Hydrogen-bond-directed supra­molecular arrays in 4,4′-bipyridinium tetra­chloro­terephthalate dihydrate and bis­(1,10-phenanthrolinium) tetra­chloro­terephthalate tetra­chloro­terephthalic acid trihydrate

The title compounds, C₁₀H₁₀N₂²⁺·C₈Cl₄O₄²⁻·2H₂O, (I), and 2C₁₂H₉N₂⁺·C₈Cl₄O₄²⁻·C₈H₂Cl₄O₄·3H₂O, (II), both crystallize as charge-transfer organic salts with the dianionic or neutral acid components lying on inversion centres. The acid and base subunits in (I) arrange alternately to generate a linear tape motif via N—H...O hydrogen bonds; these tapes are further combined into a three-dimensional architecture through multiple O—H...O and C—H...O inter­actions involving solvent water mol­ecules. In contrast, the neutral and anionic acid components in (II) are linked to form a zigzag chain by means of O—H...O hydrogen bonds between acid groups, with dangling 1,10-phenanthrolinium units connected to these chains by carboxyl­ate–pyridinium inter­actions with R₂²(7) hydrogen-bond notation. Adjacent chains are further extended to result in a two-dimensional corrugated layer network via π–π inter­actions. Inter-ion Cl...O inter­actions are also found in both (I) and (II).

S1. Comment

The supramolecular synthon approach has been widely applied to tailor desired supramolecules and molecular solids by using previously identified robust intermolecular interactions since it offers a considerable simplification in the design of crystal structures (Desiraju, 1995; Nangia & Desiraju, 1998). For the co-crystal structures of carboxylic acids with pyridyl building blocks, strong hydrogen bonds, such as O—H···N or charge-assisted N—H···O, are always essential, usually combining auxiliary weak C—H···O interactions, leading to the most familiar carboxyl/pyridyl heterosynthon [R₂²(7); Etter, 1990] (Shan et al., 2002). In this context, although aromatic dicarboxylic acids have been proven to be excellent building blocks in binary co-crystal assemblies with bipyridine-type components, terephthalic acid (H₂tp) has been less well studied than phthalic acid and isophthalic acid in this respect owing to the mismatched solubility with base components, especially because of its poor solubility (Du et al., 2005). Related efforts on its derivatives have been rare so far. Notably, it can be forecast that the substituent groups will influence the structural assemblies, since they may display different hydrogen-bonding capability and potential steric/electronic effects. A search of the Cambridge Structural Database (CSD; Version 5.30 of November 2009, plus two updates; Allen, 2002) reveals that no organic structure based on a halogen functional terephthalic acid has been reported to date, except a supramolecular adduct of triethylammonium with tetrachloroterephthalic acid (H₂tpCl₄; Lan et al., 2008). In this present work, two charge-transfer crystalline products, that is [(H₂bipy)][tpCl₄].2H₂O], (I) (bipy = 4,4'-bipyridine), and [(Hphen)₂(H₂tpCl₄)(tpCl₄).3H₂O], (II) (phen = 1,10-phenanthroline), were prepared.

Compound (I) is shown to be a proton-transfer organic binary salt, in which the asymmetric unit is composed of half of a tpCl₄^2- anion, half of an H₂bipy²⁺ cation (both lying about independent inversion centres) and one solvent water molecule in a general position (Fig. 1). Proton transfer from the tetrachloroterephthalic acid to the 4,4'-bipyridine moiety was unequivocally established from difference map plots, and the resulting cation and anion dimensions are normal and fully in accord with this proton transfer scheme. Because the two pyridylium rings are related by an inversion centre, the dihedral angle between then is exactly 0°. In the centrosymmetric tpCl₄^2- ion the unique carboxyl group is nearly perpendicular [87.4 (2)°] to the aromatic ring as influenced by the stereo hindrance of the adjacent chloro substituents. The aromatic ring of the tpCl₄^2- anion is inclined at 3.96 (9)° to the bipy component.

In the crystal structure of (I) (Fig. 2), linear tapes are generated through strong N1—H1···O1 hydrogen bonds (Table 1) between carboxylate and pyridinium groups; these tapes run along the crystallographic [211] direction with a graph-set notation C₂²(18) (Etter, 1990). Notably, the anticipated R₂²(7) synthon of N—H···O/C—H···O is absent owing to the approximately perpendicular dihedral angle [83.52 (13)°] between the carboxylate and pyridinium groups. The solvent water molecule is involved in two strong hydrogen bonds (O3—H3A···O2 and O3—H3B···O2ⁱⁱⁱ; symmetry codes and geometric parameters are given in Table 1) with carboxylate atom O2 of tpCl₄^2-, which leads to an eight-membered hydrogen-bonded R₄²(8) ring and gives rise to a linear [(tpCl₄)^2-.2H₂O]_n chain extending along the c-axis direction. Such hydrogen-bonding interactions connect neighboring tapes, resulting in a two-dimensional layer, as shown in Fig. 2. These layers align parallel to the (120) plane with some offset to fulfill the final three-dimensional hydrogen-bonding framework which is generated via weak C—H···O interactions (C6—H6···O3^iv and C8—H8···O3^v; Table 1) between bipyridinium cations and water molecules from adjacent layers. Additionally, intermolecular C4—Cl2···O3^vi [symmetry code: (vi) x + 1, y, z - 1] interactions link water molecules to further consolidate the three-dimensional assembly, with a Cl···O distance of 3.040 (2) Å, modestly shorter than the van der Waals distance (3.12 Å) suggested by Nyburg & Faerman (1985).

Crystallization of tetrachloroterephthalic acid with phenanthroline also yields a proton-transfer organic salt, (II). The crystal structure of (II) exhibits a two-dimensional supramolecular host network with the inclusion of disordered guest water molecules (Fig. 3). The asymmetric unit is composed of half of an H₂tpCl₄ molecule, half of a tpCl₄^2- anion, (both lying about independent inversion centres), one monoprotonated Hphen⁺ cation in a general position and 1.5 disordered guest water molecules lying about another inversion centre. Proton transfer from a tetrachloroterephthalic acid molecule to the phen molecule was unequivocally established from difference map plots and the resulting cation and anion dimensions are normal and fully in accord with this proton transfer scheme.

As shown in Fig. 3, within each centrosymmetric acidic unit, the rotation angles of the the carboxylate/carboxyl groups relative to the tetrachlorinated aromatic rings are 77.8 (2)° for tpCl₄^2- and 89.9 (1)° for H₂tpCl₄, respectively. The rotation angle in the dianion moiety is smaller than the corresponding values for other polychlorinated carboxylate compounds [80.6 (4) and 89.7 (3)° (Maspoch et al., 2004), and 81.88 (13)–90.0 (1)° (Chen et al., 2008)]. Analysis of the crystal packing of (II) shows that the neutral and dianionic acid moieties are connected to by intermolecular O1—H1'···O3 hydrogen bonds to form a one-dimensional zigzag chain structure extending in the (101) direction. Meanwhile, each tpCl₄^2- dianion is linked to monoprotonated Hphen⁺ cations with an R₂²(7) ring pattern via N1—H1A···O3 and C10—H10···O4 hydrogen bonds (Table 2). Adjacent inversion-related Hphen⁺ ions take part in π–π interactions; the centroid (Cg1) of the N1/C7–C10/C12 ring is 3.556 (2) Å from the centroid (Cg2) of the C4–C7/C11/C12 ring at (1 - x,2 - y,1 - z); this also allows a further C6—H6···O2^iv (Table 2) interaction and expands the one-dimensional zigzag motif into a two-dimensional hydrogen-bonding network (Fig. 5). The disordered solvent water subunits are captured in the two-dimensional supramolecular layer with partial-occupancy water atom O52 lying 2.765 (7) Å from the adjacent carboxylate atom O4. Adjoining two-dimensional layers are further extended to a three-dimensional arrangement through intermolecular C20—Cl4···O4^v [Cl···O =3.265 (2) Å and C—Cl···O 144.42 (10)°; symmetry code: (v) x + 1, y, z] interactions.

In conclusion, this work demonstrates the first example of H₂tpCl₄ as a good participant in cocrystallization with aromatic diamines. When cocrystallizing with the rod-like 4,4'-bipyridine building block, the H₂tpCl₄ subunits reliably form N—H···O interactions, while in the case of 2,2'-bipyridine-type moieties, only one of the phenanthroline N-atom donors forms an R₂²(7) heterosynthon with anionic tpCl₄ as a result of the stereochemistry effect of the phen molecule. Both the acid–base adducts show organic binary salts behaving as charge-assisted hydrogen-bonding structures of considerable multiplicity. This result offers a new challenge in the seeking of true neutral cocrystals based on such halogen-substituted terephthalic acids.

Related literature

For related literature, see: Allen (2002); Chen et al. (2007, 2008); Desiraju (1995); Du et al. (2005); Etter (1990); Lan et al. (2008); Maspoch et al. (2004); Nangia & Desiraju (1998); Nyburg & Faerman (1985); Shan et al. (2002).

S2. Experimental

All the reagents and solvents for synthesis were commercially available and used as received, except for H₂tpCl₄, which was prepared according to the literature procedures (Chen et al., 2007). For the preparation of (I), to a methanol/water (2:1 v/v) solution (6 ml) of H₂tpCl₄ was added a solution of bipy (15.8 mg, 0.1 mmol) in methanol (5 ml). After stirring for ca 10 min, the reaction mixture was filtered and left to stand at ambient temperature. Colorless block crystals of (I) suitable for X-ray diffraction were obtained through 5 d evaporation of the filtrate with a yield of 90% (44.6 mg, based on bipy). Analysis calculated for C₁₈H₁₄Cl₄N₂O₆: C 43.58, H 2.84, N 5.65%; found: C 43.58, H 2.96, N 5.56%.

For the preparation of (II), the same synthetic procedure as that for (I) was used except that bipy was replaced by phen (18.0 mg, 0.1 mmol), affording colorless block crystals of (II) in 85% yield (43.4 mg, based on phen). Analysis calculated for C₄₀H₂₆Cl₈N₄O₁₁: C 47.00, H 2.56, N 5.48%; found: C 47.03, H 2.61, N 5.45%.

S3. Refinement

H atoms bonded to C atoms were positioned geometrically (C—H = 0.93 Å) and included in the refinement in the riding-model approximation, with U_iso(H) set at 1.2U_eq(C). In (II), a study of the electron-density maps showed that the water molecule O5 is disordered unequally over two sites, consistent with occupancies of 0.6 and 0.4; the water molecule O6 has electron density consistent with it being a half-occupancy O atom disordered equally over two sites. It was not possible to locate any of these water H atoms. All of the other water and amine H atoms were located in difference maps and allowed for as riding with U_iso(H) value of 1.5U_eq(O,N).

Computing details

For both compounds, data collection: APEX2 (Bruker, 2007); cell refinement: APEX2 and SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2005); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. The molecular structure of (I), drawn with 30% probability displacement ellipsoids. Hydrogen bonds are indicated as dashed lines. [Symmetry codes: (i) -x + 2, -y + 1, -z + 1; (ii) -x, -y + 2, -z + 2.]
	Fig. 2. The two-dimensional hydrogen-bonded layer of (I). Hydrogen bonds are indicated as dashed lines. [Symmetry codes: (i) -x + 2, -y + 1, -z + 1; (ii) -x, -y + 2, -z + 2; (iii) -x + 2, -y + 1, -z + 2.]
	Fig. 3. The molecular structure of (II), drawn with 30% probability displacement ellipsoids. Hydrogen bonds are indicated as dashed lines. [Symmetry codes: (i) -x + 2, -y + 1, -z + 1; (ii) -x + 1, -y + 1, -z; (iii) -x, -y + 2, -z.]
	Fig. 4. A partial view of the one-dimensional zigzag motif of (II). Hydrogen bonds are indicated as dashed lines. [Symmetry codes: (i) -x + 2, -y + 1, -z + 1; (ii) -x + 1, -y + 1, -z.]
	Fig. 5. The two-dimensional hydrogen-bonded layer of (II), with hydrogen bonds indicated as dashed lines. The disordered water guests within the cavities have been omitted for clarity.

(I) 4,4'-bipyridinium tetrachloroterephthalate dihydrate

Crystal data

C10H10N2^2+·C8Cl4O4^2^−·2H2O	Z = 1
Mr = 496.11	F(000) = 252
Triclinic, P1	Dx = 1.643 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.306 (2) Å	Cell parameters from 3073 reflections
b = 9.325 (3) Å	θ = 2.3–27.6°
c = 10.040 (4) Å	µ = 0.63 mm^−1
α = 62.508 (3)°	T = 296 K
β = 86.763 (4)°	Block, colorless
γ = 73.842 (4)°	0.18 × 0.15 × 0.12 mm
V = 501.3 (3) Å^3

Data collection

Bruker APEXII? CCD area-detector diffractometer	1732 independent reflections
Radiation source: fine-focus sealed tube	1590 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
phi and ω scans	θmax = 25.0°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −7→7
Tmin = 0.895, Tmax = 0.928	k = −11→11
3529 measured reflections	l = −11→11

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.128	H-atom parameters constrained
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0928P)^2 + 0.2018P] where P = (Fo^2 + 2Fc^2)/3
1732 reflections	(Δ/σ)max = 0.001
136 parameters	Δρmax = 0.40 e Å^−3
0 restraints	Δρmin = −0.47 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
O1	0.6388 (3)	0.8256 (2)	0.58191 (18)	0.0333 (4)
C1	0.7975 (4)	0.6971 (3)	0.6556 (2)	0.0255 (5)
C2	0.9041 (3)	0.5942 (3)	0.5747 (2)	0.0221 (5)
C3	1.0746 (4)	0.6338 (3)	0.4826 (2)	0.0233 (5)
C4	1.1701 (3)	0.5396 (3)	0.4087 (2)	0.0227 (5)
Cl1	1.16530 (10)	0.80187 (7)	0.46194 (6)	0.0333 (2)
Cl2	1.38021 (9)	0.58890 (7)	0.29182 (6)	0.0308 (2)
O2	0.8747 (3)	0.6456 (2)	0.78608 (19)	0.0432 (5)
C5	0.3642 (4)	1.0521 (3)	0.7790 (3)	0.0315 (5)
H5	0.4533	1.1224	0.7295	0.038*
C6	0.2182 (4)	1.0860 (3)	0.8760 (3)	0.0296 (5)
H6	0.2111	1.1774	0.8925	0.036*
C7	0.0822 (4)	0.9831 (3)	0.9485 (2)	0.0243 (5)
C8	0.1036 (5)	0.8457 (3)	0.9214 (3)	0.0371 (6)
H8	0.0160	0.7734	0.9681	0.045*
C9	0.2546 (5)	0.8177 (3)	0.8253 (3)	0.0366 (6)
H9	0.2698	0.7251	0.8089	0.044*
N1	0.3792 (3)	0.9207 (2)	0.7556 (2)	0.0281 (5)
H1	0.4759	0.8987	0.6933	0.042*
O3	0.7331 (3)	0.6041 (2)	1.07034 (19)	0.0391 (5)
H3A	0.7253	0.6329	0.9798	0.059*
H3B	0.8412	0.5318	1.1264	0.059*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0346 (10)	0.0339 (9)	0.0283 (8)	0.0003 (8)	0.0076 (7)	−0.0181 (7)
C1	0.0266 (12)	0.0316 (11)	0.0220 (10)	−0.0083 (10)	0.0085 (9)	−0.0160 (9)
C2	0.0188 (11)	0.0278 (11)	0.0191 (10)	−0.0010 (9)	0.0022 (8)	−0.0137 (9)
C3	0.0212 (11)	0.0269 (11)	0.0225 (10)	−0.0036 (9)	0.0026 (9)	−0.0139 (9)
C4	0.0181 (11)	0.0292 (11)	0.0197 (10)	−0.0026 (9)	0.0050 (8)	−0.0131 (9)
Cl1	0.0361 (4)	0.0370 (4)	0.0384 (4)	−0.0161 (3)	0.0122 (3)	−0.0249 (3)
Cl2	0.0284 (4)	0.0379 (4)	0.0302 (4)	−0.0116 (3)	0.0147 (2)	−0.0194 (3)
O2	0.0468 (11)	0.0565 (11)	0.0283 (9)	0.0000 (9)	−0.0012 (8)	−0.0290 (8)
C5	0.0340 (13)	0.0342 (12)	0.0333 (12)	−0.0141 (11)	0.0130 (10)	−0.0201 (10)
C6	0.0317 (13)	0.0321 (12)	0.0351 (12)	−0.0121 (10)	0.0122 (10)	−0.0232 (10)
C7	0.0254 (12)	0.0283 (11)	0.0212 (10)	−0.0059 (9)	0.0042 (9)	−0.0145 (9)
C8	0.0486 (16)	0.0415 (13)	0.0399 (13)	−0.0253 (12)	0.0219 (12)	−0.0292 (11)
C9	0.0456 (16)	0.0386 (13)	0.0412 (14)	−0.0174 (12)	0.0174 (12)	−0.0297 (11)
N1	0.0280 (11)	0.0315 (10)	0.0265 (10)	−0.0041 (8)	0.0084 (8)	−0.0180 (8)
O3	0.0405 (11)	0.0465 (10)	0.0348 (9)	−0.0103 (8)	0.0109 (8)	−0.0246 (8)

Geometric parameters (Å, º)

O1—C1	1.258 (3)	C6—C7	1.389 (3)
C1—O2	1.243 (3)	C6—H6	0.9300
C1—C2	1.527 (3)	C7—C8	1.399 (3)
C2—C4^i	1.388 (3)	C7—C7^ii	1.497 (4)
C2—C3	1.394 (3)	C8—C9	1.377 (4)
C3—C4	1.393 (3)	C8—H8	0.9300
C3—Cl1	1.735 (2)	C9—N1	1.329 (3)
C4—C2^i	1.388 (3)	C9—H9	0.9300
C4—Cl2	1.734 (2)	N1—H1	0.9000
C5—N1	1.329 (3)	O3—H3A	0.8202
C5—C6	1.384 (4)	O3—H3B	0.8202
C5—H5	0.9300
O2—C1—O1	127.0 (2)	C5—C6—H6	120.1
O2—C1—C2	117.3 (2)	C7—C6—H6	120.1
O1—C1—C2	115.72 (18)	C6—C7—C8	117.4 (2)
C4^i—C2—C3	119.2 (2)	C6—C7—C7^ii	121.8 (2)
C4^i—C2—C1	120.03 (19)	C8—C7—C7^ii	120.8 (3)
C3—C2—C1	120.7 (2)	C9—C8—C7	119.8 (2)
C4—C3—C2	120.3 (2)	C9—C8—H8	120.1
C4—C3—Cl1	120.83 (18)	C7—C8—H8	120.1
C2—C3—Cl1	118.85 (17)	N1—C9—C8	121.2 (2)
C2^i—C4—C3	120.4 (2)	N1—C9—H9	119.4
C2^i—C4—Cl2	118.66 (17)	C8—C9—H9	119.4
C3—C4—Cl2	120.89 (18)	C5—N1—C9	120.7 (2)
N1—C5—C6	121.1 (2)	C5—N1—H1	120.5
N1—C5—H5	119.5	C9—N1—H1	118.7
C6—C5—H5	119.5	H3A—O3—H3B	121.3
C5—C6—C7	119.8 (2)
O2—C1—C2—C4^i	87.5 (3)	C2—C3—C4—Cl2	179.20 (15)
O1—C1—C2—C4^i	−92.1 (2)	Cl1—C3—C4—Cl2	−0.8 (3)
O2—C1—C2—C3	−93.1 (3)	N1—C5—C6—C7	−1.0 (4)
O1—C1—C2—C3	87.3 (3)	C5—C6—C7—C8	1.2 (3)
C4^i—C2—C3—C4	−0.3 (3)	C5—C6—C7—C7^ii	−178.5 (3)
C1—C2—C3—C4	−179.72 (18)	C6—C7—C8—C9	−0.3 (4)
C4^i—C2—C3—Cl1	179.73 (15)	C7^ii—C7—C8—C9	179.5 (3)
C1—C2—C3—Cl1	0.3 (3)	C7—C8—C9—N1	−1.0 (4)
C2—C3—C4—C2^i	0.3 (3)	C6—C5—N1—C9	−0.3 (4)
Cl1—C3—C4—C2^i	−179.73 (15)	C8—C9—N1—C5	1.3 (4)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.90	1.72	2.609 (3)	169
O3—H3A···O2	0.82	2.08	2.824 (3)	151
O3—H3B···O2^iii	0.82	1.98	2.778 (3)	165
C6—H6···O3^iv	0.93	2.35	3.269 (4)	169
C8—H8···O3^v	0.93	2.57	3.492 (4)	172

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

(II) bis(1,10-phenanthrolinium) tetrachloroterephthalate tetrachloroterephthalic acid trihydrate

Crystal data

2C12H9N2^+·C8Cl4O4^2^−·C8H2Cl4O4·3H2O	Z = 1
Mr = 1022.25	F(000) = 518
Triclinic, P1	Dx = 1.610 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.2931 (11) Å	Cell parameters from 4670 reflections
b = 12.0916 (16) Å	θ = 2.1–27.5°
c = 12.3108 (16) Å	µ = 0.60 mm^−1
α = 102.127 (2)°	T = 295 K
β = 109.454 (1)°	Block, colorless
γ = 106.072 (2)°	0.28 × 0.22 × 0.15 mm
V = 1054.4 (2) Å^3

Data collection

Bruker APEXII CCD area-detector diffractometer	3677 independent reflections
Radiation source: fine-focus sealed tube	3201 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.020
phi and ω scans	θmax = 25.0°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −9→9
Tmin = 0.850, Tmax = 0.915	k = −14→14
7609 measured reflections	l = −14→14

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.147	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.085P)^2 + 0.8354P] where P = (Fo^2 + 2Fc^2)/3
3677 reflections	(Δ/σ)max < 0.001
288 parameters	Δρmax = 0.73 e Å^−3
0 restraints	Δρmin = −0.38 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	Occ. (<1)
C13	0.8004 (4)	0.6428 (2)	0.3931 (3)	0.0349 (6)
C14	0.9036 (4)	0.5691 (2)	0.4489 (2)	0.0327 (6)
C15	0.9437 (4)	0.4846 (3)	0.3768 (2)	0.0354 (6)
C16	1.0369 (4)	0.4155 (2)	0.4264 (2)	0.0345 (6)
C17	0.3805 (4)	0.6728 (2)	0.1275 (2)	0.0328 (6)
C18	0.4441 (3)	0.5832 (2)	0.0631 (2)	0.0310 (6)
C19	0.5945 (4)	0.6239 (2)	0.0353 (2)	0.0337 (6)
C20	0.6511 (3)	0.5427 (2)	−0.0266 (2)	0.0316 (6)
Cl1	0.87168 (13)	0.46445 (9)	0.22274 (7)	0.0581 (3)
Cl2	1.08249 (13)	0.30984 (8)	0.33555 (7)	0.0551 (3)
Cl3	0.71191 (12)	0.78008 (7)	0.07764 (8)	0.0540 (3)
Cl4	0.84232 (11)	0.59513 (7)	−0.05612 (9)	0.0551 (3)
O1	0.6217 (3)	0.58790 (18)	0.3543 (2)	0.0429 (5)
H1'	0.5692	0.6279	0.3211	0.064*
O2	0.8792 (3)	0.7397 (2)	0.3880 (3)	0.0637 (7)
O3	0.4225 (3)	0.68953 (18)	0.24061 (17)	0.0389 (5)
O4	0.2923 (3)	0.7218 (2)	0.06687 (19)	0.0474 (5)
C1	0.4661 (4)	0.6718 (3)	0.5789 (3)	0.0478 (7)
H1	0.4955	0.6056	0.5512	0.057*
C2	0.4929 (5)	0.7087 (3)	0.7015 (3)	0.0552 (8)
H2	0.5405	0.6685	0.7531	0.066*
C3	0.4483 (5)	0.8047 (3)	0.7442 (3)	0.0530 (8)
H3	0.4651	0.8306	0.8253	0.064*
C4	0.3759 (4)	0.8639 (3)	0.6632 (3)	0.0426 (7)
C5	0.3258 (5)	0.9656 (3)	0.6993 (3)	0.0494 (8)
H5	0.3370	0.9933	0.7789	0.059*
C6	0.2628 (4)	1.0217 (3)	0.6203 (3)	0.0432 (7)
H6	0.2320	1.0878	0.6462	0.052*
C7	0.2427 (4)	0.9811 (2)	0.4973 (3)	0.0369 (6)
C8	0.1782 (4)	1.0353 (3)	0.4106 (3)	0.0449 (7)
H8	0.1465	1.1019	0.4327	0.054*
C9	0.1613 (5)	0.9916 (3)	0.2938 (3)	0.0489 (7)
H9	0.1163	1.0272	0.2365	0.059*
C10	0.2122 (4)	0.8929 (3)	0.2614 (3)	0.0464 (7)
H10	0.2014	0.8628	0.1822	0.056*
C11	0.3581 (4)	0.8207 (2)	0.5431 (3)	0.0361 (6)
C12	0.2910 (3)	0.8807 (2)	0.4601 (3)	0.0342 (6)
N1	0.2759 (3)	0.8421 (2)	0.3436 (2)	0.0389 (5)
H1A	0.3070	0.7780	0.3214	0.058*
N2	0.4023 (3)	0.7248 (2)	0.5005 (2)	0.0423 (6)
O51	0.2373 (14)	0.9245 (9)	−0.0266 (9)	0.095 (3)*	0.40
O52	0.3445 (8)	0.9208 (5)	−0.0130 (5)	0.0779 (14)*	0.60
O61	−0.023 (2)	0.9425 (14)	−0.0330 (15)	0.103 (5)*	0.25
O62	0.022 (2)	0.8996 (14)	−0.0653 (14)	0.093 (4)*	0.25

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C13	0.0356 (14)	0.0339 (14)	0.0365 (14)	0.0191 (12)	0.0129 (12)	0.0098 (11)
C14	0.0313 (13)	0.0345 (14)	0.0345 (14)	0.0175 (11)	0.0124 (11)	0.0108 (11)
C15	0.0339 (14)	0.0413 (15)	0.0296 (13)	0.0188 (12)	0.0089 (11)	0.0100 (11)
C16	0.0328 (14)	0.0368 (14)	0.0342 (14)	0.0188 (11)	0.0123 (11)	0.0074 (11)
C17	0.0324 (14)	0.0352 (14)	0.0297 (13)	0.0167 (11)	0.0116 (11)	0.0059 (11)
C18	0.0325 (14)	0.0361 (14)	0.0272 (13)	0.0183 (11)	0.0123 (11)	0.0089 (11)
C19	0.0371 (14)	0.0301 (13)	0.0329 (14)	0.0134 (11)	0.0146 (12)	0.0073 (11)
C20	0.0286 (13)	0.0383 (14)	0.0304 (13)	0.0154 (11)	0.0139 (11)	0.0098 (11)
Cl1	0.0725 (6)	0.0879 (6)	0.0315 (4)	0.0536 (5)	0.0208 (4)	0.0236 (4)
Cl2	0.0693 (5)	0.0635 (5)	0.0435 (4)	0.0480 (4)	0.0228 (4)	0.0093 (4)
Cl3	0.0559 (5)	0.0309 (4)	0.0732 (6)	0.0106 (3)	0.0360 (4)	0.0061 (4)
Cl4	0.0508 (5)	0.0479 (4)	0.0822 (6)	0.0189 (4)	0.0475 (5)	0.0183 (4)
O1	0.0373 (11)	0.0443 (11)	0.0526 (13)	0.0243 (9)	0.0139 (10)	0.0226 (10)
O2	0.0476 (13)	0.0464 (13)	0.100 (2)	0.0221 (11)	0.0222 (13)	0.0385 (14)
O3	0.0457 (11)	0.0493 (11)	0.0304 (10)	0.0326 (9)	0.0161 (9)	0.0096 (9)
O4	0.0563 (13)	0.0586 (13)	0.0450 (12)	0.0406 (11)	0.0228 (10)	0.0229 (10)
C1	0.0466 (17)	0.0391 (16)	0.065 (2)	0.0236 (14)	0.0247 (16)	0.0179 (15)
C2	0.058 (2)	0.0472 (18)	0.065 (2)	0.0242 (16)	0.0251 (18)	0.0245 (17)
C3	0.064 (2)	0.0506 (18)	0.0454 (18)	0.0231 (16)	0.0236 (16)	0.0144 (15)
C4	0.0403 (16)	0.0368 (15)	0.0467 (17)	0.0130 (12)	0.0185 (13)	0.0071 (13)
C5	0.0549 (19)	0.0441 (17)	0.0492 (18)	0.0217 (15)	0.0262 (15)	0.0037 (14)
C6	0.0436 (16)	0.0352 (15)	0.0524 (18)	0.0186 (13)	0.0251 (14)	0.0043 (13)
C7	0.0277 (13)	0.0293 (13)	0.0494 (17)	0.0098 (11)	0.0172 (12)	0.0046 (12)
C8	0.0401 (16)	0.0348 (15)	0.062 (2)	0.0204 (13)	0.0216 (15)	0.0111 (14)
C9	0.0491 (18)	0.0493 (18)	0.0549 (19)	0.0275 (15)	0.0212 (15)	0.0187 (15)
C10	0.0486 (18)	0.0525 (18)	0.0444 (17)	0.0278 (15)	0.0201 (14)	0.0149 (14)
C11	0.0300 (13)	0.0313 (13)	0.0450 (16)	0.0121 (11)	0.0172 (12)	0.0056 (12)
C12	0.0257 (13)	0.0282 (13)	0.0437 (15)	0.0087 (10)	0.0153 (12)	0.0030 (11)
N1	0.0358 (12)	0.0370 (12)	0.0436 (14)	0.0188 (10)	0.0167 (11)	0.0059 (11)
N2	0.0445 (14)	0.0349 (12)	0.0514 (15)	0.0207 (11)	0.0227 (12)	0.0095 (11)

Geometric parameters (Å, º)

C13—O2	1.200 (4)	C3—C4	1.416 (5)
C13—O1	1.310 (3)	C3—H3	0.9300
C13—C14	1.512 (4)	C4—C11	1.403 (4)
C14—C15	1.395 (4)	C4—C5	1.435 (4)
C14—C16^i	1.400 (4)	C5—C6	1.347 (5)
C15—C16	1.388 (4)	C5—H5	0.9300
C15—Cl1	1.727 (3)	C6—C7	1.427 (4)
C16—C14^i	1.400 (4)	C6—H6	0.9300
C16—Cl2	1.724 (3)	C7—C8	1.401 (4)
C17—O4	1.227 (3)	C7—C12	1.414 (4)
C17—O3	1.273 (3)	C8—C9	1.368 (5)
C17—C18	1.522 (3)	C8—H8	0.9300
C18—C19	1.389 (4)	C9—C10	1.397 (4)
C18—C20^ii	1.398 (4)	C9—H9	0.9300
C19—C20	1.395 (4)	C10—N1	1.329 (4)
C19—Cl3	1.737 (3)	C10—H10	0.9300
C20—C18^ii	1.398 (4)	C11—N2	1.364 (3)
C20—Cl4	1.724 (3)	C11—C12	1.427 (4)
O1—H1'	0.8200	C12—N1	1.364 (4)
C1—N2	1.314 (4)	N1—H1A	0.9000
C1—C2	1.402 (5)	O51—O52	0.864 (10)
C1—H1	0.9300	O51—O62	1.603 (18)
C2—C3	1.368 (5)	O61—O62	0.831 (19)
C2—H2	0.9300	O61—O61^iii	1.33 (3)
O2—C13—O1	126.5 (3)	C11—C4—C3	116.9 (3)
O2—C13—C14	121.8 (3)	C11—C4—C5	119.8 (3)
O1—C13—C14	111.7 (2)	C3—C4—C5	123.3 (3)
C15—C14—C16^i	118.4 (2)	C6—C5—C4	121.3 (3)
C15—C14—C13	120.4 (2)	C6—C5—H5	119.3
C16^i—C14—C13	121.2 (2)	C4—C5—H5	119.3
C16—C15—C14	121.1 (3)	C5—C6—C7	120.8 (3)
C16—C15—Cl1	119.9 (2)	C5—C6—H6	119.6
C14—C15—Cl1	119.0 (2)	C7—C6—H6	119.6
C15—C16—C14^i	120.5 (2)	C8—C7—C12	117.8 (3)
C15—C16—Cl2	120.6 (2)	C8—C7—C6	123.7 (3)
C14^i—C16—Cl2	118.9 (2)	C12—C7—C6	118.5 (3)
O4—C17—O3	125.5 (2)	C9—C8—C7	120.9 (3)
O4—C17—C18	117.9 (2)	C9—C8—H8	119.6
O3—C17—C18	116.6 (2)	C7—C8—H8	119.6
C19—C18—C20^ii	118.1 (2)	C8—C9—C10	119.5 (3)
C19—C18—C17	121.1 (2)	C8—C9—H9	120.3
C20^ii—C18—C17	120.8 (2)	C10—C9—H9	120.3
C18—C19—C20	121.7 (2)	N1—C10—C9	120.0 (3)
C18—C19—Cl3	118.7 (2)	N1—C10—H10	120.0
C20—C19—Cl3	119.6 (2)	C9—C10—H10	120.0
C19—C20—C18^ii	120.2 (2)	N2—C11—C4	124.0 (3)
C19—C20—Cl4	120.9 (2)	N2—C11—C12	117.6 (3)
C18^ii—C20—Cl4	118.85 (19)	C4—C11—C12	118.4 (2)
C13—O1—H1'	109.5	N1—C12—C7	119.3 (3)
N2—C1—C2	124.3 (3)	N1—C12—C11	119.6 (2)
N2—C1—H1	117.9	C7—C12—C11	121.1 (3)
C2—C1—H1	117.9	C10—N1—C12	122.6 (2)
C3—C2—C1	119.1 (3)	C10—N1—H1A	119.2
C3—C2—H2	120.4	C12—N1—H1A	118.2
C1—C2—H2	120.4	C1—N2—C11	116.7 (3)
C2—C3—C4	119.0 (3)	O52—O51—O62	167.4 (13)
C2—C3—H3	120.5	O62—O61—O61^iii	139 (3)
C4—C3—H3	120.5	O61—O62—O51	127 (2)
O2—C13—C14—C15	−89.7 (4)	C3—C4—C5—C6	177.9 (3)
O1—C13—C14—C15	90.7 (3)	C4—C5—C6—C7	0.4 (5)
O2—C13—C14—C16^i	89.5 (4)	C5—C6—C7—C8	−179.9 (3)
O1—C13—C14—C16^i	−90.1 (3)	C5—C6—C7—C12	−0.2 (4)
C16^i—C14—C15—C16	1.3 (5)	C12—C7—C8—C9	0.6 (4)
C13—C14—C15—C16	−179.5 (2)	C6—C7—C8—C9	−179.7 (3)
C16^i—C14—C15—Cl1	−179.9 (2)	C7—C8—C9—C10	−1.2 (5)
C13—C14—C15—Cl1	−0.7 (4)	C8—C9—C10—N1	0.2 (5)
C14—C15—C16—C14^i	−1.3 (5)	C3—C4—C11—N2	1.5 (4)
Cl1—C15—C16—C14^i	179.9 (2)	C5—C4—C11—N2	180.0 (3)
C14—C15—C16—Cl2	179.0 (2)	C3—C4—C11—C12	−178.1 (3)
Cl1—C15—C16—Cl2	0.3 (3)	C5—C4—C11—C12	0.4 (4)
O4—C17—C18—C19	77.1 (3)	C8—C7—C12—N1	1.0 (4)
O3—C17—C18—C19	−103.6 (3)	C6—C7—C12—N1	−178.8 (2)
O4—C17—C18—C20^ii	−100.9 (3)	C8—C7—C12—C11	179.9 (2)
O3—C17—C18—C20^ii	78.5 (3)	C6—C7—C12—C11	0.1 (4)
C20^ii—C18—C19—C20	−0.3 (4)	N2—C11—C12—N1	−0.9 (4)
C17—C18—C19—C20	−178.3 (2)	C4—C11—C12—N1	178.7 (2)
C20^ii—C18—C19—Cl3	178.91 (19)	N2—C11—C12—C7	−179.8 (2)
C17—C18—C19—Cl3	0.9 (3)	C4—C11—C12—C7	−0.2 (4)
C18—C19—C20—C18^ii	0.3 (4)	C9—C10—N1—C12	1.4 (5)
Cl3—C19—C20—C18^ii	−178.9 (2)	C7—C12—N1—C10	−2.0 (4)
C18—C19—C20—Cl4	−178.0 (2)	C11—C12—N1—C10	179.1 (3)
Cl3—C19—C20—Cl4	2.8 (3)	C2—C1—N2—C11	−0.8 (5)
N2—C1—C2—C3	1.0 (5)	C4—C11—N2—C1	−0.5 (4)
C1—C2—C3—C4	0.1 (5)	C12—C11—N2—C1	179.1 (3)
C2—C3—C4—C11	−1.2 (5)	O61^iii—O61—O62—O51	24 (6)
C2—C3—C4—C5	−179.7 (3)	O52—O51—O62—O61	155 (5)
C11—C4—C5—C6	−0.5 (5)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1′···O3	0.82	1.74	2.550 (3)	170
N1—H1A···O3	0.90	1.95	2.788 (4)	154
C6—H6···O2^iv	0.93	2.56	3.413 (5)	152
C10—H10···O4	0.93	2.43	3.193 (4)	139

Symmetry code: (iv) −x+1, −y+2, −z+1.