Three-dimensional hydrogen-bonded framework in bis­(melamin-1-ium) naphthalene-1,5-disulfonate melamine penta­hydrate

Crystals of the title compound, 2C₃H₇N₆⁺·C₁₀H₆O₆S₂²⁻·C₃H₆N₆·5H₂O, are built up of neutral 2,4,6-triamino-1,3,5-triazine (melamine), singly protonated melaminium cations, naphthalene-1,5-disulfonate dianions and water mol­ecules. Two independent anions lie across centres of inversion in the space group P. The melamine molecules are connected by N—H...N hydrogen bonds into two different one-dimensional polymers almost parallel to the (010) plane, forming a stacking structure along the b axis. The centrosymmetric naphthalene-1,5-disulfonate anions inter­act with water mol­ecules via O—H...O hydrogen bonds, forming layers parallel to the (001) plane. The cations and anions are connected by N—H...O and O—H...N hydrogen bonds to form a three-dimensional supra­molecular framework.

S1. Comment

The present study is a continuation of our investigations of the hydrogen-bonding systems formed by triazine derivatives in the solid state (Perpétuo & Janczak, 2007; Janczak & Kubiak, 2005a,b). Triazine and its derivatives, especially 2,4,6-triamino-1,3,5-triazine (melamine) and its organic and inorganic complexes or salts, are widely used in crystal engineering to built up extended frameworks, since they contain components of complementary arrays of hydrogen-bonding sites (Perpétuo & Janczak, 2004; Janczak & Perpétuo, 2003; Desiraju, 2002; Sherrington & Taskinen, 2001; Krische & Lehn, 2000; Row, 1999; MacDonald & Whitesides, 1994). Hydrogen bonds are widely used as the principal interactions in crystal engineering since they are directional and relatively strong (Steiner, 2002; Moulton & Zaworotko, 2001; Desiraju, 1990). Our interest in these types of compounds arises from the possibility of obtaining materials suitable for nonlinear optics (Janczak & Perpétuo, 2002; Marchewka et al. 2003; Perpétuo & Janczak, 2006). In order to expand the understanding of the solid-state physical–organic chemistry of compounds that form multiple N—H···N and N—H···O hydrogen-bonding systems, we present here the solid-state structure of bis(melamin-1-ium) naphthalene-1,5-disulfonate (1,5-NDS) melamine pentahydrate, (I).

The asymmetric unit of (I) consists of a neutral melamine molecule, two melaminium cations, each singly protonated at one of three ring N atoms, five water molecules, all in general positions, and two independent anions, each lying across a centre of inversion (Fig. 1). Thus, (I) is an example of a compound containing both a neutral melamine molecule and protonated melaminium cations, and to the best of our knowledge it is only the second example of this type (Cambridge Structural Database, Version?; Allen, 2002).

The triazine rings of the neutral melamine and the two protonated melaminium cations are essentially planar [the deviation of the N and C atoms from the mean plane is less than 0.033 (3) Å], but both exhibit significant distortion from the ideal hexagonal form (Table 1). In the neutral melamine molecule, the internal C—N—C angles are significantly greater than 120° and the internal N—C—N angles are significantly smaller than 120°. However, in the protonated melaminium units, only the C—N—C angles at the non-protonated N atoms are smaller than 120°, while the C—N—C angles at the protonated ring atoms are almost equal to 120°. This distortion results from the steric effect of the lone-pair electrons, predicted by the valence-shell electron-pair repulsion model (Gillespie, 1963, 1992), according to which the lone-pair of electrons on the N ring atoms occupies a wider region than the bonding pair N—H, causing the internal angle of the latter to be greater than on the non-protonated N ring atoms. As a result of the protonation of the triazine ring at one of three N ring atoms, the internal N—C—N angle involving only non-protonated N atoms is significantly greater than the remaining two N—C—N angles involving both protonated and non-protonated N atoms (Table 1).

The gas-phase geometry calculated ab initio for an isolated neutral melamine molecule and for a singly protonated melaminium cation shows similar trends in the internal C—N—C and N—C—N angles within the ring (Drozd & Marchewka, 2005). Thus, the ring distortions result mainly from the steric effect of a lone-pair of electrons and additionally in melaminium cations from the protonation and, to a lesser degree, from the hydrogen-bonding system, interionic interactions and crystal packing forces. Protonation of the triazine ring also disturbs the C—N bonds within the ring when compared with the neutral 2,4,6-triamino-1,3,5-triazine molecule (Aoki et al. 1994).

The two 1,5-NDS anions are quite similar in bond lengths and angles. However, a small difference caused by the hydrogen-bonding interaction can be found in the orientation of the SO₃ group in relation to the naphthalene ring system. The O3—S1—C2—C1 torsion angle is 0.6 (1)°, while in the second dianion the respective O5—S2—C7—C6 torsion angle is -10.2 (1)°. The S—O distances in both 1,5-NDS anions, with an average value of 1.456 Å, are intermediate between double S═O and single S—O bonds (Allen et al. 1987), indicating charge delocalization on all O atoms in the SO₃ groups. The average C—S bond length of 1.775 (3) Å in (I) is comparable with those found in naphthalene-1,5-disulfonic acid tetrahydrate, in which the H atoms are transferred to the water molecules forming H₅O⁺ cations (Perpétuo & Janczak, 2008). The C—S bond length in the crystal structure of (I) is shorter than those for the gas-phase structure obtained by molecular orbital calculations (1.841 Å), due to the interaction of the negatively charged SO₃^- groups with the π-aromatic ring system (Perpétuo & Janczak, 2008). In the crystal structure, this interaction is diminished due to the hydrogen-bonding system, which reduces the charge on the SO₃^- groups.

The melamine moieties of (I) are interconnected by two pairs of almost linear N—H···N hydrogen bonds forming two different one-dimensional polymers, each characterized by an R₂²(8) motif, which is one of the 24 most frequently observed bimolecular cyclic hydrogen-bonded units in organic crystal structures (Steiner, 2002). One of the chains contains only protonated melaminium cations (M1⁺), while the other contains both neutral melamine (M3) and melaminium (M2⁺) residues which alternate along the chain. Both chains run parallel to the [100] direction and they are stacked along [010] (Fig. 2). Within the stacks the two types of melamine chain alternate, and the average distance between the planes of the (M3M2⁺)_n and (M1⁺M1⁺)_n chains is shorter (~3.25 Å) than that between the (M3M2⁺)_n and (M3M2⁺)_n chains (~3.40 Å), indicating π–π interactions between the aromatic triazine rings. This distance is comparable with the sum of the van der Waals radii of C and N atoms of the π-aromatic ring system (Pauling, 1967) and longer than the distance at which the steric interaction between the π-aromatic ring system becomes predominantly repulsive (~3.08 Å; Scheidt & Lee, 1987).

The centrosymmetric 1,5-NDS anions are joined by the water molecules into a sheet parallel to the (001) plane (Fig. 2). The water molecules containing atoms O7, O9 and O10 are joined together by O—H···O hydrogen bonds into a trimeric structure (O7···O9···O10). The water molecules containing atoms O8 and O11 do not interact with other water molecules, but act as donors to the anions only and as acceptors from melamine moieties only. The trimeric structure of water molecules acts as a donor in hydrogen bonds with three 1,5-NDS anions, namely two 1,5-NDS anions A2 and one A1 (where A1 contains atom S1 and A2 contains atom S2). In addition, water atom O9 is the acceptor in a hydrogen bond with a neutral melamine, while water atoms O7 and O10 act as acceptors in hydrogen bonds with different melaminium cations, O7 with N19 and O10 with N28. Thus, the O atoms in the trimeric structure of water molecules possess distorted tetrahedral environments. Water atoms O8 and O11 also exhibit tetrahedral environments, since they each act as donor and acceptor in two hydrogen bonds, O8 as donor to two different 1,5-NDS anions (A1 and A2) and as acceptor from two symmetry-equivalent melaminium cations (with NH₂ groups N18 and N19), and O11 as donor to two different 1,5-NDS anions (A1 and A2) and as acceptor from both a neutral melamine and a melaminium cation (in both it forms a hydrogen bond with an amine group). The positively charged melamine stacks and the negatively charged sheets of anions and water molecules are linked by N—H···O and O—H···O hydrogen bonds to form a three-dimensional supramolecular framework structure (Fig. 2 and Table 2).

Related literature

For related literature, see: Allen (2002); Allen et al. (1987); Aoki et al. (1994); Desiraju (1990, 2002); Drozd & Marchewka (2005); Gillespie (1963, 1992); Janczak & Kubiak (2005a, 2005b); Janczak & Perpétuo (2002, 2003); Krische & Lehn (2000); MacDonald & Whitesides (1994); Marchewka et al. (2003); Moulton & Zaworotko (2001); Pauling (1967); Perpétuo & Janczak (2004, 2006, 2007, 2008); Row (1999); Scheidt & Lee (1987); Sherrington & Taskinen (2001); Steiner (2002).

S2. Experimental

2,4,6-Triamino-1,3,5-triazine (98%) was resolved [dissolved?] in 10% aqueous solution of naphthalene-1,5-disulfonic acid. After several days, colourless crystals of (I) had formed, which proved to be suitable for single-crystal X-ray diffraction analysis.

S3. Refinement

All H atoms were located in difference maps and then treated as riding atoms, with distances C—H = 0.93 Å, N—H = 0.86 Å and O—H = 0.82 Å, and with U_iso(H) = kU_eq(carrier), where k = 1.2 for H atoms bonded to C and 1.5 for H atoms bonded to N or O.

Computing details

Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis CCD (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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. A view of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. A view of the crystal packing in (I), showing the stack of melaminium moieties and the hydrogen-bonded sheets of anions and water molecules. Distances are in Å.

bis(melamin-1-ium) naphthalene-1,5-disulfonate melamine pentahydrate

Crystal data

2C3H7N6^+·C10H6O6S2^2^−·C3H6N6·5H2O	Z = 2
Mr = 756.78	F(000) = 792
Triclinic, P1	Dx = 1.512 Mg m^−3 Dm = 1.51 Mg m^−3 Dm measured by flotation
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.8320 (18) Å	Cell parameters from 1065 reflections
b = 10.9131 (19) Å	θ = 2.9–28.0°
c = 16.470 (3) Å	µ = 0.24 mm^−1
α = 77.302 (11)°	T = 295 K
β = 74.481 (12)°	Plate, colourless
γ = 63.112 (11)°	0.40 × 0.38 × 0.14 mm
V = 1662.0 (5) Å^3

Data collection

Kuma KM-4 with CCD area-detector diffractometer	8240 independent reflections
Radiation source: fine-focus sealed tube	4664 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.056
Detector resolution: 1024x1024 with blocks 2x2 pixels mm^-1	θmax = 29.3°, θmin = 2.9°
ω scans	h = −14→13
Absorption correction: analytical [face-indexed; SHELXTL (Sheldrick, 2008)]	k = −14→11
Tmin = 0.911, Tmax = 0.969	l = −22→21
22496 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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.088	H-atom parameters constrained
S = 1.00	w = 1/[σ^2(Fo^2) + (0.021P)^2] where P = (Fo^2 + 2Fc^2)/3
8240 reflections	(Δ/σ)max = 0.001
481 parameters	Δρmax = 0.43 e Å^−3
0 restraints	Δρmin = −0.30 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	0.31260 (9)	0.46077 (9)	0.20079 (5)	0.0362 (2)
O1	0.4359 (2)	0.3846 (2)	0.24008 (12)	0.0540 (6)
O2	0.2438 (2)	0.6067 (2)	0.21401 (12)	0.0476 (6)
O3	0.2171 (2)	0.3936 (2)	0.22548 (11)	0.0503 (6)
C1	0.3245 (2)	0.3936 (2)	0.04988 (17)	0.0365 (8)
H1	0.2588	0.3594	0.0804	0.044*
C2	0.3743 (2)	0.4543 (2)	0.09010 (16)	0.0261 (7)
C3	0.4758 (2)	0.5061 (2)	0.04420 (14)	0.0235 (6)
C4	0.5314 (2)	0.5691 (2)	0.08364 (17)	0.0303 (7)
H4	0.5015	0.5773	0.1414	0.036*
C5	0.6274 (2)	0.6169 (2)	0.03735 (18)	0.0429 (8)
H5	0.6624	0.6578	0.0640	0.052*
S2	0.17384 (9)	0.06502 (9)	0.12092 (5)	0.0388 (2)
O4	0.1499 (2)	0.2044 (2)	0.08072 (12)	0.0463 (6)
O5	0.3199 (2)	−0.0187 (2)	0.13292 (12)	0.0526 (6)
O6	0.0727 (2)	0.0648 (2)	0.19905 (11)	0.0513 (6)
C6	0.2580 (3)	−0.1162 (3)	0.0075 (2)	0.0452 (8)
H6	0.3469	−0.1436	0.0191	0.054*
C7	0.1459 (2)	−0.0146 (2)	0.04836 (16)	0.0299 (7)
C8	0.0066 (2)	0.0346 (2)	0.02965 (16)	0.0291 (7)
C9	−0.1136 (2)	0.1417 (2)	0.06841 (18)	0.0377 (8)
H9	−0.1042	0.1870	0.1065	0.045*
C10	−0.2440 (2)	0.1810 (2)	0.0514 (2)	0.0505 (9)
H10	−0.3227	0.2503	0.0790	0.061*
N11	0.8426 (2)	−0.0084 (2)	0.47321 (13)	0.0267 (6)
C12	0.9155 (2)	−0.0011 (2)	0.39558 (18)	0.0267 (7)
N13	0.8631 (2)	0.0102 (2)	0.32628 (13)	0.0289 (6)
H13	0.9134	0.0122	0.2762	0.035*
C14	0.7298 (2)	0.0183 (2)	0.33704 (19)	0.0282 (7)
N15	0.6529 (2)	0.0108 (2)	0.41300 (14)	0.0287 (6)
C16	0.7131 (2)	−0.0030 (2)	0.47859 (17)	0.0255 (7)
N17	1.0426 (2)	−0.0027 (2)	0.38154 (13)	0.0375 (7)
H17A	1.0789	−0.0087	0.4235	0.045*
H17B	1.0887	0.0021	0.3305	0.045*
N18	0.6387 (2)	−0.0131 (2)	0.55563 (14)	0.0375 (7)
H18A	0.5562	−0.0108	0.5622	0.045*
H18B	0.6727	−0.0220	0.5992	0.045*
N19	0.6830 (2)	0.0338 (2)	0.26742 (14)	0.0412 (7)
H19A	0.6000	0.0392	0.2711	0.049*
H19B	0.7356	0.0384	0.2184	0.049*
N21	0.8479 (2)	0.3220 (2)	0.47006 (13)	0.0264 (6)
C22	0.9194 (2)	0.3406 (2)	0.39354 (17)	0.0259 (7)
N23	0.8659 (2)	0.3615 (2)	0.32267 (13)	0.0271 (6)
H23	0.9125	0.3761	0.2732	0.033*
C24	0.7385 (2)	0.3591 (2)	0.33086 (18)	0.0261 (7)
N25	0.6632 (2)	0.3389 (2)	0.40523 (14)	0.0302 (6)
C26	0.7205 (2)	0.3247 (2)	0.47293 (17)	0.0301 (7)
N27	1.0437 (2)	0.3406 (2)	0.38229 (13)	0.0349 (6)
H27A	1.0804	0.3284	0.4254	0.042*
H27B	1.0887	0.3529	0.3318	0.042*
N28	0.6950 (2)	0.3749 (2)	0.25997 (14)	0.0404 (7)
H28A	0.6162	0.3721	0.2621	0.048*
H28B	0.7456	0.3880	0.2117	0.048*
N29	0.6448 (2)	0.3096 (2)	0.54847 (14)	0.0361 (6)
H29A	0.6769	0.2987	0.5933	0.043*
H29B	0.5634	0.3107	0.5530	0.043*
N31	0.8367 (2)	0.6599 (2)	0.47723 (13)	0.0271 (6)
C32	0.9036 (2)	0.6691 (2)	0.39613 (17)	0.0250 (7)
N33	0.8527 (2)	0.6856 (2)	0.32704 (13)	0.0271 (6)
C34	0.7216 (2)	0.6903 (2)	0.34370 (18)	0.0280 (7)
N35	0.6445 (2)	0.6781 (2)	0.42087 (13)	0.0268 (6)
C36	0.7076 (2)	0.6644 (2)	0.48516 (17)	0.0248 (7)
N37	1.0339 (2)	0.6631 (2)	0.38359 (13)	0.0342 (6)
H37A	1.0805	0.6697	0.3328	0.041*
H37B	1.0706	0.6526	0.4263	0.041*
N38	0.6355 (2)	0.6533 (2)	0.56350 (13)	0.0396 (7)
H38A	0.6716	0.6437	0.6063	0.048*
H38B	0.5527	0.6558	0.5714	0.048*
N39	0.6632 (2)	0.7100 (2)	0.27678 (14)	0.0392 (7)
H39A	0.5797	0.7142	0.2847	0.047*
H39B	0.7093	0.7183	0.2261	0.047*
O7	0.9655 (2)	0.8146 (3)	0.18120 (14)	0.0532 (6)
H71	0.9470	0.769	0.2255	0.080*
H72	1.0516	0.776	0.1670	0.080*
O8	0.3873 (3)	0.0865 (3)	0.25782 (16)	0.0627 (7)
H81	0.353	0.1708	0.2470	0.094*
H82	0.376	0.0620	0.2176	0.094*
O9	0.8600 (3)	0.7077 (3)	0.09459 (15)	0.0704 (8)
H91	0.897	0.749	0.1090	0.106*
H92	0.874	0.725	0.0427	0.106*
O10	0.9253 (3)	0.4313 (2)	0.15093 (14)	0.0532 (6)
H101	0.920	0.5095	0.1330	0.080*
H102	0.991	0.3730	0.1227	0.080*
O11	0.3621 (3)	0.7544 (3)	0.26750 (15)	0.0581 (6)
H111	0.345	0.822	0.2315	0.087*
H112	0.321	0.715	0.2550	0.087*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0335 (15)	0.0505 (16)	0.0303 (19)	−0.0274 (2)	0.0005 (2)	−0.0023 (2)
O1	0.0511 (15)	0.0653 (17)	0.0494 (12)	−0.0317 (14)	−0.0195 (12)	0.0108 (12)
O2	0.0470 (15)	0.0509 (15)	0.0453 (13)	−0.0244 (12)	0.0088 (11)	−0.0101 (11)
O3	0.0533 (15)	0.0602 (16)	0.0511 (13)	−0.0476 (14)	0.0067 (11)	−0.0044 (12)
C1	0.0339 (19)	0.0500 (19)	0.0372 (18)	−0.0309 (17)	−0.0031 (15)	−0.0024 (16)
C2	0.0241 (16)	0.0348 (18)	0.0238 (15)	−0.0171 (15)	−0.0036 (13)	−0.0025 (13)
C3	0.0212 (15)	0.0272 (16)	0.0246 (15)	−0.0126 (14)	−0.0037 (13)	−0.0033 (14)
C4	0.0337 (18)	0.0378 (19)	0.0273 (15)	−0.0210 (16)	−0.0041 (14)	−0.0073 (14)
C5	0.0510 (18)	0.0520 (19)	0.0431 (18)	−0.039 (2)	−0.0028 (16)	−0.0087 (17)
S2	0.0433 (15)	0.0501 (19)	0.0349 (19)	−0.0305 (2)	−0.0107 (2)	0.0013 (2)
O4	0.0622 (17)	0.0477 (14)	0.0452 (13)	−0.0306 (13)	−0.0107 (12)	0.0021 (11)
O5	0.0462 (15)	0.0618 (16)	0.0593 (15)	−0.0291 (13)	−0.0122 (12)	0.0029 (12)
O6	0.0575 (16)	0.0650 (17)	0.0478 (12)	−0.0491 (14)	−0.0007 (11)	−0.0039 (11)
C6	0.0360 (19)	0.0480 (19)	0.0490 (19)	−0.0114 (18)	−0.0116 (17)	−0.0081 (18)
C7	0.0323 (19)	0.0311 (19)	0.0323 (17)	−0.0176 (16)	−0.0074 (14)	−0.0039 (15)
C8	0.0332 (18)	0.0312 (19)	0.0279 (16)	−0.0194 (16)	−0.0089 (14)	0.0040 (14)
C9	0.0390 (19)	0.0330 (19)	0.0373 (18)	−0.0094 (17)	−0.0027 (16)	−0.0039 (15)
C10	0.0440 (19)	0.0460 (19)	0.0530 (18)	0.0012 (18)	−0.0141 (18)	−0.0236 (18)
N11	0.0225 (14)	0.0336 (16)	0.0264 (13)	−0.0148 (13)	−0.0022 (11)	−0.0044 (12)
C12	0.0231 (17)	0.0273 (18)	0.0326 (18)	−0.0109 (16)	−0.0071 (15)	−0.0054 (15)
N13	0.0237 (15)	0.0390 (16)	0.0267 (13)	−0.0169 (13)	−0.0039 (12)	−0.0014 (12)
C14	0.0279 (18)	0.0237 (18)	0.0388 (18)	−0.0115 (15)	−0.0060 (16)	−0.0017 (15)
N15	0.0263 (15)	0.0369 (16)	0.0267 (13)	−0.0137 (13)	−0.0032 (12)	−0.0034 (12)
C16	0.0269 (18)	0.0251 (18)	0.0273 (16)	−0.0133 (15)	−0.0029 (15)	−0.0058 (14)
N17	0.0339 (16)	0.0567 (19)	0.0324 (14)	−0.0304 (15)	−0.0026 (12)	−0.0065 (13)
N18	0.0346 (16)	0.0527 (18)	0.0345 (14)	−0.0280 (15)	−0.0033 (12)	−0.0062 (13)
N19	0.0373 (16)	0.0518 (19)	0.0404 (15)	−0.0235 (14)	−0.0117 (13)	−0.0004 (14)
N21	0.0260 (13)	0.0337 (15)	0.0265 (13)	−0.0187 (13)	−0.0010 (11)	0.0031 (12)
C22	0.0285 (18)	0.0272 (18)	0.0272 (16)	−0.0151 (16)	−0.0088 (15)	−0.0012 (14)
N23	0.0207 (14)	0.0343 (15)	0.0248 (13)	−0.0145 (12)	−0.0006 (11)	0.0017 (11)
C24	0.0286 (19)	0.0216 (17)	0.0319 (17)	−0.0159 (15)	−0.0037 (15)	0.0009 (14)
N25	0.0312 (15)	0.0382 (16)	0.0287 (13)	−0.0148 (14)	−0.0042 (12)	0.0017 (12)
C26	0.0338 (19)	0.0251 (18)	0.0259 (16)	−0.0184 (16)	−0.0012 (15)	0.0027 (14)
N27	0.0341 (15)	0.0444 (18)	0.0335 (13)	−0.0272 (15)	−0.0047 (11)	0.0013 (12)
N28	0.0423 (17)	0.0511 (19)	0.0399 (14)	−0.0334 (15)	−0.0101 (13)	0.0008 (13)
N29	0.0365 (14)	0.0483 (19)	0.0357 (14)	−0.0279 (14)	−0.0074 (12)	−0.0009 (13)
N31	0.0225 (14)	0.0399 (16)	0.0244 (13)	−0.0186 (13)	−0.0017 (11)	−0.0051 (11)
C32	0.0207 (17)	0.0282 (18)	0.0329 (17)	−0.0147 (15)	−0.0099 (14)	−0.0011 (15)
N33	0.0263 (14)	0.0321 (15)	0.0287 (13)	−0.0121 (13)	−0.0075 (11)	0.0013 (11)
C34	0.0291 (19)	0.0244 (17)	0.0305 (18)	−0.0097 (16)	−0.0088 (15)	0.0035 (14)
N35	0.0249 (14)	0.0397 (16)	0.0252 (13)	−0.0219 (13)	−0.0036 (11)	−0.0049 (12)
C36	0.0209 (17)	0.0263 (17)	0.0243 (15)	−0.0085 (15)	−0.0010 (14)	−0.0046 (13)
N37	0.0278 (15)	0.0445 (17)	0.0340 (13)	−0.0215 (14)	−0.0053 (11)	−0.0017 (12)
N38	0.0369 (15)	0.0497 (19)	0.0373 (14)	−0.0273 (15)	−0.0025 (12)	−0.0027 (13)
N39	0.0397 (15)	0.0574 (19)	0.0323 (14)	−0.0295 (14)	−0.0139 (12)	0.0020 (13)
O7	0.0566 (16)	0.0648 (18)	0.0402 (14)	−0.0353 (15)	−0.0070 (14)	0.0094 (13)
O8	0.0725 (19)	0.0568 (16)	0.0640 (17)	−0.0213 (16)	−0.0342 (15)	−0.0037 (16)
O9	0.0900 (19)	0.0910 (19)	0.0628 (16)	−0.0721 (17)	−0.0259 (17)	0.0135 (17)
O10	0.0541 (18)	0.0588 (18)	0.0409 (15)	−0.0261 (16)	0.0021 (12)	−0.0031 (13)
O11	0.0639 (18)	0.0687 (19)	0.0478 (15)	−0.0304 (15)	−0.0214 (13)	0.0007 (13)

Geometric parameters (Å, º)

S1—O3	1.450 (2)	N19—H19B	0.8600
S1—O1	1.454 (2)	N21—C22	1.318 (3)
S1—O2	1.460 (2)	N21—C26	1.356 (3)
S1—C2	1.771 (3)	C22—N27	1.310 (3)
C1—C2	1.369 (3)	C22—N23	1.370 (3)
C1—C5^i	1.402 (3)	N23—C24	1.361 (3)
C1—H1	0.9300	N23—H23	0.8600
C2—C3	1.425 (3)	C24—N25	1.313 (3)
C3—C3^i	1.424 (3)	C24—N28	1.322 (3)
C3—C4	1.428 (3)	N25—C26	1.363 (3)
C4—C5	1.350 (3)	C26—N29	1.316 (3)
C4—H4	0.9300	N27—H27A	0.8600
C5—C1^i	1.402 (3)	N27—H27B	0.8600
C5—H5	0.9300	N28—H28A	0.8600
S2—O6	1.450 (2)	N28—H28B	0.8600
S2—O4	1.453 (2)	N29—H29A	0.8600
S2—O5	1.469 (2)	N29—H29B	0.8600
S2—C7	1.779 (3)	N31—C32	1.345 (3)
C6—C7	1.353 (3)	N31—C36	1.348 (3)
C6—C10^ii	1.394 (3)	C32—N33	1.337 (3)
C6—H6	0.9300	C32—N37	1.343 (3)
C7—C8	1.450 (3)	N33—C34	1.351 (3)
C8—C9	1.405 (3)	C34—N35	1.337 (3)
C8—C8^ii	1.429 (3)	C34—N39	1.345 (3)
C9—C10	1.367 (3)	N35—C36	1.355 (3)
C9—H9	0.9300	C36—N38	1.329 (3)
C10—C6^ii	1.394 (3)	N37—H37A	0.8600
C10—H10	0.9300	N37—H37B	0.8600
N11—C12	1.318 (3)	N38—H38A	0.8600
N11—C16	1.356 (3)	N38—H38B	0.8600
C12—N17	1.326 (3)	N39—H39A	0.8600
C12—N13	1.364 (3)	N39—H39B	0.8600
N13—C14	1.370 (3)	O7—H71	0.820
N13—H13	0.8600	O7—H72	0.820
C14—N15	1.313 (3)	O8—H81	0.820
C14—N19	1.322 (3)	O8—H82	0.820
N15—C16	1.353 (3)	O9—H91	0.820
C16—N18	1.320 (3)	O9—H92	0.820
N17—H17A	0.8600	O10—H101	0.820
N17—H17B	0.8600	O10—H102	0.820
N18—H18A	0.8600	O11—H111	0.820
N18—H18B	0.8600	O11—H112	0.820
N19—H19A	0.8600
O3—S1—O1	111.59 (13)	C12—N17—H17B	120.0
O3—S1—O2	113.36 (13)	H17A—N17—H17B	120.0
O1—S1—O2	112.14 (13)	C16—N18—H18A	120.0
O3—S1—C2	105.91 (12)	C16—N18—H18B	120.0
O1—S1—C2	106.60 (13)	H18A—N18—H18B	120.0
O2—S1—C2	106.67 (13)	C14—N19—H19A	120.0
C2—C1—C5^i	120.0 (2)	C14—N19—H19B	120.0
C2—C1—H1	120.0	H19A—N19—H19B	120.0
C5^i—C1—H1	120.0	C22—N21—C26	115.5 (2)
C1—C2—C3	120.6 (2)	N27—C22—N21	121.4 (3)
C1—C2—S1	117.8 (2)	N27—C22—N23	117.4 (3)
C3—C2—S1	121.6 (2)	N21—C22—N23	121.2 (3)
C3^i—C3—C2	118.8 (3)	C24—N23—C22	119.7 (2)
C3^i—C3—C4	118.7 (3)	C24—N23—H23	120.1
C2—C3—C4	122.5 (2)	C22—N23—H23	120.1
C5—C4—C3	120.3 (3)	N25—C24—N28	121.1 (3)
C5—C4—H4	119.9	N25—C24—N23	122.0 (3)
C3—C4—H4	119.9	N28—C24—N23	116.8 (3)
C4—C5—C1^i	121.7 (3)	C24—N25—C26	114.9 (2)
C4—C5—H5	119.1	N29—C26—N21	117.1 (3)
C1^i—C5—H5	119.1	N29—C26—N25	116.3 (3)
O6—S2—O4	112.02 (13)	N21—C26—N25	126.6 (3)
O6—S2—O5	112.01 (13)	C22—N27—H27A	120.0
O4—S2—O5	112.87 (13)	C22—N27—H27B	120.0
O6—S2—C7	107.40 (12)	H27A—N27—H27B	120.0
O4—S2—C7	105.60 (12)	C24—N28—H28A	120.0
O5—S2—C7	106.41 (14)	C24—N28—H28B	120.0
C7—C6—C10^ii	121.8 (3)	H28A—N28—H28B	120.0
C7—C6—H6	119.1	C26—N29—H29A	120.0
C10^ii—C6—H6	119.1	C26—N29—H29B	120.0
C6—C7—C8	120.7 (3)	H29A—N29—H29B	120.0
C6—C7—S2	118.8 (2)	C32—N31—C36	113.3 (2)
C8—C7—S2	120.4 (2)	N33—C32—N37	117.0 (3)
C9—C8—C8^ii	119.6 (3)	N33—C32—N31	126.6 (3)
C9—C8—C7	123.6 (3)	N37—C32—N31	116.4 (2)
C8^ii—C8—C7	116.8 (3)	C32—N33—C34	114.2 (2)
C10—C9—C8	121.6 (3)	N35—C34—N39	117.2 (3)
C10—C9—H9	119.2	N35—C34—N33	125.7 (2)
C8—C9—H9	119.2	N39—C34—N33	117.1 (3)
C9—C10—C6^ii	119.4 (3)	C34—N35—C36	113.9 (2)
C9—C10—H10	120.3	N38—C36—N31	117.0 (2)
C6^ii—C10—H10	120.3	N38—C36—N35	116.7 (3)
C12—N11—C16	115.2 (2)	N31—C36—N35	126.2 (2)
N11—C12—N17	121.2 (3)	C32—N37—H37A	120.0
N11—C12—N13	121.6 (3)	C32—N37—H37B	120.0
N17—C12—N13	117.1 (3)	H37A—N37—H37B	120.0
C12—N13—C14	119.5 (2)	C36—N38—H38A	120.0
C12—N13—H13	120.2	C36—N38—H38B	120.0
C14—N13—H13	120.2	H38A—N38—H38B	120.0
N15—C14—N19	121.9 (3)	C34—N39—H39A	120.0
N15—C14—N13	121.3 (3)	C34—N39—H39B	120.0
N19—C14—N13	116.8 (3)	H39A—N39—H39B	120.0
C14—N15—C16	115.7 (2)	H71—O7—H72	104.0
N18—C16—N15	116.8 (3)	H81—O8—H82	101.0
N18—C16—N11	116.7 (3)	H91—O9—H92	103.0
N15—C16—N11	126.6 (3)	H101—O10—H102	112.0
C12—N17—H17A	120.0	H111—O11—H112	100.0

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N13—H13···O6^iii	0.86	2.08	2.833 (3)	146
N17—H17A···N11^iv	0.86	2.17	3.024 (3)	172
N17—H17B···O6^iii	0.86	2.15	2.899 (3)	145
N18—H18A···N15^v	0.86	2.19	3.050 (3)	177
N18—H18B···O8^v	0.86	2.31	2.970 (3)	134
N19—H19A···O8	0.86	2.18	3.030 (4)	168
N23—H23···O10	0.86	1.96	2.742 (3)	151
N27—H27A···N31^vi	0.86	2.09	2.936 (3)	168
N27—H27B···O3^iii	0.86	2.03	2.874 (3)	168
N28—H28A···O1	0.86	2.02	2.864 (3)	167
N28—H28B···O10	0.86	2.14	2.887 (3)	144
N29—H29A···O11^vii	0.86	2.21	2.945 (3)	143
N29—H29B···N35^vii	0.86	2.13	2.983 (3)	173
N37—H37A···O2^iii	0.86	2.25	3.073 (3)	160
N37—H37B···N21^vi	0.86	2.24	3.080 (3)	167
N38—H38A···O1^vii	0.86	2.50	3.098 (3)	127
N38—H38B···N25^vii	0.86	2.24	3.102 (3)	179
N39—H39A···O11	0.86	2.28	3.114 (3)	164
N39—H39B···O9	0.86	2.33	3.180 (4)	171
O7—H71···N33	0.82	1.98	2.783 (3)	165
O7—H72···O2^iii	0.82	2.26	2.944 (3)	142
O8—H81···O3	0.82	2.21	3.011 (3)	168
O8—H82···O5	0.82	2.14	2.947 (3)	168
O9—H91···O7	0.82	1.96	2.741 (3)	160
O9—H92···O4^i	0.82	2.05	2.850 (3)	164
O10—H101···O9	0.82	1.96	2.766 (4)	167
O10—H102···O4^iii	0.82	1.97	2.774 (3)	166
O11—H111···O5^viii	0.82	2.07	2.891 (3)	174
O11—H112···O2	0.82	2.03	2.848 (3)	173

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