Solid-state architecture of saccharin salts of some diamines

Hydrazinium saccharinate, N₂H₅⁺·C₇H₄NO₃S^-, crystallizes in a 1:1 ratio, while ethyl­ene­diaminium bis­(saccharinate), C₂H₁₀N₂²⁺·2C₇H₄NO₃S^-, and butane-1,4-diaminium bis­(sac­charin­ate), C₄H₁₄N₂²⁺·2C₇H₄NO₃S^-, form in a 1:2 cation-anion stoichiometry. The structures contain many strong hydrogen bonds of the N⁺-H...N^-, N⁺-H...O, N-H...O and N-H...N types, with auxiliary C-H...O inter­actions.

S1. Comment

Saccharin is a moderately strong acid and its salts have been used as sweeteners for around 125 years (Fahlberg & List, 1887). In recent years, there has been increased interest in the reactivity and structural properties of metal saccharinates because of the potential use of saccharin as an antidote for metal poisoning in the human body (Yilmaz et al., 2004 or ??? 2005). The corresponding deprotonated saccharinate anion (sac⁻) acts as a polyfunctional ligand owing to the presence of the imine N, carbonyl O and sulfonyl O atoms. We have recently reported the use of saccharin as a salt former in active pharmaceutical ingredient (API) formulation and development (Banerjee et al., 2005; Bhatt et al., 2005). In this paper, we describe the solid-state architecture of three different amine salts of saccharin, namely hydrazine saccharinate, (I), ethylenediaminium bis(saccharinate), (II), and butane-1,4-diaminium bis(saccharinate), (III). The amine and saccharin fragments are rich in hydrogen-bond donor and acceptor functionalities. Therefore, it is no surprise that the crystal structures contain many strong hydrogen bonds. Typically, one finds, N⁺—H···N⁻, N⁺—H···O, N—H···O and N—H···N bonds, with auxiliary C–H···O interactions in some cases.

Compound (I) crystallizes from methanol in the centrosymmetric space group P1 with three hydrazinium cations and three saccharinate anions in the asymmetric unit. This structure contains four different types of hydrogen bonds. The molecular geometry and atom numbering of (I) are given in Fig. 1. In this structure the symmetry independent hydrazinium cations are connected to each other via N⁺—H···N hydrogen bonds and form a zigzag array that propagates along the a axis. The saccharinate anions are connected with this zigzag chain via various N⁺—H···O, N—H···O, N—H···N and N⁺—H···N interactions, giving rise to a complex hydrogen bonding network (Fig. 2).

Compound (II) likewise crystallizes in the centrosymmetric space group P1. However, in this case the asymmetric unit contains one ethylenediaminium cation and two saccharinate anions (Fig. 3). The ethylenediamine molecule adopts the gauche conformation, with a dihedral angle between the two best planes of 78°. In general, the ethylenediamine molecule adopts the more stable staggered conformation. Among 24 examples in the Cambridge Structural Database (Version 5.27 of November 2005; Allen, 2002), the less stable gauche conformation is seen only in seven cases. The crystal structure of the salt is characterized by an eight-membered supramolecular synthon consisting of N⁺—H···N⁻ hydrogen bonds, which propagates along the a axis via N⁺—H···O═C hydrogen bonds (Fig. 4). These hydrogen-bonded layers are connected to each other via C–H···O═S hydrogen bonds. Because there are many more hydrogen-bond acceptors than donors in the system, one C═O acceptor of one of the symmetry-independent saccharinate anions remains unsatisfied in terms of hydrogen-bond formation.

Compound (III) crystallizes in the centrosymmetric space group P2₁/n. Unlike the ethylenediamine molecule, the butane-1,4-diaminium cation occupies a special position in the unit cell and the asymmetric unit contains one-half of a butane-1,4-diaminium cation and one saccharinate anion (Fig. 5). The saccharinate ions form a layered structure, which is characterized by a very stable four-point synthon formed via N⁺—H···O═S hydrogen bonds. These synthons are connected to each other via another set of N⁺—H···O═S hydrogen bonds and the pattern propagates along the ab plane (Fig. 6). In the crystal structure, the hydrophobic and hydrophilic regions remain separated.

Each of these salts possess a different crystal packing although the major intermolecular interactions are similar. The structures described in this paper show that even the smallest structural modification to a molecular component can lead to a completely different crystal structure. A major aim of crystal engineering is to understand the relationship between molecular structure and crystal structure and to control molecular packing through non-covalent interactions. However, our inability to guide the assembly of many molecules into pre-desired solid-state architectures reflects the delicate nature of the intermolecular interactions that affect molecular assembly. In this sense, prediction of organic crystal structures (Sarma & Desiraju 2002; Dey et al., 2005) remains a major scientific challenge.

S2. Experimental

Saccharin (100 mg) was dissolved in EtOAc (20 ml) and to the solution were added a few drops of the respective amines until the salt precipitated out. This was filtered off, and the residue was dissolved in methanol by warming in a water bath for ten minutes and then filtered. The filtrate was allowed to cool to room temperature. X-ray quality single crystals were obtained after two days.

S3. Refinement

H atoms on C atoms were refined using a riding model starting from idealized geometries [C—H = 0.93 and 0.99 Å, for aromatic and methylene H atoms, respectively, with U_iso(H) =1.2U_eq(H). The positions of all H atoms on N atoms were taken from a difference Fourier map and refined isotropically.

Computing details

For all compounds, data collection: SMART (Bruker, 1997); cell refinement: SMART; data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. A view of the molecular structure of (I), with the atom-numbering scheme. Displacement ellipsoids for non-H atoms are drawn at the 50% probability level.
	Fig. 2. The packing of (I). Note the zigzag chain of hydrazinium cations and the orientations of the saccarinate anions along this helical chain.
	Fig. 3. A view of the molecular structure of (II), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 4. The packing of (II). Note the N^+—H···N^− tetramer synthon.
	Fig. 5. A view of the molecular structure of (III), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 6. The packing of the (III). Note the symmetrical N^+—H···O═ S tetramer synthon. These synthons are connected to each other via another set of N^+—H···O═S interactions.

(I) hydrazinium saccharinate

Crystal data

H5N2^+·C7H4NO3S^−	Z = 6
Mr = 215.23	F(000) = 672
Triclinic, P1	Dx = 1.578 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.8647 (18) Å	Cell parameters from 1508 reflections
b = 11.776 (3) Å	θ = 2.7–23.9°
c = 15.904 (4) Å	µ = 0.34 mm^−1
α = 70.095 (3)°	T = 100 K
β = 87.137 (4)°	Plate, colorless
γ = 78.855 (4)°	0.34 × 0.29 × 0.28 mm
V = 1358.7 (6) Å^3

Data collection

Bruker SMART CCD area-detector diffractometer	4779 independent reflections
Radiation source: fine-focus sealed tube	3386 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.052
ϕ and ω scans	θmax = 25.0°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Siemens, 1996)	h = −9→9
Tmin = 0.888, Tmax = 0.910	k = −13→13
10154 measured reflections	l = −18→18

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.118	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0524P)^2] where P = (Fo^2 + 2Fc^2)/3
4779 reflections	(Δ/σ)max < 0.001
439 parameters	Δρmax = 0.40 e Å^−3
1 restraint	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	0.43721 (11)	0.51577 (7)	0.37136 (6)	0.0141 (2)
O1	0.5183 (3)	0.1926 (2)	0.38993 (15)	0.0171 (6)
O2	0.2960 (3)	0.5642 (2)	0.41817 (15)	0.0167 (6)
O3	0.5790 (3)	0.5812 (2)	0.35422 (16)	0.0178 (6)
N1	0.5010 (4)	0.3699 (2)	0.42089 (19)	0.0161 (7)
C1	0.4787 (4)	0.3064 (3)	0.3674 (2)	0.0149 (8)
C2	0.3953 (4)	0.3856 (3)	0.2788 (2)	0.0138 (8)
C3	0.3476 (4)	0.3507 (3)	0.2105 (2)	0.0184 (8)
H3	0.3728	0.2669	0.2141	0.022*
C4	0.2616 (5)	0.4410 (3)	0.1360 (2)	0.0202 (8)
H4	0.2271	0.4183	0.0885	0.024*
C5	0.2251 (5)	0.5641 (3)	0.1300 (2)	0.0193 (8)
H5	0.1652	0.6242	0.0788	0.023*
C6	0.2757 (4)	0.5994 (3)	0.1984 (2)	0.0167 (8)
H6	0.2523	0.6830	0.1951	0.020*
C7	0.3616 (4)	0.5079 (3)	0.2714 (2)	0.0140 (8)
S2	1.01651 (11)	0.15255 (7)	0.33852 (6)	0.0162 (2)
O4	0.9872 (3)	0.4238 (2)	0.40252 (16)	0.0208 (6)
O5	1.1805 (3)	0.1060 (2)	0.30606 (16)	0.0205 (6)
O6	0.9140 (3)	0.0580 (2)	0.37705 (17)	0.0236 (6)
N2	1.0392 (4)	0.2241 (2)	0.40554 (19)	0.0192 (7)
C8	0.9780 (4)	0.3469 (3)	0.3665 (2)	0.0164 (8)
C9	0.8977 (4)	0.3809 (3)	0.2766 (2)	0.0137 (8)
C10	0.8223 (4)	0.4959 (3)	0.2191 (2)	0.0168 (8)
H10	0.8170	0.5674	0.2349	0.020*
C11	0.7549 (5)	0.5037 (3)	0.1380 (2)	0.0212 (9)
H11	0.7043	0.5819	0.0974	0.025*
C12	0.7600 (5)	0.3997 (3)	0.1152 (2)	0.0216 (9)
H12	0.7099	0.4075	0.0599	0.026*
C13	0.8364 (5)	0.2847 (3)	0.1712 (2)	0.0220 (9)
H13	0.8428	0.2134	0.1551	0.026*
C14	0.9030 (4)	0.2782 (3)	0.2518 (2)	0.0155 (8)
S3	0.82108 (11)	0.91636 (8)	0.15239 (6)	0.0156 (2)
O7	0.3872 (3)	0.8515 (2)	0.21589 (16)	0.0184 (6)
O8	0.9742 (3)	0.8300 (2)	0.19372 (16)	0.0223 (6)
O9	0.8415 (3)	1.0427 (2)	0.11867 (16)	0.0211 (6)
N3	0.6570 (4)	0.8982 (2)	0.21801 (18)	0.0151 (7)
C15	0.5282 (5)	0.8675 (3)	0.1812 (2)	0.0148 (8)
C16	0.5749 (4)	0.8540 (3)	0.0920 (2)	0.0132 (8)
C17	0.4753 (5)	0.8281 (3)	0.0343 (2)	0.0163 (8)
H17	0.3610	0.8142	0.0495	0.020*
C18	0.5460 (5)	0.8229 (3)	−0.0464 (2)	0.0179 (8)
H18	0.4795	0.8040	−0.0864	0.021*
C19	0.7121 (5)	0.8449 (3)	−0.0697 (2)	0.0211 (9)
H19	0.7574	0.8413	−0.1254	0.025*
C20	0.8126 (4)	0.8722 (3)	−0.0126 (2)	0.0155 (8)
H20	0.9265	0.8872	−0.0278	0.019*
C21	0.7397 (4)	0.8765 (3)	0.0674 (2)	0.0127 (8)
N4	0.2596 (4)	0.8238 (3)	0.4320 (2)	0.0178 (7)
H4A	0.306 (4)	0.7463 (19)	0.455 (2)	0.027 (11)*
H4B	0.183 (4)	0.836 (4)	0.472 (2)	0.040 (13)*
N5	0.1543 (4)	0.8380 (3)	0.3556 (2)	0.0149 (7)
H5A	0.086 (4)	0.911 (2)	0.343 (2)	0.017 (10)*
H5B	0.085 (4)	0.783 (3)	0.365 (2)	0.023 (11)*
H5C	0.223 (4)	0.839 (3)	0.3088 (17)	0.020 (10)*
N6	0.8035 (4)	0.6511 (3)	0.4494 (2)	0.0166 (7)
H6A	0.738 (4)	0.721 (2)	0.452 (2)	0.031 (11)*
H6B	0.732 (4)	0.606 (3)	0.442 (3)	0.046 (14)*
H6C	0.872 (4)	0.620 (3)	0.4985 (17)	0.024 (11)*
N7	0.9106 (4)	0.6846 (3)	0.3721 (2)	0.0168 (7)
H7A	0.838 (4)	0.723 (3)	0.3252 (19)	0.032 (12)*
H7B	0.946 (4)	0.619 (2)	0.358 (2)	0.027 (11)*
N8	0.5255 (4)	0.9718 (3)	0.3678 (2)	0.0156 (7)
H8A	0.514 (5)	1.049 (2)	0.366 (3)	0.035 (12)*
H8B	0.431 (3)	0.939 (3)	0.383 (2)	0.014 (10)*
H8C	0.557 (5)	0.962 (3)	0.3149 (16)	0.031 (12)*
N9	0.6507 (4)	0.8980 (3)	0.4386 (2)	0.0181 (7)
H9A	0.723 (4)	0.946 (3)	0.439 (2)	0.025 (11)*
H9B	0.604 (5)	0.891 (4)	0.4906 (17)	0.039 (14)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0158 (5)	0.0123 (4)	0.0148 (5)	−0.0031 (4)	0.0001 (4)	−0.0050 (4)
O1	0.0202 (14)	0.0110 (13)	0.0189 (14)	−0.0012 (10)	0.0022 (11)	−0.0047 (11)
O2	0.0187 (13)	0.0147 (12)	0.0185 (14)	−0.0030 (10)	0.0048 (11)	−0.0086 (11)
O3	0.0163 (13)	0.0188 (13)	0.0202 (14)	−0.0085 (11)	0.0010 (11)	−0.0061 (11)
N1	0.0176 (16)	0.0135 (15)	0.0165 (17)	−0.0029 (13)	0.0015 (13)	−0.0046 (13)
C1	0.0124 (19)	0.0159 (19)	0.018 (2)	−0.0041 (15)	0.0065 (16)	−0.0073 (16)
C2	0.0123 (18)	0.0146 (18)	0.017 (2)	−0.0072 (15)	0.0056 (15)	−0.0062 (15)
C3	0.018 (2)	0.0164 (19)	0.023 (2)	−0.0072 (16)	0.0013 (17)	−0.0080 (17)
C4	0.027 (2)	0.023 (2)	0.015 (2)	−0.0118 (17)	0.0030 (17)	−0.0093 (17)
C5	0.020 (2)	0.023 (2)	0.013 (2)	−0.0033 (16)	−0.0025 (16)	−0.0026 (16)
C6	0.0133 (19)	0.0140 (18)	0.022 (2)	−0.0017 (15)	0.0019 (16)	−0.0056 (16)
C7	0.0095 (18)	0.0185 (19)	0.016 (2)	−0.0068 (15)	0.0044 (15)	−0.0063 (16)
S2	0.0161 (5)	0.0114 (5)	0.0198 (5)	−0.0017 (4)	0.0005 (4)	−0.0040 (4)
O4	0.0275 (15)	0.0163 (13)	0.0210 (15)	−0.0019 (11)	−0.0048 (12)	−0.0099 (12)
O5	0.0167 (14)	0.0161 (13)	0.0255 (15)	0.0012 (11)	0.0030 (12)	−0.0058 (11)
O6	0.0226 (15)	0.0144 (13)	0.0314 (16)	−0.0065 (11)	0.0047 (12)	−0.0037 (12)
N2	0.0212 (17)	0.0138 (16)	0.0186 (17)	−0.0004 (13)	−0.0028 (14)	−0.0015 (13)
C8	0.0129 (19)	0.0190 (19)	0.018 (2)	−0.0050 (15)	0.0054 (16)	−0.0063 (16)
C9	0.0115 (18)	0.0149 (18)	0.015 (2)	−0.0031 (15)	0.0020 (15)	−0.0051 (15)
C10	0.0168 (19)	0.0123 (18)	0.020 (2)	−0.0006 (15)	0.0032 (16)	−0.0053 (16)
C11	0.023 (2)	0.0169 (19)	0.015 (2)	0.0032 (16)	0.0007 (17)	0.0018 (16)
C12	0.023 (2)	0.025 (2)	0.015 (2)	0.0010 (17)	−0.0027 (17)	−0.0071 (17)
C13	0.022 (2)	0.022 (2)	0.027 (2)	−0.0046 (17)	0.0000 (18)	−0.0151 (18)
C14	0.0101 (18)	0.0155 (18)	0.020 (2)	−0.0027 (15)	0.0002 (16)	−0.0047 (16)
S3	0.0146 (5)	0.0178 (5)	0.0152 (5)	−0.0035 (4)	0.0015 (4)	−0.0065 (4)
O7	0.0135 (14)	0.0213 (14)	0.0201 (14)	−0.0052 (11)	0.0055 (11)	−0.0062 (11)
O8	0.0158 (14)	0.0278 (15)	0.0211 (14)	−0.0007 (11)	0.0006 (11)	−0.0071 (12)
O9	0.0209 (14)	0.0191 (14)	0.0260 (15)	−0.0087 (11)	0.0053 (12)	−0.0088 (12)
N3	0.0141 (16)	0.0189 (16)	0.0136 (16)	−0.0035 (13)	0.0037 (13)	−0.0076 (13)
C15	0.018 (2)	0.0064 (17)	0.016 (2)	0.0003 (15)	0.0024 (16)	−0.0010 (15)
C16	0.0173 (19)	0.0053 (16)	0.0144 (19)	0.0004 (14)	0.0025 (15)	−0.0017 (14)
C17	0.0170 (19)	0.0113 (18)	0.019 (2)	−0.0032 (15)	−0.0008 (16)	−0.0032 (16)
C18	0.025 (2)	0.0136 (18)	0.015 (2)	−0.0013 (16)	−0.0036 (17)	−0.0049 (16)
C19	0.025 (2)	0.022 (2)	0.017 (2)	−0.0015 (17)	0.0054 (17)	−0.0088 (17)
C20	0.0146 (19)	0.0140 (18)	0.017 (2)	−0.0021 (15)	0.0041 (16)	−0.0052 (16)
C21	0.0166 (19)	0.0108 (17)	0.0112 (19)	−0.0056 (14)	0.0011 (15)	−0.0028 (15)
N4	0.0210 (18)	0.0148 (17)	0.0146 (18)	−0.0003 (14)	−0.0007 (15)	−0.0027 (14)
N5	0.0142 (17)	0.0143 (17)	0.0162 (18)	−0.0040 (14)	0.0027 (14)	−0.0047 (14)
N6	0.0161 (18)	0.0188 (18)	0.0136 (18)	−0.0032 (15)	0.0009 (14)	−0.0041 (15)
N7	0.0182 (18)	0.0155 (17)	0.0159 (18)	−0.0037 (14)	0.0057 (14)	−0.0049 (14)
N8	0.0167 (18)	0.0127 (17)	0.0179 (19)	−0.0020 (14)	0.0005 (15)	−0.0060 (14)
N9	0.0196 (18)	0.0174 (17)	0.0182 (19)	−0.0056 (14)	−0.0003 (15)	−0.0058 (15)

Geometric parameters (Å, º)

S1—O3	1.439 (2)	S3—O8	1.437 (2)
S1—O2	1.441 (2)	S3—N3	1.619 (3)
S1—N1	1.615 (3)	S3—C21	1.758 (3)
S1—C7	1.762 (3)	O7—C15	1.232 (4)
O1—C1	1.243 (4)	N3—C15	1.358 (4)
N1—C1	1.347 (4)	C15—C16	1.501 (5)
C1—C2	1.499 (5)	C16—C17	1.379 (4)
C2—C3	1.376 (5)	C16—C21	1.384 (5)
C2—C7	1.377 (4)	C17—C18	1.390 (5)
C3—C4	1.391 (5)	C17—H17	0.9500
C3—H3	0.9500	C18—C19	1.388 (5)
C4—C5	1.393 (5)	C18—H18	0.9500
C4—H4	0.9500	C19—C20	1.385 (5)
C5—C6	1.388 (5)	C19—H19	0.9500
C5—H5	0.9500	C20—C21	1.382 (5)
C6—C7	1.383 (5)	C20—H20	0.9500
C6—H6	0.9500	N4—N5	1.449 (4)
S2—O5	1.444 (2)	N4—H4A	0.870 (18)
S2—O6	1.448 (2)	N4—H4B	0.88 (4)
S2—N2	1.602 (3)	N5—H5A	0.886 (18)
S2—C14	1.764 (3)	N5—H5B	0.894 (18)
O4—C8	1.239 (4)	N5—H5C	0.894 (18)
N2—C8	1.364 (4)	N6—N7	1.440 (4)
C8—C9	1.486 (5)	N6—H6A	0.892 (18)
C9—C10	1.386 (4)	N6—H6B	0.878 (19)
C9—C14	1.388 (4)	N6—H6C	0.897 (18)
C10—C11	1.386 (5)	N7—H7A	0.894 (18)
C10—H10	0.9500	N7—H7B	0.870 (18)
C11—C12	1.385 (5)	N8—N9	1.451 (4)
C11—H11	0.9500	N8—H8A	0.888 (18)
C12—C13	1.380 (5)	N8—H8B	0.887 (18)
C12—H12	0.9500	N8—H8C	0.903 (18)
C13—C14	1.381 (5)	N9—H9A	0.882 (18)
C13—H13	0.9500	N9—H9B	0.871 (19)
S3—O9	1.437 (2)
O3—S1—O2	114.07 (14)	O9—S3—O8	114.76 (14)
O3—S1—N1	112.04 (15)	O9—S3—N3	111.49 (14)
O2—S1—N1	111.00 (14)	O8—S3—N3	111.03 (15)
O3—S1—C7	110.76 (15)	O9—S3—C21	110.05 (15)
O2—S1—C7	110.47 (15)	O8—S3—C21	110.99 (15)
N1—S1—C7	97.28 (15)	N3—S3—C21	97.18 (15)
C1—N1—S1	111.0 (2)	C15—N3—S3	111.5 (2)
O1—C1—N1	123.5 (3)	O7—C15—N3	124.9 (3)
O1—C1—C2	122.8 (3)	O7—C15—C16	122.3 (3)
N1—C1—C2	113.6 (3)	N3—C15—C16	112.8 (3)
C3—C2—C7	120.0 (3)	C17—C16—C21	119.5 (3)
C3—C2—C1	128.8 (3)	C17—C16—C15	128.9 (3)
C7—C2—C1	111.1 (3)	C21—C16—C15	111.5 (3)
C2—C3—C4	118.4 (3)	C16—C17—C18	118.5 (3)
C2—C3—H3	120.8	C16—C17—H17	120.7
C4—C3—H3	120.8	C18—C17—H17	120.7
C3—C4—C5	121.1 (3)	C19—C18—C17	121.1 (3)
C3—C4—H4	119.4	C19—C18—H18	119.4
C5—C4—H4	119.4	C17—C18—H18	119.4
C6—C5—C4	120.4 (3)	C20—C19—C18	120.8 (3)
C6—C5—H5	119.8	C20—C19—H19	119.6
C4—C5—H5	119.8	C18—C19—H19	119.6
C7—C6—C5	117.3 (3)	C21—C20—C19	117.0 (3)
C7—C6—H6	121.3	C21—C20—H20	121.5
C5—C6—H6	121.3	C19—C20—H20	121.5
C2—C7—C6	122.7 (3)	C20—C21—C16	123.0 (3)
C2—C7—S1	106.8 (2)	C20—C21—S3	130.0 (3)
C6—C7—S1	130.4 (3)	C16—C21—S3	107.0 (2)
O5—S2—O6	112.37 (14)	N5—N4—H4A	107 (2)
O5—S2—N2	112.20 (15)	N5—N4—H4B	104 (3)
O6—S2—N2	111.86 (16)	H4A—N4—H4B	104 (3)
O5—S2—C14	109.65 (15)	N4—N5—H5A	106 (2)
O6—S2—C14	111.87 (15)	N4—N5—H5B	115 (2)
N2—S2—C14	98.06 (15)	H5A—N5—H5B	106 (3)
C8—N2—S2	110.3 (2)	N4—N5—H5C	109 (2)
O4—C8—N2	123.4 (3)	H5A—N5—H5C	108 (3)
O4—C8—C9	122.6 (3)	H5B—N5—H5C	112 (3)
N2—C8—C9	113.9 (3)	N7—N6—H6A	107 (2)
C10—C9—C14	119.5 (3)	N7—N6—H6B	110 (3)
C10—C9—C8	129.1 (3)	H6A—N6—H6B	107 (4)
C14—C9—C8	111.3 (3)	N7—N6—H6C	109 (2)
C9—C10—C11	118.2 (3)	H6A—N6—H6C	107 (3)
C9—C10—H10	120.9	H6B—N6—H6C	117 (4)
C11—C10—H10	120.9	N6—N7—H7A	106 (2)
C12—C11—C10	121.2 (3)	N6—N7—H7B	107 (2)
C12—C11—H11	119.4	H7A—N7—H7B	95 (3)
C10—C11—H11	119.4	N9—N8—H8A	107 (3)
C13—C12—C11	121.3 (3)	N9—N8—H8B	105 (2)
C13—C12—H12	119.4	H8A—N8—H8B	115 (3)
C11—C12—H12	119.4	N9—N8—H8C	112 (2)
C14—C13—C12	116.9 (3)	H8A—N8—H8C	113 (3)
C14—C13—H13	121.6	H8B—N8—H8C	105 (3)
C12—C13—H13	121.6	N8—N9—H9A	105 (2)
C13—C14—C9	122.9 (3)	N8—N9—H9B	110 (3)
C13—C14—S2	131.0 (3)	H9A—N9—H9B	99 (3)
C9—C14—S2	106.1 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···O2	0.87 (2)	2.42 (3)	3.097 (4)	135 (3)
N4—H4A···N1^i	0.87 (2)	2.40 (3)	3.061 (4)	133 (3)
N4—H4B···N2^i	0.88 (4)	2.56 (2)	3.381 (4)	155 (3)
N5—H5A···O6^ii	0.89 (2)	2.19 (2)	3.008 (4)	154 (3)
N5—H5C···O7	0.89 (2)	1.90 (2)	2.789 (4)	172 (3)
N6—H6B···O3	0.88 (2)	2.02 (3)	2.787 (4)	145 (4)
N6—H6C···O4^iii	0.90 (2)	1.84 (2)	2.728 (4)	172 (3)
N7—H7A···N3	0.89 (2)	2.43 (2)	3.265 (4)	156 (3)
N7—H7B···O4	0.87 (2)	2.12 (3)	2.886 (4)	146 (3)
N8—H8A···O1^iv	0.89 (2)	1.86 (2)	2.730 (4)	166 (4)
N8—H8C···N3	0.90 (2)	2.00 (2)	2.882 (4)	165 (3)
N9—H9A···O6^iv	0.88 (2)	2.17 (2)	2.975 (4)	152 (3)
N9—H9B···O1^i	0.87 (2)	2.10 (2)	2.924 (4)	157 (4)

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

(II) ethylenediaminium bis(saccharinate)

Crystal data

C2H10N2^2+·2C7H4NO3S^−	Z = 2
Mr = 426.46	F(000) = 444
Triclinic, P1	Dx = 1.557 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.1684 (19) Å	Cell parameters from 1782 reflections
b = 9.964 (3) Å	θ = 2.5–25.7°
c = 13.185 (4) Å	µ = 0.34 mm^−1
α = 84.557 (4)°	T = 100 K
β = 86.387 (4)°	Block, colorless
γ = 76.149 (4)°	0.15 × 0.11 × 0.06 mm
V = 909.4 (5) Å^3

Data collection

Bruker SMART CCD area-detector diffractometer	3575 independent reflections
Radiation source: fine-focus sealed tube	2479 reflections with I > 2σa(I)
Graphite monochromator	Rint = 0.056
ϕ and ω scans	θmax = 26.0°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Siemens, 1996)	h = −8→8
Tmin = 0.949, Tmax = 0.979	k = −12→11
10467 measured 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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.130	H atoms treated by a mixture of independent and constrained refinement
S = 0.99	w = 1/[σ^2(Fo^2) + (0.071P)^2] where P = (Fo^2 + 2Fc^2)/3
3575 reflections	(Δ/σ)max = 0.001
277 parameters	Δρmax = 0.67 e Å^−3
0 restraints	Δρmin = −0.40 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	1.00098 (11)	0.55402 (8)	0.63461 (6)	0.0213 (2)
O1	0.7398 (3)	0.9162 (2)	0.60423 (16)	0.0281 (5)
O2	1.1932 (3)	0.5163 (2)	0.58962 (17)	0.0325 (6)
O3	0.9016 (3)	0.4433 (2)	0.64721 (17)	0.0328 (6)
N1	0.8778 (3)	0.6908 (3)	0.57465 (18)	0.0204 (6)
C1	0.8326 (4)	0.8001 (3)	0.6335 (2)	0.0191 (7)
C2	0.9067 (4)	0.7618 (3)	0.7398 (2)	0.0185 (7)
C3	0.8867 (4)	0.8437 (3)	0.8203 (2)	0.0221 (7)
H3	0.8221	0.9389	0.8130	0.027*
C4	0.9638 (4)	0.7831 (4)	0.9126 (2)	0.0264 (8)
H4	0.9519	0.8381	0.9688	0.032*
C5	1.0575 (4)	0.6444 (4)	0.9241 (2)	0.0276 (8)
H5	1.1085	0.6055	0.9880	0.033*
C6	1.0780 (4)	0.5613 (3)	0.8433 (2)	0.0243 (7)
H6	1.1409	0.4657	0.8506	0.029*
C7	1.0029 (4)	0.6238 (3)	0.7518 (2)	0.0180 (6)
S2	0.24528 (11)	1.07048 (8)	0.80957 (5)	0.0219 (2)
O4	0.2940 (3)	0.8525 (2)	0.59627 (15)	0.0226 (5)
O5	0.0572 (3)	1.1122 (2)	0.85781 (16)	0.0292 (6)
O6	0.3704 (3)	1.1634 (2)	0.81506 (16)	0.0298 (5)
N2	0.2282 (3)	1.0397 (3)	0.69197 (17)	0.0206 (6)
C8	0.3005 (4)	0.9043 (3)	0.6775 (2)	0.0203 (7)
C9	0.3867 (4)	0.8197 (3)	0.7706 (2)	0.0209 (7)
C10	0.4789 (4)	0.6808 (3)	0.7814 (3)	0.0273 (8)
H10	0.4947	0.6250	0.7255	0.033*
C11	0.5483 (5)	0.6245 (4)	0.8769 (3)	0.0341 (9)
H11	0.6137	0.5295	0.8857	0.041*
C12	0.5229 (5)	0.7052 (4)	0.9583 (3)	0.0370 (9)
H12	0.5716	0.6647	1.0223	0.044*
C13	0.4271 (4)	0.8454 (4)	0.9487 (2)	0.0305 (8)
H13	0.4069	0.9006	1.0051	0.037*
C14	0.3633 (4)	0.8997 (3)	0.8534 (2)	0.0244 (7)
N3	0.5623 (4)	0.7663 (3)	0.4382 (2)	0.0213 (6)
H3A	0.490 (4)	0.809 (3)	0.486 (3)	0.022 (9)*
H3B	0.670 (5)	0.709 (3)	0.465 (2)	0.018 (8)*
H3C	0.595 (5)	0.838 (4)	0.398 (3)	0.032 (10)*
N4	0.1159 (4)	0.8237 (3)	0.4154 (2)	0.0207 (6)
H4A	0.148 (5)	0.869 (4)	0.468 (3)	0.053 (12)*
H4B	0.008 (3)	0.876 (3)	0.387 (2)	0.033 (10)*
H4C	0.087 (5)	0.745 (4)	0.443 (3)	0.034 (10)*
C15	0.4502 (4)	0.6947 (3)	0.3801 (2)	0.0202 (7)
H15A	0.4110	0.6205	0.4256	0.024*
H15B	0.5331	0.6505	0.3238	0.024*
C16	0.2744 (4)	0.7914 (3)	0.3368 (2)	0.0196 (7)
H16A	0.3073	0.8786	0.3078	0.023*
H16B	0.2304	0.7485	0.2808	0.023*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0256 (4)	0.0187 (4)	0.0188 (4)	−0.0024 (3)	−0.0020 (3)	−0.0041 (3)
O1	0.0402 (13)	0.0183 (12)	0.0222 (12)	−0.0003 (11)	−0.0066 (10)	0.0025 (9)
O2	0.0275 (12)	0.0357 (14)	0.0300 (13)	0.0044 (11)	0.0025 (10)	−0.0137 (11)
O3	0.0503 (15)	0.0220 (13)	0.0304 (13)	−0.0147 (11)	−0.0091 (11)	−0.0022 (10)
N1	0.0253 (14)	0.0192 (14)	0.0173 (13)	−0.0051 (12)	−0.0019 (11)	−0.0042 (11)
C1	0.0177 (15)	0.0243 (18)	0.0165 (15)	−0.0076 (14)	−0.0002 (12)	−0.0003 (13)
C2	0.0174 (15)	0.0232 (17)	0.0164 (15)	−0.0084 (13)	0.0043 (12)	−0.0041 (13)
C3	0.0216 (16)	0.0258 (18)	0.0205 (15)	−0.0089 (14)	0.0056 (12)	−0.0052 (13)
C4	0.0268 (17)	0.043 (2)	0.0147 (15)	−0.0171 (16)	0.0048 (13)	−0.0084 (14)
C5	0.0229 (17)	0.047 (2)	0.0153 (15)	−0.0142 (16)	−0.0041 (13)	0.0046 (15)
C6	0.0205 (16)	0.0295 (19)	0.0223 (16)	−0.0066 (14)	−0.0013 (13)	0.0031 (14)
C7	0.0175 (15)	0.0212 (17)	0.0164 (14)	−0.0076 (13)	0.0014 (12)	−0.0014 (12)
S2	0.0235 (4)	0.0303 (5)	0.0132 (4)	−0.0085 (4)	0.0013 (3)	−0.0043 (3)
O4	0.0261 (11)	0.0265 (12)	0.0160 (11)	−0.0072 (10)	0.0015 (9)	−0.0045 (9)
O5	0.0288 (12)	0.0379 (14)	0.0223 (12)	−0.0088 (11)	0.0067 (9)	−0.0122 (10)
O6	0.0353 (13)	0.0377 (14)	0.0222 (11)	−0.0190 (11)	−0.0005 (10)	−0.0053 (10)
N2	0.0239 (14)	0.0253 (15)	0.0113 (12)	−0.0043 (12)	0.0010 (10)	−0.0008 (10)
C8	0.0168 (15)	0.0306 (19)	0.0145 (14)	−0.0088 (14)	0.0018 (11)	−0.0006 (13)
C9	0.0159 (15)	0.0292 (19)	0.0182 (15)	−0.0087 (14)	−0.0010 (12)	0.0050 (13)
C10	0.0187 (16)	0.030 (2)	0.0331 (19)	−0.0090 (15)	0.0023 (13)	0.0043 (15)
C11	0.0238 (18)	0.035 (2)	0.044 (2)	−0.0129 (16)	−0.0075 (16)	0.0163 (17)
C12	0.0307 (19)	0.055 (3)	0.0278 (19)	−0.0228 (19)	−0.0130 (15)	0.0233 (18)
C13	0.0262 (17)	0.053 (2)	0.0177 (16)	−0.0230 (17)	−0.0038 (13)	0.0070 (15)
C14	0.0192 (16)	0.035 (2)	0.0215 (16)	−0.0128 (15)	−0.0011 (13)	0.0030 (14)
N3	0.0178 (14)	0.0283 (17)	0.0171 (14)	−0.0047 (13)	0.0023 (11)	−0.0017 (13)
N4	0.0192 (15)	0.0250 (17)	0.0189 (14)	−0.0066 (13)	−0.0006 (11)	−0.0026 (13)
C15	0.0206 (16)	0.0192 (17)	0.0211 (15)	−0.0049 (13)	0.0008 (12)	−0.0038 (13)
C16	0.0195 (15)	0.0202 (17)	0.0184 (15)	−0.0036 (13)	0.0024 (12)	−0.0029 (13)

Geometric parameters (Å, º)

S1—O3	1.442 (2)	C8—C9	1.500 (4)
S1—O2	1.443 (2)	C9—C10	1.381 (4)
S1—N1	1.603 (3)	C9—C14	1.390 (4)
S1—C7	1.755 (3)	C10—C11	1.400 (5)
O1—C1	1.228 (4)	C10—H10	0.9500
N1—C1	1.361 (4)	C11—C12	1.379 (5)
C1—C2	1.513 (4)	C11—H11	0.9500
C2—C3	1.379 (4)	C12—C13	1.399 (5)
C2—C7	1.382 (4)	C12—H12	0.9500
C3—C4	1.391 (4)	C13—C14	1.380 (4)
C3—H3	0.9500	C13—H13	0.9500
C4—C5	1.383 (5)	N3—C15	1.483 (4)
C4—H4	0.9500	N3—H3A	0.87 (3)
C5—C6	1.390 (4)	N3—H3B	0.91 (3)
C5—H5	0.9500	N3—H3C	0.92 (4)
C6—C7	1.382 (4)	N4—C16	1.487 (4)
C6—H6	0.9500	N4—H4A	0.92 (4)
S2—O5	1.438 (2)	N4—H4B	0.906 (18)
S2—O6	1.445 (2)	N4—H4C	0.90 (4)
S2—N2	1.626 (2)	C15—C16	1.499 (4)
S2—C14	1.769 (3)	C15—H15A	0.9900
O4—C8	1.240 (3)	C15—H15B	0.9900
N2—C8	1.352 (4)	C16—H16A	0.9900
C8—O4	1.240 (3)	C16—H16B	0.9900
O3—S1—O2	114.65 (14)	C14—C9—C8	111.1 (3)
O3—S1—N1	112.23 (14)	C9—C10—C11	118.2 (3)
O2—S1—N1	110.64 (14)	C9—C10—H10	120.9
O3—S1—C7	109.92 (13)	C11—C10—H10	120.9
O2—S1—C7	110.59 (14)	C12—C11—C10	120.8 (3)
N1—S1—C7	97.51 (13)	C12—C11—H11	119.6
C1—N1—S1	111.9 (2)	C10—C11—H11	119.6
O1—C1—N1	124.0 (3)	C11—C12—C13	121.5 (3)
O1—C1—C2	123.7 (3)	C11—C12—H12	119.3
N1—C1—C2	112.3 (3)	C13—C12—H12	119.3
C3—C2—C7	120.0 (3)	C14—C13—C12	116.8 (3)
C3—C2—C1	128.9 (3)	C14—C13—H13	121.6
C7—C2—C1	111.1 (2)	C12—C13—H13	121.6
C2—C3—C4	118.3 (3)	C13—C14—C9	122.4 (3)
C2—C3—H3	120.9	C13—C14—S2	130.6 (3)
C4—C3—H3	120.9	C9—C14—S2	107.0 (2)
C5—C4—C3	121.2 (3)	C15—N3—H3A	110 (2)
C5—C4—H4	119.4	C15—N3—H3B	113.8 (19)
C3—C4—H4	119.4	H3A—N3—H3B	110 (3)
C4—C5—C6	120.8 (3)	C15—N3—H3C	110 (2)
C4—C5—H5	119.6	H3A—N3—H3C	102 (3)
C6—C5—H5	119.6	H3B—N3—H3C	110 (3)
C7—C6—C5	117.1 (3)	C16—N4—H4A	113 (2)
C7—C6—H6	121.4	C16—N4—H4B	111 (2)
C5—C6—H6	121.4	H4A—N4—H4B	110 (3)
C2—C7—C6	122.6 (3)	C16—N4—H4C	110 (2)
C2—C7—S1	107.2 (2)	H4A—N4—H4C	107 (3)
C6—C7—S1	130.2 (2)	H4B—N4—H4C	107 (3)
O5—S2—O6	115.66 (13)	N3—C15—C16	112.5 (2)
O5—S2—N2	110.38 (13)	N3—C15—H15A	109.1
O6—S2—N2	110.57 (13)	C16—C15—H15A	109.1
O5—S2—C14	111.71 (14)	N3—C15—H15B	109.1
O6—S2—C14	110.08 (14)	C16—C15—H15B	109.1
N2—S2—C14	96.87 (14)	H15A—C15—H15B	107.8
C8—N2—S2	111.4 (2)	N4—C16—C15	111.8 (2)
O4—C8—N2	124.1 (3)	N4—C16—H16A	109.3
O4—C8—C9	122.3 (3)	C15—C16—H16A	109.3
N2—C8—C9	113.5 (3)	N4—C16—H16B	109.3
C10—C9—C14	120.2 (3)	C15—C16—H16B	109.3
C10—C9—C8	128.7 (3)	H16A—C16—H16B	107.9

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O4	0.87 (3)	1.96 (3)	2.797 (3)	161 (3)
N3—H3B···N1	0.91 (3)	2.10 (3)	2.891 (4)	144 (3)
N3—H3B···O2^i	0.91 (3)	2.38 (3)	2.981 (4)	123 (2)
N3—H3C···N2^ii	0.92 (4)	2.19 (4)	3.061 (4)	160 (3)
N4—H4A···O4	0.92 (4)	2.02 (4)	2.844 (3)	147 (3)
N4—H4C···N1^iii	0.90 (4)	2.33 (4)	3.029 (4)	135 (3)
N4—H4B···N2^iv	0.91 (2)	2.00 (2)	2.899 (4)	169 (3)
N4—H4C···O3^v	0.90 (4)	2.30 (4)	2.892 (4)	123 (3)

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

(III) butane-1,4-diaminium bis(saccharinate)

Crystal data

C4H14N2^2+·2C7H4NO3S^−	F(000) = 476
Mr = 454.52	Dx = 1.574 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 4341 reflections
a = 9.0016 (11) Å	θ = 2.6–28.1°
b = 11.2539 (13) Å	µ = 0.33 mm^−1
c = 10.0269 (12) Å	T = 100 K
β = 109.196 (1)°	Block, colorless
V = 959.3 (2) Å^3	0.49 × 0.37 × 0.26 mm
Z = 2

Data collection

Bruker SMART CCD area-detector diffractometer	1871 independent reflections
Radiation source: fine-focus sealed tube	1780 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.017
ϕ and ω scans	θmax = 26.0°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Siemens, 1996)	h = −9→11
Tmin = 0.857, Tmax = 0.920	k = −10→13
5206 measured reflections	l = −12→12

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)] = 0.032	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.083	w = 1/[σ^2(Fo^2) + (0.0438P)^2 + 0.7096P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.003
1871 reflections	Δρmax = 0.35 e Å^−3
149 parameters	Δρmin = −0.45 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.036 (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
N2	0.77564 (15)	0.50781 (13)	0.18396 (14)	0.0162 (3)
C9	0.92744 (17)	0.52218 (14)	0.01673 (15)	0.0163 (3)
H9A	0.9365	0.6089	0.0339	0.020*
H9B	0.8320	0.5075	−0.0656	0.020*
C8	0.91076 (18)	0.45989 (14)	0.14593 (16)	0.0171 (3)
H8A	0.8952	0.3737	0.1265	0.021*
H8B	1.0089	0.4704	0.2268	0.021*
O3	0.47033 (12)	0.38723 (10)	0.06019 (11)	0.0179 (3)
S1	0.48326 (4)	0.26812 (3)	0.11793 (4)	0.01339 (15)
O2	0.64212 (12)	0.23881 (10)	0.20604 (11)	0.0175 (3)
C7	0.34846 (17)	0.25008 (13)	0.20967 (15)	0.0133 (3)
C2	0.24053 (17)	0.16557 (13)	0.13613 (14)	0.0139 (3)
C1	0.28125 (17)	0.12043 (13)	0.01075 (15)	0.0150 (3)
C3	0.11468 (17)	0.13566 (14)	0.18006 (15)	0.0160 (3)
H3	0.0395	0.0781	0.1307	0.019*
C6	0.33885 (18)	0.30757 (14)	0.32847 (15)	0.0161 (3)
H6	0.4146	0.3650	0.3774	0.019*
C4	0.10214 (18)	0.19295 (14)	0.29909 (16)	0.0181 (3)
H4	0.0164	0.1743	0.3308	0.022*
C5	0.21249 (18)	0.27709 (14)	0.37284 (16)	0.0183 (3)
H5	0.2014	0.3140	0.4542	0.022*
N1	0.41263 (15)	0.17045 (12)	−0.00215 (13)	0.0172 (3)
H2C	0.789 (2)	0.585 (2)	0.205 (2)	0.028 (5)*
H2B	0.762 (2)	0.4708 (19)	0.265 (2)	0.033 (6)*
O1	0.20080 (12)	0.04441 (10)	−0.07077 (11)	0.0179 (3)
H2A	0.689 (2)	0.4967 (18)	0.115 (2)	0.026 (5)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N2	0.0149 (6)	0.0183 (7)	0.0156 (6)	−0.0021 (5)	0.0052 (5)	0.0001 (5)
C9	0.0148 (7)	0.0165 (7)	0.0176 (7)	0.0005 (6)	0.0052 (6)	0.0002 (6)
C8	0.0152 (7)	0.0177 (8)	0.0189 (7)	0.0013 (6)	0.0062 (6)	0.0009 (6)
O3	0.0166 (5)	0.0170 (6)	0.0193 (5)	−0.0015 (4)	0.0049 (4)	0.0043 (4)
S1	0.0117 (2)	0.0149 (2)	0.0137 (2)	−0.00089 (13)	0.00433 (15)	0.00097 (13)
O2	0.0114 (5)	0.0202 (6)	0.0193 (6)	0.0002 (4)	0.0031 (4)	0.0014 (4)
C7	0.0108 (7)	0.0145 (7)	0.0146 (7)	0.0009 (5)	0.0041 (6)	0.0034 (5)
C2	0.0142 (7)	0.0128 (7)	0.0137 (7)	0.0018 (5)	0.0031 (5)	0.0020 (5)
C1	0.0146 (7)	0.0154 (7)	0.0143 (7)	0.0025 (6)	0.0040 (6)	0.0029 (6)
C3	0.0146 (7)	0.0155 (7)	0.0172 (7)	−0.0008 (6)	0.0042 (6)	0.0007 (6)
C6	0.0169 (7)	0.0148 (7)	0.0150 (7)	0.0006 (6)	0.0029 (6)	0.0002 (6)
C4	0.0166 (7)	0.0202 (8)	0.0196 (7)	−0.0002 (6)	0.0087 (6)	0.0023 (6)
C5	0.0200 (8)	0.0202 (8)	0.0154 (7)	0.0021 (6)	0.0068 (6)	−0.0005 (6)
N1	0.0160 (6)	0.0202 (7)	0.0163 (6)	−0.0034 (5)	0.0064 (5)	−0.0035 (5)
O1	0.0182 (5)	0.0186 (6)	0.0168 (5)	−0.0039 (4)	0.0057 (4)	−0.0039 (4)

Geometric parameters (Å, º)

N2—C8	1.4902 (19)	C7—C6	1.383 (2)
N2—H2C	0.89 (2)	C7—C2	1.386 (2)
N2—H2B	0.96 (2)	C2—C3	1.385 (2)
N2—H2A	0.87 (2)	C2—C1	1.509 (2)
C9—C8	1.523 (2)	C1—O1	1.2391 (18)
C9—H9A	0.9900	C1—N1	1.3538 (19)
C9—H9B	0.9900	C3—C4	1.393 (2)
C8—H8A	0.9900	C3—H3	0.9500
C8—H8B	0.9900	C6—C5	1.394 (2)
O3—S1	1.4495 (11)	C6—H6	0.9500
S1—O2	1.4504 (11)	C4—C5	1.395 (2)
S1—N1	1.5996 (13)	C4—H4	0.9500
S1—C7	1.7589 (15)	C5—H5	0.9500
C8—N2—H2C	110.7 (13)	C6—C7—C2	123.21 (14)
C8—N2—H2B	113.9 (13)	C6—C7—S1	130.22 (12)
H2C—N2—H2B	105.4 (18)	C2—C7—S1	106.52 (11)
C8—N2—H2A	110.1 (13)	C3—C2—C7	120.07 (13)
H2C—N2—H2A	110.5 (19)	C3—C2—C1	129.15 (13)
H2B—N2—H2A	106.1 (18)	C7—C2—C1	110.76 (13)
C8—C9—H9A	109.3	O1—C1—N1	124.30 (13)
C8—C9—H9B	109.3	O1—C1—C2	122.20 (13)
H9A—C9—H9B	108.0	N1—C1—C2	113.51 (13)
N2—C8—C9	111.60 (12)	C2—C3—C4	117.71 (14)
N2—C8—H8A	109.3	C7—C6—C5	116.65 (14)
C9—C8—H8A	109.3	C7—C6—H6	121.7
N2—C8—H8B	109.3	C5—C6—H6	121.7
C9—C8—H8B	109.3	C3—C4—C5	121.59 (14)
H8A—C8—H8B	108.0	C3—C4—H4	119.2
O3—S1—O2	112.78 (6)	C5—C4—H4	119.2
O3—S1—N1	112.03 (7)	C6—C5—C4	120.76 (14)
O2—S1—N1	111.74 (7)	C6—C5—H5	119.6
O3—S1—C7	109.70 (7)	C4—C5—H5	119.6
O2—S1—C7	111.51 (7)	C1—N1—S1	110.94 (10)
N1—S1—C7	98.19 (7)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···O1^i	0.96 (2)	1.91 (2)	2.8173 (17)	158.0 (19)
N2—H2C···O2^ii	0.89 (2)	1.96 (2)	2.8259 (18)	166.0 (19)
N2—H2A···O3^iii	0.87 (2)	2.28 (2)	2.9540 (17)	134.9 (18)
N2—H2A···O3	0.87 (2)	2.23 (2)	2.9482 (17)	140.3 (17)

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