The title compound, 4Na
+·C
24H
12O
16S
84−·14H
2O (Na
4TCAS·14H
2O), was found to crystallize in the triclinic space group
P. The X-ray structure revealed that the centrosymmetric TCAS
4− anion adopts the 1,2-alternate conformation. The sodium cations are surrounded by five or six O atoms in the crystal structure. All sodium ions form centrosymmetric aqua-bridged dimers, Na(μ-H
2O)
2Na, which are also coordinated by sulfonate O atoms and contribute to the formation of a three-dimensional network. The compound exists in the solid state as layers of anionic thiacalixarenes, alternating with inorganic layers that contain sodium cations and water molecules. Intercalation of metal ions into the solid-state layered structure was observed.
Supporting information
CCDC reference: 214780
Key indicators
- Single-crystal X-ray study
- T = 93 K
- Mean (C-C) = 0.004 Å
- R factor = 0.031
- wR factor = 0.091
- Data-to-parameter ratio = 11.8
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
Alert Level C:
REFLT_03
From the CIF: _diffrn_reflns_theta_max 27.48
From the CIF: _reflns_number_total 4678
TEST2: Reflns within _diffrn_reflns_theta_max
Count of symmetry unique reflns 5098
Completeness (_total/calc) 91.76%
Alert C: < 95% complete
PLAT_728 Alert C D-H..A Calc 144.94, Rep 146.00, Dev. 1.06 Deg.
O5 -H4 -O15 1.555 1.555 1.455
General Notes
ABSTY_01 Extra text has been found in the _exptl_absorpt_correction_type
field, which should be only a single keyword. A literature
citation should be included in the _exptl_absorpt_process_details
field.
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
2 Alert Level C = Please check
A sample of sodium thiacalix[4]arenetetrasulfonate (Na4TCAS), was obtained from Cosmo Oil Co. Ltd. Crystals suitable for single-crystal X-ray diffraction were recrystallized by adding sodium chloride to a water solution of Na4(TCAS).
The positions of all the H atoms were initially located from a difference map. The coordinate parameters for all H atoms are refined. All water O—H distances and H—O—H angles were restrained to be 0.9 Å and 104°, respectively. The isotropic displacement parameters for all H atoms were fixed at 1.2 times the value of the equivalent isotropic displacement parameter of their carrier atom.
Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: CrystalStructure (Rigaku/MSC 2001); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: CrystalStructure (Rigaku/MSC 2001).
Crystal data top
4Na+·C24H12O16S84−·14H2O | Z = 1 |
Mr = 1157.00 | F(000) = 596.00 |
Triclinic, P1 | Dx = 1.730 Mg m−3 |
a = 8.2974 (7) Å | Mo Kα radiation, λ = 0.7107 Å |
b = 8.8446 (6) Å | Cell parameters from 4591 reflections |
c = 15.789 (1) Å | θ = 2.5–27.5° |
α = 95.743 (4)° | µ = 0.54 mm−1 |
β = 102.490 (2)° | T = 93 K |
γ = 97.897 (4)° | Plate, colorless |
V = 1110.4 (1) Å3 | 0.30 × 0.20 × 0.10 mm |
Data collection top
Rigaku R-AXIS-IV diffractometer | 3541 reflections with F2 > 2σ(F2) |
Detector resolution: 10.00 pixels mm-1 | Rint = 0.018 |
ω scans | θmax = 27.5° |
Absorption correction: multi-scan (higashi, 1995) ? | h = −10→10 |
Tmin = 0.848, Tmax = 0.948 | k = −11→11 |
8541 measured reflections | l = −20→20 |
4678 independent reflections | |
Refinement top
Refinement on F2 | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.031 | w = 1/[0.001Fo2 + σ2(Fo) + 0.5]/(4Fo2) |
wR(F2) = 0.091 | (Δ/σ)max < 0.001 |
S = 0.84 | Δρmax = 0.46 e Å−3 |
4233 reflections | Δρmin = −0.54 e Å−3 |
358 parameters | |
Crystal data top
4Na+·C24H12O16S84−·14H2O | γ = 97.897 (4)° |
Mr = 1157.00 | V = 1110.4 (1) Å3 |
Triclinic, P1 | Z = 1 |
a = 8.2974 (7) Å | Mo Kα radiation |
b = 8.8446 (6) Å | µ = 0.54 mm−1 |
c = 15.789 (1) Å | T = 93 K |
α = 95.743 (4)° | 0.30 × 0.20 × 0.10 mm |
β = 102.490 (2)° | |
Data collection top
Rigaku R-AXIS-IV diffractometer | 4678 independent reflections |
Absorption correction: multi-scan (higashi, 1995) ? | 3541 reflections with F2 > 2σ(F2) |
Tmin = 0.848, Tmax = 0.948 | Rint = 0.018 |
8541 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.031 | 358 parameters |
wR(F2) = 0.091 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.84 | Δρmax = 0.46 e Å−3 |
4233 reflections | Δρmin = −0.54 e Å−3 |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
S1 | 0.43010 (7) | 0.27994 (7) | 0.45382 (4) | 0.0055 (1) | |
S2 | 0.16572 (7) | −0.33281 (7) | 0.45344 (4) | 0.0051 (1) | |
S3 | 0.21040 (7) | −0.09787 (7) | 0.14849 (4) | 0.0053 (1) | |
S4 | 0.43052 (7) | 0.52342 (7) | 0.78607 (4) | 0.0055 (1) | |
Na1 | 0.5968 (1) | 0.0805 (1) | 0.11192 (6) | 0.0091 (2) | |
Na2 | 0.1760 (1) | −0.5027 (1) | 0.08505 (6) | 0.0102 (2) | |
O1 | 0.3103 (2) | 0.0041 (2) | 0.5319 (1) | 0.0080 (4) | |
O2 | 0.3151 (2) | 0.0318 (2) | 0.1264 (1) | 0.0086 (4) | |
O3 | 0.2526 (2) | −0.2459 (2) | 0.1205 (1) | 0.0096 (4) | |
O4 | 0.0314 (2) | −0.0916 (2) | 0.1168 (1) | 0.0105 (4) | |
O5 | 0.0644 (2) | 0.2550 (2) | 0.4269 (1) | 0.0079 (4) | |
O6 | 0.3848 (2) | 0.6765 (2) | 0.7965 (1) | 0.0105 (4) | |
O7 | 0.3704 (2) | 0.4248 (2) | 0.8457 (1) | 0.0108 (5) | |
O8 | 0.6086 (2) | 0.5273 (2) | 0.7907 (1) | 0.0096 (4) | |
O9 | 0.8835 (2) | 0.1779 (2) | 0.1251 (1) | 0.0127 (5) | |
O10 | 0.7461 (2) | −0.0932 (2) | 0.2088 (1) | 0.0134 (5) | |
O11 | 0.4993 (2) | 0.1736 (2) | −0.0206 (1) | 0.0108 (5) | |
O12 | 0.2069 (2) | −0.7417 (2) | 0.0265 (1) | 0.0107 (4) | |
O13 | 0.1253 (2) | −0.4631 (2) | −0.0651 (1) | 0.0114 (5) | |
O14 | 0.1040 (2) | 0.3651 (2) | 0.2638 (1) | 0.0136 (5) | |
O15 | 0.7472 (2) | 0.1531 (2) | 0.3372 (1) | 0.0101 (4) | |
C1 | 0.2861 (3) | −0.0281 (3) | 0.4445 (1) | 0.0057 (6) | |
C2 | 0.2199 (3) | −0.1744 (3) | 0.3970 (2) | 0.0062 (6) | |
C3 | 0.2034 (3) | −0.1983 (3) | 0.3067 (2) | 0.0072 (6) | |
C4 | 0.2483 (3) | −0.0743 (3) | 0.2637 (2) | 0.0060 (6) | |
C5 | 0.3118 (3) | 0.0708 (3) | 0.3097 (2) | 0.0063 (6) | |
C6 | 0.3312 (3) | 0.0948 (3) | 0.3997 (2) | 0.0054 (6) | |
C7 | 0.1421 (3) | 0.3105 (3) | 0.5108 (2) | 0.0060 (6) | |
C8 | 0.0573 (3) | 0.3548 (3) | 0.5748 (2) | 0.0056 (6) | |
C9 | 0.1484 (3) | 0.4215 (3) | 0.6580 (2) | 0.0069 (6) | |
C10 | 0.3220 (3) | 0.4378 (3) | 0.6790 (2) | 0.0065 (6) | |
C11 | 0.4065 (3) | 0.3875 (3) | 0.6173 (2) | 0.0060 (6) | |
C12 | 0.3166 (3) | 0.3260 (3) | 0.5330 (2) | 0.0054 (6) | |
H1 | 0.285 | −0.083 | 0.554 | 0.0100* | |
H2 | 0.157 | −0.301 | 0.279 | 0.0086* | |
H3 | 0.345 | 0.161 | 0.280 | 0.0073* | |
H4 | −0.038 | 0.244 | 0.419 | 0.0095* | |
H5 | 0.096 | 0.455 | 0.701 | 0.0083* | |
H6 | 0.528 | 0.402 | 0.636 | 0.0075* | |
H7 | 0.938 | 0.101 | 0.111 | 0.0162* | |
H8 | 0.955 | 0.235 | 0.172 | 0.0162* | |
H9 | 0.842 | −0.092 | 0.191 | 0.0168* | |
H10 | 0.700 | −0.193 | 0.200 | 0.0169* | |
H11 | 0.554 | 0.218 | −0.058 | 0.0143* | |
H12 | 0.427 | 0.236 | −0.012 | 0.0144* | |
H13 | 0.234 | −0.812 | 0.062 | 0.0126* | |
H14 | 0.121 | −0.793 | −0.016 | 0.0127* | |
H15 | 0.193 | −0.502 | −0.096 | 0.0150* | |
H16 | 0.139 | −0.363 | −0.071 | 0.0149* | |
H17 | 0.112 | 0.343 | 0.3188 | 0.0168* | |
H18 | 0.211 | 0.389 | 0.260 | 0.0169* | |
H19 | 0.698 | 0.215 | 0.302 | 0.0126* | |
H20 | 0.742 | 0.066 | 0.302 | 0.0125* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0046 (3) | 0.0053 (3) | 0.0066 (3) | −0.0015 (2) | 0.0032 (2) | −0.0003 (2) |
S2 | 0.0031 (3) | 0.0056 (3) | 0.0067 (3) | −0.0002 (2) | 0.0015 (2) | 0.0022 (2) |
S3 | 0.0059 (3) | 0.0055 (3) | 0.0049 (3) | 0.0003 (2) | 0.0022 (2) | 0.0009 (2) |
S4 | 0.0050 (3) | 0.0062 (3) | 0.0048 (3) | −0.0001 (2) | 0.0008 (2) | 0.0004 (2) |
Na1 | 0.0076 (5) | 0.0103 (5) | 0.0090 (5) | 0.0004 (4) | 0.0019 (4) | 0.0010 (4) |
Na2 | 0.0114 (5) | 0.0080 (5) | 0.0104 (5) | 0.0014 (4) | 0.0010 (4) | 0.0007 (4) |
O1 | 0.0119 (9) | 0.0058 (9) | 0.0061 (8) | −0.0013 (6) | 0.0032 (7) | 0.0008 (7) |
O2 | 0.0107 (9) | 0.0078 (9) | 0.0078 (8) | −0.0001 (7) | 0.0039 (7) | 0.0023 (7) |
O3 | 0.0147 (9) | 0.0054 (9) | 0.0105 (9) | 0.0030 (7) | 0.0066 (7) | 0.0003 (7) |
O4 | 0.0062 (9) | 0.015 (1) | 0.0096 (9) | 0.0019 (7) | 0.0010 (7) | 0.0004 (7) |
O5 | 0.0034 (8) | 0.013 (1) | 0.0053 (8) | −0.0015 (7) | −0.0001 (7) | −0.0024 (7) |
O6 | 0.0129 (9) | 0.0073 (9) | 0.0094 (9) | 0.0026 (7) | −0.0006 (7) | −0.0014 (7) |
O7 | 0.0133 (9) | 0.012 (1) | 0.0078 (8) | −0.0006 (7) | 0.0042 (7) | 0.0039 (7) |
O8 | 0.0062 (9) | 0.014 (1) | 0.0078 (8) | −0.0000 (7) | 0.0004 (7) | −0.0004 (7) |
O9 | 0.0097 (9) | 0.010 (1) | 0.019 (1) | 0.0021 (7) | 0.0046 (8) | 0.0010 (8) |
O10 | 0.015 (1) | 0.009 (1) | 0.017 (1) | 0.0009 (7) | 0.0051 (8) | 0.0021 (8) |
O11 | 0.0115 (9) | 0.012 (1) | 0.0109 (9) | 0.0034 (7) | 0.0063 (7) | 0.0035 (7) |
O12 | 0.0110 (9) | 0.0098 (9) | 0.0100 (9) | 0.0022 (7) | −0.0009 (7) | 0.0018 (7) |
O13 | 0.0145 (9) | 0.009 (1) | 0.0124 (9) | 0.0032 (7) | 0.0060 (7) | 0.0031 (7) |
O14 | 0.0101 (9) | 0.020 (1) | 0.0121 (9) | 0.0030 (7) | 0.0038 (7) | 0.0044 (8) |
O15 | 0.0118 (9) | 0.0103 (9) | 0.0074 (8) | 0.0009 (7) | 0.0007 (7) | 0.0013 (7) |
C1 | 0.002 (1) | 0.010 (1) | 0.005 (1) | 0.0028 (8) | 0.0005 (8) | 0.0011 (9) |
C2 | 0.005 (1) | 0.006 (1) | 0.009 (1) | 0.0008 (8) | 0.0038 (9) | 0.0029 (9) |
C3 | 0.006 (1) | 0.006 (1) | 0.010 (1) | 0.0006 (9) | 0.0018 (9) | −0.000 (1) |
C4 | 0.004 (1) | 0.007 (1) | 0.008 (1) | 0.0012 (8) | 0.0024 (9) | 0.0004 (9) |
C5 | 0.005 (1) | 0.007 (1) | 0.007 (1) | 0.0005 (8) | 0.0021 (9) | 0.0026 (9) |
C6 | 0.004 (1) | 0.005 (1) | 0.007 (1) | 0.0011 (8) | 0.0014 (9) | −0.0015 (9) |
C7 | 0.006 (1) | 0.004 (1) | 0.008 (1) | −0.0001 (8) | 0.0012 (9) | 0.0018 (9) |
C8 | 0.004 (1) | 0.004 (1) | 0.009 (1) | 0.0001 (8) | 0.0024 (9) | 0.0027 (9) |
C9 | 0.007 (1) | 0.005 (1) | 0.009 (1) | 0.0001 (9) | 0.0039 (9) | 0.0017 (9) |
C10 | 0.009 (1) | 0.003 (1) | 0.007 (1) | 0.0005 (8) | 0.0011 (9) | 0.0012 (9) |
C11 | 0.004 (1) | 0.006 (1) | 0.009 (1) | 0.0006 (8) | 0.0025 (9) | 0.0029 (9) |
C12 | 0.008 (1) | 0.002 (1) | 0.006 (1) | −0.0013 (8) | 0.0026 (9) | 0.0008 (9) |
Geometric parameters (Å, º) top
S1—C6 | 1.770 (2) | O15—H20 | 0.90 |
S1—C12 | 1.769 (2) | C1—C2 | 1.404 (4) |
S2—C2 | 1.792 (2) | C1—C6 | 1.406 (3) |
S2—C8i | 1.785 (2) | C2—C3 | 1.395 (3) |
S3—O2 | 1.4590 (18) | C3—C4 | 1.396 (3) |
S3—O3 | 1.4524 (18) | C3—H2 | 0.96 |
S3—O4 | 1.4715 (18) | C4—C5 | 1.383 (4) |
S3—C4 | 1.763 (2) | C5—C6 | 1.386 (3) |
S4—O6 | 1.4590 (18) | C5—H3 | 1.00 |
S4—O7 | 1.4635 (18) | C7—C8 | 1.405 (3) |
S4—O8 | 1.4593 (18) | C7—C12 | 1.398 (3) |
S4—C10 | 1.772 (2) | C8—C9 | 1.393 (3) |
O1—C1 | 1.347 (3) | C9—C10 | 1.390 (3) |
O1—H1 | 0.89 | C9—H5 | 0.92 |
O5—C7 | 1.350 (3) | C10—C11 | 1.390 (3) |
O5—H4 | 0.82 | C11—C12 | 1.392 (3) |
O9—H7 | 0.90 | C11—H6 | 0.98 |
O9—H8 | 0.90 | Na1—O2 | 2.382 (2) |
O10—H9 | 0.90 | Na1—O6ii | 2.434 (2) |
O10—H10 | 0.90 | Na1—O9 | 2.373 (2) |
O11—H11 | 0.90 | Na1—O10 | 2.531 (2) |
O11—H12 | 0.90 | Na1—O11 | 2.347 (2) |
O12—H13 | 0.90 | Na1—O11iii | 2.475 (2) |
O12—H14 | 0.90 | Na2—O3 | 2.252 (2) |
O13—H15 | 0.90 | Na2—O8iv | 2.402 (2) |
O13—H16 | 0.898 | Na2—O12 | 2.292 (2) |
O14—H17 | 0.90 | Na2—O13 | 2.387 (2) |
O14—H18 | 0.90 | Na2—O13v | 2.423 (2) |
O15—H19 | 0.90 | | |
| | | |
C6—S1—C12 | 105.61 (11) | S1—C6—C1 | 122.96 (18) |
C2—S2—C8i | 100.93 (11) | S1—C6—C5 | 116.68 (19) |
O2—S3—O3 | 112.97 (11) | C1—C6—C5 | 120.1 (2) |
O2—S3—O4 | 111.40 (11) | O5—C7—C8 | 123.5 (2) |
O3—S3—O4 | 112.24 (11) | O5—C7—C12 | 117.0 (2) |
O2—S3—C4 | 106.15 (11) | C8—C7—C12 | 119.4 (2) |
O3—S3—C4 | 107.77 (11) | S2i—C8—C9 | 120.93 (18) |
O4—S3—C4 | 105.79 (11) | S2i—C8—C7 | 119.39 (18) |
O6—S4—O7 | 112.21 (11) | C7—C8—C9 | 119.6 (2) |
O6—S4—O8 | 113.01 (11) | C8—C9—C10 | 120.2 (2) |
O7—S4—O8 | 112.27 (11) | C8—C9—H5 | 121.4 |
O6—S4—C10 | 105.68 (11) | C10—C9—H5 | 118.3 |
O7—S4—C10 | 106.04 (11) | S4—C10—C9 | 118.03 (18) |
O8—S4—C10 | 107.00 (11) | S4—C10—C11 | 121.50 (18) |
C1—O1—H1 | 108.8 | C9—C10—C11 | 120.5 (2) |
S3—O2—Na1 | 134.69 (11) | C10—C11—C12 | 119.5 (2) |
S3—O3—Na2 | 148.88 (12) | C10—C11—H6 | 116.6 |
C7—O5—H4 | 112.6 | C12—C11—H6 | 123.8 |
S4—O6—Na1ii | 149.38 (11) | S1—C12—C7 | 121.24 (18) |
S4—O8—Na2iv | 127.9 (1) | S1—C12—C11 | 118.07 (18) |
H7—O9—H8 | 104.5 | C7—C12—C11 | 120.6 (2) |
H9—O10—H10 | 104.5 | O2—Na1—O6ii | 85.21 (7) |
Na1—O11—Na1iii | 96.80 (7) | O2—Na1—O9 | 166.16 (8) |
H11—O11—H12 | 104.5 | O2—Na1—O10 | 104.32 (7) |
H13—O12—H14 | 104.5 | O2—Na1—O11 | 88.49 (7) |
Na2—O13—Na2v | 94.18 (7) | O2—Na1—O11iii | 79.91 (7) |
H15—O13—H16 | 104.5 | O6ii—Na1—O9 | 81.28 (7) |
H17—O14—H18 | 104.5 | O9—Na1—O10 | 76.97 (7) |
H19—O15—H20 | 104.5 | O9—Na1—O11 | 95.64 (7) |
O1—C1—C2 | 124.1 (2) | O9—Na1—O11iii | 113.65 (7) |
O1—C1—C6 | 116.6 (2) | O10—Na1—O11 | 155.35 (8) |
C2—C1—C6 | 119.3 (2) | O11—Na1—O11iii | 83.20 (7) |
S2—C2—C1 | 119.80 (18) | S3—Na2—O12 | 165.22 (6) |
S2—C2—C3 | 119.92 (19) | O3—Na2—O12 | 153.71 (8) |
C1—C2—C3 | 120.2 (2) | O3—Na2—O13 | 87.89 (7) |
C2—C3—C4 | 119.4 (2) | O3—Na2—O8iv | 87.03 (7) |
C2—C3—H2 | 114.9 | O3—Na2—O12 | 153.71 (8) |
C4—C3—H2 | 125.7 | O3—Na2—O13v | 102.85 (7) |
S3—C4—C3 | 120.07 (19) | O8iv—Na2—O12 | 87.12 (7) |
S3—C4—C5 | 118.89 (19) | O8iv—Na2—O13 | 143.44 (7) |
C3—C4—C5 | 120.9 (2) | O8iv—Na2—O13v | 130.56 (7) |
C4—C5—C6 | 120.1 (2) | O12—Na2—O13 | 81.71 (7) |
C4—C5—H3 | 121.7 | O12—Na2—O13v | 100.41 (7) |
C6—C5—H3 | 118.2 | O13—Na2—O13v | 85.82 (7) |
Symmetry codes: (i) −x, −y, −z+1; (ii) −x+1, −y+1, −z+1; (iii) −x+1, −y, −z; (iv) −x+1, −y, −z+1; (v) −x, −y−1, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O15iv | 0.90 | 1.95 | 2.693 (2) | 140 |
O5—H4···O15vi | 0.82 | 1.97 | 2.688 (2) | 146 |
O9—H7···O4vii | 0.90 | 1.97 | 2.831 (3) | 159 |
O9—H8···O14vii | 0.90 | 1.86 | 2.756 (3) | 176 |
O10—H9···O4vii | 0.90 | 2.16 | 3.033 (3) | 166 |
O10—H9···O9 | 0.90 | 2.71 | 3.055 (3) | 104 |
O10—H10···O7iv | 0.90 | 2.06 | 2.939 (3) | 165 |
O11—H11···O3iii | 0.90 | 2.06 | 2.894 (2) | 153 |
O11—H12···O12viii | 0.90 | 2.07 | 2.858 (3) | 146 |
O12—H13···O2ix | 0.90 | 1.91 | 2.796 (3) | 171 |
O12—H14···O4v | 0.90 | 1.90 | 2.793 (3) | 170 |
O13—H15···O7x | 0.90 | 2.04 | 2.935 (3) | 173 |
O13—H16···O9iii | 0.90 | 1.93 | 2.787 (3) | 159 |
O14—H17···O5 | 0.90 | 2.04 | 2.910 (3) | 163 |
Symmetry codes: (iii) −x+1, −y, −z; (iv) −x+1, −y, −z+1; (v) −x, −y−1, −z; (vi) x−1, y, z; (vii) x+1, y, z; (viii) x, y+1, z; (ix) x, y−1, z; (x) x, y−1, z−1. |
Experimental details
Crystal data |
Chemical formula | 4Na+·C24H12O16S84−·14H2O |
Mr | 1157.00 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 93 |
a, b, c (Å) | 8.2974 (7), 8.8446 (6), 15.789 (1) |
α, β, γ (°) | 95.743 (4), 102.490 (2), 97.897 (4) |
V (Å3) | 1110.4 (1) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 0.54 |
Crystal size (mm) | 0.30 × 0.20 × 0.10 |
|
Data collection |
Diffractometer | Rigaku R-AXIS-IV diffractometer |
Absorption correction | Multi-scan (Higashi, 1995) |
Tmin, Tmax | 0.848, 0.948 |
No. of measured, independent and observed [F2 > 2σ(F2)] reflections | 8541, 4678, 3541 |
Rint | 0.018 |
(sin θ/λ)max (Å−1) | 0.649 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.031, 0.091, 0.84 |
No. of reflections | 4233 |
No. of parameters | 358 |
No. of restraints | ? |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.46, −0.54 |
Selected geometric parameters (Å, º) topS1—C6 | 1.770 (2) | C5—C6 | 1.386 (3) |
S1—C12 | 1.769 (2) | C7—C8 | 1.405 (3) |
S2—C2 | 1.792 (2) | C7—C12 | 1.398 (3) |
S2—C8i | 1.785 (2) | C8—C9 | 1.393 (3) |
S3—O2 | 1.4590 (18) | C9—C10 | 1.390 (3) |
S3—O3 | 1.4524 (18) | C10—C11 | 1.390 (3) |
S3—O4 | 1.4715 (18) | C11—C12 | 1.392 (3) |
S3—C4 | 1.763 (2) | Na1—O2 | 2.382 (2) |
S4—O6 | 1.4590 (18) | Na1—O6ii | 2.434 (2) |
S4—O7 | 1.4635 (18) | Na1—O9 | 2.373 (2) |
S4—O8 | 1.4593 (18) | Na1—O10 | 2.531 (2) |
S4—C10 | 1.772 (2) | Na1—O11 | 2.347 (2) |
O1—C1 | 1.347 (3) | Na1—O11iii | 2.475 (2) |
O5—C7 | 1.350 (3) | Na2—O3 | 2.252 (2) |
C1—C2 | 1.404 (4) | Na2—O8iv | 2.402 (2) |
C1—C6 | 1.406 (3) | Na2—O12 | 2.292 (2) |
C2—C3 | 1.395 (3) | Na2—O13 | 2.387 (2) |
C3—C4 | 1.396 (3) | Na2—O13v | 2.423 (2) |
C4—C5 | 1.383 (4) | | |
| | | |
C6—S1—C12 | 105.61 (11) | C8—C7—C12 | 119.4 (2) |
C2—S2—C8i | 100.93 (11) | S2i—C8—C9 | 120.93 (18) |
O2—S3—O3 | 112.97 (11) | S2i—C8—C7 | 119.39 (18) |
O2—S3—O4 | 111.40 (11) | C7—C8—C9 | 119.6 (2) |
O3—S3—O4 | 112.24 (11) | C8—C9—C10 | 120.2 (2) |
O2—S3—C4 | 106.15 (11) | S4—C10—C9 | 118.03 (18) |
O3—S3—C4 | 107.77 (11) | S4—C10—C11 | 121.50 (18) |
O4—S3—C4 | 105.79 (11) | C9—C10—C11 | 120.5 (2) |
O6—S4—O7 | 112.21 (11) | C10—C11—C12 | 119.5 (2) |
O6—S4—O8 | 113.01 (11) | S1—C12—C7 | 121.24 (18) |
O7—S4—O8 | 112.27 (11) | S1—C12—C11 | 118.07 (18) |
O6—S4—C10 | 105.68 (11) | C7—C12—C11 | 120.6 (2) |
O7—S4—C10 | 106.04 (11) | O2—Na1—O6ii | 85.21 (7) |
O8—S4—C10 | 107.00 (11) | O2—Na1—O9 | 166.16 (8) |
S3—O2—Na1 | 134.69 (11) | O2—Na1—O10 | 104.32 (7) |
S3—O3—Na2 | 148.88 (12) | O2—Na1—O11 | 88.49 (7) |
S4—O6—Na1ii | 149.38 (11) | O2—Na1—O11iii | 79.91 (7) |
S4—O8—Na2iv | 127.9 (1) | O6ii—Na1—O9 | 81.28 (7) |
Na1—O11—Na1iii | 96.80 (7) | O9—Na1—O10 | 76.97 (7) |
Na2—O13—Na2v | 94.18 (7) | O9—Na1—O11 | 95.64 (7) |
O1—C1—C2 | 124.1 (2) | O9—Na1—O11iii | 113.65 (7) |
O1—C1—C6 | 116.6 (2) | O10—Na1—O11 | 155.35 (8) |
C2—C1—C6 | 119.3 (2) | O11—Na1—O11iii | 83.20 (7) |
S2—C2—C1 | 119.80 (18) | S3—Na2—O12 | 165.22 (6) |
S2—C2—C3 | 119.92 (19) | O3—Na2—O12 | 153.71 (8) |
C1—C2—C3 | 120.2 (2) | O3—Na2—O13 | 87.89 (7) |
C2—C3—C4 | 119.4 (2) | O3—Na2—O8iv | 87.03 (7) |
S3—C4—C3 | 120.07 (19) | O3—Na2—O12 | 153.71 (8) |
S3—C4—C5 | 118.89 (19) | O3—Na2—O13v | 102.85 (7) |
C3—C4—C5 | 120.9 (2) | O8iv—Na2—O12 | 87.12 (7) |
C4—C5—C6 | 120.1 (2) | O8iv—Na2—O13 | 143.44 (7) |
S1—C6—C1 | 122.96 (18) | O8iv—Na2—O13v | 130.56 (7) |
S1—C6—C5 | 116.68 (19) | O12—Na2—O13 | 81.71 (7) |
C1—C6—C5 | 120.1 (2) | O12—Na2—O13v | 100.41 (7) |
O5—C7—C8 | 123.5 (2) | O13—Na2—O13v | 85.82 (7) |
O5—C7—C12 | 117.0 (2) | | |
Symmetry codes: (i) −x, −y, −z+1; (ii) −x+1, −y+1, −z+1; (iii) −x+1, −y, −z; (iv) −x+1, −y, −z+1; (v) −x, −y−1, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O15iv | 0.90 | 1.95 | 2.693 (2) | 140 |
O5—H4···O15vi | 0.82 | 1.97 | 2.688 (2) | 146 |
O9—H7···O4vii | 0.90 | 1.97 | 2.831 (3) | 159 |
O9—H8···O14vii | 0.90 | 1.86 | 2.756 (3) | 176 |
O10—H9···O4vii | 0.90 | 2.16 | 3.033 (3) | 166 |
O10—H9···O9 | 0.90 | 2.71 | 3.055 (3) | 104 |
O10—H10···O7iv | 0.90 | 2.06 | 2.939 (3) | 165 |
O11—H11···O3iii | 0.90 | 2.06 | 2.894 (2) | 153 |
O11—H12···O12viii | 0.90 | 2.07 | 2.858 (3) | 146 |
O12—H13···O2ix | 0.90 | 1.91 | 2.796 (3) | 171 |
O12—H14···O4v | 0.90 | 1.90 | 2.793 (3) | 170 |
O13—H15···O7x | 0.90 | 2.04 | 2.935 (3) | 173 |
O13—H16···O9iii | 0.90 | 1.93 | 2.787 (3) | 159 |
O14—H17···O5 | 0.90 | 2.04 | 2.910 (3) | 163 |
Symmetry codes: (iii) −x+1, −y, −z; (iv) −x+1, −y, −z+1; (v) −x, −y−1, −z; (vi) x−1, y, z; (vii) x+1, y, z; (viii) x, y+1, z; (ix) x, y−1, z; (x) x, y−1, z−1. |
The title compound, (I) (Na4TCAS.14H2O), gives the first crystal structure of Na4TCAS without organic solvents as guest molecules, while crystal structures of Na4TCAS with acetone or 1,4-dioxane (Iki et al., 2001) and analogue of thiacalix[4]arenetetrasulfonate, Na5[S8C24O24H11]·EtOH·9H2O (Iki et al., 2002), are known.
A view of the TCAS4− anion is shown in Fig. 1. Selected bond distances and angles are tabulated in Table 1. The TCAS4− molecule adopted the 1,2-alternate conformation. The center of symmetry resides on the mid-point of two S atoms (S1 and S1*). The bond distances and angles in the TCAS4− molecule are similar to those observed in Na4[C24H12O16S8]·2C4H8O2·9H2O (Iki et al., 2001).
The environments around Na1 and Na2 atoms are different. The Na1 atom is coordinated by six O atoms (O2 and O6ii from sulfonate O atoms, and O9, O10, O11 and O11iii from water molecules; see Table 1 for symmetry codes) in a distorted octahedral manner. The NaO6 polyhedra share a common edge. The bridging positions are occupied by water molecules (O11 and O11iii). The center of symmetry resides on the midpoint of two aqua-bridges. The Na1···O11 [2.346 (2) Å] and Na1···O11iii [2.474 (2) Å] distances are in the range of the usual Na···µ-H2O distances (2.35–2.48 Å) [for examples, see Dressick et al. (2000) and Achour et al. (1998)]. The Na2 atom is coordinated by five O atoms (O3 and O8iv from sulfonate O atoms, and O12, O13 and O13v from water molecules; see Table 1 for symmetry codes) in a distorted trigonalbipyramidal manner. The NaO5 polyhedra share a common edge. The bridging positions are occupied by water molecules (O13 and O13v). The center of symmetry resides on the mid-point of two aqua bridges. The Na2···O13 [2.388 (2) Å] and Na2···O13v [2.388 (2) Å] distances are in the usual range for Na···µ-H2O distances (2.27–2.44 Å) (for examples, see Hauptmann et al. (1999) and Jeon et al. (1996)].
The crystal structure of (I), viewed along the b axis, is shown in Fig. 2. Since sulfonate O atoms are coordinated to Na+ cations, TCAS4− molecules are further connected by sodium aqua dimmers, Na–(µ-H2O)2–Na, forming a three-dimensional network.
The compound exists in the solid state as layers of anionic thiacalixarenes in the 1,2-alternate configuration. These layers alternate with inorganic layers that contain sodium cations and water molecules. The overall structure bears a close resemblance to those found in clay minerals. This similarity has also been reported in studies of calixarene compounds (Atwood et al., 1988; Coleman et al., 1988).
Several metal (Fe, Co, Ni, Cu, Zn) complexes of water-soluble thiacalix[4]arenetetrasulfonate have been prepared by the incorporation of the metal ions into the solid-state layered structure. There have also been several reports of the intercalation of metal ions with water-soluble calix[4]arenes (Atwood et al., 1992). X-ray structure analyses of the metal complexes of water-soluble thiacalix[4]arenetetrasulfonate are in progress.