Hydrogen-bonded structures of the isomeric 2-, 3- and 4-carbamoyl­pyridinium hydrogen chloranilates

In the three isomeric salts, all C₆H₇N₂O⁺·C₆HCl₂O₄⁻, of chloranilic acid (2,5-dichloro-3,6-dihydr­oxy-1,4-benzoquin­one) with 2-, 3- and 4-carbamoylpyridine, namely, 2-car­bamoyl­pyridinium hydrogen chloranilate (systematic name: 2-carbamoylpyridinium 2,5-dichloro-4-hydr­oxy-3,6-dioxocyclo­hexa-1,4-dienolate), (I), 3-carbamoylpyridinium hydrogen chloranilate, (II), and 4-carbamoylpyridinium hydrogen chloranilate, (III), acid–base inter­actions involving H-atom transfer are observed. The shortest inter­actions between the cation and the anion in (I) and (II) are pyridinium N—H...(O,O) bifurcated hydrogen bonds, which act as the primary inter­molecular inter­action in each crystal structure. In (III), an amide N—H...(O,O) bifurcated hydrogen bond, which is much weaker than the bifurcated hydrogen bonds in (I) and (II), connects the cation and the anion.

S1. Comment

Chloranilic acid (2,5-dichloro-3,6-dihydroxy-1,4-benzoquinone), a strong dibasic acid with hydrogen-bond donor and acceptor groups, appears particularly attractive as a template for generating tightly bound self-assemblies with various pyridine derivatives (Ishida & Kashino, 1999a,b,c, 2002; Zaman et al., 1999, 2000, 2001, 2004), and as a model compound for investigating H-atom transfer in O—H···N and N—H···O hydrogen-bond systems (Nihei et al., 2000a,b; Ikeda et al., 2005; Suzuki et al., 2007; Gotoh et al., 2008; Seliger et al., 2009). Furthermore, salts and co-crystals of chloranilic acid with pyridine derivatives have recently attracted much interest with respect to organic ferroelectrics (Horiuchi, Ishii et al., 2005; Horiuchi, Kumai & Tokura, 2005; Asaji et al., 2007; Gotoh et al., 2007; Horiuchi & Tokura, 2008). In the present study, we have prepared three isomeric salts, C₆H₇N₂O⁺.C₆HCl₂O₄^-, of chloranilic acid with picolinamide, nicotinamide and isonicotinamide, namely, 2-carbamoylpyridinium hydrogen chloranilate, (I), 3-carbamoylpyridinium hydrogen chloranilate, (II), and 4-carbamoylpyridinium hydrogen chloranilate, (III), in order to extend our studies of D—H···A hydrogen bonding (D = N, O, or C; A = N, O or Cl) in chloranilic acid–substituted-pyridine systems (Tabuchi et al., 2005; Gotoh et al., 2006, 2009).

Compound (I) contains one protonated picolinamide cation and one hydrogen chloranilate monoanion, which are linked by a bifurcated pyridinium N1—H1···(O1,O4) hydrogen bond (Table 1). There is a dihedral angle of 64.42 (6)° between the pyridine N1/C7—C11 ring and the anion C1–C6 ring (Fig. 1). In the cation, the acetamide C12/O5/N2 plane makes a dihedral angle of 11.62 (4)° with the pyridine ring, which is comparable with the equivalent angles of 9.84 (8) and 19.35 (4)° in compounds (II) and (III), respectively. This suggests that the contribution of the intramolecular N—H···O hydrogen bond (N1—H1···O5) to the molecular conformation of (I) is small. Similar angles of 11.44 (6), 2.74 (6) and 10.61 (3)° between the carboxy plane and the pyridine ring are observed in, respectively, 2-carboxypyridinium hydrogen chloranilate (Gotoh et al., 2009), 3-carboxypyridinium hydrogen chloranilate (Ishida, 2009a) and 4-carboxypyridinium hydrogen chloranilate monohydrate (Ishida, 2009b), which also suggests a weak intramolecular N—H···O hydrogen bond between the pyridininum N—H and the carboxy O atom in 2-carboxypyridinium hydrogen chloranilate. The two components in (I) are further connected through a pair of O2—H2···(O3,O5ⁱⁱⁱ) bifurcated hydrogen bonds (symmetry code as in Table 1), to form a centrosymmetric 2+2 aggregate (Fig. 2). One of the amide N—H···O hydrogen bonds (N2—H2B···O4ⁱⁱ; Table 1) connects the aggregates into a chain along the [101] direction (Fig. 3). The second amide N—H···O hydrogen bond (N2—H2A···O1ⁱ; Table 1) further connects the chains, forming a three-dimensional network. A weak C—H···(O,O) bifurcated interaction is also present (Table 1).

Although all intermolecular N—H···O and O—H···O hydrogen bonds corresponding to those in (I) are observed in (II) (Table 2), all the D···A distances of the hydrogen bonds in (II) are shorter than those in (I), so that the molecular packing motifs are quite different from each other (Figs. 4–6). In (II), the cations and the anions are separately stacked in columns along the b axis. Between the two components a bifurcated pyridinium N1—H1···(O1,O4) hydrogen bond and an O2—H2···(O3,O5ⁱⁱⁱ) hydrogen bond (symmetry code as in Table 2) are present as the primary interactions, forming a zigzag supramolecular chain along the [111] direction (Fig. 5). The dihedral angle between the pyridine N1/C7—C11 ring and the anion C1–C6 ring is 71.59 (10)°. This packing motif is similar to that of 3-carboxypyridinium hydrogen chloranilate, which crystallizes in the same space group, Pc, and is effectively isostuctural (Tabuchi et al., 2005). The cations and anions are linked by the equivalent hydrogen bonds to form a chain. In 3-carboxypyridinium hydrogen chloranilate, the carboxy group of the cation and the carbonyl O of the anion form an additional strong O—H···O hydrogen bond, which further connects the supramolecular chains related to each other by a c-glide plane to form a three-dimensional hydrogen-bond network. On the other hand, in (II) the amide group of the cation forms two weak N—H···O hydrogen bonds as the secondary interaction. One amide N—H···O hydrogen bond (N2—H2A···O1ⁱ; Table 2) connects the neighbouring chains related by a b translation, giving a wavy layer expanding parallel to the (101) plane (Fig. 6). The neighbouring layers related to each other by a c-glide plane are further linked by the second amide N—H···O hydrogen bond (N2—H2B···O4ⁱⁱ; Table 2) to form a three-dimensional hydrogen-bond network.

Compound (III) also crystallizes in a non-centrosymmetric space group, Cc, where the basic hydrogen-bonded structure is quite different from those of (I) and (II). In (III), primary hydrogen bonds are formed between the cations (N1—H1···O5ⁱ; symmetry code as in Table 3) and between the anions [O2—H2···(O3,O4ⁱⁱⁱ); Table 3], and each component affords a supramolecular zigzag chain along the [101] direction (Figs. 7 and 8). The cation and anion chains are alternately arranged and linked together through amide N—H···O hydrogen bonds [N2—H2A···(O1,O4) and N2—H2B···O3ⁱⁱ] and C—H···O hydrogen bonds (Table 3), forming a layer parallel to the (101) plane. In the layer, the cation and anion molecules are approximately coplanar, with a dihedral angle of 4.61 (5)° between the N1/C7–C11 and C1–C6 rings. A short Cl···Cl contact [Cl1···Cl2^v = 3.1634 (5) Å; symmetry code: (v) x + 1/2, y + 1/2, z] is also observed in the layer. Between the layers, no significant interaction is observed; the shortest contact is C4···C7^vi = 3.167 (2) Å [symmetry code: (vi) x + 1/2, y - 1/2, z + 1].

S2. Experimental

Crystals of (I) and (III) were obtained by slow evaporation from methanol solutions [40 and 100 ml for (I) and (III), respectively] of chloranilic acid with picolinamide or isonicotinamide in a 1:1 molar ratio [0.300 g of chloranilic acid and 0.176 g of picolinamide for (I), and 0.100 g of chloranilic acid and 0.058 g of isonicotinamide for (III)] at room temperature. Crystals of (II) were obtained by slow evaporation from a water–methanol (1:1 v/v) solution (140 ml) of chloranilic acid (0.302 g) and nicotinamide (0.179 g) at room temperature.

S3. Refinement

H atoms attached to O and N atoms were found in a difference Fourier map and refined isotropically (refined O—H and N—H distances are given in Tables 1–3). Other H atoms were treated as riding, with C—H = 0.95 Å and with U_iso(H) = 1.2U_eq(C). For compounds (II) and (III), the correct orientations of the structures with respect to the polar-axis directions were determined by use of the Flack x parameters (Flack, 1983) [0.09 (6) and 0.00 (3) for (II) and (III), respectively]. The Hooft y parameters (Hooft et al., 2008) were evaluated to be 0.14 (2) and -0.008 (18), respectively, for (II) and (III).

Computing details

For all compounds, data collection: PROCESS-AUTO (Rigaku/MSC, 2004); cell refinement: PROCESS-AUTO (Rigaku/MSC, 2004); data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: CrystalStructure (Rigaku/MSC, 2004) and PLATON (Spek, 2009).

Figures

	Fig. 1. A molecular view of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. The bifurcated N—H···(O,O) hydrogen bond is indicated by dashed lines.
	Fig. 2. The 2+2 aggregate of (I), formed by N—H···(O,O) and O—H···(O,O) bifurcated hydrogen bonds (dashed lines). [See Table 1 for symmetry code (iii)].
	Fig. 3. A partial packing diagram for (I), viewed approximately along the a axis, showing the hydrogen-bonded chain structure. Dashed lines show N—H···O and O—H···O hydrogen bonds. H atoms not involved in the hydrogen bonds have been omitted. [Symmetry code: (vi) x + 1, y, z + 1; see Table 1 for symmetry codes (ii) and (iii)].
	Fig. 4. A molecular view of (II), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. The bifurcated N—H···(O,O) hydrogen bond is indicated by dashed lines.
	Fig. 5. The supramolecular chain of (II), formed by N—H···(O,O) and O—H···(O,O) bifurcated hydrogen bonds (dashed lines). [Symmetry code: (vi) x + 1, y + 1, z + 1; see Table 2 for symmetry code (iii)].
	Fig. 6. A partial packing diagram for (II), viewed approximately along the a axis, showing the hydrogen-bonded layer structure. Dashed lines show N—H···O, O—H···O and C—H···O hydrogen bonds. H atoms not involved in the hydrogen bonds have been omitted. [Symmetry code: (vii) x, y - 1, z; see Table 2 for symmetry codes (i) and (iii)].
	Fig. 7. A molecular view of (III), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. The bifurcated N—H···(O,O) hydrogen bond is indicated by dashed lines.
	Fig. 8. A packing diagram for (III), viewed along the c axis, showing the hydrogen-bonded layer structure. Dashed lines show N—H···O, O—H···O and C—H···O hydrogen bonds. H atoms not involved in the hydrogen bonds have been omitted. [Symmetry code: (iv) x + 1/2, -y + 3/2, z + 1/2; see Table 3 for symmetry codes (i), (ii) and (iii)].

(I) 2-carbamoylpyridinium 2,5-dichloro-4-hydroxy-3,6-dioxocyclohexa-1,4-dienolate

Crystal data

C6H7N2O^+·C6HCl2O4^−	F(000) = 672.00
Mr = 331.11	Dx = 1.750 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71075 Å
Hall symbol: -P 2ybc	Cell parameters from 9451 reflections
a = 9.3420 (5) Å	θ = 3.3–30.0°
b = 12.4483 (8) Å	µ = 0.54 mm^−1
c = 11.4167 (7) Å	T = 100 K
β = 108.8014 (17)°	Platelet, black
V = 1256.83 (13) Å^3	0.27 × 0.25 × 0.19 mm
Z = 4

Data collection

Rigaku R-AXIS RAPID II diffractometer	2830 reflections with I > 2σ(I)
Detector resolution: 10.00 pixels mm^-1	Rint = 0.046
ω scans	θmax = 30.0°
Absorption correction: numerical (ABSCOR; Higashi, 1995)	h = −12→13
Tmin = 0.875, Tmax = 0.902	k = −17→17
11008 measured reflections	l = −16→16
3596 independent 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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.111	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	w = 1/[σ^2(Fo^2) + (0.0528P)^2 + 0.2416P] where P = (Fo^2 + 2Fc^2)/3
3596 reflections	(Δ/σ)max < 0.001
206 parameters	Δρmax = 0.48 e Å^−3
0 restraints	Δρmin = −0.54 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
Cl1	0.47394 (5)	0.18306 (4)	−0.08442 (4)	0.02225 (12)
Cl2	0.44480 (5)	0.58121 (4)	0.25351 (4)	0.02029 (12)
O1	0.71431 (14)	0.26018 (11)	0.14520 (11)	0.0184 (3)
O2	0.24147 (14)	0.35825 (11)	−0.13720 (11)	0.0185 (3)
O3	0.23405 (14)	0.52153 (11)	0.00192 (12)	0.0206 (3)
O4	0.70566 (14)	0.42813 (11)	0.28934 (11)	0.0184 (3)
O5	1.02131 (15)	0.48625 (12)	0.26541 (12)	0.0224 (3)
N1	0.96303 (17)	0.31153 (12)	0.38111 (14)	0.0169 (3)
N2	1.19419 (18)	0.54872 (14)	0.44191 (15)	0.0200 (3)
C1	0.60070 (19)	0.31695 (14)	0.11242 (16)	0.0148 (3)
C2	0.47235 (19)	0.29625 (14)	0.00183 (16)	0.0158 (3)
C3	0.35756 (18)	0.36800 (14)	−0.03305 (15)	0.0152 (3)
C4	0.34676 (19)	0.46261 (14)	0.04543 (16)	0.0155 (3)
C5	0.46284 (19)	0.47734 (14)	0.15914 (15)	0.0148 (3)
C6	0.59349 (19)	0.41393 (14)	0.19496 (15)	0.0152 (3)
C7	1.08111 (18)	0.37466 (15)	0.44296 (16)	0.0153 (3)
C8	1.1733 (2)	0.34217 (15)	0.55865 (16)	0.0180 (4)
H8	1.2567	0.3851	0.6043	0.022*
C9	1.1421 (2)	0.24578 (15)	0.60717 (16)	0.0185 (4)
H9	1.2052	0.2227	0.6863	0.022*
C10	1.0200 (2)	0.18294 (15)	0.54139 (17)	0.0194 (4)
H10	0.9986	0.1170	0.5742	0.023*
C11	0.9297 (2)	0.21924 (16)	0.42613 (17)	0.0199 (4)
H11	0.8445	0.1785	0.3794	0.024*
C12	1.09694 (19)	0.47626 (15)	0.37548 (16)	0.0169 (3)
H1	0.898 (3)	0.338 (2)	0.311 (3)	0.037 (7)*
H2	0.186 (3)	0.417 (2)	−0.138 (3)	0.042 (8)*
H2A	1.210 (3)	0.605 (2)	0.407 (2)	0.028 (6)*
H2B	1.242 (3)	0.541 (2)	0.519 (2)	0.026 (6)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0244 (2)	0.0201 (2)	0.0202 (2)	0.00393 (17)	0.00431 (17)	−0.00576 (16)
Cl2	0.0193 (2)	0.0223 (2)	0.0184 (2)	0.00231 (16)	0.00478 (17)	−0.00651 (16)
O1	0.0182 (6)	0.0175 (6)	0.0190 (6)	0.0024 (5)	0.0053 (5)	0.0011 (5)
O2	0.0175 (6)	0.0195 (7)	0.0155 (6)	0.0009 (5)	0.0010 (5)	−0.0024 (5)
O3	0.0175 (6)	0.0224 (7)	0.0192 (6)	0.0051 (5)	0.0023 (5)	−0.0007 (5)
O4	0.0159 (6)	0.0218 (7)	0.0148 (6)	0.0006 (5)	0.0013 (5)	−0.0003 (5)
O5	0.0257 (7)	0.0233 (7)	0.0158 (6)	−0.0040 (6)	0.0033 (5)	0.0018 (5)
N1	0.0159 (7)	0.0171 (7)	0.0156 (6)	−0.0010 (6)	0.0019 (6)	0.0002 (6)
N2	0.0236 (8)	0.0188 (8)	0.0167 (7)	−0.0036 (6)	0.0053 (6)	0.0016 (6)
C1	0.0157 (8)	0.0150 (8)	0.0143 (7)	0.0001 (6)	0.0056 (6)	0.0028 (6)
C2	0.0178 (8)	0.0139 (8)	0.0152 (7)	0.0005 (6)	0.0047 (6)	−0.0022 (6)
C3	0.0150 (8)	0.0173 (8)	0.0131 (7)	−0.0014 (6)	0.0044 (6)	0.0001 (6)
C4	0.0167 (8)	0.0153 (8)	0.0150 (7)	−0.0016 (6)	0.0059 (6)	0.0000 (6)
C5	0.0177 (8)	0.0131 (8)	0.0137 (7)	0.0005 (6)	0.0052 (6)	−0.0023 (6)
C6	0.0157 (8)	0.0166 (8)	0.0137 (7)	−0.0014 (6)	0.0054 (6)	0.0015 (6)
C7	0.0130 (7)	0.0175 (8)	0.0157 (7)	0.0001 (6)	0.0049 (6)	−0.0011 (6)
C8	0.0158 (8)	0.0209 (9)	0.0155 (7)	−0.0004 (7)	0.0024 (6)	−0.0027 (7)
C9	0.0205 (9)	0.0181 (9)	0.0154 (7)	0.0017 (7)	0.0035 (7)	0.0009 (7)
C10	0.0195 (9)	0.0195 (9)	0.0193 (8)	0.0002 (7)	0.0063 (7)	0.0017 (7)
C11	0.0161 (8)	0.0225 (9)	0.0195 (8)	−0.0029 (7)	0.0033 (7)	−0.0004 (7)
C12	0.0162 (8)	0.0169 (8)	0.0181 (8)	−0.0007 (6)	0.0065 (7)	−0.0006 (7)

Geometric parameters (Å, º)

Cl1—C2	1.7218 (18)	C1—C2	1.457 (3)
Cl2—C5	1.7257 (18)	C2—C3	1.353 (3)
O1—C1	1.229 (2)	C3—C4	1.503 (2)
O2—C3	1.332 (2)	C4—C5	1.410 (2)
O2—H2	0.90 (3)	C5—C6	1.399 (3)
O3—C4	1.248 (2)	C7—C8	1.384 (2)
O4—C6	1.250 (2)	C7—C12	1.513 (3)
O5—C12	1.233 (2)	C8—C9	1.391 (3)
N1—C11	1.336 (2)	C8—H8	0.9500
N1—C7	1.353 (2)	C9—C10	1.388 (3)
N1—H1	0.89 (3)	C9—H9	0.9500
N2—C12	1.330 (2)	C10—C11	1.390 (3)
N2—H2A	0.84 (2)	C10—H10	0.9500
N2—H2B	0.85 (2)	C11—H11	0.9500
C1—C6	1.546 (2)
C3—O2—H2	104 (2)	O4—C6—C5	125.59 (16)
C11—N1—C7	123.41 (16)	C1—C6—C5	117.87 (15)
C11—N1—H1	119.0 (17)	O4—C6—C1	116.53 (16)
C7—N1—H1	117.1 (17)	N1—C7—C8	118.69 (17)
C12—N2—H2A	118.8 (17)	N1—C7—C12	114.64 (15)
C12—N2—H2B	123.1 (17)	C8—C7—C12	126.67 (16)
H2A—N2—H2B	118 (2)	C7—C8—C9	119.08 (16)
O1—C1—C2	123.44 (16)	C7—C8—H8	120.5
O1—C1—C6	117.80 (15)	C9—C8—H8	120.5
C2—C1—C6	118.75 (15)	C10—C9—C8	120.79 (16)
Cl1—C2—C1	118.95 (13)	C10—C9—H9	119.6
Cl1—C2—C3	121.60 (14)	C8—C9—H9	119.6
C1—C2—C3	119.42 (16)	C9—C10—C11	118.12 (18)
O2—C3—C2	122.87 (16)	C9—C10—H10	120.9
O2—C3—C4	114.33 (15)	C11—C10—H10	120.9
C2—C3—C4	122.75 (15)	N1—C11—C10	119.90 (17)
O3—C4—C3	115.70 (15)	N1—C11—H11	120.0
O3—C4—C5	126.17 (16)	C10—C11—H11	120.1
C3—C4—C5	118.13 (16)	O5—C12—N2	125.04 (18)
Cl2—C5—C4	118.13 (14)	O5—C12—C7	119.02 (16)
Cl2—C5—C6	119.45 (13)	N2—C12—C7	115.94 (15)
C4—C5—C6	122.37 (16)
O1—C1—C2—Cl1	3.3 (3)	C3—C4—C5—Cl2	−176.18 (13)
O1—C1—C2—C3	−174.38 (17)	C3—C4—C5—C6	6.5 (3)
C6—C1—C2—Cl1	−175.43 (13)	Cl2—C5—C6—O4	−3.4 (3)
C6—C1—C2—C3	6.9 (3)	Cl2—C5—C6—C1	175.92 (13)
O1—C1—C6—O4	0.7 (2)	C4—C5—C6—O4	173.89 (17)
O1—C1—C6—C5	−178.69 (16)	C4—C5—C6—C1	−6.8 (3)
C2—C1—C6—O4	179.49 (16)	C11—N1—C7—C8	0.4 (3)
C2—C1—C6—C5	0.1 (2)	C11—N1—C7—C12	−179.28 (16)
Cl1—C2—C3—O2	−2.2 (3)	N1—C7—C8—C9	0.3 (3)
Cl1—C2—C3—C4	174.88 (14)	C12—C7—C8—C9	179.94 (17)
C1—C2—C3—O2	175.44 (16)	C7—C8—C9—C10	−0.4 (3)
C1—C2—C3—C4	−7.5 (3)	C8—C9—C10—C11	−0.2 (3)
O2—C3—C4—O3	−2.2 (2)	C7—N1—C11—C10	−1.0 (3)
O2—C3—C4—C5	178.25 (16)	C9—C10—C11—N1	0.9 (3)
C2—C3—C4—O3	−179.45 (17)	N1—C7—C12—O5	−11.7 (2)
C2—C3—C4—C5	1.0 (3)	C8—C7—C12—O5	168.63 (18)
O3—C4—C5—Cl2	4.3 (3)	N1—C7—C12—N2	168.49 (16)
O3—C4—C5—C6	−173.02 (18)	C8—C7—C12—N2	−11.2 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.90 (3)	2.32 (3)	3.005 (2)	133 (2)
N1—H1···O4	0.90 (3)	2.07 (3)	2.713 (2)	128 (3)
N1—H1···O5	0.90 (3)	2.32 (3)	2.690 (2)	105 (2)
N2—H2A···O1^i	0.84 (2)	2.20 (3)	3.033 (2)	168 (2)
N2—H2B···O4^ii	0.85 (2)	2.12 (2)	2.919 (2)	156 (3)
O2—H2···O3	0.90 (3)	2.00 (3)	2.5942 (19)	123 (3)
O2—H2···O5^iii	0.90 (3)	2.35 (3)	3.098 (2)	142 (3)
C10—H10···O3^iv	0.95	2.38	3.026 (2)	125
C10—H10···O5^v	0.95	2.48	3.310 (2)	146

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

(II) 3-carbamoylpyridinium 2,5-dichloro-4-hydroxy-3,6-dioxocyclohexa-1,4-dienolate

Crystal data

C6H7N2O^+·C6HCl2O4^−	F(000) = 336.00
Mr = 331.11	Dx = 1.702 Mg m^−3
Monoclinic, Pc	Mo Kα radiation, λ = 0.71075 Å
Hall symbol: P -2yc	Cell parameters from 5350 reflections
a = 9.9861 (5) Å	θ = 3.3–29.9°
b = 6.1438 (3) Å	µ = 0.53 mm^−1
c = 11.6027 (5) Å	T = 100 K
β = 114.8583 (16)°	Platelet, black
V = 645.90 (5) Å^3	0.38 × 0.27 × 0.08 mm
Z = 2

Data collection

Rigaku R-AXIS RAPID II diffractometer	2991 reflections with I > 2σ(I)
Detector resolution: 10.00 pixels mm^-1	Rint = 0.019
ω scans	θmax = 29.9°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −14→13
Tmin = 0.753, Tmax = 0.959	k = −8→8
5606 measured reflections	l = −16→16
3191 independent 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)] = 0.033	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.149	w = 1/[σ^2(Fo^2) + (0.1346P)^2 + 0.041P] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max < 0.001
3191 reflections	Δρmax = 0.45 e Å^−3
206 parameters	Δρmin = −0.34 e Å^−3
2 restraints	Absolute structure: Flack (1983), with 1354 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.09 (6)

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	−0.22309 (7)	−0.16092 (10)	0.27861 (6)	0.02023 (18)
Cl2	−0.21745 (6)	0.66069 (10)	−0.05064 (5)	0.02024 (18)
O1	0.0159 (3)	0.1613 (3)	0.3310 (2)	0.0165 (4)
O2	−0.4633 (2)	−0.0115 (4)	0.0309 (2)	0.0195 (4)
O3	−0.4588 (3)	0.3384 (3)	−0.0955 (2)	0.0201 (5)
O4	0.0276 (2)	0.5097 (3)	0.1963 (2)	0.0178 (4)
O5	0.2959 (3)	0.9866 (3)	0.7990 (2)	0.0192 (4)
N1	0.2091 (3)	0.5482 (4)	0.4386 (2)	0.0161 (4)
N2	0.1189 (3)	1.0973 (4)	0.6108 (2)	0.0217 (5)
C1	−0.0932 (3)	0.1973 (5)	0.2316 (2)	0.0118 (5)
C2	−0.2246 (3)	0.0611 (4)	0.1873 (3)	0.0159 (5)
C3	−0.3419 (3)	0.1077 (5)	0.0779 (3)	0.0160 (5)
C4	−0.3420 (3)	0.3060 (4)	0.0000 (3)	0.0145 (5)
C5	−0.2134 (3)	0.4371 (4)	0.0417 (3)	0.0148 (5)
C6	−0.0904 (3)	0.3968 (4)	0.1522 (3)	0.0143 (5)
C7	0.1760 (3)	0.7230 (4)	0.4914 (3)	0.0168 (5)
H7	0.0920	0.8089	0.4428	0.020*
C8	0.2640 (3)	0.7784 (4)	0.6164 (3)	0.0143 (5)
C9	0.3863 (3)	0.6481 (4)	0.6843 (3)	0.0163 (5)
H9	0.4473	0.6803	0.7707	0.020*
C10	0.4192 (3)	0.4712 (5)	0.6260 (3)	0.0204 (5)
H10	0.5039	0.3845	0.6714	0.024*
C11	0.3276 (3)	0.4232 (4)	0.5019 (3)	0.0194 (5)
H11	0.3482	0.3019	0.4612	0.023*
C12	0.2275 (3)	0.9650 (4)	0.6827 (2)	0.0145 (5)
H1	0.147 (6)	0.513 (7)	0.366 (5)	0.030 (11)*
H2	−0.528 (6)	0.043 (8)	−0.046 (6)	0.038 (12)*
H2A	0.068 (5)	1.065 (6)	0.530 (4)	0.016 (8)*
H2B	0.092 (8)	1.220 (9)	0.647 (7)	0.055 (17)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0191 (3)	0.0185 (3)	0.0185 (3)	−0.0036 (2)	0.0034 (3)	0.0064 (2)
Cl2	0.0216 (4)	0.0187 (3)	0.0161 (3)	−0.0033 (2)	0.0037 (2)	0.0062 (2)
O1	0.0161 (10)	0.0164 (10)	0.0140 (9)	−0.0004 (7)	0.0034 (8)	0.0007 (7)
O2	0.0146 (9)	0.0210 (10)	0.0184 (9)	−0.0045 (8)	0.0024 (8)	0.0034 (8)
O3	0.0181 (11)	0.0227 (11)	0.0148 (9)	−0.0013 (8)	0.0021 (8)	0.0036 (7)
O4	0.0154 (9)	0.0178 (10)	0.0160 (9)	−0.0061 (8)	0.0026 (7)	0.0008 (7)
O5	0.0187 (9)	0.0209 (9)	0.0138 (9)	−0.0009 (8)	0.0028 (7)	−0.0014 (7)
N1	0.0162 (10)	0.0165 (9)	0.0132 (9)	−0.0002 (9)	0.0038 (8)	−0.0015 (8)
N2	0.0237 (12)	0.0220 (12)	0.0155 (11)	0.0097 (10)	0.0043 (10)	0.0010 (10)
C1	0.0101 (12)	0.0137 (10)	0.0110 (10)	0.0009 (9)	0.0037 (9)	−0.0003 (9)
C2	0.0174 (12)	0.0133 (10)	0.0175 (11)	−0.0003 (10)	0.0079 (10)	0.0016 (10)
C3	0.0170 (13)	0.0172 (11)	0.0135 (11)	−0.0023 (11)	0.0061 (10)	−0.0025 (10)
C4	0.0163 (14)	0.0142 (10)	0.0123 (11)	0.0022 (10)	0.0052 (10)	0.0011 (10)
C5	0.0151 (12)	0.0157 (11)	0.0119 (10)	−0.0005 (10)	0.0040 (10)	0.0021 (10)
C6	0.0170 (12)	0.0133 (10)	0.0115 (10)	−0.0002 (10)	0.0049 (9)	0.0023 (10)
C7	0.0175 (11)	0.0144 (10)	0.0158 (11)	−0.0001 (9)	0.0043 (9)	−0.0019 (9)
C8	0.0105 (12)	0.0150 (10)	0.0167 (10)	0.0003 (10)	0.0050 (9)	0.0018 (10)
C9	0.0098 (11)	0.0217 (12)	0.0132 (10)	0.0043 (9)	0.0006 (9)	0.0019 (9)
C10	0.0198 (13)	0.0221 (12)	0.0161 (12)	0.0088 (11)	0.0043 (10)	0.0034 (10)
C11	0.0222 (13)	0.0182 (11)	0.0174 (12)	0.0010 (10)	0.0080 (10)	−0.0011 (10)
C12	0.0126 (11)	0.0162 (11)	0.0124 (10)	−0.0001 (9)	0.0032 (9)	0.0001 (8)

Geometric parameters (Å, º)

Cl1—C2	1.723 (3)	C1—C6	1.541 (4)
Cl2—C5	1.732 (3)	C2—C3	1.347 (5)
O1—C1	1.229 (3)	C3—C4	1.517 (4)
O2—C3	1.322 (4)	C4—C5	1.418 (4)
O2—H2	0.92 (6)	C5—C6	1.375 (5)
O3—C4	1.242 (4)	C7—C8	1.386 (4)
O4—C6	1.275 (4)	C7—H7	0.9500
O5—C12	1.237 (3)	C8—C9	1.394 (3)
N1—C11	1.341 (4)	C8—C12	1.508 (3)
N1—C7	1.345 (3)	C9—C10	1.391 (4)
N1—H1	0.84 (6)	C9—H9	0.9500
N2—C12	1.331 (4)	C10—C11	1.374 (4)
N2—H2A	0.88 (4)	C10—H10	0.9500
N2—H2B	0.96 (7)	C11—H11	0.9500
C1—C2	1.456 (4)
C3—O2—H2	110 (4)	O4—C6—C5	126.1 (3)
C11—N1—C7	122.5 (2)	C1—C6—C5	117.9 (3)
C11—N1—H1	121 (3)	O4—C6—C1	116.0 (3)
C7—N1—H1	116 (3)	N1—C7—C8	120.3 (2)
C12—N2—H2A	119 (3)	N1—C7—H7	119.9
C12—N2—H2B	121 (4)	C8—C7—H7	119.9
H2A—N2—H2B	120 (5)	C7—C8—C9	118.0 (2)
O1—C1—C2	122.7 (3)	C7—C8—C12	122.6 (2)
O1—C1—C6	118.2 (3)	C9—C8—C12	119.4 (2)
C2—C1—C6	119.1 (2)	C10—C9—C8	120.2 (3)
Cl1—C2—C3	121.8 (2)	C10—C9—H9	119.9
C1—C2—C3	120.5 (3)	C8—C9—H9	119.9
Cl1—C2—C1	117.7 (2)	C11—C10—C9	119.2 (3)
O2—C3—C2	123.7 (3)	C11—C10—H10	120.4
O2—C3—C4	115.4 (3)	C9—C10—H10	120.4
C2—C3—C4	121.0 (3)	N1—C11—C10	119.8 (3)
O3—C4—C3	115.2 (3)	N1—C11—H11	120.1
O3—C4—C5	126.2 (3)	C10—C11—H11	120.1
C3—C4—C5	118.7 (3)	O5—C12—N2	123.3 (3)
Cl2—C5—C6	119.9 (2)	O5—C12—C8	119.8 (2)
C4—C5—C6	122.8 (3)	N2—C12—C8	116.9 (2)
Cl2—C5—C4	117.2 (2)
O1—C1—C2—Cl1	−1.0 (4)	C3—C4—C5—Cl2	179.5 (2)
O1—C1—C2—C3	179.7 (3)	C3—C4—C5—C6	−2.4 (5)
C6—C1—C2—Cl1	179.8 (2)	Cl2—C5—C6—O4	−0.7 (5)
C6—C1—C2—C3	0.5 (4)	Cl2—C5—C6—C1	179.3 (2)
O1—C1—C6—O4	0.6 (4)	C4—C5—C6—O4	−178.7 (3)
O1—C1—C6—C5	−179.4 (3)	C4—C5—C6—C1	1.2 (4)
C2—C1—C6—O4	179.8 (3)	C11—N1—C7—C8	−1.1 (4)
C2—C1—C6—C5	−0.2 (4)	N1—C7—C8—C9	0.1 (4)
Cl1—C2—C3—O2	−0.8 (5)	N1—C7—C8—C12	−176.5 (2)
Cl1—C2—C3—C4	179.0 (2)	C7—C8—C9—C10	1.3 (4)
C1—C2—C3—O2	178.5 (3)	C12—C8—C9—C10	178.0 (3)
C1—C2—C3—C4	−1.7 (5)	C8—C9—C10—C11	−1.7 (4)
O2—C3—C4—O3	3.3 (4)	C7—N1—C11—C10	0.8 (4)
O2—C3—C4—C5	−177.6 (3)	C9—C10—C11—N1	0.7 (4)
C2—C3—C4—O3	−176.5 (3)	C7—C8—C12—O5	168.7 (3)
C2—C3—C4—C5	2.7 (5)	C9—C8—C12—O5	−7.9 (4)
O3—C4—C5—Cl2	−1.5 (4)	C7—C8—C12—N2	−10.0 (4)
O3—C4—C5—C6	176.7 (3)	C9—C8—C12—N2	173.4 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.84 (5)	2.47 (5)	2.984 (3)	121 (4)
N1—H1···O4	0.84 (5)	1.82 (5)	2.638 (3)	164 (4)
N2—H2A···O1^i	0.88 (4)	2.22 (4)	2.991 (3)	146 (4)
N2—H2B···O4^ii	0.96 (7)	1.95 (6)	2.899 (3)	172 (6)
O2—H2···O3	0.92 (6)	2.11 (5)	2.613 (3)	114 (5)
O2—H2···O5^iii	0.92 (6)	1.95 (6)	2.754 (3)	146 (5)
C7—H7···O1^i	0.95	2.47	3.282 (3)	143
C11—H11···O2^iv	0.95	2.47	3.206 (4)	134
C11—H11···O5^v	0.95	2.48	3.370 (3)	157

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

(III) 4-carbamoylpyridinium 2,5-dichloro-4-hydroxy-3,6-dioxocyclohexa-1,4-dienolate

Crystal data

C6H7N2O^+·C6HCl2O4^−	F(000) = 672.00
Mr = 331.11	Dx = 1.780 Mg m^−3
Monoclinic, Cc	Mo Kα radiation, λ = 0.71075 Å
Hall symbol: C -2yc	Cell parameters from 5726 reflections
a = 12.9482 (4) Å	θ = 3.0–30.0°
b = 13.4993 (5) Å	µ = 0.55 mm^−1
c = 7.0726 (3) Å	T = 100 K
β = 92.0130 (11)°	Platelet, brown
V = 1235.47 (8) Å^3	0.30 × 0.15 × 0.12 mm
Z = 4

Data collection

Rigaku R-AXIS RAPID II diffractometer	3029 reflections with I > 2σ(I)
Detector resolution: 10.00 pixels mm^-1	Rint = 0.016
ω scans	θmax = 30.0°, θmin = 3.0°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −18→17
Tmin = 0.767, Tmax = 0.936	k = −18→18
5840 measured reflections	l = −9→9
3185 independent 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)] = 0.022	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.061	w = 1/[σ^2(Fo^2) + (0.0391P)^2 + 0.1632P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max = 0.001
3185 reflections	Δρmax = 0.32 e Å^−3
206 parameters	Δρmin = −0.23 e Å^−3
2 restraints	Absolute structure: Flack (1983), with 1411 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.00 (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
Cl1	0.82353 (3)	0.49898 (2)	0.62098 (4)	0.01496 (8)
Cl2	0.52574 (3)	0.12870 (2)	0.67726 (4)	0.01469 (8)
O1	0.60208 (10)	0.48768 (9)	0.50689 (19)	0.0168 (2)
O2	0.87005 (8)	0.30674 (8)	0.80235 (16)	0.0135 (2)
O3	0.74709 (8)	0.14775 (9)	0.80503 (15)	0.0135 (2)
O4	0.47454 (9)	0.33097 (8)	0.50806 (15)	0.0144 (2)
O5	0.42357 (9)	0.68220 (9)	0.45444 (16)	0.0169 (2)
N1	0.08597 (10)	0.72797 (10)	0.13127 (18)	0.0137 (2)
N2	0.38330 (11)	0.52215 (10)	0.3900 (2)	0.0156 (2)
C1	0.63604 (11)	0.40974 (11)	0.5729 (2)	0.0109 (3)
C2	0.74192 (11)	0.39932 (11)	0.6435 (2)	0.0111 (3)
C3	0.77542 (11)	0.31451 (11)	0.72668 (19)	0.0103 (3)
C4	0.70662 (11)	0.22381 (11)	0.73503 (19)	0.0109 (3)
C5	0.60406 (11)	0.23260 (11)	0.6640 (2)	0.0114 (3)
C6	0.56272 (11)	0.31904 (11)	0.5798 (2)	0.0110 (3)
C7	0.16801 (12)	0.78916 (11)	0.1567 (2)	0.0137 (3)
H7	0.1630	0.8568	0.1202	0.016*
C8	0.25895 (12)	0.75244 (11)	0.2362 (2)	0.0127 (3)
H8	0.3172	0.7946	0.2552	0.015*
C9	0.26472 (11)	0.65279 (11)	0.28849 (19)	0.0103 (3)
C10	0.17939 (12)	0.59147 (11)	0.2575 (2)	0.0132 (3)
H10	0.1827	0.5232	0.2902	0.016*
C11	0.08945 (13)	0.63181 (11)	0.1781 (2)	0.0156 (3)
H11	0.0302	0.5912	0.1569	0.019*
C12	0.36499 (11)	0.61842 (11)	0.3846 (2)	0.0114 (3)
H1	0.030 (2)	0.7538 (18)	0.066 (3)	0.026 (6)*
H2	0.881 (2)	0.247 (2)	0.851 (4)	0.036 (7)*
H2A	0.445 (2)	0.497 (2)	0.444 (4)	0.031 (7)*
H2B	0.343 (2)	0.482 (2)	0.343 (4)	0.037 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.01137 (15)	0.01028 (15)	0.02300 (17)	−0.00293 (11)	−0.00284 (12)	0.00281 (12)
Cl2	0.01059 (15)	0.00918 (14)	0.02406 (17)	−0.00280 (12)	−0.00274 (12)	0.00177 (13)
O1	0.0139 (5)	0.0105 (5)	0.0255 (6)	−0.0001 (4)	−0.0053 (4)	0.0036 (4)
O2	0.0087 (5)	0.0119 (5)	0.0197 (5)	0.0006 (4)	−0.0038 (4)	0.0027 (4)
O3	0.0123 (5)	0.0088 (5)	0.0194 (5)	0.0002 (4)	−0.0014 (4)	0.0018 (4)
O4	0.0101 (5)	0.0123 (5)	0.0204 (5)	0.0001 (4)	−0.0060 (4)	−0.0001 (4)
O5	0.0145 (5)	0.0135 (5)	0.0223 (5)	−0.0028 (4)	−0.0058 (4)	−0.0014 (4)
N1	0.0102 (6)	0.0150 (6)	0.0158 (5)	0.0036 (4)	−0.0022 (5)	0.0008 (5)
N2	0.0112 (6)	0.0112 (6)	0.0238 (6)	0.0014 (5)	−0.0064 (5)	−0.0006 (5)
C1	0.0101 (6)	0.0104 (6)	0.0121 (6)	0.0006 (5)	−0.0010 (5)	−0.0002 (5)
C2	0.0096 (6)	0.0088 (6)	0.0148 (6)	−0.0027 (5)	−0.0021 (5)	0.0004 (5)
C3	0.0083 (6)	0.0110 (6)	0.0114 (6)	−0.0001 (5)	−0.0009 (5)	−0.0016 (5)
C4	0.0112 (6)	0.0095 (6)	0.0120 (6)	0.0011 (5)	−0.0008 (5)	−0.0011 (5)
C5	0.0093 (6)	0.0084 (6)	0.0164 (6)	−0.0027 (5)	−0.0005 (5)	−0.0001 (5)
C6	0.0095 (6)	0.0103 (7)	0.0131 (6)	−0.0001 (5)	0.0007 (5)	−0.0011 (5)
C7	0.0161 (7)	0.0101 (6)	0.0149 (6)	0.0024 (5)	0.0002 (5)	0.0013 (5)
C8	0.0133 (6)	0.0105 (6)	0.0144 (6)	−0.0004 (5)	−0.0005 (5)	0.0000 (5)
C9	0.0097 (6)	0.0103 (6)	0.0106 (6)	0.0013 (5)	−0.0016 (5)	−0.0005 (5)
C10	0.0110 (6)	0.0116 (7)	0.0168 (6)	−0.0002 (5)	−0.0020 (5)	0.0013 (5)
C11	0.0124 (7)	0.0139 (7)	0.0204 (7)	−0.0015 (5)	−0.0026 (6)	−0.0017 (5)
C12	0.0085 (6)	0.0135 (7)	0.0120 (6)	−0.0007 (5)	−0.0011 (5)	0.0008 (5)

Geometric parameters (Å, º)

Cl1—C2	1.7216 (15)	C1—C2	1.449 (2)
Cl2—C5	1.7353 (15)	C2—C3	1.352 (2)
O1—C1	1.2263 (19)	C3—C4	1.517 (2)
O2—C3	1.3239 (18)	C4—C5	1.408 (2)
O2—H2	0.89 (3)	C5—C6	1.407 (2)
O3—C4	1.2473 (19)	C7—C8	1.379 (2)
O4—C6	1.2435 (18)	C7—H7	0.9500
O5—C12	1.2388 (18)	C8—C9	1.396 (2)
N1—C11	1.340 (2)	C8—H8	0.9500
N1—C7	1.353 (2)	C9—C10	1.392 (2)
N1—H1	0.92 (2)	C9—C12	1.5168 (19)
N2—C12	1.321 (2)	C10—C11	1.386 (2)
N2—H2A	0.94 (3)	C10—H10	0.9500
N2—H2B	0.82 (3)	C11—H11	0.9500
C1—C6	1.551 (2)
C3—O2—H2	111.2 (17)	O4—C6—C5	127.60 (14)
C11—N1—C7	122.63 (13)	C1—C6—C5	116.34 (12)
C11—N1—H1	120.8 (15)	O4—C6—C1	116.05 (13)
C7—N1—H1	116.1 (15)	N1—C7—C8	119.34 (13)
C12—N2—H2A	120.9 (16)	N1—C7—H7	120.3
C12—N2—H2B	122 (2)	C8—C7—H7	120.3
H2A—N2—H2B	117 (3)	C7—C8—C9	119.43 (14)
O1—C1—C6	118.52 (13)	C7—C8—H8	120.3
C2—C1—C6	119.02 (13)	C9—C8—H8	120.3
O1—C1—C2	122.45 (14)	C10—C9—C8	119.76 (13)
Cl1—C2—C3	120.90 (11)	C10—C9—C12	123.42 (13)
C1—C2—C3	121.16 (13)	C8—C9—C12	116.77 (13)
Cl1—C2—C1	117.94 (11)	C11—C10—C9	118.75 (14)
O2—C3—C2	121.42 (13)	C11—C10—H10	120.6
O2—C3—C4	117.19 (12)	C9—C10—H10	120.6
C2—C3—C4	121.39 (13)	N1—C11—C10	120.07 (14)
O3—C4—C3	116.16 (12)	N1—C11—H11	120.0
O3—C4—C5	126.07 (14)	C10—C11—H11	120.0
C3—C4—C5	117.77 (13)	O5—C12—N2	124.42 (14)
Cl2—C5—C6	118.61 (11)	O5—C12—C9	117.94 (13)
C4—C5—C6	124.11 (13)	N2—C12—C9	117.63 (13)
Cl2—C5—C4	117.27 (11)
O1—C1—C2—Cl1	−3.5 (2)	C3—C4—C5—Cl2	−179.19 (10)
O1—C1—C2—C3	175.66 (15)	C3—C4—C5—C6	2.4 (2)
C6—C1—C2—Cl1	176.17 (10)	Cl2—C5—C6—O4	−1.3 (2)
C6—C1—C2—C3	−4.7 (2)	Cl2—C5—C6—C1	179.67 (10)
O1—C1—C6—O4	3.4 (2)	C4—C5—C6—O4	177.12 (14)
O1—C1—C6—C5	−177.43 (14)	C4—C5—C6—C1	−1.9 (2)
C2—C1—C6—O4	−176.29 (13)	C11—N1—C7—C8	−0.9 (2)
C2—C1—C6—C5	2.87 (19)	N1—C7—C8—C9	0.1 (2)
Cl1—C2—C3—O2	3.6 (2)	C7—C8—C9—C10	0.9 (2)
Cl1—C2—C3—C4	−175.63 (10)	C7—C8—C9—C12	−176.85 (13)
C1—C2—C3—O2	−175.57 (13)	C8—C9—C10—C11	−1.2 (2)
C1—C2—C3—C4	5.2 (2)	C12—C9—C10—C11	176.37 (14)
O2—C3—C4—O3	−3.29 (19)	C7—N1—C11—C10	0.5 (2)
O2—C3—C4—C5	176.74 (12)	C9—C10—C11—N1	0.5 (2)
C2—C3—C4—O3	175.95 (13)	C10—C9—C12—O5	−159.29 (15)
C2—C3—C4—C5	−4.0 (2)	C8—C9—C12—O5	18.4 (2)
O3—C4—C5—Cl2	0.9 (2)	C10—C9—C12—N2	19.9 (2)
O3—C4—C5—C6	−177.57 (14)	C8—C9—C12—N2	−162.45 (14)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O5^i	0.92 (2)	1.79 (2)	2.6966 (18)	173 (2)
N2—H2A···O1	0.94 (3)	2.07 (3)	2.9598 (19)	158 (2)
N2—H2A···O4	0.94 (3)	2.32 (3)	2.9469 (18)	124 (2)
N2—H2B···O3^ii	0.82 (3)	2.16 (3)	2.9424 (18)	161 (3)
O2—H2···O3	0.89 (3)	2.21 (3)	2.6728 (16)	112 (2)
O2—H2···O4^iii	0.89 (3)	1.93 (3)	2.6953 (15)	144 (2)
C7—H7···O1^i	0.95	2.37	3.2959 (19)	164
C10—H10···O3^ii	0.95	2.45	3.3599 (19)	159

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