Tri­tosyl­ate of diethano­lamine

The crystal structure of the tri­tosyl­ated diethano­lamine N,N-bis­(tosyl­oxy­ethyl)-p-toluene­sulfon­amide, C₂₅H₂₉NO₈S₃, has been determined. The conformation of the mol­ecule is such that the tosyl groups are as far apart as possible. The mol­ecules are interconnected by C-H...O hydrogen bonds and form columns in the crystal structure.

S1. Comment

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 NS₂X_n (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.

Related literature

For related literature, see: Adam et al. (1995); Blake et al. (1998); Searle & Geue (1984); Taylor & Kennard (1982).

S2. Experimental

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.

S3. Refinement

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.

Computing details

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.

Figures

	Fig. 1. Perspective view of the molecule with atom numbering; displacement ellipsoids are drawn at 30% probability level and H atoms have been omitted for clarity.
	Fig. 2. Stereoview of one column of the molecules stabilized by alternating aromatic(dashed lines) and aliphatic(dotted lines) C—H···O hydrogen bonds. Non-hydrogen-bonded H atoms have been omitted for clarity.

N-(tolyl-p-sulfonyl)-3-aza-1,5-bis(tolyl-p-sulfonyloxy)pentane

Crystal data

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) Å^3	Plate, colorless
Z = 4	0.40 × 0.30 × 0.10 mm

Data collection

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

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.136	H-atom parameters constrained
S = 1.00	w = 1/[σ^2(Fo^2) + (0.068P)^2] where P = (Fo^2 + 2Fc^2)/3
6572 reflections	(Δ/σ)max < 0.001
334 parameters	Δρmax = 0.28 e Å^−3
0 restraints	Δρmin = −0.29 e Å^−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	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*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

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)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4A···O8^i	0.96	2.50	3.451 (4)	174
C20—H20···O6^ii	0.96	2.53	3.376 (3)	148

Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x, −y+1, −z+2.