Similar sulfonamides with different crystal structures: sulfasymazine and sulfatriazine

The crystal structures of 4-amino-N-(4,6-diethyl-1,3,5-triazin-2-yl)benzene­sulfonamide, C₁₃H₁₇N₅O₂S, and 4-amino-N-(4,6-dimeth­oxy-1,3,5-triazin-2-yl)benzene­sulfonamide, C₁₁H₁₃N₅O₄S, also known as sulfasymazine and sulfatriazine, respectively, are dominated by hydrogen-bond inter­actions. All three potential hydrogen-bond donors are employed in each case, resulting in a three-dimensional network for sulfasymazine, while an entirely different hydrogen-bonded layer structure is obtained for sulfatriazine. This study demonstrates the versatile nature of the hydrogen-bonding capabilities in sulfonamides, even in structurally very similar mol­ecules.

S1. Comment

Structurally related compounds may form isomorphous crystal structures. For example a series of 22 isostructural 4,4'-disubstituted benzenesulfonamidobenzenes have been identitified (Gelbrich et al., 2007). Sulfasymazine, (I), and sulfatriazine, (II), are closely related historical drugs of the sulfonamide family with antibacterial properties (Frisk & Hultman, 1965, Nabert-Bock, 1958). These compounds differ only in the nature of R, but their crystal structures display very different packing arrangements despite the fact that the O atoms in the methoxy substituents of (II) do not take part in hydrogen bonding.

As can be seen in Figs. 1 and 2, the molecules of (I) and (II) adopt slightly different conformations. The S1—N2—C7—N3 torsion angle is 8.4 (3)° in sulfasymazine and 39.7 (3)° in sulfatriazine, and the methoxy and ethyl substitutents adopt different conformations relative to the triazine ring. It is well known that the low-energy conformations differ for ethyl and methoxy substituents on phenyl rings, with ethyl substituents preferentially lying out of plane (with a minimum energy when the C_ar—C_ar—C_Et—C_Et torsion angle is 90°), and methoxy substituents prefentially lying in-plane (Cinacchi & Prampolini, 2003). The N4—C8—C10—C11 and N4—C9—C12—C13 torsion angles in sulfasymazine are 128.1 (2) and 93.2 (2)°, respectively, whereas the equivalent torsion angles in sulfatriazine, N4—C8—O3—C10 and N4—C9—O4—C11, are 179.4 (2) and 1.2 (3)°, respectively; thus the methoxy and ethyl groups adopt approximately the low-energy conformation expected for each compound.

Both (I) and (II) have three potential hydrogen-bond donors, all of which are employed in both structures. In sulfasymazine, one of the amine H atoms bifurcates to form hydrogen bonds to both an N atom in the triazine ring and an O atom of the sulfone. The crystal structure of (I) displays an infinite three-dimensional hydrogen-bonded network, where each molecule is connected to five others. The two N—H···N interactions result in layers which contain dimers with a central R²₂(24) ring, and four such rings are linked by a larger ring, the graph-set notation (Bernstein et al., 1995) of which is R⁶₆(32) (Fig. 3a). Each layer is connected to those above and below it by NH₂···O₂S hydrogen bonding (Fig. 3b) with rather long H···O distances (see Table 1). This type of hydrogen bonding, where each of the H atoms in the NH₂ group is hydrogen bonded to an O atom in the same sulfone group, is not novel but is unusual. In the Cambridge Structural Database (Version 5.29 of 2007; Allen, 2002), this feature is found in only one other N1-substituted sulfonamide, a 1:1 cocrystal of sulfadimidine with aspirin (Caira, 1992). A simplified hydrogen-bonded diagram of the overall three-dimensional hydrogen-bonded network is shown in Fig. 3(c), where each molecule has been collapsed to a point and hydrogen bonds are represented by arrows (which point to the hydrogen-bond acceptor). The rings are off-set such that atom N3 lies directly above the centre of the other ring, and atoms C9 and C7 eclipse each other. The shortest hydrogen bond in the structure is that between the amide H atom and amine N atom, at 2.029 (18) Å.

Sulfatriazine, on the other hand, exhibits a two-dimensional hydrogen-bonding pattern, which is composed of two layers of molecules. Each layer (Fig. 4a) consists of R⁴₄(26) rings that result from two interactions, both involving the NH₂ group as a hydrogen-bond donor; HNH···O═S and HNH···N_triazine. The sulfonamide units of each layer are linked by dimeric SNH···O═S contacts to those of the other layer, resulting in R²₂(8) rings and additionally in R⁴₄(24) rings (Fig. 4b). A visualization of the overall double-layer topology where each molecule of (II) is hydrogen bonded to five other molecules is given in Fig. 4(c). The triazine rings, which are aligned parallel to each other on the outer faces of the double layer, slot together with the triazine rings of the adjacent double layer. The triazine rings do not, however, show any π stacking; the rings are off-set by more than the width of a triazine ring. The sulfonamide dimer formed by the mutual donation of the amide H atom to the sulfonamide O atom of the other molecule is also seen in at least four other crystal structures of sulfonamides (Rambaud et al., 1985; Giuseppetti et al., 1977; Patel et al., 1983; Liu et al., 1994), plus a series of isomorphous crystal structures of 22 related sulfonamides (Gelbrich et al., 2007).

Polymorphism in sulfonamides is a well known phenomenon, and one reason for this is the number of possible combinations between potential hydrogen-bond donor and acceptor groups. Thermomicroscopic analysis of pure sulfasymazine showed the substance to melt without change at 461–463 K. Sulfatriazine showed decomposition upon melting at 442 K, also without previous transformation. However, for sulfatriazine, two crystal morphologies with different melting points have been observed: needles and rods (405–408 K), and rhombuses and prisms (431–439 K) (Kuhnert-Branstätter et al., 1970), in addition to the monohydrate which is present in the commercial product. From hot stage microscopy experiments we have confirmed the existence of needles that melt at 412 K, but we did not obtain single crystals of this form. Thus the possibility of isostructural polymorphs of (I) and (II) cannot be discounted, although this would probably require the energy of a higher conformation of either the methoxy or the ethyl groups being overcome.

Related literature

For related literature, see: Allen (2002); Bernstein et al. (1995); Caira (1992); Cinacchi & Prampolini (2003); Frisk & Hultman (1965); Gelbrich et al. (2007); Liu et al. (1994); Nabert-Bock (1958); Rambaud et al. (1985).

S2. Experimental

Sulfasymazine was supplied by Lederle (now Wyeth–Lederle Pharma). Single crystals suitable for diffraction were prepared by slowly cooling a saturated acetonitrile solution of the commercial product. Sulfatriazine monohydrate was supplied by Stickstoffwerke Linz; single crystals of anhydrous sulfatriazine were prepared by dissolving sulfatriazine monohydrate in acetonitrile and allowing the solution to evaporate slowly to dryness.

S3. Refinement

All H atoms were identified in a difference map. Methyl H atoms were idealized and included as rigid groups allowed to rotate but not tip (C—H = 0.98 Å). The H atoms of CH₂ (C—H = 0.99 Å) and benzene (C—H = 0.95 Å) groups were positioned geometricallly. The U_iso(H) parameters were set at 1.5U_eq(C) for CH₃ H atoms and 1.2U_eq(C) for other C-bound H atoms. H atoms attached to N atoms were refined with restrained distances [N—H = 0.88 (2) Å] and their U_iso parameters were refined freely.

Computing details

For both compounds, data collection: COLLECT (Hooft, 1998); cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); data reduction: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP (Bruker, 1998) and Mercury (Bruno et al., 2002); software used to prepare material for publication: publCIF (Westrip, 2008).

Figures

	Fig. 1. The molecular geometry of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level, with H atoms shown as spheres of arbitrary size.
	Fig. 2. The molecular geometry of (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level, with H atoms shown as spheres of arbitrary size.
	Fig. 3. The hydrogen-bonded network of (I). (a) A detail of the two-dimensional structure arising from NH···N interactions, namely four R^22(24) rings linked by a central R^66(32) ring. (b) An NH2···O2S hydrogen-bonded chain with R^22(6) rings. (c) The topology of the overall three-dimensional hydrogen-bonding network. Key: single solid arrow: NH···NH2; double solid arrow: NH2···O2S (two hydrogen bonds); dashed arrow: HNH···Ntriazine.
	Fig. 4. The hydrogen-bonded network of (II). (a) A single hydrogen-bonded layer held together by R^44(26) rings. The hanging bonds marked with arrows indicate the dimeric link to the second layer. (b) Two pairs of molecules (top and bottom) belonging to different layers and connected by two dimeric R^22(8) rings and one R^44(24) ring. (c) The topology of the overall three-dimensional hydrogen-bonding network in (II). Key: solid arrow: HNH···O═S; dashed arrow: HNH···Ntriazine; dotted arrow: SNH···O═S.

(I) 4-amino-N-(4,6-diethyl-1,3,5-triazin-2-yl)benzenesulfonamide

Crystal data

C13H17N5O2S	F(000) = 648
Mr = 307.38	Dx = 1.413 Mg m^−3
Monoclinic, P21/n	Melting point = 188–190 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 9.3257 (2) Å	Cell parameters from 2906 reflections
b = 16.7918 (4) Å	θ = 2.9–26.0°
c = 9.8600 (2) Å	µ = 0.24 mm^−1
β = 110.693 (1)°	T = 120 K
V = 1444.42 (6) Å^3	Block, colourless
Z = 4	0.20 × 0.20 × 0.20 mm

Data collection

Bruker–Nonius KappaCCD diffractometer	2805 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode	2342 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.055
Detector resolution: 9.091 pixels mm^-1	θmax = 26.0°, θmin = 3.3°
ϕ & ω scans	h = −10→11
Absorption correction: multi-scan (SADABS; Sheldrick, 2007)	k = −20→20
Tmin = 0.932, Tmax = 0.954	l = −12→12
17818 measured 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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.114	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0629P)^2 + 0.9906P] where P = (Fo^2 + 2Fc^2)/3
2805 reflections	(Δ/σ)max < 0.001
204 parameters	Δρmax = 0.84 e Å^−3
3 restraints	Δρmin = −0.57 e Å^−3

Special details

Experimental. Thermomicroscopic investigations were performed using a Reichert Thermovar polarized light microscope (Reichert, Vienna, Austria) equipped with a Kofler hot stage (Reichert, Vienna, Austria).

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	0.43317 (5)	0.21502 (3)	0.62389 (5)	0.01829 (16)
O1	0.53740 (15)	0.16874 (8)	0.73809 (15)	0.0233 (3)
O2	0.47689 (16)	0.29344 (8)	0.59530 (16)	0.0244 (3)
N1	−0.16295 (19)	0.23374 (11)	0.71105 (19)	0.0217 (4)
H1A	−0.229 (3)	0.2670 (14)	0.651 (3)	0.038 (7)*
H1B	−0.204 (3)	0.1869 (11)	0.715 (3)	0.031 (6)*
N2	0.39968 (19)	0.16916 (10)	0.46775 (18)	0.0199 (4)
H2	0.383 (3)	0.2026 (14)	0.397 (2)	0.041 (7)*
N3	0.33623 (18)	0.04459 (10)	0.53926 (18)	0.0205 (4)
N4	0.24030 (19)	−0.05390 (10)	0.35607 (19)	0.0241 (4)
N5	0.31081 (18)	0.07315 (10)	0.29414 (18)	0.0212 (4)
C1	0.2574 (2)	0.21997 (11)	0.6502 (2)	0.0172 (4)
C2	0.2227 (2)	0.16509 (12)	0.7403 (2)	0.0194 (4)
H2A	0.2943	0.1249	0.7882	0.023*
C3	0.0824 (2)	0.16987 (12)	0.7593 (2)	0.0210 (4)
H3	0.0586	0.1333	0.8218	0.025*
C4	−0.0241 (2)	0.22824 (11)	0.6871 (2)	0.0191 (4)
C5	0.0120 (2)	0.28208 (11)	0.5962 (2)	0.0213 (4)
H5	−0.0602	0.3217	0.5466	0.026*
C6	0.1521 (2)	0.27816 (11)	0.5776 (2)	0.0203 (4)
H6	0.1762	0.3150	0.5156	0.024*
C7	0.3466 (2)	0.09213 (11)	0.4345 (2)	0.0187 (4)
C8	0.2575 (2)	−0.00074 (12)	0.2614 (2)	0.0225 (4)
C9	0.2824 (2)	−0.02833 (12)	0.4936 (2)	0.0214 (4)
C10	0.2137 (3)	−0.02522 (15)	0.1051 (2)	0.0340 (5)
H10A	0.1208	0.0045	0.0464	0.041*
H10B	0.1879	−0.0826	0.0963	0.041*
C11	0.3400 (4)	−0.01014 (16)	0.0440 (3)	0.0488 (7)
H11A	0.3032	−0.0243	−0.0590	0.073*
H11B	0.4297	−0.0427	0.0965	0.073*
H11C	0.3685	0.0463	0.0553	0.073*
C12	0.2667 (2)	−0.08498 (12)	0.6058 (2)	0.0263 (5)
H12A	0.3512	−0.0755	0.6990	0.032*
H12B	0.2760	−0.1403	0.5752	0.032*
C13	0.1138 (3)	−0.07543 (13)	0.6278 (2)	0.0297 (5)
H13A	0.1101	−0.1118	0.7042	0.044*
H13B	0.0299	−0.0879	0.5372	0.044*
H13C	0.1032	−0.0204	0.6561	0.044*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0174 (3)	0.0192 (3)	0.0207 (3)	−0.00228 (18)	0.0098 (2)	−0.00277 (18)
O1	0.0175 (7)	0.0301 (8)	0.0224 (7)	0.0006 (6)	0.0071 (6)	−0.0003 (6)
O2	0.0244 (7)	0.0209 (7)	0.0330 (8)	−0.0067 (6)	0.0163 (7)	−0.0036 (6)
N1	0.0179 (8)	0.0207 (9)	0.0292 (10)	−0.0021 (7)	0.0116 (8)	−0.0037 (7)
N2	0.0255 (9)	0.0184 (8)	0.0196 (8)	−0.0012 (7)	0.0128 (7)	−0.0011 (7)
N3	0.0209 (8)	0.0199 (8)	0.0227 (8)	0.0013 (7)	0.0100 (7)	0.0003 (7)
N4	0.0201 (9)	0.0219 (9)	0.0303 (9)	0.0000 (7)	0.0090 (7)	−0.0050 (7)
N5	0.0198 (8)	0.0235 (9)	0.0219 (8)	0.0009 (7)	0.0096 (7)	−0.0031 (7)
C1	0.0171 (9)	0.0186 (9)	0.0174 (9)	−0.0018 (7)	0.0081 (8)	−0.0037 (7)
C2	0.0199 (10)	0.0189 (9)	0.0195 (9)	0.0026 (8)	0.0073 (8)	0.0009 (7)
C3	0.0239 (10)	0.0206 (10)	0.0211 (10)	−0.0010 (8)	0.0111 (8)	0.0022 (8)
C4	0.0182 (9)	0.0206 (9)	0.0198 (9)	−0.0034 (8)	0.0085 (8)	−0.0089 (8)
C5	0.0224 (10)	0.0185 (10)	0.0222 (10)	0.0031 (8)	0.0069 (8)	0.0006 (8)
C6	0.0233 (10)	0.0194 (10)	0.0207 (10)	−0.0006 (8)	0.0109 (8)	0.0009 (8)
C7	0.0155 (9)	0.0205 (10)	0.0217 (9)	0.0023 (7)	0.0087 (8)	−0.0013 (8)
C8	0.0165 (9)	0.0245 (11)	0.0277 (11)	0.0008 (8)	0.0094 (8)	−0.0053 (8)
C9	0.0173 (9)	0.0188 (10)	0.0293 (10)	0.0032 (8)	0.0098 (8)	−0.0005 (8)
C10	0.0298 (12)	0.0394 (13)	0.0290 (12)	−0.0007 (10)	0.0056 (10)	−0.0124 (10)
C11	0.087 (2)	0.0386 (14)	0.0298 (12)	−0.0228 (14)	0.0320 (14)	−0.0077 (11)
C12	0.0281 (11)	0.0182 (10)	0.0332 (12)	0.0006 (8)	0.0118 (9)	0.0037 (9)
C13	0.0316 (12)	0.0289 (12)	0.0320 (12)	0.0024 (9)	0.0156 (10)	0.0077 (9)

Geometric parameters (Å, º)

S1—O1	1.4293 (15)	C3—H3	0.9500
S1—O2	1.4355 (14)	C4—C5	1.396 (3)
S1—N2	1.6495 (16)	C5—C6	1.384 (3)
S1—C1	1.7492 (19)	C5—H5	0.9500
N1—C4	1.399 (2)	C6—H6	0.9500
N1—H1A	0.884 (17)	C8—C10	1.506 (3)
N1—H1B	0.883 (16)	C9—C12	1.504 (3)
N2—C7	1.382 (3)	C10—C11	1.522 (3)
N2—H2	0.869 (17)	C10—H10A	0.9900
N3—C7	1.335 (3)	C10—H10B	0.9900
N3—C9	1.340 (3)	C11—H11A	0.9800
N4—C8	1.342 (3)	C11—H11B	0.9800
N4—C9	1.342 (3)	C11—H11C	0.9800
N5—C8	1.333 (3)	C12—C13	1.525 (3)
N5—C7	1.343 (2)	C12—H12A	0.9900
C1—C6	1.391 (3)	C12—H12B	0.9900
C1—C2	1.396 (3)	C13—H13A	0.9800
C2—C3	1.388 (3)	C13—H13B	0.9800
C2—H2A	0.9500	C13—H13C	0.9800
C3—C4	1.398 (3)
O1—S1—O2	119.48 (9)	N3—C7—N5	126.57 (18)
O1—S1—N2	109.47 (9)	N3—C7—N2	119.60 (17)
O2—S1—N2	102.60 (9)	N5—C7—N2	113.83 (17)
O1—S1—C1	108.73 (9)	N5—C8—N4	125.23 (18)
O2—S1—C1	109.35 (9)	N5—C8—C10	116.44 (19)
N2—S1—C1	106.39 (9)	N4—C8—C10	118.33 (19)
C4—N1—H1A	113.4 (18)	N3—C9—N4	124.95 (19)
C4—N1—H1B	113.2 (16)	N3—C9—C12	116.97 (18)
H1A—N1—H1B	112 (2)	N4—C9—C12	118.08 (18)
C7—N2—S1	126.28 (14)	C8—C10—C11	113.04 (19)
C7—N2—H2	117.8 (18)	C8—C10—H10A	109.0
S1—N2—H2	111.9 (18)	C11—C10—H10A	109.0
C7—N3—C9	114.07 (17)	C8—C10—H10B	109.0
C8—N4—C9	115.21 (17)	C11—C10—H10B	109.0
C8—N5—C7	113.96 (17)	H10A—C10—H10B	107.8
C6—C1—C2	120.70 (18)	C10—C11—H11A	109.5
C6—C1—S1	119.04 (15)	C10—C11—H11B	109.5
C2—C1—S1	120.24 (15)	H11A—C11—H11B	109.5
C3—C2—C1	119.35 (18)	C10—C11—H11C	109.5
C3—C2—H2A	120.3	H11A—C11—H11C	109.5
C1—C2—H2A	120.3	H11B—C11—H11C	109.5
C2—C3—C4	120.38 (18)	C9—C12—C13	112.14 (17)
C2—C3—H3	119.8	C9—C12—H12A	109.2
C4—C3—H3	119.8	C13—C12—H12A	109.2
C5—C4—C3	119.47 (18)	C9—C12—H12B	109.2
C5—C4—N1	120.90 (18)	C13—C12—H12B	109.2
C3—C4—N1	119.59 (18)	H12A—C12—H12B	107.9
C6—C5—C4	120.52 (18)	C12—C13—H13A	109.5
C6—C5—H5	119.7	C12—C13—H13B	109.5
C4—C5—H5	119.7	H13A—C13—H13B	109.5
C5—C6—C1	119.57 (18)	C12—C13—H13C	109.5
C5—C6—H6	120.2	H13A—C13—H13C	109.5
C1—C6—H6	120.2	H13B—C13—H13C	109.5

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2^i	0.88 (2)	2.64 (2)	3.298 (2)	132 (2)
N1—H1B···N4^ii	0.88 (2)	2.33 (2)	3.121 (2)	149 (2)
N1—H1B···O1^i	0.88 (2)	2.52 (2)	3.098 (2)	124 (2)
N2—H2···N1^iii	0.87 (2)	2.03 (2)	2.891 (2)	171 (2)

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

(II) 4-amino-N-(4,6-diethyl-1,3,5-triazin-2-yl)benzenesulfonamide

Crystal data

C11H13N5O4S	Z = 2
Mr = 311.32	F(000) = 324
Triclinic, P1	Dx = 1.550 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.1566 (3) Å	Cell parameters from 2381 reflections
b = 8.6577 (4) Å	θ = 2.9–27.5°
c = 10.5410 (4) Å	µ = 0.27 mm^−1
α = 97.180 (3)°	T = 120 K
β = 103.374 (2)°	Block, colourless
γ = 109.255 (2)°	0.30 × 0.20 × 0.20 mm
V = 667.06 (5) Å^3

Data collection

Bruker–Nonius KappaCCD diffractometer	2448 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode	2122 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.073
Detector resolution: 9.091 pixels mm^-1	θmax = 25.5°, θmin = 2.9°
ϕ & ω scans	h = −9→9
Absorption correction: multi-scan SADABS V2007/2 (Sheldrick, 2007)	k = −10→10
Tmin = 0.914, Tmax = 0.948	l = −12→12
7268 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)] = 0.052	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.157	w = 1/[σ^2(Fo^2) + (0.0941P)^2 + 0.2249P] where P = (Fo^2 + 2Fc^2)/3
S = 1.09	(Δ/σ)max < 0.001
2448 reflections	Δρmax = 0.43 e Å^−3
203 parameters	Δρmin = −0.61 e Å^−3
3 restraints	Extinction correction: SHELXL, Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.047 (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	0.25571 (7)	0.78437 (7)	0.40711 (5)	0.0156 (3)
O1	0.3490 (2)	0.8722 (2)	0.54379 (16)	0.0208 (4)
O2	0.3282 (2)	0.6771 (2)	0.34282 (17)	0.0212 (4)
O3	−0.1273 (2)	0.6577 (2)	−0.08832 (16)	0.0203 (4)
O4	0.3625 (2)	1.1247 (2)	−0.04302 (17)	0.0219 (4)
N1	−0.5182 (3)	0.4070 (3)	0.3306 (2)	0.0213 (5)
H1A	−0.569 (4)	0.311 (3)	0.273 (3)	0.033 (8)*
H1B	−0.585 (3)	0.463 (3)	0.346 (3)	0.025 (7)*
N2	0.2664 (3)	0.9441 (2)	0.32898 (19)	0.0171 (5)
H2	0.367 (3)	1.027 (3)	0.370 (3)	0.029 (8)*
N3	0.0650 (2)	0.7873 (2)	0.12208 (19)	0.0162 (5)
N4	0.1115 (3)	0.8860 (2)	−0.07328 (19)	0.0184 (5)
N5	0.3155 (3)	1.0390 (2)	0.1415 (2)	0.0183 (5)
C1	0.0286 (3)	0.6738 (3)	0.3880 (2)	0.0152 (5)
C2	−0.0537 (3)	0.5101 (3)	0.3105 (2)	0.0174 (5)
H2A	0.0155	0.4599	0.2714	0.021*
C3	−0.2350 (3)	0.4221 (3)	0.2911 (2)	0.0169 (5)
H3	−0.2911	0.3114	0.2376	0.020*
C4	−0.3383 (3)	0.4948 (3)	0.3500 (2)	0.0165 (5)
C5	−0.2505 (3)	0.6584 (3)	0.4324 (2)	0.0180 (5)
H5	−0.3176	0.7081	0.4747	0.022*
C6	−0.0687 (3)	0.7456 (3)	0.4515 (2)	0.0182 (5)
H6	−0.0100	0.8546	0.5078	0.022*
C7	0.2143 (3)	0.9217 (3)	0.1915 (2)	0.0153 (5)
C8	0.0221 (3)	0.7810 (3)	−0.0082 (2)	0.0154 (5)
C9	0.2577 (3)	1.0113 (3)	0.0085 (2)	0.0158 (5)
C10	−0.2354 (3)	0.5375 (3)	−0.0266 (2)	0.0230 (6)
H10A	−0.3402	0.4536	−0.0959	0.034*
H10B	−0.2776	0.5960	0.0369	0.034*
H10C	−0.1611	0.4818	0.0207	0.034*
C11	0.3104 (4)	1.1010 (3)	−0.1879 (2)	0.0251 (6)
H11A	0.3966	1.1917	−0.2135	0.038*
H11B	0.1882	1.1023	−0.2197	0.038*
H11C	0.3115	0.9930	−0.2279	0.038*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0124 (4)	0.0172 (4)	0.0139 (4)	0.0029 (3)	0.0021 (2)	0.0030 (2)
O1	0.0173 (9)	0.0247 (9)	0.0122 (9)	0.0004 (7)	−0.0003 (7)	0.0040 (7)
O2	0.0164 (9)	0.0238 (9)	0.0244 (10)	0.0076 (7)	0.0076 (7)	0.0052 (7)
O3	0.0183 (9)	0.0181 (9)	0.0154 (9)	−0.0007 (7)	0.0010 (7)	−0.0003 (7)
O4	0.0234 (9)	0.0215 (9)	0.0165 (9)	0.0024 (7)	0.0063 (7)	0.0051 (7)
N1	0.0147 (10)	0.0192 (11)	0.0265 (12)	0.0034 (9)	0.0053 (9)	0.0020 (9)
N2	0.0155 (10)	0.0150 (10)	0.0130 (10)	−0.0015 (8)	0.0009 (8)	0.0013 (8)
N3	0.0136 (10)	0.0140 (10)	0.0168 (11)	0.0021 (8)	0.0020 (8)	0.0013 (8)
N4	0.0170 (10)	0.0185 (11)	0.0165 (11)	0.0047 (8)	0.0032 (8)	0.0009 (8)
N5	0.0172 (10)	0.0181 (10)	0.0176 (11)	0.0049 (8)	0.0048 (8)	0.0023 (8)
C1	0.0125 (11)	0.0151 (11)	0.0134 (11)	0.0013 (9)	0.0016 (8)	0.0019 (9)
C2	0.0180 (12)	0.0175 (12)	0.0161 (12)	0.0067 (10)	0.0058 (9)	0.0002 (9)
C3	0.0197 (12)	0.0137 (11)	0.0148 (12)	0.0036 (9)	0.0050 (9)	0.0021 (9)
C4	0.0149 (11)	0.0174 (12)	0.0154 (12)	0.0042 (10)	0.0025 (9)	0.0057 (9)
C5	0.0161 (12)	0.0199 (12)	0.0197 (13)	0.0078 (10)	0.0068 (9)	0.0040 (10)
C6	0.0214 (12)	0.0142 (11)	0.0164 (12)	0.0057 (10)	0.0037 (9)	0.0004 (9)
C7	0.0135 (11)	0.0152 (11)	0.0164 (12)	0.0061 (9)	0.0030 (9)	0.0018 (9)
C8	0.0155 (11)	0.0150 (12)	0.0155 (12)	0.0076 (9)	0.0027 (9)	0.0009 (9)
C9	0.0164 (12)	0.0164 (11)	0.0157 (12)	0.0076 (9)	0.0052 (9)	0.0022 (9)
C10	0.0215 (13)	0.0181 (12)	0.0198 (13)	−0.0008 (10)	0.0030 (10)	−0.0010 (10)
C11	0.0273 (14)	0.0314 (14)	0.0151 (13)	0.0066 (11)	0.0080 (10)	0.0086 (11)

Geometric parameters (Å, º)

S1—O2	1.4359 (17)	N5—C9	1.335 (3)
S1—O1	1.4388 (17)	C1—C6	1.390 (3)
S1—N2	1.684 (2)	C1—C2	1.399 (3)
S1—C1	1.731 (2)	C2—C3	1.373 (3)
O3—C8	1.334 (3)	C2—H2A	0.9500
O3—C10	1.453 (3)	C3—C4	1.409 (3)
O4—C9	1.335 (3)	C3—H3	0.9500
O4—C11	1.455 (3)	C4—C5	1.417 (3)
N1—C4	1.363 (3)	C5—C6	1.377 (3)
N1—H1A	0.876 (18)	C5—H5	0.9500
N1—H1B	0.869 (17)	C6—H6	0.9500
N2—C7	1.382 (3)	C10—H10A	0.9800
N2—H2	0.861 (18)	C10—H10B	0.9800
N3—C8	1.326 (3)	C10—H10C	0.9800
N3—C7	1.346 (3)	C11—H11A	0.9800
N4—C8	1.334 (3)	C11—H11B	0.9800
N4—C9	1.334 (3)	C11—H11C	0.9800
N5—C7	1.331 (3)
O2—S1—O1	118.76 (10)	C3—C4—C5	118.8 (2)
O2—S1—N2	108.57 (10)	C6—C5—C4	120.4 (2)
O1—S1—N2	101.73 (10)	C6—C5—H5	119.8
O2—S1—C1	109.19 (11)	C4—C5—H5	119.8
O1—S1—C1	110.64 (11)	C5—C6—C1	119.8 (2)
N2—S1—C1	107.14 (11)	C5—C6—H6	120.1
C8—O3—C10	117.52 (18)	C1—C6—H6	120.1
C9—O4—C11	116.97 (19)	N5—C7—N3	126.7 (2)
C4—N1—H1A	118 (2)	N5—C7—N2	116.0 (2)
C4—N1—H1B	117.8 (19)	N3—C7—N2	117.3 (2)
H1A—N1—H1B	119 (3)	N3—C8—O3	118.9 (2)
C7—N2—S1	122.97 (16)	N3—C8—N4	127.8 (2)
C7—N2—H2	115 (2)	O3—C8—N4	113.3 (2)
S1—N2—H2	108 (2)	N4—C9—N5	127.0 (2)
C8—N3—C7	112.6 (2)	N4—C9—O4	119.3 (2)
C8—N4—C9	112.7 (2)	N5—C9—O4	113.7 (2)
C7—N5—C9	113.2 (2)	O3—C10—H10A	109.5
C6—C1—C2	120.7 (2)	O3—C10—H10B	109.5
C6—C1—S1	120.33 (18)	H10A—C10—H10B	109.5
C2—C1—S1	118.98 (18)	O3—C10—H10C	109.5
C3—C2—C1	119.8 (2)	H10A—C10—H10C	109.5
C3—C2—H2A	120.1	H10B—C10—H10C	109.5
C1—C2—H2A	120.1	O4—C11—H11A	109.5
C2—C3—C4	120.5 (2)	O4—C11—H11B	109.5
C2—C3—H3	119.8	H11A—C11—H11B	109.5
C4—C3—H3	119.8	O4—C11—H11C	109.5
N1—C4—C3	120.3 (2)	H11A—C11—H11C	109.5
N1—C4—C5	120.9 (2)	H11B—C11—H11C	109.5

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···N5^i	0.88 (2)	2.34 (2)	3.206 (3)	172 (3)
N1—H1B···O2^ii	0.87 (2)	2.19 (2)	2.998 (3)	154 (3)
N2—H2···O1^iii	0.86 (2)	2.11 (2)	2.899 (2)	152 (3)

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