21-(4-Methyl­phenyl­sulfon­yl)-4,7,13,16-tetra­oxa-1,10,21-triaza­bicyclo­[8.8.5]tricosane-19,23-dione: an N-tosyl­ated macrobicyclic dilactam

Ellis, T.K.; Clayton, S.M.; Powell, D.R.; Taylor, R.W.

doi:10.1107/S1600536811018873

organic compounds

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ISSN: 2056-9890

Volume 67| Part 6| June 2011| Page o1533

doi:10.1107/S1600536811018873

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21-(4-Methylphenylsulfonyl)-4,7,13,16-tetraoxa-1,10,21-triazabicyclo[8.8.5]tricosane-19,23-dione: an N-tosylated macrobicyclic dilactam

Trevor K. Ellis,^a Stephen M. Clayton Jr,^a Douglas R. Powell ^a and Richard W. Taylor ^a ^*

^aUniversity of Oklahoma, Department of Chemistry and Biochemistry, 101 Stephenson Pkwy, Norman, OK 73019-5251, USA
^*Correspondence e-mail: rwtaylor@ou.edu

(Received 29 April 2011; accepted 17 May 2011; online 28 May 2011)

The macrobicyclic title compound, C₂₃H₃₅N₃O₈S, contains two tertiary amide bridgehead N atoms and a toluenesulfonamide N atom in the center of the five-atom bridging strand. The molecule has a central cavity that is defined by the 18-membered ring identified by the N₂O₄ donor atom set and two 15-membered rings with N₃O₂ donor atom sets. The toluenesulfonamide N atom adopts an exo orientation with respect to the central cavity, and the tosyl group is oriented on one side of the aza-bridging strand that connects the bridgehead N atoms.

Related literature

For general background to bicyclic dilactams as cation receptors, see: Hourdakis & Popov (1977 ); Tümmler et al. (1977 ); Buschmann, (1986 ); Pietraszkiewicz et al. (1992 ); Wanichacheva et al. (2006a ,b ). For related structures, see: Fields et al. (1986 ); Tarnowska et al. (2004 ). For the synthesis, see: Lehn & Montavon (1976 , 1978 ); Lehn et al. (1977 ); Frère & Gramain (1982 ); Pietraszkiewicz et al. (1992); Wanichacheva et al. (2006a,b).

Experimental

Crystal data

C₂₃H₃₅N₃O₈S
M_r = 513.60
Monoclinic, P 2₁ /c
a = 12.807 (2) Å
b = 20.096 (3) Å
c = 10.3305 (17) Å
β = 112.949 (3)°
V = 2448.3 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.19 mm⁻¹
T = 100 K
0.45 × 0.34 × 0.02 mm

Data collection

Bruker APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2001 ) T_min = 0.921, T_max = 0.996
22174 measured reflections
5330 independent reflections
3651 reflections with I > 2σ(I)
R_int = 0.078

Refinement

R[F² > 2σ(F²)] = 0.056
wR(F²) = 0.152
S = 1.00
5330 reflections
316 parameters
H-atom parameters constrained
Δρ_max = 0.87 e Å⁻³
Δρ_min = −0.74 e Å⁻³

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811018873/pk2323sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811018873/pk2323Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811018873/pk2323Isup3.cml

checkCIF report

Comment top

The title compound (I) was isolated as an intermediate in the synthesis of the corresponding azacryptand, 2.2.1_NH (II, see Figure 1). An analogous bicyclic diamide, 2.2.1* (III), containing only oxygen donor atoms in the bridging strands, has been reported (Tarnowska, et al., 2004). Cryptands where one or more O atoms have been replaced by N atoms are of interest because of their selectivity for transition- and heavy-metal cations (Lehn & Montavon, 1978). In addition, the nitrogen atom may serve as a point of attachment for sensor chromophores (Wanichacheva, et al., 2006a) or cryptand-based polymer resins (Frère & Gramain, 1982). The bicyclic 2.2.1*_NR dilactam with R = (CH₂)₉CH₃ (Pietraszkiewicz et al., 1992) or R = –C(=O)(CH₂)₁₅SCH₃ (Wanichacheva, et al., 2006b) has been used in the construction of ion selective electrodes.

Figure 2 shows that (I) consists of an 18-membered ring (donor atoms N1, O4, O7, N10, O13, O16) and two 15-membered rings with N₃O₂ donor atom sets (N1, O4, O7, N21, N10 and N1, O13, O16, N10, N21). With respect to the molecular cavity formed by these rings, donor atoms N1, O3, O13, O16 and N10 have an endodentate orientation, while N21, O7 and the carbonyl O atoms, O33 and O34, are exodentate. The oxygen donor atoms of the 18-membered ring (O4, O7, O13, O16) form a plane (average deviation = 0.314 Å) that is nearly perpendicular to the plane defined by nitrogen atoms N1, N10, N21 (dihedral angle = 83.7 (3)°). The toluenesulfonamide group is oriented over the face of one 15-membered ring (N1, O13, O16, N10, N21) and the plane of the benzene ring (C24—C29), average deviation = 0.0042 Å) is almost coplanar with the oxygen donor plane defined by O4, O7, O13, O16 (dihedral angle = 16.5 (3)°). The N1···N10 nonbonding distance is 5.299 (4)Å which is less than the value of 5.643 (4)Å found for 2.2.1* (Tarnowska et al., 2004). The aza bridging strand consists of three planar subunits: N1, C19, O33, C20, average deviation = 0.0021 Å; C20, N21, S1, C22, average deviation = 0.0255 Å; and C22, C23, O34, N10, average deviation = 0.0068 Å. The limited conformational freedom of this bridge may explain the shorter N1···N10 nonbonding distance compared to the more flexible 2.2.1* and the extensive splitting in the ¹H-NMR spectrum due to the non-equivalence of the methylene protons.

Related literature top

For general background of bicyclic dilactams as cation receptors, see: Hourdakis & Popov (1977); Tümmler et al. (1977); Buschmann, (1986); Pietraszkiewicz et al. (1992);Wanichacheva et al. (2006a,b). For related structures, see: Fields et al. (1986); Tarnowska et al. (2004). For the synthesis, see: Lehn & Montavon (1976, 1978); Lehn et al. (1977); Frère & Gramain (1982); Pietraszkiewicz et al. (1992); Wanichacheva et al. (2006a,b).

Experimental top

The bicyclic diamide was obtained by the high-dilution condensation of 1,10-diaza-4,7,13,16-tetraoxacyclooctadecane with 2,2'-(N-tosyl)diacetyl chloride according to reported methods (Lehn & Montavon, 1976). The N-protected diacid chloride was prepared following literature procedures (Lehn, et al., 1977). The crude dilactam was purified by flash column chromatography on silica gel using a mixture of CHCl₃ and acetone (4:1) as the eluent. Spectroscopic Analysis: ¹H-NMR (CDCl₃, 300 MHz) δ 2.38 (s, 3H), δ 2.57–2.64 (ddd, 2H), δ 2.90–3.00 (ddd, 2H), δ 3.49–3.65 (m, 10H), δ 3.67–3.80 (m, 8H), δ 4.36 (d, 4H), δ 4.53 (ddd, 2H), δ 7.25, 7.90 (q, 4H); ESI-MS: m/z = 536.2 (M + Na⁺) and 1049.5 (2M + Na⁺). Crystals suitable for X-ray crystallography were obtained by slow evaporation of a solution of the compound dissolved in toluene-methanol (1:1).

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Structural formulae of the title compound (I) and related 2.2.1-type cryptands.
	Fig. 2. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level.

21-(4-Methylphenylsulfonyl)-4,7,13,16-tetraoxa-1,10,21- triazabicyclo[8.8.5]tricosane-19,23-dione top

Crystal data top

C₂₃H₃₅N₃O₈S	F(000) = 1096
M_r = 513.60	D_x = 1.393 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 7056 reflections
a = 12.807 (2) Å	θ = 2.4–26.8°
b = 20.096 (3) Å	µ = 0.19 mm⁻¹
c = 10.3305 (17) Å	T = 100 K
β = 112.949 (3)°	Plate, colorless
V = 2448.3 (7) Å³	0.45 × 0.34 × 0.02 mm
Z = 4

Data collection top

Bruker APEX CCD diffractometer	5330 independent reflections
Radiation source: fine-focus sealed tube	3651 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.078
ω scans	θ_max = 27.0°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	h = −16→16
T_min = 0.921, T_max = 0.996	k = −25→25
22174 measured reflections	l = −13→13

Refinement top

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)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.152	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.090P)² + ] where P = (F_o² + 2F_c²)/3
5330 reflections	(Δ/σ)_max = 0.001
316 parameters	Δρ_max = 0.87 e Å⁻³
0 restraints	Δρ_min = −0.74 e Å⁻³

Crystal data top

C₂₃H₃₅N₃O₈S	V = 2448.3 (7) Å³
M_r = 513.60	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.807 (2) Å	µ = 0.19 mm⁻¹
b = 20.096 (3) Å	T = 100 K
c = 10.3305 (17) Å	0.45 × 0.34 × 0.02 mm
β = 112.949 (3)°

Data collection top

Bruker APEX CCD diffractometer	5330 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	3651 reflections with I > 2σ(I)
T_min = 0.921, T_max = 0.996	R_int = 0.078
22174 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.056	0 restraints
wR(F²) = 0.152	H-atom parameters constrained
S = 1.00	Δρ_max = 0.87 e Å⁻³
5330 reflections	Δρ_min = −0.74 e Å⁻³
316 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
S1	1.09333 (5)	0.25045 (3)	0.83451 (6)	0.01752 (16)
O31	1.09605 (15)	0.22025 (8)	0.71044 (17)	0.0212 (4)
O32	1.08925 (14)	0.20910 (8)	0.94505 (17)	0.0213 (4)
O33	0.79170 (15)	0.24397 (8)	0.79188 (18)	0.0237 (4)
O34	1.03764 (15)	0.42449 (8)	0.72294 (18)	0.0233 (4)
N1	0.77810 (17)	0.31622 (9)	0.9521 (2)	0.0190 (4)
C2	0.6686 (2)	0.28984 (12)	0.9424 (3)	0.0235 (6)
H2A	0.6390	0.3198	0.9962	0.028*
H2B	0.6823	0.2460	0.9897	0.028*
C3	0.5777 (2)	0.28131 (12)	0.7980 (3)	0.0232 (6)
H3A	0.5988	0.2448	0.7484	0.028*
H3B	0.5054	0.2691	0.8057	0.028*
O4	0.56315 (14)	0.34114 (8)	0.72001 (18)	0.0247 (4)
C5	0.4764 (2)	0.33533 (14)	0.5853 (3)	0.0296 (6)
H5A	0.4018	0.3350	0.5931	0.036*
H5B	0.4850	0.2928	0.5419	0.036*
C6	0.4817 (2)	0.39256 (15)	0.4942 (3)	0.0322 (7)
H6A	0.4072	0.3971	0.4149	0.039*
H6B	0.4961	0.4341	0.5499	0.039*
O7	0.56706 (15)	0.38508 (10)	0.43936 (19)	0.0326 (5)
C8	0.6766 (2)	0.40118 (12)	0.5372 (3)	0.0240 (6)
H8A	0.7052	0.3655	0.6084	0.029*
H8B	0.6745	0.4433	0.5859	0.029*
C9	0.7540 (2)	0.40869 (12)	0.4576 (3)	0.0215 (5)
H9A	0.7651	0.3647	0.4217	0.026*
H9B	0.7177	0.4384	0.3759	0.026*
N10	0.86434 (17)	0.43611 (9)	0.5476 (2)	0.0200 (4)
C11	0.8809 (2)	0.50799 (11)	0.5374 (3)	0.0230 (6)
H11A	0.8792	0.5180	0.4428	0.028*
H11B	0.9570	0.5203	0.6070	0.028*
C12	0.7929 (2)	0.55061 (12)	0.5623 (3)	0.0244 (6)
H12A	0.8161	0.5978	0.5666	0.029*
H12B	0.7198	0.5457	0.4808	0.029*
O13	0.77576 (15)	0.53522 (8)	0.68612 (17)	0.0226 (4)
C14	0.8673 (2)	0.55091 (12)	0.8130 (3)	0.0239 (6)
H14A	0.8822	0.5994	0.8183	0.029*
H14B	0.9367	0.5275	0.8177	0.029*
C15	0.8367 (2)	0.52969 (11)	0.9315 (3)	0.0236 (6)
H15A	0.8870	0.5517	1.0194	0.028*
H15B	0.7574	0.5426	0.9125	0.028*
O16	0.84885 (15)	0.45891 (8)	0.94636 (17)	0.0215 (4)
C17	0.8009 (2)	0.43394 (11)	1.0383 (3)	0.0229 (5)
H17A	0.7174	0.4381	0.9943	0.027*
H17B	0.8286	0.4601	1.1265	0.027*
C18	0.8337 (2)	0.36153 (11)	1.0704 (3)	0.0207 (5)
H18A	0.9168	0.3574	1.1002	0.025*
H18B	0.8146	0.3474	1.1504	0.025*
C19	0.8310 (2)	0.29040 (11)	0.8733 (2)	0.0192 (5)
C20	0.9430 (2)	0.32263 (11)	0.8889 (2)	0.0180 (5)
H20A	0.9327	0.3714	0.8783	0.022*
H20B	1.0005	0.3135	0.9842	0.022*
N21	0.98335 (17)	0.29775 (9)	0.7851 (2)	0.0180 (4)
C22	0.9321 (2)	0.32465 (11)	0.6440 (2)	0.0195 (5)
H22A	0.8500	0.3144	0.6043	0.023*
H22B	0.9664	0.3031	0.5838	0.023*
C23	0.9485 (2)	0.40027 (12)	0.6426 (2)	0.0197 (5)
C24	1.2164 (2)	0.29981 (11)	0.9071 (3)	0.0189 (5)
C25	1.2716 (2)	0.30417 (12)	1.0509 (3)	0.0219 (5)
H25	1.2430	0.2814	1.1107	0.026*
C26	1.3687 (2)	0.34197 (12)	1.1071 (3)	0.0251 (6)
H26	1.4071	0.3450	1.2063	0.030*
C27	1.4114 (2)	0.37568 (12)	1.0212 (3)	0.0254 (6)
C28	1.3541 (2)	0.37067 (12)	0.8774 (3)	0.0278 (6)
H28	1.3826	0.3936	0.8176	0.033*
C29	1.2567 (2)	0.33334 (12)	0.8185 (3)	0.0238 (6)
H29	1.2180	0.3306	0.7193	0.029*
C30	1.5165 (2)	0.41723 (14)	1.0863 (3)	0.0348 (7)
H30A	1.5386	0.4349	1.0123	0.052*
H30B	1.5780	0.3897	1.1507	0.052*
H30C	1.5014	0.4542	1.1385	0.052*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0290 (3)	0.0091 (3)	0.0181 (3)	0.0008 (2)	0.0132 (3)	−0.0004 (2)
O31	0.0373 (10)	0.0126 (8)	0.0184 (9)	0.0015 (7)	0.0160 (8)	−0.0042 (7)
O32	0.0362 (10)	0.0119 (8)	0.0200 (9)	0.0016 (7)	0.0155 (8)	0.0034 (7)
O33	0.0359 (10)	0.0133 (8)	0.0255 (10)	−0.0022 (7)	0.0158 (8)	−0.0042 (7)
O34	0.0326 (10)	0.0158 (9)	0.0217 (9)	−0.0019 (7)	0.0108 (8)	−0.0001 (7)
N1	0.0296 (11)	0.0125 (9)	0.0193 (11)	−0.0011 (8)	0.0143 (9)	−0.0009 (8)
C2	0.0327 (14)	0.0172 (12)	0.0270 (14)	0.0007 (10)	0.0186 (12)	0.0030 (10)
C3	0.0315 (14)	0.0138 (12)	0.0304 (14)	−0.0014 (10)	0.0188 (12)	−0.0003 (10)
O4	0.0329 (10)	0.0184 (9)	0.0236 (9)	−0.0005 (7)	0.0119 (8)	0.0039 (7)
C5	0.0305 (14)	0.0334 (15)	0.0270 (15)	−0.0026 (12)	0.0134 (12)	−0.0004 (12)
C6	0.0277 (14)	0.0426 (17)	0.0285 (15)	0.0059 (12)	0.0134 (12)	0.0094 (13)
O7	0.0289 (10)	0.0479 (13)	0.0237 (10)	−0.0007 (9)	0.0131 (8)	0.0017 (9)
C8	0.0320 (14)	0.0182 (12)	0.0228 (14)	0.0010 (10)	0.0119 (11)	0.0004 (10)
C9	0.0287 (13)	0.0159 (12)	0.0204 (13)	0.0017 (10)	0.0099 (11)	0.0023 (10)
N10	0.0296 (11)	0.0105 (9)	0.0223 (11)	0.0007 (8)	0.0127 (9)	0.0024 (8)
C11	0.0365 (15)	0.0117 (11)	0.0246 (14)	0.0013 (10)	0.0161 (12)	0.0053 (10)
C12	0.0400 (15)	0.0124 (11)	0.0245 (14)	0.0022 (10)	0.0168 (12)	0.0045 (10)
O13	0.0340 (10)	0.0158 (8)	0.0212 (9)	0.0001 (7)	0.0142 (8)	0.0000 (7)
C14	0.0351 (15)	0.0114 (11)	0.0267 (14)	−0.0007 (10)	0.0137 (12)	0.0016 (10)
C15	0.0405 (15)	0.0077 (11)	0.0252 (14)	−0.0001 (10)	0.0156 (12)	−0.0003 (9)
O16	0.0379 (10)	0.0083 (8)	0.0264 (10)	0.0010 (7)	0.0213 (8)	0.0004 (7)
C17	0.0378 (15)	0.0130 (11)	0.0265 (14)	−0.0007 (10)	0.0221 (12)	−0.0006 (10)
C18	0.0321 (14)	0.0152 (11)	0.0199 (13)	0.0001 (10)	0.0157 (11)	−0.0003 (9)
C19	0.0310 (14)	0.0102 (11)	0.0188 (13)	0.0041 (9)	0.0121 (11)	0.0042 (9)
C20	0.0285 (13)	0.0114 (11)	0.0177 (12)	0.0027 (9)	0.0129 (10)	0.0004 (9)
N21	0.0296 (11)	0.0134 (9)	0.0152 (10)	0.0022 (8)	0.0132 (9)	0.0014 (8)
C22	0.0311 (13)	0.0125 (11)	0.0167 (12)	0.0011 (9)	0.0112 (11)	−0.0005 (9)
C23	0.0340 (14)	0.0143 (11)	0.0165 (12)	0.0031 (10)	0.0162 (11)	0.0017 (9)
C24	0.0268 (13)	0.0113 (11)	0.0214 (13)	0.0034 (9)	0.0123 (11)	0.0001 (9)
C25	0.0301 (14)	0.0159 (12)	0.0225 (13)	0.0032 (10)	0.0134 (11)	0.0007 (10)
C26	0.0335 (14)	0.0186 (12)	0.0242 (14)	0.0028 (11)	0.0124 (12)	0.0008 (10)
C27	0.0294 (14)	0.0155 (12)	0.0326 (15)	0.0022 (10)	0.0136 (12)	−0.0038 (11)
C28	0.0378 (15)	0.0202 (13)	0.0333 (16)	−0.0015 (11)	0.0225 (13)	0.0001 (11)
C29	0.0339 (14)	0.0193 (12)	0.0224 (13)	0.0002 (10)	0.0155 (12)	−0.0005 (10)
C30	0.0361 (16)	0.0299 (15)	0.0413 (18)	−0.0059 (12)	0.0181 (14)	−0.0068 (13)

Geometric parameters (Å, º) top

S1—O32	1.4295 (16)	C12—H12B	0.9900
S1—O31	1.4308 (16)	O13—C14	1.412 (3)
S1—N21	1.608 (2)	C14—C15	1.486 (3)
S1—C24	1.763 (2)	C14—H14A	0.9900
O33—C19	1.226 (3)	C14—H14B	0.9900
O34—C23	1.220 (3)	C15—O16	1.433 (3)
N1—C19	1.349 (3)	C15—H15A	0.9900
N1—C2	1.465 (3)	C15—H15B	0.9900
N1—C18	1.467 (3)	O16—C17	1.408 (3)
C2—C3	1.502 (4)	C17—C18	1.515 (3)
C2—H2A	0.9900	C17—H17A	0.9900
C2—H2B	0.9900	C17—H17B	0.9900
C3—O4	1.418 (3)	C18—H18A	0.9900
C3—H3A	0.9900	C18—H18B	0.9900
C3—H3B	0.9900	C19—C20	1.523 (3)
O4—C5	1.406 (3)	C20—N21	1.449 (3)
C5—C6	1.505 (4)	C20—H20A	0.9900
C5—H5A	0.9900	C20—H20B	0.9900
C5—H5B	0.9900	N21—C22	1.450 (3)
C6—O7	1.421 (3)	C22—C23	1.535 (3)
C6—H6A	0.9900	C22—H22A	0.9900
C6—H6B	0.9900	C22—H22B	0.9900
O7—C8	1.410 (3)	C24—C25	1.377 (3)
C8—C9	1.523 (3)	C24—C29	1.388 (3)
C8—H8A	0.9900	C25—C26	1.378 (4)
C8—H8B	0.9900	C25—H25	0.9500
C9—N10	1.463 (3)	C26—C27	1.386 (4)
C9—H9A	0.9900	C26—H26	0.9500
C9—H9B	0.9900	C27—C28	1.380 (4)
N10—C23	1.349 (3)	C27—C30	1.502 (4)
N10—C11	1.470 (3)	C28—C29	1.377 (4)
C11—C12	1.516 (3)	C28—H28	0.9500
C11—H11A	0.9900	C29—H29	0.9500
C11—H11B	0.9900	C30—H30A	0.9800
C12—O13	1.414 (3)	C30—H30B	0.9800
C12—H12A	0.9900	C30—H30C	0.9800

O32—S1—O31	119.36 (10)	C15—C14—H14B	110.1
O32—S1—N21	107.27 (10)	H14A—C14—H14B	108.4
O31—S1—N21	106.89 (10)	O16—C15—C14	108.70 (19)
O32—S1—C24	107.00 (11)	O16—C15—H15A	109.9
O31—S1—C24	106.83 (11)	C14—C15—H15A	109.9
N21—S1—C24	109.24 (11)	O16—C15—H15B	109.9
C19—N1—C2	120.8 (2)	C14—C15—H15B	109.9
C19—N1—C18	123.1 (2)	H15A—C15—H15B	108.3
C2—N1—C18	114.95 (19)	C17—O16—C15	111.61 (17)
N1—C2—C3	117.4 (2)	O16—C17—C18	109.52 (19)
N1—C2—H2A	108.0	O16—C17—H17A	109.8
C3—C2—H2A	108.0	C18—C17—H17A	109.8
N1—C2—H2B	108.0	O16—C17—H17B	109.8
C3—C2—H2B	108.0	C18—C17—H17B	109.8
H2A—C2—H2B	107.2	H17A—C17—H17B	108.2
O4—C3—C2	110.3 (2)	N1—C18—C17	114.2 (2)
O4—C3—H3A	109.6	N1—C18—H18A	108.7
C2—C3—H3A	109.6	C17—C18—H18A	108.7
O4—C3—H3B	109.6	N1—C18—H18B	108.7
C2—C3—H3B	109.6	C17—C18—H18B	108.7
H3A—C3—H3B	108.1	H18A—C18—H18B	107.6
C5—O4—C3	111.67 (19)	O33—C19—N1	122.5 (2)
O4—C5—C6	110.2 (2)	O33—C19—C20	120.9 (2)
O4—C5—H5A	109.6	N1—C19—C20	116.5 (2)
C6—C5—H5A	109.6	N21—C20—C19	111.60 (19)
O4—C5—H5B	109.6	N21—C20—H20A	109.3
C6—C5—H5B	109.6	C19—C20—H20A	109.3
H5A—C5—H5B	108.1	N21—C20—H20B	109.3
O7—C6—C5	113.4 (2)	C19—C20—H20B	109.3
O7—C6—H6A	108.9	H20A—C20—H20B	108.0
C5—C6—H6A	108.9	C20—N21—C22	117.56 (18)
O7—C6—H6B	108.9	C20—N21—S1	119.35 (16)
C5—C6—H6B	108.9	C22—N21—S1	122.47 (16)
H6A—C6—H6B	107.7	N21—C22—C23	111.63 (19)
C8—O7—C6	113.3 (2)	N21—C22—H22A	109.3
O7—C8—C9	108.1 (2)	C23—C22—H22A	109.3
O7—C8—H8A	110.1	N21—C22—H22B	109.3
C9—C8—H8A	110.1	C23—C22—H22B	109.3
O7—C8—H8B	110.1	H22A—C22—H22B	108.0
C9—C8—H8B	110.1	O34—C23—N10	123.5 (2)
H8A—C8—H8B	108.4	O34—C23—C22	118.9 (2)
N10—C9—C8	111.4 (2)	N10—C23—C22	117.5 (2)
N10—C9—H9A	109.3	C25—C24—C29	120.9 (2)
C8—C9—H9A	109.3	C25—C24—S1	119.50 (19)
N10—C9—H9B	109.3	C29—C24—S1	119.57 (19)
C8—C9—H9B	109.3	C24—C25—C26	119.3 (2)
H9A—C9—H9B	108.0	C24—C25—H25	120.4
C23—N10—C9	124.1 (2)	C26—C25—H25	120.4
C23—N10—C11	118.7 (2)	C25—C26—C27	121.1 (2)
C9—N10—C11	117.10 (19)	C25—C26—H26	119.5
N10—C11—C12	113.9 (2)	C27—C26—H26	119.5
N10—C11—H11A	108.8	C28—C27—C26	118.5 (2)
C12—C11—H11A	108.8	C28—C27—C30	122.0 (2)
N10—C11—H11B	108.8	C26—C27—C30	119.6 (2)
C12—C11—H11B	108.8	C29—C28—C27	121.7 (2)
H11A—C11—H11B	107.7	C29—C28—H28	119.2
O13—C12—C11	114.7 (2)	C27—C28—H28	119.2
O13—C12—H12A	108.6	C28—C29—C24	118.6 (2)
C11—C12—H12A	108.6	C28—C29—H29	120.7
O13—C12—H12B	108.6	C24—C29—H29	120.7
C11—C12—H12B	108.6	C27—C30—H30A	109.5
H12A—C12—H12B	107.6	C27—C30—H30B	109.5
C14—O13—C12	115.17 (19)	H30A—C30—H30B	109.5
O13—C14—C15	108.1 (2)	C27—C30—H30C	109.5
O13—C14—H14A	110.1	H30A—C30—H30C	109.5
C15—C14—H14A	110.1	H30B—C30—H30C	109.5
O13—C14—H14B	110.1

C19—N1—C2—C3	−49.0 (3)	O32—S1—N21—C20	36.3 (2)
C18—N1—C2—C3	142.7 (2)	O31—S1—N21—C20	165.43 (17)
N1—C2—C3—O4	−51.6 (3)	C24—S1—N21—C20	−79.33 (19)
C2—C3—O4—C5	−178.5 (2)	O32—S1—N21—C22	−152.89 (18)
C3—O4—C5—C6	−166.4 (2)	O31—S1—N21—C22	−23.8 (2)
O4—C5—C6—O7	78.8 (3)	C24—S1—N21—C22	91.5 (2)
C5—C6—O7—C8	−79.4 (3)	C20—N21—C22—C23	59.8 (3)
C6—O7—C8—C9	−165.6 (2)	S1—N21—C22—C23	−111.2 (2)
O7—C8—C9—N10	170.55 (19)	C9—N10—C23—O34	−175.5 (2)
C8—C9—N10—C23	79.0 (3)	C11—N10—C23—O34	1.3 (4)
C8—C9—N10—C11	−97.8 (2)	C9—N10—C23—C22	7.2 (3)
C23—N10—C11—C12	−121.6 (2)	C11—N10—C23—C22	−176.0 (2)
C9—N10—C11—C12	55.4 (3)	N21—C22—C23—O34	36.9 (3)
N10—C11—C12—O13	50.6 (3)	N21—C22—C23—N10	−145.7 (2)
C11—C12—O13—C14	68.8 (3)	O32—S1—C24—C25	−14.6 (2)
C12—O13—C14—C15	−178.22 (18)	O31—S1—C24—C25	−143.47 (19)
O13—C14—C15—O16	76.8 (2)	N21—S1—C24—C25	101.2 (2)
C14—C15—O16—C17	−168.7 (2)	O32—S1—C24—C29	164.98 (18)
C15—O16—C17—C18	−170.2 (2)	O31—S1—C24—C29	36.1 (2)
C19—N1—C18—C17	103.2 (3)	N21—S1—C24—C29	−79.2 (2)
C2—N1—C18—C17	−88.9 (2)	C29—C24—C25—C26	−0.5 (4)
O16—C17—C18—N1	−70.9 (3)	S1—C24—C25—C26	178.99 (18)
C2—N1—C19—O33	−0.6 (4)	C24—C25—C26—C27	0.2 (4)
C18—N1—C19—O33	166.6 (2)	C25—C26—C27—C28	0.1 (4)
C2—N1—C19—C20	178.53 (19)	C25—C26—C27—C30	179.1 (2)
C18—N1—C19—C20	−14.2 (3)	C26—C27—C28—C29	0.0 (4)
O33—C19—C20—N21	7.8 (3)	C30—C27—C28—C29	−178.9 (2)
N1—C19—C20—N21	−171.41 (19)	C27—C28—C29—C24	−0.4 (4)
C19—C20—N21—C22	79.0 (2)	C25—C24—C29—C28	0.7 (4)
C19—C20—N21—S1	−109.7 (2)	S1—C24—C29—C28	−178.89 (19)

Experimental details

Crystal data
Chemical formula	C₂₃H₃₅N₃O₈S
M_r	513.60
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	12.807 (2), 20.096 (3), 10.3305 (17)
β (°)	112.949 (3)
V (Å³)	2448.3 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.19
Crystal size (mm)	0.45 × 0.34 × 0.02

Data collection
Diffractometer	Bruker APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2001)
T_min, T_max	0.921, 0.996
No. of measured, independent and observed [I > 2σ(I)] reflections	22174, 5330, 3651
R_int	0.078
(sin θ/λ)_max (Å⁻¹)	0.638

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.056, 0.152, 1.00
No. of reflections	5330
No. of parameters	316
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.87, −0.74

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXTL (Sheldrick, 2008).

Acknowledgements

This work was supported by the Oklahoma Center for the Advancement of Science and Technology (grant HR06–113). The authors also thank the National Science Foundation (CHE-0130835) and the University of Oklahoma for funds to acquire the diffractometer and computers used in this work.

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