4-Pyridone-terephthalic acid-water (2/1/2) and bis­(3-hy­droxy­pyridinium) terephthalate

4-Hy­droxy­pyridine and terephthalic acid cocrystallize as a hy­drate, 4-pyridone-terephthalic acid-water (2/1/2), 2C₅H₅NO·C₈H₆O₄·2H₂O, from a methanol-water solution. The mol­ecules form a two-dimensional hydrogen-bonded network resulting in sheets of hydrogen-bonded mol­ecules that lie parallel to the (10) plane. In contrast, 3-hy­droxy­pyridine and terephthalic acid form the salt bis­(3-hy­droxy­pyridinium) terephthalate, 2C₅H₆NO⁺·C₈H₄O₄^2-, giving rise to two-dimensional hydrogen-bonded sheets extending through the lattice parallel to the (10) plane.

S1. Comment

Crystal engineering is a rapidly evolving field of chemistry that relies on intermolecular interactions such as hydrogen-bonds to form new materials (Desiraju, 2003). The cocrystallization of two dissimilar compounds has led to a wide body of work (see, for example, Bucar et al., 2007; MacGillivray, 2008; Ugono et al., 2011). Subtle differences in electronegativity and pK_a can influence the packing arrangement of these cocrystallant molecules (Aakeröy et al., 2009). Terephthalic acid has been used successfully as a co-crystallant in crystal engineering studies (Lemmerer, 2011). Both 3- and 4-hydroxypyridine and derivatives thereof have been incorporated as linker and spacer molecules in metal–organic frameworks (Castillo et al., 2001; Gao et al., 2006). Here, we present the structural study of the combination of terephthalic acid with 3-hydroxypyridine and 4-hydroxypyridine.

Terephthalic acid and 4-hydroxypyridine were found to cocrystallize with a water molecule in the lattice, viz. 4-pyridone–terephthalic acid–water (2/1/2), (I) (Fig. 1). 4-Hydroxypyridine was found to rearrange to 4-pyridone, a rearrangement which has been previously reported (Tyl et al., 2008). The 4-pyridone molecule presented here displays identical derived parameters to that of Tyl's work. The terephthalic acid crystallizes on a centre of symmetry at (1/2, 1/2, 1/2).

The terephthalic acid forms hydrogen-bonded chains incorporating the water molecule that extend parallel to the b axis. The 4-pyridone also forms hydrogen-bonded chains, with hydrogen bonds from the N atom to the pyridone O atom of an adjacent pyridone molecule (Table 1 and Fig. 2a). The water H atom not involved in the carboxylic acid chain forms a hydrogen bond to the pyridone O atom, linking the two chains together. This results in two-dimensional sheets of hydrogen-bonded molecules extending through the lattice parallel to the [101] plane (Fig. 2b).

Similarly, terephthalic acid and 3-hydroxypyridine were also found to cocrystallize, as bis(3-hydroxypyridinium) terephthalate, (II) (Fig. 3). This mixture has been previously reported as a room-temperature analysis [Yao et al., 2008; Cambridge Structural Database (CSD, Version 5.32?; Allen, 2002) refcode DIWXOX]. The derived metrics reported here are similar to those found within Yao's work. As expected, upon cooling there is distortion of the unit cell, with a and c contracting [4.9245 (4) and 10.3256 (9) Å, respectively, compared with 4.978 (1) and 10.623 (1) Å in Yao's work]. However, the b axis remains the same and β distorts significantly [b = 15.7128 (14) Å and β = 98.386 (5)° in this work, compared with b = 15.705 (3) Å and β = 100.20 (1)° in Yao's work]. These distortions of the unit cell are not readily recognized by data-mining software and the values reported here expand the current body of information regarding (II). The cocrystallization of (II) was also found to occur under milder conditions than those previously reported (see Experimental for details, cf. hydrothermal techniques for Yao's synthesis). Presumably, the 3-hydroxypyridine is a strong enough Lewis base to abstract the H atom from the carboxylic acid under ambient conditions [pK_a(3-hydroxypyridine) = 4.80 (Güven, 2005); pK_a(terephthalic acid) = 3.51 and 4.82 (Braude & Nachod, 1955)].

Unlike (I), water is not incorporated into the lattice of (II) and it is a purely binary cocrystal. Similar to (I), the terephthalate in (II) is found to crystallize about an inversion centre at (0, 1/2, 0). Presumably due to electronic constraints, the 3-hydroxypyridine does not rearrange to form a pyridone. Instead, 3-hydroxypyridine abstracts the carboxyl H atom from terephthalic acid, forming a cation–anion pair. Unlike 4-hydoxypyridine, which can rearrange and localize its formal electronic structure to the pyridone, 3-hydroxypyridine cannot readily localize the aromatic bonds to incorporate a carbonyl group at the 3-position. Hence, it retains the 3-hydroxy substituent and forms a cation. A similar hydrogen abstraction was observed by Lemmerer (2011), wherein a series of primary amines were cocrystallized with terephthalic acid yielding similar cation–anion pairs.

One carboxylate O atom of (II) (O2) accepts a hydrogen bond from the pyridinium N atom related by the c-glide plane. Atom O3 accepts a hydrogen bond from the hydroxy O atom (O1) of the 3-hydroxypyridinium cation. This generates a two-dimensional sheet of hydrogen-bonded molecules (Fig. 4a). Formally, the framework is a 2,4-connected square net, with the pyridinium forming the edges of the square and the terephthalate the corners (analysis using TOPOS; Blatov, 2006). The sheets lie in a plane parallel to the [201] crystallographic plane. The topology viewed along the [201] plane is depicted in Fig. 4(b).

In the previous characterization (Yao et al., 2008), the dihedral angle formed by the pyridinium and benzene rings was reported to be 2.2°. Yao et al. appear to have overlooked the extended packing of (II) in their report. The compounds form a two-dimensional network (described above), yielding additional information about the intermolecular geometry. For example, the interplanar angle formed by the terephthalate and the pyridinium moiety is dependent upon the choice of location of the pyridinium and terephthalate within the lattice. We found that the plane of one pyridinium cation within the network forms one angle perpendicular to the plane of the benzene ring of the terephthalate [angle formed by the planes of the pyrinidium and benzene rings = 78.79 (7)°] and one that is closer to coplanar with the benzene ring [interplanar angle = 9.61 (16)°]. This choice depends on which hydrogen-bonding group (amide or hydroxy) is selected as the orienting group.

Related literature

For related literature, see: Aakeröy et al. (2009); Allen (2002); Blatov (2006); Braude & Nachod (1955); Bucar et al. (2007); Castillo et al. (2001); Desiraju (2003); Güven (2005); Gao et al. (2006); Lemmerer (2011); MacGillivray (2008); Tyl et al. (2008); Ugono et al. (2011); Yao et al. (2008).

S2. Experimental

To 4-hydryoxypyridine (12 mg) and terephthalic acid (15 mg) were added methanol (5 ml) and water (5 ml) in a 20 ml vial. This solution was allowed to evaporate and colourless blade-like crystals of (I) were harvested. In the same manner, 3-hydroxypyridine (27 mg) and therephthalic acid (33 mg) were dissolved in methanol (5 ml) and water (5 ml) in a 20 ml vial and the solvents allowed to evaporate. Colourless columnar crystals of (II) were harvested.

S3. Refinement

All C-bound H atoms were included in geometrically calculated positions, with C—H = 0.95 Å. The pyridone, carboxylic acid, water and hydroxy H atoms were initially located from a difference Fourier map in positions that form good hydrogen bonds to nearby acceptors. Water O—H distances were restrained to 0.84 (1) Å, carboxylic acid and hydroxy O—H distances were constrained to 0.84 Å and amine N—H distances were constrained to 0.88 Å. All O-bound H atoms were refined with U_iso(H) = 1.5U_eq(O). All other H atoms were refined with U_iso(H) = 1.2U_eq(parent atom).

Computing details

For both compounds, data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP (Sheldrick, 2008), POV-RAY (Cason, 2003) and DIAMOND (Brandenburg, 2009). Software used to prepare material for publication: XCIF (Sheldrick, 2008), enCIFer (Allen et al., 2004) and publCIF (Westrip, 2010) for (I); XCIF (Sheldrick, 2008), enCIFer (Allen et al., 2004), publCIF (Westrip, 2010) and TOPOS (Blatov, 2006) for (II).

Figures

	Fig. 1. The atom-labelling scheme for (I). Displacement ellipsoids are depicted at the 50% probability level. [Symmetry code: (i) -x + 1, -y + 1, -z + 1.]
	Fig. 2. Packing diagrams for (I), viewed (a) along the a axis, depicting one layer of the two-dimensional network, and (b) along the b axis, depicting the two-dimensional sheets running parallel to the [101] plane. Hydrogen bonds are represented by dashed lines.
	Fig. 3. The atom-abelling scheme for (II). Displacement ellipsoids are depicted at the 50% probability level. [Symmetry code: (iv) -x + 1, -y + 1, -z.]
	Fig. 4. Packing diagrams for (II), viewed (a) along the a axis of the square net subunit within the layers and (b) along the [201] plane, showing the overall packing of the sheets (in the electronic version of the paper, alternate sheets are coloured blue and gold for clarity). Hydrogen bonds are represented by dashed lines.

(I) 4-Pyridone–terephthalic acid–water (2/1/2)

Crystal data

2C5H5NO·C8H6O4·2H2O	F(000) = 412
Mr = 392.36	Dx = 1.468 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1679 reflections
a = 10.412 (2) Å	θ = 3.3–22.3°
b = 11.994 (3) Å	µ = 0.12 mm^−1
c = 7.1077 (17) Å	T = 120 K
β = 90.743 (4)°	Blade, colourless
V = 887.6 (4) Å^3	0.23 × 0.05 × 0.02 mm
Z = 2

Data collection

Bruker APEXII Kappa X8 area-detector diffractometer	2214 independent reflections
Radiation source: fine-focus sealed tube	1589 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.070
Detector resolution: 8.33 pixels mm^-1	θmax = 28.4°, θmin = 2.0°
combination of ω and ϕ scans	h = −13→13
Absorption correction: numerical (SADABS; Sheldrick, 2008)	k = −16→15
Tmin = 0.907, Tmax = 1.000	l = −9→9
15289 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.104	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0387P)^2 + 0.353P] where P = (Fo^2 + 2Fc^2)/3
2214 reflections	(Δ/σ)max = 0.001
134 parameters	Δρmax = 0.26 e Å^−3
2 restraints	Δρmin = −0.27 e Å^−3

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.

Hydrogen atoms bonded to carbon were placed in geometric positions with C—H bonded distances constrained to 0.95 Å. Water, hydroxyl, and carboxylic acid H atoms were included initially in their observed positions. Water H atoms were restrained to have O—H distances of 0.84 (1) Å while the carboxylic acid and amine N atoms were refined with distances constrained to 0.84 and 0.88 Å, respectively. Thermal perameters of water and carboxylic acid H atoms were constrained to be 1.5 × the U_eq of the oxygen to which they are bonded. The thermal perameters of all remaining H atoms were constrained to be 1.2 × the U_eq of the atom to which they are bonded.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O1	0.12796 (12)	0.03948 (10)	0.35315 (18)	0.0213 (3)
O2	0.63524 (11)	0.22373 (10)	0.42134 (18)	0.0198 (3)
H2	0.6367	0.1537	0.4250	0.030*
O3	0.44719 (11)	0.19946 (10)	0.56596 (18)	0.0200 (3)
O4	0.67459 (12)	0.01180 (10)	0.41366 (19)	0.0211 (3)
H4Y	0.6180 (16)	−0.0389 (14)	0.411 (3)	0.032*
H4Z	0.7349 (15)	−0.0067 (17)	0.488 (2)	0.032*
N1	−0.01048 (14)	0.35054 (12)	0.24445 (19)	0.0172 (3)
H1N	−0.0397	0.4179	0.2194	0.021*
C2	0.11007 (16)	0.33728 (14)	0.3134 (2)	0.0174 (4)
H2A	0.1621	0.4012	0.3343	0.021*
C3	0.15869 (16)	0.23485 (14)	0.3534 (2)	0.0163 (4)
H3A	0.2434	0.2281	0.4036	0.020*
C4	0.08341 (16)	0.13732 (14)	0.3207 (2)	0.0157 (4)
C5	−0.04364 (16)	0.15581 (14)	0.2505 (2)	0.0176 (4)
H5A	−0.0991	0.0941	0.2292	0.021*
C6	−0.08636 (16)	0.26089 (14)	0.2138 (2)	0.0178 (4)
H6A	−0.1711	0.2714	0.1658	0.021*
C7	0.52848 (16)	0.26034 (14)	0.4995 (2)	0.0154 (3)
C8	0.51602 (16)	0.38450 (14)	0.4988 (2)	0.0151 (3)
C9	0.60678 (16)	0.45297 (14)	0.4148 (2)	0.0169 (4)
H9A	0.6798	0.4210	0.3569	0.020*
C10	0.40925 (17)	0.43222 (14)	0.5845 (2)	0.0179 (4)
H10A	0.3473	0.3858	0.6425	0.022*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0190 (6)	0.0135 (6)	0.0313 (7)	0.0022 (5)	−0.0043 (5)	−0.0011 (5)
O2	0.0199 (6)	0.0115 (6)	0.0280 (7)	0.0018 (5)	0.0023 (5)	0.0001 (5)
O3	0.0184 (6)	0.0145 (6)	0.0272 (7)	−0.0025 (5)	0.0007 (5)	0.0028 (5)
O4	0.0196 (7)	0.0136 (6)	0.0298 (7)	−0.0002 (5)	−0.0071 (6)	0.0008 (5)
N1	0.0195 (7)	0.0131 (7)	0.0189 (7)	0.0039 (6)	−0.0001 (6)	0.0013 (6)
C2	0.0177 (8)	0.0163 (9)	0.0181 (8)	−0.0030 (7)	−0.0008 (7)	−0.0011 (7)
C3	0.0145 (8)	0.0173 (9)	0.0173 (8)	−0.0005 (7)	0.0002 (7)	0.0001 (7)
C4	0.0163 (8)	0.0154 (8)	0.0155 (8)	0.0011 (6)	0.0024 (7)	−0.0001 (6)
C5	0.0166 (8)	0.0166 (9)	0.0196 (9)	−0.0036 (7)	−0.0004 (7)	−0.0007 (7)
C6	0.0153 (8)	0.0201 (9)	0.0181 (8)	0.0004 (7)	−0.0003 (7)	0.0009 (7)
C7	0.0142 (8)	0.0160 (8)	0.0159 (8)	0.0019 (7)	−0.0050 (7)	−0.0013 (7)
C8	0.0159 (8)	0.0134 (8)	0.0159 (8)	−0.0002 (6)	−0.0026 (6)	−0.0006 (7)
C9	0.0144 (8)	0.0159 (8)	0.0206 (9)	−0.0001 (7)	0.0013 (7)	−0.0002 (7)
C10	0.0167 (8)	0.0170 (9)	0.0202 (9)	−0.0033 (7)	0.0016 (7)	0.0012 (7)

Geometric parameters (Å, º)

O1—C4	1.282 (2)	C9—C10^i	1.387 (2)
O2—C7	1.324 (2)	C10—C9^i	1.387 (2)
O3—C7	1.218 (2)	O2—H2	0.8400
N1—C6	1.350 (2)	O4—H4Y	0.846 (9)
N1—C2	1.351 (2)	O4—H4Z	0.847 (9)
C2—C3	1.358 (2)	N1—H1N	0.8800
C3—C4	1.426 (2)	C2—H2A	0.9500
C4—C5	1.425 (2)	C3—H3A	0.9500
C5—C6	1.361 (2)	C5—H5A	0.9500
C7—C8	1.495 (2)	C6—H6A	0.9500
C8—C9	1.392 (2)	C9—H9A	0.9500
C8—C10	1.397 (2)	C10—H10A	0.9500
C6—N1—C2	120.25 (15)	C7—O2—H2	109.5
N1—C2—C3	121.66 (16)	H4Y—O4—H4Z	110 (2)
C2—C3—C4	120.37 (16)	C6—N1—H1N	119.9
O1—C4—C5	122.52 (16)	C2—N1—H1N	119.9
O1—C4—C3	121.67 (16)	N1—C2—H2A	119.2
C5—C4—C3	115.81 (15)	C3—C2—H2A	119.2
C6—C5—C4	120.73 (16)	C2—C3—H3A	119.8
N1—C6—C5	121.17 (16)	C4—C3—H3A	119.8
O3—C7—O2	123.74 (15)	C6—C5—H5A	119.6
O3—C7—C8	122.55 (15)	C4—C5—H5A	119.6
O2—C7—C8	113.71 (14)	N1—C6—H6A	119.4
C9—C8—C10	119.57 (16)	C5—C6—H6A	119.4
C9—C8—C7	121.99 (15)	C10^i—C9—H9A	119.9
C10—C8—C7	118.43 (15)	C8—C9—H9A	119.9
C10^i—C9—C8	120.11 (16)	C9^i—C10—H10A	119.8
C9^i—C10—C8	120.32 (16)	C8—C10—H10A	119.8
C6—N1—C2—C3	0.1 (2)	O3—C7—C8—C9	−177.02 (16)
N1—C2—C3—C4	1.0 (3)	O2—C7—C8—C9	2.8 (2)
C2—C3—C4—O1	178.36 (16)	O3—C7—C8—C10	2.6 (2)
C2—C3—C4—C5	−1.8 (2)	O2—C7—C8—C10	−177.56 (15)
O1—C4—C5—C6	−178.49 (16)	C10—C8—C9—C10^i	−0.3 (3)
C3—C4—C5—C6	1.7 (2)	C7—C8—C9—C10^i	179.28 (16)
C2—N1—C6—C5	−0.2 (2)	C9—C8—C10—C9^i	0.3 (3)
C4—C5—C6—N1	−0.7 (3)	C7—C8—C10—C9^i	−179.30 (16)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O4	0.84	1.75	2.5753 (17)	167
O4—H4Y···O3^ii	0.85 (1)	2.05 (1)	2.8379 (18)	155 (2)
O4—H4Z···O1^ii	0.85 (1)	1.85 (1)	2.6951 (18)	176 (2)
N1—H1N···O1^iii	0.88	1.80	2.6628 (19)	168

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

(II) bis(3-hydroxypyridinium) terephthalate

Crystal data

2C5H6NO^+·C8H4O4^2^−	F(000) = 372
Mr = 356.33	Dx = 1.497 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6172 reflections
a = 4.9245 (4) Å	θ = 2.4–28.2°
b = 15.7128 (14) Å	µ = 0.11 mm^−1
c = 10.3256 (9) Å	T = 120 K
β = 98.386 (5)°	Columnar, colourless
V = 790.43 (12) Å^3	0.25 × 0.23 × 0.15 mm
Z = 2

Data collection

Bruker APEXII Kappa X8 area-detector diffractometer	1979 independent reflections
Radiation source: fine-focus sealed tube	1735 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.024
Detector resolution: 8.33 pixels mm^-1	θmax = 28.4°, θmin = 2.4°
combination of ω and ϕ scans	h = −6→6
Absorption correction: numerical (SADABS; Sheldrick, 2008)	k = −21→20
Tmin = 0.927, Tmax = 1.000	l = −13→13
16777 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.094	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0484P)^2 + 0.3112P] where P = (Fo^2 + 2Fc^2)/3
1979 reflections	(Δ/σ)max < 0.001
119 parameters	Δρmax = 0.37 e Å^−3
0 restraints	Δρmin = −0.22 e Å^−3

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.

Hydrogen atoms bonded to carbon were placed in geometric positions with C—H bonded distances constrained to 0.95 Å. Amide and hydroxyl H atoms were included in their observed positions and were subsequently refined with O—H and N—H distances constrained to 0.84 and 0.88 Å, respectively. The hydroxyl hydrogen thermal parameters were tied to be 1.5 × the U_eq of the oxygen to which they are bonded, all remaining hydrogen thermal parameters were set to 1.2 × U_eq of the atom to which they are bonded.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O1	0.10205 (17)	0.40959 (6)	0.35614 (8)	0.0250 (2)
H1O	0.1087	0.3861	0.2836	0.037*
N1	0.67723 (18)	0.28650 (6)	0.50705 (9)	0.0181 (2)
H1N	0.7822	0.2446	0.4869	0.022*
O2	−0.01389 (17)	0.33229 (5)	−0.07064 (8)	0.02153 (19)
C2	0.4745 (2)	0.31338 (7)	0.41693 (10)	0.0181 (2)
H2A	0.4448	0.2871	0.3332	0.022*
O3	0.13620 (16)	0.32831 (5)	0.14238 (8)	0.02073 (19)
C3	0.3062 (2)	0.37982 (7)	0.44493 (10)	0.0185 (2)
C4	0.3529 (2)	0.41592 (7)	0.56924 (11)	0.0217 (2)
H4A	0.2397	0.4610	0.5915	0.026*
C5	0.5648 (2)	0.38580 (7)	0.66004 (11)	0.0221 (2)
H5A	0.5981	0.4101	0.7451	0.027*
C6	0.7282 (2)	0.32029 (7)	0.62669 (11)	0.0204 (2)
H6A	0.8754	0.2995	0.6883	0.024*
C7	0.1356 (2)	0.35924 (7)	0.03023 (10)	0.0164 (2)
C8	0.3251 (2)	0.43209 (6)	0.01420 (10)	0.0155 (2)
C9	0.2775 (2)	0.48412 (7)	−0.09551 (10)	0.0165 (2)
H9A	0.1250	0.4733	−0.1610	0.020*
C10	0.5487 (2)	0.44838 (7)	0.10982 (10)	0.0170 (2)
H10A	0.5822	0.4131	0.1852	0.020*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0237 (4)	0.0306 (4)	0.0190 (4)	0.0095 (3)	−0.0028 (3)	−0.0004 (3)
N1	0.0187 (4)	0.0176 (4)	0.0182 (4)	0.0028 (3)	0.0029 (3)	0.0001 (3)
O2	0.0235 (4)	0.0235 (4)	0.0165 (4)	−0.0080 (3)	−0.0005 (3)	−0.0008 (3)
C2	0.0193 (5)	0.0192 (5)	0.0157 (5)	0.0003 (4)	0.0021 (4)	−0.0004 (4)
O3	0.0232 (4)	0.0214 (4)	0.0166 (4)	−0.0049 (3)	−0.0003 (3)	0.0028 (3)
C3	0.0169 (5)	0.0206 (5)	0.0174 (5)	0.0013 (4)	0.0010 (4)	0.0021 (4)
C4	0.0231 (5)	0.0213 (5)	0.0208 (5)	0.0045 (4)	0.0037 (4)	−0.0017 (4)
C5	0.0242 (5)	0.0249 (5)	0.0167 (5)	0.0028 (4)	0.0012 (4)	−0.0042 (4)
C6	0.0193 (5)	0.0236 (5)	0.0175 (5)	0.0021 (4)	−0.0002 (4)	−0.0004 (4)
C7	0.0155 (5)	0.0164 (5)	0.0171 (5)	0.0006 (4)	0.0020 (4)	−0.0007 (4)
C8	0.0148 (5)	0.0161 (5)	0.0159 (5)	0.0003 (3)	0.0031 (4)	−0.0019 (4)
C9	0.0143 (4)	0.0203 (5)	0.0142 (5)	0.0002 (4)	0.0000 (3)	−0.0016 (4)
C10	0.0172 (5)	0.0183 (5)	0.0153 (5)	0.0010 (4)	0.0016 (4)	0.0011 (4)

Geometric parameters (Å, º)

O1—C3	1.3420 (13)	C8—C10	1.3913 (14)
N1—C2	1.3304 (14)	C9—C10^i	1.3840 (14)
N1—C6	1.3344 (14)	C10—C9^i	1.3841 (14)
O2—C7	1.2579 (13)	O1—H1O	0.8400
C2—C3	1.3894 (15)	N1—H1N	0.8800
O3—C7	1.2555 (13)	C2—H2A	0.9500
C3—C4	1.3915 (15)	C4—H4A	0.9500
C4—C5	1.3809 (15)	C5—H5A	0.9500
C5—C6	1.3806 (15)	C6—H6A	0.9500
C7—C8	1.5013 (14)	C9—H9A	0.9500
C8—C9	1.3889 (14)	C10—H10A	0.9500
C2—N1—C6	122.82 (9)	C9^i—C10—C8	120.19 (10)
C3—O1—H1O	109.5	C2—N1—H1N	118.6
N1—C2—C3	120.17 (10)	C6—N1—H1N	118.6
O1—C3—C2	122.00 (10)	N1—C2—H2A	119.9
O1—C3—C4	119.65 (10)	C3—C2—H2A	119.9
C2—C3—C4	118.35 (10)	C5—C4—H4A	120.2
C5—C4—C3	119.57 (10)	C3—C4—H4A	120.2
C6—C5—C4	119.76 (10)	C6—C5—H5A	120.1
N1—C6—C5	119.32 (10)	C4—C5—H5A	120.1
O3—C7—O2	123.77 (10)	N1—C6—H6A	120.3
O3—C7—C8	118.61 (9)	C5—C6—H6A	120.3
O2—C7—C8	117.61 (9)	C10^i—C9—H9A	119.8
C9—C8—C10	119.50 (9)	C8—C9—H9A	119.8
C9—C8—C7	120.34 (9)	C9^i—C10—H10A	119.9
C10—C8—C7	120.16 (9)	C8—C10—H10A	119.9
C10^i—C9—C8	120.31 (9)
C6—N1—C2—C3	0.56 (16)	O3—C7—C8—C9	−160.84 (10)
N1—C2—C3—O1	179.02 (10)	O2—C7—C8—C9	19.69 (14)
N1—C2—C3—C4	−1.03 (16)	O3—C7—C8—C10	18.64 (14)
O1—C3—C4—C5	−179.32 (10)	O2—C7—C8—C10	−160.83 (10)
C2—C3—C4—C5	0.73 (17)	C10—C8—C9—C10^i	0.09 (16)
C3—C4—C5—C6	0.03 (17)	C7—C8—C9—C10^i	179.58 (9)
C2—N1—C6—C5	0.23 (17)	C9—C8—C10—C9^i	−0.09 (16)
C4—C5—C6—N1	−0.52 (17)	C7—C8—C10—C9^i	−179.58 (9)

Symmetry code: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···O3	0.84	1.74	2.5767 (12)	174
N1—H1N···O2^ii	0.88	1.73	2.6072 (12)	173
N1—H1N···O3^ii	0.88	2.47	3.0651 (12)	125

Symmetry code: (ii) x+1, −y+1/2, z+1/2.