Two hydration products of 3,4,5,6-tetra­chloro-N-(methyl-2-pyrid­yl)phthalmic acids

In 2-amino-6-methyl­pyridin-1-ium 2-carb­oxy-3,4,5,6-tetra­chloro­benzoate, C₆H₉N₂⁺·C₈HCl₄O₄⁻, there are two perpendicular chains of hydrogen-bonded ions, one arising from the inter­action between 2-carb­oxy-3,4,5,6-tetra­chloro­benzoate ions and the other from the inter­action between the 2-am­ino-6-methyl­pyridin-1-ium and 2-carb­oxy-3,4,5,6-tetra­chloro­ben­zo­ate ions. These chains combine to form a two-dimensional network of hydrogen-bonded ions. Cocrystals of bis­(2-amino-3-methyl­pyridin-1-ium) 3,4,5,6-tetra­chloro­phtha­late–3,4,5,6-tetra­chloro­phthalic acid (1/1), 2C₆H₉N₂⁺·C₈Cl₄O₄²⁻·C₈H₂Cl₄O₄, form finite aggregates of hydrogen-bonded ions. π–π inter­actions are observed between 2-amino-3-methyl­pyridin-1-ium cations. Both structures exhibit the characteristic R₂²(8) motif as a result of the hydrogen bonding between the 2-amino­pyridinium and carboxyl­ate units.

S1. Comment

N-(3-methyl-2-pyridyl)-3,4,5,6-tetrachlorophthalmic acid and N-(6-methyl-2-pyridyl)-3,4,5,6-tetrachlorophthalmic acid are known to be pharamacologically active having been shown to exhibit a hypertensive effect in biological systems (Dolzhenko et al., 2003). In the context of this study, these materials are of interest for their potential as a UV-active dye for dye-sensitized solar cell applications. Heating these compounds to 333 K in hydrated methanol produces crystals of two salts: 2-amino-6-methylpyridin-1-ium 2-carboxy-3,4,5,6-tetrachlorobenzoate, [C₆H₉N₂][C₈HO₄Cl₄], (I) (Fig. 1), and 2-amino-3-methylpyridin-1-ium 3,4,5,6-tetrachlorophthalate co-crystallized with 3,4,5,6-tetrachlorophthalic acid, ([C₆H₉N₂]₂[C₈O₄Cl₄].C₈H₂O₄Cl₄), (II) (Fig. 2). These salts are the result of the reaction of the starting material with water present in the methanol solution (Figs. 3, 4) and the equilibrium that exists between amides and water and the corresponding amines and carboxylic acids. In (I) and (II) protonation of the pyridyl nitrogen results in pyridinium salts stabilized by imino resonance. Interestingly, as 3,4,5,6-tetrachlorophthalic acid co-crystallizes with 2-amino-3-methylpyridin-1-ium phthalate all the products of this reaction are represented stoichiometrically in the crystal structure.

The molecular geometry of the 2-amino-6-methylpyridin-1-ium cation in the structure of (I) can be compared with that of the non-halogenated 2-amino-6-methylpyridinium 2-formylbenzoate monohydrate (Büyükgüngör & Odabaşoǧlu, 2006). This geometry is similar in both compounds, with the characteristic bond-length alternation within the pyridyl ring, which demonstrates the imino resonance stabilizing the positive charge (Fig. 5) (Zhi et al., 2002). The bond geometry of the aromatic ring in the 2-carboxy-3,4,5,6-tetrachlorobenzoate anion in (I) resembles more closely that of the hemihydrate of 3,4,5,6-tetrachlorophthalic acid (Ito et al., 1975) than that of the 2-carboxy-3,4,5,6-tetrachlorobenzoate in a similar salt, 2-methyl-5-ethylpyridinium 3,4,5,6-tetrachlorophthalate (Galloy et al., 1976). This indicates a contribution from the neutral canonical form, which is also observed in the carboxylate group, where O3—C8 is observed to be shorter than O4—C8. The bond distances in the aromatic ring of 2-carboxy-3,4,5,6-tetrachlorobenzoate in (I) range from 1.374 (9) to 1.403 (9) Å.

Compound (I) forms continuous sheets of hydrogen-bonded ions parallel to (010). These sheets contain the characteristic rings with the graph set R₂² (8) (Etter, 1990; Bernstein et al., 1995) with amine and pyridinium N atoms acting as donors and the two carboxylate O atoms acting as acceptors (N1—H1N···O4 and N2—H2A···O3), as is well documented in this type of compound (Quah et al., 2010; Hemamalini & Fun, 2010). These rings are linked by chain motifs to form the sheets. The 2-carboxy-3,4,5,6-tetrachlorobenzoate anions form chains with the graph set C₁¹(7) in the [001] direction through O1—H1···O4 (Fig. 6) and the 2-amino-6-methylpyridin-1-ium cations link via the anions forming chains with the graph set C₂²(9) (through N2—H2A···O3 and N2—H2B···O2) and C₂²(11) (through N1—H1N···O4 and N2—H2B···O2), giving overall a C₂²(9)C₂²(11)[R₂²(8)] chain of rings parallel to the [100] direction (Fig. 7).

The aromatic rings in the 2-amino-3-methylpyridin-1-ium cations of compound (II) exhibit similar geometry to those in (I) with regard to the bond distances. The distances in the benzene rings of the 3,4,5,6-tetrachlorophthalate dianion and the 3,4,5,6-tetrachlorophthalic acid molecule range between 1.387 (3) and 1.403 (2) Å and 1.389 (3) and 1.399 (3) Å, respectively, altogether more consistent than the bond distances of the 2-carboxy-3,4,5,6-tetrachlorobenzoate anion in (I) or the hemihydrate of 3,4,5,6-tetrachlorophthalic acid. This similarity in bond geometry between the dianion and the neutral acid in (II) strengthens the argument for the contribution of the neutral canonical forms in these compounds. As is observed in similar structures (Ni et al., 2007; Zhi et al., 2002) there are π–π interactions between 2-amino-3-methylpyridin-1-ium cations; the dihedral angle between the two pyridinium rings in the selected asymmetric unit is only 3.8 (2)°, and the corresponding centroid separation is 3.834 (2) Å.

Unlike the two-dimensional network observed in (I), the hydrogen-bonded system in (II) consists of a finite array of four 2-amino-3-methylpyridin-1-ium cations, two 3,4,5,6-tetrachlorophthalate dianions and two molecules of 3,4,5,6-tetrachlorophthalic acid (Fig. 8). The R₂²(8) ring motifs formed between the pyridinium and the phthalate are once again present with each phthalate dianion forming two such rings parallel to each other because of the π–π interactions between the pyridinium cations, i.e. through N2—H2A···O1 and N1—H1N···O2 for one ring and N4—H4A···O3 and N3—H3N···O4 for the other. In addition to this, each of these rings is connected to an adjacent R₂²(8) ring through N2—H2B···O1 and N4—H4B···O3 forming an [R₂²(8)R₄²(8)R₂²(8)] motif within an outer R₄⁴(16) ring. Further motifs are observed when considering that there are two parallel [R₂²(8)R₄²(8)R₂²(8)] motifs linked by the phthalate dianions; this gives rise to rings with graph sets R₄⁴(18) and R₄⁴(22).

The 3,4,5,6-tetrachlorophthalic acid molecules and 3,4,5,6-tetrachlorophthalate dianions are also connected by hydrogen bonds with the acid protons donating to carboxylate oxygen acceptors through O5—H5O···O2 and O7—H7O···O4 to create R₂²(14) motifs. Though there is no direct hydrogen bonding between the acid molecules and the pyridinium cations, rings with the graph set R₈⁶(34) are formed between acid molecules through the [R₂²(8)R₄²(8)R₂²(8)] motif.

Related literature

For similar structures containing methyl-2-amino-pyridinium cations see Büyükgüngör & Odabaşoǧlu (2006), Quah et al., (2010), Hemamalini & Fun, (2010), Ni et al., (2007) and Zhi et al., (2002). For structures pertaining to 3,4,5,6-tetrachlorophthalmic acid and related ions see Galloy et al., (1976), Hosomi et al., (2000) and Ito et al., (1975). A description of hydrogen bonding in terms of graph sets is given by Etter, (1990) and Bernstein et al., (1995).

S2. Experimental

N-(3-methyl-2-pyridyl)-3,4,5,6-tetrachlorophthalic acid (10 mg, 0.026 mmol) and N-(6-methyl-2-pyridyl)-3,4,5,6-tetrachlorophthalmic acid (10 mg, 0.026 mmol) were heated to 333 K in hydrated methanol (5 ml) until a clear solution was afforded. Colourless plate-like crystals of (I) were grown upon cooling to room temperature and colourless prism-like crystals of (II) were grown after the solution was allowed to stand for 1 week.

S3. Refinement

H atoms were positioned geometrically and refined as riding on their parent atoms, with C—H = 0.95 Å and U_iso(H) = 1.2U_eq(C) and N—H = 0.88 Å and U_iso(H) = 1.2U_eq(N). Hydroxy and methyl hydrogen atoms were modelled in a similar fashion with O—H = 0.84 Å and U_iso(H) = 1.5U_eq(C) and C—H = 0.98 Å and U_iso(H) = 1.5U_eq(N). The most disagreeable reflections were omitted with those exhibiting a Δ(F²) value greater than 5 s.u. being removed. The refinement was further improved by restricting the reflections considered to 25.68° and below. The Flack parameter gives the expected values for a correct structure within 3 s.u.s. Nonetheless since the s.u. is moderate, the inverted structure was tested. This yielded a Flack parameter, x = 1.21 (13) by the 'hole in one' method and x = 1.34 (13) using TWIN/BASF, giving us confidence that we have presented the correct orientation of the structure with respect to the polar axis direction. These checks were particularly important given that the precision of the Flack x parameter is poor owing to a low Friedel coverage of 60%. Refinement for (II) was reduced to θ = 25.68° to reduce the number of missing data; however, a number of missing data remain (171 reflections between THmin and STh/L = 0.600). Analysis of reciprocal-space plots reveal that these missing portions are fairly randomly dispersed which gives us confidence that this is not a systematic error.

Computing details

For both compounds, data collection: CrystalClear (Rigaku, 2008); cell refinement: CrystalClear (Rigaku, 2008); data reduction: CrystalClear (Rigaku, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. The structure of the asymmetric unit of (I), with atomic displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. Structure of the asymmetric unit of (II), with atomic displacement ellipsoids drawn at the 50% probability level.
	Fig. 3. The resonance exhibited by (I).
	Fig. 4. View of the C1^1(7) hydrogen-bonding motif in the [001] direction in (I). H atoms not involved in hydrogen bonding (dashed lines) have been omitted.
	Fig. 5. View of the C2^2(9)C2^2(11)[R2^2(8)] chain of rings along [100] in (I). H atoms not involved in hydrogen bonding (dashed lines) have been omitted.
	Fig. 6. Stereoview of the finite hydrogen-bonding network in the structure of (II). H atoms not involved in hydrogen bonding (dashed lines) have been omitted.

(I) 2-amino-6-methylpyridin-1-ium 2-carboxy-3,4,5,6-tetrachlorobenzoate

Crystal data

C6H9N2^+·C8HCl4O4^−	F(000) = 832
Mr = 412.04	Dx = 1.686 Mg m^−3
Orthorhombic, Pca21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2ac	Cell parameters from 3604 reflections
a = 9.441 (14) Å	θ = 1.6–32.9°
b = 12.56 (2) Å	µ = 0.75 mm^−1
c = 13.69 (2) Å	T = 120 K
V = 1623 (4) Å^3	Prism, colorless
Z = 4	0.33 × 0.16 × 0.06 mm

Data collection

Rigaku Saturn724+ (2x2 bin mode) diffractometer	2495 independent reflections
Radiation source: Sealed Tube	2302 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.048
Detector resolution: 28.5714 pixels mm^-1	θmax = 25.7°, θmin = 3.0°
profile data from ω–scans	h = −11→9
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −11→15
Tmin = 0.866, Tmax = 0.956	l = −16→13
5083 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)] = 0.057	H-atom parameters constrained
wR(F^2) = 0.127	w = 1/[σ^2(Fo^2) + (0.0307P)^2 + 5.8163P] where P = (Fo^2 + 2Fc^2)/3
S = 1.10	(Δ/σ)max < 0.001
2495 reflections	Δρmax = 0.44 e Å^−3
218 parameters	Δρmin = −0.50 e Å^−3
1 restraint	Absolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.31 (13)

Special details

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
C1	0.1965 (6)	0.8453 (4)	0.4565 (5)	0.0244 (14)
C2	0.1106 (7)	0.8102 (5)	0.3749 (5)	0.0257 (14)
C3	0.0338 (6)	0.8757 (4)	0.3139 (5)	0.0243 (14)
C4	0.0453 (6)	0.9762 (5)	0.3322 (5)	0.0294 (16)
C5	0.1356 (6)	1.0098 (4)	0.4085 (5)	0.0208 (13)
C6	0.2106 (6)	0.9452 (5)	0.4727 (5)	0.0242 (14)
C7	0.2715 (7)	0.7738 (5)	0.5294 (5)	0.0247 (13)
C8	0.0983 (7)	0.6986 (5)	0.3543 (5)	0.0259 (14)
Cl3	−0.07756 (17)	0.83183 (12)	0.21553 (14)	0.0323 (4)
Cl4	−0.05791 (15)	1.05582 (12)	0.25660 (13)	0.0297 (4)
Cl5	0.15292 (18)	1.13515 (11)	0.42892 (13)	0.0324 (4)
Cl6	0.33018 (16)	0.99037 (11)	0.56559 (12)	0.0279 (4)
O1	0.2370 (5)	0.7841 (3)	0.6294 (3)	0.0271 (10)
H1O	0.2834	0.7413	0.6613	0.041*
O2	0.3531 (5)	0.7112 (3)	0.4936 (4)	0.0330 (11)
O3	0.0374 (5)	0.6502 (3)	0.4219 (4)	0.0355 (11)
O4	0.1554 (5)	0.6685 (3)	0.2687 (4)	0.0300 (11)
C9	0.0473 (7)	0.4127 (5)	0.2843 (6)	0.0360 (17)
C10	0.0329 (7)	0.3149 (5)	0.2538 (6)	0.0378 (17)
H10	−0.0233	0.2671	0.2882	0.045*
C11	0.1047 (8)	0.2821 (5)	0.1664 (7)	0.044 (2)
H11	0.0883	0.2127	0.1456	0.053*
C12	0.1965 (8)	0.3433 (5)	0.1093 (6)	0.043 (2)
H12	0.2403	0.318	0.0531	0.051*
C13	0.2140 (7)	0.4380 (5)	0.1424 (6)	0.0345 (17)
C14	0.3065 (8)	0.5108 (5)	0.0875 (6)	0.042 (2)
H14A	0.3629	0.5515	0.1324	0.063*
H14B	0.2496	0.5582	0.0489	0.063*
H14C	0.3675	0.4703	0.0454	0.063*
N1	0.1376 (6)	0.4701 (4)	0.2274 (4)	0.0308 (13)
H1N	0.1505	0.5351	0.2453	0.037*
N2	−0.0249 (7)	0.4523 (4)	0.3661 (5)	0.0428 (16)
H2A	−0.0813	0.4116	0.3983	0.051*
H2B	−0.0127	0.5173	0.3841	0.051*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.020 (3)	0.021 (3)	0.032 (4)	0.001 (2)	−0.002 (3)	−0.002 (3)
C2	0.027 (3)	0.023 (3)	0.027 (4)	0.004 (2)	−0.002 (3)	0.000 (3)
C3	0.023 (3)	0.017 (3)	0.033 (4)	−0.003 (2)	−0.003 (3)	0.000 (3)
C4	0.023 (3)	0.033 (3)	0.032 (4)	0.005 (3)	0.013 (3)	0.007 (3)
C5	0.026 (3)	0.018 (2)	0.019 (3)	0.000 (2)	0.005 (3)	0.001 (2)
C6	0.024 (3)	0.024 (3)	0.024 (4)	0.001 (2)	−0.003 (3)	−0.003 (3)
C7	0.026 (3)	0.024 (3)	0.024 (4)	0.001 (2)	0.002 (3)	0.003 (3)
C8	0.029 (3)	0.020 (3)	0.028 (4)	−0.002 (2)	−0.003 (3)	0.002 (3)
Cl3	0.0319 (8)	0.0295 (7)	0.0355 (10)	−0.0023 (6)	−0.0069 (8)	−0.0030 (7)
Cl4	0.0288 (7)	0.0251 (7)	0.0353 (10)	0.0041 (6)	−0.0013 (8)	0.0014 (7)
Cl5	0.0411 (9)	0.0179 (6)	0.0382 (10)	−0.0001 (6)	−0.0025 (8)	−0.0005 (7)
Cl6	0.0284 (7)	0.0236 (7)	0.0316 (9)	−0.0023 (6)	−0.0025 (7)	−0.0018 (6)
O1	0.033 (2)	0.0199 (19)	0.029 (3)	0.0067 (18)	0.003 (2)	−0.0008 (18)
O2	0.040 (3)	0.021 (2)	0.037 (3)	0.0079 (19)	0.002 (2)	−0.002 (2)
O3	0.052 (3)	0.020 (2)	0.034 (3)	−0.0048 (19)	0.009 (3)	0.002 (2)
O4	0.040 (3)	0.0178 (19)	0.032 (3)	−0.0039 (17)	0.003 (2)	−0.0023 (19)
C9	0.037 (4)	0.031 (3)	0.041 (5)	−0.005 (3)	−0.006 (4)	0.003 (3)
C10	0.039 (4)	0.019 (3)	0.055 (5)	−0.004 (3)	−0.008 (4)	0.002 (3)
C11	0.044 (4)	0.022 (3)	0.067 (6)	−0.001 (3)	0.000 (4)	−0.005 (3)
C12	0.048 (4)	0.022 (3)	0.058 (6)	0.003 (3)	−0.009 (4)	−0.003 (3)
C13	0.036 (4)	0.024 (3)	0.044 (5)	0.000 (3)	−0.009 (3)	0.008 (3)
C14	0.048 (4)	0.026 (3)	0.052 (6)	−0.002 (3)	0.005 (4)	0.004 (3)
N1	0.042 (3)	0.016 (2)	0.034 (4)	−0.006 (2)	−0.003 (3)	0.001 (2)
N2	0.051 (4)	0.023 (3)	0.055 (5)	−0.016 (3)	0.003 (3)	0.007 (3)

Geometric parameters (Å, º)

C1—C6	1.282 (8)	C9—C10	1.304 (10)
C1—C2	1.449 (9)	C9—N1	1.361 (9)
C1—C7	1.518 (9)	C9—N2	1.402 (10)
C2—C3	1.380 (9)	C10—C11	1.435 (12)
C2—C8	1.434 (8)	C10—H10	0.93
C3—C4	1.291 (9)	C11—C12	1.397 (11)
C3—Cl3	1.795 (7)	C11—H11	0.93
C4—C5	1.413 (9)	C12—C13	1.284 (9)
C4—Cl4	1.738 (7)	C12—H12	0.93
C5—C6	1.390 (8)	C13—N1	1.427 (10)
C5—Cl5	1.607 (6)	C13—C14	1.471 (9)
C6—Cl6	1.793 (7)	C14—H14A	0.96
C7—O2	1.205 (7)	C14—H14B	0.96
C7—O1	1.413 (8)	C14—H14C	0.96
C8—O3	1.248 (8)	N1—H1N	0.86
C8—O4	1.344 (8)	N2—H2A	0.86
O1—H1O	0.82	N2—H2B	0.86
C6—C1—C2	119.3 (6)	C10—C9—N2	122.6 (7)
C6—C1—C7	114.7 (6)	N1—C9—N2	124.9 (6)
C2—C1—C7	126.0 (5)	C9—C10—C11	119.2 (7)
C3—C2—C8	114.9 (6)	C9—C10—H10	120.4
C3—C2—C1	125.4 (6)	C11—C10—H10	120.4
C8—C2—C1	119.7 (6)	C12—C11—C10	127.0 (7)
C4—C3—C2	114.9 (7)	C12—C11—H11	116.5
C4—C3—Cl3	119.7 (5)	C10—C11—H11	116.5
C2—C3—Cl3	125.4 (5)	C13—C12—C11	113.1 (8)
C3—C4—C5	119.1 (6)	C13—C12—H12	123.5
C3—C4—Cl4	113.5 (6)	C11—C12—H12	123.5
C5—C4—Cl4	127.4 (5)	C12—C13—N1	119.0 (7)
C6—C5—C4	126.9 (5)	C12—C13—C14	118.2 (8)
C6—C5—Cl5	114.2 (5)	N1—C13—C14	122.8 (6)
C4—C5—Cl5	118.9 (5)	C13—C14—H14A	109.5
C1—C6—C5	114.2 (6)	C13—C14—H14B	109.5
C1—C6—Cl6	119.9 (5)	H14A—C14—H14B	109.5
C5—C6—Cl6	125.8 (4)	C13—C14—H14C	109.5
O2—C7—O1	127.0 (6)	H14A—C14—H14C	109.5
O2—C7—C1	114.6 (6)	H14B—C14—H14C	109.5
O1—C7—C1	118.3 (5)	C9—N1—C13	129.2 (5)
O3—C8—O4	134.0 (5)	C9—N1—H1N	115.4
O3—C8—C2	111.5 (6)	C13—N1—H1N	115.4
O4—C8—C2	114.5 (6)	C9—N2—H2A	120
C7—O1—H1O	109.5	C9—N2—H2B	120
C10—C9—N1	112.4 (7)	H2A—N2—H2B	120

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···O3	0.86	1.81	2.666 (8)	173
N2—H2A···O2^i	0.86	2.11	2.931 (8)	159
N1—H1N···O4	0.86	1.71	2.559 (7)	171
O1—H1O···O4^ii	0.82	1.83	2.604 (7)	158

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

(II) bis(2-amino-3-methylpyridin-1-ium) 3,4,5,6-tetrachlorophthalate– 3,4,5,6-tetrachlorophthalic acid (1/1)

Crystal data

2C6H9N2^+·C8Cl4O4^2^−·C8H2Cl4O4	Z = 2
Mr = 824.08	F(000) = 832
Triclinic, P1	Dx = 1.688 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.6972 (17) Å	Cell parameters from 4445 reflections
b = 13.762 (3) Å	θ = 1.4–33.2°
c = 15.381 (3) Å	µ = 0.75 mm^−1
α = 69.388 (9)°	T = 120 K
β = 75.342 (10)°	Prism, colorless
γ = 72.618 (1)°	0.41 × 0.14 × 0.12 mm
V = 1621.7 (6) Å^3

Data collection

Rigaku Saturn724+ (2x2 bin mode) diffractometer	5964 independent reflections
Radiation source: Sealed Tube	5551 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
Detector resolution: 28.5714 pixels mm^-1	θmax = 25.7°, θmin = 2.8°
profile data from ω–scans	h = −10→10
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −14→16
Tmin = 0.881, Tmax = 0.914	l = −18→18
9810 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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.090	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0428P)^2 + 1.0334P] where P = (Fo^2 + 2Fc^2)/3
5964 reflections	(Δ/σ)max = 0.002
435 parameters	Δρmax = 0.43 e Å^−3
0 restraints	Δρmin = −0.34 e Å^−3

Special details

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
C1	0.8219 (2)	0.48117 (15)	0.23232 (14)	0.0168 (4)
C2	0.6754 (2)	0.50100 (16)	0.20006 (14)	0.0171 (4)
C3	0.6594 (2)	0.56477 (16)	0.10873 (14)	0.0177 (4)
C4	0.7887 (2)	0.60750 (16)	0.04846 (14)	0.0177 (4)
C5	0.9371 (2)	0.58356 (15)	0.07930 (14)	0.0174 (4)
C6	0.9521 (2)	0.52174 (16)	0.17141 (14)	0.0175 (4)
C7	0.8361 (2)	0.41522 (16)	0.33390 (14)	0.0179 (4)
C8	0.5333 (2)	0.45776 (16)	0.26918 (14)	0.0182 (4)
Cl3	0.47607 (6)	0.59516 (4)	0.06984 (4)	0.02412 (13)
Cl4	0.76717 (6)	0.68803 (4)	−0.06430 (3)	0.02502 (13)
Cl5	1.09952 (6)	0.63103 (4)	0.00283 (3)	0.02045 (12)
Cl6	1.13483 (6)	0.49143 (4)	0.21082 (3)	0.02290 (12)
O1	0.82904 (19)	0.46105 (12)	0.39140 (10)	0.0237 (3)
O2	0.84842 (18)	0.31577 (11)	0.35278 (10)	0.0215 (3)
O3	0.4826 (2)	0.49028 (13)	0.33959 (11)	0.0291 (4)
O4	0.47819 (17)	0.39221 (11)	0.25293 (10)	0.0198 (3)
C9	0.9232 (3)	0.05523 (16)	0.20767 (14)	0.0195 (4)
C10	0.7747 (3)	0.08973 (16)	0.17426 (14)	0.0200 (4)
C11	0.7426 (3)	0.03654 (17)	0.12159 (14)	0.0212 (4)
C12	0.8591 (3)	−0.05110 (17)	0.10079 (14)	0.0210 (4)
C13	1.0081 (3)	−0.08466 (16)	0.13277 (14)	0.0218 (4)
C14	1.0403 (3)	−0.03074 (17)	0.18561 (14)	0.0206 (4)
C15	0.9463 (3)	0.10950 (17)	0.27186 (15)	0.0219 (4)
C16	0.6457 (2)	0.17577 (17)	0.20869 (15)	0.0211 (4)
Cl11	0.55442 (7)	0.07527 (5)	0.08695 (4)	0.02970 (14)
Cl12	0.81806 (7)	−0.11799 (4)	0.03655 (4)	0.02806 (13)
Cl13	1.15223 (7)	−0.19198 (4)	0.10737 (4)	0.02924 (14)
Cl14	1.22773 (6)	−0.06856 (5)	0.22118 (4)	0.02861 (13)
O5	0.92425 (19)	0.21231 (12)	0.23277 (10)	0.0247 (3)
H5O	0.9377	0.2404	0.2699	0.037*
O6	0.9736 (2)	0.06017 (13)	0.35098 (11)	0.0332 (4)
O7	0.62076 (18)	0.26954 (12)	0.14668 (10)	0.0223 (3)
H7O	0.5479	0.3125	0.1711	0.033*
O8	0.5784 (2)	0.15309 (13)	0.29054 (11)	0.0304 (4)
C17	0.5891 (2)	0.26491 (16)	0.57298 (14)	0.0197 (4)
C18	0.4778 (3)	0.21799 (17)	0.65167 (14)	0.0207 (4)
C19	0.4450 (3)	0.12603 (17)	0.65291 (15)	0.0248 (5)
H19	0.3697	0.0943	0.7038	0.03*
C20	0.5186 (3)	0.07690 (18)	0.58151 (16)	0.0263 (5)
H20	0.4948	0.0128	0.5841	0.032*
C21	0.6247 (3)	0.12387 (18)	0.50867 (16)	0.0261 (5)
H21	0.6763	0.0925	0.4595	0.031*
C22	0.4052 (3)	0.27119 (18)	0.72747 (16)	0.0275 (5)
H22A	0.3441	0.344	0.7003	0.041*
H22B	0.4927	0.2737	0.7556	0.041*
H22C	0.3313	0.2307	0.7761	0.041*
N1	0.6569 (2)	0.21554 (14)	0.50616 (12)	0.0221 (4)
H1N	0.726	0.2443	0.4582	0.027*
N2	0.6282 (2)	0.35485 (15)	0.56363 (13)	0.0246 (4)
H2A	0.6974	0.3812	0.5143	0.029*
H2B	0.5849	0.388	0.6067	0.029*
C23	0.1964 (2)	0.32552 (16)	0.48343 (14)	0.0193 (4)
C24	0.0836 (2)	0.27476 (17)	0.55759 (14)	0.0201 (4)
C25	0.0513 (3)	0.18660 (17)	0.55150 (15)	0.0226 (4)
H25	−0.0225	0.1513	0.6007	0.027*
C26	0.1240 (3)	0.14623 (17)	0.47443 (16)	0.0246 (5)
H26	0.1008	0.0842	0.4717	0.03*
C27	0.2282 (3)	0.19830 (17)	0.40407 (16)	0.0229 (4)
H27	0.2764	0.1739	0.3505	0.028*
C28	0.0050 (3)	0.32028 (19)	0.63791 (15)	0.0268 (5)
H28A	−0.0464	0.3961	0.6132	0.04*
H28B	0.0881	0.3125	0.6741	0.04*
H28C	−0.0782	0.282	0.6788	0.04*
N3	0.2634 (2)	0.28547 (14)	0.41032 (12)	0.0201 (4)
H3N	0.3329	0.317	0.3647	0.024*
N4	0.2406 (2)	0.41012 (15)	0.48375 (13)	0.0247 (4)
H4A	0.3119	0.4384	0.437	0.03*
H4B	0.1986	0.4377	0.5307	0.03*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0170 (9)	0.0137 (9)	0.0191 (10)	−0.0038 (7)	−0.0003 (7)	−0.0061 (8)
C2	0.0157 (9)	0.0159 (9)	0.0197 (10)	−0.0043 (8)	0.0008 (8)	−0.0074 (8)
C3	0.0135 (9)	0.0190 (10)	0.0219 (10)	−0.0019 (8)	−0.0025 (7)	−0.0093 (8)
C4	0.0188 (10)	0.0162 (10)	0.0163 (9)	−0.0027 (8)	−0.0007 (8)	−0.0052 (8)
C5	0.0167 (9)	0.0151 (9)	0.0201 (10)	−0.0054 (8)	0.0026 (8)	−0.0073 (8)
C6	0.0153 (9)	0.0180 (10)	0.0193 (10)	−0.0028 (8)	−0.0025 (8)	−0.0067 (8)
C7	0.0133 (9)	0.0206 (10)	0.0176 (9)	−0.0039 (8)	0.0004 (7)	−0.0053 (8)
C8	0.0151 (9)	0.0166 (10)	0.0214 (10)	−0.0037 (8)	−0.0026 (8)	−0.0041 (8)
Cl3	0.0170 (2)	0.0295 (3)	0.0243 (3)	−0.0051 (2)	−0.00616 (19)	−0.0046 (2)
Cl4	0.0252 (3)	0.0278 (3)	0.0169 (2)	−0.0065 (2)	−0.00372 (19)	−0.0002 (2)
Cl5	0.0183 (2)	0.0220 (2)	0.0195 (2)	−0.00859 (19)	0.00323 (18)	−0.00555 (19)
Cl6	0.0160 (2)	0.0299 (3)	0.0222 (2)	−0.0078 (2)	−0.00399 (18)	−0.0045 (2)
O1	0.0288 (8)	0.0248 (8)	0.0191 (7)	−0.0095 (6)	−0.0013 (6)	−0.0074 (6)
O2	0.0271 (8)	0.0172 (7)	0.0181 (7)	−0.0050 (6)	−0.0015 (6)	−0.0043 (6)
O3	0.0304 (8)	0.0336 (9)	0.0280 (8)	−0.0179 (7)	0.0118 (7)	−0.0179 (7)
O4	0.0179 (7)	0.0195 (7)	0.0226 (7)	−0.0069 (6)	−0.0007 (6)	−0.0067 (6)
C9	0.0229 (10)	0.0165 (10)	0.0165 (9)	−0.0074 (8)	0.0002 (8)	−0.0020 (8)
C10	0.0226 (10)	0.0186 (10)	0.0160 (9)	−0.0074 (8)	0.0015 (8)	−0.0031 (8)
C11	0.0194 (10)	0.0230 (11)	0.0196 (10)	−0.0070 (8)	−0.0013 (8)	−0.0043 (8)
C12	0.0274 (11)	0.0220 (11)	0.0152 (9)	−0.0118 (9)	0.0012 (8)	−0.0056 (8)
C13	0.0259 (11)	0.0185 (10)	0.0169 (10)	−0.0047 (8)	0.0030 (8)	−0.0053 (8)
C14	0.0198 (10)	0.0212 (10)	0.0174 (10)	−0.0063 (8)	−0.0001 (8)	−0.0025 (8)
C15	0.0224 (10)	0.0218 (11)	0.0213 (10)	−0.0081 (8)	−0.0006 (8)	−0.0059 (9)
C16	0.0188 (10)	0.0222 (11)	0.0221 (10)	−0.0073 (8)	−0.0001 (8)	−0.0065 (8)
Cl11	0.0230 (3)	0.0352 (3)	0.0328 (3)	−0.0075 (2)	−0.0077 (2)	−0.0096 (2)
Cl12	0.0392 (3)	0.0279 (3)	0.0221 (3)	−0.0144 (2)	−0.0023 (2)	−0.0100 (2)
Cl13	0.0328 (3)	0.0232 (3)	0.0260 (3)	0.0001 (2)	0.0011 (2)	−0.0102 (2)
Cl14	0.0206 (3)	0.0322 (3)	0.0304 (3)	−0.0043 (2)	−0.0056 (2)	−0.0068 (2)
O5	0.0352 (9)	0.0203 (8)	0.0200 (7)	−0.0102 (6)	−0.0034 (6)	−0.0053 (6)
O6	0.0543 (11)	0.0257 (8)	0.0235 (8)	−0.0112 (8)	−0.0154 (8)	−0.0041 (7)
O7	0.0224 (7)	0.0196 (7)	0.0203 (7)	−0.0021 (6)	−0.0008 (6)	−0.0048 (6)
O8	0.0328 (9)	0.0247 (8)	0.0240 (8)	−0.0054 (7)	0.0080 (7)	−0.0055 (7)
C17	0.0192 (10)	0.0199 (10)	0.0185 (10)	−0.0031 (8)	−0.0055 (8)	−0.0036 (8)
C18	0.0197 (10)	0.0204 (10)	0.0190 (10)	−0.0041 (8)	−0.0033 (8)	−0.0027 (8)
C19	0.0259 (11)	0.0236 (11)	0.0203 (10)	−0.0089 (9)	−0.0020 (8)	0.0003 (9)
C20	0.0324 (12)	0.0201 (11)	0.0281 (11)	−0.0093 (9)	−0.0068 (9)	−0.0051 (9)
C21	0.0313 (12)	0.0240 (11)	0.0232 (11)	−0.0063 (9)	−0.0036 (9)	−0.0078 (9)
C22	0.0294 (12)	0.0263 (12)	0.0232 (11)	−0.0102 (9)	0.0037 (9)	−0.0056 (9)
N1	0.0263 (9)	0.0213 (9)	0.0178 (8)	−0.0085 (7)	0.0006 (7)	−0.0052 (7)
N2	0.0290 (10)	0.0240 (9)	0.0218 (9)	−0.0122 (8)	0.0042 (7)	−0.0089 (7)
C23	0.0177 (10)	0.0181 (10)	0.0198 (10)	−0.0032 (8)	−0.0041 (8)	−0.0029 (8)
C24	0.0174 (10)	0.0209 (10)	0.0186 (10)	−0.0047 (8)	−0.0034 (8)	−0.0013 (8)
C25	0.0198 (10)	0.0214 (10)	0.0233 (10)	−0.0071 (8)	−0.0053 (8)	0.0003 (8)
C26	0.0249 (11)	0.0212 (11)	0.0295 (11)	−0.0079 (9)	−0.0068 (9)	−0.0060 (9)
C27	0.0237 (11)	0.0217 (11)	0.0247 (11)	−0.0048 (8)	−0.0057 (8)	−0.0076 (9)
C28	0.0263 (11)	0.0300 (12)	0.0222 (11)	−0.0099 (9)	0.0011 (9)	−0.0064 (9)
N3	0.0177 (8)	0.0203 (9)	0.0203 (8)	−0.0053 (7)	−0.0009 (7)	−0.0046 (7)
N4	0.0270 (10)	0.0248 (10)	0.0230 (9)	−0.0131 (8)	0.0042 (7)	−0.0079 (8)

Geometric parameters (Å, º)

C1—C6	1.394 (3)	C17—N2	1.330 (3)
C1—C2	1.401 (3)	C17—N1	1.346 (3)
C1—C7	1.521 (3)	C17—C18	1.431 (3)
C2—C3	1.386 (3)	C18—C19	1.371 (3)
C2—C8	1.530 (3)	C18—C22	1.499 (3)
C3—C4	1.398 (3)	C19—C20	1.408 (3)
C3—Cl3	1.727 (2)	C19—H19	0.95
C4—C5	1.395 (3)	C20—C21	1.359 (3)
C4—Cl4	1.720 (2)	C20—H20	0.95
C5—C6	1.388 (3)	C21—N1	1.358 (3)
C5—Cl5	1.725 (2)	C21—H21	0.95
C6—Cl6	1.727 (2)	C22—H22A	0.98
C7—O1	1.235 (3)	C22—H22B	0.98
C7—O2	1.272 (3)	C22—H22C	0.98
C8—O3	1.245 (3)	N1—H1N	0.88
C8—O4	1.258 (3)	N2—H2A	0.88
C9—C14	1.393 (3)	N2—H2B	0.88
C9—C10	1.398 (3)	C23—N4	1.333 (3)
C9—C15	1.511 (3)	C23—N3	1.349 (3)
C10—C11	1.387 (3)	C23—C24	1.426 (3)
C10—C16	1.513 (3)	C24—C25	1.363 (3)
C11—C12	1.401 (3)	C24—C28	1.499 (3)
C11—Cl11	1.722 (2)	C25—C26	1.410 (3)
C12—C13	1.392 (3)	C25—H25	0.95
C12—Cl12	1.722 (2)	C26—C27	1.361 (3)
C13—C14	1.398 (3)	C26—H26	0.95
C13—Cl13	1.720 (2)	C27—N3	1.363 (3)
C14—Cl14	1.724 (2)	C27—H27	0.95
C15—O6	1.211 (3)	C28—H28A	0.98
C15—O5	1.303 (3)	C28—H28B	0.98
C16—O8	1.218 (3)	C28—H28C	0.98
C16—O7	1.301 (3)	N3—H3N	0.88
O5—H5O	0.84	N4—H4A	0.88
O7—H7O	0.84	N4—H4B	0.88
C6—C1—C2	119.90 (18)	N1—C17—C18	118.42 (19)
C6—C1—C7	121.00 (18)	C19—C18—C17	117.4 (2)
C2—C1—C7	119.10 (17)	C19—C18—C22	124.00 (19)
C3—C2—C1	119.32 (18)	C17—C18—C22	118.63 (19)
C3—C2—C8	121.83 (18)	C18—C19—C20	122.4 (2)
C1—C2—C8	118.71 (18)	C18—C19—H19	118.8
C2—C3—C4	120.66 (18)	C20—C19—H19	118.8
C2—C3—Cl3	119.81 (15)	C21—C20—C19	118.1 (2)
C4—C3—Cl3	119.50 (16)	C21—C20—H20	121
C5—C4—C3	119.92 (18)	C19—C20—H20	121
C5—C4—Cl4	119.63 (15)	N1—C21—C20	120.1 (2)
C3—C4—Cl4	120.44 (16)	N1—C21—H21	120
C6—C5—C4	119.44 (18)	C20—C21—H21	120
C6—C5—Cl5	120.81 (16)	C18—C22—H22A	109.5
C4—C5—Cl5	119.76 (15)	C18—C22—H22B	109.5
C5—C6—C1	120.66 (18)	H22A—C22—H22B	109.5
C5—C6—Cl6	120.07 (15)	C18—C22—H22C	109.5
C1—C6—Cl6	119.25 (15)	H22A—C22—H22C	109.5
O1—C7—O2	125.39 (19)	H22B—C22—H22C	109.5
O1—C7—C1	118.96 (18)	C17—N1—C21	123.66 (18)
O2—C7—C1	115.59 (17)	C17—N1—H1N	118.2
O3—C8—O4	124.88 (19)	C21—N1—H1N	118.2
O3—C8—C2	115.69 (18)	C17—N2—H2A	120
O4—C8—C2	119.41 (18)	C17—N2—H2B	120
C14—C9—C10	119.72 (19)	H2A—N2—H2B	120
C14—C9—C15	122.20 (19)	N4—C23—N3	118.35 (18)
C10—C9—C15	117.98 (18)	N4—C23—C24	122.8 (2)
C11—C10—C9	120.03 (19)	N3—C23—C24	118.80 (19)
C11—C10—C16	122.16 (19)	C25—C24—C23	117.9 (2)
C9—C10—C16	117.30 (18)	C25—C24—C28	122.84 (19)
C10—C11—C12	120.3 (2)	C23—C24—C28	119.27 (19)
C10—C11—Cl11	119.35 (17)	C24—C25—C26	122.0 (2)
C12—C11—Cl11	120.33 (16)	C24—C25—H25	119
C13—C12—C11	119.85 (19)	C26—C25—H25	119
C13—C12—Cl12	119.96 (17)	C27—C26—C25	118.3 (2)
C11—C12—Cl12	120.19 (17)	C27—C26—H26	120.8
C12—C13—C14	119.76 (19)	C25—C26—H26	120.8
C12—C13—Cl13	120.22 (16)	C26—C27—N3	120.1 (2)
C14—C13—Cl13	120.02 (17)	C26—C27—H27	120
C9—C14—C13	120.4 (2)	N3—C27—H27	120
C9—C14—Cl14	119.73 (17)	C24—C28—H28A	109.5
C13—C14—Cl14	119.89 (17)	C24—C28—H28B	109.5
O6—C15—O5	126.7 (2)	H28A—C28—H28B	109.5
O6—C15—C9	121.63 (19)	C24—C28—H28C	109.5
O5—C15—C9	111.51 (18)	H28A—C28—H28C	109.5
O8—C16—O7	126.1 (2)	H28B—C28—H28C	109.5
O8—C16—C10	118.59 (19)	C23—N3—C27	122.89 (18)
O7—C16—C10	115.32 (17)	C23—N3—H3N	118.6
C15—O5—H5O	109.5	C27—N3—H3N	118.6
C16—O7—H7O	109.5	C23—N4—H4A	120
N2—C17—N1	118.96 (19)	C23—N4—H4B	120
N2—C17—C18	122.6 (2)	H4A—N4—H4B	120

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5O···O2	0.84	1.80	2.558 (2)	149
O7—H7O···O4	0.84	1.83	2.593 (2)	151
N1—H1N···O2	0.88	1.83	2.708 (2)	173
N2—H2A···O1	0.88	2.07	2.943 (2)	171
N3—H3N···O4	0.88	2.01	2.891 (2)	175
N4—H4A···O3	0.88	1.93	2.805 (2)	175
N2—H2B···O3^i	0.88	1.99	2.823 (2)	157
N4—H4B···O1^i	0.88	2.07	2.892 (2)	156

Symmetry code: (i) −x+1, −y+1, −z+1.