Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100019788/vj1127sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100019788/vj1127Isup2.hkl |
CCDC reference: 162584
For related literature, see: Adam et al. (1995); Blake et al. (1998); Searle & Geue (1984); Taylor & Kennard (1982).
Compound (I) was prepared by the reaction of diethanolamine and tosyl chloride according to the published procedure (Searle & Geue, 1984). Single crystals suitable for X-ray crystallography were prepared by vapor diffusion of diethyl ether into the acetonitrile solution of compound (I) at room temperature.
H atoms were added at calculated positions (C—H 0.96 Å) and refined using a riding model. They were assigned isotropic displacement parameters equal to 1.2 times the equivalent isotropic displacement parameter of the atom to which they are attached.
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SHELXTL (Sheldrick, 1996b); program(s) used to solve structure: SHELXTL; program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
C25H29NO8S3 | F(000) = 1192 |
Mr = 567.67 | Dx = 1.394 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 11.3887 (10) Å | Cell parameters from 17590 reflections |
b = 22.0576 (19) Å | θ = 1.9–28.4° |
c = 11.7301 (10) Å | µ = 0.32 mm−1 |
β = 113.330 (1)° | T = 293 K |
V = 2705.8 (4) Å3 | Plate, colorless |
Z = 4 | 0.40 × 0.30 × 0.10 mm |
CCD area detector diffractometer | 3614 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.047 |
Graphite monochromator | θmax = 28.4°, θmin = 1.9° |
ϕ and ω scans | h = −15→13 |
17590 measured reflections | k = −29→23 |
6572 independent reflections | l = −14→14 |
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)] = 0.047 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.136 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.068P)2] where P = (Fo2 + 2Fc2)/3 |
6572 reflections | (Δ/σ)max < 0.001 |
334 parameters | Δρmax = 0.28 e Å−3 |
0 restraints | Δρmin = −0.29 e Å−3 |
C25H29NO8S3 | V = 2705.8 (4) Å3 |
Mr = 567.67 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 11.3887 (10) Å | µ = 0.32 mm−1 |
b = 22.0576 (19) Å | T = 293 K |
c = 11.7301 (10) Å | 0.40 × 0.30 × 0.10 mm |
β = 113.330 (1)° |
CCD area detector diffractometer | 3614 reflections with I > 2σ(I) |
17590 measured reflections | Rint = 0.047 |
6572 independent reflections |
R[F2 > 2σ(F2)] = 0.047 | 0 restraints |
wR(F2) = 0.136 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.28 e Å−3 |
6572 reflections | Δρmin = −0.29 e Å−3 |
334 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 | ||
S1 | 0.37323 (6) | 0.40954 (3) | 0.81419 (6) | 0.04859 (18) | |
S2 | 0.07641 (7) | 0.61162 (3) | 0.96867 (6) | 0.05512 (19) | |
S3 | −0.18899 (7) | 0.38665 (3) | 0.49546 (6) | 0.0623 (2) | |
O1 | −0.06145 (17) | 0.36808 (8) | 0.60595 (15) | 0.0614 (5) | |
O2 | 0.18674 (18) | 0.57087 (8) | 0.96467 (16) | 0.0636 (5) | |
O3 | 0.45664 (17) | 0.46049 (8) | 0.84379 (17) | 0.0640 (5) | |
O4 | 0.33576 (18) | 0.38053 (8) | 0.69667 (15) | 0.0644 (5) | |
O5 | −0.0241 (2) | 0.57494 (9) | 0.97176 (19) | 0.0791 (6) | |
O6 | 0.1396 (2) | 0.65128 (8) | 1.06877 (16) | 0.0811 (6) | |
O7 | −0.26634 (19) | 0.33362 (9) | 0.47450 (19) | 0.0853 (6) | |
O8 | −0.1611 (2) | 0.41154 (10) | 0.39737 (17) | 0.0836 (6) | |
N | 0.24073 (17) | 0.43264 (8) | 0.82231 (17) | 0.0471 (5) | |
C1 | 0.0429 (2) | 0.41098 (12) | 0.6444 (2) | 0.0598 (7) | |
H1A | 0.0119 | 0.4515 | 0.6439 | 0.072* | |
H1B | 0.0874 | 0.4093 | 0.5900 | 0.072* | |
C2 | 0.1302 (2) | 0.39234 (11) | 0.7747 (2) | 0.0500 (6) | |
H2A | 0.0843 | 0.3941 | 0.8278 | 0.060* | |
H2B | 0.1584 | 0.3514 | 0.7741 | 0.060* | |
C3 | 0.2489 (2) | 0.47456 (10) | 0.9228 (2) | 0.0489 (6) | |
H3A | 0.3340 | 0.4906 | 0.9614 | 0.059* | |
H3B | 0.2296 | 0.4534 | 0.9848 | 0.059* | |
C4 | 0.1552 (3) | 0.52530 (12) | 0.8695 (2) | 0.0671 (8) | |
H4A | 0.1624 | 0.5414 | 0.7965 | 0.081* | |
H4B | 0.0693 | 0.5111 | 0.8476 | 0.081* | |
C5 | 0.4402 (2) | 0.35443 (10) | 0.9291 (2) | 0.0452 (5) | |
C6 | 0.4132 (3) | 0.29397 (12) | 0.9028 (3) | 0.0668 (8) | |
H6 | 0.3572 | 0.2815 | 0.8208 | 0.080* | |
C7 | 0.4670 (3) | 0.25161 (12) | 0.9944 (3) | 0.0730 (8) | |
H7 | 0.4473 | 0.2095 | 0.9753 | 0.088* | |
C8 | 0.5484 (2) | 0.26772 (12) | 1.1131 (2) | 0.0577 (7) | |
C9 | 0.5742 (3) | 0.32818 (12) | 1.1366 (2) | 0.0643 (7) | |
H9 | 0.6311 | 0.3405 | 1.2184 | 0.077* | |
C10 | 0.5215 (2) | 0.37172 (12) | 1.0471 (2) | 0.0562 (6) | |
H10 | 0.5409 | 0.4138 | 1.0665 | 0.067* | |
C11 | 0.6083 (3) | 0.22042 (15) | 1.2105 (3) | 0.0885 (10) | |
H11A | 0.5784 | 0.1811 | 1.1765 | 0.106* | |
H11B | 0.5854 | 0.2278 | 1.2797 | 0.106* | |
H11C | 0.6997 | 0.2221 | 1.2378 | 0.106* | |
C12 | 0.0198 (2) | 0.65134 (10) | 0.8280 (2) | 0.0441 (5) | |
C13 | −0.0861 (2) | 0.63005 (11) | 0.7304 (2) | 0.0564 (7) | |
H13 | −0.1268 | 0.5932 | 0.7385 | 0.068* | |
C14 | −0.1328 (3) | 0.66221 (12) | 0.6213 (2) | 0.0605 (7) | |
H14 | −0.2066 | 0.6472 | 0.5534 | 0.073* | |
C15 | −0.0773 (3) | 0.71512 (11) | 0.6063 (2) | 0.0533 (6) | |
C16 | 0.0292 (3) | 0.73507 (11) | 0.7055 (2) | 0.0606 (7) | |
H16 | 0.0703 | 0.7718 | 0.6969 | 0.073* | |
C17 | 0.0786 (2) | 0.70413 (11) | 0.8163 (2) | 0.0559 (6) | |
H17 | 0.1527 | 0.7191 | 0.8842 | 0.067* | |
C18 | −0.1304 (3) | 0.74921 (13) | 0.4865 (3) | 0.0778 (9) | |
H18A | −0.0801 | 0.7850 | 0.4929 | 0.093* | |
H18B | −0.2173 | 0.7606 | 0.4688 | 0.093* | |
H18C | −0.1280 | 0.7240 | 0.4208 | 0.093* | |
C19 | −0.2501 (2) | 0.44420 (11) | 0.5588 (2) | 0.0517 (6) | |
C20 | −0.2557 (3) | 0.43598 (12) | 0.6741 (2) | 0.0597 (7) | |
H20 | −0.2214 | 0.3999 | 0.7215 | 0.072* | |
C21 | −0.3106 (3) | 0.48001 (13) | 0.7190 (2) | 0.0613 (7) | |
H21 | −0.3146 | 0.4743 | 0.7985 | 0.074* | |
C22 | −0.3604 (2) | 0.53219 (12) | 0.6537 (2) | 0.0556 (6) | |
C23 | −0.3551 (2) | 0.53909 (12) | 0.5378 (2) | 0.0566 (7) | |
H23 | −0.3910 | 0.5747 | 0.4896 | 0.068* | |
C24 | −0.2997 (2) | 0.49590 (12) | 0.4915 (2) | 0.0543 (6) | |
H24 | −0.2955 | 0.5017 | 0.4121 | 0.065* | |
C25 | −0.4185 (3) | 0.58014 (14) | 0.7057 (3) | 0.0791 (9) | |
H25A | −0.4140 | 0.5676 | 0.7857 | 0.095* | |
H25B | −0.5064 | 0.5860 | 0.6508 | 0.095* | |
H25C | −0.3725 | 0.6175 | 0.7139 | 0.095* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0483 (3) | 0.0542 (4) | 0.0458 (3) | 0.0090 (3) | 0.0214 (3) | 0.0081 (3) |
S2 | 0.0721 (4) | 0.0486 (4) | 0.0493 (4) | 0.0125 (3) | 0.0289 (3) | 0.0048 (3) |
S3 | 0.0580 (4) | 0.0741 (5) | 0.0430 (4) | 0.0003 (4) | 0.0073 (3) | −0.0048 (3) |
O1 | 0.0548 (11) | 0.0618 (11) | 0.0538 (10) | −0.0011 (9) | 0.0069 (8) | 0.0014 (8) |
O2 | 0.0683 (12) | 0.0601 (11) | 0.0549 (10) | 0.0180 (9) | 0.0163 (9) | −0.0046 (8) |
O3 | 0.0556 (10) | 0.0624 (11) | 0.0790 (12) | −0.0030 (9) | 0.0320 (9) | 0.0159 (9) |
O4 | 0.0719 (12) | 0.0822 (13) | 0.0418 (10) | 0.0207 (10) | 0.0255 (9) | 0.0042 (9) |
O5 | 0.0896 (15) | 0.0773 (13) | 0.0860 (14) | −0.0006 (11) | 0.0513 (12) | 0.0240 (11) |
O6 | 0.1198 (17) | 0.0647 (12) | 0.0459 (10) | 0.0169 (12) | 0.0191 (11) | −0.0078 (9) |
O7 | 0.0759 (14) | 0.0760 (13) | 0.0819 (14) | −0.0190 (11) | 0.0078 (11) | −0.0256 (11) |
O8 | 0.0899 (15) | 0.1155 (17) | 0.0463 (11) | 0.0188 (13) | 0.0280 (10) | 0.0076 (10) |
N | 0.0425 (11) | 0.0484 (11) | 0.0477 (11) | 0.0084 (9) | 0.0151 (9) | −0.0033 (9) |
C1 | 0.0537 (15) | 0.0672 (16) | 0.0517 (15) | −0.0017 (13) | 0.0135 (12) | 0.0063 (13) |
C2 | 0.0474 (14) | 0.0523 (14) | 0.0474 (13) | 0.0020 (12) | 0.0158 (11) | 0.0018 (11) |
C3 | 0.0521 (14) | 0.0464 (13) | 0.0449 (13) | 0.0056 (11) | 0.0158 (11) | −0.0001 (10) |
C4 | 0.083 (2) | 0.0641 (17) | 0.0469 (15) | 0.0216 (15) | 0.0177 (14) | −0.0047 (13) |
C5 | 0.0433 (13) | 0.0484 (14) | 0.0452 (13) | 0.0054 (11) | 0.0188 (11) | 0.0010 (10) |
C6 | 0.0675 (18) | 0.0529 (16) | 0.0624 (17) | 0.0056 (14) | 0.0072 (14) | −0.0048 (13) |
C7 | 0.0749 (19) | 0.0446 (15) | 0.083 (2) | 0.0033 (14) | 0.0141 (16) | 0.0070 (14) |
C8 | 0.0538 (16) | 0.0602 (17) | 0.0617 (16) | 0.0151 (13) | 0.0257 (13) | 0.0152 (13) |
C9 | 0.0681 (18) | 0.0662 (18) | 0.0460 (14) | 0.0089 (15) | 0.0093 (13) | 0.0023 (13) |
C10 | 0.0584 (16) | 0.0532 (15) | 0.0483 (14) | 0.0011 (12) | 0.0119 (12) | −0.0018 (12) |
C11 | 0.088 (2) | 0.085 (2) | 0.093 (2) | 0.0257 (18) | 0.0356 (19) | 0.0404 (18) |
C12 | 0.0516 (14) | 0.0405 (13) | 0.0448 (13) | 0.0033 (11) | 0.0239 (11) | −0.0004 (10) |
C13 | 0.0571 (16) | 0.0478 (14) | 0.0611 (16) | −0.0113 (12) | 0.0201 (13) | 0.0048 (12) |
C14 | 0.0570 (16) | 0.0595 (16) | 0.0551 (15) | −0.0106 (13) | 0.0116 (13) | 0.0017 (13) |
C15 | 0.0599 (15) | 0.0533 (14) | 0.0473 (14) | −0.0027 (13) | 0.0219 (12) | 0.0038 (12) |
C16 | 0.0657 (17) | 0.0510 (15) | 0.0636 (17) | −0.0150 (13) | 0.0240 (14) | 0.0052 (13) |
C17 | 0.0585 (15) | 0.0515 (15) | 0.0527 (15) | −0.0089 (12) | 0.0167 (12) | −0.0028 (12) |
C18 | 0.088 (2) | 0.077 (2) | 0.0593 (17) | −0.0085 (18) | 0.0198 (15) | 0.0128 (15) |
C19 | 0.0461 (13) | 0.0628 (16) | 0.0386 (13) | −0.0090 (12) | 0.0089 (10) | 0.0023 (11) |
C20 | 0.0645 (17) | 0.0652 (17) | 0.0432 (14) | −0.0005 (14) | 0.0148 (12) | 0.0133 (12) |
C21 | 0.0645 (17) | 0.0751 (18) | 0.0443 (14) | −0.0062 (15) | 0.0217 (13) | 0.0033 (14) |
C22 | 0.0418 (13) | 0.0666 (17) | 0.0547 (15) | −0.0102 (12) | 0.0152 (12) | −0.0032 (13) |
C23 | 0.0501 (14) | 0.0583 (16) | 0.0526 (15) | −0.0070 (12) | 0.0108 (12) | 0.0087 (12) |
C24 | 0.0551 (15) | 0.0628 (16) | 0.0403 (13) | −0.0089 (13) | 0.0140 (11) | 0.0080 (12) |
C25 | 0.0664 (19) | 0.091 (2) | 0.078 (2) | −0.0045 (17) | 0.0270 (16) | −0.0083 (17) |
S1—O3 | 1.4228 (18) | C6—C7 | 1.372 (4) |
S1—O4 | 1.4234 (18) | C7—C8 | 1.379 (4) |
S1—N | 1.6307 (19) | C8—C9 | 1.370 (4) |
S1—C5 | 1.750 (2) | C8—C11 | 1.498 (3) |
S2—O6 | 1.4117 (18) | C9—C10 | 1.373 (3) |
S2—O5 | 1.414 (2) | C12—C13 | 1.375 (3) |
S2—O2 | 1.5606 (18) | C12—C17 | 1.377 (3) |
S2—C12 | 1.750 (2) | C13—C14 | 1.373 (3) |
S3—O8 | 1.420 (2) | C14—C15 | 1.371 (3) |
S3—O7 | 1.426 (2) | C15—C16 | 1.379 (4) |
S3—O1 | 1.5704 (18) | C15—C18 | 1.494 (3) |
S3—C19 | 1.749 (3) | C16—C17 | 1.376 (3) |
O1—C1 | 1.445 (3) | C19—C24 | 1.374 (3) |
O2—C4 | 1.438 (3) | C19—C20 | 1.390 (3) |
N—C2 | 1.459 (3) | C20—C21 | 1.369 (4) |
N—C3 | 1.472 (3) | C21—C22 | 1.374 (4) |
C1—C2 | 1.513 (3) | C22—C23 | 1.392 (3) |
C3—C4 | 1.502 (3) | C22—C25 | 1.500 (4) |
C5—C6 | 1.376 (3) | C23—C24 | 1.368 (4) |
C5—C10 | 1.379 (3) | ||
O3—S1—O4 | 120.43 (12) | C10—C5—S1 | 119.70 (18) |
O3—S1—N | 106.43 (10) | C7—C6—C5 | 119.6 (2) |
O4—S1—N | 105.52 (11) | C6—C7—C8 | 121.9 (3) |
O3—S1—C5 | 108.39 (11) | C9—C8—C7 | 117.3 (2) |
O4—S1—C5 | 107.81 (11) | C9—C8—C11 | 121.8 (3) |
N—S1—C5 | 107.64 (11) | C7—C8—C11 | 120.8 (3) |
O6—S2—O5 | 119.00 (14) | C8—C9—C10 | 122.2 (2) |
O6—S2—O2 | 103.32 (12) | C9—C10—C5 | 119.4 (2) |
O5—S2—O2 | 109.93 (12) | C13—C12—C17 | 120.4 (2) |
O6—S2—C12 | 110.48 (11) | C13—C12—S2 | 119.20 (18) |
O5—S2—C12 | 108.12 (12) | C17—C12—S2 | 120.34 (18) |
O2—S2—C12 | 105.09 (10) | C14—C13—C12 | 119.2 (2) |
O8—S3—O7 | 119.92 (13) | C15—C14—C13 | 122.1 (2) |
O8—S3—O1 | 109.81 (12) | C14—C15—C16 | 117.4 (2) |
O7—S3—O1 | 103.57 (11) | C14—C15—C18 | 120.9 (2) |
O8—S3—C19 | 108.54 (13) | C16—C15—C18 | 121.7 (2) |
O7—S3—C19 | 110.24 (13) | C17—C16—C15 | 122.2 (2) |
O1—S3—C19 | 103.45 (10) | C16—C17—C12 | 118.7 (2) |
C1—O1—S3 | 117.68 (15) | C24—C19—C20 | 120.0 (3) |
C4—O2—S2 | 117.98 (16) | C24—C19—S3 | 120.03 (19) |
C2—N—C3 | 117.43 (19) | C20—C19—S3 | 119.8 (2) |
C2—N—S1 | 117.72 (15) | C21—C20—C19 | 119.1 (2) |
C3—N—S1 | 118.45 (15) | C20—C21—C22 | 122.0 (2) |
O1—C1—C2 | 105.52 (19) | C21—C22—C23 | 117.9 (2) |
N—C2—C1 | 110.08 (19) | C21—C22—C25 | 120.9 (3) |
N—C3—C4 | 108.99 (18) | C23—C22—C25 | 121.1 (3) |
O2—C4—C3 | 106.2 (2) | C24—C23—C22 | 121.1 (2) |
C6—C5—C10 | 119.7 (2) | C23—C24—C19 | 119.9 (2) |
C6—C5—S1 | 120.64 (18) | ||
O1—C1—C2—N | 179.29 (19) | O2—C4—C3—N | −167.7 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4A···O8i | 0.96 | 2.50 | 3.451 (4) | 174 |
C20—H20···O6ii | 0.96 | 2.53 | 3.376 (3) | 148 |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x, −y+1, −z+2. |
Experimental details
Crystal data | |
Chemical formula | C25H29NO8S3 |
Mr | 567.67 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 11.3887 (10), 22.0576 (19), 11.7301 (10) |
β (°) | 113.330 (1) |
V (Å3) | 2705.8 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.32 |
Crystal size (mm) | 0.40 × 0.30 × 0.10 |
Data collection | |
Diffractometer | CCD area detector diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 17590, 6572, 3614 |
Rint | 0.047 |
(sin θ/λ)max (Å−1) | 0.669 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.136, 1.00 |
No. of reflections | 6572 |
No. of parameters | 334 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.28, −0.29 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXTL (Sheldrick, 1996b), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4A···O8i | .96 | 2.495 | 3.451 (4) | 174.4 |
C20—H20···O6ii | .96 | 2.526 | 3.376 (3) | 147.5 |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x, −y+1, −z+2. |
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The development of mixed donor cyclic ligands have received considerable attention due to their ability to discriminate between metal ions (Adam et al., 1995). Of tridentate cyclic ligands, [9]aneNS2 is interesting since it has both hard N-donor and soft S-donor atoms (Blake et al., 1998). One strategy for the synthesis of the macrocycles based on an NS2 donor set involves the title compound as an important precursor followed by the macrocyclization with corresponding dithiol and detosylation (Blake et al., 1998). During our search for new macrocycles containing NS2Xn (X = O or S, n = 0–4) mixed donor atoms, we have determined the crystal structure of this compound, (I). \sch
The back bone of the molecule is fully stretched and the torsion angles in both the –NCH2CH2O– units correspond to the anti conformation [179.3 (2) and 167.7 (2)°]. The three tosyl groups are separated from one another as much as possible, presumably to minimize steric repulsion. The interplanar angles between the two O-tosyl aromatic rings is 76.7 (1)° and those between O-tosyl and N-tosyl aromaic rings are 53.3 (1) and 27.9 (1)°.
Although H atoms have been included in their idealized positions, some aromatic and methylene H atoms are situated close to the sulfonyl O atoms of O-tosyl groups, providing evidence for C—H···O hydrogen bonds (Taylor & Kennard, 1982). As illustrated in Fig. 2, the molecules are interconnected by hydrogen bonds in such a way that they form columns parallel to the crystallographic c axis. Aromatic and aliphatic C—H···O hydrogen bonds alternate in the column. Their parameters are given in Table 1.