with an Elementar Vario EL III elemental analyzer. Thermogravimetric analysis (TGA) was performed in air atmosphere from 28 to 1000 °C, with a heating rate of 15 °C min-1. |
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 | ||
Ba1 | −0.076480 (17) | 0.39968 (2) | 0.748920 (4) | 0.01830 (6) | |
S1 | −0.28054 (7) | 0.45888 (8) | 0.313430 (19) | 0.01904 (13) | |
O1 | −0.1679 (3) | 0.5005 (2) | 0.66410 (6) | 0.0286 (4) | |
O1W | −0.3912 (2) | 0.2895 (3) | 0.72688 (7) | 0.0328 (5) | |
H1A | −0.4298 | 0.2416 | 0.7484 | 0.049* | |
H1B | −0.4487 | 0.3726 | 0.7234 | 0.049* | |
O2 | −0.1832 (2) | 0.7063 (2) | 0.70998 (6) | 0.0254 (4) | |
O2W | −0.2821 (3) | 0.5626 (3) | 0.80199 (7) | 0.0353 (5) | |
H2A | −0.3778 | 0.5309 | 0.8050 | 0.053* | |
H2B | −0.2681 | 0.6625 | 0.8014 | 0.053* | |
O3 | −0.3938 (2) | 0.9210 (2) | 0.68900 (6) | 0.0270 (4) | |
H3 | −0.3366 | 0.8635 | 0.7053 | 0.041* | |
O3W | 0.0969 (2) | 0.6219 (2) | 0.80128 (6) | 0.0250 (4) | |
H3A | 0.0765 | 0.6246 | 0.8284 | 0.037* | |
H3B | 0.1965 | 0.5986 | 0.8041 | 0.037* | |
O4 | −0.1754 (3) | 0.3224 (3) | 0.31004 (7) | 0.0349 (5) | |
O5 | −0.4470 (2) | 0.4280 (2) | 0.29741 (6) | 0.0266 (4) | |
O6 | −0.2156 (3) | 0.6001 (3) | 0.29246 (6) | 0.0305 (5) | |
N1 | −0.3759 (3) | 0.7384 (3) | 0.51350 (7) | 0.0328 (6) | |
N2 | −0.2800 (3) | 0.6312 (3) | 0.50395 (8) | 0.0352 (6) | |
N3 | 0.0237 (4) | 0.6017 (4) | 0.88700 (9) | 0.0486 (8) | |
C1 | −0.2098 (3) | 0.6385 (3) | 0.67206 (8) | 0.0206 (5) | |
C2 | −0.2963 (3) | 0.7360 (3) | 0.63637 (8) | 0.0196 (5) | |
C3 | −0.3863 (3) | 0.8713 (3) | 0.64659 (8) | 0.0231 (5) | |
C4 | −0.4710 (4) | 0.9568 (4) | 0.61356 (10) | 0.0364 (7) | |
H4 | −0.5332 | 1.0472 | 0.6208 | 0.044* | |
C5 | −0.4644 (4) | 0.9096 (4) | 0.56994 (10) | 0.0385 (8) | |
H5 | −0.5221 | 0.9681 | 0.5472 | 0.046* | |
C6 | −0.3738 (4) | 0.7770 (4) | 0.55930 (8) | 0.0281 (6) | |
C7 | −0.2921 (3) | 0.6893 (3) | 0.59254 (8) | 0.0237 (5) | |
H7 | −0.2331 | 0.5967 | 0.5852 | 0.028* | |
C8 | −0.2891 (4) | 0.5913 (4) | 0.45795 (9) | 0.0294 (6) | |
C9 | −0.4188 (4) | 0.6296 (4) | 0.42900 (9) | 0.0352 (7) | |
H9 | −0.5085 | 0.6859 | 0.4394 | 0.042* | |
C10 | −0.4186 (4) | 0.5863 (4) | 0.38498 (9) | 0.0317 (7) | |
H10 | −0.5083 | 0.6114 | 0.3651 | 0.038* | |
C11 | −0.2860 (3) | 0.5059 (3) | 0.37020 (8) | 0.0205 (5) | |
C12 | −0.1569 (4) | 0.4667 (5) | 0.39885 (10) | 0.0443 (9) | |
H12 | −0.0667 | 0.4112 | 0.3884 | 0.053* | |
C13 | −0.1588 (4) | 0.5083 (5) | 0.44291 (10) | 0.0471 (10) | |
H13 | −0.0706 | 0.4798 | 0.4629 | 0.056* | |
C14 | 0.1093 (6) | 0.6769 (6) | 0.91837 (13) | 0.0669 (13) | |
H14 | 0.1791 | 0.7601 | 0.9100 | 0.080* | |
C15 | 0.1043 (6) | 0.6425 (6) | 0.96302 (13) | 0.0684 (14) | |
H15 | 0.1690 | 0.7013 | 0.9843 | 0.082* | |
C16 | 0.0046 (4) | 0.5221 (4) | 0.97626 (9) | 0.0369 (7) | |
C17 | −0.0848 (5) | 0.4443 (6) | 0.94332 (12) | 0.0576 (11) | |
H17 | −0.1560 | 0.3608 | 0.9506 | 0.069* | |
C18 | −0.0720 (6) | 0.4867 (6) | 0.89973 (12) | 0.0640 (12) | |
H18 | −0.1354 | 0.4302 | 0.8777 | 0.077* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ba1 | 0.01949 (9) | 0.01653 (9) | 0.01903 (8) | 0.00006 (5) | 0.00238 (5) | 0.00095 (5) |
S1 | 0.0177 (3) | 0.0233 (3) | 0.0164 (3) | 0.0021 (2) | 0.0031 (2) | −0.0030 (2) |
O1 | 0.0376 (11) | 0.0243 (11) | 0.0235 (9) | 0.0082 (9) | −0.0009 (8) | 0.0000 (8) |
O1W | 0.0255 (10) | 0.0332 (12) | 0.0396 (11) | 0.0051 (9) | 0.0008 (8) | 0.0092 (9) |
O2 | 0.0279 (10) | 0.0307 (11) | 0.0176 (8) | 0.0019 (8) | 0.0002 (7) | −0.0036 (7) |
O2W | 0.0301 (11) | 0.0363 (13) | 0.0409 (12) | −0.0011 (9) | 0.0122 (9) | 0.0004 (9) |
O3 | 0.0320 (11) | 0.0306 (11) | 0.0187 (9) | 0.0069 (9) | 0.0038 (8) | −0.0057 (8) |
O3W | 0.0268 (10) | 0.0260 (11) | 0.0220 (9) | −0.0009 (8) | 0.0007 (7) | 0.0021 (7) |
O4 | 0.0345 (11) | 0.0385 (13) | 0.0311 (10) | 0.0178 (10) | −0.0024 (9) | −0.0145 (9) |
O5 | 0.0203 (9) | 0.0341 (12) | 0.0252 (9) | 0.0000 (8) | −0.0010 (7) | −0.0058 (8) |
O6 | 0.0322 (11) | 0.0334 (12) | 0.0270 (10) | −0.0061 (9) | 0.0098 (8) | 0.0038 (8) |
N1 | 0.0421 (15) | 0.0398 (16) | 0.0163 (10) | 0.0108 (12) | 0.0002 (10) | −0.0018 (10) |
N2 | 0.0420 (15) | 0.0467 (17) | 0.0167 (11) | 0.0126 (13) | 0.0007 (10) | −0.0031 (10) |
N3 | 0.0516 (18) | 0.068 (2) | 0.0266 (13) | 0.0024 (16) | 0.0057 (12) | 0.0059 (14) |
C1 | 0.0196 (12) | 0.0251 (14) | 0.0174 (11) | −0.0016 (10) | 0.0030 (9) | 0.0008 (9) |
C2 | 0.0214 (12) | 0.0186 (13) | 0.0190 (11) | 0.0003 (10) | 0.0030 (9) | 0.0001 (9) |
C3 | 0.0265 (13) | 0.0244 (15) | 0.0188 (12) | 0.0004 (11) | 0.0038 (10) | −0.0021 (10) |
C4 | 0.0468 (19) | 0.0381 (18) | 0.0246 (14) | 0.0213 (15) | 0.0042 (13) | −0.0017 (12) |
C5 | 0.0495 (19) | 0.043 (2) | 0.0220 (14) | 0.0217 (16) | −0.0019 (13) | 0.0012 (13) |
C6 | 0.0344 (15) | 0.0333 (16) | 0.0167 (12) | 0.0076 (12) | 0.0023 (10) | −0.0018 (11) |
C7 | 0.0267 (14) | 0.0238 (14) | 0.0207 (12) | 0.0058 (11) | 0.0019 (10) | −0.0016 (10) |
C8 | 0.0348 (15) | 0.0373 (17) | 0.0160 (12) | 0.0045 (13) | 0.0020 (11) | −0.0013 (11) |
C9 | 0.0317 (15) | 0.051 (2) | 0.0230 (14) | 0.0159 (14) | 0.0020 (11) | −0.0094 (13) |
C10 | 0.0270 (14) | 0.0463 (19) | 0.0214 (13) | 0.0129 (13) | −0.0012 (11) | −0.0067 (12) |
C11 | 0.0225 (12) | 0.0230 (14) | 0.0165 (11) | 0.0024 (10) | 0.0041 (9) | −0.0018 (9) |
C12 | 0.0348 (17) | 0.074 (3) | 0.0242 (14) | 0.0251 (17) | −0.0021 (12) | −0.0098 (15) |
C13 | 0.0408 (18) | 0.077 (3) | 0.0226 (14) | 0.0275 (19) | −0.0072 (13) | −0.0078 (16) |
C14 | 0.083 (3) | 0.083 (3) | 0.036 (2) | −0.029 (3) | 0.011 (2) | 0.005 (2) |
C15 | 0.086 (3) | 0.090 (4) | 0.0300 (18) | −0.035 (3) | 0.0039 (19) | 0.000 (2) |
C16 | 0.0352 (16) | 0.050 (2) | 0.0260 (15) | 0.0078 (15) | 0.0052 (12) | 0.0017 (14) |
C17 | 0.066 (3) | 0.076 (3) | 0.0309 (17) | −0.024 (2) | −0.0017 (17) | 0.0067 (18) |
C18 | 0.075 (3) | 0.085 (3) | 0.0303 (18) | −0.023 (3) | −0.0051 (18) | 0.0037 (19) |
Ba1—O1 | 2.770 (2) | N2—C8 | 1.433 (3) |
Ba1—O2W | 2.773 (2) | N3—C14 | 1.312 (5) |
Ba1—O3Wi | 2.7830 (19) | N3—C18 | 1.320 (5) |
Ba1—O4ii | 2.786 (2) | C1—C2 | 1.503 (4) |
Ba1—O3W | 2.788 (2) | C2—C7 | 1.389 (3) |
Ba1—O6iii | 2.791 (2) | C2—C3 | 1.402 (4) |
Ba1—O1W | 2.804 (2) | C3—C4 | 1.386 (4) |
Ba1—O2i | 2.910 (2) | C4—C5 | 1.386 (4) |
Ba1—O2 | 2.943 (2) | C4—H4 | 0.9500 |
Ba1—C1 | 3.217 (3) | C5—C6 | 1.391 (4) |
Ba1—Ba1iv | 4.3799 (8) | C5—H5 | 0.9500 |
Ba1—Ba1i | 4.3799 (8) | C6—C7 | 1.389 (4) |
S1—O4 | 1.446 (2) | C7—H7 | 0.9500 |
S1—O5 | 1.455 (2) | C8—C9 | 1.382 (4) |
S1—O6 | 1.462 (2) | C8—C13 | 1.384 (4) |
S1—C11 | 1.770 (2) | C9—C10 | 1.384 (4) |
O1—C1 | 1.236 (3) | C9—H9 | 0.9500 |
O1W—H1A | 0.8467 | C10—C11 | 1.385 (4) |
O1W—H1B | 0.8469 | C10—H10 | 0.9500 |
O2—C1 | 1.290 (3) | C11—C12 | 1.375 (4) |
O2—Ba1iv | 2.910 (2) | C12—C13 | 1.383 (4) |
O2W—H2A | 0.8456 | C12—H12 | 0.9500 |
O2W—H2B | 0.8463 | C13—H13 | 0.9500 |
O3—C3 | 1.358 (3) | C14—C15 | 1.388 (5) |
O3—H3 | 0.8200 | C14—H14 | 0.9500 |
O3W—Ba1iv | 2.7830 (19) | C15—C16 | 1.379 (6) |
O3W—H3A | 0.8501 | C15—H15 | 0.9500 |
O3W—H3B | 0.8458 | C16—C17 | 1.371 (5) |
O4—Ba1v | 2.786 (2) | C16—C16vi | 1.494 (6) |
O6—Ba1iii | 2.791 (2) | C17—C18 | 1.380 (5) |
N1—N2 | 1.245 (4) | C17—H17 | 0.9500 |
N1—C6 | 1.426 (3) | C18—H18 | 0.9500 |
O1—Ba1—O2W | 104.30 (6) | C1—O2—Ba1iv | 135.11 (16) |
O1—Ba1—O3Wi | 75.12 (6) | C1—O2—Ba1 | 90.19 (16) |
O2W—Ba1—O3Wi | 135.38 (6) | Ba1iv—O2—Ba1 | 96.89 (6) |
O1—Ba1—O4ii | 138.42 (6) | Ba1—O2W—H2A | 121.3 |
O2W—Ba1—O4ii | 74.18 (7) | Ba1—O2W—H2B | 112.7 |
O3Wi—Ba1—O4ii | 78.13 (6) | H2A—O2W—H2B | 116.4 |
O1—Ba1—O3W | 115.26 (6) | C3—O3—H3 | 109.5 |
O2W—Ba1—O3W | 69.63 (6) | Ba1iv—O3W—Ba1 | 103.66 (6) |
O3Wi—Ba1—O3W | 152.04 (3) | Ba1iv—O3W—H3A | 119.9 |
O4ii—Ba1—O3W | 103.26 (6) | Ba1—O3W—H3A | 116.3 |
O1—Ba1—O6iii | 77.06 (6) | Ba1iv—O3W—H3B | 105.9 |
O2W—Ba1—O6iii | 147.12 (7) | Ba1—O3W—H3B | 111.5 |
O3Wi—Ba1—O6iii | 77.25 (6) | H3A—O3W—H3B | 99.2 |
O4ii—Ba1—O6iii | 126.71 (7) | S1—O4—Ba1v | 141.21 (12) |
O3W—Ba1—O6iii | 80.03 (6) | S1—O6—Ba1iii | 123.20 (12) |
O1—Ba1—O1W | 71.50 (6) | N2—N1—C6 | 114.9 (2) |
O2W—Ba1—O1W | 72.99 (7) | N1—N2—C8 | 113.6 (2) |
O3Wi—Ba1—O1W | 64.50 (6) | C14—N3—C18 | 116.4 (3) |
O4ii—Ba1—O1W | 68.42 (6) | O1—C1—O2 | 123.6 (2) |
O3W—Ba1—O1W | 142.51 (6) | O1—C1—C2 | 119.7 (2) |
O6iii—Ba1—O1W | 135.20 (6) | O2—C1—C2 | 116.8 (2) |
O1—Ba1—O2i | 136.09 (5) | O1—C1—Ba1 | 58.06 (14) |
O2W—Ba1—O2i | 119.25 (6) | O2—C1—Ba1 | 66.18 (14) |
O3Wi—Ba1—O2i | 77.65 (6) | C2—C1—Ba1 | 171.09 (17) |
O4ii—Ba1—O2i | 65.25 (6) | C7—C2—C3 | 119.0 (2) |
O3W—Ba1—O2i | 77.78 (6) | C7—C2—C1 | 119.8 (2) |
O6iii—Ba1—O2i | 63.68 (6) | C3—C2—C1 | 121.1 (2) |
O1W—Ba1—O2i | 124.63 (6) | O3—C3—C4 | 118.4 (2) |
O1—Ba1—O2 | 45.74 (5) | O3—C3—C2 | 120.9 (2) |
O2W—Ba1—O2 | 67.85 (6) | C4—C3—C2 | 120.7 (2) |
O3Wi—Ba1—O2 | 120.36 (5) | C5—C4—C3 | 119.7 (3) |
O4ii—Ba1—O2 | 139.31 (6) | C5—C4—H4 | 120.2 |
O3W—Ba1—O2 | 77.02 (6) | C3—C4—H4 | 120.2 |
O6iii—Ba1—O2 | 93.74 (6) | C4—C5—C6 | 120.2 (3) |
O1W—Ba1—O2 | 86.63 (6) | C4—C5—H5 | 119.9 |
O2i—Ba1—O2 | 148.68 (5) | C6—C5—H5 | 119.9 |
O1—Ba1—C1 | 22.26 (6) | C7—C6—C5 | 120.0 (2) |
O2W—Ba1—C1 | 85.35 (7) | C7—C6—N1 | 124.3 (3) |
O3Wi—Ba1—C1 | 96.79 (6) | C5—C6—N1 | 115.7 (3) |
O4ii—Ba1—C1 | 142.86 (6) | C2—C7—C6 | 120.4 (3) |
O3W—Ba1—C1 | 97.92 (6) | C2—C7—H7 | 119.8 |
O6iii—Ba1—C1 | 86.61 (6) | C6—C7—H7 | 119.8 |
O1W—Ba1—C1 | 76.17 (6) | C9—C8—C13 | 119.8 (3) |
O2i—Ba1—C1 | 150.29 (6) | C9—C8—N2 | 123.9 (3) |
O2—Ba1—C1 | 23.64 (6) | C13—C8—N2 | 116.4 (3) |
O1—Ba1—Ba1iv | 77.50 (4) | C8—C9—C10 | 120.4 (3) |
O2W—Ba1—Ba1iv | 72.92 (5) | C8—C9—H9 | 119.8 |
O3Wi—Ba1—Ba1iv | 144.84 (4) | C10—C9—H9 | 119.8 |
O4ii—Ba1—Ba1iv | 136.59 (5) | C9—C10—C11 | 119.2 (3) |
O3W—Ba1—Ba1iv | 38.13 (4) | C9—C10—H10 | 120.4 |
O6iii—Ba1—Ba1iv | 75.45 (5) | C11—C10—H10 | 120.4 |
O1W—Ba1—Ba1iv | 125.61 (5) | C12—C11—C10 | 120.8 (2) |
O2i—Ba1—Ba1iv | 108.81 (4) | C12—C11—S1 | 119.8 (2) |
O2—Ba1—Ba1iv | 41.27 (4) | C10—C11—S1 | 119.5 (2) |
C1—Ba1—Ba1iv | 60.02 (5) | C11—C12—C13 | 119.7 (3) |
O1—Ba1—Ba1i | 111.61 (4) | C11—C12—H12 | 120.1 |
O2W—Ba1—Ba1i | 130.55 (5) | C13—C12—H12 | 120.1 |
O3Wi—Ba1—Ba1i | 38.21 (4) | C12—C13—C8 | 120.1 (3) |
O4ii—Ba1—Ba1i | 56.38 (5) | C12—C13—H13 | 119.9 |
O3W—Ba1—Ba1i | 119.59 (4) | C8—C13—H13 | 119.9 |
O6iii—Ba1—Ba1i | 75.53 (5) | N3—C14—C15 | 124.1 (4) |
O1W—Ba1—Ba1i | 87.19 (5) | N3—C14—H14 | 117.9 |
O2i—Ba1—Ba1i | 41.84 (4) | C15—C14—H14 | 117.9 |
O2—Ba1—Ba1i | 157.22 (4) | C16—C15—C14 | 119.4 (4) |
C1—Ba1—Ba1i | 133.86 (5) | C16—C15—H15 | 120.3 |
Ba1iv—Ba1—Ba1i | 146.487 (11) | C14—C15—H15 | 120.3 |
O4—S1—O5 | 113.35 (13) | C17—C16—C15 | 116.2 (3) |
O4—S1—O6 | 111.84 (13) | C17—C16—C16vi | 121.8 (4) |
O5—S1—O6 | 111.36 (12) | C15—C16—C16vi | 122.0 (4) |
O4—S1—C11 | 107.30 (12) | C16—C17—C18 | 120.4 (4) |
O5—S1—C11 | 106.51 (12) | C16—C17—H17 | 119.8 |
O6—S1—C11 | 105.96 (13) | C18—C17—H17 | 119.8 |
C1—O1—Ba1 | 99.67 (15) | N3—C18—C17 | 123.5 (4) |
Ba1—O1W—H1A | 111.2 | N3—C18—H18 | 118.3 |
Ba1—O1W—H1B | 105.3 | C17—C18—H18 | 118.3 |
H1A—O1W—H1B | 104.6 |
Symmetry codes: (i) −x, y−1/2, −z+3/2; (ii) x, −y+1/2, z+1/2; (iii) −x, −y+1, −z+1; (iv) −x, y+1/2, −z+3/2; (v) x, −y+1/2, z−1/2; (vi) −x, −y+1, −z+2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O2 | 0.82 | 1.83 | 2.558 (3) | 147 |
O1W—H1A···O5ii | 0.85 | 2.07 | 2.871 (3) | 158 |
O1W—H1B···O5vii | 0.85 | 1.97 | 2.798 (3) | 166 |
O2W—H2A···O3viii | 0.85 | 2.12 | 2.960 (3) | 173 |
O2W—H2B···O6ix | 0.85 | 2.06 | 2.900 (3) | 172 |
O3W—H3A···N3 | 0.85 | 1.87 | 2.712 (3) | 172 |
O3W—H3B···O3i | 0.85 | 2.21 | 2.977 (3) | 151 |
O3W—H3B···O1Wiv | 0.85 | 2.49 | 2.981 (3) | 118 |
Symmetry codes: (i) −x, y−1/2, −z+3/2; (ii) x, −y+1/2, z+1/2; (iv) −x, y+1/2, −z+3/2; (vii) −x−1, −y+1, −z+1; (viii) −x−1, y−1/2, −z+3/2; (ix) x, −y+3/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Ba2(C13H8N2O6S)2(H2O)6]·C10H8N2 |
Mr | 1179.5 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 8.2706 (16), 8.3878 (16), 30.342 (6) |
β (°) | 93.542 (2) |
V (Å3) | 2100.8 (7) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 2.05 |
Crystal size (mm) | 0.38 × 0.27 × 0.18 |
Data collection | |
Diffractometer | Rigaku? Model? CCD area-detector diffractometer |
Absorption correction | Multi-scan (Blessing, 1995) |
Tmin, Tmax | 0.736, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13373, 4594, 4420 |
Rint | 0.019 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.025, 0.061, 1.07 |
No. of reflections | 4594 |
No. of parameters | 290 |
No. of restraints | 6 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.83, −0.61 |
Computer programs: CrystalClear (Rigaku/MSC, 2000), CrystalClear, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), DIAMOND (Brandenburg, 1999), SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O2 | 0.82 | 1.83 | 2.558 (3) | 147.4 |
O1W—H1A···O5i | 0.85 | 2.07 | 2.871 (3) | 158.0 |
O1W—H1B···O5ii | 0.85 | 1.97 | 2.798 (3) | 166.3 |
O2W—H2A···O3iii | 0.85 | 2.12 | 2.960 (3) | 172.5 |
O2W—H2B···O6iv | 0.85 | 2.06 | 2.900 (3) | 172.1 |
O3W—H3A···N3 | 0.85 | 1.87 | 2.712 (3) | 172.2 |
O3W—H3B···O3v | 0.85 | 2.21 | 2.977 (3) | 150.9 |
O3W—H3B···O1Wvi | 0.85 | 2.49 | 2.981 (3) | 117.5 |
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) −x−1, −y+1, −z+1; (iii) −x−1, y−1/2, −z+3/2; (iv) x, −y+3/2, z+1/2; (v) −x, y−1/2, −z+3/2; (vi) −x, y+1/2, −z+3/2. |
The self-assemblies of metal–organic frameworks (MOFs) are of great interest owing to their fascinating structural topologies and potential application in materials science (Moulton & Zaworotko, 2001; Leininger et al., 2000; Belanger et al., 1999; Eddaoudi et al., 2001; Evans & Lin, 2002). Accordingly, the judicious choice of organic building blocks with various assembly modes and unique functional properties is very significant in optimizing structural topology and desired functions (Cote & Shimizu, 2003; Makinen et al., 2001; Hix et al., 2001; Drumel, Janvier, Barboux et al., 1995; Drumel, Janvier, Deniaud & Bujoli, 1995). In recent years, azo-benzene derivatives as building blocks have attracted attention because the combination of these photo-functional molecules with transition metals (TMs) may result in interesting magnetic, optical and electronic properties (Otsuki et al., 2003; Nishihara, 2005). So far, most metal cations in the reported azo-based metal complexes are the d-block TM ions, while such complexes with alkaline-earth metals (the s-block metals), specially barium-containing MOFs, are rare (Kennedy et al., 2001, 2004). Azo-based s-block metal complexes are of general interest to structural chemists, because they have more flexible configurations than azo-based TM complexes in forming MOFs, but the s-block complexes are still less common than the TM complexes in supramolecular chemistry and crystal engineering. In addition, the structures of these compounds as colourants are also of specific interest to the dye and pigment industries (Kennedy et al., 2004, and references therein). 5-(4-Sulfophenylazo) salicylic acid disodium salt (abbreviated as Na2Sasa), (Ia), an azobenzene-containing building block which exhibits versatile coordination modes and can form directional hydrogen bonds based on the different binding abilities of salicylate and sulfonate groups, may provide great opportunities for constructing functional molecular assemblies with interesting networks. However, the structures and properties of metal complexes with the Sasa ligand are still less explored so far. The Sasa ligand is used here for the first time to prepare a barium-based MOF, a two-dimensional coordination polymer with one-dimensional channels, [Ba2(Sasa)2(H2O)6]·Bpy (Bpy is 4,4'-bipyridine) (Ib), in which the salicylate group of Sasa coordinates to the Ba ions in a µ3-η2,η1-bimetallic bridging–chelating mode. Such a coordination mode is not only rare for salicylate-based complexes but has also never been observed in the associated Ba-based MOFs.
The asymmetric unit of the title compound is composed of one BaII ion, one Sasa anion, one-half of a Bpy molecule and three coordinated water molecules (Fig. 1). Atom Ba1 is nine-coordinate with an irregular coordination environment containing three carboxylate O atoms (O1, O2 and O2ii) and two sulfonate O atoms (O4iii and O6i) in two Sasa ligands [Ba1—O = 2.7687 (19)–2.943 (2) Å], two bridging (O3W and O3Wii) and two terminal (O1W and O2W) water molecules [Ba1—OW = 2.773 (2)–2.804 (2) Å]. Each BaII ion is bridged through water molecules to form a {Ba—O3W}n backbone chain running along the b axis. These backbone chains are further connected to each other by O atoms from the salicylate and sulfonate groups in the Sasa ligands, coordinated to two BaII ions in µ3-η2,η1-bimetallic bridging–chelating mode and syn–syn bridging fashion, respectively, giving rise to a two-dimensional layer in the bc plane (Fig. 2a). Sulfonate atom O5 atom and the OH group of the Sasa ligand remain uncoordinated in the structure (see scheme). It is interesting to note that this layer not only is characteristic of a slab with a thickness of 8.27 Å (the length of the a axis) but also contains one-dimensional channels along the b axis (Fig. 2b), with an approximate free-pore diameter of 11.35 × 2.86 Å (the O3W···O3W and C13···C13 distances not including the van der Waals radii), in which Bpy molecules are situated. Calculations using PLATON (Spek, 2003) show that there are no residual solvent accessible voids in the prototype unit, but 23.9% of the volume of the unit cell is available after removing the Bpy molecules. The slabs stack in –AAA– modes along the a axis. Hydrogen bonds (Table 1) between the coordinated water molecules and the O atoms of the SO3-/OH- groups link adjacent slabs into a three-dimensional supramolecular framework (Fig. 2b). Like the structure-directing agents in porous materials (Liu et al., 2007), the Bpy molecules as the guest are only located in the channels (Fig. 2b) and are in contact with the pore wall via strong hydrogen-bonding interactions [N3···O3W = 2.712 (3) Å] and weak π–π interactions (the centroid–centroid distance is 3.825 Å [s.u. values available for these values?], and the interplanar distance between the pyridyl rings and the aromatic rings of Sasa ligands is ca 3.70 Å, resulting in an offset angle of 14.5°; Fig. 3).
The framework collapsed when the Bpy molecules were removed from the channels at 628 K, perhaps because of the strong hydrogen-bonding interactions and π–π stacking interactions between the host and guest molecules. Attempts to replace Bpy with low boiling or/and low-conjugated N-heterocycle molecules, such as pyridine and methylpyridine, are in progress. For the construction of porous metal-organic frameworks, the frequent occurrence of interpenetration or uncontrollable interlayer stacking in staggered mode generally leads to no void space in the molecular packing structure despite the fact that porous coordination networks can be obtained more easily. Such a two-dimensional slab-layer structure with one-dimensional channels in the title compound is undoubtedly of great advantage in avoiding nonporous structures resulted from interpenetration or staggered stacking, and may shed some light on the design and construction of new porous materials. Until now, only a few simple complexes including s-block metals and sulfonated azo anions have been reported, and these exhibit ion-pair, discrete, one-dimensional chain/ladder-like and two-dimensional structures (Kennedy et al., 2001, 2004); the title compound is the first two-dimensional slab-layer compound with one-dimensional channels, and this type of structure is also rare in metal-organic coordination complexes.