Melaminium acetate acetic acid solvate monohydrate

The crystals of the title new melaminium salt, 2,4,6-tri­amino-1,3,5-triazin-1-ium acetate acetic acid solvate monohydrate, C₃H₇N₆⁺·CH₃COO⁻·CH₃COOH·H₂O, are built up from singly protonated melaminium residues, acetate anions, and acetic acid and water mol­ecules. The melaminium residues are interconnected by N—H...N hydrogen bonds to form chains along the [010] direction. These chains of melaminium residues form stacks aligned along the a axis. The acetic acid mol­ecules interact with the acetate anions via the H atom of their carboxylic acid groups and, together with the water mol­ecules, form layers that are parallel to the (001) plane. The oppositely charged moieties interact via multiple N—H...O hydrogen bonds that stabilize a pseudo-two-dimensional stacking structure.

S1. Comment

This study forms part of our investigation of the characterization of the hydrogen bonds formed by the melamine molecule in the solid state (Janczak & Perpétuo, 2001a,b,c,d). The melamine molecule and its organic and inorganic complexes or salts can, via multiple hydrogen bonds, develop supramolecular structures by self-assembly of components which contain complementary arrays of hydrogen-bonding sites (MacDonald & Whitesides, 1994; Row, 1999; Krische & Lehn, 2000; Sherrington & Taskinen, 2001). To expand understanding of the solid state physical organic chemistry of compounds containing multiple and different hydrogen-bonding systems, we have studied the solid state structure of single-protonated melaminium acetate monohydrate acetic acid solvate, (I), and the results are presented here. \sch

The asymmetric unit of (I) consists of two molecules, namely two melaminium residues protonated at one ring N atom, two acetate anions, two acetic acid molecules and two water molecules (Fig. 1). The two independent melaminium cations do not differ significantly, but the six-membered aromatic rings exhibit significant distortion from the ideal hexagonal form. The internal C—N—C angle at the protonated N atom (N2) is significantly greater than the other two ring C—N—C angles (Table 1). This is a result of the steric effect of a lone-pair electron, predicted by the valence-shell electron pair repulsion theory (VSEPR; Gillespie, 1963, 1992).

As a result of the protonation of the melamine ring at atom N2, the internal N—C—N angle containing only non-protonated N atoms is significantly greater than either of the N—C—N angles containing both protonated and non-protonated N atoms. This correlation between the internal C—N—C angles within the melaminium rings is quite similar to those reported for the crystals of barbituric acid with melamine (Zerkowski et al., 1994), melaminium phthalate (Janczak & Perpétuo, 2001a), melaminium chloride hemihydrate (Janczak & Perpétuo, 2001c) and bis(melaminium) sulfate dihydrate (Janczak & Perpétuo, 2001 d), i.e. those singly protonated melaminium salts that have been structurally characterized to date.

The melaminium residues in the crystal of (I) are involved in nine hydrogen bonds, in seven of them as donor H and in the remaining two as acceptor H. The four N—H···N bonds link the melaminium residue with two neighbouring melaminium residues to form a chain (Fig. 2), while the five N—H···O bonds link a melaminium residue with two acetate ions, two acetic acid molecules and one water molecule. The N—H···N hydrogen bonds are much more linear than the N—H···O bonds.

The geometries of the two independent acetate ions do not differ significantly. The C—O bond lengths in the acetate moieties indicate delocalization of the charge on both O atoms, since the C—O bond lengths are intermediate between single Csp²—O and double Csp²═O, and correlate well with values for carboxylate anions (1.247–1.262 Å; Allen et al., 1987). One of the two independent acetate ions is involved as acceptor in four hydrogen bonds (O11 and O12), while the other acetate ion is involved in five hydrogen bonds.

Both independent acetic acid molecules exhibit similar geometry. The OH group of the COOH in both acetic acid molecules joins the acetate ions via O—H···O hydrogen bonds. The carbonyl O atom of the COOH groups acts as acceptor in hydrogen bonds with the amine groups of two different melaminium residues. The slight differences in C—O distances for equivalent bonds in the acetate ions, as well as in the acetic acid molecules, correlate with the number and strengh of the hydrogen bonds in which the O atoms are involved (see Table 2).

The water molecules form a hydrogen-bonded dimeric structure (O1W-H2W1···O2W), with an O···O distance of 2.853 (3) Å, joining the hydrogen-bonded acetic acid-acetate moieties. The first water molecule (O1W) is involved in three hydrogen bonds, in two of which it acts as donor H, with O2W of a water molecule and O32 of an acetate ion, and in the other as acceptor H, with the amine group of a melaminium residue. The second water molecule is involved in four hydrogen bonds, with two acetate ions, a water molecule and an amine group of a melaminium residue. Details of this hydrogen-bonding geometry are given in Table 2.

In the crystal of (I), the melaminium residues form complementary planar positively charged chains interconnected by N—H···N hydrogen bonds, and these chains form stacks parallel to the (001) plane (Fig. 3). Within one stack, the melaminium residues are separated by ~3.25 Å. This is slightly shorter than the distance between π-aromatic ring systems (~3.4 Å; Pauling, 1960) and indicates π–π interaction between the melaminium rings. The hydrogen-bonded acetic acid-acetate moieties are interconnected by the dimeric structure of the hydrogen-bonded water, forming negatively charged layers that are located parallel to the (001) plane. These oppositely charged moieties are extensively interconnected by multiple hydrogen bonds to form columnar supramolecular aggregates which are aligned along the a axis.

S2. Experimental

Melamine was dissolved in a 20% solution of acetic acid and the resulting solution was slowly evaporated. After several days, colourless crystals of (I) appeared.

S3. Refinement

H atoms bonded to C and N were treated as riding, with C—H = 0.96 and N—H = 0.86 Å. The coordinates of H atoms bonded to O were refined, and the resulting range of O—H distances was 0.80 (2)–0.83 (2) Å.

Computing details

Data collection: XSCANS (Siemens, 1991); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 1990); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. A view of the molecular structure of (I) showing 50% probability displacement ellipsoids and the atom-numbering scheme. H atoms are shown as spheres of arbitrary radii.
	Fig. 2. An [010] projection of the packing in (I) showing an N—H···N interconnected melaminium chain, which interacts via N—H···O hydrogen bonds with the acetate anions and acetic acid and water molecules.
	Fig. 3. A stereoview of the molecular arrangement in the unit cell of (I), showing the hydrogen-bonding interactions (dashed lines).

2,4,6-triamino-1,3,5-triazine-1-ium acetate monohydrate acetic acid solvate

Crystal data

C3H7N6^+·C2H3O2^−·H2O·C2H4O2	F(000) = 560
Mr = 264.26	Dx = 1.393 Mg m^−3 Dm = 1.39 Mg m^−3 Dm measured by flotation
Triclinic, P1	Melting point: decomposition K
a = 6.859 (1) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.427 (2) Å	Cell parameters from 69 reflections
c = 15.307 (3) Å	θ = 9–16°
α = 92.31 (3)°	µ = 0.12 mm^−1
β = 95.87 (3)°	T = 293 K
γ = 103.36 (3)°	Parallelepiped, colourless
V = 1260.0 (4) Å^3	0.33 × 0.18 × 0.15 mm
Z = 4

Data collection

Siemens P4 diffractometer	2141 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.017
Graphite monochromator	θmax = 25.1°, θmin = 2.7°
ω/2θ scans	h = −8→7
Absorption correction: analytical face-indexed (SHELXTL; Sheldrick, 1990)	k = −14→14
Tmin = 0.962, Tmax = 0.983	l = −18→18
7979 measured reflections	2 standard reflections every 50 reflections
4252 independent reflections	intensity decay: 0.8%

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.057	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ^2(Fo^2) + (0.012P)^2 + 0.0133P] where P = (Fo^2 + 2Fc^2)/3
4252 reflections	(Δ/σ)max = 0.001
347 parameters	Δρmax = 0.15 e Å^−3
7 restraints	Δρmin = −0.14 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
N1	0.7302 (2)	0.73967 (13)	0.07260 (10)	0.0383 (4)
C1	0.7510 (3)	0.74024 (16)	−0.01294 (13)	0.0390 (5)
N2	0.7618 (2)	0.83469 (12)	−0.05616 (10)	0.0395 (4)
H2	0.7757	0.8342	−0.1114	0.047*
C2	0.7506 (3)	0.92940 (16)	−0.01208 (13)	0.0391 (5)
N3	0.7294 (2)	0.93343 (12)	0.07279 (10)	0.0399 (4)
C3	0.7167 (3)	0.83667 (16)	0.11264 (12)	0.0400 (5)
N4	0.7604 (2)	0.64910 (13)	−0.05881 (10)	0.0472 (4)
H4NA	0.7531	0.5881	−0.0334	0.057*
H4NB	0.7739	0.6510	−0.1140	0.057*
N5	0.7608 (2)	1.01746 (13)	−0.05790 (11)	0.0517 (5)
H5NA	0.7537	1.0793	−0.0327	0.062*
H5NB	0.7746	1.0132	−0.1131	0.062*
N6	0.6870 (2)	0.83755 (13)	0.19614 (10)	0.0515 (5)
H6NA	0.6767	0.7778	0.2236	0.062*
H6NB	0.6778	0.8978	0.2233	0.062*
N7	0.7479 (2)	0.43301 (12)	0.02400 (9)	0.0363 (4)
C4	0.7303 (3)	0.43256 (15)	0.10949 (12)	0.0395 (5)
N8	0.7258 (2)	0.33975 (12)	0.15358 (10)	0.0420 (4)
H8	0.7183	0.3415	0.2093	0.050*
C5	0.7333 (3)	0.24469 (16)	0.10974 (12)	0.0398 (5)
N9	0.7468 (2)	0.23932 (12)	0.02295 (10)	0.0370 (4)
C6	0.7577 (3)	0.33557 (16)	−0.01601 (12)	0.0376 (5)
N10	0.7144 (3)	0.52247 (13)	0.15485 (10)	0.0538 (5)
H10N	0.7153	0.5827	0.1289	0.065*
H11N	0.7031	0.5207	0.2102	0.065*
N11	0.7217 (2)	0.15435 (13)	0.15410 (10)	0.0469 (5)
H12N	0.7229	0.0924	0.1272	0.056*
H13N	0.7131	0.1577	0.2098	0.056*
N12	0.7821 (2)	0.33424 (13)	−0.10091 (9)	0.0486 (5)
H14N	0.7901	0.2739	−0.1283	0.058*
H15N	0.7898	0.3937	−0.1285	0.058*
O11	0.2293 (2)	0.14468 (11)	0.23549 (9)	0.0601 (4)
O12	0.2431 (3)	0.32386 (12)	0.23777 (10)	0.0740 (5)
C12	0.2128 (4)	0.23704 (18)	0.37108 (13)	0.0604 (6)
H12A	0.2037	0.3094	0.3920	0.091*
H12B	0.3307	0.2197	0.4009	0.091*
H12C	0.0949	0.1832	0.3826	0.091*
C11	0.2267 (4)	0.23530 (19)	0.27535 (14)	0.0533 (6)
O21	0.1982 (2)	−0.12903 (12)	0.21138 (9)	0.0630 (5)
O22	0.1663 (3)	−0.02558 (13)	0.32902 (10)	0.0701 (5)
H222	0.193 (4)	0.0254 (18)	0.2955 (15)	0.105*
C21	0.1693 (3)	−0.12000 (18)	0.28757 (14)	0.0494 (6)
C22	0.1230 (4)	−0.21590 (18)	0.34284 (14)	0.0704 (7)
H22A	0.0044	−0.2684	0.3159	0.106*
H22B	0.0999	−0.1908	0.4002	0.106*
H22C	0.2347	−0.2506	0.3482	0.106*
O31	0.7270 (2)	0.31449 (12)	0.33567 (9)	0.0583 (4)
O32	0.7976 (2)	0.49755 (12)	0.34265 (9)	0.0603 (4)
C32	0.7335 (4)	0.4099 (2)	0.47417 (13)	0.0736 (8)
H32A	0.6244	0.3506	0.4863	0.110*
H32B	0.7074	0.4796	0.4922	0.110*
H32C	0.8569	0.4020	0.5060	0.110*
C31	0.7519 (3)	0.40599 (19)	0.37780 (14)	0.0516 (6)
O41	0.6790 (3)	0.04125 (12)	0.30406 (9)	0.0705 (5)
O42	0.6978 (3)	0.14033 (13)	0.42910 (10)	0.0705 (5)
H421	0.724 (4)	0.192 (2)	0.4006 (17)	0.106*
C41	0.6890 (4)	0.04655 (19)	0.38352 (15)	0.0544 (6)
C42	0.6989 (4)	−0.04788 (19)	0.43843 (14)	0.0727 (8)
H42A	0.7579	−0.0993	0.4081	0.109*
H42B	0.5653	−0.0845	0.4495	0.109*
H42C	0.7800	−0.0211	0.4933	0.109*
O1W	0.5787 (3)	0.66472 (14)	0.31972 (14)	0.0789 (5)
H1W1	0.609 (4)	0.614 (2)	0.3467 (18)	0.118*
H2W1	0.460 (2)	0.639 (2)	0.312 (2)	0.118*
O2W	0.1872 (3)	0.52752 (13)	0.26407 (14)	0.0756 (5)
H1W2	0.207 (4)	0.4646 (16)	0.2660 (18)	0.113*
H2W2	0.082 (3)	0.517 (2)	0.2843 (19)	0.113*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0425 (10)	0.0321 (10)	0.0426 (9)	0.0136 (8)	0.0045 (8)	0.0023 (8)
C1	0.0422 (13)	0.0289 (11)	0.0481 (12)	0.0145 (10)	0.0022 (10)	0.0022 (9)
N2	0.0552 (11)	0.0284 (9)	0.0368 (9)	0.0127 (8)	0.0081 (8)	0.0001 (7)
C2	0.0481 (13)	0.0244 (11)	0.0456 (11)	0.0108 (10)	0.0030 (10)	0.0039 (9)
N3	0.0498 (11)	0.0257 (9)	0.0468 (10)	0.0132 (8)	0.0086 (8)	0.0009 (8)
C3	0.0480 (13)	0.0320 (12)	0.0417 (11)	0.0115 (10)	0.0084 (10)	0.0030 (9)
N4	0.0660 (12)	0.0377 (10)	0.0401 (9)	0.0178 (9)	0.0025 (9)	0.0041 (8)
N5	0.0683 (13)	0.0382 (11)	0.0524 (11)	0.0193 (10)	0.0096 (10)	0.0002 (9)
N6	0.0778 (14)	0.0326 (10)	0.0480 (10)	0.0188 (10)	0.0112 (10)	0.0034 (8)
N7	0.0467 (11)	0.0259 (9)	0.0364 (9)	0.0088 (8)	0.0044 (8)	0.0019 (7)
C4	0.0523 (14)	0.0282 (11)	0.0377 (11)	0.0118 (10)	0.0005 (10)	−0.0038 (9)
N8	0.0624 (12)	0.0279 (9)	0.0354 (9)	0.0116 (9)	0.0020 (9)	0.0003 (7)
C5	0.0477 (13)	0.0316 (12)	0.0404 (11)	0.0097 (10)	0.0052 (10)	0.0035 (9)
N9	0.0486 (11)	0.0210 (9)	0.0428 (9)	0.0095 (8)	0.0083 (8)	0.0042 (7)
C6	0.0442 (13)	0.0311 (11)	0.0369 (10)	0.0098 (10)	0.0016 (10)	0.0004 (9)
N10	0.0857 (14)	0.0334 (10)	0.0453 (10)	0.0195 (10)	0.0089 (10)	0.0036 (8)
N11	0.0757 (13)	0.0290 (9)	0.0371 (9)	0.0152 (9)	0.0040 (9)	0.0036 (8)
N12	0.0790 (14)	0.0337 (10)	0.0365 (9)	0.0172 (10)	0.0133 (9)	0.0023 (8)
O11	0.0890 (12)	0.0428 (9)	0.0515 (9)	0.0210 (9)	0.0096 (9)	0.0019 (8)
O12	0.1318 (15)	0.0412 (9)	0.0580 (10)	0.0334 (10)	0.0206 (10)	0.0113 (8)
C12	0.0780 (17)	0.0528 (15)	0.0533 (14)	0.0205 (14)	0.0094 (13)	0.0042 (12)
C11	0.0709 (17)	0.0421 (14)	0.0503 (13)	0.0189 (12)	0.0100 (12)	0.0014 (11)
O21	0.0918 (13)	0.0504 (10)	0.0501 (9)	0.0229 (9)	0.0114 (9)	−0.0010 (8)
O22	0.1105 (14)	0.0511 (11)	0.0513 (10)	0.0230 (11)	0.0130 (10)	0.0031 (8)
C21	0.0632 (16)	0.0411 (13)	0.0447 (12)	0.0184 (12)	−0.0015 (12)	−0.0023 (10)
C22	0.103 (2)	0.0556 (15)	0.0556 (14)	0.0239 (15)	0.0103 (14)	0.0035 (12)
O31	0.0830 (12)	0.0458 (9)	0.0453 (8)	0.0139 (9)	0.0073 (8)	−0.0009 (8)
O32	0.0874 (12)	0.0443 (9)	0.0511 (9)	0.0192 (9)	0.0079 (8)	0.0033 (8)
C32	0.098 (2)	0.0642 (17)	0.0515 (15)	0.0017 (15)	0.0193 (14)	−0.0027 (13)
C31	0.0599 (16)	0.0484 (15)	0.0469 (13)	0.0139 (12)	0.0065 (12)	0.0012 (11)
O41	0.1204 (15)	0.0510 (10)	0.0458 (9)	0.0315 (10)	0.0088 (10)	0.0066 (8)
O42	0.1133 (15)	0.0493 (11)	0.0466 (9)	0.0133 (11)	0.0109 (10)	0.0050 (8)
C41	0.0654 (16)	0.0465 (15)	0.0518 (14)	0.0119 (13)	0.0113 (12)	0.0043 (12)
C42	0.108 (2)	0.0598 (16)	0.0559 (14)	0.0281 (16)	0.0170 (15)	0.0101 (13)
O1W	0.0855 (13)	0.0611 (12)	0.0975 (14)	0.0249 (11)	0.0231 (13)	0.0166 (10)
O2W	0.0815 (14)	0.0488 (11)	0.1016 (14)	0.0178 (10)	0.0233 (11)	0.0169 (11)

Geometric parameters (Å, º)

N1—C1	1.332 (2)	N12—H15N	0.8600
N1—C3	1.357 (2)	O11—C11	1.264 (2)
C1—N4	1.326 (2)	O12—C11	1.250 (2)
C1—N2	1.361 (2)	C12—C11	1.478 (3)
N2—C2	1.354 (2)	C12—H12A	0.9600
N2—H2	0.8600	C12—H12B	0.9600
C2—N5	1.316 (2)	C12—H12C	0.9600
C2—N3	1.322 (2)	O21—C21	1.208 (2)
N3—C3	1.359 (2)	O22—C21	1.317 (2)
C3—N6	1.315 (2)	O22—H222	0.831 (16)
N4—H4NA	0.8600	C21—C22	1.483 (3)
N4—H4NB	0.8600	C22—H22A	0.9600
N5—H5NA	0.8600	C22—H22B	0.9600
N5—H5NB	0.8600	C22—H22C	0.9600
N6—H6NA	0.8600	O31—C31	1.252 (2)
N6—H6NB	0.8600	O32—C31	1.266 (2)
N7—C4	1.326 (2)	C32—C31	1.493 (3)
N7—C6	1.354 (2)	C32—H32A	0.9600
C4—N10	1.324 (2)	C32—H32B	0.9600
C4—N8	1.355 (2)	C32—H32C	0.9600
N8—C5	1.349 (2)	O41—C41	1.209 (2)
N8—H8	0.8600	O42—C41	1.320 (3)
C5—N11	1.326 (2)	O42—H421	0.79 (3)
C5—N9	1.341 (2)	C41—C42	1.481 (3)
N9—C6	1.348 (2)	C42—H42A	0.9600
C6—N12	1.327 (2)	C42—H42B	0.9600
N10—H10N	0.8600	C42—H42C	0.9600
N10—H11N	0.8600	O1W—H1W1	0.823 (16)
N11—H12N	0.8600	O1W—H2W1	0.798 (16)
N11—H13N	0.8600	O2W—H1W2	0.825 (16)
N12—H14N	0.8600	O2W—H2W2	0.798 (16)
C1—N1—C3	116.4 (2)	C6—N12—H14N	120.0
N4—C1—N1	121.3 (2)	C6—N12—H15N	120.0
N4—C1—N2	117.92 (18)	H14N—N12—H15N	120.0
N1—C1—N2	120.8 (2)	C11—C12—H12A	109.5
C2—N2—C1	119.9 (2)	C11—C12—H12A	109.5
C2—N2—H2	120.0	H12A—C12—H12B	109.5
C1—N2—H2	120.0	C11—C12—H12C	109.5
N5—C2—N3	121.40 (19)	H12A—C12—H12C	109.5
N5—C2—N2	116.78 (18)	H12B—C12—H12C	109.5
N3—C2—N2	121.8 (2)	O12—C11—O11	122.7 (2)
C2—N3—C3	116.0 (2)	O12—C11—C12	118.9 (2)
N6—C3—N1	117.91 (18)	O11—C11—C12	118.3 (2)
N6—C3—N3	117.08 (18)	C21—O22—H222	109.3 (19)
N1—C3—N3	125.0 (2)	O21—C21—O22	123.9 (2)
C1—N4—H4NA	120.0	O21—C21—C22	123.1 (2)
C1—N4—H4NB	120.0	O22—C21—C22	112.96 (19)
H4NA—N4—H4NB	120.0	C21—C22—H22A	109.5
C2—N5—H5NA	120.0	C21—C22—H22B	109.5
C2—N5—H5NB	120.0	H22A—C22—H22B	109.5
H5NA—N5—H5NB	120.0	C21—C22—H22C	109.5
C3—N6—H6NA	120.0	H22A—C22—H22C	109.5
C3—N6—H6NB	120.0	H22B—C22—H22C	109.5
H6NA—N6—H6NB	120.0	C31—C32—H32A	109.5
C4—N7—C6	116.1 (2)	C31—C32—H32B	109.5
N10—C4—N7	121.25 (17)	H32A—C32—H32B	109.5
N10—C4—N8	117.42 (17)	C31—C32—H32C	109.5
N7—C4—N8	121.3 (2)	H32A—C32—H32C	109.5
C5—N8—C4	119.8 (2)	H32B—C32—H32C	109.5
C5—N8—H8	120.1	O31—C31—O32	122.8 (2)
C4—N8—H8	120.1	O31—C31—C32	119.8 (2)
N11—C5—N9	119.92 (18)	O32—C31—C32	117.4 (2)
N11—C5—N8	118.41 (17)	C41—O42—H421	112 (2)
N9—C5—N8	121.7 (2)	O41—C41—O42	121.7 (2)
C5—N9—C6	115.3 (2)	O41—C41—C42	124.3 (2)
N12—C6—N9	116.72 (17)	O42—C41—C42	114.01 (19)
N12—C6—N7	117.51 (17)	C41—C42—H42A	109.5
N9—C6—N7	125.8 (2)	C41—C42—H42B	109.5
C4—N10—H10N	120.0	H42A—C42—H42B	109.5
C4—N10—H11N	120.0	C41—C42—H42C	109.5
H10N—N10—H11N	120.0	H42A—C42—H42C	109.5
C5—N11—H12N	120.0	H42B—C42—H42C	109.5
C5—N11—H13N	120.0	H1W1—O1W—H2W1	97 (2)
H12N—N11—H13N	120.0	H1W2—O2W—H2W2	99 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O11^i	0.86	1.93	2.773 (2)	168
N4—H4NA···N7	0.86	2.14	3.002 (2)	176
N4—H4NB···O12^i	0.86	1.93	2.772 (2)	166
N5—H5NA···N9^ii	0.86	2.14	3.002 (2)	176
N5—H5NB···O21^i	0.86	2.12	2.782 (2)	133
N6—H6NA···O1W	0.86	2.13	2.936 (2)	157
N6—H6NB···O41^ii	0.86	2.13	2.981 (2)	173
N8—H8···O31	0.86	1.97	2.817 (2)	167
N10—H10N···N1	0.86	2.15	3.008 (2)	176
N10—H11N···O32	0.86	2.12	2.916 (2)	155
N11—H12N···N3^iii	0.86	2.13	2.982 (2)	175
N11—H13N···O41	0.86	2.08	2.746 (2)	134
N12—H14N···O21^iv	0.86	2.18	3.040 (2)	174
N12—H15N···O2W^i	0.86	2.33	3.085 (2)	146
O22—H222···O11	0.83 (2)	1.76 (2)	2.581 (2)	171 (3)
O42—H421···O31	0.79 (3)	1.85 (2)	2.622 (2)	167 (3)
O1W—H1W1···O32	0.82 (2)	2.16 (2)	2.844 (2)	141 (3)
O1W—H2W1···O2W	0.80 (2)	2.10 (2)	2.853 (2)	158 (3)
O2W—H1W2···O12	0.82 (2)	1.86 (2)	2.667 (2)	165 (3)
O2W—H2W2···O32^v	0.80 (2)	2.20 (2)	2.993 (2)	177 (3)

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