Diisopropyl­ammonium 2-[(2,4-dinitro­phenyl)­sulfanyl­amino­carbonyl]­benzoate

The structure of title compound, C₆H₁₆N⁺·C₁₄H₈N₃O₇S⁻, comprises discrete ions which are inter­connected by N—H...O⁻ and N—H⁺...O⁻ hydrogen bonds, leading to a neutral one-dimensional network along [100]. These hydrogen bonds appear to complement the Coulombic inter­action and help to stabilize the structure further.

S1. Comment

Sulfenamides are important compounds with versatile industrial applications (Kuhle, 1973). Bond polarization in sulfenamide derivatives, resulting from the difference in electronegativity between S and N, activates the S—N bond for attack by both nucleophiles and electrophiles, and appears to be the factor primarily responsible for the chemistry of these compounds. The title compound, (I), is the result of the condensation reaction of 2,4-dinitrophenylsulfenyl chloride and 2-carbamoyl benzoic acid. As part of our work involving the study of the synthesis and structural characterization of divalent-sulfur compounds (Brito et al., 2004, 2005; Brito, López-Rodríguez, Cárdenas & Vargas, 2006; Brito, López-Rodríguez, Vargas & León, 2006), we report here the molecular and supramolecular structure of (I). To our knowledge (Cambridge Structural Database, version 5.27; Allen, 2002), this is the first reported structure of an ionic sulfenamide.

The structure of compound (I) comprises discrete ions (Fig. 1 and Table 1). The cation in (I) has an approximate C₂ symmetry and the molecular dimensions are within normal ranges (Allen et al., 1987), with mean Csp³—Csp³ = 1.508 (4) Å and mean Csp³—N = 1.504 (3) Å.

The benzene rings are slightly distorted and the nitro groups are slightly twisted with respect to the ring to which they are bonded (Table 1). The C—S and N—S bond distances [1.760 (2) and 1.6885 (18) Å, respectively] are normal for this type of compound [literature values are in the ranges C—S = 1.763–1.791 Å and S—N = 1.679–1.695 Å (Mahmoudkhani & Vargas-Baca, 2003; Glidewell et al., 2003; Lee et al., 1995; Zhang et al., 2005; Bao et al., 2003)]. The S—N distance is shorter than the normal S—N single-bond length (1.74 Å; Pauling, 1960), but is normal for this type of structure as a result of the π character of the S—N bond.

The C—O bond distances in the carboxylate group are nearly equal and lie midway between the usual single and double C—O bond lengths found in a carboxylate fragment, as a consequence of the virtually complete electron delocalization. These lengths also compare favourably with those reported [1.2593 (16)–1.259 (2) Å] by Parvez et al. (2004), as a representative example. In the anion, the C6/S1/N3 plane makes a dihedral angle of 88.4 (8)° with the H3/N3/C7 plane, in good agreement with the value of 90.0° for the torsional ground state of this type of species. The conformation of the anion is stabilized by two intramolecular hydrogen bonds involving atom C5 as a donor, C5—H5···N3 and C5—H5···O7 (Fig. 1). The crystal packing also shows a weak intramolecular C—H···π interaction between pairs of cations and anions (Fig. 1, Table 2).

Two cations in (I) bridge two anions through N⁺—H···O⁻ hydrogen bonds (Table 2). The ammonium atom N4 forms hydrogen bonds to a different carboxylate O atom in each of two adjacent anions, to form a centrosymmetric macroring at (0, 0, 1/2) characterized by the R⁴₄(12) motif (labelled A in Fig. 2) (Bernstein et al., 1995). Pairs of anions are then connected via hydrogen bonds involving atom N3 as the donor in one anion and atom O6 of the carboxylate group of the other anion as the acceptor, thereby generating an R²₂(14) centrosymmetric ring (labelled B in Fig. 2) at (1/2, 0, 1/2). These two types of rings combine alternately in an ···ABAB··· fashion to form a one-dimensional supramolecular aggregate (Fig. 2).

S2. Experimental

All reactions were carried out under an atmosphere of purified nitrogen. Solvents used were dried and distilled prior to use. 2,4-Dinitrophenylsulfenyl chloride and phthalimide were purchased from Aldrich. The precursor compound, 2-carbamoylbenzoic acid, C₈H₇NO₃, was prepared in situ by a hydrolysis reaction at room temperature of the phthalimide compound (see scheme). The title compound, (I), was prepared according to the method of Wunderly (1972). A methanol solution of 2,4-dinitrophenyl chloride (2.487 g, 0.010 mol) was added dropwise to a stirred solution of phthalimide (1.176 g, 0.008 mol) and diisopropylamine (1.13 ml, 0.008 mol) in dimethylformamide–H₂O (5:1 v/v, Volume?) under a nitrogen atmosphere. Stirring was continued for 30 min at 298 K. The colourless crystals which formed were filtered off, washed with pentane and dried at room temperature. Colourless crystals suitable for single-crystal X-ray diffraction studies were obtained by slow evaporation of a solution of (I) in methanol [m.p. 423 K (decomposition)]. FT–IR (KBr pellet, cm⁻¹): ν(w, C—S) 735; ν(s, C═O) 1568; ν(s, N—H) 3106; ν(s, NO₂) 1521; ν(s, C—O) 1307; ν(m, S—N) 967; ν(s, C—H disubstitution, Ar) 830; ν(m, N—H amine) 2942.

S3. Refinement

H atoms bonded to atoms N3 and N4 were located in difference density maps and refined with an isotropic model, giving N—H distances in the range 0.82 (3)–0.93 (3) Å. H atoms bonded to C were positioned geometrically and then allowed to ride on their parent atoms, with C—H distances of 0.94 Å for aromatic H atoms, 0.96 Å for methyl H atoms and 0.98 Å for methylene H atoms, with U_iso(H) = 1.2U_eq(C) or 1.5U_eq(C) for methyl groups. 55 unique reflections with sinθ/λ < 0.6 were not included in the data set as they were either partially obscured by the beam stop or were eliminated during data reduction.

Computing details

Data collection: COLLECT (Nonius, 1998); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997), Mercury (Macrae et al., 2006) and PLATON (Spek, 2003); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. The structure of (I), showing the atom-numbering scheme and with 30% probability displacement ellipsoids. H atoms are shown as small spheres of arbitrary radii. The dashed lines denote the hydrogen-bonding interactions and the C—H···π interaction (centroid C9—C14 ring) within the asymmetric unit.
	Fig. 2. A view of the one-dimensional supramolecular aggregate, showing the formation of R^44(12) and R^22(14) rings (labelled A and B, respectively). H atoms not involved in the N—H···O interactions have been omitted. [Symmetry codes: (i) −x, −y, 1 − z; (ii) 1 − x, −y, 1 − z.]

Diisopropylammonium 2-[(2,4-dinitrophenyl)sulfanylaminocarbonyl]benzoate

Crystal data

C6H16N^+·C14H8N3O7S^−	F(000) = 976
Mr = 464.49	Dx = 1.36 Mg m^−3
Monoclinic, P21/n	Melting point: 422.8 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 9.435 (1) Å	Cell parameters from 6570 reflections
b = 18.098 (8) Å	θ = 2.0–26.5°
c = 13.612 (2) Å	µ = 0.19 mm^−1
β = 102.485 (9)°	T = 298 K
V = 2269.3 (11) Å^3	Prism, colourless
Z = 4	0.35 × 0.23 × 0.19 mm

Data collection

Nonius KappaCCD area-detector diffractometer	4866 independent reflections
Radiation source: fine-focus sealed tube	4116 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.037
ϕ scans, and ω scans with κ offsets	θmax = 27°, θmin = 1.9°
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	h = −10→12
Tmin = 0.951, Tmax = 0.963	k = −23→20
12285 measured reflections	l = −17→10

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.059	w = 1/[σ^2(Fo^2) + (0.0801P)^2 + 0.6445P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.166	(Δ/σ)max = 0.006
S = 1.17	Δρmax = 0.41 e Å^−3
4866 reflections	Δρmin = −0.36 e Å^−3
307 parameters

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	0.44359 (6)	0.11628 (3)	0.21640 (4)	0.04332 (19)
O1	−0.0037 (3)	−0.13080 (11)	−0.05426 (14)	0.0715 (6)
O2	−0.0615 (2)	−0.14362 (12)	0.08809 (16)	0.0764 (6)
O3	0.3719 (3)	0.03832 (13)	−0.08998 (14)	0.0764 (6)
O4	0.4464 (3)	0.11826 (12)	0.02576 (15)	0.0773 (7)
O5	0.2862 (2)	0.19101 (11)	0.35562 (13)	0.0628 (5)
O6	0.29183 (16)	−0.03871 (8)	0.55993 (12)	0.0457 (4)
O7	0.18012 (16)	0.04121 (9)	0.44480 (11)	0.0449 (4)
N1	0.0121 (2)	−0.11651 (11)	0.03470 (16)	0.0524 (5)
N2	0.3767 (2)	0.06355 (12)	−0.00645 (15)	0.0517 (5)
N3	0.4509 (2)	0.10309 (10)	0.34020 (13)	0.0373 (4)
N4	−0.0550 (2)	0.13591 (10)	0.44750 (13)	0.0368 (4)
C1	0.2976 (2)	0.02649 (12)	0.06055 (15)	0.0383 (5)
C2	0.2025 (2)	−0.02849 (12)	0.01862 (16)	0.0411 (5)
H2	0.1941	−0.043	−0.0479	0.056 (2)*
C3	0.1205 (2)	−0.06105 (12)	0.07883 (16)	0.0410 (5)
C4	0.1334 (3)	−0.04063 (13)	0.17770 (16)	0.0435 (5)
H4	0.0755	−0.0629	0.2164	0.056 (2)*
C5	0.2315 (2)	0.01249 (12)	0.21916 (15)	0.0402 (5)
H5	0.2413	0.025	0.2866	0.056 (2)*
C6	0.3175 (2)	0.04828 (11)	0.16185 (15)	0.0355 (4)
C7	0.3781 (2)	0.14691 (11)	0.39419 (16)	0.0379 (5)
C8	0.2780 (2)	0.02379 (11)	0.51882 (15)	0.0347 (4)
C9	0.4302 (2)	0.13935 (11)	0.50707 (15)	0.0354 (4)
C10	0.3862 (2)	0.08276 (11)	0.56444 (15)	0.0359 (4)
C11	0.4381 (3)	0.08354 (13)	0.66844 (16)	0.0458 (5)
H11	0.4105	0.0462	0.7074	0.056 (2)*
C12	0.5298 (3)	0.13888 (15)	0.71471 (19)	0.0578 (7)
H12	0.5607	0.1394	0.7844	0.056 (2)*
C13	0.5754 (3)	0.19301 (14)	0.6581 (2)	0.0577 (7)
H13	0.6387	0.2297	0.6889	0.056 (2)*
C14	0.5262 (3)	0.19261 (13)	0.55454 (19)	0.0491 (6)
H14	0.5584	0.2289	0.5161	0.056 (2)*
C15	−0.1145 (3)	0.11360 (19)	0.2671 (2)	0.0703 (8)
H15A	−0.0364	0.0785	0.2784	0.096 (3)*
H15B	−0.1236	0.1355	0.2018	0.096 (3)*
H15C	−0.2034	0.089	0.2706	0.096 (3)*
C16	−0.0833 (2)	0.17312 (14)	0.34648 (15)	0.0443 (5)
H16	0.0047	0.1996	0.3397	0.056 (2)*
C17	−0.2064 (3)	0.22806 (16)	0.3359 (2)	0.0628 (7)
H17A	−0.2902	0.2041	0.3505	0.096 (3)*
H17B	−0.2293	0.2468	0.2683	0.096 (3)*
H17C	−0.1777	0.2682	0.3821	0.096 (3)*
C18	−0.0283 (3)	0.18572 (13)	0.53829 (16)	0.0452 (5)
H18	−0.112	0.2187	0.5332	0.056 (2)*
C19	0.1054 (3)	0.23224 (14)	0.54382 (19)	0.0531 (6)
H19A	0.1893	0.2008	0.5533	0.096 (3)*
H19B	0.1153	0.266	0.5993	0.096 (3)*
H19C	0.0969	0.2595	0.4824	0.096 (3)*
C20	−0.0176 (5)	0.1380 (2)	0.6301 (2)	0.0895 (12)
H20A	0.0659	0.1065	0.6375	0.096 (3)*
H20B	−0.1035	0.1082	0.6229	0.096 (3)*
H20C	−0.0086	0.1688	0.6886	0.096 (3)*
H4A	0.021 (3)	0.1094 (13)	0.4526 (17)	0.039 (6)*
H4B	−0.132 (3)	0.1046 (14)	0.4519 (19)	0.049 (7)*
H3	0.521 (3)	0.0801 (15)	0.372 (2)	0.051 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0447 (3)	0.0502 (3)	0.0336 (3)	−0.0110 (2)	0.0053 (2)	0.0020 (2)
O1	0.1023 (16)	0.0657 (12)	0.0452 (11)	−0.0299 (11)	0.0132 (10)	−0.0135 (9)
O2	0.0890 (15)	0.0809 (14)	0.0649 (13)	−0.0454 (12)	0.0290 (11)	−0.0103 (11)
O3	0.1006 (16)	0.0985 (15)	0.0398 (10)	−0.0286 (13)	0.0367 (10)	−0.0082 (10)
O4	0.0996 (16)	0.0828 (14)	0.0534 (12)	−0.0474 (13)	0.0254 (11)	0.0010 (10)
O5	0.0665 (11)	0.0694 (12)	0.0503 (10)	0.0330 (10)	0.0077 (9)	0.0136 (9)
O6	0.0413 (8)	0.0415 (8)	0.0501 (10)	0.0000 (7)	0.0012 (7)	0.0113 (7)
O7	0.0423 (8)	0.0494 (9)	0.0371 (8)	0.0069 (7)	−0.0044 (6)	0.0018 (7)
N1	0.0665 (13)	0.0458 (11)	0.0444 (12)	−0.0159 (10)	0.0105 (10)	−0.0043 (9)
N2	0.0590 (12)	0.0622 (12)	0.0366 (11)	−0.0116 (10)	0.0162 (9)	0.0057 (9)
N3	0.0375 (9)	0.0405 (9)	0.0302 (9)	0.0045 (8)	−0.0005 (7)	0.0009 (7)
N4	0.0361 (9)	0.0425 (10)	0.0302 (9)	0.0041 (9)	0.0034 (7)	0.0014 (7)
C1	0.0422 (11)	0.0444 (11)	0.0303 (10)	−0.0004 (9)	0.0119 (8)	0.0042 (8)
C2	0.0533 (13)	0.0434 (11)	0.0277 (10)	−0.0030 (10)	0.0108 (9)	−0.0021 (8)
C3	0.0487 (12)	0.0388 (11)	0.0347 (11)	−0.0059 (9)	0.0072 (9)	−0.0009 (9)
C4	0.0501 (12)	0.0503 (12)	0.0311 (11)	−0.0095 (10)	0.0113 (9)	0.0046 (9)
C5	0.0441 (11)	0.0506 (12)	0.0260 (10)	−0.0061 (10)	0.0078 (8)	−0.0010 (9)
C6	0.0370 (10)	0.0392 (10)	0.0292 (10)	0.0011 (8)	0.0052 (8)	0.0037 (8)
C7	0.0359 (10)	0.0371 (10)	0.0382 (11)	0.0024 (9)	0.0025 (8)	0.0027 (9)
C8	0.0330 (10)	0.0393 (10)	0.0316 (10)	0.0076 (8)	0.0067 (8)	−0.0002 (8)
C9	0.0356 (10)	0.0328 (10)	0.0352 (11)	0.0071 (8)	0.0018 (8)	−0.0036 (8)
C10	0.0368 (10)	0.0352 (10)	0.0326 (10)	0.0099 (8)	0.0010 (8)	−0.0023 (8)
C11	0.0577 (14)	0.0436 (12)	0.0326 (11)	0.0114 (11)	0.0023 (10)	−0.0025 (9)
C12	0.0685 (16)	0.0583 (15)	0.0375 (13)	0.0141 (13)	−0.0087 (11)	−0.0145 (11)
C13	0.0619 (15)	0.0480 (13)	0.0547 (15)	−0.0006 (12)	−0.0064 (12)	−0.0207 (12)
C14	0.0527 (13)	0.0384 (11)	0.0535 (14)	0.0006 (10)	0.0055 (11)	−0.0061 (10)
C15	0.0662 (17)	0.107 (2)	0.0353 (13)	0.0155 (16)	0.0067 (12)	−0.0129 (14)
C16	0.0389 (11)	0.0651 (14)	0.0282 (10)	−0.0009 (10)	0.0053 (8)	0.0080 (10)
C17	0.0643 (16)	0.0630 (16)	0.0523 (15)	0.0136 (13)	−0.0070 (12)	0.0094 (13)
C18	0.0519 (13)	0.0530 (13)	0.0306 (11)	0.0043 (11)	0.0086 (9)	−0.0032 (9)
C19	0.0551 (14)	0.0481 (13)	0.0535 (15)	0.0001 (11)	0.0057 (11)	−0.0119 (11)
C20	0.131 (3)	0.101 (3)	0.0317 (14)	−0.037 (2)	0.0074 (16)	0.0059 (15)

Geometric parameters (Å, º)

S1—N3	1.6885 (18)	C9—C14	1.384 (3)
S1—C6	1.760 (2)	C9—C10	1.404 (3)
O1—N1	1.215 (3)	C10—C11	1.394 (3)
O2—N1	1.212 (3)	C11—C12	1.383 (4)
O3—N2	1.217 (3)	C11—H11	0.93
O4—N2	1.217 (3)	C12—C13	1.372 (4)
O5—C7	1.212 (3)	C12—H12	0.93
O6—C8	1.256 (3)	C13—C14	1.385 (3)
O7—C8	1.251 (2)	C13—H13	0.93
N1—C3	1.466 (3)	C14—H14	0.93
N2—C1	1.461 (3)	C15—C16	1.509 (4)
N3—C7	1.363 (3)	C15—H15A	0.96
N3—H3	0.82 (3)	C15—H15B	0.96
N4—C16	1.502 (3)	C15—H15C	0.96
N4—C18	1.506 (3)	C16—C17	1.511 (4)
N4—H4A	0.85 (3)	C16—H16	0.98
N4—H4B	0.93 (3)	C17—H17A	0.96
C1—C2	1.378 (3)	C17—H17B	0.96
C1—C6	1.407 (3)	C17—H17C	0.96
C2—C3	1.375 (3)	C18—C20	1.505 (4)
C2—H2	0.93	C18—C19	1.505 (3)
C3—C4	1.375 (3)	C18—H18	0.98
C4—C5	1.369 (3)	C19—H19A	0.96
C4—H4	0.93	C19—H19B	0.96
C5—C6	1.400 (3)	C19—H19C	0.96
C5—H5	0.93	C20—H20A	0.96
C7—C9	1.515 (3)	C20—H20B	0.96
C8—C10	1.514 (3)	C20—H20C	0.96
N3—S1—C6	101.56 (9)	C12—C11—H11	119.4
O2—N1—O1	123.2 (2)	C10—C11—H11	119.4
O2—N1—C3	118.1 (2)	C13—C12—C11	120.2 (2)
O1—N1—C3	118.6 (2)	C13—C12—H12	119.9
O4—N2—O3	123.4 (2)	C11—C12—H12	119.9
O4—N2—C1	117.26 (19)	C12—C13—C14	119.4 (2)
O3—N2—C1	119.4 (2)	C12—C13—H13	120.3
C7—N3—S1	122.62 (15)	C14—C13—H13	120.3
C7—N3—H3	117.2 (19)	C9—C14—C13	121.4 (2)
S1—N3—H3	116.7 (19)	C9—C14—H14	119.3
C16—N4—C18	116.60 (18)	C13—C14—H14	119.3
C16—N4—H4A	107.9 (16)	C16—C15—H15A	109.5
C18—N4—H4A	106.4 (16)	C16—C15—H15B	109.5
C16—N4—H4B	110.2 (15)	H15A—C15—H15B	109.5
C18—N4—H4B	107.8 (16)	C16—C15—H15C	109.5
H4A—N4—H4B	108 (2)	H15A—C15—H15C	109.5
C2—C1—C6	123.04 (19)	H15B—C15—H15C	109.5
C2—C1—N2	116.60 (19)	N4—C16—C15	107.7 (2)
C6—C1—N2	120.34 (19)	N4—C16—C17	111.30 (19)
C3—C2—C1	117.5 (2)	C15—C16—C17	112.0 (2)
C3—C2—H2	121.2	N4—C16—H16	108.6
C1—C2—H2	121.2	C15—C16—H16	108.6
C2—C3—C4	121.7 (2)	C17—C16—H16	108.6
C2—C3—N1	118.8 (2)	C16—C17—H17A	109.5
C4—C3—N1	119.43 (19)	C16—C17—H17B	109.5
C5—C4—C3	120.1 (2)	H17A—C17—H17B	109.5
C5—C4—H4	120	C16—C17—H17C	109.5
C3—C4—H4	120	H17A—C17—H17C	109.5
C4—C5—C6	121.12 (19)	H17B—C17—H17C	109.5
C4—C5—H5	119.4	C20—C18—C19	112.0 (2)
C6—C5—H5	119.4	C20—C18—N4	107.9 (2)
C5—C6—C1	116.47 (19)	C19—C18—N4	111.44 (19)
C5—C6—S1	120.57 (16)	C20—C18—H18	108.5
C1—C6—S1	122.96 (16)	C19—C18—H18	108.5
O5—C7—N3	123.1 (2)	N4—C18—H18	108.5
O5—C7—C9	122.93 (19)	C18—C19—H19A	109.5
N3—C7—C9	113.81 (17)	C18—C19—H19B	109.5
O7—C8—O6	125.0 (2)	H19A—C19—H19B	109.5
O7—C8—C10	117.87 (18)	C18—C19—H19C	109.5
O6—C8—C10	117.15 (17)	H19A—C19—H19C	109.5
C14—C9—C10	119.40 (19)	H19B—C19—H19C	109.5
C14—C9—C7	116.53 (19)	C18—C20—H20A	109.5
C10—C9—C7	124.07 (18)	C18—C20—H20B	109.5
C11—C10—C9	118.44 (19)	H20A—C20—H20B	109.5
C11—C10—C8	118.76 (19)	C18—C20—H20C	109.5
C9—C10—C8	122.69 (17)	H20A—C20—H20C	109.5
C12—C11—C10	121.2 (2)	H20B—C20—H20C	109.5
C6—S1—N3—C7	−100.66 (18)	S1—N3—C7—C9	−164.32 (14)
O4—N2—C1—C2	170.7 (2)	O5—C7—C9—C14	−77.4 (3)
O3—N2—C1—C2	−10.3 (3)	N3—C7—C9—C14	98.5 (2)
O4—N2—C1—C6	−7.9 (3)	O5—C7—C9—C10	102.2 (3)
O3—N2—C1—C6	171.1 (2)	N3—C7—C9—C10	−81.9 (2)
C6—C1—C2—C3	2.4 (3)	C14—C9—C10—C11	1.9 (3)
N2—C1—C2—C3	−176.2 (2)	C7—C9—C10—C11	−177.71 (19)
C1—C2—C3—C4	−0.9 (3)	C14—C9—C10—C8	178.08 (19)
C1—C2—C3—N1	176.3 (2)	C7—C9—C10—C8	−1.5 (3)
O2—N1—C3—C2	−178.5 (2)	O7—C8—C10—C11	143.9 (2)
O1—N1—C3—C2	−1.5 (3)	O6—C8—C10—C11	−34.5 (3)
O2—N1—C3—C4	−1.2 (4)	O7—C8—C10—C9	−32.3 (3)
O1—N1—C3—C4	175.8 (2)	O6—C8—C10—C9	149.25 (19)
C2—C3—C4—C5	−1.1 (4)	C9—C10—C11—C12	0.5 (3)
N1—C3—C4—C5	−178.3 (2)	C8—C10—C11—C12	−175.9 (2)
C3—C4—C5—C6	1.6 (3)	C10—C11—C12—C13	−2.2 (4)
C4—C5—C6—C1	−0.2 (3)	C11—C12—C13—C14	1.4 (4)
C4—C5—C6—S1	−179.79 (17)	C10—C9—C14—C13	−2.6 (3)
C2—C1—C6—C5	−1.9 (3)	C7—C9—C14—C13	176.9 (2)
N2—C1—C6—C5	176.66 (19)	C12—C13—C14—C9	1.0 (4)
C2—C1—C6—S1	177.71 (17)	C18—N4—C16—C15	−177.1 (2)
N2—C1—C6—S1	−3.8 (3)	C18—N4—C16—C17	−54.0 (3)
N3—S1—C6—C5	13.6 (2)	C16—N4—C18—C20	174.4 (2)
N3—S1—C6—C1	−165.92 (17)	C16—N4—C18—C19	−62.3 (3)
S1—N3—C7—O5	11.6 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O6^i	0.82 (3)	1.96 (3)	2.770 (3)	170 (3)
N4—H4A···O7	0.85 (3)	1.96 (3)	2.810 (3)	171 (2)
N4—H4B···O6^ii	0.93 (3)	1.90 (3)	2.828 (3)	172 (2)
C5—H5···O7	0.93	2.37	3.253 (3)	160
C5—H5···N3	0.93	2.41	2.866 (3)	110
C19—H19A···Cg1	0.96	2.92	3.857 (3)	165

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