Two hydrate pseudopolymorphs of thi­amine pyrophosphate: a dihydrate and a trihydrate

Two hydrate pseudopolymorphs of 3-[(4-amino-2-methylpyrimidin-1-ium-5-yl)meth­yl]-4-methyl-1,3-thia­zol-3-ium-5-yl hydrogen pyrophosphate (TPP), viz. a dihydrate, C₁₂H₁₈N₄O₇P₂S·2H₂O, (I), and a trihydrate, C₁₂H₁₈N₄O₇P₂S·3H₂O, (II), were obtained during a structural study of vitamin B1 coenzyme. In both compounds, TPP is a neutral zwitterion, with its pyrophosphate group doubly deprotonated and its pyrimidine ring protonated, and it assumes the usual `F' conformation in terms of the two torsion angles about the bonds by which the methyl­ene group links the thia­zolium and pyrimidinium rings [1.1 (3) and 79.7 (3)° for (I), and 2.0 (3) and 75.5 (3)° for (II)]. In (I), two TPP mol­ecules are linked by a pair of O-H...O hydrogen bonds into a phosphate-pairing dimer. N-H...O hydrogen bonds connect the dimers into a sheet parallel to (101). In (II), the TPP mol­ecules are self-assembled solely by N-H...O hydrogen bonds, generating a tape structure along [001]. A comparison of the four known hydrate pseudopolymorphs of TPP shows that the phosphate-pairing dimers are basic building units for the formation of two-dimensional networks.

S1. Comment

Pseudopolymorphs are solvated forms of a compound which differ in the nature or stoichiometry of the included solvent molecules (Nangia, 2006). Like polymorphs, pseudopolymorphs are of importance in pharmaceutical science and solid-state chemistry because physical properties and bioavailability can be critically dependent on crystal forms. Thiamine (vitamin B1) in its pyrophosphate form (thiamine pyrophosphate, TPP) is a coenzyme for a number of enzyme systems which catalyse a number of important metabolic reactions, including the transfer of aldehyde groups and the oxidative and non-oxidative decarboxylation of α-keto acids (Breslow, 1958; Krampitz, 1969). The catalytic processes involve the recognition and reaction of a substrate electrophile such as pyruvate at nucleophilic site C1 of the deprotonated thiazolium group (see Fig. 1 for atomic numbering). Thiamine and TPP are not only biologically important molecules but potential building blocks for constructing hydrogen-bonded supramolecular arrays, on which anionic or electronegative guests are adsorbed (Aoki et al., 1993; Hu et al., 2001; Li & Hu, 2010), as they provide multiple sites that serve as hydrogen-bond donors and acceptors. A large number of crystal structures of thiamine compounds have been reported as models of host–guest interactions [65 hits from the Cambridge Structural Database (CSD), Version 5.33; Allen, 2002], including thiamine–anion salt compounds (43 hits) and thiamine–metal complexes (22 hits). However, only limited structural studies can be found for TPP (six hits from the CSD). In three of these compounds, TPP exists as a monovalent cation with a protonated pyrimidine ring and a deprotonated phosphate group (Bai et al., 2009; Pletcher & Sax, 1972), and in the others TPP acts as a neutral zwitterion with a doubly deprotonated pyrophosphate group. The structure of neutral TPP has been determined in its tetrahydrate form, (III) (CSD refcode THPPTH01; Pletcher et al., 1977), and 4.5-hydrate form, (IV) (THPPTI; Pletcher et al., 1979). Interestingly, both pseudopolymorphs (III) and (IV) show a two-dimensional hydrogen-bonded network, with similar N—H···O hydrogen-bonding interactions between the pyrimidine and pyrophosphate groups but different O—H···O hydrogen-bonding interactions between the pyrophosphate groups. This prompted us to examine the supramolecular structures in different hydrate pseudopolymorphs of TPP. We report here the crystal structures of a dihydrate form, (I), and a trihydrate form, (II).

The molecular dimensions in (I) (Fig. 1) and (II) (Fig. 2) are in agreement with each other. The C9—N2—C10 angles of the pyrimidinium ring are 120.3 (2) and 119.5 (2)°, respectively, for the two compounds, which are comparable with the reported value for a protonated pyrimidine ring (Hu et al., 2005; Pletcher & Sax, 1972) but larger than in derivatives in which the pyriminine ring is not protonated [115.8 (6) and 115.0 (7)°; Li & Hu, 2010]. It is evident from the P—O bond lengths and the location of the H atoms that both the inner and terminal phosphate groups are deprotonated, and thus the TPP molecule is a neutral zwitterion in both (I) and (II). As is usually observed in thiamine compounds, the TPP molecules adopt an F conformation in terms of the torsion angles: ϕ_T = 1.1 (3)° and ϕ_P = 79.7 (3)° for (I), with corresponding values of 2.0 (3) and 75.5 (3)° for (II) (ϕ_T = C8—C7—N1—C1 ≈ 0° and ϕ_P = N1—C7—C8—C11 ≈ ±90° for the F conformation; Blank et al., 1976). It has been shown that the manner in which thiamine is associated with anions or electronegative atoms is closely related to the molecular conformation (Aoki et al., 1993; Cramer et al., 1988). Two distinct types of anion-bridging interactions are observed, which link the thiazolium and pyrimidine rings of a thiamine molecule via hydrogen bonds and electrostatic contacts. They have been defined as type I and type II anion bridges, respectively (Hu et al., 1999). In (I), phosphate atom O7ⁱ (symmetry code as in Table 1) acts as a type-I anion bridge to link the two aromatic rings by accepting a hydrogen bond from atom C1 (Table 1) and making a close contact with the pyrimidine ring [O7ⁱ···centroid distance = 3.354 (3) Å] (Fig. 1). Water molecule O1W occupies the site of a type-II anion bridge to accept a hydrogen bond from atom N4 and making a close contact with the thiazolium ring [O1W···centroid distance = 3.389 (3) Å].

These two anion bridges also occur in (II) (Fig. 2 and Table 2). The role of type-I anion bridge is performed by a phosphate O atom, being of the form C1—H···O6ⁱ···pyrimidinium ring [O6ⁱ···centroid distance = 3.485 (3) Å; symmetry code as in Table 2], and the type-II anion bridge is another phosphate O atom, not a water molecule, being of the form N4—H···O3ⁱⁱⁱ···thiazolium ring [O3ⁱⁱⁱ···centroid distance = 3.653 (3) Å; symmetry code as in Table 2]. These two types of interaction stabilize the molecular conformation and the type-I anion bridge is characteristic of a thiamine molecule in the F conformation. Our results confirm that TPP hydrates follow this rule.

The conformations of the pyrophosphate groups differ significantly in (I) and (II). From the P1—O1—C6—C5 and O2—P1—O1—C6 torsion angles [-173.5 (2) and -169.7 (2)° in (I), and 113.0 (2) and -73.0 (2)° in (II), respectively], (I) has a more extended pyrophosphate side chain than (II). We note that the role of type-II anion bridge played by a water molecule is also present in tetrahydrate (III) and 4.5-hydrate (IV), similar to that in (I) but different from that played by a phosphate O atom in (II). This may lead to the difference in hydrogen-bonded supramolecular structures between these compounds, a two-dimensional network in (I), (III) and (IV) and a one-dimensional tape in (II), as described below.

The crystal packing in (I) and (II) is dominated by intermolecular hydrogen bonds involving TPP and water molecules. As shown in Fig. 3, the TPP molecules in (I) are self-assembled into a two-dimensional network which is stabilized by three types of hydrogen bonds, O_t—H···O_i, N_p—H···O_t and N_a—H···O_t (O_t is an O atom of the terminal phosphate, O_i is an O atom of the inner phosphate, N_p is the protonated N atom of the pyrimidine ring and N_a is the N atom of the amino group). Firstly, a dimer is formed through a pair of O5—H···O3^iv hydrogen bonds between two pyrophosphate groups across an inversion centre in an R₂²(12) motif (Bernstein et al., 1995). N2—H···O6ⁱⁱ and N4—H···O7ⁱⁱⁱ hydrogen bonds then link the dimers to complete a sheet parallel to (101) (symmetry codes as in Table 1). The sheet is further stabilized by π–π interactions between the thiazolium rings [centroid-to-centroid distance = 3.8877 (14) Å]. These sheets are packed with the meshes aligned, thus forming channels along [100]. The solvent water molecules lie in the channels and act as both hydrogen-bond donors and acceptors to interact with the TPP molecules (Table 1). In (II), two TPP molecules form a centrosymmetric cyclic dimer by a pair of N4—H···O3ⁱⁱⁱ hydrogen bonds in an R₂²(26) motif. The dimers are further connected by a pair of N2—H···O6ⁱⁱ hydrogen bonds (symmetry codes as in Table 2), leading to a one-dimensional tape structure along [001] (Fig. 4). The tapes are linked by water molecules through hydrogen bonds (Table 2).

We examined the structural details of the previously reported pseudopolymorphs (III) and (IV) in order to make a comparison of the supramolecular structures in the TPP hydrates. It is interesting to note that (III) and (IV) also exhibit two-dimensional networks built by three types of hydrogen bond, similar to the case of (I). The structure of (III), containing two crystallographically independent molecules A and B, is composed of two different molecular sheets. Two molecules A are linked by a pair of O_t—H···O_t hydrogen bonds in an R₂²(8) motif, forming a phosphate-pairing dimer. N_p—H···O_t and N_a—H···O_i hydrogen bonds connect the dimers into a sheet. Molecules B are self-assembled into a second sheet in a similar way, except the phosphate-pairing dimer is formed by a single O_t—H···O_t hydrogen bond in a D motif. Compound (IV) displays a sheet structure constructed in a similar way to molecules A in (III); a pair of O_t—H···O_t hydrogen bonds results in an R₂²(8) dimer, and N_p—H···O_t and N_a—H···O_i hydrogen bonds complete the sheet. Altogether, (I), (III) and (IV) show three kinds of phosphate-pairing dimer, as illustrated in Fig. 5. Despite the differences in these dimers, sheet structures are present in all three pseudopolymorphs. In contrast, there are no phosphate-pairing interactions in (II) and a tape structure is observed.

In summary, two types of anion bridge that have been frequently observed in thiamine compounds are present in the title TPP hydrates (I) and (II). The results could be helpful for understanding the interactions between the TPP coenzyme and substrate. The formation of two-dimensional networks in the neutral TPP zwitterion hydrates is closely related to the existence of hydrogen-bonded phosphate-pairing dimers exhibiting R₂²(12), R₂²(8) and D motifs. In the TPP systems, several phosphate O atoms can serve as hydrogen-bond acceptors from water donors, as it is observed that three O(water)—H···O(phosphate) hydrogen bonds are formed in (I) and five in (II). At the same time, a water molecule in (II) competes for the acceptor site on a phosphate group, thus interrupting the self-assembly of a phosphate-pairing dimer. However, from the four neutral TPP hydrates available at present, supramolecular synthons between the pyrophosphate groups are obviously predominant in the crystal packing of two-dimensional networks. Further work is needed to understand the factors that govern the crystal packing in TPP systems.

Related literature

For related literature, see: Allen (2002); Aoki et al. (1993); Bai et al. (2009); Bernstein et al. (1995); Blank et al. (1976); Breslow (1958); Cramer et al. (1988); Hu et al. (1999, 2001, 2005); Krampitz (1969); Li & Hu (2010); Nangia (2006); Pletcher & Sax (1972); Pletcher et al. (1977, 1979).

S2. Experimental

Compound (I) was prepared by mixing thiamine pyrophosphate hydrochloride (0.092 g, 0.2 mmol) and KNO₃ (0.020 g, 0.2 mmol) in water–methanol (8 ml, 1:1 v/v). Diffusing acetone into the mixture gave colourless crystals. Compound (II) was obtained by diffusing acetone into a solution of thiamine pyrophosphate hydrochloride (0.092 g, 0.2 mmol) in water–ethyl acetate (8 ml, 1:3 v/v) to afford colourless crystals.

S3. Refinement

C- and N-bound H atoms were positioned geometrically and refined as riding, with C—H = 0.93 (aromatic), 0.97 (CH₂) and 0.96 Å (CH₃) and N—H = 0.86 Å, and with U_iso(H) = 1.2(1.5 for methyl)U_eq(C,N). H atoms of the hydroxy groups and water molecules were located in difference Fourier maps and refined as riding, with U_iso(H) = 1.5U_eq(O).

Computing details

For both compounds, data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS (Siemens, 1996); data reduction: XSCANS (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. The molecular structure of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Dashed lines denote hydrogen bonds and dotted lines denote close contacts. [Symmetry code: (i) 2 - x, 1 - y, 1 - z.]
	Fig. 2. The molecular structure of (II), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Dashed lines denote hydrogen bonds and dotted lines denote close contacts. [Symmetry codes: (i) 1 - x, 1 - y, 2 - z; (iii) 1 - x, 2 - y, 2 - z.]
	Fig. 3. The two-dimensional hydrogen-bonded network in (I). Dashed lines denote hydrogen bonds. H atoms bonded to C atoms have been omitted for clarity.
	Fig. 4. The hydrogen-bonded tape in (II). Dashed lines denote hydrogen bonds. H atoms bonded to C atoms have been omitted for clarity.
	Fig. 5. Three kinds of phosphate-pairing dimers, formed (a) by a pair of Ot—H···Oi hydrogen bonds in (I), (b) by a pair of Ot—H···Ot hydrogen bonds for molecules A in (III) and in (IV), and (c) by a single Ot—H···Ot hydrogen bond for molecules B in (III). Dashed lines denote hydrogen bonds. H atoms not involved in hydrogen bonds have been omitted for clarity.

(I) 3-[(4-Amino-2-methylpyrimidin-1-ium-5-yl)methyl]-4-methyl-1,3-thiazol-3-ium-5-yl hydrogen pyrophosphate dihydrate

Crystal data

C12H18N4O7P2S·2H2O	Z = 2
Mr = 460.34	F(000) = 480
Triclinic, P1	Dx = 1.643 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.8778 (12) Å	Cell parameters from 30 reflections
b = 11.2134 (14) Å	θ = 6.7–20.0°
c = 11.7613 (14) Å	µ = 0.40 mm^−1
α = 69.368 (12)°	T = 295 K
β = 73.893 (12)°	Prism, colourless
γ = 89.070 (11)°	0.41 × 0.20 × 0.18 mm
V = 930.3 (2) Å^3

Data collection

Siemens P4 four-circle diffractometer	2647 reflections with I > 2σ(I)
Radiation source: sealed tube	Rint = 0.024
Graphite monochromator	θmax = 25.0°, θmin = 1.9°
2θ and ω scans	h = −1→9
Absorption correction: ψ scan (XSCANS; Siemens, 1996)	k = −12→12
Tmin = 0.852, Tmax = 0.931	l = −13→13
4169 measured reflections	3 standard reflections every 150 reflections
3259 independent reflections	intensity decay: 2.0%

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.116	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.070P)^2] where P = (Fo^2 + 2Fc^2)/3
3259 reflections	(Δ/σ)max = 0.001
256 parameters	Δρmax = 0.26 e Å^−3
6 restraints	Δρmin = −0.33 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	0.60227 (8)	0.62188 (7)	0.57391 (6)	0.03270 (19)
P1	0.92737 (9)	0.87753 (6)	0.27302 (6)	0.02922 (19)
P2	1.23877 (9)	0.80004 (6)	0.12596 (6)	0.02772 (19)
O1	0.7447 (2)	0.78904 (16)	0.31641 (17)	0.0343 (4)
O2	1.0549 (2)	0.77456 (17)	0.24144 (18)	0.0375 (5)
O3	0.9345 (3)	0.98886 (19)	0.15739 (18)	0.0451 (5)
O4	0.9537 (3)	0.8990 (2)	0.3838 (2)	0.0543 (6)
O5	1.1735 (3)	0.82538 (19)	0.0060 (2)	0.0484 (6)
H5	1.1553	0.9009	−0.0225	0.073*
O6	1.3444 (3)	0.91110 (17)	0.12017 (19)	0.0389 (5)
O7	1.3120 (2)	0.67384 (16)	0.15106 (17)	0.0342 (4)
N1	0.3092 (3)	0.50824 (18)	0.71860 (18)	0.0245 (5)
N2	0.3001 (3)	0.1603 (2)	1.0786 (2)	0.0325 (5)
H2	0.3162	0.0805	1.0959	0.039*
N3	0.3059 (3)	0.34223 (19)	1.13225 (19)	0.0297 (5)
N4	0.2547 (3)	0.5357 (2)	1.0012 (2)	0.0319 (5)
H4A	0.2735	0.5686	1.0530	0.038*
H4B	0.2290	0.5833	0.9339	0.038*
C1	0.4783 (3)	0.5184 (2)	0.7135 (2)	0.0298 (6)
H1	0.5234	0.4730	0.7800	0.036*
C2	0.2706 (3)	0.5854 (2)	0.6088 (2)	0.0258 (5)
C3	0.4176 (3)	0.6555 (2)	0.5193 (2)	0.0269 (5)
C4	0.0860 (4)	0.5818 (3)	0.5998 (3)	0.0379 (7)
H4C	0.0838	0.6365	0.5165	0.057*
H4D	0.0096	0.6108	0.6621	0.057*
H4E	0.0457	0.4957	0.6149	0.057*
C5	0.4287 (4)	0.7511 (3)	0.3891 (2)	0.0317 (6)
H5A	0.4372	0.7054	0.3317	0.038*
H5B	0.3196	0.7929	0.3935	0.038*
C6	0.5817 (4)	0.8512 (3)	0.3350 (3)	0.0355 (6)
H6A	0.5753	0.9131	0.2547	0.043*
H6B	0.5784	0.8958	0.3927	0.043*
C7	0.1683 (3)	0.4247 (3)	0.8313 (2)	0.0299 (6)
H7A	0.1140	0.3637	0.8074	0.036*
H7B	0.0772	0.4771	0.8568	0.036*
C8	0.2335 (3)	0.3532 (2)	0.9420 (2)	0.0259 (5)
C9	0.2538 (3)	0.2258 (2)	0.9745 (2)	0.0311 (6)
H9	0.2349	0.1836	0.9230	0.037*
C10	0.3217 (3)	0.2184 (2)	1.1568 (2)	0.0316 (6)
C11	0.2651 (3)	0.4125 (2)	1.0249 (2)	0.0255 (5)
C12	0.3648 (5)	0.1384 (3)	1.2736 (3)	0.0501 (8)
H12A	0.4907	0.1472	1.2598	0.075*
H12B	0.3264	0.0505	1.2947	0.075*
H12C	0.3055	0.1657	1.3421	0.075*
O1W	0.1593 (4)	0.7354 (2)	0.8001 (2)	0.0619 (7)
H1A	0.1427	0.7762	0.7276	0.093*
H1B	0.1380	0.7834	0.8445	0.093*
O2W	0.8689 (4)	1.1173 (2)	0.4343 (2)	0.0760 (8)
H2A	0.9049	1.0533	0.4118	0.114*
H2B	0.9379	1.1301	0.4757	0.114*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0243 (3)	0.0375 (4)	0.0313 (4)	0.0020 (3)	−0.0077 (3)	−0.0068 (3)
P1	0.0328 (4)	0.0263 (4)	0.0304 (4)	0.0030 (3)	−0.0106 (3)	−0.0113 (3)
P2	0.0298 (4)	0.0233 (4)	0.0340 (4)	0.0045 (3)	−0.0122 (3)	−0.0128 (3)
O1	0.0307 (10)	0.0276 (10)	0.0384 (10)	0.0025 (8)	−0.0032 (8)	−0.0099 (8)
O2	0.0330 (10)	0.0283 (10)	0.0496 (12)	0.0012 (8)	−0.0062 (9)	−0.0165 (9)
O3	0.0460 (12)	0.0350 (11)	0.0408 (11)	0.0012 (9)	−0.0114 (9)	0.0015 (9)
O4	0.0807 (17)	0.0496 (13)	0.0537 (13)	0.0134 (12)	−0.0364 (13)	−0.0312 (11)
O5	0.0770 (16)	0.0372 (12)	0.0476 (12)	0.0218 (11)	−0.0352 (12)	−0.0225 (10)
O6	0.0365 (11)	0.0259 (10)	0.0537 (12)	−0.0013 (8)	−0.0098 (9)	−0.0159 (9)
O7	0.0410 (11)	0.0258 (10)	0.0449 (11)	0.0107 (8)	−0.0204 (9)	−0.0177 (8)
N1	0.0262 (11)	0.0235 (11)	0.0266 (11)	0.0027 (8)	−0.0087 (9)	−0.0118 (9)
N2	0.0417 (13)	0.0199 (11)	0.0359 (12)	−0.0010 (9)	−0.0103 (10)	−0.0105 (9)
N3	0.0358 (12)	0.0257 (11)	0.0295 (11)	0.0025 (9)	−0.0117 (10)	−0.0105 (9)
N4	0.0437 (14)	0.0266 (12)	0.0303 (11)	0.0050 (10)	−0.0155 (10)	−0.0127 (9)
C1	0.0279 (13)	0.0327 (14)	0.0290 (13)	0.0044 (11)	−0.0113 (11)	−0.0091 (11)
C2	0.0311 (13)	0.0248 (13)	0.0266 (12)	0.0049 (10)	−0.0109 (11)	−0.0133 (10)
C3	0.0259 (13)	0.0287 (13)	0.0284 (13)	0.0056 (10)	−0.0078 (11)	−0.0133 (11)
C4	0.0310 (15)	0.0425 (16)	0.0403 (15)	0.0017 (12)	−0.0142 (12)	−0.0121 (13)
C5	0.0314 (14)	0.0363 (15)	0.0265 (13)	0.0078 (12)	−0.0093 (11)	−0.0097 (11)
C6	0.0359 (15)	0.0305 (14)	0.0355 (15)	0.0083 (12)	−0.0080 (12)	−0.0083 (12)
C7	0.0275 (13)	0.0322 (14)	0.0293 (13)	−0.0032 (11)	−0.0065 (11)	−0.0112 (11)
C8	0.0238 (12)	0.0272 (13)	0.0252 (12)	−0.0028 (10)	−0.0033 (10)	−0.0103 (10)
C9	0.0359 (15)	0.0292 (14)	0.0298 (13)	−0.0032 (11)	−0.0076 (11)	−0.0139 (11)
C10	0.0333 (14)	0.0276 (14)	0.0325 (14)	−0.0012 (11)	−0.0081 (11)	−0.0100 (11)
C11	0.0221 (12)	0.0250 (13)	0.0267 (12)	−0.0024 (10)	−0.0027 (10)	−0.0093 (10)
C12	0.078 (2)	0.0298 (15)	0.0455 (18)	0.0058 (16)	−0.0297 (17)	−0.0078 (13)
O1W	0.106 (2)	0.0445 (13)	0.0482 (13)	0.0214 (13)	−0.0354 (14)	−0.0233 (11)
O2W	0.130 (3)	0.0522 (15)	0.0764 (17)	0.0467 (16)	−0.0632 (18)	−0.0364 (13)

Geometric parameters (Å, º)

S1—C1	1.673 (3)	C2—C4	1.490 (4)
S1—C3	1.733 (3)	C3—C5	1.507 (3)
P1—O4	1.473 (2)	C4—H4C	0.9600
P1—O3	1.4746 (19)	C4—H4D	0.9600
P1—O2	1.5933 (19)	C4—H4E	0.9600
P1—O1	1.6119 (19)	C5—C6	1.495 (4)
P2—O6	1.4802 (19)	C5—H5A	0.9700
P2—O7	1.4821 (18)	C5—H5B	0.9700
P2—O5	1.566 (2)	C6—H6A	0.9700
P2—O2	1.635 (2)	C6—H6B	0.9700
O1—C6	1.451 (3)	C7—C8	1.491 (4)
O5—H5	0.8200	C7—H7A	0.9700
N1—C1	1.322 (3)	C7—H7B	0.9700
N1—C2	1.390 (3)	C8—C9	1.363 (3)
N1—C7	1.486 (3)	C8—C11	1.432 (3)
N2—C9	1.333 (3)	C9—H9	0.9300
N2—C10	1.347 (3)	C10—C12	1.479 (4)
N2—H2	0.8600	C12—H12A	0.9600
N3—C10	1.326 (3)	C12—H12B	0.9600
N3—C11	1.354 (3)	C12—H12C	0.9600
N4—C11	1.315 (3)	O1W—H1A	0.8598
N4—H4A	0.8600	O1W—H1B	0.8586
N4—H4B	0.8600	O2W—H2A	0.8664
C1—H1	0.9300	O2W—H2B	0.8667
C2—C3	1.355 (3)
C1—S1—C3	91.14 (12)	H4D—C4—H4E	109.5
O4—P1—O3	119.05 (13)	C6—C5—C3	114.5 (2)
O4—P1—O2	109.23 (12)	C6—C5—H5A	108.6
O3—P1—O2	111.35 (12)	C3—C5—H5A	108.6
O4—P1—O1	109.30 (13)	C6—C5—H5B	108.6
O3—P1—O1	109.49 (11)	C3—C5—H5B	108.6
O2—P1—O1	95.96 (10)	H5A—C5—H5B	107.6
O6—P2—O7	119.75 (11)	O1—C6—C5	108.4 (2)
O6—P2—O5	113.58 (12)	O1—C6—H6A	110.0
O7—P2—O5	105.91 (11)	C5—C6—H6A	110.0
O6—P2—O2	107.88 (11)	O1—C6—H6B	110.0
O7—P2—O2	104.54 (10)	C5—C6—H6B	110.0
O5—P2—O2	103.69 (12)	H6A—C6—H6B	108.4
C6—O1—P1	116.73 (16)	N1—C7—C8	113.8 (2)
P1—O2—P2	127.76 (12)	N1—C7—H7A	108.8
P2—O5—H5	109.5	C8—C7—H7A	108.8
C1—N1—C2	114.2 (2)	N1—C7—H7B	108.8
C1—N1—C7	124.3 (2)	C8—C7—H7B	108.8
C2—N1—C7	121.5 (2)	H7A—C7—H7B	107.7
C9—N2—C10	120.3 (2)	C9—C8—C11	116.6 (2)
C9—N2—H2	119.8	C9—C8—C7	121.4 (2)
C10—N2—H2	119.8	C11—C8—C7	121.8 (2)
C10—N3—C11	118.7 (2)	N2—C9—C8	121.3 (2)
C11—N4—H4A	120.0	N2—C9—H9	119.4
C11—N4—H4B	120.0	C8—C9—H9	119.4
H4A—N4—H4B	120.0	N3—C10—N2	122.5 (2)
N1—C1—S1	112.47 (19)	N3—C10—C12	120.2 (2)
N1—C1—H1	123.8	N2—C10—C12	117.3 (2)
S1—C1—H1	123.8	N4—C11—N3	117.4 (2)
C3—C2—N1	111.7 (2)	N4—C11—C8	122.0 (2)
C3—C2—C4	128.1 (2)	N3—C11—C8	120.6 (2)
N1—C2—C4	120.2 (2)	C10—C12—H12A	109.5
C2—C3—C5	127.3 (2)	C10—C12—H12B	109.5
C2—C3—S1	110.50 (19)	H12A—C12—H12B	109.5
C5—C3—S1	122.20 (18)	C10—C12—H12C	109.5
C2—C4—H4C	109.5	H12A—C12—H12C	109.5
C2—C4—H4D	109.5	H12B—C12—H12C	109.5
H4C—C4—H4D	109.5	H1A—O1W—H1B	108.7
C2—C4—H4E	109.5	H2A—O2W—H2B	107.2
H4C—C4—H4E	109.5
O4—P1—O1—C6	77.5 (2)	C2—C3—C5—C6	154.8 (3)
O3—P1—O1—C6	−54.5 (2)	S1—C3—C5—C6	−24.9 (3)
O2—P1—O1—C6	−169.68 (18)	P1—O1—C6—C5	−173.47 (16)
O4—P1—O2—P2	−104.39 (18)	C3—C5—C6—O1	64.2 (3)
O3—P1—O2—P2	29.1 (2)	C1—N1—C7—C8	1.1 (3)
O1—P1—O2—P2	142.77 (15)	C2—N1—C7—C8	−177.5 (2)
O6—P2—O2—P1	45.00 (19)	N1—C7—C8—C9	−105.1 (3)
O7—P2—O2—P1	173.48 (14)	N1—C7—C8—C11	79.7 (3)
O5—P2—O2—P1	−75.74 (17)	C10—N2—C9—C8	2.4 (4)
C2—N1—C1—S1	−0.5 (3)	C11—C8—C9—N2	0.2 (4)
C7—N1—C1—S1	−179.20 (18)	C7—C8—C9—N2	−175.2 (2)
C3—S1—C1—N1	0.7 (2)	C11—N3—C10—N2	0.6 (4)
C1—N1—C2—C3	−0.1 (3)	C11—N3—C10—C12	−179.6 (3)
C7—N1—C2—C3	178.7 (2)	C9—N2—C10—N3	−2.9 (4)
C1—N1—C2—C4	178.6 (2)	C9—N2—C10—C12	177.2 (3)
C7—N1—C2—C4	−2.7 (3)	C10—N3—C11—N4	−178.3 (2)
N1—C2—C3—C5	−179.1 (2)	C10—N3—C11—C8	2.2 (4)
C4—C2—C3—C5	2.4 (4)	C9—C8—C11—N4	178.0 (2)
N1—C2—C3—S1	0.6 (3)	C7—C8—C11—N4	−6.6 (4)
C4—C2—C3—S1	−177.9 (2)	C9—C8—C11—N3	−2.5 (3)
C1—S1—C3—C2	−0.8 (2)	C7—C8—C11—N3	172.9 (2)
C1—S1—C3—C5	179.0 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O7^i	0.93	2.15	2.972 (3)	147
N2—H2···O6^ii	0.86	1.84	2.696 (3)	175
N4—H4A···O7^iii	0.86	2.00	2.846 (3)	170
N4—H4B···O1W	0.86	2.06	2.893 (3)	163
O5—H5···O3^iv	0.82	1.94	2.605 (3)	138
O1W—H1A···O2W^v	0.86	1.88	2.738 (3)	172
O1W—H1B···O5^iii	0.86	2.20	2.962 (3)	148
O2W—H2A···O4	0.87	1.89	2.746 (3)	171
O2W—H2B···O4^vi	0.87	1.99	2.818 (3)	159

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

(II) 3-[(4-Amino-2-methylpyrimidin-1-ium-5-yl)methyl]-4-methyl-1,3-thiazol-3-ium-5-yl hydrogen pyrophosphate trihydrate

Crystal data

C12H18N4O7P2S·3H2O	Z = 2
Mr = 478.35	F(000) = 500
Triclinic, P1	Dx = 1.550 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.3776 (12) Å	Cell parameters from 30 reflections
b = 9.2397 (13) Å	θ = 9.7–19.9°
c = 14.208 (2) Å	µ = 0.37 mm^−1
α = 87.896 (11)°	T = 295 K
β = 74.324 (13)°	Plate, colourless
γ = 75.559 (11)°	0.47 × 0.38 × 0.13 mm
V = 1024.8 (3) Å^3

Data collection

Siemens P4 four-circle diffractometer	2953 reflections with I > 2σ(I)
Radiation source: sealed tube	Rint = 0.017
Graphite monochromator	θmax = 25.0°, θmin = 1.5°
2θ and ω scans	h = −1→9
Absorption correction: ψ scan (XSCANS; Siemens, 1996)	k = −10→10
Tmin = 0.844, Tmax = 0.953	l = −16→16
4473 measured reflections	3 standard reflections every 150 reflections
3593 independent reflections	intensity decay: 2.5%

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.111	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0566P)^2 + 0.4384P] where P = (Fo^2 + 2Fc^2)/3
3593 reflections	(Δ/σ)max = 0.001
265 parameters	Δρmax = 0.45 e Å^−3
0 restraints	Δρmin = −0.38 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	0.56965 (10)	0.68932 (9)	0.88403 (5)	0.0446 (2)
P1	0.45328 (8)	0.76825 (7)	1.17304 (4)	0.02809 (17)
P2	0.72596 (8)	0.51133 (7)	1.20239 (4)	0.02943 (18)
O1	0.5264 (2)	0.8371 (3)	1.07179 (13)	0.0469 (5)
O2	0.5695 (3)	0.6016 (2)	1.16260 (17)	0.0574 (6)
O3	0.4726 (2)	0.8499 (2)	1.25489 (13)	0.0395 (4)
O4	0.2808 (2)	0.7564 (2)	1.17169 (14)	0.0466 (5)
O5	0.7733 (2)	0.3606 (2)	1.14276 (13)	0.0375 (4)
H5	0.7955	0.3769	1.0841	0.056*
O6	0.6629 (3)	0.4770 (2)	1.30680 (13)	0.0526 (6)
O7	0.8613 (3)	0.5935 (3)	1.17575 (16)	0.0586 (6)
N1	0.6884 (2)	0.7951 (2)	0.72405 (13)	0.0258 (4)
N2	0.5270 (3)	0.6725 (2)	0.45746 (14)	0.0364 (5)
H2	0.5614	0.6032	0.4125	0.044*
N3	0.3039 (3)	0.8628 (2)	0.54785 (14)	0.0326 (5)
N4	0.3484 (3)	1.0109 (2)	0.65830 (15)	0.0339 (5)
H4A	0.2430	1.0593	0.6686	0.041*
H4B	0.4122	1.0367	0.6896	0.041*
C1	0.5710 (3)	0.7256 (3)	0.76771 (17)	0.0341 (6)
H1	0.4965	0.6994	0.7372	0.041*
C2	0.7878 (3)	0.8217 (3)	0.78318 (17)	0.0278 (5)
C3	0.7374 (3)	0.7706 (3)	0.87406 (17)	0.0314 (5)
C4	0.9316 (3)	0.8927 (3)	0.7429 (2)	0.0400 (6)
H4C	0.9900	0.8970	0.7919	0.060*
H4D	0.8878	0.9922	0.7236	0.060*
H4E	1.0101	0.8349	0.6870	0.060*
C5	0.8092 (3)	0.7750 (3)	0.96008 (18)	0.0366 (6)
H5A	0.9139	0.8084	0.9384	0.044*
H5B	0.8384	0.6745	0.9835	0.044*
C6	0.6873 (3)	0.8767 (3)	1.04385 (18)	0.0364 (6)
H6A	0.7359	0.8676	1.0992	0.044*
H6B	0.6701	0.9798	1.0241	0.044*
C7	0.7134 (3)	0.8448 (3)	0.62156 (17)	0.0297 (5)
H7A	0.8280	0.7952	0.5837	0.036*
H7B	0.7043	0.9516	0.6210	0.036*
C8	0.5868 (3)	0.8125 (3)	0.57386 (16)	0.0280 (5)
C9	0.6374 (3)	0.7029 (3)	0.50307 (17)	0.0338 (6)
H9	0.7508	0.6476	0.4856	0.041*
C10	0.3627 (3)	0.7515 (3)	0.48273 (17)	0.0338 (6)
C11	0.4122 (3)	0.8973 (3)	0.59463 (16)	0.0272 (5)
C12	0.2417 (4)	0.7084 (4)	0.4354 (2)	0.0477 (7)
H12A	0.1805	0.7954	0.4093	0.072*
H12B	0.1621	0.6661	0.4830	0.072*
H12C	0.3048	0.6359	0.3834	0.072*
O1W	0.9665 (2)	0.7524 (2)	1.29550 (15)	0.0498 (5)
H1A	1.0652	0.7622	1.2606	0.075*
H1B	0.9246	0.7084	1.2587	0.075*
O2W	0.8420 (3)	0.3743 (3)	0.95506 (14)	0.0632 (7)
H2A	0.8023	0.3276	0.9197	0.095*
H2B	0.9399	0.3861	0.9237	0.095*
O3W	0.9915 (3)	0.4591 (3)	1.37667 (17)	0.0718 (7)
H3A	1.0225	0.5385	1.3511	0.108*
H3B	0.9124	0.4475	1.3507	0.108*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0507 (4)	0.0698 (5)	0.0282 (3)	−0.0382 (4)	−0.0159 (3)	0.0142 (3)
P1	0.0252 (3)	0.0359 (3)	0.0233 (3)	−0.0069 (3)	−0.0063 (2)	−0.0072 (2)
P2	0.0273 (3)	0.0336 (3)	0.0287 (3)	−0.0099 (3)	−0.0067 (3)	−0.0056 (3)
O1	0.0374 (11)	0.0802 (15)	0.0284 (10)	−0.0222 (10)	−0.0112 (8)	0.0057 (9)
O2	0.0645 (14)	0.0364 (11)	0.0809 (16)	−0.0014 (10)	−0.0435 (13)	−0.0151 (10)
O3	0.0422 (10)	0.0472 (11)	0.0309 (9)	−0.0146 (9)	−0.0078 (8)	−0.0139 (8)
O4	0.0317 (10)	0.0694 (14)	0.0415 (11)	−0.0178 (9)	−0.0075 (8)	−0.0146 (10)
O5	0.0387 (10)	0.0391 (10)	0.0309 (9)	−0.0057 (8)	−0.0053 (8)	−0.0086 (8)
O6	0.0810 (16)	0.0443 (11)	0.0269 (10)	−0.0178 (11)	−0.0022 (10)	−0.0067 (8)
O7	0.0468 (12)	0.0752 (15)	0.0612 (14)	−0.0339 (11)	−0.0075 (11)	−0.0137 (12)
N1	0.0261 (10)	0.0294 (10)	0.0215 (9)	−0.0072 (8)	−0.0053 (8)	0.0002 (8)
N2	0.0511 (14)	0.0360 (12)	0.0204 (10)	−0.0127 (10)	−0.0043 (9)	−0.0065 (9)
N3	0.0346 (11)	0.0402 (12)	0.0254 (10)	−0.0140 (9)	−0.0080 (9)	−0.0002 (9)
N4	0.0279 (11)	0.0386 (12)	0.0341 (11)	−0.0029 (9)	−0.0098 (9)	−0.0111 (9)
C1	0.0381 (14)	0.0437 (14)	0.0283 (13)	−0.0204 (12)	−0.0133 (11)	0.0051 (11)
C2	0.0233 (12)	0.0294 (12)	0.0300 (12)	−0.0048 (9)	−0.0071 (10)	−0.0028 (10)
C3	0.0283 (13)	0.0384 (13)	0.0289 (12)	−0.0099 (10)	−0.0084 (10)	−0.0004 (10)
C4	0.0305 (14)	0.0491 (16)	0.0431 (15)	−0.0151 (12)	−0.0100 (12)	0.0046 (12)
C5	0.0296 (13)	0.0506 (16)	0.0320 (13)	−0.0094 (12)	−0.0129 (11)	0.0023 (12)
C6	0.0395 (14)	0.0441 (15)	0.0296 (13)	−0.0139 (12)	−0.0131 (11)	0.0020 (11)
C7	0.0277 (12)	0.0346 (13)	0.0239 (11)	−0.0069 (10)	−0.0032 (10)	0.0023 (9)
C8	0.0315 (13)	0.0310 (12)	0.0191 (11)	−0.0072 (10)	−0.0035 (9)	0.0011 (9)
C9	0.0391 (14)	0.0329 (13)	0.0240 (12)	−0.0052 (11)	−0.0027 (11)	−0.0006 (10)
C10	0.0473 (16)	0.0398 (14)	0.0180 (11)	−0.0200 (12)	−0.0069 (11)	0.0022 (10)
C11	0.0319 (12)	0.0317 (12)	0.0184 (11)	−0.0101 (10)	−0.0055 (9)	0.0011 (9)
C12	0.0597 (19)	0.0611 (19)	0.0329 (14)	−0.0333 (16)	−0.0128 (13)	−0.0023 (13)
O1W	0.0370 (11)	0.0633 (13)	0.0491 (12)	−0.0172 (10)	−0.0050 (9)	−0.0147 (10)
O2W	0.0565 (14)	0.113 (2)	0.0310 (11)	−0.0417 (14)	−0.0082 (10)	−0.0129 (12)
O3W	0.0761 (17)	0.0641 (15)	0.0636 (15)	0.0021 (13)	−0.0180 (13)	0.0050 (12)

Geometric parameters (Å, º)

S1—C1	1.672 (2)	C3—C5	1.507 (3)
S1—C3	1.723 (2)	C4—H4C	0.9600
P1—O3	1.4746 (17)	C4—H4D	0.9600
P1—O4	1.4812 (19)	C4—H4E	0.9600
P1—O1	1.5813 (19)	C5—C6	1.513 (4)
P1—O2	1.591 (2)	C5—H5A	0.9700
P2—O7	1.477 (2)	C5—H5B	0.9700
P2—O6	1.485 (2)	C6—H6A	0.9700
P2—O5	1.5633 (18)	C6—H6B	0.9700
P2—O2	1.598 (2)	C7—C8	1.496 (3)
O1—C6	1.433 (3)	C7—H7A	0.9700
O5—H5	0.8200	C7—H7B	0.9700
N1—C1	1.311 (3)	C8—C9	1.359 (3)
N1—C2	1.398 (3)	C8—C11	1.433 (3)
N1—C7	1.486 (3)	C9—H9	0.9300
N2—C10	1.344 (4)	C10—C12	1.492 (4)
N2—C9	1.350 (3)	C12—H12A	0.9600
N2—H2	0.8600	C12—H12B	0.9600
N3—C10	1.314 (3)	C12—H12C	0.9600
N3—C11	1.361 (3)	O1W—H1A	0.8665
N4—C11	1.317 (3)	O1W—H1B	0.8645
N4—H4A	0.8600	O2W—H2A	0.8523
N4—H4B	0.8600	O2W—H2B	0.8522
C1—H1	0.9300	O3W—H3A	0.8736
C2—C3	1.353 (3)	O3W—H3B	0.8700
C2—C4	1.485 (3)
C1—S1—C3	91.07 (12)	H4D—C4—H4E	109.5
O3—P1—O4	119.48 (11)	C3—C5—C6	113.5 (2)
O3—P1—O1	111.00 (11)	C3—C5—H5A	108.9
O4—P1—O1	105.10 (11)	C6—C5—H5A	108.9
O3—P1—O2	110.61 (11)	C3—C5—H5B	108.9
O4—P1—O2	106.06 (12)	C6—C5—H5B	108.9
O1—P1—O2	103.23 (13)	H5A—C5—H5B	107.7
O7—P2—O6	118.21 (13)	O1—C6—C5	109.9 (2)
O7—P2—O5	113.21 (12)	O1—C6—H6A	109.7
O6—P2—O5	106.48 (11)	C5—C6—H6A	109.7
O7—P2—O2	107.72 (13)	O1—C6—H6B	109.7
O6—P2—O2	109.95 (14)	C5—C6—H6B	109.7
O5—P2—O2	99.71 (10)	H6A—C6—H6B	108.2
C6—O1—P1	124.44 (16)	N1—C7—C8	113.11 (19)
P1—O2—P2	136.32 (13)	N1—C7—H7A	109.0
P2—O5—H5	109.5	C8—C7—H7A	109.0
C1—N1—C2	114.1 (2)	N1—C7—H7B	109.0
C1—N1—C7	123.8 (2)	C8—C7—H7B	109.0
C2—N1—C7	122.14 (19)	H7A—C7—H7B	107.8
C10—N2—C9	119.5 (2)	C9—C8—C11	116.5 (2)
C10—N2—H2	120.2	C9—C8—C7	120.0 (2)
C9—N2—H2	120.2	C11—C8—C7	123.4 (2)
C10—N3—C11	118.9 (2)	N2—C9—C8	121.5 (2)
C11—N4—H4A	120.0	N2—C9—H9	119.3
C11—N4—H4B	120.0	C8—C9—H9	119.3
H4A—N4—H4B	120.0	N3—C10—N2	123.1 (2)
N1—C1—S1	112.75 (18)	N3—C10—C12	118.9 (2)
N1—C1—H1	123.6	N2—C10—C12	118.1 (2)
S1—C1—H1	123.6	N4—C11—N3	116.8 (2)
C3—C2—N1	111.2 (2)	N4—C11—C8	122.8 (2)
C3—C2—C4	128.2 (2)	N3—C11—C8	120.4 (2)
N1—C2—C4	120.5 (2)	C10—C12—H12A	109.5
C2—C3—C5	128.9 (2)	C10—C12—H12B	109.5
C2—C3—S1	110.89 (18)	H12A—C12—H12B	109.5
C5—C3—S1	120.16 (18)	C10—C12—H12C	109.5
C2—C4—H4C	109.5	H12A—C12—H12C	109.5
C2—C4—H4D	109.5	H12B—C12—H12C	109.5
H4C—C4—H4D	109.5	H1A—O1W—H1B	107.4
C2—C4—H4E	109.5	H2A—O2W—H2B	111.0
H4C—C4—H4E	109.5	H3A—O3W—H3B	106.4
O3—P1—O1—C6	45.5 (2)	C2—C3—C5—C6	112.7 (3)
O4—P1—O1—C6	176.1 (2)	S1—C3—C5—C6	−68.3 (3)
O2—P1—O1—C6	−73.0 (2)	P1—O1—C6—C5	113.0 (2)
O3—P1—O2—P2	−15.2 (3)	C3—C5—C6—O1	53.9 (3)
O4—P1—O2—P2	−146.1 (2)	C1—N1—C7—C8	2.0 (3)
O1—P1—O2—P2	103.6 (2)	C2—N1—C7—C8	−176.7 (2)
O7—P2—O2—P1	−54.2 (3)	N1—C7—C8—C9	−108.1 (2)
O6—P2—O2—P1	75.9 (3)	N1—C7—C8—C11	75.5 (3)
O5—P2—O2—P1	−172.5 (2)	C10—N2—C9—C8	−0.4 (4)
C2—N1—C1—S1	0.8 (3)	C11—C8—C9—N2	−2.3 (3)
C7—N1—C1—S1	−177.98 (17)	C7—C8—C9—N2	−178.9 (2)
C3—S1—C1—N1	−0.4 (2)	C11—N3—C10—N2	−2.3 (4)
C1—N1—C2—C3	−0.9 (3)	C11—N3—C10—C12	176.7 (2)
C7—N1—C2—C3	178.0 (2)	C9—N2—C10—N3	2.9 (4)
C1—N1—C2—C4	177.0 (2)	C9—N2—C10—C12	−176.1 (2)
C7—N1—C2—C4	−4.2 (3)	C10—N3—C11—N4	179.1 (2)
N1—C2—C3—C5	179.5 (2)	C10—N3—C11—C8	−0.7 (3)
C4—C2—C3—C5	1.9 (4)	C9—C8—C11—N4	−176.9 (2)
N1—C2—C3—S1	0.5 (3)	C7—C8—C11—N4	−0.4 (4)
C4—C2—C3—S1	−177.1 (2)	C9—C8—C11—N3	2.9 (3)
C1—S1—C3—C2	−0.1 (2)	C7—C8—C11—N3	179.4 (2)
C1—S1—C3—C5	−179.2 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O6^i	0.93	2.54	3.400 (3)	154
N2—H2···O6^ii	0.86	1.81	2.662 (3)	169
N4—H4A···O1W^iii	0.86	2.10	2.910 (3)	156
N4—H4B···O3^iii	0.86	1.90	2.739 (3)	163
O5—H5···O2W	0.82	1.77	2.577 (3)	169
O1W—H1A···O4^iv	0.87	1.89	2.751 (3)	171
O1W—H1B···O7	0.86	1.87	2.733 (3)	172
O2W—H2A···O4^i	0.85	1.90	2.746 (3)	172
O2W—H2B···O7^v	0.85	1.92	2.748 (3)	165
O3W—H3A···O1W	0.87	2.09	2.888 (3)	151
O3W—H3B···O6	0.87	2.29	3.135 (4)	164

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