(3-Hydr­­oxy-2-pyridylmeth­yl)di­methyl­ammonium di­hydrogenphosphate

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; 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 ammonium 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 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 (to atoms O3 and O4) show the expected lengthening (Table 1) 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, 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 + , 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 π–π stacking inter­actions are present in (I).

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 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 + , z + ; (ii) x + 1, −y + , z + ; (iii) x, y, z + 1.]

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 − , −z + .]

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⁻

• M_r = 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) ų

• Z = 4

• D_x = 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)T_min = 0.914, T_max = 0.914

• 22984 measured reflections

• 2481 independent reflections

• 2282 reflections with I > 2σ(I)

• R_int = 0.029

• θ_max = 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(F_o²) + (0.0283P)² + 0.7457P] where P = (F_o² + 2F_c²)/3

• (Δ/σ)_max = 0.001

• Δρ_max = 0.32 e Å⁻³

• Δρ_min = −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	D⋯A	D—H⋯A
O3—H1⋯N1^v	0.787 (18)	1.955 (18)	2.7243 (14)	166 (2)
O4—H2⋯O2^vi	0.848 (18)	1.749 (18)	2.5813 (13)	167 (2)
N2—H3⋯O1^vii	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⋯O1^ii	0.99	2.30	3.2663 (15)	165
Symmetry codes: (ii) ; (v) ; (vi) ; (vii) .

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 U_iso(H) = 1.2U_eq(carrier) or 1.5U_eq(methyl carrier) was applied and the methyl groups were allowed to rotate to fit the electron density.

Data collection: COLLECT (Nonius, 1998); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: 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.

Supporting information

S1. 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; 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···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, 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 π–π stacking interactions are present in (I).

S2. Experimental

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.

S3. Refinement

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 U_iso(H) = 1.2U_eq(carrier) or 1.5U_eq(methyl carrier) was applied and the methyl groups were allowed to rotate to fit the electron density.

Computing details

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

	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.
	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.]
	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

Crystal data

C8H13N2O^+·H2O4P^−	F(000) = 528
Mr = 250.19	Dx = 1.534 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4901 reflections
a = 10.7601 (2) Å	θ = 2.9–27.5°
b = 11.9724 (2) Å	µ = 0.26 mm^−1
c = 8.9122 (1) Å	T = 120 K
β = 109.3578 (11)°	Cube, colourless
V = 1083.20 (3) Å^3	0.35 × 0.35 × 0.35 mm
Z = 4

Data collection

Nonius KappaCCD diffractometer	2481 independent reflections
Radiation source: fine-focus sealed tube	2282 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
ω and ϕ scans	θmax = 27.5°, θmin = 3.0°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −13→13
Tmin = 0.914, Tmax = 0.914	k = −15→15
22984 measured reflections	l = −10→11

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.027	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.070	w = 1/[σ^2(Fo^2) + (0.0283P)^2 + 0.7457P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.001
2481 reflections	Δρmax = 0.32 e Å^−3
160 parameters	Δρmin = −0.39 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.034 (2)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
P1	0.16330 (3)	0.71981 (2)	0.04893 (3)	0.00932 (11)
O1	0.07862 (8)	0.63731 (7)	0.09668 (10)	0.01391 (19)
O2	0.27118 (8)	0.77220 (7)	0.18593 (10)	0.0140 (2)
O3	0.07854 (9)	0.81843 (7)	−0.05028 (11)	0.01291 (19)
H1	0.0063 (18)	0.8024 (13)	−0.103 (2)	0.015*
O4	0.22776 (9)	0.65744 (7)	−0.06218 (11)	0.0161 (2)
H2	0.2383 (16)	0.6904 (14)	−0.141 (2)	0.019*
C1	0.59183 (12)	0.75960 (10)	0.22578 (14)	0.0122 (2)
C2	0.54888 (12)	0.65224 (10)	0.17002 (15)	0.0146 (2)
H2A	0.4575	0.6351	0.1312	0.017*
C3	0.64144 (12)	0.57163 (10)	0.17232 (15)	0.0149 (3)
H3A	0.6146	0.4983	0.1345	0.018*
C4	0.77402 (12)	0.59911 (10)	0.23047 (15)	0.0141 (2)
H4A	0.8372	0.5434	0.2317	0.017*
C5	0.72734 (12)	0.78147 (10)	0.28192 (14)	0.0108 (2)
C6	0.78105 (12)	0.89447 (10)	0.34491 (14)	0.0116 (2)
H6A	0.8630	0.8842	0.4363	0.014*
H6B	0.7165	0.9329	0.3843	0.014*
C7	0.91019 (12)	0.91808 (10)	0.16085 (15)	0.0149 (3)
H7A	0.9909	0.9022	0.2496	0.022*
H7B	0.9298	0.9708	0.0876	0.022*
H7C	0.8757	0.8486	0.1043	0.022*
C8	0.68967 (12)	1.00072 (11)	0.09135 (15)	0.0173 (3)
H8A	0.7137	1.0513	0.0189	0.026*
H8B	0.6286	1.0387	0.1351	0.026*
H8C	0.6472	0.9339	0.0331	0.026*
N1	0.81642 (10)	0.70141 (9)	0.28498 (12)	0.0124 (2)
N2	0.81024 (10)	0.96771 (8)	0.22321 (12)	0.0112 (2)
H3	0.8478 (15)	1.0340 (13)	0.2821 (18)	0.013*
O5	0.50784 (9)	0.84319 (7)	0.22640 (12)	0.0173 (2)
H4	0.4285 (18)	0.8154 (14)	0.205 (2)	0.021*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P1	0.00841 (16)	0.00994 (16)	0.00926 (16)	0.00023 (10)	0.00246 (11)	0.00080 (10)
O1	0.0108 (4)	0.0137 (4)	0.0159 (4)	−0.0009 (3)	0.0026 (3)	0.0048 (3)
O2	0.0093 (4)	0.0201 (5)	0.0121 (4)	−0.0032 (3)	0.0029 (3)	−0.0024 (3)
O3	0.0098 (4)	0.0108 (4)	0.0162 (4)	0.0004 (3)	0.0017 (3)	0.0024 (3)
O4	0.0211 (5)	0.0158 (4)	0.0132 (4)	0.0059 (4)	0.0083 (4)	0.0017 (3)
C1	0.0109 (5)	0.0129 (6)	0.0131 (5)	0.0009 (4)	0.0044 (4)	0.0011 (4)
C2	0.0116 (6)	0.0153 (6)	0.0162 (6)	−0.0027 (5)	0.0038 (5)	−0.0005 (5)
C3	0.0165 (6)	0.0120 (6)	0.0154 (6)	−0.0016 (5)	0.0041 (5)	−0.0011 (4)
C4	0.0134 (6)	0.0128 (6)	0.0155 (6)	0.0018 (4)	0.0041 (5)	−0.0003 (5)
C5	0.0109 (6)	0.0118 (5)	0.0098 (5)	−0.0006 (4)	0.0036 (4)	0.0006 (4)
C6	0.0115 (5)	0.0123 (5)	0.0111 (5)	−0.0012 (4)	0.0042 (4)	−0.0015 (4)
C7	0.0151 (6)	0.0136 (6)	0.0191 (6)	−0.0001 (5)	0.0100 (5)	−0.0007 (5)
C8	0.0131 (6)	0.0184 (6)	0.0169 (6)	−0.0006 (5)	0.0001 (5)	0.0033 (5)
N1	0.0110 (5)	0.0130 (5)	0.0124 (5)	0.0006 (4)	0.0029 (4)	0.0004 (4)
N2	0.0106 (5)	0.0099 (5)	0.0123 (5)	−0.0007 (4)	0.0029 (4)	−0.0009 (4)
O5	0.0084 (4)	0.0138 (4)	0.0298 (5)	0.0003 (3)	0.0065 (4)	−0.0026 (4)

Geometric parameters (Å, º)

P1—O1	1.4980 (9)	C5—N1	1.3493 (15)
P1—O2	1.5139 (9)	C5—C6	1.5048 (16)
P1—O3	1.5726 (9)	C6—N2	1.5066 (15)
P1—O4	1.5731 (9)	C6—H6A	0.9900
O3—H1	0.787 (18)	C6—H6B	0.9900
O4—H2	0.848 (18)	C7—N2	1.4882 (15)
C1—O5	1.3497 (15)	C7—H7A	0.9800
C1—C2	1.4001 (17)	C7—H7B	0.9800
C1—C5	1.4005 (17)	C7—H7C	0.9800
C2—C3	1.3822 (17)	C8—N2	1.4865 (15)
C2—H2A	0.9500	C8—H8A	0.9800
C3—C4	1.3863 (17)	C8—H8B	0.9800
C3—H3A	0.9500	C8—H8C	0.9800
C4—N1	1.3406 (16)	N2—H3	0.963 (15)
C4—H4A	0.9500	O5—H4	0.877 (18)
O1—P1—O2	114.83 (5)	N2—C6—H6A	108.8
O1—P1—O3	111.14 (5)	C5—C6—H6B	108.8
O2—P1—O3	106.81 (5)	N2—C6—H6B	108.8
O1—P1—O4	107.61 (5)	H6A—C6—H6B	107.7
O2—P1—O4	108.91 (5)	N2—C7—H7A	109.5
O3—P1—O4	107.28 (5)	N2—C7—H7B	109.5
P1—O3—H1	115.3 (12)	H7A—C7—H7B	109.5
P1—O4—H2	120.8 (11)	N2—C7—H7C	109.5
O5—C1—C2	122.65 (11)	H7A—C7—H7C	109.5
O5—C1—C5	118.63 (11)	H7B—C7—H7C	109.5
C2—C1—C5	118.72 (11)	N2—C8—H8A	109.5
C3—C2—C1	118.97 (11)	N2—C8—H8B	109.5
C3—C2—H2A	120.5	H8A—C8—H8B	109.5
C1—C2—H2A	120.5	N2—C8—H8C	109.5
C2—C3—C4	119.14 (11)	H8A—C8—H8C	109.5
C2—C3—H3A	120.4	H8B—C8—H8C	109.5
C4—C3—H3A	120.4	C4—N1—C5	119.18 (10)
N1—C4—C3	122.46 (11)	C8—N2—C7	111.12 (10)
N1—C4—H4A	118.8	C8—N2—C6	112.85 (9)
C3—C4—H4A	118.8	C7—N2—C6	112.67 (9)
N1—C5—C1	121.53 (11)	C8—N2—H3	108.1 (9)
N1—C5—C6	116.66 (10)	C7—N2—H3	107.9 (9)
C1—C5—C6	121.80 (11)	C6—N2—H3	103.7 (9)
C5—C6—N2	113.62 (9)	C1—O5—H4	108.9 (11)
C5—C6—H6A	108.8
O5—C1—C2—C3	179.47 (11)	N1—C5—C6—N2	85.24 (13)
C5—C1—C2—C3	0.03 (18)	C1—C5—C6—N2	−95.99 (13)
C1—C2—C3—C4	0.34 (18)	C3—C4—N1—C5	−0.77 (18)
C2—C3—C4—N1	0.02 (19)	C1—C5—N1—C4	1.15 (17)
O5—C1—C5—N1	179.75 (11)	C6—C5—N1—C4	179.93 (10)
C2—C1—C5—N1	−0.79 (18)	C5—C6—N2—C8	66.40 (13)
O5—C1—C5—C6	1.04 (17)	C5—C6—N2—C7	−60.45 (13)
C2—C1—C5—C6	−179.50 (11)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H1···N1^i	0.787 (18)	1.955 (18)	2.7243 (14)	166 (2)
O4—H2···O2^ii	0.848 (18)	1.749 (18)	2.5813 (13)	167 (2)
N2—H3···O1^iii	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···O1^iv	0.99	2.30	3.2663 (15)	165

Symmetry codes: (i) x−1, −y+3/2, z−1/2; (ii) x, −y+3/2, z−1/2; (iii) −x+1, y+1/2, −z+1/2; (iv) x+1, −y+3/2, z+1/2.