organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

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

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[Farrell, D. M. M. (2001). Acta Cryst. C57, 952-954.]; Ferguson et al., 1998[Ferguson, G., Glidewell, C., Gregson, R. M. & Meehan, P. R. (1998). Acta Cryst. B54, 129-138.]; Glidewell et al., 2000[Glidewell, C., Ferguson, G. & Lough, A. J. (2000). Acta Cryst. C56, 855-858.]; Wheatley et al., 2001[Wheatley, P. S., Lough, A. J., Ferguson, G., Burchell, C. J. & Glidewell, C. (2001). Acta Cryst. B57, 95-102.]). 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[DeLaMatter, D., McCullough, J. J. & Calvo, C. (1973). J. Phys. Chem. 77, 1146-1148.]) consists of a three-dimensional hydrogen-bonded network.

[Scheme 1]

The title compound, (I)[link], 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[Beugelmans, R., Benadjila-Iguertsira, L., Chastanet, J., Negron, G. & Roussi, G. (1985). Can. J. Chem. 63, 725-34.]).

The asymmetric unit of (I)[link] contains two anions and two half-cations, each cation lying on an inversion centre (Fig. 1[link]). 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[link]). 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[Hmimid, N., Besse, J. P. & Chevalier, R. (1987). Mater. Chem. Phys. 16, 175-180.]); 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)[link] (Fig. 2[link], Table 2[link]). 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]
Figure 1
The two cations (completed by inversion symmetry) and two anions in the asymmetric unit of (I)[link], 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]
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)[link], 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

  • Mr = 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

  • Dx = 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[Sheldrick, G. M. (2002). SADABS. University of Göttingen, Germany.])Tmin = 0.800, Tmax = 0.915

  • 12295 measured reflections

  • 4037 independent reflections

  • 3592 reflections with I > 2σ(I)

  • Rint = 0.028

  • θmax = 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(Fo2) + (0.0315P)2 + 0.7406P] where P = (Fo2 + 2Fc2)/3

  • (Δ/σ)max = 0.001

  • Δρmax = 0.55 e Å−3

  • Δρmin = −0.50 e Å−3

  • Extinction correction: SHELXTL (Sheldrick, 2001[Sheldrick, G. M. (2001). SHELXTL. Bruker AXS Inc., Madison, Wisconsin, USA.])

  • Extinction coefficient: 0.011 (2)

Table 1
Selected bond lengths (Å)[link]

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, °)[link]

D—H⋯A D—H H⋯A DA D—H⋯A
O1—H1O⋯O6iii 0.81 (2) 1.73 (2) 2.5287 (16) 169 (2)
O4—H4O⋯O8iv 0.83 (2) 1.76 (2) 2.5799 (17) 174 (2)
O5—H5O⋯O3v 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⋯O8vi 0.82 (2) 1.73 (2) 2.5228 (17) 163 (2)
O11—H11O⋯O9vii 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 Uiso(H) = 1.2 (1.5 for methyl groups) times Ueq(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 Uiso(H) = 1.2Ueq(N,O).

Data collection: COLLECT (Nonius, 1998[Nonius (1998). COLLECT. Nonius BV, Delft, The Netherlands.]); cell refinement: DIRAX (Duisenberg, 1992[Duisenberg, A. J. M. (1992). J. Appl. Cryst. 25, 92-96.]); data reduction: EVALCCD (Duisenberg et al., 2003[Duisenberg, A. J. M., Kroon-Batenburg, L. M. J. & Schreurs, A. M. M. (2003). J. Appl. Cryst. 36, 220-229.]); program(s) used to solve structure: SHELXTL (Sheldrick, 2001[Sheldrick, G. M. (2001). SHELXTL. Bruker AXS Inc., Madison, Wisconsin, USA.]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and local programs.

Supporting information


Comment top

Phosphonic 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 hydroxyls in the –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) is a three-dimensional hydrogen-bonded network.

The title compound, (I), obtained unintentionally in one of a series of hydrothermal syntheses of aluminium diphosponate 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 H-free O atoms (Table 1). The shortest P—O bonds, to atoms O6 and O12, involve the intact P(O)(OH)2 phosphonic acid groups of atoms P2 and P4, and these can be assigned as PO double bonds. The other P—O bonds to unprotonated O atoms are intermediate in length, and are in the deprotonated P(O)2(OH) phosphonate groups of atoms P1 and P3; these are delocalized and intermediate between single and double bonds, while the P—OH bonds are single. Methyldiphosphonate is usually found in crystal structures with both groups deprotonated, as a doubly charged anion; the only previous report of the singly charged H2O3PCH2PO3H anion is in a trithallium(I) mixed salt of this and the doubly charged species (Hmimid et al., 1987), in which the two proposed anionic species are crystallographically equivalent and, therefore, 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.

Experimental top

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.

Refinement top

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 Uiso(H) = 1.2 (1.5 for methyl groups) times Ueq(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 Uiso(H) = 1.2Ueq(N,O).

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.

Figures top
[Figure 1] Fig. 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 for unlabelled atoms: (1 − x, 1 − y, −z) for cation of N1 and (1 − x, 1 − y, 1 − z) for cation of N2.]
[Figure 2] Fig. 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.
N,N'-Dimethylpiperazinium(2+) bis[methylenehydrogendiphosphonate(1-)] top
Crystal data top
C6H16N22+·2CH5O6P2Z = 2
Mr = 466.19F(000) = 488
Triclinic, P1Dx = 1.661 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 6.9881 (6) ÅCell parameters from 59 reflections
b = 8.9148 (6) Åθ = 2.5–27.5°
c = 16.6251 (10) ŵ = 0.47 mm1
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 tube3592 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.028
ϕ and ω scansθmax = 27.5°, θmin = 4.7°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2002)
h = 99
Tmin = 0.800, Tmax = 0.915k = 1111
12295 measured reflectionsl = 2121
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.028H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.075 w = 1/[σ2(Fo2) + (0.0315P)2 + 0.7406P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max = 0.001
4037 reflectionsΔρmax = 0.55 e Å3
262 parametersΔρmin = 0.50 e Å3
8 restraintsExtinction correction: SHELXTL (Sheldrick, 2001), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.011 (2)
Crystal data top
C6H16N22+·2CH5O6P2γ = 112.244 (6)°
Mr = 466.19V = 932.24 (12) Å3
Triclinic, P1Z = 2
a = 6.9881 (6) ÅMo Kα radiation
b = 8.9148 (6) ŵ = 0.47 mm1
c = 16.6251 (10) ÅT = 120 K
α = 98.910 (5)°0.50 × 0.50 × 0.20 mm
β = 95.882 (6)°
Data collection top
Nonius KappaCCD area-detector
diffractometer
4037 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2002)
3592 reflections with I > 2σ(I)
Tmin = 0.800, Tmax = 0.915Rint = 0.028
12295 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0288 restraints
wR(F2) = 0.075H atoms treated by a mixture of independent and constrained refinement
S = 1.06Δρmax = 0.55 e Å3
4037 reflectionsΔρmin = 0.50 e Å3
262 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
P10.72874 (6)0.26531 (5)0.14321 (2)0.01031 (10)
P20.25336 (6)0.05401 (5)0.11556 (2)0.01102 (10)
C10.5149 (2)0.08775 (19)0.16149 (10)0.0132 (3)
H1A0.53920.01270.14090.016*
H1B0.52120.09930.22200.016*
O10.92324 (18)0.27350 (16)0.20257 (7)0.0175 (3)
H1O1.003 (3)0.242 (3)0.1799 (13)0.021*
O20.68992 (18)0.41979 (14)0.16996 (7)0.0157 (2)
O30.75543 (18)0.23748 (14)0.05337 (7)0.0155 (2)
O40.10390 (18)0.11161 (15)0.13683 (7)0.0175 (2)
H4O0.134 (3)0.123 (3)0.1844 (10)0.021*
O50.23587 (19)0.02151 (14)0.02082 (7)0.0152 (2)
H5O0.241 (3)0.067 (2)0.0027 (12)0.018*
O60.20780 (18)0.20123 (15)0.14673 (7)0.0187 (3)
P31.01122 (6)0.79458 (5)0.33650 (2)0.01223 (11)
P40.72510 (6)0.96071 (5)0.39958 (2)0.01142 (11)
C20.9692 (2)0.98231 (19)0.36560 (10)0.0131 (3)
H2A1.08561.05830.41050.016*
H2B0.97881.03640.31760.016*
O70.79361 (19)0.67144 (16)0.28394 (8)0.0228 (3)
H7O0.785 (4)0.590 (2)0.2495 (12)0.027*
O81.17930 (18)0.83067 (16)0.28150 (7)0.0191 (3)
O91.0655 (2)0.73429 (14)0.41184 (7)0.0186 (3)
O100.56949 (19)0.90998 (16)0.31701 (7)0.0191 (3)
H10O0.444 (3)0.888 (3)0.3155 (13)0.023*
O110.7503 (2)1.13825 (15)0.44042 (7)0.0194 (3)
H11O0.801 (3)1.169 (3)0.4905 (10)0.023*
O120.66895 (18)0.84128 (14)0.45641 (7)0.0151 (2)
N10.4264 (2)0.52382 (16)0.07827 (8)0.0121 (3)
H1N0.476 (3)0.467 (2)0.1047 (11)0.014*
C30.6069 (2)0.65879 (19)0.05574 (10)0.0139 (3)
H3A0.70630.72940.10670.017*
H3B0.55330.72940.02810.017*
C40.2785 (2)0.41262 (19)0.00124 (10)0.0140 (3)
H4A0.21570.47640.02780.017*
H4B0.16350.32120.01620.017*
C50.3156 (3)0.5972 (2)0.13405 (10)0.0181 (3)
H5A0.25600.66150.10500.027*
H5B0.41550.67000.18360.027*
H5C0.20260.50820.15020.027*
N20.4365 (2)0.51721 (17)0.41761 (8)0.0143 (3)
H2N0.513 (3)0.6236 (19)0.4239 (12)0.017*
C60.5842 (3)0.4356 (2)0.43334 (10)0.0167 (3)
H6A0.68150.45440.39310.020*
H6B0.50370.31460.42590.020*
C70.2916 (3)0.4945 (2)0.47959 (10)0.0161 (3)
H7A0.20370.37500.47340.019*
H7B0.19720.55150.46920.019*
C80.3153 (3)0.4548 (2)0.33170 (11)0.0248 (4)
H8A0.22220.33750.32440.037*
H8B0.41270.46690.29230.037*
H8C0.23130.51880.32180.037*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
P10.0091 (2)0.01140 (19)0.00927 (18)0.00425 (15)0.00039 (14)0.00018 (14)
P20.0095 (2)0.0112 (2)0.01111 (19)0.00410 (15)0.00016 (14)0.00013 (14)
C10.0130 (8)0.0132 (7)0.0141 (7)0.0060 (6)0.0006 (6)0.0040 (6)
O10.0107 (6)0.0273 (6)0.0142 (5)0.0097 (5)0.0008 (4)0.0005 (5)
O20.0152 (6)0.0122 (5)0.0168 (6)0.0057 (4)0.0021 (4)0.0022 (4)
O30.0182 (6)0.0181 (6)0.0109 (5)0.0083 (5)0.0028 (4)0.0024 (4)
O40.0143 (6)0.0189 (6)0.0139 (6)0.0011 (5)0.0006 (5)0.0049 (5)
O50.0198 (6)0.0138 (6)0.0106 (5)0.0064 (5)0.0002 (4)0.0013 (4)
O60.0139 (6)0.0188 (6)0.0229 (6)0.0095 (5)0.0006 (5)0.0030 (5)
P30.0101 (2)0.0138 (2)0.01052 (19)0.00387 (16)0.00048 (14)0.00079 (14)
P40.0123 (2)0.0119 (2)0.00977 (18)0.00505 (15)0.00051 (14)0.00160 (14)
C20.0117 (8)0.0113 (7)0.0137 (7)0.0027 (6)0.0001 (6)0.0020 (6)
O70.0124 (6)0.0216 (6)0.0251 (7)0.0046 (5)0.0014 (5)0.0130 (5)
O80.0127 (6)0.0325 (7)0.0137 (5)0.0107 (5)0.0024 (4)0.0051 (5)
O90.0268 (7)0.0155 (6)0.0160 (6)0.0111 (5)0.0032 (5)0.0037 (4)
O100.0120 (6)0.0320 (7)0.0128 (5)0.0093 (5)0.0004 (5)0.0039 (5)
O110.0300 (7)0.0160 (6)0.0157 (6)0.0136 (5)0.0035 (5)0.0027 (5)
O120.0176 (6)0.0129 (5)0.0131 (5)0.0045 (5)0.0026 (4)0.0025 (4)
N10.0129 (7)0.0118 (6)0.0112 (6)0.0049 (5)0.0010 (5)0.0025 (5)
C30.0130 (8)0.0104 (7)0.0147 (7)0.0017 (6)0.0012 (6)0.0013 (6)
C40.0111 (8)0.0144 (7)0.0132 (7)0.0026 (6)0.0002 (6)0.0015 (6)
C50.0215 (9)0.0168 (8)0.0187 (8)0.0094 (7)0.0082 (7)0.0032 (6)
N20.0150 (7)0.0110 (6)0.0133 (6)0.0021 (5)0.0024 (5)0.0035 (5)
C60.0198 (9)0.0159 (8)0.0157 (8)0.0086 (7)0.0026 (6)0.0029 (6)
C70.0129 (8)0.0148 (8)0.0197 (8)0.0047 (6)0.0001 (6)0.0049 (6)
C80.0276 (10)0.0234 (9)0.0135 (8)0.0025 (7)0.0075 (7)0.0028 (7)
Geometric parameters (Å, º) top
P1—C11.8118 (16)N1—H1N0.857 (15)
P1—O11.5666 (12)N1—C31.505 (2)
P1—O21.5119 (11)N1—C41.5002 (19)
P1—O31.5180 (11)N1—C51.493 (2)
P2—C11.8000 (16)C3—H3A0.990
P2—O41.5703 (12)C3—H3B0.990
P2—O51.5401 (11)C3—C4i1.516 (2)
P2—O61.4939 (12)C4—C3i1.516 (2)
C1—H1A0.990C4—H4A0.990
C1—H1B0.990C4—H4B0.990
O1—H1O0.813 (15)C5—H5A0.980
O4—H4O0.827 (15)C5—H5B0.980
O5—H5O0.837 (15)C5—H5C0.980
P3—C21.8088 (16)N2—H2N0.877 (15)
P3—O71.5646 (13)N2—C61.495 (2)
P3—O81.5312 (12)N2—C71.501 (2)
P3—O91.5055 (12)N2—C81.489 (2)
P4—C21.8021 (16)C6—H6A0.990
P4—O101.5494 (12)C6—H6B0.990
P4—O111.5583 (12)C6—C7ii1.514 (2)
P4—O121.5005 (12)C7—C6ii1.514 (2)
C2—H2A0.990C7—H7A0.990
C2—H2B0.990C7—H7B0.990
O7—H7O0.832 (16)C8—H8A0.980
O10—H10O0.818 (16)C8—H8B0.980
O11—H11O0.829 (16)C8—H8C0.980
C1—P1—O1103.11 (7)C3—N1—C4109.82 (12)
C1—P1—O2109.22 (7)C3—N1—C5110.34 (12)
C1—P1—O3110.38 (7)C4—N1—C5110.96 (13)
O1—P1—O2109.23 (7)N1—C3—H3A109.4
O1—P1—O3111.51 (7)N1—C3—H3B109.4
O2—P1—O3112.92 (7)N1—C3—C4i111.34 (12)
C1—P2—O4105.78 (7)H3A—C3—H3B108.0
C1—P2—O5108.65 (7)H3A—C3—C4i109.4
C1—P2—O6109.88 (7)H3B—C3—C4i109.4
O4—P2—O5106.64 (6)N1—C4—C3i110.63 (13)
O4—P2—O6114.36 (7)N1—C4—H4A109.5
O5—P2—O6111.23 (7)N1—C4—H4B109.5
P1—C1—P2116.93 (9)C3i—C4—H4A109.5
P1—C1—H1A108.1C3i—C4—H4B109.5
P1—C1—H1B108.1H4A—C4—H4B108.1
P2—C1—H1A108.1N1—C5—H5A109.5
P2—C1—H1B108.1N1—C5—H5B109.5
H1A—C1—H1B107.3N1—C5—H5C109.5
P1—O1—H1O115.0 (15)H5A—C5—H5B109.5
P2—O4—H4O115.0 (15)H5A—C5—H5C109.5
P2—O5—H5O117.6 (14)H5B—C5—H5C109.5
C2—P3—O7102.53 (7)H2N—N2—C6107.1 (13)
C2—P3—O8107.44 (7)H2N—N2—C7108.3 (13)
C2—P3—O9110.87 (7)H2N—N2—C8108.2 (13)
O7—P3—O8109.91 (7)C6—N2—C7110.51 (12)
O7—P3—O9111.51 (8)C6—N2—C8111.70 (14)
O8—P3—O9113.90 (7)C7—N2—C8110.83 (13)
C2—P4—O10102.76 (7)N2—C6—H6A109.6
C2—P4—O11106.61 (7)N2—C6—H6B109.6
C2—P4—O12111.73 (7)N2—C6—C7ii110.13 (13)
O10—P4—O11106.19 (7)H6A—C6—H6B108.1
O10—P4—O12115.59 (7)H6A—C6—C7ii109.6
O11—P4—O12113.07 (7)H6B—C6—C7ii109.6
P3—C2—P4117.02 (9)N2—C7—C6ii110.51 (13)
P3—C2—H2A108.0N2—C7—H7A109.5
P3—C2—H2B108.0N2—C7—H7B109.5
P4—C2—H2A108.0C6ii—C7—H7A109.5
P4—C2—H2B108.0C6ii—C7—H7B109.5
H2A—C2—H2B107.3H7A—C7—H7B108.1
P3—O7—H7O120.5 (16)N2—C8—H8A109.5
P4—O10—H10O122.2 (15)N2—C8—H8B109.5
P4—O11—H11O115.4 (15)N2—C8—H8C109.5
H1N—N1—C3108.3 (13)H8A—C8—H8B109.5
H1N—N1—C4109.5 (13)H8A—C8—H8C109.5
H1N—N1—C5107.9 (13)H8B—C8—H8C109.5
O4—P2—C1—P1176.67 (8)O8—P3—C2—P4159.45 (8)
O5—P2—C1—P162.49 (10)O9—P3—C2—P475.49 (10)
O6—P2—C1—P159.41 (11)C4—N1—C3—C4i57.12 (18)
O1—P1—C1—P2171.03 (8)C5—N1—C3—C4i179.74 (13)
O2—P1—C1—P254.97 (11)C3—N1—C4—C3i56.70 (18)
O3—P1—C1—P269.75 (10)C5—N1—C4—C3i178.95 (13)
O10—P4—C2—P381.93 (10)C7—N2—C6—C7ii57.62 (18)
O11—P4—C2—P3166.60 (8)C8—N2—C6—C7ii178.50 (14)
O12—P4—C2—P342.61 (11)C6—N2—C7—C6ii57.84 (18)
O7—P3—C2—P443.63 (11)C8—N2—C7—C6ii177.78 (14)
Symmetry codes: (i) x+1, y+1, z; (ii) x+1, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1O···O6iii0.81 (2)1.73 (2)2.5287 (16)169 (2)
O4—H4O···O8iv0.83 (2)1.76 (2)2.5799 (17)174 (2)
O5—H5O···O3v0.84 (2)1.63 (2)2.4689 (16)177 (2)
O7—H7O···O20.83 (2)1.71 (2)2.5139 (16)162 (2)
O10—H10O···O8vi0.82 (2)1.73 (2)2.5228 (17)163 (2)
O11—H11O···O9vii0.83 (2)1.70 (2)2.5222 (17)169 (2)
N1—H1N···O20.86 (2)1.97 (2)2.7802 (18)157 (2)
N2—H2N···O120.88 (2)1.79 (2)2.6563 (18)170 (2)
Symmetry codes: (iii) x+1, y, z; (iv) x1, y1, z; (v) x+1, y, z; (vi) x1, y, z; (vii) x+2, y+2, z+1.

Experimental details

Crystal data
Chemical formulaC6H16N22+·2CH5O6P2
Mr466.19
Crystal system, space groupTriclinic, P1
Temperature (K)120
a, b, c (Å)6.9881 (6), 8.9148 (6), 16.6251 (10)
α, β, γ (°)98.910 (5), 95.882 (6), 112.244 (6)
V3)932.24 (12)
Z2
Radiation typeMo Kα
µ (mm1)0.47
Crystal size (mm)0.50 × 0.50 × 0.20
Data collection
DiffractometerNonius KappaCCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2002)
Tmin, Tmax0.800, 0.915
No. of measured, independent and
observed [I > 2σ(I)] reflections
12295, 4037, 3592
Rint0.028
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.028, 0.075, 1.06
No. of reflections4037
No. of parameters262
No. of restraints8
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.55, 0.50

Computer programs: COLLECT (Nonius, 1998), DIRAX (Duisenberg, 1992), EVALCCD (Duisenberg et al., 2003), SHELXTL (Sheldrick, 2001), SHELXTL and local programs.

Selected bond lengths (Å) top
P1—C11.8118 (16)P3—C21.8088 (16)
P1—O11.5666 (12)P3—O71.5646 (13)
P1—O21.5119 (11)P3—O81.5312 (12)
P1—O31.5180 (11)P3—O91.5055 (12)
P2—C11.8000 (16)P4—C21.8021 (16)
P2—O41.5703 (12)P4—O101.5494 (12)
P2—O51.5401 (11)P4—O111.5583 (12)
P2—O61.4939 (12)P4—O121.5005 (12)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1O···O6i0.813 (15)1.725 (16)2.5287 (16)169 (2)
O4—H4O···O8ii0.827 (15)1.756 (16)2.5799 (17)174 (2)
O5—H5O···O3iii0.837 (15)1.632 (15)2.4689 (16)177 (2)
O7—H7O···O20.832 (16)1.709 (17)2.5139 (16)162 (2)
O10—H10O···O8iv0.818 (16)1.728 (17)2.5228 (17)163 (2)
O11—H11O···O9v0.829 (16)1.703 (16)2.5222 (17)169 (2)
N1—H1N···O20.857 (15)1.971 (16)2.7802 (18)157 (2)
N2—H2N···O120.877 (15)1.789 (15)2.6563 (18)170 (2)
Symmetry codes: (i) x+1, y, z; (ii) x1, y1, z; (iii) x+1, y, z; (iv) x1, y, z; (v) x+2, y+2, z+1.
 

Acknowledgements

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

References

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