Hydrogen-bonded networks in trans-3-(3-pyrid­yl)acrylic acid and rctt-3,3′-(3,4-dicarboxy­cyclo­butane-1,2-diyl)­dipyridinium dichloride

The structure of trans-3-(3-pyridyl)acrylic acid, C₈H₇NO₂, (I), possesses a two-dimensional hydrogen-bonded array of supra­molecular ribbons assembled via heterodimeric synthons between the pyridine and carboxyl groups. This compound is photoreactive in the solid state as a result of close contacts between the double bonds of neighbouring mol­ecules [3.821 (1) Å] along the a axis. The crystal structure of the photoproduct, rctt-3,3′-(3,4-dicarboxy­cyclo­butane-1,2-diyl)­dipyridinium dichloride, C₁₆H₁₆N₂O₄²⁺·2Cl⁻, (II), consists of a three-dimensional hydrogen-bonded network built from crosslinking of helical chains integrated by self-assembly of dipyridinium cations and Cl⁻ anions via different O—H...Cl, C—H...Cl and N⁺—H...Cl hydrogen-bond inter­actions.

S1. Comment

Organic reactions performed in the solid state are considered an important green alternative for the preparation of both new and conventional compounds (Toda, 2005; MacGillivray et al., 2004; Gao et al., 2004; Tanaka & Toda, 2000; Xiao et al., 2000; Garcia-Garibay, 2003; Ramamurthy & Venkatesan, 1987; Díaz de Delgado et al., 1991). A particular case of solid-state reactions is [2 + 2] photocycloaddition, in which the nature and features of the products can be controlled by topochemical parameters (Schmidt, 1971). This alternative offers regio- and stereoselective control combined with quantitative yields. These advantages make the assembly of olefins in the solid state an efficient route for regiocontrolled access to versatile multitopic organic molecules. Such compounds turn out to be very interesting as building blocks for designing novel supramolecular metal assemblies with unusual topologies (Papaefstathiou & MacGillivray, 2002; Papaefstathiou et al., 2005; Papaefstathiou, Milios & MacGillivray, 2004; Papaefstathiou, Hamilton et al., 2004; Lee et al., 2005; Kim & Jung, 2002). As part of our interest in the study of potentially photo- and thermally reactive solids (Briceño et al., 2006, 2002, 1999), we have re-investigated the photoreactivity of trans-3-(3-pyridyl)acrylic acid, (I), to prepare a tetratopic ligand containing either pyridyl or carboxylic acid groups. The solid-state reactivity of the title compound, (I), was previously studied by Lahav & Schmidt (1967). However, neither the crystal structure of the starting material nor that of the dimer have yet been reported in the literature. Here, the crystal structures of (I) and a hydrogen-bonded supramolecular array based on the photoproduct, (II), are reported.

The molecule of (I) (Fig. 1) adopts a nearly planar conformation with a maximum deviation from the mean molecular plane of 0.007 (2) Å. The molecule displays a C—H···O intramolecular hydrogen bond [C···O = 2.765 (2) Å, C3—H3···O1 = 102.2°], which leads to the formation of a five-membered ring described by the S(5) graph-set symbol (Bernstein et al., 1995).

The crystal structure of (I) consists of the self-assembly of molecules via a heterodimeric hydrogen-bonded synthon based on the interaction between the pyridine and carboxylic groups. This supramolecular motif, described as R²₂(7), is repeated along the b direction to generate zigzag supramolecular ribbons with distances O1···N1ⁱ = 2.660 (2) Å and C5···O2ⁱ = 3.263 (2) Å [symmetry code: (i) 1 - x, -1/2 + y, 3/2 - z]. Adjacent ribbons are linked by two complementary C—H···O hydrogen bonds [C8···O2ⁱⁱ = 3.299 (3) Å; symmetry code: (ii) -x, 1 - y, 1 - z]. These interactions induce self-assembly of parallel ribbons in an alternating head-to-tail fashion, resulting in a two-dimensional hydrogen-bonded array in the bc plane (Fig. 2a). The three-dimensional network is achieved by stacking of the sheets through π–π interactions along the a axis (interlayer distance ca 3.8 Å).

A remarkable feature of the structure of (I) is the presence of close contacts between the double bonds of neighbouring molecules related by translation along the a axis [centroid-to-centroid distance = 3.812 (1) Å]. This structural feature is responsible for the photoreactivity that is displayed by (I) in the solid state (Fig. 2b).

As expected, UV irradiation of (I) produces the dimer. The ¹H NMR spectrum confirms the photocycloaddition (see Experimental section) The stereochemistry of the product was confirmed by the single-crystal structure analysis of compound (II), which revealed the formation of a typical truxinic acid analogue (head-to-head dimer). This result is in agreement with the expected topochemical control by the crystalline starting structure, and with the results previously reported by Lahav & Schmidt (1967), based on the characterization of the compound by ¹H NMR spectroscopy and other chemicophysical observations.

The asymmetric unit of (II) consists of the diprotonated β-dimer, C₁₆H₁₆N₂O₄²⁺ (Fig. 3), and two Cl^- anions. The cyclobutane ring is slightly puckered; the flap C4 atom deviates 0.354 (5) Å from the plane of the other three atoms of the four-membered ring. This value is similar to those observed for other substituted cyclobutanes that do not crystallize on a centre of symmetry (Abdelmoty et al., 2005; Kanao et al., 1990; Pani et al., 1995). Both pyridinium rings, as well as the carboxylic acid groups, are twisted out of the mean plane of the cyclobutane ring: the mean planes of the pyridinium rings based on N1 (C7–C11) and N2 (C12–C16), and the carboxylic acid groups O1/C5/O2 and O4/C6/O3, are rotated by 69.0 (1), 79.1 (1), 35.9 (3) and 86.2 (3)°, respectively (Fig. 3).

An analysis of the bond distances and angles of the pyridyl rings in (I) and (II) only reveals significant differences in the internal C—N—C angle of both protonated N atoms. These values are greater in (II) than those found for (I) (Tables 1 and 2).

The structure of (II) consists of a three-dimensional hydrogen-bonded network, which is built up by self-assembly of the cations and Cl^- anions via different C—H···Cl, O—H···Cl and N⁺—H···Cl hydrogen-bonding interactions. In this structure, the Cl^- anions act as structure-directing agents of this assembly, and each Cl^- anion is an acceptor of multiple hydrogen-bonding interactions. Atom Cl1 is acceptor of four hydrogen bonds from different adjacent dications, whereas atom Cl2 accepts only three hydrogen bonds. Details of the hydrogen-bonding geometry in (II) are given in Table 2. The cations are self-assembled through O—H···Cl interactions between carboxylic acid groups and Cl1 atoms, generating one-dimensional helical chains running along the a axis (Fig. 4). The central axis about each chain is a twofold screw axis. Neighbouring helical arrangements (shown dark in Fig. 5) are cross-linked by additional N⁺—H···Cl hydrogen bonds, involving pyridinium units through the H atom of the protonated ring, and C—H···Cl interactions, to afford a three-dimensional hydrogen-bonded assembly (Fig. 5).

Related literature

For related literature, see: Abdelmoty et al. (2005); Bernstein et al. (1995); Briceño et al. (1999, 2002, 2006); Díaz de Delgado, Wheeler, Snider & Foxman (1991); Gao et al. (2004); Garcia-Garibay (2003); Kanao et al. (1990); Kim & Jung (2002); Lahav & Schmidt (1967); Lee et al. (2005); MacGillivray et al. (2004); Pani et al. (1995); Papaefstathiou & MacGillivray (2002); Papaefstathiou et al. (2005); Papaefstathiou, Hamilton, Friščič & MacGillivray (2004); Papaefstathiou, Milios & MacGillivray (2004); Ramamurthy & Venkatesan (1987); Schmidt (1971); Tanaka & Toda (2000); Toda (2005); Xiao et al. (2000).

S2. Experimental

trans-3-(3-Pyridyl) acrylic acid, (I), was obtained commercially (Aldrich). Crystals of (I) were obtained by slow evaporation of a methanol solution. IR (KBr disc, ν, cm^-1): 3500–2300 (O—H), 3052 (═C—H), 1702 (C═O), 1635 (C═C), 1580 and 1418 (C═C and C═N), 1284 (C—O).

The photodimer was prepared by topochemical reaction of (I). Crystals and powered crystalline material of (I) were irradiated with a 100 W H g lamp above 302 nm for 3 d. The product was purified as described in the literature (Lahav & Schmidt, 1967) (yield: 55–60%). IR (Medium?, ν, cm^-1): 3500–2300 (O—H), 3057 (═C—H), 2955–2857 (C—H), 1717 (C═O), 1583 and 1422 (C═C and C═N), 1277(C—O); ¹H NMR (Solvent?, δ, p.p.m.): 8.25 (2H, s, J = 1.86 Hz), 8.17 (2H, d, J = 3.84 Hz), 7.45 (2H, d, J = 6.24 Hz), 7.08 (2H, dd, J = 7.83 Hz), 4.25 (2H, d), 3.89 (2H, d, J = 6.24 Hz). Crystals of (II) were obtained by dissolving the dimer (200 mg) in distilled water (50 ml) and adjusting the pH to 1 with HCl. The resultant solution was allowed to evaporate slowly at room temperature. After 2–3 weeks, pale-yellow crystals suitable for X-ray analysis were formed. Attempts were made to optimize the exposure time, and thus ensure the maximum yield, by monitoring the degree of conversion of the photoreaction by FT–IR spectroscopy. It was found that compound (I) in the presence of KBr is photodegraded by decarboxylation. Interestingly, the CO₂ released is partially trapped in the KBr disc. The CO₂ band is enhanced as a function of the exposure time, and simultaneously a decrease in the relative intensity of the absorption band corresponding to the C═O stretch at 1702 cm^-1 was observed. After 4 h of irradiation, a loss of resolution in the FT–IR spectrum was observed. This behaviour was not observed during direct UV irradiation of (I); apparently, the KBr matrix induced this process.

S3. Refinement

For (I), all H atoms bound to carbon were included in calculated positions. The H atom of the carboxylic acid group was located in a difference Fourier map. The H atoms were refined using a riding model, with C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C,O). For (II), all H atoms bound to carbon were included in calculated positions. H atoms on N and O atoms (carboxyl groups) were located in a difference Fourier map. The H atoms were refined using a riding model, with C—H = 0.93–0.98 Å and U_iso(H) = 1.2U_eq(C,N,O).

Computing details

Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1993) for (I); CrystalClear (Rigaku/MSC, 2000) for (II). Cell refinement: MSC/AFC Diffractometer Control Software for (I); CrystalClear for (II). Data reduction: TEXSAN (Molecular Structure Corporation, 1999) for (I); CrystalStructure (Rigaku/MSC and Rigaku Corporation, 2004) for (II). For both compounds, program(s) used to solve structure: SHELXTL-NT (Bruker, 1998); program(s) used to refine structure: SHELXTL-NT; molecular graphics: SHELXTL-NT and DIAMOND (Brandenburg, 1998); software used to prepare material for publication: SHELXTL-NT and PLATON (Spek, 2003).

Figures

	Fig. 1. The molecular structure of the compound (I), showing the atom-labelling scheme and the intramolecular hydrogen bond (dashed line). Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. (a) View of the hydrogen-bonded network observed in the crystal structure of (I). (b) Close contacts between adjacent molecules along the a axis. [Symmetry codes: (i) 1 - x, -1/2 + y, 3/2 - z; (ii) -x, 1 - y, 1 - z.]
	Fig. 3. The molecular structure of the dication of (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 4. A view of the one-dimensional helical chains along the a axis, generated by O—H···Cl interactions (dashed lines). Most H atoms have been omitted for clarity. [Symmetry codes: (i) 0.5 + x, 0.5 - y, 2 - z; (viii) -0.5 - x, 0.5 - y, 2 - z.]
	Fig. 5. A view of the crystal structure of (II) in the bc plane, showing C—H···Cl, O—H···Cl and N—H···Cl interactions (dashed lines). Most H atoms have been omitted for clarity. The darker molecules indicate one of the neighbouring helical arrangements (see text).

(I) trans-3-(3-pyridyl)acrylic acid

Crystal data

C8H7NO2	F(000) = 312
Mr = 149.15	Dx = 1.397 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 3.8205 (6) Å	θ = 34.4–38.6°
b = 15.986 (2) Å	µ = 0.10 mm^−1
c = 11.6080 (12) Å	T = 295 K
β = 90.546 (11)°	Prism, colourless
V = 708.90 (16) Å^3	0.48 × 0.26 × 0.18 mm
Z = 4

Data collection

Rigaku AFC-7S diffractometer	876 reflections with I > 2σ(I)
Radiation source: normal-focus sealed tube	Rint = 0.017
Graphite monochromator	θmax = 25.0°, θmin = 2.2°
ω/2θ scans	h = 0→4
Absorption correction: ψ scan (North et al., 1968)	k = 0→19
Tmin = 0.900, Tmax = 0.960	l = −13→13
1451 measured reflections	3 standard reflections every 150 reflections
1255 independent reflections	intensity decay: none

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.112	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0558P)^2 + 0.1155P] where P = (Fo^2 + 2Fc^2)/3
1255 reflections	(Δ/σ)max < 0.001
100 parameters	Δρmax = 0.13 e Å^−3
0 restraints	Δρmin = −0.16 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.

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

	x	y	z	Uiso*/Ueq
N1	0.2544 (4)	0.87148 (9)	0.59595 (14)	0.0499 (5)
O1	0.5537 (4)	0.50929 (8)	0.79155 (12)	0.0588 (5)
H1	0.6246	0.4509	0.8284	0.071*
O2	0.3462 (5)	0.42225 (9)	0.65764 (13)	0.0720 (5)
C1	0.3989 (5)	0.49277 (11)	0.69220 (17)	0.0486 (5)
C2	0.2953 (5)	0.56700 (12)	0.62555 (16)	0.0502 (5)
H2	0.1827	0.5585	0.5551	0.060*
C3	0.3505 (5)	0.64459 (11)	0.65851 (16)	0.0441 (5)
H3	0.4635	0.6518	0.7291	0.053*
C4	0.2535 (5)	0.72095 (11)	0.59628 (15)	0.0406 (5)
C5	0.3264 (5)	0.79799 (11)	0.64613 (16)	0.0456 (5)
H5	0.4314	0.7986	0.7187	0.055*
C6	0.1018 (5)	0.87005 (13)	0.49228 (17)	0.0531 (6)
H6	0.0503	0.9205	0.4561	0.064*
C7	0.0175 (5)	0.79662 (13)	0.43674 (16)	0.0529 (5)
H7	−0.0905	0.7980	0.3646	0.063*
C8	0.0934 (5)	0.72107 (13)	0.48824 (16)	0.0478 (5)
H8	0.0385	0.6710	0.4514	0.057*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0623 (11)	0.0384 (9)	0.0490 (10)	0.0007 (7)	−0.0056 (8)	0.0015 (7)
O1	0.0873 (11)	0.0351 (7)	0.0536 (8)	0.0005 (7)	−0.0211 (7)	−0.0038 (6)
O2	0.1110 (14)	0.0370 (8)	0.0676 (10)	−0.0033 (8)	−0.0249 (9)	−0.0098 (7)
C1	0.0593 (12)	0.0382 (11)	0.0482 (11)	−0.0027 (9)	−0.0049 (9)	−0.0061 (8)
C2	0.0632 (13)	0.0419 (11)	0.0453 (11)	−0.0015 (9)	−0.0142 (9)	−0.0042 (9)
C3	0.0486 (11)	0.0422 (11)	0.0415 (10)	−0.0012 (9)	−0.0089 (8)	−0.0015 (8)
C4	0.0400 (10)	0.0420 (10)	0.0397 (9)	−0.0012 (8)	−0.0022 (8)	−0.0020 (7)
C5	0.0545 (12)	0.0401 (10)	0.0419 (10)	−0.0009 (9)	−0.0083 (9)	−0.0001 (8)
C6	0.0593 (13)	0.0483 (12)	0.0515 (12)	0.0050 (9)	−0.0065 (10)	0.0081 (9)
C7	0.0548 (13)	0.0600 (13)	0.0436 (11)	0.0022 (10)	−0.0115 (9)	0.0019 (9)
C8	0.0491 (12)	0.0484 (12)	0.0459 (11)	−0.0028 (9)	−0.0080 (9)	−0.0048 (8)

Geometric parameters (Å, º)

N1—C6	1.332 (2)	C3—H3	0.9300
N1—C5	1.339 (2)	C4—C5	1.388 (2)
O1—C1	1.318 (2)	C4—C8	1.390 (2)
O1—H1	1.0608	C5—H5	0.9300
O2—C1	1.213 (2)	C6—C7	1.376 (3)
C1—C2	1.469 (3)	C6—H6	0.9300
C2—C3	1.314 (2)	C7—C8	1.377 (3)
C2—H2	0.9300	C7—H7	0.9300
C3—C4	1.464 (2)	C8—H8	0.9300
C6—N1—C5	117.66 (17)	C8—C4—C3	123.59 (17)
C1—O1—H1	106.7	N1—C5—C4	123.90 (17)
O2—C1—O1	123.19 (18)	N1—C5—H5	118.0
O2—C1—C2	122.25 (18)	C4—C5—H5	118.0
O1—C1—C2	114.55 (16)	N1—C6—C7	122.43 (18)
C3—C2—C1	124.56 (18)	N1—C6—H6	118.8
C3—C2—H2	117.7	C7—C6—H6	118.8
C1—C2—H2	117.7	C6—C7—C8	119.82 (17)
C2—C3—C4	127.16 (18)	C6—C7—H7	120.1
C2—C3—H3	116.4	C8—C7—H7	120.1
C4—C3—H3	116.4	C7—C8—C4	118.80 (18)
C5—C4—C8	117.37 (17)	C7—C8—H8	120.6
C5—C4—C3	119.04 (16)	C4—C8—H8	120.6

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1^i	1.06	1.61	2.660 (2)	170
C5—H5···O2^ii	0.93	2.58	3.263 (2)	130
C8—H8···O2^iii	0.93	2.44	3.299 (2)	154
C3—H3···O1	0.93	2.41	2.765 (2)	102

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

(II) rctt-3,3'-(3,4-dicarboxycyclobutane-1,2-diyl)dipyridinium dichloride

Crystal data

C16H16N2O4^2+·2Cl^−	F(000) = 768
Mr = 371.21	Dx = 1.475 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71070 Å
Hall symbol: P 2ac 2ab	Cell parameters from 1256 reflections
a = 7.3938 (13) Å	θ = 1.9–28.0°
b = 14.829 (3) Å	µ = 0.41 mm^−1
c = 15.250 (3) Å	T = 295 K
V = 1672.1 (6) Å^3	Prism, pale yellow
Z = 4	0.48 × 0.23 × 0.16 mm

Data collection

Rigaku AFC-7S Mercury diffractometer	3310 independent reflections
Radiation source: normal-focus sealed tube	2872 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.036
Detector resolution: 14.6306 pixels mm^-1	θmax = 28.2°, θmin = 1.9°
ω scans	h = −8→8
Absorption correction: multi-scan (Jacobson, 1998)	k = −17→17
Tmin = 0.820, Tmax = 0.912	l = −17→13
19377 measured reflections

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)] = 0.038	H-atom parameters constrained
wR(F^2) = 0.103	w = 1/[σ^2(Fo^2) + (0.0456P)^2 + 0.4231P] where P = (Fo^2 + 2Fc^2)/3
S = 1.15	(Δ/σ)max = 0.001
3310 reflections	Δρmax = 0.22 e Å^−3
220 parameters	Δρmin = −0.32 e Å^−3
0 restraints	Absolute structure: Flack (1983), with how many Friedel pairs?
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.01 (7)

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
Cl1	0.01679 (10)	0.02345 (5)	1.10215 (4)	0.04509 (19)
Cl2	1.01910 (11)	0.20072 (6)	0.42467 (5)	0.0527 (2)
O1	0.6160 (4)	0.27763 (14)	0.88370 (14)	0.0617 (7)
H1OH	0.5740	0.3327	0.9010	0.074*
O2	0.5483 (4)	0.22581 (14)	1.01689 (13)	0.0618 (7)
O3	0.4059 (3)	0.01199 (14)	1.04300 (12)	0.0465 (5)
H3OH	0.2824	0.0161	1.0553	0.094 (14)*
O4	0.3283 (3)	0.06142 (17)	0.91129 (14)	0.0572 (6)
N1	0.9711 (4)	0.16586 (16)	0.61851 (14)	0.0433 (6)
H1N	0.9446	0.1787	0.5611	0.087 (13)*
N2	1.1274 (3)	−0.11219 (16)	0.85947 (15)	0.0405 (6)
H2N	1.2144	−0.1244	0.8980	0.044 (8)*
C1	0.6404 (3)	0.03711 (17)	0.94119 (17)	0.0322 (6)
H1	0.7141	0.0062	0.9854	0.039*
C2	0.7131 (3)	0.13231 (18)	0.91619 (16)	0.0341 (6)
H2	0.8401	0.1366	0.9341	0.041*
C3	0.7057 (4)	0.10716 (17)	0.81825 (16)	0.0314 (6)
H3	0.5932	0.1301	0.7927	0.038*
C4	0.6789 (4)	0.00538 (17)	0.84576 (16)	0.0315 (6)
H4	0.5700	−0.0200	0.8188	0.038*
C5	0.6163 (4)	0.21536 (19)	0.94606 (19)	0.0417 (7)
C6	0.4421 (4)	0.03832 (18)	0.96247 (18)	0.0360 (6)
C7	0.8620 (4)	0.13203 (17)	0.75994 (17)	0.0310 (6)
C8	0.8338 (4)	0.14348 (18)	0.67147 (18)	0.0381 (6)
H8	0.7185	0.1356	0.6483	0.046*
C9	1.1398 (5)	0.1771 (2)	0.6472 (2)	0.0516 (8)
H9	1.2318	0.1924	0.6084	0.062*
C10	1.1758 (4)	0.1658 (3)	0.7343 (2)	0.0559 (9)
H10	1.2927	0.1737	0.7555	0.067*
C11	1.0377 (4)	0.1428 (2)	0.79064 (19)	0.0439 (7)
H11	1.0623	0.1343	0.8499	0.053*
C12	0.8412 (4)	−0.05184 (17)	0.82664 (17)	0.0324 (6)
C13	0.9783 (4)	−0.06920 (18)	0.88566 (17)	0.0371 (6)
H13	0.9668	−0.0509	0.9437	0.045*
C14	1.1542 (4)	−0.1396 (2)	0.77667 (18)	0.0413 (7)
H14	1.2624	−0.1670	0.7606	0.050*
C15	1.0205 (5)	−0.12671 (18)	0.71637 (17)	0.0435 (7)
H15	1.0345	−0.1469	0.6591	0.052*
C16	0.8643 (4)	−0.08322 (19)	0.74177 (18)	0.0406 (7)
H16	0.7723	−0.0747	0.7010	0.049*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0383 (4)	0.0477 (4)	0.0492 (4)	−0.0055 (3)	0.0098 (3)	−0.0064 (3)
Cl2	0.0459 (4)	0.0678 (5)	0.0445 (4)	0.0131 (4)	0.0092 (3)	0.0119 (3)
O1	0.0921 (18)	0.0366 (12)	0.0566 (14)	0.0125 (12)	0.0291 (13)	0.0054 (10)
O2	0.0878 (17)	0.0493 (13)	0.0482 (13)	0.0095 (13)	0.0308 (12)	−0.0033 (9)
O3	0.0408 (12)	0.0561 (13)	0.0425 (11)	0.0053 (10)	0.0129 (8)	0.0109 (10)
O4	0.0308 (11)	0.0906 (18)	0.0504 (13)	0.0043 (12)	−0.0001 (9)	0.0131 (12)
N1	0.0547 (16)	0.0414 (14)	0.0339 (13)	−0.0042 (12)	0.0111 (12)	0.0008 (9)
N2	0.0327 (13)	0.0424 (14)	0.0465 (14)	0.0053 (11)	−0.0063 (10)	−0.0069 (10)
C1	0.0278 (13)	0.0335 (14)	0.0352 (15)	0.0039 (11)	0.0013 (10)	0.0001 (10)
C2	0.0295 (13)	0.0380 (15)	0.0348 (14)	−0.0018 (12)	0.0052 (10)	−0.0036 (11)
C3	0.0275 (14)	0.0311 (14)	0.0355 (14)	0.0035 (11)	0.0023 (11)	0.0002 (11)
C4	0.0272 (13)	0.0322 (14)	0.0352 (13)	−0.0014 (11)	−0.0007 (10)	0.0010 (10)
C5	0.0453 (17)	0.0373 (15)	0.0425 (17)	−0.0057 (13)	0.0087 (13)	−0.0019 (12)
C6	0.0365 (15)	0.0332 (15)	0.0383 (14)	−0.0017 (12)	0.0049 (12)	−0.0006 (11)
C7	0.0293 (13)	0.0279 (13)	0.0359 (15)	0.0040 (11)	0.0029 (10)	0.0018 (10)
C8	0.0403 (16)	0.0336 (15)	0.0405 (16)	−0.0030 (13)	0.0039 (12)	−0.0032 (11)
C9	0.048 (2)	0.054 (2)	0.053 (2)	−0.0022 (16)	0.0245 (15)	0.0034 (15)
C10	0.0297 (17)	0.078 (2)	0.060 (2)	−0.0001 (16)	0.0066 (14)	0.0048 (17)
C11	0.0370 (16)	0.0548 (18)	0.0397 (15)	0.0031 (15)	0.0015 (12)	0.0073 (13)
C12	0.0310 (14)	0.0284 (13)	0.0377 (14)	−0.0034 (11)	0.0020 (11)	−0.0014 (10)
C13	0.0361 (14)	0.0379 (15)	0.0373 (14)	0.0039 (13)	−0.0006 (12)	−0.0077 (10)
C14	0.0401 (17)	0.0380 (15)	0.0459 (17)	0.0051 (14)	0.0090 (13)	−0.0076 (12)
C15	0.0568 (19)	0.0405 (15)	0.0333 (14)	0.0119 (16)	0.0031 (14)	−0.0057 (11)
C16	0.0472 (18)	0.0380 (15)	0.0366 (15)	0.0059 (14)	−0.0048 (13)	−0.0026 (11)

Geometric parameters (Å, º)

O1—C5	1.326 (4)	C3—C4	1.579 (4)
O1—H1OH	0.9131	C3—H3	0.9800
O2—C5	1.201 (3)	C4—C12	1.498 (4)
O3—C6	1.316 (3)	C4—H4	0.9800
O3—H3OH	0.9344	C7—C8	1.376 (4)
O4—C6	1.198 (3)	C7—C11	1.390 (4)
N1—C9	1.333 (4)	C8—H8	0.9300
N1—C8	1.339 (3)	C9—C10	1.364 (5)
N1—H1N	0.9166	C9—H9	0.9300
N2—C13	1.335 (3)	C10—C11	1.378 (4)
N2—C14	1.341 (3)	C10—H10	0.9300
N2—H2N	0.8900	C11—H11	0.9300
C1—C6	1.502 (4)	C12—C13	1.380 (4)
C1—C4	1.556 (3)	C12—C16	1.386 (4)
C1—C2	1.558 (4)	C13—H13	0.9300
C1—H1	0.9800	C14—C15	1.363 (4)
C2—C5	1.496 (4)	C14—H14	0.9300
C2—C3	1.540 (4)	C15—C16	1.378 (4)
C2—H2	0.9800	C15—H15	0.9300
C3—C7	1.504 (4)	C16—H16	0.9300
C5—O1—H1OH	114.6	O1—C5—C2	110.8 (2)
C6—O3—H3OH	111.5	O4—C6—O3	123.4 (3)
C9—N1—C8	122.8 (3)	O4—C6—C1	123.3 (3)
C9—N1—H1N	119.2	O3—C6—C1	113.4 (2)
C8—N1—H1N	117.7	C8—C7—C11	117.2 (3)
C13—N2—C14	123.3 (3)	C8—C7—C3	119.6 (2)
C13—N2—H2N	119.8	C11—C7—C3	123.2 (2)
C14—N2—H2N	116.9	N1—C8—C7	120.5 (3)
C6—C1—C4	112.6 (2)	N1—C8—H8	119.8
C6—C1—C2	112.3 (2)	C7—C8—H8	119.8
C4—C1—C2	88.97 (18)	N1—C9—C10	119.2 (3)
C6—C1—H1	113.6	N1—C9—H9	120.4
C4—C1—H1	113.6	C10—C9—H9	120.4
C2—C1—H1	113.6	C9—C10—C11	119.5 (3)
C5—C2—C3	118.5 (2)	C9—C10—H10	120.2
C5—C2—C1	120.4 (2)	C11—C10—H10	120.2
C3—C2—C1	90.33 (19)	C10—C11—C7	120.7 (3)
C5—C2—H2	108.7	C10—C11—H11	119.6
C3—C2—H2	108.7	C7—C11—H11	119.6
C1—C2—H2	108.7	C13—C12—C16	117.1 (3)
C7—C3—C2	119.1 (2)	C13—C12—C4	124.5 (2)
C7—C3—C4	119.2 (2)	C16—C12—C4	118.1 (2)
C2—C3—C4	88.75 (19)	N2—C13—C12	120.1 (2)
C7—C3—H3	109.4	N2—C13—H13	120.0
C2—C3—H3	109.4	C12—C13—H13	120.0
C4—C3—H3	109.4	N2—C14—C15	119.0 (3)
C12—C4—C1	120.0 (2)	N2—C14—H14	120.5
C12—C4—C3	112.9 (2)	C15—C14—H14	120.5
C1—C4—C3	88.99 (19)	C14—C15—C16	118.9 (2)
C12—C4—H4	111.0	C14—C15—H15	120.5
C1—C4—H4	111.0	C16—C15—H15	120.5
C3—C4—H4	111.0	C15—C16—C12	121.5 (3)
O2—C5—O1	123.7 (3)	C15—C16—H16	119.2
O2—C5—C2	125.5 (3)	C12—C16—H16	119.2

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1OH···Cl1^i	0.91	2.17	3.047 (2)	160
O3—H3OH···Cl1	0.93	2.09	3.020 (2)	172
N1—H1N···Cl2	0.92	2.18	3.022 (2)	153
N2—H2N···Cl2^ii	0.89	2.31	3.089 (3)	146
C9—H9···Cl2^iii	0.93	2.70	3.514 (3)	147
C11—H11···O4^iv	0.93	2.43	3.075 (3)	126
C13—H13···Cl1^iv	0.93	2.68	3.587 (3)	165
C14—H14···O1^v	0.93	2.52	3.221 (3)	133
C15—H15···O2^vi	0.93	2.54	3.417 (3)	158
C16—H16···Cl1^vii	0.93	2.72	3.641 (3)	169

Symmetry codes: (i) x+1/2, −y+1/2, −z+2; (ii) −x+5/2, −y, z+1/2; (iii) x+1/2, −y+1/2, −z+1; (iv) x+1, y, z; (v) −x+2, y−1/2, −z+3/2; (vi) −x+3/2, −y, z−1/2; (vii) −x+1/2, −y, z−1/2.