Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102016712/av1115sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102016712/av1115Isup2.hkl |
CCDC reference: 199404
The title complex was prepared by thoroughly mixing Ba(OH)2·8H2O (1.58 g, 5 mmol), sodium saccharine (2.05 g, 10 mmol) and 18-crown-6 (2.64 g, 5 mmol) in ethanol (50 ml). Distilled water (5 ml) was then added and the mixture was warmed until a solution was obtained. The solution was filtered and left to evaporate slowly in air. Colourless single crystals of (I) suitable for X-ray data collection were obtained from the solution after a few days.
All H atoms were geometrically fixed with ideal bond lengths and angles, and were treated as riding atoms. The highest peak of 2.18 e Å-3 and deepest hole of -0.74 e Å-3 were 0.78 and 0.53 Å from Ba1, respectively.
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 1990).
[Ba2(C12H24O6)2(H2O)4S2](C7H5NO3S)2 | Z = 1 |
Mr = 1305.85 | F(000) = 660 |
Triclinic, P1 | Dx = 1.679 Mg m−3 |
a = 8.5668 (5) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 11.9073 (6) Å | Cell parameters from 6797 reflections |
c = 14.0768 (8) Å | θ = 2.6–28.3° |
α = 109.195 (1)° | µ = 1.75 mm−1 |
β = 103.383 (1)° | T = 293 K |
γ = 96.374 (1)° | Block, colourless |
V = 1291.6 (1) Å3 | 0.28 × 0.26 × 0.24 mm |
Siemens SMART CCD area-detector diffractometer | 6090 independent reflections |
Radiation source: fine-focus sealed tube | 5704 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.012 |
Detector resolution: 8.33 pixels mm-1 | θmax = 28.3°, θmin = 2.6° |
ω scans | h = −11→8 |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | k = −15→15 |
Tmin = 0.639, Tmax = 0.678 | l = −13→18 |
8231 measured reflections |
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)] = 0.034 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.102 | H-atom parameters constrained |
S = 1.10 | w = 1/[σ2(Fo2) + (0.0544P)2 + 2.0593P] where P = (Fo2 + 2Fc2)/3 |
6090 reflections | (Δ/σ)max = 0.001 |
307 parameters | Δρmax = 2.18 e Å−3 |
0 restraints | Δρmin = −0.74 e Å−3 |
[Ba2(C12H24O6)2(H2O)4S2](C7H5NO3S)2 | γ = 96.374 (1)° |
Mr = 1305.85 | V = 1291.6 (1) Å3 |
Triclinic, P1 | Z = 1 |
a = 8.5668 (5) Å | Mo Kα radiation |
b = 11.9073 (6) Å | µ = 1.75 mm−1 |
c = 14.0768 (8) Å | T = 293 K |
α = 109.195 (1)° | 0.28 × 0.26 × 0.24 mm |
β = 103.383 (1)° |
Siemens SMART CCD area-detector diffractometer | 6090 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 5704 reflections with I > 2σ(I) |
Tmin = 0.639, Tmax = 0.678 | Rint = 0.012 |
8231 measured reflections |
R[F2 > 2σ(F2)] = 0.034 | 0 restraints |
wR(F2) = 0.102 | H-atom parameters constrained |
S = 1.10 | Δρmax = 2.18 e Å−3 |
6090 reflections | Δρmin = −0.74 e Å−3 |
307 parameters |
Experimental. The data collection covered over a hemisphere of reciprocal space by a combination of three sets of exposures; each set had a different ϕ angle (0, 88 and 180°) for the crystal and each exposure of 30 s covered 0.3° in ω. The crystal-to-detector distance was 5 cm and the detector swing angle was -35°. Crystal decay was monitored by repeating fifty initial frames at the end of data collection and analysing the intensity of duplicate reflections, and was found to be negligible. |
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 | 0.14244 (2) | 0.159804 (17) | 0.692474 (15) | 0.03004 (8) | |
S1 | 0.15027 (12) | −0.09419 (9) | 0.51629 (8) | 0.0426 (2) | |
S2 | 0.30448 (14) | 0.27839 (10) | 0.24311 (8) | 0.0450 (2) | |
O1 | 0.1432 (4) | 0.1522 (2) | 0.8984 (2) | 0.0414 (6) | |
O2 | 0.3742 (3) | 0.0563 (2) | 0.8046 (2) | 0.0380 (6) | |
O3 | 0.4661 (3) | 0.1670 (3) | 0.6711 (2) | 0.0411 (6) | |
O4 | 0.2645 (3) | 0.2891 (3) | 0.5733 (2) | 0.0420 (6) | |
O5 | 0.0451 (3) | 0.3811 (2) | 0.6795 (2) | 0.0378 (5) | |
O6 | −0.0633 (3) | 0.2806 (2) | 0.8142 (2) | 0.0410 (6) | |
O1W | −0.0826 (5) | −0.0491 (3) | 0.6702 (3) | 0.0604 (9) | |
H2W1 | −0.0994 | −0.1011 | 0.6076 | 0.091* | |
H1W1 | −0.1309 | −0.0852 | 0.7020 | 0.091* | |
O2W | 0.3686 (4) | 0.3481 (3) | 0.8633 (2) | 0.0532 (8) | |
H2W2 | 0.4539 | 0.3881 | 0.8595 | 0.080* | |
H1W2 | 0.3881 | 0.3462 | 0.9246 | 0.080* | |
O7 | 0.2985 (6) | 0.3452 (4) | 0.3476 (3) | 0.0804 (13) | |
O8 | 0.2163 (5) | 0.1528 (3) | 0.1988 (3) | 0.0648 (9) | |
O9 | 0.3644 (4) | 0.4444 (3) | 0.0744 (2) | 0.0430 (6) | |
N1 | 0.2496 (4) | 0.3486 (3) | 0.1664 (3) | 0.0394 (7) | |
H1 | 0.1530 | 0.3634 | 0.1500 | 0.047* | |
C1 | 0.1993 (6) | 0.0491 (4) | 0.9130 (3) | 0.0493 (10) | |
H1A | 0.1293 | −0.0251 | 0.8597 | 0.059* | |
H1B | 0.1967 | 0.0485 | 0.9814 | 0.059* | |
C2 | 0.3703 (6) | 0.0570 (4) | 0.9050 (3) | 0.0512 (11) | |
H2A | 0.4396 | 0.1310 | 0.9588 | 0.061* | |
H2B | 0.4126 | −0.0114 | 0.9162 | 0.061* | |
C3 | 0.5389 (5) | 0.0803 (4) | 0.7998 (4) | 0.0492 (10) | |
H3A | 0.5975 | 0.0220 | 0.8186 | 0.059* | |
H3B | 0.5944 | 0.1609 | 0.8496 | 0.059* | |
C4 | 0.5390 (5) | 0.0716 (4) | 0.6922 (4) | 0.0479 (10) | |
H4A | 0.6503 | 0.0803 | 0.6870 | 0.057* | |
H4B | 0.4768 | −0.0068 | 0.6415 | 0.057* | |
C5 | 0.4674 (5) | 0.1703 (4) | 0.5711 (3) | 0.0486 (10) | |
H5A | 0.3860 | 0.1035 | 0.5160 | 0.058* | |
H5B | 0.5742 | 0.1628 | 0.5604 | 0.058* | |
C6 | 0.4297 (5) | 0.2875 (5) | 0.5683 (4) | 0.0521 (10) | |
H6A | 0.5051 | 0.3542 | 0.6273 | 0.062* | |
H6B | 0.4411 | 0.2965 | 0.5040 | 0.062* | |
C7 | 0.2221 (6) | 0.4034 (4) | 0.5788 (3) | 0.0492 (10) | |
H7A | 0.2307 | 0.4192 | 0.5167 | 0.059* | |
H7B | 0.2971 | 0.4680 | 0.6397 | 0.059* | |
C8 | 0.0531 (6) | 0.4007 (4) | 0.5862 (3) | 0.0472 (9) | |
H8A | 0.0220 | 0.4771 | 0.5880 | 0.057* | |
H8B | −0.0220 | 0.3359 | 0.5255 | 0.057* | |
C9 | −0.1102 (5) | 0.3895 (4) | 0.6980 (4) | 0.0506 (10) | |
H9A | −0.1925 | 0.3201 | 0.6471 | 0.061* | |
H9B | −0.1422 | 0.4627 | 0.6909 | 0.061* | |
C10 | −0.0981 (6) | 0.3926 (4) | 0.8062 (4) | 0.0547 (11) | |
H10A | −0.0118 | 0.4597 | 0.8565 | 0.066* | |
H10B | −0.2005 | 0.4051 | 0.8222 | 0.066* | |
C11 | −0.0416 (5) | 0.2840 (4) | 0.9186 (3) | 0.0474 (10) | |
H11A | −0.1401 | 0.2984 | 0.9395 | 0.057* | |
H11B | 0.0485 | 0.3497 | 0.9666 | 0.057* | |
C12 | −0.0060 (5) | 0.1650 (4) | 0.9232 (3) | 0.0471 (9) | |
H12A | 0.0031 | 0.1640 | 0.9929 | 0.057* | |
H12B | −0.0937 | 0.0987 | 0.8732 | 0.057* | |
C13 | 0.5089 (5) | 0.2828 (3) | 0.2368 (3) | 0.0408 (8) | |
C14 | 0.6367 (7) | 0.2418 (4) | 0.2864 (4) | 0.0586 (12) | |
H14 | 0.6252 | 0.2052 | 0.3341 | 0.070* | |
C15 | 0.7825 (6) | 0.2581 (4) | 0.2616 (5) | 0.0695 (16) | |
H15 | 0.8709 | 0.2311 | 0.2930 | 0.083* | |
C16 | 0.8001 (6) | 0.3130 (5) | 0.1919 (5) | 0.0667 (15) | |
H16 | 0.8997 | 0.3218 | 0.1767 | 0.080* | |
C17 | 0.6726 (5) | 0.3555 (4) | 0.1439 (4) | 0.0494 (10) | |
H17 | 0.6849 | 0.3930 | 0.0969 | 0.059* | |
C18 | 0.5253 (5) | 0.3401 (3) | 0.1684 (3) | 0.0360 (7) | |
C19 | 0.3718 (4) | 0.3821 (3) | 0.1305 (3) | 0.0342 (7) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ba1 | 0.02802 (11) | 0.03112 (11) | 0.03217 (12) | 0.00826 (7) | 0.00949 (8) | 0.01178 (8) |
S1 | 0.0339 (4) | 0.0371 (5) | 0.0441 (5) | 0.0103 (4) | 0.0026 (4) | 0.0037 (4) |
S2 | 0.0570 (6) | 0.0471 (5) | 0.0427 (5) | 0.0129 (4) | 0.0246 (4) | 0.0237 (4) |
O1 | 0.0491 (15) | 0.0393 (14) | 0.0429 (14) | 0.0105 (12) | 0.0200 (12) | 0.0190 (12) |
O2 | 0.0346 (13) | 0.0389 (13) | 0.0345 (13) | 0.0126 (10) | −0.0009 (10) | 0.0115 (10) |
O3 | 0.0356 (13) | 0.0446 (14) | 0.0439 (14) | 0.0153 (11) | 0.0161 (11) | 0.0116 (12) |
O4 | 0.0408 (14) | 0.0417 (14) | 0.0460 (15) | 0.0037 (11) | 0.0151 (12) | 0.0189 (12) |
O5 | 0.0379 (13) | 0.0368 (13) | 0.0417 (14) | 0.0140 (10) | 0.0102 (11) | 0.0168 (11) |
O6 | 0.0393 (14) | 0.0353 (13) | 0.0488 (15) | 0.0130 (11) | 0.0193 (12) | 0.0097 (11) |
O1W | 0.073 (2) | 0.0573 (19) | 0.0478 (17) | −0.0077 (16) | 0.0218 (16) | 0.0189 (15) |
O2W | 0.067 (2) | 0.0466 (16) | 0.0396 (15) | −0.0089 (14) | 0.0204 (14) | 0.0111 (12) |
O7 | 0.125 (4) | 0.097 (3) | 0.0462 (19) | 0.049 (3) | 0.050 (2) | 0.034 (2) |
O8 | 0.064 (2) | 0.0550 (19) | 0.088 (3) | 0.0003 (16) | 0.0297 (19) | 0.0399 (19) |
O9 | 0.0486 (15) | 0.0450 (15) | 0.0432 (15) | 0.0077 (12) | 0.0181 (12) | 0.0230 (12) |
N1 | 0.0373 (16) | 0.0469 (17) | 0.0441 (17) | 0.0126 (13) | 0.0194 (13) | 0.0229 (14) |
C1 | 0.071 (3) | 0.042 (2) | 0.0360 (19) | 0.0096 (19) | 0.0103 (19) | 0.0190 (17) |
C2 | 0.063 (3) | 0.049 (2) | 0.0345 (19) | 0.020 (2) | −0.0032 (18) | 0.0161 (17) |
C3 | 0.0308 (18) | 0.048 (2) | 0.059 (2) | 0.0143 (16) | −0.0026 (17) | 0.0149 (19) |
C4 | 0.0292 (17) | 0.044 (2) | 0.066 (3) | 0.0162 (16) | 0.0135 (17) | 0.0118 (19) |
C5 | 0.040 (2) | 0.059 (2) | 0.045 (2) | 0.0046 (18) | 0.0226 (17) | 0.0095 (19) |
C6 | 0.044 (2) | 0.066 (3) | 0.052 (2) | 0.002 (2) | 0.0215 (19) | 0.026 (2) |
C7 | 0.072 (3) | 0.0374 (19) | 0.043 (2) | 0.0071 (19) | 0.020 (2) | 0.0186 (17) |
C8 | 0.063 (3) | 0.0374 (19) | 0.040 (2) | 0.0170 (18) | 0.0055 (18) | 0.0165 (16) |
C9 | 0.040 (2) | 0.044 (2) | 0.072 (3) | 0.0240 (17) | 0.016 (2) | 0.021 (2) |
C10 | 0.054 (2) | 0.040 (2) | 0.076 (3) | 0.0228 (19) | 0.035 (2) | 0.014 (2) |
C11 | 0.039 (2) | 0.051 (2) | 0.047 (2) | 0.0048 (17) | 0.0236 (17) | 0.0040 (18) |
C12 | 0.048 (2) | 0.055 (2) | 0.040 (2) | 0.0005 (18) | 0.0205 (17) | 0.0181 (18) |
C13 | 0.046 (2) | 0.0274 (16) | 0.043 (2) | 0.0074 (15) | 0.0082 (16) | 0.0088 (14) |
C14 | 0.067 (3) | 0.035 (2) | 0.062 (3) | 0.013 (2) | −0.001 (2) | 0.0164 (19) |
C15 | 0.053 (3) | 0.039 (2) | 0.091 (4) | 0.019 (2) | −0.007 (3) | 0.006 (2) |
C16 | 0.039 (2) | 0.045 (2) | 0.095 (4) | 0.0099 (19) | 0.017 (2) | 0.001 (3) |
C17 | 0.041 (2) | 0.039 (2) | 0.062 (3) | 0.0043 (16) | 0.0205 (19) | 0.0071 (18) |
C18 | 0.0371 (18) | 0.0271 (15) | 0.0378 (18) | 0.0045 (13) | 0.0106 (14) | 0.0049 (13) |
C19 | 0.0386 (18) | 0.0305 (16) | 0.0304 (16) | 0.0049 (13) | 0.0131 (14) | 0.0058 (13) |
Ba1—O2W | 2.810 (3) | C2—H2B | 0.9700 |
Ba1—O3 | 2.852 (3) | C3—C4 | 1.485 (7) |
Ba1—O1W | 2.854 (3) | C3—H3A | 0.9700 |
Ba1—O2 | 2.885 (2) | C3—H3B | 0.9700 |
Ba1—O5 | 2.900 (3) | C4—H4A | 0.9700 |
Ba1—O4 | 2.903 (3) | C4—H4B | 0.9700 |
Ba1—O6 | 2.907 (3) | C5—C6 | 1.478 (7) |
Ba1—O1 | 2.929 (3) | C5—H5A | 0.9700 |
Ba1—S1i | 3.1904 (10) | C5—H5B | 0.9700 |
Ba1—S1 | 3.2391 (10) | C6—H6A | 0.9700 |
S1—Ba1i | 3.1904 (10) | C6—H6B | 0.9700 |
S2—O7 | 1.440 (4) | C7—C8 | 1.473 (7) |
S2—O8 | 1.454 (4) | C7—H7A | 0.9700 |
S2—N1 | 1.591 (3) | C7—H7B | 0.9700 |
S2—C13 | 1.770 (4) | C8—H8A | 0.9700 |
O1—C12 | 1.412 (5) | C8—H8B | 0.9700 |
O1—C1 | 1.425 (5) | C9—C10 | 1.490 (7) |
O2—C2 | 1.418 (5) | C9—H9A | 0.9700 |
O2—C3 | 1.429 (5) | C9—H9B | 0.9700 |
O3—C5 | 1.424 (5) | C10—H10A | 0.9700 |
O3—C4 | 1.435 (5) | C10—H10B | 0.9700 |
O4—C7 | 1.430 (5) | C11—C12 | 1.501 (7) |
O4—C6 | 1.436 (5) | C11—H11A | 0.9700 |
O5—C8 | 1.422 (5) | C11—H11B | 0.9700 |
O5—C9 | 1.422 (5) | C12—H12A | 0.9700 |
O6—C11 | 1.425 (5) | C12—H12B | 0.9700 |
O6—C10 | 1.433 (5) | C13—C18 | 1.374 (5) |
O1W—H2W1 | 0.8619 | C13—C14 | 1.383 (6) |
O1W—H1W1 | 0.8533 | C14—C15 | 1.383 (8) |
O2W—H2W2 | 0.8494 | C14—H14 | 0.9300 |
O2W—H1W2 | 0.8491 | C15—C16 | 1.371 (9) |
O9—C19 | 1.244 (4) | C15—H15 | 0.9300 |
N1—C19 | 1.340 (5) | C16—C17 | 1.382 (7) |
N1—H1 | 0.8600 | C16—H16 | 0.9300 |
C1—C2 | 1.491 (7) | C17—C18 | 1.392 (5) |
C1—H1A | 0.9700 | C17—H17 | 0.9300 |
C1—H1B | 0.9700 | C18—C19 | 1.503 (5) |
C2—H2A | 0.9700 | ||
O2W—Ba1—O3 | 68.96 (9) | O2—C2—H2A | 109.6 |
O2W—Ba1—O1W | 134.69 (9) | C1—C2—H2A | 109.6 |
O3—Ba1—O1W | 126.57 (10) | O2—C2—H2B | 109.6 |
O2W—Ba1—O2 | 70.95 (9) | C1—C2—H2B | 109.6 |
O3—Ba1—O2 | 58.95 (8) | H2A—C2—H2B | 108.1 |
O1W—Ba1—O2 | 82.74 (10) | O2—C3—C4 | 110.0 (3) |
O2W—Ba1—O5 | 75.12 (9) | O2—C3—H3A | 109.7 |
O3—Ba1—O5 | 107.66 (8) | C4—C3—H3A | 109.7 |
O1W—Ba1—O5 | 123.58 (10) | O2—C3—H3B | 109.7 |
O2—Ba1—O5 | 146.06 (8) | C4—C3—H3B | 109.7 |
O2W—Ba1—O4 | 82.65 (8) | H3A—C3—H3B | 108.2 |
O3—Ba1—O4 | 57.91 (8) | O3—C4—C3 | 108.1 (3) |
O1W—Ba1—O4 | 142.66 (9) | O3—C4—H4A | 110.1 |
O2—Ba1—O4 | 116.64 (8) | C3—C4—H4A | 110.1 |
O5—Ba1—O4 | 56.91 (8) | O3—C4—H4B | 110.1 |
O2W—Ba1—O6 | 76.76 (9) | C3—C4—H4B | 110.1 |
O3—Ba1—O6 | 145.50 (8) | H4A—C4—H4B | 108.4 |
O1W—Ba1—O6 | 81.04 (9) | O3—C5—C6 | 107.9 (3) |
O2—Ba1—O6 | 113.32 (8) | O3—C5—H5A | 110.1 |
O5—Ba1—O6 | 58.12 (8) | C6—C5—H5A | 110.1 |
O4—Ba1—O6 | 114.81 (8) | O3—C5—H5B | 110.1 |
O2W—Ba1—O1 | 65.38 (8) | C6—C5—H5B | 110.1 |
O3—Ba1—O1 | 109.46 (8) | H5A—C5—H5B | 108.4 |
O1W—Ba1—O1 | 69.38 (9) | O4—C6—C5 | 108.1 (3) |
O2—Ba1—O1 | 56.94 (8) | O4—C6—H6A | 110.1 |
O5—Ba1—O1 | 108.85 (8) | C5—C6—H6A | 110.1 |
O4—Ba1—O1 | 147.89 (8) | O4—C6—H6B | 110.1 |
O6—Ba1—O1 | 56.76 (8) | C5—C6—H6B | 110.1 |
O2W—Ba1—S1i | 145.47 (7) | H6A—C6—H6B | 108.4 |
O3—Ba1—S1i | 117.17 (6) | O4—C7—C8 | 109.3 (3) |
O1W—Ba1—S1i | 71.69 (7) | O4—C7—H7A | 109.8 |
O2—Ba1—S1i | 142.93 (6) | C8—C7—H7A | 109.8 |
O5—Ba1—S1i | 70.70 (6) | O4—C7—H7B | 109.8 |
O4—Ba1—S1i | 74.86 (6) | C8—C7—H7B | 109.8 |
O6—Ba1—S1i | 89.17 (6) | H7A—C7—H7B | 108.3 |
O1—Ba1—S1i | 131.13 (6) | O5—C8—C7 | 108.7 (3) |
O2W—Ba1—S1 | 137.28 (8) | O5—C8—H8A | 110.0 |
O3—Ba1—S1 | 71.25 (6) | C7—C8—H8A | 110.0 |
O1W—Ba1—S1 | 63.67 (8) | O5—C8—H8B | 110.0 |
O2—Ba1—S1 | 75.74 (6) | C7—C8—H8B | 110.0 |
O5—Ba1—S1 | 132.79 (6) | H8A—C8—H8B | 108.3 |
O4—Ba1—S1 | 89.23 (6) | O5—C9—C10 | 108.6 (3) |
O6—Ba1—S1 | 142.60 (6) | O5—C9—H9A | 110.0 |
O1—Ba1—S1 | 115.90 (6) | C10—C9—H9A | 110.0 |
S1i—Ba1—S1 | 69.06 (3) | O5—C9—H9B | 110.0 |
Ba1i—S1—Ba1 | 110.94 (3) | C10—C9—H9B | 110.0 |
O7—S2—O8 | 114.7 (3) | H9A—C9—H9B | 108.3 |
O7—S2—N1 | 111.1 (2) | O6—C10—C9 | 109.9 (3) |
O8—S2—N1 | 111.5 (2) | O6—C10—H10A | 109.7 |
O7—S2—C13 | 111.5 (2) | C9—C10—H10A | 109.7 |
O8—S2—C13 | 109.2 (2) | O6—C10—H10B | 109.7 |
N1—S2—C13 | 97.60 (18) | C9—C10—H10B | 109.7 |
C12—O1—C1 | 112.2 (3) | H10A—C10—H10B | 108.2 |
C12—O1—Ba1 | 114.2 (2) | O6—C11—C12 | 109.0 (3) |
C1—O1—Ba1 | 112.1 (2) | O6—C11—H11A | 109.9 |
C2—O2—C3 | 111.2 (3) | C12—C11—H11A | 109.9 |
C2—O2—Ba1 | 120.5 (2) | O6—C11—H11B | 109.9 |
C3—O2—Ba1 | 116.1 (2) | C12—C11—H11B | 109.9 |
C5—O3—C4 | 112.5 (3) | H11A—C11—H11B | 108.3 |
C5—O3—Ba1 | 110.1 (2) | O1—C12—C11 | 107.5 (3) |
C4—O3—Ba1 | 113.3 (2) | O1—C12—H12A | 110.2 |
C7—O4—C6 | 111.7 (3) | C11—C12—H12A | 110.2 |
C7—O4—Ba1 | 119.5 (2) | O1—C12—H12B | 110.2 |
C6—O4—Ba1 | 117.5 (2) | C11—C12—H12B | 110.2 |
C8—O5—C9 | 112.1 (3) | H12A—C12—H12B | 108.5 |
C8—O5—Ba1 | 114.3 (2) | C18—C13—C14 | 122.4 (4) |
C9—O5—Ba1 | 111.3 (2) | C18—C13—S2 | 105.8 (3) |
C11—O6—C10 | 110.9 (3) | C14—C13—S2 | 131.8 (4) |
C11—O6—Ba1 | 119.5 (2) | C13—C14—C15 | 116.6 (5) |
C10—O6—Ba1 | 117.6 (2) | C13—C14—H14 | 121.7 |
Ba1—O1W—H2W1 | 107.3 | C15—C14—H14 | 121.7 |
Ba1—O1W—H1W1 | 145.7 | C16—C15—C14 | 121.8 (5) |
H2W1—O1W—H1W1 | 106.3 | C16—C15—H15 | 119.1 |
Ba1—O2W—H2W2 | 124.5 | C14—C15—H15 | 119.1 |
Ba1—O2W—H1W2 | 120.6 | C15—C16—C17 | 121.3 (5) |
H2W2—O2W—H1W2 | 107.8 | C15—C16—H16 | 119.4 |
C19—N1—S2 | 112.0 (3) | C17—C16—H16 | 119.4 |
C19—N1—H1 | 124.0 | C16—C17—C18 | 117.6 (5) |
S2—N1—H1 | 124.0 | C16—C17—H17 | 121.2 |
O1—C1—C2 | 107.8 (3) | C18—C17—H17 | 121.2 |
O1—C1—H1A | 110.1 | C13—C18—C17 | 120.3 (4) |
C2—C1—H1A | 110.1 | C13—C18—C19 | 111.8 (3) |
O1—C1—H1B | 110.1 | C17—C18—C19 | 128.0 (4) |
C2—C1—H1B | 110.1 | O9—C19—N1 | 124.9 (4) |
H1A—C1—H1B | 108.5 | O9—C19—C18 | 122.3 (3) |
O2—C2—C1 | 110.3 (3) | N1—C19—C18 | 112.7 (3) |
O2W—Ba1—S1—Ba1i | −152.35 (9) | O1—Ba1—O5—C8 | 175.0 (2) |
O3—Ba1—S1—Ba1i | −130.26 (7) | S1i—Ba1—O5—C8 | −56.9 (2) |
O1W—Ba1—S1—Ba1i | 79.28 (9) | S1—Ba1—O5—C8 | −24.1 (3) |
O2—Ba1—S1—Ba1i | 168.15 (7) | O2W—Ba1—O5—C9 | −113.6 (3) |
O5—Ba1—S1—Ba1i | −33.22 (8) | O3—Ba1—O5—C9 | −175.2 (3) |
O4—Ba1—S1—Ba1i | −74.07 (6) | O1W—Ba1—O5—C9 | 20.6 (3) |
O6—Ba1—S1—Ba1i | 58.26 (11) | O2—Ba1—O5—C9 | −115.0 (3) |
O1—Ba1—S1—Ba1i | 126.67 (7) | O4—Ba1—O5—C9 | 155.6 (3) |
S1i—Ba1—S1—Ba1i | 0.0 | O6—Ba1—O5—C9 | −30.1 (3) |
O2W—Ba1—O1—C12 | 117.3 (3) | O1—Ba1—O5—C9 | −56.7 (3) |
O3—Ba1—O1—C12 | 171.8 (2) | S1i—Ba1—O5—C9 | 71.4 (3) |
O1W—Ba1—O1—C12 | −65.3 (3) | S1—Ba1—O5—C9 | 104.3 (3) |
O2—Ba1—O1—C12 | −160.1 (3) | O2W—Ba1—O6—C11 | −61.8 (3) |
O5—Ba1—O1—C12 | 54.4 (3) | O3—Ba1—O6—C11 | −68.3 (3) |
O4—Ba1—O1—C12 | 111.6 (3) | O1W—Ba1—O6—C11 | 78.4 (3) |
O6—Ba1—O1—C12 | 27.4 (2) | O2—Ba1—O6—C11 | 0.4 (3) |
S1i—Ba1—O1—C12 | −26.1 (3) | O5—Ba1—O6—C11 | −142.4 (3) |
S1—Ba1—O1—C12 | −110.1 (2) | O4—Ba1—O6—C11 | −137.1 (3) |
O2W—Ba1—O1—C1 | −113.6 (3) | O1—Ba1—O6—C11 | 7.2 (2) |
O3—Ba1—O1—C1 | −59.1 (3) | S1i—Ba1—O6—C11 | 150.0 (3) |
O1W—Ba1—O1—C1 | 63.7 (3) | S1—Ba1—O6—C11 | 97.4 (3) |
O2—Ba1—O1—C1 | −31.1 (3) | O2W—Ba1—O6—C10 | 77.6 (3) |
O5—Ba1—O1—C1 | −176.6 (3) | O3—Ba1—O6—C10 | 71.1 (3) |
O4—Ba1—O1—C1 | −119.3 (3) | O1W—Ba1—O6—C10 | −142.2 (3) |
O6—Ba1—O1—C1 | 156.4 (3) | O2—Ba1—O6—C10 | 139.8 (3) |
S1i—Ba1—O1—C1 | 103.0 (3) | O5—Ba1—O6—C10 | −3.0 (3) |
S1—Ba1—O1—C1 | 18.9 (3) | O4—Ba1—O6—C10 | 2.3 (3) |
O2W—Ba1—O2—C2 | 71.4 (3) | O1—Ba1—O6—C10 | 146.6 (3) |
O3—Ba1—O2—C2 | 147.8 (3) | S1i—Ba1—O6—C10 | −70.6 (3) |
O1W—Ba1—O2—C2 | −71.1 (3) | S1—Ba1—O6—C10 | −123.2 (3) |
O5—Ba1—O2—C2 | 72.9 (3) | O7—S2—N1—C19 | 116.1 (3) |
O4—Ba1—O2—C2 | 142.5 (3) | O8—S2—N1—C19 | −114.7 (3) |
O6—Ba1—O2—C2 | 5.8 (3) | C13—S2—N1—C19 | −0.5 (3) |
O1—Ba1—O2—C2 | −1.0 (3) | C12—O1—C1—C2 | −169.3 (3) |
S1i—Ba1—O2—C2 | −117.2 (3) | Ba1—O1—C1—C2 | 60.6 (3) |
S1—Ba1—O2—C2 | −135.7 (3) | C3—O2—C2—C1 | 172.1 (3) |
O2W—Ba1—O2—C3 | −67.8 (3) | Ba1—O2—C2—C1 | 31.2 (4) |
O3—Ba1—O2—C3 | 8.6 (2) | O1—C1—C2—O2 | −60.5 (4) |
O1W—Ba1—O2—C3 | 149.7 (3) | C2—O2—C3—C4 | 176.6 (3) |
O5—Ba1—O2—C3 | −66.3 (3) | Ba1—O2—C3—C4 | −40.5 (4) |
O4—Ba1—O2—C3 | 3.3 (3) | C5—O3—C4—C3 | 177.2 (3) |
O6—Ba1—O2—C3 | −133.4 (3) | Ba1—O3—C4—C3 | −57.1 (4) |
O1—Ba1—O2—C3 | −140.2 (3) | O2—C3—C4—O3 | 65.1 (4) |
S1i—Ba1—O2—C3 | 103.6 (3) | C4—O3—C5—C6 | −165.9 (3) |
S1—Ba1—O2—C3 | 85.1 (3) | Ba1—O3—C5—C6 | 66.7 (3) |
O2W—Ba1—O3—C5 | −127.8 (3) | C7—O4—C6—C5 | 175.7 (3) |
O1W—Ba1—O3—C5 | 101.5 (3) | Ba1—O4—C6—C5 | 32.2 (4) |
O2—Ba1—O3—C5 | 152.4 (3) | O3—C5—C6—O4 | −65.8 (4) |
O5—Ba1—O3—C5 | −62.1 (3) | C6—O4—C7—C8 | −178.7 (3) |
O4—Ba1—O3—C5 | −33.2 (2) | Ba1—O4—C7—C8 | −36.1 (4) |
O6—Ba1—O3—C5 | −121.0 (3) | C9—O5—C8—C7 | 174.1 (3) |
O1—Ba1—O3—C5 | 179.8 (2) | Ba1—O5—C8—C7 | −58.0 (4) |
S1i—Ba1—O3—C5 | 14.9 (3) | O4—C7—C8—O5 | 61.2 (4) |
S1—Ba1—O3—C5 | 68.1 (2) | C8—O5—C9—C10 | −168.9 (3) |
O2W—Ba1—O3—C4 | 105.3 (3) | Ba1—O5—C9—C10 | 61.6 (4) |
O1W—Ba1—O3—C4 | −25.5 (3) | C11—O6—C10—C9 | 176.6 (3) |
O2—Ba1—O3—C4 | 25.4 (2) | Ba1—O6—C10—C9 | 33.9 (4) |
O5—Ba1—O3—C4 | 171.0 (2) | O5—C9—C10—O6 | −64.0 (5) |
O4—Ba1—O3—C4 | −160.2 (3) | C10—O6—C11—C12 | 179.9 (3) |
O6—Ba1—O3—C4 | 112.0 (3) | Ba1—O6—C11—C12 | −38.3 (4) |
O1—Ba1—O3—C4 | 52.8 (3) | C1—O1—C12—C11 | 172.7 (3) |
S1i—Ba1—O3—C4 | −112.1 (2) | Ba1—O1—C12—C11 | −58.3 (4) |
S1—Ba1—O3—C4 | −58.9 (2) | O6—C11—C12—O1 | 63.0 (4) |
O2W—Ba1—O4—C7 | −71.3 (3) | O7—S2—C13—C18 | −117.9 (3) |
O3—Ba1—O4—C7 | −141.0 (3) | O8—S2—C13—C18 | 114.4 (3) |
O1W—Ba1—O4—C7 | 109.3 (3) | N1—S2—C13—C18 | −1.6 (3) |
O2—Ba1—O4—C7 | −135.6 (3) | O7—S2—C13—C14 | 61.5 (5) |
O5—Ba1—O4—C7 | 5.7 (3) | O8—S2—C13—C14 | −66.2 (5) |
O6—Ba1—O4—C7 | 0.4 (3) | N1—S2—C13—C14 | 177.9 (4) |
O1—Ba1—O4—C7 | −66.0 (3) | C18—C13—C14—C15 | −1.8 (6) |
S1i—Ba1—O4—C7 | 82.3 (3) | S2—C13—C14—C15 | 178.8 (4) |
S1—Ba1—O4—C7 | 150.8 (3) | C13—C14—C15—C16 | 0.5 (7) |
O2W—Ba1—O4—C6 | 69.3 (3) | C14—C15—C16—C17 | 0.5 (8) |
O3—Ba1—O4—C6 | −0.4 (3) | C15—C16—C17—C18 | −0.3 (7) |
O1W—Ba1—O4—C6 | −110.2 (3) | C14—C13—C18—C17 | 2.1 (6) |
O2—Ba1—O4—C6 | 5.0 (3) | S2—C13—C18—C17 | −178.4 (3) |
O5—Ba1—O4—C6 | 146.3 (3) | C14—C13—C18—C19 | −176.5 (4) |
O6—Ba1—O4—C6 | 141.0 (3) | S2—C13—C18—C19 | 3.0 (4) |
O1—Ba1—O4—C6 | 74.5 (3) | C16—C17—C18—C13 | −1.0 (6) |
S1i—Ba1—O4—C6 | −137.1 (3) | C16—C17—C18—C19 | 177.4 (4) |
S1—Ba1—O4—C6 | −68.6 (3) | S2—N1—C19—O9 | −175.5 (3) |
O2W—Ba1—O5—C8 | 118.1 (3) | S2—N1—C19—C18 | 2.4 (4) |
O3—Ba1—O5—C8 | 56.4 (3) | C13—C18—C19—O9 | 174.3 (3) |
O1W—Ba1—O5—C8 | −107.7 (3) | C17—C18—C19—O9 | −4.2 (6) |
O2—Ba1—O5—C8 | 116.7 (3) | C13—C18—C19—N1 | −3.7 (4) |
O4—Ba1—O5—C8 | 27.2 (2) | C17—C18—C19—N1 | 177.8 (4) |
O6—Ba1—O5—C8 | −158.4 (3) |
Symmetry code: (i) −x, −y, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1W1···O8i | 0.85 | 2.05 | 2.898 (7) | 170 |
O2W—H1W2···O9ii | 0.85 | 2.12 | 2.822 (4) | 140 |
O2W—H2W2···O9iii | 0.85 | 2.16 | 2.915 (5) | 147 |
Symmetry codes: (i) −x, −y, −z+1; (ii) x, y, z+1; (iii) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Ba2(C12H24O6)2(H2O)4S2](C7H5NO3S)2 |
Mr | 1305.85 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 8.5668 (5), 11.9073 (6), 14.0768 (8) |
α, β, γ (°) | 109.195 (1), 103.383 (1), 96.374 (1) |
V (Å3) | 1291.6 (1) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 1.75 |
Crystal size (mm) | 0.28 × 0.26 × 0.24 |
Data collection | |
Diffractometer | Siemens SMART CCD area-detector diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.639, 0.678 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8231, 6090, 5704 |
Rint | 0.012 |
(sin θ/λ)max (Å−1) | 0.668 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.102, 1.10 |
No. of reflections | 6090 |
No. of parameters | 307 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 2.18, −0.74 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXTL (Sheldrick, 1997), SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 1990).
Ba1—S1i | 3.1904 (10) | Ba1—S1 | 3.2391 (10) |
C12—O1—C1—C2 | −169.3 (3) | C6—O4—C7—C8 | −178.7 (3) |
C3—O2—C2—C1 | 172.1 (3) | C9—O5—C8—C7 | 174.1 (3) |
O1—C1—C2—O2 | −60.5 (4) | O4—C7—C8—O5 | 61.2 (4) |
C2—O2—C3—C4 | 176.6 (3) | C8—O5—C9—C10 | −168.9 (3) |
C5—O3—C4—C3 | 177.2 (3) | C11—O6—C10—C9 | 176.6 (3) |
O2—C3—C4—O3 | 65.1 (4) | O5—C9—C10—O6 | −64.0 (5) |
C4—O3—C5—C6 | −165.9 (3) | C10—O6—C11—C12 | 179.9 (3) |
C7—O4—C6—C5 | 175.7 (3) | C1—O1—C12—C11 | 172.7 (3) |
O3—C5—C6—O4 | −65.8 (4) | O6—C11—C12—O1 | 63.0 (4) |
Symmetry code: (i) −x, −y, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1W1···O8i | 0.85 | 2.05 | 2.898 (7) | 170 |
O2W—H1W2···O9ii | 0.85 | 2.12 | 2.822 (4) | 140 |
O2W—H2W2···O9iii | 0.85 | 2.16 | 2.915 (5) | 147 |
Symmetry codes: (i) −x, −y, −z+1; (ii) x, y, z+1; (iii) −x+1, −y+1, −z+1. |
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Complexes of alkaline earth metal cations with 1,4,7,10,13,16-hexaoxacyclooctadecane (18-crown-6) have been investigated intensively (Dyer et al., 1986; Wei et al., 1988; Luger et al., 1992; Rheingold et al., 1993; Usman et al., 2002). Generally, these studies have been devoted to the structures of the complexes, including the conformation of the macrocycle and the position of the metal cation relative to the crown centre, due to the different nature of the metal cation and the counteranion.
In continuing our interest on the variation with temperature of the cell parameters of barium-18-crown-6 complexes, we have prepared the title complex, (I), which is a 2:2 complex of diaquo(18-crown-6)barium(II)sulfide and saccharin. However, for this complex, the cell parameters are almost constant in the temperature range 183–300 K. An X-ray crystal structure determination of (I) was undertaken at 293 K, and the result is reported here. \sch
The asymmetric unit of (I) contains only one half of the molecule, and the other half is generated by a centre of inversion. The BaII atom is encapsulated by an 18-crown-6 ring and is coordinated to the six O atoms of the crown, two water O atoms and two bridging S atoms. The atomic numbering scheme and molecular conformation of (I) are shown in Fig. 1. The bond lengths and angles have normal values (Allen et al., 1987).
The average Ba—Ocrown distance is 2.896 Å, which is slightly elongated when compared with that in barium-bis(trimethylacetate)-18-crown-6 [2.823 (6) Å; Rheingold et al., 1993] or barium-2,4-dinitrophenolate-18-crown-6 [2.794 (3) Å; Usman et al., 2002]. The average Ba—Owater distance [2.832 Å] is comparable with that in aqua(18-crown-6)barium(II)bis(o-nitrophenolate) [2.836 (4) Å; Chantrapromma et al., 2002].
The aromatic ring systems of the saccharin moieties in (I) are essentially planar, with a maximum deviation of 0.042 (4) Å for atom C19, and the dihedral angle between the five- and six-membered rings is 2.2 (2)°. The bond lengths and angles within this moiety are comparable with those in free saccharin (Deng et al., 2001). Atom O9 is displaced by 0.153 (3) Å from the saccharin plane, whereas atoms O7 and O8 are conditioned by the tetrahedral conformation of the S2 atom, with the average angle subtended at S2 being 109.2°.
In the crown of (I), the C atoms deviate from the least-squares plane by -0.352 (4) to 0.443 (5) Å, with the BaII atom displaced from the crown ring by 0.908 (1) Å. The average C—O and C—C bond distances are 1.426 and 1.486 Å, respectively. The average C—O distance is normal for a C—O single bond (Allen et al., 1987), whereas that of the C—C bond is shorter than the average for a Csp3—Csp3 single bond, due to the macrocyclic C—C shortening of the crown ether (Shoham et al., 1983).
The O—C—C and C—O—C angles are almost tetrahedral, with average values of 108.7 and 111.8°, respectively. The O atoms of the crown ring form a regular hexagon, with nonbonded O···O distances in the range 2.766 (4)–2.824 (4) Å, and their maximum deviations from the mean plane are 0.12 and -0.28 Å. For which atoms?
The conformation of the crown in (I) is that of the typical crown ether arrangement, i.e. approximately D3 d symmetry, determined by the +sc or -sc and ap conformations of the O—C—C—O and C—O—C—C torsion angles. The mean plane of the crown makes a dihedral angle of 67.1 (1)° with respect to the Ba1/Ba1A/S1/S1A plane.
The symmetry-related molecules are linked by intermolcular O2W-H1W2···O9ii and O2W-H2W2···O9iii hydrogen bonds into molecular columns, which are interconnected by O1W-H1W1···O8i hydrogen bonds into molecular layers (Fig. 2).