Crystal structure of 2,4-di­nitro­phenyl 4-methyl­benzene­sulfonate: a new polymorph

Cooley, T.A.; Riley, S.; Biros, S.M.; Staples, R.J.; Ngassa, F.N.

doi:10.1107/S2056989015015650

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Volume 71| Part 9| September 2015| Pages 1085-1088

https://doi.org/10.1107/S2056989015015650

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Crystal structure of 2,4-dinitrophenyl 4-methylbenzenesulfonate: a new polymorph

Tyler A. Cooley,^a Sean Riley,^a Shannon M. Biros,^a Richard J. Staples ^b and Felix N. Ngassa ^a ^*

^aDepartment of Chemistry, Grand Valley State University, 1 Campus Dr., Allendale, MI 49401, USA, and ^bCenter for Crystallographic Research, Department of Chemistry, Michigan State University, 578 S. Shaw Lane, East Lansing, MI, 48824, USA
^*Correspondence e-mail: ngassaf@gvsu.edu

Edited by S. Parkin, University of Kentucky, USA (Received 4 August 2015; accepted 20 August 2015; online 26 August 2015)

The title compound, C₁₃H₁₀N₂O₇S, was synthesized via a nucleophilic substitution reaction between 2,4-dinitrophenol and p-toluenesulfonyl chloride. This crystal structure is a polymorph of CSD entry WUVYUH [Vembu et al. (2003). Acta Cryst, E59, o378–380]. The aromatic substituents on the sulfonate group are oriented gauche to one another with a C—O—S—C torsion angle of −62.0 (3)°. The supramolecular features that contribute to the crystal stability are offset π–π [centroid–centroid distance = 3.729 (2) Å] and multiple C—H⋯O interactions.

Keywords: crystal structure; aryl sulfonate; π–π interactions; C—H⋯O interactions; p-toluenesulfonyl chloride.

CCDC reference: 1419864

1. Chemical context

Nucleophilic substitution reactions at the carbonyl carbon atom are an important class of reactions in biological processes. Analogous to the carbonyl group, nucleophilic substitution reactions of sulfonyl derivatives have also been reported (Castro et al., 2003 ; Terrier et al., 2003 ; Um et al., 2004 , 2013 ; Qrareya et al., 2014 ). The mechanism of nucleophilic substitution reactions at the carbonyl group is well understood (Stefanidis et al., 1993 ; Lee et al., 2002 ). However, the mechanism for nucleophilic substitution reactions at the sulfonyl group is not fully understood (Morales-Rojas & Moss, 2002 ; Um et al., 2013).

A review of the current literature lends credence to both a concerted mechanism and a non-concerted mechanism (Guthrie, 1991 ; Colthurst & Williams, 1997 ; Spillane et al., 2001 ; Um et al., 2003 , 2004, 2013). Using primary and secondary amines as nucleophiles, the factors influencing regioselectivity of nucleophilic substitution reactions at the sulfonyl group have been reported (Um et al., 2004). It has been demonstrated that the regioselectivity and S—O bond-fission mechanism depends on the basicity of the amine and the electronic nature of the sulfonyl substituent. Based on the current state of knowledge in the field, we have sought to capitalize on the chemistry learned on the mechanistic insight of S—O vs C—O bond fission by investigating the effect of different substituents on the reactivity of sulfonates. In our work, we are interested in using various sulfonate analogues (Fig. 1) as electrophilic substrates in nucleophilic aromatic substitution (S_NAr) reactions similar to those reported by others (Qrareya et al., 2014). As the title compound is of interest in our ongoing effort on probing the mechanism of S_NAr reactions with sulfonate derivatives, we report here on the synthesis and crystal structure of a new polymorph of 2,4-dinitrophenyl 4-methylbenzenesulfonate (Fig. 2).

Figure 1
General structure of sulfonate analogues. R represents electron-donating and electron-withdrawing substituents.

Figure 2
(a) The asymmetric unit of the title compound along with the atom-numbering scheme, showing displacement ellipsoids at the 50% probability level; (b) the structure and atom-numbering scheme of a polymorph of the title compound WUVYUH (Vembu, et al., 2003a

). All hydrogen atoms have been omitted for clarity.

2. Structural commentary

The central sulfur atom (S1) is tetrahedral with S=O bond lengths of 1.415 (3) and 1.414 (3) Å, and an S—O bond length of 1.634 (3) Å (Fig. 2a). The bond angle between the S=O groups (O1—S1—O2) is 121.20 (17)°, while that of the aromatic substituents (O3—S1—C5) is 103.27 (15)°. The two aromatic rings are in a gauche orientation about the O3—S1 bond with a torsion angle (C8—O3—S1—C5) of −62.0 (3)°.

For comparison, the polymorph WUVYUH (Vembu et al., 2003a ) has S=O bond lengths of 1.4204 (10) and 1.4246 (10) Å, and the S—O bond length is 1.6195 (9) Å (Fig. 2b). While the bond lengths of the two polymorphs agree within 0.01 Å of each other, there are some differences between bond angles. The aromatic rings in WUVYUH are in an anti orientation along the S—O bond, with a torsion angle of 141.02 (9)°. The bond angle between the S=O groups (O1—S1—O2) is 119.80 (6)°, while that of the aromatic substituents (O3—S1—C5) is 98.17 (5)°.

3. Supramolecular features

There are no classical hydrogen-bonding interactions in this crystal. There are, however, several intermolecular C—H⋯O interactions with D⋯A distances less than 3.5 Å and D—H⋯A angles greater than 120° (Table 1, Fig. 3). An offset π–π stacking interaction is present between the relatively electron-poor ring C8–C13 and the relatively electron-rich ring C2–C7^v (Fig. 4). The centroid–centroid distance is 3.729 (2) Å, the C2–C7 ring is offset by 1.529 (5) Å and tilted 5.74 (12)° out of the plane defined by the C8–C13 ring [symmetry code: (v) $[{3\over 2}]$ − x, − $[{1\over 2}]$ + y, − $[{1\over 2}]$ + z].

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯O2ⁱ	0.95	2.42	3.273 (5)	149
C4—H4⋯O6ⁱⁱ	0.95	2.57	3.486 (5)	162
C7—H7⋯O7ⁱⁱⁱ	0.95	2.75	3.499 (5)	137
C10—H10⋯O7^iv	0.95	2.51	3.233 (5)	133
C12—H12⋯O4^v	0.95	2.34	3.087 (5)	135
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z]$ ; (iii) $[-x+1, -y+1, z+{\script{1\over 2}}]$ ; (iv) $[-x+1, -y+1, z-{\script{1\over 2}}]$ ; (v) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Figure 3
A drawing of a selection of the C—H⋯O interactions present in the crystal lattice using a ball and stick model. Symmetry codes: (i) −x + 1, −y + 1, z + $[{1\over 2}]$ ; (ii) −x + $[{3\over 2}]$ , y + $[{1\over 2}]$ , z − $[{1\over 2}]$ ; (iii) −x + 2, −y + 2, z − $[{1\over 2}]$ .

Figure 4
A drawing of the intermolecular π–π stacking and nitro–sulfonic ester interactions present in the crystal using a ball and stick model. Symmetry code (v) −x + $[{3\over 2}]$ , y − $[{1\over 2}]$ , z + $[{1\over 2}]$ .

One nitro group (N2,O6,O7) is in proximity to the sulfonic ester of the C2–C7^v ring of a nearby π–π dimer. Fig. 4 also shows that the atoms of these two functional groups are oriented to align the electron-poor N2(nitro) with the electron-rich O1(sulfonic ester), and the electron-poor S1(sulfonic ester) with the electron-rich O7(nitro). Interatomic distances are N2(nitro)⋯O17^v(sulfonic ester) = 3.379 (4) Å, and O7(nitro)⋯S1^v(sulfonic ester) = 3.877 (3) Å. The relatively short intermolecular distance between N2 and O17 suggests the presence of favorable N⋯O interactions in the crystal (Daszkiewicz, 2013 ).

4. Database survey

The Cambridge Structural Database (CSD, version 5.36, May 2015: Groom and Allen, 2014 ) contains 171 aromatic 4-toluenesulfonic esters. Of these, there are 14 structures where the aromatic ring bears substituents at both the 2- and 4-positions. One of these structures is quite similar to the title compound (GOFTIF: Ji et al., 2008 ) where the ortho-substituent is a nitro group and the para-position bears a second tosylate group. The remaining entries have various electron-rich groups in the ortho-position including methoxy (e.g. FEMROF: Ichikawa et al., 2004 ), ethoxy (e.g. HIRHOG: Ramachandran et al., 2007 ), chlorine (OJENEW: Vembu et al., 2003b ) and alkyl amine (PERFEZ: Zhao et al., 2013 ).

The CSD contains three additional structures where the position ortho to the sulfonic ester bears a nitro group. In FAYBAJ (Manivannan et al., 2005 ), this o-nitro group is the only substituent. The aromatic ring in XIYZIP is part of a naphthalene system and also bears a 4-nitro group (Ramachandran et al., 2008 ). The third structure in this set is a polymorph of the title compound (WUVYUH: Vembu et al., 2003a) that was solved in the orthorhombic space group Pbca. One significant difference between WUVYUH and the title compound is the orientation of the groups around the S—O bond (see the Structural commentary section for more details).

5. Synthesis and crystallization

The title compound was prepared by stirring 2,4-dinitrophenol (5 mmol), p-toluenesulfonyl chloride (5 mmol) and pyridine (3 mmol) in 10 mL of dichloromethane for 30 minutes at room temperature. The reaction was heated to 353 K for 30 minutes in a microwave reactor, then cooled to room temperature and stirred overnight in a fume hood. The reaction mixture was transferred to a scintillation vial where the pale yellow product crystallized upon standing after several days and was filtered from the mother liquor (m.p. 393.4–394.7 K).

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. Hydrogen atoms were placed in calculated positions and constrained to ride on their parent atoms, with U_iso(H) = 1.2U_eq(C) for CH groups and U_iso(H) = 1.5 U_eq(C) for methyl groups.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₃H₁₀N₂O₇S
M_r	338.29
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	173
a, b, c (Å)	14.7716 (12), 12.6403 (11), 7.6734 (6)
V (Å³)	1432.8 (2)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.27
Crystal size (mm)	0.27 × 0.21 × 0.20

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2014 )
T_min, T_max	0.686, 0.745
No. of measured, independent and observed [I > 2σ(I)] reflections	11432, 2624, 2326
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.603

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.088, 1.05
No. of reflections	2624
No. of parameters	209
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.18
Absolute structure	Flack x determined using 970 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013 ).
Absolute structure parameter	−0.02 (4)
Computer programs: APEX2 and SAINT (Bruker, 2013 ), XS (Sheldrick, 2008 ), SHELXL (Sheldrick, 2015 ), CrystalMaker (Palmer, 2007 ) and OLEX2 (Dolomanov et al., 2009 ; Bourhis et al., 2015 ).

Supporting information

CCDC reference: 1419864

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989015015650/pk2562sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015015650/pk2562Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989015015650/pk2562Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: XS (Sheldrick, 2008); program(s) used to refine structure: SHELXL (Sheldrick, 2015); molecular graphics: CrystalMaker (Palmer, 2007); software used to prepare material for publication: Olex2 (Dolomanov et al., 2009; Bourhis et al., 2015).

2,4-Dinitrophenyl 4-methylbenzenesulfonate top

Crystal data top

C₁₃H₁₀N₂O₇S	D_x = 1.568 Mg m⁻³
M_r = 338.29	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pna2₁	Cell parameters from 5781 reflections
a = 14.7716 (12) Å	θ = 2.8–25.4°
b = 12.6403 (11) Å	µ = 0.27 mm⁻¹
c = 7.6734 (6) Å	T = 173 K
V = 1432.8 (2) Å³	Chunk, yellow
Z = 4	0.27 × 0.21 × 0.20 mm
F(000) = 696

Data collection top

Bruker APEXII CCD diffractometer	2624 independent reflections
Radiation source: sealed tube	2326 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.036
Detector resolution: 8 pixels mm^-1	θ_max = 25.4°, θ_min = 2.1°
φ and ω scans	h = −17→17
Absorption correction: multi-scan (SADABS; Bruker, 2014)	k = −15→15
T_min = 0.686, T_max = 0.745	l = −9→9
11432 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.034	w = 1/[σ²(F_o²) + (0.0448P)² + 0.2683P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.088	(Δ/σ)_max < 0.001
S = 1.05	Δρ_max = 0.18 e Å⁻³
2624 reflections	Δρ_min = −0.18 e Å⁻³
209 parameters	Absolute structure: Flack x determined using 970 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013).
1 restraint	Absolute structure parameter: −0.02 (4)

Special details top

Experimental. SADABS (Bruker, 2014) was used for absorption correction. wR2(int) was 0.0928 before and 0.0535 after correction. The Ratio of minimum to maximum transmission is 0.9202. The λ/2 correction factor is 0.00150.

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.

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

	x	y	z	U_iso*/U_eq
S1	0.84591 (5)	0.72917 (7)	0.62435 (14)	0.0377 (2)
O1	0.92559 (18)	0.7834 (2)	0.5749 (4)	0.0520 (8)
O2	0.84576 (18)	0.6573 (2)	0.7657 (4)	0.0480 (8)
O3	0.82059 (18)	0.6622 (2)	0.4489 (3)	0.0393 (6)
O4	0.7331 (2)	0.7555 (3)	0.1741 (4)	0.0698 (10)
O5	0.6041 (2)	0.8003 (2)	0.2866 (5)	0.0622 (9)
O6	0.43774 (19)	0.4573 (2)	0.3474 (4)	0.0569 (8)
O7	0.5026 (2)	0.3344 (2)	0.4987 (4)	0.0552 (8)
N1	0.6675 (2)	0.7407 (3)	0.2684 (5)	0.0447 (8)
N2	0.5033 (2)	0.4212 (3)	0.4265 (4)	0.0409 (7)
C1	0.5319 (3)	1.0307 (3)	0.6779 (6)	0.0526 (11)
H1A	0.4769	0.9950	0.6376	0.079*
H1B	0.5436	1.0927	0.6047	0.079*
H1C	0.5240	1.0531	0.7991	0.079*
C2	0.6109 (2)	0.9555 (3)	0.6659 (5)	0.0383 (9)
C3	0.6881 (3)	0.9821 (3)	0.5730 (5)	0.0391 (9)
H3	0.6911	1.0490	0.5167	0.047*
C4	0.7608 (2)	0.9138 (3)	0.5602 (4)	0.0360 (8)
H4	0.8130	0.9328	0.4950	0.043*
C5	0.7559 (2)	0.8168 (2)	0.6448 (4)	0.0299 (7)
C6	0.6796 (2)	0.7879 (3)	0.7391 (4)	0.0345 (8)
H6	0.6770	0.7214	0.7966	0.041*
C7	0.6077 (2)	0.8575 (3)	0.7480 (5)	0.0373 (8)
H7	0.5551	0.8380	0.8114	0.045*
C8	0.7418 (2)	0.6020 (3)	0.4478 (5)	0.0323 (8)
C9	0.6651 (2)	0.6401 (3)	0.3637 (4)	0.0307 (7)
C10	0.5859 (2)	0.5833 (3)	0.3596 (5)	0.0337 (8)
H10	0.5329	0.6110	0.3061	0.040*
C11	0.5861 (2)	0.4846 (3)	0.4361 (5)	0.0323 (8)
C12	0.6613 (2)	0.4440 (3)	0.5188 (5)	0.0363 (8)
H12	0.6593	0.3754	0.5693	0.044*
C13	0.7395 (2)	0.5035 (3)	0.5279 (5)	0.0362 (8)
H13	0.7911	0.4774	0.5880	0.043*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0284 (4)	0.0403 (4)	0.0443 (5)	0.0001 (4)	−0.0037 (5)	0.0048 (5)
O1	0.0275 (12)	0.0566 (16)	0.072 (2)	−0.0066 (12)	0.0026 (13)	0.0053 (15)
O2	0.0478 (17)	0.0453 (15)	0.0507 (17)	0.0058 (12)	−0.0094 (13)	0.0130 (13)
O3	0.0330 (13)	0.0407 (14)	0.0444 (15)	0.0004 (12)	0.0077 (11)	−0.0014 (12)
O4	0.077 (2)	0.069 (2)	0.063 (2)	−0.0155 (17)	0.0088 (18)	0.0306 (17)
O5	0.073 (2)	0.0364 (14)	0.077 (2)	0.0159 (15)	−0.0244 (17)	0.0065 (15)
O6	0.0387 (16)	0.0549 (17)	0.077 (2)	−0.0012 (14)	−0.0106 (16)	−0.0068 (17)
O7	0.070 (2)	0.0441 (15)	0.0517 (17)	−0.0187 (14)	0.0021 (15)	0.0053 (14)
N1	0.058 (2)	0.0326 (16)	0.044 (2)	−0.0040 (16)	−0.0153 (17)	0.0052 (14)
N2	0.044 (2)	0.0391 (16)	0.0391 (18)	−0.0051 (15)	0.0050 (16)	−0.0065 (15)
C1	0.051 (2)	0.047 (2)	0.059 (3)	0.0125 (18)	−0.009 (2)	−0.011 (2)
C2	0.0358 (19)	0.0371 (18)	0.042 (2)	0.0007 (16)	−0.0077 (16)	−0.0076 (17)
C3	0.050 (2)	0.0285 (17)	0.039 (2)	−0.0011 (16)	−0.0090 (17)	0.0033 (15)
C4	0.0358 (19)	0.0388 (19)	0.0335 (19)	−0.0086 (16)	0.0015 (15)	0.0028 (15)
C5	0.0268 (16)	0.0322 (15)	0.0307 (18)	−0.0046 (13)	−0.0045 (15)	0.0029 (17)
C6	0.037 (2)	0.0323 (18)	0.0342 (19)	−0.0063 (15)	−0.0001 (16)	0.0020 (16)
C7	0.0304 (18)	0.042 (2)	0.039 (2)	−0.0069 (16)	0.0000 (16)	−0.0065 (17)
C8	0.0294 (18)	0.0328 (18)	0.0346 (17)	0.0035 (14)	0.0080 (15)	0.0015 (16)
C9	0.0383 (19)	0.0254 (16)	0.0283 (16)	0.0049 (15)	0.0017 (15)	0.0020 (14)
C10	0.036 (2)	0.0325 (17)	0.0324 (18)	0.0090 (15)	−0.0008 (16)	−0.0015 (15)
C11	0.0328 (19)	0.0326 (17)	0.0315 (18)	−0.0003 (15)	0.0062 (15)	−0.0024 (15)
C12	0.044 (2)	0.0280 (17)	0.0366 (19)	0.0059 (15)	0.0014 (17)	0.0056 (15)
C13	0.0362 (19)	0.0326 (17)	0.0397 (19)	0.0112 (15)	0.0006 (16)	0.0040 (16)

Geometric parameters (Å, º) top

S1—O1	1.414 (3)	C3—H3	0.9500
S1—O2	1.415 (3)	C3—C4	1.381 (5)
S1—O3	1.634 (3)	C4—H4	0.9500
S1—C5	1.737 (3)	C4—C5	1.390 (4)
O3—C8	1.391 (4)	C5—C6	1.388 (5)
O4—N1	1.224 (4)	C6—H6	0.9500
O5—N1	1.210 (4)	C6—C7	1.381 (5)
O6—N2	1.231 (4)	C7—H7	0.9500
O7—N2	1.228 (4)	C8—C9	1.389 (5)
N1—C9	1.468 (5)	C8—C13	1.389 (5)
N2—C11	1.465 (4)	C9—C10	1.374 (5)
C1—H1A	0.9800	C10—H10	0.9500
C1—H1B	0.9800	C10—C11	1.378 (5)
C1—H1C	0.9800	C11—C12	1.379 (5)
C1—C2	1.507 (5)	C12—H12	0.9500
C2—C3	1.387 (5)	C12—C13	1.379 (5)
C2—C7	1.391 (5)	C13—H13	0.9500

O1—S1—O2	121.20 (17)	C4—C5—S1	118.8 (3)
O1—S1—O3	102.73 (16)	C6—C5—S1	120.0 (2)
O1—S1—C5	110.64 (16)	C6—C5—C4	121.2 (3)
O2—S1—O3	107.40 (14)	C5—C6—H6	120.6
O2—S1—C5	109.80 (17)	C7—C6—C5	118.8 (3)
O3—S1—C5	103.27 (15)	C7—C6—H6	120.6
C8—O3—S1	118.7 (2)	C2—C7—H7	119.4
O4—N1—C9	116.5 (3)	C6—C7—C2	121.3 (3)
O5—N1—O4	125.9 (3)	C6—C7—H7	119.4
O5—N1—C9	117.6 (4)	C9—C8—O3	119.7 (3)
O6—N2—C11	118.6 (3)	C13—C8—O3	120.6 (3)
O7—N2—O6	123.2 (3)	C13—C8—C9	119.8 (3)
O7—N2—C11	118.3 (3)	C8—C9—N1	120.8 (3)
H1A—C1—H1B	109.5	C10—C9—N1	117.5 (3)
H1A—C1—H1C	109.5	C10—C9—C8	121.6 (3)
H1B—C1—H1C	109.5	C9—C10—H10	121.3
C2—C1—H1A	109.5	C9—C10—C11	117.5 (3)
C2—C1—H1B	109.5	C11—C10—H10	121.3
C2—C1—H1C	109.5	C10—C11—N2	118.2 (3)
C3—C2—C1	121.0 (3)	C10—C11—C12	122.3 (3)
C3—C2—C7	118.5 (3)	C12—C11—N2	119.5 (3)
C7—C2—C1	120.5 (3)	C11—C12—H12	120.2
C2—C3—H3	119.2	C11—C12—C13	119.7 (3)
C4—C3—C2	121.6 (3)	C13—C12—H12	120.2
C4—C3—H3	119.2	C8—C13—H13	120.5
C3—C4—H4	120.7	C12—C13—C8	119.1 (3)
C3—C4—C5	118.6 (3)	C12—C13—H13	120.5
C5—C4—H4	120.7

S1—O3—C8—C9	101.6 (3)	O7—N2—C11—C12	2.6 (5)
S1—O3—C8—C13	−79.5 (4)	N1—C9—C10—C11	174.5 (3)
S1—C5—C6—C7	−177.7 (3)	N2—C11—C12—C13	179.9 (3)
O1—S1—O3—C8	−177.1 (2)	C1—C2—C3—C4	−179.7 (3)
O1—S1—C5—C4	21.1 (3)	C1—C2—C7—C6	−179.7 (4)
O1—S1—C5—C6	−161.2 (3)	C2—C3—C4—C5	−0.7 (5)
O2—S1—O3—C8	54.0 (3)	C3—C2—C7—C6	0.5 (5)
O2—S1—C5—C4	157.5 (3)	C3—C4—C5—S1	178.3 (3)
O2—S1—C5—C6	−24.8 (3)	C3—C4—C5—C6	0.6 (5)
O3—S1—C5—C4	−88.2 (3)	C4—C5—C6—C7	0.0 (5)
O3—S1—C5—C6	89.5 (3)	C5—S1—O3—C8	−62.0 (3)
O3—C8—C9—N1	3.0 (5)	C5—C6—C7—C2	−0.6 (5)
O3—C8—C9—C10	−179.9 (3)	C7—C2—C3—C4	0.2 (5)
O3—C8—C13—C12	−177.6 (3)	C8—C9—C10—C11	−2.7 (5)
O4—N1—C9—C8	44.8 (5)	C9—C8—C13—C12	1.4 (5)
O4—N1—C9—C10	−132.4 (4)	C9—C10—C11—N2	−177.5 (3)
O5—N1—C9—C8	−136.9 (4)	C9—C10—C11—C12	1.9 (5)
O5—N1—C9—C10	46.0 (5)	C10—C11—C12—C13	0.5 (5)
O6—N2—C11—C10	1.6 (5)	C11—C12—C13—C8	−2.2 (5)
O6—N2—C11—C12	−177.8 (3)	C13—C8—C9—N1	−176.0 (3)
O7—N2—C11—C10	−178.0 (3)	C13—C8—C9—C10	1.1 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O2ⁱ	0.95	2.42	3.273 (5)	149
C4—H4···O6ⁱⁱ	0.95	2.57	3.486 (5)	162
C7—H7···O7ⁱⁱⁱ	0.95	2.75	3.499 (5)	137
C10—H10···O7^iv	0.95	2.51	3.233 (5)	133
C12—H12···O4^v	0.95	2.34	3.087 (5)	135

Symmetry codes: (i) −x+3/2, y+1/2, z−1/2; (ii) x+1/2, −y+3/2, z; (iii) −x+1, −y+1, z+1/2; (iv) −x+1, −y+1, z−1/2; (v) −x+3/2, y−1/2, z+1/2.

Acknowledgements

The authors thank the GVSU for financial support (Weldon Fund, CSCE), the NSF for a 300 MHz Jeol FT–NMR (CCLI-0087655) and Pfizer, Inc. for the donation of a Varian Inova 400 FT–NMR. The CCD-based X-ray diffractometers at Michigan State University were upgraded and/or replaced by departmental funds.

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