Crystal structure of poly[[di-μ2-aqua-aqua­sodium] 4-amino-3,5,6-tri­chloro­pyridine-2-carboxyl­ate trihydrate], the sodium salt of the herbicide picloram

Smith, G.

doi:10.1107/S2056989015012633

research communications

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ISSN: 2056-9890

Volume 71| Part 8| August 2015| Pages 931-933

https://doi.org/10.1107/S2056989015012633

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Crystal structure of poly[[di-μ₂-aqua-aquasodium] 4-amino-3,5,6-trichloropyridine-2-carboxylate trihydrate], the sodium salt of the herbicide picloram

Graham Smith ^a ^*

^aScience and Engineering Faculty, Queensland University of Technology, GPO Box 2434, Brisbane, Queensland 4001, Australia
^*Correspondence e-mail: g.smith@qut.edu.au

Edited by M. Weil, Vienna University of Technology, Austria (Received 3 June 2015; accepted 30 June 2015; online 15 July 2015)

In the structure of the title complex, {[Na(H₂O)₃](C₆H₂Cl₃N₂O₂)·3H₂O}_n, the sodium salt of the herbicide picloram, the cation adopts a polymeric chain structure, based on μ₂-aqua-bridged NaO₅ trigonal–bipyramidal complex units which have, in addition, a singly bonded water molecule. Each of the bridges within the chain, which extends parallel to the a axis, is centrosymmetric, with Na⋯Na separations of 3.4807 (16) and 3.5109 (16) Å. In the crystal, there are three water molecules of solvation and these, as well as the coordinating water molecules and the amino group of the 4-amino-3,5,6-trichloropicolinate anion, are involved in extensive inter-species hydrogen-bonding interactions with carboxyl and water O atoms, as well as the pyridine N atom. Among these associations is a centrosymmetric cyclic tetrawater R₄⁴(8) motif, resulting in an overall three-dimensional structure.

Keywords: crystal structure; picloram; Tordon; herbicide; sodium salt; coordination polymer; sodium–water cationic chain; hydrogen bonding.

CCDC reference: 1409779

1. Chemical context

4-Amino-3,5,6-trichloropyridine-2-carboxylic acid (picloram) is a commercial herbicide (Mullinson, 1985 ) introduced by Dow Chemicals as Tordon (O'Neil, 2001 ). Although it has potential as a metal-chelating ligand similar to picolinic acid, there are only five metal complexes with picloramate anions in the crystallographic literature. Examples include picloram as a bidentate N,O chelating ligand with Mn^II (Smith et al., 1981a ) and Cu^II (two structures, one a mixed-ligand complex with 2-aminopyrimidine; O'Reilly et al., 1983 ) and caesium (Smith, 2013 ). In the Mg complex (Smith et al., 1981b ), the picloramate anions act as counter-ions to the [Mg(H₂O)₆]²⁺ cation. Although the structure of picloram has not been reported, that of the guanidinium salt is known (Parthasarathi et al., 1982 ). The reaction of picloram with sodium bicarbonate in aqueous ethanol gave crystals of the title complex salt {[Na(H₂O)₃]⁺·C₆H₂Cl₃N₂O₂⁻·3H₂O}_n, and the structure is reported herein.

2. Structural commentary

In the structure of the title salt, (Fig. 1), polymeric cationic chains based on μ₂-water-bridged NaO₅ trigonal–bipyramidal complex units are formed, comprising centrosymmetric four-membered water-bridged Na₂O₂ rings with both O1W and O3W [Na⋯Naⁱ and Na⋯Naⁱⁱ = 3.4807 (16) and 3.5109 (16) Å, respectively; for symmetry codes, see Table 1]. In the fifth Na coordination site is the third water molecule (O2W) in a non-bridging mode [overall Na—O range, 2.3183 (17)–2.4185 (16) Å: Table 1]. Although the μ₂-water-bridged cationic chains are relatively common, the NaO₅ coordination with one non-bridging water is rare, compared to the more usual octahedral NaO₆ coordination involving two non-bridging water molecules in other examples, e.g. in the biphenyl-4,4′-diphosphonate salt (Kinnibrugh et al., 2012 ).

Table 1
Selected bond lengths (Å)

Na1—O1Wⁱ	2.4185 (16)	Na1—O2W	2.3183 (17)
Na1—O3Wⁱⁱ	2.3803 (16)	Na1—O3W	2.3530 (16)
Na1—O1W	2.3529 (16)
Symmetry codes: (i) -x, -y+1, -z+2; (ii) -x+1, -y+1, -z+2.

Figure 1
The atom-numbering scheme for the hydrated title salt, with non-H atoms drawn as 40% probability ellipsoids. Inter-species hydrogen bonds are shown as dashed lines. Symmetry codes: (ix) x + 1, y, z; (x) x − 1, y, z. For other symmetry codes, see Table 1

The structure of the title salt also contains non-coordinating picloramate anions and three water molecules of solvation (O4W–O6W). In this anion, the carboxyl group lies close to perpendicular to the pyridine ring [torsion angle N1—C2—C21—O21 = 89.1 (2)°], which is similar to that in the anhydrous guanidinium picloramate salt (73.3°) (Parthasarathi et al., 1982), while the amine group gives lateral intramolecular N4—H41⋯Cl3 and N4—H41⋯O6W interactions [2.9956 (17), 3.080 (2) Å].

3. Supramolecular features

In the crystal there are numerous inter-species water O—H⋯O_{carboxyl,water}, O—H⋯N_pyridine and O—H⋯Cl hydrogen-bonding interactions (Table 2), including a centrosymmetric tetra-water cyclic ring involving O2W—H⋯O5W and O5W—H⋯O2W^vi [graph set R₄⁴(8)], giving a three-dimensional structure (Fig. 2). Cyclic tetra-water moieties such as found in the present structure are being identified in an increasing number in labile water-stabilized salt hydrates, e.g. in the brucinium L-glycerate 4.75-hydrate salt (Białońska et al., 2005 ). Also found in the structure of the title salt is a short intermolecular Cl3⋯Cl5^xi contact [3.2108 (7) Å; symmetry code (xi): x, y − 1, z].

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H11W⋯O4W	0.82	1.97	2.786 (2)	178
O1W—H12W⋯O6W	0.89	1.99	2.877 (2)	174
O2W—H21W⋯O22ⁱⁱⁱ	0.94	1.79	2.721 (2)	171
O2W—H22W⋯O5W	0.84	1.98	2.816 (2)	172
O3W—H31W⋯O5W^iv	0.88	1.93	2.781 (2)	163
O3W—H32W⋯N1ⁱⁱ	0.90	2.02	2.910 (2)	170
O4W—H41W⋯O22^v	0.99	1.93	2.916 (2)	173
O4W—H42W⋯O21	0.93	1.99	2.918 (2)	174
O5W—H51W⋯O21	0.90	1.87	2.748 (2)	166
O5W—H52W⋯O2W^vi	0.90	2.01	2.8481 (19)	155
O6W—H61W⋯O22^vii	0.93	2.10	2.972 (2)	156
O6W—H62W⋯O21^iv	0.93	2.19	2.996 (2)	144
N4—H41⋯O6W^viii	0.96	2.18	3.080 (2)	156
N4—H42⋯O4W^viii	0.97	2.22	3.146 (2)	160
Symmetry codes: (ii) -x+1, -y+1, -z+2; (iii) -x+1, -y, -z+2; (iv) x, y+1, z; (v) x-1, y, z; (vi) -x, -y, -z+2; (vii) x-1, y+1, z; (viii) -x+1, -y+1, -z+1.

Figure 2
The three-dimensional hydrogen-bonded structure, with inter-species hydrogen bonds and intramolecular N—H⋯Cl associations shown as dashed lines. For symmetry codes, see Fig. 1

and Table 2

4. Database survey

The (μ₂-aqua)-bridged Na₂(H₂O)₂ units in the coordination polymeric cationic chains in the title structure have precedents in a large number of reported crystal structures. However, with few exceptions, these are based on NaO₆ polyhedra, with octahedral or distorted octahedral stereochemistry, having two non-bridging water molecules [Na₂(H₂O)₈²⁺], compared to one non-bridging water molecule in the NaO₅ coordination [Na₂(H₂O)₆²⁺] of the title complex. The [Na₂(H₂O)₈²⁺] dications may be discrete, such as found in the anionic aryltelluronic anhydride salt (Beckmann et al., 2012 ) and the anionic dimethylarsenate (cacodylate) salt (Lennartson & Håkansson, 2008 ), or they may be found as [Na₄(H₂O)₁₆⁴⁺] tetra-cations as found in the dianionic biphenyl-4,4′-diphosphonate salt (Kinnibrugh et al., 2012) and the monoanionic salt of luminol (5-amino-2,3-dihydro-1,4-phthalazinedione; Guzei et al., 2013 ). However, more commonly, they are polymeric [Na₂(H₂O)₈]_n, e.g. in the monoanionic salt of the anti-allergic drug tranilast ({2-[3-(3,4-dimethoxyphenyl)acrolyl]amino}benzoic acid; Geng et al., 2013 ), but often associated with metal complex anions, e.g. the Cu^II complex with pyrophosphate, [Cu(H₂O)(phen)(P₂O₇)]²⁻ (phen = 1,10-phenanthroline; Marino et al., 2010 ), the mixed-valent di-Ru^II,III complex with 1-hydroxyethane 1,1-diphosphonate (hedp) [Ru₂(hedp)₂X]⁴⁻ (X = Cl, Br; Yi et al., 2005 ) and the dioxo-Np complex anion salt with dipicolinate (dipic), [NpO₂(dipic)(H₂O)₂]⁻ (Tian et al., 2009 ).

5. Synthesis and crystallization

The title compound was synthesized by briefly heating together 0.5 mmol of 4-amino-3,5,6-trichloropicolinic acid (picloram) with excess NaHCO₃ in 10 ml of 10% (v/v) ethanol–water. Room temperature evaporation of the solution to dryness gave minor colourless crystal blocks of the title complex from which a specimen was cleaved for the X-ray analysis.

6. Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 3. Hydrogen atoms of the water molecules and the amine group were located in a difference-Fourier synthesis but were subsequently constrained in the refinement with the isotropic displacement parameters allowed to ride, with U_iso(H) = 1.2U_eq(N) or 1.5U_eq(O).

Table 3
Experimental details

Crystal data
Chemical formula	[Na(H₂O)₃](C₆H₂Cl₃N₂O₂)·3H₂O
M_r	371.53
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	200
a, b, c (Å)	6.5625 (5), 8.4574 (6), 13.8553 (10)
α, β, γ (°)	78.747 (6), 79.374 (6), 88.864 (6)
V (Å³)	741.17 (9)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.68
Crystal size (mm)	0.35 × 0.35 × 0.22

Data collection
Diffractometer	Oxford Diffraction Gemini-S CCD detector
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2014 )
T_min, T_max	0.947, 0.980
No. of measured, independent and observed [I > 2σ(I)] reflections	6040, 2905, 2487
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.088, 1.00
No. of reflections	2905
No. of parameters	182
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.28
Computer programs: CrysAlis PRO (Agilent, 2014), SIR92 (Altomare et al., 1993 ), SHELXL97 (Sheldrick, 2008 ) within WinGX (Farrugia, 2012 ), PLATON (Spek, 2009 ).

Supporting information

CCDC reference: 1409779

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2056989015012633/wm5173sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015012633/wm5173Isup2.hkl

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Agilent, 2014); cell refinement: CrysAlis PRO (Agilent, 2014); data reduction: CrysAlis PRO (Agilent, 2014); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) within WinGX (Farrugia, 2012); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: PLATON (Spek, 2009).

Poly[[di-µ₂-aqua-aquasodium] 4-amino-3,5,6-trichloropyridine-2-carboxylate trihydrate] top

Crystal data top

[Na(H₂O)₃](C₆H₂Cl₃N₂O₂)·3H₂O	Z = 2
M_r = 371.53	F(000) = 380
Triclinic, P1	D_x = 1.665 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.5625 (5) Å	Cell parameters from 2548 reflections
b = 8.4574 (6) Å	θ = 3.8–28.8°
c = 13.8553 (10) Å	µ = 0.68 mm⁻¹
α = 78.747 (6)°	T = 200 K
β = 79.374 (6)°	Block, colourless
γ = 88.864 (6)°	0.35 × 0.35 × 0.22 mm
V = 741.17 (9) Å³

Data collection top

Oxford Diffraction Gemini-S CCD-detector diffractometer	2905 independent reflections
Radiation source: Enhance (Mo) X-ray source	2487 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
Detector resolution: 16.077 pixels mm^-1	θ_max = 26.0°, θ_min = 3.3°
ω scans	h = −8→7
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	k = −10→10
T_min = 0.947, T_max = 0.980	l = −17→13
6040 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.031	H-atom parameters constrained
wR(F²) = 0.088	w = 1/[σ²(F_o²) + (0.0478P)² + 0.2264P] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max = 0.001
2905 reflections	Δρ_max = 0.30 e Å⁻³
182 parameters	Δρ_min = −0.28 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008) within WinGX (Farrugia, 2012)
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.050 (3)

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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 (Å²) top

	x	y	z	U_iso*/U_eq
Cl3	0.73580 (8)	0.09272 (5)	0.52593 (4)	0.0257 (2)
Cl5	0.76678 (8)	0.74102 (5)	0.46993 (4)	0.0240 (2)
Cl6	0.67863 (9)	0.70381 (6)	0.70472 (4)	0.0295 (2)
O21	0.4767 (2)	0.04778 (17)	0.77535 (11)	0.0287 (5)
O22	0.8188 (2)	0.04407 (17)	0.77067 (11)	0.0292 (5)
N1	0.6684 (2)	0.39495 (18)	0.71307 (12)	0.0196 (5)
N4	0.7849 (3)	0.42747 (19)	0.40294 (12)	0.0213 (5)
C2	0.6814 (3)	0.2631 (2)	0.67196 (14)	0.0172 (5)
C3	0.7193 (3)	0.2696 (2)	0.57064 (14)	0.0170 (5)
C4	0.7473 (3)	0.4178 (2)	0.50250 (14)	0.0168 (6)
C5	0.7335 (3)	0.5539 (2)	0.54712 (14)	0.0173 (5)
C6	0.6946 (3)	0.5361 (2)	0.64975 (15)	0.0186 (6)
C21	0.6561 (3)	0.1034 (2)	0.74534 (14)	0.0204 (6)
Na1	0.24455 (12)	0.42819 (9)	1.01558 (6)	0.0268 (3)
O1W	0.0817 (2)	0.53070 (17)	0.87914 (10)	0.0299 (5)
O2W	0.1503 (2)	0.15728 (17)	1.05390 (11)	0.0300 (5)
O3W	0.4202 (2)	0.62279 (17)	1.07140 (10)	0.0272 (5)
O4W	0.1371 (2)	0.27585 (17)	0.77676 (12)	0.0317 (5)
O5W	0.2700 (2)	−0.10534 (18)	0.95986 (11)	0.0325 (5)
O6W	0.1709 (2)	0.82429 (17)	0.73270 (11)	0.0298 (5)
H41	0.80460	0.32820	0.37840	0.0260*
H42	0.80680	0.53330	0.36040	0.0260*
H11W	0.09740	0.45450	0.85000	0.0450*
H12W	0.10510	0.62480	0.83710	0.0450*
H21W	0.15180	0.09520	1.11820	0.0450*
H22W	0.19310	0.08550	1.02150	0.0450*
H31W	0.38250	0.71930	1.04480	0.0410*
H32W	0.40980	0.61800	1.13770	0.0410*
H41W	0.02360	0.20490	0.77150	0.0480*
H42W	0.25100	0.20920	0.77350	0.0480*
H51W	0.34890	−0.07030	0.89970	0.0490*
H52W	0.15590	−0.13130	0.93860	0.18 (2)*
H61W	0.06160	0.89510	0.72480	0.0450*
H62W	0.30130	0.87260	0.72460	0.0450*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl3	0.0359 (3)	0.0159 (2)	0.0269 (3)	0.0007 (2)	−0.0044 (2)	−0.0091 (2)
Cl5	0.0280 (3)	0.0146 (2)	0.0282 (3)	−0.0001 (2)	−0.0049 (2)	−0.0012 (2)
Cl6	0.0412 (3)	0.0196 (3)	0.0309 (3)	0.0023 (2)	−0.0063 (2)	−0.0131 (2)
O21	0.0247 (8)	0.0260 (8)	0.0314 (9)	−0.0065 (6)	−0.0013 (6)	0.0013 (6)
O22	0.0290 (8)	0.0250 (8)	0.0318 (9)	0.0043 (6)	−0.0089 (7)	0.0013 (6)
N1	0.0202 (9)	0.0195 (8)	0.0195 (9)	0.0004 (6)	−0.0025 (7)	−0.0060 (7)
N4	0.0263 (9)	0.0197 (8)	0.0178 (8)	0.0009 (7)	−0.0031 (7)	−0.0042 (6)
C2	0.0128 (9)	0.0164 (9)	0.0220 (10)	0.0008 (7)	−0.0024 (7)	−0.0037 (7)
C3	0.0152 (9)	0.0147 (9)	0.0224 (10)	0.0005 (7)	−0.0038 (7)	−0.0063 (7)
C4	0.0106 (9)	0.0193 (10)	0.0216 (10)	0.0008 (7)	−0.0044 (7)	−0.0053 (8)
C5	0.0141 (9)	0.0144 (9)	0.0228 (10)	0.0002 (7)	−0.0041 (7)	−0.0019 (7)
C6	0.0160 (10)	0.0167 (9)	0.0252 (10)	0.0015 (7)	−0.0040 (8)	−0.0090 (8)
C21	0.0251 (11)	0.0192 (9)	0.0177 (10)	0.0014 (8)	−0.0028 (8)	−0.0068 (7)
Na1	0.0249 (5)	0.0264 (4)	0.0291 (5)	−0.0002 (3)	−0.0031 (3)	−0.0068 (3)
O1W	0.0360 (9)	0.0275 (8)	0.0252 (8)	0.0022 (6)	−0.0021 (7)	−0.0065 (6)
O2W	0.0390 (9)	0.0239 (8)	0.0246 (8)	0.0020 (6)	−0.0008 (7)	−0.0039 (6)
O3W	0.0322 (9)	0.0264 (8)	0.0223 (8)	0.0022 (6)	−0.0020 (6)	−0.0064 (6)
O4W	0.0282 (8)	0.0283 (8)	0.0399 (9)	0.0023 (6)	−0.0067 (7)	−0.0097 (7)
O5W	0.0342 (9)	0.0353 (9)	0.0247 (8)	0.0009 (7)	−0.0010 (7)	−0.0020 (7)
O6W	0.0257 (8)	0.0311 (8)	0.0330 (9)	−0.0003 (6)	−0.0043 (7)	−0.0079 (6)

Geometric parameters (Å, º) top

Na1—O1Wⁱ	2.4185 (16)	O4W—H42W	0.9300
Na1—O3Wⁱⁱ	2.3803 (16)	O4W—H41W	0.9900
Na1—O1W	2.3529 (16)	O5W—H52W	0.9000
Na1—O2W	2.3183 (17)	O5W—H51W	0.9000
Na1—O3W	2.3530 (16)	O6W—H61W	0.9300
Cl3—C3	1.7216 (18)	O6W—H62W	0.9300
Cl5—C5	1.7213 (18)	N1—C2	1.342 (2)
Cl6—C6	1.7289 (19)	N1—C6	1.330 (2)
O21—C21	1.243 (2)	N4—C4	1.342 (2)
O22—C21	1.250 (2)	N4—H41	0.9600
O1W—H12W	0.8900	N4—H42	0.9700
O1W—H11W	0.8200	C2—C3	1.370 (3)
O2W—H21W	0.9400	C2—C21	1.515 (3)
O2W—H22W	0.8400	C3—C4	1.407 (3)
O3W—H31W	0.8800	C4—C5	1.403 (2)
O3W—H32W	0.9000	C5—C6	1.376 (3)

O1Wⁱ—Na1—O3Wⁱⁱ	173.66 (6)	H41W—O4W—H42W	103.00
O1W—Na1—O3W	114.69 (6)	H51W—O5W—H52W	98.00
O1W—Na1—O1Wⁱ	86.32 (5)	H61W—O6W—H62W	116.00
O1W—Na1—O3Wⁱⁱ	100.02 (6)	C2—N1—C6	116.35 (16)
O2W—Na1—O3W	141.97 (6)	C4—N4—H41	118.00
O1Wⁱ—Na1—O2W	85.88 (6)	C4—N4—H42	118.00
O2W—Na1—O3Wⁱⁱ	92.71 (6)	H41—N4—H42	124.00
O1W—Na1—O2W	103.20 (6)	N1—C2—C3	123.14 (17)
O3W—Na1—O3Wⁱⁱ	84.24 (5)	N1—C2—C21	115.53 (16)
O1Wⁱ—Na1—O3W	93.06 (5)	C3—C2—C21	121.32 (16)
Na1—O1W—Na1ⁱ	93.68 (5)	Cl3—C3—C2	119.28 (14)
Na1—O3W—Na1ⁱⁱ	95.76 (6)	Cl3—C3—C4	119.39 (14)
Na1—O1W—H11W	100.00	C2—C3—C4	121.32 (16)
Na1ⁱ—O1W—H11W	121.00	N4—C4—C3	122.49 (16)
Na1—O1W—H12W	128.00	N4—C4—C5	122.95 (17)
H11W—O1W—H12W	112.00	C3—C4—C5	114.55 (17)
Na1ⁱ—O1W—H12W	103.00	Cl5—C5—C4	118.07 (14)
Na1—O2W—H22W	128.00	Cl5—C5—C6	121.71 (14)
H21W—O2W—H22W	97.00	C4—C5—C6	120.22 (16)
Na1—O2W—H21W	121.00	Cl6—C6—N1	115.37 (15)
Na1—O3W—H32W	119.00	Cl6—C6—C5	120.21 (14)
H31W—O3W—H32W	108.00	N1—C6—C5	124.42 (17)
Na1—O3W—H31W	109.00	O21—C21—O22	127.24 (18)
Na1ⁱⁱ—O3W—H32W	115.00	O21—C21—C2	116.83 (17)
Na1ⁱⁱ—O3W—H31W	109.00	O22—C21—C2	115.91 (17)

O3Wⁱⁱ—Na1—O3W—Na1ⁱⁱ	0.00 (6)	N1—C2—C21—O21	89.1 (2)
O1W—Na1—O1Wⁱ—Na1ⁱ	0.00 (6)	N1—C2—C3—Cl3	179.26 (15)
O2W—Na1—O1Wⁱ—Na1ⁱ	−103.53 (6)	N1—C2—C3—C4	0.0 (3)
O3W—Na1—O1Wⁱ—Na1ⁱ	114.57 (6)	C21—C2—C3—Cl3	0.7 (3)
O1W—Na1—O3Wⁱⁱ—Na1ⁱⁱ	114.11 (6)	C3—C2—C21—O22	89.4 (2)
O2W—Na1—O3Wⁱⁱ—Na1ⁱⁱ	−141.98 (6)	N1—C2—C21—O22	−89.3 (2)
O3W—Na1—O3Wⁱⁱ—Na1ⁱⁱ	−0.02 (8)	C3—C2—C21—O21	−92.2 (2)
O2W—Na1—O3W—Na1ⁱⁱ	87.03 (10)	C2—C3—C4—C5	0.1 (3)
O1Wⁱ—Na1—O3W—Na1ⁱⁱ	174.25 (5)	Cl3—C3—C4—N4	0.6 (3)
O2W—Na1—O1W—Na1ⁱ	84.89 (6)	Cl3—C3—C4—C5	−179.13 (15)
O3W—Na1—O1W—Na1ⁱ	−91.68 (6)	C2—C3—C4—N4	179.9 (2)
O1Wⁱ—Na1—O1W—Na1ⁱ	0.00 (5)	C3—C4—C5—Cl5	179.71 (15)
O3Wⁱⁱ—Na1—O1W—Na1ⁱ	−179.91 (5)	N4—C4—C5—Cl5	−0.1 (3)
O1W—Na1—O3W—Na1ⁱⁱ	−98.40 (6)	N4—C4—C5—C6	−180.0 (2)
C6—N1—C2—C21	178.63 (17)	C3—C4—C5—C6	−0.2 (3)
C2—N1—C6—Cl6	−179.62 (14)	C4—C5—C6—N1	0.2 (3)
C6—N1—C2—C3	0.0 (3)	Cl5—C5—C6—Cl6	−0.2 (3)
C2—N1—C6—C5	−0.1 (3)	Cl5—C5—C6—N1	−179.72 (15)
C21—C2—C3—C4	−178.59 (18)	C4—C5—C6—Cl6	179.74 (16)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H11W···O4W	0.82	1.97	2.786 (2)	178
O1W—H12W···O6W	0.89	1.99	2.877 (2)	174
O2W—H21W···O22ⁱⁱⁱ	0.94	1.79	2.721 (2)	171
O2W—H22W···O5W	0.84	1.98	2.816 (2)	172
O3W—H31W···O5W^iv	0.88	1.93	2.781 (2)	163
O3W—H32W···N1ⁱⁱ	0.90	2.02	2.910 (2)	170
O4W—H41W···O22^v	0.99	1.93	2.916 (2)	173
O4W—H42W···O21	0.93	1.99	2.918 (2)	174
O5W—H51W···O21	0.90	1.87	2.748 (2)	166
O5W—H52W···O2W^vi	0.90	2.01	2.8481 (19)	155
O6W—H61W···O22^vii	0.93	2.10	2.972 (2)	156
O6W—H62W···Cl6	0.93	2.83	3.4400 (15)	124
O6W—H62W···O21^iv	0.93	2.19	2.996 (2)	144
N4—H41···Cl3	0.96	2.54	2.9956 (17)	109
N4—H41···O6W^viii	0.96	2.18	3.080 (2)	156
N4—H42···Cl5	0.97	2.52	2.9690 (17)	108
N4—H42···O4W^viii	0.97	2.22	3.146 (2)	160

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

Acknowledgements

The author acknowledges financial support from the Science and Engineering Faculty, Queensland University of Technology, Brisbane.

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