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

Journal logoSTRUCTURAL
CHEMISTRY
ISSN: 2053-2296

(3-Hydr­­oxy-2-pyridylmeth­yl)di­methyl­ammonium di­hydrogenphosphate

aDepartment of Chemistry, Faculty of Arts and Sciences, Ondokuz Mayis University, 55139 Kurupelit Samsun, Turkey, and bDepartment of Chemistry, University of Aberdeen, Meston Walk, Aberdeen AB24 3UE, Scotland
*Correspondence e-mail: vtyilmaz@omu.edu.tr

(Received 7 February 2006; accepted 16 February 2006; online 18 March 2006)

The title compound, C8H13N2O+·H2PO4, is an ionic salt. The organic species is protonated at the N atom of the dimethyl­amino­methyl group. The dihydrogenphosphate moieties are connected into infinite chains by way of O—H⋯O links. The H2PO4 group also makes an O—H⋯N hydrogen bond to the pyridine N atom of the organic species. The organic cations crosslink the phosphate chains into a three-dimensional network by way of strong N—H⋯O and O—H⋯O inter­actions.

Comment

Organic ammonium phosphates are formed as inter­mediates or by-products in the syntheses of metal phosphate frameworks templated by organic amines (Oliver et al., 1998[Oliver, S., Lough, A. J. & Ozin, G. A. (1998). Inorg. Chem. 37, 5021-5028.]; Neeraj et al., 1999[Neeraj, S., Natarajan, S. & Rao, C. N. R. (1999). Angew. Chem. Int. Ed. 38, 3480-3483.]; Rao et al., 2000[Rao, C. N. R., Natarajan, S. & Neeraj, S. (2000). J. Solid State Chem. 152, 302-321.]). In the formation of organic templated metal phosphates, the protonated organic amines play an important role. The amines can act as structure-directing agents, usually occupying the available voids or channels, and stabilize the structure through hydrogen bonding and other inter­actions (Choudhury et al., 2000[Choudhury, A., Natarajan, S. & Rao, C. N. R. (2000). Inorg. Chem. 39, 4295-4304.]; Harrison et al., 2002[Harrison, W. T. A., Rodgers, J. A., Phillips, M. L. F. & Nenoff, T. M. (2002). Solid State Sci. 4, 969-972.]; Yilmaz et al., 2005[Yilmaz, V. T., Demir, S., Kazak, C. & Harrison, W. T. A. (2005). Solid State Sci. 7, 1247-1255.]; Dorn et al. 2005[Dorn, T., Janiak, C. & Abu-Shandi, K. (2005). CrystEngComm, 7, 633-641.]). The charge and size of the organic cations also have significant influences on the structure of the anionic inorganic framework.

[Scheme 1]

The organic ammonium phosphates show inter­esting crystal packing motifs strongly influenced by N—H⋯O and O—H⋯O hydrogen bonds (Demir et al., 2002[Demir, S., Yilmaz, V. T., Andac, O. & Harrison, W. T. A. (2002). Acta Cryst. C58, o407-o408.], 2003a[Demir, S., Yilmaz, V. T. & Harrison, W. T. A. (2003a). Acta Cryst. C59, o378-o380.],b[Demir, S., Yilmaz, V. T. & Harrison, W. T. A. (2003b). Acta Cryst. E59, o907-o909.], 2005[Demir, S., Yilmaz, V. T. & Harrison, W. T. A. (2005). Acta Cryst. C61, o565-o567.]). Sometimes, a three-dimensional supramolecular array of phosphate ions encapsulates the organic amine cations in channels (Czapla et al., 2003[Czapla, Z., Dacko, S. & Waskowska, A. (2003). J. Phys. Condens. Matter, 15, 3793-3803.]; Dakhlaoui et al., 2004[Dakhlaoui, A., Smiri, L. S. & Driss, A. (2004). Acta Cryst. E60, o2241-o2243.]). As a continuation of our work on the preparation and structural characterization of organic ammonium phosphates, in this paper, we report the structure of the title compound, C8H13N2O+·H2PO4, (I)[link] (Fig. 1[link]).

The amine mol­ecule in (I)[link] has two potential N atoms for protonation. Here, the N atom of the 2-dimethyl­amino­methyl (2-dmam) group is protonated. The inductive effect of the alkyl groups around the 2-dmam N atom presumably favours protonation of this N atom rather than the pyridine N atom. The protonation of the 2-dmam N atom results in a slight lengthening of the three N—C bonds [the mean for (I)[link] is 1.494 (2) Å] relative to the unprotonated form of the amine [mean 1.466 (3) Å; Yilmaz et al. 2006[Yilmaz, V. T., Hamamci, S., Gumus, S. & Büyükgüngör, O. (2006). J. Mol. Struct. In the press.]]. As expected, the pyridine ring in (I)[link] is essentially planar (for atoms N1 and C1–C5, the r.m.s. deviation from the least-squares plane is 0.003 Å).

For the tetra­hedral dihydrogenphosphate group, the protonated P—O vertices (to atoms O3 and O4) show the expected lengthening (Table 1[link]) relative to the other P—O bonds (to atoms O1 and O2), which are of similar length as a result of delocalization of the negative charge between them.

As well as electrostatic forces, an extensive network of hydrogen bonds, listed in Table 2[link], appears to be a key factor in the stabilization of this structure. The dihydrogenphosphate anions are linked into one-dimensional chains by way of P—O—H⋯O=P bonds, running parallel to the c axis (i.e. generated by the c-glide operation). The intra­chain P1⋯P1i separation [symmetry code: (i) x, −y + [{3\over 2}], z + [{1\over 2}]] is 4.5144 (4) Å, which is similar to those found in β-(C5H7N2)(H2PO4) [4.526 (1) and 4.536 (2) Å; Demir et al., 2005[Demir, S., Yilmaz, V. T. & Harrison, W. T. A. (2005). Acta Cryst. C61, o565-o567.]]. Unusually, the H2PO4 group in (I)[link] makes an O—H⋯N hydrogen bond to the organic cation. In related compounds, the dihydrogen­phos­phate moiety usually makes O—H⋯O bonds to other anions (Demir et al., 2005[Demir, S., Yilmaz, V. T. & Harrison, W. T. A. (2005). Acta Cryst. C61, o565-o567.]).

In turn, the organic cation makes an O—H⋯O hydrogen bond from its phenol group to a phosphate O atom. This hydrogen bonding results in an extended sheet structure (Fig. 2[link]) propagating in the (010) plane. A short C—H⋯O inter­action (Table 2[link]) may also help to consolidate this extended sheet. Finally, the protonated 2-dmam N atom makes an N—H⋯O bond to a phosphate O atom displaced in the b direction (Fig. 3[link]), resulting in a three-dimensional network. No aromatic ππ stacking inter­actions are present in (I)[link].

[Figure 1]
Figure 1
A view of (I), showing 50% probability displacement ellipsoids. H atoms are drawn as spheres of arbitrary radii and the hydrogen bond is indicated by double dashed lines.
[Figure 2]
Figure 2
Part of an extended (010) hydrogen-bonded sheet in (I), showing hydrogen-bonded phosphate chains propagating in the c direction, cross­linked by phosphate-to-organic O—H⋯N and organic-to-phosphate O—H⋯O bonds (double dashed lines) in the a direction. The C—H⋯O inter­actions are indicated by single dashed lines. H atoms not involved in hydrogen bonds have been omitted for clarity (50% probability displacement ellipsoids and arbitrary spheres for H atoms). [Symmetry codes: (i) x, −y + [{3\over 2}], z + [{1\over 2}]; (ii) x + 1, −y + [{3\over 2}], z + [{1\over 2}]; (iii) x, y, z + 1.]
[Figure 3]
Figure 3
Part of an extended (001) hydrogen-bonding sheet in (I). Only the H atoms involved in hydrogen bonds are shown (50% probability displacement ellipsoids and arbitrary spheres for H atoms). [Symmetry code: (iv) −x + 1, y[{1\over 2}], −z + [{1\over 2}].]

Experimental

H3PO4 (0.17 ml, 2.5 mmol) (aqueous 85 wt%) was added dropwise to a solution of 2-(dimethyl­amino­meth­yl)-3-hydroxy­pyridine (0.30 g, 2 mmol) in methanol (30 ml) and stirred at 363 K for 15 min. The resulting mixture was left to crystallize at room temperature. Colourless cubic crystals of the title compound were washed with a small amount of methanol and dried in air.

Crystal data
  • C8H13N2O+·H2PO4

  • Mr = 250.19

  • Monoclinic, P 21 /c

  • a = 10.7601 (2) Å

  • b = 11.9724 (2) Å

  • c = 8.9122 (1) Å

  • β = 109.3578 (11)°

  • V = 1083.20 (3) Å3

  • Z = 4

  • Dx = 1.534 Mg m−3

  • Mo Kα radiation

  • Cell parameters from 4901 reflections

  • θ = 2.9–27.5°

  • μ = 0.26 mm−1

  • T = 120 (2) K

  • Cube, colourless

  • 0.35 × 0.35 × 0.35 mm

Data collection
  • Nonius KappaCCD diffractometer

  • ω and φ scans

  • Absorption correction: multi-scan(SADABS; Bruker, 2003[Bruker (2003). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.])Tmin = 0.914, Tmax = 0.914

  • 22984 measured reflections

  • 2481 independent reflections

  • 2282 reflections with I > 2σ(I)

  • Rint = 0.029

  • θmax = 27.5°

  • h = −13 → 13

  • k = −15 → 15

  • l = −10 → 11

Refinement
  • Refinement on F2

  • R[F2 > 2σ(F2)] = 0.027

  • wR(F2) = 0.070

  • S = 1.05

  • 2481 reflections

  • 160 parameters

  • H atoms treated by a mixture of independent and constrained refinement

  • w = 1/[σ2(Fo2) + (0.0283P)2 + 0.7457P] where P = (Fo2 + 2Fc2)/3

  • (Δ/σ)max = 0.001

  • Δρmax = 0.32 e Å−3

  • Δρmin = −0.39 e Å−3

  • Extinction correction: SHELXL97

  • Extinction coefficient: 0.034 (2)

Table 1
Selected geometric parameters (Å, °)

P1—O1 1.4980 (9)
P1—O2 1.5139 (9)
P1—O3 1.5726 (9)
P1—O4 1.5731 (9)
O1—P1—O2 114.83 (5)
O1—P1—O3 111.14 (5)
O2—P1—O3 106.81 (5)
O1—P1—O4 107.61 (5)
O2—P1—O4 108.91 (5)
O3—P1—O4 107.28 (5)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
O3—H1⋯N1v 0.787 (18) 1.955 (18) 2.7243 (14) 166 (2)
O4—H2⋯O2vi 0.848 (18) 1.749 (18) 2.5813 (13) 167 (2)
N2—H3⋯O1vii 0.963 (15) 1.661 (16) 2.6187 (13) 173 (1)
O5—H4⋯O2 0.877 (18) 1.723 (18) 2.5939 (12) 172 (2)
C6—H6A⋯O1ii 0.99 2.30 3.2663 (15) 165
Symmetry codes: (ii) [x+1, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]; (v) [x-1, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]; (vi) [x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]; (vii) [-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}].

N- and O-bound H atoms were found in difference maps and their positions were refined freely. C-bound H atoms were placed in idealized locations (C—H = 0.95–0.99 Å) and refined as riding. The constraint Uiso(H) = 1.2Ueq(carrier) or 1.5Ueq(methyl carrier) was applied and the methyl groups were allowed to rotate to fit the electron density.

Data collection: COLLECT (Nonius, 1998[Nonius (1998). COLLECT. Nonius BV, Delft, The Netherlands.]); cell refinement: SCALEPACK (Otwinowski & Minor, 1997[Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307-326. New York: Academic Press.]); data reduction: DENZO (Otwinowski & Minor, 1997[Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307-326. New York: Academic Press.]) and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.]); molecular graphics: ORTEP-3 (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]); software used to prepare material for publication: SHELXL97.

Supporting information


Comment top

Organic ammonium phosphates are formed as intermediates or by-products in the syntheses of metal phosphate frameworks templated by organic amines (Oliver et al., 1998; Neeraj et al., 1999; Rao et al., 2000). In the formation of organic templated metal phosphates, the protonated organic amines play an important role. The amines can act as structure-directing agents, usually occupying the available voids or channels, and stabilize the structure through hydrogen bonding and other interactions (Choudhury et al., 2000; Harrison et al., 2002; Yilmaz et al., 2005; Dorn et al. 2005). The charge and size of the organic cations also have significant influences on the structure of the anionic inorganic framework.

The organic ammmonium phosphates show interesting crystal packing motifs strongly influenced by N—H···O and O—H···O hydrogen bonds (Demir et al., 2002, 2003a,b, 2005). Sometimes, a three-dimensional supramolecular array of phosphate ions encapsulates the organic amine cations in channels (Czapla et al., 2003; Dakhlaoui, et al., 2004). As a continuation of our work on the preparation and structural characterization of organic ammonium phosphates, in this paper, we report the structure of the title compound, C8H13N2O+·H2PO4, (I) (Fig. 1).

The amine molecule in (I) has two potential N atoms for protonation. Here the N atom of the 2-dimethylaminomethyl (2-dmam) group is protonated. The inductive effect of the three alkyl groups around the 2-dmam N atom presumably favours protonation of this N atom rather than the pyridine N atom. The protonation of the 2-dmam N atom results in a slight lengthening of the three N—C bonds [the mean for (I) is 1.494 (2) Å] relative to the unprotonated form of the amine [mean 1.466 (3) Å; Yilmaz et al. 2006]. As expected, the pyridine ring in (I) is essentially planar (for atoms N1 and C1–C5, the r.m.s. deviation from the least-squares plane is 0.003 Å).

For the tetrahedral dihydrogenphosphate group, the protonated P—O vertices (O3 and O4) show their expected lengthening (Table 1) relative to the other P—O bonds (O1 and O2), which are of similar length as a result of delocalization of the negative charge between them.

As well as electrostatic forces, an extensive network of hydrogen bonds, listed in Table 2, appears to be a key factor in the stabilization of this structure. The dihydrogenphosphate anions are linked into one-dimensional chains by way of P—O—H···OP bonds, running parallel to the c axis (i.e. generated by the c-glide operation). The intrachain P1···P1i separation [symmetry code: (i) x, 3/2 − y, 1/2 + z) is 4.5144 (4) Å, which is similar to those found in β-(C5H7N2)(H2PO4) [4.526 (1) and 4.536 (2) Å; Demir et al., 2005]. Unusually, the H2PO4 group in (I) makes an O—H···N hydrogen bond to the organic cation. In related compounds, the dihydrogenphosphate moiety usually makes O—H···O bonds to other anions (Demir et al., 2005).

In turn, the organic cation makes an O—H···O hydrogen bond from its phenol group to a phosphate O atom. This hydrogen bonding results in an extended sheet structure (Fig. 2) propagating in the (010) plane. A short C—H···O interaction (Table 2) may also help to consolidate this extended sheet. Finally, the protonated 2-dmam N atom makes an N—H···O bond to a phosphate O atom displaced in the b direction (Fig. 3), resulting in a three-dimensional network. No aromatic ππ stacking interactions are present in (I).

Experimental top

H3PO4 (0.17 ml, 2.5 mmol) (aq 85 wt%) was added dropwise to a solution of 2-(dimethylaminomethyl)-3-hydroxypyridine (0.30 g, 2 mmol) in methanol (30 ml) and stirred at 363 K for 15 min. The resulting mixture was left to crystallize at room temperature. Colourless cubic crystals of the title compound were washed with a small amount of methanol and dried in air.

Refinement top

N-and O-bound H atoms were found in difference maps and their positions were freely refined. C-bound H atoms were placed in idealized locations (C—H = 0.95–0.99 Å) and refined as riding. The constraint Uiso(H) = 1.2Ueq(carrier) or 1.5Ueq(methyl carrier) was applied and the methyl groups were allowed to rotate to fit the electron density.

Computing details top

Data collection: Collect (Nonius, 1998); cell refinement: HKL SCALEPACK (Otwinowski & Minor ,1997); data reduction: HKL DENZO (Otwinowski & Minor, 1997) and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. A view of (I), showing 50% probability displacement ellipsoids. H atoms are drawn as spheres of arbitrary radii and the hydrogen bond is indicated by dashed lines.
[Figure 2] Fig. 2. Part of an extented (010) hydrogen-bonded sheet in (I), showing hydrogen-bonded phosphate chains propagating in the c direction, cross-linked by phosphate-to-organic O—H···N and organic to-phosphate O—H···O bonds (double dashed lines) in the a direction. The C—H···O interactions are indicated by single dashed lines. H atoms not involved in hydrogen bonds have been omitted for clarity (50% probability displacement ellipsoids, and arbitrary spheres for the H atoms). [Symmetry codes: (i) x, −y + 3/2, z + 1/2; (ii) x + 1, −y + 3/2, z + 1/2; (iii) x, y, z + 1.]
[Figure 3] Fig. 3. Part of an extended (001) hydrogen-bonding sheet in (I). Only the H atoms involved in hydrogen bonds are shown (50% probability displacement ellipsoids and arbitrary spheres for the H atoms). [Symmetry code: (i) −x + 1, y − 1/2, −z + 1/2.]
(3-Hydroxy-2-pyridylmethyl)dimethylammonium dihydrogenphosphate top
Crystal data top
C8H13N2O+·H2O4PF(000) = 528
Mr = 250.19Dx = 1.534 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 4901 reflections
a = 10.7601 (2) Åθ = 2.9–27.5°
b = 11.9724 (2) ŵ = 0.26 mm1
c = 8.9122 (1) ÅT = 120 K
β = 109.3578 (11)°Cube, colourless
V = 1083.20 (3) Å30.35 × 0.35 × 0.35 mm
Z = 4
Data collection top
Nonius KappaCCD
diffractometer
2481 independent reflections
Radiation source: fine-focus sealed tube2282 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.029
ω and ϕ scansθmax = 27.5°, θmin = 3.0°
Absorption correction: multi-scan
(SADABS; Bruker, 2003)
h = 1313
Tmin = 0.914, Tmax = 0.914k = 1515
22984 measured reflectionsl = 1011
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.027H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.070 w = 1/[σ2(Fo2) + (0.0283P)2 + 0.7457P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max = 0.001
2481 reflectionsΔρmax = 0.32 e Å3
160 parametersΔρmin = 0.39 e Å3
0 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.034 (2)
Crystal data top
C8H13N2O+·H2O4PV = 1083.20 (3) Å3
Mr = 250.19Z = 4
Monoclinic, P21/cMo Kα radiation
a = 10.7601 (2) ŵ = 0.26 mm1
b = 11.9724 (2) ÅT = 120 K
c = 8.9122 (1) Å0.35 × 0.35 × 0.35 mm
β = 109.3578 (11)°
Data collection top
Nonius KappaCCD
diffractometer
2481 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2003)
2282 reflections with I > 2σ(I)
Tmin = 0.914, Tmax = 0.914Rint = 0.029
22984 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0270 restraints
wR(F2) = 0.070H atoms treated by a mixture of independent and constrained refinement
S = 1.05Δρmax = 0.32 e Å3
2481 reflectionsΔρmin = 0.39 e Å3
160 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
xyzUiso*/Ueq
P10.16330 (3)0.71981 (2)0.04893 (3)0.00932 (11)
O10.07862 (8)0.63731 (7)0.09668 (10)0.01391 (19)
O20.27118 (8)0.77220 (7)0.18593 (10)0.0140 (2)
O30.07854 (9)0.81843 (7)0.05028 (11)0.01291 (19)
H10.0063 (18)0.8024 (13)0.103 (2)0.015*
O40.22776 (9)0.65744 (7)0.06218 (11)0.0161 (2)
H20.2383 (16)0.6904 (14)0.141 (2)0.019*
C10.59183 (12)0.75960 (10)0.22578 (14)0.0122 (2)
C20.54888 (12)0.65224 (10)0.17002 (15)0.0146 (2)
H2A0.45750.63510.13120.017*
C30.64144 (12)0.57163 (10)0.17232 (15)0.0149 (3)
H3A0.61460.49830.13450.018*
C40.77402 (12)0.59911 (10)0.23047 (15)0.0141 (2)
H4A0.83720.54340.23170.017*
C50.72734 (12)0.78147 (10)0.28192 (14)0.0108 (2)
C60.78105 (12)0.89447 (10)0.34491 (14)0.0116 (2)
H6A0.86300.88420.43630.014*
H6B0.71650.93290.38430.014*
C70.91019 (12)0.91808 (10)0.16085 (15)0.0149 (3)
H7A0.99090.90220.24960.022*
H7B0.92980.97080.08760.022*
H7C0.87570.84860.10430.022*
C80.68967 (12)1.00072 (11)0.09135 (15)0.0173 (3)
H8A0.71371.05130.01890.026*
H8B0.62861.03870.13510.026*
H8C0.64720.93390.03310.026*
N10.81642 (10)0.70141 (9)0.28498 (12)0.0124 (2)
N20.81024 (10)0.96771 (8)0.22321 (12)0.0112 (2)
H30.8478 (15)1.0340 (13)0.2821 (18)0.013*
O50.50784 (9)0.84319 (7)0.22640 (12)0.0173 (2)
H40.4285 (18)0.8154 (14)0.205 (2)0.021*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
P10.00841 (16)0.00994 (16)0.00926 (16)0.00023 (10)0.00246 (11)0.00080 (10)
O10.0108 (4)0.0137 (4)0.0159 (4)0.0009 (3)0.0026 (3)0.0048 (3)
O20.0093 (4)0.0201 (5)0.0121 (4)0.0032 (3)0.0029 (3)0.0024 (3)
O30.0098 (4)0.0108 (4)0.0162 (4)0.0004 (3)0.0017 (3)0.0024 (3)
O40.0211 (5)0.0158 (4)0.0132 (4)0.0059 (4)0.0083 (4)0.0017 (3)
C10.0109 (5)0.0129 (6)0.0131 (5)0.0009 (4)0.0044 (4)0.0011 (4)
C20.0116 (6)0.0153 (6)0.0162 (6)0.0027 (5)0.0038 (5)0.0005 (5)
C30.0165 (6)0.0120 (6)0.0154 (6)0.0016 (5)0.0041 (5)0.0011 (4)
C40.0134 (6)0.0128 (6)0.0155 (6)0.0018 (4)0.0041 (5)0.0003 (5)
C50.0109 (6)0.0118 (5)0.0098 (5)0.0006 (4)0.0036 (4)0.0006 (4)
C60.0115 (5)0.0123 (5)0.0111 (5)0.0012 (4)0.0042 (4)0.0015 (4)
C70.0151 (6)0.0136 (6)0.0191 (6)0.0001 (5)0.0100 (5)0.0007 (5)
C80.0131 (6)0.0184 (6)0.0169 (6)0.0006 (5)0.0001 (5)0.0033 (5)
N10.0110 (5)0.0130 (5)0.0124 (5)0.0006 (4)0.0029 (4)0.0004 (4)
N20.0106 (5)0.0099 (5)0.0123 (5)0.0007 (4)0.0029 (4)0.0009 (4)
O50.0084 (4)0.0138 (4)0.0298 (5)0.0003 (3)0.0065 (4)0.0026 (4)
Geometric parameters (Å, º) top
P1—O11.4980 (9)C5—N11.3493 (15)
P1—O21.5139 (9)C5—C61.5048 (16)
P1—O31.5726 (9)C6—N21.5066 (15)
P1—O41.5731 (9)C6—H6A0.9900
O3—H10.787 (18)C6—H6B0.9900
O4—H20.848 (18)C7—N21.4882 (15)
C1—O51.3497 (15)C7—H7A0.9800
C1—C21.4001 (17)C7—H7B0.9800
C1—C51.4005 (17)C7—H7C0.9800
C2—C31.3822 (17)C8—N21.4865 (15)
C2—H2A0.9500C8—H8A0.9800
C3—C41.3863 (17)C8—H8B0.9800
C3—H3A0.9500C8—H8C0.9800
C4—N11.3406 (16)N2—H30.963 (15)
C4—H4A0.9500O5—H40.877 (18)
O1—P1—O2114.83 (5)N2—C6—H6A108.8
O1—P1—O3111.14 (5)C5—C6—H6B108.8
O2—P1—O3106.81 (5)N2—C6—H6B108.8
O1—P1—O4107.61 (5)H6A—C6—H6B107.7
O2—P1—O4108.91 (5)N2—C7—H7A109.5
O3—P1—O4107.28 (5)N2—C7—H7B109.5
P1—O3—H1115.3 (12)H7A—C7—H7B109.5
P1—O4—H2120.8 (11)N2—C7—H7C109.5
O5—C1—C2122.65 (11)H7A—C7—H7C109.5
O5—C1—C5118.63 (11)H7B—C7—H7C109.5
C2—C1—C5118.72 (11)N2—C8—H8A109.5
C3—C2—C1118.97 (11)N2—C8—H8B109.5
C3—C2—H2A120.5H8A—C8—H8B109.5
C1—C2—H2A120.5N2—C8—H8C109.5
C2—C3—C4119.14 (11)H8A—C8—H8C109.5
C2—C3—H3A120.4H8B—C8—H8C109.5
C4—C3—H3A120.4C4—N1—C5119.18 (10)
N1—C4—C3122.46 (11)C8—N2—C7111.12 (10)
N1—C4—H4A118.8C8—N2—C6112.85 (9)
C3—C4—H4A118.8C7—N2—C6112.67 (9)
N1—C5—C1121.53 (11)C8—N2—H3108.1 (9)
N1—C5—C6116.66 (10)C7—N2—H3107.9 (9)
C1—C5—C6121.80 (11)C6—N2—H3103.7 (9)
C5—C6—N2113.62 (9)C1—O5—H4108.9 (11)
C5—C6—H6A108.8
O5—C1—C2—C3179.47 (11)N1—C5—C6—N285.24 (13)
C5—C1—C2—C30.03 (18)C1—C5—C6—N295.99 (13)
C1—C2—C3—C40.34 (18)C3—C4—N1—C50.77 (18)
C2—C3—C4—N10.02 (19)C1—C5—N1—C41.15 (17)
O5—C1—C5—N1179.75 (11)C6—C5—N1—C4179.93 (10)
C2—C1—C5—N10.79 (18)C5—C6—N2—C866.40 (13)
O5—C1—C5—C61.04 (17)C5—C6—N2—C760.45 (13)
C2—C1—C5—C6179.50 (11)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H1···N1i0.787 (18)1.955 (18)2.7243 (14)166 (2)
O4—H2···O2ii0.848 (18)1.749 (18)2.5813 (13)167 (2)
N2—H3···O1iii0.963 (15)1.661 (16)2.6187 (13)173 (1)
O5—H4···O20.877 (18)1.723 (18)2.5939 (12)172 (2)
C6—H6A···O1iv0.992.303.2663 (15)165
Symmetry codes: (i) x1, y+3/2, z1/2; (ii) x, y+3/2, z1/2; (iii) x+1, y+1/2, z+1/2; (iv) x+1, y+3/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC8H13N2O+·H2O4P
Mr250.19
Crystal system, space groupMonoclinic, P21/c
Temperature (K)120
a, b, c (Å)10.7601 (2), 11.9724 (2), 8.9122 (1)
β (°) 109.3578 (11)
V3)1083.20 (3)
Z4
Radiation typeMo Kα
µ (mm1)0.26
Crystal size (mm)0.35 × 0.35 × 0.35
Data collection
DiffractometerNonius KappaCCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2003)
Tmin, Tmax0.914, 0.914
No. of measured, independent and
observed [I > 2σ(I)] reflections
22984, 2481, 2282
Rint0.029
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.027, 0.070, 1.05
No. of reflections2481
No. of parameters160
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.32, 0.39

Computer programs: Collect (Nonius, 1998), HKL SCALEPACK (Otwinowski & Minor ,1997), HKL DENZO (Otwinowski & Minor, 1997) and SCALEPACK, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), SHELXL97.

Selected geometric parameters (Å, º) top
P1—O11.4980 (9)P1—O31.5726 (9)
P1—O21.5139 (9)P1—O41.5731 (9)
O1—P1—O2114.83 (5)O1—P1—O4107.61 (5)
O1—P1—O3111.14 (5)O2—P1—O4108.91 (5)
O2—P1—O3106.81 (5)O3—P1—O4107.28 (5)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H1···N1i0.787 (18)1.955 (18)2.7243 (14)166 (2)
O4—H2···O2ii0.848 (18)1.749 (18)2.5813 (13)167 (2)
N2—H3···O1iii0.963 (15)1.661 (16)2.6187 (13)173 (1)
O5—H4···O20.877 (18)1.723 (18)2.5939 (12)172 (2)
C6—H6A···O1iv0.992.303.2663 (15)165
Symmetry codes: (i) x1, y+3/2, z1/2; (ii) x, y+3/2, z1/2; (iii) x+1, y+1/2, z+1/2; (iv) x+1, y+3/2, z+1/2.
 

Acknowledgements

The authors thank Ondokuz Mayis University for financial support and the EPSRC National Crystallography Service (University of Southampton, England) for the data collection.

References

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