Mixed dicationic and monocationic benzidine species in the proton-transfer compound of benzidine with 3,5-dinitro­salicylic acid

The crystal structure of the proton-transfer compound of 1,1′-biphenyl-4,4′-diamine (benzidine) with 3,5-dinitro­salicylic acid, viz. 1,1′-biphenyl-4,4′-diaminium bis­(4′-amino-1,1′-bi­phenyl-4-aminium) tetra­kis(2-carb­oxy-4,6-dinitro­phenol­ate) ethanol disolvate, C₁₂H₁₄N₂²⁺·2C₁₂H₁₃N₂⁺·4C₇H₃N₂O₇⁻·2C₂H₆O, shows the presence of both diprotonated and monoprotonated benzidine cations. The diprotonated species lie across crystallographic inversion centres in the unit cell, while the monoprotonated species occupy general sites. All amine H atoms participate in hydrogen bonding with carboxyl, phenolate and nitro O-atom acceptors of the salicylate anions, which also participate in hydrogen bonding with the disordered ethanol solvent mol­ecules. Significant inter-ring anion–anion and anion–monocation π–π inter­actions are also present, giving a three-dimensional framework structure.

S1. Comment

3,5-Dinitrosalicylic acid (DNSA) has proved to be a particularly useful compound for the promotion of the crystallization of Lewis bases as chemically stable proton-transfer compounds. We have previously determined the crystal structures of more than 40 of these compounds (Smith et al., 1995, 2002, 2003, 2006) while adduct formation has been found with molecules such as urea (Smith et al., 1997), 1,1-diethylurea (Smith et al., 2000) and phenazine (Kumar et al., 2002). These are analogous to the set of pseudopolymorphic solvates formed with DNSA, namely two monohydrates (Smith et al., 1995; Kumar et al., 1999), four dioxine solvates and a tert-butyl alcohol solvate (Kumar et al., 1999). However, among the proton-transfer compounds of DNSA for which the crystal structures are known, only rarely are solvates formed, although most compounds are obtained from ethanol or ethanol–water mixtures. The only known examples of solvates are 2-aminopyridinium–3,5-dinitrosalicylate–ethanol (4/4/1) (Smith et al., 2002) and brucinium 3,5-dinitrosalicylate monohydrate (Smith et al., 2006). Generally, reaction of DNSA with aniline-type Lewis bases results in the formation of 1:1 anilinium cations, which usually enhance molecular self-assembly through extensive hydrogen-bonding interactions. Seldom are π–π interactions significant in this process, occurring only among polycyclic heteroaromatic Lewis base–DNSA compounds (Smith et al., 2006).

To extend the investigation of the systematics of the hydrogen bonding in proton-transfer compounds of DNSA with Lewis bases, we decided to prepare and crystallographically characterize the compounds with certain aromatic polyamines. The 1:1 and 2:1 compounds of DNSA with 1,1'-biphenyl-4,4'-diamine (benzidine, BD) had been synthesized and investigated spectroscopically by Issa et al. (1981). However, our attempted preparation of the 1:1 compound in 80% ethanol–water solvent surprisingly gave instead the compound reported here, the ethanol solvate of the proton-transfer compound, (I), which contains both dicationic and monocationic benzidine cation species, and corresponds to neither of the compounds reported by Issa et al. (1981). Compound (I) is best described in terms of the centrosymmetric molecular unit, [BD²⁺·2(BD⁺)·4(DNSA⁻)·2(EtOH)] (Fig. 1). The crystallographic asymmetric unit of (I) comprises two DNSA anions (anions A and B), a BD⁺ monocation (cation C), a BD²⁺ dication (cation D) lying across an inversion centre in the cell, and a disordered ethanol molecule of solvation (molecule E). The methyl group of the ethanol molecule occupies two partial sites, C2E [0.806 (17) occupancy] and C21E [0.194 (17) occupancy]. The monoprotonated C cations differ conformationally from the essentially planar doubly protonated D cations [C2C—C1C—C11C—C61C = 15.7 (3)°, cf. 0.2 (4)° for the equivalent angle in D]. The six aminium H atoms on cation D are involved in eight hydrogen-bonding interactions, viz. six to DNSA anions (carboxyl, phenol and nitro groups) and two to the unprotonated N-acceptors of benzidine cations C (Table 1). Included in this set is the primary linear H(aminium)···O(carboxyl) interaction [N4D—H43D···O71A^vi; symmetry code: (vi) −x + 1, y − 1/2, −z + 1/2], whereas the carboxyl group of the second DNSA anion is not involved in any such interaction. Instead it forms a three-centred asymmetric R²₁(4) interaction with the hydroxyl H atom of the ethanol molecule of solvation [O1E—H1E··· O71Bⁱ,O72Bⁱ; symmetry code: (i) x + 1, y, z]. Anion C participates in four interactions via the protonated amine group (N4C), including two to ethanol (E) molecules. The unprotonated amine (N41C) forms only weak interactions with O atoms of the nitro groups but acts as an acceptor to a C-cation aminium H atom.

The result is a stable three-dimensional cage structure (Fig. 2), which has in addition significant π–π interactions between adjacent DNSA anion species [A···B; the ring centroid separation (Cg_A···Cg_B) is 3.605 (3) Å; the dihedral angle (α) is 4.7 (1)°] and A-anion–unprotonated C-cation species [Cg_A···Cg_C = 3.753 (3) Å and α = 6.2 (1)°]. Similar interactions have been found in the structures of a number of benzidine compounds (Herbstein, 1971), where it was observed that in the formation of ternary complexes involvement of the third species in π bonding did not occur. This is apparent in the series of pseudopolymorphic 1:1 benzidene complexes with 7,7,8,8-tetracyano-p-quinodimethane (TCNQ), the solvent-free complex (Yakushi et al., 1974a), the benzene solvate (Yakushi et al., 1974b) and the dichloromethane solvate (Ikemoto et al., 1972). These structures are somewhat analogous to the structure of (I), where, in addition, it would appear that the lack of flexibility of the protonated benzidine molecule together with the enforced π–π interactions place constraints on the availability of suitable O-acceptor sites on DNSA, resulting in the incorporation of the unusual molecule of ethanol in the structure. As indicated previously, ethanol or water solvent molecules are rare in DNSA proton-transfer compounds and it can only be speculated that ethanol incorporation in (I) (rather than water) has to do with a space-filling requirement.

With the DNSA anions, the expected intramolecular hydrogen bond is found between the phenol and carboxylate substituent groups of the DNSA anions [O72—H72···O2 = 2.479 (3) Å [−173.2 (2)?] (A) and 2.487 (3) Å (B)], with the H atoms located on the carboxylate O atoms. The carboxyl group is therefore essentially coplanar with the benzene ring [C2—C1—C7—O71 = 177.6 (2) [−173.2 (2)?] (A) and −178.9 (3)° (B)], as are the nitro substituent groups at C5 [C4—C5—N5—O52 = −177.8 (2) (A) and −175.7 (2)° (B)]. However, in both anion species, the nitro group at C3 is rotated out of the plane [C2—C3—N3—O32 = −149.5 (3) (A) and 147.7 (2)° (B)].

S2. Experimental

The title compound was synthesized by heating 1 mmol quantities of DNSA and benzidine in 80% ethanol/water (50 ml) for 10 min under reflux. After concentration to ca 30 ml, partial room-temperature evaporation of the hot-filtered solution gave yellow–brown prismatic crystals of (I) (m.p. 480–483 K).

S3. Refinement

H atoms potentially involved in hydrogen-bonding interactions were located by difference methods and their positional and isotropic displacement parameters were refined. Other H atoms were included in the refinement in calculated positions [C—H = 0.93–0.99 Å], using the riding-model approximation, with U_iso(H) fixed at 1.2U_eq(C).

Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SMART; data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXTL (Bruker, 1997); program(s) used to refine structure: SHELXTL (Bruker, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: PLATON.

Figures

Fig. 1. The molecular configuration and atom-naming scheme for the two DNSA anions (A and B), the benzidine monocation (C) and dication (D), and the disordered ethanol molecule of solvation (E) in (I). The dication lies across a crystallographic inversion centre [symmetry code: (viii) −x + 1, −y + 1, −z]. The intramolecular hydrogen bonds in anions A and B are shown as dashed lines. Displacement ellipsoids are drawn at the 30% probability level.

Fig. 2. A perspective view of the partial packing in the unit cell, showing hydrogen-bonding associations as dashed lines. In addition, π–π interactions are present between the DNSA A and B anions, as well as between A anions and unprotonated C benzidine rings. [Symmetry codes: (ix) −x + 1, −y + 2, −z; (x) x, y + 1, z; for other symmetry codes, see Table 1 and Fig. 1.]

1,1'-biphenyl-4,4'-diaminium bis(4'-amino-1,1'-biphenyl-4-aminium) tetrakis(2-carboxy-4,6-dinitrophenolate) ethanol disolvate

Crystal data

C12H14N2^2+·2C12H13N2^+·4C7H3N2O7^−·2C2H6O	F(000) = 1620
Mr = 1557.34	Dx = 1.447 Mg m^−3
Monoclinic, P21/c	Melting point: 479.7–482.9 (dec) K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 18.862 (2) Å	Cell parameters from 1773 reflections
b = 10.5138 (11) Å	θ = 2.3–19.1°
c = 19.081 (2) Å	µ = 0.12 mm^−1
β = 109.154 (2)°	T = 295 K
V = 3574.6 (7) Å^3	Prism, yellow–brown
Z = 2	0.45 × 0.15 × 0.08 mm

Data collection

Bruker SMART CCD diffractometer	3072 reflections with I > 2σ(I)
Radiation source: sealed tube	Rint = 0.063
Graphite monochromator	θmax = 27.6°, θmin = 2.2°
ϕ and ω scans	h = −24→16
22178 measured reflections	k = −11→13
8165 independent reflections	l = −24→24

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.098	H atoms treated by a mixture of independent and constrained refinement
S = 0.87	w = 1/[σ^2(Fo^2) + (0.0239P)^2] where P = (Fo^2 + 2Fc^2)/3
8165 reflections	(Δ/σ)max = 0.002
549 parameters	Δρmax = 0.19 e Å^−3
0 restraints	Δρmin = −0.15 e Å^−3

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All e.s.d.'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)
N4D	0.43574 (15)	0.1927 (2)	0.16941 (13)	0.0429 (9)
C1D	0.48955 (14)	0.4535 (2)	0.02470 (12)	0.0369 (9)
C2D	0.51012 (13)	0.3270 (2)	0.02723 (12)	0.0431 (10)
C3D	0.49182 (14)	0.2413 (2)	0.07314 (13)	0.0455 (10)
C4D	0.45242 (13)	0.2816 (2)	0.11734 (13)	0.0374 (9)
C5D	0.43044 (15)	0.4054 (2)	0.11621 (14)	0.0558 (11)
C6D	0.44887 (15)	0.4898 (2)	0.06944 (14)	0.0602 (11)
N4C	0.10555 (16)	0.9872 (3)	0.49959 (14)	0.0598 (11)
N41C	0.37076 (18)	0.9499 (2)	0.12627 (17)	0.0549 (11)
C1C	0.21828 (15)	0.9816 (2)	0.33928 (14)	0.0406 (9)
C2C	0.14193 (16)	0.9628 (3)	0.32006 (14)	0.0620 (11)
C3C	0.10484 (16)	0.9647 (3)	0.37120 (15)	0.0686 (13)
C4C	0.14459 (16)	0.9866 (2)	0.44408 (15)	0.0497 (11)
C5C	0.21944 (17)	1.0045 (2)	0.46612 (14)	0.0607 (11)
C6C	0.25613 (15)	1.0023 (2)	0.41433 (14)	0.0598 (11)
C11C	0.25797 (15)	0.9758 (2)	0.28410 (13)	0.0405 (9)
C21C	0.33445 (15)	0.9617 (2)	0.30435 (14)	0.0518 (11)
C31C	0.37132 (15)	0.9513 (2)	0.25312 (14)	0.0502 (10)
C41C	0.33200 (16)	0.9548 (2)	0.17830 (14)	0.0421 (10)
C51C	0.25602 (16)	0.9707 (2)	0.15665 (14)	0.0554 (11)
C61C	0.21961 (15)	0.9815 (2)	0.20846 (14)	0.0531 (11)
O2A	0.19965 (10)	0.64259 (16)	0.12008 (10)	0.0568 (7)
O31A	0.05855 (11)	0.5914 (2)	0.12155 (11)	0.0813 (9)
O32A	0.03550 (13)	0.6965 (3)	0.20652 (14)	0.1420 (13)
O51A	0.21813 (15)	0.6419 (2)	0.45221 (12)	0.1118 (11)
O52A	0.33430 (15)	0.6507 (2)	0.46371 (11)	0.1010 (11)
O71A	0.41757 (11)	0.62515 (18)	0.24999 (11)	0.0737 (8)
O72A	0.33586 (13)	0.64814 (18)	0.13806 (13)	0.0607 (8)
N3A	0.07911 (15)	0.6437 (3)	0.18152 (15)	0.0747 (11)
N5A	0.2681 (2)	0.6474 (2)	0.42585 (14)	0.0732 (13)
C1A	0.28934 (15)	0.6402 (2)	0.23949 (14)	0.0435 (10)
C2A	0.21433 (15)	0.6406 (2)	0.19032 (15)	0.0449 (10)
C3A	0.15841 (15)	0.6422 (2)	0.22624 (15)	0.0490 (10)
C4A	0.17515 (16)	0.6464 (2)	0.30195 (15)	0.0549 (11)
C5A	0.24900 (18)	0.6458 (2)	0.34559 (14)	0.0509 (10)
C6A	0.30597 (15)	0.6427 (2)	0.31512 (14)	0.0496 (11)
C7A	0.35296 (18)	0.6370 (2)	0.21045 (18)	0.0516 (11)
O2B	0.32386 (10)	0.31570 (15)	0.21442 (9)	0.0537 (7)
O31B	0.46337 (11)	0.2989 (2)	0.31660 (12)	0.0854 (10)
O32B	0.47081 (11)	0.41536 (17)	0.41125 (11)	0.0698 (8)
O51B	0.28318 (12)	0.3210 (2)	0.52540 (11)	0.0820 (9)
O52B	0.16754 (13)	0.3205 (2)	0.45598 (11)	0.0973 (10)
O71B	0.10119 (11)	0.3095 (2)	0.18682 (10)	0.0835 (9)
O72B	0.18955 (13)	0.31358 (19)	0.13545 (10)	0.0701 (9)
N3B	0.43459 (14)	0.3500 (2)	0.35821 (13)	0.0566 (10)
N5B	0.23424 (17)	0.3226 (2)	0.46471 (14)	0.0654 (11)
C1B	0.22656 (15)	0.3139 (2)	0.26719 (14)	0.0430 (10)
C2B	0.30369 (15)	0.3182 (2)	0.27207 (14)	0.0436 (10)
C3B	0.35465 (15)	0.3321 (2)	0.34556 (14)	0.0445 (12)
C4B	0.33251 (16)	0.3351 (2)	0.40770 (14)	0.0517 (10)
C5B	0.25779 (16)	0.3243 (2)	0.39910 (14)	0.0468 (10)
C6B	0.20481 (15)	0.3158 (2)	0.32950 (15)	0.0501 (11)
C7B	0.16737 (18)	0.3113 (3)	0.19375 (16)	0.0546 (11)
O1E	1.01662 (12)	0.3206 (2)	0.04173 (12)	0.0744 (9)
C1E	1.0060 (3)	0.1916 (4)	0.0164 (3)	0.144 (3)
C2E	0.9594 (6)	0.1286 (6)	0.0536 (9)	0.246 (8)	0.806 (13)
C21E	0.9356 (12)	0.1340 (19)	−0.0278 (18)	0.149 (11)	0.194 (13)
H2D	0.537000	0.298900	−0.002800	0.0520*
H3D	0.506200	0.156600	0.074000	0.0550*
H5D	0.403500	0.432600	0.146400	0.0670*
H6D	0.433300	0.573900	0.068100	0.0720*
H41D	0.4132 (13)	0.125 (2)	0.1462 (12)	0.047 (9)*
H42D	0.3982 (17)	0.234 (2)	0.1845 (15)	0.106 (11)*
H43D	0.4864 (18)	0.169 (2)	0.1972 (16)	0.118 (12)*
H2C	0.114400	0.948200	0.270500	0.0750*
H3C	0.053300	0.951300	0.356300	0.0820*
H5C	0.246200	1.018200	0.516000	0.0730*
H6C	0.307800	1.015100	0.430100	0.0720*
H21C	0.362400	0.959000	0.354600	0.0620*
H31C	0.423200	0.942000	0.269200	0.0600*
H41C	0.0900 (17)	1.065 (3)	0.5050 (16)	0.097 (14)*
H42C	0.138 (2)	0.943 (3)	0.541 (2)	0.192 (16)*
H43C	0.0659 (15)	0.928 (2)	0.4857 (13)	0.061 (10)*
H44C	0.3401 (17)	0.926 (3)	0.0798 (17)	0.114 (14)*
H45C	0.4122 (16)	0.907 (3)	0.1402 (16)	0.094 (14)*
H51C	0.228400	0.974300	0.106400	0.0660*
H61C	0.167900	0.993100	0.192200	0.0640*
H4A	0.137200	0.649500	0.323000	0.0660*
H6A	0.355800	0.642300	0.345900	0.0600*
H72A	0.2861 (16)	0.647 (3)	0.1215 (15)	0.084 (12)*
H4B	0.367800	0.344400	0.454700	0.0620*
H6B	0.154100	0.311300	0.324500	0.0600*
H72B	0.2409 (17)	0.314 (2)	0.1548 (16)	0.094 (11)*
H1E	1.0476 (17)	0.315 (3)	0.0904 (17)	0.106 (13)*
H3E	0.958600	0.038700	0.044400	0.296*	0.806
H4E	0.909200	0.161600	0.034900	0.296*	0.806
H2E	0.979600	0.143900	0.106000	0.296*	0.806
H5E	0.930400	0.140300	−0.079500	0.180*	0.194
H6E	0.894700	0.177500	−0.018800	0.180*	0.194
H7E	0.935200	0.046000	−0.014400	0.180*	0.194
H11E	0.98200	0.190000	−0.03600	0.170*
H12E	1.05300	0.150000	0.02800	0.170*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N4D	0.0479 (17)	0.0407 (15)	0.0429 (14)	−0.0037 (14)	0.0185 (13)	0.0036 (12)
C1D	0.0386 (16)	0.0345 (15)	0.0401 (16)	0.0010 (13)	0.0164 (13)	0.0017 (12)
C2D	0.0507 (18)	0.0438 (16)	0.0424 (16)	−0.0011 (14)	0.0257 (14)	−0.0039 (13)
C3D	0.0579 (19)	0.0367 (15)	0.0443 (16)	0.0037 (14)	0.0201 (15)	0.0035 (13)
C4D	0.0361 (16)	0.0414 (16)	0.0332 (15)	−0.0038 (13)	0.0093 (13)	0.0032 (12)
C5D	0.071 (2)	0.0463 (17)	0.070 (2)	0.0127 (16)	0.0501 (18)	0.0107 (15)
C6D	0.081 (2)	0.0393 (17)	0.081 (2)	0.0166 (16)	0.0547 (19)	0.0164 (15)
N4C	0.0563 (19)	0.079 (2)	0.0497 (17)	0.0005 (19)	0.0251 (15)	0.0004 (16)
N41C	0.061 (2)	0.0577 (17)	0.0569 (19)	−0.0035 (17)	0.0341 (16)	−0.0013 (15)
C1C	0.0441 (17)	0.0402 (15)	0.0394 (16)	0.0011 (14)	0.0161 (14)	0.0037 (12)
C2C	0.051 (2)	0.100 (2)	0.0339 (16)	0.0123 (19)	0.0124 (16)	0.0000 (16)
C3C	0.0442 (19)	0.115 (3)	0.0471 (19)	0.0146 (18)	0.0158 (17)	0.0069 (18)
C4C	0.053 (2)	0.0585 (18)	0.0437 (18)	0.0085 (16)	0.0243 (16)	0.0055 (14)
C5C	0.060 (2)	0.086 (2)	0.0377 (17)	−0.0112 (19)	0.0184 (16)	−0.0024 (15)
C6C	0.0485 (19)	0.084 (2)	0.0488 (19)	−0.0149 (16)	0.0187 (16)	−0.0010 (16)
C11C	0.0448 (17)	0.0386 (15)	0.0387 (16)	0.0036 (14)	0.0145 (14)	0.0050 (12)
C21C	0.052 (2)	0.0630 (19)	0.0385 (16)	0.0090 (16)	0.0122 (15)	0.0058 (14)
C31C	0.0439 (18)	0.0593 (18)	0.0504 (18)	0.0081 (14)	0.0196 (16)	0.0098 (15)
C41C	0.0538 (19)	0.0335 (15)	0.0455 (17)	−0.0051 (14)	0.0250 (16)	−0.0001 (13)
C51C	0.052 (2)	0.077 (2)	0.0385 (16)	−0.0123 (17)	0.0166 (16)	0.0017 (15)
C61C	0.0418 (18)	0.073 (2)	0.0463 (18)	0.0000 (15)	0.0171 (15)	0.0066 (15)
O2A	0.0540 (13)	0.0783 (13)	0.0401 (11)	−0.0069 (11)	0.0181 (10)	−0.0070 (10)
O31A	0.0558 (14)	0.1349 (19)	0.0545 (14)	−0.0151 (13)	0.0197 (12)	−0.0188 (13)
O32A	0.0570 (16)	0.238 (3)	0.131 (2)	0.0069 (19)	0.0310 (16)	−0.087 (2)
O51A	0.128 (2)	0.162 (2)	0.0612 (16)	−0.0241 (19)	0.0526 (16)	−0.0012 (14)
O52A	0.101 (2)	0.136 (2)	0.0519 (15)	−0.0118 (18)	0.0058 (14)	0.0054 (14)
O71A	0.0436 (13)	0.0902 (15)	0.0834 (16)	−0.0006 (12)	0.0155 (12)	−0.0240 (12)
O72A	0.0537 (15)	0.0681 (14)	0.0687 (15)	−0.0027 (13)	0.0317 (13)	−0.0060 (11)
N3A	0.0533 (19)	0.106 (2)	0.072 (2)	−0.0087 (17)	0.0304 (17)	−0.0237 (17)
N5A	0.098 (3)	0.0713 (18)	0.0501 (19)	−0.009 (2)	0.0242 (19)	0.0021 (15)
C1A	0.0471 (19)	0.0390 (16)	0.0443 (17)	−0.0009 (14)	0.0148 (15)	−0.0053 (13)
C2A	0.0488 (19)	0.0424 (16)	0.0451 (18)	−0.0038 (14)	0.0177 (16)	−0.0040 (14)
C3A	0.0419 (18)	0.0584 (18)	0.0476 (18)	−0.0056 (15)	0.0159 (15)	−0.0060 (14)
C4A	0.064 (2)	0.0582 (19)	0.0520 (19)	−0.0116 (17)	0.0320 (17)	−0.0039 (15)
C5A	0.065 (2)	0.0490 (17)	0.0375 (17)	−0.0043 (17)	0.0151 (17)	−0.0006 (14)
C6A	0.051 (2)	0.0400 (16)	0.0511 (19)	−0.0013 (14)	0.0075 (16)	0.0004 (14)
C7A	0.052 (2)	0.0439 (17)	0.058 (2)	−0.0024 (16)	0.0169 (18)	−0.0139 (16)
O2B	0.0551 (13)	0.0680 (12)	0.0443 (11)	0.0039 (10)	0.0247 (11)	0.0039 (10)
O31B	0.0567 (14)	0.1201 (19)	0.0827 (16)	0.0006 (13)	0.0275 (13)	−0.0318 (14)
O32B	0.0694 (15)	0.0759 (14)	0.0603 (13)	−0.0220 (12)	0.0163 (11)	−0.0080 (11)
O51B	0.0876 (18)	0.1149 (17)	0.0446 (13)	−0.0044 (14)	0.0233 (13)	−0.0028 (13)
O52B	0.0708 (16)	0.158 (2)	0.0768 (16)	0.0065 (18)	0.0428 (15)	0.0089 (14)
O71B	0.0468 (14)	0.142 (2)	0.0579 (14)	0.0004 (14)	0.0119 (12)	0.0100 (13)
O72B	0.0578 (15)	0.1067 (17)	0.0455 (13)	0.0117 (14)	0.0166 (12)	0.0081 (11)
N3B	0.0587 (19)	0.0587 (17)	0.0517 (16)	−0.0043 (15)	0.0170 (15)	−0.0003 (13)
N5B	0.075 (2)	0.0756 (18)	0.0532 (18)	0.0017 (18)	0.0313 (18)	0.0016 (15)
C1B	0.0466 (18)	0.0446 (16)	0.0412 (16)	0.0041 (14)	0.0190 (15)	0.0062 (13)
C2B	0.0527 (19)	0.0386 (16)	0.0422 (17)	0.0036 (15)	0.0194 (16)	0.0061 (13)
C3B	0.0413 (18)	0.0427 (16)	0.0503 (18)	−0.0003 (14)	0.0161 (15)	0.0034 (14)
C4B	0.060 (2)	0.0477 (17)	0.0450 (17)	0.0014 (16)	0.0139 (16)	0.0031 (14)
C5B	0.0527 (19)	0.0506 (17)	0.0397 (17)	−0.0002 (16)	0.0186 (16)	0.0011 (14)
C6B	0.0484 (19)	0.0472 (17)	0.0596 (19)	0.0046 (14)	0.0245 (17)	0.0058 (15)
C7B	0.053 (2)	0.066 (2)	0.0477 (19)	0.0038 (18)	0.0205 (18)	0.0082 (16)
O1E	0.0632 (15)	0.0954 (18)	0.0551 (15)	0.0043 (14)	0.0063 (12)	0.0036 (14)
C1E	0.160 (5)	0.098 (4)	0.173 (5)	−0.034 (3)	0.053 (4)	−0.030 (3)
C2E	0.210 (10)	0.148 (6)	0.46 (2)	−0.106 (6)	0.218 (15)	−0.143 (9)
C21E	0.14 (2)	0.123 (19)	0.11 (2)	0.008 (17)	−0.061 (17)	−0.056 (15)

Geometric parameters (Å, º)

O2A—C2A	1.277 (3)	C2C—C3C	1.375 (4)
O31A—N3A	1.213 (3)	C3C—C4C	1.366 (4)
O32A—N3A	1.212 (4)	C4C—C5C	1.348 (4)
O51A—N5A	1.207 (5)	C5C—C6C	1.380 (4)
O52A—N5A	1.221 (4)	C11C—C21C	1.374 (4)
O71A—C7A	1.211 (4)	C11C—C61C	1.387 (3)
O72A—C7A	1.317 (4)	C21C—C31C	1.377 (4)
O72A—H72A	0.89 (3)	C31C—C41C	1.377 (4)
O2B—C2B	1.277 (3)	C41C—C51C	1.365 (4)
O31B—N3B	1.223 (3)	C51C—C61C	1.381 (4)
O32B—N3B	1.229 (3)	C2C—H2C	0.9300
O51B—N5B	1.222 (3)	C3C—H3C	0.9300
O52B—N5B	1.214 (4)	C5C—H5C	0.9300
O71B—C7B	1.212 (4)	C6C—H6C	0.9300
O72B—C7B	1.311 (4)	C21C—H21C	0.9300
O72B—H72B	0.92 (3)	C31C—H31C	0.9300
O1E—C1E	1.432 (5)	C51C—H51C	0.9300
O1E—H1E	0.92 (3)	C61C—H61C	0.9300
N4D—C4D	1.471 (3)	C1A—C6A	1.373 (4)
N4D—H41D	0.87 (2)	C1A—C2A	1.418 (4)
N4D—H43D	0.96 (3)	C1A—C7A	1.478 (5)
N4D—H42D	0.95 (3)	C2A—C3A	1.434 (4)
N4C—C4C	1.475 (4)	C3A—C4A	1.375 (4)
N41C—C41C	1.414 (4)	C4A—C5A	1.368 (4)
N4C—H43C	0.94 (3)	C5A—C6A	1.380 (4)
N4C—H41C	0.89 (3)	C4A—H4A	0.9300
N4C—H42C	0.95 (4)	C6A—H6A	0.9300
N41C—H45C	0.87 (3)	C1B—C6B	1.379 (4)
N41C—H44C	0.92 (3)	C1B—C7B	1.478 (4)
N3A—C3A	1.459 (4)	C1B—C2B	1.428 (4)
N5A—C5A	1.454 (4)	C2B—C3B	1.424 (4)
N3B—C3B	1.459 (4)	C3B—C4B	1.381 (4)
N5B—C5B	1.459 (4)	C4B—C5B	1.369 (4)
C1D—C6D	1.376 (4)	C5B—C6B	1.378 (4)
C1D—C1D^i	1.498 (3)	C4B—H4B	0.9300
C1D—C2D	1.382 (3)	C6B—H6B	0.9300
C2D—C3D	1.377 (3)	C1E—C2E	1.458 (14)
C3D—C4D	1.362 (4)	C1E—C21E	1.45 (3)
C4D—C5D	1.364 (3)	C1E—H11E	0.9500
C5D—C6D	1.381 (3)	C1E—H12E	0.9500
C2D—H2D	0.9300	C2E—H2E	0.9600
C3D—H3D	0.9300	C2E—H3E	0.9600
C5D—H5D	0.9300	C2E—H4E	0.9600
C6D—H6D	0.9300	C21E—H5E	0.9600
C1C—C6C	1.392 (4)	C21E—H6E	0.9600
C1C—C2C	1.379 (4)	C21E—H7E	0.9600
C1C—C11C	1.480 (4)
C7A—O72A—H72A	103.8 (18)	C4C—C5C—H5C	120.00
C7B—O72B—H72B	104.3 (18)	C6C—C5C—H5C	120.00
C1E—O1E—H1E	105 (2)	C1C—C6C—H6C	119.00
C4D—N4D—H43D	98.2 (17)	C5C—C6C—H6C	119.00
C4D—N4D—H41D	110.6 (15)	C11C—C21C—H21C	119.00
H41D—N4D—H43D	107 (2)	C31C—C21C—H21C	119.00
H41D—N4D—H42D	104 (2)	C41C—C31C—H31C	120.00
H42D—N4D—H43D	131 (2)	C21C—C31C—H31C	120.00
C4D—N4D—H42D	105.0 (14)	C61C—C51C—H51C	120.00
H41C—N4C—H43C	112 (3)	C41C—C51C—H51C	120.00
H42C—N4C—H43C	98 (3)	C11C—C61C—H61C	119.00
C4C—N4C—H41C	111 (2)	C51C—C61C—H61C	119.00
C4C—N4C—H43C	109.4 (16)	C2A—C1A—C7A	120.6 (2)
C4C—N4C—H42C	105 (2)	C6A—C1A—C7A	117.5 (3)
H41C—N4C—H42C	120 (3)	C2A—C1A—C6A	122.0 (3)
C41C—N41C—H44C	112 (2)	C1A—C2A—C3A	114.5 (2)
H44C—N41C—H45C	112 (3)	O2A—C2A—C3A	124.2 (3)
C41C—N41C—H45C	115 (2)	O2A—C2A—C1A	121.4 (3)
O31A—N3A—C3A	119.7 (3)	C2A—C3A—C4A	123.5 (3)
O31A—N3A—O32A	122.1 (3)	N3A—C3A—C4A	116.9 (3)
O32A—N3A—C3A	118.2 (3)	N3A—C3A—C2A	119.6 (2)
O51A—N5A—C5A	118.8 (3)	C3A—C4A—C5A	118.5 (3)
O51A—N5A—O52A	122.8 (3)	C4A—C5A—C6A	121.5 (2)
O52A—N5A—C5A	118.4 (3)	N5A—C5A—C6A	119.1 (3)
O31B—N3B—C3B	119.4 (2)	N5A—C5A—C4A	119.5 (3)
O31B—N3B—O32B	122.4 (3)	C1A—C6A—C5A	120.2 (3)
O32B—N3B—C3B	118.3 (2)	O71A—C7A—C1A	122.9 (3)
O52B—N5B—C5B	118.4 (2)	O72A—C7A—C1A	116.2 (3)
O51B—N5B—C5B	117.7 (3)	O71A—C7A—O72A	120.9 (3)
O51B—N5B—O52B	123.8 (3)	C3A—C4A—H4A	121.00
C1D^i—C1D—C6D	121.7 (2)	C5A—C4A—H4A	121.00
C1D^i—C1D—C2D	121.4 (2)	C5A—C6A—H6A	120.00
C2D—C1D—C6D	116.9 (2)	C1A—C6A—H6A	120.00
C1D—C2D—C3D	121.7 (2)	C2B—C1B—C7B	119.9 (2)
C2D—C3D—C4D	119.5 (2)	C2B—C1B—C6B	121.9 (2)
N4D—C4D—C5D	119.1 (2)	C6B—C1B—C7B	118.2 (3)
N4D—C4D—C3D	120.1 (2)	O2B—C2B—C3B	123.7 (3)
C3D—C4D—C5D	120.8 (2)	C1B—C2B—C3B	114.3 (2)
C4D—C5D—C6D	118.9 (2)	O2B—C2B—C1B	121.9 (2)
C1D—C6D—C5D	122.2 (2)	C2B—C3B—C4B	123.5 (3)
C1D—C2D—H2D	119.00	N3B—C3B—C2B	120.2 (2)
C3D—C2D—H2D	119.00	N3B—C3B—C4B	116.3 (2)
C4D—C3D—H3D	120.00	C3B—C4B—C5B	119.0 (2)
C2D—C3D—H3D	120.00	C4B—C5B—C6B	120.9 (3)
C6D—C5D—H5D	120.00	N5B—C5B—C6B	119.8 (3)
C4D—C5D—H5D	121.00	N5B—C5B—C4B	119.3 (2)
C5D—C6D—H6D	119.00	C1B—C6B—C5B	120.3 (3)
C1D—C6D—H6D	119.00	O72B—C7B—C1B	116.9 (3)
C6C—C1C—C11C	122.0 (3)	O71B—C7B—O72B	120.8 (3)
C2C—C1C—C6C	115.8 (3)	O71B—C7B—C1B	122.3 (3)
C2C—C1C—C11C	122.2 (2)	C5B—C4B—H4B	120.00
C1C—C2C—C3C	122.7 (2)	C3B—C4B—H4B	121.00
C2C—C3C—C4C	119.2 (3)	C1B—C6B—H6B	120.00
C3C—C4C—C5C	120.7 (3)	C5B—C6B—H6B	120.00
N4C—C4C—C5C	119.6 (2)	O1E—C1E—C2E	107.8 (5)
N4C—C4C—C3C	119.7 (3)	O1E—C1E—C21E	126.3 (9)
C4C—C5C—C6C	119.6 (2)	O1E—C1E—H11E	109.9
C1C—C6C—C5C	122.1 (3)	O1E—C1E—H12E	109.9
C21C—C11C—C61C	116.0 (2)	C2E—C1E—H11E	109.9
C1C—C11C—C21C	122.3 (2)	C2E—C1E—H12E	109.9
C1C—C11C—C61C	121.7 (3)	H11E—C1E—H12E	109.5
C11C—C21C—C31C	122.5 (2)	C1E—C2E—H3E	110.00
C21C—C31C—C41C	120.6 (3)	C1E—C2E—H4E	109.00
N41C—C41C—C51C	121.7 (3)	H2E—C2E—H3E	109.00
C31C—C41C—C51C	118.2 (3)	H2E—C2E—H4E	109.00
N41C—C41C—C31C	120.0 (3)	H3E—C2E—H4E	109.00
C41C—C51C—C61C	120.8 (2)	C1E—C21E—H5E	109.00
C11C—C61C—C51C	121.9 (3)	C1E—C21E—H6E	109.00
C3C—C2C—H2C	119.00	C1E—C21E—H7E	109.00
C1C—C2C—H2C	119.00	H5E—C21E—H6E	109.00
C4C—C3C—H3C	120.00	H5E—C21E—H7E	109.00
C2C—C3C—H3C	120.00	H6E—C21E—H7E	110.00
O32A—N3A—C3A—C4A	28.5 (4)	C21C—C11C—C61C—C51C	1.4 (3)
O31A—N3A—C3A—C4A	−150.5 (3)	C11C—C21C—C31C—C41C	0.0 (3)
O31A—N3A—C3A—C2A	31.5 (4)	C21C—C31C—C41C—N41C	177.1 (2)
O32A—N3A—C3A—C2A	−149.5 (3)	C21C—C31C—C41C—C51C	1.0 (3)
O52A—N5A—C5A—C4A	−177.8 (2)	C31C—C41C—C51C—C61C	−0.7 (3)
O52A—N5A—C5A—C6A	2.7 (3)	N41C—C41C—C51C—C61C	−176.8 (2)
O51A—N5A—C5A—C6A	−175.3 (2)	C41C—C51C—C61C—C11C	−0.5 (3)
O51A—N5A—C5A—C4A	4.2 (3)	C6A—C1A—C7A—O72A	−173.1 (2)
O32B—N3B—C3B—C2B	147.7 (2)	C6A—C1A—C2A—C3A	−0.7 (3)
O31B—N3B—C3B—C2B	−33.0 (3)	C6A—C1A—C7A—O71A	6.8 (3)
O32B—N3B—C3B—C4B	−29.6 (3)	C6A—C1A—C2A—O2A	177.6 (2)
O31B—N3B—C3B—C4B	149.6 (2)	C7A—C1A—C2A—O2A	−2.4 (3)
O51B—N5B—C5B—C6B	174.8 (2)	C2A—C1A—C7A—O72A	6.9 (3)
O51B—N5B—C5B—C4B	−5.6 (3)	C2A—C1A—C7A—O71A	−173.2 (2)
O52B—N5B—C5B—C6B	−3.9 (3)	C7A—C1A—C6A—C5A	180.0 (2)
O52B—N5B—C5B—C4B	175.7 (2)	C2A—C1A—C6A—C5A	0.0 (3)
C6D—C1D—C1D^i—C6D^i	180.0 (3)	C7A—C1A—C2A—C3A	179.25 (19)
C2D—C1D—C6D—C5D	1.4 (4)	C1A—C2A—C3A—N3A	179.6 (2)
C2D—C1D—C1D^i—C6D^i	−0.2 (4)	O2A—C2A—C3A—C4A	−176.7 (2)
C6D—C1D—C1D^i—C2D^i	0.2 (4)	C1A—C2A—C3A—C4A	1.6 (3)
C2D—C1D—C1D^i—C2D^i	180.0 (2)	O2A—C2A—C3A—N3A	1.3 (3)
C1D^i—C1D—C2D—C3D	179.3 (2)	N3A—C3A—C4A—C5A	−179.7 (2)
C1D^i—C1D—C6D—C5D	−178.8 (2)	C2A—C3A—C4A—C5A	−1.7 (3)
C6D—C1D—C2D—C3D	−0.9 (4)	C3A—C4A—C5A—N5A	−178.7 (2)
C1D—C2D—C3D—C4D	0.0 (4)	C3A—C4A—C5A—C6A	0.8 (3)
C2D—C3D—C4D—C5D	0.5 (4)	N5A—C5A—C6A—C1A	179.5 (2)
C2D—C3D—C4D—N4D	−176.9 (2)	C4A—C5A—C6A—C1A	0.0 (3)
C3D—C4D—C5D—C6D	−0.1 (4)	C7B—C1B—C2B—O2B	−2.3 (3)
N4D—C4D—C5D—C6D	177.4 (2)	C6B—C1B—C2B—C3B	−3.5 (3)
C4D—C5D—C6D—C1D	−0.9 (4)	C7B—C1B—C6B—C5B	−176.9 (2)
C2C—C1C—C11C—C21C	−162.9 (2)	C7B—C1B—C2B—C3B	174.5 (2)
C6C—C1C—C11C—C61C	−166.5 (2)	C2B—C1B—C6B—C5B	1.2 (3)
C2C—C1C—C6C—C5C	−0.3 (3)	C6B—C1B—C7B—O71B	−0.8 (4)
C2C—C1C—C11C—C61C	15.7 (3)	C6B—C1B—C7B—O72B	177.9 (2)
C11C—C1C—C6C—C5C	−178.3 (2)	C2B—C1B—C7B—O71B	−178.9 (3)
C6C—C1C—C11C—C21C	15.0 (3)	C2B—C1B—C7B—O72B	−0.2 (4)
C6C—C1C—C2C—C3C	0.3 (4)	C6B—C1B—C2B—O2B	179.6 (2)
C11C—C1C—C2C—C3C	178.3 (3)	O2B—C2B—C3B—N3B	2.6 (3)
C1C—C2C—C3C—C4C	0.3 (5)	O2B—C2B—C3B—C4B	179.8 (2)
C2C—C3C—C4C—C5C	−0.9 (4)	C1B—C2B—C3B—N3B	−174.17 (19)
C2C—C3C—C4C—N4C	−179.2 (3)	C1B—C2B—C3B—C4B	3.0 (3)
N4C—C4C—C5C—C6C	179.2 (2)	C2B—C3B—C4B—C5B	0.0 (3)
C3C—C4C—C5C—C6C	0.8 (3)	N3B—C3B—C4B—C5B	177.25 (19)
C4C—C5C—C6C—C1C	−0.2 (3)	C3B—C4B—C5B—C6B	−2.7 (3)
C61C—C11C—C21C—C31C	−1.2 (3)	C3B—C4B—C5B—N5B	177.7 (2)
C1C—C11C—C21C—C31C	177.4 (2)	N5B—C5B—C6B—C1B	−178.3 (2)
C1C—C11C—C61C—C51C	−177.2 (2)	C4B—C5B—C6B—C1B	2.1 (3)

Symmetry code: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O72A—H72A···O2A	0.89 (3)	1.62 (3)	2.479 (3)	161 (3)
O72B—H72B···O2B	0.92 (3)	1.61 (3)	2.487 (3)	160 (3)
O1E—H1E···O71B^ii	0.92 (3)	1.79 (3)	2.706 (3)	175 (3)
O1E—H1E···O72B^ii	0.92 (3)	2.53 (3)	3.165 (3)	126 (3)
N4C—H41C···O1E^iii	0.89 (3)	2.12 (3)	2.903 (4)	147 (3)
N4C—H42C···O2A^iv	0.95 (4)	1.81 (4)	2.761 (3)	180 (4)
N4C—H42C···O31A^iv	0.95 (4)	2.50 (4)	2.870 (3)	103 (3)
N4C—H43C···O1E^v	0.94 (3)	1.85 (3)	2.794 (4)	176 (2)
N4D—H41D···N41C^vi	0.87 (2)	1.99 (2)	2.835 (3)	162 (2)
N4D—H42D···O2B	0.95 (3)	1.89 (3)	2.838 (3)	180 (3)
N4D—H42D···O31B	0.95 (3)	2.51 (3)	2.906 (3)	105 (2)
N4D—H43D···O71A^vii	0.96 (3)	1.82 (3)	2.781 (3)	180 (3)
N41C—H44C···O52A^viii	0.92 (3)	2.33 (3)	3.133 (4)	146 (3)
N41C—H45C···O31B^v	0.87 (3)	2.49 (3)	3.356 (4)	176 (3)

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