Tetra­kis(2-amino-5-chloro­pyridinium) di­hydrogen cyclo­hexa­phosphate

Hamdi, A.; Khederi, L.; Rzaigui, M.

doi:10.1107/S1600536814003584

organic compounds

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ISSN: 2056-9890

Volume 70| Part 3| March 2014| Pages o342-o343

doi:10.1107/S1600536814003584

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Tetrakis(2-amino-5-chloropyridinium) dihydrogen cyclohexaphosphate

Ahmed Hamdi,^a Lamia Khederi ^a ^* and Mohamed Rzaigui ^a

^aChemistry Laboratory of Materials, Sciences Faculty of Bizerta, 7021 Jarzouna, Bizerta, Tunisia
^*Correspondence e-mail: lamia.khederi@fsb.rnu.tn

(Received 3 February 2014; accepted 17 February 2014; online 22 February 2014)

In the crystal structure of the title compound, 4C₅H₆ClN₂⁺·H₂P₆O₁₈⁴⁻, the [H₂P₆O₁₈]⁴⁻ anions are interconnected by O—H⋯O hydrogen bonds, leading to the formation of infinite ribbons extending along the a-axis direction. These ribbons are linked to the organic cations, via N—H⋯O and C—H⋯O hydrogen bonds, into a three-dimensional network. The six P atoms of the [H₂P₆O₁₈]⁴⁻ anion form a chair conformation. The complete cyclohexaphosphate anion is generated by inversion symmetry.

CCDC reference: 987420

Related literature

For properties of hybrid materials, see: Ozin (1992 ); Teraski et al. (1987 ). For related structures containing cyclohexaphosphate rings, see: Bel Haj Salah et al. (2014 ); Khedhiri et al. (2007 , 2012 ); Amri et al. (2009 ); Abid et al. (2012 ). For bond lengths in pyridine, see: Bak et al. (1959 ); Hemissi et al. (2010 ); Toumi Akriche et al. (2010 ); Akriche & Rzaigui (2005 ); Janiak (2000 ). For the preparation of cyclohexaphosphoric acid, see: Schulke & Kayser (1985 ).

Experimental

Crystal data

4C₅H₆ClN₂⁺·H₂O₁₈P₆⁴⁻
M_r = 994.11
Triclinic, $[P \overline 1]$
a = 9.199 (3) Å
b = 9.304 (2) Å
c = 11.327 (3) Å
α = 74.98 (3)°
β = 85.17 (2)°
γ = 75.20 (2)°
V = 905.1 (5) Å³
Z = 1
Ag Kα radiation
λ = 0.56087 Å
μ = 0.35 mm⁻¹
T = 293 K
0.32 × 0.22 × 0.15 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
11291 measured reflections
8865 independent reflections
5387 reflections with I > 2σ(I)
R_int = 0.020
2 standard reflections every 120 min intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.056
wR(F²) = 0.155
S = 1.02
8865 reflections
305 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.82 e Å⁻³
Δρ_min = −0.65 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O5ⁱ	0.96 (3)	1.78 (3)	2.736 (3)	177 (3)
O1—H1A⋯O8ⁱⁱ	0.78 (5)	1.66 (5)	2.418 (3)	165 (5)
N2—H2A⋯O6ⁱ	0.82 (4)	2.02 (4)	2.844 (3)	173 (3)
N2—H2B⋯O9ⁱⁱⁱ	0.80 (3)	2.29 (3)	3.000 (3)	149 (4)
N3—H3⋯O2	0.78 (4)	2.03 (3)	2.781 (3)	161 (3)
N4—H4A⋯O2	0.80 (3)	2.57 (3)	3.179 (3)	134 (2)
N4—H4A⋯O6	0.80 (3)	2.16 (3)	2.827 (3)	142 (3)
N4—H4B⋯O9^iv	0.93 (4)	1.95 (4)	2.852 (3)	162 (3)
C5—H5⋯O5^v	0.87 (3)	2.51 (3)	3.322 (3)	157 (3)
C10—H10⋯O1ⁱⁱ	0.96 (4)	2.42 (4)	3.262 (3)	146 (3)
Symmetry codes: (i) -x, -y, -z+1; (ii) -x+1, -y+1, -z+1; (iii) -x, -y+1, -z+1; (iv) x, y-1, z; (v) x, y, z-1.

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ); software used to prepare material for publication: WinGX (Farrugia, 2012).

Supporting information

CCDC reference: 987420

Crystal structure: contains datablock I. DOI: 10.1107/S1600536814003584/fj2662sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814003584/fj2662Isup2.hkl

checkCIF report

Comment top

Research in organic-inorganic materials has experienced considerable growth in recent years for the purpose of generating desirable properties and functionalities. An important strategy employed in studying such systems has been to take advantage of hydrogen-bond interactions between organic cations and inorganic anions, since they have been recognized as the most powerful force to generate supramolecular network in one, two and three dimensions (Ozin, 1992, Teraski et al., 1987).

In this context, our aims have been focused on the organic salts of cyclohexaphosphates systems. The title compound (I) provides another example of these kinds of materials.

The partial three-dimensional plot in Figure 1 illustrates the geometrical configuration of the [H₂P₆O₁₈]^4- ring and the two independent organic cations [C₅H₆ClN₂]⁺ in the (I) structure. The dihydrogen-cyclohexaphosphate anions are connected through strong hydrogen bonds characterized by short distances (d_O···O = 2.418 (3) Å) leading to the formation of infinite and parallel [H₂P₆O₁₈]_n^4- slabs (Figure 2). It is worth noting that the strong H-bond between phosphoric rings (Table 1) (d_O···O < 2.73 Å) is rather observed in cyclohexaphosphates.

Two crystallographically independent cations coexist in this structure. They are arranged in pairs and anchored onto the anionic ribbons via N—H···O and C—H···O hydrogen bonds to keep up the three-dimensional network cohesion (Figure 3, Figure 4).

The [H₂P₆O₁₈]^4-, group with chair conformation shows its standard geometry, the longest bonds length ranging between 1.580 (2) and 1.608 (2) Å, correspond to the bridging oxygen atom, the intermediate one, P1—O1 = 1.502 (2) Å, correspond to the P—OH bonding and the shortest ones spreading between 1.460 (2) and 1.498 (2) Å, correspond to the external oxygen atoms. The P—P—P angles of 111.0 (1), 120.5 (1) and 125.1 (4)° show that the rings are slightly distorted from the ideal threefold symmetry. The P—P distances as well as P—O—P or O—P—O angles show that these features are similar to those commonly observed in condensed phosphate anions (Bel Haj Salah et al., 2014, Khedhiri et al., 2012, Khedhiri et al., 2007, Amri et al., 2009, Abid et al., 2012).

Despite the limited number of organic cation cyclohexaphosphates (about forty related structures), we can distinguish only few acidic cyclohexaphosphates such as the title compound (I).

The examination of pyridinium rings shows that these units are planar with mean deviation of 0.0036 and 0.0038 Å from least-square plane defined by the six constituent atoms. The average C—N distances in pyridinium rings is 1.353 Å and the C—C bond lengths are 1.380 Å. The latter value, being shorter than 1.39–1.41 Å, reported for non-substituent pyridine, may indicate some aromatic bond characters (Bak et al., 1959). These values are in accordance with those observed in others compounds (Hemissi et al., 2010, Toumi Akriche et al., 2010, Akriche et al., 2005). The inter-planar distance between the pyridine rings is in the vicinity of 4.00 Å, which is significantly longer than 3.80 Å for the p-p interaction (Janiak, 2000). In addition to electrostatic and van der Waals interactions, the structure is further stabilized with a three-dimensional network of O—H···O, N—H···O and the weaker C—H···O hydrogen bonds (Table 1, Figure 3).

Related literature top

For properties of hybrid materials, see: Ozin (1992); Teraski et al. (1987). For related structures containing cyclohexaphosphate rings, see: Bel Haj Salah et al. (2014); Khedhiri et al. (2007, 2012); Amri et al. (2009); Abid et al. (2012). For bond lengths in pyridine, see: Bak et al. (1959); Hemissi et al. (2010); Toumi Akriche et al. (2010); Akriche & Rzaigui (2005); Janiak (2000). For the preparation of cyclohexaphosphoric acid, see: Schulke & Kayser (1985).

Experimental top

Single crystals of the title compound were prepared in two steps. In the first one, 50 ml of an aqueous solution of cyclohexaphosphoric acid was prepared by protonation of 4 g of Li₆P₆O₁₈, obtained by the Schulke process (Schulke et al., 1985), with an ion exchange resin (Amberlite IR 120). In the second one, the frech acidic solution (20 ml, 2.6 mmol) was immediately neutralized with a solution of 2-amino-5-chloropyridine (2.8 mmol in 10 ml of ehanol) under continuous stirring. Good quality of prismatic-shaped crystals were obtained after a slow evaporation during few days at ambient temperature

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012).

Figures top

	Fig. 1. ORTEP drawing of the cyclic anion [H₂P₆O₁₈]^4- and the two independent 2-amino-5-chloropyridinium cations. Displacement ellipsoids for non H-atoms are drawn at the 40% probability level. [Symmetry code: (i) x, y, z]
	Fig. 2. Projection of the [H₂P₆O₁₈]^4- anions running along the a axis
	Fig. 3. Projection of the structure along the a direction
	Fig. 4. Projection of the structure along the b direction

Tetrakis(2-amino-5-chloropyridinium) dihydrogen cyclohexaphosphate top

Crystal data top

4C₅H₆ClN₂⁺·H₂O₁₈P₆⁴⁻	Z = 1
M_r = 994.11	F(000) = 504
Triclinic, P1	D_x = 1.824 Mg m⁻³
Hall symbol: -P 1	Ag Kα radiation, λ = 0.56087 Å
a = 9.199 (3) Å	Cell parameters from 25 reflections
b = 9.304 (2) Å	θ = 9–11°
c = 11.327 (3) Å	µ = 0.35 mm⁻¹
α = 74.98 (3)°	T = 293 K
β = 85.17 (2)°	Rectangular, colorless
γ = 75.20 (2)°	0.32 × 0.22 × 0.15 mm
V = 905.1 (5) Å³

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.020
Radiation source: fine-focus sealed tube	θ_max = 28.0°, θ_min = 2.1°
Graphite monochromator	h = −15→15
non–profiled ω scans	k = −15→15
11291 measured reflections	l = −18→3
8865 independent reflections	2 standard reflections every 120 min
5387 reflections with I > 2σ(I)	intensity decay: 1%

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.155	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0798P)² + 0.0876P] where P = (F_o² + 2F_c²)/3
8865 reflections	(Δ/σ)_max = 0.001
305 parameters	Δρ_max = 0.82 e Å⁻³
0 restraints	Δρ_min = −0.65 e Å⁻³

Crystal data top

4C₅H₆ClN₂⁺·H₂O₁₈P₆⁴⁻	γ = 75.20 (2)°
M_r = 994.11	V = 905.1 (5) Å³
Triclinic, P1	Z = 1
a = 9.199 (3) Å	Ag Kα radiation, λ = 0.56087 Å
b = 9.304 (2) Å	µ = 0.35 mm⁻¹
c = 11.327 (3) Å	T = 293 K
α = 74.98 (3)°	0.32 × 0.22 × 0.15 mm
β = 85.17 (2)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.020
11291 measured reflections	2 standard reflections every 120 min
8865 independent reflections	intensity decay: 1%
5387 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.056	0 restraints
wR(F²) = 0.155	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.82 e Å⁻³
8865 reflections	Δρ_min = −0.65 e Å⁻³
305 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
P1	0.31788 (5)	0.39966 (6)	0.59770 (5)	0.0246 (1)
P2	0.09221 (5)	0.22559 (6)	0.68658 (5)	0.0249 (1)
P3	0.21377 (5)	0.64715 (6)	0.38126 (5)	0.0261 (1)
O1	0.39658 (19)	0.4679 (2)	0.67218 (19)	0.0454 (6)
O2	0.40900 (17)	0.29457 (17)	0.52877 (14)	0.0335 (4)
O3	0.20301 (19)	0.5379 (2)	0.51466 (15)	0.0455 (5)
O4	0.20430 (16)	0.32887 (17)	0.69374 (13)	0.0297 (4)
O5	0.08853 (19)	0.11700 (18)	0.80701 (15)	0.0375 (5)
O6	0.12380 (17)	0.16793 (19)	0.57518 (15)	0.0353 (4)
O7	0.06189 (16)	0.64266 (17)	0.32794 (16)	0.0359 (5)
O8	0.33616 (16)	0.56632 (18)	0.30855 (14)	0.0333 (4)
O9	0.21174 (18)	0.80107 (18)	0.39100 (17)	0.0407 (5)
Cl1	0.26706 (10)	0.37124 (10)	−0.05308 (6)	0.0606 (3)
N1	0.0267 (2)	0.1302 (2)	0.18049 (17)	0.0341 (5)
N2	−0.0748 (3)	0.1321 (3)	0.3732 (2)	0.0430 (7)
C1	0.0017 (3)	0.1920 (2)	0.2777 (2)	0.0319 (5)
C2	0.0596 (3)	0.3211 (3)	0.2711 (2)	0.0382 (7)
C3	0.1390 (3)	0.3761 (3)	0.1712 (2)	0.0396 (7)
C4	0.1628 (3)	0.3061 (3)	0.0732 (2)	0.0377 (6)
C5	0.1044 (3)	0.1844 (3)	0.0791 (2)	0.0376 (6)
Cl2	0.71034 (11)	0.24071 (11)	−0.00108 (7)	0.0685 (3)
N3	0.4844 (2)	0.2016 (2)	0.31254 (19)	0.0370 (6)
N4	0.3444 (2)	0.0352 (2)	0.4197 (2)	0.0387 (6)
C6	0.4320 (2)	0.0752 (2)	0.3261 (2)	0.0298 (5)
C7	0.4751 (2)	−0.0097 (2)	0.2364 (2)	0.0325 (6)
C8	0.5622 (3)	0.0394 (3)	0.1400 (2)	0.0373 (6)
C9	0.6083 (3)	0.1751 (3)	0.1271 (2)	0.0405 (7)
C10	0.5705 (3)	0.2533 (3)	0.2150 (2)	0.0434 (7)
H1A	0.483 (5)	0.441 (5)	0.680 (4)	0.113 (17)*
H1	−0.010 (3)	0.041 (3)	0.186 (3)	0.047 (8)*
H2	0.041 (3)	0.362 (3)	0.333 (3)	0.053 (9)*
H2A	−0.089 (3)	0.046 (4)	0.382 (3)	0.044 (8)*
H2B	−0.083 (4)	0.164 (4)	0.433 (3)	0.055 (9)*
H3A	0.174 (3)	0.469 (4)	0.162 (3)	0.055 (9)*
H5	0.107 (3)	0.139 (4)	0.021 (3)	0.053 (9)*
H3	0.457 (4)	0.247 (4)	0.363 (3)	0.054 (9)*
H4A	0.319 (3)	0.082 (3)	0.471 (2)	0.033 (7)*
H4B	0.312 (4)	−0.053 (5)	0.425 (3)	0.075 (11)*
H7	0.442 (3)	−0.106 (3)	0.249 (3)	0.044 (8)*
H8	0.592 (3)	−0.006 (3)	0.082 (2)	0.031 (6)*
H10	0.607 (4)	0.340 (4)	0.218 (3)	0.058 (9)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
P1	0.0202 (2)	0.0277 (2)	0.0285 (2)	−0.0090 (2)	0.0034 (2)	−0.0097 (2)
P2	0.0230 (2)	0.0271 (2)	0.0294 (2)	−0.0115 (2)	0.0022 (2)	−0.0111 (2)
P3	0.0231 (2)	0.0274 (2)	0.0304 (2)	−0.0090 (2)	−0.0001 (2)	−0.0093 (2)
O1	0.0284 (7)	0.0669 (11)	0.0609 (12)	−0.0270 (8)	0.0119 (7)	−0.0393 (10)
O2	0.0306 (7)	0.0335 (7)	0.0360 (8)	−0.0039 (6)	0.0058 (6)	−0.0135 (6)
O3	0.0387 (8)	0.0452 (9)	0.0345 (8)	0.0062 (7)	0.0107 (7)	0.0020 (7)
O4	0.0297 (6)	0.0388 (7)	0.0294 (7)	−0.0210 (6)	0.0047 (5)	−0.0129 (6)
O5	0.0454 (9)	0.0366 (8)	0.0343 (8)	−0.0224 (7)	−0.0015 (7)	−0.0028 (6)
O6	0.0351 (7)	0.0438 (8)	0.0376 (8)	−0.0184 (6)	0.0078 (6)	−0.0226 (7)
O7	0.0243 (6)	0.0320 (7)	0.0589 (10)	−0.0077 (5)	−0.0042 (6)	−0.0224 (7)
O8	0.0254 (6)	0.0452 (8)	0.0339 (8)	−0.0124 (6)	0.0046 (5)	−0.0158 (7)
O9	0.0367 (8)	0.0351 (8)	0.0601 (11)	−0.0175 (6)	−0.0027 (7)	−0.0196 (7)
Cl1	0.0841 (5)	0.0739 (5)	0.0387 (3)	−0.0499 (4)	0.0169 (3)	−0.0155 (3)
N1	0.0451 (10)	0.0335 (8)	0.0322 (9)	−0.0198 (8)	0.0038 (7)	−0.0142 (7)
N2	0.0648 (14)	0.0380 (10)	0.0362 (10)	−0.0264 (10)	0.0150 (9)	−0.0182 (9)
C1	0.0409 (10)	0.0271 (8)	0.0313 (10)	−0.0126 (8)	0.0012 (8)	−0.0100 (7)
C2	0.0574 (14)	0.0313 (10)	0.0330 (11)	−0.0199 (10)	0.0031 (10)	−0.0127 (8)
C3	0.0558 (14)	0.0339 (10)	0.0365 (11)	−0.0217 (10)	0.0022 (10)	−0.0120 (9)
C4	0.0482 (12)	0.0406 (11)	0.0300 (10)	−0.0220 (10)	0.0017 (9)	−0.0086 (9)
C5	0.0477 (12)	0.0426 (11)	0.0323 (10)	−0.0222 (10)	0.0044 (9)	−0.0169 (9)
Cl2	0.0848 (6)	0.0781 (5)	0.0483 (4)	−0.0413 (5)	0.0239 (4)	−0.0125 (4)
N3	0.0453 (10)	0.0351 (9)	0.0389 (10)	−0.0173 (8)	0.0078 (8)	−0.0190 (8)
N4	0.0389 (10)	0.0384 (10)	0.0450 (11)	−0.0143 (8)	0.0103 (8)	−0.0197 (9)
C6	0.0299 (9)	0.0282 (8)	0.0343 (10)	−0.0084 (7)	−0.0007 (7)	−0.0114 (7)
C7	0.0354 (10)	0.0296 (9)	0.0368 (10)	−0.0082 (8)	−0.0022 (8)	−0.0147 (8)
C8	0.0414 (11)	0.0421 (11)	0.0333 (11)	−0.0111 (9)	0.0019 (9)	−0.0177 (9)
C9	0.0447 (12)	0.0461 (12)	0.0333 (11)	−0.0171 (10)	0.0064 (9)	−0.0107 (10)
C10	0.0554 (14)	0.0379 (11)	0.0444 (13)	−0.0242 (10)	0.0065 (11)	−0.0127 (10)

Geometric parameters (Å, º) top

Cl1—C4	1.718 (3)	N3—C6	1.350 (3)
Cl2—C9	1.722 (3)	N3—C10	1.361 (3)
P1—O2	1.4612 (17)	N4—C6	1.310 (3)
P1—O1	1.501 (2)	N3—H3	0.78 (4)
P1—O3	1.5816 (19)	N4—H4B	0.93 (4)
P1—O4	1.5804 (17)	N4—H4A	0.80 (3)
P2—O4	1.5981 (17)	C1—C2	1.416 (4)
P2—O7ⁱ	1.6082 (17)	C2—C3	1.352 (3)
P2—O5	1.4758 (18)	C3—C4	1.402 (3)
P2—O6	1.4744 (18)	C4—C5	1.357 (4)
P3—O3	1.5989 (18)	C2—H2	0.87 (3)
P3—O9	1.4599 (18)	C3—H3A	0.98 (4)
P3—O7	1.5823 (17)	C5—H5	0.87 (3)
P3—O8	1.4979 (17)	C6—C7	1.415 (3)
O1—H1A	0.78 (5)	C7—C8	1.351 (3)
N1—C5	1.353 (3)	C8—C9	1.401 (4)
N1—C1	1.347 (3)	C9—C10	1.353 (4)
N2—C1	1.317 (3)	C7—H7	0.99 (3)
N1—H1	0.96 (3)	C8—H8	0.86 (2)
N2—H2A	0.82 (4)	C10—H10	0.96 (4)
N2—H2B	0.80 (3)

O1—P1—O2	118.53 (10)	C6—N4—H4A	123.5 (19)
O1—P1—O3	106.68 (11)	C6—N4—H4B	117 (2)
O1—P1—O4	102.68 (10)	N1—C1—N2	119.7 (2)
O2—P1—O3	112.61 (10)	N2—C1—C2	123.0 (2)
O2—P1—O4	114.52 (10)	N1—C1—C2	117.3 (2)
O3—P1—O4	99.74 (9)	C1—C2—C3	120.3 (2)
O4—P2—O5	108.10 (10)	C2—C3—C4	119.9 (3)
O4—P2—O6	110.40 (9)	C3—C4—C5	119.5 (2)
O4—P2—O7ⁱ	98.08 (9)	Cl1—C4—C3	120.7 (2)
O5—P2—O6	119.81 (10)	Cl1—C4—C5	119.78 (19)
O5—P2—O7ⁱ	108.31 (10)	N1—C5—C4	119.6 (2)
O6—P2—O7ⁱ	109.93 (10)	C1—C2—H2	117.0 (19)
O3—P3—O7	99.05 (10)	C3—C2—H2	123 (2)
O3—P3—O8	109.32 (10)	C2—C3—H3A	121.8 (19)
O3—P3—O9	109.78 (11)	C4—C3—H3A	118.2 (19)
O7—P3—O8	105.20 (10)	C4—C5—H5	126 (2)
O7—P3—O9	111.56 (10)	N1—C5—H5	114 (2)
O8—P3—O9	119.86 (10)	N3—C6—C7	117.59 (19)
P1—O3—P3	134.02 (13)	N3—C6—N4	120.0 (2)
P1—O4—P2	132.54 (10)	N4—C6—C7	122.37 (18)
P2ⁱ—O7—P3	126.34 (11)	C6—C7—C8	119.8 (2)
P1—O1—H1A	121 (3)	C7—C8—C9	120.5 (2)
C1—N1—C5	123.4 (2)	C8—C9—C10	119.4 (2)
C5—N1—H1	119.3 (19)	Cl2—C9—C8	119.51 (19)
C1—N1—H1	117.3 (19)	Cl2—C9—C10	121.1 (2)
C1—N2—H2A	121 (2)	N3—C10—C9	119.5 (2)
H2A—N2—H2B	117 (3)	C6—C7—H7	117.6 (18)
C1—N2—H2B	119 (3)	C8—C7—H7	122.6 (18)
C6—N3—C10	123.1 (2)	C7—C8—H8	124.7 (18)
C6—N3—H3	115 (3)	C9—C8—H8	114.7 (18)
C10—N3—H3	122 (3)	N3—C10—H10	116 (2)
H4A—N4—H4B	120 (3)	C9—C10—H10	125 (2)

O1—P1—O3—P3	89.53 (18)	C5—N1—C1—C2	0.6 (4)
O2—P1—O3—P3	−42.1 (2)	C1—N1—C5—C4	0.8 (4)
O4—P1—O3—P3	−163.97 (16)	C10—N3—C6—N4	−177.2 (2)
O1—P1—O4—P2	−174.03 (14)	C10—N3—C6—C7	2.8 (3)
O2—P1—O4—P2	−44.19 (17)	C6—N3—C10—C9	−0.8 (4)
O3—P1—O4—P2	76.27 (15)	N1—C1—C2—C3	−1.3 (4)
O5—P2—O4—P1	144.47 (14)	N2—C1—C2—C3	179.1 (3)
O6—P2—O4—P1	11.66 (17)	C1—C2—C3—C4	0.7 (4)
O7ⁱ—P2—O4—P1	−103.18 (15)	C2—C3—C4—Cl1	−178.5 (2)
O4—P2—O7ⁱ—P3ⁱ	159.29 (13)	C2—C3—C4—C5	0.7 (4)
O5—P2—O7ⁱ—P3ⁱ	−88.53 (15)	Cl1—C4—C5—N1	177.8 (2)
O6—P2—O7ⁱ—P3ⁱ	44.08 (16)	C3—C4—C5—N1	−1.4 (4)
O7—P3—O3—P1	134.37 (16)	N3—C6—C7—C8	−1.8 (3)
O8—P3—O3—P1	24.7 (2)	N4—C6—C7—C8	178.1 (2)
O9—P3—O3—P1	−108.72 (17)	C6—C7—C8—C9	−1.0 (4)
O3—P3—O7—P2ⁱ	102.22 (14)	C7—C8—C9—Cl2	−176.3 (2)
O8—P3—O7—P2ⁱ	−144.80 (13)	C7—C8—C9—C10	3.0 (4)
O9—P3—O7—P2ⁱ	−13.34 (18)	Cl2—C9—C10—N3	177.2 (2)
C5—N1—C1—N2	−179.8 (3)	C8—C9—C10—N3	−2.1 (4)

Symmetry code: (i) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O5ⁱⁱ	0.96 (3)	1.78 (3)	2.736 (3)	177 (3)
O1—H1A···O8ⁱⁱⁱ	0.78 (5)	1.66 (5)	2.418 (3)	165 (5)
N2—H2A···O6ⁱⁱ	0.82 (4)	2.02 (4)	2.844 (3)	173 (3)
N2—H2B···O9ⁱ	0.80 (3)	2.29 (3)	3.000 (3)	149 (4)
N3—H3···O2	0.78 (4)	2.03 (3)	2.781 (3)	161 (3)
N4—H4A···O2	0.80 (3)	2.57 (3)	3.179 (3)	134 (2)
N4—H4A···O6	0.80 (3)	2.16 (3)	2.827 (3)	142 (3)
N4—H4B···O9^iv	0.93 (4)	1.95 (4)	2.852 (3)	162 (3)
C5—H5···O5^v	0.87 (3)	2.51 (3)	3.322 (3)	157 (3)
C10—H10···O1ⁱⁱⁱ	0.96 (4)	2.42 (4)	3.262 (3)	146 (3)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O5ⁱ	0.96 (3)	1.78 (3)	2.736 (3)	177 (3)
O1—H1A···O8ⁱⁱ	0.78 (5)	1.66 (5)	2.418 (3)	165 (5)
N2—H2A···O6ⁱ	0.82 (4)	2.02 (4)	2.844 (3)	173 (3)
N2—H2B···O9ⁱⁱⁱ	0.80 (3)	2.29 (3)	3.000 (3)	149 (4)
N3—H3···O2	0.78 (4)	2.03 (3)	2.781 (3)	161 (3)
N4—H4A···O2	0.80 (3)	2.57 (3)	3.179 (3)	134 (2)
N4—H4A···O6	0.80 (3)	2.16 (3)	2.827 (3)	142 (3)
N4—H4B···O9^iv	0.93 (4)	1.95 (4)	2.852 (3)	162 (3)
C5—H5···O5^v	0.87 (3)	2.51 (3)	3.322 (3)	157 (3)
C10—H10···O1ⁱⁱ	0.96 (4)	2.42 (4)	3.262 (3)	146 (3)

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

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Volume 70| Part 3| March 2014| Pages o342-o343

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