Crystal structure of methyl (S)-2-{(R)-4-[(tert-but-oxy-carbon-yl)amino]-3-oxo-1,2-thia-zolidin-2-yl}-3-methyl-butano-ate: a chemical model for oxidized protein tyrosine phosphatase 1B (PTP1B).

The asymmetric unit of the title compound, C14H24N2O5S, contains two independent mol-ecules (A and B). In each mol-ecule, the iso-thia-zolidin-3-one ring adopts an envelope conformation with the methyl-ene C atom as the flap. In the crystal, the A mol-ecules are linked to one another by N-H⋯O hydrogen bonds, forming columns along [010]. The B mol-ecules are also linked to one another by N-H⋯O hydrogen bonds, forming columns along the same direction, i.e. [010]. Within the individual columns, there are also C-H⋯S and C-H⋯O hydrogen bonds present. The columns of A and B mol-ecules are linked by C-H⋯O hydrogen bonds, forming sheets parallel to (10-1). The absolute structure was determined by resonant scattering [Flack parameter = 0.00 (3)].

Chemical context

X-ray crystallographic analyses of the enzyme PTP1B have revealed an unprecedented post-translational modification that may be important in redox regulation of protein function (Zhou et al., 2011 ▸; Salmeen et al., 2003 ▸; van Montfort et al., 2003 ▸; Tanner et al., 2011 ▸; Sivaramakrishnan et al., 2010 ▸). Specifically, oxidation converts the catalytic cysteine in this enzyme to an iso­thia­zolidin-3-one heterocycle that is commonly referred to as a sulfenyl amide residue. As part of early efforts in the area of cephalosporin synthesis, a dipeptide containing a protein sulfenyl amide residue was synthesized (Morin et al., 1973 ▸). However, to the best of our knowledge, there are no examples of low mol­ecular weight sulfenyl amides that have been characterized crystallographically, although structures of related 1,2-benziso­thia­zol-3(2H)-ones have been reported (Kim et al., 1996 ▸; Ranganathan et al., 2002 ▸; Wang et al., 2011 ▸). Herein we describe the synthesis and crystal structure of the title compound, a low mol­ecular weight mimic of oxidized PTP1B.

Structural commentary

The mol­ecular structures of the two independent mol­ecules (A and B) of the title compound are shown in Fig. 1 ▸. The two mol­ecules differ only in the orientation of the isopropyl group (Fig. 1 ▸). The bond lengths and angles are very similar to those seen in the crystal structures of the oxidized enzyme PTP1B (see: pdb codes 1oem, 1oes, 3sme). In both mol­ecules, the iso­thio­zolidin-3-one ring adopts an envelope conformation with the methyl­ene C atom (C1A in mol­ecule A and C1B in mol­ecule B) as the flap, similar to the conformation of oxidized PTP1B (pdb code: 1oem). In previously reported chemical models (1,2-benziso­thia­zole compounds) of PTP1B, the five-membered ring is planar (Kim et al., 1996 ▸; Ranganathan et al., 2002 ▸; Wang et al., 2011 ▸; Sivaramakrishnan et al., 2005 ▸). The S—N bond lengths in the title compound [S1A—N1A = 1.740 (2) Å and S1B—N1B = 1.733 (2) Å], are similar to the same bond distance of ca 1.71 Å in oxidized PTP1B (pdb code: 1oem).

Figure 1

A view of the mol­ecular structure of the two independent mol­ecules (A and B) of the title compound. Displacement ellipsoids are drawn at the 50% probability level.

Supra­molecular features

In the crystal, N—H⋯O hydrogen-bonding inter­actions give infinite, separate columns of A and B mol­ecules along the b-axis (Table 1 ▸ and Fig. 2 ▸). Within the columns there are C—H⋯S and C—H⋯O hydrogen bonds present (Table 1 ▸). The columns of A and B mol­ecules are linked by C—H⋯O hydrogen bonds, forming sheets parallel to (10); see Fig. 2 ▸.

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
N2AH2ANO1A i	0.88	2.07	2.925(3)	164
N2BH2BNO1B ii	0.88	2.05	2.921(3)	169
C2AH2AO5A i	1.00	2.57	3.549(3)	167
C1BH1B2O1B iii	0.99	2.56	3.371(4)	139
C4AH4AS1A iv	1.00	2.70	3.526(3)	140
C4BH4BS1B iv	1.00	2.70	3.488(3)	136
C9BH9B3O2A v	0.98	2.52	3.400(4)	149

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .

Figure 2

A view along the b axis of the crystal packing of the title compound. Hydrogen bonds are shown as dashed lines (see Table 1 ▸ for details; A mol­ecules are blue and B mol­ecules are red).

Database survey

A search in the Cambridge Structural Database (Version 5.36; Groom & Allen, 2014 ▸) for the substructure 1,2-benziso­thia­zole-3-one resulted in over twenty hits, which include three structures similar to the title compound: methyl 2-hy­droxy-2-(3-oxobenzo[d]iso­thia­zol-2(3H)-yl)propano­ate (Ranganathan et al., 2002 ▸), 2-(3-oxobenzo[d]iso­thia­zol-2(3H)-yl)acetic acid (Wang et al., 2011 ▸) and 2-phenethyl­benzo[d]iso­thia­zol-3(2H)-one (Kim et al., 1996 ▸). In all three compounds, the five-membered isothizolinone ring is planar. However, the S—N bond lengths are similar to that in the title compound; see Structural commentary.

Synthesis and crystallization

The title compound was prepared by a modification of a previously published procedure (Shiau et al., 2006 ▸). Pyridine (20 eq) was added to a solution of l-valine ester of N,N-di-tert-butyl­oxycarbonyl-l-cystine (1.0 g, 1.5 mmol) in 50 mL of anhydrous CH2Cl2. The solution was cooled in a liquid nitro­gen bath, under an N2 atmosphere, and stirred for 15 min. Bromine (135 µL, 2.6 mmol) in dry CH2Cl2 was added dropwise over a period of 30 min. The solution was allowed to warm to 273 K over 1 h, and then CH2Cl2 was evaporated in vacuo using a rotatory evaporator to afford the crude material. Flash chromatography (50% EtOAc/hexa­nes) of the crude material gave the title compound as a white solid (360 mg, 72% yield). Crystals suitable for X-ray diffraction analysis were obtained by slow evaporation of a solution of title compound in DMF.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. The H atoms were included in calculated positions and treated as riding atoms: N—H = 0.88 Å, C—H = 0.98–1.00 Å with U iso(H) = 1.5U eq(C) for methyl H atoms and 1.2U eq(N,C) for other H atoms.

Table 2

Experimental details

Crystal data
Chemical formula	C14H24N2O5S
M r	332.41
Crystal system, space group	Monoclinic, P21
Temperature (K)	173
a, b, c ()	11.509(3), 5.9290(18), 25.751(8)
()	98.307(3)
V (3)	1738.7(9)
Z	4
Radiation type	Mo K
(mm1)	0.21
Crystal size (mm)	0.50 0.15 0.05
Data collection
Diffractometer	Bruker APEXII CCD area detector
Absorption correction	Multi-scan (SADABS; Bruker, 2008 ▸)
T min, T max	0.88, 0.99
No. of measured, independent and observed [I > 2(I)] reflections	19532, 7699, 6307
R int	0.026
(sin /)max (1)	0.650
Refinement
R[F 2 > 2(F 2)], wR(F 2), S	0.040, 0.086, 1.05
No. of reflections	7699
No. of parameters	409
No. of restraints	1
H-atom treatment	H-atom parameters constrained
max, min (e 3)	0.22, 0.25
Absolute structure	Flack x determined using 2415 quotients [(I +)(I )]/[(I +)+(I )] (Parsons et al., 2013 ▸)
Absolute structure parameter	0.00(3)

Computer programs: APEX2 and SAINT (Bruker, 2008 ▸), SHELXS2014 (Sheldrick, 2008 ▸), SHELXL2014 (Sheldrick, 2015 ▸), Mercury (Macrae et al., 2008 ▸) and publCIF (Westrip, 2010 ▸).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015010051/su5136sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015010051/su5136Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015010051/su5136Isup3.cml

CCDC reference: 1402668

Additional supporting information: crystallographic information; 3D view; checkCIF report

C14H24N2O5S	F(000) = 712
Mr = 332.41	Dx = 1.270 Mg m−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 7090 reflections
a = 11.509 (3) Å	θ = 2.6–22.2°
b = 5.9290 (18) Å	µ = 0.21 mm−1
c = 25.751 (8) Å	T = 173 K
β = 98.307 (3)°	Needle, colourless
V = 1738.7 (9) Å3	0.50 × 0.15 × 0.05 mm
Z = 4

Bruker APEXII CCD area-detector diffractometer	7699 independent reflections
Radiation source: fine-focus sealed tube	6307 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.026
ω scans	θmax = 27.5°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −14→14
Tmin = 0.88, Tmax = 0.99	k = −7→7
19532 measured reflections	l = −32→33

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.040	H-atom parameters constrained
wR(F2) = 0.086	w = 1/[σ2(Fo2) + (0.0332P)2 + 0.3913P] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max = 0.001
7699 reflections	Δρmax = 0.22 e Å−3
409 parameters	Δρmin = −0.25 e Å−3
1 restraint	Absolute structure: Flack x determined using 2415 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.00 (3)

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.

	x	y	z	Uiso*/Ueq
S1A	0.17551 (7)	0.37685 (12)	0.89628 (3)	0.0306 (2)
O1A	0.37713 (16)	0.8791 (4)	0.92762 (7)	0.0258 (5)
O2A	−0.04290 (17)	0.8246 (4)	0.84881 (8)	0.0391 (6)
O3A	0.07144 (17)	0.8801 (4)	0.92603 (8)	0.0334 (5)
O4A	0.25361 (16)	0.8018 (3)	1.02566 (7)	0.0287 (5)
O5A	0.40692 (16)	0.7475 (3)	1.09140 (7)	0.0277 (5)
N1A	0.23825 (18)	0.6385 (4)	0.88732 (9)	0.0217 (5)
N2A	0.40950 (19)	0.5788 (4)	1.01516 (8)	0.0249 (5)
H2AN	0.4807	0.5362	1.0286	0.030*
C1A	0.2486 (2)	0.3592 (5)	0.96298 (11)	0.0276 (6)
H1A1	0.1983	0.4206	0.9877	0.033*
H1A2	0.2687	0.2009	0.9727	0.033*
C2A	0.3596 (2)	0.5013 (5)	0.96366 (10)	0.0222 (6)
H2A	0.4199	0.4062	0.9497	0.027*
C3A	0.3281 (2)	0.6971 (5)	0.92527 (10)	0.0202 (6)
C4A	0.1701 (2)	0.8095 (5)	0.85499 (10)	0.0224 (6)
H4A	0.2129	0.9552	0.8627	0.027*
C5A	0.0523 (2)	0.8373 (5)	0.87466 (11)	0.0255 (6)
C6A	−0.0312 (3)	0.8925 (7)	0.95220 (12)	0.0433 (9)
H6A1	−0.0795	0.7577	0.9439	0.065*
H6A2	−0.0769	1.0270	0.9403	0.065*
H6A3	−0.0068	0.9012	0.9902	0.065*
C7A	0.1596 (3)	0.7759 (5)	0.79545 (11)	0.0300 (7)
H7A	0.1022	0.8904	0.7788	0.036*
C8A	0.1133 (3)	0.5449 (6)	0.77637 (12)	0.0399 (8)
H8A1	0.0416	0.5108	0.7913	0.060*
H8A2	0.1728	0.4299	0.7876	0.060*
H8A3	0.0958	0.5455	0.7380	0.060*
C9A	0.2768 (3)	0.8254 (7)	0.77685 (13)	0.0466 (9)
H9A1	0.3349	0.7131	0.7916	0.070*
H9A2	0.3037	0.9763	0.7886	0.070*
H9A3	0.2672	0.8186	0.7384	0.070*
C10A	0.3474 (2)	0.7172 (5)	1.04305 (10)	0.0226 (6)
C11A	0.3593 (3)	0.8922 (5)	1.13002 (11)	0.0299 (7)
C12A	0.3575 (3)	1.1359 (6)	1.11241 (13)	0.0390 (8)
H12A	0.3039	1.1522	1.0794	0.058*
H12B	0.4368	1.1816	1.1071	0.058*
H12C	0.3308	1.2317	1.1393	0.058*
C13A	0.4492 (3)	0.8548 (8)	1.17880 (12)	0.0547 (11)
H13A	0.5272	0.8994	1.1715	0.082*
H13B	0.4501	0.6949	1.1885	0.082*
H13C	0.4280	0.9459	1.2078	0.082*
C14A	0.2390 (3)	0.8122 (6)	1.13960 (13)	0.0423 (9)
H14A	0.2411	0.6490	1.1458	0.063*
H14B	0.1811	0.8464	1.1088	0.063*
H14C	0.2171	0.8894	1.1704	0.063*
S1B	0.82980 (7)	0.48748 (12)	0.60817 (3)	0.0323 (2)
O1B	0.61995 (16)	0.9736 (4)	0.57159 (7)	0.0273 (5)
O2B	1.03914 (18)	0.9218 (4)	0.65232 (9)	0.0431 (7)
O3B	0.92605 (17)	1.0176 (4)	0.57700 (8)	0.0322 (5)
O4B	0.74978 (16)	0.8851 (4)	0.47590 (7)	0.0291 (5)
O5B	0.59660 (16)	0.8252 (4)	0.41038 (7)	0.0289 (5)
N1B	0.76343 (19)	0.7473 (4)	0.61334 (9)	0.0228 (5)
N2B	0.5954 (2)	0.6591 (4)	0.48677 (8)	0.0249 (5)
H2BN	0.5257	0.6095	0.4729	0.030*
C1B	0.7557 (3)	0.4505 (5)	0.54193 (11)	0.0281 (7)
H1B1	0.8053	0.5048	0.5161	0.034*
H1B2	0.7365	0.2897	0.5348	0.034*
C2B	0.6441 (2)	0.5915 (5)	0.53926 (10)	0.0215 (6)
H2B	0.5838	0.4986	0.5538	0.026*
C3B	0.6726 (2)	0.7945 (5)	0.57522 (10)	0.0202 (6)
C4B	0.8258 (2)	0.9234 (5)	0.64632 (10)	0.0225 (6)
H4B	0.7808	1.0668	0.6388	0.027*
C5B	0.9443 (3)	0.9547 (5)	0.62751 (11)	0.0263 (7)
C6B	1.0263 (3)	1.0160 (8)	0.54915 (13)	0.0472 (9)
H6B1	1.0737	0.8810	0.5589	0.071*
H6B2	1.0740	1.1510	0.5584	0.071*
H6B3	0.9993	1.0148	0.5113	0.071*
C7B	0.8375 (3)	0.8825 (5)	0.70572 (11)	0.0292 (6)
H7B	0.8995	0.7658	0.7156	0.035*
C8B	0.7239 (3)	0.7992 (8)	0.72175 (14)	0.0514 (10)
H8B1	0.7050	0.6502	0.7063	0.077*
H8B2	0.6606	0.9050	0.7093	0.077*
H8B3	0.7323	0.7882	0.7601	0.077*
C9B	0.8768 (3)	1.1022 (6)	0.73369 (12)	0.0405 (8)
H9B1	0.8166	1.2180	0.7245	0.061*
H9B2	0.9508	1.1521	0.7228	0.061*
H9B3	0.8883	1.0777	0.7717	0.061*
C10B	0.6558 (2)	0.7978 (5)	0.45889 (10)	0.0242 (6)
C11B	0.6433 (3)	0.9681 (6)	0.37099 (11)	0.0320 (7)
C12B	0.6446 (3)	1.2118 (6)	0.38854 (14)	0.0455 (9)
H12D	0.6719	1.3076	0.3617	0.068*
H12E	0.6977	1.2282	0.4217	0.068*
H12F	0.5652	1.2573	0.3936	0.068*
C13B	0.7631 (3)	0.8901 (7)	0.36143 (14)	0.0492 (9)
H13D	0.7624	0.7260	0.3567	0.074*
H13E	0.8214	0.9304	0.3916	0.074*
H13F	0.7833	0.9630	0.3298	0.074*
C14B	0.5525 (4)	0.9286 (8)	0.32308 (13)	0.0617 (13)
H14D	0.5547	0.7702	0.3124	0.093*
H14E	0.5697	1.0255	0.2943	0.093*
H14F	0.4742	0.9646	0.3315	0.093*

	U11	U22	U33	U12	U13	U23
S1A	0.0326 (5)	0.0190 (4)	0.0366 (4)	−0.0017 (3)	−0.0067 (4)	−0.0018 (3)
O1A	0.0176 (10)	0.0280 (12)	0.0308 (11)	−0.0052 (9)	0.0005 (8)	0.0013 (9)
O2A	0.0231 (11)	0.0551 (16)	0.0367 (12)	0.0073 (10)	−0.0034 (9)	0.0028 (11)
O3A	0.0255 (11)	0.0482 (14)	0.0262 (11)	0.0065 (10)	0.0035 (8)	−0.0077 (10)
O4A	0.0221 (10)	0.0357 (13)	0.0275 (11)	0.0075 (9)	0.0005 (8)	−0.0033 (9)
O5A	0.0258 (11)	0.0327 (12)	0.0236 (10)	0.0037 (9)	−0.0001 (8)	−0.0046 (9)
N1A	0.0168 (11)	0.0180 (12)	0.0288 (13)	0.0022 (9)	−0.0014 (9)	−0.0016 (10)
N2A	0.0201 (12)	0.0323 (14)	0.0214 (12)	0.0059 (10)	−0.0002 (9)	−0.0031 (10)
C1A	0.0310 (15)	0.0246 (15)	0.0273 (15)	−0.0011 (13)	0.0044 (12)	−0.0013 (13)
C2A	0.0183 (13)	0.0266 (15)	0.0215 (14)	0.0064 (12)	0.0025 (10)	−0.0002 (12)
C3A	0.0153 (13)	0.0251 (15)	0.0206 (14)	0.0021 (11)	0.0040 (11)	−0.0017 (11)
C4A	0.0205 (13)	0.0208 (15)	0.0247 (14)	0.0047 (11)	−0.0013 (11)	−0.0015 (11)
C5A	0.0235 (14)	0.0217 (15)	0.0302 (15)	0.0049 (11)	0.0002 (12)	0.0018 (12)
C6A	0.0353 (18)	0.060 (2)	0.0372 (18)	0.0117 (18)	0.0127 (14)	0.0000 (17)
C7A	0.0307 (15)	0.0352 (18)	0.0231 (15)	0.0053 (14)	0.0009 (12)	−0.0019 (13)
C8A	0.049 (2)	0.039 (2)	0.0301 (17)	0.0009 (16)	0.0002 (15)	−0.0087 (14)
C9A	0.044 (2)	0.059 (3)	0.0393 (19)	0.0004 (18)	0.0137 (15)	−0.0010 (17)
C10A	0.0209 (14)	0.0242 (15)	0.0226 (14)	−0.0020 (11)	0.0027 (11)	0.0008 (11)
C11A	0.0335 (16)	0.0327 (18)	0.0242 (15)	−0.0018 (14)	0.0063 (13)	−0.0067 (13)
C12A	0.0441 (19)	0.0284 (18)	0.047 (2)	−0.0075 (15)	0.0164 (16)	−0.0039 (15)
C13A	0.066 (3)	0.066 (3)	0.0271 (18)	0.007 (2)	−0.0105 (17)	−0.0095 (18)
C14A	0.053 (2)	0.042 (2)	0.0364 (18)	−0.0120 (17)	0.0213 (16)	−0.0065 (15)
S1B	0.0358 (5)	0.0192 (4)	0.0375 (5)	0.0025 (3)	−0.0100 (4)	0.0014 (3)
O1B	0.0231 (11)	0.0299 (12)	0.0273 (11)	0.0050 (9)	−0.0020 (8)	−0.0014 (9)
O2B	0.0224 (11)	0.0622 (18)	0.0414 (13)	−0.0038 (11)	−0.0060 (10)	0.0064 (12)
O3B	0.0287 (11)	0.0411 (14)	0.0273 (11)	−0.0026 (10)	0.0054 (9)	0.0025 (10)
O4B	0.0228 (10)	0.0369 (12)	0.0271 (10)	−0.0081 (10)	0.0017 (8)	0.0049 (9)
O5B	0.0277 (11)	0.0373 (13)	0.0204 (10)	−0.0046 (9)	−0.0003 (8)	0.0041 (9)
N1B	0.0228 (12)	0.0168 (12)	0.0269 (12)	−0.0019 (9)	−0.0028 (10)	0.0016 (9)
N2B	0.0213 (12)	0.0314 (14)	0.0208 (12)	−0.0082 (10)	−0.0007 (9)	0.0019 (10)
C1B	0.0312 (16)	0.0242 (16)	0.0285 (16)	0.0035 (12)	0.0034 (13)	0.0009 (12)
C2B	0.0210 (13)	0.0234 (14)	0.0198 (13)	−0.0046 (11)	0.0015 (11)	0.0019 (11)
C3B	0.0132 (12)	0.0253 (15)	0.0225 (14)	−0.0028 (11)	0.0041 (10)	0.0018 (11)
C4B	0.0239 (14)	0.0183 (14)	0.0236 (14)	−0.0009 (11)	−0.0026 (11)	0.0009 (11)
C5B	0.0268 (16)	0.0222 (15)	0.0290 (16)	−0.0040 (12)	0.0011 (12)	−0.0005 (12)
C6B	0.042 (2)	0.061 (3)	0.042 (2)	−0.0102 (19)	0.0164 (16)	−0.0010 (18)
C7B	0.0307 (15)	0.0292 (16)	0.0264 (15)	0.0029 (14)	−0.0009 (12)	0.0044 (13)
C8B	0.050 (2)	0.066 (3)	0.040 (2)	−0.011 (2)	0.0131 (16)	0.0059 (18)
C9B	0.052 (2)	0.040 (2)	0.0262 (16)	0.0019 (16)	−0.0044 (15)	−0.0033 (15)
C10B	0.0219 (14)	0.0279 (16)	0.0228 (14)	0.0028 (12)	0.0032 (11)	0.0009 (12)
C11B	0.0347 (17)	0.0374 (19)	0.0245 (16)	0.0024 (14)	0.0066 (13)	0.0086 (13)
C12B	0.053 (2)	0.037 (2)	0.050 (2)	0.0086 (17)	0.0193 (17)	0.0127 (16)
C13B	0.058 (2)	0.052 (2)	0.043 (2)	0.014 (2)	0.0264 (17)	0.0134 (18)
C14B	0.068 (3)	0.085 (4)	0.0281 (19)	−0.010 (2)	−0.0056 (18)	0.018 (2)

S1A—N1A	1.740 (2)	S1B—N1B	1.733 (2)
S1A—C1A	1.803 (3)	S1B—C1B	1.807 (3)
O1A—C3A	1.215 (3)	O1B—C3B	1.219 (3)
O2A—C5A	1.200 (3)	O2B—C5B	1.199 (3)
O3A—C5A	1.334 (3)	O3B—C5B	1.340 (3)
O3A—C6A	1.444 (4)	O3B—C6B	1.444 (4)
O4A—C10A	1.215 (3)	O4B—C10B	1.222 (3)
O5A—C10A	1.344 (3)	O5B—C10B	1.344 (3)
O5A—C11A	1.477 (3)	O5B—C11B	1.481 (4)
N1A—C3A	1.361 (3)	N1B—C3B	1.356 (3)
N1A—C4A	1.465 (3)	N1B—C4B	1.466 (3)
N2A—C10A	1.360 (4)	N2B—C10B	1.349 (4)
N2A—C2A	1.442 (3)	N2B—C2B	1.443 (3)
N2A—H2AN	0.8800	N2B—H2BN	0.8800
C1A—C2A	1.529 (4)	C1B—C2B	1.526 (4)
C1A—H1A1	0.9900	C1B—H1B1	0.9900
C1A—H1A2	0.9900	C1B—H1B2	0.9900
C2A—C3A	1.534 (4)	C2B—C3B	1.525 (4)
C2A—H2A	1.0000	C2B—H2B	1.0000
C4A—C5A	1.523 (4)	C4B—C5B	1.523 (4)
C4A—C7A	1.533 (4)	C4B—C7B	1.535 (4)
C4A—H4A	1.0000	C4B—H4B	1.0000
C6A—H6A1	0.9800	C6B—H6B1	0.9800
C6A—H6A2	0.9800	C6B—H6B2	0.9800
C6A—H6A3	0.9800	C6B—H6B3	0.9800
C7A—C9A	1.524 (4)	C7B—C8B	1.510 (4)
C7A—C8A	1.525 (5)	C7B—C9B	1.526 (5)
C7A—H7A	1.0000	C7B—H7B	1.0000
C8A—H8A1	0.9800	C8B—H8B1	0.9800
C8A—H8A2	0.9800	C8B—H8B2	0.9800
C8A—H8A3	0.9800	C8B—H8B3	0.9800
C9A—H9A1	0.9800	C9B—H9B1	0.9800
C9A—H9A2	0.9800	C9B—H9B2	0.9800
C9A—H9A3	0.9800	C9B—H9B3	0.9800
C11A—C12A	1.514 (5)	C11B—C13B	1.507 (4)
C11A—C14A	1.518 (4)	C11B—C12B	1.513 (5)
C11A—C13A	1.523 (4)	C11B—C14B	1.516 (4)
C12A—H12A	0.9800	C12B—H12D	0.9800
C12A—H12B	0.9800	C12B—H12E	0.9800
C12A—H12C	0.9800	C12B—H12F	0.9800
C13A—H13A	0.9800	C13B—H13D	0.9800
C13A—H13B	0.9800	C13B—H13E	0.9800
C13A—H13C	0.9800	C13B—H13F	0.9800
C14A—H14A	0.9800	C14B—H14D	0.9800
C14A—H14B	0.9800	C14B—H14E	0.9800
C14A—H14C	0.9800	C14B—H14F	0.9800
N1A—S1A—C1A	91.87 (13)	N1B—S1B—C1B	91.57 (12)
C5A—O3A—C6A	116.4 (2)	C5B—O3B—C6B	117.1 (2)
C10A—O5A—C11A	120.8 (2)	C10B—O5B—C11B	121.4 (2)
C3A—N1A—C4A	121.3 (2)	C3B—N1B—C4B	122.3 (2)
C3A—N1A—S1A	114.78 (19)	C3B—N1B—S1B	115.47 (19)
C4A—N1A—S1A	119.59 (17)	C4B—N1B—S1B	119.55 (17)
C10A—N2A—C2A	120.6 (2)	C10B—N2B—C2B	120.5 (2)
C10A—N2A—H2AN	119.7	C10B—N2B—H2BN	119.8
C2A—N2A—H2AN	119.7	C2B—N2B—H2BN	119.8
C2A—C1A—S1A	104.66 (19)	C2B—C1B—S1B	104.80 (19)
C2A—C1A—H1A1	110.8	C2B—C1B—H1B1	110.8
S1A—C1A—H1A1	110.8	S1B—C1B—H1B1	110.8
C2A—C1A—H1A2	110.8	C2B—C1B—H1B2	110.8
S1A—C1A—H1A2	110.8	S1B—C1B—H1B2	110.8
H1A1—C1A—H1A2	108.9	H1B1—C1B—H1B2	108.9
N2A—C2A—C1A	114.0 (2)	N2B—C2B—C3B	111.7 (2)
N2A—C2A—C3A	112.2 (2)	N2B—C2B—C1B	113.9 (2)
C1A—C2A—C3A	106.9 (2)	C3B—C2B—C1B	107.4 (2)
N2A—C2A—H2A	107.9	N2B—C2B—H2B	107.9
C1A—C2A—H2A	107.9	C3B—C2B—H2B	107.9
C3A—C2A—H2A	107.9	C1B—C2B—H2B	107.9
O1A—C3A—N1A	124.2 (2)	O1B—C3B—N1B	123.9 (3)
O1A—C3A—C2A	125.1 (2)	O1B—C3B—C2B	125.4 (2)
N1A—C3A—C2A	110.7 (2)	N1B—C3B—C2B	110.6 (2)
N1A—C4A—C5A	108.3 (2)	N1B—C4B—C5B	106.8 (2)
N1A—C4A—C7A	115.9 (2)	N1B—C4B—C7B	115.4 (2)
C5A—C4A—C7A	113.6 (2)	C5B—C4B—C7B	112.5 (2)
N1A—C4A—H4A	106.1	N1B—C4B—H4B	107.3
C5A—C4A—H4A	106.1	C5B—C4B—H4B	107.3
C7A—C4A—H4A	106.1	C7B—C4B—H4B	107.3
O2A—C5A—O3A	124.7 (3)	O2B—C5B—O3B	124.4 (3)
O2A—C5A—C4A	126.5 (3)	O2B—C5B—C4B	126.8 (3)
O3A—C5A—C4A	108.9 (2)	O3B—C5B—C4B	108.7 (2)
O3A—C6A—H6A1	109.5	O3B—C6B—H6B1	109.5
O3A—C6A—H6A2	109.5	O3B—C6B—H6B2	109.5
H6A1—C6A—H6A2	109.5	H6B1—C6B—H6B2	109.5
O3A—C6A—H6A3	109.5	O3B—C6B—H6B3	109.5
H6A1—C6A—H6A3	109.5	H6B1—C6B—H6B3	109.5
H6A2—C6A—H6A3	109.5	H6B2—C6B—H6B3	109.5
C9A—C7A—C8A	110.8 (3)	C8B—C7B—C9B	111.1 (3)
C9A—C7A—C4A	110.1 (2)	C8B—C7B—C4B	111.7 (2)
C8A—C7A—C4A	114.4 (3)	C9B—C7B—C4B	108.2 (2)
C9A—C7A—H7A	107.1	C8B—C7B—H7B	108.6
C8A—C7A—H7A	107.1	C9B—C7B—H7B	108.6
C4A—C7A—H7A	107.1	C4B—C7B—H7B	108.6
C7A—C8A—H8A1	109.5	C7B—C8B—H8B1	109.5
C7A—C8A—H8A2	109.5	C7B—C8B—H8B2	109.5
H8A1—C8A—H8A2	109.5	H8B1—C8B—H8B2	109.5
C7A—C8A—H8A3	109.5	C7B—C8B—H8B3	109.5
H8A1—C8A—H8A3	109.5	H8B1—C8B—H8B3	109.5
H8A2—C8A—H8A3	109.5	H8B2—C8B—H8B3	109.5
C7A—C9A—H9A1	109.5	C7B—C9B—H9B1	109.5
C7A—C9A—H9A2	109.5	C7B—C9B—H9B2	109.5
H9A1—C9A—H9A2	109.5	H9B1—C9B—H9B2	109.5
C7A—C9A—H9A3	109.5	C7B—C9B—H9B3	109.5
H9A1—C9A—H9A3	109.5	H9B1—C9B—H9B3	109.5
H9A2—C9A—H9A3	109.5	H9B2—C9B—H9B3	109.5
O4A—C10A—O5A	126.4 (3)	O4B—C10B—O5B	125.9 (3)
O4A—C10A—N2A	124.1 (2)	O4B—C10B—N2B	124.4 (2)
O5A—C10A—N2A	109.5 (2)	O5B—C10B—N2B	109.7 (2)
O5A—C11A—C12A	110.1 (2)	O5B—C11B—C13B	111.5 (3)
O5A—C11A—C14A	111.3 (2)	O5B—C11B—C12B	109.3 (3)
C12A—C11A—C14A	112.0 (3)	C13B—C11B—C12B	111.8 (3)
O5A—C11A—C13A	101.4 (3)	O5B—C11B—C14B	101.1 (3)
C12A—C11A—C13A	111.4 (3)	C13B—C11B—C14B	111.1 (3)
C14A—C11A—C13A	110.3 (3)	C12B—C11B—C14B	111.5 (3)
C11A—C12A—H12A	109.5	C11B—C12B—H12D	109.5
C11A—C12A—H12B	109.5	C11B—C12B—H12E	109.5
H12A—C12A—H12B	109.5	H12D—C12B—H12E	109.5
C11A—C12A—H12C	109.5	C11B—C12B—H12F	109.5
H12A—C12A—H12C	109.5	H12D—C12B—H12F	109.5
H12B—C12A—H12C	109.5	H12E—C12B—H12F	109.5
C11A—C13A—H13A	109.5	C11B—C13B—H13D	109.5
C11A—C13A—H13B	109.5	C11B—C13B—H13E	109.5
H13A—C13A—H13B	109.5	H13D—C13B—H13E	109.5
C11A—C13A—H13C	109.5	C11B—C13B—H13F	109.5
H13A—C13A—H13C	109.5	H13D—C13B—H13F	109.5
H13B—C13A—H13C	109.5	H13E—C13B—H13F	109.5
C11A—C14A—H14A	109.5	C11B—C14B—H14D	109.5
C11A—C14A—H14B	109.5	C11B—C14B—H14E	109.5
H14A—C14A—H14B	109.5	H14D—C14B—H14E	109.5
C11A—C14A—H14C	109.5	C11B—C14B—H14F	109.5
H14A—C14A—H14C	109.5	H14D—C14B—H14F	109.5
H14B—C14A—H14C	109.5	H14E—C14B—H14F	109.5
C1A—S1A—N1A—C3A	13.0 (2)	C1B—S1B—N1B—C3B	12.9 (2)
C1A—S1A—N1A—C4A	−144.0 (2)	C1B—S1B—N1B—C4B	−148.9 (2)
N1A—S1A—C1A—C2A	−27.2 (2)	N1B—S1B—C1B—C2B	−26.1 (2)
C10A—N2A—C2A—C1A	−61.9 (3)	C10B—N2B—C2B—C3B	57.7 (3)
C10A—N2A—C2A—C3A	59.8 (3)	C10B—N2B—C2B—C1B	−64.2 (3)
S1A—C1A—C2A—N2A	158.7 (2)	S1B—C1B—C2B—N2B	157.0 (2)
S1A—C1A—C2A—C3A	34.2 (3)	S1B—C1B—C2B—C3B	32.7 (3)
C4A—N1A—C3A—O1A	−18.2 (4)	C4B—N1B—C3B—O1B	−15.1 (4)
S1A—N1A—C3A—O1A	−174.7 (2)	S1B—N1B—C3B—O1B	−176.4 (2)
C4A—N1A—C3A—C2A	162.8 (2)	C4B—N1B—C3B—C2B	166.6 (2)
S1A—N1A—C3A—C2A	6.2 (3)	S1B—N1B—C3B—C2B	5.3 (3)
N2A—C2A—C3A—O1A	28.5 (4)	N2B—C2B—C3B—O1B	30.9 (4)
C1A—C2A—C3A—O1A	154.1 (3)	C1B—C2B—C3B—O1B	156.4 (3)
N2A—C2A—C3A—N1A	−152.5 (2)	N2B—C2B—C3B—N1B	−150.9 (2)
C1A—C2A—C3A—N1A	−26.8 (3)	C1B—C2B—C3B—N1B	−25.3 (3)
C3A—N1A—C4A—C5A	−103.6 (3)	C3B—N1B—C4B—C5B	−106.0 (3)
S1A—N1A—C4A—C5A	51.9 (3)	S1B—N1B—C4B—C5B	54.6 (3)
C3A—N1A—C4A—C7A	127.3 (3)	C3B—N1B—C4B—C7B	128.2 (3)
S1A—N1A—C4A—C7A	−77.2 (3)	S1B—N1B—C4B—C7B	−71.3 (3)
C6A—O3A—C5A—O2A	5.4 (5)	C6B—O3B—C5B—O2B	8.6 (5)
C6A—O3A—C5A—C4A	−174.9 (3)	C6B—O3B—C5B—C4B	−169.0 (3)
N1A—C4A—C5A—O2A	−126.7 (3)	N1B—C4B—C5B—O2B	−117.3 (3)
C7A—C4A—C5A—O2A	3.7 (4)	C7B—C4B—C5B—O2B	10.3 (4)
N1A—C4A—C5A—O3A	53.7 (3)	N1B—C4B—C5B—O3B	60.1 (3)
C7A—C4A—C5A—O3A	−176.0 (2)	C7B—C4B—C5B—O3B	−172.3 (2)
N1A—C4A—C7A—C9A	−71.8 (3)	N1B—C4B—C7B—C8B	−44.0 (4)
C5A—C4A—C7A—C9A	161.7 (3)	C5B—C4B—C7B—C8B	−166.8 (3)
N1A—C4A—C7A—C8A	53.7 (3)	N1B—C4B—C7B—C9B	−166.6 (3)
C5A—C4A—C7A—C8A	−72.8 (3)	C5B—C4B—C7B—C9B	70.6 (3)
C11A—O5A—C10A—O4A	1.1 (4)	C11B—O5B—C10B—O4B	1.0 (4)
C11A—O5A—C10A—N2A	179.7 (2)	C11B—O5B—C10B—N2B	−179.4 (2)
C2A—N2A—C10A—O4A	−7.4 (4)	C2B—N2B—C10B—O4B	−4.3 (4)
C2A—N2A—C10A—O5A	173.9 (2)	C2B—N2B—C10B—O5B	176.1 (2)
C10A—O5A—C11A—C12A	−67.5 (3)	C10B—O5B—C11B—C13B	57.3 (4)
C10A—O5A—C11A—C14A	57.3 (3)	C10B—O5B—C11B—C12B	−66.9 (4)
C10A—O5A—C11A—C13A	174.5 (3)	C10B—O5B—C11B—C14B	175.4 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N2A—H2AN···O1Ai	0.88	2.07	2.925 (3)	164
N2B—H2BN···O1Bii	0.88	2.05	2.921 (3)	169
C2A—H2A···O5Ai	1.00	2.57	3.549 (3)	167
C1B—H1B2···O1Biii	0.99	2.56	3.371 (4)	139
C4A—H4A···S1Aiv	1.00	2.70	3.526 (3)	140
C4B—H4B···S1Biv	1.00	2.70	3.488 (3)	136
C9B—H9B3···O2Av	0.98	2.52	3.400 (4)	149