Two-dimensional hydrogen-bonded networks in 1-(diamino­methyl­ene)­thio­uron-1-ium nitrate and bis­[1-(di­amino­methyl­ene)thio­uron-1-ium] phospho­nate monohydrate

Crystals of the title compounds, C₂H₇N₄S⁺·NO₃⁻, (I), and 2C₂H₇N₄S⁺·HPO₃²⁻·H₂O, (II), are built up from 1-(diamino­methyl­ene)thio­uron-1-ium cations and nitrate anions in (I), and from phospho­nate anions and water mol­ecules in (II). In both crystals, the cations and anions are linked together via N—H...O hydrogen bonds. The 1-(diamino­methyl­ene)thio­uron-1-ium cations exhibit a twisted conformation. Both arms of the cations are planar and are turned in opposite directions around the C—N bond involving the central N atom. Hydrogen-bonding inter­actions join oppositely charged units into layers in the nitrate salt and into double layers in the phospho­nate monohydrate salt. In addition, the structures are stabilized by π–π inter­actions between the delocalized π bonds of the cations. The significance of this study lies in the illustration of the differences between the supra­molecular aggregations in the nitrate and phospho­nate salts of a small organic mol­ecule. The different geometries of the counter-ions and their different potential for hydrogen-bond formation results in markedly different hydrogen-bond arrangements.

S1. Comment

As a continuation of our studies on 1-(diaminomethylene)thiourea and its imino tautomer, i.e. 2-imino-4-thiobiuret, whose utility has been described previously (Janczak & Perpétuo, 2008a,b; Perpétuo & Janczak, 2008), we have investigated the crystal structure of 1-(diaminomethylene)thiouron-1-ium nitrate, (I), and bis[1-(diaminomethylene)thiouron-1-ium] phosphonate monohydrate, (II).

The asymmetric unit of (I) consists of a 1-(diaminomethylene)thiouron-1-ium cation and a nitrate anion (Fig. 1a), while the asymmetric unit of (II) consists of two 1-(diaminomethylene)thiouron-1-ium cations, one phosphonate dianion and a water molecule (Fig.1b). The cations in these crystals are not strictly planar but are twisted. Both arms of each cation are rotated relative to the central N atom. The dihedral angle between the planes defined by the N1/C2/N3/N4 and N1/C1/N2/S1 atoms is 7.2 (1)° in (I), while the eqivalent angles in (II) are 9.1 (1) and 3.7 (1)° in (II) for the independent M1 and M2 units, respectively (for the M1 unit the planes are N11/C12/N13/N14 and N11/C11/N12/S11, and for M2 the planes are N21/C22/N23/N24 and N21/C21/N22/S21). For comparison, the neutral molecule of 1-(diaminomethylene)thiourea also has a twisted conformation, with a dihedral angle of 2.1 (1)° (Janczak & Perpétuo, 2008a).

The respective C—N and C═S bond lengths in (I) and in both independent cations in (II) are very similar. The average distance of the C—N bonds involving the central N atom [1.374 (12) Å] is significantly longer than the average distance of the other C—N bonds linking the amine groups [1.313 (9) Å]. The values of the C═S bonds in these salts are intermediate between the pure double C═S bond [1.6109 (8) Å; Johnson et al., 1971] and the distance of ca. 1.74 Å which represents 50% double-bond character (Abrahams, 1956; Allen et al. 1987). The elongation of the C═S bond and the shortening of the C—NH₂ bonds indicate partial delocalization of the π bonds (C═S and C═N) over the whole 1-(diaminomethylene)thiouron-1-ium cation. The anionic species of the (I) and (II) crystals exhibit a slightly distorted C_3h geometry for the NO₃^- anion and C_3v geometry for the HPO₃^2- anion, with N—O and P—O values typical for bond lengths and angles found in several crystals of this type (Allen, 2002).

In the crystal structures of (I) and (II), the oppositely charged units are linked through hydrogen bonds. In both crystals, 1-(diaminomethylene)thiouron-1-ium cations, related by inversion, are linked via a pair of N—H···S hydrogen bonds (Tables 1 and 2) forming R₂²(8) dimeric structures. In (I), these dimers are linked by NO₃^- anions via N—H···O hydrogen bonds into layers that lie parallel to the (301) plane (Fig. 2). The layers are separated by a distance of ~3.37 Å. In (II), the dimers of the independent M1 and M2 units are located essentially perpendicular, (M1)₂, and parallel, (M2)₂, to the (001) plane (Fig. 3). Within one layer the M2 dimeric cations are interconnected by HPO₃^2- anions via N—H···O hydrogen bonds, while in the second layer M1 dimers are linked via N—H···O interactions with water molecules as well as with HPO₃^2- anions. The dimeric units of M1 and M2 are arranged into layers located parallel to the (001) crystallographic plane at z = 0 (M1 layer) and at z = 0.50 (15) (M2 layer) (Fig. 3). The layer of M1 units is surrounded by two layers of M2 units, forming a sheet parallel to the (001) plane (Fig. 3). The adjacent M2 sheets are separated by a distance of ~3.27 Å. Owing to the partial delocalization of the π electrons of the double C═S and N21═C22 bonds of the M2 cation over the whole cation, the π–π interaction between the M2 units stabilizes the structure and makes it more planar than the M1 unit [the greatest deviations of the non-H atoms observed in the M2 cation are 0.042 (2) Å, while in the M1 cation they are 0.122 (2) Å]. The distance of 3.27 Å between the layers of M2 units is nearly intermediate between the sum of the van der Waals radii for C atoms of π-interacting aromatic rings (~3.4 Å) and the distance of 3.08 Å at which the steric interactions between the π systems become predominantly repulsive (Pauling, 1960; Scheidt & Lee, 1987).

This study illustrates the usefulness of 1-(diaminomethylene)thiourea in crystal engineering for developing supramolecular structures. Protonation of the molecule at the central N atom offers seven active donor sites for hydrogen bonds. Depending on the form of the anion, hydrogen-bonding interactions lead to the formation of layers in nitrate salts or double layers in phosphonate salts.

Related literature

For related literature, see: Abrahams (1956); Allen (2002); Allen et al. (1987); Janczak & Perpétuo (2008a, 2008b); Johnson et al. (1971); Pauling (1960); Perpétuo & Janczak (2008); Scheidt & Lee (1987).

S2. Experimental

Crystals of (I) and (II) were obtained from 2-imino-4-thiobiuret (purchased from Aldrich, 99% purity) dissolved in 5% aqueous solutions of the respective acids (HNO₃ or H₃PO₃). After several days at room temperature, suitable crystals were formed.

S3. Refinement

The H atom of the HPO₃^2- anion was located from a difference Fourier map and was refined [P1—H1 = 1.36 (2) Å]. All other H atoms were located from difference Fourier maps and were constrained [N—H = 0.86 Å with U_iso(H) = 1.2U_eq(N), and O—H = 0.82 Å with U_iso(H) = 1.5U_eq(O)].

Computing details

For both compounds, data collection: CrysAlis CCD (Oxford Diffraction, 2006). Cell refinement: CrysAlis RED (Oxford Diffraction, 2006) for (I); CrysAlis CCD (Oxford Diffraction, 2006) for (II). Data reduction: CrysAlis RED (Oxford Diffraction, 2006) for (I); CrysAlis CCD (Oxford Diffraction, 2006) for (II). For both compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Diamond (Brandenburg & Putz, 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. A view of (a) (I) and (b) (II), with the labelling scheme. Displacement ellipsoids are shown at the 50% probability level.
	Fig. 2. A view of the hydrogen bonded layers in (I). Symmetry codes as in Table 1.
	Fig. 3. A view of the crystal packing of (II), showing N—H···O and O—H···O hydrogen-bonded double layers.

(I) 1-(diaminomethylene)thiouron-1-ium nitrate

Crystal data

C2H7N4S^+·NO3^−	F(000) = 376
Mr = 181.19	Dx = 1.631 Mg m^−3 Dm = 1.63 Mg m^−3 Dm measured by flotation
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1307 reflections
a = 9.776 (2) Å	θ = 3.0–28.3°
b = 8.3320 (17) Å	µ = 0.41 mm^−1
c = 10.003 (2) Å	T = 295 K
β = 115.08 (3)°	Paralellepiped, colourless
V = 738.0 (3) Å^3	0.36 × 0.32 × 0.14 mm
Z = 4

Data collection

Kuma KM-4 with area CCD detector diffractometer	1915 independent reflections
Radiation source: fine-focus sealed tube	1307 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.026
Detector resolution: 1024x1024 with blocks 2x2 pixels mm^-1	θmax = 29.3°, θmin = 3.3°
ω–scan	h = −13→13
Absorption correction: numerical (CrysAlis RED; Oxford Diffraction, 2006)	k = −10→11
Tmin = 0.865, Tmax = 0.942	l = −13→13
8419 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)] = 0.032	H-atom parameters constrained
wR(F^2) = 0.087	w = 1/[σ^2(Fo^2) + (0.0474P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.00	(Δ/σ)max < 0.001
1915 reflections	Δρmax = 0.18 e Å^−3
104 parameters	Δρmin = −0.16 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: 0.0029 (4)

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
N5	0.69428 (14)	0.65872 (13)	1.07747 (13)	0.0462 (3)
O1	0.59382 (13)	0.69920 (12)	0.95482 (11)	0.0506 (3)
O2	0.72641 (15)	0.51615 (11)	1.10551 (11)	0.0621 (4)
O3	0.75985 (17)	0.76409 (11)	1.17092 (12)	0.0602 (4)
S1	0.54164 (6)	0.23394 (4)	0.57070 (4)	0.05162 (16)
C1	0.56851 (16)	0.33955 (15)	0.72214 (14)	0.0363 (3)
N1	0.61549 (15)	0.27710 (14)	0.86351 (11)	0.0386 (3)
H1	0.6390	0.3432	0.9360	0.046*
C2	0.63273 (16)	0.12143 (15)	0.90974 (15)	0.0363 (3)
N2	0.54808 (15)	0.49519 (13)	0.71795 (13)	0.0494 (3)
H21	0.5638	0.5468	0.7976	0.059*
H22	0.5189	0.5458	0.6355	0.059*
N3	0.67546 (14)	0.09650 (15)	1.05159 (13)	0.0471 (3)
H31	0.6875	0.0001	1.0854	0.057*
H32	0.6914	0.1766	1.1106	0.057*
N4	0.60813 (17)	0.00144 (14)	0.81904 (14)	0.0546 (4)
H41	0.6198	−0.0954	0.8517	0.066*
H42	0.5802	0.0190	0.7264	0.066*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N5	0.0567 (8)	0.0397 (6)	0.0407 (6)	−0.0002 (5)	0.0177 (6)	0.0010 (5)
O1	0.0609 (7)	0.0412 (5)	0.0375 (6)	0.0087 (5)	0.0092 (5)	0.0013 (5)
O2	0.0718 (9)	0.0430 (5)	0.0509 (7)	0.0028 (5)	0.0095 (6)	0.0046 (5)
O3	0.0788 (10)	0.0402 (6)	0.0413 (6)	−0.0101 (6)	0.0102 (6)	−0.0067 (4)
S1	0.0629 (4)	0.0480 (2)	0.0454 (2)	0.00012 (19)	0.0264 (2)	−0.00206 (15)
C1	0.0409 (8)	0.0313 (7)	0.0351 (7)	0.0004 (6)	0.0116 (6)	0.0025 (6)
N1	0.0541 (8)	0.0292 (6)	0.0293 (6)	0.0007 (5)	0.0146 (6)	−0.0026 (5)
C2	0.0386 (8)	0.0327 (7)	0.0373 (7)	0.0019 (6)	0.0157 (6)	0.0024 (6)
N2	0.0755 (10)	0.0309 (6)	0.0353 (6)	0.0046 (6)	0.0174 (6)	0.0014 (5)
N3	0.0616 (9)	0.0364 (6)	0.0371 (6)	0.0022 (6)	0.0150 (6)	0.0048 (5)
N4	0.0907 (11)	0.0294 (6)	0.0423 (7)	0.0059 (6)	0.0266 (7)	0.0030 (5)

Geometric parameters (Å, º)

N5—O2	1.2303 (15)	C2—N4	1.3021 (17)
N5—O3	1.2440 (15)	C2—N3	1.3148 (18)
N5—O1	1.2498 (15)	N2—H21	0.8600
S1—C1	1.6736 (14)	N2—H22	0.8600
C1—N2	1.3100 (17)	N3—H31	0.8600
C1—N1	1.3896 (17)	N3—H32	0.8600
N1—C2	1.3632 (16)	N4—H41	0.8600
N1—H1	0.8600	N4—H42	0.8600
O2—N5—O3	120.64 (12)	N3—C2—N1	116.97 (12)
O2—N5—O1	120.18 (12)	C1—N2—H21	120.0
O3—N5—O1	119.17 (12)	C1—N2—H22	120.0
N2—C1—N1	112.54 (12)	H21—N2—H22	120.0
N2—C1—S1	121.89 (10)	C2—N3—H31	120.0
N1—C1—S1	125.56 (10)	C2—N3—H32	120.0
C2—N1—C1	129.90 (11)	H31—N3—H32	120.0
C2—N1—H1	112	C2—N4—H41	120.0
C1—N1—H1	118	C2—N4—H42	120.0
N4—C2—N3	120.73 (13)	H41—N4—H42	120.0
N4—C2—N1	122.31 (13)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	0.86	2.11	2.9627 (16)	171
N2—H21···O1	0.86	1.94	2.7938 (16)	169
N2—H22···S1^i	0.86	2.63	3.4717 (14)	165
N3—H31···O3^ii	0.86	2.14	2.9903 (17)	169
N3—H32···O3^iii	0.86	2.16	2.9268 (18)	149
N4—H41···O1^ii	0.86	2.07	2.8927 (16)	160
N4—H42···S1	0.86	2.30	2.9962 (14)	139

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, y−1, z; (iii) −x+3/2, y−1/2, −z+5/2.

(II) bis[1-(diaminomethylene)thiouron-1-ium] phosphonate monohydrate

Crystal data

2C2H7N4S^+·HPO3^2^−·H2O	Z = 2
Mr = 336.35	F(000) = 352
Triclinic, P1	Dx = 1.600 Mg m^−3 Dm = 1.594 Mg m^−3 Dm measured by floatation
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.6109 (12) Å	Cell parameters from 852 reflections
b = 7.8771 (14) Å	θ = 2.9–29.5°
c = 12.758 (2) Å	µ = 0.52 mm^−1
α = 72.700 (16)°	T = 295 K
β = 72.961 (15)°	Paralellepiped, colourless
γ = 85.842 (14)°	0.38 × 0.27 × 0.22 mm
V = 698.1 (2) Å^3

Data collection

Kuma KM-4 with area CCD detector diffractometer	3529 independent reflections
Radiation source: fine-focus sealed tube	1950 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.037
Detector resolution: 1024x1024 with blocks 2x2 pixels mm^-1	θmax = 29.5°, θmin = 2.9°
ω–scan	h = −10→10
Absorption correction: numerical (CrysAlis RED; Oxford Diffraction, 2006)	k = −7→10
Tmin = 0.850, Tmax = 0.923	l = −16→16
8542 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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.089	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ^2(Fo^2) + (0.028P)^2] where P = (Fo^2 + 2Fc^2)/3
3529 reflections	(Δ/σ)max = 0.001
188 parameters	Δρmax = 0.43 e Å^−3
0 restraints	Δρmin = −0.35 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
P1	0.37123 (9)	0.14677 (9)	0.64056 (6)	0.02563 (18)
H1	0.430 (3)	0.146 (3)	0.5294 (18)	0.017 (6)*
O1	0.3364 (2)	0.3387 (2)	0.63694 (17)	0.0362 (5)
O2	0.1971 (2)	0.0318 (2)	0.69163 (16)	0.0331 (5)
O3	0.5187 (2)	0.0705 (2)	0.69932 (16)	0.0338 (5)
S11	0.22758 (10)	−0.45085 (10)	1.07379 (7)	0.0407 (2)
C11	0.2605 (4)	−0.2956 (3)	0.9465 (2)	0.0306 (7)
N11	0.1256 (3)	−0.1898 (3)	0.90960 (19)	0.0301 (6)
H11	0.1540	−0.1260	0.8385	0.036*
N12	0.4235 (3)	−0.2654 (3)	0.8699 (2)	0.0410 (7)
H121	0.4364	−0.1862	0.8049	0.049*
H122	0.5168	−0.3250	0.8850	0.049*
C12	−0.0556 (4)	−0.1779 (3)	0.9673 (2)	0.0301 (7)
N14	−0.1252 (3)	−0.2582 (3)	1.0754 (2)	0.0443 (7)
H141	−0.2384	−0.2428	1.1089	0.053*
H142	−0.0581	−0.3269	1.1136	0.053*
N13	−0.1568 (3)	−0.0726 (3)	0.9080 (2)	0.0442 (7)
H131	−0.2702	−0.0564	0.9408	0.053*
H132	−0.1096	−0.0199	0.8364	0.053*
S21	−0.15934 (10)	0.79949 (9)	0.64775 (7)	0.0371 (2)
C21	0.0111 (3)	0.6542 (3)	0.6403 (2)	0.0253 (6)
N21	−0.0014 (3)	0.4810 (3)	0.63714 (19)	0.0243 (5)
H21	0.1010	0.4230	0.6310	0.029*
N22	0.1791 (3)	0.6955 (3)	0.6381 (2)	0.0396 (7)
H221	0.2644	0.6178	0.6350	0.048*
H222	0.2022	0.7998	0.6397	0.048*
C22	−0.1487 (3)	0.3912 (3)	0.6396 (2)	0.0199 (6)
N24	−0.3072 (3)	0.4674 (3)	0.6383 (2)	0.0347 (6)
H241	−0.3976	0.4077	0.6385	0.042*
H242	−0.3209	0.5772	0.6372	0.042*
N23	−0.1257 (3)	0.2238 (3)	0.64123 (18)	0.0294 (6)
H231	−0.2153	0.1629	0.6415	0.035*
H232	−0.0212	0.1750	0.6421	0.035*
O4W	0.5009 (3)	0.1613 (3)	0.89006 (19)	0.0471 (6)
H1W	0.5500	0.2580	0.8750	0.071*
H2W	0.5070	0.1360	0.8310	0.071*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P1	0.0176 (4)	0.0247 (4)	0.0297 (5)	−0.0002 (3)	−0.0073 (3)	−0.0086 (3)
O1	0.0377 (11)	0.0313 (10)	0.0406 (14)	−0.0011 (8)	−0.0179 (10)	−0.0079 (10)
O2	0.0260 (10)	0.0266 (10)	0.0473 (13)	−0.0045 (8)	−0.0128 (9)	−0.0080 (9)
O3	0.0269 (11)	0.0278 (11)	0.0478 (13)	0.0050 (8)	−0.0151 (9)	−0.0092 (9)
S11	0.0374 (5)	0.0398 (5)	0.0362 (5)	0.0022 (4)	−0.0089 (4)	−0.0002 (4)
C11	0.0293 (16)	0.0264 (15)	0.0378 (18)	0.0037 (12)	−0.0090 (13)	−0.0131 (13)
N11	0.0265 (13)	0.0305 (14)	0.0274 (14)	0.0032 (10)	−0.0059 (11)	−0.0022 (11)
N12	0.0298 (14)	0.0381 (15)	0.0395 (16)	0.0082 (11)	−0.0016 (11)	0.0019 (12)
C12	0.0285 (16)	0.0276 (16)	0.0360 (19)	0.0018 (13)	−0.0081 (13)	−0.0135 (14)
N14	0.0265 (14)	0.0615 (18)	0.0384 (16)	0.0067 (12)	−0.0032 (12)	−0.0121 (14)
N13	0.0320 (15)	0.0496 (16)	0.0461 (17)	0.0107 (12)	−0.0118 (12)	−0.0081 (13)
S21	0.0376 (4)	0.0349 (4)	0.0413 (6)	0.0037 (3)	−0.0117 (4)	−0.0182 (4)
C21	0.0238 (14)	0.0238 (15)	0.0271 (16)	−0.0008 (11)	−0.0062 (11)	−0.0062 (12)
N21	0.0210 (12)	0.0226 (12)	0.0301 (14)	0.0002 (9)	−0.0074 (10)	−0.0099 (10)
N22	0.0233 (13)	0.0278 (13)	0.074 (2)	0.0013 (10)	−0.0162 (12)	−0.0220 (13)
C22	0.0169 (13)	0.0227 (14)	0.0183 (14)	−0.0008 (11)	−0.0052 (10)	−0.0028 (11)
N24	0.0265 (13)	0.0236 (12)	0.0607 (18)	0.0004 (10)	−0.0195 (12)	−0.0149 (12)
N23	0.0253 (12)	0.0231 (12)	0.0441 (16)	−0.0004 (9)	−0.0115 (11)	−0.0151 (11)
O4W	0.0381 (13)	0.0594 (15)	0.0428 (15)	−0.0057 (11)	−0.0082 (11)	−0.0152 (13)

Geometric parameters (Å, º)

P1—O1	1.5051 (18)	N13—H132	0.8600
P1—O3	1.5195 (19)	S21—C21	1.667 (3)
P1—O2	1.5226 (18)	C21—N22	1.332 (3)
P1—H1	1.36 (2)	C21—N21	1.388 (3)
S11—C11	1.679 (3)	N21—C22	1.357 (3)
C11—N12	1.321 (3)	N21—H21	0.8700
C11—N11	1.376 (3)	N22—H221	0.8600
N11—C12	1.372 (3)	N22—H222	0.8600
N11—H11	0.8700	C22—N24	1.311 (3)
N12—H121	0.8600	C22—N23	1.312 (3)
N12—H122	0.8600	N24—H241	0.8600
C12—N14	1.298 (3)	N24—H242	0.8600
C12—N13	1.315 (3)	N23—H231	0.8600
N14—H141	0.8600	N23—H232	0.8600
N14—H142	0.8600	O4W—H1W	0.8200
N13—H131	0.8600	O4W—H2W	0.8200
O1—P1—O3	111.38 (11)	C12—N13—H132	120.0
O1—P1—O2	113.20 (10)	H131—N13—H132	120.0
O3—P1—O2	111.99 (10)	N22—C21—N21	112.2 (2)
O1—P1—H1	105.4 (8)	N22—C21—S21	121.7 (2)
O3—P1—H1	109.6 (9)	N21—C21—S21	126.02 (19)
O2—P1—H1	104.7 (9)	C22—N21—C21	129.4 (2)
N12—C11—N11	113.0 (2)	C22—N21—H21	115.7
N12—C11—S11	121.8 (2)	C21—N21—H21	114.9
N11—C11—S11	125.2 (2)	C21—N22—H221	120.0
C12—N11—C11	129.3 (2)	C21—N22—H222	120.0
C12—N11—H11	113.4	H221—N22—H222	120.0
C11—N11—H11	117.2	N24—C22—N23	120.7 (2)
C11—N12—H121	120.0	N24—C22—N21	122.1 (2)
C11—N12—H122	120.0	N23—C22—N21	117.2 (2)
H121—N12—H122	120.0	C22—N24—H241	120.0
N14—C12—N13	120.6 (3)	C22—N24—H242	120.0
N14—C12—N11	123.2 (3)	H241—N24—H242	120.0
N13—C12—N11	116.2 (3)	C22—N23—H231	120.0
C12—N14—H141	120.0	C22—N23—H232	120.0
C12—N14—H142	120.0	H231—N23—H232	120.0
H141—N14—H142	120.0	H1W—O4W—H2W	111
C12—N13—H131	120.0

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N11—H11···O2	0.87	1.87	2.728 (3)	173
N12—H121···O3	0.86	2.09	2.862 (3)	149
N12—H122···S11^i	0.86	2.59	3.444 (2)	170
N14—H141···O4W^ii	0.86	2.05	2.846 (3)	153
N14—H142···S11	0.86	2.30	2.984 (3)	137
N13—H131···O4W^ii	0.86	2.31	3.037 (3)	142
N13—H131···O4W^iii	0.86	2.44	3.104 (3)	134
N13—H132···O2	0.86	2.49	3.188 (3)	139
N21—H21···O1	0.87	1.88	2.729 (3)	165
N22—H221···O1	0.86	2.22	2.976 (3)	146
N22—H222···O2^iv	0.86	2.12	2.948 (3)	163
N24—H241···O1^iii	0.86	2.14	2.970 (3)	162
N24—H242···S21	0.86	2.27	2.969 (2)	139
N23—H231···O3^iii	0.86	2.05	2.846 (3)	154
N23—H231···S21^v	0.86	2.84	3.345 (2)	119
N23—H232···O2	0.86	2.09	2.923 (3)	164
O4W—H1W···S11^vi	0.82	2.68	3.399 (2)	147
O4W—H2W···O3	0.82	1.88	2.698 (3)	178

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