Ethyl 2-[2,2-bis­(ethoxy­carbon­yl)eth­yl]-1-(phenyl­sulfon­yl)indole-3-carboxyl­ate

In the title compound, C₂₅H₂₇NO₈S, the phenyl ring forms a dihedral angle of 83.28 (7)° with the indole ring system. The methyl C atoms of the ester groups and one of the carbonyl O atoms are each disordered over two positions; the site occupancies for the C atoms are 0.75/0.25, 0.87/0.13, 0.64/0.36 and for the O atom 0.57/0.43. The mol­ecular structure is stabilized by weak intra­molecular C–H...O inter­actions.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.003 Å
• Disorder in main residue
• R factor = 0.060
• wR factor = 0.191
• Data-to-parameter ratio = 17.9

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT220_ALERT_2_A Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       6.03 Ratio

Author Response: This is because the disordered side-chains are very dynamic.

PLAT222_ALERT_3_A Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       6.33 Ratio

Author Response: This is because the disordered side-chains are very dynamic.

Alert level C
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C24
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C15
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C16
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C20
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C23
PLAT301_ALERT_3_C Main Residue  Disorder .........................      10.00 Perc.

Alert level G
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......         10

   2 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   6 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   6 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

---

S1. Comment

Benzenesulfonamide derivatives exhibit significant biological activities, such as antibacterial (Nieto et al., 2005), anticancer and anti - HIV (Pomarnacka & Kozlarska-Kedra, 2003) and antitumor (Yang et al., 2002). Sulfur containing compounds mostly act as simple narcotics (Schultz et al., 2001).

Geometric parameters in the title compound (Fig. 1) agree with the reported values of similar structures (Chakkaravarthi et al., 2007; Liu et al., 2007). The sum of the bond angles around N1 (358.19°) indicates sp² hybridization.

The torsion angles C14—N1—S1—O1 and C7—N1—S1—O2 [-54.54 (17)° and 13.62 (2)°, respectively] indicate the syn conformation of the sulfonyl moiety with indole ring system.

The molecular structure is stabilized by weak intramolecular C - H···O interactions (Table 1). A similar compound with ethoxycarbonyl group has been reported (Chakkaravarthi et al., 2007).

Related literature

For related literature, see: Liu et al. (2007); Nieto et al. (2005); Pomarnacka & Kozlarska-Kedra (2003); Schultz et al. (2001); Yang et al. (2002). A similar compound with ethoxycarbonyl group has been reported (Chakkaravarthi et al., 2007).

S2. Experimental

To a well stirred suspension of sodium hydride (0.27 g, 5.62 mmol) in dry tetrahydrofuron (15 ml) at room temperature, a solution of diethyl malonate (1.4 ml, 9.47 mmol) in dry tetrahydrofuron (10 ml) was slowly added over a period of 20 min. After the evolution of hydrogen gas ceased, a solution of ethyl-1-phenyl sulfonyl-2-bromo methyl indole-3-carboxylate (2 g, 4.73 mmol) in dry THF (20 ml) was added in dropwise with vigorous stirring. Then the reaction mixture was stirred for 3 h. The reaction mixture was quenched with ice containing few drop of concentrated HCl, extracted with dichloro methane (3 X 5 ml) and dried (Na₂SO₄). The solvent was removed under vacuum. Then the crude product was purified by column chromatography on siliga gel (hexane-ethyl acetate 9:1). Single crystals suitable for X-ray analysis were grown by slow evaporation of ethyl acetate solution at room temperature.

S3. Refinement

The site occupancy factors for disordered C and O atoms were refined as C22 = 0.25 (2), C22A = 0.75 (2), C25 = 0.134 (10), C25A = 0.866 (10), C17 = 0.36 (2), C17A = 0.64 (2), O3 = 0.43 (6) and O3A = 0.57 (6) during anisotropic refinement. The distances C16—C17, C21—C22, C21—C22A, C24—C25 and C24—C25A were restrained to 1.55 (1) Å; the bond distances C24—C25/C24—C25A and C21—C22/C21—C22A were restrained to be equal within 0.02 Å and the non-bonding distances O6—C25/O6—C25A and O8—C22/O8—C22A were restrained to be equal within 0.04 Å. H atoms were positioned geometrically and refined using riding model with C—H = 0.93 Å and U_iso(H) = 1.2Ueq(C) for aromatic C—H, C—H = 0.98 Å and U_iso(H) = 1.2Ueq(C) for C—H, C—H = 0.97 Å and U_iso(H) = 1.2Ueq(C) for CH₂ and C—H = 0.96 Å and U_iso(H) = 1.5Ueq(C) for CH_3.

Computing details

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 (Bruker, 2004); data reduction: APEX2 (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures

Fig. 1. The molecular structure of (I), with atom labels and 50% probability displacement ellipsoids for non-H atoms.

Ethyl 2-[2,2-bis(ethoxycarbonyl)ethyl]-1-(phenylsulfonyl)indole-3-carboxylate

Crystal data

C25H27NO8S	F(000) = 1056
Mr = 501.54	Dx = 1.289 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 7119 reflections
a = 7.9066 (2) Å	θ = 2.7–24.6°
b = 27.9935 (6) Å	µ = 0.17 mm^−1
c = 11.8849 (2) Å	T = 295 K
β = 100.832 (1)°	Block, colourless
V = 2583.66 (10) Å^3	0.26 × 0.18 × 0.14 mm
Z = 4

Data collection

Bruker Kappa APEX2 diffractometer	6381 independent reflections
Radiation source: fine-focus sealed tube	4267 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.032
ω and ϕ scan	θmax = 28.2°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→10
Tmin = 0.892, Tmax = 0.976	k = −37→37
29408 measured reflections	l = −15→15

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)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.192	H-atom parameters constrained
S = 1.09	w = 1/[σ^2(Fo^2) + (0.1023P)^2 + 0.2706P] where P = (Fo^2 + 2Fc^2)/3
6381 reflections	(Δ/σ)max < 0.001
356 parameters	Δρmax = 0.38 e Å^−3
10 restraints	Δρmin = −0.34 e Å^−3

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
O8	0.4654 (3)	0.06412 (9)	0.6271 (2)	0.1218 (9)
C21	0.3304 (9)	0.0330 (2)	0.6543 (5)	0.183 (2)
H21A	0.2246	0.0507	0.6533	0.219*	0.25 (2)
H21B	0.3657	0.0183	0.7290	0.219*	0.25 (2)
H21C	0.3080	0.0386	0.7307	0.219*	0.75 (2)
H21D	0.3644	−0.0001	0.6489	0.219*	0.75 (2)
C22	0.308 (4)	−0.0035 (6)	0.5616 (17)	0.131 (11)	0.25 (2)
H22A	0.2206	−0.0258	0.5726	0.197*	0.25 (2)
H22B	0.4149	−0.0202	0.5637	0.197*	0.25 (2)
H22C	0.2749	0.0119	0.4887	0.197*	0.25 (2)
C22A	0.1991 (19)	0.0263 (9)	0.5545 (10)	0.278 (10)	0.75 (2)
H22D	0.1128	0.0050	0.5723	0.418*	0.75 (2)
H22E	0.2493	0.0130	0.4940	0.418*	0.75 (2)
H22F	0.1473	0.0566	0.5305	0.418*	0.75 (2)
O6	0.4575 (3)	0.14642 (9)	0.45463 (15)	0.1016 (7)
C24	0.4363 (5)	0.1513 (2)	0.3289 (3)	0.1361 (17)
H24A	0.5340	0.1402	0.2976	0.163*	0.134 (10)
H24B	0.3991	0.1827	0.3000	0.163*	0.134 (10)
H24C	0.5035	0.1781	0.3099	0.163*	0.866 (10)
H24D	0.4758	0.1226	0.2963	0.163*	0.866 (10)
C25	0.292 (4)	0.1152 (11)	0.322 (2)	0.141 (17)	0.134 (10)
H25A	0.2418	0.1094	0.2429	0.211*	0.134 (10)
H25B	0.2052	0.1274	0.3609	0.211*	0.134 (10)
H25C	0.3368	0.0858	0.3569	0.211*	0.134 (10)
C25A	0.2606 (6)	0.1588 (2)	0.2843 (3)	0.119 (2)	0.866 (10)
H25D	0.2435	0.1612	0.2024	0.179*	0.866 (10)
H25E	0.2235	0.1878	0.3152	0.179*	0.866 (10)
H25F	0.1949	0.1325	0.3050	0.179*	0.866 (10)
O4	0.7444 (3)	0.00175 (6)	0.93343 (16)	0.0833 (6)
C16	0.7172 (5)	−0.04847 (10)	0.9064 (3)	0.1012 (10)
H16A	0.6205	−0.0525	0.8435	0.121*	0.64 (2)
H16B	0.8188	−0.0621	0.8841	0.121*	0.64 (2)
H16C	0.8276	−0.0636	0.9064	0.121*	0.36 (2)
H16D	0.6486	−0.0516	0.8300	0.121*	0.36 (2)
C17A	0.6831 (15)	−0.0717 (3)	1.0072 (9)	0.103 (3)	0.64 (2)
H17A	0.6643	−0.1052	0.9921	0.155*	0.64 (2)
H17B	0.5823	−0.0580	1.0284	0.155*	0.64 (2)
H17C	0.7797	−0.0675	1.0687	0.155*	0.64 (2)
C17	0.626 (4)	−0.0743 (8)	0.991 (2)	0.200 (15)	0.36 (2)
H17D	0.6391	−0.1082	0.9835	0.300*	0.36 (2)
H17E	0.5064	−0.0662	0.9761	0.300*	0.36 (2)
H17F	0.6769	−0.0649	1.0680	0.300*	0.36 (2)
O3A	0.864 (3)	0.0147 (5)	0.7829 (16)	0.086 (5)	0.43 (6)
O3	0.811 (5)	0.0131 (5)	0.7638 (18)	0.147 (6)	0.57 (6)
C1	1.0656 (3)	0.22467 (7)	0.92948 (18)	0.0498 (5)
C2	1.0958 (3)	0.25755 (9)	1.0163 (2)	0.0696 (7)
H2	1.0057	0.2748	1.0367	0.084*
C3	1.2626 (4)	0.26446 (13)	1.0724 (3)	0.0914 (9)
H3	1.2856	0.2865	1.1320	0.110*
C4	1.3943 (4)	0.23944 (13)	1.0417 (3)	0.0927 (9)
H4	1.5065	0.2447	1.0801	0.111*
C5	1.3637 (3)	0.20698 (11)	0.9559 (3)	0.0828 (8)
H5	1.4547	0.1899	0.9362	0.099*
C6	1.1983 (3)	0.19911 (8)	0.8978 (2)	0.0630 (6)
H6	1.1765	0.1770	0.8384	0.076*
C7	0.8124 (3)	0.11715 (8)	0.82435 (16)	0.0495 (5)
C8	0.8111 (3)	0.07924 (8)	0.89519 (17)	0.0530 (5)
C9	0.8128 (3)	0.09659 (8)	1.00985 (16)	0.0500 (5)
C10	0.8153 (3)	0.07444 (9)	1.11520 (19)	0.0665 (6)
H10	0.8151	0.0413	1.1210	0.080*
C11	0.8179 (4)	0.10257 (10)	1.2106 (2)	0.0746 (7)
H11	0.8195	0.0882	1.2813	0.089*
C12	0.8183 (3)	0.15172 (10)	1.2030 (2)	0.0675 (6)
H12	0.8189	0.1698	1.2687	0.081*
C13	0.8178 (3)	0.17465 (8)	1.10046 (17)	0.0552 (5)
H13	0.8196	0.2078	1.0956	0.066*
C14	0.8145 (2)	0.14609 (7)	1.00462 (16)	0.0459 (4)
C15	0.7996 (4)	0.02893 (9)	0.8579 (2)	0.0707 (7)
C18	0.7955 (3)	0.11677 (9)	0.69716 (17)	0.0602 (6)
H18A	0.8128	0.0845	0.6720	0.072*
H18B	0.8846	0.1368	0.6759	0.072*
C19	0.6184 (3)	0.13479 (9)	0.63587 (17)	0.0592 (6)
H19	0.6076	0.1680	0.6598	0.071*
C20	0.4725 (4)	0.10741 (11)	0.6689 (2)	0.0766 (7)
C23	0.6122 (4)	0.13528 (11)	0.5078 (2)	0.0769 (7)
N1	0.8127 (2)	0.15922 (6)	0.88973 (13)	0.0476 (4)
O1	0.7418 (2)	0.24538 (6)	0.90117 (16)	0.0747 (5)
O2	0.8539 (2)	0.21559 (6)	0.73534 (14)	0.0744 (5)
O5	0.7302 (3)	0.12815 (12)	0.46237 (18)	0.1306 (11)
O7	0.3763 (3)	0.12298 (10)	0.7269 (2)	0.1108 (8)
S1	0.85601 (7)	0.215323 (19)	0.85505 (5)	0.05376 (19)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O8	0.1224 (19)	0.0987 (18)	0.153 (2)	−0.0370 (15)	0.0491 (16)	−0.0315 (16)
C21	0.183 (5)	0.166 (5)	0.208 (6)	−0.085 (4)	0.062 (5)	−0.022 (4)
C22	0.145 (19)	0.073 (11)	0.176 (19)	−0.059 (11)	0.030 (14)	−0.044 (10)
C22A	0.154 (11)	0.36 (2)	0.300 (15)	−0.119 (15)	−0.001 (9)	0.009 (14)
O6	0.0976 (14)	0.156 (2)	0.0446 (9)	0.0306 (14)	−0.0028 (9)	−0.0103 (11)
C24	0.121 (3)	0.228 (6)	0.0530 (17)	0.026 (3)	−0.0003 (18)	−0.009 (2)
C25	0.23 (5)	0.13 (3)	0.081 (18)	0.04 (3)	0.07 (2)	0.027 (18)
C25A	0.123 (4)	0.161 (5)	0.061 (2)	0.031 (3)	−0.016 (2)	−0.007 (2)
O4	0.1192 (16)	0.0486 (10)	0.0908 (13)	−0.0107 (9)	0.0415 (11)	−0.0058 (8)
C16	0.131 (3)	0.0452 (15)	0.128 (3)	−0.0072 (16)	0.025 (2)	−0.0089 (16)
C17A	0.112 (6)	0.045 (3)	0.154 (6)	−0.013 (3)	0.030 (4)	0.032 (4)
C17	0.18 (2)	0.145 (17)	0.32 (3)	−0.077 (14)	0.16 (2)	−0.086 (19)
O3A	0.142 (11)	0.055 (5)	0.074 (6)	0.033 (5)	0.052 (5)	−0.004 (4)
O3	0.294 (16)	0.067 (4)	0.078 (5)	−0.004 (7)	0.032 (9)	−0.017 (3)
C1	0.0519 (11)	0.0445 (11)	0.0572 (11)	−0.0058 (8)	0.0207 (9)	0.0034 (8)
C2	0.0670 (15)	0.0653 (15)	0.0847 (16)	−0.0141 (12)	0.0351 (12)	−0.0182 (12)
C3	0.0797 (19)	0.104 (2)	0.093 (2)	−0.0374 (17)	0.0241 (15)	−0.0354 (17)
C4	0.0608 (16)	0.104 (2)	0.111 (2)	−0.0208 (16)	0.0101 (15)	−0.0108 (19)
C5	0.0522 (14)	0.0758 (18)	0.124 (3)	−0.0012 (12)	0.0265 (14)	−0.0021 (16)
C6	0.0608 (14)	0.0551 (13)	0.0788 (15)	−0.0043 (10)	0.0277 (11)	−0.0037 (11)
C7	0.0520 (11)	0.0522 (12)	0.0454 (10)	0.0024 (9)	0.0118 (8)	0.0022 (8)
C8	0.0620 (12)	0.0482 (12)	0.0501 (11)	0.0037 (9)	0.0138 (9)	0.0014 (9)
C9	0.0546 (11)	0.0490 (12)	0.0472 (10)	−0.0020 (9)	0.0120 (8)	0.0046 (8)
C10	0.0927 (17)	0.0560 (13)	0.0531 (12)	−0.0010 (12)	0.0198 (11)	0.0119 (10)
C11	0.0991 (19)	0.0809 (19)	0.0462 (12)	−0.0054 (15)	0.0203 (12)	0.0097 (11)
C12	0.0818 (16)	0.0740 (16)	0.0485 (12)	−0.0100 (13)	0.0166 (11)	−0.0077 (11)
C13	0.0605 (13)	0.0527 (12)	0.0530 (11)	−0.0096 (10)	0.0124 (9)	−0.0042 (9)
C14	0.0444 (10)	0.0499 (11)	0.0439 (10)	−0.0039 (8)	0.0093 (7)	0.0035 (8)
C15	0.1019 (19)	0.0535 (14)	0.0579 (13)	0.0065 (13)	0.0182 (14)	0.0002 (11)
C18	0.0746 (15)	0.0650 (14)	0.0438 (11)	0.0060 (11)	0.0184 (10)	0.0018 (9)
C19	0.0708 (14)	0.0671 (14)	0.0395 (10)	0.0045 (11)	0.0102 (9)	−0.0031 (9)
C20	0.0836 (18)	0.089 (2)	0.0559 (14)	−0.0028 (15)	0.0091 (12)	−0.0058 (13)
C23	0.0880 (19)	0.095 (2)	0.0470 (13)	0.0132 (15)	0.0102 (13)	−0.0012 (12)
N1	0.0553 (10)	0.0449 (9)	0.0426 (8)	−0.0067 (7)	0.0091 (7)	0.0054 (7)
O1	0.0578 (9)	0.0539 (10)	0.1148 (14)	0.0109 (8)	0.0222 (9)	0.0140 (9)
O2	0.0931 (12)	0.0708 (11)	0.0568 (9)	−0.0131 (9)	0.0077 (8)	0.0229 (8)
O5	0.1146 (18)	0.231 (3)	0.0512 (11)	0.0421 (19)	0.0288 (11)	0.0124 (14)
O7	0.1057 (17)	0.141 (2)	0.0982 (16)	−0.0020 (14)	0.0508 (13)	−0.0124 (14)
S1	0.0543 (3)	0.0467 (3)	0.0604 (3)	−0.0007 (2)	0.0111 (2)	0.0133 (2)

Geometric parameters (Å, º)

O8—C20	1.307 (4)	C17—H17F	0.9600
O8—C21	1.459 (5)	O3A—C15	1.176 (11)
C21—C22A	1.434 (7)	O3—C15	1.222 (14)
C21—C22	1.489 (8)	C1—C2	1.369 (3)
C21—H21A	0.9700	C1—C6	1.380 (3)
C21—H21B	0.9700	C1—S1	1.745 (2)
C21—H21C	0.9700	C2—C3	1.375 (4)
C21—H21D	0.9700	C2—H2	0.9300
C22—H21D	1.0530	C3—C4	1.361 (4)
C22—H22A	0.9600	C3—H3	0.9300
C22—H22B	0.9600	C4—C5	1.353 (4)
C22—H22C	0.9600	C4—H4	0.9300
C22A—H22D	0.9600	C5—C6	1.377 (4)
C22A—H22E	0.9600	C5—H5	0.9300
C22A—H22F	0.9600	C6—H6	0.9300
O6—C23	1.305 (3)	C7—C8	1.356 (3)
O6—C24	1.479 (4)	C7—N1	1.411 (3)
C24—C25A	1.406 (5)	C7—C18	1.492 (3)
C24—C25	1.516 (9)	C8—C9	1.444 (3)
C24—H24A	0.9700	C8—C15	1.474 (3)
C24—H24B	0.9700	C9—C14	1.387 (3)
C24—H24C	0.9700	C9—C10	1.394 (3)
C24—H24D	0.9700	C10—C11	1.378 (3)
C25—H25A	0.9600	C10—H10	0.9300
C25—H25B	0.9600	C11—C12	1.379 (4)
C25—H25C	0.9600	C11—H11	0.9300
C25A—H25D	0.9600	C12—C13	1.377 (3)
C25A—H25E	0.9600	C12—H12	0.9300
C25A—H25F	0.9600	C13—C14	1.388 (3)
O4—C15	1.312 (3)	C13—H13	0.9300
O4—C16	1.449 (3)	C14—N1	1.411 (2)
C16—C17A	1.433 (8)	C18—C19	1.537 (3)
C16—C17	1.527 (10)	C18—H18A	0.9700
C16—H16A	0.9700	C18—H18B	0.9700
C16—H16B	0.9700	C19—C20	1.498 (4)
C16—H16C	0.9700	C19—C23	1.514 (3)
C16—H16D	0.9700	C19—H19	0.9800
C17A—H17A	0.9600	C20—O7	1.200 (3)
C17A—H17B	0.9600	C23—O5	1.179 (3)
C17A—H17C	0.9600	N1—S1	1.6754 (17)
C17—H17D	0.9600	O1—S1	1.4178 (18)
C17—H17E	0.9600	O2—S1	1.4197 (17)
C20—O8—C21	116.7 (3)	H17A—C17A—H17C	109.5
C22A—C21—O8	109.9 (6)	H17B—C17A—H17C	109.5
O8—C21—C22	103.6 (9)	C16—C17—H17D	109.5
O8—C21—H21A	111.0	C16—C17—H17E	109.5
C22—C21—H21A	111.0	H17D—C17—H17E	109.5
C22A—C21—H21B	137.7	C16—C17—H17F	109.5
O8—C21—H21B	111.0	H17D—C17—H17F	109.5
C22—C21—H21B	111.0	H17E—C17—H17F	109.5
H21A—C21—H21B	109.0	C2—C1—C6	121.3 (2)
C22A—C21—H21C	124.3	C2—C1—S1	119.81 (17)
O8—C21—H21C	112.4	C6—C1—S1	118.83 (17)
C22—C21—H21C	141.9	C1—C2—C3	118.4 (2)
O8—C21—H21D	109.4	C1—C2—H2	120.8
H21A—C21—H21D	137.2	C3—C2—H2	120.8
H21C—C21—H21D	108.5	C4—C3—C2	120.7 (3)
C21—C22—H22A	109.5	C4—C3—H3	119.7
H21D—C22—H22A	96.1	C2—C3—H3	119.7
C21—C22—H22B	109.5	C5—C4—C3	120.7 (3)
H21D—C22—H22B	79.2	C5—C4—H4	119.7
H22A—C22—H22B	109.5	C3—C4—H4	119.7
C21—C22—H22C	109.5	C4—C5—C6	120.3 (3)
H21D—C22—H22C	147.3	C4—C5—H5	119.9
H22A—C22—H22C	109.5	C6—C5—H5	119.9
H22B—C22—H22C	109.5	C5—C6—C1	118.6 (2)
C21—C22A—H22D	109.5	C5—C6—H6	120.7
C21—C22A—H22E	109.5	C1—C6—H6	120.7
H22D—C22A—H22E	109.5	C8—C7—N1	108.11 (17)
C21—C22A—H22F	109.5	C8—C7—C18	127.9 (2)
H22D—C22A—H22F	109.5	N1—C7—C18	123.68 (18)
H22E—C22A—H22F	109.5	C7—C8—C9	108.83 (19)
C23—O6—C24	115.4 (2)	C7—C8—C15	124.7 (2)
C25A—C24—O6	108.1 (3)	C9—C8—C15	126.4 (2)
O6—C24—C25	86.3 (10)	C14—C9—C10	119.08 (19)
C25A—C24—H24A	134.8	C14—C9—C8	106.99 (17)
O6—C24—H24A	114.3	C10—C9—C8	133.9 (2)
C25—C24—H24A	114.3	C11—C10—C9	118.7 (2)
C25A—C24—H24B	61.3	C11—C10—H10	120.6
O6—C24—H24B	114.3	C9—C10—H10	120.6
C25—C24—H24B	114.3	C10—C11—C12	121.1 (2)
H24A—C24—H24B	111.4	C10—C11—H11	119.5
C25A—C24—H24C	110.1	C12—C11—H11	119.5
O6—C24—H24C	110.1	C13—C12—C11	121.6 (2)
C25—C24—H24C	160.6	C13—C12—H12	119.2
C25A—C24—H24D	110.1	C11—C12—H12	119.2
O6—C24—H24D	110.1	C12—C13—C14	117.0 (2)
C25—C24—H24D	73.8	C12—C13—H13	121.5
H24B—C24—H24D	135.2	C14—C13—H13	121.5
H24C—C24—H24D	108.4	C9—C14—C13	122.51 (18)
C24—C25—H25A	109.5	C9—C14—N1	107.75 (16)
C24—C25—H25B	109.5	C13—C14—N1	129.74 (19)
H25A—C25—H25B	109.5	O3A—C15—O4	124.6 (8)
C24—C25—H25C	109.5	O3—C15—O4	120.5 (9)
H25A—C25—H25C	109.5	O3A—C15—C8	122.8 (9)
H25B—C25—H25C	109.5	O3—C15—C8	127.6 (8)
C24—C25A—H25D	109.5	O4—C15—C8	111.0 (2)
C24—C25A—H25E	109.5	C7—C18—C19	112.18 (18)
H25D—C25A—H25E	109.5	C7—C18—H18A	109.2
C24—C25A—H25F	109.5	C19—C18—H18A	109.2
H25D—C25A—H25F	109.5	C7—C18—H18B	109.2
H25E—C25A—H25F	109.5	C19—C18—H18B	109.2
C15—O4—C16	117.8 (2)	H18A—C18—H18B	107.9
C17A—C16—O4	107.4 (5)	C20—C19—C23	112.8 (2)
O4—C16—C17	112.5 (10)	C20—C19—C18	112.7 (2)
C17A—C16—H16A	110.2	C23—C19—C18	109.50 (19)
O4—C16—H16A	110.2	C20—C19—H19	107.2
C17—C16—H16A	93.1	C23—C19—H19	107.2
C17A—C16—H16B	110.2	C18—C19—H19	107.2
O4—C16—H16B	110.2	O7—C20—O8	124.6 (3)
C17—C16—H16B	120.7	O7—C20—C19	124.6 (3)
H16A—C16—H16B	108.5	O8—C20—C19	110.8 (3)
C17A—C16—H16C	96.5	O5—C23—O6	124.7 (2)
O4—C16—H16C	109.1	O5—C23—C19	125.5 (2)
C17—C16—H16C	109.1	O6—C23—C19	109.8 (2)
H16A—C16—H16C	121.9	C7—N1—C14	108.31 (15)
C17A—C16—H16D	125.6	C7—N1—S1	128.78 (14)
O4—C16—H16D	109.1	C14—N1—S1	121.10 (13)
C17—C16—H16D	109.1	O1—S1—O2	119.72 (11)
H16B—C16—H16D	93.2	O1—S1—N1	106.66 (9)
H16C—C16—H16D	107.8	O2—S1—N1	106.67 (9)
C16—C17A—H17A	109.5	O1—S1—C1	109.16 (11)
C16—C17A—H17B	109.5	O2—S1—C1	109.79 (10)
H17A—C17A—H17B	109.5	N1—S1—C1	103.56 (9)
C16—C17A—H17C	109.5
C20—O8—C21—C22A	107.7 (14)	C9—C8—C15—O3	−174 (2)
C20—O8—C21—C22	157.7 (14)	C7—C8—C15—O4	−159.0 (2)
C23—O6—C24—C25A	174.5 (4)	C9—C8—C15—O4	17.2 (4)
C23—O6—C24—C25	125.5 (15)	C8—C7—C18—C19	106.4 (3)
C15—O4—C16—C17A	171.4 (5)	N1—C7—C18—C19	−65.8 (3)
C15—O4—C16—C17	−170.9 (16)	C7—C18—C19—C20	−55.7 (3)
C6—C1—C2—C3	−0.4 (4)	C7—C18—C19—C23	177.9 (2)
S1—C1—C2—C3	−179.3 (2)	C21—O8—C20—O7	−0.3 (5)
C1—C2—C3—C4	0.5 (5)	C21—O8—C20—C19	179.0 (4)
C2—C3—C4—C5	−0.5 (5)	C23—C19—C20—O7	−126.3 (3)
C3—C4—C5—C6	0.5 (5)	C18—C19—C20—O7	109.0 (3)
C4—C5—C6—C1	−0.5 (4)	C23—C19—C20—O8	54.3 (3)
C2—C1—C6—C5	0.4 (4)	C18—C19—C20—O8	−70.3 (3)
S1—C1—C6—C5	179.3 (2)	C24—O6—C23—O5	−1.7 (5)
N1—C7—C8—C9	−0.7 (2)	C24—O6—C23—C19	176.1 (3)
C18—C7—C8—C9	−174.0 (2)	C20—C19—C23—O5	−134.2 (4)
N1—C7—C8—C15	176.0 (2)	C18—C19—C23—O5	−7.8 (4)
C18—C7—C8—C15	2.8 (4)	C20—C19—C23—O6	48.0 (3)
C7—C8—C9—C14	0.2 (2)	C18—C19—C23—O6	174.3 (2)
C15—C8—C9—C14	−176.5 (2)	C8—C7—N1—C14	1.0 (2)
C7—C8—C9—C10	−178.8 (2)	C18—C7—N1—C14	174.60 (18)
C15—C8—C9—C10	4.5 (4)	C8—C7—N1—S1	165.55 (15)
C14—C9—C10—C11	0.5 (4)	C18—C7—N1—S1	−20.9 (3)
C8—C9—C10—C11	179.4 (2)	C9—C14—N1—C7	−0.9 (2)
C9—C10—C11—C12	−0.1 (4)	C13—C14—N1—C7	179.0 (2)
C10—C11—C12—C13	−0.7 (4)	C9—C14—N1—S1	−166.83 (14)
C11—C12—C13—C14	0.9 (4)	C13—C14—N1—S1	13.1 (3)
C10—C9—C14—C13	−0.3 (3)	C7—N1—S1—O1	142.65 (18)
C8—C9—C14—C13	−179.48 (19)	C14—N1—S1—O1	−54.54 (17)
C10—C9—C14—N1	179.60 (19)	C7—N1—S1—O2	13.6 (2)
C8—C9—C14—N1	0.4 (2)	C14—N1—S1—O2	176.42 (15)
C12—C13—C14—C9	−0.4 (3)	C7—N1—S1—C1	−102.22 (18)
C12—C13—C14—N1	179.7 (2)	C14—N1—S1—C1	60.59 (17)
C16—O4—C15—O3A	−17.5 (15)	C2—C1—S1—O1	−0.7 (2)
C16—O4—C15—O3	7 (2)	C6—C1—S1—O1	−179.55 (17)
C16—O4—C15—C8	176.8 (2)	C2—C1—S1—O2	132.41 (19)
C7—C8—C15—O3A	34.9 (14)	C6—C1—S1—O2	−46.5 (2)
C9—C8—C15—O3A	−148.9 (13)	C2—C1—S1—N1	−114.0 (2)
C7—C8—C15—O3	10 (2)	C6—C1—S1—N1	67.12 (19)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O1	0.93	2.52	2.895 (3)	104
C10—H10···O4	0.93	2.46	2.944 (3)	113
C13—H13···O1	0.93	2.51	3.059 (3)	118
C18—H18A···O3	0.97	2.28	3.004 (15)	131
C18—H18B···O2	0.97	2.34	2.827 (3)	110
C19—H19···O2	0.98	2.39	3.025 (3)	122