Products of the oxidation of 1-(di­amino­methyl­ene)thio­urea with hydrogen peroxide

Two oxidation products of 1-(diamino­methyl­ene)thio­urea (HATU) are reported, obtained from reactions with hydrogen peroxide at two different concentrations; these are 3,5-diamino-1,2,4-thia­diazole, C₂H₄N₄S, (I), related to HATU by intra­molecular N—S bond formation, and 1-(diamino­methyl­ene)uronium hydrogen sulfate, C₂H₇N₄O⁺·HSO₄⁻, (II). In (I), mol­ecular hydrogen-bonded chains could be distinguished, further organized in a herring-bone-like pattern. The structure of (II) is stabilized by an extensive network of N—H...O and O—H...O hydrogen bonds, where hydrogen-bonded anion chains and characteristic cation–anion motifs are present. The compounds are of importance not only with respect to crystal engineering, but also in the design of new synthetic routes to HATU transition metal complexes.

S1. Comment

1-(Diaminomethylene)thiourea (HATU) is a derivative of biuret, in which one O atom has been notionally replaced by an S atom while the remaining amide group has been replaced by –CH(NH₂)₂. This simple molecule has attracted interest in its use as a starting compound to obtain the so-called `metallacages', e.g. [Ni₆(ATU)₈Cl][ClO₄]₃ (where ATU is the deprotonated form of HATU; Diaz et al., 2004; Gale & Quesada, 2006; Gimeno & Vilar, 2006; Lankshear & Beer, 2006). Such compounds are formed only in the presence of chloride ions, so that the reaction could serve as a method of colorimetric chloride detection. HATU has also been used as a component of resins chelating such ions as Ag⁺ (Trochimczuk & Kolarz, 2000). The reported transition metal complexes containing HATU as a ligand with known structure include the complexes of Ni (Kabir et al., 2002; Vilar et al., 1998, 1999; Diaz et al., 2004), Pd (Chakrabarty et al., 1990; Doxiadi et al., 2003), Ni and Pd (Sang-Ting et al., 2001; Vilar et al., 1999; Doxiadi et al., 2003). Metal complexes with HATU of so far unknown structure include the nitrosyl complexes with Co, Fe and Ru (Roy & Saha, 1980); the complexes with Co and Hg (Poddar & Ray, 1952); and the complexes with Cu, Ag and Zn (Roy & Saha, 1980). The structures of HATU itself and of some simple salts derived from HATU have recently been reported (Janczak & Perpétuo, 2008a,b; Perpétuo & Janczak, 2008).

As a thiourea, HATU can be expected undergo oxidation reactions yielding different products depending on the reaction conditions. Structure determinations undertaken so far concern the oxidation products only of substituted thioureas (e.g. Mamaeva & Bakibaev, 2003). In particular, Butler et al. (1978) determined the crystal structure of the so-called Hector's base (Hector, 1889), 5-imino-4-phenyl-3-phenylamino-4H-1,2,4-thiadiazoline, which was controversial for 100 years. Hector's bases are formed on oxidation of monoarylthioureas and on base-catalyzed rearrangement yield 3,5-bis(arylamino)-1,2,4-thiadiazoles, known as Dost's bases (Christophersen et al., 1975; Butler et al., 1980, 1986).

Chilmana & Simoy (2004) investigated the kinetics of 1-(diaminomethylene)thiourea oxidation with bromate(V) and iodate(VII) ions. In the case of the reaction with bromate(V) ions, 1-(diaminomethylene)urea was mentioned as the final product, whereas the reaction with iodate(VII) ions yields 3,5-diamino- 1,2,4-thiadiazole, (I). The latter oxidation product is interestingly related to HATU as its cyclization product; however, no crystal structure determination has been attempted so far.

In this paper the crystal structure of (I), obtained as a HATU oxidation product with 3% aqueous solution of hydrogen peroxide, is reported. When 30% hydrogen peroxide was used, compound (II) could be isolated. Both (I) and (II) are of importance not only with respect to crystal engineering, but also in the design of new synthetic routes leading to HATU transition metal complexes. Compound (I) could be considered as the product of N—S intramolecular bond formation in the 1-(diaminomethylene)thiourea molecule (Fig. 1 and Table 1). This cyclization apparently does not lead to charge delocalization. As a result, the N1—C1 and N1—C2 bond lengths are not equal (Table 1). A literature survey leads to the conclusion that the most similar compound with available crystal structure data is 3,5-bis(diphenylamino)-1,2,4- thiadiazole (Senda & Maruha, 1985), investigated during systematic studies on oxidation of substituted thioureas by the iron(III) ion. This compound can be considered as the derivative of (I) with both amine groups replaced by two phenyl rings. The 1,2,4-thiadiazole ring geometric parameters are in good agreement in the two compounds. In (I), all atoms constituting the 1,2,4-thiadiazole ring lie in one plane, whereas the two amine substituents (containing atoms N2 and N3) deviate from the ring plane by 0.036 (2) and 0.054 (2) Å (above and below the plane), respectively.

Molecules of (I) form hydrogen-bonded dimers linked through an N2—H21···N1ⁱ (symmetry code as in Table 2) hydrogen bond to form R²₂(8) rings (Etter et al., 1990), which are further linked through an N3—H31···N4ⁱⁱ hydrogen bond with the formation of a second type of R²₂(8) ring (Fig. 2). The resulting molecular chains along [001] adopt a herringbone-like arrangement in (I). Adjacent chains form very weak contacts between atom H32 at (x, y, z) and atom S1 at (-x + 3/2, y - 1/2, -z + 1/2).

Compound (II) is a salt consisting of 1-(diaminomethylene)oxouron-1-ium cations and hydrogensulfate anions. The cation, in comparison to the similar [HATUH]⁺ cation present, for example, in 1-(diaminomethylene)thiouron-1-ium chloride (Perpétuo & Janczak, 2008), differs by the presence of an O atom (O1) instead of an S atom (Fig. 3). Atom O1 is involved in an intramolecular N—H···O hydrogen bond as an acceptor (Table 3). Thus a hydrogen-bonded ring consisting of atoms N1, C1, C2, O1 and N4, lying in one plane, is formed. Atoms N2 and N3 from the amine groups bonded to atoms C1 and C2 deviate from this plane by 0.028 (2) and 0.035 (2) Å, respectively. The 1-(diaminomethylene)oxouron-1-ium cation geometrical parameters are consistent with the data reported for other salts [e.g. the sulfate hydrate (Lotsch & Schnick, 2005) and hydrogen chloride (Scoponi et al., 1991)]. It is assumed that the cation is stabilized by π-electron delocalization, which is reflected by the C1—N1 and C2—N1 bond length values [1.406 (2) and 1.366 (2) Å, respectively].

In the hydrogensulfate anion, the H atom is statistically disordered over two half-occupied positions; in one position it is bonded to atom O31 and in the second position to atom O21. In both positions, this H atom participates in O—H···O hydrogen bonds, with the hydrogensulfate anion O atom involved as acceptor, to form anionic chains (Table 3). Similar hydrogen-bonded anionic chains were described for 1-(diaminomethylene)thiouron-1-ium hydrogensulfate by Janczak & Perpétuo (2008b). Compound (II) is stabilized by an extensive network of N—H···O and O—H···O hydrogen bonds (Fig. 4). All amine H atoms from the organic cation are involved in these hydrogen bonds as donors. Characteristic motifs formed by the N2—H21···O11, N1—H1···O11 and N3—H32···O41 hydrogen bonds could be distinguished. Such motifs, within which R²₁(8) rings can be detected, are also present, for example, in 1-(diaminomethylene)thiouron-1-ium dihydrogenphosphate and dihydrogenarsenate (Janczak & Perpétuo, 2008b).

Related literature

For related literature, see: Butler et al. (1978); Chakrabarty et al. (1990); Christophersen et al. (1975); Diaz et al. (2004); Doxiadi et al. (2003); Etter et al. (1990); Gale & Quesada (2006); Gimeno & Vilar (2006); Janczak & Perpétuo (2008, 2008); Kabir et al. (2002); Lankshear & Beer (2006); Lotsch & Schnick (2005); Mamaeva & Bakibaev (2003); Perpétuo & Janczak (2008); Poddar & Ray (1952); Roy & Saha (1980); Scoponi et al. (1991); Senda & Maruha (1985); Sheldrick (2008); Trochimczuk & Kolarz (2000); Vilar et al. (1998, 1999).

S2. Experimental

HATU (0.5 g) was dissolved in 10 ml of a hydrogen peroxide aqueous solution. An exothermal reaction occurred with evolution of colourless gas. The product was obtained in the form of colourless crystals on slow evaporation of the reaction mixture. Compounds (I) and (II) formed when 3 or 30% hydrogen peroxide solutions were used, respectively. Analyses: for (I), found: C 20.7, H 3.3, N 48.1, S 28.0%; C₂H₄N₄S requires: C 20.7, H 3.4, N 48.3, S 27.6%; for (2), found: C 13.1, H 4.3, N 30.9, S 14.4%; C₂H₈N₄O₅S requires: C 12.0, H 4.0, N 28.0, S 16.0%.

S3. Refinement

All H atoms were easily found in a difference Fourier map. For (I), all H-atom positions and isotropic displacement parameters were refined [N—H = 0.813 (19)–0.86 (2) Å]. For (II), DFIX restraints were used for all N—H bond lengths (0.87 Å with an allowed deviation of 0.002 [or 0.02?]). Subsequently, the parameters for H atoms involved in N—H bonds were constrained using the AFIX 3 constraint. The hydrogen sulfate H atom was found to be disordered over two positions. Half-occupancy factors were assumed for both positions and AFIX 147 constraints were used for both disorder components. All H atoms were refined with U_eq set at 1.2 U_eq (parent atom). In the final difference maps the following highest peaks were found: for (I) the maximum is 0.76 Å from atom C1, and for (II) the maximum is 0.69 Å from atom O21 and 0.86 Å from atom S1 atom.

Computing details

For both compounds, data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis RED (Oxford Diffraction, 2006); data reduction: CrysAlis RED (Oxford Diffraction, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005) and SHELXTL-NT (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. The molecular structure of (I). Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. Hydrogen bonds stabilizing molecular chains in (I). [Symmetry codes: (i) -x + 1, -y + 1, -z; (ii) -x + 1, -y + 1, -z + 1.]
	Fig. 3. The cation and anion structure in (II). Hydrogen bonds and disordered H atom are denoted with dashed lines.
	Fig. 4. Two differenct views of the three-dimensional hydrogen-bonding network in (II). The disordered anion H atoms have been omitted for clarity. Hydrogen bonds are denoted with dashed lines.

(I) 3,5-diamino-1,2,4-thiadiazole

Crystal data

C2H4N4S	F(000) = 240
Mr = 116.15	Dx = 1.712 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3013 reflections
a = 3.923 (4) Å	θ = 3–35°
b = 10.701 (9) Å	µ = 0.56 mm^−1
c = 10.754 (9) Å	T = 100 K
β = 93.40 (8)°	Needle, colourless
V = 450.7 (7) Å^3	0.21 × 0.19 × 0.18 mm
Z = 4

Data collection

Kuma KM-4 CCD diffractometer	960 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.017
Graphite monochromator	θmax = 28.5°, θmin = 3.8°
ω scans	h = −4→5
3267 measured reflections	k = −13→14
1076 independent reflections	l = −14→14

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)] = 0.025	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.060	All H-atom parameters refined
S = 0.96	w = 1/[σ^2(Fo^2) + (0.0333P)^2 + 0.2859P] where P = (Fo^2 + 2Fc^2)/3
1076 reflections	(Δ/σ)max < 0.001
80 parameters	Δρmax = 0.30 e Å^−3
0 restraints	Δρmin = −0.21 e Å^−3

Special details

Experimental. Elemental analysis was carried out on Elementar 2400 CHNS vario EL III elemental analyser. For (1) - Calc.: 20.7% C, 3.4% H, 48.3% N, 27.6% S; Obs.: 20.7% C, 3.3% H, 48.1% N, 28.0% S.

IR spectra were collected for samples prepared as KBr pellets on BRUKER spectrometer.

(1) 452.3 (s), 475.7 (s), 589.4 (m), 689.0 (m), 705.1 (m), 734.4 (s), 835.7 (s), 1016.5 (m), 1106.4 (s), 1127.7 (s), 1303.3 (s), 1413.5 (vs), 1521.8 (vs), 1544.2 (vs), 1626.7 (vs), 2745.9 (m), 3115.4 (vs), 3191.4 (vs), 3292.1 (vs), 3413.9 (vs).

The device used for ESI-MS spectra collection was micrOTOF-Q. The samples were prepared as aqueous solutions. Results for (1) [m/Z (I, a.u.)]: positive ions at 117 (3000) corresponding to the [HATUH]⁺ cation (M), 119 (1000) correponding to M+2, 107.0 (600), 90.1 (200).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
S1	0.20111 (8)	0.70583 (3)	0.21750 (3)	0.01227 (11)
N1	0.5024 (3)	0.52103 (10)	0.32630 (10)	0.0128 (2)
N2	0.2856 (3)	0.66364 (12)	0.46799 (11)	0.0169 (3)
N3	0.6654 (3)	0.40908 (11)	0.15040 (11)	0.0148 (2)
N4	0.3744 (3)	0.59912 (10)	0.12569 (10)	0.0133 (2)
C1	0.3375 (3)	0.62463 (12)	0.35233 (12)	0.0125 (3)
C2	0.5153 (3)	0.51205 (12)	0.19893 (12)	0.0119 (2)
H21	0.337 (4)	0.6141 (18)	0.5289 (18)	0.022 (4)*
H22	0.173 (5)	0.7263 (18)	0.4780 (17)	0.019 (4)*
H31	0.703 (5)	0.4123 (17)	0.0762 (19)	0.023 (5)*
H32	0.827 (5)	0.3757 (18)	0.1971 (17)	0.025 (5)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.01515 (18)	0.01198 (17)	0.00955 (16)	0.00151 (12)	−0.00030 (11)	0.00057 (11)
N1	0.0155 (5)	0.0125 (5)	0.0103 (5)	−0.0008 (4)	0.0006 (4)	0.0006 (4)
N2	0.0250 (6)	0.0154 (6)	0.0104 (5)	0.0055 (5)	0.0008 (4)	0.0002 (5)
N3	0.0193 (6)	0.0151 (5)	0.0102 (6)	0.0039 (5)	0.0015 (4)	0.0012 (4)
N4	0.0159 (5)	0.0134 (5)	0.0106 (5)	0.0013 (4)	0.0012 (4)	−0.0004 (4)
C1	0.0129 (6)	0.0128 (6)	0.0117 (6)	−0.0030 (5)	−0.0004 (4)	0.0008 (5)
C2	0.0114 (6)	0.0126 (6)	0.0116 (6)	−0.0027 (5)	0.0005 (4)	0.0002 (5)

Geometric parameters (Å, º)

S1—N4	1.6794 (15)	N2—H22	0.813 (19)
S1—C1	1.7469 (18)	N3—C2	1.3674 (19)
N1—C1	1.3219 (19)	N3—H31	0.82 (2)
N1—C2	1.377 (2)	N3—H32	0.86 (2)
N2—C1	1.3389 (19)	N4—C2	1.3199 (19)
N2—H21	0.86 (2)
N4—S1—C1	92.01 (8)	N2—C1—S1	124.06 (12)
C2—N4—S1	107.40 (11)	C2—N3—H32	115.5 (12)
C1—N1—C2	108.45 (11)	C2—N3—H31	116.3 (13)
N4—C2—N3	121.05 (13)	H32—N3—H31	114.6 (17)
N4—C2—N1	120.37 (12)	C1—N2—H22	119.5 (13)
N3—C2—N1	118.54 (12)	C1—N2—H21	118.4 (12)
N1—C1—N2	124.16 (12)	H22—N2—H21	120.9 (17)
N1—C1—S1	111.78 (10)
C1—S1—N4—C2	0.58 (10)	C2—N1—C1—N2	−178.42 (12)
S1—N4—C2—N3	177.20 (10)	C2—N1—C1—S1	0.64 (13)
S1—N4—C2—N1	−0.34 (15)	N4—S1—C1—N1	−0.74 (10)
C1—N1—C2—N4	−0.21 (17)	N4—S1—C1—N2	178.32 (12)
C1—N1—C2—N3	−177.81 (11)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H21···N1^i	0.86 (2)	2.19 (2)	3.045 (3)	175 (2)
N3—H31···N4^ii	0.82 (2)	2.18 (2)	2.965 (3)	161 (2)

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

(II) 1-(diaminomethylene)uronium hydrogen sulfate

Crystal data

C2H7N4O^+·HO4S^−	Z = 2
Mr = 200.18	F(000) = 208
Triclinic, P1	Dx = 1.857 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.840 (6) Å	Cell parameters from 2828 reflections
b = 7.374 (7) Å	θ = 3–35°
c = 8.019 (4) Å	µ = 0.45 mm^−1
α = 76.48 (8)°	T = 100 K
β = 66.48 (6)°	Block, colourless
γ = 78.43 (8)°	0.35 × 0.26 × 0.24 mm
V = 358.0 (5) Å^3

Data collection

Kuma KM-4 CCD diffractometer	1633 independent reflections
Radiation source: fine-focus sealed tube	1530 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.017
/w scans	θmax = 28.5°, θmin = 3.3°
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2006)	h = −9→9
Tmin = 0.893, Tmax = 0.904	k = −9→9
2901 measured reflections	l = −8→10

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)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.077	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.047P)^2 + 0.2148P] where P = (Fo^2 + 2Fc^2)/3
1633 reflections	(Δ/σ)max = 0.001
111 parameters	Δρmax = 0.39 e Å^−3
0 restraints	Δρmin = −0.37 e Å^−3

Special details

Experimental. Elemental analysis was carried out on Elementar 2400 CHNS vario EL III elemental analyser. For (2) - Calc.: 12.0% C, 4.0% H, 28.0% N, 16.0% S; Obs.: 13.1% C, 4.3% H, 30.9% N, 14.4% S.

IR spectra were collected for samples prepared as KBr pellets on BRUKER spectrometer.

(2) 428.1 (s), 444.7 (s), 558.1 (s), 591.8 (vs), 714.6 (m), 759.8 (w), 886.1 (m), 935.1 (w), 1053.1 (s), 1079.9 (s), 1123.0 (s), 1190.4 (vs), 1343.5 (vs), 1399.1 (w), 1456.9 (s), 1524.8 (m), 1583.5 (vs), 1627.2 (s), 1678.3 (vs), 1742.4 (vs), 3006.8 (s), 3184.7 (vs), 3253.5 (vs), 3377.1 (vs).

The device used for ESI-MS spectra collection was micrOTOF-Q. The samples were prepared as aqueous solutions. Results for (2) [m/Z (I, a.u.)]: positive ions at 103.1 (8*10⁴) corresponding to the organic cation, 303.1 (1200); negative ions at 97.0 (420) corresponding to the HSO₄^- anion, 194.9 (1.2*10⁴) likely to correspond to the partially deprotonated ion pair of cation and anion.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1	0.38828 (17)	0.16796 (14)	0.65866 (13)	0.0159 (2)
N1	0.24983 (18)	0.45200 (15)	0.53251 (15)	0.0122 (2)
H1	0.2288	0.5094	0.4322	0.015*
N2	0.37580 (19)	0.20491 (16)	0.37377 (16)	0.0148 (2)
H21	0.3523	0.2801	0.2807	0.018*
H22	0.4427	0.0932	0.3576	0.018*
N3	0.1228 (2)	0.72788 (16)	0.64743 (16)	0.0157 (2)
H31	0.1023	0.7946	0.7305	0.019*
H32	0.1170	0.7773	0.5396	0.019*
N4	0.24148 (19)	0.46847 (16)	0.82226 (15)	0.0139 (2)
H41	0.2996	0.3520	0.8289	0.017*
H42	0.2153	0.5329	0.9085	0.017*
C1	0.3424 (2)	0.26396 (18)	0.52916 (18)	0.0120 (3)
C2	0.2044 (2)	0.54974 (19)	0.67150 (18)	0.0119 (3)
S1	0.23640 (5)	0.78776 (4)	0.11996 (4)	0.01217 (12)
O11	0.24205 (16)	0.58494 (13)	0.17215 (13)	0.0147 (2)
O21	0.46556 (15)	0.83046 (13)	0.02064 (13)	0.0143 (2)
H211	0.4709	0.9442	0.0171	0.017*	0.50
O31	0.12814 (16)	0.84814 (14)	−0.01924 (13)	0.0148 (2)
H311	0.0406	0.9448	0.0054	0.018*	0.50
O41	0.12590 (16)	0.88941 (14)	0.27315 (13)	0.0159 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0220 (5)	0.0128 (4)	0.0136 (5)	0.0027 (4)	−0.0094 (4)	−0.0027 (4)
N1	0.0164 (5)	0.0107 (5)	0.0106 (5)	0.0005 (4)	−0.0069 (4)	−0.0020 (4)
N2	0.0199 (6)	0.0127 (5)	0.0126 (5)	0.0024 (5)	−0.0079 (5)	−0.0039 (4)
N3	0.0202 (6)	0.0125 (5)	0.0151 (6)	0.0011 (4)	−0.0077 (5)	−0.0042 (4)
N4	0.0175 (6)	0.0134 (5)	0.0123 (5)	−0.0002 (4)	−0.0066 (4)	−0.0047 (4)
C1	0.0112 (6)	0.0118 (6)	0.0127 (6)	−0.0010 (5)	−0.0039 (5)	−0.0026 (5)
C2	0.0098 (6)	0.0130 (6)	0.0127 (6)	−0.0020 (5)	−0.0031 (5)	−0.0033 (5)
S1	0.01633 (19)	0.00969 (17)	0.00997 (17)	−0.00130 (12)	−0.00441 (13)	−0.00176 (12)
O11	0.0187 (5)	0.0100 (5)	0.0157 (5)	−0.0025 (4)	−0.0079 (4)	0.0006 (4)
O21	0.0131 (5)	0.0138 (4)	0.0154 (5)	−0.0024 (4)	−0.0042 (4)	−0.0031 (4)
O31	0.0184 (5)	0.0142 (4)	0.0152 (5)	0.0033 (4)	−0.0107 (4)	−0.0055 (4)
O41	0.0180 (5)	0.0171 (5)	0.0130 (5)	0.0010 (4)	−0.0058 (4)	−0.0059 (4)

Geometric parameters (Å, º)

O1—C1	1.2268 (19)	C1—N2	1.3346 (19)
N3—C2	1.322 (2)	N2—H21	0.8698
N3—H31	0.8696	N2—H22	0.8698
N3—H32	0.8698	S1—O41	1.4506 (17)
N4—C2	1.315 (2)	S1—O11	1.4528 (18)
N4—H41	0.8700	S1—O21	1.5082 (18)
N4—H42	0.8697	S1—O31	1.5125 (14)
C2—N1	1.366 (2)	O21—H211	0.8400
N1—C1	1.406 (2)	O31—H311	0.8400
N1—H1	0.8696
C2—N3—H31	118.5	O1—C1—N1	121.54 (14)
C2—N3—H32	117.5	N2—C1—N1	113.64 (14)
H31—N3—H32	122.8	C1—N2—H21	122.1
C2—N4—H41	117.9	C1—N2—H22	118.9
C2—N4—H42	120.0	H21—N2—H22	118.2
H41—N4—H42	121.9	O41—S1—O11	114.30 (10)
N4—C2—N3	121.89 (14)	O41—S1—O21	110.88 (9)
N4—C2—N1	120.82 (13)	O11—S1—O21	107.33 (11)
N3—C2—N1	117.29 (14)	O41—S1—O31	110.01 (8)
C2—N1—C1	126.00 (13)	O11—S1—O31	107.02 (9)
C2—N1—H1	119.4	O21—S1—O31	106.98 (9)
C1—N1—H1	114.5	S1—O21—H211	109.5
O1—C1—N2	124.81 (14)	S1—O31—H311	109.5
N4—C2—N1—C1	−1.8 (2)	C2—N1—C1—O1	1.3 (2)
N3—C2—N1—C1	178.06 (12)	C2—N1—C1—N2	−177.97 (12)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O11	0.87	2.00	2.845 (2)	164
N2—H21···O11	0.87	2.30	3.056 (3)	145
N2—H21···O21^i	0.87	2.48	2.963 (2)	116
N2—H22···O1^ii	0.87	2.04	2.907 (3)	174
N3—H31···O31^iii	0.87	2.21	3.022 (2)	155
N3—H31···O41^iv	0.87	2.53	3.052 (4)	119
N3—H32···O41	0.87	2.08	2.952 (3)	176
N4—H41···O1	0.87	1.99	2.656 (3)	133
N4—H41···O21^v	0.87	2.40	3.067 (3)	134
N4—H42···O11^iii	0.87	2.32	3.122 (2)	154
N4—H42···O31^iii	0.87	2.43	3.172 (3)	144
O21—H211···O21^vi	0.84	1.73	2.558 (3)	168
O31—H311···O31^vii	0.84	1.72	2.550 (3)	171

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