Helical supra­molecular assembly of N²,N^2'-bis­[3-(morpholin-4-yl)prop­yl]-N¹,N^1'-(1,2-phenyl­ene)dioxalamide dimethyl sulfoxide monosolvate

In the title compound, C₂₄H₃₆N₆O₆·C₂H₆OS, the carbonyl groups are in an anti­periplanar conformation, with O=C-C=O torsion angles of 178.59 (15) and -172.08 (16)°. An intra­molecular hydrogen-bonding pattern is depicted by four N-H...O inter­actions, which form two adjacent S(5)S(5) motifs, and an N-H...N inter­action, which forms an S(6) ring motif. Inter­molecular N-H...O hydrogen bonding and C-H...O soft inter­actions allow the formation of a meso-helix. The title compound is the first example of a helical 1,2-phenyl­enedioxalamide. The oxalamide traps one mol­ecule of dimethyl sulfoxide through N-H...O hydrogen bonding. C-H...O soft inter­actions give rise to the two-dimensional structure.

S1. Comment

In supramolecular chemistry, the design and synthesis of model molecules for donor–acceptor interaction studies continues being an area of interest (Steed & Atwood, 2009). Hydrogen bonding (HB) is the most important noncovalent interaction used in the design of host–guest systems. HB is particularly important from a biological point of view, because of its participation in several biological processes such as the stabilization of the double helix of DNA (Kool, 1997), peptide three-dimensional structures (helices, sheets or turns) (Sewald & Hans-Dieter, 2002), enzyme–substrate interactions (Bugg, 2004), recognition among proteins (Keskin et al., 2008) and drug-acceptor interactions (Sarker & Nahar, 2007). The development of simple hydrogen-bonding motifs for anion recognition, that are easy to make and functionalize, has lead to the design and synthesis of amide, pyrrole and urea-based hosts with conventional hydrogen-bond donors (Brooks et al., 2006; Brooks et al., 2007). The supramolecular versatility of oxalamides has been demonstrated previously as formers of columns, sheets, tapes, helixes and layers (González-González, Martínez-Martínez, García-Báez et al., 2011; González-González, Martínez-Martínez, Peraza-Campos et al., 2011). In this context, the N—H and C═O groups of oxalamides can be exploited as recognition sites in the design of molecular hosts. In this contribution, we report the molecular structure and the helical supramolecular assembly complex, (I) (Fig. 1), formed between N²,N^2'-bis[2-(morpholin-4-yl)propyl]-N¹,N^1'-(1,2-phenylene)dioxalamide and dimethyl sulfoxide (DMSO).

The title compound forms triclinic crystals (P1, Z = 2). Selected bond lengths and angles are listed in Table 1 and are in the normal range found in related structures (Martínez-Martínez et al., 1998). The carbonyl groups are antiperiplanar, with O8—C8—C9—O9 and O28—C28—C29—O29 torsion angles of 178.62 (19) and -171.9 (2)°, respectively. The oxalamide group is almost planar, with N7—C8—C9—N10 and N27—C28—C29—N30 torsion angles of -177.76 (17) and -170.66 (16)°, respectively. These values are in agreement with those reported for oxalamides (Bernés et al., 2010). Both oxalyl arms are twisted from the mean plane of the phenylene ring and adopt an anticlinal conformation with C6—C1—N7—C8 and C1—C6—N27—C28 torsion angles of 137.6 (2) and -126.0 (2)°, respectively. The N7—H and N27—H amide groups point towards the cavity, thus the two oxalamidyl groups are cis-positioned between them, in relation to the mean plane of the phenylene ring. According to graph-set notation (Bernstein et al., 1995), four S(5) rings are formed between amide NH and carbonyl groups, through N7—H7···O9, N10—H10···O8, N27—H27···O29 and N30—H30···O28 interactions, and one S(6) ring is formed between an amide NH group and the N atom of one morpholine residue, through N30—H30···N34 interactions, displaying only one N—H stretch maximum, at 3272 cm^-1. N···A distances and N—H···A angles (A = O and N) are in the range of intramolecular hydrogen bonding (HB) (Taylor & Kennard, 1982; Desiraju, 1996), in agreement with similar structures (Desseyn et al., 2004; Martín et al., 2002; Blay et al., 2003) and also in agreement with values reported for intramolecular HB in other systems (Zhu et al., 2007; Yang & Gellman, 1998). The geometric parameters associated with HB interactions are summarized in Table 2. The S(5)S(5)S(6) intramolecular hydrogen-bonded side arm is twisted from the mean aromatic ring plane with N30—C31—C32—C33 and C31—C32—C33—N34 torsion angles values of 54.4 (2) and -70.5 (2)°, respectively, whereas the S(5)S(5) side arm is twisted to the opposite side, with N10—C11—C12—C13 and C11—C12—C13—N14 torsion angles values of -168.58 (16) and 56.5 (2)°, respectively. One molecule of DMSO is situated outside the cavity formed by the pair of oxalamide side arms and bonded to the dioxalamide molecule by means of N7—H7···O1 and N27—H27···O1 HB interactions and C40—H40C···O29 and C41—H41C···O29 soft interactions to form a 1:1 complex. C—H···O interactions are weak HB interactions classified between electrostatic and van der Waals limits (Desiraju, 2002), herein they are called `soft interactions', as suggested by Desiraju (1996).

The zero-dimensional array is given by pairing of two molecules complex (I) (Fig. 2) through self-complementary strong N10—H10···O8 hydrogen bonding, to form the R₂²(10) motif characteristic of oxalamides. This motif is developed in one-dimensional meso-helix by C35—H35A···O29 soft interaction forming an R₂²(18) ring motif along the (001) direction. In the crystal lattice, the perfect alignment of the helical molecules of the same chirality in the meso-helix is observed (Fig. 3).

The turn of the helix measured as the spacing between the aromatic rings on neighbouring homochiral molecules is 16.328 (2) Å, which match the exact value of the lattice c parameter. Adjacent meso-helices are interlinked through C4—H4···O37 soft interactions to form an infinite sheet on the [441] family of planes separated by 5.329 (2) Å. DMSO molecules not only act as a template to form the cavity between the two oxalamide arms, but also facilitate the development of the second dimension linking the meso-helices through C40—H40B···O28 soft interactions and fill the voids left between the layers.

The softness of DMSO is not capable interrupting the formation of the typical R₂²(10) (N—H···O) ring motif of oxalamides, in contrast to that observed with the use of the 2-(4-nitrophenyl)acetic acid (Arman et al., 2012). As a final remark, is worth mentioning that a search was performed in the Cambridge Structural Database (CSD, Version 5.33, November 2011; Allen, 2002) for the 1,2-fenilenedioxalyl moiety and the only hit found was for the crystal structure of ethyl 1,2-fenilenedioxalamate (Martín et al., 2002). Thus, the title compound is the first example of a 1,2-fenilenedioxalamide crystal structure which, in addition, presents a meso-helix supramolecular architecture.

Related literature

For related literature, see: Allen (2002); Arman et al. (2012); Bernés et al. (2010); Bernstein et al. (1995); Blay et al. (2003); Brooks et al. (2006, 2007); Bugg (2004); Desiraju (1996, 2002); Desseyn et al. (2004); González-González, Martínez-Martínez, Peraza-Campos, Rosales-Hoz, García-Báez & Padilla-Martínez (2011); Keskin et al. (2008); Kool (1997); Martín et al. (2002); Martínez-Martínez, Padilla-Martínez, Brito, Geniz, Rojas, Saavedra, Höpfl, Tlahuextl & Contreras (1998); Sarker & Nahar (2007); Sewald & Hans-Dieter (2002); Sheldrick (2008); Steed & Atwood (2009); Taylor & Kennard (1982); Yang & Gellman (1998); Zhu et al. (2007).

S2. Experimental

A solution of diethyl 1,2-phenylenedioxalamate (0.5 g, 1.6 mmol) in methanol (30 ml) and 3-(morpholin-4-yl)propylamine (0.474 ml, 3.2 mmol) was refluxed for 24 h. The suspension was filtered off and the resulting solid was washed with acetone (3 ml) and dried to yield 0.49 g (61%) of a white solid (m.p. 238–440 K). Good quality crystals were grown from DMSO solution by slow evaporation. IR ν (neat) (cm^-1): 3272 (N—H), 1667 (C═O). ¹H NMR (300 MHz, DMSO_d-6): δ 7.27 (m, 2H), 7.59 (m, 2H), 10.52 (s, 2H, Ar–NH), 8.87 (t, 2H, NH–CH₂), 3.24 (m, 4H, NH–CH₂), 1.64 (m, 4H, NH–CH₂–CH₂), 2.32 (m, 4H, CH₂–N), 2.30 [m, 8H, N–(CH₂)₂], 3.56 [m, 8H, O–(CH₂)₂]. ¹³C NMR (75.46 MHz, DMSO_d-6): δ 130.5 (C1,6), 126.2 (C2,5), 126.8 (C3,4), 159.3 (C8), 160.1 (C9), 38.9 (C11), 25.6 (C12), 57.0 (C13), 53.9 (N–CH₂), 66.8 (CH₂—O). ESI–MS (m/z): calculated 504.27, found 526.9 [M + Na]⁺.

S3. Refinement

All H atoms were found by Fourier difference synthesis and refined. The DMSO S atom is disordered over two positions with occupancies of 0.931 (2) and 0.069 (2). The disorder was treated using PART 1, PART 2 and PART 0 SHELXL97 (Sheldrick, 2008) instructions.

Computing details

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008) and WinGX (Farrugia, 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2006); software used to prepare material for publication: PLATON (Spek, 2009).

Figures

The molecular structure of the title DMSO-solvated complex, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.

Two molecules of the title DMSO-solvated complex are paired through self-complementary strong N10—H10···O8 hydrogen bonding to form the R₂²(10) motif characteristic of oxalamides.

The linkage of the title DMSO-solvated complex dimer through C35—H35A···O29 soft interactions developing a meso helix along the direction of the c axis. H atoms have been omitted for clarity.

N²,N^2'-bis[2-(morpholin-4-yl)propyl]- N¹,N^1'-(1,2-phenylene)dioxalamide dimethyl sulfoxide monosolvate

Crystal data

C24H36N6O6·C2H6OS	Z = 2
Mr = 582.72	F(000) = 624
Triclinic, P1	Dx = 1.318 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.6704 (8) Å	Cell parameters from 600 reflections
b = 11.0052 (10) Å	θ = 20–25°
c = 16.3277 (15) Å	µ = 0.16 mm^−1
α = 107.425 (2)°	T = 173 K
β = 98.036 (2)°	Block, yellow
γ = 91.517 (2)°	0.30 × 0.26 × 0.22 × 0.12 (radius) mm
V = 1468.0 (2) Å^3

Data collection

Bruker APEXII area-detector diffractometer	5081 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.021
ϕ and ω scans	θmax = 26.0°, θmin = 1.3°
Absorption correction: for a sphere (Dwiggins, 1975)	h = −10→10
Tmin = 0.861, Tmax = 0.862	k = −12→13
11574 measured reflections	l = −19→20
5722 independent reflections

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.099	All H-atom parameters refined
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0453P)^2 + 0.6256P] where P = (Fo^2 + 2Fc^2)/3
5722 reflections	(Δ/σ)max = 0.001
539 parameters	Δρmax = 0.41 e Å^−3
0 restraints	Δρmin = −0.28 e Å^−3

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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	Occ. (<1)
O8	0.53574 (12)	0.60848 (11)	0.10601 (7)	0.0264 (3)
O9	0.17690 (13)	0.50921 (11)	0.15060 (7)	0.0262 (3)
O17	−0.37434 (15)	0.17201 (13)	0.08340 (9)	0.0391 (4)
O28	0.64360 (13)	0.75925 (12)	0.47845 (8)	0.0302 (4)
O29	0.25116 (12)	0.65877 (11)	0.46500 (7)	0.0252 (3)
O37	1.02189 (14)	0.80083 (12)	0.67308 (9)	0.0385 (4)
N7	0.38959 (15)	0.70657 (12)	0.21044 (8)	0.0187 (4)
N10	0.31850 (16)	0.40636 (12)	0.04669 (9)	0.0225 (4)
N14	−0.10812 (15)	0.18090 (12)	−0.00197 (8)	0.0227 (4)
N27	0.42871 (15)	0.79070 (12)	0.39127 (8)	0.0188 (3)
N30	0.46105 (15)	0.65750 (13)	0.56521 (9)	0.0215 (4)
N34	0.71514 (14)	0.73241 (12)	0.69766 (8)	0.0207 (4)
C1	0.48849 (16)	0.81794 (14)	0.25568 (10)	0.0185 (4)
C2	0.56534 (17)	0.88637 (15)	0.21224 (10)	0.0213 (5)
C3	0.66111 (18)	0.99471 (15)	0.25899 (11)	0.0231 (5)
C4	0.68062 (18)	1.03634 (15)	0.34891 (10)	0.0221 (4)
C5	0.60312 (17)	0.96937 (15)	0.39263 (10)	0.0212 (5)
C6	0.50729 (16)	0.85992 (14)	0.34636 (10)	0.0180 (4)
C8	0.41987 (17)	0.61291 (14)	0.14196 (9)	0.0194 (4)
C9	0.29006 (17)	0.50367 (14)	0.11262 (10)	0.0196 (4)
C11	0.21399 (19)	0.29092 (15)	0.01338 (11)	0.0237 (5)
C12	0.0849 (2)	0.29545 (17)	−0.05828 (11)	0.0274 (5)
C13	−0.0393 (2)	0.18562 (17)	−0.07818 (10)	0.0258 (5)
C15	−0.1936 (2)	0.29349 (17)	0.03148 (12)	0.0303 (5)
C16	−0.2704 (2)	0.28347 (19)	0.10682 (13)	0.0369 (6)
C18	−0.2899 (2)	0.06255 (19)	0.05283 (14)	0.0357 (6)
C19	−0.21447 (19)	0.06680 (16)	−0.02420 (11)	0.0267 (5)
C28	0.50291 (17)	0.74814 (14)	0.45403 (10)	0.0201 (4)
C29	0.39051 (17)	0.68233 (14)	0.49543 (10)	0.0198 (4)
C31	0.37658 (18)	0.60791 (16)	0.62106 (11)	0.0235 (5)
C32	0.49037 (18)	0.58436 (16)	0.69399 (11)	0.0235 (5)
C33	0.59856 (19)	0.70112 (16)	0.74713 (10)	0.0238 (5)
C35	0.83681 (19)	0.64169 (16)	0.68605 (13)	0.0282 (5)
C36	0.9470 (2)	0.67591 (18)	0.63104 (15)	0.0364 (6)
C38	0.9057 (2)	0.89093 (17)	0.68587 (14)	0.0342 (6)
C39	0.7904 (2)	0.86114 (16)	0.73967 (12)	0.0299 (5)
S1A	0.03282 (4)	0.22525 (4)	0.69145 (3)	0.0201 (1)	0.931 (2)
O1	−0.13537 (12)	0.21701 (11)	0.70381 (7)	0.0256 (3)
C40	0.0296 (2)	0.1563 (2)	0.57760 (12)	0.0359 (6)
C41	0.0781 (3)	0.3874 (2)	0.69737 (18)	0.0477 (8)
S1B	−0.0121 (11)	0.3196 (8)	0.6628 (6)	0.055 (3)	0.069 (2)
H2	0.553 (2)	0.8566 (17)	0.1505 (12)	0.025 (4)*
H3	0.7147 (19)	1.0425 (16)	0.2299 (11)	0.020 (4)*
H4	0.748 (2)	1.1113 (17)	0.3810 (11)	0.022 (4)*
H5	0.6172 (19)	0.9953 (16)	0.4560 (12)	0.022 (4)*
H7	0.304 (2)	0.6964 (18)	0.2256 (12)	0.029 (5)*
H10	0.392 (2)	0.4154 (18)	0.0200 (12)	0.030 (5)*
H11A	0.1675 (19)	0.2798 (15)	0.0609 (11)	0.016 (4)*
H11B	0.277 (2)	0.2198 (18)	−0.0084 (12)	0.026 (4)*
H12A	0.127 (2)	0.2889 (18)	−0.1108 (12)	0.029 (5)*
H12B	0.037 (2)	0.3779 (19)	−0.0421 (12)	0.030 (5)*
H13A	−0.121 (2)	0.1896 (17)	−0.1243 (12)	0.027 (5)*
H13B	0.011 (2)	0.1042 (18)	−0.0995 (11)	0.024 (4)*
H15A	−0.279 (2)	0.3041 (19)	−0.0144 (13)	0.039 (5)*
H15B	−0.123 (2)	0.3694 (19)	0.0496 (12)	0.031 (5)*
H16A	−0.192 (2)	0.2795 (18)	0.1533 (13)	0.033 (5)*
H16B	−0.334 (2)	0.355 (2)	0.1251 (13)	0.040 (5)*
H18A	−0.364 (2)	−0.011 (2)	0.0377 (13)	0.039 (5)*
H18B	−0.205 (2)	0.0586 (18)	0.0998 (12)	0.031 (5)*
H19A	−0.157 (2)	−0.0075 (18)	−0.0427 (11)	0.024 (4)*
H19B	−0.300 (2)	0.0644 (17)	−0.0731 (12)	0.028 (5)*
H27	0.327 (2)	0.7744 (17)	0.3771 (12)	0.027 (5)*
H30	0.553 (2)	0.6837 (18)	0.5860 (12)	0.026 (5)*
H31A	0.317 (2)	0.5292 (19)	0.5866 (12)	0.030 (5)*
H31B	0.305 (2)	0.6694 (17)	0.6469 (11)	0.024 (4)*
H32A	0.428 (2)	0.5591 (18)	0.7342 (12)	0.030 (5)*
H32B	0.551 (2)	0.5113 (17)	0.6699 (11)	0.022 (4)*
H33A	0.540 (2)	0.7767 (19)	0.7655 (12)	0.030 (5)*
H33B	0.651 (2)	0.6867 (17)	0.8013 (12)	0.025 (4)*
H35A	0.790 (2)	0.5578 (19)	0.6568 (12)	0.030 (5)*
H35B	0.892 (2)	0.6453 (18)	0.7439 (13)	0.034 (5)*
H36A	1.028 (2)	0.6189 (19)	0.6228 (13)	0.037 (5)*
H36B	0.886 (2)	0.675 (2)	0.5718 (14)	0.044 (6)*
H38A	0.848 (2)	0.8922 (19)	0.6298 (13)	0.036 (5)*
H38B	0.962 (2)	0.975 (2)	0.7173 (13)	0.042 (6)*
H39A	0.846 (2)	0.8695 (19)	0.7996 (13)	0.034 (5)*
H39B	0.707 (2)	0.9221 (19)	0.7458 (12)	0.034 (5)*
H40A	−0.001 (3)	0.059 (3)	0.5650 (16)	0.066 (7)*
H40B	0.132 (3)	0.169 (2)	0.5635 (13)	0.043 (6)*
H40C	−0.045 (2)	0.1964 (19)	0.5472 (13)	0.035 (5)*
H41A	0.072 (3)	0.442 (3)	0.7620 (18)	0.070 (8)*
H41B	−0.005 (3)	0.414 (3)	0.6513 (18)	0.072 (8)*
H41C	0.186 (3)	0.391 (2)	0.6899 (16)	0.065 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O8	0.0256 (6)	0.0259 (6)	0.0243 (6)	−0.0022 (5)	0.0091 (5)	0.0006 (5)
O9	0.0270 (6)	0.0253 (6)	0.0255 (6)	−0.0015 (5)	0.0092 (5)	0.0046 (5)
O17	0.0332 (7)	0.0382 (7)	0.0491 (8)	0.0076 (6)	0.0181 (6)	0.0127 (6)
O28	0.0213 (6)	0.0423 (7)	0.0339 (7)	−0.0003 (5)	0.0026 (5)	0.0228 (6)
O29	0.0214 (5)	0.0296 (6)	0.0251 (6)	−0.0032 (4)	−0.0004 (4)	0.0115 (5)
O37	0.0247 (6)	0.0297 (7)	0.0607 (9)	−0.0060 (5)	0.0067 (6)	0.0141 (6)
N7	0.0191 (6)	0.0204 (7)	0.0170 (6)	0.0002 (5)	0.0049 (5)	0.0054 (5)
N10	0.0256 (7)	0.0203 (7)	0.0210 (7)	−0.0013 (5)	0.0077 (5)	0.0037 (5)
N14	0.0259 (7)	0.0214 (7)	0.0201 (7)	0.0011 (5)	0.0031 (5)	0.0057 (5)
N27	0.0193 (6)	0.0198 (6)	0.0167 (6)	−0.0019 (5)	0.0025 (5)	0.0051 (5)
N30	0.0184 (6)	0.0258 (7)	0.0219 (7)	−0.0022 (5)	0.0017 (5)	0.0108 (6)
N34	0.0215 (6)	0.0181 (6)	0.0225 (7)	0.0009 (5)	0.0031 (5)	0.0063 (5)
C1	0.0184 (7)	0.0176 (7)	0.0191 (7)	0.0043 (6)	0.0031 (6)	0.0047 (6)
C2	0.0235 (8)	0.0231 (8)	0.0189 (8)	0.0040 (6)	0.0049 (6)	0.0078 (6)
C3	0.0237 (8)	0.0216 (8)	0.0278 (9)	0.0027 (6)	0.0080 (6)	0.0116 (7)
C4	0.0215 (7)	0.0167 (7)	0.0269 (8)	0.0009 (6)	0.0033 (6)	0.0053 (6)
C5	0.0237 (8)	0.0202 (8)	0.0187 (8)	0.0022 (6)	0.0030 (6)	0.0044 (6)
C6	0.0186 (7)	0.0169 (7)	0.0202 (7)	0.0035 (5)	0.0049 (6)	0.0070 (6)
C8	0.0222 (7)	0.0203 (8)	0.0170 (7)	0.0019 (6)	0.0023 (6)	0.0080 (6)
C9	0.0219 (7)	0.0201 (8)	0.0179 (7)	0.0012 (6)	0.0023 (6)	0.0079 (6)
C11	0.0290 (8)	0.0179 (8)	0.0227 (8)	−0.0019 (6)	0.0049 (7)	0.0037 (7)
C12	0.0351 (9)	0.0279 (9)	0.0203 (8)	−0.0036 (7)	0.0041 (7)	0.0097 (7)
C13	0.0308 (8)	0.0275 (9)	0.0172 (8)	−0.0020 (7)	0.0000 (7)	0.0060 (7)
C15	0.0345 (9)	0.0229 (9)	0.0325 (10)	0.0034 (7)	0.0052 (8)	0.0070 (7)
C16	0.0361 (10)	0.0357 (10)	0.0363 (11)	0.0082 (8)	0.0110 (8)	0.0043 (8)
C18	0.0339 (10)	0.0340 (10)	0.0464 (12)	0.0054 (8)	0.0157 (9)	0.0186 (9)
C19	0.0267 (8)	0.0221 (8)	0.0311 (9)	0.0009 (7)	0.0039 (7)	0.0081 (7)
C28	0.0233 (8)	0.0187 (7)	0.0183 (8)	0.0014 (6)	0.0048 (6)	0.0052 (6)
C29	0.0231 (7)	0.0165 (7)	0.0189 (8)	0.0011 (6)	0.0041 (6)	0.0039 (6)
C31	0.0217 (8)	0.0269 (8)	0.0252 (8)	−0.0012 (7)	0.0045 (6)	0.0127 (7)
C32	0.0242 (8)	0.0265 (8)	0.0243 (8)	0.0012 (7)	0.0066 (6)	0.0132 (7)
C33	0.0266 (8)	0.0261 (8)	0.0198 (8)	0.0032 (7)	0.0044 (6)	0.0083 (7)
C35	0.0220 (8)	0.0204 (8)	0.0410 (10)	0.0013 (6)	0.0028 (7)	0.0086 (8)
C36	0.0237 (8)	0.0263 (9)	0.0571 (13)	−0.0005 (7)	0.0133 (9)	0.0069 (9)
C38	0.0337 (9)	0.0235 (9)	0.0447 (11)	−0.0048 (7)	0.0029 (8)	0.0116 (8)
C39	0.0349 (9)	0.0200 (8)	0.0310 (10)	−0.0011 (7)	0.0030 (8)	0.0033 (7)
S1A	0.0172 (2)	0.0196 (2)	0.0239 (2)	0.0025 (2)	0.0024 (2)	0.0074 (2)
O1	0.0214 (5)	0.0300 (6)	0.0243 (6)	0.0040 (4)	0.0062 (4)	0.0053 (5)
C40	0.0313 (10)	0.0466 (12)	0.0290 (10)	0.0066 (9)	0.0122 (8)	0.0065 (9)
C41	0.0379 (11)	0.0256 (10)	0.0763 (17)	−0.0078 (9)	0.0077 (11)	0.0120 (11)
S1B	0.066 (6)	0.037 (5)	0.065 (6)	−0.005 (4)	0.021 (5)	0.017 (4)

Geometric parameters (Å, º)

S1A—C41	1.788 (2)	C28—C29	1.540 (2)
S1A—O1	1.5039 (11)	C31—C32	1.526 (2)
S1A—C40	1.7809 (19)	C32—C33	1.525 (2)
S1B—C40	1.993 (10)	C35—C36	1.512 (3)
S1B—C41	1.039 (10)	C38—C39	1.510 (3)
S1B—O1	1.859 (9)	C2—H2	0.951 (19)
S1B—H41B	1.11 (4)	C3—H3	0.957 (18)
O8—C8	1.2274 (18)	C4—H4	0.963 (19)
O9—C9	1.2254 (19)	C5—H5	0.976 (19)
O17—C18	1.423 (3)	C11—H11A	0.960 (17)
O17—C16	1.424 (3)	C11—H11B	0.974 (19)
O28—C28	1.2202 (19)	C12—H12A	0.962 (18)
O29—C29	1.2298 (18)	C12—H12B	0.99 (2)
O37—C36	1.430 (3)	C13—H13B	0.995 (19)
O37—C38	1.425 (2)	C13—H13A	0.971 (18)
N7—C8	1.3371 (19)	C15—H15B	0.97 (2)
N7—C1	1.417 (2)	C15—H15A	1.012 (19)
N10—C9	1.328 (2)	C16—H16A	0.958 (19)
N10—C11	1.456 (2)	C16—H16B	0.97 (2)
N14—C13	1.467 (2)	C18—H18B	0.998 (18)
N14—C19	1.460 (2)	C18—H18A	0.97 (2)
N14—C15	1.463 (2)	C19—H19A	0.961 (19)
N27—C6	1.424 (2)	C19—H19B	1.004 (18)
N27—C28	1.343 (2)	C31—H31B	0.972 (18)
N30—C29	1.322 (2)	C31—H31A	0.97 (2)
N30—C31	1.459 (2)	C32—H32B	0.984 (18)
N34—C35	1.464 (2)	C32—H32A	1.001 (19)
N34—C33	1.473 (2)	C33—H33B	0.995 (19)
N34—C39	1.465 (2)	C33—H33A	0.98 (2)
N7—H7	0.830 (18)	C35—H35B	0.99 (2)
N10—H10	0.840 (18)	C35—H35A	0.95 (2)
N27—H27	0.879 (18)	C36—H36B	1.03 (2)
N30—H30	0.829 (18)	C36—H36A	0.951 (19)
C1—C6	1.397 (2)	C38—H38B	0.99 (2)
C1—C2	1.393 (2)	C38—H38A	0.98 (2)
C2—C3	1.385 (2)	C39—H39B	0.99 (2)
C3—C4	1.385 (2)	C39—H39A	1.01 (2)
C4—C5	1.388 (2)	C40—H40B	0.97 (3)
C5—C6	1.392 (2)	C40—H40C	0.96 (2)
C8—C9	1.541 (2)	C40—H40A	1.05 (3)
C11—C12	1.515 (2)	C41—H41B	1.08 (3)
C12—C13	1.525 (3)	C41—H41C	0.96 (3)
C15—C16	1.508 (3)	C41—H41A	1.06 (3)
C18—C19	1.508 (3)
O1—S1A—C40	104.66 (7)	C13—C12—H12A	107.8 (12)
O1—S1A—C41	106.01 (10)	C13—C12—H12B	110.2 (11)
C40—S1A—C41	97.54 (12)	H13A—C13—H13B	107.4 (15)
O1—S1B—C40	85.1 (4)	N14—C13—H13A	109.9 (11)
O1—S1B—C41	128.5 (7)	C12—C13—H13A	110.5 (11)
C40—S1B—C41	121.3 (7)	C12—C13—H13B	108.0 (11)
C41—S1B—H41B	60.1 (15)	N14—C13—H13B	107.4 (11)
O1—S1B—H41B	142.5 (16)	H15A—C15—H15B	107.3 (17)
C40—S1B—H41B	124.0 (16)	N14—C15—H15A	111.8 (12)
C16—O17—C18	108.97 (14)	C16—C15—H15A	107.2 (11)
C36—O37—C38	108.90 (13)	C16—C15—H15B	109.8 (11)
C1—N7—C8	125.64 (13)	N14—C15—H15B	109.7 (11)
C9—N10—C11	121.27 (14)	C15—C16—H16B	110.1 (12)
C15—N14—C19	108.92 (13)	O17—C16—H16A	108.1 (12)
C13—N14—C19	110.08 (13)	O17—C16—H16B	105.7 (12)
C13—N14—C15	111.82 (14)	C15—C16—H16A	109.5 (11)
C6—N27—C28	123.04 (13)	H16A—C16—H16B	111.6 (17)
C29—N30—C31	122.74 (13)	O17—C18—H18B	109.6 (11)
C33—N34—C39	111.71 (13)	C19—C18—H18A	111.0 (12)
C33—N34—C35	112.25 (13)	H18A—C18—H18B	110.3 (17)
C35—N34—C39	108.39 (13)	O17—C18—H18A	106.6 (12)
C8—N7—H7	114.6 (13)	C19—C18—H18B	107.5 (10)
C1—N7—H7	119.8 (14)	H19A—C19—H19B	107.9 (15)
C11—N10—H10	119.3 (13)	N14—C19—H19A	109.0 (11)
C9—N10—H10	119.0 (14)	C18—C19—H19B	107.8 (10)
C28—N27—H27	118.2 (13)	C18—C19—H19A	109.9 (11)
C6—N27—H27	118.7 (13)	N14—C19—H19B	111.5 (11)
C29—N30—H30	121.3 (13)	C32—C31—H31B	108.5 (10)
C31—N30—H30	114.7 (13)	C32—C31—H31A	110.1 (12)
N7—C1—C2	121.86 (14)	N30—C31—H31B	109.8 (11)
C2—C1—C6	119.66 (14)	N30—C31—H31A	109.3 (11)
N7—C1—C6	118.48 (14)	H31A—C31—H31B	108.8 (15)
C1—C2—C3	120.00 (14)	H32A—C32—H32B	106.5 (16)
C2—C3—C4	120.53 (15)	C31—C32—H32A	108.1 (10)
C3—C4—C5	119.80 (15)	C33—C32—H32A	108.0 (11)
C4—C5—C6	120.19 (14)	C33—C32—H32B	110.7 (10)
N27—C6—C5	120.17 (14)	C31—C32—H32B	109.7 (10)
C1—C6—C5	119.83 (14)	C32—C33—H33A	111.3 (11)
N27—C6—C1	120.00 (14)	N34—C33—H33B	110.5 (10)
O8—C8—C9	122.06 (13)	N34—C33—H33A	106.8 (12)
N7—C8—C9	111.30 (13)	C32—C33—H33B	109.6 (11)
O8—C8—N7	126.63 (15)	H33A—C33—H33B	106.3 (15)
N10—C9—C8	113.24 (13)	C36—C35—H35A	108.7 (11)
O9—C9—N10	125.86 (15)	H35A—C35—H35B	109.8 (17)
O9—C9—C8	120.86 (14)	N34—C35—H35B	108.4 (11)
N10—C11—C12	113.53 (14)	N34—C35—H35A	109.4 (11)
C11—C12—C13	111.46 (15)	C36—C35—H35B	111.4 (11)
N14—C13—C12	113.34 (13)	H36A—C36—H36B	110.3 (17)
N14—C15—C16	110.94 (16)	O37—C36—H36B	108.3 (13)
O17—C16—C15	111.85 (16)	C35—C36—H36B	110.0 (11)
O17—C18—C19	111.82 (17)	O37—C36—H36A	106.4 (12)
N14—C19—C18	110.72 (14)	C35—C36—H36A	111.1 (13)
O28—C28—N27	125.74 (15)	C39—C38—H38A	108.6 (11)
N27—C28—C29	112.80 (13)	O37—C38—H38B	106.2 (11)
O28—C28—C29	121.46 (14)	O37—C38—H38A	110.8 (12)
O29—C29—C28	121.55 (14)	H38A—C38—H38B	110.4 (17)
N30—C29—C28	112.43 (13)	C39—C38—H38B	109.3 (11)
O29—C29—N30	126.02 (15)	H39A—C39—H39B	107.6 (16)
N30—C31—C32	110.38 (13)	C38—C39—H39A	109.4 (11)
C31—C32—C33	113.61 (15)	C38—C39—H39B	111.0 (11)
N34—C33—C32	112.28 (13)	N34—C39—H39B	107.7 (11)
N34—C35—C36	109.19 (15)	N34—C39—H39A	111.0 (12)
O37—C36—C35	110.65 (17)	S1A—C40—H40A	105.0 (14)
O37—C38—C39	111.71 (16)	S1A—C40—H40B	109.4 (12)
N34—C39—C38	110.11 (15)	S1A—C40—H40C	109.0 (12)
C1—C2—H2	119.2 (11)	H40A—C40—H40B	111 (2)
C3—C2—H2	120.8 (12)	H40A—C40—H40C	112.5 (19)
C4—C3—H3	118.7 (10)	H40B—C40—H40C	109.9 (18)
C2—C3—H3	120.8 (10)	S1B—C40—H40B	106.6 (13)
C5—C4—H4	120.1 (10)	S1B—C40—H40C	73.1 (13)
C3—C4—H4	120.1 (10)	S1B—C40—H40A	136.5 (14)
C6—C5—H5	118.4 (11)	S1A—C41—H41A	105.7 (18)
C4—C5—H5	121.4 (11)	S1A—C41—H41B	109.5 (17)
C12—C11—H11A	108.6 (10)	S1B—C41—H41C	129.3 (15)
C12—C11—H11B	109.6 (11)	H41A—C41—H41B	112 (2)
H11A—C11—H11B	109.9 (16)	H41A—C41—H41C	107 (2)
N10—C11—H11A	107.7 (10)	H41B—C41—H41C	117 (2)
N10—C11—H11B	107.5 (11)	S1A—C41—H41C	104.8 (14)
C11—C12—H12B	110.2 (11)	S1B—C41—H41A	119.6 (16)
C11—C12—H12A	110.1 (11)	S1B—C41—H41B	63.3 (18)
H12A—C12—H12B	107.0 (16)
C18—O17—C16—C15	58.2 (2)	C39—N34—C35—C36	−59.01 (18)
C16—O17—C18—C19	−58.57 (19)	N7—C1—C6—N27	0.4 (2)
C38—O37—C36—C35	−60.2 (2)	C2—C1—C6—N27	179.80 (14)
C36—O37—C38—C39	58.5 (2)	N7—C1—C2—C3	−179.93 (14)
C8—N7—C1—C6	−137.65 (16)	C6—C1—C2—C3	0.7 (2)
C1—N7—C8—O8	−1.4 (3)	N7—C1—C6—C5	−179.70 (14)
C8—N7—C1—C2	43.0 (2)	C2—C1—C6—C5	−0.3 (2)
C1—N7—C8—C9	177.00 (14)	C1—C2—C3—C4	−0.4 (2)
C11—N10—C9—C8	176.20 (13)	C2—C3—C4—C5	−0.3 (2)
C11—N10—C9—O9	−1.4 (3)	C3—C4—C5—C6	0.7 (2)
C9—N10—C11—C12	89.77 (18)	C4—C5—C6—N27	179.53 (14)
C19—N14—C13—C12	−174.58 (14)	C4—C5—C6—C1	−0.4 (2)
C15—N14—C13—C12	64.21 (18)	N7—C8—C9—O9	0.1 (2)
C15—N14—C19—C18	−55.40 (18)	N7—C8—C9—N10	−177.62 (13)
C19—N14—C15—C16	55.15 (18)	O8—C8—C9—O9	178.59 (15)
C13—N14—C19—C18	−178.32 (14)	O8—C8—C9—N10	0.9 (2)
C13—N14—C15—C16	177.03 (14)	N10—C11—C12—C13	−168.49 (14)
C6—N27—C28—O28	−2.3 (3)	C11—C12—C13—N14	56.32 (19)
C28—N27—C6—C5	−54.0 (2)	N14—C15—C16—O17	−57.85 (19)
C6—N27—C28—C29	177.02 (13)	O17—C18—C19—N14	58.55 (19)
C28—N27—C6—C1	125.88 (16)	O28—C28—C29—N30	8.6 (2)
C31—N30—C29—C28	173.34 (14)	O28—C28—C29—O29	−172.08 (16)
C29—N30—C31—C32	177.84 (15)	N27—C28—C29—O29	8.6 (2)
C31—N30—C29—O29	−5.9 (3)	N27—C28—C29—N30	−170.71 (14)
C33—N34—C35—C36	177.14 (14)	N30—C31—C32—C33	54.54 (18)
C39—N34—C33—C32	165.05 (14)	C31—C32—C33—N34	−70.39 (18)
C35—N34—C39—C38	57.35 (18)	N34—C35—C36—O37	61.52 (19)
C33—N34—C39—C38	−178.47 (14)	O37—C38—C39—N34	−58.1 (2)
C35—N34—C33—C32	−72.96 (17)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N7—H7···O9	0.830 (18)	2.23 (2)	2.6620 (18)	113.1 (16)
N7—H7···O1^i	0.830 (18)	2.064 (18)	2.7896 (17)	145.8 (19)
N10—H10···O8	0.840 (18)	2.372 (19)	2.7224 (18)	105.8 (15)
N10—H10···O8^ii	0.840 (18)	2.177 (18)	2.9134 (18)	146.2 (17)
N27—H27···O29	0.879 (18)	2.329 (19)	2.7155 (18)	106.7 (14)
N27—H27···O1^i	0.879 (18)	1.996 (18)	2.7734 (17)	146.7 (17)
N30—H30···O28	0.829 (18)	2.370 (19)	2.6924 (19)	103.9 (15)
N30—H30···N34	0.829 (18)	2.061 (18)	2.7774 (18)	144.5 (17)
C4—H4···O37^iii	0.963 (19)	2.569 (18)	3.224 (2)	125.5 (13)
C11—H11A···N14	0.960 (17)	2.541 (17)	2.962 (2)	106.6 (12)
C35—H35A···O29^iv	0.95 (2)	2.59 (2)	3.472 (2)	155.1 (15)
C40—H40B···O28^iv	0.97 (3)	2.34 (3)	3.290 (2)	166.7 (19)
C40—H40C···O29^i	0.96 (2)	2.45 (2)	3.345 (2)	155.0 (16)
C41—H41B···O29^i	1.08 (3)	2.58 (3)	3.527 (3)	146 (2)

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