Disodium 2,5-bis(phenylamino)terephthalate deca­hydrate, an inter­mediate in the industrial synthesis of quinacridone pigments

The title compound, 2Na⁺·C₂₀H₁₄N₂O₄^2-·10H₂O, is an inter­mediate in the industrial synthesis of red and violet quinacridone pigments. The structure is remarkable for two reasons. First, one of the Na⁺ ions is surrounded octa­hedrally by five water mol­ecules and a phenyl group, although the crystal contains many more water mol­ecules than are required for complete coordination of both Na⁺ ions with six water mol­ecules each. Secondly, although the anion has almost exact mol­ecular inversion symmetry, it is positioned on a general position; this is one of the very few exceptions to the observation of Kitajgorodskij [Advances in Structure Research by Diffraction Methods - Fortschritte der Strukturforschung mit Beugungsmethoden (1970), Vol. 3, pp. 173-247] that mol­ecules with inversion centres always lie on crystallographic inversion centres.

S1. Comment

Quinacridone (VII), worldwide registered as C·I. Pigment Violet 19, is the most important pigment for red–violet shades (Herbst & Hunger, 2004). The pigment is produced in an amount of several thousand tons per year; the annual sales are more than 100 million euros. It is used for automotive finishes, powder coatings, paints, plastics and high-grade printing inks. The industrially most common synthetic route starts with a condensation of aniline (II) and succinylosuccinic ester (dimethyl 1,4-cyclohexanedione-2,5-dicarboxylate, III) (see scheme), followed by oxidation and alkali treatment, yielding disodium 2,5-bis(phenylamino)terephthalate decahydrate, (I), as intermediate. This intermediate is converted to the corresponding acid (VI) and treated with molten polyphosphoric acid to yield the quinacridone (VII) in the α, β or γ phase, depending on the synthetic conditions (Urban et al., 1998; Urban et al., 2000; Herbst & Hunger, 2004). The violet β phase and the red γ phase are commercially used as pigments.

Quinacridone has been known since 1935 (Liebermann et al., 1935) and industrially produced since 1958 (Reeve & Botti, 1958). The crystal structures of β and γquinacridone are known (Paulus et al., 1989; Potts et al., 1994), but – despite their industrial relevance – not one solitary crystal structure of any intermediate has been determined hitherto (Cambridge Crystallographic Database; Version 5.26 of November 2004 plus three updates; Allen, 2002). We report here the crystal structure of the intermediate (I), also called `anilic acid sodium salt'. The molecular structure is shown in Fig. 1.

The crystal structure consists of 2,5-bis(phenylamino)terephthalate di-anions and sodium cations, which are coordinated by water molecules (see Fig. 2). There is no direct sodium–carboxylate contact.

The anion shows two intramolecular hydrogen bonds from the NH groups to the carboxylate moieties. The total bis(amino)terephthalate unit is almost planar (the r.m.s. deviation for all non H atoms is 0.0706 Å). In contrast, the two phenyl rings are twisted against the central terephthalate unit by 58.44 (6) and 51.08 (6)° for the rings C21–C26 and C51–C56, respectively. For the final synthetic step, i.e. the ring closure, the intramolecular hydrogen bonds have to be broken and the phenylamine moiety must be rotated by about approximately 150° (Table 1). Under the applied synthetic conditions (molten polyphosphoric acid at 373–473 K) these rotations are easily possible.

The anion adopts almost exact inversion symmetry. According to the observation of Kitajgorodskij (1970), all molecules with molecular inversion symmetry maintain this symmetry in the crystal, i.e. they are always positioned on crystallographic inversion centres. Hence the 2,5-bis(phenylamino)terephthalate di-anions should be on an inversion centre, and there should be either one Na atom on a general position or, for example, two Na atoms on inversion centres. Astonishingly, in the present structure the anion is not situated on an inversion centre, but on a general position. This is one of the very few exceptions to Kitajgorodski's rule.

A thorough examination of the Cambridge Structural Database shows that 99% of all molecules with point group 1 are actually situated on crystallographic inversion centres (Pidcock et al., 2003). If the molecules have even higher symmetry, e.g. 2/m, then the occupancy of 1 drops to 97% as other special positions (e.g. 2 or m) are possible. The remaining 3% may include some structures with overlooked symmetry, but there are a few accurately determined structures where a molecule with inversion symmetry is definitely situated on a general position, e.g. 1,5-dimethylnaphthalene (P2₁/c, Z = 4, Z' = 1; Beintema, 1965; Ferraris et al., 1972; Wilson, 1997) or 2,2'-diaminodibenzyl (P2₁2₁2₁, Z = 4, Z' = 1; Narasegowda et al., 2005). In these cases, the intramolecular inversion centre is only a local symmetry element, not a crystallographic one; this situation is comparable to the case of an asymmetric unit containing two crystallographically independent molecules, which are connected only by a local symmetry operation.

In the crystal structure of (I) we carefully checked that there is no erroneously missed crystallographic symmetry. A further indication is the existence of two symmetrically and chemically inequivalent sodium cations; atom Na1 is coordinated octahedrally by six water molecules (Fig. 2), whereas Na2 is octahedrally surrounded by five water molecules and a phenyl ring at a longer distance, which is bound only by van der Waals forces (Fig. 3). Sodium–phenyl contacts are also known for other compounds; these compounds contain either no water or only one water molecule per Na⁺ ion (e.g. Hu et al., 2002). It is very surprising that in compound (I) the Na2 atom prefers the neighbourhood of a phenyl group instead of being surrounded by water molecules only. Compound (I) is a decahydrate and contains many more water molecules than necessary for a complete coordination of both Na⁺ ions; there is even one water molecule not bonded to any Na atoms. The reason for this unexpected coordination of Na2 remains obscure.

The structure is a double-layered structure (Fig. 4). The non-polar layer is formed by the phenyl rings; the polar layer contains the cations, the water molecules and the carboxy groups. The water molecules show a variety of coordination modes. Seven water molecules are coordinated to just one Na atom, two water molecules are shared between the sodium ions, and the tenth water molecule is not directly bound to any cation. Two (O2 and O3) of the nine water molecules that are coordinated to the Na cations bridge two anions via hydrogen bonds, four (O1, O5, O6 and O8) form hydrogen bonds between an anion and a water molecule, atom O4 is hydrogen bonded to the anion and to the water molecule that is not bonded to an Na atom, atom O7 forms hydrogen bonds to two Na-coordinating water molecules, and atom O9 is hydrogen bonded to a water molecule coordinating a sodium cation and the water molecule that is not bonded to a sodium cation. The water molecule (O1W) that is not coordinating a sodium cation forms hydrogen bonds to an anion and an Na-coordinating water molecule (Table 1).

S2. Experimental

Industrially produced 2,5-bis(phenylamino)terephthalic acid (`anilic acid'), (VI), from the quinacridone plant of Clariant GmbH at Frankfurt–Höchst was converted into the sodium salt (I) by stirring anilic acid (50 g) in a solution of NaHCO₃ (50 g) and water (450 ml) water for 2 h. The mixture was filtrated through a 20 µ filter to remove all particles. The solution was allowed to stand at room temperature in a open one litre Erlenmeyer flask for several weeks. The resulting small pale-brown crystals were isolated from the solution and carefully dried with tissue paper.

S3. Refinement

All H atoms were located in a difference map. Those bonded to C atoms were refined with fixed individual displacement parameters [U_iso(H) = 1.2U_eq(C)] using a riding model with C—H = 0.95 Å. H atoms bonded to N atoms were refined isotropically. H atoms bonded to O atoms were refined with restraints of 0.84 (1) Å for O—H and 1.40 (1) Å for H···H distances. One of the H atoms bonded to O7 could not be clearly located and was omitted from the refinement.

Computing details

Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 1991) and SCHAKAL (Keller, 1980); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2003).

Figures

	Fig. 1. A perspective view of the title compound, with the atom numbering; displacement ellipsoids are shown at the 50% probability level. One of the H atoms bonded to O7 is not drawn because it could not be clearly located and was therefore omitted from the refinement.
	Fig. 2. The coordination of Na1.
	Fig. 3. The coordination of Na2 [Na2···C21^i = 4.7320 (19) Å, Na2···C22^i = 4.072 (2) Å, Na2···C23^i = 3.240 (3) Å, Na2···C24^i = 3.162 (2) Å, Na2···C25^i = 3.943 (2) Å, Na···C26^i = 4.654 (2) Å, Na2···cog^i = 3.765 Å; symmetry code: (i) −x, 1 − y, 1 − z].
	Fig. 4. : A projection of the layer structure of (I). The view direction is [010], with [100] vertical.

Disodium 2,5-dianilinoterephthalate decahydrate

Crystal data

2Na^+·C20H14N2O4^2^−·10H2O	Z = 2
Mr = 572.47	F(000) = 604
Triclinic, P1	Dx = 1.438 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.7638 (7) Å	Cell parameters from 21410 reflections
b = 12.4371 (10) Å	θ = 3.6–27.2°
c = 13.5720 (11) Å	µ = 0.15 mm^−1
α = 110.550 (6)°	T = 173 K
β = 97.483 (7)°	Block, brown
γ = 101.857 (6)°	0.19 × 0.11 × 0.09 mm
V = 1322.14 (19) Å^3

Data collection

Stoe IPDS-II two-circle diffractometer	5789 independent reflections
Radiation source: fine-focus sealed tube	4837 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.078
ω scans	θmax = 27.2°, θmin = 3.6°
Absorption correction: multi-scan (MULABS; Spek, 2003; Blessing, 1995)	h = −11→11
Tmin = 0.973, Tmax = 0.981	k = −15→15
21410 measured reflections	l = −17→17

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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.141	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0765P)^2 + 0.5265P] where P = (Fo^2 + 2Fc^2)/3
5789 reflections	(Δ/σ)max = 0.001
427 parameters	Δρmax = 0.37 e Å^−3
28 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
Na1	0.53040 (8)	0.26076 (6)	1.00816 (5)	0.01921 (17)
Na2	0.11567 (9)	0.18887 (7)	0.92297 (6)	0.02589 (19)
O1	0.68370 (17)	0.10616 (13)	1.00759 (11)	0.0272 (3)
H1A	0.638 (3)	0.059 (2)	0.9435 (12)	0.063 (10)*
H1B	0.7835 (12)	0.127 (2)	1.015 (2)	0.047 (8)*
O2	0.61030 (15)	0.25796 (12)	0.84887 (10)	0.0211 (3)
H2A	0.601 (3)	0.3141 (14)	0.8287 (19)	0.037 (7)*
H2B	0.565 (3)	0.1911 (10)	0.7992 (15)	0.037 (7)*
O3	0.41397 (17)	0.25111 (11)	1.15494 (10)	0.0232 (3)
H3A	0.420 (3)	0.1970 (14)	1.1779 (18)	0.036 (7)*
H3B	0.455 (3)	0.3194 (10)	1.2043 (15)	0.041 (7)*
O4	0.69974 (15)	0.45652 (12)	1.11449 (10)	0.0226 (3)
H4A	0.658 (3)	0.465 (3)	1.1683 (15)	0.056 (9)*
H4B	0.7989 (12)	0.465 (2)	1.1320 (19)	0.037 (7)*
O5	0.32948 (16)	0.37672 (11)	0.99626 (10)	0.0212 (3)
H5A	0.349 (3)	0.4215 (19)	1.0624 (8)	0.047 (8)*
H5B	0.322 (3)	0.4160 (19)	0.9573 (15)	0.035 (7)*
O6	0.32014 (15)	0.08084 (11)	0.89872 (10)	0.0203 (3)
H6A	0.347 (3)	0.061 (2)	0.8389 (13)	0.047 (8)*
H6B	0.320 (3)	0.0281 (19)	0.9242 (19)	0.044 (8)*
O7	0.09037 (19)	0.22157 (14)	1.10965 (12)	0.0343 (3)
H7B	0.1895 (14)	0.236 (3)	1.133 (2)	0.049 (8)*
O8	−0.07510 (18)	0.00806 (14)	0.87289 (14)	0.0355 (4)
H8A	−0.048 (3)	−0.048 (2)	0.886 (3)	0.079 (12)*
H8B	−0.1679 (17)	−0.014 (2)	0.8340 (19)	0.039 (7)*
O9	−0.05840 (17)	0.30603 (14)	0.91775 (13)	0.0309 (3)
H9A	−0.029 (4)	0.359 (3)	0.893 (4)	0.118 (18)*
H9B	−0.1598 (12)	0.284 (2)	0.904 (2)	0.046 (8)*
O1W	0.03178 (17)	0.48841 (14)	0.13037 (12)	0.0307 (3)
H1WA	0.1278 (17)	0.508 (3)	0.166 (2)	0.052 (8)*
H1WB	0.012 (4)	0.424 (2)	0.076 (2)	0.121 (18)*
C1	0.49982 (19)	0.84814 (14)	0.59739 (12)	0.0138 (3)
C2	0.39469 (19)	0.83052 (14)	0.50050 (13)	0.0143 (3)
C3	0.39014 (19)	0.73286 (14)	0.40676 (13)	0.0149 (3)
H3	0.3189	0.7194	0.3419	0.018*
C4	0.48525 (18)	0.65437 (14)	0.40403 (12)	0.0133 (3)
C5	0.59294 (19)	0.67363 (14)	0.50066 (13)	0.0145 (3)
C6	0.59442 (19)	0.76949 (14)	0.59452 (13)	0.0148 (3)
H6	0.6635	0.7817	0.6598	0.018*
C11	0.51197 (19)	0.94655 (14)	0.70528 (13)	0.0147 (3)
O11	0.44370 (16)	1.02777 (11)	0.70804 (10)	0.0214 (3)
O12	0.58942 (16)	0.94275 (11)	0.78949 (9)	0.0210 (3)
N21	0.30325 (17)	0.90888 (13)	0.49500 (12)	0.0186 (3)
H21	0.325 (3)	0.978 (2)	0.554 (2)	0.029 (6)*
C21	0.15037 (19)	0.87519 (15)	0.42758 (13)	0.0158 (3)
C22	0.0993 (2)	0.95982 (18)	0.39655 (18)	0.0279 (4)
H22	0.1709	1.0362	0.4157	0.033*
C23	−0.0563 (2)	0.93346 (19)	0.33745 (19)	0.0313 (5)
H23	−0.0900	0.9925	0.3179	0.038*
C24	−0.1618 (2)	0.82185 (18)	0.30719 (15)	0.0249 (4)
H24	−0.2674	0.8039	0.2668	0.030*
C25	−0.1108 (2)	0.73690 (17)	0.33681 (17)	0.0273 (4)
H25	−0.1822	0.6602	0.3164	0.033*
C26	0.0433 (2)	0.76245 (16)	0.39595 (16)	0.0230 (4)
H26	0.0763	0.7029	0.4151	0.028*
C41	0.46847 (19)	0.55337 (14)	0.29684 (13)	0.0146 (3)
O41	0.55209 (15)	0.48038 (11)	0.29349 (10)	0.0202 (3)
O42	0.37382 (15)	0.54691 (11)	0.21424 (10)	0.0209 (3)
N51	0.68861 (18)	0.59750 (13)	0.50526 (12)	0.0188 (3)
H51	0.661 (3)	0.526 (3)	0.450 (2)	0.036 (7)*
C51	0.83863 (19)	0.62940 (15)	0.57529 (13)	0.0155 (3)
C52	0.9415 (2)	0.74526 (17)	0.62019 (16)	0.0255 (4)
H52	0.9076	0.8081	0.6078	0.031*
C53	1.0926 (2)	0.76896 (18)	0.68275 (18)	0.0305 (4)
H53	1.1606	0.8480	0.7127	0.037*
C54	1.1457 (2)	0.67906 (19)	0.70221 (16)	0.0271 (4)
H54	1.2492	0.6958	0.7450	0.032*
C55	1.0444 (2)	0.56394 (18)	0.65779 (16)	0.0265 (4)
H55	1.0796	0.5014	0.6699	0.032*
C56	0.8916 (2)	0.53892 (16)	0.59562 (15)	0.0218 (4)
H56	0.8233	0.4600	0.5670	0.026*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Na1	0.0218 (3)	0.0168 (3)	0.0137 (3)	0.0013 (3)	0.0035 (3)	0.0021 (3)
Na2	0.0222 (4)	0.0216 (4)	0.0316 (4)	0.0048 (3)	0.0068 (3)	0.0080 (3)
O1	0.0288 (7)	0.0285 (7)	0.0182 (6)	0.0071 (6)	0.0033 (5)	0.0030 (6)
O2	0.0252 (6)	0.0179 (6)	0.0154 (6)	0.0009 (5)	0.0020 (5)	0.0047 (5)
O3	0.0352 (7)	0.0146 (6)	0.0168 (6)	0.0038 (5)	0.0052 (5)	0.0046 (5)
O4	0.0197 (6)	0.0248 (7)	0.0171 (6)	0.0024 (5)	0.0027 (5)	0.0036 (5)
O5	0.0255 (6)	0.0182 (6)	0.0163 (6)	0.0043 (5)	0.0022 (5)	0.0041 (5)
O6	0.0224 (6)	0.0183 (6)	0.0168 (6)	0.0048 (5)	0.0039 (5)	0.0032 (5)
O7	0.0368 (8)	0.0353 (8)	0.0273 (7)	0.0059 (7)	0.0008 (6)	0.0124 (6)
O8	0.0250 (7)	0.0277 (8)	0.0467 (9)	0.0002 (6)	−0.0024 (6)	0.0137 (7)
O9	0.0231 (7)	0.0291 (8)	0.0373 (8)	0.0058 (6)	−0.0004 (6)	0.0121 (6)
O1W	0.0234 (7)	0.0367 (8)	0.0284 (7)	0.0053 (6)	0.0035 (6)	0.0110 (7)
C1	0.0149 (7)	0.0112 (7)	0.0112 (7)	0.0012 (6)	0.0020 (6)	0.0013 (6)
C2	0.0142 (7)	0.0125 (7)	0.0146 (7)	0.0036 (6)	0.0016 (6)	0.0039 (6)
C3	0.0149 (7)	0.0159 (8)	0.0105 (7)	0.0026 (6)	−0.0009 (6)	0.0031 (6)
C4	0.0137 (7)	0.0126 (7)	0.0110 (7)	0.0026 (6)	0.0025 (5)	0.0019 (6)
C5	0.0143 (7)	0.0123 (7)	0.0142 (7)	0.0024 (6)	0.0012 (6)	0.0032 (6)
C6	0.0166 (7)	0.0144 (7)	0.0102 (7)	0.0035 (6)	−0.0010 (6)	0.0027 (6)
C11	0.0160 (7)	0.0124 (7)	0.0119 (7)	0.0026 (6)	0.0019 (6)	0.0013 (6)
O11	0.0273 (6)	0.0164 (6)	0.0151 (6)	0.0099 (5)	−0.0001 (5)	−0.0007 (5)
O12	0.0294 (7)	0.0189 (6)	0.0107 (5)	0.0086 (5)	−0.0001 (5)	0.0015 (5)
N21	0.0195 (7)	0.0133 (7)	0.0160 (7)	0.0068 (6)	−0.0037 (5)	−0.0011 (6)
C21	0.0164 (7)	0.0173 (8)	0.0122 (7)	0.0063 (6)	0.0016 (6)	0.0036 (6)
C22	0.0207 (9)	0.0217 (9)	0.0412 (11)	0.0010 (7)	−0.0039 (8)	0.0188 (9)
C23	0.0227 (9)	0.0316 (11)	0.0445 (12)	0.0070 (8)	−0.0039 (8)	0.0247 (10)
C24	0.0178 (8)	0.0286 (10)	0.0239 (9)	0.0059 (7)	−0.0032 (7)	0.0078 (8)
C25	0.0192 (9)	0.0189 (9)	0.0356 (11)	0.0017 (7)	0.0003 (7)	0.0050 (8)
C26	0.0206 (8)	0.0160 (8)	0.0308 (10)	0.0057 (7)	0.0015 (7)	0.0083 (7)
C41	0.0153 (7)	0.0130 (7)	0.0117 (7)	0.0011 (6)	0.0026 (6)	0.0019 (6)
O41	0.0245 (6)	0.0165 (6)	0.0151 (6)	0.0098 (5)	0.0008 (5)	−0.0003 (5)
O42	0.0255 (6)	0.0193 (6)	0.0118 (5)	0.0070 (5)	−0.0020 (5)	0.0006 (5)
N51	0.0197 (7)	0.0143 (7)	0.0163 (7)	0.0074 (6)	−0.0028 (6)	−0.0002 (6)
C51	0.0165 (7)	0.0182 (8)	0.0108 (7)	0.0060 (6)	0.0020 (6)	0.0040 (6)
C52	0.0233 (9)	0.0166 (8)	0.0323 (10)	0.0056 (7)	−0.0025 (7)	0.0073 (7)
C53	0.0231 (9)	0.0197 (9)	0.0378 (11)	0.0011 (7)	−0.0049 (8)	0.0053 (8)
C54	0.0195 (8)	0.0306 (10)	0.0253 (9)	0.0059 (7)	−0.0054 (7)	0.0082 (8)
C55	0.0258 (9)	0.0269 (10)	0.0294 (10)	0.0095 (8)	−0.0012 (7)	0.0152 (8)
C56	0.0223 (8)	0.0172 (8)	0.0249 (9)	0.0036 (7)	0.0002 (7)	0.0096 (7)

Geometric parameters (Å, º)

Na1—O2	2.3487 (14)	C3—C4	1.402 (2)
Na1—O3	2.3815 (15)	C3—H3	0.9500
Na1—O4	2.3882 (15)	C4—C5	1.426 (2)
Na1—O6	2.4224 (14)	C4—C41	1.517 (2)
Na1—O5	2.5178 (15)	C5—N51	1.399 (2)
Na1—O1	2.5605 (17)	C5—C6	1.403 (2)
Na1—Na2	3.4915 (11)	C6—H6	0.9500
Na1—H4A	2.60 (3)	C11—O11	1.268 (2)
Na2—O8	2.3237 (16)	C11—O12	1.272 (2)
Na2—O9	2.3266 (17)	N21—C21	1.410 (2)
Na2—O6	2.4407 (15)	N21—H21	0.91 (3)
Na2—O5	2.4582 (15)	C21—C22	1.393 (2)
Na2—O7	2.4685 (18)	C21—C26	1.401 (2)
Na2—H7B	2.66 (3)	C22—C23	1.399 (3)
O1—H1A	0.846 (10)	C22—H22	0.9500
O1—H1B	0.841 (10)	C23—C24	1.387 (3)
O2—H2A	0.85 (2)	C23—H23	0.9500
O2—H2B	0.840 (9)	C24—C25	1.387 (3)
O3—H3A	0.84 (2)	C24—H24	0.9500
O3—H3B	0.844 (10)	C25—C26	1.390 (3)
O4—H4A	0.845 (10)	C25—H25	0.9500
O4—H4B	0.845 (10)	C26—H26	0.9500
O5—H5A	0.846 (10)	C41—O41	1.271 (2)
O5—H5B	0.84 (2)	C41—O42	1.272 (2)
O6—H6A	0.844 (10)	N51—C51	1.409 (2)
O6—H6B	0.84 (3)	N51—H51	0.90 (3)
O7—H7B	0.843 (10)	C51—C56	1.399 (2)
O8—H8A	0.85 (3)	C51—C52	1.402 (2)
O8—H8B	0.843 (10)	C52—C53	1.390 (3)
O9—H9A	0.85 (4)	C52—H52	0.9500
O9—H9B	0.849 (10)	C53—C54	1.388 (3)
O1W—H1WA	0.851 (10)	C53—H53	0.9500
O1W—H1WB	0.84 (3)	C54—C55	1.391 (3)
C1—C6	1.400 (2)	C54—H54	0.9500
C1—C2	1.423 (2)	C55—C56	1.397 (3)
C1—C11	1.517 (2)	C55—H55	0.9500
C2—N21	1.398 (2)	C56—H56	0.9500
C2—C3	1.406 (2)
O2—Na1—O3	172.29 (5)	Na2—O8—H8A	119 (2)
O2—Na1—O4	93.61 (5)	Na2—O8—H8B	127.7 (17)
O3—Na1—O4	92.21 (5)	H8A—O8—H8B	112.7 (17)
O2—Na1—O6	87.91 (5)	Na2—O9—H9A	115 (3)
O3—Na1—O6	85.44 (5)	Na2—O9—H9B	126.8 (19)
O4—Na1—O6	169.36 (6)	H9A—O9—H9B	109.2 (16)
O2—Na1—O5	95.27 (5)	H1WA—O1W—H1WB	111.1 (17)
O3—Na1—O5	80.58 (5)	C6—C1—C2	118.91 (14)
O4—Na1—O5	81.63 (5)	C6—C1—C11	117.82 (14)
O6—Na1—O5	87.75 (5)	C2—C1—C11	123.25 (15)
O2—Na1—O1	87.81 (5)	N21—C2—C3	119.86 (14)
O3—Na1—O1	94.99 (5)	N21—C2—C1	122.52 (15)
O4—Na1—O1	109.64 (5)	C3—C2—C1	117.56 (15)
O6—Na1—O1	80.93 (5)	C4—C3—C2	123.42 (14)
O5—Na1—O1	168.17 (5)	C4—C3—H3	118.3
O2—Na1—Na2	100.70 (4)	C2—C3—H3	118.3
O3—Na1—Na2	71.77 (4)	C3—C4—C5	118.94 (14)
O4—Na1—Na2	125.15 (4)	C3—C4—C41	117.61 (14)
O6—Na1—Na2	44.32 (4)	C5—C4—C41	123.45 (15)
O5—Na1—Na2	44.75 (3)	N51—C5—C6	120.07 (14)
O1—Na1—Na2	123.45 (4)	N51—C5—C4	122.39 (15)
O2—Na1—H4A	112.1 (4)	C6—C5—C4	117.45 (15)
O3—Na1—H4A	73.4 (3)	C1—C6—C5	123.69 (15)
O4—Na1—H4A	18.9 (3)	C1—C6—H6	118.2
O6—Na1—H4A	155.4 (3)	C5—C6—H6	118.2
O5—Na1—H4A	76.7 (6)	O11—C11—O12	122.92 (15)
O1—Na1—H4A	112.7 (6)	O11—C11—C1	119.06 (14)
Na2—Na1—H4A	114.9 (5)	O12—C11—C1	118.01 (14)
O8—Na2—O9	97.88 (6)	C2—N21—C21	124.85 (14)
O8—Na2—O6	88.77 (6)	C2—N21—H21	116.2 (16)
O9—Na2—O6	167.29 (6)	C21—N21—H21	115.0 (16)
O8—Na2—O5	172.95 (7)	C22—C21—C26	118.32 (16)
O9—Na2—O5	85.88 (5)	C22—C21—N21	118.73 (15)
O6—Na2—O5	88.70 (5)	C26—C21—N21	122.82 (15)
O8—Na2—O7	86.00 (6)	C21—C22—C23	120.66 (17)
O9—Na2—O7	88.40 (6)	C21—C22—H22	119.7
O6—Na2—O7	102.93 (6)	C23—C22—H22	119.7
O5—Na2—O7	88.15 (6)	C24—C23—C22	120.56 (18)
O8—Na2—Na1	129.74 (5)	C24—C23—H23	119.7
O9—Na2—Na1	132.02 (5)	C22—C23—H23	119.7
O6—Na2—Na1	43.91 (3)	C25—C24—C23	118.93 (17)
O5—Na2—Na1	46.14 (4)	C25—C24—H24	120.5
O7—Na2—Na1	89.35 (5)	C23—C24—H24	120.5
O8—Na2—H7B	97.2 (6)	C24—C25—C26	120.92 (17)
O9—Na2—H7B	101.3 (5)	C24—C25—H25	119.5
O6—Na2—H7B	88.5 (5)	C26—C25—H25	119.5
O5—Na2—H7B	76.2 (6)	C25—C26—C21	120.59 (17)
O7—Na2—H7B	18.5 (3)	C25—C26—H26	119.7
Na1—Na2—H7B	70.9 (3)	C21—C26—H26	119.7
Na1—O1—H1A	95 (2)	O41—C41—O42	123.09 (15)
Na1—O1—H1B	118 (2)	O41—C41—C4	118.32 (14)
H1A—O1—H1B	111.3 (16)	O42—C41—C4	118.58 (15)
Na1—O2—H2A	117.9 (18)	C5—N51—C51	126.27 (14)
Na1—O2—H2B	108.8 (18)	C5—N51—H51	115.9 (17)
H2A—O2—H2B	111.0 (15)	C51—N51—H51	116.6 (17)
Na1—O3—H3A	120.5 (18)	C56—C51—C52	118.36 (16)
Na1—O3—H3B	103.7 (18)	C56—C51—N51	117.98 (15)
H3A—O3—H3B	111.2 (15)	C52—C51—N51	123.53 (16)
Na1—O4—H4A	95 (2)	C53—C52—C51	120.57 (17)
Na1—O4—H4B	118.4 (19)	C53—C52—H52	119.7
H4A—O4—H4B	110.9 (15)	C51—C52—H52	119.7
Na2—O5—Na1	89.11 (5)	C54—C53—C52	121.09 (18)
Na2—O5—H5A	120.1 (19)	C54—C53—H53	119.5
Na1—O5—H5A	98.0 (19)	C52—C53—H53	119.5
Na2—O5—H5B	110.8 (17)	C53—C54—C55	118.61 (17)
Na1—O5—H5B	127.0 (18)	C53—C54—H54	120.7
H5A—O5—H5B	111.0 (15)	C55—C54—H54	120.7
Na1—O6—Na2	91.77 (5)	C54—C55—C56	120.98 (17)
Na1—O6—H6A	102 (2)	C54—C55—H55	119.5
Na2—O6—H6A	118.0 (18)	C56—C55—H55	119.5
Na1—O6—H6B	110.5 (19)	C55—C56—C51	120.38 (17)
Na2—O6—H6B	119.8 (18)	C55—C56—H56	119.8
H6A—O6—H6B	111.2 (16)	C51—C56—H56	119.8
Na2—O7—H7B	94 (2)
O2—Na1—Na2—O8	101.00 (8)	C6—C1—C2—C3	1.0 (2)
O3—Na1—Na2—O8	−77.29 (8)	C11—C1—C2—C3	−177.39 (14)
O4—Na1—Na2—O8	−156.79 (8)	N21—C2—C3—C4	176.04 (15)
O6—Na1—Na2—O8	25.28 (8)	C1—C2—C3—C4	−1.2 (2)
O5—Na1—Na2—O8	−172.32 (9)	C2—C3—C4—C5	−0.1 (2)
O1—Na1—Na2—O8	6.52 (9)	C2—C3—C4—C41	−179.55 (15)
O2—Na1—Na2—O9	−87.49 (8)	C3—C4—C5—N51	178.21 (15)
O3—Na1—Na2—O9	94.22 (8)	C41—C4—C5—N51	−2.4 (2)
O4—Na1—Na2—O9	14.72 (9)	C3—C4—C5—C6	1.6 (2)
O6—Na1—Na2—O9	−163.21 (9)	C41—C4—C5—C6	−179.05 (14)
O5—Na1—Na2—O9	−0.81 (7)	C2—C1—C6—C5	0.5 (2)
O1—Na1—Na2—O9	178.03 (7)	C11—C1—C6—C5	178.96 (15)
O2—Na1—Na2—O6	75.72 (6)	N51—C5—C6—C1	−178.52 (15)
O3—Na1—Na2—O6	−102.57 (6)	C4—C5—C6—C1	−1.8 (2)
O4—Na1—Na2—O6	177.93 (7)	C6—C1—C11—O11	171.11 (15)
O5—Na1—Na2—O6	162.40 (7)	C2—C1—C11—O11	−10.5 (2)
O1—Na1—Na2—O6	−18.76 (6)	C6—C1—C11—O12	−9.7 (2)
O2—Na1—Na2—O5	−86.68 (6)	C2—C1—C11—O12	168.70 (15)
O3—Na1—Na2—O5	95.03 (6)	C3—C2—N21—C21	35.5 (2)
O4—Na1—Na2—O5	15.53 (6)	C1—C2—N21—C21	−147.42 (17)
O6—Na1—Na2—O5	−162.40 (7)	C2—N21—C21—C22	−154.71 (18)
O1—Na1—Na2—O5	178.84 (6)	C2—N21—C21—C26	29.5 (3)
O2—Na1—Na2—O7	−174.75 (6)	C26—C21—C22—C23	1.5 (3)
O3—Na1—Na2—O7	6.97 (5)	N21—C21—C22—C23	−174.51 (19)
O4—Na1—Na2—O7	−72.53 (6)	C21—C22—C23—C24	−1.0 (4)
O6—Na1—Na2—O7	109.53 (6)	C22—C23—C24—C25	0.2 (3)
O5—Na1—Na2—O7	−88.06 (6)	C23—C24—C25—C26	0.1 (3)
O1—Na1—Na2—O7	90.77 (6)	C24—C25—C26—C21	0.4 (3)
O9—Na2—O5—Na1	179.40 (6)	C22—C21—C26—C25	−1.2 (3)
O6—Na2—O5—Na1	−12.11 (5)	N21—C21—C26—C25	174.65 (17)
O7—Na2—O5—Na1	90.87 (5)	C3—C4—C41—O41	−178.91 (14)
O2—Na1—O5—Na2	99.89 (5)	C5—C4—C41—O41	1.7 (2)
O3—Na1—O5—Na2	−73.55 (5)	C3—C4—C41—O42	2.4 (2)
O4—Na1—O5—Na2	−167.22 (5)	C5—C4—C41—O42	−177.02 (15)
O6—Na1—O5—Na2	12.20 (5)	C6—C5—N51—C51	−32.0 (2)
O1—Na1—O5—Na2	−4.7 (3)	C4—C5—N51—C51	151.39 (17)
O2—Na1—O6—Na2	−107.66 (5)	C5—N51—C51—C56	158.36 (17)
O3—Na1—O6—Na2	68.43 (5)	C5—N51—C51—C52	−25.7 (3)
O4—Na1—O6—Na2	−9.2 (3)	C56—C51—C52—C53	0.4 (3)
O5—Na1—O6—Na2	−12.30 (5)	N51—C51—C52—C53	−175.51 (18)
O1—Na1—O6—Na2	164.23 (5)	C51—C52—C53—C54	0.1 (3)
O8—Na2—O6—Na1	−160.82 (6)	C52—C53—C54—C55	0.0 (3)
O9—Na2—O6—Na1	77.3 (3)	C53—C54—C55—C56	−0.6 (3)
O5—Na2—O6—Na1	12.59 (5)	C54—C55—C56—C51	1.1 (3)
O7—Na2—O6—Na1	−75.21 (6)	C52—C51—C56—C55	−1.0 (3)
C6—C1—C2—N21	−176.15 (15)	N51—C51—C56—C55	175.13 (17)
C11—C1—C2—N21	5.5 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O12^i	0.85 (1)	2.01 (1)	2.8328 (18)	165 (3)
O1—H1B···O8^ii	0.84 (1)	2.61 (2)	3.130 (2)	121 (2)
O2—H2A···O42^iii	0.85 (2)	1.99 (1)	2.8275 (18)	168 (3)
O2—H2B···O11^i	0.84 (1)	1.95 (1)	2.7740 (18)	168 (2)
O3—H3A···O12^iv	0.84 (2)	1.93 (1)	2.7632 (18)	171 (2)
O3—H3B···O41^v	0.84 (1)	1.88 (1)	2.7123 (18)	170 (2)
O4—H4A···O41^v	0.85 (1)	2.01 (1)	2.8522 (19)	178 (3)
O4—H4B···O1W^vi	0.85 (1)	2.01 (1)	2.824 (2)	163 (2)
O5—H5A···O42^v	0.85 (1)	2.05 (1)	2.8895 (18)	170 (2)
O5—H5B···O4^iv	0.84 (2)	2.16 (1)	2.9889 (19)	169 (2)
O6—H6A···O11^i	0.84 (1)	2.01 (1)	2.8513 (18)	172 (3)
O6—H6B···O1^vii	0.84 (3)	2.17 (1)	3.014 (2)	178 (2)
O7—H7B···O3	0.84 (1)	1.91 (1)	2.741 (2)	168 (3)
O8—H8A···O7^viii	0.85 (3)	2.15 (2)	2.925 (2)	154 (3)
O8—H8B···O12^ix	0.84 (1)	2.04 (1)	2.845 (2)	161 (3)
O9—H9A···O1W^x	0.85 (4)	2.03 (2)	2.826 (2)	155 (4)
O9—H9B···O2^xi	0.85 (1)	1.98 (1)	2.8015 (19)	164 (3)
O1W—H1WA···O42	0.85 (1)	2.07 (1)	2.9059 (19)	166 (3)
O1W—H1WB···O9^xii	0.84 (3)	2.05 (2)	2.858 (2)	159 (4)
N21—H21···O11	0.91 (3)	2.03 (3)	2.7176 (19)	132 (2)
N51—H51···O41	0.90 (3)	2.03 (3)	2.6950 (19)	130 (2)

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