In-house and synchrotron X-ray diffraction studies of 2-phenyl-1,10-phenanthroline, protonated salts, com­plexes with gold(III) and copper(II), and an orthometallation product with palladium(II)

Different salts of the 2-phenyl-1,10-phenanthrolin-1-ium cation, (pnpH)⁺, are obtained by reacting 2-phenyl-1,10-phen­anthroline (pnp), C₁₈H₁₂N₂, (I), with a variety of anions, such as hexa­fluorido­phosphate, C₁₈H₁₃N₂⁺·PF₆⁻, (II), tri­fluoro­methane­sulfonate, C₁₈H₁₃N₂⁺·CF₃SO₃⁻, (III), tetra­chlorido­aurate, (C₁₈H₁₃N₂)[AuCl₄], (IV), and bromide (as the dihydrate), C₁₈H₁₃N₂⁺·Br⁻·2H₂O, (V). Compound (I) crystallizes with Z′ = 2, with both independent mol­ecules adopting a coplanar conformation. In (II)–(IV), a hydrogen bond exists between the cation and anion, while one of the lattice water mol­ecules serves as a hydrogen-bonded bridge between the cation and anion in (V). Reaction of (I) with HAuCl₄ gives the salt complex (IV); however, reaction with KAuCl₄ produces the monodentate complex tri­chlorido­(2-phenyl-1,10-phenanthroline-κN¹⁰)gold(III), [AuCl₃(C₁₈H₁₂N₂)], (VI). Di­chlorido­(2-phenyl-1,10-phenanthroline-κ²N,N′)copper(II), [CuCl₂(C₁₈H₁₂N₂)], (VII), results from the reaction of CuCl₂·2H₂O and (I), in which the Cu^II center adopts a tetra­hedrally distorted square-planar geometry. The pendent phenyl ring twists to a bis­ecting position relative to the phenanthroline plane. The square-planar Pd^II complex, bromido­[2-(phenanthrolin-2-yl)phenyl-κ³C¹,N,N′]palladium(II), [PdBr(C₁₈H₁₁N₂)], (VIII), is obtained from the reaction of (I) with [PdCl₂(cyclo­octa-1,5-diene)], followed by addition of bromine. A coplanar geometry for the pendent ring is adopted as a result of the tridentate bonding motif.

S1. Introduction

2-Phenyl-1,10-phenanthroline [pnp, (I)] was first reported by Case & Sasin (1955) and later by Riesgo et al. (1996). Studies involving (I), other substituted phenanthroline (phen) ligands, as well as substituted 2,2'-bi­pyridine (bpy) ligands and their complexes, are centered primarily around the variable chelating ability of these ligands and how this can influence the electronic and steric properties of the resulting complexes. The consensus is that the disposition of the pendent group with respect to the phen or bpy moiety (dihedral angle, α, defined by rotation about the 2,2' bond) influences key inter- and intra-ligand communication via π stacking inter­actions (Constable et al., 2008; Goodman et al., 1995; Jeffrey et al., 1995; Shishkin et al., 2011; Wu et al., 1999; Yang et al., 2009).

Energy-minimized molecular mechanics calculations carried out by Wu et al. (1999) on (I) show that α = 28° is preferred by the uncomplexed ligand while upon complexation the calculated α angle expands, for example in [Ru(pnp)(bpy)₂](PF₆)₂ α = 54.7°. On the other hand, researchers have investigated the reactivity of pnp–metal complexes as model systems for metal–DNA inter­actions. For example, Suggs et al. (1993) found that [(RPd)₂(µ-adenine)]⁺ (R = pnp and derivatives thereof) can act as nucleases generating nicks in DNA; the planarity of the ligand is presumed to give rise to a favorable geometry for inter­calation.

In this paper, we report the structure of (I) and several protonated salts of the type, (pnpH)X [X = PF₆, (II), CF₃SO₃, (III), AuCl₄, (IV), and Br, (V)]. In addition, the structures of three pnp–metal complexes are reported (see Scheme), where the ligand adopts a monodentate, [AuCl₃(pnp)], (VI), a bidentate, [CuCl₂(pnp)], (VII), or tridentate, [PdBr(pnp)] (VIII), bonding motif.

S2. Experimental

S2.1. Synthesis and crystallization

Compound (I) was prepared according to the literature method of Riesgo et al. (1996). Colorless single crystals were grown at room temperature by slow evaporation of a methyl­ene chloride solution or slow evaporation of a layered di­chloro­methane–hexane solution (1:1 v/v).

Compound (II) was isolated as a side product during the reaction of PtCl(pip₂NCN) with AgPF₆ (Chatterjee et al., 2012), followed by the addition of (I). Colorless crystals were harvested from slow evaporation of a solution of acetone–di­ethyl ether (1:1 v/v) kept at room temperature.

Colorless single crystals of (III) were obtained upon reacting [La(CF₃SO₃)₃] with (I) at room temperature in aceto­nitrile–di­chloro­methane solution [1:1 molar ratio of rea­cta­nts (typically 0.1 mmol of each rea­ctant), 5 ml of each solvent]. Crystals grew in the test tube over the course of 1–2 weeks.

After approximately one week at room temperature, a solution of HAuCl₄ in methanol and (I) in di­chloro­methane [1:1 molar ratio of rea­cta­nts (typically 0.1 mmol of each rea­ctant), 5 ml of each solvent, testtube reaction] yielded golden-yellow crystals of (IV).

Compound (V) was obtained as a by-product from th Cheers fnow Dil

——————————————————- e reaction of PtCl(pnp) and bromine. Colorless crystals were obtained from aceto­nitrile–di­ethyl ether solutions (1:1 v/v) maintained at room temperature.

In a test tube, a clear yellow solution of KAuCl₄ in methanol was layered over a solution of (I) in di­chloro­methane [1:1 molar ratio of rea­cta­nts (typically 0.08 mmol of each rea­ctant), 5 ml of each solvent] and allowed to sit at room temperature. Golden yellow plates of (VI) were harvested after two weeks.

Orange crystals of (VII) were obtained from a room temperature test tube reaction of CuCl₂.2H₂O dissolved in methanol and (I) dissolved in di­chloro­methane [1:1 molar ratio of rea­cta­nts (typically 0.05–0.1 mmol of each rea­ctant), 5 ml of each solvent]. Crystals of a suitable size for diffraction analysis grew in 5–10 d.

Compound (VIII) was otained as follows. [PdCl₂(COD)] and (I) in methanol–aceto­nitrile (0.2 mmol of each rea­ctant, 1:1 solvent ratio, 50 ml total solvent volume) were refluxed for 4 h. The resulting yellow precipitate was filtered off, washed with di­ethyl ether and subsequently dissolved in methanol–aceto­nitrile (1:1 v/v). Bromine (10 equivalents) was added and refluxed for 4 h. The resulting product was filtered off and washed with di­ethyl ether. Yellow crystals were obtained from a layered aceto­nitrile–di­ethyl ether solution (1:1 v/v) maintained at room temperature.

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. The PF₆^- counter-ion in (II) shows typical disorder in four F atoms in the equatorial plane that have been refined with a two-component disorder model. The refined major occupancy is 0.53 (2). However, it appears that the electron density in the equatorial place could be described as a ring of electron density with multiple options for partial-occupancy F-atom placement.

Atom H1 for (II)–(V), as well as the water H atoms for (V), were located directly from the difference map and the coordinates refined. All distances and angles associated with hydrogen-bond inter­actions are summarized in Tables 2 and 3. All C-bound H atoms for (I)–(VIII) were calculated based on geometric criteria, and treated with a riding model, with C—H = 0.95 Å. Isotropic displacement parameters for all H atoms were defined as kU_eq(C,N,O) where k = 1.5 for solvent H atoms and 1.2 for all others.

S3. Results and discussion

Compound (I) (Fig. 1) crystallizes with two independent molecules in the asymmetric unit. Both molecules adopt a nearly coplanar conformation [α = 8.92 (7)° for molecule A and 9.70 (10)° for molecule B]. Similar coplanarity is found for 2-(2-hy­droxy­phenyl)-1,10-phenanthroline (two independent molecules with reported α angles of 15.6 and 20.8°; Jeffrey et al., 1995) and 2-(4-iodo­phenyl)-1,10-phenanthroline [α = 11.1 (2)°; Shishkin et al., 2011]. This is also observed for the 1:1 hydrogen-bonded cocrystal 2,2,6,6-tetra­methyl-4-oxopiperidinium hexa­fluoro­phosphate–php [php = 2-(pyridin-2-yl)-1,10-phenanthroline], where α = 10.97 (12)° (Krause et al., 2013). As expected, increased steric bulk on the pendent ring favors larger values of α. For example, the reported angle for 2-(2,4,6-tri­methyl­phenyl)-1,10-phenanthroline (Zhao et al., 2009) is α = 82.69 (4)°.

Reaction of (I) with various metal complexes produces (II)–(V) (Figs. 2–5). The pnpH⁺ cation, (I)H⁺, is protonated at atom N1, resulting in an inter­molecular hydrogen bond (Table 2) with the anion as in (II) and (III). A similar but weak hydrogen-bonding inter­action occurs for (IV). The N—H···Cl inter­action for (IV) is longer than observed for the related [^n-BuphenH]AuCl₄ (2.91 Å) and [^sec-BuphenH]AuCl₄ (3.00 Å) but shorter than the value of 3.55 Å observed for [^tBuphenH]AuCl₂ (Hudson et al., 2009). In the case of (V), a lattice water molecule serves as a hydrogen-bonded bridge between the cation and anion (Table 3). Additionally, a second lattice water (O2W) is present which hydrogen bonds with both Br1 and O1W to form a one-dimensional chain which runs parallel to the aaxis (Fig. 6 and Table 3). Each cation in (II), (III) and (V) retains the nearly coplanar arrangement of the pendent phenyl ring [α = 5.14 (11)° for (II), 2.71 (7)° for (III), and 3.68 (16)° for (V)], while the disposition of the ring is twisted to 12.49 (12)° for (IV). The more planar arrangement observed for (II), (III), and (V) may be attributed to a favorable C—H···anion–solvate inter­action [C18···F1 = 3.537 (3) Å for (II), C18···O2 = 3.452 (2) Å for (III), and C18···O1W = 3.593 (7) Å for (V)], whereas the related C—H···anion distance is >4.0 Å for (IV).

As a ligand, (I) is rather versatile in its coordination to metals. Reaction of (I) with KAuCl₄ produces (VI) (Fig. 7). The ligand coordinates to the square-planar Au^III metal center in a monodentate fashion and approaches a perpendicular orientation with respect to the AuCl₃ moiety [72.05 (3)°]. The bond lengths and angles involving the gold (Table 4) are comparable to other square-planar AuCl₃-containing complexes such as trichlorido[2-(2,5-di­methyl­phenyl)­pyridine]­gold(III) and trichlorido[2-(2-meth­oxy­phenyl)­pyridine]­gold(III) (Hashmi et al., 2010), (dpo)AuCl₃ (dpo = di-2-pyridyl ether; Hodges et al., 2011), and (acridine-N)trichloridogold(III) (Sloufova & Slouf, 2001). The orientation of the pendent phenyl ring [α = 30.57 (7)°] is twisted away from a coplanar arrangement. In contrast, the substituted phenanthroline ligand in ^n-BuphenAuCl₃ and ^sec-BuphenAuCl₃ binds in a bidentate fashion to the gold (Hudson et al., 2009).

Reaction of CuCl₂.2H₂O and (I) forms (VII) (Fig. 8) in which the ligand coordinates through the N atoms in a bidentate fashion with a bite angle of 82.56 (7)°. The Cu^II center in (VII) adopts a tetra­hedrally distorted square-planar geometry. The angles about the Cu are in the range 82–155° (Table 5), with the Cl1—Cu1—Cl2 angle [99.74 (2)°] midway between the expected square-planar and tetra­hedral angles. Perhaps a better indicator of the degree of distortion in (VII) is reflected in the dihedral angle [53.34 (4)°] about the Cu-containing planes N1—Cu1—N1 and Cl1—Cu1—Cl2 (90° for tetra­hedral and 0° for square planar). Such distortion is frequently observed in four-coordinate Cu complexes (Raithby et al., 2000), particularly those having bidentate ligands and can be rationalized in terms of electronic and steric effects, i.e. increased π-back-bonding of the chelating ligand favors a square planar geometry, while bulky substituents tend to cause tetra­hedral distortions. However, the degree of distortion is highly variable, e.g. [Cu{R-bis­(oxazoline)}(H₂O)₂](SbF₆)₂ (R = tert-butyl, ave. distortion reported as 33.3°; R = iso­propyl, ave. distortion = 7°) (Johnson & Evans, 2000), [CuCl₂{^tBu-bis­(oxazoline)}] (37°; Evans et al., 1999), [Cu(tbz)₂](CF₃SO₃)₂.H₂O [tbz = bis­(2-benzimidazolyl)propane; 62°;Albada et al., 2000], [CuCl₂(5,5'-di­amino-2,2'-bi­pyridine)] (41.1°; Janiak et al., 1999), [CuCl₂(2,2'-bi­quinoline)] (65.4°; Muranishi et al., 2005) and [CuCl₂(BL^iPr)] [BL^iPr = bis­(1,3-diiso­propyl-4,5-di­methyl­imidazolin-2-yl­idene)-1,2-ethanedi­amine; reported distortion of 53.9°; Glöge et al., 2010]. Another way of describing the distortion at the four-coordinate metal center is the τ₄ geometry index (Yang et al., 2007), similar to the τ₅ index popularized by Addison et al. (1984) for the description of five-coordinate metal centers. As pointed out, (VII) is a difficult case that appears to be an average of a number of geometries, the τ₄ index of 0.52 suggests a tetra­hedrally distorted seesaw geometry. As with the triclinic and monoclinic forms of [CuCl₂(php)] [2.4336 (7) and 2.4461 (9) versus 2.2393 (8) and 2.2578 (6) Å; Krause et al., 2013], there is an elongation of the Cu—Cl_apical bond in (V) [Cu—Cl2 = 2.2458 (6) versus Cu—Cl1 = 2.2180 (6) Å]. In addition, the Cu atom in (VII) is displaced 0.1218 (14) Å out of the plane generated by the phen ring. Taken together, one may speculate a pyramidal distortion is also contributing to the observed asymmetry. The orientation of the pendent phenyl ring is significantly canted away from coplanarity [α = 45.63 (5)°], similar angles are observed for [AuCl(dpp)]C₇H₇SO₃.0.5CH₃OH [55.1 (2)°; Chan et al., 1994], [Cu(dpp)₂](PF₆)₂ and [Cu(dpp)₂](ClO₄)₂ (dpp = 2,9-di­phenyl-1,10-phenanthroline; 42.6–61.4 and 39.9–43.3°, respectively; Miller et al., 1998). In contrast, an α = 10.3° orientation is reported by Constable et al. (2008) for [Cu(Rphen)₂]PF₆ [Rphen = 2-(4-meth­oxy­phenyl)-1,10-phenanthroline].

Refluxing [PdCl₂(COD)] (COD = 1,5-cyclo­octa­diene) and (I) in methanol–aceto­nitrile followed by the addition of bromine results in (VIII) (Fig. 9). The Pd^II geometry is square planar, with (I) acting as a tridentate ligand to the metal atom. This is a popular chelating mode of aromatic polypyridine ligands such as 2,2':6,2''-terpyridine (tpy), php, pnp and related derivatives. The bonding about the Pd^II atom is asymmetric, with the central Pd—N bond shorter than the distal Pd—N or Pd—C bonds (Table 6). For representative complexes such as [AuCl(dpp)](C₇H₇SO₃).0.5CH₃OH (Chan et al., 1994), [CuCl₂(php)] (Krause et al., 2013), [PtCl(4,7-Me₂-php)]CF₃SO₃ (Moore et al., 2002), [PtCl(php)]X (X = ClO₄^-, ReO₄^-, PF₆^- and AsF₆^-; Norton et al., 2014), [PtCl(tpy)]ClO₄ (Taylor et al., 2013), [PtCl(tpy)]PF₆ and [PtCl(tpy)]ClO₄.H₂O (Taylor et al., 2010), shortening of the central bond is typical (1.92–1.97 Å range), while the distal bonds fall in the range 2.01–2.22 Å. The customary contraction of the angle between the distal atoms of the chelating ligand and the metal [N1—Pd1—C18 = 160.04 (11)°] is observed, comparable to that for the above-mentioned four- and five-coordinate examples (154–163° range). As expected, the disposition [α = 1.25 (11)°] of the pendent phenyl ring is small; values of 0.3–6.0° are adopted for similar ligands in [PtCl(4,7-Me₂-php)]CF₃SO₃ (Moore et al., 2002), [PtCl(php)]X (X = ClO₄^-, ReO₄^-, PF₆^- and AsF₆^-; Norton et al., 2014) and [CuCl₂(php)] (Krause et al., 2013).

The packing arrangement for (II), (III) and (V) maximizes π-inter­actions but with the conventional offset stacking pattern [the centroid distances between the central ring defined by atoms C4–C9 of the phenanthroline system and the pendent phenyl ring are 3.582 (2) Å for (II), 3.6770 (10) Å for (III), and 3.711 (3) Å for (V)]. The closest inter­planar distance for (IV) is 3.757 (3) Å between the distal ring defined by atoms N1–C5 of the phenanthroline system and the pendent phenyl ring. The displacement angles for these inter­actions range from 18.7 to 29.7°. The more planar the metal complex, the less slippage is associated with the C4–C9 phenanthroline centroid-to-centroid π-inter­action. As a result, stacking distances of 3.487 (2) Å for (VIII), 3.713 (2) Å for (VI), and 3.8983 (13) Å for (VII) are observed with associated displacement angles in the range 9.3–26.2°. As reported by Janiak (2000), distances and displacement angles clustered about 3.8 Å and 20°, respectively, are common.

Related literature

For related literature, see:van Albada et al. (2000); Case & Sasin (1955); Chan et al. (1994); Chatterjee et al. (2012); Constable et al. (2008); Evans et al. (1999); Glöge et al. (2010); Goodman et al. (1995); Hashmi et al. (2010); Hodges et al. (2011); Hudson et al. (2009); Janiak (2000); Janiak et al. (1999); Jeffrey et al. (1995); Johnson & Evans (2000); Krause et al. (2013); Miller et al. (1998); Moore et al. (2002); Muranishi et al. (2005); Norton et al. (2014); Raithby et al. (2000); Riesgo et al. (1996); Shishkin et al. (2011); Sloufova & Slouf (2001); Suggs et al. (1993); Taylor et al. (2010, 2013); Wu et al. (1999); Yang et al. (2007, 2009); Zhao et al. (2009).

Computing details

Data collection: SMART (Bruker, 2003) for (I), (III), (IV), (VI), (VII); APEX2 (Bruker, 2005) for (II), (V), (VIII). For all compounds, cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008b); program(s) used to refine structure: SHELXTL (Sheldrick, 2008b). Molecular graphics: SHELXTL (Sheldrick, 2008b) for (I), (II), (III), (IV), (VI), (VII), (VIII); SHELXTL (Sheldrick, 2008b) and DIAMOND (Brandenburg, 2012) for (V). For all compounds, software used to prepare material for publication: SHELXTL (Sheldrick, 2008b).

Figures

	Fig. 1. The molecular structure of (I), showing the atomic labelling scheme and 50% probability displacement ellipsoids.
	Fig. 2. The molecular structure of (II), showing the atomic labelling scheme and 50% probability displacement ellipsoids. The dashed line indicates a hydrogen-bonding interaction.
	Fig. 3. The molecular structure of (III), showing the atomic labelling scheme and 50% probability displacement ellipsoids. The dashed line indicates a hydrogen-bonding interaction.
	Fig. 4. The molecular structure of (IV), showing the atomic labelling scheme and 50% probability displacement ellipsoids. The dashed line indicates a hydrogen-bonding interaction.
	Fig. 5. The molecular structure of (V), showing the atomic labelling scheme and 50% probability displacement ellipsoids. The dashed line indicates a hydrogen-bonding interaction.
	Fig. 6. The hydrogen-bonded network of (V), viewed in the ab plane. Only H atoms involved in hydrogen bonding are shown.
	Fig. 7. The molecular structure of (VI), showing the atomic labelling scheme and 50% probability displacement ellipsoids.
	Fig. 8. The molecular structure of (VII), showing the atomic labelling scheme and 50% probability displacement ellipsoids.
	Fig. 9. The molecular structure of (VIII), showing the atomic labelling scheme and 50% probability displacement ellipsoids.

(I) 2-Phenyl-1,10-phenanthroline

Crystal data

C18H12N2	F(000) = 1072
Mr = 256.30	Dx = 1.283 Mg m^−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2ybc	Cell parameters from 4494 reflections
a = 10.8180 (4) Å	θ = 4.2–66.1°
b = 21.0893 (8) Å	µ = 0.59 mm^−1
c = 12.2199 (5) Å	T = 150 K
β = 107.844 (2)°	Rectangular block, colorless
V = 2653.78 (18) Å^3	0.27 × 0.15 × 0.08 mm
Z = 8

Data collection

Bruker SMART6000 CCD diffractometer	4740 independent reflections
Radiation source: fine-focus sealed tube	3118 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.056
ω scans	θmax = 67.9°, θmin = 4.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a)	h = −12→12
Tmin = 0.856, Tmax = 0.954	k = −25→25
22260 measured reflections	l = −14→14

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.129	H-atom parameters constrained
S = 0.99	w = 1/[σ^2(Fo^2) + (0.0711P)^2] where P = (Fo^2 + 2Fc^2)/3
4740 reflections	(Δ/σ)max < 0.001
361 parameters	Δρmax = 0.18 e Å^−3
0 restraints	Δρmin = −0.19 e Å^−3

Special details

Experimental. A suitable crystal was mounted in a loop with paratone-N and transferred immediately to the goniostat bathed in a cold stream.

Our standard practice is to collect a full sphere of data out to a theta angle of 67° (0.83 Å resolution).

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

All C-bound H atoms were calculated based on geometric criteria, and treated with a riding model.

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

	x	y	z	Uiso*/Ueq
N1A	−0.12251 (15)	0.15229 (8)	0.45401 (14)	0.0470 (4)
N2A	0.04455 (14)	0.13877 (7)	0.67646 (13)	0.0377 (4)
C1A	−0.1944 (2)	0.15945 (10)	0.34590 (18)	0.0533 (6)
H1A	−0.2461	0.1245	0.3094	0.064*
C2A	−0.2002 (2)	0.21454 (11)	0.28122 (19)	0.0540 (6)
H2A	−0.2521	0.2164	0.2029	0.065*
C3A	−0.12897 (19)	0.26581 (10)	0.33380 (18)	0.0469 (5)
H3A	−0.1323	0.3043	0.2926	0.056*
C4A	−0.05098 (18)	0.26126 (9)	0.44877 (16)	0.0400 (5)
C5A	−0.04914 (18)	0.20270 (9)	0.50624 (16)	0.0385 (4)
C6A	0.02822 (19)	0.31283 (9)	0.50664 (17)	0.0432 (5)
H6A	0.0235	0.3524	0.4683	0.052*
C7A	0.10937 (19)	0.30652 (9)	0.61433 (17)	0.0433 (5)
H7A	0.1608	0.3415	0.6510	0.052*
C8A	0.11873 (18)	0.24752 (9)	0.67391 (16)	0.0390 (5)
C9A	0.03899 (17)	0.19563 (9)	0.62228 (16)	0.0363 (4)
C10A	0.20892 (19)	0.23771 (10)	0.78248 (17)	0.0446 (5)
H10A	0.2647	0.2712	0.8198	0.054*
C11A	0.21667 (19)	0.18000 (9)	0.83469 (17)	0.0437 (5)
H11A	0.2792	0.1728	0.9074	0.052*
C12A	0.13096 (17)	0.13109 (9)	0.77974 (16)	0.0377 (4)
C13A	0.13207 (18)	0.06815 (9)	0.83550 (16)	0.0387 (4)
C14A	0.19725 (18)	0.05835 (9)	0.95183 (17)	0.0420 (5)
H14A	0.2444	0.0923	0.9968	0.050*
C15A	0.19433 (19)	−0.00001 (10)	1.00268 (18)	0.0462 (5)
H15A	0.2379	−0.0056	1.0823	0.055*
C16A	0.1285 (2)	−0.04993 (10)	0.93812 (19)	0.0504 (5)
H16A	0.1279	−0.0902	0.9729	0.060*
C17A	0.0634 (2)	−0.04145 (10)	0.82305 (19)	0.0526 (6)
H17A	0.0175	−0.0758	0.7785	0.063*
C18A	0.0648 (2)	0.01707 (9)	0.77234 (18)	0.0455 (5)
H18A	0.0192	0.0225	0.6931	0.055*
N1B	0.27871 (15)	0.10705 (7)	0.37739 (13)	0.0419 (4)
N2B	0.42869 (15)	0.09526 (7)	0.23349 (13)	0.0371 (4)
C1B	0.1995 (2)	0.11041 (10)	0.44147 (18)	0.0494 (5)
H1B	0.1655	0.1508	0.4512	0.059*
C2B	0.1626 (2)	0.05864 (10)	0.49556 (18)	0.0514 (5)
H2B	0.1042	0.0639	0.5392	0.062*
C3B	0.2120 (2)	0.00048 (10)	0.48445 (17)	0.0505 (5)
H3B	0.1888	−0.0354	0.5208	0.061*
C4B	0.2978 (2)	−0.00603 (9)	0.41880 (17)	0.0427 (5)
C5B	0.32680 (18)	0.04888 (9)	0.36455 (16)	0.0383 (4)
C6B	0.3541 (2)	−0.06563 (10)	0.40425 (19)	0.0535 (6)
H6B	0.3334	−0.1024	0.4399	0.064*
C7B	0.4362 (2)	−0.07043 (9)	0.34075 (19)	0.0529 (6)
H7B	0.4740	−0.1103	0.3340	0.064*
C8B	0.46700 (19)	−0.01637 (9)	0.28361 (17)	0.0432 (5)
C9B	0.41088 (17)	0.04314 (8)	0.29247 (15)	0.0362 (4)
C10B	0.5490 (2)	−0.01912 (10)	0.21416 (18)	0.0494 (5)
H10B	0.5916	−0.0577	0.2079	0.059*
C11B	0.56791 (19)	0.03308 (9)	0.15570 (18)	0.0455 (5)
H11B	0.6239	0.0312	0.1092	0.055*
C12B	0.50319 (17)	0.09024 (9)	0.16500 (16)	0.0380 (4)
C13B	0.51281 (18)	0.14813 (9)	0.09817 (16)	0.0402 (5)
C14B	0.5724 (2)	0.14761 (11)	0.01166 (18)	0.0512 (5)
H14B	0.6087	0.1093	−0.0057	0.061*
C15B	0.5792 (2)	0.20261 (12)	−0.0494 (2)	0.0611 (6)
H15B	0.6208	0.2016	−0.1075	0.073*
C16B	0.5260 (2)	0.25845 (11)	−0.02609 (19)	0.0583 (6)
H16B	0.5309	0.2958	−0.0679	0.070*
C17B	0.4655 (2)	0.25979 (10)	0.05852 (18)	0.0510 (5)
H17B	0.4279	0.2981	0.0741	0.061*
C18B	0.45963 (19)	0.20550 (9)	0.12064 (17)	0.0435 (5)
H18B	0.4190	0.2072	0.1793	0.052*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1A	0.0412 (9)	0.0460 (10)	0.0481 (10)	−0.0065 (8)	0.0054 (8)	−0.0017 (8)
N2A	0.0348 (8)	0.0372 (9)	0.0413 (9)	−0.0014 (7)	0.0120 (7)	−0.0039 (7)
C1A	0.0446 (12)	0.0535 (13)	0.0520 (13)	−0.0113 (11)	0.0004 (10)	−0.0003 (10)
C2A	0.0433 (12)	0.0640 (15)	0.0490 (13)	−0.0042 (11)	0.0055 (10)	0.0056 (11)
C3A	0.0390 (11)	0.0508 (13)	0.0525 (13)	−0.0016 (10)	0.0163 (10)	0.0080 (10)
C4A	0.0342 (10)	0.0443 (11)	0.0452 (12)	0.0001 (9)	0.0177 (9)	−0.0007 (9)
C5A	0.0325 (10)	0.0394 (11)	0.0451 (12)	−0.0012 (9)	0.0140 (8)	−0.0025 (8)
C6A	0.0458 (11)	0.0375 (11)	0.0510 (13)	−0.0022 (9)	0.0219 (10)	−0.0005 (9)
C7A	0.0459 (11)	0.0385 (11)	0.0496 (13)	−0.0082 (9)	0.0208 (10)	−0.0081 (9)
C8A	0.0371 (10)	0.0397 (11)	0.0435 (11)	−0.0037 (9)	0.0172 (9)	−0.0070 (8)
C9A	0.0340 (10)	0.0370 (10)	0.0411 (11)	0.0004 (8)	0.0160 (8)	−0.0024 (8)
C10A	0.0445 (11)	0.0447 (12)	0.0451 (12)	−0.0108 (10)	0.0143 (9)	−0.0107 (9)
C11A	0.0401 (11)	0.0465 (12)	0.0418 (11)	−0.0066 (9)	0.0085 (9)	−0.0072 (9)
C12A	0.0332 (10)	0.0411 (11)	0.0393 (11)	−0.0015 (9)	0.0121 (8)	−0.0066 (8)
C13A	0.0353 (10)	0.0398 (11)	0.0424 (11)	0.0008 (9)	0.0141 (8)	−0.0029 (8)
C14A	0.0363 (10)	0.0412 (11)	0.0464 (12)	0.0019 (9)	0.0097 (9)	−0.0073 (9)
C15A	0.0400 (11)	0.0506 (12)	0.0463 (12)	0.0037 (10)	0.0106 (9)	0.0007 (10)
C16A	0.0430 (12)	0.0444 (12)	0.0639 (15)	−0.0011 (10)	0.0165 (10)	0.0087 (10)
C17A	0.0498 (13)	0.0445 (12)	0.0600 (14)	−0.0137 (11)	0.0114 (11)	−0.0028 (10)
C18A	0.0441 (11)	0.0477 (12)	0.0427 (12)	−0.0072 (10)	0.0102 (9)	−0.0025 (9)
N1B	0.0458 (10)	0.0358 (9)	0.0456 (10)	−0.0001 (8)	0.0160 (8)	−0.0032 (7)
N2B	0.0345 (8)	0.0340 (9)	0.0399 (9)	−0.0002 (7)	0.0070 (7)	−0.0024 (7)
C1B	0.0541 (13)	0.0434 (12)	0.0547 (13)	−0.0022 (10)	0.0228 (11)	−0.0078 (10)
C2B	0.0573 (13)	0.0530 (13)	0.0480 (13)	−0.0106 (11)	0.0225 (11)	−0.0069 (10)
C3B	0.0557 (13)	0.0497 (13)	0.0442 (12)	−0.0118 (11)	0.0125 (10)	0.0033 (10)
C4B	0.0457 (11)	0.0373 (11)	0.0404 (11)	−0.0054 (9)	0.0062 (9)	0.0005 (8)
C5B	0.0375 (10)	0.0362 (11)	0.0365 (11)	−0.0018 (9)	0.0046 (8)	−0.0020 (8)
C6B	0.0621 (14)	0.0385 (12)	0.0564 (14)	−0.0007 (11)	0.0129 (11)	0.0096 (10)
C7B	0.0574 (14)	0.0344 (11)	0.0632 (15)	0.0108 (10)	0.0128 (11)	0.0060 (10)
C8B	0.0396 (11)	0.0364 (11)	0.0479 (12)	0.0040 (9)	0.0048 (9)	0.0000 (9)
C9B	0.0343 (10)	0.0311 (10)	0.0375 (11)	−0.0010 (8)	0.0026 (8)	−0.0016 (8)
C10B	0.0419 (12)	0.0392 (12)	0.0635 (15)	0.0098 (10)	0.0109 (10)	−0.0028 (10)
C11B	0.0376 (11)	0.0447 (12)	0.0556 (13)	0.0038 (10)	0.0163 (10)	−0.0049 (10)
C12B	0.0303 (9)	0.0402 (11)	0.0398 (11)	−0.0010 (8)	0.0055 (8)	−0.0053 (8)
C13B	0.0328 (10)	0.0438 (11)	0.0402 (11)	−0.0046 (9)	0.0058 (8)	−0.0014 (9)
C14B	0.0412 (11)	0.0598 (14)	0.0519 (13)	−0.0007 (11)	0.0131 (10)	−0.0013 (11)
C15B	0.0526 (14)	0.0784 (18)	0.0542 (15)	−0.0125 (13)	0.0193 (11)	0.0071 (12)
C16B	0.0559 (14)	0.0559 (14)	0.0540 (14)	−0.0201 (12)	0.0035 (11)	0.0092 (11)
C17B	0.0548 (13)	0.0388 (11)	0.0504 (13)	−0.0094 (10)	0.0026 (10)	−0.0022 (9)
C18B	0.0424 (11)	0.0407 (11)	0.0440 (12)	−0.0060 (9)	0.0081 (9)	−0.0040 (9)

Geometric parameters (Å, º)

N1A—C1A	1.320 (3)	N1B—C1B	1.328 (2)
N1A—C5A	1.363 (2)	N1B—C5B	1.360 (2)
N2A—C12A	1.330 (2)	N2B—C12B	1.332 (2)
N2A—C9A	1.362 (2)	N2B—C9B	1.360 (2)
C1A—C2A	1.396 (3)	C1B—C2B	1.396 (3)
C1A—H1A	0.9500	C1B—H1B	0.9500
C2A—C3A	1.368 (3)	C2B—C3B	1.361 (3)
C2A—H2A	0.9500	C2B—H2B	0.9500
C3A—C4A	1.403 (3)	C3B—C4B	1.407 (3)
C3A—H3A	0.9500	C3B—H3B	0.9500
C4A—C5A	1.418 (3)	C4B—C5B	1.416 (3)
C4A—C6A	1.430 (3)	C4B—C6B	1.432 (3)
C5A—C9A	1.454 (3)	C5B—C9B	1.452 (3)
C6A—C7A	1.346 (3)	C6B—C7B	1.351 (3)
C6A—H6A	0.9500	C6B—H6B	0.9500
C7A—C8A	1.430 (3)	C7B—C8B	1.429 (3)
C7A—H7A	0.9500	C7B—H7B	0.9500
C8A—C10A	1.400 (3)	C8B—C10B	1.404 (3)
C8A—C9A	1.416 (3)	C8B—C9B	1.413 (3)
C10A—C11A	1.365 (3)	C10B—C11B	1.362 (3)
C10A—H10A	0.9500	C10B—H10B	0.9500
C11A—C12A	1.412 (3)	C11B—C12B	1.416 (3)
C11A—H11A	0.9500	C11B—H11B	0.9500
C12A—C13A	1.490 (3)	C12B—C13B	1.490 (3)
C13A—C18A	1.393 (3)	C13B—C14B	1.397 (3)
C13A—C14A	1.395 (3)	C13B—C18B	1.402 (3)
C14A—C15A	1.383 (3)	C14B—C15B	1.393 (3)
C14A—H14A	0.9500	C14B—H14B	0.9500
C15A—C16A	1.376 (3)	C15B—C16B	1.378 (3)
C15A—H15A	0.9500	C15B—H15B	0.9500
C16A—C17A	1.378 (3)	C16B—C17B	1.383 (3)
C16A—H16A	0.9500	C16B—H16B	0.9500
C17A—C18A	1.383 (3)	C17B—C18B	1.386 (3)
C17A—H17A	0.9500	C17B—H17B	0.9500
C18A—H18A	0.9500	C18B—H18B	0.9500
C1A—N1A—C5A	117.35 (18)	C1B—N1B—C5B	117.06 (17)
C12A—N2A—C9A	118.81 (16)	C12B—N2B—C9B	118.68 (16)
N1A—C1A—C2A	124.9 (2)	N1B—C1B—C2B	124.5 (2)
N1A—C1A—H1A	117.6	N1B—C1B—H1B	117.7
C2A—C1A—H1A	117.6	C2B—C1B—H1B	117.7
C3A—C2A—C1A	118.1 (2)	C3B—C2B—C1B	118.7 (2)
C3A—C2A—H2A	121.0	C3B—C2B—H2B	120.7
C1A—C2A—H2A	121.0	C1B—C2B—H2B	120.7
C2A—C3A—C4A	119.70 (19)	C2B—C3B—C4B	119.50 (19)
C2A—C3A—H3A	120.2	C2B—C3B—H3B	120.2
C4A—C3A—H3A	120.1	C4B—C3B—H3B	120.2
C3A—C4A—C5A	117.93 (18)	C3B—C4B—C5B	117.82 (18)
C3A—C4A—C6A	121.90 (18)	C3B—C4B—C6B	122.46 (19)
C5A—C4A—C6A	120.14 (18)	C5B—C4B—C6B	119.72 (19)
N1A—C5A—C4A	121.99 (18)	N1B—C5B—C4B	122.39 (18)
N1A—C5A—C9A	119.37 (17)	N1B—C5B—C9B	118.55 (16)
C4A—C5A—C9A	118.55 (17)	C4B—C5B—C9B	119.06 (17)
C7A—C6A—C4A	121.37 (18)	C7B—C6B—C4B	121.15 (19)
C7A—C6A—H6A	119.3	C7B—C6B—H6B	119.4
C4A—C6A—H6A	119.3	C4B—C6B—H6B	119.4
C6A—C7A—C8A	120.47 (18)	C6B—C7B—C8B	120.91 (19)
C6A—C7A—H7A	119.8	C6B—C7B—H7B	119.5
C8A—C7A—H7A	119.8	C8B—C7B—H7B	119.5
C10A—C8A—C9A	117.41 (18)	C10B—C8B—C9B	116.67 (18)
C10A—C8A—C7A	122.07 (18)	C10B—C8B—C7B	123.19 (19)
C9A—C8A—C7A	120.48 (18)	C9B—C8B—C7B	120.1 (2)
N2A—C9A—C8A	122.24 (17)	N2B—C9B—C8B	122.91 (18)
N2A—C9A—C5A	118.86 (16)	N2B—C9B—C5B	118.09 (16)
C8A—C9A—C5A	118.89 (17)	C8B—C9B—C5B	118.96 (17)
C11A—C10A—C8A	119.98 (18)	C11B—C10B—C8B	120.55 (19)
C11A—C10A—H10A	120.0	C11B—C10B—H10B	119.7
C8A—C10A—H10A	120.0	C8B—C10B—H10B	119.7
C10A—C11A—C12A	119.46 (19)	C10B—C11B—C12B	119.24 (19)
C10A—C11A—H11A	120.3	C10B—C11B—H11B	120.4
C12A—C11A—H11A	120.3	C12B—C11B—H11B	120.4
N2A—C12A—C11A	122.04 (18)	N2B—C12B—C11B	121.82 (18)
N2A—C12A—C13A	116.55 (16)	N2B—C12B—C13B	115.88 (17)
C11A—C12A—C13A	121.41 (17)	C11B—C12B—C13B	122.29 (17)
C18A—C13A—C14A	117.71 (18)	C14B—C13B—C18B	117.84 (19)
C18A—C13A—C12A	120.38 (18)	C14B—C13B—C12B	122.30 (18)
C14A—C13A—C12A	121.90 (17)	C18B—C13B—C12B	119.86 (17)
C15A—C14A—C13A	121.03 (19)	C15B—C14B—C13B	120.8 (2)
C15A—C14A—H14A	119.5	C15B—C14B—H14B	119.6
C13A—C14A—H14A	119.5	C13B—C14B—H14B	119.6
C16A—C15A—C14A	120.1 (2)	C16B—C15B—C14B	120.4 (2)
C16A—C15A—H15A	119.9	C16B—C15B—H15B	119.8
C14A—C15A—H15A	119.9	C14B—C15B—H15B	119.8
C15A—C16A—C17A	119.9 (2)	C15B—C16B—C17B	119.7 (2)
C15A—C16A—H16A	120.0	C15B—C16B—H16B	120.2
C17A—C16A—H16A	120.0	C17B—C16B—H16B	120.2
C16A—C17A—C18A	120.0 (2)	C16B—C17B—C18B	120.3 (2)
C16A—C17A—H17A	120.0	C16B—C17B—H17B	119.9
C18A—C17A—H17A	120.0	C18B—C17B—H17B	119.9
C17A—C18A—C13A	121.16 (19)	C17B—C18B—C13B	121.0 (2)
C17A—C18A—H18A	119.4	C17B—C18B—H18B	119.5
C13A—C18A—H18A	119.4	C13B—C18B—H18B	119.5
C5A—N1A—C1A—C2A	0.4 (3)	C5B—N1B—C1B—C2B	−0.2 (3)
N1A—C1A—C2A—C3A	−1.8 (4)	N1B—C1B—C2B—C3B	1.2 (3)
C1A—C2A—C3A—C4A	1.4 (3)	C1B—C2B—C3B—C4B	−0.3 (3)
C2A—C3A—C4A—C5A	0.2 (3)	C2B—C3B—C4B—C5B	−1.4 (3)
C2A—C3A—C4A—C6A	178.13 (19)	C2B—C3B—C4B—C6B	179.5 (2)
C1A—N1A—C5A—C4A	1.3 (3)	C1B—N1B—C5B—C4B	−1.7 (3)
C1A—N1A—C5A—C9A	−175.40 (18)	C1B—N1B—C5B—C9B	178.33 (17)
C3A—C4A—C5A—N1A	−1.6 (3)	C3B—C4B—C5B—N1B	2.4 (3)
C6A—C4A—C5A—N1A	−179.62 (17)	C6B—C4B—C5B—N1B	−178.40 (18)
C3A—C4A—C5A—C9A	175.15 (16)	C3B—C4B—C5B—C9B	−177.55 (17)
C6A—C4A—C5A—C9A	−2.9 (3)	C6B—C4B—C5B—C9B	1.6 (3)
C3A—C4A—C6A—C7A	−175.37 (18)	C3B—C4B—C6B—C7B	−180.0 (2)
C5A—C4A—C6A—C7A	2.6 (3)	C5B—C4B—C6B—C7B	0.9 (3)
C4A—C6A—C7A—C8A	0.2 (3)	C4B—C6B—C7B—C8B	−1.6 (3)
C6A—C7A—C8A—C10A	175.10 (18)	C6B—C7B—C8B—C10B	−178.3 (2)
C6A—C7A—C8A—C9A	−2.6 (3)	C6B—C7B—C8B—C9B	−0.3 (3)
C12A—N2A—C9A—C8A	−2.4 (3)	C12B—N2B—C9B—C8B	−0.6 (3)
C12A—N2A—C9A—C5A	175.84 (16)	C12B—N2B—C9B—C5B	−178.47 (16)
C10A—C8A—C9A—N2A	2.6 (3)	C10B—C8B—C9B—N2B	3.0 (3)
C7A—C8A—C9A—N2A	−179.66 (17)	C7B—C8B—C9B—N2B	−175.04 (18)
C10A—C8A—C9A—C5A	−175.62 (16)	C10B—C8B—C9B—C5B	−179.11 (17)
C7A—C8A—C9A—C5A	2.1 (3)	C7B—C8B—C9B—C5B	2.8 (3)
N1A—C5A—C9A—N2A	−0.9 (3)	N1B—C5B—C9B—N2B	−5.5 (2)
C4A—C5A—C9A—N2A	−177.72 (16)	C4B—C5B—C9B—N2B	174.54 (16)
N1A—C5A—C9A—C8A	177.39 (16)	N1B—C5B—C9B—C8B	176.58 (16)
C4A—C5A—C9A—C8A	0.5 (3)	C4B—C5B—C9B—C8B	−3.4 (3)
C9A—C8A—C10A—C11A	−0.5 (3)	C9B—C8B—C10B—C11B	−2.4 (3)
C7A—C8A—C10A—C11A	−178.22 (18)	C7B—C8B—C10B—C11B	175.6 (2)
C8A—C10A—C11A—C12A	−1.7 (3)	C8B—C10B—C11B—C12B	−0.5 (3)
C9A—N2A—C12A—C11A	0.1 (3)	C9B—N2B—C12B—C11B	−2.5 (3)
C9A—N2A—C12A—C13A	179.50 (15)	C9B—N2B—C12B—C13B	176.82 (15)
C10A—C11A—C12A—N2A	2.0 (3)	C10B—C11B—C12B—N2B	3.1 (3)
C10A—C11A—C12A—C13A	−177.45 (18)	C10B—C11B—C12B—C13B	−176.23 (18)
N2A—C12A—C13A—C18A	12.6 (3)	N2B—C12B—C13B—C14B	−171.08 (17)
C11A—C12A—C13A—C18A	−167.99 (18)	C11B—C12B—C13B—C14B	8.3 (3)
N2A—C12A—C13A—C14A	−166.13 (17)	N2B—C12B—C13B—C18B	8.2 (2)
C11A—C12A—C13A—C14A	13.3 (3)	C11B—C12B—C13B—C18B	−172.42 (17)
C18A—C13A—C14A—C15A	−0.4 (3)	C18B—C13B—C14B—C15B	0.4 (3)
C12A—C13A—C14A—C15A	178.31 (17)	C12B—C13B—C14B—C15B	179.75 (19)
C13A—C14A—C15A—C16A	1.2 (3)	C13B—C14B—C15B—C16B	−0.6 (3)
C14A—C15A—C16A—C17A	−1.2 (3)	C14B—C15B—C16B—C17B	0.0 (3)
C15A—C16A—C17A—C18A	0.3 (3)	C15B—C16B—C17B—C18B	0.8 (3)
C16A—C17A—C18A—C13A	0.4 (3)	C16B—C17B—C18B—C13B	−0.9 (3)
C14A—C13A—C18A—C17A	−0.4 (3)	C14B—C13B—C18B—C17B	0.3 (3)
C12A—C13A—C18A—C17A	−179.15 (19)	C12B—C13B—C18B—C17B	−179.01 (18)

(II) 2-Phenyl-1,10-phenanthrolin-1-ium hexafluoridophosphate

Crystal data

C18H13N2^+·PF6^−	Z = 2
Mr = 402.27	F(000) = 408
Triclinic, P1	Dx = 1.612 Mg m^−3
Hall symbol: -P 1	Synchrotron radiation, λ = 0.77500 Å
a = 7.5798 (8) Å	Cell parameters from 3494 reflections
b = 10.6930 (12) Å	θ = 2.1–27.1°
c = 10.9157 (12) Å	µ = 0.29 mm^−1
α = 103.713 (3)°	T = 173 K
β = 90.801 (3)°	Plate, colorless
γ = 104.707 (3)°	0.08 × 0.04 × 0.01 mm
V = 828.75 (16) Å^3

Data collection

Bruker Platinum 200 diffractometer	3316 independent reflections
Radiation source: synchrotron	2793 reflections with I > 2σ(I)
Si-<111> channel cut crystal monochromator	Rint = 0.056
ω scans	θmax = 29.0°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a)	h = −9→9
Tmin = 0.977, Tmax = 0.997	k = −13→13
8626 measured reflections	l = −13→13

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: mixed
wR(F^2) = 0.174	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0894P)^2 + 0.3941P] where P = (Fo^2 + 2Fc^2)/3
3316 reflections	(Δ/σ)max < 0.001
284 parameters	Δρmax = 0.62 e Å^−3
0 restraints	Δρmin = −0.33 e Å^−3

Special details

Experimental. A suitable crystal was mounted in a loop with paratone-N and transferred immediately to the goniostat bathed in a cold stream.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Data resolution to 0.85 Å in refinement.

Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

The PF6^- counterion in (II) shows typical disorder in 4 F-atoms in the equatorial plane that have been refined with a two-component disorder model. The refined major occupancy is 0.53 (2). However it appears that the electron density in the equatorial plane could be described as a ring of electron density with multiple options for partial-occupancy F-atom placement.

H1 involved in H-bonding (N1—H1···F1) was located directly from the difference map and the coordinates refined. U_iso(H1)=1.2U_eq(N1).

All C-bound H atoms were calculated based on geometric criteria, and treated with a riding model.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
N1	0.7359 (3)	0.59376 (19)	0.75184 (19)	0.0362 (4)
H1	0.756 (4)	0.523 (3)	0.723 (3)	0.043*
N2	0.7615 (2)	0.48032 (18)	0.50441 (17)	0.0307 (4)
C1	0.7269 (4)	0.6403 (2)	0.8742 (2)	0.0443 (6)
H1A	0.7542	0.5931	0.9324	0.053*
C2	0.6773 (4)	0.7589 (3)	0.9176 (3)	0.0519 (7)
H2A	0.6685	0.7926	1.0054	0.062*
C3	0.6412 (4)	0.8265 (2)	0.8321 (3)	0.0506 (7)
H3A	0.6078	0.9077	0.8612	0.061*
C4	0.6531 (3)	0.7775 (2)	0.7022 (3)	0.0408 (6)
C5	0.7025 (3)	0.6562 (2)	0.6628 (2)	0.0349 (5)
C6	0.6169 (3)	0.8416 (2)	0.6068 (3)	0.0478 (7)
H6A	0.5826	0.9230	0.6308	0.057*
C7	0.6308 (3)	0.7880 (2)	0.4836 (3)	0.0461 (6)
H7A	0.6050	0.8323	0.4224	0.055*
C8	0.6834 (3)	0.6660 (2)	0.4427 (2)	0.0382 (5)
C9	0.7164 (3)	0.5974 (2)	0.5326 (2)	0.0324 (5)
C10	0.7069 (3)	0.6075 (2)	0.3170 (2)	0.0434 (6)
H10A	0.6892	0.6498	0.2522	0.052*
C11	0.7550 (3)	0.4900 (3)	0.2875 (2)	0.0404 (5)
H11A	0.7729	0.4514	0.2024	0.049*
C12	0.7783 (3)	0.4252 (2)	0.3841 (2)	0.0323 (5)
C13	0.8206 (3)	0.2936 (2)	0.3549 (2)	0.0320 (5)
C14	0.8288 (3)	0.2228 (3)	0.2312 (2)	0.0417 (6)
H14A	0.8111	0.2606	0.1630	0.050*
C15	0.8625 (4)	0.0983 (3)	0.2063 (3)	0.0481 (6)
H15A	0.8685	0.0515	0.1215	0.058*
C16	0.8874 (4)	0.0415 (3)	0.3047 (3)	0.0460 (6)
H16A	0.9099	−0.0442	0.2877	0.055*
C17	0.8792 (3)	0.1107 (2)	0.4281 (2)	0.0405 (5)
H17A	0.8965	0.0721	0.4957	0.049*
C18	0.8461 (3)	0.2352 (2)	0.4537 (2)	0.0333 (5)
H18A	0.8405	0.2814	0.5388	0.040*
P1	0.76724 (9)	0.26099 (6)	0.85587 (5)	0.0384 (2)
F1	0.8521 (3)	0.37312 (18)	0.78258 (17)	0.0690 (6)
F2	0.6793 (3)	0.15248 (18)	0.92971 (18)	0.0784 (6)
F3A	0.804 (2)	0.1568 (13)	0.7420 (13)	0.091 (4)	0.474 (19)
F4A	0.5819 (13)	0.2950 (13)	0.8368 (14)	0.116 (5)	0.474 (19)
F5A	0.820 (2)	0.3753 (10)	0.9812 (9)	0.080 (3)	0.474 (19)
F6A	0.9509 (18)	0.2294 (14)	0.8745 (16)	0.119 (5)	0.474 (19)
F3B	0.734 (3)	0.1532 (11)	0.7280 (11)	0.121 (5)	0.526 (19)
F4B	0.5768 (15)	0.2410 (19)	0.7973 (12)	0.157 (5)	0.526 (19)
F5B	0.725 (2)	0.3637 (10)	0.9730 (10)	0.091 (3)	0.526 (19)
F6B	0.9614 (15)	0.2823 (16)	0.9148 (14)	0.139 (5)	0.526 (19)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0400 (10)	0.0288 (9)	0.0394 (11)	0.0091 (8)	0.0056 (8)	0.0075 (8)
N2	0.0272 (9)	0.0311 (9)	0.0342 (10)	0.0053 (7)	0.0009 (7)	0.0114 (7)
C1	0.0496 (14)	0.0400 (13)	0.0391 (13)	0.0073 (10)	0.0076 (11)	0.0067 (10)
C2	0.0575 (16)	0.0414 (14)	0.0487 (15)	0.0094 (12)	0.0121 (13)	−0.0010 (11)
C3	0.0444 (14)	0.0330 (12)	0.0684 (18)	0.0095 (10)	0.0087 (13)	0.0016 (12)
C4	0.0306 (11)	0.0285 (11)	0.0606 (16)	0.0050 (9)	0.0028 (10)	0.0090 (10)
C5	0.0270 (10)	0.0289 (11)	0.0479 (13)	0.0039 (8)	0.0015 (9)	0.0116 (9)
C6	0.0351 (12)	0.0284 (11)	0.080 (2)	0.0074 (9)	−0.0009 (12)	0.0144 (12)
C7	0.0346 (12)	0.0357 (12)	0.0712 (18)	0.0051 (10)	−0.0058 (12)	0.0246 (12)
C8	0.0291 (10)	0.0346 (11)	0.0527 (14)	0.0034 (9)	−0.0041 (10)	0.0203 (10)
C9	0.0240 (10)	0.0289 (10)	0.0444 (13)	0.0027 (8)	−0.0006 (9)	0.0143 (9)
C10	0.0404 (12)	0.0463 (14)	0.0481 (15)	0.0051 (10)	−0.0042 (11)	0.0274 (11)
C11	0.0405 (12)	0.0480 (14)	0.0346 (12)	0.0075 (10)	0.0005 (10)	0.0184 (10)
C12	0.0254 (10)	0.0366 (11)	0.0355 (11)	0.0043 (8)	−0.0003 (9)	0.0146 (9)
C13	0.0260 (10)	0.0378 (11)	0.0312 (11)	0.0065 (8)	0.0007 (8)	0.0091 (9)
C14	0.0423 (13)	0.0487 (14)	0.0332 (12)	0.0115 (11)	0.0007 (10)	0.0092 (10)
C15	0.0494 (14)	0.0509 (15)	0.0376 (13)	0.0133 (12)	0.0037 (11)	−0.0013 (11)
C16	0.0430 (13)	0.0398 (13)	0.0538 (15)	0.0148 (10)	0.0053 (11)	0.0048 (11)
C17	0.0393 (12)	0.0407 (13)	0.0453 (13)	0.0149 (10)	0.0035 (10)	0.0135 (10)
C18	0.0332 (11)	0.0360 (11)	0.0319 (11)	0.0107 (9)	0.0023 (9)	0.0092 (9)
P1	0.0545 (4)	0.0348 (4)	0.0276 (4)	0.0145 (3)	0.0003 (3)	0.0080 (3)
F1	0.1086 (16)	0.0549 (10)	0.0568 (11)	0.0306 (10)	0.0309 (10)	0.0281 (8)
F2	0.1279 (19)	0.0463 (10)	0.0592 (11)	0.0107 (10)	0.0183 (11)	0.0225 (8)
F3A	0.162 (9)	0.059 (6)	0.071 (8)	0.064 (7)	0.051 (7)	0.015 (5)
F4A	0.058 (4)	0.165 (8)	0.194 (12)	0.058 (5)	0.043 (6)	0.143 (9)
F5A	0.145 (8)	0.046 (3)	0.027 (2)	−0.009 (5)	0.003 (4)	0.0034 (17)
F6A	0.100 (8)	0.139 (8)	0.178 (13)	0.086 (7)	0.036 (7)	0.092 (8)
F3B	0.246 (14)	0.045 (4)	0.034 (3)	−0.016 (5)	0.002 (6)	−0.005 (2)
F4B	0.077 (5)	0.292 (14)	0.102 (6)	0.049 (7)	−0.027 (4)	0.051 (8)
F5B	0.164 (9)	0.047 (4)	0.057 (4)	0.024 (5)	0.054 (6)	0.007 (3)
F6B	0.073 (5)	0.189 (11)	0.141 (8)	−0.008 (6)	−0.063 (6)	0.065 (8)

Geometric parameters (Å, º)

N1—C1	1.320 (3)	C11—H11A	0.9500
N1—C5	1.357 (3)	C12—C13	1.484 (3)
N1—H1	0.80 (3)	C13—C14	1.393 (3)
N2—C12	1.329 (3)	C13—C18	1.403 (3)
N2—C9	1.347 (3)	C14—C15	1.384 (4)
C1—C2	1.391 (4)	C14—H14A	0.9500
C1—H1A	0.9500	C15—C16	1.385 (4)
C2—C3	1.372 (4)	C15—H15A	0.9500
C2—H2A	0.9500	C16—C17	1.385 (4)
C3—C4	1.403 (4)	C16—H16A	0.9500
C3—H3A	0.9500	C17—C18	1.381 (3)
C4—C5	1.412 (3)	C17—H17A	0.9500
C4—C6	1.434 (4)	C18—H18A	0.9500
C5—C9	1.428 (3)	P1—F4B	1.514 (10)
C6—C7	1.348 (4)	P1—F6A	1.535 (9)
C6—H6A	0.9500	P1—F6B	1.538 (8)
C7—C8	1.433 (3)	P1—F3A	1.541 (9)
C7—H7A	0.9500	P1—F3B	1.555 (10)
C8—C10	1.401 (4)	P1—F4A	1.561 (8)
C8—C9	1.411 (3)	P1—F5B	1.571 (9)
C10—C11	1.364 (4)	P1—F5A	1.571 (9)
C10—H10A	0.9500	P1—F2	1.5830 (18)
C11—C12	1.423 (3)	P1—F1	1.6027 (17)
C1—N1—C5	123.9 (2)	C16—C15—H15A	119.9
C1—N1—H1	122 (2)	C15—C16—C17	119.5 (2)
C5—N1—H1	114 (2)	C15—C16—H16A	120.3
C12—N2—C9	118.40 (19)	C17—C16—H16A	120.3
N1—C1—C2	119.7 (3)	C18—C17—C16	120.7 (2)
N1—C1—H1A	120.2	C18—C17—H17A	119.6
C2—C1—H1A	120.2	C16—C17—H17A	119.6
C3—C2—C1	119.2 (3)	C17—C18—C13	120.3 (2)
C3—C2—H2A	120.4	C17—C18—H18A	119.8
C1—C2—H2A	120.4	C13—C18—H18A	119.8
C2—C3—C4	120.9 (2)	F4B—P1—F6A	157.0 (7)
C2—C3—H3A	119.5	F4B—P1—F6B	179.5 (8)
C4—C3—H3A	119.5	F4B—P1—F3A	90.4 (10)
C3—C4—C5	117.8 (2)	F6B—P1—F3A	89.5 (10)
C3—C4—C6	124.4 (2)	F6A—P1—F3B	87.2 (11)
C5—C4—C6	117.8 (2)	F6B—P1—F3B	109.5 (12)
N1—C5—C4	118.6 (2)	F6A—P1—F4A	179.2 (6)
N1—C5—C9	119.4 (2)	F6B—P1—F4A	156.5 (7)
C4—C5—C9	122.0 (2)	F3A—P1—F4A	112.8 (9)
C7—C6—C4	121.0 (2)	F3B—P1—F4A	93.1 (11)
C7—C6—H6A	119.5	F4B—P1—F5B	88.8 (6)
C4—C6—H6A	119.5	F6A—P1—F5B	113.1 (6)
C6—C7—C8	121.7 (2)	F6B—P1—F5B	91.2 (6)
C6—C7—H7A	119.2	F3A—P1—F5B	178.3 (8)
C8—C7—H7A	119.2	F3B—P1—F5B	159.2 (12)
C10—C8—C9	115.8 (2)	F4B—P1—F5A	113.7 (6)
C10—C8—C7	124.6 (2)	F6A—P1—F5A	88.9 (6)
C9—C8—C7	119.6 (2)	F3A—P1—F5A	155.4 (10)
N2—C9—C8	124.6 (2)	F3B—P1—F5A	174.4 (10)
N2—C9—C5	117.49 (19)	F4A—P1—F5A	90.7 (6)
C8—C9—C5	117.9 (2)	F4B—P1—F2	87.4 (6)
C11—C10—C8	120.1 (2)	F6A—P1—F2	87.9 (5)
C11—C10—H10A	119.9	F6B—P1—F2	93.1 (6)
C8—C10—H10A	119.9	F3A—P1—F2	93.4 (6)
C10—C11—C12	120.1 (2)	F3B—P1—F2	91.5 (5)
C10—C11—H11A	119.9	F4A—P1—F2	92.8 (3)
C12—C11—H11A	119.9	F5B—P1—F2	85.0 (4)
N2—C12—C11	120.9 (2)	F5A—P1—F2	92.5 (4)
N2—C12—C13	117.37 (18)	F4B—P1—F1	91.6 (6)
C11—C12—C13	121.7 (2)	F6A—P1—F1	93.5 (5)
C14—C13—C18	118.3 (2)	F6B—P1—F1	87.9 (6)
C14—C13—C12	122.1 (2)	F3A—P1—F1	87.9 (6)
C18—C13—C12	119.5 (2)	F3B—P1—F1	89.4 (5)
C15—C14—C13	120.9 (2)	F4A—P1—F1	85.8 (3)
C15—C14—H14A	119.5	F5B—P1—F1	93.7 (4)
C13—C14—H14A	119.5	F5A—P1—F1	86.8 (4)
C14—C15—C16	120.2 (2)	F2—P1—F1	178.37 (12)
C14—C15—H15A	119.9
C5—N1—C1—C2	1.3 (4)	C4—C5—C9—N2	−178.88 (19)
N1—C1—C2—C3	−1.0 (4)	N1—C5—C9—C8	−179.09 (19)
C1—C2—C3—C4	0.2 (4)	C4—C5—C9—C8	1.5 (3)
C2—C3—C4—C5	0.3 (4)	C9—C8—C10—C11	1.3 (3)
C2—C3—C4—C6	179.7 (2)	C7—C8—C10—C11	−179.1 (2)
C1—N1—C5—C4	−0.8 (3)	C8—C10—C11—C12	1.1 (4)
C1—N1—C5—C9	179.8 (2)	C9—N2—C12—C11	1.9 (3)
C3—C4—C5—N1	0.0 (3)	C9—N2—C12—C13	−177.57 (18)
C6—C4—C5—N1	−179.5 (2)	C10—C11—C12—N2	−2.9 (3)
C3—C4—C5—C9	179.3 (2)	C10—C11—C12—C13	176.6 (2)
C6—C4—C5—C9	−0.1 (3)	N2—C12—C13—C14	175.5 (2)
C3—C4—C6—C7	−179.8 (2)	C11—C12—C13—C14	−3.9 (3)
C5—C4—C6—C7	−0.4 (4)	N2—C12—C13—C18	−1.9 (3)
C4—C6—C7—C8	−0.5 (4)	C11—C12—C13—C18	178.7 (2)
C6—C7—C8—C10	−177.6 (2)	C18—C13—C14—C15	−0.4 (4)
C6—C7—C8—C9	2.0 (4)	C12—C13—C14—C15	−177.8 (2)
C12—N2—C9—C8	0.7 (3)	C13—C14—C15—C16	0.4 (4)
C12—N2—C9—C5	−178.81 (18)	C14—C15—C16—C17	−0.3 (4)
C10—C8—C9—N2	−2.4 (3)	C15—C16—C17—C18	0.2 (4)
C7—C8—C9—N2	178.04 (19)	C16—C17—C18—C13	−0.1 (4)
C10—C8—C9—C5	177.2 (2)	C14—C13—C18—C17	0.2 (3)
C7—C8—C9—C5	−2.4 (3)	C12—C13—C18—C17	177.8 (2)
N1—C5—C9—N2	0.5 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···F1	0.80 (3)	2.14 (3)	2.806 (3)	140 (3)

(III) 2-Phenyl-1,10-phenanthrolin-1-ium trifluoromethanesulfonate

Crystal data

C18H13N2^+·CF3SO3^−	Z = 2
Mr = 406.37	F(000) = 416
Triclinic, P1	Dx = 1.568 Mg m^−3
Hall symbol: -P 1	Cu Kα radiation, λ = 1.54178 Å
a = 7.6682 (2) Å	Cell parameters from 4788 reflections
b = 10.7446 (4) Å	θ = 4.2–67.7°
c = 11.1174 (4) Å	µ = 2.19 mm^−1
α = 104.848 (2)°	T = 150 K
β = 95.687 (2)°	Block, colorless
γ = 100.439 (2)°	0.11 × 0.10 × 0.05 mm
V = 860.48 (5) Å^3

Data collection

Bruker SMART6000 CCD diffractometer	2976 independent reflections
Radiation source: fine-focus sealed tube	2658 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.021
ω scans	θmax = 67.9°, θmin = 4.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a)	h = −9→9
Tmin = 0.794, Tmax = 0.898	k = −11→12
7396 measured reflections	l = −13→13

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)] = 0.035	Hydrogen site location: mixed
wR(F^2) = 0.102	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0628P)^2 + 0.2088P] where P = (Fo^2 + 2Fc^2)/3
2976 reflections	(Δ/σ)max < 0.001
256 parameters	Δρmax = 0.32 e Å^−3
0 restraints	Δρmin = −0.28 e Å^−3

Special details

Experimental. A suitable crystal was mounted in a loop with paratone-N and transferred immediately to the goniostat bathed in a cold stream.

Our standard practice is to collect a full sphere of data out to a theta angle of 67° (0.83 Å resolution).

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

H1 involved in H-bonding (N1—H1···O2) was located directly from the difference map and the coordinates refined. U_iso(H1)=1.2U_eq(N1).

All C-bound H atoms were calculated based on geometric criteria, and treated with a riding model.

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

	x	y	z	Uiso*/Ueq
N1	0.82129 (19)	0.37096 (14)	0.24790 (13)	0.0278 (3)
H1	0.801 (3)	0.444 (2)	0.2719 (19)	0.033*
N2	0.75786 (18)	0.48085 (13)	0.48577 (12)	0.0263 (3)
C1	0.8476 (2)	0.32438 (17)	0.12979 (16)	0.0320 (4)
H1A	0.8439	0.3771	0.0732	0.038*
C2	0.8804 (2)	0.19852 (18)	0.08934 (17)	0.0354 (4)
H2A	0.8968	0.1638	0.0046	0.042*
C3	0.8890 (2)	0.12466 (17)	0.17333 (17)	0.0337 (4)
H3A	0.9116	0.0386	0.1462	0.040*
C4	0.8646 (2)	0.17512 (16)	0.29892 (16)	0.0289 (4)
C5	0.8277 (2)	0.30197 (16)	0.33458 (15)	0.0265 (3)
C6	0.8778 (2)	0.10544 (17)	0.39261 (17)	0.0323 (4)
H6A	0.9027	0.0197	0.3703	0.039*
C7	0.8553 (2)	0.16056 (17)	0.51205 (17)	0.0324 (4)
H7A	0.8684	0.1139	0.5732	0.039*
C8	0.8121 (2)	0.28787 (17)	0.54848 (16)	0.0288 (4)
C9	0.7979 (2)	0.36027 (16)	0.46050 (15)	0.0258 (3)
C10	0.7793 (2)	0.34725 (17)	0.67040 (16)	0.0316 (4)
H10A	0.7877	0.3034	0.7342	0.038*
C11	0.7354 (2)	0.46834 (17)	0.69647 (16)	0.0311 (4)
H11A	0.7110	0.5080	0.7780	0.037*
C12	0.7264 (2)	0.53452 (16)	0.60124 (15)	0.0266 (3)
C13	0.6835 (2)	0.66778 (16)	0.62633 (15)	0.0272 (4)
C14	0.6588 (2)	0.73704 (18)	0.74594 (16)	0.0342 (4)
H14A	0.6665	0.6981	0.8134	0.041*
C15	0.6233 (3)	0.86216 (19)	0.76683 (17)	0.0385 (4)
H15A	0.6072	0.9085	0.8486	0.046*
C16	0.6112 (2)	0.92001 (18)	0.66934 (17)	0.0362 (4)
H16A	0.5878	1.0061	0.6841	0.043*
C17	0.6335 (2)	0.85149 (17)	0.54991 (17)	0.0342 (4)
H17A	0.6237	0.8905	0.4826	0.041*
C18	0.6698 (2)	0.72677 (16)	0.52804 (15)	0.0296 (4)
H18A	0.6854	0.6809	0.4460	0.035*
S1	0.81504 (5)	0.69060 (4)	0.14034 (4)	0.02846 (15)
O1	0.82534 (18)	0.61105 (12)	0.01695 (12)	0.0398 (3)
F1	0.60625 (17)	0.82031 (13)	0.04384 (11)	0.0519 (3)
F2	0.57104 (16)	0.81289 (12)	0.23124 (11)	0.0504 (3)
F3	0.46595 (16)	0.64175 (12)	0.07531 (12)	0.0553 (3)
O2	0.78871 (19)	0.61981 (13)	0.23348 (12)	0.0413 (3)
O3	0.94529 (17)	0.81352 (12)	0.18409 (11)	0.0367 (3)
C19	0.6034 (2)	0.74334 (18)	0.12102 (16)	0.0340 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0312 (7)	0.0241 (7)	0.0291 (7)	0.0070 (6)	0.0066 (6)	0.0079 (6)
N2	0.0253 (7)	0.0263 (7)	0.0271 (7)	0.0034 (5)	0.0035 (5)	0.0085 (5)
C1	0.0349 (9)	0.0332 (9)	0.0294 (8)	0.0061 (7)	0.0076 (7)	0.0111 (7)
C2	0.0404 (10)	0.0340 (10)	0.0312 (9)	0.0080 (7)	0.0115 (7)	0.0057 (7)
C3	0.0319 (9)	0.0276 (9)	0.0407 (10)	0.0072 (7)	0.0089 (7)	0.0061 (7)
C4	0.0238 (8)	0.0279 (9)	0.0348 (9)	0.0053 (6)	0.0046 (7)	0.0089 (7)
C5	0.0224 (8)	0.0266 (8)	0.0305 (8)	0.0029 (6)	0.0030 (6)	0.0102 (6)
C6	0.0300 (9)	0.0265 (9)	0.0432 (10)	0.0084 (7)	0.0056 (7)	0.0133 (7)
C7	0.0311 (9)	0.0321 (9)	0.0378 (9)	0.0075 (7)	0.0030 (7)	0.0168 (7)
C8	0.0247 (8)	0.0295 (9)	0.0326 (9)	0.0036 (6)	0.0012 (6)	0.0123 (7)
C9	0.0229 (8)	0.0245 (8)	0.0290 (8)	0.0021 (6)	0.0025 (6)	0.0084 (6)
C10	0.0330 (9)	0.0352 (10)	0.0290 (8)	0.0062 (7)	0.0024 (7)	0.0149 (7)
C11	0.0332 (9)	0.0338 (9)	0.0258 (8)	0.0052 (7)	0.0036 (7)	0.0090 (7)
C12	0.0236 (8)	0.0274 (9)	0.0266 (8)	0.0022 (6)	0.0017 (6)	0.0068 (6)
C13	0.0238 (8)	0.0274 (9)	0.0282 (8)	0.0026 (6)	0.0031 (6)	0.0062 (6)
C14	0.0402 (10)	0.0348 (10)	0.0287 (9)	0.0095 (7)	0.0067 (7)	0.0094 (7)
C15	0.0458 (10)	0.0379 (10)	0.0313 (9)	0.0123 (8)	0.0104 (8)	0.0046 (7)
C16	0.0390 (10)	0.0277 (9)	0.0425 (10)	0.0114 (7)	0.0090 (8)	0.0067 (7)
C17	0.0366 (9)	0.0318 (9)	0.0354 (9)	0.0066 (7)	0.0057 (7)	0.0117 (7)
C18	0.0313 (9)	0.0288 (9)	0.0269 (8)	0.0047 (7)	0.0042 (7)	0.0061 (6)
S1	0.0371 (2)	0.0252 (2)	0.0251 (2)	0.00996 (17)	0.00670 (16)	0.00760 (16)
O1	0.0496 (8)	0.0348 (7)	0.0342 (7)	0.0107 (6)	0.0146 (6)	0.0041 (5)
F1	0.0618 (8)	0.0588 (8)	0.0487 (7)	0.0256 (6)	0.0063 (6)	0.0311 (6)
F2	0.0560 (7)	0.0569 (7)	0.0433 (7)	0.0290 (6)	0.0176 (5)	0.0073 (5)
F3	0.0392 (6)	0.0509 (7)	0.0676 (8)	0.0025 (5)	−0.0008 (6)	0.0102 (6)
O2	0.0588 (8)	0.0378 (7)	0.0389 (7)	0.0212 (6)	0.0144 (6)	0.0212 (6)
O3	0.0397 (7)	0.0318 (7)	0.0367 (7)	0.0066 (5)	0.0032 (5)	0.0080 (5)
C19	0.0379 (10)	0.0342 (10)	0.0319 (9)	0.0105 (7)	0.0057 (7)	0.0111 (7)

Geometric parameters (Å, º)

N1—C1	1.329 (2)	C11—C12	1.421 (2)
N1—C5	1.360 (2)	C11—H11A	0.9500
N1—H1	0.81 (2)	C12—C13	1.490 (2)
N2—C12	1.331 (2)	C13—C14	1.397 (2)
N2—C9	1.351 (2)	C13—C18	1.401 (2)
C1—C2	1.389 (2)	C14—C15	1.386 (3)
C1—H1A	0.9500	C14—H14A	0.9500
C2—C3	1.376 (3)	C15—C16	1.384 (3)
C2—H2A	0.9500	C15—H15A	0.9500
C3—C4	1.407 (2)	C16—C17	1.387 (2)
C3—H3A	0.9500	C16—H16A	0.9500
C4—C5	1.407 (2)	C17—C18	1.383 (2)
C4—C6	1.436 (2)	C17—H17A	0.9500
C5—C9	1.439 (2)	C18—H18A	0.9500
C6—C7	1.350 (2)	S1—O1	1.4366 (12)
C6—H6A	0.9500	S1—O3	1.4404 (13)
C7—C8	1.432 (2)	S1—O2	1.4425 (13)
C7—H7A	0.9500	S1—C19	1.8238 (19)
C8—C9	1.405 (2)	F1—C19	1.335 (2)
C8—C10	1.411 (2)	F2—C19	1.334 (2)
C10—C11	1.369 (2)	F3—C19	1.324 (2)
C10—H10A	0.9500
C1—N1—C5	123.25 (15)	C10—C11—H11A	120.1
C1—N1—H1	120.3 (15)	C12—C11—H11A	120.1
C5—N1—H1	116.4 (15)	N2—C12—C11	121.48 (15)
C12—N2—C9	118.16 (14)	N2—C12—C13	116.88 (14)
N1—C1—C2	119.86 (16)	C11—C12—C13	121.64 (14)
N1—C1—H1A	120.1	C14—C13—C18	118.69 (15)
C2—C1—H1A	120.1	C14—C13—C12	121.89 (15)
C3—C2—C1	119.26 (16)	C18—C13—C12	119.42 (14)
C3—C2—H2A	120.4	C15—C14—C13	120.46 (16)
C1—C2—H2A	120.4	C15—C14—H14A	119.8
C2—C3—C4	120.78 (16)	C13—C14—H14A	119.8
C2—C3—H3A	119.6	C16—C15—C14	120.44 (16)
C4—C3—H3A	119.6	C16—C15—H15A	119.8
C3—C4—C5	117.80 (15)	C14—C15—H15A	119.8
C3—C4—C6	123.76 (15)	C15—C16—C17	119.56 (16)
C5—C4—C6	118.44 (15)	C15—C16—H16A	120.2
N1—C5—C4	119.02 (15)	C17—C16—H16A	120.2
N1—C5—C9	119.48 (15)	C18—C17—C16	120.52 (16)
C4—C5—C9	121.50 (15)	C18—C17—H17A	119.7
C7—C6—C4	120.67 (15)	C16—C17—H17A	119.7
C7—C6—H6A	119.7	C17—C18—C13	120.33 (15)
C4—C6—H6A	119.7	C17—C18—H18A	119.8
C6—C7—C8	121.38 (16)	C13—C18—H18A	119.8
C6—C7—H7A	119.3	O1—S1—O3	115.13 (8)
C8—C7—H7A	119.3	O1—S1—O2	115.22 (8)
C9—C8—C10	116.17 (15)	O3—S1—O2	114.60 (8)
C9—C8—C7	120.19 (15)	O1—S1—C19	104.23 (8)
C10—C8—C7	123.63 (15)	O3—S1—C19	102.96 (8)
N2—C9—C8	124.57 (15)	O2—S1—C19	102.26 (8)
N2—C9—C5	117.66 (14)	F3—C19—F2	107.36 (15)
C8—C9—C5	117.76 (15)	F3—C19—F1	108.06 (15)
C11—C10—C8	119.77 (15)	F2—C19—F1	107.10 (14)
C11—C10—H10A	120.1	F3—C19—S1	111.83 (13)
C8—C10—H10A	120.1	F2—C19—S1	110.79 (12)
C10—C11—C12	119.82 (15)	F1—C19—S1	111.48 (12)
C5—N1—C1—C2	1.2 (3)	C4—C5—C9—N2	−178.00 (14)
N1—C1—C2—C3	−1.3 (3)	N1—C5—C9—C8	−177.74 (14)
C1—C2—C3—C4	0.1 (3)	C4—C5—C9—C8	1.9 (2)
C2—C3—C4—C5	1.3 (2)	C9—C8—C10—C11	0.4 (2)
C2—C3—C4—C6	−177.75 (16)	C7—C8—C10—C11	−178.73 (16)
C1—N1—C5—C4	0.2 (2)	C8—C10—C11—C12	−1.2 (2)
C1—N1—C5—C9	179.88 (14)	C9—N2—C12—C11	0.4 (2)
C3—C4—C5—N1	−1.4 (2)	C9—N2—C12—C13	179.70 (14)
C6—C4—C5—N1	177.62 (14)	C10—C11—C12—N2	0.8 (2)
C3—C4—C5—C9	178.93 (14)	C10—C11—C12—C13	−178.47 (15)
C6—C4—C5—C9	−2.0 (2)	N2—C12—C13—C14	−176.04 (14)
C3—C4—C6—C7	179.05 (15)	C11—C12—C13—C14	3.2 (2)
C5—C4—C6—C7	0.0 (2)	N2—C12—C13—C18	3.1 (2)
C4—C6—C7—C8	2.0 (3)	C11—C12—C13—C18	−177.67 (15)
C6—C7—C8—C9	−2.1 (3)	C18—C13—C14—C15	−0.7 (3)
C6—C7—C8—C10	177.06 (16)	C12—C13—C14—C15	178.46 (16)
C12—N2—C9—C8	−1.3 (2)	C13—C14—C15—C16	0.2 (3)
C12—N2—C9—C5	178.63 (13)	C14—C15—C16—C17	0.5 (3)
C10—C8—C9—N2	0.8 (2)	C15—C16—C17—C18	−0.8 (3)
C7—C8—C9—N2	−179.99 (15)	C16—C17—C18—C13	0.3 (3)
C10—C8—C9—C5	−179.07 (13)	C14—C13—C18—C17	0.4 (2)
C7—C8—C9—C5	0.1 (2)	C12—C13—C18—C17	−178.77 (15)
N1—C5—C9—N2	2.4 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	0.81 (2)	2.06 (2)	2.773 (2)	147 (2)

(IV) 2-Phenyl-1,10-phenanthrolin-1-ium tetrachloridoaurate(III)

Crystal data

(C18H13N2)[AuCl4]	F(000) = 2256
Mr = 596.07	Dx = 2.142 Mg m^−3
Monoclinic, C2/c	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -C 2yc	Cell parameters from 9263 reflections
a = 14.7934 (3) Å	θ = 3.8–67.6°
b = 10.7307 (3) Å	µ = 20.31 mm^−1
c = 23.3067 (5) Å	T = 150 K
β = 92.593 (2)°	Blade, golden-yellow
V = 3696.00 (15) Å^3	0.13 × 0.04 × 0.01 mm
Z = 8

Data collection

Bruker SMART6000 CCD diffractometer	3259 independent reflections
Radiation source: fine-focus sealed tube	2946 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.042
ω scans	θmax = 67.8°, θmin = 3.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a)	h = −17→17
Tmin = 0.178, Tmax = 0.823	k = −12→12
15346 measured reflections	l = −27→27

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)] = 0.025	Hydrogen site location: mixed
wR(F^2) = 0.066	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0412P)^2 + 2.1988P] where P = (Fo^2 + 2Fc^2)/3
3259 reflections	(Δ/σ)max = 0.001
229 parameters	Δρmax = 1.12 e Å^−3
0 restraints	Δρmin = −0.58 e Å^−3

Special details

Experimental. A suitable crystal was mounted in a loop with paratone-N and transferred immediately to the goniostat bathed in a cold stream.

Our standard practice is to collect a full sphere of data out to a theta angle of 67° (0.83 Å resolution).

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

H1 involved in H-bonding (N1—H1···F1) was located directly from the difference map and the coordinates refined. U_iso(H1)=1.2U_eq(N1).

All C-bound H atoms were calculated based on geometric criteria, and treated with a riding model.

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

	x	y	z	Uiso*/Ueq
Au	0.171156 (10)	−0.031329 (16)	0.375453 (7)	0.02849 (8)
Cl1	0.23443 (6)	−0.16649 (10)	0.44143 (4)	0.0340 (2)
Cl2	0.09533 (7)	0.06282 (12)	0.44699 (5)	0.0401 (3)
Cl3	0.10036 (7)	0.09831 (12)	0.30966 (5)	0.0445 (3)
Cl4	0.25302 (8)	−0.11992 (11)	0.30562 (4)	0.0408 (3)
N1	0.2199 (2)	0.0036 (4)	0.56608 (16)	0.0317 (8)
H1	0.222 (3)	0.031 (4)	0.524 (2)	0.038*
N2	0.3654 (2)	0.1073 (3)	0.51642 (14)	0.0270 (7)
C1	0.1443 (3)	−0.0428 (4)	0.5871 (2)	0.0342 (10)
H1A	0.0913	−0.0518	0.5629	0.041*
C2	0.1435 (3)	−0.0777 (5)	0.6445 (2)	0.0390 (10)
H2A	0.0898	−0.1096	0.6599	0.047*
C3	0.2210 (3)	−0.0658 (4)	0.67873 (19)	0.0377 (10)
H3A	0.2210	−0.0912	0.7178	0.045*
C4	0.3003 (3)	−0.0166 (4)	0.6567 (2)	0.0324 (9)
C5	0.2982 (3)	0.0186 (4)	0.59833 (18)	0.0285 (9)
C6	0.3827 (3)	0.0024 (5)	0.6904 (2)	0.0400 (11)
H6A	0.3859	−0.0201	0.7298	0.048*
C7	0.4561 (3)	0.0522 (4)	0.6663 (2)	0.0371 (10)
H7A	0.5101	0.0640	0.6893	0.045*
C8	0.4546 (3)	0.0873 (4)	0.60755 (18)	0.0304 (9)
C9	0.3747 (3)	0.0735 (4)	0.57280 (17)	0.0279 (8)
C10	0.5294 (3)	0.1369 (4)	0.57954 (19)	0.0347 (10)
H10A	0.5858	0.1468	0.6002	0.042*
C11	0.5211 (3)	0.1706 (4)	0.52304 (18)	0.0319 (9)
H11A	0.5717	0.2038	0.5045	0.038*
C12	0.4372 (3)	0.1562 (4)	0.49207 (17)	0.0278 (8)
C13	0.4250 (3)	0.1951 (4)	0.43142 (17)	0.0295 (9)
C14	0.4979 (3)	0.2270 (4)	0.39810 (19)	0.0360 (10)
H14A	0.5576	0.2233	0.4148	0.043*
C15	0.4850 (3)	0.2637 (5)	0.3412 (2)	0.0434 (11)
H15A	0.5355	0.2852	0.3195	0.052*
C16	0.3983 (3)	0.2692 (4)	0.31605 (19)	0.0403 (11)
H16A	0.3891	0.2950	0.2772	0.048*
C17	0.3257 (3)	0.2368 (4)	0.34779 (19)	0.0389 (10)
H17A	0.2665	0.2386	0.3303	0.047*
C18	0.3376 (3)	0.2015 (4)	0.40493 (18)	0.0339 (9)
H18A	0.2864	0.1815	0.4263	0.041*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Au	0.02213 (11)	0.03765 (13)	0.02557 (11)	0.00113 (6)	−0.00035 (7)	−0.00189 (6)
Cl1	0.0273 (5)	0.0455 (6)	0.0292 (5)	0.0044 (4)	0.0002 (4)	0.0030 (4)
Cl2	0.0299 (5)	0.0564 (7)	0.0342 (5)	0.0101 (5)	0.0022 (4)	−0.0091 (5)
Cl3	0.0341 (5)	0.0610 (7)	0.0383 (5)	0.0116 (5)	−0.0006 (5)	0.0119 (5)
Cl4	0.0442 (6)	0.0517 (7)	0.0271 (5)	0.0107 (5)	0.0062 (5)	−0.0022 (4)
N1	0.0277 (19)	0.040 (2)	0.0275 (19)	−0.0021 (16)	0.0031 (16)	−0.0039 (15)
N2	0.0237 (16)	0.0301 (18)	0.0274 (16)	0.0002 (13)	0.0022 (14)	−0.0052 (14)
C1	0.023 (2)	0.046 (3)	0.035 (2)	−0.0039 (17)	0.0041 (19)	−0.0069 (18)
C2	0.035 (2)	0.040 (3)	0.043 (2)	−0.007 (2)	0.013 (2)	−0.003 (2)
C3	0.046 (3)	0.038 (2)	0.030 (2)	0.000 (2)	0.010 (2)	−0.0061 (18)
C4	0.032 (2)	0.033 (2)	0.032 (2)	0.0051 (18)	0.0045 (19)	−0.0058 (18)
C5	0.026 (2)	0.032 (2)	0.028 (2)	0.0032 (16)	0.0031 (18)	−0.0055 (16)
C6	0.045 (3)	0.046 (3)	0.028 (2)	0.003 (2)	−0.001 (2)	−0.002 (2)
C7	0.030 (2)	0.048 (3)	0.032 (2)	0.0012 (19)	−0.007 (2)	−0.0036 (19)
C8	0.027 (2)	0.029 (2)	0.035 (2)	0.0053 (17)	0.0000 (18)	−0.0051 (18)
C9	0.025 (2)	0.029 (2)	0.030 (2)	0.0018 (17)	0.0006 (17)	−0.0062 (17)
C10	0.0199 (19)	0.045 (3)	0.039 (2)	0.0031 (18)	−0.0050 (18)	−0.005 (2)
C11	0.0193 (19)	0.037 (2)	0.040 (2)	0.0007 (17)	0.0046 (18)	−0.0035 (18)
C12	0.0214 (19)	0.028 (2)	0.034 (2)	0.0013 (16)	0.0036 (17)	−0.0064 (17)
C13	0.025 (2)	0.032 (2)	0.031 (2)	−0.0032 (16)	0.0002 (17)	−0.0041 (17)
C14	0.027 (2)	0.041 (3)	0.040 (2)	−0.0049 (18)	0.0040 (19)	0.001 (2)
C15	0.043 (3)	0.049 (3)	0.039 (2)	−0.008 (2)	0.013 (2)	0.001 (2)
C16	0.053 (3)	0.036 (3)	0.033 (2)	−0.005 (2)	0.006 (2)	0.0008 (19)
C17	0.038 (2)	0.040 (3)	0.037 (2)	−0.004 (2)	−0.007 (2)	0.004 (2)
C18	0.030 (2)	0.036 (2)	0.035 (2)	−0.0042 (18)	0.0031 (19)	−0.0006 (18)

Geometric parameters (Å, º)

Au—Cl4	2.2800 (10)	C7—C8	1.419 (6)
Au—Cl1	2.2834 (10)	C7—H7A	0.9500
Au—Cl2	2.2865 (10)	C8—C9	1.410 (6)
Au—Cl3	2.2887 (11)	C8—C10	1.414 (6)
N1—C1	1.337 (6)	C10—C11	1.366 (6)
N1—C5	1.362 (6)	C10—H10A	0.9500
N1—H1	1.02 (5)	C11—C12	1.417 (6)
N2—C12	1.333 (5)	C11—H11A	0.9500
N2—C9	1.364 (5)	C12—C13	1.477 (6)
C1—C2	1.390 (7)	C13—C14	1.400 (6)
C1—H1A	0.9500	C13—C18	1.409 (6)
C2—C3	1.373 (7)	C14—C15	1.389 (6)
C2—H2A	0.9500	C14—H14A	0.9500
C3—C4	1.405 (7)	C15—C16	1.387 (7)
C3—H3A	0.9500	C15—H15A	0.9500
C4—C5	1.410 (6)	C16—C17	1.376 (7)
C4—C6	1.435 (7)	C16—H16A	0.9500
C5—C9	1.429 (6)	C17—C18	1.388 (6)
C6—C7	1.355 (7)	C17—H17A	0.9500
C6—H6A	0.9500	C18—H18A	0.9500
Cl4—Au—Cl1	90.06 (4)	C9—C8—C7	120.2 (4)
Cl4—Au—Cl2	177.17 (4)	C10—C8—C7	124.5 (4)
Cl1—Au—Cl2	89.39 (4)	N2—C9—C8	124.8 (4)
Cl4—Au—Cl3	90.97 (4)	N2—C9—C5	117.6 (4)
Cl1—Au—Cl3	176.84 (4)	C8—C9—C5	117.6 (4)
Cl2—Au—Cl3	89.73 (4)	C11—C10—C8	120.5 (4)
C1—N1—C5	123.1 (4)	C11—C10—H10A	119.8
C1—N1—H1	121 (3)	C8—C10—H10A	119.8
C5—N1—H1	116 (3)	C10—C11—C12	120.0 (4)
C12—N2—C9	117.9 (3)	C10—C11—H11A	120.0
N1—C1—C2	119.8 (4)	C12—C11—H11A	120.0
N1—C1—H1A	120.1	N2—C12—C11	121.5 (4)
C2—C1—H1A	120.1	N2—C12—C13	117.0 (3)
C3—C2—C1	119.4 (4)	C11—C12—C13	121.5 (4)
C3—C2—H2A	120.3	C14—C13—C18	117.4 (4)
C1—C2—H2A	120.3	C14—C13—C12	122.4 (4)
C2—C3—C4	120.8 (4)	C18—C13—C12	120.2 (4)
C2—C3—H3A	119.6	C15—C14—C13	121.5 (4)
C4—C3—H3A	119.6	C15—C14—H14A	119.2
C3—C4—C5	118.1 (4)	C13—C14—H14A	119.2
C3—C4—C6	123.8 (4)	C16—C15—C14	120.0 (4)
C5—C4—C6	118.1 (4)	C16—C15—H15A	120.0
N1—C5—C4	118.8 (4)	C14—C15—H15A	120.0
N1—C5—C9	119.3 (4)	C17—C16—C15	119.4 (4)
C4—C5—C9	121.9 (4)	C17—C16—H16A	120.3
C7—C6—C4	120.4 (4)	C15—C16—H16A	120.3
C7—C6—H6A	119.8	C16—C17—C18	121.2 (4)
C4—C6—H6A	119.8	C16—C17—H17A	119.4
C6—C7—C8	121.7 (4)	C18—C17—H17A	119.4
C6—C7—H7A	119.1	C17—C18—C13	120.5 (4)
C8—C7—H7A	119.1	C17—C18—H18A	119.8
C9—C8—C10	115.3 (4)	C13—C18—H18A	119.8
C5—N1—C1—C2	0.2 (7)	C4—C5—C9—N2	−178.4 (4)
N1—C1—C2—C3	−0.9 (7)	N1—C5—C9—C8	−179.9 (4)
C1—C2—C3—C4	1.3 (7)	C4—C5—C9—C8	2.4 (6)
C2—C3—C4—C5	−0.8 (7)	C9—C8—C10—C11	1.5 (6)
C2—C3—C4—C6	177.9 (5)	C7—C8—C10—C11	−178.6 (4)
C1—N1—C5—C4	0.2 (6)	C8—C10—C11—C12	0.1 (7)
C1—N1—C5—C9	−177.5 (4)	C9—N2—C12—C11	1.2 (6)
C3—C4—C5—N1	0.1 (6)	C9—N2—C12—C13	−178.5 (4)
C6—C4—C5—N1	−178.7 (4)	C10—C11—C12—N2	−1.5 (6)
C3—C4—C5—C9	177.8 (4)	C10—C11—C12—C13	178.1 (4)
C6—C4—C5—C9	−1.0 (6)	N2—C12—C13—C14	−168.5 (4)
C3—C4—C6—C7	−179.0 (5)	C11—C12—C13—C14	11.8 (7)
C5—C4—C6—C7	−0.3 (7)	N2—C12—C13—C18	11.5 (6)
C4—C6—C7—C8	0.0 (7)	C11—C12—C13—C18	−168.1 (4)
C6—C7—C8—C9	1.5 (7)	C18—C13—C14—C15	0.2 (7)
C6—C7—C8—C10	−178.4 (4)	C12—C13—C14—C15	−179.8 (4)
C12—N2—C9—C8	0.5 (6)	C13—C14—C15—C16	−0.2 (8)
C12—N2—C9—C5	−178.6 (4)	C14—C15—C16—C17	−0.6 (7)
C10—C8—C9—N2	−1.9 (6)	C15—C16—C17—C18	1.5 (7)
C7—C8—C9—N2	178.2 (4)	C16—C17—C18—C13	−1.6 (7)
C10—C8—C9—C5	177.3 (4)	C14—C13—C18—C17	0.7 (6)
C7—C8—C9—C5	−2.6 (6)	C12—C13—C18—C17	−179.3 (4)
N1—C5—C9—N2	−0.7 (6)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl2	1.02 (5)	2.56 (5)	3.323 (4)	131 (4)

(V) 2-Phenyl-1,10-phenanthrolin-1-ium bromide dihydrate

Crystal data

C18H13N2^+·Br^−·2H2O	F(000) = 760
Mr = 373.25	Dx = 1.547 Mg m^−3
Monoclinic, P21/n	Synchrotron radiation, λ = 0.77490 Å
Hall symbol: -P 2yn	Cell parameters from 4500 reflections
a = 7.2285 (11) Å	θ = 3.0–28.7°
b = 19.897 (3) Å	µ = 3.17 mm^−1
c = 11.2322 (16) Å	T = 150 K
β = 97.283 (2)°	Block, colorless
V = 1602.4 (4) Å^3	0.04 × 0.03 × 0.03 mm
Z = 4

Data collection

Bruker APEXII diffractometer	2828 independent reflections
Radiation source: synchrotron	2518 reflections with I > 2σ(I)
Si-<111> channel cut crystal monochromator	Rint = 0.046
ω scans	θmax = 27.5°, θmin = 3.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a)	h = −8→8
Tmin = 0.884, Tmax = 0.911	k = −23→23
15887 measured reflections	l = −13→13

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)] = 0.062	Hydrogen site location: mixed
wR(F^2) = 0.132	H atoms treated by a mixture of independent and constrained refinement
S = 1.17	w = 1/[σ^2(Fo^2) + (0.0061P)^2 + 9.1211P] where P = (Fo^2 + 2Fc^2)/3
2828 reflections	(Δ/σ)max < 0.001
223 parameters	Δρmax = 1.37 e Å^−3
0 restraints	Δρmin = −0.59 e Å^−3

Special details

Experimental. Marginal quality crystals obtained from acetonitrile-diethyl ether.

A suitable crystal was mounted in a loop with paratone-N and transferred immediately to the goniostat bathed in a cold stream.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Data resolution to 0.84 Å in refinement.

Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

H1 and the water H-atoms were located directly from the difference map and the coordinates refined. U_iso(H1)=1.2U_eq(N1), U_iso(H_solvent)=1.5U_eq(O)

All C-bound H atoms were calculated based on geometric criteria, and treated with a riding model.

_vrf_PLAT926_V Reported and Calculated R1 Differ by ········· -0.0176 _vrf_PLAT927_V Reported and Calculated wR2 Differ by ········· -0.0329 _vrf_PLAT928_V Reported and Calculated S value Differ by. -0.290 RESPONSE: For each of the above listed alerts, the issue lies with checkcif incorrectly interpreting the wavelength of the experiment even though it is correctly identified in the CIF. When one uses incorrect Mo Kα radiation (λ = 0.71073 Å) instead of the correct wavelength of 0.77490 Å in the refinement, the alert goes away.

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

	x	y	z	Uiso*/Ueq
N1	0.6028 (6)	−0.0548 (3)	0.3217 (4)	0.0360 (11)
H1	0.608 (8)	−0.005 (3)	0.298 (5)	0.043*
N2	0.7587 (6)	0.0284 (2)	0.5004 (4)	0.0278 (10)
C1	0.5233 (7)	−0.0912 (3)	0.2314 (5)	0.0336 (12)
H1A	0.4805	−0.0707	0.1566	0.040*
C2	0.5028 (8)	−0.1607 (3)	0.2473 (6)	0.0433 (15)
H2A	0.4425	−0.1869	0.1831	0.052*
C3	0.5676 (8)	−0.1912 (3)	0.3530 (6)	0.0446 (15)
H3A	0.5569	−0.2385	0.3622	0.054*
C4	0.6501 (7)	−0.1513 (3)	0.4474 (5)	0.0335 (13)
C5	0.6693 (7)	−0.0825 (3)	0.4349 (5)	0.0279 (11)
C6	0.7218 (8)	−0.1812 (3)	0.5658 (6)	0.0403 (14)
H6A	0.7107	−0.2281	0.5796	0.048*
C7	0.8024 (7)	−0.1405 (3)	0.6525 (5)	0.0316 (12)
H7A	0.8479	−0.1590	0.7286	0.038*
C8	0.8210 (8)	−0.0707 (3)	0.6333 (5)	0.0370 (13)
C9	0.7531 (7)	−0.0393 (3)	0.5258 (5)	0.0306 (12)
C10	0.9131 (8)	−0.0247 (3)	0.7278 (5)	0.0412 (14)
H10A	0.9652	−0.0418	0.8036	0.049*
C11	0.9209 (8)	0.0406 (3)	0.7042 (5)	0.0401 (14)
H11A	0.9794	0.0701	0.7639	0.048*
C12	0.8437 (7)	0.0670 (3)	0.5917 (5)	0.0331 (12)
C13	0.8487 (7)	0.1413 (3)	0.5652 (5)	0.0338 (13)
C14	0.9224 (8)	0.1877 (3)	0.6532 (5)	0.0390 (14)
H14A	0.9744	0.1724	0.7304	0.047*
C15	0.9189 (8)	0.2563 (3)	0.6270 (6)	0.0417 (14)
H15A	0.9675	0.2879	0.6862	0.050*
C16	0.8439 (8)	0.2776 (3)	0.5141 (6)	0.0425 (14)
H16A	0.8429	0.3241	0.4949	0.051*
C17	0.7701 (8)	0.2314 (3)	0.4290 (6)	0.0429 (14)
H17A	0.7160	0.2469	0.3524	0.052*
C18	0.7735 (8)	0.1632 (3)	0.4528 (5)	0.0370 (13)
H18A	0.7249	0.1320	0.3929	0.044*
Br1	0.86250 (8)	0.12250 (3)	0.00993 (6)	0.0403 (2)
O1W	0.5609 (7)	0.0664 (2)	0.2021 (4)	0.0446 (10)
H1W	0.454 (11)	0.062 (4)	0.140 (7)	0.067*
H2W	0.655 (11)	0.082 (4)	0.164 (7)	0.067*
O2W	0.2722 (6)	0.0428 (2)	0.0064 (4)	0.0445 (11)
H3W	0.246 (10)	0.003 (4)	0.018 (7)	0.067*
H4W	0.181 (11)	0.064 (4)	−0.016 (7)	0.067*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.028 (2)	0.046 (3)	0.034 (3)	0.001 (2)	0.003 (2)	−0.002 (2)
N2	0.024 (2)	0.028 (2)	0.033 (2)	−0.0011 (18)	0.0095 (18)	−0.0060 (19)
C1	0.028 (3)	0.045 (3)	0.029 (3)	0.001 (2)	0.003 (2)	−0.004 (2)
C2	0.036 (3)	0.048 (4)	0.047 (4)	0.002 (3)	0.009 (3)	0.005 (3)
C3	0.038 (3)	0.034 (3)	0.063 (4)	−0.001 (3)	0.016 (3)	−0.006 (3)
C4	0.023 (3)	0.032 (3)	0.048 (3)	−0.002 (2)	0.014 (2)	−0.006 (2)
C5	0.021 (2)	0.027 (3)	0.038 (3)	0.003 (2)	0.010 (2)	0.002 (2)
C6	0.032 (3)	0.040 (3)	0.050 (4)	0.006 (3)	0.010 (3)	0.002 (3)
C7	0.035 (3)	0.033 (3)	0.026 (3)	0.004 (2)	0.002 (2)	0.011 (2)
C8	0.035 (3)	0.041 (3)	0.037 (3)	0.013 (3)	0.014 (3)	0.015 (3)
C9	0.024 (3)	0.038 (3)	0.030 (3)	0.003 (2)	0.005 (2)	0.003 (2)
C10	0.035 (3)	0.052 (4)	0.038 (3)	0.007 (3)	0.007 (3)	0.016 (3)
C11	0.037 (3)	0.047 (4)	0.035 (3)	−0.002 (3)	0.001 (3)	−0.007 (3)
C12	0.031 (3)	0.040 (3)	0.029 (3)	0.002 (2)	0.007 (2)	0.003 (2)
C13	0.027 (3)	0.025 (3)	0.054 (4)	0.000 (2)	0.018 (3)	−0.008 (2)
C14	0.037 (3)	0.041 (3)	0.039 (3)	0.003 (3)	0.008 (3)	−0.002 (3)
C15	0.039 (3)	0.034 (3)	0.053 (4)	−0.004 (3)	0.011 (3)	−0.016 (3)
C16	0.039 (3)	0.026 (3)	0.062 (4)	0.003 (2)	0.006 (3)	−0.003 (3)
C17	0.039 (3)	0.039 (3)	0.049 (4)	−0.001 (3)	0.002 (3)	0.000 (3)
C18	0.033 (3)	0.036 (3)	0.042 (3)	−0.005 (2)	0.007 (3)	−0.008 (3)
Br1	0.0375 (3)	0.0304 (3)	0.0509 (4)	0.0003 (3)	−0.0025 (2)	0.0069 (3)
O1W	0.048 (3)	0.045 (3)	0.042 (3)	−0.004 (2)	0.008 (2)	−0.001 (2)
O2W	0.043 (2)	0.036 (2)	0.055 (3)	−0.001 (2)	0.008 (2)	−0.002 (2)

Geometric parameters (Å, º)

N1—C1	1.317 (7)	C10—C11	1.328 (8)
N1—C5	1.412 (7)	C10—H10A	0.9500
N1—H1	1.03 (6)	C11—C12	1.417 (8)
N2—C12	1.364 (7)	C11—H11A	0.9500
N2—C9	1.379 (7)	C12—C13	1.510 (8)
C1—C2	1.405 (8)	C13—C18	1.380 (8)
C1—H1A	0.9500	C13—C14	1.407 (8)
C2—C3	1.363 (9)	C14—C15	1.395 (8)
C2—H2A	0.9500	C14—H14A	0.9500
C3—C4	1.397 (8)	C15—C16	1.381 (9)
C3—H3A	0.9500	C15—H15A	0.9500
C4—C5	1.384 (7)	C16—C17	1.384 (8)
C4—C6	1.489 (8)	C16—H16A	0.9500
C5—C9	1.410 (7)	C17—C18	1.382 (8)
C6—C7	1.343 (8)	C17—H17A	0.9500
C6—H6A	0.9500	C18—H18A	0.9500
C7—C8	1.415 (8)	O1W—H1W	0.98 (8)
C7—H7A	0.9500	O1W—H2W	0.90 (8)
C8—C9	1.392 (7)	O2W—H3W	0.83 (8)
C8—C10	1.493 (9)	O2W—H4W	0.79 (8)
C1—N1—C5	123.0 (5)	C8—C9—C5	115.3 (5)
C1—N1—H1	111 (3)	C11—C10—C8	118.9 (5)
C5—N1—H1	126 (3)	C11—C10—H10A	120.5
C12—N2—C9	114.7 (5)	C8—C10—H10A	120.5
N1—C1—C2	119.1 (6)	C10—C11—C12	121.3 (6)
N1—C1—H1A	120.5	C10—C11—H11A	119.3
C2—C1—H1A	120.5	C12—C11—H11A	119.3
C3—C2—C1	121.3 (6)	N2—C12—C11	123.4 (5)
C3—C2—H2A	119.4	N2—C12—C13	115.1 (5)
C1—C2—H2A	119.4	C11—C12—C13	121.5 (5)
C2—C3—C4	118.3 (6)	C18—C13—C14	120.4 (5)
C2—C3—H3A	120.8	C18—C13—C12	118.2 (5)
C4—C3—H3A	120.8	C14—C13—C12	121.4 (5)
C5—C4—C3	121.6 (6)	C15—C14—C13	119.8 (6)
C5—C4—C6	117.3 (5)	C15—C14—H14A	120.1
C3—C4—C6	121.1 (5)	C13—C14—H14A	120.1
C4—C5—C9	124.6 (5)	C16—C15—C14	119.3 (6)
C4—C5—N1	116.7 (5)	C16—C15—H15A	120.4
C9—C5—N1	118.7 (5)	C14—C15—H15A	120.4
C7—C6—C4	118.4 (5)	C15—C16—C17	120.1 (6)
C7—C6—H6A	120.8	C15—C16—H16A	119.9
C4—C6—H6A	120.8	C17—C16—H16A	119.9
C6—C7—C8	121.5 (5)	C18—C17—C16	121.5 (6)
C6—C7—H7A	119.3	C18—C17—H17A	119.3
C8—C7—H7A	119.2	C16—C17—H17A	119.3
C9—C8—C7	122.9 (6)	C13—C18—C17	118.9 (5)
C9—C8—C10	114.7 (5)	C13—C18—H18A	120.6
C7—C8—C10	122.4 (5)	C17—C18—H18A	120.6
N2—C9—C8	126.9 (5)	H1W—O1W—H2W	105 (6)
N2—C9—C5	117.8 (5)	H3W—O2W—H4W	111 (8)
C5—N1—C1—C2	0.1 (8)	N1—C5—C9—N2	2.6 (7)
N1—C1—C2—C3	−1.7 (9)	C4—C5—C9—C8	0.8 (8)
C1—C2—C3—C4	2.1 (9)	N1—C5—C9—C8	−177.8 (5)
C2—C3—C4—C5	−1.0 (8)	C9—C8—C10—C11	1.0 (8)
C2—C3—C4—C6	179.3 (5)	C7—C8—C10—C11	−178.2 (6)
C3—C4—C5—C9	−179.1 (5)	C8—C10—C11—C12	0.1 (9)
C6—C4—C5—C9	0.6 (8)	C9—N2—C12—C11	0.0 (7)
C3—C4—C5—N1	−0.5 (7)	C9—N2—C12—C13	−179.4 (4)
C6—C4—C5—N1	179.2 (4)	C10—C11—C12—N2	−0.6 (9)
C1—N1—C5—C4	1.0 (7)	C10—C11—C12—C13	178.8 (5)
C1—N1—C5—C9	179.7 (5)	N2—C12—C13—C18	−1.6 (7)
C5—C4—C6—C7	−0.8 (8)	C11—C12—C13—C18	178.9 (5)
C3—C4—C6—C7	178.9 (5)	N2—C12—C13—C14	176.3 (5)
C4—C6—C7—C8	−0.4 (8)	C11—C12—C13—C14	−3.1 (8)
C6—C7—C8—C9	2.0 (9)	C18—C13—C14—C15	0.2 (8)
C6—C7—C8—C10	−178.9 (5)	C12—C13—C14—C15	−177.7 (5)
C12—N2—C9—C8	1.3 (7)	C13—C14—C15—C16	−0.5 (9)
C12—N2—C9—C5	−179.2 (4)	C14—C15—C16—C17	1.2 (9)
C7—C8—C9—N2	177.4 (5)	C15—C16—C17—C18	−1.7 (9)
C10—C8—C9—N2	−1.7 (8)	C14—C13—C18—C17	−0.7 (8)
C7—C8—C9—C5	−2.1 (8)	C12—C13—C18—C17	177.3 (5)
C10—C8—C9—C5	178.7 (5)	C16—C17—C18—C13	1.4 (9)
C4—C5—C9—N2	−178.8 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W···O2W	0.98 (8)	1.90 (8)	2.871 (7)	171 (7)
O1W—H2W···Br1	0.90 (8)	2.56 (8)	3.443 (5)	166 (6)
O2W—H3W···Br1^i	0.83 (8)	2.63 (8)	3.428 (5)	164 (7)
O2W—H4W···Br1^ii	0.79 (8)	2.63 (8)	3.364 (5)	154 (7)

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

(VI) Trichlorido(2-phenyl-1,10-phenanthroline-κN¹⁰)gold(III)

Crystal data

[AuCl3(C18H12N2)]	F(000) = 1056
Mr = 559.61	Dx = 2.210 Mg m^−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2ybc	Cell parameters from 8557 reflections
a = 7.1497 (1) Å	θ = 4.2–67.7°
b = 18.4625 (3) Å	µ = 20.83 mm^−1
c = 13.0648 (2) Å	T = 150 K
β = 102.727 (1)°	Plate, golden-yellow
V = 1682.20 (4) Å^3	0.09 × 0.05 × 0.01 mm
Z = 4

Data collection

Bruker SMART6000 CCD diffractometer	2949 independent reflections
Radiation source: fine-focus sealed tube	2672 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.044
ω scans	θmax = 67.9°, θmin = 4.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a)	h = −7→8
Tmin = 0.256, Tmax = 0.819	k = −21→21
14259 measured reflections	l = −15→15

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) = 0.061	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0363P)^2 + 1.2779P] where P = (Fo^2 + 2Fc^2)/3
2949 reflections	(Δ/σ)max = 0.001
217 parameters	Δρmax = 1.16 e Å^−3
0 restraints	Δρmin = −0.63 e Å^−3

Special details

Experimental. A suitable crystal was mounted in a loop with paratone-N and transferred immediately to the goniostat bathed in a cold stream.

Our standard practice is to collect a full sphere of data out to a theta angle of 67° (0.83 Å resolution).

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

All C-bound H atoms were calculated based on geometric criteria, and treated with a riding model.

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

	x	y	z	Uiso*/Ueq
Au1	0.61946 (2)	0.255111 (7)	0.142802 (12)	0.01728 (8)
Cl1	0.46392 (15)	0.31020 (5)	0.25622 (8)	0.0288 (2)
Cl2	0.71561 (15)	0.36489 (5)	0.09566 (8)	0.0298 (2)
Cl3	0.79301 (14)	0.19870 (5)	0.03755 (8)	0.0267 (2)
N1	0.5524 (4)	0.15577 (16)	0.1970 (2)	0.0192 (7)
N2	0.3043 (4)	0.19790 (16)	0.0101 (2)	0.0169 (6)
C1	0.6375 (5)	0.1392 (2)	0.2964 (3)	0.0208 (8)
H1	0.7043	0.1757	0.3412	0.025*
C2	0.6294 (6)	0.0693 (2)	0.3347 (3)	0.0254 (9)
H2	0.6849	0.0589	0.4062	0.031*
C3	0.5419 (6)	0.0157 (2)	0.2699 (3)	0.0242 (9)
H3	0.5452	−0.0329	0.2942	0.029*
C4	0.4462 (5)	0.0329 (2)	0.1664 (3)	0.0202 (8)
C5	0.4463 (5)	0.1052 (2)	0.1325 (3)	0.0181 (8)
C6	0.3448 (6)	−0.0213 (2)	0.0964 (3)	0.0231 (8)
H6	0.3502	−0.0706	0.1177	0.028*
C7	0.2421 (5)	−0.0024 (2)	0.0008 (3)	0.0215 (8)
H7	0.1793	−0.0389	−0.0454	0.026*
C8	0.2257 (6)	0.0713 (2)	−0.0324 (3)	0.0207 (8)
C9	0.3243 (5)	0.1264 (2)	0.0329 (3)	0.0172 (7)
C10	0.1050 (6)	0.0947 (2)	−0.1281 (3)	0.0242 (9)
H10	0.0379	0.0600	−0.1762	0.029*
C11	0.0850 (5)	0.1657 (2)	−0.1512 (3)	0.0218 (8)
H11	0.0031	0.1811	−0.2150	0.026*
C12	0.1873 (5)	0.2179 (2)	−0.0794 (3)	0.0184 (8)
C13	0.1618 (6)	0.2962 (2)	−0.1003 (3)	0.0207 (8)
C14	0.1236 (5)	0.3241 (2)	−0.2029 (3)	0.0228 (9)
H14	0.1141	0.2919	−0.2606	0.027*
C15	0.0997 (6)	0.3976 (2)	−0.2208 (4)	0.0275 (9)
H15	0.0740	0.4157	−0.2906	0.033*
C16	0.1131 (6)	0.4453 (2)	−0.1367 (4)	0.0309 (10)
H16	0.0992	0.4960	−0.1486	0.037*
C17	0.1471 (6)	0.4177 (2)	−0.0350 (4)	0.0331 (11)
H17	0.1536	0.4498	0.0226	0.040*
C18	0.1713 (6)	0.3445 (2)	−0.0172 (3)	0.0238 (9)
H18	0.1948	0.3266	0.0526	0.029*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Au1	0.01965 (12)	0.01319 (11)	0.01835 (12)	−0.00284 (5)	0.00278 (7)	−0.00061 (5)
Cl1	0.0418 (6)	0.0185 (5)	0.0295 (5)	−0.0024 (4)	0.0153 (4)	−0.0055 (4)
Cl2	0.0384 (6)	0.0174 (5)	0.0333 (6)	−0.0091 (4)	0.0075 (4)	0.0040 (4)
Cl3	0.0268 (5)	0.0250 (5)	0.0306 (5)	0.0003 (4)	0.0117 (4)	−0.0022 (4)
N1	0.0229 (18)	0.0114 (15)	0.0243 (18)	−0.0009 (12)	0.0073 (13)	−0.0007 (13)
N2	0.0147 (16)	0.0176 (15)	0.0184 (16)	−0.0015 (12)	0.0037 (12)	0.0007 (12)
C1	0.025 (2)	0.0188 (19)	0.018 (2)	0.0009 (14)	0.0025 (15)	0.0003 (15)
C2	0.029 (2)	0.024 (2)	0.022 (2)	0.0034 (16)	0.0037 (17)	0.0064 (16)
C3	0.027 (2)	0.0160 (19)	0.030 (2)	0.0037 (15)	0.0071 (17)	0.0054 (16)
C4	0.017 (2)	0.0158 (18)	0.029 (2)	0.0009 (14)	0.0069 (15)	0.0005 (16)
C5	0.016 (2)	0.0181 (19)	0.021 (2)	0.0003 (14)	0.0044 (15)	−0.0006 (15)
C6	0.027 (2)	0.0123 (19)	0.032 (2)	0.0012 (15)	0.0106 (17)	0.0015 (15)
C7	0.023 (2)	0.0128 (18)	0.030 (2)	−0.0046 (14)	0.0081 (17)	−0.0069 (16)
C8	0.019 (2)	0.021 (2)	0.024 (2)	−0.0015 (14)	0.0070 (15)	−0.0025 (16)
C9	0.016 (2)	0.0171 (18)	0.020 (2)	−0.0002 (13)	0.0063 (14)	−0.0007 (15)
C10	0.023 (2)	0.025 (2)	0.024 (2)	−0.0064 (16)	0.0036 (16)	−0.0061 (17)
C11	0.017 (2)	0.024 (2)	0.021 (2)	−0.0036 (15)	−0.0008 (15)	−0.0008 (16)
C12	0.014 (2)	0.0179 (19)	0.022 (2)	−0.0020 (14)	0.0018 (15)	−0.0016 (16)
C13	0.0126 (19)	0.020 (2)	0.029 (2)	0.0001 (15)	0.0032 (15)	0.0026 (16)
C14	0.014 (2)	0.024 (2)	0.030 (2)	0.0014 (14)	0.0047 (16)	0.0009 (17)
C15	0.020 (2)	0.026 (2)	0.035 (2)	0.0022 (16)	0.0033 (17)	0.0127 (18)
C16	0.025 (2)	0.017 (2)	0.047 (3)	−0.0030 (16)	0.0001 (18)	0.007 (2)
C17	0.033 (3)	0.023 (2)	0.039 (3)	−0.0010 (17)	−0.002 (2)	−0.0070 (19)
C18	0.021 (2)	0.020 (2)	0.028 (2)	0.0028 (15)	−0.0016 (16)	0.0016 (16)

Geometric parameters (Å, º)

Au1—N1	2.060 (3)	C7—H7	0.9500
Au1—Cl2	2.2686 (9)	C8—C9	1.412 (5)
Au1—Cl1	2.2788 (10)	C8—C10	1.421 (6)
Au1—Cl3	2.2950 (9)	C10—C11	1.345 (6)
N1—C1	1.342 (5)	C10—H10	0.9500
N1—C5	1.370 (5)	C11—C12	1.429 (5)
N2—C12	1.331 (5)	C11—H11	0.9500
N2—C9	1.355 (5)	C12—C13	1.475 (6)
C1—C2	1.390 (5)	C13—C18	1.394 (6)
C1—H1	0.9500	C13—C14	1.405 (6)
C2—C3	1.361 (6)	C14—C15	1.382 (6)
C2—H2	0.9500	C14—H14	0.9500
C3—C4	1.411 (6)	C15—C16	1.395 (6)
C3—H3	0.9500	C15—H15	0.9500
C4—C5	1.407 (5)	C16—C17	1.394 (7)
C4—C6	1.438 (5)	C16—H16	0.9500
C5—C9	1.451 (5)	C17—C18	1.376 (6)
C6—C7	1.348 (6)	C17—H17	0.9500
C6—H6	0.9500	C18—H18	0.9500
C7—C8	1.425 (5)
N1—Au1—Cl2	174.89 (9)	C9—C8—C7	120.4 (4)
N1—Au1—Cl1	89.43 (9)	C10—C8—C7	123.4 (4)
Cl2—Au1—Cl1	89.90 (4)	N2—C9—C8	123.6 (3)
N1—Au1—Cl3	89.96 (9)	N2—C9—C5	118.3 (3)
Cl2—Au1—Cl3	90.38 (4)	C8—C9—C5	118.0 (3)
Cl1—Au1—Cl3	176.26 (4)	C11—C10—C8	120.5 (4)
C1—N1—C5	120.7 (3)	C11—C10—H10	119.8
C1—N1—Au1	116.5 (2)	C8—C10—H10	119.8
C5—N1—Au1	122.3 (3)	C10—C11—C12	119.7 (4)
C12—N2—C9	118.7 (3)	C10—C11—H11	120.1
N1—C1—C2	121.0 (4)	C12—C11—H11	120.1
N1—C1—H1	119.5	N2—C12—C11	121.4 (4)
C2—C1—H1	119.5	N2—C12—C13	117.6 (3)
C3—C2—C1	120.0 (4)	C11—C12—C13	121.0 (3)
C3—C2—H2	120.0	C18—C13—C14	118.4 (4)
C1—C2—H2	120.0	C18—C13—C12	120.0 (3)
C2—C3—C4	119.5 (4)	C14—C13—C12	121.7 (3)
C2—C3—H3	120.3	C15—C14—C13	120.8 (4)
C4—C3—H3	120.3	C15—C14—H14	119.6
C5—C4—C3	118.8 (4)	C13—C14—H14	119.6
C5—C4—C6	119.6 (4)	C14—C15—C16	120.2 (4)
C3—C4—C6	121.6 (3)	C14—C15—H15	119.9
N1—C5—C4	119.5 (3)	C16—C15—H15	119.9
N1—C5—C9	120.7 (3)	C17—C16—C15	119.2 (4)
C4—C5—C9	119.7 (3)	C17—C16—H16	120.4
C7—C6—C4	120.3 (3)	C15—C16—H16	120.4
C7—C6—H6	119.8	C18—C17—C16	120.6 (4)
C4—C6—H6	119.8	C18—C17—H17	119.7
C6—C7—C8	121.4 (4)	C16—C17—H17	119.7
C6—C7—H7	119.3	C17—C18—C13	120.9 (4)
C8—C7—H7	119.3	C17—C18—H18	119.6
C9—C8—C10	116.0 (3)	C13—C18—H18	119.6
Cl2—Au1—N1—C1	14.8 (12)	C10—C8—C9—N2	2.0 (6)
Cl1—Au1—N1—C1	−67.6 (3)	C7—C8—C9—N2	−174.8 (3)
Cl3—Au1—N1—C1	108.7 (3)	C10—C8—C9—C5	178.8 (3)
Cl2—Au1—N1—C5	−157.2 (8)	C7—C8—C9—C5	1.9 (5)
Cl1—Au1—N1—C5	120.3 (3)	N1—C5—C9—N2	−6.1 (5)
Cl3—Au1—N1—C5	−63.4 (3)	C4—C5—C9—N2	169.7 (3)
C5—N1—C1—C2	3.6 (6)	N1—C5—C9—C8	177.0 (3)
Au1—N1—C1—C2	−168.6 (3)	C4—C5—C9—C8	−7.2 (5)
N1—C1—C2—C3	3.1 (6)	C9—C8—C10—C11	−1.8 (6)
C1—C2—C3—C4	−5.2 (6)	C7—C8—C10—C11	175.0 (4)
C2—C3—C4—C5	0.9 (6)	C8—C10—C11—C12	0.6 (6)
C2—C3—C4—C6	−177.3 (4)	C9—N2—C12—C11	−0.4 (5)
C1—N1—C5—C4	−8.0 (5)	C9—N2—C12—C13	177.5 (3)
Au1—N1—C5—C4	163.8 (3)	C10—C11—C12—N2	0.6 (6)
C1—N1—C5—C9	167.8 (3)	C10—C11—C12—C13	−177.2 (4)
Au1—N1—C5—C9	−20.4 (5)	N2—C12—C13—C18	−32.0 (5)
C3—C4—C5—N1	5.7 (5)	C11—C12—C13—C18	145.9 (4)
C6—C4—C5—N1	−176.1 (3)	N2—C12—C13—C14	149.3 (4)
C3—C4—C5—C9	−170.2 (3)	C11—C12—C13—C14	−32.7 (5)
C6—C4—C5—C9	8.1 (5)	C18—C13—C14—C15	1.2 (6)
C5—C4—C6—C7	−3.4 (6)	C12—C13—C14—C15	179.9 (3)
C3—C4—C6—C7	174.8 (4)	C13—C14—C15—C16	−0.1 (6)
C4—C6—C7—C8	−2.0 (6)	C14—C15—C16—C17	−1.2 (6)
C6—C7—C8—C9	2.8 (6)	C15—C16—C17—C18	1.4 (7)
C6—C7—C8—C10	−173.9 (4)	C16—C17—C18—C13	−0.2 (7)
C12—N2—C9—C8	−0.9 (5)	C14—C13—C18—C17	−1.1 (6)
C12—N2—C9—C5	−177.7 (3)	C12—C13—C18—C17	−179.7 (4)

(VII) Dichlorido(2-phenyl-1,10-phenanthroline-κ²N,N')copper(II)

Crystal data

[CuCl2(C18H12N2)]	F(000) = 788
Mr = 390.74	Dx = 1.667 Mg m^−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2ybc	Cell parameters from 7410 reflections
a = 7.9946 (2) Å	θ = 4.4–67.6°
b = 19.2773 (5) Å	µ = 5.12 mm^−1
c = 10.3823 (2) Å	T = 150 K
β = 103.408 (1)°	Blade, orange
V = 1556.45 (6) Å^3	0.20 × 0.09 × 0.01 mm
Z = 4

Data collection

Bruker SMART6000 CCD diffractometer	2755 independent reflections
Radiation source: fine-focus sealed tube	2444 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.034
ω scans	θmax = 68.0°, θmin = 4.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a)	h = −9→9
Tmin = 0.428, Tmax = 0.951	k = −18→21
13203 measured reflections	l = −12→12

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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.078	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.044P)^2 + 0.9787P] where P = (Fo^2 + 2Fc^2)/3
2755 reflections	(Δ/σ)max = 0.001
208 parameters	Δρmax = 0.34 e Å^−3
0 restraints	Δρmin = −0.26 e Å^−3

Special details

Experimental. A suitable crystal was mounted in a loop with paratone-N and transferred immediately to the goniostat bathed in a cold stream.

Our standard practice is to collect a full sphere of data out to a theta angle of 67° (0.83 Å resolution).

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

All C-bound H atoms were calculated based on geometric criteria, and treated with a riding model.

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

	x	y	z	Uiso*/Ueq
Cu1	0.26805 (4)	0.547963 (15)	0.87148 (3)	0.02034 (12)
Cl1	0.34828 (7)	0.53638 (3)	1.08968 (5)	0.02637 (14)
Cl2	0.14664 (7)	0.65355 (3)	0.85895 (5)	0.02490 (14)
N1	0.1660 (2)	0.45241 (9)	0.82921 (18)	0.0194 (4)
N2	0.2993 (2)	0.54171 (9)	0.68323 (17)	0.0182 (4)
C1	0.0952 (3)	0.41107 (12)	0.9035 (2)	0.0244 (5)
H1	0.1016	0.4236	0.9930	0.029*
C2	0.0112 (3)	0.34939 (12)	0.8546 (3)	0.0292 (5)
H2	−0.0394	0.3211	0.9102	0.035*
C3	0.0024 (3)	0.33003 (12)	0.7260 (2)	0.0273 (5)
H3	−0.0516	0.2877	0.6926	0.033*
C4	0.0744 (3)	0.37363 (11)	0.6438 (2)	0.0227 (5)
C5	0.1560 (3)	0.43456 (11)	0.7007 (2)	0.0191 (4)
C6	0.0666 (3)	0.35997 (12)	0.5069 (2)	0.0281 (5)
H6	0.0129	0.3187	0.4676	0.034*
C7	0.1345 (3)	0.40485 (13)	0.4326 (2)	0.0281 (5)
H7	0.1283	0.3944	0.3422	0.034*
C8	0.2156 (3)	0.46797 (12)	0.4878 (2)	0.0226 (5)
C9	0.2276 (2)	0.48253 (11)	0.6227 (2)	0.0191 (4)
C10	0.2806 (3)	0.51850 (13)	0.4144 (2)	0.0257 (5)
H10	0.2744	0.5115	0.3228	0.031*
C11	0.3524 (3)	0.57743 (12)	0.4754 (2)	0.0261 (5)
H11	0.3965	0.6114	0.4258	0.031*
C12	0.3624 (3)	0.58885 (11)	0.6120 (2)	0.0207 (4)
C13	0.4401 (3)	0.65285 (11)	0.6773 (2)	0.0224 (5)
C14	0.3999 (3)	0.71634 (12)	0.6127 (2)	0.0278 (5)
H14	0.3309	0.7174	0.5249	0.033*
C15	0.4601 (3)	0.77756 (13)	0.6758 (3)	0.0333 (6)
H15	0.4296	0.8207	0.6327	0.040*
C16	0.5651 (3)	0.77571 (13)	0.8022 (3)	0.0324 (6)
H16	0.6056	0.8178	0.8460	0.039*
C17	0.6118 (3)	0.71253 (13)	0.8657 (2)	0.0303 (5)
H17	0.6868	0.7116	0.9513	0.036*
C18	0.5491 (3)	0.65125 (12)	0.8042 (2)	0.0261 (5)
H18	0.5796	0.6082	0.8477	0.031*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0302 (2)	0.01531 (19)	0.01613 (18)	−0.00138 (12)	0.00661 (13)	−0.00030 (11)
Cl1	0.0408 (3)	0.0219 (3)	0.0164 (3)	0.0015 (2)	0.0066 (2)	0.00073 (18)
Cl2	0.0322 (3)	0.0178 (3)	0.0242 (3)	0.00344 (19)	0.0056 (2)	−0.00065 (19)
N1	0.0208 (9)	0.0148 (9)	0.0222 (9)	0.0006 (6)	0.0043 (7)	−0.0008 (7)
N2	0.0187 (9)	0.0184 (9)	0.0167 (9)	0.0022 (6)	0.0028 (7)	0.0015 (6)
C1	0.0270 (11)	0.0226 (12)	0.0248 (11)	0.0015 (9)	0.0079 (9)	0.0014 (9)
C2	0.0279 (12)	0.0218 (12)	0.0391 (14)	−0.0040 (9)	0.0102 (10)	0.0039 (10)
C3	0.0244 (11)	0.0177 (12)	0.0379 (13)	−0.0021 (8)	0.0037 (10)	−0.0033 (9)
C4	0.0196 (10)	0.0179 (11)	0.0295 (12)	0.0039 (8)	0.0033 (9)	−0.0036 (9)
C5	0.0172 (10)	0.0187 (11)	0.0207 (11)	0.0033 (8)	0.0032 (8)	−0.0008 (8)
C6	0.0240 (12)	0.0259 (13)	0.0316 (13)	0.0019 (9)	0.0005 (9)	−0.0109 (10)
C7	0.0245 (12)	0.0344 (14)	0.0233 (11)	0.0042 (9)	0.0012 (9)	−0.0092 (10)
C8	0.0175 (10)	0.0297 (13)	0.0194 (11)	0.0056 (8)	0.0021 (8)	−0.0021 (9)
C9	0.0154 (10)	0.0201 (11)	0.0209 (11)	0.0040 (8)	0.0028 (8)	−0.0010 (8)
C10	0.0226 (11)	0.0364 (14)	0.0177 (11)	0.0072 (9)	0.0041 (9)	0.0013 (9)
C11	0.0238 (11)	0.0312 (13)	0.0245 (11)	0.0057 (9)	0.0081 (9)	0.0099 (9)
C12	0.0169 (10)	0.0224 (12)	0.0225 (11)	0.0049 (8)	0.0038 (8)	0.0045 (8)
C13	0.0193 (11)	0.0222 (12)	0.0267 (11)	0.0002 (8)	0.0073 (9)	0.0061 (9)
C14	0.0277 (12)	0.0270 (13)	0.0294 (12)	0.0015 (9)	0.0083 (10)	0.0095 (9)
C15	0.0325 (13)	0.0227 (13)	0.0484 (16)	0.0012 (9)	0.0169 (11)	0.0101 (11)
C16	0.0257 (12)	0.0229 (13)	0.0513 (16)	−0.0056 (9)	0.0143 (11)	−0.0054 (11)
C17	0.0231 (12)	0.0318 (14)	0.0346 (13)	−0.0023 (9)	0.0036 (10)	−0.0033 (10)
C18	0.0227 (11)	0.0258 (13)	0.0292 (12)	0.0012 (9)	0.0051 (9)	0.0055 (9)

Geometric parameters (Å, º)

Cu1—N1	2.0212 (17)	C7—H7	0.9500
Cu1—N2	2.0306 (18)	C8—C10	1.409 (3)
Cu1—Cl1	2.2180 (6)	C8—C9	1.410 (3)
Cu1—Cl2	2.2458 (6)	C10—C11	1.361 (3)
N1—C1	1.324 (3)	C10—H10	0.9500
N1—C5	1.362 (3)	C11—C12	1.420 (3)
N2—C12	1.341 (3)	C11—H11	0.9500
N2—C9	1.363 (3)	C12—C13	1.474 (3)
C1—C2	1.402 (3)	C13—C14	1.397 (3)
C1—H1	0.9500	C13—C18	1.401 (3)
C2—C3	1.372 (3)	C14—C15	1.381 (4)
C2—H2	0.9500	C14—H14	0.9500
C3—C4	1.412 (3)	C15—C16	1.385 (4)
C3—H3	0.9500	C15—H15	0.9500
C4—C5	1.406 (3)	C16—C17	1.394 (4)
C4—C6	1.433 (3)	C16—H16	0.9500
C5—C9	1.433 (3)	C17—C18	1.381 (3)
C6—C7	1.354 (3)	C17—H17	0.9500
C6—H6	0.9500	C18—H18	0.9500
C7—C8	1.434 (3)
N1—Cu1—N2	82.56 (7)	C10—C8—C9	116.8 (2)
N1—Cu1—Cl1	97.85 (5)	C10—C8—C7	124.0 (2)
N2—Cu1—Cl1	154.97 (5)	C9—C8—C7	119.1 (2)
N1—Cu1—Cl2	131.77 (5)	N2—C9—C8	123.3 (2)
N2—Cu1—Cl2	98.40 (5)	N2—C9—C5	117.39 (18)
Cl1—Cu1—Cl2	99.74 (2)	C8—C9—C5	119.3 (2)
C1—N1—C5	118.86 (19)	C11—C10—C8	119.6 (2)
C1—N1—Cu1	128.88 (15)	C11—C10—H10	120.2
C5—N1—Cu1	111.83 (14)	C8—C10—H10	120.2
C12—N2—C9	118.98 (18)	C10—C11—C12	121.0 (2)
C12—N2—Cu1	129.50 (15)	C10—C11—H11	119.5
C9—N2—Cu1	111.16 (14)	C12—C11—H11	119.5
N1—C1—C2	122.2 (2)	N2—C12—C11	120.3 (2)
N1—C1—H1	118.9	N2—C12—C13	119.09 (19)
C2—C1—H1	118.9	C11—C12—C13	120.6 (2)
C3—C2—C1	119.7 (2)	C14—C13—C18	119.6 (2)
C3—C2—H2	120.1	C14—C13—C12	119.2 (2)
C1—C2—H2	120.1	C18—C13—C12	121.18 (19)
C2—C3—C4	119.3 (2)	C15—C14—C13	120.4 (2)
C2—C3—H3	120.3	C15—C14—H14	119.8
C4—C3—H3	120.3	C13—C14—H14	119.8
C5—C4—C3	117.2 (2)	C14—C15—C16	119.7 (2)
C5—C4—C6	118.7 (2)	C14—C15—H15	120.2
C3—C4—C6	124.1 (2)	C16—C15—H15	120.2
N1—C5—C4	122.6 (2)	C15—C16—C17	120.5 (2)
N1—C5—C9	116.75 (19)	C15—C16—H16	119.7
C4—C5—C9	120.6 (2)	C17—C16—H16	119.7
C7—C6—C4	121.1 (2)	C18—C17—C16	120.0 (2)
C7—C6—H6	119.4	C18—C17—H17	120.0
C4—C6—H6	119.4	C16—C17—H17	120.0
C6—C7—C8	121.2 (2)	C17—C18—C13	119.7 (2)
C6—C7—H7	119.4	C17—C18—H18	120.1
C8—C7—H7	119.4	C13—C18—H18	120.1
N2—Cu1—N1—C1	−177.1 (2)	Cu1—N2—C9—C8	173.68 (16)
Cl1—Cu1—N1—C1	28.13 (19)	C12—N2—C9—C5	−177.77 (18)
Cl2—Cu1—N1—C1	−82.5 (2)	Cu1—N2—C9—C5	−4.0 (2)
N2—Cu1—N1—C5	−4.79 (14)	C10—C8—C9—N2	−0.7 (3)
Cl1—Cu1—N1—C5	−159.53 (13)	C7—C8—C9—N2	−178.67 (19)
Cl2—Cu1—N1—C5	89.86 (14)	C10—C8—C9—C5	176.96 (18)
N1—Cu1—N2—C12	177.69 (18)	C7—C8—C9—C5	−1.0 (3)
Cl1—Cu1—N2—C12	−89.7 (2)	N1—C5—C9—N2	0.0 (3)
Cl2—Cu1—N2—C12	46.41 (18)	C4—C5—C9—N2	177.69 (18)
N1—Cu1—N2—C9	4.74 (13)	N1—C5—C9—C8	−177.79 (18)
Cl1—Cu1—N2—C9	97.38 (17)	C4—C5—C9—C8	−0.1 (3)
Cl2—Cu1—N2—C9	−126.54 (13)	C9—C8—C10—C11	0.8 (3)
C5—N1—C1—C2	0.3 (3)	C7—C8—C10—C11	178.7 (2)
Cu1—N1—C1—C2	172.20 (16)	C8—C10—C11—C12	−0.2 (3)
N1—C1—C2—C3	0.7 (3)	C9—N2—C12—C11	0.7 (3)
C1—C2—C3—C4	−1.7 (3)	Cu1—N2—C12—C11	−171.73 (15)
C2—C3—C4—C5	1.6 (3)	C9—N2—C12—C13	−179.94 (18)
C2—C3—C4—C6	−177.4 (2)	Cu1—N2—C12—C13	7.6 (3)
C1—N1—C5—C4	−0.4 (3)	C10—C11—C12—N2	−0.6 (3)
Cu1—N1—C5—C4	−173.61 (16)	C10—C11—C12—C13	−179.9 (2)
C1—N1—C5—C9	177.24 (18)	N2—C12—C13—C14	−135.8 (2)
Cu1—N1—C5—C9	4.0 (2)	C11—C12—C13—C14	43.5 (3)
C3—C4—C5—N1	−0.5 (3)	N2—C12—C13—C18	42.2 (3)
C6—C4—C5—N1	178.51 (19)	C11—C12—C13—C18	−138.5 (2)
C3—C4—C5—C9	−178.09 (19)	C18—C13—C14—C15	−3.2 (3)
C6—C4—C5—C9	0.9 (3)	C12—C13—C14—C15	174.9 (2)
C5—C4—C6—C7	−0.7 (3)	C13—C14—C15—C16	2.0 (4)
C3—C4—C6—C7	178.3 (2)	C14—C15—C16—C17	0.6 (4)
C4—C6—C7—C8	−0.4 (3)	C15—C16—C17—C18	−2.0 (4)
C6—C7—C8—C10	−176.5 (2)	C16—C17—C18—C13	0.8 (3)
C6—C7—C8—C9	1.3 (3)	C14—C13—C18—C17	1.8 (3)
C12—N2—C9—C8	−0.1 (3)	C12—C13—C18—C17	−176.2 (2)

(VIII) Bromido[2-(phenanthrolin-2-yl)phenyl-κ³C¹,N,N')palladium(II)

Crystal data

[PdBr(C18H11N2)]	F(000) = 856
Mr = 441.60	Dx = 2.049 Mg m^−3
Monoclinic, P21/n	Synchrotron radiation, λ = 0.77490 Å
Hall symbol: -P 2yn	Cell parameters from 6253 reflections
a = 7.8956 (7) Å	θ = 3.3–33.2°
b = 9.6681 (8) Å	µ = 5.05 mm^−1
c = 19.0436 (16) Å	T = 150 K
β = 99.960 (1)°	Needle, yellow
V = 1431.8 (2) Å^3	0.09 × 0.02 × 0.01 mm
Z = 4

Data collection

Bruker APEXII diffractometer	4329 independent reflections
Radiation source: synchrotron	3673 reflections with I > 2σ(I)
Si-<111> channel cut crystal monochromator	Rint = 0.049
ω scans	θmax = 33.6°, θmin = 2.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a)	h = −11→11
Tmin = 0.659, Tmax = 0.951	k = −13→13
19447 measured reflections	l = −27→27

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.084	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0279P)^2 + 2.2043P] where P = (Fo^2 + 2Fc^2)/3
4329 reflections	(Δ/σ)max < 0.001
199 parameters	Δρmax = 1.97 e Å^−3
0 restraints	Δρmin = −1.32 e Å^−3

Special details

Experimental. A suitable crystal was mounted in a loop with paratone-N and transferred immediately to the goniostat bathed in a cold stream.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

PLAT927_ALERT_1_C Reported and Calculated wR2 Differ by ········· -0.0019 RESPONSE: For the alert above, the issue lies with checkcif incorrectly interpreting the wavelength of the experiment even though it is correctly identified in the CIF. When one uses incorrect Mo Kα radiation (λ = 0.71073 Å) instead of the correct wavelength of 0.7749 Å in the refinement, the alert goes away.

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

	x	y	z	Uiso*/Ueq
Pd1	0.30417 (3)	0.35433 (2)	0.049625 (11)	0.02670 (7)
Br1	0.36791 (5)	0.13412 (4)	0.11219 (2)	0.04374 (10)
N1	0.1294 (3)	0.2827 (2)	−0.04421 (13)	0.0295 (5)
N2	0.2511 (3)	0.5294 (2)	−0.00139 (12)	0.0255 (4)
C1	0.0699 (4)	0.1580 (3)	−0.06638 (18)	0.0368 (6)
H1	0.1035	0.0802	−0.0368	0.044*
C2	−0.0401 (5)	0.1375 (4)	−0.13169 (19)	0.0421 (7)
H2	−0.0789	0.0470	−0.1457	0.051*
C3	−0.0918 (4)	0.2475 (4)	−0.17528 (18)	0.0393 (7)
H3	−0.1661	0.2337	−0.2196	0.047*
C4	−0.0340 (4)	0.3814 (3)	−0.15402 (16)	0.0322 (6)
C5	0.0773 (4)	0.3931 (3)	−0.08795 (15)	0.0274 (5)
C6	−0.0795 (4)	0.5056 (4)	−0.19475 (16)	0.0385 (7)
H6	−0.1539	0.4991	−0.2395	0.046*
C7	−0.0192 (4)	0.6315 (3)	−0.17107 (17)	0.0374 (7)
H7	−0.0546	0.7113	−0.1989	0.045*
C8	0.0977 (4)	0.6467 (3)	−0.10438 (16)	0.0308 (6)
C9	0.1420 (3)	0.5260 (3)	−0.06472 (14)	0.0263 (5)
C10	0.1745 (4)	0.7708 (3)	−0.07658 (17)	0.0360 (6)
H10	0.1497	0.8546	−0.1024	0.043*
C11	0.2861 (4)	0.7721 (3)	−0.01197 (17)	0.0351 (6)
H11	0.3367	0.8565	0.0067	0.042*
C12	0.3244 (4)	0.6473 (3)	0.02629 (15)	0.0284 (5)
C13	0.4378 (4)	0.6226 (3)	0.09449 (16)	0.0301 (6)
C14	0.5294 (4)	0.7276 (4)	0.13469 (17)	0.0376 (7)
H14	0.5195	0.8209	0.1188	0.045*
C15	0.6359 (4)	0.6929 (4)	0.19875 (18)	0.0436 (8)
H15	0.7004	0.7628	0.2265	0.052*
C16	0.6477 (4)	0.5561 (4)	0.22202 (17)	0.0438 (8)
H16	0.7198	0.5335	0.2658	0.053*
C17	0.5550 (4)	0.4523 (4)	0.18179 (16)	0.0366 (6)
H17	0.5645	0.3596	0.1986	0.044*
C18	0.4486 (4)	0.4818 (3)	0.11746 (15)	0.0301 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pd1	0.02900 (11)	0.02766 (11)	0.02409 (10)	0.00047 (8)	0.00645 (7)	0.00217 (7)
Br1	0.0526 (2)	0.03584 (18)	0.04332 (19)	0.00233 (14)	0.00989 (15)	0.01310 (13)
N1	0.0311 (12)	0.0278 (11)	0.0303 (12)	−0.0022 (9)	0.0078 (9)	−0.0028 (9)
N2	0.0264 (10)	0.0267 (10)	0.0242 (10)	−0.0008 (9)	0.0063 (8)	−0.0036 (8)
C1	0.0399 (16)	0.0302 (14)	0.0416 (17)	−0.0040 (12)	0.0113 (13)	−0.0041 (12)
C2	0.0404 (17)	0.0408 (17)	0.0456 (18)	−0.0098 (14)	0.0091 (14)	−0.0156 (14)
C3	0.0321 (15)	0.0476 (18)	0.0376 (16)	−0.0027 (13)	0.0045 (12)	−0.0146 (14)
C4	0.0267 (13)	0.0407 (16)	0.0298 (14)	0.0025 (11)	0.0065 (11)	−0.0049 (11)
C5	0.0268 (12)	0.0299 (13)	0.0266 (12)	−0.0007 (10)	0.0081 (10)	−0.0039 (10)
C6	0.0325 (15)	0.0534 (19)	0.0290 (14)	0.0082 (14)	0.0037 (11)	−0.0006 (13)
C7	0.0365 (16)	0.0440 (17)	0.0317 (15)	0.0093 (13)	0.0061 (12)	0.0053 (12)
C8	0.0309 (13)	0.0319 (14)	0.0311 (13)	0.0044 (11)	0.0099 (11)	0.0038 (11)
C9	0.0257 (12)	0.0286 (12)	0.0259 (12)	0.0018 (10)	0.0084 (10)	−0.0003 (10)
C10	0.0405 (16)	0.0276 (14)	0.0414 (16)	0.0027 (12)	0.0114 (13)	0.0043 (12)
C11	0.0385 (16)	0.0268 (13)	0.0418 (16)	−0.0033 (12)	0.0124 (13)	−0.0007 (12)
C12	0.0267 (12)	0.0294 (13)	0.0301 (13)	−0.0009 (10)	0.0077 (10)	−0.0040 (10)
C13	0.0264 (13)	0.0330 (14)	0.0318 (14)	−0.0013 (10)	0.0078 (10)	−0.0061 (11)
C14	0.0310 (14)	0.0410 (17)	0.0413 (17)	−0.0033 (12)	0.0074 (12)	−0.0131 (13)
C15	0.0307 (15)	0.059 (2)	0.0398 (17)	−0.0063 (14)	0.0037 (13)	−0.0214 (16)
C16	0.0321 (15)	0.066 (2)	0.0319 (15)	0.0025 (15)	0.0012 (12)	−0.0098 (15)
C17	0.0337 (15)	0.0488 (18)	0.0271 (13)	0.0045 (13)	0.0050 (11)	0.0020 (12)
C18	0.0260 (12)	0.0390 (15)	0.0261 (13)	0.0016 (11)	0.0066 (10)	−0.0031 (11)

Geometric parameters (Å, º)

Pd1—N2	1.961 (2)	C7—C8	1.443 (4)
Pd1—C18	1.995 (3)	C7—H7	0.9500
Pd1—N1	2.173 (2)	C8—C9	1.401 (4)
Pd1—Br1	2.4490 (4)	C8—C10	1.406 (4)
N1—C1	1.335 (4)	C10—C11	1.384 (4)
N1—C5	1.373 (4)	C10—H10	0.9500
N2—C12	1.344 (3)	C11—C12	1.415 (4)
N2—C9	1.356 (3)	C11—H11	0.9500
C1—C2	1.403 (5)	C12—C13	1.464 (4)
C1—H1	0.9500	C13—C14	1.396 (4)
C2—C3	1.367 (5)	C13—C18	1.428 (4)
C2—H2	0.9500	C14—C15	1.398 (5)
C3—C4	1.409 (4)	C14—H14	0.9500
C3—H3	0.9500	C15—C16	1.393 (6)
C4—C5	1.410 (4)	C15—H15	0.9500
C4—C6	1.441 (5)	C16—C17	1.392 (5)
C5—C9	1.424 (4)	C16—H16	0.9500
C6—C7	1.355 (5)	C17—C18	1.390 (4)
C6—H6	0.9500	C17—H17	0.9500
N2—Pd1—C18	80.61 (11)	C9—C8—C10	117.2 (3)
N2—Pd1—N1	79.44 (9)	C9—C8—C7	116.8 (3)
C18—Pd1—N1	160.04 (11)	C10—C8—C7	125.9 (3)
N2—Pd1—Br1	179.28 (7)	N2—C9—C8	121.3 (3)
C18—Pd1—Br1	100.12 (9)	N2—C9—C5	115.9 (2)
N1—Pd1—Br1	99.83 (7)	C8—C9—C5	122.8 (3)
C1—N1—C5	117.3 (3)	C11—C10—C8	120.6 (3)
C1—N1—Pd1	133.3 (2)	C11—C10—H10	119.7
C5—N1—Pd1	109.39 (18)	C8—C10—H10	119.7
C12—N2—C9	122.3 (2)	C10—C11—C12	119.8 (3)
C12—N2—Pd1	119.81 (19)	C10—C11—H11	120.1
C9—N2—Pd1	117.90 (18)	C12—C11—H11	120.1
N1—C1—C2	122.5 (3)	N2—C12—C11	118.8 (3)
N1—C1—H1	118.7	N2—C12—C13	111.4 (2)
C2—C1—H1	118.7	C11—C12—C13	129.7 (3)
C3—C2—C1	120.2 (3)	C14—C13—C18	121.9 (3)
C3—C2—H2	119.9	C14—C13—C12	123.2 (3)
C1—C2—H2	119.9	C18—C13—C12	115.0 (2)
C2—C3—C4	119.5 (3)	C13—C14—C15	118.7 (3)
C2—C3—H3	120.2	C13—C14—H14	120.6
C4—C3—H3	120.2	C15—C14—H14	120.6
C3—C4—C5	116.8 (3)	C16—C15—C14	120.2 (3)
C3—C4—C6	125.0 (3)	C16—C15—H15	119.9
C5—C4—C6	118.2 (3)	C14—C15—H15	119.9
N1—C5—C4	123.7 (3)	C17—C16—C15	120.7 (3)
N1—C5—C9	117.4 (2)	C17—C16—H16	119.7
C4—C5—C9	119.0 (3)	C15—C16—H16	119.7
C7—C6—C4	121.9 (3)	C18—C17—C16	121.1 (3)
C7—C6—H6	119.0	C18—C17—H17	119.4
C4—C6—H6	119.0	C16—C17—H17	119.4
C6—C7—C8	121.3 (3)	C17—C18—C13	117.4 (3)
C6—C7—H7	119.4	C17—C18—Pd1	129.4 (2)
C8—C7—H7	119.4	C13—C18—Pd1	113.2 (2)
N2—Pd1—N1—C1	178.8 (3)	C10—C8—C9—C5	−178.1 (3)
C18—Pd1—N1—C1	176.9 (3)	C7—C8—C9—C5	0.3 (4)
Br1—Pd1—N1—C1	−1.3 (3)	N1—C5—C9—N2	0.7 (4)
N2—Pd1—N1—C5	0.39 (18)	C4—C5—C9—N2	−178.7 (2)
C18—Pd1—N1—C5	−1.5 (4)	N1—C5—C9—C8	−179.7 (2)
Br1—Pd1—N1—C5	−179.66 (17)	C4—C5—C9—C8	0.9 (4)
C18—Pd1—N2—C12	0.3 (2)	C9—C8—C10—C11	−1.3 (4)
N1—Pd1—N2—C12	−179.1 (2)	C7—C8—C10—C11	−179.5 (3)
Br1—Pd1—N2—C12	177 (100)	C8—C10—C11—C12	0.5 (5)
C18—Pd1—N2—C9	179.3 (2)	C9—N2—C12—C11	0.1 (4)
N1—Pd1—N2—C9	−0.02 (19)	Pd1—N2—C12—C11	179.1 (2)
Br1—Pd1—N2—C9	−4 (6)	C9—N2—C12—C13	−179.4 (2)
C5—N1—C1—C2	0.5 (5)	Pd1—N2—C12—C13	−0.4 (3)
Pd1—N1—C1—C2	−177.8 (2)	C10—C11—C12—N2	0.1 (4)
N1—C1—C2—C3	−0.5 (5)	C10—C11—C12—C13	179.5 (3)
C1—C2—C3—C4	−0.2 (5)	N2—C12—C13—C14	−179.7 (3)
C2—C3—C4—C5	0.7 (4)	C11—C12—C13—C14	0.9 (5)
C2—C3—C4—C6	−179.7 (3)	N2—C12—C13—C18	0.2 (3)
C1—N1—C5—C4	0.0 (4)	C11—C12—C13—C18	−179.2 (3)
Pd1—N1—C5—C4	178.7 (2)	C18—C13—C14—C15	0.8 (5)
C1—N1—C5—C9	−179.4 (3)	C12—C13—C14—C15	−179.3 (3)
Pd1—N1—C5—C9	−0.7 (3)	C13—C14—C15—C16	−0.9 (5)
C3—C4—C5—N1	−0.6 (4)	C14—C15—C16—C17	0.4 (5)
C6—C4—C5—N1	179.7 (3)	C15—C16—C17—C18	0.1 (5)
C3—C4—C5—C9	178.8 (3)	C16—C17—C18—C13	−0.2 (4)
C6—C4—C5—C9	−0.9 (4)	C16—C17—C18—Pd1	179.6 (2)
C3—C4—C6—C7	180.0 (3)	C14—C13—C18—C17	−0.2 (4)
C5—C4—C6—C7	−0.4 (4)	C12—C13—C18—C17	179.8 (3)
C4—C6—C7—C8	1.6 (5)	C14—C13—C18—Pd1	179.9 (2)
C6—C7—C8—C9	−1.6 (4)	C12—C13—C18—Pd1	0.0 (3)
C6—C7—C8—C10	176.6 (3)	N2—Pd1—C18—C17	−179.9 (3)
C12—N2—C9—C8	−1.0 (4)	N1—Pd1—C18—C17	−178.1 (2)
Pd1—N2—C9—C8	−180.0 (2)	Br1—Pd1—C18—C17	0.1 (3)
C12—N2—C9—C5	178.7 (2)	N2—Pd1—C18—C13	−0.1 (2)
Pd1—N2—C9—C5	−0.4 (3)	N1—Pd1—C18—C13	1.7 (4)
C10—C8—C9—N2	1.5 (4)	Br1—Pd1—C18—C13	179.91 (19)
C7—C8—C9—N2	179.9 (3)