3-(1-Pyridinio)propane­sulfonate and 3-(benzyl­dimethyl­ammonio)propane­sulfonate monohydrate

3-(1-Pyridinio)propane­sulfonate, C₈H₁₁NO₃S, and 3-(benzyl­dimethyl­ammonio)propane­sulfonate monohydrate, C₁₂H₁₉NO₃S·H₂O, used as additives during protein refolding and crystallization, both crystallize in the monoclinic system in the P2₁/c space group, with one mol­ecule (or one set of mol­ecules) per asymmetric unit. The solvent water mol­ecule present in the second crystal structure results in the formation of a dimer through hydrogen bonds. The conformation of the propane­sulfonate moiety is similar in both structures.

S1. Comment

Non-detergent sulfobetaines (NDSBs), to which the title compounds belong, are zwitterionic molecules. NDSB-201 or 3-(1-pyridino)-1-propane sulfonate, (I), and NDSB-256 or 3-(benzyldimethylammonio)propane sulfonate, of which the monohydrate structure, (II), is reported here, are members of a larger family of compounds that was mainly developed to facilitate protein solubilization, as well as for improvement of protein stability (Vuillard et al., 1995). It was discovered that compounds from this group are very useful during protein refolding (Goldberg et al. 1995; Vuillard et al., 1998; Expert-Bezançon et al. 2003; Swope Willis et al., 2006) and purification (Vuillard et al., 1995). NDSBs prevent protein aggregation and are used as additives to protein solution in isoelectric focusing. Recently, Collins et al. (2006) demonstrated the usefulness of NDSB-201 in differential scanning calorimetry. The properties of NDSBs with respect to protein solutions have also been noticed by protein crystallographers (Vuillard et al., 1994, 1996). During crystallization, a protein has to be stable in highly concentrated solution for a prolonged period of time, and the presence of chemicals preventing the formation of an amorphous precipitate could be crucial for the success of a crystallization experiment.

NDSB-201 and NDSB-256 crystallize in the P2₁/c space group, with one molecule or one set of molecules per asymmetric unit (Fig. 1). Both compounds have aromatic rings that influence packing in the crystal structures. Weak interactions also play an important role in crystal packing, especially in the case of the structure of (I). Listed in Table 1 are the contacts between H and O atoms that are at least 0.3 Å shorter than the sum of the van der Waals radii. In the case of (II), important for the packing are hydrogen bonds mediated by water molecules (Table 2). The NDSB-256 molecule in the structure of (II) forms dimers, and their formation is intermediated by water molecules (Fig. 2). The hydrogen-bonding pattern corresponds to an R₄⁴(12) motif as described by Bernstein et al. (1995). Atom O1, which does not form hydogen bonds with water molecules, is involved in short contacts with benzyl atom H6B and atom H9 from the aromatic ring. The distances H6B···O1(-x, 1/2 + y, 1/2 - z) and H9···O1(1 + x, y, z) are 2.35 and 2.48 Å, respectively, while the distances C6···O1(-x, 1/2 + y, 1/2 - z) and C9···O1(1 + x, y, z) are 3.262 (2) and 3.167 (2) Å, respectively. The angles C6—H6B···O1(-x, 1/2 + y, 1/2 - z) and C9—H9···O1(1 + x, y, z) are 156 and 131°, respectively.

NDSBs with a three-carbon bridge between the S and N atoms (sulfopropyl non-detergent betaines) have been found to be superior for work with proteins (Vuillard et al., 1995). It was proposed that a sulfopropyl NDSB may adopt a cyclic conformation, with a six-atom ring and an ionic link between N⁺ and SO₃^- in a solution. The resulting hydrocarbon cluster might take part in hydrophobic protein–protein interactions. Our results show that for NDSB-201 and NDSB-256 such a conformation of the sulfopropyl moiety is not observed in the crystal structures, but of course it cannot be concluded that at least some of the molecules do not adopt the cyclic conformation in solution. In the crystal structures reported by us, the torsion angles S1—C1—C2—C3 and C1—C2—C3—N1 are -178.3 (1) and 171.3 (1)°, respectively, for NDSB-201, while for NDSB-256 they are 178.8 (1) and 169.2 (1)°, respectively.

In the Cambridge Structural Database (CSD, Version 5.27, updated January 2006; Allen, 2002), there are 12 structures with the sulfopropyl moiety attached to an N atom, forming ternary or quaternary amines. In the structures reported in the CSD, there is also no example in which the cyclic conformation of the ⁺N—CH₂—CH₂—CH₂—SO₃^- fragment is observed. It is also quite surprising that, although NDSB molecules are quite often used during protein refolding, there are only a few structures in the Protein Data Bank (PDB; Berman et al., 2000) for which the use of non-detergent sulfobetaines is reported in REMARK 280 (REMARK 280 contains information about crystals, solvent content and crystallization conditions) [Is this a program or a book? Reference?]. A sarch of the PDB in September 2006 revealed that for only six structures were NDSBs used for crystallization. NDSB-195 was used in two cases (PDB codes 2AUW and 2 G4B), NDSB-201 was used in three cases (PDB codes 1 NAX, 1UA2 and 2 F GC), and the usage of NDSB-256 was reported in only one case (PDB code 2 F96). It was noted that the application of NDSB-201 (Lolli et al., 2004) helped to prevent excessive nucleation and promoted crystal growth. Most probably the influence of compounds from the NDSB family in protein solution is similar to that observed in the case of arginine (Baynes & Trout, 2004) and NDSBs may be treated as `neutral crowder' additives (Baynes & Trout, 2004).

Related literature

For related literature, see: Allen (2002); Baynes & Trout (2004); Berman et al. (2000); Bernstein et al. (1995); Collins et al. (2006); Expert-Bezançon, Rabilloud, Vuillard & Goldberg (2003); Goldberg et al. (1995); Lolli et al. (2004); Swope Willis, Hogan, Prabhakar, Liu, Tsai, Wei & Fox (2006); Vuillard et al. (1994, 1995, 1996, 1998).

S2. Experimental

Both NDSB-201 and NDSB-256 were purchased from ANATRACE. Crystallization was performed at room temperature and the crystals used for X-ray diffraction experiments were obtained by a slow evaporation method. NDSB-201 was crystallized from a 1:1 mixture of methanol and 70% ethanol, while NDSB-256 was crystallized from 10% propionic acid.

S3. Refinement

All H atoms in NDSB-201, (I), were located in a difference map and their position and isotropic displacement parameters were refined. In the case of NDSB-256 monohydrate, (II), water H atoms were located in a difference map and their positional and isotropic displacement parameters were refined. All other H atoms were included in the refinement in calculated positions and refined using a riding-model approximation, with C—H = 0.93 (aromatic CH), 0.96 (CH₃) or 0.97 Å (CH₂), and with U_iso(H) = 1.2U_eq(C) for aromatic CH and CH₂, or 1.5U_eq(C) for CH₃.

Computing details

For both compounds, data collection: HKL-2000 (Otwinowski & Minor, 1997); cell refinement: HKL-2000; data reduction: HKL-2000; program(s) used to solve structure: HKL-3000SM (Minor et al., 2006) and SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: HKL-3000SM and SHELXL97 (Sheldrick, 1997); molecular graphics: HKL-3000SM, ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: HKL-3000SM.

Figures

	Fig. 1. The molecular structure of compound (I). Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. The molecular structure of compound (II). Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 3. Hydrogen bonds (dashed lines) in the crystal structure of (II). Labelled and unlabelled molecules are related by the symmetry operator (-x, 1 - y, -z).

(I) 3-(1-Pyridinio)propanesulfonate

Crystal data

C8H11NO3S	F(000) = 424
Mr = 201.24	Dx = 1.577 Mg m^−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54179 Å
Hall symbol: -P 2ybc	Cell parameters from 3268 reflections
a = 5.699 (1) Å	θ = 4.4–72.2°
b = 7.428 (1) Å	µ = 3.20 mm^−1
c = 20.053 (2) Å	T = 103 K
β = 93.384 (7)°	Prism, colourless
V = 847.4 (2) Å^3	0.5 × 0.4 × 0.3 mm
Z = 4

Data collection

Rigaku R-AXIS RAPID diffractometer	1641 independent reflections
Radiation source: fine-focus sealed tube	1636 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.040
Detector resolution: 10 pixels mm^-1	θmax = 72.2°, θmin = 4.4°
ω scan with χ offset	h = −6→6
Absorption correction: multi-scan (Otwinowski et al., 2003)	k = −9→9
Tmin = 0.27, Tmax = 0.38	l = −24→24
78761 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.030	All H-atom parameters refined
wR(F^2) = 0.082	w = 1/[σ^2(Fo^2) + (0.0455P)^2 + 0.5835P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max < 0.001
1641 reflections	Δρmax = 0.41 e Å^−3
163 parameters	Δρmin = −0.45 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0253 (12)

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	−0.00770 (6)	0.83978 (5)	0.159230 (16)	0.01668 (17)
N1	0.4608 (2)	0.84861 (16)	0.39284 (6)	0.0167 (3)
O1	0.0688 (2)	0.66014 (14)	0.14014 (5)	0.0230 (3)
O2	−0.0243 (2)	0.96490 (16)	0.10312 (5)	0.0261 (3)
O3	−0.2196 (2)	0.83503 (15)	0.19639 (6)	0.0226 (3)
C1	0.2196 (3)	0.9280 (2)	0.21447 (7)	0.0174 (3)
C2	0.2502 (3)	0.8275 (2)	0.28063 (7)	0.0187 (3)
C3	0.4438 (3)	0.9207 (2)	0.32337 (7)	0.0178 (3)
C4	0.2831 (3)	0.8816 (2)	0.43264 (7)	0.0186 (3)
C5	0.2941 (3)	0.8204 (2)	0.49755 (8)	0.0212 (3)
C6	0.4912 (3)	0.7266 (2)	0.52197 (8)	0.0220 (3)
C7	0.6703 (3)	0.6924 (2)	0.48025 (8)	0.0213 (3)
C8	0.6512 (3)	0.7542 (2)	0.41522 (7)	0.0188 (3)
H1A	0.177 (3)	1.052 (3)	0.2221 (9)	0.024 (5)*
H1B	0.359 (3)	0.925 (3)	0.1905 (9)	0.021 (4)*
H2A	0.111 (3)	0.832 (2)	0.3021 (10)	0.020 (5)*
H2B	0.290 (4)	0.704 (3)	0.2750 (10)	0.026 (5)*
H3A	0.409 (3)	1.052 (3)	0.3265 (9)	0.016 (4)*
H3B	0.588 (4)	0.902 (3)	0.3068 (9)	0.022 (5)*
H4	0.158 (3)	0.951 (3)	0.4142 (9)	0.023 (5)*
H5	0.167 (4)	0.845 (3)	0.5242 (10)	0.026 (5)*
H6	0.501 (4)	0.683 (3)	0.5671 (11)	0.032 (5)*
H7	0.802 (4)	0.627 (3)	0.4957 (10)	0.028 (5)*
H8	0.765 (3)	0.734 (2)	0.3841 (9)	0.011 (4)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0178 (3)	0.0191 (2)	0.0129 (2)	−0.00300 (12)	−0.00102 (14)	−0.00004 (12)
N1	0.0193 (7)	0.0171 (6)	0.0135 (6)	−0.0007 (5)	−0.0007 (5)	−0.0008 (5)
O1	0.0256 (6)	0.0223 (6)	0.0210 (6)	−0.0026 (4)	0.0011 (5)	−0.0066 (4)
O2	0.0314 (7)	0.0287 (6)	0.0172 (5)	−0.0092 (5)	−0.0074 (5)	0.0071 (4)
O3	0.0182 (6)	0.0268 (6)	0.0230 (6)	−0.0017 (4)	0.0022 (5)	−0.0012 (4)
C1	0.0190 (8)	0.0189 (7)	0.0138 (7)	−0.0019 (6)	−0.0012 (6)	−0.0003 (5)
C2	0.0215 (9)	0.0191 (8)	0.0152 (7)	−0.0012 (5)	−0.0009 (6)	0.0002 (5)
C3	0.0204 (8)	0.0212 (8)	0.0118 (7)	−0.0008 (6)	−0.0001 (6)	0.0014 (5)
C4	0.0199 (8)	0.0184 (7)	0.0173 (7)	0.0002 (6)	−0.0009 (6)	−0.0018 (6)
C5	0.0248 (9)	0.0219 (8)	0.0172 (7)	−0.0036 (6)	0.0040 (6)	−0.0021 (6)
C6	0.0314 (9)	0.0182 (7)	0.0159 (7)	−0.0053 (6)	−0.0028 (6)	0.0012 (6)
C7	0.0259 (9)	0.0172 (7)	0.0200 (7)	0.0009 (6)	−0.0065 (6)	0.0003 (6)
C8	0.0197 (8)	0.0182 (7)	0.0182 (7)	0.0016 (6)	−0.0011 (6)	−0.0028 (6)

Geometric parameters (Å, º)

S1—O3	1.4564 (12)	C2—H2A	0.92 (2)
S1—O2	1.4581 (11)	C2—H2B	0.96 (2)
S1—O1	1.4618 (11)	C4—C5	1.377 (2)
S1—C1	1.7791 (15)	C4—H4	0.94 (2)
N1—C8	1.347 (2)	C3—H3A	0.998 (19)
N1—C4	1.348 (2)	C3—H3B	0.91 (2)
N1—C3	1.4901 (18)	C1—H1A	0.96 (2)
C7—C8	1.381 (2)	C1—H1B	0.955 (19)
C7—C6	1.381 (2)	C5—C6	1.387 (2)
C7—H7	0.93 (2)	C5—H5	0.94 (2)
C2—C3	1.523 (2)	C8—H8	0.939 (17)
C2—C1	1.523 (2)	C6—H6	0.96 (2)
O3—S1—O2	113.08 (7)	N1—C3—C2	111.59 (12)
O3—S1—O1	112.40 (7)	N1—C3—H3A	107.2 (10)
O2—S1—O1	112.74 (7)	C2—C3—H3A	109.9 (10)
O3—S1—C1	106.59 (7)	N1—C3—H3B	105.9 (12)
O2—S1—C1	104.91 (7)	C2—C3—H3B	111.2 (12)
O1—S1—C1	106.38 (7)	H3A—C3—H3B	111.0 (16)
C8—N1—C4	121.06 (13)	C2—C1—S1	113.79 (11)
C8—N1—C3	120.34 (13)	C2—C1—H1A	110.2 (11)
C4—N1—C3	118.59 (13)	S1—C1—H1A	105.6 (11)
C8—C7—C6	119.42 (15)	C2—C1—H1B	111.8 (11)
C8—C7—H7	120.3 (12)	S1—C1—H1B	106.1 (11)
C6—C7—H7	120.2 (12)	H1A—C1—H1B	109.0 (16)
C3—C2—C1	108.02 (12)	C4—C5—C6	119.38 (15)
C3—C2—H2A	109.4 (12)	C4—C5—H5	118.5 (12)
C1—C2—H2A	109.2 (12)	C6—C5—H5	122.1 (12)
C3—C2—H2B	109.6 (12)	N1—C8—C7	120.32 (14)
C1—C2—H2B	112.7 (12)	N1—C8—H8	115.9 (10)
H2A—C2—H2B	107.9 (17)	C7—C8—H8	123.7 (10)
N1—C4—C5	120.39 (14)	C7—C6—C5	119.40 (14)
N1—C4—H4	116.5 (11)	C7—C6—H6	120.4 (13)
C5—C4—H4	123.1 (11)	C5—C6—H6	120.2 (13)
C8—N1—C4—C5	0.6 (2)	O1—S1—C1—C2	−66.24 (13)
C3—N1—C4—C5	−178.76 (13)	N1—C4—C5—C6	0.9 (2)
C8—N1—C3—C2	112.58 (15)	C4—N1—C8—C7	−1.4 (2)
C4—N1—C3—C2	−68.08 (17)	C3—N1—C8—C7	177.94 (13)
C1—C2—C3—N1	171.33 (12)	C6—C7—C8—N1	0.7 (2)
C3—C2—C1—S1	−178.26 (11)	C8—C7—C6—C5	0.8 (2)
O3—S1—C1—C2	53.89 (13)	C4—C5—C6—C7	−1.6 (2)
O2—S1—C1—C2	174.07 (11)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O1^i	0.94 (2)	2.26 (2)	3.175 (2)	165.6 (16)
C3—H3A···O3^i	0.996 (19)	2.397 (19)	3.347 (2)	159.2 (14)
C7—H7···O2^ii	0.93 (2)	2.41 (2)	3.155 (2)	136.5 (16)
C5—H5···O1^iii	0.96 (2)	2.41 (2)	3.206 (2)	139.8 (16)

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

(II) 3-(benzyldimethylammonio)propanesulfonate monohydrate

Crystal data

C12H19NO3S·H2O	F(000) = 592.0
Mr = 275.37	Dx = 1.356 Mg m^−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54179 Å
Hall symbol: -P 2ybc	Cell parameters from 4731 reflections
a = 12.628 (1) Å	θ = 3.7–72.1°
b = 11.209 (1) Å	µ = 2.21 mm^−1
c = 9.982 (1) Å	T = 103 K
β = 107.260 (4)°	Block, colourless
V = 1349.3 (2) Å^3	0.45 × 0.15 × 0.11 mm
Z = 4

Data collection

Rigaku R-AXIS RAPID diffractometer	2600 independent reflections
Radiation source: fine-focus sealed tube	2449 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.057
Detector resolution: 10.0 pixels mm^-1	θmax = 72.1°, θmin = 3.7°
ω scans with χ offset	h = −15→15
Absorption correction: multi-scan (Otwinowski et al., 2003)	k = −13→12
Tmin = 0.710, Tmax = 0.780	l = −12→12
36458 measured 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)] = 0.039	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.102	w = 1/[σ^2(Fo^2) + (0.0464P)^2 + 0.8011P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max < 0.001
2600 reflections	Δρmax = 0.36 e Å^−3
172 parameters	Δρmin = −0.47 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0169 (8)

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	−0.16405 (3)	0.45690 (3)	0.11564 (4)	0.01951 (16)
O1	−0.25915 (9)	0.43190 (11)	0.16517 (13)	0.0254 (3)
O3	−0.18342 (10)	0.55699 (11)	0.01727 (13)	0.0272 (3)
O2	−0.12445 (9)	0.35111 (11)	0.05952 (12)	0.0246 (3)
N1	0.25781 (11)	0.55913 (12)	0.38614 (14)	0.0196 (3)
O4	0.07127 (14)	0.23489 (13)	0.02042 (17)	0.0386 (4)
C4	0.29428 (14)	0.43633 (15)	0.36072 (19)	0.0252 (4)
H4A	0.2534	0.4108	0.2680	0.038*
H4B	0.2807	0.3823	0.4284	0.038*
H4C	0.3721	0.4372	0.3695	0.038*
C7	0.39272 (13)	0.65770 (14)	0.27477 (16)	0.0199 (3)
C8	0.43173 (13)	0.58489 (15)	0.18618 (17)	0.0220 (3)
H8	0.3847	0.5291	0.1295	0.026*
C9	0.54056 (14)	0.59521 (16)	0.18203 (18)	0.0248 (4)
H9	0.5662	0.5459	0.1234	0.030*
C5	0.32094 (14)	0.60027 (17)	0.53048 (16)	0.0265 (4)
H5A	0.2969	0.6790	0.5458	0.040*
H5B	0.3988	0.6016	0.5396	0.040*
H5C	0.3076	0.5466	0.5986	0.040*
C12	0.46323 (14)	0.74345 (14)	0.35624 (18)	0.0230 (4)
H12	0.4374	0.7940	0.4134	0.028*
C6	0.27397 (12)	0.64691 (14)	0.27689 (16)	0.0199 (3)
H6A	0.2284	0.6217	0.1848	0.024*
H6B	0.2481	0.7249	0.2953	0.024*
C2	0.05522 (13)	0.51886 (17)	0.24237 (17)	0.0236 (4)
H2A	0.0802	0.4457	0.2095	0.028*
H2B	0.0493	0.5803	0.1721	0.028*
C10	0.61085 (14)	0.67918 (16)	0.26542 (18)	0.0260 (4)
H10	0.6837	0.6856	0.2632	0.031*
C1	−0.05666 (12)	0.49942 (15)	0.26788 (16)	0.0217 (3)
H1A	−0.0783	0.5725	0.3047	0.026*
H1B	−0.0486	0.4381	0.3387	0.026*
C11	0.57233 (14)	0.75362 (15)	0.35221 (18)	0.0253 (4)
H11	0.6193	0.8102	0.4076	0.030*
C3	0.13626 (13)	0.55687 (15)	0.38096 (17)	0.0212 (4)
H3A	0.1281	0.5032	0.4535	0.025*
H3B	0.1157	0.6360	0.4036	0.025*
H1	0.110 (2)	0.289 (3)	0.004 (3)	0.051 (7)*
H2	0.013 (3)	0.270 (3)	0.030 (3)	0.065 (9)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0173 (2)	0.0194 (2)	0.0217 (2)	−0.00192 (13)	0.00557 (16)	0.00048 (13)
O1	0.0181 (6)	0.0280 (6)	0.0319 (6)	−0.0030 (5)	0.0103 (5)	0.0004 (5)
O3	0.0259 (6)	0.0238 (6)	0.0288 (7)	−0.0029 (5)	0.0031 (5)	0.0074 (5)
O2	0.0236 (6)	0.0248 (6)	0.0253 (6)	−0.0004 (5)	0.0071 (5)	−0.0052 (5)
N1	0.0179 (7)	0.0210 (7)	0.0192 (7)	0.0008 (5)	0.0043 (5)	0.0002 (5)
O4	0.0414 (9)	0.0231 (7)	0.0574 (9)	0.0000 (6)	0.0240 (7)	0.0062 (6)
C4	0.0247 (9)	0.0202 (8)	0.0313 (9)	0.0050 (6)	0.0093 (7)	0.0034 (7)
C7	0.0185 (8)	0.0200 (8)	0.0198 (7)	0.0015 (6)	0.0036 (6)	0.0039 (6)
C8	0.0217 (8)	0.0222 (8)	0.0214 (8)	0.0008 (6)	0.0052 (6)	0.0019 (6)
C9	0.0243 (8)	0.0262 (9)	0.0252 (8)	0.0040 (7)	0.0097 (7)	0.0046 (7)
C5	0.0231 (8)	0.0356 (10)	0.0183 (8)	−0.0035 (7)	0.0022 (6)	−0.0004 (7)
C12	0.0231 (8)	0.0198 (8)	0.0248 (8)	0.0010 (6)	0.0053 (6)	0.0013 (6)
C6	0.0196 (8)	0.0197 (8)	0.0198 (7)	0.0008 (6)	0.0050 (6)	0.0008 (6)
C2	0.0183 (8)	0.0309 (9)	0.0211 (8)	−0.0016 (7)	0.0049 (6)	−0.0003 (7)
C10	0.0199 (8)	0.0278 (9)	0.0305 (9)	0.0026 (7)	0.0081 (7)	0.0092 (7)
C1	0.0200 (8)	0.0245 (9)	0.0208 (8)	−0.0016 (6)	0.0065 (6)	−0.0018 (6)
C11	0.0217 (8)	0.0224 (9)	0.0290 (9)	−0.0024 (6)	0.0034 (7)	0.0041 (6)
C3	0.0173 (8)	0.0244 (8)	0.0230 (8)	−0.0001 (6)	0.0079 (6)	−0.0008 (6)

Geometric parameters (Å, º)

S1—O1	1.4552 (11)	C9—H9	0.9300
S1—O2	1.4616 (12)	C5—H5A	0.9600
S1—O3	1.4629 (12)	C5—H5B	0.9600
S1—C1	1.7756 (16)	C5—H5C	0.9600
N1—C4	1.497 (2)	C12—C11	1.395 (2)
N1—C5	1.497 (2)	C12—H12	0.9300
N1—C3	1.5207 (19)	C6—H6A	0.9700
N1—C6	1.527 (2)	C6—H6B	0.9700
O4—H1	0.83 (3)	C2—C3	1.517 (2)
O4—H2	0.87 (3)	C2—C1	1.524 (2)
C4—H4A	0.9600	C2—H2A	0.9700
C4—H4B	0.9600	C2—H2B	0.9700
C4—H4C	0.9600	C10—C11	1.390 (2)
C7—C12	1.396 (2)	C10—H10	0.9300
C7—C8	1.396 (2)	C1—H1A	0.9700
C7—C6	1.511 (2)	C1—H1B	0.9700
C8—C9	1.392 (2)	C11—H11	0.9300
C8—H8	0.9300	C3—H3A	0.9700
C9—C10	1.389 (3)	C3—H3B	0.9700
O1—S1—O2	112.62 (7)	C11—C12—C7	120.29 (16)
O1—S1—O3	112.66 (7)	C11—C12—H12	119.9
O2—S1—O3	111.90 (7)	C7—C12—H12	119.9
O1—S1—C1	104.99 (7)	C7—C6—N1	113.90 (12)
O2—S1—C1	106.53 (7)	C7—C6—H6A	108.8
O3—S1—C1	107.57 (7)	N1—C6—H6A	108.8
C4—N1—C5	110.09 (13)	C7—C6—H6B	108.8
C4—N1—C3	109.70 (12)	N1—C6—H6B	108.8
C5—N1—C3	106.36 (12)	H6A—C6—H6B	107.7
C4—N1—C6	111.01 (12)	C3—C2—C1	107.20 (13)
C5—N1—C6	110.06 (12)	C3—C2—H2A	110.3
C3—N1—C6	109.51 (12)	C1—C2—H2A	110.3
H1—O4—H2	106 (3)	C3—C2—H2B	110.3
N1—C4—H4A	109.5	C1—C2—H2B	110.3
N1—C4—H4B	109.5	H2A—C2—H2B	108.5
H4A—C4—H4B	109.5	C9—C10—C11	120.05 (15)
N1—C4—H4C	109.5	C9—C10—H10	120.0
H4A—C4—H4C	109.5	C11—C10—H10	120.0
H4B—C4—H4C	109.5	C2—C1—S1	113.95 (11)
C12—C7—C8	119.18 (15)	C2—C1—H1A	108.8
C12—C7—C6	120.75 (14)	S1—C1—H1A	108.8
C8—C7—C6	120.02 (14)	C2—C1—H1B	108.8
C9—C8—C7	120.48 (15)	S1—C1—H1B	108.8
C9—C8—H8	119.8	H1A—C1—H1B	107.7
C7—C8—H8	119.8	C10—C11—C12	120.00 (16)
C10—C9—C8	119.98 (16)	C10—C11—H11	120.0
C10—C9—H9	120.0	C12—C11—H11	120.0
C8—C9—H9	120.0	C2—C3—N1	115.89 (13)
N1—C5—H5A	109.5	C2—C3—H3A	108.3
N1—C5—H5B	109.5	N1—C3—H3A	108.3
H5A—C5—H5B	109.5	C2—C3—H3B	108.3
N1—C5—H5C	109.5	N1—C3—H3B	108.3
H5A—C5—H5C	109.5	H3A—C3—H3B	107.4
H5B—C5—H5C	109.5
C12—C7—C8—C9	1.8 (2)	C3—C2—C1—S1	178.84 (11)
C6—C7—C8—C9	179.13 (14)	O1—S1—C1—C2	174.61 (12)
C7—C8—C9—C10	−0.6 (2)	O2—S1—C1—C2	54.95 (14)
C8—C7—C12—C11	−1.9 (2)	O3—S1—C1—C2	−65.18 (14)
C6—C7—C12—C11	−179.21 (14)	C9—C10—C11—C12	0.4 (2)
C12—C7—C6—N1	−91.30 (18)	C7—C12—C11—C10	0.8 (2)
C8—C7—C6—N1	91.45 (17)	C1—C2—C3—N1	169.21 (13)
C4—N1—C6—C7	−59.71 (17)	C4—N1—C3—C2	−61.69 (18)
C5—N1—C6—C7	62.44 (17)	C5—N1—C3—C2	179.27 (14)
C3—N1—C6—C7	179.02 (13)	C6—N1—C3—C2	60.38 (18)
C8—C9—C10—C11	−0.5 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H1···O3^i	0.83 (3)	2.00 (3)	2.812 (2)	167 (3)
O4—H2···O2	0.87 (3)	2.05 (3)	2.921 (2)	178 (3)

Symmetry code: (i) −x, −y+1, −z.