Nine N-aryl-2-chloronicotinamides: supramolecular structures in one, two and three dimensions

Structures are reported here for eight further substituted N-aryl-2-chloronicotinamides, 2-ClC₅H₃NCONHC₆H₄X-4′. When X = H, compound (I) (C₁₂H₉ClN₂O), the molecules are linked into sheets by N—H⋯N, C—H⋯π(pyridyl) and C—H⋯π(arene) hydrogen bonds. For X = CH₃, compound (II) (C₁₃H₁₁ClN₂O, triclinic with Z′ = 2), the molecules are linked into sheets by N—H⋯O, C—H⋯O and C—H⋯π(arene) hydrogen bonds. Compound (III), where X = F, crystallizes as a monohydrate (C₁₂H₈ClFN₂O·H₂O) and sheets are formed by N—H⋯O, O—H⋯O and O—H⋯N hydrogen bonds and aromatic π⋯π stacking interactions. Crystals of compound (IV), where X = Cl (C₁₂H₈Cl₂N₂O, monoclinic P2₁ with Z′ = 4) exhibit inversion twinning: the molecules are linked by N—H⋯O hydrogen bonds into four independent chains, linked in pairs by C—H⋯π(arene) hydrogen bonds. When X = Br, compound (V) (C₁₂H₈BrClN₂O), the molecules are linked into sheets by N—H⋯O and C—H⋯N hydrogen bonds, while in compound (VI), where X = I (C₁₂H₈ClIN₂O), the molecules are linked into a three-dimensional framework by N—H⋯O and C—H⋯π(arene) hydrogen bonds and an iodo⋯N(pyridyl) interaction. For X = CH₃O, compound (VII) (C₁₃H₁₁ClN₂O₂), the molecules are linked into chains by a single N—H⋯O hydrogen bond. Compound (VIII) (C₁₃H₈ClN₃O, triclinic with Z′ = 2), where X = CN, forms a complex three-dimensional framework by N—H⋯N, C—H⋯N and C—H⋯O hydrogen bonds and two independent aromatic π⋯π stacking interactions.

1. Introduction

Nicotinic acid (pyridine-3-carboxylic acid) and nicotinamide (niacinamide, pyridine-3-carboxamide) are two of the principal members of the B-vitamin complex. Niacin, nicotinamide and nicotinic acid have identical vitamin activities, but they have very different pharmacological activities. Nicotinamide, via its major metabolite nicotinamide adenine dinucleotide, is involved in a wide range of biological processes including the production of energy, the synthesis of fatty acids, cholesterol and steroids, signal transduction, and the maintenance of the integrity of the genome. Nicotinic acid in pharmacological doses is used as an antihyperlipidemic agent: it also causes vasodilation of cutaneous blood vessels. Nicotinamide has been investigated as an agent for the prevention or delay of the onset of type 1 diabetes mellitus. It also has anti-oxidant, anti-inflammatory and anti-carcinogenic activities, and has putative activity against osteoarthritis and granuloma annulare. We have made a study of the properties and activities of substituted derivatives, 2-chloro-N-(4-X-phenyl)nicotinamides, and here we report the structures and supramolecular arrangements of nine examples having X = H (I), Me (II), F (III), Cl (IV), Br (V), I (VI), OMe (VII) and CN (VIII), and including the recently reported analogue with X = NO₂, (IX) (de Souza et al., 2005).

Here we report the molecular and supramolecular structures of eight closely related N-aryl-2-chloronicotinamides, 2-ClC₅H₃NCONHC₆H₄X-4′, whose crystallization characteristics prove to be all different, even within the halogen-substituted subset, (III)–(VI), and whose supramolecular structures all prove to be different, with no two utilizing the same combination of direction-specific intermolecular interactions.

2. Experimental

2.1. Synthesis

Samples of (I)–(VIII) were prepared by reaction of equimolar quantities of 2-chloronicotinoyl chloride and the appropriate substituted aniline in tetrahydrofuran solution at ambient temperature in the presence of a catalytic quantity of triethylamine. After stirring for 8 h, the reaction mixtures were neutralized with saturated aqueous sodium hydrogencarbonate solution and the resulting aqueous mixtures were extracted with ethyl acetate (2 × 30 cm³). For each preparation, the organic extracts were combined, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. Chromatography on silica, using hexane:ethyl acetate gradients (up to 50% ethyl acetate), then yielded the pure products, with yields in the range 80–90%. Crystals of (I), (II) and (IV)–(VIII) suitable for single-crystal X-ray diffraction were grown from solution in ethanol, and crystals of (III) were grown from an aqueous solution: m.p.s: (I) 395–397 K, (II) 432–433 K, (III) 366–367 K, (IV) 421–422 K, (V) 399–400 K, (VI) 448–450 K, (VII) 383–384 K and (VIII) 445–446 K.

2.2. Data collection, structure solution and refinement

Details of cell data, data collection and structure solution and refinement are summarized in Table 1 (Bruker, 2004; Cernik et al., 1997; Ferguson, 1999; McArdle, 2003; Otwinowski & Minor, 1997; Sheldrick, 1997a,b, 2003; Hooft, 1999). The space groups for (I), (IV), (V), VI) and (VII) were all assigned uniquely from the systematic absences: crystals of (II), (III) and (VIII) are triclinic, and for each the space group was selected, and confirmed by the successful structure analysis. The structures were all solved by direct methods using SHELXS97 (Sheldrick, 1997a) and refined on F² with all data using SHELXL97 (Sheldrick, 1997b). A weighting scheme based upon P = [F_o² + 2F_c²]/3 was employed in order to reduce statistical bias (Wilson, 1976). All H atoms were located from difference maps and all were included in the refinements as riding atoms, with distances C—H 0.95 and N—H 0.88 Å, and with U_iso(H) = 1.2U_eq(C,N). For (V) and (VII), the correct enantiomorph was selected using the Flack parameter (Flack, 1983): the final values were 0.031 (7) and −0.05 (7), respectively. For (IV), where the crystals were all of very poor quality, the Flack parameter 0.54 (11) indicated inversion twinning.

Table 1
Experimental details

	(I)	(II)	(III)	(IV)
Crystal data
Chemical formula	C12H9ClN2O	C13H11ClN2O	C12H8ClFN2O·H2O	C12H8Cl2N2O
Mr	232.66	246.69	268.67	267.10
Cell setting, space group	Orthorhombic, Pccn	Triclinic,	Triclinic,	Monoclinic, P21
Temperature (K)	120 (2)	120 (2)	120 (2)	120 (2)
a, b, c (Å)	13.2296 (6), 21.0744 (10), 7.6898 (16)	9.6824 (6), 11.3082 (7), 11.5139 (7)	6.8033 (4), 8.1303 (3), 11.5356 (6)	5.0855 (8), 28.982 (8), 15.607 (4)
α, β, γ (°)	90, 90, 90	77.453 (2), 73.445 (2), 87.978 (2)	84.032 (3), 84.297 (2), 69.569 (3)	90, 90.37 (2), 90
V (Å^3)	2144.0 (5)	1179.07 (13)	593.32 (5)	2300.2 (9)
Z	8	4	2	8
Dx (Mg m^−3)	1.442	1.390	1.504	1.543
Radiation type	Mo Kα	Synchrotron, λ = 0.67510 Å	Mo Kα	Mo Kα
No. of reflections for cell parameters	2446	6881	2720	9787
θ range (°)	3.1–27.5	2.1–28.8	3.3–27.8	3.0–27.5
μ (mm^−1)	0.33	0.31	0.33	0.55
Crystal form, colour	Needle, colourless	Needle, colourless	Plate, colourless	Plate, colourless
Crystal size (mm)	0.24 × 0.09 × 0.02	0.10 × 0.02 × 0.02	0.18 × 0.16 × 0.03	0.28 × 0.07 × 0.03
Data collection
Diffractometer	Bruker–Nonius 95 mm CCD camera on κ goniostat	Bruker SMART APEX2 CCD diffractometer	Bruker–Nonius 95 mm CCD camera on κ goniostat	Bruker–Nonius 95 mm CCD camera on κ goniostat
Data collection method	φ and ω scans	Fine-slice ω scans	φ and ω scans	φ and ω scans
Absorption correction	Multi-scan	Multi-scan	Multi-scan	Multi-scan
Tmin	0.943	0.970	0.933	0.862
Tmax	0.993	0.994	0.990	0.984
No. of measured, independent and observed reflections	17 837, 2446, 1724	12 982, 6881, 5217	12 303, 2720, 1943	24 726, 9787, 6370
Criterion for observed reflections	I > 2σ(I)	I > 2σ(I)	I > 2σ(I)	I > 2σ(I)
Rint	0.104	0.022	0.052	0.053
θmax (°)	27.5	28.8	27.8	27.5
Range of h, k, l	−16 → h → 17	−13 → h → 13	−8 → h → 8	−6 → h → 6
	−27 → k → 27	−16 → k → 16	−9 → k → 10	−37 → k → 37
	−9 → l → 9	−16 → l → 16	−14 → l → 14	−20 → l → 20
Refinement
Refinement on	F^2	F^2	F^2	F^2
R[F^2 > 2σ(F^2)], wR(F^2), S	0.059, 0.129, 1.07	0.044, 0.124, 1.02	0.044, 0.113, 1.05	0.069, 0.169, 1.04
No. of reflections	2446	6881	2720	9787
No. of parameters	145	309	163	254
H-atom treatment	Constrained to parent site	Constrained to parent site	Constrained to parent site	Constrained to parent site
Weighting scheme	w = 1/[σ^2(Fo^2) + (0.0479P)^2 + 1.6007P], where P = (Fo^2 + 2Fc^2)/3	w = 1/[σ^2(Fo^2) + (0.0648P)^2 + 0.3225P], where P = (Fo^2 + 2Fc^2)/3	w = 1/[σ^2(Fo^2) + (0.0536P)^2 + 0.1705P], where P = (Fo^2 + 2Fc^2)/3	w = 1/[σ^2(Fo^2) + (0.0454P)^2 + 5.774P], where P = (Fo^2 + 2Fc^2)/3
(Δ/σ)max	0.001	0.001	<0.0001	0.001
Δρmax, Δρmin (e Å^−3)	0.28, −0.28	0.43, −0.30	0.26, −0.29	0.79, −0.54
Absolute structure	–	–	–	Flack (1983), 4396 Friedel pairs
Flack parameter	–	–	–	0.54 (11)

	(V)	(VI)	(VII)	(VIII)
Crystal data
Chemical formula	C12H8BrClN2O	C12H8ClIN2O	C13H11ClN2O2	C13H8ClN3O
Mr	311.56	358.55	262.69	257.67
Cell setting, space group	Orthorhombic, P212121	Orthorhombic, Pbca	Orthorhombic, P212121	Triclinic,
Temperature (K)	120 (2)	120 (2)	120 (2)	120 (2)
a, b, c (Å)	4.8810 (2), 13.3448 (2), 18.3974 (3)	10.6597 (2), 25.9833 (3), 9.2044 (6)	4.8536 (2), 11.8437 (4), 21.0612 (7)	7.2885 (3), 7.7607 (3), 20.8849 (9)
α, β, γ (°)	90, 90, 90	90, 90, 90	90, 90, 90	96.456 (2), 92.913 (2), 91.810 (2)
V (Å^3)	1198.33 (6)	2549.38 (18)	1210.69 (6)	1171.49 (8)
Z	4	8	4	4
Dx (Mg m^−3)	1.727	1.868	1.441	1.461
Radiation type	Mo Kα	Mo Kα	Mo Kα	Mo Kα
No. of reflections for cell parameters	2736	2909	2661	5365
θ range (°)	3.0–27.5	3.0–27.5	3.6–27.5	2.9–27.6
μ (mm^−1)	3.64	2.71	0.31	0.32
Crystal form, colour	Block, colourless	Plate, colourless	Block, colourless	Block, colourless
Crystal size (mm)	0.16 × 0.16 × 0.16	0.33 × 0.18 × 0.07	0.34 × 0.22 × 0.12	0.40 × 0.10 × 0.10
Data collection
Diffractometer	Bruker–Nonius 95 mm CCD camera on κ goniostat	Bruker–Nonius 95 mm CCD camera on κ goniostat	Bruker–Nonius 95 mm CCD camera on κ goniostat	Bruker–Nonius 95 mm CCD camera on κ goniostat
Data collection method	φ and ω scans	φ and ω scans	φ and ω scans	φ and ω scans
Absorption correction	Multi-scan	Multi-scan	Multi-scan	Multi-scan
Tmin	0.558	0.469	0.921	0.899
Tmax	0.558	0.833	0.964	0.969
No. of measured, independent and observed reflections	36 201, 2736, 2597	19 649, 2909, 2314	7884, 2661, 2184	21 639, 5365, 3760
Criterion for observed reflections	I > 2σ(I)	I > 2σ(I)	I > 2σ(I)	I > 2σ(I)
Rint	0.047	0.038	0.040	0.060
θmax (°)	27.5	27.5	27.5	27.6
Range of h, k, l	−6 → h → 6	−13 → h → 13	−5 → h → 6	−9 → h → 9
	−17 → k → 17	−32 → k → 33	−15 → k → 11	−10 → k → 10
	−23 → l → 23	−11 → l → 11	−21 → l → 27	−27 → l → 26
Refinement
Refinement on	F^2	F^2	F^2	F^2
R[F^2 > 2σ(F^2)], wR(F^2), S	0.023, 0.060, 1.07	0.023, 0.056, 1.04	0.042, 0.104, 1.04	0.059, 0.171, 1.06
No. of reflections	2736	2909	2661	5365
No. of parameters	154	154	164	325
H-atom treatment	Constrained to parent site	Constrained to parent site	Constrained to parent site	Constrained to parent site
Weighting scheme	w = 1/[σ^2(Fo^2) + (0.0339P)^2 + 0.2964P], where P = (Fo^2 + 2Fc^2)/3	w = 1/[σ^2(Fo^2) + (0.026P)^2 + 0.5926P], where P = (Fo^2 + 2Fc^2)/3	w = 1/[σ^2(Fo^2) + (0.0579P)^2], where P = (Fo^2 + 2Fc^2)/3	w = 1/[σ^2(Fo^2) + (0.0844P)^2 + 1.0407P], where P = (Fo^2 + 2Fc^2)/3
(Δ/σ)max	0.001	0.005	<0.0001	<0.0001
Δρmax, Δρmin (e Å^−3)	0.43, −0.52	0.39, −0.78	0.24, −0.35	0.74, −0.35
Absolute structure	Flack (1983), 1098 Friedel pairs	–	Flack (1983), 1013 Friedel pairs	–
Flack parameter	0.031 (7)	–	−0.05 (7)	–

Supramolecular analyses were made and the diagrams were prepared with the aid of PLATON (Spek, 2003). Figs. 1–30 show the independent components of (I)–(VIII) and aspects of their supramolecular structures. Selected torsional angles are given in Table 2 and details of the hydrogen bonding are in Table 3.¹

Table 2
Selected torsional and dihedral angles (°)

C13—C17—N21—C21	C12—C13—C17—N21	C17—N21—C21—C22	Δ†
(I)
178.8 (2)	−56.2 (4)	−171.8 (2)	48.2 (2)
(II)
175.30 (13)	−99.53 (16)	−141.82 (15)	59.8 (2)
175.77 (13)‡	−103.14 (16)†	166.05 (14)†	62.9 (2)
(III)
171.39 (18)	130.5 (2)	174.60 (18)	62.6 (2)
(IV)
175.0 (6)	135.5 (8)	149.0 (6)	78.2 (3)
−176.7 (6)‡	−137.9 (8)†	−148.6 (5)†	77.8 (3)
173.9 (6)‡	134.4 (8)†	−141.9 (6)†	12.4 (3)
−176.9 (6)‡	−138.0 (8)†	144.9 (5)†	11.5 (3)
(V)
178.86 (17)	51.3 (3)	143.6 (2)	17.2 (2)
(VI)
172.75 (19)	−77.3 (2)	−135.9 (2)	35.4 (2)
(VII)
−179.41 (18)	−134.5 (2)	141.0 (2)	10.2 (2)
(VIII)
170.3 (3)	−73.7 (4)	−163.6 (3)	60.9 (2)
−174.2 (3)‡	90.9 (3)†	177.8 (3)†	89.4 (3)
(IX)§
173.29 (19)	78.1 (3)	−179.8 (2)	73.3 (2)
−173.4 (2)‡	−71.5 (3)†	173.6 (2)†	73.6 (3)

†Δ is the dihedral angle between the two rings in each independent molecule.
‡In molecule 2 of (II), (IV), (VIII) and (IX) the relevant atom sequence is C32—C33—C37—N41—C41—C42; in molecules 3 and 4 of (IV) the relevant atom sequences are C52—C53—C57—N61—C61—C62 and C72—C73—C77—N81—C81—C82, respectively (see Figs. 5, 12 and 25).
§Data from de Souza et al. (2005).

Table 3
Hydrogen-bond parameters (Å, °)

D—H⋯A	H⋯A	D⋯A	D—H⋯A
(I)
N21—H21⋯N11^i	2.25	3.101 (3)	164
C15—H15⋯Cg1^ii†	2.89	3.535 (3)	126
C16—H16⋯Cg2^iii‡	2.87	3.464 (3)	121
(II)
N21—H21⋯O3	1.96	2.827 (2)	170
N41—H41⋯O1^iv	1.99	2.847 (2)	163
C35—H35⋯O1^ii	2.48	3.424 (2)	174
C14—H14⋯Cg3^v§	2.69	3.398 (2)	132
C34—H34⋯Cg2^ii‡	2.63	3.398 (2)	138
(III)
N21—H21⋯O2	1.91	2.837 (2)	179
O2—H2A⋯N11^vi	1.97	2.887 (2)	161
O2—H2B⋯O1^iv	1.95	2.780 (2)	173
(IV)
N21—H21⋯O1^iv	2.11	2.925 (8)	153
N41—H41⋯O3^iv	2.00	2.833 (8)	157
N61—H61⋯O5^vii	2.11	2.925 (8)	153
N81—H81⋯O7^vii	2.00	2.841 (8)	159
C26—H26⋯Cg5¶	2.76	3.444 (8)	130
C46—H46⋯Cg4††	2.75	3.448 (8)	131
C62—H62⋯Cg3^vii§	2.88	3.588 (8)	132
C82—H82⋯Cg2^vii‡	2.87	3.579 (8)	132
(V)
N21—H21⋯O1^iv	2.03	2.825 (2)	169
C22—H22⋯N11^viii	2.56	3.405 (3)	148
(VI)
N21—H21⋯O1^ix	2.01	2.853 (2)	160
C15—H15⋯Cg2^x‡	2.65	3.404 (2)	137
(VII)
N21—H21⋯O1^ii	1.92	2.785 (2)	168
(VIII)
N21—H21⋯N44	2.15	3.006 (4)	164
N41—H41⋯N24^xi	2.10	2.978 (4)	173
C14—H14⋯O11^xii	2.49	3.334 (4)	148
C15—H15⋯O11^ii	2.60	3.507 (4)	160
C25—H25⋯N11^xiii	2.52	3.348 (4)	146
C34—H34⋯O31^xiv	2.53	3.327 (4)	142
C35—H35⋯O31^ii	2.45	3.366 (4)	161
C45—H45⋯N31^xiii	2.53	3.300 (4)	138
Symmetry codes: (i) ; (ii) 1 - x, 1 - y, 1 - z; (iii) ; (iv) -1 +x, y, z; (v) 1 - x, 2 - y, -z; (vi) 1 - x, 2 - y, 1 - z; (vii) 1 + x, y, z; (viii) ; (ix) ; (x) ; (xi) -2 + x, 1 + y, z; (xii) 1 - x, -y, 1 - z; (xiii) 1 + x, -1 + y, z; (xiv) -1 - x, 1 - y, -z.

†Cg1 is the centroid of ring N11, C12–C16.
‡Cg2 is the centroid of ring C21–C26.
§Cg3 is the centroid of ring C41–C46.
¶Cg5 is the centroid of ring C81–C86.
††Cg4 is the centroid of ring C61–C66.

3. Results and discussion

3.1. Crystallization characteristics

Compounds (II) and (VIII) both crystallize with Z′ = 2, while (IV) has Z′= 4; similarly, the 4-nitrophenyl derivative (IX) crystallizes with Z′ = 2 (de Souza et al., 2005). Of the compounds (I)–(VIII) reported here, the 4-fluorophenyl derivative is unique in crystallizing as a monohydrate, although the 2-nitrophenyl analogue reported recently (de Souza et al., 2005) also crystallizes as a stoichiometric monohydrate.

3.2. Molecular conformations

In each of compounds (I)–(VIII), as well as in (IX) (de Souza et al., 2005), the central C—C—N—C spacer unit is nearly planar, as shown by the torsional angles for this unit which are all close to 180°, ranging between 170.0 (3) and −173.4 (2)° (Table 2). However, the aryl ring is often markedly twisted out of this plane, particularly in (II), (IV), (V), (VI) and (VII), while the chloropyridyl is always twisted well away from the plane of the central spacer, being nearly orthogonal to this plane in (II), (VI), (VIII) and (IX). An alternative way to consider the overall conformations is by means of the dihedral angle denoted Δ between the two rings of each molecule, also shown in Table 2. It is striking to note the relationships between the conformations of the four independent molecules in (IV), shown particularly clearly by the dihedral angles Δ: molecules 1 and 2, containing N21 and N41 respectively, are close to being enantiomorphs, as are molecules 3 and 4 containing N61 and N81. However, the relationships between molecules 1 and 3, and between molecules 2 and 4 is that of diastereoisomers. The wide range of the dihedral angles Δ in (I)–(IX), varying from 10.2 (2)° in (VII) to 89.4 (2)° in molecule 2 of (VIII), indicates that the intramolecular barriers to rotation about the C—C bonds connecting the rings to the central spacer unit are rather readily overcome by the intermolecular forces, in particular by the direction-specific hydrogen bonds. In this way the observed conformations are an indirect reflection of the action of the hydrogen bonds, just as the detailed supramolecular aggregation patterns are a direct reflection of the action of the hydrogen bonds. The bond lengths and angles present no unusual features.

3.3. Supramolecular structures

3.3.1. Compound (I)

In the unsubstituted parent compound, (I) (Fig. 1), the molecules are linked into sheets by a combination of N—H⋯N, C—H⋯π(pyridyl) and C—H⋯π(arene) hydrogen bonds, but N—H⋯O hydrogen bonds are absent (Table 3). The formation of the sheets is most conveniently analysed and described in terms of the chains formed by the N—H⋯N and C—H⋯π(pyridyl) hydrogen bonds, and the linkage of the chains by the C—H⋯π(arene) hydrogen bonds.

Figure 1 The molecule of (I) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.

The amidic N21 atom in the molecule at (x, y, z) acts as a hydrogen-bond donor to the pyridyl N11 atom in the molecule at (), thus forming a C(7) (Bernstein et al., 1995) chain running parallel to the [001] direction and generated by the c glide plane at x = 0.25. This chain is reinforced by the —H⋯π(pyridyl) hydrogen bond, where the C16 atom in the molecule at (x, y, z) acts as a donor to the pyridyl ring in the molecule at (), thus forming a [001] chain of rings generated by the c glide plane at y = 0.25 (Fig. 2). Four chains of this type pass though each unit cell, two each in the domains 0.25 < y < 0.75 and −0.25 < y < 0.25, and within each domain, one chain is generated by the c glide plane at 0.25, and the other, antiparallel to the first, is generated by the c glide plane at y = 0.75. A simple centrosymmetric motif serves to link the antiparallel pairs of [001] chains in each domain to form sheets. The C15 atom in the molecule at (x, y, z), which is part of a chain generated by the glide plane at x = 0.25, acts as a hydrogen-bond donor to the phenyl ring in the molecule at (1 - x, 1 - y, 1 - z), which is part of a chain generated by the glide plane at x = 0.75 (Fig. 3). Propagation of this interaction then links all the chains in a given domain of y into a (010) sheet (Fig. 4): two sheets, related to one another by the twofold rotation axes parallel to [001], pass through each unit cell, but there are no direction-specific interactions between adjacent sheets.

Figure 2 Part of the crystal structure of (I) showing the formation of a hydrogen-bonded chain of rings along [001]. For the sake of clarity, the H atoms not involved in the motifs shown have been omitted. The atoms marked with an asterisk (*), a hash (#) or a dollar sign ($) are at the symmetry positions (), () and (x, y, -1 + z), respectively.

Figure 3 Part of the crystal structure of (I) showing the centrosymmetric ring built from C—H⋯π(arene) hydrogen bonds, which link the [001] chains into (010) sheets. For the sake of clarity, the H atoms not involved in the motif shown have been omitted. The atom marked with an asterisk (*) is at the symmetry position (1 - x, 1 - y, 1 - z).

Figure 4 Stereoview of part of the crystal structure of (I), showing a hydrogen-bonded (010) sheet. For the sake of clarity, the H atoms not involved in the motifs shown have been omitted.

3.3.2. Compound (II)

In the 4-methylphenyl derivative (II), where Z′ = 2 (Fig. 5), the molecules are linked by two independent N—H⋯O hydrogen bonds (Table 3) into C₂²(8) chains (Fig. 6): it is convenient to refer to molecules containing atoms O1 and O3 as 1 and 2, respectively. Two antiparallel C₂²(8) chains pass through each unit cell and these chains are linked into a chain of edge-fused rings by a single, nearly linear C—H⋯O hydrogen bond, where the pyridyl C35 atom in molecule 2 at (x, y, z) acts as a hydrogen-bond donor to the O1 atom in molecule 1 at (1 - x, 1 - y, 1 - z). Propagation by translation and inversion of these three hydrogen bonds, two of the N—H⋯O type and one of the C—H⋯O type, generates a chain of centrosymmetric, edge-fused rings along (), with R²₄(16) rings centred at () (n = zero or integer) and R₄⁴(20) rings centred at () (n = zero or integer; Fig. 7).

Figure 5 The two independent molecules of (II) showing the atom-labelling scheme and the N—H⋯O hydrogen bond within the asymmetric unit. Displacement ellipsoids are drawn at the 30% probability level.

Figure 6 Part of the crystal structure of (II), showing the formation of a C2^2(8) chain along [100]. For the sake of clarity, the H atoms bonded to C atoms have been omitted. The atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (-1 + x, y, z) and (1 + x, y, z), respectively.

Figure 7 Stereoview of part of the crystal structure of (II) showing the formation of a chain of edge fused R^24(16) and R4^4(20) rings along [100]. For the sake of clarity, the H atoms not involved in the motifs shown have been omitted.

There are two C—H⋯π(arene) hydrogen bonds in the structure of (II) (Table 3): one, having the C34 atom as the donor, lies within the [100] chain of rings, but the other, having C14 as the donor, links the [100] chains into sheets. The C14 atom in molecule 1 at (x, y, z) lies in the chain along (): this atom acts as a donor to the phenyl ring C41–C46 in molecule 2 at (1 - x, 2 - y, -z), which lies in the chain along (). Propagation by inversion of this C—H⋯π(arene) hydrogen bond then links [100] chains into a (011) sheet (Fig. 8). There are no direction-specific interactions between adjacent sheets.

Figure 8 Stereoview of part of the crystal structure of (II) showing the linking, by means of a single C—H⋯π(arene) hydrogen bond, of the [100] chains of rings into a (011) sheet. For the sake of clarity, the H atoms not involved in the motifs shown have been omitted.

3.3.3. Compound (III)

The 4-fluorophenyl derivative crystallizes as a monohydrate, compound (III), and in the selected asymmetric unit (Fig. 9) the two components are linked by an N—H⋯O hydrogen bond: this utilization of the N—H donor site immediately precludes the formation of the characteristic amidic C(4) chain. Instead the molecules are linked into chains of edge-fused rings by a combination of O—H⋯O and O—H⋯N hydrogen bonds (Table 3), and these chains are linked into sheets by a single aromatic π⋯π stacking interaction.

Figure 9 The molecular components of (III) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.

The water atom O2 at (x, y, z) acts as a hydrogen-bond donor, via H2B, to the amidic atom O1 at (-1 + x, y, z), thus generating by translation a C₂²(6) chain running parallel to the [100] direction. An antiparallel pair of these C₂²(6) chains is linked by the N—H⋯O hydrogen bond: the O2 atom at (x, y, z) acts as a donor, via H2A, to the pyridyl N11 atom at (1 - x, 2 - y, 1 - z), thus generating a centrosymmetric R₄⁴(16) ring, centred at (). The combination of all the hydrogen bonds then generates, by translation and inversion, a chain of edge-fused R₄⁴(16) rings along () (Fig. 10). There are two types of ring within this chain and both are centrosymmetric: those having amidic O atoms as two of the acceptor sites are centred at () (n = zero or integer), and those having water O atoms as two of the acceptor sites are centred at () (n = zero or integer).

Figure 10 Part of the crystal structure of (III) showing the formation of a hydrogen-bonded chain of edge-fused rings along [100]. For the sake of clarity, the H atoms bonded to C atoms have been omitted. The atoms marked with an asterisk (*), a hash (#) or a dollar sign ($) are at the symmetry positions (1 - x, 2 - y, 1 - z), (-1 + x, y, z) and (-x, 2 - y, 1 - z), respectively.

The pyridyl rings in the amide molecules at (x, y, z) and (1 - x, 1 - y, 2 - z) are strictly parallel with an interplanar spacing of 3.352 (2) Å; the ring-centroid separation is 3.618 (2) Å, corresponding to a nearly ideal ring offset of 1.362 (2) Å. These two amide molecules form parts of the chains of fused rings along () and (), so that propagation by inversion of this stacking interaction forms a [01] chain (Fig. 11), which links the chains of rings into a (011) sheet.

Figure 11 Stereoview of part of the crystal structure of (III) showing the centrosymmetric π-stacking interaction which links the [100] chains into (011) sheets. For the sake of clarity, the H atoms bonded to C atoms have been omitted.

3.3.4. Compound (IV)

We comment here only briefly on the supramolecular aggregation of the 4-chlorophenyl compound (IV). This compound crystallizes in the non-centrosymmetric space group P2₁ with Z′ = 4 (Fig. 12), but the crystal quality was extremely poor, with extensive twinning. Nonetheless, the main features of the structure are clear enough: each of the four independent molecules forms a C(4) chain by translation along [100], built from N—H⋯O hydrogen bonds (Fig. 13), and these chains are linked in pairs by the C—H⋯ π(arene) hydrogen bonds (Table 3).

Figure 12 The four independent molecules of (IV) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. The atom labelling for the other three molecules and the conformational differences between the molecules are defined in Table 2.

Figure 13 Stereoview of part of the crystal structure of (IV) showing the formation of four independent C(4) chains along [100]. For the sake of clarity, the H atoms bonded to C atoms have been omitted.

3.3.5. Compound (V)

In the 4-bromophenyl compound (V) (Fig. 14), the molecules are linked into isolated sheets by a combination of one N—H⋯O and one C—H⋯N hydrogen bond (Table 3). The amidic N21 atom in the molecule at (x, y, z) acts as a hydrogen-bond donor to the amidic O1 in the molecule at (-1 + x, y, z), so generating by translation a C(4) chain running parallel to the [100] direction (Fig. 15). Four chains of this type pass through each unit cell, two in each of the domains 0 < z < 0.5 and 0.5 < z < 1.0, and within each of these domains the chains are linked into sheets by a single C—H⋯N hydrogen bond. The aryl C22 atom in the molecule at (x, y, z) acts as a hydrogen-bond donor to the pyridyl N11 atom in the molecule at (), so forming a C(8) chain running parallel to the [010] direction, and generated by the 2₁ screw axis along () (Fig. 16). The combination of the [100] and [010] chains then generates a (001) sheet in the form of a (4,4) net built from a single type of R₄⁴(22) ring (Fig. 17). Two sheets of this type pass through each unit cell, generated by screw axes at y = 0.25 and y = 0.75, respectively, but there are no direction-specific interactions between adjacent sheets: in particular, aromatic π⋯π stacking interactions and C—H⋯π(arene) hydrogen bonds are absent.

Figure 14 The molecule of (V) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.

Figure 15 Part of the crystal structure of (V) showing the formation of a hydrogen-bonded C(4) chain along [100]. For the sake of clarity, the H atoms bonded to C atoms have been omitted. The atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (-1 + x, y, z) and (1 + x, y, z), respectively.

Figure 16 Part of the crystal structure of (V) showing the formation of a hydrogen-bonded C(8) chain along [010]. For the sake of clarity, the H atoms not involved in the motif shown have been omitted. The atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions () and (), respectively.

Figure 17 Stereoview of part of the crystal structure of (V) showing the formation of a hydrogen-bonded (001) sheet of R4^4(22) rings. For the sake of clarity, the H atoms not involved in the motifs shown have been omitted.

3.3.6. Compound (VI)

The molecules of the 4-iodophenyl compound (VI) (Fig. 18) are linked into sheets by a combination of one N—H⋯O hydrogen bond and one C—H⋯π(arene) hydrogen bond (Table 3) and these sheets are themselves linked by a single iodo⋯N(pyridyl) interaction. The N21 atom in the molecule at (x, y, z) acts as a hydrogen-bond donor to the O1 atom in the molecule at (), so forming a C(4) chain running parallel to the [001] direction, and generated by the c-glide plane at y = 0.25 (Fig. 19). In addition, the pyridyl C15 atom in the molecule at (x, y, z) acts as a hydrogen-bond donor to the aryl ring C21—C26 in the molecule at (), so forming a chain running parallel to the [100] direction and generated by the 2₁ screw axis along () (Fig. 20). The combination of these two hydrogen-bonded motifs then generates a (010) sheet (Fig. 21): two sheets of this type pass through each unit cell, in the domains −0.02 < y < 0.52 and 0.48 < y < 1.02. The sole direction-specific interaction between adjacent sheets is an iodo⋯N(pyridyl) interaction, somewhat analogous electronically to an iodo⋯nitro interaction: the I24 atom in the molecule at (x, y, z) forms a short contact with the pyridyl N11 atom in the molecule at (), with dimensions I⋯Nⁱ 3.116 (2) Å, C—I⋯Nⁱ 167.5 (2)° [symmetry code (i) ]. This interaction thus forms a C(10) chain (Starbuck et al., 1999) running parallel to the [010] direction and generated by a b-glide plane at y = 0.75 (Fig. 22): in this manner all the (010) sheets are linked into a continuous three-dimensional array.

Figure 18 The molecule of (VI) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.

Figure 19 Part of the crystal structure of (VI) showing the formation of a hydrogen-bonded C(4) chain along [001]. For the sake of clarity, the H atoms bonded to C atoms have been omitted. The atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions () and (), respectively.

Figure 20 Part of the crystal structure of (VI) showing the formation of a hydrogen-bonded chain along [100]. For the sake of clarity, the H atoms not involved in the motif shown have been omitted. The atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions () and (), respectively.

Figure 21 Stereoview of part of the crystal structure of (VI) showing the formation of a hydrogen-bonded (010) sheet. For the sake of clarity, the H atoms not involved in the motifs shown have been omitted.

Figure 22 Part of the crystal structure of (VI) showing the formation of an iodo⋯N(pyridyl) chain along [010]. For the sake of clarity, the H atoms have been omitted. The atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions () and (), respectively.

3.3.7. Compound (VII)

The supramolecular aggregation of the 4-methoxyphenyl derivative, compound (VII) (Fig. 23), is exceptionally simple. A single N—H⋯O hydrogen bond (Table 3) links the molecules into C(4) chains generated by translation (Fig. 24). Four chain of this type pass through each unit cell, but there are no direction-specific interactions between adjacent chains: in particular, C—H⋯π(arene) hydrogen bonds and aromatic π⋯π stacking interactions are both absent.

Figure 23 The molecule of (VII) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.

Figure 24 Part of the crystal structure of (VII) showing the formation of a hydrogen-bonded C(4) chain along [100]. For the sake of clarity, the H atoms bonded to C atoms have been omitted. The atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (-1 + x, y, z) and (1 + x, y, z), respectively.

3.3.8. Compound (VIII)

The structure of the 4-cyanophenyl compound (VIII) (Fig. 25) contains N—H⋯N, C—H⋯N and C—H⋯O hydrogen bonds (Table 3), as well as aromatic π⋯π stacking interactions; the resulting three-dimensional structure is of considerable complexity, although it is readily analysed in terms of its constituent one-dimensional sub-structures. Within the asymmetric unit, the amido N21 atom acts as a hydrogen-bond donor to the cyano N44 atom: similarly, the amido atom N41 at (x, y, z) acts as a donor to the cyano N24 atom at (-2 + x, 1 + y, z), so generating by translation a C₂²(16) chain running parallel to the [20] direction (Fig. 26). In contrast to the simple chain generated by the hard hydrogen bonds, the soft hydrogen bonds generate both molecular ladders and chains of rings (Bernstein et al., 1995).

Figure 25 The two independent molecules of (VIII) showing the atom-labelling scheme and the N—H⋯N hydrogen bond within the asymmetric unit. Displacement ellipsoids are drawn at the 30% probability level.

Figure 26 Stereoview of part of the crystal structure of (VIII) showing the formation of a C2^2(16) chain along [20] built from N—H⋯N hydrogen bonds. For the sake of clarity, the H atoms bonded to C atoms have been omitted.

Atoms C15 and C35 in the bimolecular aggregate at (x, y, z) act as hydrogen-bond donors respectively to atoms O11 and O31 in the aggregate at (-1 + x, y, z). The individual C—H⋯O hydrogen bonds each generate by translation a C(6) chain along [100] and, together with the N—H⋯N hydrogen bond within the bimolecular aggregate, they generate a chain of edge-fused R₄⁴(32) rings (Fig. 27). Alternatively, this motif can be regarded as a molecular ladder, in which the C(6) chains form the uprights, and N—H⋯N hydrogen bonds form part of each rung.

Figure 27 Stereoview of part of the crystal structure of (VIII) showing the formation of a chain of edge-fused R4^4(32) rings along [100] built from N—H⋯N and C—H⋯O hydrogen bonds. For the sake of clarity, the H atoms bonded to C atoms, but not involved in the motif shown, have been omitted.

In a similar way, the C25 and C45 atoms in the bimolecular aggregate at (x, y, z) act as hydrogen-bond donors respectively to pyridyl atoms N11 and N31 in the aggregate at (1 + x, -1 + y, z). The individual C—H⋯N hydrogen bonds each generate by translation a C(9) chain along [10] and together with the N—H⋯N hydrogen bond within the bimolecular aggregate they generate a chain of edge-fused R₄⁴(28) rings (Fig. 28). As before, this motif can be regarded as a molecular ladder, with the C(9) chains now forming the uprights and with the N—H⋯N hydrogen bonds in the rungs.

Figure 28 Stereoview of part of the crystal structure of (VIII) showing the formation of a chain of edge-fused R4^4(28) rings along [10] built from N—H⋯N and C—H⋯N hydrogen bonds. For the sake of clarity, the H atoms bonded to C atoms, but not involved in the motif shown, have been omitted.

Finally, atoms C14 and C34 at (x, y, z) acts as hydrogen-bond donors respectively to atoms O11 at (1 - x, -y, 1 - z) and O31 at (-1 - x, 1 - y, -z), so generating two distinct R₂²(10) rings, both centrosymmetric, and centred respectively at () and (). The combination of these two rings, together with the N—H⋯N hydrogen bond within the asymmetric unit, then generates by inversion a chain of rings running parallel to the [21] direction (Fig. 29). This chain, in turn, is reinforced by a combination of two π⋯π stacking interactions. The pyridyl rings containing N11 in the molecules are (x, y, z) and (1 - x, 1 - y, 1 - z) and are parallel with an interplanar spacing of 3.426 (2) Å; the ring-centroid separation is 3.589 (2) Å, corresponding to a ring offset of 1.069 (2) Å; similarly, the pyridyl rings containing N31 in the molecules at (x, y, z) and (-1 - x, 2 - y, -z) have an interplanar spacing of 3.334 (2) Å, with a ring-centroid separation of 3.658 (2) Å and ring offset of 1.505 (2) Å. These two interactions are centred across the inversion centres at () and (), respectively, and their combination thus generates a second [21] substructure (Fig. 30). The combination of chains along [100], [10], [20] and [21] suffices to generate a continuous three-dimensional framework structure.

Figure 29 Stereoview of part of the crystal structure of (VIII) showing the formation of a chain of R2^2(10) rings along [21] built from N—H⋯N and C—H⋯O hydrogen bonds. For the sake of clarity, the H atoms bonded to C atoms, but not involved in the motif shown, have been omitted.

Figure 30 Stereoview of part of the crystal structure of (VIII) showing the formation of a π-stacked chain along [21]. For the sake of clarity, the H atoms have been omitted.

3.3.9. Compound (IX)

The structure of the 4-nitrophenyl analogue (IX) has recently been described (de Souza et al., 2005) and here we briefly summarize its supramolecular behaviour. Compound (IX) crystallizes in the space group P2₁/n with Z′ = 2, and the molecules are linked by two independent N—H⋯N hydrogen bonds into C₂²(12) chains in which the two independent molecules alternate: however, the amidic N—H⋯O hydrogen bonds which characterize (II)–(VIII), although not (I), are absent from the structure of (IX).

3.3.10. General comments on the structures

Although the approximately isosteric requirements of methyl and chloro substituents on aryl rings often lead to the isomorphism of corresponding pairs of compounds, the unit-cell dimension and Z′ values (Table 1) for (II) (X = CH₃) and (IV) (X = Cl) here are entirely distinct. Likewise, the four 4-halogenophenyl derivatives (III)–(VI) all crystallize in different space groups, one triclinic, two monoclinic and one orthorhombic. In contrast to this, we have recently observed:

• (i) that the 4-substituted anilinium 2-carboxy-4-nitrobenzoates [4-XC₆H₄NH₃]⁺·[C₈H₄NO₆]⁻, for X = H, Cl, Br and I, are all isomorphous and approximately isostructural (Glidewell et al., 2005);

• (ii) that a series of cyclopenta[g]pyrazolo[1,5-a]pyrimidines carrying 4-methylphenyl, 4-chlorophenyl or 4-bromophenyl substituents are all strictly isostructural (Portilla et al., 2005); and

• (iii) that a pair of benzo[f]pyrazolo[3,4-b]quinolines carrying 4-chlorophenyl or 4-bromophenyl substituents are also strictly isostructural (Serrano et al., 2005a,b).

As the single substituent in the aryl ring is varied within the series (I)–(IX), so too are the direction-specific intermolecular interactions which are manifested in the supramolecular structures. A very common supramolecular motif found in the crystal structures of simple amides is the formation of simple C(4) chains built from N—H⋯O hydrogen bonds, with corresponding C₂²(8) chains in some cases where Z′ = 2. Such chains occur in (II), where the chain is of C₂²(8) type; in (IV), where there are four independent C(4) chains, and in (V), (VI) and (VII), each of which forms a single C(4) chain. It is striking how readily this motif can be disrupted when alternative hydrogen-bond acceptor sites are available, so that the amidic N—H donor has a pyridyl N acceptor in each of (I), (VIII) and (IX), while in (III) the water O atom acts as the acceptor to form the amidic N—H bond (Table 3). Despite the acceptor role for the pyridyl N atom manifested in (I), (VIII) and (IX), this potential acceptor is completely inactive in each of (II), (IV) and (VI), while in (III) and (V) this site acts as the acceptor in O—H⋯N and C—H⋯N hydrogen bonds, respectively. No obvious pattern of behaviour can be discerned here and any attempt to rationalize such behaviour would necessarily be largely, if not entirely, speculative: in this connection, it should perhaps be emphasized that the intermolecular forces involved here are all fairly weak and soft, and not readily susceptible to quantitative modelling.

For (IV), where X = Cl, (VII) where X = OMe and (IX) where X = NO₂ (de Souza et al., 2005), the supramolecular structures are all one-dimensional, with isolated chains built from N—H⋯O hydrogen bonds in (VII), similar chains linked in pairs by C—H⋯π(arene) hydrogen bonds in (IV), and chains built from N—H⋯N hydrogen bonds in (IX). Compounds (IV) and (IX) differ further in that (IV), where Z′ = 4, contains four independent chains, each containing a single molecular type, whereas (IX), where Z′ = 2, contains a single chain where the two independent molecules alternate.

The structures of compounds (I), where X = H, (II), where X = Me, (III), where X = F, and (V), where X = Br, are all two-dimensional. N—H⋯N hydrogen bonds are present only in the structure of (I); C—H⋯O and C—H⋯π(arene) hydrogen bonds are present only in the structure of (II); O—H⋯O and O—H⋯N hydrogen bonds, and aromatic π⋯π stacking interactions are present only in the structure of (III); and C—H⋯N hydrogen bonds are present only in the structure of (V). For the two compounds with three-dimensional supramolecular structures, there are no direction-specific intermolecular interactions in common: the structure of (VI), where X = I, is built from N—H⋯O and C—H⋯π(arene) hydrogen bonds, and iodo⋯pyridyl interactions, while the structure of (VIII), where X = CN, is built from N—H⋯N, C—H⋯N and C—H⋯O hydrogen bonds.

3.3.11. Compounds closely related to (I)–(IX)

Here we briefly comment on the supramolecular structures of some closely related compounds, including two isomers (X) and (XI) of (IX) (de Souza et al., 2005), and (XII)–(XV) retrieved from the Cambridge Structural Database (CSD; Allen, 2002).

In (X), the only N—H⋯O hydrogen bond is intramolecular, so that again the formation of a C(4) chain has readily been prevented: the molecules of (X) are linked into chains of centrosymmetric edge-fused R₂²(14) and R₄⁴(24) rings by two independent C—H⋯.O hydrogen bonds, while the pyridyl N atom is inactive as an acceptor. In the isomeric compound (XI), which unexpectedly crystallizes as a stoichiometric monohydrate just like compound (III), the amidic N—H bond acts as a hydrogen-bond donor to the water molecule, and these bimolecular aggregates are linked by a combination of O—H⋯N and O—H⋯O hydrogen bonds to form a chain of edge-fused rings containing two different types of R₄⁴(16) ring. Thus, despite the different composition and constitutions of (III) and (XI), their supramolecular aggregation patterns show a considerable degree of similarity.

The unsubstituted amide (XII) (CSD code PYDCXA10; Gdaniec et al., 1979), which may be regarded as the parent compound for this whole series, forms simple C(4) chains built from N—H⋯O hydrogen bonds, and these chains are linked in pairs by a centrosymmetric π⋯π stacking interaction. In the dichloro compound (XIII) (CSD code HIFWUO; Jethmalani et al., 1996), a combination of N—H⋯N and C—H⋯N hydrogen bonds generates a C(3)C(6)[R¹₂(7)] chain of rings, but no N—H⋯O hydrogen bonds are present.

The ease with which the C(4) motif can be disrupted, not only by the presence of water molecules in the structure, but also by intramolecular hydrogen bonds, is shown both by (X), and by (XIV) (CSD code MURWUR; Zhang et al., 2002) and (XV) (CSD code ZIKWEX; Pèpe et al., 1995), where the amidic N—H bonds participate respectively in intramolecular N—H⋯N and N—H⋯O hydrogen bonds. The supramolecular structure of (XIV) consists of simple C(6) chains built from C—H⋯O hydrogen bonds, while the structure of (XV) consists of effectively isolated molecules with no direction-specific intermolecular interactions of any kind.

4. Concluding remarks

The variations in the unit-cell dimensions in (I)–(IX) and the consequent absence of any isomorphisms, together with the very wide variations in the active intermolecular interactions and in the resulting supramolecular structures, both for these compounds and for the related compounds (X)–(XV), raise the question of whether supramolecular structures of this type, dependent on weak intermolecular forces, are likely to become reliably predictable in the foreseeable future.

Supporting information

S1. Comment

In full text version

S2. Experimental

In full text version

S3. Refinement

In full text version

Computing details

Data collection: COLLECT (Hooft, 1999) for (I), (III), (IV), (V), (VI), (VII), (VIII); Bruker APEX2 (Bruker, 2004) for (II). Cell refinement: DENZO (Otwinowski & Minor, 1997) & COLLECT for (I), (III), (IV), (V), (VI), (VII), (VIII); SAINT (Bruker, 2004) for (II). Data reduction: DENZO & COLLECT for (I), (III), (IV), (V), (VI), (VII), (VIII); SAINT for (II). For all compounds, program(s) used to solve structure: OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: OSCAIL and SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).

Figures

In full text version

(I) N-phenyl-2-chloronicotinamide

Crystal data

C12H9ClN2O	F(000) = 960
Mr = 232.66	Dx = 1.442 Mg m^−3
Orthorhombic, Pccn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ab 2ac	Cell parameters from 2446 reflections
a = 13.2296 (6) Å	θ = 3.1–27.5°
b = 21.0744 (10) Å	µ = 0.33 mm^−1
c = 7.6898 (16) Å	T = 120 K
V = 2144.0 (5) Å^3	Needle, colourless
Z = 8	0.24 × 0.09 × 0.02 mm

Data collection

Bruker-Nonius 95mm CCD camera on κ goniostat diffractometer	2446 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode	1724 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.104
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 3.1°
ϕ & ω scans	h = −16→17
Absorption correction: multi-scan SADABS 2.10 (Sheldrick, 2003)	k = −27→27
Tmin = 0.943, Tmax = 0.993	l = −9→9
17837 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)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.129	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0479P)^2 + 1.6007P] where P = (Fo^2 + 2Fc^2)/3
2446 reflections	(Δ/σ)max = 0.001
145 parameters	Δρmax = 0.28 e Å^−3
0 restraints	Δρmin = −0.28 e Å^−3

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

	x	y	z	Uiso*/Ueq
N11	0.25408 (16)	0.57579 (10)	0.9067 (3)	0.0262 (5)
C12	0.32767 (18)	0.60070 (12)	0.8111 (4)	0.0238 (6)
Cl1	0.31180 (5)	0.68016 (3)	0.75558 (10)	0.0305 (2)
C13	0.41523 (18)	0.56871 (12)	0.7615 (3)	0.0220 (5)
C14	0.42677 (19)	0.50752 (12)	0.8256 (3)	0.0248 (6)
C15	0.3523 (2)	0.48067 (13)	0.9271 (3)	0.0282 (6)
C16	0.2668 (2)	0.51593 (13)	0.9605 (4)	0.0288 (6)
C17	0.49778 (19)	0.59498 (12)	0.6469 (4)	0.0246 (6)
O1	0.58540 (13)	0.59291 (10)	0.6968 (3)	0.0390 (5)
N21	0.46640 (16)	0.61551 (10)	0.4897 (3)	0.0249 (5)
C21	0.52498 (19)	0.64341 (12)	0.3554 (3)	0.0235 (6)
C22	0.4731 (2)	0.66828 (13)	0.2137 (4)	0.0296 (7)
C23	0.5248 (2)	0.69702 (13)	0.0789 (4)	0.0331 (7)
C24	0.6292 (2)	0.70101 (13)	0.0842 (4)	0.0295 (6)
C25	0.6809 (2)	0.67565 (13)	0.2231 (4)	0.0293 (6)
C26	0.63023 (19)	0.64704 (12)	0.3598 (4)	0.0252 (6)
H14	0.4862	0.4841	0.7995	0.030*
H15	0.3597	0.4390	0.9727	0.034*
H16	0.2139	0.4967	1.0252	0.035*
H21	0.4012	0.6125	0.4688	0.030*
H22	0.4015	0.6655	0.2096	0.035*
H23	0.4887	0.7140	−0.0173	0.040*
H24	0.6650	0.7212	−0.0076	0.035*
H25	0.7526	0.6778	0.2253	0.035*
H26	0.6667	0.6301	0.4555	0.030*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N11	0.0225 (11)	0.0302 (12)	0.0261 (13)	0.0000 (10)	0.0039 (10)	−0.0002 (10)
C12	0.0234 (13)	0.0253 (13)	0.0227 (14)	0.0002 (10)	−0.0028 (11)	0.0013 (11)
Cl1	0.0259 (3)	0.0258 (3)	0.0400 (4)	0.0033 (3)	0.0028 (3)	0.0040 (3)
C13	0.0183 (12)	0.0277 (13)	0.0202 (14)	0.0002 (10)	−0.0021 (11)	0.0010 (11)
C14	0.0241 (13)	0.0294 (14)	0.0210 (14)	0.0029 (12)	−0.0052 (12)	−0.0030 (11)
C15	0.0333 (15)	0.0256 (14)	0.0257 (15)	−0.0025 (12)	−0.0002 (13)	0.0023 (11)
C16	0.0299 (15)	0.0317 (14)	0.0247 (15)	−0.0057 (12)	0.0040 (12)	0.0001 (12)
C17	0.0205 (12)	0.0282 (14)	0.0250 (15)	0.0045 (11)	0.0003 (11)	0.0008 (11)
O1	0.0193 (10)	0.0645 (14)	0.0333 (12)	0.0000 (10)	−0.0020 (9)	0.0148 (10)
N21	0.0162 (10)	0.0334 (13)	0.0250 (13)	−0.0001 (9)	−0.0004 (10)	0.0055 (10)
C21	0.0225 (13)	0.0269 (14)	0.0213 (15)	−0.0016 (11)	0.0008 (12)	−0.0021 (11)
C22	0.0198 (13)	0.0369 (16)	0.0319 (17)	−0.0011 (11)	−0.0009 (12)	0.0045 (12)
C23	0.0312 (16)	0.0367 (16)	0.0315 (17)	−0.0011 (13)	−0.0018 (13)	0.0092 (13)
C24	0.0300 (15)	0.0328 (15)	0.0257 (15)	−0.0044 (12)	0.0061 (13)	0.0018 (12)
C25	0.0237 (14)	0.0344 (15)	0.0297 (16)	−0.0042 (12)	0.0036 (12)	−0.0046 (12)
C26	0.0224 (13)	0.0280 (14)	0.0251 (15)	−0.0006 (11)	0.0002 (12)	−0.0027 (11)

Geometric parameters (Å, º)

N11—C12	1.328 (3)	N21—C21	1.419 (3)
N11—C16	1.338 (3)	N21—H21	0.8796
C12—C13	1.394 (3)	C21—C22	1.390 (4)
C12—Cl1	1.741 (3)	C21—C26	1.395 (3)
C13—C14	1.389 (3)	C22—C23	1.382 (4)
C13—C17	1.509 (4)	C22—H22	0.95
C14—C15	1.378 (4)	C23—C24	1.385 (4)
C14—H14	0.95	C23—H23	0.95
C15—C16	1.378 (4)	C24—C25	1.376 (4)
C15—H15	0.95	C24—H24	0.95
C16—H16	0.95	C25—C26	1.385 (4)
C17—O1	1.222 (3)	C25—H25	0.95
C17—N21	1.349 (3)	C26—H26	0.95
C12—N11—C16	116.9 (2)	C17—N21—H21	116.3
N11—C12—C13	124.7 (2)	C21—N21—H21	115.6
N11—C12—Cl1	115.32 (19)	C22—C21—C26	119.4 (2)
C13—C12—Cl1	119.9 (2)	C22—C21—N21	117.2 (2)
C14—C13—C12	116.3 (2)	C26—C21—N21	123.4 (2)
C14—C13—C17	117.9 (2)	C23—C22—C21	120.6 (2)
C12—C13—C17	125.8 (2)	C23—C22—H22	119.7
C15—C14—C13	120.2 (2)	C21—C22—H22	119.7
C15—C14—H14	119.9	C22—C23—C24	119.8 (3)
C13—C14—H14	119.9	C22—C23—H23	120.1
C16—C15—C14	118.1 (2)	C24—C23—H23	120.1
C16—C15—H15	120.9	C25—C24—C23	119.7 (3)
C14—C15—H15	120.9	C25—C24—H24	120.2
N11—C16—C15	123.6 (3)	C23—C24—H24	120.2
N11—C16—H16	118.2	C24—C25—C26	121.2 (2)
C15—C16—H16	118.2	C24—C25—H25	119.4
O1—C17—N21	125.8 (2)	C26—C25—H25	119.4
O1—C17—C13	119.4 (2)	C25—C26—C21	119.3 (3)
N21—C17—C13	114.7 (2)	C25—C26—H26	120.4
C17—N21—C21	128.1 (2)	C21—C26—H26	120.4
C16—N11—C12—C13	1.1 (4)	C12—C13—C17—N21	−56.2 (4)
C16—N11—C12—Cl1	−176.12 (19)	O1—C17—N21—C21	−5.5 (4)
N11—C12—C13—C14	−3.4 (4)	C13—C17—N21—C21	178.8 (2)
Cl1—C12—C13—C14	173.71 (19)	C17—N21—C21—C22	−171.8 (2)
N11—C12—C13—C17	177.3 (2)	C17—N21—C21—C26	8.0 (4)
Cl1—C12—C13—C17	−5.7 (4)	C26—C21—C22—C23	−0.7 (4)
C12—C13—C14—C15	2.3 (4)	N21—C21—C22—C23	179.1 (2)
C17—C13—C14—C15	−178.3 (2)	C21—C22—C23—C24	0.2 (4)
C13—C14—C15—C16	0.7 (4)	C22—C23—C24—C25	0.7 (4)
C12—N11—C16—C15	2.4 (4)	C23—C24—C25—C26	−1.1 (4)
C14—C15—C16—N11	−3.2 (4)	C24—C25—C26—C21	0.6 (4)
C14—C13—C17—O1	−51.6 (4)	C22—C21—C26—C25	0.3 (4)
C12—C13—C17—O1	127.8 (3)	N21—C21—C26—C25	−179.5 (2)
C14—C13—C17—N21	124.4 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N21—H21···N11^i	0.88	2.25	3.101 (3)	164
C15—H15···Cg1^ii	0.95	2.89	3.535 (3)	126
C16—H16···Cg2^iii	0.95	2.87	3.464 (3)	121

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

(II) N-(4-Methylphenyl)-2-chloronicotinamide

Crystal data

C13H11ClN2O	Z = 4
Mr = 246.69	F(000) = 512
Triclinic, P1	Dx = 1.390 Mg m^−3
Hall symbol: -P 1	Synchrotron radiation, λ = 0.67510 Å
a = 9.6824 (6) Å	Cell parameters from 6881 reflections
b = 11.3082 (7) Å	θ = 2.1–28.8°
c = 11.5139 (7) Å	µ = 0.31 mm^−1
α = 77.453 (2)°	T = 120 K
β = 73.445 (2)°	Needle, colourless
γ = 87.978 (2)°	0.10 × 0.02 × 0.02 mm
V = 1179.07 (13) Å^3

Data collection

Bruker SMART APEX2 CCD diffractometer	6881 independent reflections
Radiation source: Daresbury SRS station 9.8, (Cernik et al., 1997)	5217 reflections with ( > 2σ(I)
Silicon 111 monochromator	Rint = 0.022
fine–slice ω scans	θmax = 28.8°, θmin = 2.1°
Absorption correction: multi-scan Bruker SADABS (Bruker, 2004)	h = −13→13
Tmin = 0.970, Tmax = 0.994	k = −16→16
12982 measured reflections	l = −16→16

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) = 0.124	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0648P)^2 + 0.3225P] where P = (Fo^2 + 2Fc^2)/3
6881 reflections	(Δ/σ)max = 0.001
309 parameters	Δρmax = 0.43 e Å^−3
0 restraints	Δρmin = −0.30 e Å^−3

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

	x	y	z	Uiso*/Ueq
N11	0.86915 (14)	0.73134 (12)	−0.08967 (11)	0.0221 (3)
C12	0.84419 (15)	0.70831 (13)	0.03187 (12)	0.0183 (3)
Cl1	0.83100 (5)	0.55573 (3)	0.10547 (3)	0.02910 (11)
C13	0.83069 (14)	0.79583 (13)	0.10341 (12)	0.0168 (3)
C14	0.83825 (17)	0.91586 (14)	0.04073 (13)	0.0220 (3)
C15	0.86423 (18)	0.94293 (14)	−0.08708 (13)	0.0245 (3)
C16	0.88058 (17)	0.84842 (14)	−0.14807 (13)	0.0236 (3)
C17	0.82579 (15)	0.76179 (13)	0.23844 (12)	0.0173 (3)
O1	0.93912 (11)	0.74347 (11)	0.26770 (9)	0.0255 (2)
N21	0.69517 (13)	0.75458 (11)	0.31986 (10)	0.0182 (2)
C21	0.66503 (14)	0.71569 (13)	0.45110 (12)	0.0168 (3)
C22	0.54054 (15)	0.64547 (14)	0.51422 (13)	0.0201 (3)
C23	0.50576 (16)	0.60308 (14)	0.64181 (13)	0.0223 (3)
C24	0.59492 (16)	0.62974 (14)	0.70977 (12)	0.0209 (3)
C25	0.71711 (16)	0.70342 (14)	0.64523 (13)	0.0214 (3)
C26	0.75349 (15)	0.74657 (14)	0.51730 (13)	0.0196 (3)
C241	0.56166 (18)	0.57879 (16)	0.84700 (13)	0.0274 (3)
N31	0.09859 (14)	0.76364 (12)	0.58897 (11)	0.0225 (3)
C32	0.17080 (16)	0.79085 (13)	0.47011 (13)	0.0192 (3)
Cl3	0.20022 (5)	0.94486 (3)	0.40386 (4)	0.03240 (11)
C33	0.22193 (15)	0.70691 (13)	0.39653 (12)	0.0175 (3)
C34	0.19083 (15)	0.58576 (13)	0.45303 (13)	0.0200 (3)
C35	0.11540 (16)	0.55384 (14)	0.57837 (13)	0.0215 (3)
C36	0.07258 (16)	0.64550 (14)	0.64210 (13)	0.0219 (3)
C37	0.31481 (15)	0.74411 (14)	0.26399 (12)	0.0194 (3)
O3	0.44343 (12)	0.76878 (14)	0.24022 (10)	0.0373 (3)
N41	0.24535 (12)	0.74497 (11)	0.17848 (10)	0.0171 (2)
C41	0.30028 (14)	0.78264 (13)	0.04773 (12)	0.0164 (3)
C42	0.21841 (15)	0.75010 (13)	−0.02321 (12)	0.0192 (3)
C43	0.25670 (16)	0.79412 (14)	−0.15074 (13)	0.0211 (3)
C44	0.37751 (16)	0.87086 (14)	−0.21107 (12)	0.0205 (3)
C441	0.41532 (19)	0.92274 (16)	−0.34831 (13)	0.0274 (3)
C45	0.46144 (16)	0.89806 (14)	−0.13930 (13)	0.0222 (3)
C46	0.42436 (15)	0.85517 (14)	−0.01134 (12)	0.0204 (3)
H14	0.8257	0.9791	0.0850	0.026*
H15	0.8707	1.0247	−0.1318	0.029*
H16	0.9010	0.8674	−0.2359	0.028*
H21	0.6227	0.7543	0.2879	0.022*
H22	0.4787	0.6263	0.4696	0.024*
H23	0.4201	0.5553	0.6836	0.027*
H25	0.7774	0.7248	0.6901	0.026*
H26	0.8375	0.7964	0.4756	0.024*
H24A	0.5336	0.4928	0.8650	0.041*
H24B	0.4824	0.6230	0.8913	0.041*
H24C	0.6473	0.5873	0.8741	0.041*
H34	0.2208	0.5249	0.4065	0.024*
H35	0.0939	0.4713	0.6190	0.026*
H36	0.0222	0.6238	0.7279	0.026*
H41	0.1522	0.7281	0.2078	0.021*
H42	0.1362	0.6976	0.0160	0.023*
H43	0.1997	0.7717	−0.1978	0.025*
H44A	0.3280	0.9264	−0.3758	0.041*
H44B	0.4851	0.8711	−0.3923	0.041*
H44C	0.4575	1.0045	−0.3663	0.041*
H45	0.5464	0.9473	−0.1790	0.027*
H46	0.4832	0.8752	0.0354	0.024*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N11	0.0278 (7)	0.0255 (6)	0.0147 (5)	0.0004 (5)	−0.0070 (5)	−0.0064 (5)
C12	0.0191 (6)	0.0206 (7)	0.0149 (6)	−0.0015 (5)	−0.0044 (5)	−0.0036 (5)
Cl1	0.0429 (2)	0.02044 (19)	0.02131 (18)	−0.00353 (15)	−0.00605 (15)	−0.00230 (14)
C13	0.0156 (6)	0.0228 (7)	0.0118 (6)	0.0001 (5)	−0.0032 (5)	−0.0044 (5)
C14	0.0279 (7)	0.0226 (7)	0.0160 (6)	0.0040 (6)	−0.0058 (5)	−0.0067 (5)
C15	0.0337 (8)	0.0229 (7)	0.0154 (6)	0.0049 (6)	−0.0068 (6)	−0.0021 (5)
C16	0.0298 (8)	0.0280 (8)	0.0131 (6)	0.0044 (6)	−0.0067 (5)	−0.0043 (5)
C17	0.0175 (6)	0.0214 (7)	0.0132 (6)	−0.0003 (5)	−0.0043 (5)	−0.0043 (5)
O1	0.0162 (5)	0.0439 (7)	0.0158 (5)	0.0009 (4)	−0.0056 (4)	−0.0039 (4)
N21	0.0159 (5)	0.0283 (6)	0.0115 (5)	0.0006 (4)	−0.0051 (4)	−0.0050 (4)
C21	0.0171 (6)	0.0238 (7)	0.0103 (5)	0.0021 (5)	−0.0033 (5)	−0.0066 (5)
C22	0.0180 (6)	0.0285 (7)	0.0147 (6)	−0.0018 (5)	−0.0052 (5)	−0.0054 (5)
C23	0.0203 (7)	0.0289 (8)	0.0152 (6)	−0.0019 (6)	−0.0019 (5)	−0.0032 (5)
C24	0.0238 (7)	0.0260 (7)	0.0124 (6)	0.0050 (5)	−0.0039 (5)	−0.0056 (5)
C25	0.0220 (7)	0.0302 (8)	0.0153 (6)	0.0020 (6)	−0.0071 (5)	−0.0095 (5)
C26	0.0181 (6)	0.0270 (7)	0.0157 (6)	−0.0011 (5)	−0.0052 (5)	−0.0075 (5)
C241	0.0318 (8)	0.0363 (9)	0.0125 (6)	0.0040 (7)	−0.0049 (6)	−0.0042 (6)
N31	0.0278 (7)	0.0256 (6)	0.0133 (5)	0.0024 (5)	−0.0043 (5)	−0.0048 (5)
C32	0.0227 (7)	0.0205 (7)	0.0141 (6)	0.0004 (5)	−0.0063 (5)	−0.0016 (5)
Cl3	0.0471 (3)	0.0213 (2)	0.02420 (19)	−0.00033 (16)	−0.00680 (17)	0.00040 (14)
C33	0.0159 (6)	0.0259 (7)	0.0115 (5)	0.0000 (5)	−0.0056 (5)	−0.0029 (5)
C34	0.0197 (7)	0.0243 (7)	0.0172 (6)	0.0008 (5)	−0.0054 (5)	−0.0071 (5)
C35	0.0220 (7)	0.0228 (7)	0.0177 (6)	−0.0005 (5)	−0.0055 (5)	−0.0001 (5)
C36	0.0228 (7)	0.0281 (8)	0.0133 (6)	0.0004 (6)	−0.0045 (5)	−0.0024 (5)
C37	0.0170 (6)	0.0294 (7)	0.0116 (6)	0.0009 (5)	−0.0048 (5)	−0.0029 (5)
O3	0.0172 (5)	0.0745 (10)	0.0175 (5)	−0.0082 (5)	−0.0072 (4)	0.0001 (6)
N41	0.0150 (5)	0.0259 (6)	0.0103 (5)	−0.0014 (4)	−0.0032 (4)	−0.0039 (4)
C41	0.0167 (6)	0.0229 (7)	0.0101 (5)	0.0019 (5)	−0.0038 (5)	−0.0049 (5)
C42	0.0178 (6)	0.0260 (7)	0.0147 (6)	−0.0001 (5)	−0.0046 (5)	−0.0060 (5)
C43	0.0226 (7)	0.0303 (8)	0.0137 (6)	0.0034 (6)	−0.0076 (5)	−0.0089 (5)
C44	0.0242 (7)	0.0251 (7)	0.0116 (6)	0.0037 (5)	−0.0040 (5)	−0.0045 (5)
C441	0.0341 (9)	0.0335 (9)	0.0121 (6)	0.0041 (7)	−0.0046 (6)	−0.0031 (6)
C45	0.0226 (7)	0.0287 (8)	0.0132 (6)	−0.0036 (6)	−0.0024 (5)	−0.0027 (5)
C46	0.0197 (7)	0.0281 (7)	0.0139 (6)	−0.0034 (5)	−0.0048 (5)	−0.0051 (5)

Geometric parameters (Å, º)

N11—C12	1.3182 (17)	N31—C32	1.3203 (17)
N11—C16	1.341 (2)	N31—C36	1.3428 (19)
C12—C13	1.3996 (19)	C32—C33	1.393 (2)
C12—Cl1	1.7407 (15)	C32—Cl3	1.7407 (15)
C13—C14	1.386 (2)	C33—C34	1.386 (2)
C13—C17	1.5056 (18)	C33—C37	1.5101 (18)
C14—C15	1.3861 (19)	C34—C35	1.3921 (19)
C14—H14	0.95	C34—H34	0.95
C15—C16	1.382 (2)	C35—C36	1.383 (2)
C15—H15	0.95	C35—H35	0.95
C16—H16	0.95	C36—H36	0.95
C17—O1	1.2348 (16)	C37—O3	1.2251 (18)
C17—N21	1.3355 (17)	C37—N41	1.3395 (17)
N21—C21	1.4251 (16)	N41—C41	1.4184 (16)
N21—H21	0.8803	N41—H41	0.8803
C21—C22	1.3890 (19)	C41—C46	1.3928 (19)
C21—C26	1.3948 (18)	C41—C42	1.3969 (18)
C22—C23	1.3874 (19)	C42—C43	1.3880 (19)
C22—H22	0.95	C42—H42	0.95
C23—C24	1.398 (2)	C43—C44	1.397 (2)
C23—H23	0.95	C43—H43	0.95
C24—C25	1.395 (2)	C44—C45	1.396 (2)
C24—C241	1.5032 (19)	C44—C441	1.5026 (19)
C25—C26	1.3914 (19)	C441—H44A	0.98
C25—H25	0.95	C441—H44B	0.98
C26—H26	0.95	C441—H44C	0.98
C241—H24A	0.98	C45—C46	1.3911 (19)
C241—H24B	0.98	C45—H45	0.95
C241—H24C	0.98	C46—H46	0.95
C12—N11—C16	116.68 (13)	C32—N31—C36	116.89 (13)
N11—C12—C13	125.25 (13)	N31—C32—C33	125.15 (13)
N11—C12—Cl1	115.85 (11)	N31—C32—Cl3	115.60 (11)
C13—C12—Cl1	118.90 (10)	C33—C32—Cl3	119.24 (11)
C14—C13—C12	116.57 (12)	C34—C33—C32	116.74 (12)
C14—C13—C17	121.50 (12)	C34—C33—C37	120.95 (13)
C12—C13—C17	121.55 (12)	C32—C33—C37	122.20 (13)
C13—C14—C15	119.45 (13)	C33—C34—C35	119.58 (13)
C13—C14—H14	120.3	C33—C34—H34	120.2
C15—C14—H14	120.3	C35—C34—H34	120.2
C16—C15—C14	118.57 (14)	C36—C35—C34	118.23 (14)
C16—C15—H15	120.7	C36—C35—H35	120.9
C14—C15—H15	120.7	C34—C35—H35	120.9
N11—C16—C15	123.40 (13)	N31—C36—C35	123.37 (13)
N11—C16—H16	118.3	N31—C36—H36	118.3
C15—C16—H16	118.3	C35—C36—H36	118.3
O1—C17—N21	124.14 (12)	O3—C37—N41	124.47 (13)
O1—C17—C13	119.67 (12)	O3—C37—C33	121.01 (12)
N21—C17—C13	116.18 (12)	N41—C37—C33	114.51 (12)
C17—N21—C21	125.42 (12)	C37—N41—C41	127.77 (12)
C17—N21—H21	114.9	C37—N41—H41	115.4
C21—N21—H21	117.4	C41—N41—H41	116.4
C22—C21—C26	119.55 (12)	C46—C41—C42	119.37 (12)
C22—C21—N21	117.58 (12)	C46—C41—N41	123.70 (12)
C26—C21—N21	122.86 (12)	C42—C41—N41	116.80 (12)
C23—C22—C21	120.59 (13)	C43—C42—C41	120.29 (13)
C23—C22—H22	119.7	C43—C42—H42	119.9
C21—C22—H22	119.7	C41—C42—H42	119.9
C22—C23—C24	120.94 (14)	C42—C43—C44	121.15 (13)
C22—C23—H23	119.5	C42—C43—H43	119.4
C24—C23—H23	119.5	C44—C43—H43	119.4
C25—C24—C23	117.58 (13)	C45—C44—C43	117.66 (12)
C25—C24—C241	121.29 (14)	C45—C44—C441	121.21 (14)
C23—C24—C241	121.12 (14)	C43—C44—C441	121.13 (13)
C26—C25—C24	122.13 (13)	C44—C441—H44A	109.5
C26—C25—H25	118.9	C44—C441—H44B	109.5
C24—C25—H25	118.9	H44A—C441—H44B	109.5
C25—C26—C21	119.15 (13)	C44—C441—H44C	109.5
C25—C26—H26	120.4	H44A—C441—H44C	109.5
C21—C26—H26	120.4	H44B—C441—H44C	109.5
C24—C241—H24A	109.5	C46—C45—C44	121.91 (13)
C24—C241—H24B	109.5	C46—C45—H45	119.0
H24A—C241—H24B	109.5	C44—C45—H45	119.0
C24—C241—H24C	109.5	C45—C46—C41	119.50 (13)
H24A—C241—H24C	109.5	C45—C46—H46	120.2
H24B—C241—H24C	109.5	C41—C46—H46	120.2
C16—N11—C12—C13	−0.8 (2)	C36—N31—C32—C33	−0.2 (2)
C16—N11—C12—Cl1	−179.58 (11)	C36—N31—C32—Cl3	179.10 (11)
N11—C12—C13—C14	2.9 (2)	N31—C32—C33—C34	1.6 (2)
Cl1—C12—C13—C14	−178.36 (11)	Cl3—C32—C33—C34	−177.70 (10)
N11—C12—C13—C17	−170.10 (13)	N31—C32—C33—C37	−174.61 (13)
Cl1—C12—C13—C17	8.60 (18)	Cl3—C32—C33—C37	6.09 (19)
C12—C13—C14—C15	−2.7 (2)	C32—C33—C34—C35	−1.8 (2)
C17—C13—C14—C15	170.38 (14)	C37—C33—C34—C35	174.50 (13)
C13—C14—C15—C16	0.6 (2)	C33—C34—C35—C36	0.7 (2)
C12—N11—C16—C15	−1.6 (2)	C32—N31—C36—C35	−1.0 (2)
C14—C15—C16—N11	1.7 (2)	C34—C35—C36—N31	0.8 (2)
C14—C13—C17—O1	−91.64 (18)	C34—C33—C37—O3	−97.98 (19)
C12—C13—C17—O1	81.05 (18)	C32—C33—C37—O3	78.1 (2)
C14—C13—C17—N21	87.78 (17)	C34—C33—C37—N41	80.81 (17)
C12—C13—C17—N21	−99.53 (16)	C32—C33—C37—N41	−103.14 (16)
O1—C17—N21—C21	−5.3 (2)	O3—C37—N41—C41	−5.5 (3)
C13—C17—N21—C21	175.30 (13)	C33—C37—N41—C41	175.77 (13)
C17—N21—C21—C22	−141.82 (15)	C37—N41—C41—C46	−18.0 (2)
C17—N21—C21—C26	39.1 (2)	C37—N41—C41—C42	166.05 (14)
C26—C21—C22—C23	−1.8 (2)	C46—C41—C42—C43	−2.9 (2)
N21—C21—C22—C23	179.06 (13)	N41—C41—C42—C43	173.22 (13)
C21—C22—C23—C24	−0.1 (2)	C41—C42—C43—C44	0.4 (2)
C22—C23—C24—C25	2.0 (2)	C42—C43—C44—C45	2.4 (2)
C22—C23—C24—C241	−176.85 (14)	C42—C43—C44—C441	−177.36 (14)
C23—C24—C25—C26	−2.1 (2)	C43—C44—C45—C46	−2.6 (2)
C241—C24—C25—C26	176.79 (14)	C441—C44—C45—C46	177.08 (14)
C24—C25—C26—C21	0.2 (2)	C44—C45—C46—C41	0.2 (2)
C22—C21—C26—C25	1.8 (2)	C42—C41—C46—C45	2.6 (2)
N21—C21—C26—C25	−179.17 (13)	N41—C41—C46—C45	−173.22 (14)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N21—H21···O3	0.88	1.96	2.827 (2)	170
N41—H41···O1^i	0.88	1.99	2.847 (2)	163
C35—H35···O1^ii	0.95	2.48	3.424 (2)	174
C14—H14···Cg3^iii	0.95	2.69	3.398 (2)	132
C34—H34···Cg2^ii	0.95	2.63	3.398 (2)	138

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

(III) N-(4-Fluorophenyl)-2-chloronicotinamide monohydrate

Crystal data

C12H8ClFN2O·H2O	Z = 2
Mr = 268.67	F(000) = 276
Triclinic, P1	Dx = 1.504 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.8033 (4) Å	Cell parameters from 2720 reflections
b = 8.1303 (3) Å	θ = 3.3–27.8°
c = 11.5356 (6) Å	µ = 0.33 mm^−1
α = 84.032 (3)°	T = 120 K
β = 84.297 (2)°	Plate, colourless
γ = 69.569 (3)°	0.18 × 0.16 × 0.03 mm
V = 593.32 (5) Å^3

Data collection

Bruker-Nonius 95mm CCD camera on κ goniostat diffractometer	2720 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode	1943 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.052
Detector resolution: 9.091 pixels mm^-1	θmax = 27.8°, θmin = 3.3°
ϕ & ω scans	h = −8→8
Absorption correction: multi-scan SADABS 2.10 (Sheldrick,. 2003)	k = −9→10
Tmin = 0.933, Tmax = 0.990	l = −14→14
12303 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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.113	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0536P)^2 + 0.1705P] where P = (Fo^2 + 2Fc^2)/3
2720 reflections	(Δ/σ)max < 0.001
163 parameters	Δρmax = 0.26 e Å^−3
0 restraints	Δρmin = −0.29 e Å^−3

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

	x	y	z	Uiso*/Ueq
N11	0.7571 (3)	0.9978 (2)	0.48546 (15)	0.0235 (4)
C12	0.7752 (3)	0.9063 (3)	0.58821 (17)	0.0199 (4)
Cl1	0.78295 (8)	1.02152 (7)	0.70544 (5)	0.02776 (17)
C13	0.7785 (3)	0.7329 (2)	0.60679 (17)	0.0197 (4)
C14	0.7568 (3)	0.6539 (3)	0.50950 (18)	0.0234 (5)
C15	0.7400 (3)	0.7458 (3)	0.40094 (18)	0.0258 (5)
C16	0.7432 (3)	0.9155 (3)	0.39284 (19)	0.0258 (5)
C17	0.8196 (3)	0.6272 (3)	0.72202 (17)	0.0209 (4)
O1	0.9775 (2)	0.61153 (18)	0.77274 (12)	0.0271 (4)
N21	0.6788 (3)	0.5477 (2)	0.75786 (14)	0.0209 (4)
C21	0.6875 (3)	0.4219 (2)	0.85440 (17)	0.0205 (4)
C22	0.5108 (3)	0.3715 (3)	0.87844 (18)	0.0231 (5)
C23	0.5070 (4)	0.2461 (3)	0.96891 (18)	0.0270 (5)
C24	0.6789 (4)	0.1759 (3)	1.03364 (18)	0.0277 (5)
F24	0.6761 (2)	0.05172 (17)	1.12278 (11)	0.0396 (4)
C25	0.8533 (4)	0.2245 (3)	1.01359 (19)	0.0288 (5)
C26	0.8583 (3)	0.3489 (3)	0.92234 (19)	0.0268 (5)
O2	0.3127 (2)	0.65660 (18)	0.63096 (13)	0.0276 (4)
H14	0.7534	0.5374	0.5177	0.028*
H15	0.7267	0.6935	0.3336	0.031*
H16	0.7353	0.9775	0.3180	0.031*
H21	0.5606	0.5839	0.7159	0.025*
H22	0.3927	0.4232	0.8327	0.028*
H23	0.3880	0.2098	0.9855	0.032*
H25	0.9689	0.1740	1.0612	0.035*
H26	0.9784	0.3839	0.9066	0.032*
H2A	0.2798	0.7599	0.5792	0.041*
H2B	0.2058	0.6458	0.6689	0.041*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N11	0.0174 (9)	0.0273 (9)	0.0255 (10)	−0.0077 (7)	−0.0038 (7)	0.0021 (7)
C12	0.0127 (10)	0.0235 (10)	0.0238 (11)	−0.0060 (8)	−0.0026 (8)	−0.0026 (8)
Cl1	0.0311 (3)	0.0269 (3)	0.0277 (3)	−0.0113 (2)	−0.0042 (2)	−0.0056 (2)
C13	0.0122 (10)	0.0223 (10)	0.0235 (11)	−0.0052 (8)	−0.0003 (8)	−0.0001 (8)
C14	0.0182 (11)	0.0239 (11)	0.0277 (12)	−0.0062 (8)	−0.0033 (9)	−0.0027 (9)
C15	0.0214 (11)	0.0311 (12)	0.0245 (12)	−0.0075 (9)	−0.0033 (9)	−0.0048 (9)
C16	0.0199 (11)	0.0321 (12)	0.0229 (11)	−0.0068 (9)	−0.0020 (9)	0.0027 (9)
C17	0.0181 (11)	0.0223 (10)	0.0221 (11)	−0.0063 (8)	−0.0025 (8)	−0.0021 (8)
O1	0.0237 (8)	0.0326 (8)	0.0279 (8)	−0.0134 (6)	−0.0084 (6)	0.0044 (6)
N21	0.0169 (9)	0.0217 (9)	0.0249 (10)	−0.0078 (7)	−0.0061 (7)	0.0039 (7)
C21	0.0226 (11)	0.0171 (10)	0.0211 (11)	−0.0057 (8)	−0.0015 (8)	−0.0026 (8)
C22	0.0234 (11)	0.0254 (11)	0.0227 (11)	−0.0105 (9)	−0.0028 (9)	−0.0031 (8)
C23	0.0325 (13)	0.0292 (11)	0.0240 (12)	−0.0168 (10)	−0.0002 (10)	−0.0033 (9)
C24	0.0413 (14)	0.0222 (11)	0.0197 (11)	−0.0123 (10)	−0.0010 (10)	0.0012 (8)
F24	0.0566 (9)	0.0359 (7)	0.0300 (8)	−0.0230 (7)	−0.0073 (7)	0.0111 (6)
C25	0.0285 (12)	0.0275 (12)	0.0277 (12)	−0.0056 (9)	−0.0081 (10)	0.0022 (9)
C26	0.0233 (12)	0.0271 (11)	0.0297 (12)	−0.0086 (9)	−0.0046 (9)	0.0016 (9)
O2	0.0212 (8)	0.0271 (8)	0.0357 (9)	−0.0111 (6)	−0.0052 (6)	0.0057 (6)

Geometric parameters (Å, º)

N11—C12	1.325 (3)	N21—H21	0.9217
N11—C16	1.345 (3)	C21—C26	1.386 (3)
C12—C13	1.397 (3)	C21—C22	1.394 (3)
C12—Cl1	1.738 (2)	C22—C23	1.386 (3)
C13—C14	1.394 (3)	C22—H22	0.95
C13—C17	1.501 (3)	C23—C24	1.368 (3)
C14—C15	1.384 (3)	C23—H23	0.95
C14—H14	0.95	C24—C25	1.367 (3)
C15—C16	1.381 (3)	C24—F24	1.368 (2)
C15—H15	0.95	C25—C26	1.389 (3)
C16—H16	0.95	C25—H25	0.95
C17—O1	1.235 (2)	C26—H26	0.95
C17—N21	1.343 (2)	O2—H2A	0.9508
N21—C21	1.423 (2)	O2—H2B	0.8371
C12—N11—C16	117.01 (17)	C21—N21—H21	117.2
N11—C12—C13	124.72 (19)	C26—C21—C22	120.02 (19)
N11—C12—Cl1	115.00 (15)	C26—C21—N21	123.98 (18)
C13—C12—Cl1	120.21 (15)	C22—C21—N21	116.00 (18)
C14—C13—C12	116.67 (18)	C23—C22—C21	120.2 (2)
C14—C13—C17	119.78 (18)	C23—C22—H22	119.9
C12—C13—C17	123.38 (18)	C21—C22—H22	119.9
C15—C14—C13	119.74 (19)	C24—C23—C22	118.3 (2)
C15—C14—H14	120.1	C24—C23—H23	120.9
C13—C14—H14	120.1	C22—C23—H23	120.9
C16—C15—C14	118.4 (2)	C25—C24—C23	123.1 (2)
C16—C15—H15	120.8	C25—C24—F24	118.5 (2)
C14—C15—H15	120.8	C23—C24—F24	118.43 (19)
N11—C16—C15	123.42 (19)	C24—C25—C26	118.8 (2)
N11—C16—H16	118.3	C24—C25—H25	120.6
C15—C16—H16	118.3	C26—C25—H25	120.6
O1—C17—N21	125.40 (18)	C21—C26—C25	119.7 (2)
O1—C17—C13	120.50 (17)	C21—C26—H26	120.2
N21—C17—C13	113.99 (17)	C25—C26—H26	120.2
C17—N21—C21	127.79 (17)	H2A—O2—H2B	112.3
C17—N21—H21	114.9
C16—N11—C12—C13	−0.7 (3)	O1—C17—N21—C21	−4.9 (3)
C16—N11—C12—Cl1	−177.79 (14)	C13—C17—N21—C21	171.39 (18)
N11—C12—C13—C14	−1.4 (3)	C17—N21—C21—C26	−5.9 (3)
Cl1—C12—C13—C14	175.56 (14)	C17—N21—C21—C22	174.60 (18)
N11—C12—C13—C17	174.01 (18)	C26—C21—C22—C23	−1.2 (3)
Cl1—C12—C13—C17	−9.1 (3)	N21—C21—C22—C23	178.30 (17)
C12—C13—C14—C15	2.0 (3)	C21—C22—C23—C24	0.7 (3)
C17—C13—C14—C15	−173.52 (18)	C22—C23—C24—C25	0.4 (3)
C13—C14—C15—C16	−0.7 (3)	C22—C23—C24—F24	−179.80 (18)
C12—N11—C16—C15	2.2 (3)	C23—C24—C25—C26	−1.0 (3)
C14—C15—C16—N11	−1.5 (3)	F24—C24—C25—C26	179.21 (18)
C14—C13—C17—O1	122.2 (2)	C22—C21—C26—C25	0.6 (3)
C12—C13—C17—O1	−53.0 (3)	N21—C21—C26—C25	−178.85 (19)
C14—C13—C17—N21	−54.2 (2)	C24—C25—C26—C21	0.5 (3)
C12—C13—C17—N21	130.5 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···N11^i	0.95	1.97	2.887 (2)	161
O2—H2B···O1^ii	0.84	1.95	2.780 (2)	173
N21—H21···O2	0.92	1.91	2.837 (2)	179

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

(IV) N-(4-Chlorophenyl-2-chloronicotinamide

Crystal data

C12H8Cl2N2O	F(000) = 1088
Mr = 267.10	Dx = 1.543 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 9787 reflections
a = 5.0855 (8) Å	θ = 3.0–27.5°
b = 28.982 (8) Å	µ = 0.55 mm^−1
c = 15.607 (4) Å	T = 120 K
β = 90.37 (2)°	Plate, colourless
V = 2300.2 (9) Å^3	0.28 × 0.07 × 0.03 mm
Z = 8

Data collection

Bruker-Nonius 95mm CCD camera on κ goniostat diffractometer	9787 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode	6370 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.053
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 3.0°
ϕ & ω scans	h = −6→6
Absorption correction: multi-scan SADABS 2.10 (Sheldrick, 2003)	k = −37→37
Tmin = 0.862, Tmax = 0.984	l = −20→20
24726 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)] = 0.069	H-atom parameters constrained
wR(F^2) = 0.169	w = 1/[σ^2(Fo^2) + (0.0454P)^2 + 5.774P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.001
9787 reflections	Δρmax = 0.79 e Å^−3
254 parameters	Δρmin = −0.54 e Å^−3
1 restraint	Absolute structure: Flack (1983), 4396 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.54 (11)

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

	x	y	z	Uiso*/Ueq
N11	1.0930 (11)	−0.1416 (2)	−0.0684 (4)	0.0249 (6)
C12	1.1545 (15)	−0.0970 (3)	−0.0642 (5)	0.0249 (6)
Cl1	1.3934 (4)	−0.07776 (6)	−0.13183 (11)	0.0255 (4)
C13	1.0218 (16)	−0.0653 (3)	−0.0091 (5)	0.0249 (6)
C14	0.8354 (15)	−0.0820 (3)	0.0465 (4)	0.0249 (6)
C15	0.7658 (14)	−0.1313 (3)	0.0424 (5)	0.0249 (6)
C16	0.8947 (12)	−0.1561 (3)	−0.0104 (4)	0.0249 (6)
C17	1.0824 (14)	−0.0137 (3)	−0.0081 (5)	0.0249 (6)
O1	1.3151 (10)	−0.00037 (17)	−0.0012 (3)	0.0249 (6)
N21	0.8848 (12)	0.0131 (2)	−0.0071 (4)	0.0193 (5)
Cl24	0.8822 (4)	0.21692 (6)	0.02990 (14)	0.0324 (5)
C21	0.8859 (7)	0.06241 (12)	0.0004 (2)	0.0193 (5)
C22	0.6884 (6)	0.08819 (14)	−0.0387 (2)	0.0193 (5)
C23	0.6872 (6)	0.13596 (14)	−0.0308 (2)	0.0193 (5)
C24	0.8835 (7)	0.15795 (12)	0.0162 (2)	0.0193 (5)
C25	1.0810 (6)	0.13216 (14)	0.0554 (2)	0.0193 (5)
C26	1.0822 (6)	0.08439 (14)	0.0474 (2)	0.0193 (5)
N31	0.3668 (10)	0.8114 (2)	0.1869 (4)	0.0231 (5)
C32	0.4029 (15)	0.7668 (3)	0.1884 (5)	0.0231 (5)
Cl3	0.6478 (4)	0.74925 (6)	0.11518 (12)	0.0285 (5)
C33	0.2773 (16)	0.7352 (3)	0.2393 (5)	0.0231 (5)
C34	0.0798 (15)	0.7547 (3)	0.2904 (5)	0.0231 (5)
C35	0.0404 (13)	0.7987 (2)	0.2935 (5)	0.0231 (5)
C36	0.1852 (12)	0.8288 (2)	0.2357 (4)	0.0231 (5)
C37	0.3454 (14)	0.6860 (3)	0.2416 (5)	0.0231 (5)
O3	0.5701 (9)	0.67153 (16)	0.2390 (3)	0.0231 (5)
N41	0.1203 (12)	0.6564 (2)	0.2434 (4)	0.0211 (5)
Cl44	0.1270 (4)	0.45328 (6)	0.27721 (12)	0.0280 (5)
C41	0.1364 (7)	0.60846 (12)	0.2500 (2)	0.0211 (5)
C42	−0.0605 (6)	0.58283 (15)	0.2102 (2)	0.0211 (5)
C43	−0.0640 (6)	0.53508 (14)	0.2184 (2)	0.0211 (5)
C44	0.1295 (7)	0.51296 (12)	0.2665 (3)	0.0211 (5)
C45	0.3263 (6)	0.53858 (14)	0.3063 (2)	0.0211 (5)
C46	0.3298 (6)	0.58633 (14)	0.2981 (2)	0.0211 (5)
N51	0.4263 (11)	0.3580 (2)	0.5740 (4)	0.0252 (6)
C52	0.3620 (15)	0.4025 (3)	0.5697 (5)	0.0252 (6)
Cl5	0.1300 (4)	0.42136 (6)	0.64060 (11)	0.0272 (4)
C53	0.4881 (16)	0.4344 (3)	0.5147 (5)	0.0252 (6)
C54	0.6738 (15)	0.4183 (3)	0.4579 (5)	0.0252 (6)
C55	0.7478 (13)	0.3695 (2)	0.4609 (5)	0.0252 (6)
C56	0.6201 (12)	0.3440 (3)	0.5145 (4)	0.0252 (6)
C57	0.4242 (14)	0.4860 (3)	0.5140 (5)	0.0252 (6)
O5	0.1900 (10)	0.49896 (17)	0.5091 (3)	0.0252 (6)
Cl64	0.5855 (4)	0.71624 (6)	0.46495 (13)	0.0298 (5)
N61	0.6203 (12)	0.5126 (2)	0.5135 (4)	0.0201 (5)
C61	0.6177 (7)	0.56264 (12)	0.5049 (2)	0.0201 (5)
C62	0.8107 (6)	0.58460 (14)	0.4572 (2)	0.0201 (5)
C63	0.8043 (6)	0.63223 (15)	0.4470 (2)	0.0201 (5)
C64	0.6049 (7)	0.65791 (12)	0.4845 (2)	0.0201 (5)
C65	0.4120 (6)	0.63595 (15)	0.5322 (2)	0.0201 (5)
C66	0.4184 (6)	0.58832 (15)	0.5424 (2)	0.0201 (5)
N71	1.1553 (11)	0.3130 (2)	0.3173 (4)	0.0249 (6)
C72	1.1159 (15)	0.2685 (3)	0.3159 (5)	0.0249 (6)
Cl7	0.8784 (4)	0.25131 (6)	0.39206 (12)	0.0293 (5)
C73	1.2365 (16)	0.2368 (3)	0.2649 (5)	0.0249 (6)
C74	1.4280 (15)	0.2551 (3)	0.2109 (5)	0.0249 (6)
C75	1.4668 (13)	0.2994 (2)	0.2065 (5)	0.0249 (6)
C76	1.3311 (12)	0.3301 (2)	0.2677 (4)	0.0249 (6)
C77	1.1627 (14)	0.1876 (3)	0.2631 (5)	0.0249 (6)
O7	0.9370 (9)	0.17332 (16)	0.2669 (3)	0.0249 (6)
N81	1.3862 (12)	0.1571 (2)	0.2606 (4)	0.0208 (5)
Cl84	1.3420 (4)	−0.04497 (6)	0.21810 (13)	0.0297 (5)
C81	1.3679 (7)	0.10957 (12)	0.2546 (2)	0.0208 (5)
C82	1.5613 (6)	0.08769 (14)	0.2070 (2)	0.0208 (5)
C83	1.5558 (6)	0.04005 (14)	0.1969 (2)	0.0208 (5)
C84	1.3569 (7)	0.01429 (12)	0.2344 (3)	0.0208 (5)
C85	1.1634 (6)	0.03616 (15)	0.2820 (2)	0.0208 (5)
C86	1.1690 (6)	0.08381 (15)	0.2921 (2)	0.0208 (5)
H14	0.7533	−0.0621	0.0866	0.030*
H15	0.6315	−0.1440	0.0772	0.030*
H16	0.8533	−0.1881	−0.0109	0.030*
H21	0.7294	−0.0001	−0.0116	0.023*
H22	0.5542	0.0732	−0.0709	0.023*
H23	0.5522	0.1536	−0.0575	0.023*
H25	1.2152	0.1472	0.0875	0.023*
H26	1.2172	0.0668	0.0742	0.023*
H34	−0.0280	0.7349	0.3236	0.028*
H35	−0.0815	0.8113	0.3330	0.028*
H36	0.1473	0.8608	0.2337	0.028*
H41	−0.0366	0.6690	0.2401	0.025*
H42	−0.1927	0.5980	0.1773	0.025*
H43	−0.1985	0.5176	0.1912	0.025*
H45	0.4585	0.5235	0.3392	0.025*
H46	0.4644	0.6038	0.3253	0.025*
H54	0.7521	0.4385	0.4176	0.030*
H55	0.8820	0.3573	0.4255	0.030*
H56	0.6612	0.3121	0.5140	0.030*
H61	0.7756	0.4995	0.5189	0.024*
H62	0.9469	0.5670	0.4315	0.024*
H63	0.9362	0.6472	0.4144	0.024*
H65	0.2757	0.6535	0.5579	0.024*
H66	0.2865	0.5733	0.5750	0.024*
H74	1.5312	0.2349	0.1769	0.030*
H75	1.5809	0.3119	0.1646	0.030*
H76	1.3733	0.3620	0.2703	0.030*
H81	1.5441	0.1695	0.2629	0.025*
H82	1.6973	0.1053	0.1813	0.025*
H83	1.6880	0.0251	0.1643	0.025*
H85	1.0275	0.0186	0.3077	0.025*
H86	1.0368	0.0988	0.3247	0.025*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N11	0.0242 (13)	0.0245 (15)	0.0262 (12)	−0.0006 (11)	0.0013 (10)	−0.0009 (11)
C12	0.0242 (13)	0.0245 (15)	0.0262 (12)	−0.0006 (11)	0.0013 (10)	−0.0009 (11)
Cl1	0.0312 (10)	0.0205 (10)	0.0249 (9)	0.0036 (8)	0.0083 (7)	0.0004 (8)
C13	0.0242 (13)	0.0245 (15)	0.0262 (12)	−0.0006 (11)	0.0013 (10)	−0.0009 (11)
C14	0.0242 (13)	0.0245 (15)	0.0262 (12)	−0.0006 (11)	0.0013 (10)	−0.0009 (11)
C15	0.0242 (13)	0.0245 (15)	0.0262 (12)	−0.0006 (11)	0.0013 (10)	−0.0009 (11)
C16	0.0242 (13)	0.0245 (15)	0.0262 (12)	−0.0006 (11)	0.0013 (10)	−0.0009 (11)
C17	0.0242 (13)	0.0245 (15)	0.0262 (12)	−0.0006 (11)	0.0013 (10)	−0.0009 (11)
O1	0.0242 (13)	0.0245 (15)	0.0262 (12)	−0.0006 (11)	0.0013 (10)	−0.0009 (11)
N21	0.0169 (11)	0.0209 (12)	0.0202 (12)	−0.0001 (10)	0.0027 (9)	0.0005 (9)
Cl24	0.0369 (12)	0.0165 (11)	0.0438 (12)	−0.0031 (9)	0.0072 (9)	0.0017 (9)
C21	0.0169 (11)	0.0209 (12)	0.0202 (12)	−0.0001 (10)	0.0027 (9)	0.0005 (9)
C22	0.0169 (11)	0.0209 (12)	0.0202 (12)	−0.0001 (10)	0.0027 (9)	0.0005 (9)
C23	0.0169 (11)	0.0209 (12)	0.0202 (12)	−0.0001 (10)	0.0027 (9)	0.0005 (9)
C24	0.0169 (11)	0.0209 (12)	0.0202 (12)	−0.0001 (10)	0.0027 (9)	0.0005 (9)
C25	0.0169 (11)	0.0209 (12)	0.0202 (12)	−0.0001 (10)	0.0027 (9)	0.0005 (9)
C26	0.0169 (11)	0.0209 (12)	0.0202 (12)	−0.0001 (10)	0.0027 (9)	0.0005 (9)
N31	0.0225 (12)	0.0146 (12)	0.0324 (13)	0.0002 (10)	0.0059 (10)	−0.0015 (10)
C32	0.0225 (12)	0.0146 (12)	0.0324 (13)	0.0002 (10)	0.0059 (10)	−0.0015 (10)
Cl3	0.0264 (10)	0.0245 (11)	0.0347 (11)	−0.0019 (9)	0.0116 (8)	−0.0006 (9)
C33	0.0225 (12)	0.0146 (12)	0.0324 (13)	0.0002 (10)	0.0059 (10)	−0.0015 (10)
C34	0.0225 (12)	0.0146 (12)	0.0324 (13)	0.0002 (10)	0.0059 (10)	−0.0015 (10)
C35	0.0225 (12)	0.0146 (12)	0.0324 (13)	0.0002 (10)	0.0059 (10)	−0.0015 (10)
C36	0.0225 (12)	0.0146 (12)	0.0324 (13)	0.0002 (10)	0.0059 (10)	−0.0015 (10)
C37	0.0225 (12)	0.0146 (12)	0.0324 (13)	0.0002 (10)	0.0059 (10)	−0.0015 (10)
O3	0.0225 (12)	0.0146 (12)	0.0324 (13)	0.0002 (10)	0.0059 (10)	−0.0015 (10)
N41	0.0228 (12)	0.0173 (12)	0.0233 (12)	0.0005 (10)	0.0042 (9)	−0.0003 (10)
Cl44	0.0373 (12)	0.0153 (10)	0.0314 (10)	−0.0023 (8)	0.0044 (8)	0.0018 (8)
C41	0.0228 (12)	0.0173 (12)	0.0233 (12)	0.0005 (10)	0.0042 (9)	−0.0003 (10)
C42	0.0228 (12)	0.0173 (12)	0.0233 (12)	0.0005 (10)	0.0042 (9)	−0.0003 (10)
C43	0.0228 (12)	0.0173 (12)	0.0233 (12)	0.0005 (10)	0.0042 (9)	−0.0003 (10)
C44	0.0228 (12)	0.0173 (12)	0.0233 (12)	0.0005 (10)	0.0042 (9)	−0.0003 (10)
C45	0.0228 (12)	0.0173 (12)	0.0233 (12)	0.0005 (10)	0.0042 (9)	−0.0003 (10)
C46	0.0228 (12)	0.0173 (12)	0.0233 (12)	0.0005 (10)	0.0042 (9)	−0.0003 (10)
N51	0.0209 (13)	0.0243 (15)	0.0304 (13)	0.0018 (10)	−0.0007 (10)	0.0006 (11)
C52	0.0209 (13)	0.0243 (15)	0.0304 (13)	0.0018 (10)	−0.0007 (10)	0.0006 (11)
Cl5	0.0313 (10)	0.0197 (10)	0.0308 (10)	−0.0008 (9)	0.0123 (8)	0.0001 (9)
C53	0.0209 (13)	0.0243 (15)	0.0304 (13)	0.0018 (10)	−0.0007 (10)	0.0006 (11)
C54	0.0209 (13)	0.0243 (15)	0.0304 (13)	0.0018 (10)	−0.0007 (10)	0.0006 (11)
C55	0.0209 (13)	0.0243 (15)	0.0304 (13)	0.0018 (10)	−0.0007 (10)	0.0006 (11)
C56	0.0209 (13)	0.0243 (15)	0.0304 (13)	0.0018 (10)	−0.0007 (10)	0.0006 (11)
C57	0.0209 (13)	0.0243 (15)	0.0304 (13)	0.0018 (10)	−0.0007 (10)	0.0006 (11)
O5	0.0209 (13)	0.0243 (15)	0.0304 (13)	0.0018 (10)	−0.0007 (10)	0.0006 (11)
Cl64	0.0330 (11)	0.0164 (10)	0.0400 (11)	0.0020 (8)	0.0040 (9)	−0.0033 (8)
N61	0.0169 (11)	0.0228 (13)	0.0207 (12)	0.0021 (10)	0.0004 (9)	−0.0001 (10)
C61	0.0169 (11)	0.0228 (13)	0.0207 (12)	0.0021 (10)	0.0004 (9)	−0.0001 (10)
C62	0.0169 (11)	0.0228 (13)	0.0207 (12)	0.0021 (10)	0.0004 (9)	−0.0001 (10)
C63	0.0169 (11)	0.0228 (13)	0.0207 (12)	0.0021 (10)	0.0004 (9)	−0.0001 (10)
C64	0.0169 (11)	0.0228 (13)	0.0207 (12)	0.0021 (10)	0.0004 (9)	−0.0001 (10)
C65	0.0169 (11)	0.0228 (13)	0.0207 (12)	0.0021 (10)	0.0004 (9)	−0.0001 (10)
C66	0.0169 (11)	0.0228 (13)	0.0207 (12)	0.0021 (10)	0.0004 (9)	−0.0001 (10)
N71	0.0249 (13)	0.0151 (13)	0.0347 (13)	−0.0005 (10)	0.0085 (10)	−0.0005 (10)
C72	0.0249 (13)	0.0151 (13)	0.0347 (13)	−0.0005 (10)	0.0085 (10)	−0.0005 (10)
Cl7	0.0345 (11)	0.0208 (10)	0.0328 (10)	−0.0023 (9)	0.0145 (8)	−0.0038 (8)
C73	0.0249 (13)	0.0151 (13)	0.0347 (13)	−0.0005 (10)	0.0085 (10)	−0.0005 (10)
C74	0.0249 (13)	0.0151 (13)	0.0347 (13)	−0.0005 (10)	0.0085 (10)	−0.0005 (10)
C75	0.0249 (13)	0.0151 (13)	0.0347 (13)	−0.0005 (10)	0.0085 (10)	−0.0005 (10)
C76	0.0249 (13)	0.0151 (13)	0.0347 (13)	−0.0005 (10)	0.0085 (10)	−0.0005 (10)
C77	0.0249 (13)	0.0151 (13)	0.0347 (13)	−0.0005 (10)	0.0085 (10)	−0.0005 (10)
O7	0.0249 (13)	0.0151 (13)	0.0347 (13)	−0.0005 (10)	0.0085 (10)	−0.0005 (10)
N81	0.0216 (12)	0.0169 (12)	0.0239 (12)	−0.0014 (10)	−0.0002 (9)	0.0019 (9)
Cl84	0.0394 (12)	0.0163 (10)	0.0335 (10)	−0.0024 (9)	0.0101 (9)	−0.0031 (8)
C81	0.0216 (12)	0.0169 (12)	0.0239 (12)	−0.0014 (10)	−0.0002 (9)	0.0019 (9)
C82	0.0216 (12)	0.0169 (12)	0.0239 (12)	−0.0014 (10)	−0.0002 (9)	0.0019 (9)
C83	0.0216 (12)	0.0169 (12)	0.0239 (12)	−0.0014 (10)	−0.0002 (9)	0.0019 (9)
C84	0.0216 (12)	0.0169 (12)	0.0239 (12)	−0.0014 (10)	−0.0002 (9)	0.0019 (9)
C85	0.0216 (12)	0.0169 (12)	0.0239 (12)	−0.0014 (10)	−0.0002 (9)	0.0019 (9)
C86	0.0216 (12)	0.0169 (12)	0.0239 (12)	−0.0014 (10)	−0.0002 (9)	0.0019 (9)

Geometric parameters (Å, º)

N11—C12	1.330 (10)	N51—C52	1.330 (10)
N11—C16	1.424 (9)	N51—C56	1.418 (9)
C12—C13	1.432 (12)	C52—C53	1.418 (12)
C12—Cl1	1.709 (8)	C52—Cl5	1.713 (8)
C13—C14	1.376 (11)	C53—C54	1.382 (11)
C13—C17	1.525 (11)	C53—C57	1.530 (11)
C14—C15	1.474 (11)	C54—C55	1.462 (11)
C14—H14	0.95	C54—H54	0.95
C15—C16	1.278 (10)	C55—C56	1.295 (10)
C15—H15	0.95	C55—H55	0.95
C16—H16	0.95	C56—H56	0.95
C17—O1	1.249 (9)	C57—O5	1.251 (9)
C17—N21	1.270 (9)	C57—N61	1.260 (9)
N21—C21	1.435 (7)	Cl64—C64	1.721 (4)
N21—H21	0.88	N61—C61	1.456 (7)
Cl24—C24	1.722 (4)	N61—H61	0.88
C21—C22	1.39	C61—C62	1.39
C21—C26	1.39	C61—C66	1.39
C22—C23	1.39	C62—C63	1.39
C22—H22	0.95	C62—H62	0.95
C23—C24	1.39	C63—C64	1.39
C23—H23	0.95	C63—H63	0.95
C24—C25	1.39	C64—C65	1.39
C25—C26	1.39	C65—C66	1.39
C25—H25	0.95	C65—H65	0.95
C26—H26	0.95	C66—H66	0.95
N31—C36	1.302 (8)	N71—C76	1.285 (9)
N31—C32	1.307 (10)	N71—C72	1.305 (10)
C32—C33	1.372 (11)	C72—C73	1.365 (11)
C32—Cl3	1.770 (8)	C72—Cl7	1.771 (8)
C33—C34	1.405 (11)	C73—C74	1.396 (11)
C33—C37	1.469 (10)	C73—C77	1.474 (11)
C34—C35	1.290 (11)	C74—C75	1.300 (11)
C34—H34	0.95	C74—H74	0.95
C35—C36	1.458 (9)	C75—C76	1.479 (10)
C35—H35	0.95	C75—H75	0.95
C36—H36	0.95	C76—H76	0.95
C37—O3	1.218 (8)	C77—O7	1.222 (8)
C37—N41	1.431 (9)	C77—N81	1.441 (9)
N41—C41	1.394 (7)	N81—C81	1.384 (7)
N41—H41	0.88	N81—H81	0.88
Cl44—C44	1.738 (4)	Cl84—C84	1.738 (4)
C41—C42	1.39	C81—C82	1.39
C41—C46	1.39	C81—C86	1.39
C42—C43	1.39	C82—C83	1.39
C42—H42	0.95	C82—H82	0.95
C43—C44	1.39	C83—C84	1.39
C43—H43	0.95	C83—H83	0.95
C44—C45	1.39	C84—C85	1.39
C45—C46	1.39	C85—C86	1.39
C45—H45	0.95	C85—H85	0.95
C46—H46	0.95	C86—H86	0.95
C12—N11—C16	115.0 (6)	C52—N51—C56	114.5 (6)
N11—C12—C13	122.9 (7)	N51—C52—C53	123.4 (7)
N11—C12—Cl1	117.0 (6)	N51—C52—Cl5	116.5 (6)
C13—C12—Cl1	120.0 (6)	C53—C52—Cl5	119.9 (6)
C14—C13—C12	118.8 (8)	C54—C53—C52	118.7 (8)
C14—C13—C17	118.5 (7)	C54—C53—C57	118.2 (7)
C12—C13—C17	122.7 (7)	C52—C53—C57	123.1 (7)
C13—C14—C15	118.7 (7)	C53—C54—C55	118.9 (7)
C13—C14—H14	120.7	C53—C54—H54	120.5
C15—C14—H14	120.7	C55—C54—H54	120.5
C16—C15—C14	116.8 (7)	C56—C55—C54	116.2 (7)
C16—C15—H15	121.6	C56—C55—H55	121.9
C14—C15—H15	121.6	C54—C55—H55	121.9
C15—C16—N11	127.7 (7)	C55—C56—N51	127.9 (7)
C15—C16—H16	116.2	C55—C56—H56	116.1
N11—C16—H16	116.2	N51—C56—H56	116.1
O1—C17—N21	124.0 (8)	O5—C57—N61	124.7 (8)
O1—C17—C13	119.7 (7)	O5—C57—C53	119.7 (7)
N21—C17—C13	116.0 (7)	N61—C57—C53	115.4 (7)
C17—N21—C21	127.4 (6)	C57—N61—C61	127.1 (6)
C17—N21—H21	116.3	C57—N61—H61	116.5
C21—N21—H21	116.3	C61—N61—H61	116.5
C22—C21—C26	120.0	C62—C61—C66	120.0
C22—C21—N21	119.8 (3)	C62—C61—N61	120.0 (3)
C26—C21—N21	120.2 (3)	C66—C61—N61	120.0 (3)
C21—C22—C23	120.0	C61—C62—C63	120.0
C21—C22—H22	120.0	C61—C62—H62	120.0
C23—C22—H22	120.0	C63—C62—H62	120.0
C24—C23—C22	120.0	C64—C63—C62	120.0
C24—C23—H23	120.0	C64—C63—H63	120.0
C22—C23—H23	120.0	C62—C63—H63	120.0
C25—C24—C23	120.0	C65—C64—C63	120.0
C25—C24—Cl24	118.8 (2)	C65—C64—Cl64	120.3 (2)
C23—C24—Cl24	121.1 (2)	C63—C64—Cl64	119.5 (2)
C24—C25—C26	120.0	C66—C65—C64	120.0
C24—C25—H25	120.0	C66—C65—H65	120.0
C26—C25—H25	120.0	C64—C65—H65	120.0
C25—C26—C21	120.0	C65—C66—C61	120.0
C25—C26—H26	120.0	C65—C66—H66	120.0
C21—C26—H26	120.0	C61—C66—H66	120.0
C36—N31—C32	118.2 (6)	C76—N71—C72	118.6 (7)
N31—C32—C33	127.1 (7)	N71—C72—C73	127.2 (8)
N31—C32—Cl3	111.9 (6)	N71—C72—Cl7	111.9 (6)
C33—C32—Cl3	121.0 (6)	C73—C72—Cl7	120.9 (6)
C32—C33—C34	113.4 (7)	C72—C73—C74	114.5 (7)
C32—C33—C37	123.5 (7)	C72—C73—C77	123.1 (7)
C34—C33—C37	123.1 (7)	C74—C73—C77	122.3 (7)
C35—C34—C33	122.0 (8)	C75—C74—C73	120.8 (8)
C35—C34—H34	119.0	C75—C74—H74	119.6
C33—C34—H34	119.0	C73—C74—H74	119.6
C34—C35—C36	119.2 (7)	C74—C75—C76	119.3 (7)
C34—C35—H35	120.4	C74—C75—H75	120.4
C36—C35—H35	120.4	C76—C75—H75	120.4
N31—C36—C35	119.6 (6)	N71—C76—C75	119.0 (6)
N31—C36—H36	120.2	N71—C76—H76	120.5
C35—C36—H36	120.2	C75—C76—H76	120.5
O3—C37—N41	123.0 (7)	O7—C77—N81	122.3 (7)
O3—C37—C33	123.6 (7)	O7—C77—C73	124.5 (7)
N41—C37—C33	113.3 (6)	N81—C77—C73	113.1 (6)
C41—N41—C37	123.5 (6)	C81—N81—C77	124.1 (6)
C41—N41—H41	118.2	C81—N81—H81	118.0
C37—N41—H41	118.2	C77—N81—H81	118.0
C42—C41—C46	120.0	N81—C81—C82	116.3 (3)
C42—C41—N41	117.2 (3)	N81—C81—C86	123.7 (3)
C46—C41—N41	122.7 (3)	C82—C81—C86	120.0
C43—C42—C41	120.0	C81—C82—C83	120.0
C43—C42—H42	120.0	C81—C82—H82	120.0
C41—C42—H42	120.0	C83—C82—H82	120.0
C42—C43—C44	120.0	C84—C83—C82	120.0
C42—C43—H43	120.0	C84—C83—H83	120.0
C44—C43—H43	120.0	C82—C83—H83	120.0
C45—C44—C43	120.0	C83—C84—C85	120.0
C45—C44—Cl44	119.6 (2)	C83—C84—Cl84	120.0 (2)
C43—C44—Cl44	120.4 (2)	C85—C84—Cl84	119.9 (2)
C44—C45—C46	120.0	C84—C85—C86	120.0
C44—C45—H45	120.0	C84—C85—H85	120.0
C46—C45—H45	120.0	C86—C85—H85	120.0
C45—C46—C41	120.0	C85—C86—C81	120.0
C45—C46—H46	120.0	C85—C86—H86	120.0
C41—C46—H46	120.0	C81—C86—H86	120.0
C16—N11—C12—C13	−3.4 (10)	C56—N51—C52—C53	−4.3 (10)
C16—N11—C12—Cl1	179.5 (5)	C56—N51—C52—Cl5	−179.6 (5)
N11—C12—C13—C14	4.8 (11)	N51—C52—C53—C54	5.1 (12)
Cl1—C12—C13—C14	−178.2 (5)	Cl5—C52—C53—C54	−179.8 (6)
N11—C12—C13—C17	−176.5 (7)	N51—C52—C53—C57	−176.2 (6)
Cl1—C12—C13—C17	0.5 (10)	Cl5—C52—C53—C57	−1.1 (10)
C12—C13—C14—C15	−4.6 (10)	C52—C53—C54—C55	−4.6 (11)
C17—C13—C14—C15	176.7 (6)	C57—C53—C54—C55	176.7 (6)
C13—C14—C15—C16	3.5 (10)	C53—C54—C55—C56	3.9 (10)
C14—C15—C16—N11	−2.4 (10)	C54—C55—C56—N51	−3.6 (10)
C12—N11—C16—C15	2.5 (10)	C52—N51—C56—C55	3.8 (10)
C14—C13—C17—O1	128.4 (8)	C54—C53—C57—O5	129.1 (8)
C12—C13—C17—O1	−50.3 (10)	C52—C53—C57—O5	−49.6 (11)
C14—C13—C17—N21	−45.8 (9)	C54—C53—C57—N61	−46.9 (10)
C12—C13—C17—N21	135.5 (8)	C52—C53—C57—N61	134.4 (8)
O1—C17—N21—C21	1.0 (12)	O5—C57—N61—C61	−1.8 (12)
C13—C17—N21—C21	175.0 (6)	C53—C57—N61—C61	173.9 (6)
C17—N21—C21—C22	149.0 (6)	C57—N61—C61—C62	−141.9 (6)
C17—N21—C21—C26	−31.7 (8)	C57—N61—C61—C66	36.4 (8)
C26—C21—C22—C23	0.0	C66—C61—C62—C63	0.0
N21—C21—C22—C23	179.3 (4)	N61—C61—C62—C63	178.2 (4)
C21—C22—C23—C24	0.0	C61—C62—C63—C64	0.0
C22—C23—C24—C25	0.0	C62—C63—C64—C65	0.0
C22—C23—C24—Cl24	−178.1 (3)	C62—C63—C64—Cl64	−175.3 (3)
C23—C24—C25—C26	0.0	C63—C64—C65—C66	0.0
Cl24—C24—C25—C26	178.1 (3)	Cl64—C64—C65—C66	175.2 (3)
C24—C25—C26—C21	0.0	C64—C65—C66—C61	0.0
C22—C21—C26—C25	0.0	C62—C61—C66—C65	0.0
N21—C21—C26—C25	−179.3 (4)	N61—C61—C66—C65	−178.2 (4)
C36—N31—C32—C33	−3.2 (11)	C76—N71—C72—C73	−2.2 (12)
C36—N31—C32—Cl3	177.7 (5)	C76—N71—C72—Cl7	177.1 (5)
N31—C32—C33—C34	4.0 (12)	N71—C72—C73—C74	2.2 (12)
Cl3—C32—C33—C34	−177.0 (5)	Cl7—C72—C73—C74	−177.1 (6)
N31—C32—C33—C37	−174.9 (7)	N71—C72—C73—C77	−174.8 (7)
Cl3—C32—C33—C37	4.1 (11)	Cl7—C72—C73—C77	5.9 (11)
C32—C33—C34—C35	−5.8 (11)	C72—C73—C74—C75	−5.3 (11)
C37—C33—C34—C35	173.1 (7)	C77—C73—C74—C75	171.7 (7)
C33—C34—C35—C36	6.7 (11)	C73—C74—C75—C76	8.1 (11)
C32—N31—C36—C35	3.6 (9)	C72—N71—C76—C75	4.7 (10)
C34—C35—C36—N31	−5.6 (10)	C74—C75—C76—N71	−7.9 (10)
C32—C33—C37—O3	39.5 (12)	C72—C73—C77—O7	39.2 (12)
C34—C33—C37—O3	−139.3 (8)	C74—C73—C77—O7	−137.6 (8)
C32—C33—C37—N41	−137.9 (8)	C72—C73—C77—N81	−138.0 (8)
C34—C33—C37—N41	43.3 (10)	C74—C73—C77—N81	45.2 (10)
O3—C37—N41—C41	5.9 (11)	O7—C77—N81—C81	5.8 (11)
C33—C37—N41—C41	−176.7 (6)	C73—C77—N81—C81	−176.9 (6)
C37—N41—C41—C42	−148.6 (5)	C77—N81—C81—C82	144.9 (5)
C37—N41—C41—C46	35.1 (7)	C77—N81—C81—C86	−34.2 (8)
C46—C41—C42—C43	0.0	N81—C81—C82—C83	−179.2 (4)
N41—C41—C42—C43	−176.4 (4)	C86—C81—C82—C83	0.0
C41—C42—C43—C44	0.0	C81—C82—C83—C84	0.0
C42—C43—C44—C45	0.0	C82—C83—C84—C85	0.0
C42—C43—C44—Cl44	180.0 (3)	C82—C83—C84—Cl84	177.3 (3)
C43—C44—C45—C46	0.0	C83—C84—C85—C86	0.0
Cl44—C44—C45—C46	180.0 (3)	Cl84—C84—C85—C86	−177.3 (3)
C44—C45—C46—C41	0.0	C84—C85—C86—C81	0.0
C42—C41—C46—C45	0.0	N81—C81—C86—C85	179.2 (5)
N41—C41—C46—C45	176.2 (5)	C82—C81—C86—C85	0.0

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N21—H21···O1^i	0.88	2.11	2.925 (8)	153
N41—H41···O3^i	0.88	2.00	2.833 (8)	157
N61—H61···O5^ii	0.88	2.11	2.925 (8)	153
N81—H81···O7^ii	0.88	2.00	2.841 (8)	159
C26—H26···Cg5	0.95	2.76	3.444 (8)	130
C46—H46···Cg4	0.95	2.75	3.448 (8)	131
C62—H62···Cg3^ii	0.95	2.88	3.588 (8)	132
C82—H82···Cg2^ii	0.95	2.87	3.579 (8)	132

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

(V) N-(4-bromophenyl)-2-chloronicotinamide

Crystal data

C12H8BrClN2O	F(000) = 616
Mr = 311.56	Dx = 1.727 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 2736 reflections
a = 4.8810 (2) Å	θ = 3.1–27.5°
b = 13.3448 (2) Å	µ = 3.64 mm^−1
c = 18.3974 (3) Å	T = 120 K
V = 1198.33 (6) Å^3	Block, colourless
Z = 4	0.16 × 0.16 × 0.16 mm

Data collection

Bruker-Nonius 95mm CCD camera on κ goniostat diffractometer	2736 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode	2597 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.047
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 3.1°
ϕ & ω scans	h = −6→6
Absorption correction: multi-scan SADABS 2.10 (Sheldrick, 2003)	k = −17→17
Tmin = 0.558, Tmax = 0.558	l = −23→23
36201 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)] = 0.023	H-atom parameters constrained
wR(F^2) = 0.060	w = 1/[σ^2(Fo^2) + (0.0339P)^2 + 0.2964P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max = 0.001
2736 reflections	Δρmax = 0.43 e Å^−3
154 parameters	Δρmin = −0.52 e Å^−3
0 restraints	Absolute structure: Flack (1983), 1098 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.031 (7)

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

	x	y	z	Uiso*/Ueq
N11	0.2251 (4)	0.44892 (15)	0.25022 (11)	0.0305 (4)
C12	0.3184 (4)	0.53761 (16)	0.27104 (11)	0.0233 (4)
Cl1	0.20925 (12)	0.63776 (4)	0.21708 (3)	0.03344 (13)
C13	0.5004 (4)	0.55387 (15)	0.32813 (11)	0.0212 (4)
C14	0.6017 (5)	0.46884 (16)	0.36219 (12)	0.0282 (5)
C15	0.5092 (5)	0.37504 (17)	0.34193 (13)	0.0350 (5)
C16	0.3191 (5)	0.36907 (17)	0.28653 (13)	0.0344 (5)
C17	0.5980 (4)	0.65411 (16)	0.35532 (10)	0.0218 (4)
O1	0.8431 (3)	0.66775 (13)	0.36577 (10)	0.0359 (4)
N21	0.4029 (3)	0.72119 (12)	0.37036 (9)	0.0212 (3)
C21	0.4464 (4)	0.81970 (14)	0.39778 (10)	0.0201 (4)
C22	0.2741 (4)	0.89596 (16)	0.37318 (12)	0.0261 (4)
C23	0.3060 (5)	0.99245 (16)	0.39955 (12)	0.0275 (5)
C24	0.5085 (4)	1.01185 (14)	0.44999 (11)	0.0242 (4)
Br24	0.55925 (5)	1.144725 (15)	0.484926 (12)	0.03552 (8)
C25	0.6793 (4)	0.93690 (16)	0.47524 (11)	0.0256 (4)
C26	0.6465 (4)	0.83994 (16)	0.44923 (11)	0.0236 (4)
H14	0.7351	0.4751	0.3995	0.037*
H15	0.5746	0.3163	0.3654	0.045*
H16	0.2512	0.3048	0.2735	0.045*
H21	0.2466	0.7057	0.3631	0.025*
H22	0.1355	0.8817	0.3385	0.034*
H23	0.1895	1.0448	0.3831	0.036*
H25	0.8176	0.9516	0.5100	0.033*
H26	0.7609	0.7876	0.4666	0.031*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N11	0.0325 (10)	0.0286 (10)	0.0305 (10)	−0.0047 (8)	0.0013 (8)	−0.0098 (8)
C12	0.0242 (10)	0.0250 (10)	0.0206 (10)	0.0007 (8)	0.0021 (8)	−0.0028 (8)
Cl1	0.0459 (3)	0.0307 (3)	0.0237 (2)	0.0034 (3)	−0.0106 (2)	−0.0017 (2)
C13	0.0205 (9)	0.0238 (10)	0.0192 (9)	0.0000 (7)	0.0044 (7)	−0.0029 (8)
C14	0.0332 (11)	0.0288 (11)	0.0225 (10)	0.0030 (9)	0.0007 (9)	−0.0021 (8)
C15	0.0501 (14)	0.0249 (11)	0.0299 (11)	0.0034 (10)	0.0038 (10)	0.0000 (9)
C16	0.0425 (12)	0.0213 (11)	0.0393 (13)	−0.0059 (10)	0.0090 (10)	−0.0085 (10)
C17	0.0199 (9)	0.0259 (10)	0.0196 (9)	−0.0037 (9)	0.0019 (7)	−0.0015 (8)
O1	0.0187 (7)	0.0393 (10)	0.0497 (10)	−0.0021 (7)	−0.0010 (7)	−0.0161 (8)
N21	0.0178 (8)	0.0224 (8)	0.0232 (8)	−0.0042 (7)	−0.0028 (7)	−0.0034 (7)
C21	0.0204 (9)	0.0206 (9)	0.0192 (9)	−0.0027 (8)	0.0016 (8)	−0.0006 (7)
C22	0.0243 (10)	0.0297 (11)	0.0243 (10)	0.0003 (9)	−0.0049 (8)	0.0007 (8)
C23	0.0286 (11)	0.0245 (10)	0.0293 (12)	0.0040 (9)	−0.0009 (9)	0.0017 (9)
C24	0.0340 (12)	0.0175 (9)	0.0210 (9)	−0.0035 (8)	0.0055 (8)	−0.0006 (7)
Br24	0.05752 (15)	0.01955 (11)	0.02950 (12)	−0.00444 (10)	0.00210 (10)	−0.00290 (9)
C25	0.0284 (10)	0.0255 (10)	0.0228 (10)	−0.0042 (8)	−0.0060 (8)	−0.0025 (8)
C26	0.0247 (9)	0.0235 (10)	0.0225 (9)	−0.0016 (8)	−0.0045 (8)	0.0004 (8)

Geometric parameters (Å, º)

N11—C12	1.325 (3)	N21—C21	1.424 (2)
N11—C16	1.339 (3)	N21—H21	0.8017
C12—C13	1.393 (3)	C21—C26	1.387 (3)
C12—Cl1	1.748 (2)	C21—C22	1.395 (3)
C13—C14	1.387 (3)	C22—C23	1.385 (3)
C13—C17	1.506 (3)	C22—H22	0.95
C14—C15	1.382 (3)	C23—C24	1.381 (3)
C14—H14	0.95	C23—H23	0.95
C15—C16	1.381 (4)	C24—C25	1.382 (3)
C15—H15	0.95	C24—Br24	1.9022 (19)
C16—H16	0.95	C25—C26	1.389 (3)
C17—O1	1.225 (3)	C25—H25	0.95
C17—N21	1.336 (3)	C26—H26	0.95
C12—N11—C16	116.70 (19)	C17—N21—H21	118.1
N11—C12—C13	125.2 (2)	C21—N21—H21	116.0
N11—C12—Cl1	114.47 (16)	C26—C21—C22	120.24 (19)
C13—C12—Cl1	120.23 (17)	C26—C21—N21	121.77 (18)
C14—C13—C12	116.14 (19)	C22—C21—N21	117.95 (18)
C14—C13—C17	117.63 (17)	C23—C22—C21	119.8 (2)
C12—C13—C17	126.23 (19)	C23—C22—H22	120.1
C15—C14—C13	120.2 (2)	C21—C22—H22	120.1
C15—C14—H14	119.9	C24—C23—C22	119.3 (2)
C13—C14—H14	119.9	C24—C23—H23	120.3
C16—C15—C14	118.1 (2)	C22—C23—H23	120.3
C16—C15—H15	120.9	C23—C24—C25	121.47 (19)
C14—C15—H15	120.9	C23—C24—Br24	119.68 (16)
N11—C16—C15	123.5 (2)	C25—C24—Br24	118.84 (16)
N11—C16—H16	118.2	C24—C25—C26	119.25 (19)
C15—C16—H16	118.2	C24—C25—H25	120.4
O1—C17—N21	124.3 (2)	C26—C25—H25	120.4
O1—C17—C13	119.55 (18)	C21—C26—C25	119.86 (19)
N21—C17—C13	116.01 (16)	C21—C26—H26	120.1
C17—N21—C21	125.86 (17)	C25—C26—H26	120.1
C16—N11—C12—C13	−1.3 (3)	O1—C17—N21—C21	2.7 (3)
C16—N11—C12—Cl1	175.22 (17)	C13—C17—N21—C21	178.86 (17)
N11—C12—C13—C14	4.1 (3)	C17—N21—C21—C26	−38.6 (3)
Cl1—C12—C13—C14	−172.30 (16)	C17—N21—C21—C22	143.6 (2)
N11—C12—C13—C17	−176.62 (19)	C26—C21—C22—C23	0.9 (3)
Cl1—C12—C13—C17	7.0 (3)	N21—C21—C22—C23	178.7 (2)
C12—C13—C14—C15	−3.8 (3)	C21—C22—C23—C24	0.0 (3)
C17—C13—C14—C15	176.82 (19)	C22—C23—C24—C25	−0.5 (3)
C13—C14—C15—C16	1.1 (3)	C22—C23—C24—Br24	178.60 (17)
C12—N11—C16—C15	−1.7 (3)	C23—C24—C25—C26	0.0 (3)
C14—C15—C16—N11	1.8 (4)	Br24—C24—C25—C26	−179.05 (16)
C14—C13—C17—O1	46.9 (3)	C22—C21—C26—C25	−1.3 (3)
C12—C13—C17—O1	−132.4 (2)	N21—C21—C26—C25	−179.10 (19)
C14—C13—C17—N21	−129.4 (2)	C24—C25—C26—C21	0.9 (3)
C12—C13—C17—N21	51.3 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N21—H21···O1^i	0.80	2.03	2.825 (2)	169
C22—H22···N11^ii	0.95	2.56	3.405 (3)	148

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

(VI) N-(4-Iodophenyl)-2-chloronicotinamide

Crystal data

C12H8ClIN2O	F(000) = 1376
Mr = 358.55	Dx = 1.868 Mg m^−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 2909 reflections
a = 10.6597 (2) Å	θ = 3.0–27.5°
b = 25.9833 (3) Å	µ = 2.71 mm^−1
c = 9.2044 (6) Å	T = 120 K
V = 2549.38 (18) Å^3	Plate, colourless
Z = 8	0.33 × 0.18 × 0.07 mm

Data collection

Bruker-Nonius 95mm CCD camera on κ goniostat diffractometer	2909 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode	2314 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.038
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 3.0°
ϕ & ω scans	h = −13→13
Absorption correction: multi-scan SADABS 2.10 (Sheldrick, 2003)	k = −32→33
Tmin = 0.469, Tmax = 0.833	l = −11→11
19649 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)] = 0.023	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.056	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.026P)^2 + 0.5926P] where P = (Fo^2 + 2Fc^2)/3
2909 reflections	(Δ/σ)max = 0.005
154 parameters	Δρmax = 0.39 e Å^−3
0 restraints	Δρmin = −0.78 e Å^−3

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

	x	y	z	Uiso*/Ueq
N11	0.60356 (18)	0.11949 (7)	0.62709 (19)	0.0203 (4)
C12	0.6165 (2)	0.16921 (8)	0.6038 (2)	0.0160 (5)
Cl1	0.76816 (5)	0.19337 (2)	0.62506 (6)	0.02158 (13)
C13	0.5212 (2)	0.20242 (8)	0.5592 (2)	0.0143 (4)
C14	0.4040 (2)	0.18113 (8)	0.5380 (2)	0.0203 (5)
C15	0.3866 (2)	0.12909 (8)	0.5640 (2)	0.0244 (5)
C16	0.4878 (2)	0.10011 (8)	0.6066 (3)	0.0245 (5)
C17	0.54567 (19)	0.25827 (8)	0.5278 (2)	0.0149 (4)
O1	0.55314 (15)	0.27425 (5)	0.40199 (16)	0.0207 (4)
N21	0.55734 (17)	0.28802 (7)	0.64672 (17)	0.0170 (4)
C21	0.5942 (2)	0.34079 (8)	0.6469 (2)	0.0171 (5)
C22	0.6810 (2)	0.35646 (8)	0.7503 (2)	0.0204 (5)
C23	0.7200 (2)	0.40740 (8)	0.7567 (3)	0.0220 (5)
C24	0.6721 (2)	0.44248 (8)	0.6580 (2)	0.0190 (5)
I24	0.741430 (14)	0.518368 (5)	0.656374 (16)	0.02235 (7)
C25	0.5848 (2)	0.42725 (8)	0.5546 (2)	0.0195 (5)
C26	0.5448 (2)	0.37637 (8)	0.5492 (2)	0.0186 (5)
H14	0.3361	0.2019	0.5059	0.026*
H15	0.3063	0.1138	0.5526	0.032*
H16	0.4754	0.0643	0.6226	0.032*
H21	0.5409	0.2738	0.7313	0.022*
H22	0.7140	0.3321	0.8172	0.027*
H23	0.7788	0.4181	0.8280	0.029*
H25	0.5524	0.4516	0.4875	0.025*
H26	0.4842	0.3660	0.4795	0.024*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N11	0.0209 (11)	0.0147 (10)	0.0253 (10)	0.0018 (8)	0.0015 (8)	0.0022 (8)
C12	0.0160 (12)	0.0168 (12)	0.0150 (11)	−0.0013 (9)	0.0016 (9)	−0.0029 (9)
Cl1	0.0157 (3)	0.0203 (3)	0.0288 (3)	−0.0014 (2)	−0.0015 (2)	0.0029 (2)
C13	0.0191 (12)	0.0134 (11)	0.0105 (10)	0.0016 (9)	0.0021 (9)	−0.0010 (8)
C14	0.0192 (12)	0.0188 (12)	0.0230 (12)	0.0011 (9)	−0.0050 (10)	0.0009 (9)
C15	0.0209 (13)	0.0189 (13)	0.0334 (14)	−0.0057 (10)	−0.0023 (11)	−0.0028 (10)
C16	0.0290 (15)	0.0146 (12)	0.0300 (13)	−0.0048 (10)	0.0029 (11)	0.0007 (10)
C17	0.0100 (11)	0.0154 (11)	0.0193 (12)	0.0005 (8)	−0.0004 (9)	0.0000 (9)
O1	0.0329 (10)	0.0161 (8)	0.0132 (8)	0.0007 (7)	0.0016 (7)	0.0012 (6)
N21	0.0265 (11)	0.0115 (9)	0.0131 (9)	−0.0038 (8)	0.0026 (8)	0.0005 (7)
C21	0.0208 (12)	0.0146 (11)	0.0158 (11)	−0.0007 (9)	0.0039 (9)	−0.0015 (9)
C22	0.0305 (14)	0.0171 (11)	0.0137 (10)	0.0002 (10)	0.0010 (10)	0.0015 (9)
C23	0.0304 (14)	0.0174 (12)	0.0182 (11)	−0.0048 (10)	−0.0026 (10)	−0.0036 (9)
C24	0.0241 (13)	0.0096 (11)	0.0234 (12)	−0.0018 (9)	0.0059 (10)	−0.0032 (9)
I24	0.02689 (11)	0.01153 (10)	0.02863 (11)	−0.00335 (6)	−0.00034 (7)	−0.00170 (6)
C25	0.0185 (12)	0.0138 (11)	0.0263 (12)	0.0028 (9)	0.0003 (10)	0.0024 (9)
C26	0.0162 (12)	0.0173 (11)	0.0225 (12)	0.0003 (9)	−0.0005 (9)	−0.0016 (9)

Geometric parameters (Å, º)

N11—C12	1.317 (3)	N21—C21	1.426 (3)
N11—C16	1.346 (3)	N21—H21	0.88
C12—C13	1.395 (3)	C21—C22	1.389 (3)
C12—Cl1	1.745 (2)	C21—C26	1.393 (3)
C13—C14	1.380 (3)	C22—C23	1.388 (3)
C13—C17	1.502 (3)	C22—H22	0.95
C14—C15	1.386 (3)	C23—C24	1.384 (3)
C14—H14	0.95	C23—H23	0.95
C15—C16	1.373 (3)	C24—C25	1.388 (3)
C15—H15	0.95	C24—I24	2.106 (2)
C16—H16	0.95	C25—C26	1.390 (3)
C17—O1	1.232 (2)	C25—H25	0.95
C17—N21	1.346 (3)	C26—H26	0.95
C12—N11—C16	116.14 (19)	C17—N21—H21	117.3
N11—C12—C13	125.3 (2)	C21—N21—H21	117.3
N11—C12—Cl1	115.59 (16)	C22—C21—C26	120.0 (2)
C13—C12—Cl1	119.03 (16)	C22—C21—N21	117.77 (19)
C14—C13—C12	116.93 (19)	C26—C21—N21	122.2 (2)
C14—C13—C17	121.16 (18)	C23—C22—C21	120.5 (2)
C12—C13—C17	121.83 (19)	C23—C22—H22	119.7
C13—C14—C15	119.2 (2)	C21—C22—H22	119.7
C13—C14—H14	120.4	C24—C23—C22	119.3 (2)
C15—C14—H14	120.4	C24—C23—H23	120.3
C16—C15—C14	118.6 (2)	C22—C23—H23	120.3
C16—C15—H15	120.7	C23—C24—C25	120.6 (2)
C14—C15—H15	120.7	C23—C24—I24	119.47 (16)
N11—C16—C15	123.7 (2)	C25—C24—I24	119.83 (16)
N11—C16—H16	118.1	C24—C25—C26	120.1 (2)
C15—C16—H16	118.1	C24—C25—H25	119.9
O1—C17—N21	124.37 (19)	C26—C25—H25	119.9
O1—C17—C13	121.16 (18)	C25—C26—C21	119.5 (2)
N21—C17—C13	114.47 (18)	C25—C26—H26	120.3
C17—N21—C21	125.33 (18)	C21—C26—H26	120.3
C16—N11—C12—C13	−0.6 (3)	O1—C17—N21—C21	−7.7 (3)
C16—N11—C12—Cl1	−178.02 (16)	C13—C17—N21—C21	172.75 (19)
N11—C12—C13—C14	0.0 (3)	C17—N21—C21—C22	−135.9 (2)
Cl1—C12—C13—C14	177.36 (15)	C17—N21—C21—C26	45.1 (3)
N11—C12—C13—C17	−176.83 (19)	C26—C21—C22—C23	−0.5 (3)
Cl1—C12—C13—C17	0.5 (3)	N21—C21—C22—C23	−179.6 (2)
C12—C13—C14—C15	1.1 (3)	C21—C22—C23—C24	−0.5 (3)
C17—C13—C14—C15	177.99 (19)	C22—C23—C24—C25	0.8 (3)
C13—C14—C15—C16	−1.6 (3)	C22—C23—C24—I24	−175.18 (16)
C12—N11—C16—C15	0.0 (3)	C23—C24—C25—C26	−0.1 (3)
C14—C15—C16—N11	1.1 (4)	I24—C24—C25—C26	175.85 (16)
C14—C13—C17—O1	−73.6 (3)	C24—C25—C26—C21	−0.9 (3)
C12—C13—C17—O1	103.1 (2)	C22—C21—C26—C25	1.2 (3)
C14—C13—C17—N21	106.0 (2)	N21—C21—C26—C25	−179.80 (19)
C12—C13—C17—N21	−77.3 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N21—H21···O1^i	0.88	2.01	2.853 (2)	160
C15—H15···Cg2^ii	0.95	2.65	3.404 (2)	137

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

(VII) N-(4-Methoxyphenyl)-2-chloronicotinamide

Crystal data

C13H11ClN2O2	F(000) = 544
Mr = 262.69	Dx = 1.441 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 2661 reflections
a = 4.8536 (2) Å	θ = 3.6–27.5°
b = 11.8437 (4) Å	µ = 0.31 mm^−1
c = 21.0612 (7) Å	T = 120 K
V = 1210.69 (6) Å^3	Block, colourless
Z = 4	0.34 × 0.22 × 0.12 mm

Data collection

Bruker-Nonius 95mm CCD camera on κ goniostat diffractometer	2661 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode	2184 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.040
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 3.6°
ϕ & ω scans	h = −5→6
Absorption correction: multi-scan SADABS 2.10 (Sheldrick, 2003)	k = −15→11
Tmin = 0.921, Tmax = 0.964	l = −21→27
7884 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)] = 0.042	H-atom parameters constrained
wR(F^2) = 0.104	w = 1/[σ^2(Fo^2) + (0.0579P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max < 0.001
2661 reflections	Δρmax = 0.24 e Å^−3
164 parameters	Δρmin = −0.35 e Å^−3
0 restraints	Absolute structure: Flack (1983), 1013 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.05 (7)

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

	x	y	z	Uiso*/Ueq
N11	0.2528 (4)	0.42072 (18)	0.20676 (9)	0.0307 (5)
C12	0.3347 (4)	0.3434 (2)	0.24770 (10)	0.0227 (5)
Cl1	0.56547 (12)	0.24507 (5)	0.21709 (3)	0.03297 (19)
C13	0.2436 (4)	0.33534 (18)	0.31091 (9)	0.0177 (5)
C14	0.0515 (4)	0.41567 (19)	0.33018 (10)	0.0208 (5)
C15	−0.0354 (5)	0.4982 (2)	0.28822 (11)	0.0267 (5)
C16	0.0687 (5)	0.4970 (2)	0.22747 (11)	0.0331 (6)
C17	0.3486 (4)	0.24784 (19)	0.35626 (9)	0.0182 (4)
O1	0.5965 (3)	0.22805 (14)	0.36182 (7)	0.0282 (4)
N21	0.1514 (4)	0.19607 (16)	0.39034 (8)	0.0183 (4)
C21	0.1969 (4)	0.11043 (18)	0.43713 (9)	0.0182 (5)
C22	0.0365 (5)	0.1129 (2)	0.49195 (10)	0.0215 (5)
C23	0.0673 (5)	0.0297 (2)	0.53731 (10)	0.0245 (5)
C24	0.2577 (5)	−0.0565 (2)	0.52849 (9)	0.0212 (5)
O24	0.2684 (3)	−0.13507 (14)	0.57646 (7)	0.0285 (4)
C241	0.4823 (5)	−0.2180 (2)	0.57344 (11)	0.0314 (6)
C25	0.4176 (5)	−0.0590 (2)	0.47362 (10)	0.0225 (5)
C26	0.3853 (4)	0.02478 (19)	0.42806 (10)	0.0218 (5)
H14	−0.0200	0.4138	0.3722	0.027*
H15	−0.1638	0.5543	0.3011	0.035*
H16	0.0070	0.5532	0.1986	0.043*
H21	−0.0202	0.2166	0.3833	0.022*
H22	−0.0939	0.1717	0.4981	0.028*
H23	−0.0421	0.0314	0.5747	0.032*
H24A	0.4653	−0.2610	0.5339	0.041*
H24B	0.4660	−0.2694	0.6097	0.041*
H12C	0.6622	−0.1805	0.5747	0.041*
H25	0.5482	−0.1177	0.4674	0.029*
H26	0.4934	0.0230	0.3905	0.028*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N11	0.0356 (11)	0.0325 (12)	0.0241 (10)	−0.0033 (11)	0.0013 (9)	0.0069 (9)
C12	0.0179 (11)	0.0260 (14)	0.0242 (11)	−0.0046 (10)	0.0031 (10)	−0.0039 (10)
Cl1	0.0300 (3)	0.0373 (4)	0.0316 (3)	0.0010 (3)	0.0104 (2)	−0.0087 (3)
C13	0.0130 (9)	0.0202 (13)	0.0197 (10)	−0.0033 (9)	−0.0041 (9)	−0.0016 (9)
C14	0.0181 (10)	0.0221 (13)	0.0223 (10)	−0.0025 (10)	−0.0004 (9)	−0.0023 (9)
C15	0.0256 (12)	0.0189 (12)	0.0357 (13)	0.0024 (11)	−0.0031 (12)	0.0023 (10)
C16	0.0372 (15)	0.0283 (15)	0.0337 (13)	0.0024 (13)	−0.0053 (12)	0.0109 (10)
C17	0.0166 (10)	0.0173 (11)	0.0206 (9)	−0.0010 (10)	−0.0021 (8)	−0.0040 (9)
O1	0.0124 (7)	0.0343 (10)	0.0378 (8)	−0.0011 (8)	−0.0020 (7)	0.0081 (8)
N21	0.0112 (8)	0.0225 (11)	0.0211 (9)	0.0035 (8)	−0.0011 (7)	0.0023 (8)
C21	0.0173 (11)	0.0187 (13)	0.0185 (11)	−0.0018 (9)	−0.0027 (9)	−0.0009 (9)
C22	0.0188 (11)	0.0209 (13)	0.0247 (10)	0.0025 (10)	0.0008 (9)	−0.0013 (9)
C23	0.0259 (12)	0.0280 (14)	0.0195 (10)	0.0019 (11)	0.0046 (10)	−0.0029 (9)
C24	0.0249 (11)	0.0206 (13)	0.0182 (10)	−0.0011 (11)	−0.0029 (9)	0.0010 (9)
O24	0.0347 (9)	0.0268 (10)	0.0242 (8)	0.0050 (9)	0.0021 (8)	0.0074 (7)
C241	0.0329 (13)	0.0312 (15)	0.0300 (12)	0.0041 (12)	−0.0035 (11)	0.0074 (11)
C25	0.0184 (11)	0.0216 (13)	0.0274 (11)	0.0076 (11)	−0.0007 (10)	0.0006 (9)
C26	0.0196 (11)	0.0265 (13)	0.0192 (10)	0.0031 (10)	0.0035 (9)	0.0002 (9)

Geometric parameters (Å, º)

N11—C12	1.319 (3)	C21—C26	1.379 (3)
N11—C16	1.344 (3)	C21—C22	1.393 (3)
C12—C13	1.406 (3)	C22—C23	1.381 (3)
C12—Cl1	1.740 (2)	C22—H22	0.95
C13—C14	1.393 (3)	C23—C24	1.389 (3)
C13—C17	1.499 (3)	C23—H23	0.95
C14—C15	1.384 (3)	C24—O24	1.375 (3)
C14—H14	0.95	C24—C25	1.393 (3)
C15—C16	1.376 (3)	O24—C241	1.431 (3)
C15—H15	0.95	C241—H24A	0.98
C16—H16	0.95	C241—H24B	0.98
C17—O1	1.231 (2)	C241—H12C	0.98
C17—N21	1.344 (3)	C25—C26	1.389 (3)
N21—C21	1.431 (3)	C25—H25	0.95
N21—H21	0.88	C26—H26	0.95
C12—N11—C16	117.07 (19)	C22—C21—N21	117.99 (18)
N11—C12—C13	124.9 (2)	C23—C22—C21	119.9 (2)
N11—C12—Cl1	114.61 (17)	C23—C22—H22	120.1
C13—C12—Cl1	120.50 (18)	C21—C22—H22	120.1
C14—C13—C12	116.1 (2)	C22—C23—C24	120.3 (2)
C14—C13—C17	120.95 (18)	C22—C23—H23	119.9
C12—C13—C17	122.9 (2)	C24—C23—H23	119.9
C15—C14—C13	120.1 (2)	O24—C24—C23	115.13 (19)
C15—C14—H14	120.0	O24—C24—C25	125.1 (2)
C13—C14—H14	120.0	C23—C24—C25	119.8 (2)
C16—C15—C14	118.3 (2)	C24—O24—C241	117.39 (17)
C16—C15—H15	120.8	O24—C241—H24A	109.5
C14—C15—H15	120.8	O24—C241—H24B	109.5
N11—C16—C15	123.6 (2)	H24A—C241—H24B	109.5
N11—C16—H16	118.2	O24—C241—H12C	109.5
C15—C16—H16	118.2	H24A—C241—H12C	109.5
O1—C17—N21	123.9 (2)	H24B—C241—H12C	109.5
O1—C17—C13	121.64 (19)	C26—C25—C24	119.7 (2)
N21—C17—C13	114.43 (17)	C26—C25—H25	120.2
C17—N21—C21	125.51 (17)	C24—C25—H25	120.2
C17—N21—H21	117.2	C21—C26—C25	120.30 (19)
C21—N21—H21	117.2	C21—C26—H26	119.9
C26—C21—C22	120.1 (2)	C25—C26—H26	119.9
C26—C21—N21	121.89 (17)
C16—N11—C12—C13	0.0 (3)	C13—C17—N21—C21	−179.40 (17)
C16—N11—C12—Cl1	178.26 (19)	C17—N21—C21—C26	−41.5 (3)
N11—C12—C13—C14	0.4 (3)	C17—N21—C21—C22	141.0 (2)
Cl1—C12—C13—C14	−177.73 (16)	C26—C21—C22—C23	0.3 (3)
N11—C12—C13—C17	−178.3 (2)	N21—C21—C22—C23	177.8 (2)
Cl1—C12—C13—C17	3.6 (3)	C21—C22—C23—C24	0.0 (3)
C12—C13—C14—C15	−1.0 (3)	C22—C23—C24—O24	−179.4 (2)
C17—C13—C14—C15	177.7 (2)	C22—C23—C24—C25	−0.1 (3)
C13—C14—C15—C16	1.2 (3)	C23—C24—O24—C241	−172.87 (19)
C12—N11—C16—C15	0.1 (4)	C25—C24—O24—C241	7.9 (3)
C14—C15—C16—N11	−0.8 (4)	O24—C24—C25—C26	179.2 (2)
C14—C13—C17—O1	−131.8 (2)	C23—C24—C25—C26	−0.1 (3)
C12—C13—C17—O1	46.8 (3)	C22—C21—C26—C25	−0.5 (3)
C14—C13—C17—N21	46.9 (3)	N21—C21—C26—C25	−177.90 (19)
C12—C13—C17—N21	−134.5 (2)	C24—C25—C26—C21	0.4 (3)
O1—C17—N21—C21	−0.7 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N21—H21···O1^i	0.88	1.92	2.785 (2)	168

Symmetry code: (i) x−1, y, z.

(VIII) N-(4-Cyanophenyl)-2-chloronicotinamide

Crystal data

C13H8ClN3O	Z = 4
Mr = 257.67	F(000) = 528
Triclinic, P1	Dx = 1.461 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.2885 (3) Å	Cell parameters from 5365 reflections
b = 7.7607 (3) Å	θ = 2.9–27.6°
c = 20.8849 (9) Å	µ = 0.32 mm^−1
α = 96.456 (2)°	T = 120 K
β = 92.913 (2)°	Block, colourless
γ = 91.810 (2)°	0.40 × 0.10 × 0.10 mm
V = 1171.49 (8) Å^3

Data collection

Bruker-Nonius 95mm CCD camera on κ goniostat diffractometer	5365 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode	3760 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.060
Detector resolution: 9.091 pixels mm^-1	θmax = 27.6°, θmin = 2.9°
ϕ & ω scans	h = −9→9
Absorption correction: multi-scan SADABS 2.10 (Sheldrick, 2003)	k = −10→10
Tmin = 0.899, Tmax = 0.969	l = −27→26
21639 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)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.171	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0844P)^2 + 1.0407P] where P = (Fo^2 + 2Fc^2)/3
5365 reflections	(Δ/σ)max < 0.001
325 parameters	Δρmax = 0.74 e Å^−3
0 restraints	Δρmin = −0.35 e Å^−3

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

	x	y	z	Uiso*/Ueq
N11	0.4024 (3)	0.5334 (3)	0.41399 (12)	0.0257 (6)
C12	0.5406 (4)	0.4277 (4)	0.40989 (14)	0.0225 (6)
Cl11	0.74241 (10)	0.51557 (10)	0.38256 (4)	0.0285 (2)
C13	0.5387 (4)	0.2603 (4)	0.42747 (14)	0.0206 (6)
C14	0.3775 (4)	0.2012 (4)	0.45139 (15)	0.0241 (7)
C15	0.2276 (4)	0.3077 (4)	0.45524 (15)	0.0268 (7)
C16	0.2475 (4)	0.4714 (4)	0.43607 (15)	0.0279 (7)
C17	0.7039 (4)	0.1471 (4)	0.42314 (14)	0.0211 (6)
O11	0.7924 (3)	0.1170 (3)	0.47166 (10)	0.0273 (5)
N21	0.7375 (3)	0.0842 (3)	0.36189 (12)	0.0235 (6)
C21	0.8926 (4)	−0.0042 (4)	0.33945 (14)	0.0209 (6)
C22	0.9149 (4)	−0.0138 (4)	0.27334 (15)	0.0232 (6)
C23	1.0691 (4)	−0.0867 (4)	0.24724 (15)	0.0244 (7)
C24	1.2018 (4)	−0.1517 (4)	0.28771 (15)	0.0221 (6)
C241	1.3665 (4)	−0.2196 (4)	0.26069 (15)	0.0263 (7)
N24	1.4970 (4)	−0.2700 (4)	0.23738 (14)	0.0340 (7)
C25	1.1762 (4)	−0.1476 (4)	0.35319 (15)	0.0224 (6)
C26	1.0208 (4)	−0.0761 (4)	0.37956 (15)	0.0221 (6)
N31	−0.5598 (3)	1.0705 (3)	0.08089 (12)	0.0251 (6)
C32	−0.4236 (4)	0.9650 (4)	0.08737 (14)	0.0203 (6)
Cl31	−0.21001 (10)	1.06368 (10)	0.11310 (4)	0.0268 (2)
C33	−0.4379 (4)	0.7849 (4)	0.07404 (14)	0.0194 (6)
C34	−0.6107 (4)	0.7128 (4)	0.05231 (15)	0.0244 (7)
C35	−0.7567 (4)	0.8212 (4)	0.04530 (15)	0.0266 (7)
C36	−0.7249 (4)	0.9975 (4)	0.05984 (15)	0.0279 (7)
C37	−0.2739 (4)	0.6719 (4)	0.07828 (14)	0.0193 (6)
O31	−0.1832 (3)	0.6369 (3)	0.03110 (10)	0.0257 (5)
N41	−0.2429 (3)	0.6166 (3)	0.13691 (12)	0.0221 (5)
C41	−0.0939 (4)	0.5220 (4)	0.15886 (14)	0.0192 (6)
C42	−0.0933 (4)	0.4872 (4)	0.22279 (15)	0.0238 (7)
C43	0.0521 (4)	0.4041 (4)	0.24920 (15)	0.0246 (7)
C44	0.1995 (4)	0.3559 (4)	0.21195 (15)	0.0220 (6)
C441	0.3543 (4)	0.2754 (4)	0.23969 (15)	0.0259 (7)
N44	0.4780 (4)	0.2120 (4)	0.26268 (14)	0.0326 (6)
C45	0.1955 (4)	0.3863 (4)	0.14756 (14)	0.0216 (6)
C46	0.0501 (4)	0.4687 (4)	0.12041 (14)	0.0217 (6)
H14	0.3693	0.0887	0.4651	0.029*
H15	0.1148	0.2689	0.4706	0.032*
H16	0.1453	0.5443	0.4387	0.034*
H21	0.6517	0.1005	0.3322	0.028*
H22	0.8237	0.0299	0.2460	0.028*
H23	1.0845	−0.0924	0.2022	0.029*
H25	1.2659	−0.1942	0.3803	0.027*
H26	1.0021	−0.0761	0.4242	0.027*
H34	−0.6284	0.5908	0.0424	0.029*
H35	−0.8757	0.7748	0.0308	0.032*
H36	−0.8248	1.0714	0.0547	0.033*
H41	−0.3263	0.6429	0.1651	0.026*
H42	−0.1931	0.5208	0.2483	0.029*
H43	0.0516	0.3798	0.2928	0.030*
H45	0.2940	0.3500	0.1218	0.026*
H46	0.0481	0.4887	0.0763	0.026*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N11	0.0217 (13)	0.0263 (14)	0.0300 (15)	0.0095 (11)	0.0027 (11)	0.0032 (11)
C12	0.0200 (14)	0.0251 (16)	0.0229 (15)	0.0055 (12)	0.0028 (11)	0.0029 (12)
Cl11	0.0228 (4)	0.0318 (4)	0.0330 (4)	0.0026 (3)	0.0089 (3)	0.0083 (3)
C13	0.0190 (14)	0.0238 (16)	0.0195 (14)	0.0059 (12)	0.0024 (11)	0.0023 (11)
C14	0.0186 (15)	0.0261 (17)	0.0285 (17)	0.0043 (12)	0.0035 (12)	0.0050 (12)
C15	0.0141 (14)	0.0328 (18)	0.0330 (18)	0.0029 (13)	0.0042 (12)	−0.0004 (13)
C16	0.0158 (14)	0.0325 (19)	0.0346 (18)	0.0099 (13)	0.0020 (12)	−0.0030 (14)
C17	0.0184 (14)	0.0222 (16)	0.0236 (15)	0.0023 (12)	0.0025 (12)	0.0052 (12)
O11	0.0214 (11)	0.0361 (13)	0.0254 (12)	0.0096 (9)	0.0015 (9)	0.0056 (9)
N21	0.0163 (12)	0.0305 (15)	0.0241 (13)	0.0098 (11)	0.0003 (10)	0.0029 (11)
C21	0.0162 (14)	0.0172 (15)	0.0292 (16)	0.0039 (11)	0.0021 (11)	0.0016 (12)
C22	0.0211 (15)	0.0232 (16)	0.0255 (16)	0.0065 (12)	−0.0008 (12)	0.0026 (12)
C23	0.0232 (15)	0.0248 (17)	0.0255 (16)	0.0029 (13)	0.0038 (12)	0.0019 (12)
C24	0.0151 (14)	0.0181 (15)	0.0329 (17)	0.0031 (11)	0.0031 (12)	0.0008 (12)
C241	0.0218 (16)	0.0243 (17)	0.0323 (17)	0.0034 (13)	0.0009 (13)	0.0006 (13)
N24	0.0247 (15)	0.0377 (17)	0.0402 (17)	0.0097 (13)	0.0083 (12)	0.0017 (13)
C25	0.0172 (14)	0.0184 (15)	0.0319 (17)	0.0071 (11)	−0.0006 (12)	0.0035 (12)
C26	0.0220 (15)	0.0202 (15)	0.0251 (16)	0.0057 (12)	0.0038 (12)	0.0041 (12)
N31	0.0202 (13)	0.0281 (14)	0.0280 (14)	0.0104 (11)	0.0032 (10)	0.0043 (11)
C32	0.0133 (13)	0.0264 (16)	0.0214 (15)	0.0034 (12)	0.0010 (11)	0.0024 (11)
Cl31	0.0208 (4)	0.0279 (4)	0.0309 (4)	0.0004 (3)	−0.0033 (3)	0.0022 (3)
C33	0.0174 (14)	0.0218 (15)	0.0200 (14)	0.0028 (11)	0.0035 (11)	0.0048 (11)
C34	0.0186 (15)	0.0247 (16)	0.0308 (17)	0.0024 (12)	0.0020 (12)	0.0064 (13)
C35	0.0146 (14)	0.0347 (19)	0.0317 (17)	−0.0001 (13)	0.0009 (12)	0.0097 (14)
C36	0.0211 (15)	0.0350 (19)	0.0300 (17)	0.0137 (14)	0.0043 (13)	0.0096 (14)
C37	0.0163 (14)	0.0174 (15)	0.0241 (15)	0.0001 (11)	0.0017 (11)	0.0010 (11)
O31	0.0221 (11)	0.0313 (13)	0.0247 (11)	0.0085 (9)	0.0052 (9)	0.0040 (9)
N41	0.0165 (12)	0.0280 (14)	0.0233 (13)	0.0093 (10)	0.0048 (10)	0.0060 (10)
C41	0.0129 (13)	0.0176 (15)	0.0275 (16)	0.0041 (11)	0.0013 (11)	0.0029 (11)
C42	0.0223 (15)	0.0242 (16)	0.0262 (16)	0.0086 (13)	0.0071 (12)	0.0043 (12)
C43	0.0233 (15)	0.0279 (17)	0.0237 (16)	0.0070 (13)	0.0020 (12)	0.0059 (12)
C44	0.0191 (14)	0.0155 (15)	0.0311 (17)	0.0032 (11)	−0.0015 (12)	0.0020 (12)
C441	0.0257 (16)	0.0233 (16)	0.0290 (17)	0.0034 (13)	0.0008 (13)	0.0043 (13)
N44	0.0280 (15)	0.0330 (16)	0.0376 (16)	0.0111 (12)	−0.0030 (12)	0.0074 (12)
C45	0.0166 (14)	0.0187 (15)	0.0296 (16)	0.0046 (11)	0.0030 (12)	0.0015 (12)
C46	0.0203 (15)	0.0216 (15)	0.0242 (15)	0.0062 (12)	0.0034 (12)	0.0049 (12)

Geometric parameters (Å, º)

N11—C12	1.319 (4)	N31—C32	1.318 (4)
N11—C16	1.336 (4)	N31—C36	1.345 (4)
C12—C13	1.389 (4)	C32—C33	1.394 (4)
C12—Cl11	1.751 (3)	C32—Cl31	1.745 (3)
C13—C14	1.385 (4)	C33—C34	1.395 (4)
C13—C17	1.513 (4)	C33—C37	1.510 (4)
C14—C15	1.391 (4)	C34—C35	1.389 (4)
C14—H14	0.95	C34—H34	0.95
C15—C16	1.380 (5)	C35—C36	1.377 (5)
C15—H15	0.95	C35—H35	0.95
C16—H16	0.95	C36—H36	0.95
C17—O11	1.222 (3)	C37—O31	1.224 (3)
C17—N21	1.354 (4)	C37—N41	1.353 (4)
N21—C21	1.414 (4)	N41—C41	1.415 (4)
N21—H21	0.88	N41—H41	0.88
C21—C22	1.392 (4)	C41—C42	1.391 (4)
C21—C26	1.395 (4)	C41—C46	1.399 (4)
C22—C23	1.383 (4)	C42—C43	1.381 (4)
C22—H22	0.95	C42—H42	0.95
C23—C24	1.396 (4)	C43—C44	1.395 (4)
C23—H23	0.95	C43—H43	0.95
C24—C25	1.387 (4)	C44—C45	1.390 (4)
C24—C241	1.442 (4)	C44—C441	1.434 (4)
C241—N24	1.150 (4)	C441—N44	1.150 (4)
C25—C26	1.389 (4)	C45—C46	1.385 (4)
C25—H25	0.95	C45—H45	0.95
C26—H26	0.95	C46—H46	0.95
C12—N11—C16	116.5 (3)	C32—N31—C36	117.0 (3)
N11—C12—C13	125.5 (3)	N31—C32—C33	125.0 (3)
N11—C12—Cl11	115.0 (2)	N31—C32—Cl31	116.0 (2)
C13—C12—Cl11	119.4 (2)	C33—C32—Cl31	118.9 (2)
C14—C13—C12	116.6 (3)	C32—C33—C34	116.7 (3)
C14—C13—C17	120.5 (3)	C32—C33—C37	122.5 (3)
C12—C13—C17	122.9 (3)	C34—C33—C37	120.7 (3)
C13—C14—C15	119.6 (3)	C35—C34—C33	119.4 (3)
C13—C14—H14	120.2	C35—C34—H34	120.3
C15—C14—H14	120.2	C33—C34—H34	120.3
C16—C15—C14	118.0 (3)	C36—C35—C34	118.5 (3)
C16—C15—H15	121.0	C36—C35—H35	120.8
C14—C15—H15	121.0	C34—C35—H35	120.8
N11—C16—C15	123.8 (3)	N31—C36—C35	123.4 (3)
N11—C16—H16	118.1	N31—C36—H36	118.3
C15—C16—H16	118.1	C35—C36—H36	118.3
O11—C17—N21	125.5 (3)	O31—C37—N41	125.9 (3)
O11—C17—C13	121.1 (3)	O31—C37—C33	120.3 (3)
N21—C17—C13	113.4 (2)	N41—C37—C33	113.9 (2)
C17—N21—C21	128.4 (2)	C37—N41—C41	128.5 (2)
C17—N21—H21	115.8	C37—N41—H41	115.8
C21—N21—H21	115.8	C41—N41—H41	115.8
C22—C21—C26	120.3 (3)	C42—C41—C46	120.2 (3)
C22—C21—N21	116.0 (3)	C42—C41—N41	116.4 (2)
C26—C21—N21	123.8 (3)	C46—C41—N41	123.3 (3)
C23—C22—C21	120.4 (3)	C43—C42—C41	120.2 (3)
C23—C22—H22	119.8	C43—C42—H42	119.9
C21—C22—H22	119.8	C41—C42—H42	119.9
C22—C23—C24	119.4 (3)	C42—C43—C44	120.0 (3)
C22—C23—H23	120.3	C42—C43—H43	120.0
C24—C23—H23	120.3	C44—C43—H43	120.0
C25—C24—C23	120.1 (3)	C45—C44—C43	119.5 (3)
C25—C24—C241	120.7 (3)	C45—C44—C441	120.1 (3)
C23—C24—C241	119.1 (3)	C43—C44—C441	120.4 (3)
N24—C241—C24	177.5 (3)	N44—C441—C44	179.1 (4)
C24—C25—C26	120.7 (3)	C46—C45—C44	121.0 (3)
C24—C25—H25	119.6	C46—C45—H45	119.5
C26—C25—H25	119.6	C44—C45—H45	119.5
C25—C26—C21	119.0 (3)	C45—C46—C41	119.0 (3)
C25—C26—H26	120.5	C45—C46—H46	120.5
C21—C26—H26	120.5	C41—C46—H46	120.5
C16—N11—C12—C13	−1.1 (5)	C36—N31—C32—C33	0.1 (4)
C16—N11—C12—Cl11	−178.6 (2)	C36—N31—C32—Cl31	178.7 (2)
N11—C12—C13—C14	−0.2 (5)	N31—C32—C33—C34	−0.1 (4)
Cl11—C12—C13—C14	177.2 (2)	Cl31—C32—C33—C34	−178.6 (2)
N11—C12—C13—C17	−178.4 (3)	N31—C32—C33—C37	175.9 (3)
Cl11—C12—C13—C17	−1.0 (4)	Cl31—C32—C33—C37	−2.7 (4)
C12—C13—C14—C15	1.4 (4)	C32—C33—C34—C35	−0.1 (4)
C17—C13—C14—C15	179.7 (3)	C37—C33—C34—C35	−176.2 (3)
C13—C14—C15—C16	−1.4 (5)	C33—C34—C35—C36	0.4 (4)
C12—N11—C16—C15	1.1 (5)	C32—N31—C36—C35	0.2 (4)
C14—C15—C16—N11	0.1 (5)	C34—C35—C36—N31	−0.4 (5)
C14—C13—C17—O11	−70.9 (4)	C32—C33—C37—O31	−89.6 (4)
C12—C13—C17—O11	107.3 (3)	C34—C33—C37—O31	86.2 (4)
C14—C13—C17—N21	108.1 (3)	C32—C33—C37—N41	90.9 (3)
C12—C13—C17—N21	−73.7 (4)	C34—C33—C37—N41	−93.3 (3)
O11—C17—N21—C21	−10.7 (5)	O31—C37—N41—C41	6.3 (5)
C13—C17—N21—C21	170.3 (3)	C33—C37—N41—C41	−174.2 (3)
C17—N21—C21—C22	−163.6 (3)	C37—N41—C41—C42	177.8 (3)
C17—N21—C21—C26	15.1 (5)	C37—N41—C41—C46	−0.3 (5)
C26—C21—C22—C23	−3.4 (4)	C46—C41—C42—C43	1.8 (5)
N21—C21—C22—C23	175.4 (3)	N41—C41—C42—C43	−176.4 (3)
C21—C22—C23—C24	0.4 (4)	C41—C42—C43—C44	0.5 (5)
C22—C23—C24—C25	1.9 (4)	C42—C43—C44—C45	−2.4 (5)
C22—C23—C24—C241	−177.0 (3)	C42—C43—C44—C441	177.6 (3)
C23—C24—C25—C26	−1.3 (4)	C43—C44—C45—C46	2.1 (4)
C241—C24—C25—C26	177.5 (3)	C441—C44—C45—C46	−178.0 (3)
C24—C25—C26—C21	−1.6 (4)	C44—C45—C46—C41	0.2 (4)
C22—C21—C26—C25	3.9 (4)	C42—C41—C46—C45	−2.1 (4)
N21—C21—C26—C25	−174.7 (3)	N41—C41—C46—C45	175.9 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N21—H21···N44	0.88	2.15	3.006 (4)	164
N41—H41···N24^i	0.88	2.10	2.978 (4)	173
C14—H14···O11^ii	0.95	2.49	3.334 (4)	148
C15—H15···O11^iii	0.95	2.60	3.507 (4)	160
C25—H25···N11^iv	0.95	2.52	3.348 (4)	146
C34—H34···O31^v	0.95	2.53	3.327 (4)	142
C35—H35···O31^iii	0.95	2.45	3.366 (4)	161
C45—H45···N31^iv	0.95	2.53	3.300 (4)	138

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

 

Footnotes

¹Supplementary data for this paper are available from the IUCr electronic archives (Reference: BM5033 ). Services for accessing these data are described at the back of the journal.