Crystal structure of poly[[di-μ2-aqua-aqua-sodium] 4-amino-3,5,6-tri-chloro-pyridine-2-carboxyl-ate trihydrate], the sodium salt of the herbicide picloram.

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 mol-ecule. 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 mol-ecules of solvation and these, as well as the coordinating water mol-ecules and the amino group of the 4-amino-3,5,6-tri-chloro-picolinate anion, are involved in extensive inter-species hydrogen-bonding inter-actions with carboxyl and water O atoms, as well as the pyridine N atom. Among these associations is a centrosymmetric cyclic tetra-water R 4 (4)(8) motif, resulting in an overall three-dimensional structure.

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 MnII (Smith et al., 1981a ▸) and CuII (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}, and the structure is reported herein.

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 ▸).

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 ▸.

Table 1

Selected bond lengths ()

Na1O1W i	2.4185(16)	Na1O2W	2.3183(17)
Na1O3W ii	2.3803(16)	Na1O3W	2.3530(16)
Na1O1W	2.3529(16)

Symmetry codes: (i) ; (ii) .

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].

Supra­molecular features

In the crystal there are numerous inter-species water O—H⋯Ocarboxyl,water, O—H⋯Npyridine 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 (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⋯Cl5xi contact [3.2108 (7) Å; symmetry code (xi): x, y − 1, z].

Table 2

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
O1WH11WO4W	0.82	1.97	2.786(2)	178
O1WH12WO6W	0.89	1.99	2.877(2)	174
O2WH21WO22iii	0.94	1.79	2.721(2)	171
O2WH22WO5W	0.84	1.98	2.816(2)	172
O3WH31WO5W iv	0.88	1.93	2.781(2)	163
O3WH32WN1ii	0.90	2.02	2.910(2)	170
O4WH41WO22v	0.99	1.93	2.916(2)	173
O4WH42WO21	0.93	1.99	2.918(2)	174
O5WH51WO21	0.90	1.87	2.748(2)	166
O5WH52WO2W vi	0.90	2.01	2.8481(19)	155
O6WH61WO22vii	0.93	2.10	2.972(2)	156
O6WH62WO21iv	0.93	2.19	2.996(2)	144
N4H41O6W viii	0.96	2.18	3.080(2)	156
N4H42O4W viii	0.97	2.22	3.146(2)	160

Symmetry codes: (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) ; (viii) .

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 ▸.

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)8 2+], compared to one non-bridging water mol­ecule in the NaO5 coordination [Na2(H2O)6 2+] of the title complex. The [Na2(H2O)8 2+] 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)16 4+] 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], 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 CuII complex with pyrophosphate, [Cu(H2O)(phen)(P2O7)]2− (phen = 1,10-phenanthroline; Marino et al., 2010 ▸), the mixed-valent di-RuII,III complex with 1-hy­droxy­ethane 1,1-di­phospho­nate (hedp) [Ru2(hedp)2 X]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 ▸).

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.

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
Temperature (K)	200
a, b, c ()	6.5625(5), 8.4574(6), 13.8553(10)
, , ()	78.747(6), 79.374(6), 88.864(6)
V (3)	741.17(9)
Z	2
Radiation type	Mo K
(mm1)	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 > 2(I)] reflections	6040, 2905, 2487
R int	0.025
(sin /)max (1)	0.617
Refinement
R[F 2 > 2(F 2)], wR(F 2), S	0.031, 0.088, 1.00
No. of reflections	2905
No. of parameters	182
H-atom treatment	H-atom parameters constrained
max, min (e 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 ▸).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015012633/wm5173sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015012633/wm5173Isup2.hkl

CCDC reference: 1409779

Additional supporting information: crystallographic information; 3D view; checkCIF report

[Na(H2O)3](C6H2Cl3N2O2)·3H2O	Z = 2
Mr = 371.53	F(000) = 380
Triclinic, P1	Dx = 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

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	Rint = 0.025
Detector resolution: 16.077 pixels mm-1	θmax = 26.0°, θmin = 3.3°
ω scans	h = −8→7
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	k = −10→10
Tmin = 0.947, Tmax = 0.980	l = −17→13
6040 measured reflections

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(Fo2) + (0.0478P)2 + 0.2264P] where P = (Fo2 + 2Fc2)/3
S = 1.00	(Δ/σ)max = 0.001
2905 reflections	Δρmax = 0.30 e Å−3
182 parameters	Δρmin = −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)

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.

	x	y	z	Uiso*/Ueq
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*

	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)

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)

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···O5Wiv	0.88	1.93	2.781 (2)	163
O3W—H32W···N1ii	0.90	2.02	2.910 (2)	170
O4W—H41W···O22v	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···O2Wvi	0.90	2.01	2.8481 (19)	155
O6W—H61W···O22vii	0.93	2.10	2.972 (2)	156
O6W—H62W···Cl6	0.93	2.83	3.4400 (15)	124
O6W—H62W···O21iv	0.93	2.19	2.996 (2)	144
N4—H41···Cl3	0.96	2.54	2.9956 (17)	109
N4—H41···O6Wviii	0.96	2.18	3.080 (2)	156
N4—H42···Cl5	0.97	2.52	2.9690 (17)	108
N4—H42···O4Wviii	0.97	2.22	3.146 (2)	160