N,N′-Dimethyl­piperazinium(2+) bis­[methyl­enehydrogendiphospho­nate(1−)]

Yuan, Z.; Clegg, W.

doi:10.1107/S1600536805022737

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 61| Part 8| August 2005| Pages o2635-o2637

https://doi.org/10.1107/S1600536805022737

N,N′-Dimethylpiperazinium(2+) bis[methylenehydrogendiphosphonate(1−)]

Zhanhui Yuan ^a and William Clegg ^a ^*

^aSchool of Natural Sciences (Chemistry), University of Newcastle upon Tyne, Newcastle upon Tyne NE1 7RU, England
^*Correspondence e-mail: w.clegg@ncl.ac.uk

(Received 1 July 2005; accepted 15 July 2005; online 20 July 2005)

The asymmetric unit of the title compound, C₆H₁₆N₂²⁺·2(HO)₂(O)PCH₂P(O)₂(OH)⁻, contains two singly charged diphosphonate anions and two half-cations, each doubly charged cation lying on an inversion centre. Single deprotonation of methylenediphosphonic acid to give a salt with an organic amine is unprecedented, double deprotonation being normal. All N—H and O—H groups act as hydrogen-bond donors in the crystal structure, with unprotonated O atoms as the acceptors, giving a three-dimensional network.

Comment

Phosphonic and diphosphonic acids are extremely versatile building blocks in supramolecular chemistry (Farrell et al., 2001 ; Ferguson et al., 1998 ; Glidewell et al., 2000 ; Wheatley et al., 2001 ). An important factor in the behaviour of such acids is the marked difference in acidity for stepwise deprotonation of the two hydroxyl functions in each –PO(OH)₂ group. With organic amines, typically only one proton per phosphonate group is transferred from O to N. The resulting –P(O)₂(OH)– group can thus act as a hydrogen-bond donor as well as an acceptor. The structure of methyldiphosphonic acid itself (DeLaMatter et al., 1973 ) consists of a three-dimensional hydrogen-bonded network.

The title compound, (I), obtained unintentionally in one of a series of hydrothermal syntheses of aluminium diphosphonate complexes, is a 1:2 salt of diprotonated piperazine (generated by coupling of trimethylamine under the hydrothermal conditions) and the singly charged anion of methylenediphosphonic acid obtained by removal of only one proton; the second phosphonic acid group remains uncharged. Although there appears to be no previous report of such a reaction of trimethylamine to produce N,N′-dimethylpiperazine, this product can be obtained from trimethylamine oxide by deprotonation (Beugelmans et al., 1985 ).

The asymmetric unit of (I) contains two anions and two half-cations, each cation lying on an inversion centre (Fig. 1). Both independent piperazine rings have the expected chair conformation, with the methyl substituents equatorial. All H atoms bonded to N in the cations and to O in the anions were clearly identified in a difference map. The P—O bond lengths to the OH groups are all longer than those to unprotonated O atoms (Table 1). The shortest P—O bonds (P2—O6 and P4—O12) are found in the intact P(O)(OH)₂ phosphonic acid groups of the anions and can be assigned as P=O double bonds. The P—O bonds to unprotonated O atoms in the deprotonated P(O)₂(OH) phosphonate groups are intermediate in length; these are delocalized and intermediate between single and double bonds and can be assumed to carry the delocalised negative charge, while the P—OH bonds are single. Methyldiphosphonates in crystal structures are usually dianionic, with both groups deprotonated. Only in one previous report is a singly charged H₂O₃PCH₂PO₃H⁻ anion found (Hmimid et al., 1987 ); in this trithallium(I) compound, singly and doubly charged anions occupy the same position and are, therfore, disordered.

All N—H and O—H groups act as hydrogen-bond donors in the crystal structure of (I) (Fig. 2, Table 2). The acceptors are the unprotonated O atoms of the anions; since there are only six of these for the eight donors, two (atoms O2 and O8, which carry some shared negative charge in the delocalized phosphonate groups) are double acceptors. The hydrogen bonding generates a three-dimensional network.

Figure 1
The two cations (completed by inversion symmetry) and two anions in the asymmetric unit of (I)

, showing atom labels and with 50% probability displacement ellipsoids. [Symmetry codes: (i) 1 − x, 1 − y, −z); (ii) 1 − x, 1 − y, 1 − z.]

Figure 2
The packing of the ions, viewed down the a axis, with hydrogen bonds shown as dashed lines. H atoms not involved in hydrogen bonding have been omitted.

Experimental

The title compound was obtained by hydrothermal synthesis, in an attempt to prepare an aluminium methylenediphosphonate complex. A mixture of Al₂(SO₄)₃.18H₂O (98%, Alfa Aesar), methylenediphosphonic acid (98%, Alfa Aesar), hydrofluoric acid (48 wt.% in water, Aldrich), trimethylamine (48% in water, Fluka) and ethanol was combined in the molar ratio 1:3:9.43:9.52:100. Vigorous stirring led to complete dissolution of all reagents. The solution was then placed in a 23 ml Teflon-lined stainless steel autoclave and heated at 473 K for 10 d. The title compound, (I), was collected by filtration, washed with deionized water and air-dried. It is not known whether aluminium-containing products were in the resulting solid or in the filtrate. The solid material was largely an unidentified powder mixture containing single crystals of the title compound.

Crystal data

C₆H₁₆N₂²⁺·2CH₅O₆P₂⁻
M_r = 466.19
Triclinic, $[P \overline 1]$
a = 6.9881 (6) Å
b = 8.9148 (6) Å
c = 16.6251 (10) Å
α = 98.910 (5)°
β = 95.882 (6)°
γ = 112.244 (6)°
V = 932.24 (12) Å³
Z = 2
D_x = 1.661 Mg m⁻³
Mo Kα radiation
Cell parameters from 59 reflections
θ = 2.5–27.5°
μ = 0.47 mm⁻¹
T = 120 (2) K
Block, colourless
0.50 × 0.50 × 0.20 mm

Data collection

Nonius KappaCCD area-detector diffractometer
φ and ω scans
Absorption correction: multi-scan(SADABS; Sheldrick, 2002 )T_min = 0.800, T_max = 0.915
12295 measured reflections
4037 independent reflections
3592 reflections with I > 2σ(I)
R_int = 0.028
θ_max = 27.5°
h = −9 → 9
k = −11 → 11
l = −21 → 21

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.028
wR(F²) = 0.075
S = 1.06
4037 reflections
262 parameters
H atoms treated by a mixture of independent and constrained refinement
w = 1/[σ²(F_o²) + (0.0315P)² + 0.7406P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.001
Δρ_max = 0.55 e Å⁻³
Δρ_min = −0.50 e Å⁻³
Extinction correction: SHELXTL (Sheldrick, 2001 )
Extinction coefficient: 0.011 (2)

Table 1
Selected bond lengths (Å)

P1—C1	1.8118 (16)
P1—O1	1.5666 (12)
P1—O2	1.5119 (11)
P1—O3	1.5180 (11)
P2—C1	1.8000 (16)
P2—O4	1.5703 (12)
P2—O5	1.5401 (11)
P2—O6	1.4939 (12)
P3—C2	1.8088 (16)
P3—O7	1.5646 (13)
P3—O8	1.5312 (12)
P3—O9	1.5055 (12)
P4—C2	1.8021 (16)
P4—O10	1.5494 (12)
P4—O11	1.5583 (12)
P4—O12	1.5005 (12)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O⋯O6ⁱⁱⁱ	0.81 (2)	1.73 (2)	2.5287 (16)	169 (2)
O4—H4O⋯O8^iv	0.83 (2)	1.76 (2)	2.5799 (17)	174 (2)
O5—H5O⋯O3^v	0.84 (2)	1.63 (2)	2.4689 (16)	177 (2)
O7—H7O⋯O2	0.83 (2)	1.71 (2)	2.5139 (16)	162 (2)
O10—H10O⋯O8^vi	0.82 (2)	1.73 (2)	2.5228 (17)	163 (2)
O11—H11O⋯O9^vii	0.83 (2)	1.70 (2)	2.5222 (17)	169 (2)
N1—H1N⋯O2	0.86 (2)	1.97 (2)	2.7802 (18)	157 (2)
N2—H2N⋯O12	0.88 (2)	1.79 (2)	2.6563 (18)	170 (2)
Symmetry codes: (iii) x+1, y, z; (iv) x-1, y-1, z; (v) -x+1, -y, -z; (vi) x-1, y, z; (vii) -x+2, -y+2, -z+1.

C-bound H atoms were positioned geometrically and refined with a riding model (including free rotation about C—C bonds), with C—H = 0.98 (CH₂) or 0.99 Å (CH₃) and with U_iso(H) = 1.2 (1.5 for methyl groups) times U_eq(C). H atoms bonded to N and O were located in a difference map and refined with restrained distances of N—H = 0.87 (2) Å and O—H = 0.84 (2) Å, and with U_iso(H) = 1.2U_eq(N,O).

Data collection: COLLECT (Nonius, 1998 ); cell refinement: DIRAX (Duisenberg, 1992 ); data reduction: EVALCCD (Duisenberg et al., 2003 ); program(s) used to solve structure: SHELXTL (Sheldrick, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and local programs.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536805022737/nc6040sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536805022737/nc6040Isup2.hkl

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: DIRAX (Duisenberg, 1992); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: SHELXTL (Sheldrick, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and local programs.

N,N'-Dimethylpiperazinium(2+) bis[methylenehydrogendiphosphonate(1-)] top

Crystal data top

C₆H₁₆N₂²⁺·2CH₅O₆P₂⁻	Z = 2
M_r = 466.19	F(000) = 488
Triclinic, P1	D_x = 1.661 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.9881 (6) Å	Cell parameters from 59 reflections
b = 8.9148 (6) Å	θ = 2.5–27.5°
c = 16.6251 (10) Å	µ = 0.47 mm⁻¹
α = 98.910 (5)°	T = 120 K
β = 95.882 (6)°	Block, colourless
γ = 112.244 (6)°	0.50 × 0.50 × 0.20 mm
V = 932.24 (12) Å³

Data collection top

Nonius KappaCCD area-detector diffractometer	4037 independent reflections
Radiation source: sealed tube	3592 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
φ and ω scans	θ_max = 27.5°, θ_min = 4.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	h = −9→9
T_min = 0.800, T_max = 0.915	k = −11→11
12295 measured reflections	l = −21→21

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.028	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.075	w = 1/[σ²(F_o²) + (0.0315P)² + 0.7406P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.001
4037 reflections	Δρ_max = 0.55 e Å⁻³
262 parameters	Δρ_min = −0.50 e Å⁻³
8 restraints	Extinction correction: SHELXTL (Sheldrick, 2001), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.011 (2)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
P1	0.72874 (6)	0.26531 (5)	0.14321 (2)	0.01031 (10)
P2	0.25336 (6)	0.05401 (5)	0.11556 (2)	0.01102 (10)
C1	0.5149 (2)	0.08775 (19)	0.16149 (10)	0.0132 (3)
H1A	0.5392	−0.0127	0.1409	0.016*
H1B	0.5212	0.0993	0.2220	0.016*
O1	0.92324 (18)	0.27350 (16)	0.20257 (7)	0.0175 (3)
H1O	1.003 (3)	0.242 (3)	0.1799 (13)	0.021*
O2	0.68992 (18)	0.41979 (14)	0.16996 (7)	0.0157 (2)
O3	0.75543 (18)	0.23748 (14)	0.05337 (7)	0.0155 (2)
O4	0.10390 (18)	−0.11161 (15)	0.13683 (7)	0.0175 (2)
H4O	0.134 (3)	−0.123 (3)	0.1844 (10)	0.021*
O5	0.23587 (19)	0.02151 (14)	0.02082 (7)	0.0152 (2)
H5O	0.241 (3)	−0.067 (2)	−0.0027 (12)	0.018*
O6	0.20780 (18)	0.20123 (15)	0.14673 (7)	0.0187 (3)
P3	1.01122 (6)	0.79458 (5)	0.33650 (2)	0.01223 (11)
P4	0.72510 (6)	0.96071 (5)	0.39958 (2)	0.01142 (11)
C2	0.9692 (2)	0.98231 (19)	0.36560 (10)	0.0131 (3)
H2A	1.0856	1.0583	0.4105	0.016*
H2B	0.9788	1.0364	0.3176	0.016*
O7	0.79361 (19)	0.67144 (16)	0.28394 (8)	0.0228 (3)
H7O	0.785 (4)	0.590 (2)	0.2495 (12)	0.027*
O8	1.17930 (18)	0.83067 (16)	0.28150 (7)	0.0191 (3)
O9	1.0655 (2)	0.73429 (14)	0.41184 (7)	0.0186 (3)
O10	0.56949 (19)	0.90998 (16)	0.31701 (7)	0.0191 (3)
H10O	0.444 (3)	0.888 (3)	0.3155 (13)	0.023*
O11	0.7503 (2)	1.13825 (15)	0.44042 (7)	0.0194 (3)
H11O	0.801 (3)	1.169 (3)	0.4905 (10)	0.023*
O12	0.66895 (18)	0.84128 (14)	0.45641 (7)	0.0151 (2)
N1	0.4264 (2)	0.52382 (16)	0.07827 (8)	0.0121 (3)
H1N	0.476 (3)	0.467 (2)	0.1047 (11)	0.014*
C3	0.6069 (2)	0.65879 (19)	0.05574 (10)	0.0139 (3)
H3A	0.7063	0.7294	0.1067	0.017*
H3B	0.5533	0.7294	0.0281	0.017*
C4	0.2785 (2)	0.41262 (19)	0.00124 (10)	0.0140 (3)
H4A	0.2157	0.4764	−0.0278	0.017*
H4B	0.1635	0.3212	0.0162	0.017*
C5	0.3156 (3)	0.5972 (2)	0.13405 (10)	0.0181 (3)
H5A	0.2560	0.6615	0.1050	0.027*
H5B	0.4155	0.6700	0.1836	0.027*
H5C	0.2026	0.5082	0.1502	0.027*
N2	0.4365 (2)	0.51721 (17)	0.41761 (8)	0.0143 (3)
H2N	0.513 (3)	0.6236 (19)	0.4239 (12)	0.017*
C6	0.5842 (3)	0.4356 (2)	0.43334 (10)	0.0167 (3)
H6A	0.6815	0.4544	0.3931	0.020*
H6B	0.5037	0.3146	0.4259	0.020*
C7	0.2916 (3)	0.4945 (2)	0.47959 (10)	0.0161 (3)
H7A	0.2037	0.3750	0.4734	0.019*
H7B	0.1972	0.5515	0.4692	0.019*
C8	0.3153 (3)	0.4548 (2)	0.33170 (11)	0.0248 (4)
H8A	0.2222	0.3375	0.3244	0.037*
H8B	0.4127	0.4669	0.2923	0.037*
H8C	0.2313	0.5188	0.3218	0.037*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
P1	0.0091 (2)	0.01140 (19)	0.00927 (18)	0.00425 (15)	−0.00039 (14)	−0.00018 (14)
P2	0.0095 (2)	0.0112 (2)	0.01111 (19)	0.00410 (15)	−0.00016 (14)	0.00013 (14)
C1	0.0130 (8)	0.0132 (7)	0.0141 (7)	0.0060 (6)	0.0006 (6)	0.0040 (6)
O1	0.0107 (6)	0.0273 (6)	0.0142 (5)	0.0097 (5)	−0.0008 (4)	0.0005 (5)
O2	0.0152 (6)	0.0122 (5)	0.0168 (6)	0.0057 (4)	−0.0021 (4)	−0.0022 (4)
O3	0.0182 (6)	0.0181 (6)	0.0109 (5)	0.0083 (5)	0.0028 (4)	0.0024 (4)
O4	0.0143 (6)	0.0189 (6)	0.0139 (6)	0.0011 (5)	−0.0006 (5)	0.0049 (5)
O5	0.0198 (6)	0.0138 (6)	0.0106 (5)	0.0064 (5)	−0.0002 (4)	0.0013 (4)
O6	0.0139 (6)	0.0188 (6)	0.0229 (6)	0.0095 (5)	0.0006 (5)	−0.0030 (5)
P3	0.0101 (2)	0.0138 (2)	0.01052 (19)	0.00387 (16)	0.00048 (14)	−0.00079 (14)
P4	0.0123 (2)	0.0119 (2)	0.00977 (18)	0.00505 (15)	0.00051 (14)	0.00160 (14)
C2	0.0117 (8)	0.0113 (7)	0.0137 (7)	0.0027 (6)	0.0001 (6)	0.0020 (6)
O7	0.0124 (6)	0.0216 (6)	0.0251 (7)	0.0046 (5)	−0.0014 (5)	−0.0130 (5)
O8	0.0127 (6)	0.0325 (7)	0.0137 (5)	0.0107 (5)	0.0024 (4)	0.0051 (5)
O9	0.0268 (7)	0.0155 (6)	0.0160 (6)	0.0111 (5)	0.0032 (5)	0.0037 (4)
O10	0.0120 (6)	0.0320 (7)	0.0128 (5)	0.0093 (5)	−0.0004 (5)	0.0039 (5)
O11	0.0300 (7)	0.0160 (6)	0.0157 (6)	0.0136 (5)	0.0035 (5)	0.0027 (5)
O12	0.0176 (6)	0.0129 (5)	0.0131 (5)	0.0045 (5)	0.0026 (4)	0.0025 (4)
N1	0.0129 (7)	0.0118 (6)	0.0112 (6)	0.0049 (5)	0.0010 (5)	0.0025 (5)
C3	0.0130 (8)	0.0104 (7)	0.0147 (7)	0.0017 (6)	0.0012 (6)	0.0013 (6)
C4	0.0111 (8)	0.0144 (7)	0.0132 (7)	0.0026 (6)	−0.0002 (6)	0.0015 (6)
C5	0.0215 (9)	0.0168 (8)	0.0187 (8)	0.0094 (7)	0.0082 (7)	0.0032 (6)
N2	0.0150 (7)	0.0110 (6)	0.0133 (6)	0.0021 (5)	−0.0024 (5)	0.0035 (5)
C6	0.0198 (9)	0.0159 (8)	0.0157 (8)	0.0086 (7)	0.0026 (6)	0.0029 (6)
C7	0.0129 (8)	0.0148 (8)	0.0197 (8)	0.0047 (6)	0.0001 (6)	0.0049 (6)
C8	0.0276 (10)	0.0234 (9)	0.0135 (8)	0.0025 (7)	−0.0075 (7)	0.0028 (7)

Geometric parameters (Å, º) top

P1—C1	1.8118 (16)	N1—H1N	0.857 (15)
P1—O1	1.5666 (12)	N1—C3	1.505 (2)
P1—O2	1.5119 (11)	N1—C4	1.5002 (19)
P1—O3	1.5180 (11)	N1—C5	1.493 (2)
P2—C1	1.8000 (16)	C3—H3A	0.990
P2—O4	1.5703 (12)	C3—H3B	0.990
P2—O5	1.5401 (11)	C3—C4ⁱ	1.516 (2)
P2—O6	1.4939 (12)	C4—C3ⁱ	1.516 (2)
C1—H1A	0.990	C4—H4A	0.990
C1—H1B	0.990	C4—H4B	0.990
O1—H1O	0.813 (15)	C5—H5A	0.980
O4—H4O	0.827 (15)	C5—H5B	0.980
O5—H5O	0.837 (15)	C5—H5C	0.980
P3—C2	1.8088 (16)	N2—H2N	0.877 (15)
P3—O7	1.5646 (13)	N2—C6	1.495 (2)
P3—O8	1.5312 (12)	N2—C7	1.501 (2)
P3—O9	1.5055 (12)	N2—C8	1.489 (2)
P4—C2	1.8021 (16)	C6—H6A	0.990
P4—O10	1.5494 (12)	C6—H6B	0.990
P4—O11	1.5583 (12)	C6—C7ⁱⁱ	1.514 (2)
P4—O12	1.5005 (12)	C7—C6ⁱⁱ	1.514 (2)
C2—H2A	0.990	C7—H7A	0.990
C2—H2B	0.990	C7—H7B	0.990
O7—H7O	0.832 (16)	C8—H8A	0.980
O10—H10O	0.818 (16)	C8—H8B	0.980
O11—H11O	0.829 (16)	C8—H8C	0.980

C1—P1—O1	103.11 (7)	C3—N1—C4	109.82 (12)
C1—P1—O2	109.22 (7)	C3—N1—C5	110.34 (12)
C1—P1—O3	110.38 (7)	C4—N1—C5	110.96 (13)
O1—P1—O2	109.23 (7)	N1—C3—H3A	109.4
O1—P1—O3	111.51 (7)	N1—C3—H3B	109.4
O2—P1—O3	112.92 (7)	N1—C3—C4ⁱ	111.34 (12)
C1—P2—O4	105.78 (7)	H3A—C3—H3B	108.0
C1—P2—O5	108.65 (7)	H3A—C3—C4ⁱ	109.4
C1—P2—O6	109.88 (7)	H3B—C3—C4ⁱ	109.4
O4—P2—O5	106.64 (6)	N1—C4—C3ⁱ	110.63 (13)
O4—P2—O6	114.36 (7)	N1—C4—H4A	109.5
O5—P2—O6	111.23 (7)	N1—C4—H4B	109.5
P1—C1—P2	116.93 (9)	C3ⁱ—C4—H4A	109.5
P1—C1—H1A	108.1	C3ⁱ—C4—H4B	109.5
P1—C1—H1B	108.1	H4A—C4—H4B	108.1
P2—C1—H1A	108.1	N1—C5—H5A	109.5
P2—C1—H1B	108.1	N1—C5—H5B	109.5
H1A—C1—H1B	107.3	N1—C5—H5C	109.5
P1—O1—H1O	115.0 (15)	H5A—C5—H5B	109.5
P2—O4—H4O	115.0 (15)	H5A—C5—H5C	109.5
P2—O5—H5O	117.6 (14)	H5B—C5—H5C	109.5
C2—P3—O7	102.53 (7)	H2N—N2—C6	107.1 (13)
C2—P3—O8	107.44 (7)	H2N—N2—C7	108.3 (13)
C2—P3—O9	110.87 (7)	H2N—N2—C8	108.2 (13)
O7—P3—O8	109.91 (7)	C6—N2—C7	110.51 (12)
O7—P3—O9	111.51 (8)	C6—N2—C8	111.70 (14)
O8—P3—O9	113.90 (7)	C7—N2—C8	110.83 (13)
C2—P4—O10	102.76 (7)	N2—C6—H6A	109.6
C2—P4—O11	106.61 (7)	N2—C6—H6B	109.6
C2—P4—O12	111.73 (7)	N2—C6—C7ⁱⁱ	110.13 (13)
O10—P4—O11	106.19 (7)	H6A—C6—H6B	108.1
O10—P4—O12	115.59 (7)	H6A—C6—C7ⁱⁱ	109.6
O11—P4—O12	113.07 (7)	H6B—C6—C7ⁱⁱ	109.6
P3—C2—P4	117.02 (9)	N2—C7—C6ⁱⁱ	110.51 (13)
P3—C2—H2A	108.0	N2—C7—H7A	109.5
P3—C2—H2B	108.0	N2—C7—H7B	109.5
P4—C2—H2A	108.0	C6ⁱⁱ—C7—H7A	109.5
P4—C2—H2B	108.0	C6ⁱⁱ—C7—H7B	109.5
H2A—C2—H2B	107.3	H7A—C7—H7B	108.1
P3—O7—H7O	120.5 (16)	N2—C8—H8A	109.5
P4—O10—H10O	122.2 (15)	N2—C8—H8B	109.5
P4—O11—H11O	115.4 (15)	N2—C8—H8C	109.5
H1N—N1—C3	108.3 (13)	H8A—C8—H8B	109.5
H1N—N1—C4	109.5 (13)	H8A—C8—H8C	109.5
H1N—N1—C5	107.9 (13)	H8B—C8—H8C	109.5

O4—P2—C1—P1	176.67 (8)	O8—P3—C2—P4	159.45 (8)
O5—P2—C1—P1	62.49 (10)	O9—P3—C2—P4	−75.49 (10)
O6—P2—C1—P1	−59.41 (11)	C4—N1—C3—C4ⁱ	−57.12 (18)
O1—P1—C1—P2	171.03 (8)	C5—N1—C3—C4ⁱ	−179.74 (13)
O2—P1—C1—P2	54.97 (11)	C3—N1—C4—C3ⁱ	56.70 (18)
O3—P1—C1—P2	−69.75 (10)	C5—N1—C4—C3ⁱ	178.95 (13)
O10—P4—C2—P3	−81.93 (10)	C7—N2—C6—C7ⁱⁱ	−57.62 (18)
O11—P4—C2—P3	166.60 (8)	C8—N2—C6—C7ⁱⁱ	178.50 (14)
O12—P4—C2—P3	42.61 (11)	C6—N2—C7—C6ⁱⁱ	57.84 (18)
O7—P3—C2—P4	43.63 (11)	C8—N2—C7—C6ⁱⁱ	−177.78 (14)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···O6ⁱⁱⁱ	0.81 (2)	1.73 (2)	2.5287 (16)	169 (2)
O4—H4O···O8^iv	0.83 (2)	1.76 (2)	2.5799 (17)	174 (2)
O5—H5O···O3^v	0.84 (2)	1.63 (2)	2.4689 (16)	177 (2)
O7—H7O···O2	0.83 (2)	1.71 (2)	2.5139 (16)	162 (2)
O10—H10O···O8^vi	0.82 (2)	1.73 (2)	2.5228 (17)	163 (2)
O11—H11O···O9^vii	0.83 (2)	1.70 (2)	2.5222 (17)	169 (2)
N1—H1N···O2	0.86 (2)	1.97 (2)	2.7802 (18)	157 (2)
N2—H2N···O12	0.88 (2)	1.79 (2)	2.6563 (18)	170 (2)

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

Acknowledgements

The authors thank the EPSRC, UK, for financial support.

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