Polysulfonyl­amines. CXCI. The `almost' polymorphs rac-trans-2-amino­cyclo­hexan-1-aminium di(methane­sulfon­yl)azanide and its 0.11-hydrate†

The title compound, C₆H₁₅N₂⁺·C₂H₆NO₄S₂⁻, crystallizes as a 0.11-hydrate, (I), in the space group C2; the asymmetric unit consists of two cations (one of each enanti­omer), one anion on a general position, two half anions, each with the N atom on a twofold axis, and approximately one fifth of a water mol­ecule. The general anion departs significantly from the usual conformation: it lacks one of the typical `W'-shaped sequence of O—S—N—S—O atoms. The compound also crystallizes in the solvent-free form, (II), in the space group P2₁/c, with one formula unit in the asymmetric unit. Both compounds form ribbons of hydrogen-bonded cation dimers parallel to the b axis. In (I), there are two independent ribbons of opposite chirality, each involving one anion on a special position, and these ribbons are connected by hydrogen bonds to the anion on a general position, resulting in a layer structure parallel to (100). In (II), the chains are connected by hydrogen bonds, and again a layer structure parallel to (100) results.

Comment

We are inter­ested in the supra­molecular potential of NH-acidic di(organosulfon­yl)amines, (RSO₂)₂NH, and have published numerous crystal structures of mol­ecular cocrystals, solvates, metal coordination compounds and organic salts involving (RSO₂)₂NH or (RSO₂)₂N⁻ entities. In particular, proton-transfer reactions of di(methane­sulfon­yl)amine (`dimesyl­amine'), (CH₃SO₂)₂NH, with rationally selected nitro­gen bases (amines and aza-­aromatics) afforded an extended series of ionic crystals whose packing patterns are governed by a wide variety of charge-assisted hydrogen-bonding systems in zero, one, two or three dimensions (e.g. Moers et al., 1999, 2000, 2001; Wijaya et al., 2000; Wijaya, Moers, Blaschette et al., 2004; Wijaya, Moers, Henschel et al., 2004). Our recent studies of silver complexes of rac-trans-­cyclo­hexane-1,2-diamine (Wölper et al., 2010), in turn inspired by the work of Englert (Kalf et al., 2006) on racemic and enanti­omerically pure complexes of the same amine, prompted us to use this amine to synthesize adducts with di(methane­sulfon­yl)amine. Here we present the structures of two crystal forms of the ionic 1:1 adduct rac-trans-2-amino­cyclo­hexan-1-aminium di(methane­sulfon­yl)azanide.

rac-trans-2-Amino­cyclo­hexan-1-aminium di(methane­sul­fon­­yl)azanide 0.11-hydrate, (I), crystallizes with a partially occupied water site in the monoclinic Sohnke space group C2. The asymmetric unit (Fig. 1) consists of two cations (C11 and C12 are R-, and C21 and C22 S-configured, i.e. one of each enanti­omer), one anion on a general position, two half anions, each with the N atom on a twofold axis, and approximately one fifth of a water mol­ecule. Consequently, the compound is racemic despite its Sohnke space group. The anhydrous form, (II), crystallizes in the monoclinic space group P2₁/c with one formula unit in the asymmetric unit (Fig. 2), which was chosen to contain the R,R-enanti­omer of the 2-amino­cyclo­hexan-1-aminium cation.

In the great majority of compounds containing the di(methane­sulfon­yl)azanide anion, a `W'-shaped sequence of O—S—N—S—O atoms is observed, with two O—S—N—S torsion angles of ca ±180°. However, in one of the anions in (I) the typical `W' sequence is distorted; only O7—S4—N3—S3 fits the pattern [−176.18 (8)°], whereas around S3—N3, the largest (absolute) torsion angle is O5—S3—N3—S4 [−132.00 (8)°]. The pseudo-torsion angle O5—S3⋯S4—O7 is 65.54 (8)°, resulting in a pseudo-gauche conformation in contrast to the normally observed pseudo-ecliptic arrangement. The rotation of the SO₂ group constituted by atoms S3, O5 and O6 allows the formation of additional hydrogen bonds (see below).

In the packing of (I), an extensive system of classical hydrogen bonds combines to form corrugated layers parallel to (100) (see Fig. 3, in which the layers are seen edge-on), consisting of a grid-like arrangement of ribbons parallel to the b and c axes. All potential classical hydrogen-bond donors and acceptors are involved, with the exception of the water site (see below). Parallel to the b axis, two independent ribbons are associated with the twofold axes, leading to a completion of the anions with nitro­gen on the special position and to the formation of cation dimers via N11—H3⋯N12ⁱ and N21—H8⋯N22ⁱⁱⁱ interactions, respectively [all symmetry codes used in the discussion of (I) are as in Table 1]. Each of these ribbons consists of only one enanti­omer of the cation, i.e. neighbouring ribbons are of opposite chirality (and are henceforth referred to as R,R- and S,S-ribbons according to the chirality of the respective cations). Defining the direction of the anion by the S⋯S vector and the direction of the cation by the vector joining the mid-points of both (N)C—C(N) bonds, the angle between these vectors is 30.0° for the anion based on S1 and 8.5° for the anion based on S2. As the anions of the R,R- and S,S-ribbons subtend different angles with the cation dimers the strengths of the hydrogen bonds forming them must differ, but the qualitative patterns are the same (Figs. 4 and 5). Within each ribbon, the ions are connected in one direction via the three-centred inter­actions with H2 (R,R-ribbon) or H6 (S,S-ribbon) as donors; in the opposite direction, the classical two-centre inter­actions N12—H5⋯O2 or N22—H10⋯O4 are involved, of which the former is more linear [166.1 (17)° compared to 157.6 (14)°]. The three-centred bonds are of similar strength. The different arrangement of the ions in the two ribbons has most influence on the nonclassical hydrogen bonds. In the S,S-ribbon, two longer inter­actions are observed (C21—H21⋯O4 and C22—H22⋯O3ⁱⁱ), while in the R,R-ribbon, only one short inter­action is found (C12—H12⋯O1ⁱⁱ); the corresponding hydrogen H11 shows a long contact to O6ⁱ which is strongly bent and presumably has a limited structure-determining influence.

The ribbons are connected by hydrogen bonds to the anion on a general position (Fig. 6). Both cases involve one three-centred (N11—H1⋯O6ⁱ, N11—H1⋯O8ⁱ and N21—H7⋯N3ⁱⁱⁱ and N21—H7⋯O7ⁱⁱⁱ) and one bifurcated system in which H4 and H9 share the same acceptor (O5). These inter­actions could explain the deviation from the typical conformation of this anion. Without the distortion of the `W' sequence, only one of the SO<sub>2</sub> groups could take part in inter­actions. Apparently the energy gained by the hydrogen bonds at least compensates the energy necessary to change the conformation of the anion. It should be noted that a similarly distorted anion occurs in the structure of inversion-symmetric [trans-(CH<sub>3</sub>)<sub>2</sub>Sn(urea)<sub>4</sub>]·[(CH<sub>3</sub>SO<sub>2</sub>)<sub>2</sub>N]<sub>2</sub>·6(urea), where the (SO<sub>2</sub>)<sub>2</sub>N group accepts a total of 12 hydrogen bonds with urea NH<sub>2</sub> as donors (Wirth et al., 1998). The bond patterns between the different ribbons and the anion on the general position necessarily differ, since the S,S- and R,R-ribbons approach the (distorted) `W' sequence of the anion from opposite sides, and consequently the acceptors of the three-centred hydrogen bonds are not alike. The anions on general positions connect the R,R- and S,S-ribbons to constitute a grid-like layer in whose meshes the partially occupied water mol­ecule is included (Fig. 7). The layers are corrugated because the cation dimers are mutually rotated about 38.7° [angle between vectors joining the mid-points of the (N)C—C(N) bonds]. Atom O99 is a potential acceptor for several contacts, of which only C2—H2B⋯O99 can be described unequivocally as a hydrogen bond. As the water H atoms could not be identified, no certain statement about the donor properties of O99 can be given, but O1 [3.225 (6) Å] and O5^iv, O8^iv and N3^iv [3.435 (6) to 3.512 (6) Å] lie within the range of potential acceptors. It is not clear to what extent the partially occupied water site is essential for the formation of the partial hydrate, (I), nor over what range of water occupation factors the same structure is maintained; we have conducted no experiments to investigate this. The difference in composition between structures (I) and (II) means that, strictly speaking, they are not polymorphs, but could perhaps be classified as pseudopolymorphs (Nangia, 2006, and references therein). A similar case of two crystal forms not being polymorphs because of traces of water in one of the structures was reported recently (Minkov, 2011).

The methyl H atoms of the anion are activated because of the electron-withdrawing effects of the hetero atoms, and this leads to several nonclassical hydrogen bonds that reinforce the classical hydrogen bonds. Special attention should be paid to C3—H3C⋯O7^v and C4—H4C⋯O7^v since they are inter-layer inter­actions, but the latter is weak. Further C—H donors of the cation form hydrogen bonds, of which one (C25—H25A⋯O8^viii) also connects the layers. It is noteworthy that all hydrogen bonds within the layer are formed by lattice translation and twofold rotation, while inter­actions beyond the layer always include lattice centring, i.e. lattice centring itself and the 2₁-screw axes resulting from its combination with twofold axes.

The packing of (II) is broadly similar to that of (I) in that a system of classical hydrogen bonds combines to form layers parallel to (100); again, all potential classical hydrogen-bond donors and acceptors are involved (Fig. 8). No directed inter­action can be found between these layers. The layers can best be described as parallel ribbons of alternating cation dimers and anions. The dimers are formed via inversion, with N11—H2⋯N12ⁱⁱⁱ connecting the cations, hence leading, unlike in (I), to a racemic composition of the ribbons [all symmetry codes used in the discussion of (II) are as in Table 2]. N11—H3⋯O4ⁱⁱⁱ, N12—H4⋯O3 and N12—H5⋯O4 attach the anion to the dimer, thus establishing the repeat unit of the chain (Fig. 9) while N11—H1⋯N1ⁱ, N11—H2⋯O1ⁱⁱ and N12—H5⋯O1ⁱ connect to the next unit, thus completing the chain formation parallel to b. The remaining acceptor O2 enables the connection of the ribbons by the N11—H3⋯O2^iv hydrogen bond, which is accompanied by the nonclassical C16—H16A⋯O2^iv hydrogen bond (Fig. 10). Since most of the hydrogen-bond donors inter­act with more than one acceptor, most angles at the H atoms are narrow [113.1 (16)–139.6 (14)°]; the bonds involving one acceptor only are far more linear [150.5 (16) and 161.6 (15)°]. Except for those from H5, which are both 2.62 (2) Å long, all hydrogen bonds are significantly shorter than the sum of the van der Waals radii. As N12—H5⋯O1ⁱ and N12—H5⋯O4 are not only long but also deviate the most from linearity [113.1 (16) and 116.5 (16)°, respectively], they must be regarded as weak.

In both structures, well defined layers, with a separation of the hydro­philic regions from the hydro­phobic alkyl residues of the cations, can be observed. Ribbons of alternating anions and cation dimers can be found in both cases. However, the most obvious difference between the two structures is that in (I) the layers are corrugated while in (II) they are flat. In (I), each cation dimer consists of only one enanti­omer, in contrast to (II) which is composed of racemic dimers. Because of the partially occupied water mol­ecule, the overall density of (I) is lower [1.359 Mg m⁻³ in (I) and 1.478 Mg m⁻³ in (II)]. Apart from the formation of the cation dimers, the hydrogen-bond patterns show little similarity. For this reason it seems sensible to assume that the enanti­opure or racemic dimers are responsible during nucleation for the constitution of the different structures. Alternatively, one might speculate that the water mol­ecule strongly influences the formation of the packing at an early stage of crystal growth.

Figure 1 The unique components of (I). Displacement ellipsoids represent 50% probability levels.

Figure 2 The asymmetric unit of (II). Displacement ellipsoids represent 50% probability levels.

Figure 3 The corrugated layers of (I) parallel to (100) seen from the side. The view is parallel to the b axis along the R,R- and S,S-ribbons. Classical hydrogen bonds are shown with thick dashed lines.

Figure 4 The contacts within the R,R-ribbons of (I). Classical hydrogen bonds are shown with thick and nonclassical hydrogen bonds are shown with thin dashed lines. (Symmetry codes are as in Table 1.)

Figure 5 The contacts within the S,S-ribbons of (I). Classical hydrogen bonds are shown with thick and nonclassical hydrogen bonds are shown with thin dashed lines. (Symmetry codes are as in Table 1.)

Figure 6 The contacts between the ribbons and the connecting anions in the packing of (I). Classical hydrogen bonds are shown with thick dashed lines. (Symmetry codes are as in Table 1.)

Figure 7 The grid-like arrangement of the ribbons in (I) (running vertically with an R,R-ribbon in the middle and S,S-ribbons at the sides) within the layer [seen from above, view perpendicular to (100), with b pointing up and c pointing to the right]. Classical hydrogen bonds are shown with thick and nonclassical hydrogen bonds with thin dashed lines.

Figure 8 Layers of (II) parallel to (100), seen from the side. Classical hydrogen bonds are shown with thick and nonclassical hydrogen bonds are shown with thin dashed lines.

Figure 9 The repeat unit of the ribbons in (II). Classical hydrogen bonds are shown with thick dashed lines. (Symmetry codes are as in Table 2.)

Figure 10 The contacts connecting the ribbons in (II). Classical hydrogen bonds are shown with thick and nonclassical hydrogen bonds are shown with thin dashed lines. (Symmetry codes are as in Table 2.)

Experimental

The first attempts to synthesize adducts of rac-trans-­cyclo­hexane-1,2-diamine and di(methane­sulfon­yl)amine used a 2:1 molar ratio in dichloro­methane. Despite this, only the 1:1 adduct was obtained. Liquid–liquid diffusion of diethyl ether into such solutions led to crystals of form (I), whereas the use of petroleum ether led to form (II). We did not investigate whether both crystal forms were formed from the alternative solvent mixtures. Elemental analysis of form (II) was satisfactory (found: C 33.42, H 7.30, N 14.32, S 22.18%; calculated C 33.43, H 7.36, N 14.62, S 22.31%).

Compound (I)

Crystal data

• C₆H₁₅N₂⁺·C₂H₆NO₄S₂⁻·0.11H₂O

• M_r = 289.38

• Monoclinic, C 2

• a = 21.9116 (6) Å

• b = 8.84942 (10) Å

• c = 17.2357 (4) Å

• β = 122.196 (6)°

• V = 2828.2 (2) ų

• Z = 8

• Mo Kα radiation

• μ = 0.39 mm⁻¹

• T = 100 K

• 0.25 × 0.20 × 0.10 mm

Data collection

• Oxford Diffraction Xcalibur E diffractometer

• 59469 measured reflections

• 7844 independent reflections

• 6813 reflections with I > 2σ(I)

• R_int = 0.035

Refinement

• R[F² > 2σ(F²)] = 0.026

• wR(F²) = 0.054

• S = 0.95

• 7844 reflections

• 347 parameters

• 9 restraints

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.29 e Å⁻³

• Δρ_min = −0.27 e Å⁻³

• Absolute structure: Flack (1983), 3637 Friedel pairs

• Flack parameter: 0.04 (3)

Table 1
Geometry of hydrogen bonds and interspecies contacts (Å, °) for (I)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N11—H1⋯O6^i	0.85 (1)	2.52 (2)	2.9567 (16)	112.6 (13)
N11—H1⋯O8^i	0.85 (1)	2.04 (1)	2.8721 (16)	164.1 (16)
N11—H2⋯O1^ii	0.86 (1)	2.54 (1)	3.304 (2)	149.9 (15)
N11—H2⋯N1^ii	0.86 (1)	2.30 (1)	3.076 (2)	150.6 (15)
N11—H1⋯O6^i	0.85 (1)	2.52 (2)	2.9567 (16)	112.6 (13)
N11—H3⋯N12^i	0.89 (1)	2.01 (1)	2.900 (2)	171.4 (16)
N12—H4⋯O5	0.86 (1)	2.30 (2)	3.1585 (16)	173.2 (16)
N12—H5⋯O2	0.85 (1)	2.24 (2)	3.0656 (18)	166.1 (17)
N21—H6⋯O3^ii	0.90 (1)	2.11 (1)	2.9433 (17)	154.7 (15)
N21—H6⋯N2^ii	0.90 (1)	2.49 (2)	3.2499 (19)	141.9 (14)
N21—H7⋯O7^iii	0.89 (1)	2.22 (1)	3.0613 (16)	157.3 (14)
N21—H7⋯N3^iii	0.89 (1)	2.32 (1)	3.0453 (17)	138.3 (14)
N21—H8⋯N22^iii	0.92 (1)	1.99 (1)	2.8889 (19)	166.9 (14)
N22—H9⋯O5	0.94 (1)	2.24 (2)	3.1416 (16)	159.7 (15)
N22—H10⋯O4	0.97 (1)	2.34 (2)	3.2593 (18)	157.6 (14)
C1—H1C⋯O8^iv	0.98	2.63	3.5771 (19)	162
C2—H2B⋯O99	0.98	2.62	3.578 (6)	166
C3—H3C⋯O7^v	0.98	2.61	3.5373 (19)	159
C4—H4A⋯O4^vi	0.98	2.68	3.4874 (19)	140
C4—H4C⋯O7^v	0.98	2.83	3.6972 (19)	149
C12—H12⋯O1^ii	1.00	2.48	3.353 (2)	146
C14—H14B⋯O1^vii	0.99	2.81	3.706 (3)	151
C16—H16A⋯O1^ii	0.99	2.74	3.533 (2)	138
C21—H21⋯O4	1.00	2.62	3.4812 (18)	144
C22—H22⋯O3^ii	1.00	2.74	3.5025 (18)	134
C25—H25A⋯O8^viii	0.99	2.69	3.549 (2)	145
C26—H26A⋯O3^ii	0.99	2.58	3.377 (2)	137
Interspecies contacts
N22—H9⋯O99^ii	0.94 (1)	2.83 (2)	3.312 (6)	113.2 (12)
C1—H1C⋯O99	0.98	2.87	3.452 (7)	119
C11—H11⋯O6^i	1.00	2.71	3.2789 (17)	116
C13—H13A⋯O2	0.99	2.77	3.519 (2)	133
C22—H22⋯O99^ii	1.00	2.70	3.328 (6)	121
Symmetry codes: (i) -x+1, y, -z+1; (ii) x, y+1, z; (iii) -x+1, y, -z+2; (iv) x, y-1, z; (v) ; (vi) ; (vii) ; (viii) .

Compound (II)

Crystal data

• C₆H₁₅N₂⁺·C₂H₆NO₄S₂⁻

• M_r = 287.40

• Monoclinic, P 2₁ /c

• a = 9.7958 (3) Å

• b = 8.5522 (2) Å

• c = 16.0779 (4) Å

• β = 106.455 (3)°

• V = 1291.77 (6) ų

• Z = 4

• Mo Kα radiation

• μ = 0.42 mm⁻¹

• T = 90 K

• 0.25 × 0.20 × 0.18 mm

Data collection

• Oxford Diffraction Xcalibur E diffractometer

• 39527 measured reflections

• 3620 independent reflections

• 3110 reflections with I > 2σ(I)

• R_int = 0.024

Refinement

• R[F² > 2σ(F²)] = 0.026

• wR(F²) = 0.075

• S = 1.09

• 3620 reflections

• 176 parameters

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.55 e Å⁻³

• Δρ_min = −0.32 e Å⁻³

Table 2
Hydrogen-bond geometry (Å, °) for (II)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N11—H1⋯N1^i	0.862 (17)	2.129 (18)	2.9593 (14)	161.6 (15)
N11—H2⋯O1^ii	0.848 (18)	2.403 (17)	2.9627 (13)	124.0 (14)
N11—H2⋯N12^iii	0.848 (18)	2.356 (17)	3.0408 (14)	138.1 (14)
N11—H3⋯O2^iv	0.892 (18)	2.237 (17)	2.9735 (13)	139.6 (14)
N11—H3⋯O4^iii	0.892 (18)	2.393 (17)	3.0377 (13)	129.3 (14)
N12—H4⋯O3	0.87 (2)	2.40 (2)	3.1864 (14)	150.5 (16)
N12—H5⋯O1^i	0.87 (2)	2.62 (2)	3.0667 (14)	113.1 (16)
N12—H5⋯O4	0.87 (2)	2.62 (2)	3.1029 (13)	116.5 (16)
C16—H16A⋯O2^iv	0.99	2.45	3.1891 (14)	132
Symmetry codes: (i) x, y+1, z; (ii) -x+2, -y+1, -z+1; (iii) -x+2, -y+2, -z+1; (iv) .

For (I), H atoms attached to N atoms were refined freely, but with the N—H distances at each N atom restrained to be similar and with U_iso(H) values constrained to 1.2U_eq(N). Methyl H atoms were identified in difference syntheses; the geometry was idealized (C—H = 0.98 Å and H—C—H = 109.5°) and the methyl groups were refined as rigid groups that were allowed to rotate but not to tip. Other H atoms were included at calculated positions (methine C—H = 1.00 Å and methyl­ene C—H = 0.99 Å) and refined using a riding model. U_iso(H) values were set at mU_eq(C), with m = 1.5 for methyl and 1.2 for riding H atoms.

The compound is a racemate but crystallizes by chance in a Sohnke space group. The refinement of the highest remaining Fourier peak as oxygen yielded a site-occupancy factor of 22.1 (5)%. The H atoms of the water mol­ecule could not be identified, but the short distances (3.225–3.512 Å) to potential hydrogen-bond acceptors and to H atoms of (nonclassical) donor groups (2.62–2.87 Å) strongly suggest that treating this peak as partially occupied water is justified. Ignoring the peak results in a solvent-accessible void of 36 ų at x = 0.944, y = 0.726, z = 0.713 (coordinates of the peak = 0.9622, 0.7419, 0.7383).

For (II), H atoms attached to N atoms were refined freely; other H atoms were refined as described for compound (I).

For both compounds, data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP (Bruker, 1998); software used to prepare material for publication: SHELXL97.

Supporting information

S1. Comment

We are interested in the supramolecular potential of NH-acidic di(organosulfonyl)amines, (RSO₂)₂NH, and have published numerous crystal structures of molecular cocrystals, solvates, metal coordination compounds and organic salts involving (RSO₂)₂NH or (RSO₂)₂N^- entities. In particular, proton-transfer reactions of di(methanesulfonyl)amine (`dimesylamine'), (CH₃SO₂)₂NH, with rationally selected nitrogen bases (amines and azaaromatics) afforded an extended series of ionic crystals whose packing patterns are governed by a wide variety of charge-assisted hydrogen-bonding systems in zero, one, two or three dimensions (e.g. Moers et al., 1999, 2000, 2001; Wijaya et al., 2000; Wijaya, Moers, Blaschette et al., 2004; Wijaya, Moers, Henschel et al., 2004). Our recent studies of silver complexes of rac-trans-1,2-diaminocyclohexane (Wölper et al., 2010), in turn inspired by the work of Englert (Kalf et al., 2006) on racemic and enantiomerically pure complexes of the same amine, prompted us to use this amine to synthesize adducts with di(methanesulfonyl)amine. Here we present the structures of two crystal forms of the ionic 1:1 adduct rac-trans-1-ammonio-2-aminocyclohexane di(methanesulfonyl)amide.

rac-trans-1-Ammonio-2-aminocyclohexane di(methanesulfonyl)amide 0.11-hydrate, (I), crystallizes with a partially occupied water site in the monoclinic Sohnke space group C2. The asymmetric unit (Fig. 1) consists of two cations (C11 and C12 are R- and C21 and C22 S-configured, i.e. one of each enantiomer), one anion on a general position, two half anions, each with the nitrogen atom on a twofold axis, and approximately one fifth of a water molecule. Consequently, the compound is racemic despite its Sohnke space group. The anhydrous form, (II), crystallizes in the monoclinic space group P2₁/c with one formula unit in the asymmetric unit (Fig. 2), which was chosen to contain the R,R-enantiomer of the 1-ammonium-2-aminocyclohexane cation.

In the great majority of compounds containing the di(methanesulfonyl)amide anion, a `W'-shaped sequence of atoms O—S—N—S—O is observed, with two O—S—N—S torsion angles of ca ±180°. However, in one of the anions in (I) the typical `W' sequence is distorted; only O7—S4—N3—S3 fits the pattern [-176.18 (2)°], whereas around S3—N3 the largest (absolute) torsion angle is O5—S3—N3—S4 [-132.00 (8)°]. The pseudotorsion angle O5—S3···S4—O7 is 65.54 (8)°, resulting in a pseudo-gauche conformation in contrast to the normally observed pseudo-ecliptic arrangement. The rotation of the SO₂ group constituted by S3, O5 and O6 allows the formation of additional hydrogen bonds (see below).

In the packing of (I), an extensive system of classical hydrogen bonds combines to form corrugated layers parallel to (100) (see Fig. 3, in which the layers are seen edge-on), consisting of a grid-like arrangement of ribbons parallel to the b and c axes. All potential classical hydrogen-bond donors and acceptors are involved, with the exception of the water site (see below). Parallel to the b axis, two independent ribbons are associated with the twofold axes, leading to a completion of the anions with nitrogen on the special position and to the formation of cation dimers via N11—H3···N12ⁱ and N21—H8···N22ⁱⁱⁱ, respectively. Each of these ribbons consists of only one enantiomer of the cation, i.e. neighbouring ribbons are of opposite chirality (and are henceforth referred to as R,R and S,S ribbons according to the chirality of the respective cations). Defining the direction of the anion by the S···S vector and the direction of the cation by the vector joining the midpoints of both (N)C—C(N) bonds, the angle between these vectors is 30.0° for the anion based on S1 and 8.5° for the anion based on S2. As the anions of the R,R and S,S ribbons subtend different angles with the cation dimers, the strengths of the hydrogen bonds forming them must differ, but the qualitative patterns are the same (Figs. 4 and 5). Within each ribbon the ions are connected in one direction via the three-centred interactions with H2 (R,R ribbon) or H6 (S,S ribbon) as donors; in the opposite direction the classical two-centre interactions N12—H5···O2 or N22—H10···O4 are involved, of which the former is more linear [166.1 (17)° compared to 157.6 (14)°]. The three-centred bonds are of similar strength. The different arrangement of the ions in the two ribbons has most influence on the non-classical hydrogen bonds. In the S,S ribbon two longer interactions are observed (C21—H21···O4, C22—H22···O3ⁱⁱⁱ) while in the R,R ribbon only one short interaction is found (C12—H12···O1ⁱⁱ); the corresponding hydrogen H11 shows a long contact to O6ⁱ which is strongly bent and presumably has a limited structure-determining influence.

The ribbons are connected by hydrogen bonds to the anion on a general position (Fig. 6). Both cases involve one three-centred (N11—H1···O6ⁱ, N11—H1···O8ⁱ and N21—H7···N3ⁱⁱⁱ, N21— H7···O7ⁱⁱⁱ) and one bifurcated system in which H4 and H9 share the same acceptor (O5). These interactions could explain the deviation from the typical conformation of this anion. Without the distortion of the `W' sequence only one of the SO<sub>2</sub> groups could take part in interactions. Apparently the energy gained by the hydrogen bonds at least compensates the energy necessary to change the conformation of the anion. It should be noted that a similarly distorted anion occurs in the structure of the inversion-symmetric [trans-(CH<sub>3</sub>)<sub>2</sub>Sn(urea)<sub>4</sub>]<sup>.</sup>[(CH<sub>3</sub>SO<sub>2</sub>)<sub>2</sub>N]<sub>2</sub><sup>.</sup>6(urea), where the (SO<sub>2</sub>)<sub>2</sub>N group accepts a total of 12 hydrogen bonds with urea NH<sub>2</sub> as donors (Wirth et al., 1998). The bond patterns between the different ribbons and the anion on the general position necessarily differ, since the S,S and R,R ribbons approach the (distorted) `W' sequence of the anion from opposite sides, and consequently the acceptors of the three-centred hydrogen bonds are not alike. The anions on general positions connect the R,R and S,S ribbons to constitute a grid-like layer in whose meshes the partially occupied water molecule is included (Fig. 7). The layers are corrugated because the cation dimers are mutually rotated about 38.7° [angle between vectors joining the midpoints of the (N)C—C(N) bonds]. O99 is a potential acceptor for several contacts, of which only C2—H2B···O99 can be described as a hydrogen bond without doubt. As the water hydrogen atoms could not be identified, no certain statement about the donor properties of O99 can be given, but O1 [3.225 (6) Å] and O5^iv, O8^iv, N3^iv [3.435 (6) to 3.512 (6) Å] lie within the range of potential acceptors. It is not clear to what extent the partially occupied water site is essential for the formation of the partial hydrate, (I), nor over what range of water occupation factors the same structure is maintained; we have conducted no experiments to investigate this. The difference in composition between the structures (I) and (II) means however that, strictly speaking, they are not polymorphs, but could perhaps be classified as pseudopolymorphs (Nangia, 2006, and references therein).

The methyl hydrogen atoms of the anion are activated because of the electron-withdrawing effects of the hetero atoms, and this leads to several non-classical hydrogen bonds that reinforce the classical hydrogen bonds. Special attention should be drawn to C3—H3C···O7^v and C4—H4C···O7^v since they are inter-layer interactions, but the latter is weak. Further CH donors of the cation form hydrogen bonds of which one (C25—H25A···O8^viii) also connects the layers. It is noteworthy that all hydrogen bonds within the layer are formed by lattice translation and twofold rotation, while interactions beyond the layer always include lattice centring, i.e. lattice centring itself and the 2₁-screw axes resulting from its combination with twofold axes.

The packing of (II) is broadly similar to that of (I) in that a system of classical hydrogen bonds combines to form layers parallel to (100); again, all potential classical hydrogen-bond donors and acceptors are involved (Fig. 8). Between these layers no directed interaction can be found. The layers can best be described as parallel ribbons of alternating cation dimers and anions. The dimers are formed via inversion, with N11—H2···N12ⁱⁱⁱ connecting the cations, hence leading, unlike (I), to a racemic composition of the ribbons. N11—H3···O4ⁱⁱⁱ, N12 —H4···O3 and N12—H5···O4 attach the anion to the dimer, thus establishing the repeat unit of the chain (Fig. 9) while N11—H1···N1ⁱ, N11—H2···O1ⁱⁱ and N12—H5···O1ⁱ connect to the next unit, thus completing the chain formation parallel to b. The remaining acceptor O2 enables the connection of the ribbons by the hydrogen bond N11—H3···O2^iv, which is accompanied by the non-classical bond C16—H16A···O2^iv (Fig. 10). Since most of the hydrogen-bond donors interact with more than one acceptor, most angles at the hydrogen atoms are narrow [113.1 (16) to 139.6 (14)°]; the bonds involving one acceptor only are far more linear [150.5 (16) and 161.6 (15)°]. Except for those from H5, which are both 2.62 (2) Å long, all hydrogen bonds are significantly shorter than the sum of the van der Waals radii. As N12—H5···O1ⁱ and N12—H5···O4 are not only long but also deviate the most from linearity [113.1 (16) and 116.5 (16)°, respectively] they must be regarded as weak.

In both structures well defined layers, with a separation of hydrophilic regions from the hydrophobic alkyl residues of the cations, can be observed. Ribbons of alternating anions and cation dimers can be found in both cases. However, the most obvious difference between the two structures is that in (I) the layers are corrugated while in (II) they are flat. In (I) each cation dimer consists of only one enantiomer, in contrast to (II) which is composed of racemic dimers. Because of the partially occupied water molecule the overall density of (I) is lower [(I): 1.359, (II): 1.478 Mg m^-3]. Apart from the formation of the cation dimers the hydrogen-bond patterns show little similarity. For this reason it seems sensible to assume that the enantiopure or racemic dimers are responsible during nucleation for the constitution of the different structures. Alternatively one might speculate that the water molecule strongly influences the formation of the packing at an early stage of crystal growth.

Related literature

For related literature, see: Kalf et al. (2006); Moers et al. (1999, 2000, 2001); Nangia (2006); Wölper et al. (2010); Wijaya et al. (2000); Wijaya, Moers, Blaschette et al. (2004); Wijaya, Moers, Henschel et al. 2004); Wirth et al. (1998).

S2. Experimental

First attempts to synthesize adducts of rac-trans-1,2-diaminocyclohexane and di(methanesulfonyl)amine used a 2:1 molar ratio in dichloromethane. Despite this, only the 1:1 adduct was obtained. Liquid–liquid diffusion of diethyl ether into such solutions led to crystals of form (I), whereas the use of petroleum ether led to form (II). We did not investigate whether both crystal forms were formed from the alternative solvent mixtures. Elemental analysis of form (II) was satisfactory (found: C 33.42, H 7.30, N 14.32, S 22.18; calculated C 33.43, H 7.36, N 14.62, S 22.31%).

S3. Refinement

For (I) NH hydrogen atoms were refined freely, but with N—H distance restraints and U(H) constrained to 1.2U_eq(N). Methyl H atoms were identified in difference syntheses; the geometry was idealized (C—H 0.98 Å, H—C—H 109.5°) and the methyl groups refined as rigid groups that were allowed to rotate but not tip. Other H atoms were included at calculated positions (C_methine—H 1.00, C_methylene—H 0.99 Å) and refined using a riding model. U(H) was set to mU_eq(C), with m = 1.5 for methyl and 1.2 for riding H atoms.

The compound is a racemate but crystallizes by chance in a Sohnke space group. The refinement of the highest remaining Fourier peak as oxygen yielded a site-occupancy factor of 22.1 (5)%. The hydrogen atoms of the water molecule could not be identified, but the short distances (3.225 to 3.512 Å) to potential hydrogen-bond acceptors and to H atoms of (non-classical) donor groups (2.62 to 2.87 Å) strongly suggest that treating this peak as partly occupied water is justified. Ignoring the peak results in a solvent-accessible void of 36 ų at x = 0.944, y = 0.726, z = 0.713 (coordinates of the peak 0.9622, 0.7419, 0.7383).

For (II) NH hydrogen atoms were refined freely; other H atoms were refined as described for compound (I).

Computing details

For both compounds, data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP (Bruker, 1998); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. The asymmetric unit of (I). Displacement ellipsoids represent 50% probability levels.
	Fig. 2. The asymmetric unit of (II). Displacement ellipsoids represent 50% probability levels.
	Fig. 3. The corrugated layers of (I) parallel to (100) seen from the side. The view is parallel to the b axis along the R,R and S,S ribbons. Classical hydrogen bonds are shown with thick and nonclassical hydrogen bonds are shown with thin dashed lines.
	Fig. 4. The contacts within the R,R-ribbons of (I). Classical hydrogen bonds are shown with thick and nonclassical hydrogen bonds are shown with thin dashed lines.
	Fig. 5. The contacts within the S,S-ribbons of (I). Classical hydrogen bonds are shown with thick and nonclassical hydrogen bonds are shown with thin dashed lines.
	Fig. 6. The contacts between the ribbons and the connecting anions in the packing of (I). Classical hydrogen bonds are shown with thick dashed lines.
	Fig. 7. The grid-like arrangement of the ribbons (running vertically with R,R- in the middle and S,S- at the sides) within the layer [seen from above, view perpendicular to (100)]. Classical hydrogen bonds as thick, non-classical hydrogen bonds as thin dashed lines.
	Fig. 8. Layers of (II) parallel to (100), seen from the side. Classical hydrogen bonds are shown with thick and nonclassical hydrogen bonds are shown with thin dashed lines.
	Fig. 9. The repeat unit of the ribbons in (II). Classical hydrogen bonds are shown with thick dashed lines.
	Fig. 10. The contacts connecting the ribbons in (II). Classical hydrogen bonds are shown with thick and nonclassical hydrogen bonds are shown with thin dashed lines.

(I) rac-trans-2-aminocyclohexan-1-aminium di(methanesulfonyl)amide 0.11-hydrate

Crystal data

C6H15N2^+·C2H6NO4S2^−·0.11H2O	F(000) = 1241
Mr = 289.38	Dx = 1.359 Mg m^−3
Monoclinic, C2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C 2y	Cell parameters from 26969 reflections
a = 21.9116 (6) Å	θ = 2.2–30.9°
b = 8.84942 (10) Å	µ = 0.39 mm^−1
c = 17.2357 (4) Å	T = 100 K
β = 122.196 (6)°	Tablet, colourless
V = 2828.2 (2) Å^3	0.25 × 0.20 × 0.10 mm
Z = 8

Data collection

Oxford Diffraction Xcalibur E diffractometer	6813 reflections with I > 2σ(I)
Radiation source: Enhance (Mo) X-ray Source	Rint = 0.035
Graphite monochromator	θmax = 29.6°, θmin = 2.2°
Detector resolution: 16.1419 pixels mm^-1	h = −30→30
ω scans	k = −12→12
59469 measured reflections	l = −23→23
7844 independent reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.026	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.054	w = 1/[σ^2(Fo^2) + (0.0291P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.95	(Δ/σ)max = 0.001
7844 reflections	Δρmax = 0.29 e Å^−3
347 parameters	Δρmin = −0.27 e Å^−3
9 restraints	Absolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.04 (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.

Operators for generating equivalent atoms:

$4 x, y - 1, z

Distance DIST

3.2246 (0.0064) O99 - O1 3.5124 (0.0063) O99 - O5_$4 3.5095 (0.0063) O99 - O8_$4 3.4352 (0.0063) O99 - N3_$4

Dihedral angle TORS

65.54 (0.08) O5 - S3 - S4 - O7

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)
S1	0.45268 (2)	0.16112 (4)	0.52978 (3)	0.03075 (10)
S2	0.433245 (19)	0.25381 (4)	0.91870 (2)	0.01815 (8)
S3	0.594403 (18)	0.58696 (4)	0.81208 (2)	0.01519 (7)
S4	0.664674 (18)	0.86459 (4)	0.86374 (2)	0.01797 (8)
O1	0.40533 (8)	0.05097 (17)	0.53122 (11)	0.0623 (5)
O2	0.41913 (6)	0.29327 (12)	0.47407 (7)	0.0316 (3)
O3	0.37423 (6)	0.14703 (12)	0.87663 (8)	0.0281 (3)
O4	0.41855 (6)	0.39566 (11)	0.94713 (7)	0.0241 (2)
O5	0.51769 (5)	0.56290 (12)	0.77023 (6)	0.0212 (2)
O6	0.62037 (5)	0.57944 (12)	0.75075 (6)	0.0186 (2)
O7	0.67664 (6)	0.97637 (12)	0.93183 (7)	0.0259 (2)
O8	0.63382 (6)	0.92174 (11)	0.77146 (6)	0.0233 (2)
N1	0.5000	0.0706 (2)	0.5000	0.0308 (4)
N2	0.5000	0.16351 (19)	1.0000	0.0206 (4)
N3	0.61650 (6)	0.73784 (14)	0.87115 (8)	0.0207 (3)
N11	0.41297 (8)	0.78424 (14)	0.40254 (8)	0.0245 (3)
H1	0.3974 (9)	0.8074 (19)	0.3469 (9)	0.029*
H2	0.4251 (9)	0.8649 (16)	0.4348 (10)	0.029*
H3	0.4511 (8)	0.7255 (18)	0.4185 (11)	0.029*
N12	0.46288 (7)	0.60805 (16)	0.56115 (9)	0.0265 (3)
H4	0.4741 (9)	0.597 (2)	0.6170 (10)	0.032*
H5	0.4579 (10)	0.5212 (17)	0.5379 (12)	0.032*
N21	0.40685 (7)	0.86537 (15)	0.98250 (8)	0.0196 (2)
H6	0.4107 (9)	0.9585 (16)	0.9646 (11)	0.024*
H7	0.3887 (8)	0.8755 (19)	1.0180 (10)	0.024*
H8	0.4519 (7)	0.8243 (17)	1.0201 (10)	0.024*
N22	0.46209 (7)	0.70780 (16)	0.88785 (9)	0.0243 (3)
H9	0.4752 (9)	0.6878 (19)	0.8451 (10)	0.029*
H10	0.4633 (9)	0.6094 (17)	0.9137 (11)	0.029*
C1	0.51186 (10)	0.22227 (19)	0.64361 (11)	0.0336 (4)
H1A	0.4842	0.2728	0.6658	0.050*
H1B	0.5470	0.2931	0.6456	0.050*
H1C	0.5372	0.1349	0.6826	0.050*
C2	0.45626 (9)	0.29192 (19)	0.83724 (11)	0.0284 (4)
H2A	0.4159	0.3429	0.7842	0.043*
H2B	0.4668	0.1969	0.8175	0.043*
H2C	0.4989	0.3572	0.8647	0.043*
C3	0.63838 (8)	0.44449 (18)	0.89545 (10)	0.0217 (3)
H3A	0.6272	0.3456	0.8653	0.033*
H3B	0.6218	0.4474	0.9382	0.033*
H3C	0.6906	0.4613	0.9292	0.033*
C4	0.74847 (8)	0.78314 (18)	0.89614 (10)	0.0252 (3)
H4A	0.7808	0.8615	0.8979	0.038*
H4B	0.7413	0.7053	0.8515	0.038*
H4C	0.7699	0.7373	0.9570	0.038*
C11	0.36011 (9)	0.69862 (17)	0.41493 (10)	0.0247 (3)
H11	0.3523	0.5977	0.3850	0.030*
C12	0.39027 (9)	0.67346 (19)	0.51662 (10)	0.0265 (3)
H12	0.3947	0.7746	0.5450	0.032*
C13	0.33597 (10)	0.5811 (2)	0.52659 (11)	0.0370 (4)
H13A	0.3288	0.4818	0.4964	0.044*
H13B	0.3554	0.5628	0.5924	0.044*
C14	0.26388 (11)	0.6620 (3)	0.48413 (13)	0.0494 (5)
H14A	0.2701	0.7573	0.5177	0.059*
H14B	0.2293	0.5977	0.4893	0.059*
C15	0.23391 (10)	0.6971 (3)	0.38280 (13)	0.0477 (5)
H15A	0.2204	0.6012	0.3478	0.057*
H15B	0.1897	0.7590	0.3582	0.057*
C16	0.28802 (10)	0.7810 (2)	0.36889 (11)	0.0375 (5)
H16A	0.2954	0.8841	0.3948	0.045*
H16B	0.2685	0.7905	0.3024	0.045*
C21	0.35883 (8)	0.76844 (17)	0.90083 (9)	0.0195 (3)
H21	0.3597	0.6635	0.9229	0.023*
C22	0.38748 (7)	0.76341 (17)	0.83768 (9)	0.0194 (3)
H22	0.3881	0.8694	0.8179	0.023*
C23	0.33614 (9)	0.6726 (2)	0.75208 (11)	0.0312 (4)
H23A	0.3539	0.6742	0.7099	0.037*
H23B	0.3359	0.5662	0.7696	0.037*
C24	0.25956 (9)	0.7337 (2)	0.70224 (11)	0.0351 (4)
H24A	0.2588	0.8371	0.6797	0.042*
H24B	0.2280	0.6691	0.6486	0.042*
C25	0.23124 (8)	0.7373 (2)	0.76561 (11)	0.0330 (4)
H25A	0.2266	0.6327	0.7822	0.040*
H25B	0.1828	0.7842	0.7334	0.040*
C26	0.28181 (8)	0.82695 (19)	0.85278 (11)	0.0296 (4)
H26A	0.2810	0.9347	0.8368	0.036*
H26B	0.2644	0.8200	0.8951	0.036*
O99	0.4611 (3)	−0.0585 (7)	0.7371 (4)	0.046 (2)*	0.221 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0271 (2)	0.02175 (19)	0.0313 (2)	−0.00695 (17)	0.00746 (17)	0.00276 (17)
S2	0.01731 (17)	0.01602 (16)	0.02301 (18)	−0.00121 (14)	0.01200 (14)	−0.00102 (14)
S3	0.01332 (16)	0.02095 (17)	0.01114 (15)	0.00163 (14)	0.00642 (13)	0.00217 (14)
S4	0.01646 (17)	0.02306 (18)	0.01372 (16)	−0.00059 (15)	0.00759 (14)	−0.00479 (14)
O1	0.0520 (9)	0.0511 (9)	0.0742 (11)	−0.0256 (7)	0.0271 (8)	0.0087 (8)
O2	0.0227 (6)	0.0290 (6)	0.0292 (6)	0.0036 (5)	0.0045 (5)	0.0014 (5)
O3	0.0226 (6)	0.0234 (5)	0.0380 (6)	−0.0054 (5)	0.0159 (5)	−0.0034 (5)
O4	0.0249 (5)	0.0192 (5)	0.0298 (6)	0.0035 (4)	0.0156 (5)	0.0004 (4)
O5	0.0137 (5)	0.0311 (6)	0.0149 (5)	0.0003 (4)	0.0049 (4)	0.0036 (4)
O6	0.0217 (5)	0.0224 (5)	0.0144 (5)	−0.0007 (4)	0.0113 (4)	−0.0004 (4)
O7	0.0265 (6)	0.0289 (6)	0.0201 (5)	−0.0014 (5)	0.0109 (5)	−0.0102 (5)
O8	0.0294 (6)	0.0209 (5)	0.0161 (5)	−0.0024 (4)	0.0099 (5)	−0.0007 (4)
N1	0.0368 (11)	0.0127 (9)	0.0258 (10)	0.000	0.0051 (8)	0.000
N2	0.0237 (9)	0.0140 (8)	0.0243 (9)	0.000	0.0129 (8)	0.000
N3	0.0221 (6)	0.0268 (7)	0.0186 (6)	−0.0008 (5)	0.0145 (5)	−0.0029 (5)
N11	0.0369 (8)	0.0159 (7)	0.0105 (6)	0.0057 (6)	0.0058 (6)	0.0011 (5)
N12	0.0326 (8)	0.0230 (7)	0.0132 (6)	0.0029 (6)	0.0051 (6)	0.0028 (5)
N21	0.0225 (6)	0.0222 (6)	0.0204 (6)	−0.0009 (6)	0.0157 (5)	−0.0016 (6)
N22	0.0216 (7)	0.0302 (7)	0.0241 (7)	0.0025 (5)	0.0142 (6)	−0.0045 (5)
C1	0.0392 (10)	0.0295 (9)	0.0238 (8)	0.0055 (7)	0.0113 (7)	0.0064 (7)
C2	0.0301 (9)	0.0332 (9)	0.0268 (8)	−0.0012 (7)	0.0184 (7)	0.0023 (7)
C3	0.0183 (7)	0.0277 (8)	0.0173 (7)	0.0059 (6)	0.0082 (6)	0.0108 (6)
C4	0.0154 (7)	0.0332 (9)	0.0243 (8)	−0.0019 (6)	0.0088 (6)	−0.0091 (7)
C11	0.0299 (9)	0.0254 (8)	0.0143 (7)	0.0089 (6)	0.0088 (6)	0.0003 (6)
C12	0.0362 (9)	0.0259 (8)	0.0130 (7)	0.0119 (7)	0.0102 (7)	0.0023 (6)
C13	0.0402 (10)	0.0513 (11)	0.0230 (8)	0.0142 (9)	0.0192 (8)	0.0067 (8)
C14	0.0459 (12)	0.0744 (14)	0.0365 (10)	0.0221 (11)	0.0277 (9)	0.0087 (11)
C15	0.0351 (10)	0.0716 (15)	0.0343 (10)	0.0252 (10)	0.0171 (8)	0.0068 (10)
C16	0.0386 (10)	0.0481 (11)	0.0186 (8)	0.0240 (9)	0.0105 (7)	0.0056 (7)
C21	0.0195 (7)	0.0187 (7)	0.0221 (7)	−0.0019 (6)	0.0122 (6)	−0.0009 (6)
C22	0.0190 (7)	0.0205 (7)	0.0203 (7)	−0.0001 (6)	0.0115 (6)	−0.0014 (6)
C23	0.0282 (9)	0.0378 (9)	0.0222 (8)	0.0031 (8)	0.0098 (7)	−0.0046 (7)
C24	0.0286 (9)	0.0365 (10)	0.0271 (9)	−0.0016 (8)	0.0061 (7)	−0.0025 (8)
C25	0.0185 (8)	0.0329 (9)	0.0383 (9)	−0.0028 (7)	0.0090 (7)	−0.0003 (8)
C26	0.0197 (8)	0.0336 (9)	0.0381 (9)	−0.0017 (6)	0.0171 (7)	−0.0041 (7)

Geometric parameters (Å, º)

S1—O1	1.4334 (13)	C3—H3A	0.98
S1—O2	1.4415 (11)	C3—H3B	0.98
S1—N1	1.5963 (10)	C3—H3C	0.98
S1—C1	1.7643 (16)	C4—H4A	0.98
S2—O4	1.4449 (11)	C4—H4B	0.98
S2—O3	1.4463 (11)	C4—H4C	0.98
S2—N2	1.5992 (9)	C11—C16	1.523 (2)
S2—C2	1.7589 (15)	C11—C12	1.524 (2)
S3—O6	1.4444 (10)	C11—H11	1.00
S3—O5	1.4488 (10)	C12—C13	1.527 (3)
S3—N3	1.5901 (13)	C12—H12	1.00
S3—C3	1.7628 (14)	C13—C14	1.521 (2)
S4—O7	1.4479 (10)	C13—H13A	0.99
S4—O8	1.4480 (10)	C13—H13B	0.99
S4—N3	1.5913 (13)	C14—C15	1.535 (2)
S4—C4	1.7635 (15)	C14—H14A	0.99
N1—S1^i	1.5963 (10)	C14—H14B	0.99
N2—S2^ii	1.5992 (9)	C15—C16	1.523 (3)
N11—C11	1.492 (2)	C15—H15A	0.99
N11—H1	0.854 (13)	C15—H15B	0.99
N11—H2	0.855 (13)	C16—H16A	0.99
N11—H3	0.893 (13)	C16—H16B	0.99
N12—C12	1.468 (2)	C21—C22	1.5196 (19)
N12—H4	0.862 (14)	C21—C26	1.521 (2)
N12—H5	0.847 (14)	C21—H21	1.00
N21—C21	1.4986 (19)	C22—C23	1.523 (2)
N21—H6	0.899 (13)	C22—H22	1.00
N21—H7	0.893 (12)	C23—C24	1.520 (2)
N21—H8	0.918 (12)	C23—H23A	0.99
N22—C22	1.4684 (19)	C23—H23B	0.99
N22—H9	0.940 (14)	C24—C25	1.517 (2)
N22—H10	0.972 (14)	C24—H24A	0.99
C1—H1A	0.98	C24—H24B	0.99
C1—H1B	0.98	C25—C26	1.530 (2)
C1—H1C	0.98	C25—H25A	0.99
C2—H2A	0.98	C25—H25B	0.99
C2—H2B	0.98	C26—H26A	0.99
C2—H2C	0.98	C26—H26B	0.99
O1—S1—O2	116.51 (8)	C16—C11—C12	111.27 (13)
O1—S1—N1	105.33 (9)	N11—C11—H11	108.2
O2—S1—N1	112.41 (7)	C16—C11—H11	108.2
O1—S1—C1	107.41 (9)	C12—C11—H11	108.2
O2—S1—C1	107.68 (7)	N12—C12—C11	110.13 (12)
N1—S1—C1	107.05 (7)	N12—C12—C13	114.99 (13)
O4—S2—O3	115.87 (6)	C11—C12—C13	108.73 (13)
O4—S2—N2	113.71 (7)	N12—C12—H12	107.6
O3—S2—N2	105.59 (7)	C11—C12—H12	107.6
O4—S2—C2	108.34 (7)	C13—C12—H12	107.6
O3—S2—C2	106.57 (7)	C14—C13—C12	111.44 (17)
N2—S2—C2	106.13 (6)	C14—C13—H13A	109.3
O6—S3—O5	115.71 (6)	C12—C13—H13A	109.3
O6—S3—N3	113.77 (6)	C14—C13—H13B	109.3
O5—S3—N3	108.59 (6)	C12—C13—H13B	109.3
O6—S3—C3	107.83 (7)	H13A—C13—H13B	108.0
O5—S3—C3	106.61 (7)	C13—C14—C15	110.35 (15)
N3—S3—C3	103.35 (7)	C13—C14—H14A	109.6
O7—S4—O8	115.38 (6)	C15—C14—H14A	109.6
O7—S4—N3	104.95 (6)	C13—C14—H14B	109.6
O8—S4—N3	113.14 (6)	C15—C14—H14B	109.6
O7—S4—C4	108.31 (7)	H14A—C14—H14B	108.1
O8—S4—C4	106.77 (7)	C16—C15—C14	112.38 (17)
N3—S4—C4	108.04 (7)	C16—C15—H15A	109.1
S1^i—N1—S1	119.73 (11)	C14—C15—H15A	109.1
S2^ii—N2—S2	120.04 (11)	C16—C15—H15B	109.1
S3—N3—S4	121.95 (7)	C14—C15—H15B	109.1
C11—N11—H1	113.9 (12)	H15A—C15—H15B	107.9
C11—N11—H2	109.1 (12)	C15—C16—C11	111.28 (14)
H1—N11—H2	109.2 (16)	C15—C16—H16A	109.4
C11—N11—H3	109.2 (11)	C11—C16—H16A	109.4
H1—N11—H3	103.6 (16)	C15—C16—H16B	109.4
H2—N11—H3	111.7 (15)	C11—C16—H16B	109.4
C12—N12—H4	102.3 (12)	H16A—C16—H16B	108.0
C12—N12—H5	106.2 (13)	N21—C21—C22	109.76 (11)
H4—N12—H5	108.3 (17)	N21—C21—C26	109.68 (12)
C21—N21—H6	110.5 (10)	C22—C21—C26	112.45 (12)
C21—N21—H7	110.8 (11)	N21—C21—H21	108.3
H6—N21—H7	107.4 (15)	C22—C21—H21	108.3
C21—N21—H8	112.9 (10)	C26—C21—H21	108.3
H6—N21—H8	110.0 (15)	N22—C22—C21	110.08 (12)
H7—N21—H8	104.9 (14)	N22—C22—C23	114.18 (12)
C22—N22—H9	108.2 (10)	C21—C22—C23	109.60 (12)
C22—N22—H10	108.6 (10)	N22—C22—H22	107.6
H9—N22—H10	104.2 (14)	C21—C22—H22	107.6
S1—C1—H1A	109.5	C23—C22—H22	107.6
S1—C1—H1B	109.5	C24—C23—C22	112.52 (14)
H1A—C1—H1B	109.5	C24—C23—H23A	109.1
S1—C1—H1C	109.5	C22—C23—H23A	109.1
H1A—C1—H1C	109.5	C24—C23—H23B	109.1
H1B—C1—H1C	109.5	C22—C23—H23B	109.1
S2—C2—H2A	109.5	H23A—C23—H23B	107.8
S2—C2—H2B	109.5	C25—C24—C23	110.64 (14)
H2A—C2—H2B	109.5	C25—C24—H24A	109.5
S2—C2—H2C	109.5	C23—C24—H24A	109.5
H2A—C2—H2C	109.5	C25—C24—H24B	109.5
H2B—C2—H2C	109.5	C23—C24—H24B	109.5
S3—C3—H3A	109.5	H24A—C24—H24B	108.1
S3—C3—H3B	109.5	C24—C25—C26	110.96 (14)
H3A—C3—H3B	109.5	C24—C25—H25A	109.4
S3—C3—H3C	109.5	C26—C25—H25A	109.4
H3A—C3—H3C	109.5	C24—C25—H25B	109.4
H3B—C3—H3C	109.5	C26—C25—H25B	109.4
S4—C4—H4A	109.5	H25A—C25—H25B	108.0
S4—C4—H4B	109.5	C21—C26—C25	111.79 (13)
H4A—C4—H4B	109.5	C21—C26—H26A	109.3
S4—C4—H4C	109.5	C25—C26—H26A	109.3
H4A—C4—H4C	109.5	C21—C26—H26B	109.3
H4B—C4—H4C	109.5	C25—C26—H26B	109.3
N11—C11—C16	110.56 (13)	H26A—C26—H26B	107.9
N11—C11—C12	110.17 (13)
O1—S1—N1—S1^i	167.01 (7)	C11—C12—C13—C14	−59.87 (18)
O2—S1—N1—S1^i	39.16 (5)	C12—C13—C14—C15	56.9 (2)
C1—S1—N1—S1^i	−78.87 (6)	C13—C14—C15—C16	−52.9 (2)
O4—S2—N2—S2^ii	−32.64 (5)	C14—C15—C16—C11	52.6 (2)
O3—S2—N2—S2^ii	−160.76 (5)	N11—C11—C16—C15	−178.65 (13)
C2—S2—N2—S2^ii	86.35 (6)	C12—C11—C16—C15	−55.88 (19)
O6—S3—N3—S4	−1.59 (11)	N21—C21—C22—N22	56.98 (16)
O5—S3—N3—S4	−132.00 (8)	C26—C21—C22—N22	179.37 (12)
C3—S3—N3—S4	115.05 (9)	N21—C21—C22—C23	−176.63 (12)
O7—S4—N3—S3	−176.18 (8)	C26—C21—C22—C23	−54.24 (17)
O8—S4—N3—S3	57.20 (10)	N22—C22—C23—C24	179.97 (14)
C4—S4—N3—S3	−60.78 (10)	C21—C22—C23—C24	55.95 (18)
N11—C11—C12—N12	−51.27 (17)	C22—C23—C24—C25	−57.1 (2)
C16—C11—C12—N12	−174.26 (14)	C23—C24—C25—C26	55.1 (2)
N11—C11—C12—C13	−178.10 (13)	N21—C21—C26—C25	176.73 (13)
C16—C11—C12—C13	58.91 (18)	C22—C21—C26—C25	54.29 (18)
N12—C12—C13—C14	176.14 (14)	C24—C25—C26—C21	−54.08 (19)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N11—H1···O6^i	0.85 (1)	2.52 (2)	2.9567 (16)	113 (1)
N11—H1···O8^i	0.85 (1)	2.04 (1)	2.8721 (16)	164 (2)
N11—H2···O1^iii	0.86 (1)	2.54 (1)	3.304 (2)	150 (2)
N11—H2···N1^iii	0.86 (1)	2.30 (1)	3.076 (2)	151 (2)
N11—H1···O6^i	0.85 (1)	2.52 (2)	2.9567 (16)	113 (1)
N11—H3···N12^i	0.89 (1)	2.01 (1)	2.900 (2)	171 (2)
N12—H4···O5	0.86 (1)	2.30 (2)	3.1585 (16)	173 (2)
N12—H5···O2	0.85 (1)	2.24 (2)	3.0656 (18)	166 (2)
N21—H6···O3^iii	0.90 (1)	2.11 (1)	2.9433 (17)	155 (2)
N21—H6···N2^iii	0.90 (1)	2.49 (2)	3.2499 (19)	142 (1)
N21—H7···O7^ii	0.89 (1)	2.22 (1)	3.0613 (16)	157 (1)
N21—H7···N3^ii	0.89 (1)	2.32 (1)	3.0453 (17)	138 (1)
N21—H8···N22^ii	0.92 (1)	1.99 (1)	2.8889 (19)	167 (1)
N22—H9···O5	0.94 (1)	2.24 (2)	3.1416 (16)	160 (2)
N22—H9···O99^iii	0.94 (1)	2.83 (2)	3.312 (6)	113 (1)
N22—H10···O4	0.97 (1)	2.34 (2)	3.2593 (18)	158 (1)
C1—H1C···O8^iv	0.98	2.63	3.5771 (19)	162
C1—H1C···O99	0.98	2.87	3.452 (7)	119
C2—H2B···O99	0.98	2.62	3.578 (6)	166
C3—H3C···O7^v	0.98	2.61	3.5373 (19)	159
C4—H4A···O4^vi	0.98	2.68	3.4874 (19)	140
C4—H4C···O7^v	0.98	2.83	3.6972 (19)	149
C11—H11···O6^i	1.00	2.71	3.2789 (17)	116
C12—H12···O1^iii	1.00	2.48	3.353 (2)	146
C13—H13A···O2	0.99	2.77	3.519 (2)	133
C14—H14B···O1^vii	0.99	2.81	3.706 (3)	151
C16—H16A···O1^iii	0.99	2.74	3.533 (2)	138
C21—H21···O4	1.00	2.62	3.4812 (18)	144
C22—H22···O3^iii	1.00	2.74	3.5025 (18)	134
C22—H22···O99^iii	1.00	2.70	3.328 (6)	121
C25—H25A···O8^viii	0.99	2.69	3.549 (2)	145
C26—H26A···O3^iii	0.99	2.58	3.377 (2)	137

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

(II) rac-trans-2-aminocyclohexan-1-aminium di(methanesulfonyl)amide

Crystal data

C6H15N2^+·C2H6NO4S2^−	F(000) = 616
Mr = 287.40	Dx = 1.478 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 23572 reflections
a = 9.7958 (3) Å	θ = 2.2–30.7°
b = 8.5522 (2) Å	µ = 0.42 mm^−1
c = 16.0779 (4) Å	T = 90 K
β = 106.455 (3)°	Block, colourless
V = 1291.77 (6) Å^3	0.25 × 0.20 × 0.18 mm
Z = 4

Data collection

Oxford Diffraction Xcalibur E diffractometer	3110 reflections with I > 2σ(I)
Radiation source: Enhance (Mo) X-ray Source	Rint = 0.024
Graphite monochromator	θmax = 29.6°, θmin = 2.2°
Detector resolution: 16.1419 pixels mm^-1	h = −13→13
ω scans	k = −11→11
39527 measured reflections	l = −22→22
3620 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)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.075	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ^2(Fo^2) + (0.0431P)^2 + 0.333P] where P = (Fo^2 + 2Fc^2)/3
3620 reflections	(Δ/σ)max = 0.001
176 parameters	Δρmax = 0.55 e Å^−3
0 restraints	Δρmin = −0.32 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	0.94179 (3)	0.25490 (3)	0.662708 (17)	0.01016 (7)
S2	0.79270 (3)	0.50117 (3)	0.563105 (18)	0.01104 (7)
O1	0.97415 (10)	0.09624 (10)	0.64455 (6)	0.01810 (19)
O2	0.86120 (9)	0.27277 (10)	0.72527 (5)	0.01329 (17)
O3	0.74098 (10)	0.53444 (11)	0.47114 (5)	0.01768 (19)
O4	0.88515 (10)	0.61792 (10)	0.61586 (6)	0.01702 (18)
N1	0.86231 (11)	0.33160 (11)	0.57055 (6)	0.01201 (19)
N11	0.88098 (10)	1.17174 (12)	0.41090 (7)	0.01084 (18)
H1	0.8780 (18)	1.2373 (19)	0.4510 (11)	0.021 (4)*
H2	0.9442 (18)	1.105 (2)	0.4342 (11)	0.023 (4)*
H3	0.9102 (18)	1.2202 (19)	0.3699 (11)	0.023 (4)*
N12	0.81235 (11)	0.89855 (12)	0.48862 (7)	0.0145 (2)
H4	0.795 (2)	0.807 (2)	0.4644 (12)	0.035 (5)*
H5	0.812 (2)	0.890 (2)	0.5422 (14)	0.041 (5)*
C1	1.10380 (12)	0.35498 (15)	0.70491 (8)	0.0166 (2)
H1A	1.1602	0.3019	0.7575	0.025*
H1B	1.0844	0.4626	0.7191	0.025*
H1C	1.1570	0.3561	0.6616	0.025*
C2	0.64265 (14)	0.48884 (16)	0.60308 (9)	0.0203 (3)
H2A	0.5946	0.5905	0.5967	0.030*
H2B	0.6733	0.4595	0.6645	0.030*
H2C	0.5768	0.4097	0.5702	0.030*
C11	0.74053 (12)	1.09327 (13)	0.37289 (7)	0.0122 (2)
H11	0.7507	1.0161	0.3283	0.015*
C12	0.69803 (12)	1.00569 (13)	0.44463 (7)	0.0124 (2)
H12	0.6854	1.0841	0.4880	0.015*
C13	0.55421 (12)	0.92553 (14)	0.40473 (8)	0.0144 (2)
H13A	0.5657	0.8453	0.3628	0.017*
H13B	0.5242	0.8717	0.4512	0.017*
C14	0.43783 (13)	1.04004 (15)	0.35842 (8)	0.0172 (2)
H14A	0.4170	1.1124	0.4013	0.021*
H14B	0.3497	0.9816	0.3302	0.021*
C15	0.48417 (13)	1.13384 (16)	0.29020 (8)	0.0182 (2)
H15A	0.4113	1.2140	0.2650	0.022*
H15B	0.4913	1.0631	0.2429	0.022*
C16	0.62832 (12)	1.21408 (14)	0.32923 (8)	0.0140 (2)
H16A	0.6582	1.2684	0.2829	0.017*
H16B	0.6192	1.2931	0.3723	0.017*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.01062 (13)	0.01063 (13)	0.00969 (13)	0.00139 (9)	0.00364 (9)	−0.00029 (9)
S2	0.01209 (13)	0.01053 (13)	0.01018 (13)	−0.00027 (10)	0.00265 (10)	0.00109 (9)
O1	0.0239 (5)	0.0120 (4)	0.0187 (4)	0.0057 (3)	0.0065 (4)	−0.0011 (3)
O2	0.0132 (4)	0.0167 (4)	0.0114 (4)	0.0016 (3)	0.0058 (3)	0.0013 (3)
O3	0.0227 (5)	0.0170 (4)	0.0112 (4)	−0.0005 (3)	0.0014 (3)	0.0037 (3)
O4	0.0202 (4)	0.0118 (4)	0.0163 (4)	−0.0024 (3)	0.0008 (3)	−0.0007 (3)
N1	0.0153 (5)	0.0112 (4)	0.0095 (4)	0.0018 (4)	0.0035 (4)	0.0004 (3)
N11	0.0089 (4)	0.0123 (4)	0.0116 (4)	0.0004 (4)	0.0035 (3)	0.0013 (4)
N12	0.0142 (5)	0.0134 (5)	0.0151 (5)	0.0008 (4)	0.0028 (4)	0.0031 (4)
C1	0.0110 (5)	0.0216 (6)	0.0165 (6)	−0.0004 (5)	0.0027 (4)	0.0007 (5)
C2	0.0151 (6)	0.0243 (6)	0.0236 (6)	0.0056 (5)	0.0089 (5)	0.0063 (5)
C11	0.0103 (5)	0.0131 (5)	0.0132 (5)	−0.0010 (4)	0.0034 (4)	0.0005 (4)
C12	0.0125 (5)	0.0134 (5)	0.0121 (5)	−0.0006 (4)	0.0047 (4)	0.0006 (4)
C13	0.0125 (5)	0.0141 (5)	0.0164 (5)	−0.0031 (4)	0.0039 (4)	0.0001 (4)
C14	0.0128 (5)	0.0217 (6)	0.0169 (6)	−0.0021 (5)	0.0040 (4)	0.0006 (5)
C15	0.0121 (5)	0.0255 (6)	0.0163 (6)	−0.0001 (5)	0.0030 (4)	0.0032 (5)
C16	0.0104 (5)	0.0165 (5)	0.0150 (5)	0.0009 (4)	0.0036 (4)	0.0043 (4)

Geometric parameters (Å, º)

S1—O1	1.4419 (9)	C2—H2B	0.9800
S1—O2	1.4520 (8)	C2—H2C	0.9800
S1—N1	1.6058 (10)	C11—C16	1.5269 (16)
S1—C1	1.7611 (12)	C11—C12	1.5287 (16)
S2—O3	1.4489 (9)	C11—H11	1.0000
S2—O4	1.4496 (9)	C12—C13	1.5344 (16)
S2—N1	1.5925 (10)	C12—H12	1.0000
S2—C2	1.7664 (13)	C13—C14	1.5271 (17)
N11—C11	1.4967 (15)	C13—H13A	0.9900
N11—H1	0.862 (17)	C13—H13B	0.9900
N11—H2	0.848 (18)	C14—C15	1.5279 (17)
N11—H3	0.892 (18)	C14—H14A	0.9900
N12—C12	1.4646 (15)	C14—H14B	0.9900
N12—H4	0.87 (2)	C15—C16	1.5351 (17)
N12—H5	0.87 (2)	C15—H15A	0.9900
C1—H1A	0.9800	C15—H15B	0.9900
C1—H1B	0.9800	C16—H16A	0.9900
C1—H1C	0.9800	C16—H16B	0.9900
C2—H2A	0.9800
O1—S1—O2	115.67 (5)	N11—C11—C12	109.08 (9)
O1—S1—N1	105.93 (5)	C16—C11—C12	111.35 (9)
O2—S1—N1	112.31 (5)	N11—C11—H11	108.8
O1—S1—C1	108.03 (6)	C16—C11—H11	108.8
O2—S1—C1	106.82 (6)	C12—C11—H11	108.8
N1—S1—C1	107.79 (6)	N12—C12—C11	109.66 (9)
O3—S2—O4	116.21 (5)	N12—C12—C13	114.10 (9)
O3—S2—N1	105.90 (5)	C11—C12—C13	108.51 (9)
O4—S2—N1	113.58 (5)	N12—C12—H12	108.1
O3—S2—C2	107.25 (6)	C11—C12—H12	108.1
O4—S2—C2	105.94 (6)	C13—C12—H12	108.1
N1—S2—C2	107.52 (6)	C14—C13—C12	112.80 (10)
S2—N1—S1	121.78 (6)	C14—C13—H13A	109.0
C11—N11—H1	112.0 (11)	C12—C13—H13A	109.0
C11—N11—H2	110.5 (11)	C14—C13—H13B	109.0
H1—N11—H2	106.5 (15)	C12—C13—H13B	109.0
C11—N11—H3	110.9 (11)	H13A—C13—H13B	107.8
H1—N11—H3	109.8 (15)	C13—C14—C15	110.74 (10)
H2—N11—H3	107.0 (15)	C13—C14—H14A	109.5
C12—N12—H4	108.7 (13)	C15—C14—H14A	109.5
C12—N12—H5	108.2 (13)	C13—C14—H14B	109.5
H4—N12—H5	108.4 (18)	C15—C14—H14B	109.5
S1—C1—H1A	109.5	H14A—C14—H14B	108.1
S1—C1—H1B	109.5	C14—C15—C16	111.54 (10)
H1A—C1—H1B	109.5	C14—C15—H15A	109.3
S1—C1—H1C	109.5	C16—C15—H15A	109.3
H1A—C1—H1C	109.5	C14—C15—H15B	109.3
H1B—C1—H1C	109.5	C16—C15—H15B	109.3
S2—C2—H2A	109.5	H15A—C15—H15B	108.0
S2—C2—H2B	109.5	C11—C16—C15	110.15 (10)
H2A—C2—H2B	109.5	C11—C16—H16A	109.6
S2—C2—H2C	109.5	C15—C16—H16A	109.6
H2A—C2—H2C	109.5	C11—C16—H16B	109.6
H2B—C2—H2C	109.5	C15—C16—H16B	109.6
N11—C11—C16	110.06 (9)	H16A—C16—H16B	108.1
O3—S2—N1—S1	176.00 (7)	C16—C11—C12—C13	58.49 (12)
O4—S2—N1—S1	47.29 (9)	N12—C12—C13—C14	−179.28 (10)
C2—S2—N1—S1	−69.58 (9)	C11—C12—C13—C14	−56.71 (12)
O1—S1—N1—S2	172.88 (7)	C12—C13—C14—C15	54.88 (13)
O2—S1—N1—S2	45.72 (9)	C13—C14—C15—C16	−53.63 (14)
C1—S1—N1—S2	−71.67 (8)	N11—C11—C16—C15	180.00 (9)
N11—C11—C12—N12	−54.62 (12)	C12—C11—C16—C15	−58.90 (13)
C16—C11—C12—N12	−176.28 (9)	C14—C15—C16—C11	55.85 (13)
N11—C11—C12—C13	−179.84 (9)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N11—H1···N1^i	0.862 (17)	2.129 (18)	2.9593 (14)	161.6 (15)
N11—H2···O1^ii	0.848 (18)	2.403 (17)	2.9627 (13)	124.0 (14)
N11—H2···N12^iii	0.848 (18)	2.356 (17)	3.0408 (14)	138.1 (14)
N11—H3···O2^iv	0.892 (18)	2.237 (17)	2.9735 (13)	139.6 (14)
N11—H3···O4^iii	0.892 (18)	2.393 (17)	3.0377 (13)	129.3 (14)
N12—H4···O3	0.87 (2)	2.40 (2)	3.1864 (14)	150.5 (16)
N12—H5···O1^i	0.87 (2)	2.62 (2)	3.0667 (14)	113.1 (16)
N12—H5···O4	0.87 (2)	2.62 (2)	3.1029 (13)	116.5 (16)
C16—H16A···O2^iv	0.99	2.45	3.1891 (14)	132

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

 

Footnotes

†For part CXC, see Zerbe et al. (2011).