N-{3-[(2-Ammonio­ethyl)amino]prop­yl}ethane-1,2-diaminium tris­(trifluoro­methane­sulfonate): a salt of a folded triply protonated tetramine

The structure of a trifluoro­methane­sulfonate salt of a non­typical triply protonated linear tetr­amine, C₇H₂₃N₄³⁺·3CF₃SO₃^-, with a layered crystal structure is presented. One N atom remains unprotonated. The conformation of the cation is enforced by intra- and inter­molecular hydrogen bonds. The crystal structure is built of ca 10 Å deep layers, within which cations and anions are hydrogen bonded. Each layer is only weakly bound to its neighbours. This study shows a rare example of an unsymmetrically protonated polyamine and the relation between the lack of protonation, intra­molecular hydrogen bonding and the conformation of the cation.

S1. Comment

Polyamines play a major role in many biological processes. Most eukaryotic cells have a polyamine transporter system on their cell membrane that facilitates the internalization of exogenous polyamines. This system is highly active in rapidly proliferating cells and is the target of some chemotherapeutics currently under development (Wang et al., 2003). Polyamines are also important modulators of a variety of ion channels including NMDA and AMPA receptors (Chen et al., 2005). In the course of our studies on metal complexes with polyamines, some new salts of biogenic polyamines and their derivatives have recently been described (Pospieszna-Markiewicz et al., 2006, 2007; Jazdoń et al., 2007). Here we present another example, the trifluoromethanesulfonate salt of an unexpectedly triply protonated 3,7-diazanonane-1,9-diamine, (I).

Protonated polyamines are also useful for studying the coordination properties of different anions (e.g. halides; Ilioudis et al., 2000). Linear, symmetrical tetramines in their protonated forms usually exist as di- or tetracations. For instance, in the Cambridge Structural Database (Allen, 2002; version 5.29, November 2007) there are 42 fragments containing triethylenetetramine cations: in 31 cases they are tetra-, in eight they are diprotonated, while two of three remaining structures are highly disordered (Yao et al., 1999, Zheng et al., 2003), and in only one, bis(triethylenetetramine) tris[bis(nitrilotriacetato)zirconium] tetrahydrate (Haussuhl et al., 2000), is the trication unequivocally determined. For sperminium (1,5,10,14-tetraazoniatetradecane), there are seven tetracations and one dication. The 3,7-diazanonane-1,9-diamine derivatives are represented by only one salt, in which the amine is tetra-protonated, namely benzene-1,2,4,5-tetracarboxylate (Su et al., 2002).

At room temperature, at least two of three anions in (I) display large and eccentric displacement ellipsoids, suggesting a certain degree of disorder. Lowering the temperature to 100 K significantly reduces the ellipsoids, and also improves their shapes. The 100 K structure is reported here.

The conformation of the cation is gttggggt (where t denotes trans and g gauche, cf. Fig. 1) as can be seen from the values of the torsion angles along the chain [71.00 (15)°, -178.77 (11)°, -175.46 (11)°, -66.72 (16)°, 62.13 (15)°, 71.31 (14)°, 90.19 (14)°, -170.13(11°)]. It is far from the all-trans conformation observed in some related α,ω-diaminoalkanes, e.g. in n-decylammonium chloride (Schenk & Chapuis, 1986), or 4-bromocinnamate (Ballabn et al., 2006) and also the gttttttg conformation reported for the 3,7-diazanonane-1,9-diamine tetracation (Su et al., 2002), and is probably a consequence of both inter- and intramolecular hydrogen bonds. The intramolecular N4···N8 distance is 2.8480 (16) Å (for the all-trans conformation it would be almost 5 Å), and the H8A atom is obviously involved in the interaction (Table 1); this hydrogen bond closes a six-membered chair-like ring. A different situation was observed in the other unsymmetrically protonated tetramine (Haussuhl et al., 2000), in which the N···N distance is even shorter (2.807 versus 4 Å for all-trans), but, surprisingly, hardly any hydrogen-bond interactions can be found, as the intramolecular N—H···N angle is as small as 98°. It might be noted that in both cases the N atom that might act as the hydrogen-bond acceptor has no intermolecular short contacts. The second factor that contributes to the stability of the folded conformation of the cation is the intermolecular hydrogen bonding with one of the anions (Fig. 1). The motif formed by these interactions might be described, using graph-set description (Etter et al., 1990; Bernstein et al., 1995), as R²₂(13), or R³₃(11), taking into account the intramolecular hydrogen bond. The anions are in a typical skew conformation, with the O—S—C—F torsion angles close to ±60° or 180°.

Due to the large number of hydrogen-bond donors and acceptors, the overall crystal structure would be expected to be determined by the hydrogen bonds between the ionic components (Table 1). Interestingly, this is only partly true. The crystal comprises layers expanding in the ac plane (Figs. 2 and 3) within which cations and anions are hydrogen bonded, while the layers are only held to one another by weak van der Waals interactions. The organization within a layer is quite complicated (Fig. 2). Using graph-set notation, one can find some characteristic motifs of higher rank, as all the first-rank motifs are simple dimers (D). The terminal NH₃ groups are involved in two kinds of interactions: they make centrosymmetric tetramers (of second order) with two anions R⁴₄(12) with the same NH₃ group, i.e. N1 to N1(2-x,2-y,1-z), N11 to N11(-x,2-y,2-z), and mixed, four-order rings: N1 to N11(1+x,y,z), all with the same graph set R⁴₄(12). These rings connect molecules into chains characterized by the interlinked motifs C⁴₄(32). The `internal' NH groups are also involved in ring-like structures. Two N4—H4 groups, together with the N1—H1B groups of the same molecule, and two anions close a centrosymmetric R⁴₄(14) ring; the N8—H8B group not involved in intramolecular hydrogen bonds makes a small R²₂(8) ring. All these motifs are interconnected to create the strongly bound layer, in which also some secondary, relatively short C—H···O contacts are observed (Table 1). These layers are circa 10 Å deep (almost the whole b parameter). The shortest F···F interlayer contact is 2.89 Å, indicating that only weak, unspecific interactions are involved between layers.

Related literature

For related literature, see: Allen (2002); Ballabn et al. (2006); Bernstein et al. (1995); Chen et al. (2005); Etter et al. (1990); Haussuhl et al. (2000); Ilioudis et al. (2000); Jazdoń et al. (2007); Pospieszna-Markiewicz, Radecka-Paryzek & Kubicki (2006, 2007); Schenk & Chapuis (1986); Su et al. (2002); Wang et al. (2003); Yao et al. (1999); Zheng et al. (2003).

S2. Experimental

An equimolar mixture of Eu(CF₃SO₃)₃ (18 mg, 30 µmol) in methanol (5 ml), 2,6-diacetylpyridine (4.9 mg, 30 µmol) in methanol (5 ml) and 3,7-diazanonane-1,9-diamine (5 µl, 30 µmol) in methanol (5 ml) was stirred at room temperature for 48 h. The solvent was evaporated under reduced pressure to yield a yellow powder. Yellow single crystals suitable for X-ray diffraction analysis were formed by slow diffusion of methanol into an acetonitrile solution of the compound (1 ml) at 278 K over period of a few weeks.

S3. Refinement

The positions of H atoms were freely refined. H atoms bound to the same non-H atom were constrained to have the same U_iso value, which was refined as a free variable.

Computing details

Data collection: CrysAlis CCD (Oxford Diffraction, 2007); cell refinement: CrysAlis RED (Oxford Diffraction, 2007); data reduction: CrysAlis RED (Oxford Diffraction, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Stereochemical Workstation Operation Manual (Siemens, 1989); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. Anisotropic ellipsoid representation of molecule (I) together with the atom-labelling scheme. The ellipsoids are drawn at the 50% probability level; H atoms are depicted as spheres with arbitrary radii. Hydrogen bonds are drawn as dashed lines.
	Fig. 2. The geometry of the hydrogen-bonded layer as seen along the b direction. The hydrogen bonds are depicted as dashed lines.
	Fig. 3. The crystal packing as seen along the c direction.

N-{3-[(2-Ammonioethyl)amino]propyl}ethane-1,2-diaminium tris(trifluoromethanesulfonate)

Crystal data

C7H23N4^3+·3(CF3O3S^−)	Z = 2
Mr = 610.50	F(000) = 624
Triclinic, P1	Dx = 1.731 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.1174 (8) Å	Cell parameters from 3566 reflections
b = 10.5925 (7) Å	θ = 4–24°
c = 12.2690 (13) Å	µ = 0.44 mm^−1
α = 91.964 (7)°	T = 100 K
β = 98.312 (8)°	Prism, colourless
γ = 91.333 (6)°	0.4 × 0.2 × 0.1 mm
V = 1171.28 (18) Å^3

Data collection

Kuma KM-4-CCD diffractometer	4783 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.023
Graphite monochromator	θmax = 30.0°, θmin = 2.9°
ω scans	h = −7→12
9862 measured reflections	k = −13→14
5707 independent reflections	l = −16→16

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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.080	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0435P)^2 + 0.2136P] where P = (Fo^2 + 2Fc^2)/3
5707 reflections	(Δ/σ)max = 0.001
396 parameters	Δρmax = 0.50 e Å^−3
0 restraints	Δρmin = −0.36 e Å^−3

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	0.04439 (3)	0.81188 (3)	0.47056 (3)	0.01425 (8)
O11	−0.00328 (11)	0.77912 (10)	0.57319 (8)	0.0210 (2)
O12	0.19732 (11)	0.85748 (10)	0.48011 (9)	0.0210 (2)
O13	−0.06109 (11)	0.88423 (10)	0.39893 (8)	0.0208 (2)
C11	0.04546 (17)	0.66045 (14)	0.39408 (12)	0.0215 (3)
F11	0.06872 (11)	0.67894 (9)	0.29106 (7)	0.0311 (2)
F12	−0.08463 (12)	0.59869 (10)	0.38983 (9)	0.0383 (3)
F13	0.15138 (12)	0.58691 (9)	0.44186 (8)	0.0353 (2)
S2	0.61177 (3)	1.11884 (3)	0.82741 (3)	0.01304 (8)
O21	0.76935 (11)	1.13922 (11)	0.84535 (10)	0.0276 (3)
O22	0.54565 (11)	1.08840 (9)	0.92376 (8)	0.0172 (2)
O23	0.55420 (11)	1.04119 (9)	0.72996 (8)	0.0201 (2)
C21	0.53683 (16)	1.27412 (13)	0.79207 (12)	0.0193 (3)
F21	0.38858 (10)	1.26652 (9)	0.76986 (8)	0.0314 (2)
F22	0.58719 (11)	1.31679 (8)	0.70280 (7)	0.0276 (2)
F23	0.57338 (12)	1.35918 (8)	0.87431 (8)	0.0325 (2)
S3	0.83853 (4)	0.76769 (3)	0.88814 (3)	0.01570 (8)
O31	0.68558 (12)	0.77644 (12)	0.90137 (11)	0.0336 (3)
O32	0.94525 (12)	0.80160 (11)	0.98401 (9)	0.0261 (2)
O33	0.87738 (13)	0.82070 (10)	0.78840 (9)	0.0279 (2)
C31	0.86476 (15)	0.59843 (14)	0.86740 (12)	0.0200 (3)
F31	1.00536 (10)	0.57535 (9)	0.85821 (9)	0.0350 (2)
F32	0.78046 (10)	0.55318 (9)	0.77584 (8)	0.0293 (2)
F33	0.82874 (12)	0.53495 (10)	0.95132 (9)	0.0392 (3)
N1	0.71084 (14)	0.89879 (12)	0.58829 (10)	0.0172 (2)
H1A	0.662 (2)	0.9266 (18)	0.6394 (17)	0.029 (3)*
H1B	0.742 (2)	0.9666 (19)	0.5561 (16)	0.029 (3)*
H1C	0.788 (2)	0.8612 (19)	0.6172 (16)	0.029 (3)*
C2	0.61372 (16)	0.81330 (14)	0.50741 (11)	0.0181 (3)
H2A	0.6692 (18)	0.7918 (16)	0.4496 (14)	0.020 (3)*
H2B	0.5314 (19)	0.8633 (16)	0.4746 (14)	0.020 (3)*
C3	0.56367 (15)	0.69626 (13)	0.56148 (11)	0.0166 (3)
H3A	0.5220 (19)	0.6345 (17)	0.5047 (15)	0.024 (3)*
H3B	0.6471 (19)	0.6555 (17)	0.6046 (15)	0.024 (3)*
N4	0.45559 (13)	0.72355 (11)	0.63641 (9)	0.0140 (2)
H4	0.383 (2)	0.7522 (17)	0.5973 (15)	0.026 (5)*
C5	0.41370 (16)	0.60625 (13)	0.68830 (12)	0.0169 (3)
H5A	0.5044 (18)	0.5753 (16)	0.7318 (14)	0.017 (3)*
H5B	0.3763 (18)	0.5379 (16)	0.6304 (14)	0.017 (3)*
C6	0.29230 (15)	0.62664 (13)	0.76021 (12)	0.0169 (3)
H6A	0.2658 (18)	0.5423 (16)	0.7839 (14)	0.019 (3)*
H6B	0.2055 (19)	0.6603 (16)	0.7152 (14)	0.019 (3)*
C7	0.34052 (15)	0.71161 (13)	0.86287 (11)	0.0166 (3)
H7A	0.4285 (17)	0.6824 (15)	0.9077 (13)	0.014 (3)*
H7B	0.2609 (17)	0.7238 (15)	0.9068 (13)	0.014 (3)*
N8	0.38348 (12)	0.84282 (11)	0.83262 (10)	0.0142 (2)
H8A	0.4396 (19)	0.8319 (16)	0.7830 (15)	0.020 (3)*
H8B	0.4262 (19)	0.8824 (17)	0.8886 (15)	0.020 (3)*
C9	0.25591 (15)	0.91999 (13)	0.78415 (11)	0.0154 (3)
H9A	0.1833 (18)	0.8626 (16)	0.7458 (13)	0.016 (3)*
H9B	0.2885 (18)	0.9784 (16)	0.7351 (14)	0.016 (3)*
C10	0.19455 (14)	0.99411 (13)	0.87456 (11)	0.0150 (3)
H10A	0.1686 (17)	0.9430 (16)	0.9337 (14)	0.017 (3)*
H10B	0.2614 (18)	1.0596 (16)	0.9016 (14)	0.017 (3)*
N11	0.05249 (13)	1.05109 (12)	0.82558 (10)	0.0163 (2)
H11A	0.063 (2)	1.0860 (19)	0.7659 (17)	0.031 (3)*
H11B	0.023 (2)	1.1066 (19)	0.8725 (17)	0.031 (3)*
H11C	−0.020 (2)	0.9881 (19)	0.8135 (16)	0.031 (3)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.01318 (16)	0.01632 (16)	0.01340 (15)	0.00163 (12)	0.00224 (11)	0.00074 (12)
O11	0.0210 (5)	0.0287 (6)	0.0143 (5)	0.0032 (4)	0.0048 (4)	0.0028 (4)
O12	0.0152 (5)	0.0206 (5)	0.0273 (5)	−0.0006 (4)	0.0037 (4)	0.0005 (4)
O13	0.0213 (5)	0.0246 (5)	0.0165 (5)	0.0077 (4)	0.0015 (4)	0.0025 (4)
C11	0.0265 (8)	0.0171 (7)	0.0214 (7)	−0.0015 (6)	0.0053 (6)	0.0011 (5)
F11	0.0493 (6)	0.0264 (5)	0.0198 (4)	0.0042 (4)	0.0128 (4)	−0.0032 (4)
F12	0.0413 (6)	0.0317 (5)	0.0406 (6)	−0.0205 (5)	0.0064 (5)	−0.0058 (4)
F13	0.0480 (6)	0.0208 (5)	0.0374 (6)	0.0141 (4)	0.0050 (5)	0.0040 (4)
S2	0.01088 (15)	0.01400 (15)	0.01435 (15)	0.00072 (11)	0.00192 (11)	0.00173 (11)
O21	0.0102 (5)	0.0363 (6)	0.0368 (6)	0.0015 (4)	0.0024 (4)	0.0116 (5)
O22	0.0191 (5)	0.0191 (5)	0.0140 (5)	−0.0013 (4)	0.0042 (4)	0.0014 (4)
O23	0.0274 (5)	0.0176 (5)	0.0157 (5)	0.0005 (4)	0.0048 (4)	−0.0023 (4)
C21	0.0243 (7)	0.0157 (6)	0.0164 (6)	0.0011 (5)	−0.0018 (5)	0.0004 (5)
F21	0.0217 (5)	0.0350 (5)	0.0365 (5)	0.0139 (4)	−0.0018 (4)	0.0028 (4)
F22	0.0425 (6)	0.0207 (4)	0.0194 (4)	−0.0020 (4)	0.0024 (4)	0.0079 (3)
F23	0.0572 (7)	0.0163 (4)	0.0216 (5)	0.0007 (4)	−0.0012 (4)	−0.0043 (4)
S3	0.01276 (16)	0.01917 (17)	0.01463 (16)	0.00156 (12)	0.00056 (12)	−0.00197 (12)
O31	0.0146 (5)	0.0343 (7)	0.0518 (8)	0.0050 (5)	0.0062 (5)	−0.0092 (6)
O32	0.0230 (5)	0.0348 (6)	0.0183 (5)	−0.0005 (5)	−0.0027 (4)	−0.0068 (4)
O33	0.0426 (7)	0.0218 (5)	0.0185 (5)	−0.0041 (5)	0.0024 (5)	0.0028 (4)
C31	0.0151 (6)	0.0206 (7)	0.0237 (7)	0.0008 (5)	0.0000 (5)	0.0037 (6)
F31	0.0161 (4)	0.0304 (5)	0.0576 (7)	0.0077 (4)	0.0030 (4)	−0.0061 (5)
F32	0.0283 (5)	0.0230 (5)	0.0328 (5)	0.0013 (4)	−0.0061 (4)	−0.0075 (4)
F33	0.0461 (6)	0.0338 (5)	0.0378 (6)	−0.0067 (5)	0.0033 (5)	0.0179 (5)
N1	0.0148 (6)	0.0191 (6)	0.0178 (6)	0.0012 (5)	0.0021 (5)	0.0011 (5)
C2	0.0183 (7)	0.0225 (7)	0.0135 (6)	0.0005 (5)	0.0029 (5)	0.0000 (5)
C3	0.0180 (7)	0.0163 (6)	0.0158 (6)	0.0016 (5)	0.0038 (5)	−0.0014 (5)
N4	0.0127 (5)	0.0145 (5)	0.0149 (5)	0.0022 (4)	0.0014 (4)	0.0008 (4)
C5	0.0181 (7)	0.0138 (6)	0.0190 (6)	−0.0009 (5)	0.0039 (5)	−0.0009 (5)
C6	0.0141 (6)	0.0161 (6)	0.0203 (7)	−0.0031 (5)	0.0030 (5)	−0.0006 (5)
C7	0.0157 (6)	0.0185 (7)	0.0157 (6)	−0.0011 (5)	0.0028 (5)	0.0025 (5)
N8	0.0113 (5)	0.0163 (5)	0.0148 (5)	0.0007 (4)	0.0021 (4)	−0.0028 (4)
C9	0.0136 (6)	0.0193 (7)	0.0133 (6)	0.0042 (5)	0.0016 (5)	−0.0003 (5)
C10	0.0112 (6)	0.0191 (6)	0.0143 (6)	0.0028 (5)	0.0008 (5)	−0.0019 (5)
N11	0.0132 (5)	0.0215 (6)	0.0144 (6)	0.0047 (5)	0.0025 (4)	0.0010 (5)

Geometric parameters (Å, º)

S1—O11	1.4408 (10)	C2—H2B	0.975 (17)
S1—O12	1.4521 (10)	C3—N4	1.4686 (17)
S1—O13	1.4562 (10)	C3—H3A	0.969 (18)
S1—C11	1.8313 (15)	C3—H3B	0.979 (18)
C11—F11	1.3317 (17)	N4—C5	1.4823 (18)
C11—F12	1.3346 (18)	N4—H4	0.831 (19)
C11—F13	1.3364 (17)	C5—C6	1.5267 (19)
S2—O21	1.4318 (10)	C5—H5A	0.987 (17)
S2—O22	1.4450 (10)	C5—H5B	1.014 (17)
S2—O23	1.4534 (10)	C6—C7	1.5275 (19)
S2—C21	1.8373 (15)	C6—H6A	0.984 (18)
C21—F23	1.3295 (16)	C6—H6B	0.979 (17)
C21—F22	1.3357 (17)	C7—N8	1.5083 (18)
C21—F21	1.3396 (17)	C7—H7A	0.968 (16)
S3—O31	1.4318 (11)	C7—H7B	0.973 (16)
S3—O32	1.4433 (10)	N8—C9	1.5007 (17)
S3—O33	1.4496 (12)	N8—H8A	0.856 (18)
S3—C31	1.8283 (15)	N8—H8B	0.833 (18)
C31—F33	1.3247 (18)	C9—C10	1.5166 (18)
C31—F31	1.3305 (16)	C9—H9A	0.949 (17)
C31—F32	1.3337 (16)	C9—H9B	0.950 (17)
N1—C2	1.4952 (18)	C10—N11	1.4965 (17)
N1—H1A	0.87 (2)	C10—H10A	0.973 (17)
N1—H1B	0.89 (2)	C10—H10B	0.932 (17)
N1—H1C	0.86 (2)	N11—H11A	0.85 (2)
C2—C3	1.518 (2)	N11—H11B	0.88 (2)
C2—H2A	0.953 (17)	N11—H11C	0.92 (2)
O11—S1—O12	114.75 (6)	C2—C3—H3A	109.0 (11)
O11—S1—O13	114.74 (6)	N4—C3—H3B	107.0 (10)
O12—S1—O13	114.68 (6)	C2—C3—H3B	111.8 (11)
O11—S1—C11	104.22 (7)	H3A—C3—H3B	105.9 (14)
O12—S1—C11	103.22 (6)	C3—N4—C5	110.17 (10)
O13—S1—C11	103.07 (7)	C3—N4—H4	105.5 (13)
F11—C11—F12	107.97 (12)	C5—N4—H4	110.9 (13)
F11—C11—F13	108.63 (12)	N4—C5—C6	112.59 (11)
F12—C11—F13	108.08 (13)	N4—C5—H5A	107.3 (10)
F11—C11—S1	110.38 (10)	C6—C5—H5A	111.1 (9)
F12—C11—S1	110.55 (10)	N4—C5—H5B	111.0 (10)
F13—C11—S1	111.14 (10)	C6—C5—H5B	107.5 (9)
O21—S2—O22	115.61 (6)	H5A—C5—H5B	107.2 (13)
O21—S2—O23	115.16 (7)	C5—C6—C7	114.01 (11)
O22—S2—O23	113.62 (6)	C5—C6—H6A	105.9 (9)
O21—S2—C21	104.78 (7)	C7—C6—H6A	108.4 (10)
O22—S2—C21	103.18 (6)	C5—C6—H6B	108.9 (10)
O23—S2—C21	102.21 (6)	C7—C6—H6B	110.7 (10)
F23—C21—F22	108.18 (12)	H6A—C6—H6B	108.7 (14)
F23—C21—F21	107.90 (12)	N8—C7—C6	111.30 (11)
F22—C21—F21	107.51 (11)	N8—C7—H7A	104.3 (10)
F23—C21—S2	111.50 (10)	C6—C7—H7A	112.6 (9)
F22—C21—S2	111.09 (10)	N8—C7—H7B	104.8 (10)
F21—C21—S2	110.50 (10)	C6—C7—H7B	112.4 (10)
O31—S3—O32	116.27 (7)	H7A—C7—H7B	110.8 (13)
O31—S3—O33	115.01 (8)	C9—N8—C7	114.58 (11)
O32—S3—O33	112.61 (7)	C9—N8—H8A	107.4 (11)
O31—S3—C31	104.28 (7)	C7—N8—H8A	105.2 (12)
O32—S3—C31	103.18 (7)	C9—N8—H8B	107.5 (12)
O33—S3—C31	103.40 (7)	C7—N8—H8B	109.4 (12)
F33—C31—F31	108.00 (12)	H8A—N8—H8B	112.8 (17)
F33—C31—F32	107.98 (12)	N8—C9—C10	110.26 (11)
F31—C31—F32	107.95 (12)	N8—C9—H9A	106.9 (10)
F33—C31—S3	110.92 (11)	C10—C9—H9A	111.2 (10)
F31—C31—S3	110.97 (10)	N8—C9—H9B	109.8 (10)
F32—C31—S3	110.89 (10)	C10—C9—H9B	108.2 (10)
C2—N1—H1A	110.3 (13)	H9A—C9—H9B	110.5 (14)
C2—N1—H1B	111.5 (12)	N11—C10—C9	108.38 (11)
H1A—N1—H1B	106.5 (17)	N11—C10—H10A	105.1 (9)
C2—N1—H1C	111.4 (13)	C9—C10—H10A	114.3 (10)
H1A—N1—H1C	110.1 (17)	N11—C10—H10B	108.2 (10)
H1B—N1—H1C	106.9 (17)	C9—C10—H10B	109.1 (10)
N1—C2—C3	111.49 (12)	H10A—C10—H10B	111.4 (14)
N1—C2—H2A	107.2 (10)	C10—N11—H11A	110.4 (13)
C3—C2—H2A	111.4 (10)	C10—N11—H11B	110.3 (12)
N1—C2—H2B	107.0 (10)	H11A—N11—H11B	110.1 (18)
C3—C2—H2B	113.1 (10)	C10—N11—H11C	108.5 (12)
H2A—C2—H2B	106.3 (14)	H11A—N11—H11C	110.7 (18)
N4—C3—C2	112.79 (11)	H11B—N11—H11C	106.6 (17)
N4—C3—H3A	110.1 (10)
O11—S1—C11—F11	171.71 (10)	O31—S3—C31—F33	−57.42 (12)
O12—S1—C11—F11	−68.08 (11)	O32—S3—C31—F33	64.49 (11)
O13—S1—C11—F11	51.58 (12)	O33—S3—C31—F33	−178.02 (10)
O11—S1—C11—F12	52.33 (12)	O31—S3—C31—F31	−177.48 (11)
O12—S1—C11—F12	172.54 (10)	O32—S3—C31—F31	−55.57 (12)
O13—S1—C11—F12	−67.80 (12)	O33—S3—C31—F31	61.93 (12)
O11—S1—C11—F13	−67.69 (12)	O31—S3—C31—F32	62.55 (12)
O12—S1—C11—F13	52.51 (12)	O32—S3—C31—F32	−175.54 (10)
O13—S1—C11—F13	172.17 (10)	O33—S3—C31—F32	−58.04 (12)
O21—S2—C21—F23	−61.88 (12)	N1—C2—C3—N4	71.00 (15)
O22—S2—C21—F23	59.51 (12)	C2—C3—N4—C5	−178.77 (11)
O23—S2—C21—F23	177.66 (10)	C3—N4—C5—C6	−175.46 (11)
O21—S2—C21—F22	58.88 (11)	N4—C5—C6—C7	−66.72 (16)
O22—S2—C21—F22	−179.73 (9)	C5—C6—C7—N8	62.13 (15)
O23—S2—C21—F22	−61.58 (11)	C6—C7—N8—C9	71.31 (14)
O21—S2—C21—F21	178.12 (10)	C7—N8—C9—C10	90.19 (14)
O22—S2—C21—F21	−60.49 (11)	N8—C9—C10—N11	−170.13 (11)
O23—S2—C21—F21	57.66 (11)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O23	0.87 (2)	1.99 (2)	2.8239 (16)	161.4 (18)
N1—H1B···O12^i	0.89 (2)	2.01 (2)	2.8847 (17)	165.2 (17)
N1—H1C···O33	0.86 (2)	2.20 (2)	2.8526 (17)	132.9 (16)
N1—H1C···O11^ii	0.86 (2)	2.236 (19)	2.9516 (16)	141.0 (17)
N4—H4···O12	0.831 (19)	2.380 (19)	3.2049 (16)	172.0 (17)
N8—H8A···O23	0.856 (18)	2.573 (17)	3.0034 (16)	112.2 (13)
N8—H8A···O31	0.856 (18)	2.581 (17)	2.8726 (16)	101.2 (13)
N8—H8B···O22^iii	0.833 (18)	2.288 (18)	3.0254 (15)	147.6 (16)
N8—H8B···O22	0.833 (18)	2.413 (18)	3.0573 (15)	134.7 (15)
N8—H8A···N4	0.856 (18)	2.125 (18)	2.8480 (16)	141.8 (15)
C9—H9B···O23	0.950 (17)	2.508 (16)	3.1473 (18)	124.7 (12)
C9—H9A···O11	0.949 (17)	2.631 (17)	3.5090 (17)	154.0 (13)
C10—H10B···O22	0.932 (17)	2.576 (16)	3.2955 (17)	134.3 (12)
N11—H11A···O13^iv	0.85 (2)	2.05 (2)	2.8727 (16)	161.7 (19)
N11—H11B···O32^iii	0.88 (2)	1.96 (2)	2.7618 (16)	150.3 (17)
N11—H11C···O33^v	0.92 (2)	1.98 (2)	2.8713 (18)	162.6 (16)

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