X-ray and synchrotron diffraction studies of 2-(pyridin-2-yl)-1,10-phenanthroline in the role of ligand for two copper polymorphs or hydrogen bonded with 2,2,6,6-tetra­methyl-4-oxopiperidinium hexa­fluoro­phosphate

Different extended packing motifs of dichlorido[2-(pyridin-2-yl)-1,10-phenanthroline]copper(II), [CuCl₂(C₁₇H₁₁N₃)], are obtained, depending on the crystallization conditions. A triclinic form, (I), is obtained from di­methyl­formamide–diethyl ether or methanol, whereas crystallization from di­methyl­formamide–water yields a monoclinic form, (II). In each case, the Cu^II centre is in a five-coordinate distorted square-pyramidal geometry. The extended packing for both forms can be described as a highly offset π-stacking arrangement, with inter­layer distances of 3.674 (3) and 3.679 (3) Å for forms (I) and (II), respectively. The reaction of diprotonated Pt(tmpip₂NCN)Cl [tmpip₂NCN = 2,6-bis­(2,2,6,6-tetra­methyl­piperidylmeth­yl)benzyl] with AgPF₆ under acidic conditions, followed by the addition of 2-(pyridin-2-yl)-1,10-phenanthroline, results in a hydrogen-bonded cocrystal, 2,2,6,6-tetra­methyl-4-oxopiperidinium hexa­fluoro­phosphate–2-(pyridin-2-yl)-1,10-phenanthroline (1/1), C₉H₁₈NO⁺·PF₆⁻·C₁₇H₁₁N₃, (III). The extended packing maximizes π–π inter­actions in a parallel face-to-face arrangement, with an inter­layer stacking distance of 3.4960 (14) Å.

S1. Comment

Our ongoing research efforts primarily focus on utilizing bi- and tridentate chelating imine-based ligands: (i) to tune the electronic nature of square-planar d⁸-electron and octahedral d⁶-electron late transition metals for promising multi-redox catalytic applications and to explore their photophysical properties (see, for example, Pt complexes: Chatterjee et al., 2012; Chatterjee, Krause, Connick et al., 2010; Chatterjee, Krause, Oliver et al., 2010; Green et al., 2005; Grove et al., 2008; Jude, Carroll & Connick, 2003; Jude, Krause Bauer & Connick, 2003; Pd complexes: Tastan et al., 2006); (ii) to bridge multiple metal centres to form more elaborate molecular architectures (Jude et al., 2005; Willison et al., 2008); and (iii) to continue our studies utilizing coinage metals (Collins et al., 2007). Our most recent focus has been the tridentate ligand 2-(pyridin-2-yl)-1,10-phenanthroline (php). We report here the synthesis and solid-state structure of Cu(php)Cl₂ in both triclinic, (I), and monoclinic, (II), forms, obtained from different crystallization media. In addition, the neutral php ligand can act as a hydrogen-bond acceptor to an oxopiperidinium salt, as illustrated in 2,2,6,6-tetramethyl-4-oxopiperidinium hexafluorophosphate–2-(pyridin-2-yl)-1,10-phenanthroline (1/1), (III).

The crystallization medium plays a critical role in influencing the solid-state packing motifs that molecules adopt. Most often this is accomplished by solvents participating in close-contact interactions (e.g. hydrogen-bonding or π–π interactions) with the complex of interest, or residing in channels or cavities created by the surrounding complexes, as found for vapour- and anion-sensing crystals (Grove et al., 2008; Taylor, 2011). However, there can be instances, as in the present study, where the solvent, instead of affecting the close contacts, modifies the extended motif adopted. These differences in packing can be attributed to differences in the physical properties (e.g. electronegativity and pK_a) introduced by the new solvent (Aakeröy et al., 2009, 2010).

The reaction of CuCl₂.2H₂O with php results in the formation of Cu(php)Cl₂. Two crystallographic forms of Cu(php)Cl₂ are obtained, depending on the crystallization conditions, viz. a triclinic form, (I) (Fig. 1a), when dimethylformamide–diethyl ether [Solvent ratio?] or methanol solutions were used, or a monoclinic form, (II) (Fig. 1b), when dimethylformamide–water [Solvent ratio?] was the solvent system. In each case, the Cu^II centre is in a five-coordinate distorted square-pyramidal geometry [τ = 0.11 for (I) and 0.03 for (II); Addison et al., 1984]. Atom Cu1 of (I) is 0.3915 (9) Å out of the basal plane (N1—N2—N3—Cl1), while for (II) the corresponding distance is 0.3544 (12) Å. Additionally, forms (I) and (II) both have an elongated Cu—Cl_apical bond (see Cu1—Cl2 distances summarized in Table 1), generally seen with square-pyramidal complexes (Addison et al., 1984). The disposition (dihedral angle, α) of the pyridine ring with respect to the phenanthroline system is relatively small, viz. 3.41 (8)° from coplanarity for (I) and 5.96 (13)° for (II) (Fig. 1c). Similarly, Ng (2004) and Wang et al., (2004) reported a distorted square-pyramidal geometry (τ = 0.02), with atom Cu1 above the basal plane (0.224 Å) and an elongated Cu—Cl_apical bond length [2.396 (1) Å], for Cu(dppt)Cl₂ [dppt = 3-(1,10-phenanthrolin-2-yl)-5,6-diphenyl-1,2,4-triazine]. For Cu(dppt)Cl₂, the corresponding relationship (α) between the phenanthroline system and triazine ring is 4.5°. The extended packing of forms (I) and (II) (Fig. 2) is a highly-offset π-stacking arrangement, with interlayer distances of 3.674 (3) and 3.679 (3) Å, respectively (the centroid of the pyridine ring stacks above the mid-point of the C12—C13 bond). Such an arrangement is indicative of a high degree of C—H···π attraction (Janiak, 2000).

Cocrystallization of 2,2,6,6-tetramethyl-4-oxopiperidinium hexafluorophosphate with php forms 2,2,6,6-tetramethyl-4-oxopiperidinium hexafluorophosphate–2-(pyridin-2-yl)-1,10-phenanthroline (1/1), (III), which is stabilized by two hydrogen bonds (Table 2) between the protonated N atom (N4) of the oxopiperidinium cation and two N atoms (N1 and N3) of the neutral php molecule (Fig. 3). The cation adopts the expected chair conformation, as reported by Simpson (1992) for 2,2,6,6-tetramethyl-4-oxopiperidinium hexafluorophosphate, by Breitung et al. (2003) for 2,2,6,6-tetramethyl-4-oxopiperidinium trifluoroacetate and by Campana et al., (1998) for 2,2,6,6-tetramethyl-4-oxopiperidinium bis(pentafluorophenyl)phosphinate. The pyridine ring is rotated 10.97 (12)° out of the phenanthroline plane to accommodate the hydrogen bonding to the oxopiperidinium cation. The extended packing (Fig. 4) maximizes a parallel face-to-face π–π stacking arrangement, with an interlayer stacking distance of 3.4960 (14) Å. The phenanthroline–phenanthroline centroid-to-centroid distance is 3.906 (2) Å. This arrangement is typical for aromatic nitrogen-containing ligands (Janiak, 2000; Miller et al., (1998)).

Related literature

For related literature, see: Aakeröy et al. (2009, 2010); Addison et al. (1984); Breitung et al. (2003); Campana et al. (1998); Chatterjee et al. (2012); Chatterjee, Krause, Connick, Genre, Rodrigue-Witchel & Reber (2010); Chatterjee, Krause, Oliver & Connick (2010); Collins et al. (2007); Green et al. (2005); Grove et al. (2008); Janiak (2000); Jude et al. (2002, 2005); Jude, Carroll & Connick (2003); Jude, Krause Bauer & Connick (2003); Miller et al. (1998); Moore et al. (2002); Ng (2004); Simpson (1992); Tastan et al. (2006); Taylor (2011); Wang et al. (2004); Willison et al. (2008).

S2. Experimental

2-(Pyridin-2-yl)-1,10-phenanthroline (php) was prepared using a modification of the procedure of Moore et al. (2002). Under an inert argon atmosphere, 1.2 equivalents of n-butyllithium solution (1.6M in hexanes) was added to a stirred solution of 2-bromopyridine (6.7 mmol) in tetrahydrofuran (THF) at 195 K. After stirring for 30 min, the red solution was cannula-transferred to a tetrahydrofuran solution of 1,10-phenanthroline (5.70 mmol), stirred for an additional 6 h and then quenched with water. The organics were extracted into dichloromethane and oxidized with an excess of MnO₂. After standing overnight, the solution was filtered, dried with Na₂SO₄ and concentrated to a yellow oil. The crude product was purified by column chromatography (silica gel, 8:1 v/v THF–hexane). An off-white solid was obtained and further purified via recrystallization from dichloromethane–hexane [Solvent ratio?].

Pt(tmpip₂NCN)Cl was prepared by substituting 2,2,6,6-tetramethylpiperidine as the ligand reagent in the procedure originally described by Jude et al. (2002) for Pt(pip₂NCN)Cl.

Copper(II) chloride dihydrate and php were added to a methanol–acetonitrile solution (0.2 mmol of each reactant, 25 ml of each solvent). After refluxing for 4 h, a precipitate was obtained. The crude product, Cu(php)Cl₂, was filtered off and washed with diethyl ether. X-ray quality crystals of (I) were grown from either dimethylformamide–diethyl ether [Solvent ratio?] or methanol solutions. Polymorph (II) was obtained when dimethylformamide–water [Solvent ratio?] were the crystallization solvents.

Solvated salt (III) was obtained during the reaction of Pt(tmpip₂NCN)Cl with AgPF₆ and php under acidic conditions. Trifluoroacetic acid (2 equivalents) was added to an acetonitrile solution [Volume?] of Pt(tmpip₂NCN)Cl [How much?]. AgPF₆ [How much?] was added to this mixture, followed by the addition of php [How much?]. Crystals of (III) were harvested from an acetone–diethyl ether solution [Solvent ratio?].

S3. Refinement

The N-bound H atoms of (III) were located directly from the difference map and the positions were refined. All remaining H atoms for (I), (II) and (III) were either located from the difference map or calculated based on geometric criteria, and treated with a riding model, with C—H = 0.99 for CH₂, 0.98 for CH₃ and 0.95 Å for aromatic, and with U_iso(H) = kU_eq(C,N), where k = 1.5 for methyl H atoms or 1.2 for all others.

Computing details

Data collection: SMART (Bruker, 2003) for (I), (II); APEX2 (Bruker, 2009) for (III). For all compounds, cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003) and SADABS (Sheldrick, 2008a); program(s) used to solve structure: SHELXTL (Sheldrick, 2008b); program(s) used to refine structure: SHELXTL (Sheldrick, 2008b); molecular graphics: SHELXTL (Sheldrick, 2008b) and DIAMOND (Brandenburg, 2012); software used to prepare material for publication: SHELXTL (Sheldrick, 2008b).

Figures

	Fig. 1. The structure of (a) triclinic form (I) and (b) monoclinic form (II) of Cu(php)Cl2, showing the atomic labelling scheme and 50% probability displacement ellipsoids. (c) An overlay showing the differences between forms (I) (red atoms in the electronic version of the paper) and (II) (blue atoms).
	Fig. 2. The highly-offset π-stacking arrangement in (I), viewed in the bc plane. The C12—C13 bond is shown as a thicker line (red in the electronic version of the paper). All H atoms have been omitted for clarity. The π-stacking arrangement of (II) is similar.
	Fig. 3. The molecular structure of (III), showing the atomic labelling scheme and 50% probability displacement ellipsoids. N—H···N hydrogen bonding is shown as dashed lines.
	Fig. 4. The offset face-to-face π–π stacking of (III), viewed in the bc plane. Only H atoms involved in hydrogen bonding (dashed lines) are shown.

(I) Dichlorido[2-(pyridin-2-yl)-1,10-phenanthroline]copper(II)

Crystal data

[CuCl2(C17H11N3)]	Z = 2
Mr = 391.73	F(000) = 394
Triclinic, P1	Dx = 1.750 Mg m^−3
Hall symbol: -P 1	Cu Kα radiation, λ = 1.54178 Å
a = 7.4523 (2) Å	Cell parameters from 4986 reflections
b = 8.8189 (2) Å	θ = 3.8–67.2°
c = 12.1288 (3) Å	µ = 5.38 mm^−1
α = 103.263 (1)°	T = 150 K
β = 99.042 (1)°	Rectangular block, green
γ = 101.361 (1)°	0.25 × 0.11 × 0.10 mm
V = 743.36 (3) Å^3

Data collection

Bruker SMART6000 CCD area-detector diffractometer	2545 independent reflections
Radiation source: fine-focus sealed tube	2401 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.015
Detector resolution: 0.83 pixels mm^-1	θmax = 67.4°, θmin = 3.8°
ω scans	h = −8→8
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a)	k = −10→10
Tmin = 0.346, Tmax = 0.615	l = −14→13
6228 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.083	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0451P)^2 + 0.937P] where P = (Fo^2 + 2Fc^2)/3
2545 reflections	(Δ/σ)max = 0.001
208 parameters	Δρmax = 0.78 e Å^−3
0 restraints	Δρmin = −0.35 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.

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

	x	y	z	Uiso*/Ueq
Cu1	0.49190 (5)	0.76181 (4)	0.28255 (3)	0.01994 (13)
Cl1	0.30191 (8)	0.54665 (7)	0.31009 (5)	0.02607 (16)
Cl2	0.73570 (8)	0.66442 (7)	0.19669 (5)	0.02433 (16)
N1	0.3295 (3)	0.7717 (2)	0.12892 (18)	0.0210 (4)
N2	0.5591 (3)	0.9944 (2)	0.29969 (17)	0.0195 (4)
N3	0.6562 (3)	0.8522 (2)	0.44928 (18)	0.0197 (4)
C1	0.2186 (3)	0.6548 (3)	0.0409 (2)	0.0246 (5)
H1	0.2037	0.5468	0.0450	0.030*
C2	0.1227 (4)	0.6853 (3)	−0.0580 (2)	0.0267 (6)
H2	0.0445	0.5990	−0.1194	0.032*
C3	0.1427 (4)	0.8411 (3)	−0.0655 (2)	0.0263 (6)
H3	0.0749	0.8630	−0.1308	0.032*
C4	0.2644 (3)	0.9682 (3)	0.0245 (2)	0.0231 (5)
C5	0.3542 (3)	0.9250 (3)	0.1192 (2)	0.0204 (5)
C6	0.3085 (4)	1.1340 (3)	0.0255 (2)	0.0277 (6)
H6	0.2489	1.1649	−0.0381	0.033*
C7	0.4329 (4)	1.2497 (3)	0.1143 (2)	0.0265 (6)
H7	0.4585	1.3582	0.1109	0.032*
C8	0.5250 (3)	1.2092 (3)	0.2124 (2)	0.0214 (5)
C9	0.4824 (3)	1.0467 (3)	0.2121 (2)	0.0189 (5)
C10	0.6560 (4)	1.3158 (3)	0.3099 (2)	0.0232 (5)
H10	0.6927	1.4266	0.3136	0.028*
C11	0.7310 (3)	1.2598 (3)	0.4000 (2)	0.0223 (5)
H11	0.8180	1.3316	0.4658	0.027*
C12	0.6768 (3)	1.0952 (3)	0.3930 (2)	0.0193 (5)
C13	0.7359 (3)	1.0130 (3)	0.4811 (2)	0.0194 (5)
C14	0.8588 (3)	1.0893 (3)	0.5866 (2)	0.0222 (5)
H14	0.9117	1.2018	0.6071	0.027*
C15	0.9033 (3)	0.9978 (3)	0.6618 (2)	0.0237 (5)
H15	0.9880	1.0468	0.7344	0.028*
C16	0.8220 (3)	0.8339 (3)	0.6293 (2)	0.0239 (5)
H16	0.8499	0.7694	0.6795	0.029*
C17	0.6993 (3)	0.7656 (3)	0.5224 (2)	0.0218 (5)
H17	0.6440	0.6535	0.5005	0.026*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0215 (2)	0.01345 (19)	0.0226 (2)	0.00126 (14)	0.00109 (14)	0.00543 (14)
Cl1	0.0278 (3)	0.0175 (3)	0.0300 (3)	−0.0009 (2)	0.0029 (2)	0.0084 (2)
Cl2	0.0247 (3)	0.0187 (3)	0.0287 (3)	0.0050 (2)	0.0056 (2)	0.0049 (2)
N1	0.0196 (10)	0.0192 (10)	0.0226 (10)	0.0021 (8)	0.0035 (8)	0.0055 (8)
N2	0.0190 (10)	0.0166 (10)	0.0235 (10)	0.0037 (8)	0.0050 (8)	0.0067 (8)
N3	0.0190 (10)	0.0160 (9)	0.0234 (10)	0.0037 (8)	0.0035 (8)	0.0050 (8)
C1	0.0217 (12)	0.0210 (12)	0.0280 (13)	0.0002 (10)	0.0034 (10)	0.0060 (10)
C2	0.0208 (12)	0.0301 (14)	0.0244 (13)	0.0013 (11)	0.0014 (10)	0.0045 (11)
C3	0.0204 (12)	0.0343 (14)	0.0261 (13)	0.0073 (11)	0.0049 (10)	0.0115 (11)
C4	0.0203 (12)	0.0276 (13)	0.0250 (13)	0.0081 (10)	0.0081 (10)	0.0097 (10)
C5	0.0185 (11)	0.0203 (12)	0.0239 (12)	0.0051 (10)	0.0069 (9)	0.0067 (10)
C6	0.0291 (14)	0.0324 (14)	0.0288 (14)	0.0139 (12)	0.0085 (11)	0.0152 (11)
C7	0.0306 (14)	0.0233 (13)	0.0308 (14)	0.0103 (11)	0.0100 (11)	0.0117 (11)
C8	0.0226 (12)	0.0194 (12)	0.0262 (13)	0.0081 (10)	0.0090 (10)	0.0088 (10)
C9	0.0184 (11)	0.0192 (11)	0.0209 (12)	0.0057 (10)	0.0074 (9)	0.0058 (9)
C10	0.0285 (13)	0.0148 (11)	0.0270 (13)	0.0052 (10)	0.0082 (10)	0.0055 (10)
C11	0.0230 (12)	0.0183 (12)	0.0242 (13)	0.0033 (10)	0.0047 (10)	0.0043 (10)
C12	0.0176 (11)	0.0188 (11)	0.0221 (12)	0.0047 (9)	0.0053 (9)	0.0058 (9)
C13	0.0171 (11)	0.0173 (11)	0.0252 (12)	0.0055 (9)	0.0066 (9)	0.0060 (9)
C14	0.0192 (12)	0.0182 (11)	0.0268 (13)	0.0025 (10)	0.0058 (10)	0.0023 (10)
C15	0.0190 (12)	0.0264 (13)	0.0227 (12)	0.0037 (10)	0.0025 (10)	0.0039 (10)
C16	0.0224 (12)	0.0249 (13)	0.0257 (13)	0.0066 (10)	0.0039 (10)	0.0093 (10)
C17	0.0233 (12)	0.0180 (11)	0.0250 (13)	0.0039 (10)	0.0055 (10)	0.0081 (10)

Geometric parameters (Å, º)

Cu1—N2	1.967 (2)	C6—C7	1.368 (4)
Cu1—N3	2.079 (2)	C6—H6	0.9500
Cu1—N1	2.086 (2)	C7—C8	1.431 (4)
Cu1—Cl1	2.2578 (6)	C7—H7	0.9500
Cu1—Cl2	2.4336 (7)	C8—C9	1.404 (3)
N1—C1	1.330 (3)	C8—C10	1.415 (4)
N1—C5	1.362 (3)	C10—C11	1.384 (4)
N2—C12	1.326 (3)	C10—H10	0.9500
N2—C9	1.344 (3)	C11—C12	1.407 (3)
N3—C17	1.339 (3)	C11—H11	0.9500
N3—C13	1.363 (3)	C12—C13	1.482 (3)
C1—C2	1.407 (4)	C13—C14	1.386 (4)
C1—H1	0.9500	C14—C15	1.394 (4)
C2—C3	1.378 (4)	C14—H14	0.9500
C2—H2	0.9500	C15—C16	1.389 (4)
C3—C4	1.414 (4)	C15—H15	0.9500
C3—H3	0.9500	C16—C17	1.390 (4)
C4—C5	1.405 (4)	C16—H16	0.9500
C4—C6	1.430 (4)	C17—H17	0.9500
C5—C9	1.427 (3)
N2—Cu1—N3	77.19 (8)	C7—C6—H6	118.7
N2—Cu1—N1	79.82 (8)	C4—C6—H6	118.7
N3—Cu1—N1	156.19 (8)	C6—C7—C8	120.7 (2)
N2—Cu1—Cl1	149.32 (6)	C6—C7—H7	119.6
N3—Cu1—Cl1	98.41 (6)	C8—C7—H7	119.6
N1—Cu1—Cl1	98.20 (6)	C9—C8—C10	116.2 (2)
N2—Cu1—Cl2	104.08 (6)	C9—C8—C7	117.0 (2)
N3—Cu1—Cl2	94.90 (6)	C10—C8—C7	126.8 (2)
N1—Cu1—Cl2	96.58 (6)	N2—C9—C8	122.3 (2)
Cl1—Cu1—Cl2	106.56 (2)	N2—C9—C5	115.0 (2)
C1—N1—C5	117.8 (2)	C8—C9—C5	122.7 (2)
C1—N1—Cu1	130.54 (17)	C11—C10—C8	120.5 (2)
C5—N1—Cu1	111.57 (16)	C11—C10—H10	119.8
C12—N2—C9	121.4 (2)	C8—C10—H10	119.8
C12—N2—Cu1	121.50 (16)	C10—C11—C12	119.2 (2)
C9—N2—Cu1	117.11 (16)	C10—C11—H11	120.4
C17—N3—C13	118.6 (2)	C12—C11—H11	120.4
C17—N3—Cu1	125.89 (16)	N2—C12—C11	120.3 (2)
C13—N3—Cu1	115.32 (16)	N2—C12—C13	112.3 (2)
N1—C1—C2	122.3 (2)	C11—C12—C13	127.4 (2)
N1—C1—H1	118.9	N3—C13—C14	122.2 (2)
C2—C1—H1	118.9	N3—C13—C12	113.4 (2)
C3—C2—C1	119.7 (2)	C14—C13—C12	124.4 (2)
C3—C2—H2	120.2	C13—C14—C15	118.7 (2)
C1—C2—H2	120.2	C13—C14—H14	120.7
C2—C3—C4	119.7 (2)	C15—C14—H14	120.7
C2—C3—H3	120.2	C16—C15—C14	119.1 (2)
C4—C3—H3	120.2	C16—C15—H15	120.5
C5—C4—C3	116.2 (2)	C14—C15—H15	120.5
C5—C4—C6	117.8 (2)	C15—C16—C17	119.1 (2)
C3—C4—C6	126.0 (2)	C15—C16—H16	120.5
N1—C5—C4	124.3 (2)	C17—C16—H16	120.5
N1—C5—C9	116.5 (2)	N3—C17—C16	122.3 (2)
C4—C5—C9	119.2 (2)	N3—C17—H17	118.8
C7—C6—C4	122.6 (2)	C16—C17—H17	118.8
N2—Cu1—N1—C1	177.0 (2)	C4—C6—C7—C8	−0.5 (4)
N3—Cu1—N1—C1	−167.8 (2)	C6—C7—C8—C9	0.4 (4)
Cl1—Cu1—N1—C1	−34.0 (2)	C6—C7—C8—C10	−179.9 (2)
Cl2—Cu1—N1—C1	73.8 (2)	C12—N2—C9—C8	1.6 (4)
N2—Cu1—N1—C5	0.87 (16)	Cu1—N2—C9—C8	−177.59 (18)
N3—Cu1—N1—C5	16.0 (3)	C12—N2—C9—C5	−178.2 (2)
Cl1—Cu1—N1—C5	149.84 (15)	Cu1—N2—C9—C5	2.6 (3)
Cl2—Cu1—N1—C5	−102.31 (16)	C10—C8—C9—N2	0.8 (4)
N3—Cu1—N2—C12	5.09 (18)	C7—C8—C9—N2	−179.5 (2)
N1—Cu1—N2—C12	178.9 (2)	C10—C8—C9—C5	−179.4 (2)
Cl1—Cu1—N2—C12	90.0 (2)	C7—C8—C9—C5	0.2 (4)
Cl2—Cu1—N2—C12	−86.81 (18)	N1—C5—C9—N2	−1.8 (3)
N3—Cu1—N2—C9	−175.74 (19)	C4—C5—C9—N2	179.0 (2)
N1—Cu1—N2—C9	−1.94 (17)	N1—C5—C9—C8	178.4 (2)
Cl1—Cu1—N2—C9	−90.9 (2)	C4—C5—C9—C8	−0.8 (4)
Cl2—Cu1—N2—C9	92.36 (17)	C9—C8—C10—C11	−1.8 (4)
N2—Cu1—N3—C17	179.8 (2)	C7—C8—C10—C11	178.5 (2)
N1—Cu1—N3—C17	164.5 (2)	C8—C10—C11—C12	0.6 (4)
Cl1—Cu1—N3—C17	30.7 (2)	C9—N2—C12—C11	−2.9 (4)
Cl2—Cu1—N3—C17	−76.9 (2)	Cu1—N2—C12—C11	176.24 (18)
N2—Cu1—N3—C13	−5.16 (16)	C9—N2—C12—C13	176.9 (2)
N1—Cu1—N3—C13	−20.4 (3)	Cu1—N2—C12—C13	−4.0 (3)
Cl1—Cu1—N3—C13	−154.25 (16)	C10—C11—C12—N2	1.8 (4)
Cl2—Cu1—N3—C13	98.19 (16)	C10—C11—C12—C13	−177.9 (2)
C5—N1—C1—C2	−2.4 (4)	C17—N3—C13—C14	−0.3 (4)
Cu1—N1—C1—C2	−178.36 (18)	Cu1—N3—C13—C14	−175.75 (18)
N1—C1—C2—C3	0.0 (4)	C17—N3—C13—C12	−179.9 (2)
C1—C2—C3—C4	2.2 (4)	Cu1—N3—C13—C12	4.7 (3)
C2—C3—C4—C5	−1.9 (4)	N2—C12—C13—N3	−0.7 (3)
C2—C3—C4—C6	175.8 (3)	C11—C12—C13—N3	179.0 (2)
C1—N1—C5—C4	2.7 (4)	N2—C12—C13—C14	179.7 (2)
Cu1—N1—C5—C4	179.39 (19)	C11—C12—C13—C14	−0.6 (4)
C1—N1—C5—C9	−176.5 (2)	N3—C13—C14—C15	0.6 (4)
Cu1—N1—C5—C9	0.2 (3)	C12—C13—C14—C15	−179.9 (2)
C3—C4—C5—N1	−0.5 (4)	C13—C14—C15—C16	−0.6 (4)
C6—C4—C5—N1	−178.4 (2)	C14—C15—C16—C17	0.3 (4)
C3—C4—C5—C9	178.6 (2)	C13—N3—C17—C16	0.0 (4)
C6—C4—C5—C9	0.7 (3)	Cu1—N3—C17—C16	174.91 (18)
C5—C4—C6—C7	−0.1 (4)	C15—C16—C17—N3	0.0 (4)
C3—C4—C6—C7	−177.7 (2)

(II) Dichlorido[2-(pyridin-2-yl)-1,10-phenanthroline]copper(II)

Crystal data

[CuCl2(C17H11N3)]	F(000) = 788
Mr = 391.73	Dx = 1.758 Mg m^−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2ybc	Cell parameters from 5694 reflections
a = 11.8630 (2) Å	θ = 3.9–67.0°
b = 7.7022 (2) Å	µ = 5.41 mm^−1
c = 16.8882 (3) Å	T = 150 K
β = 106.424 (1)°	Plate, green
V = 1480.13 (5) Å^3	0.13 × 0.11 × 0.03 mm
Z = 4

Data collection

Bruker SMART6000 CCD area-detector diffractometer	2578 independent reflections
Radiation source: fine-focus sealed tube	2184 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
Detector resolution: 0.83 pixels mm^-1	θmax = 67.2°, θmin = 3.9°
ω scans	h = −14→13
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a)	k = −9→9
Tmin = 0.540, Tmax = 0.855	l = −20→20
11084 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.098	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0548P)^2 + 1.8743P] where P = (Fo^2 + 2Fc^2)/3
2578 reflections	(Δ/σ)max < 0.001
208 parameters	Δρmax = 0.88 e Å^−3
0 restraints	Δρmin = −0.27 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.

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

	x	y	z	Uiso*/Ueq
Cu1	0.28679 (4)	0.06985 (6)	0.38472 (2)	0.02167 (16)
Cl1	0.31047 (7)	−0.03508 (12)	0.26680 (5)	0.0326 (2)
Cl2	0.17784 (7)	0.33979 (10)	0.34226 (5)	0.0275 (2)
N1	0.1514 (2)	−0.0974 (3)	0.39344 (15)	0.0230 (6)
N2	0.3065 (2)	0.0787 (3)	0.50377 (15)	0.0196 (5)
N3	0.4484 (2)	0.1979 (3)	0.43012 (15)	0.0213 (6)
C1	0.0751 (3)	−0.1909 (4)	0.3366 (2)	0.0263 (7)
H1	0.0791	−0.1872	0.2812	0.032*
C2	−0.0113 (3)	−0.2951 (4)	0.3553 (2)	0.0293 (8)
H2	−0.0644	−0.3598	0.3129	0.035*
C3	−0.0191 (3)	−0.3032 (4)	0.4350 (2)	0.0298 (8)
H3	−0.0767	−0.3746	0.4480	0.036*
C4	0.0592 (3)	−0.2046 (4)	0.4973 (2)	0.0250 (7)
C5	0.1420 (3)	−0.1037 (4)	0.47223 (19)	0.0226 (7)
C6	0.0604 (3)	−0.1979 (5)	0.5820 (2)	0.0307 (8)
H6	0.0048	−0.2650	0.5997	0.037*
C7	0.1389 (3)	−0.0982 (5)	0.6387 (2)	0.0316 (8)
H7	0.1352	−0.0951	0.6941	0.038*
C8	0.2275 (3)	0.0028 (5)	0.61566 (18)	0.0242 (7)
C9	0.2259 (3)	−0.0037 (4)	0.53253 (18)	0.0204 (6)
C10	0.3153 (3)	0.1064 (5)	0.66792 (19)	0.0268 (7)
H10	0.3167	0.1213	0.7240	0.032*
C11	0.3995 (3)	0.1867 (4)	0.63830 (19)	0.0263 (7)
H11	0.4602	0.2535	0.6740	0.032*
C12	0.3937 (3)	0.1676 (4)	0.55444 (18)	0.0197 (6)
C13	0.4785 (3)	0.2353 (4)	0.51206 (18)	0.0209 (6)
C14	0.5796 (3)	0.3266 (4)	0.55127 (19)	0.0230 (7)
H14	0.5999	0.3477	0.6090	0.028*
C15	0.6509 (3)	0.3870 (4)	0.5039 (2)	0.0253 (7)
H15	0.7202	0.4511	0.5289	0.030*
C16	0.6191 (3)	0.3519 (4)	0.4200 (2)	0.0262 (7)
H16	0.6657	0.3931	0.3865	0.031*
C17	0.5187 (3)	0.2563 (4)	0.38587 (19)	0.0244 (7)
H17	0.4983	0.2306	0.3285	0.029*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0230 (3)	0.0282 (3)	0.0145 (2)	0.0017 (2)	0.00656 (18)	−0.00065 (18)
Cl1	0.0371 (4)	0.0436 (5)	0.0201 (4)	−0.0008 (4)	0.0130 (3)	−0.0071 (3)
Cl2	0.0266 (4)	0.0295 (4)	0.0243 (4)	0.0050 (3)	0.0038 (3)	0.0022 (3)
N1	0.0220 (13)	0.0259 (14)	0.0216 (13)	0.0056 (12)	0.0071 (11)	0.0004 (11)
N2	0.0206 (12)	0.0219 (13)	0.0167 (12)	0.0034 (11)	0.0061 (10)	0.0005 (10)
N3	0.0204 (13)	0.0257 (14)	0.0186 (13)	0.0042 (11)	0.0066 (10)	0.0022 (11)
C1	0.0282 (17)	0.0262 (18)	0.0230 (16)	0.0061 (15)	0.0051 (13)	−0.0019 (13)
C2	0.0249 (17)	0.0269 (18)	0.0328 (18)	0.0011 (15)	0.0028 (14)	−0.0064 (15)
C3	0.0232 (16)	0.0238 (18)	0.041 (2)	0.0025 (15)	0.0066 (14)	0.0050 (15)
C4	0.0192 (15)	0.0241 (17)	0.0315 (17)	0.0063 (14)	0.0071 (13)	0.0049 (14)
C5	0.0207 (15)	0.0232 (16)	0.0233 (16)	0.0067 (14)	0.0053 (12)	0.0038 (13)
C6	0.0278 (17)	0.0304 (19)	0.0383 (19)	0.0037 (16)	0.0165 (15)	0.0077 (16)
C7	0.0331 (18)	0.037 (2)	0.0287 (18)	0.0093 (16)	0.0152 (15)	0.0079 (15)
C8	0.0250 (16)	0.0272 (17)	0.0232 (16)	0.0084 (14)	0.0114 (13)	0.0049 (14)
C9	0.0189 (15)	0.0211 (15)	0.0213 (15)	0.0068 (13)	0.0059 (12)	0.0037 (13)
C10	0.0305 (17)	0.0355 (19)	0.0155 (15)	0.0096 (15)	0.0085 (13)	0.0007 (14)
C11	0.0276 (16)	0.0307 (18)	0.0192 (15)	0.0021 (15)	0.0043 (13)	−0.0056 (14)
C12	0.0194 (15)	0.0191 (16)	0.0203 (15)	0.0050 (13)	0.0053 (12)	0.0017 (12)
C13	0.0241 (16)	0.0207 (16)	0.0197 (15)	0.0071 (13)	0.0089 (12)	0.0016 (12)
C14	0.0259 (16)	0.0221 (16)	0.0213 (15)	0.0043 (14)	0.0075 (13)	−0.0012 (12)
C15	0.0206 (15)	0.0215 (16)	0.0327 (18)	0.0027 (14)	0.0058 (13)	0.0013 (14)
C16	0.0251 (16)	0.0266 (17)	0.0308 (17)	0.0056 (14)	0.0144 (14)	0.0075 (14)
C17	0.0263 (16)	0.0293 (18)	0.0189 (15)	0.0088 (14)	0.0087 (13)	0.0051 (13)

Geometric parameters (Å, º)

Cu1—N2	1.959 (2)	C6—C7	1.366 (5)
Cu1—N1	2.096 (3)	C6—H6	0.9500
Cu1—N3	2.099 (3)	C7—C8	1.447 (5)
Cu1—Cl1	2.2393 (8)	C7—H7	0.9500
Cu1—Cl2	2.4461 (9)	C8—C9	1.399 (4)
N1—C1	1.330 (4)	C8—C10	1.407 (5)
N1—C5	1.367 (4)	C10—C11	1.383 (5)
N2—C12	1.331 (4)	C10—H10	0.9500
N2—C9	1.347 (4)	C11—C12	1.406 (4)
N3—C17	1.344 (4)	C11—H11	0.9500
N3—C13	1.359 (4)	C12—C13	1.485 (4)
C1—C2	1.406 (5)	C13—C14	1.386 (4)
C1—H1	0.9500	C14—C15	1.398 (4)
C2—C3	1.377 (5)	C14—H14	0.9500
C2—H2	0.9500	C15—C16	1.386 (5)
C3—C4	1.412 (5)	C15—H15	0.9500
C3—H3	0.9500	C16—C17	1.380 (5)
C4—C5	1.408 (4)	C16—H16	0.9500
C4—C6	1.428 (5)	C17—H17	0.9500
C5—C9	1.431 (5)
N2—Cu1—N1	79.66 (10)	C7—C6—H6	118.9
N2—Cu1—N3	77.14 (10)	C4—C6—H6	118.9
N1—Cu1—N3	154.42 (10)	C6—C7—C8	121.2 (3)
N2—Cu1—Cl1	156.48 (8)	C6—C7—H7	119.4
N1—Cu1—Cl1	97.58 (7)	C8—C7—H7	119.4
N3—Cu1—Cl1	99.38 (7)	C9—C8—C10	116.6 (3)
N2—Cu1—Cl2	99.86 (8)	C9—C8—C7	116.4 (3)
N1—Cu1—Cl2	101.03 (7)	C10—C8—C7	127.0 (3)
N3—Cu1—Cl2	93.44 (7)	N2—C9—C8	122.3 (3)
Cl1—Cu1—Cl2	103.58 (3)	N2—C9—C5	114.7 (3)
C1—N1—C5	117.2 (3)	C8—C9—C5	122.9 (3)
C1—N1—Cu1	131.4 (2)	C11—C10—C8	120.6 (3)
C5—N1—Cu1	111.4 (2)	C11—C10—H10	119.7
C12—N2—C9	120.8 (3)	C8—C10—H10	119.7
C12—N2—Cu1	121.5 (2)	C10—C11—C12	118.9 (3)
C9—N2—Cu1	117.6 (2)	C10—C11—H11	120.6
C17—N3—C13	118.0 (3)	C12—C11—H11	120.6
C17—N3—Cu1	126.9 (2)	N2—C12—C11	120.6 (3)
C13—N3—Cu1	114.9 (2)	N2—C12—C13	112.4 (3)
N1—C1—C2	122.5 (3)	C11—C12—C13	127.0 (3)
N1—C1—H1	118.7	N3—C13—C14	122.5 (3)
C2—C1—H1	118.7	N3—C13—C12	113.5 (3)
C3—C2—C1	120.0 (3)	C14—C13—C12	124.1 (3)
C3—C2—H2	120.0	C13—C14—C15	118.5 (3)
C1—C2—H2	120.0	C13—C14—H14	120.8
C2—C3—C4	119.5 (3)	C15—C14—H14	120.8
C2—C3—H3	120.3	C16—C15—C14	119.1 (3)
C4—C3—H3	120.3	C16—C15—H15	120.4
C5—C4—C3	116.2 (3)	C14—C15—H15	120.4
C5—C4—C6	118.1 (3)	C17—C16—C15	118.9 (3)
C3—C4—C6	125.7 (3)	C17—C16—H16	120.5
N1—C5—C4	124.6 (3)	C15—C16—H16	120.5
N1—C5—C9	116.2 (3)	N3—C17—C16	122.9 (3)
C4—C5—C9	119.2 (3)	N3—C17—H17	118.5
C7—C6—C4	122.2 (3)	C16—C17—H17	118.5
N2—Cu1—N1—C1	−177.6 (3)	C4—C6—C7—C8	−1.7 (5)
N3—Cu1—N1—C1	−152.4 (3)	C6—C7—C8—C9	1.8 (5)
Cl1—Cu1—N1—C1	−21.2 (3)	C6—C7—C8—C10	−178.0 (3)
Cl2—Cu1—N1—C1	84.3 (3)	C12—N2—C9—C8	1.5 (4)
N2—Cu1—N1—C5	4.2 (2)	Cu1—N2—C9—C8	−176.2 (2)
N3—Cu1—N1—C5	29.3 (4)	C12—N2—C9—C5	−175.9 (3)
Cl1—Cu1—N1—C5	160.51 (19)	Cu1—N2—C9—C5	6.4 (3)
Cl2—Cu1—N1—C5	−94.0 (2)	C10—C8—C9—N2	2.6 (5)
N1—Cu1—N2—C12	176.5 (2)	C7—C8—C9—N2	−177.2 (3)
N3—Cu1—N2—C12	7.3 (2)	C10—C8—C9—C5	179.8 (3)
Cl1—Cu1—N2—C12	91.3 (3)	C7—C8—C9—C5	0.0 (5)
Cl2—Cu1—N2—C12	−84.0 (2)	N1—C5—C9—N2	−2.5 (4)
N1—Cu1—N2—C9	−5.8 (2)	C4—C5—C9—N2	175.5 (3)
N3—Cu1—N2—C9	−175.0 (2)	N1—C5—C9—C8	−179.9 (3)
Cl1—Cu1—N2—C9	−91.0 (3)	C4—C5—C9—C8	−1.9 (5)
Cl2—Cu1—N2—C9	93.7 (2)	C9—C8—C10—C11	−4.3 (5)
N2—Cu1—N3—C17	179.6 (3)	C7—C8—C10—C11	175.5 (3)
N1—Cu1—N3—C17	154.2 (3)	C8—C10—C11—C12	2.0 (5)
Cl1—Cu1—N3—C17	23.3 (3)	C9—N2—C12—C11	−4.0 (4)
Cl2—Cu1—N3—C17	−81.1 (3)	Cu1—N2—C12—C11	173.6 (2)
N2—Cu1—N3—C13	−5.7 (2)	C9—N2—C12—C13	175.0 (3)
N1—Cu1—N3—C13	−31.0 (4)	Cu1—N2—C12—C13	−7.4 (3)
Cl1—Cu1—N3—C13	−161.9 (2)	C10—C11—C12—N2	2.2 (5)
Cl2—Cu1—N3—C13	93.7 (2)	C10—C11—C12—C13	−176.6 (3)
C5—N1—C1—C2	−1.0 (4)	C17—N3—C13—C14	−1.7 (4)
Cu1—N1—C1—C2	−179.2 (2)	Cu1—N3—C13—C14	−176.9 (2)
N1—C1—C2—C3	−0.1 (5)	C17—N3—C13—C12	178.9 (3)
C1—C2—C3—C4	0.8 (5)	Cu1—N3—C13—C12	3.6 (3)
C2—C3—C4—C5	−0.4 (4)	N2—C12—C13—N3	2.0 (4)
C2—C3—C4—C6	178.9 (3)	C11—C12—C13—N3	−179.2 (3)
C1—N1—C5—C4	1.5 (4)	N2—C12—C13—C14	−177.5 (3)
Cu1—N1—C5—C4	180.0 (2)	C11—C12—C13—C14	1.4 (5)
C1—N1—C5—C9	179.3 (3)	N3—C13—C14—C15	2.1 (5)
Cu1—N1—C5—C9	−2.1 (3)	C12—C13—C14—C15	−178.5 (3)
C3—C4—C5—N1	−0.8 (5)	C13—C14—C15—C16	−0.8 (5)
C6—C4—C5—N1	179.8 (3)	C14—C15—C16—C17	−0.9 (5)
C3—C4—C5—C9	−178.6 (3)	C13—N3—C17—C16	−0.1 (5)
C6—C4—C5—C9	2.0 (4)	Cu1—N3—C17—C16	174.5 (2)
C5—C4—C6—C7	−0.3 (5)	C15—C16—C17—N3	1.4 (5)
C3—C4—C6—C7	−179.6 (3)

(III) 2,2,6,6-Tetramethyl-4-oxopiperidinium hexafluorophosphate–2-(pyridin-2-yl)-1,10-phenanthroline

Crystal data

C9H18NO^+·PF6^−·C17H11N3	F(000) = 1160
Mr = 558.50	Dx = 1.472 Mg m^−3
Monoclinic, P21/c	Synchrotron radiation, λ = 0.77490 Å
Hall symbol: -P 2ybc	Cell parameters from 9159 reflections
a = 8.1051 (10) Å	θ = 2.6–29.0°
b = 21.714 (3) Å	µ = 0.23 mm^−1
c = 14.4087 (19) Å	T = 183 K
β = 96.337 (3)°	Block, light yellow
V = 2520.3 (6) Å^3	0.07 × 0.07 × 0.05 mm
Z = 4

Data collection

Bruker Platinum 200 diffractometer	5080 independent reflections
Radiation source: synchrotron	4268 reflections with I > 2σ(I)
Si-<111> channel-cut crystal monochromator	Rint = 0.040
ω scans	θmax = 29.1°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a)	h = −7→10
Tmin = 0.984, Tmax = 0.989	k = −21→27
26509 measured reflections	l = −17→18

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)] = 0.049	Hydrogen site location: mixed
wR(F^2) = 0.151	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0836P)^2 + 0.9747P] where P = (Fo^2 + 2Fc^2)/3
5080 reflections	(Δ/σ)max = 0.001
353 parameters	Δρmax = 0.71 e Å^−3
0 restraints	Δρmin = −0.24 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.

ABSMU01_ALERT_1_G Calculation of _exptl_absorpt_correction_mu not performed for this radiation type.

NOTE FROM AUTHORS: Synchrotron Radiation at 0.7749 Å wavelength was used in the experiment and is properly documented.

PLAT984_ALERT_1_G The C-f'= -0.002 Deviates from the B&C-Value 0.004 A nd 5 other PLAT984 Alerts More ···

NOTE FROM AUTHORS: Scattering Factors for a wavelength of 0.77490 Å were calculated using the Brennan method as employed in the WCROMER program (using the Brennan method as employed in the XDISP program calculates identical values). Reference L. Kissel & R. H. Pratt, Acta Cryst A (1990), A46, 170–175 is documented.

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.

H atoms on N4 were located directly from the difference map and their positions refined. All remaining H atoms were either located or calculated and treated with a riding model. Isotropic displacement parameters were defined as a*U_eq of the adjacent atom (a = 1.5 for methyls and 1.2 for all others).

PLAT906_ALERT_3_C Large K value in the Analysis of Variance··· 3.485

NOTE FROM AUTHORS: Section take from. lst file, there is no K value as given in the alert. Analysis of variance for reflections employed in refinement K = Mean[F_o²] / Mean[Fc²] for group

Fc/Fc(max) 0.000 0.006 0.011 0.017 0.023 0.030 0.040 0.053 0.076 0.120 1.000

Number in group 598. 460. 507. 479. 503. 529. 477. 520. 498. 509.

GooF 1.012 1.119 1.084 1.096 0.966 1.131 0.973 1.090 1.107 0.996

K 2.702 1.323 1.122 1.072 1.035 1.031 1.013 0.992 0.998 1.027

Resolution(A) 0.80 0.83 0.86 0.90 0.95 1.01 1.09 1.20 1.37 1.73 inf

Number in group 520. 497. 508. 521. 505. 494. 509. 512. 508. 506.

GooF 0.889 0.832 0.792 0.794 0.855 0.885 0.881 0.890 1.223 1.974

K 1.089 1.061 1.012 1.015 1.006 0.989 0.978 0.972 0.983 1.049

R1 0.123 0.102 0.096 0.076 0.067 0.051 0.041 0.040 0.042 0.052

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

	x	y	z	Uiso*/Ueq
N1	0.3383 (2)	0.37795 (8)	0.42059 (11)	0.0444 (4)
N2	0.1358 (2)	0.47411 (8)	0.34893 (11)	0.0409 (4)
N3	−0.0176 (2)	0.46422 (9)	0.16884 (12)	0.0493 (4)
C1	0.4361 (3)	0.33277 (11)	0.45669 (15)	0.0500 (5)
H1	0.4500	0.2977	0.4188	0.060*
C2	0.5198 (3)	0.33370 (12)	0.54726 (16)	0.0559 (6)
H2	0.5891	0.3004	0.5696	0.067*
C3	0.4995 (3)	0.38352 (13)	0.60249 (15)	0.0566 (6)
H3	0.5532	0.3848	0.6645	0.068*
C4	0.3990 (3)	0.43295 (12)	0.56757 (13)	0.0494 (5)
C5	0.3190 (2)	0.42860 (10)	0.47475 (13)	0.0423 (4)
C6	0.3817 (3)	0.48824 (14)	0.62057 (16)	0.0620 (7)
H6	0.4368	0.4912	0.6821	0.074*
C7	0.2889 (3)	0.53604 (14)	0.58487 (17)	0.0614 (6)
H7	0.2798	0.5721	0.6213	0.074*
C8	0.2040 (3)	0.53283 (11)	0.49241 (14)	0.0476 (5)
C9	0.2163 (2)	0.47943 (10)	0.43647 (13)	0.0409 (4)
C10	0.1081 (3)	0.58201 (11)	0.45294 (16)	0.0532 (5)
H10	0.0990	0.6188	0.4876	0.064*
C11	0.0276 (3)	0.57699 (11)	0.36433 (16)	0.0512 (5)
H11	−0.0370	0.6102	0.3370	0.061*
C12	0.0423 (2)	0.52139 (10)	0.31426 (14)	0.0433 (4)
C13	−0.0532 (2)	0.51358 (10)	0.22029 (14)	0.0436 (4)
C14	−0.1787 (3)	0.55492 (11)	0.18793 (16)	0.0532 (5)
H14	−0.2014	0.5898	0.2243	0.064*
C15	−0.2705 (3)	0.54452 (12)	0.10163 (17)	0.0575 (6)
H15	−0.3575	0.5718	0.0792	0.069*
C16	−0.2341 (3)	0.49471 (11)	0.04952 (16)	0.0536 (5)
H16	−0.2949	0.4866	−0.0094	0.064*
C17	−0.1055 (3)	0.45629 (11)	0.08540 (16)	0.0539 (5)
H17	−0.0783	0.4223	0.0485	0.065*
O1	0.1157 (2)	0.22508 (9)	0.03831 (12)	0.0656 (5)
N4	0.1813 (2)	0.35480 (8)	0.23412 (11)	0.0390 (4)
H4A	0.237 (3)	0.3666 (11)	0.2906 (17)	0.047*
H4B	0.121 (3)	0.3916 (11)	0.2203 (16)	0.047*
C18	0.0539 (2)	0.30358 (10)	0.24277 (14)	0.0439 (5)
C19	−0.0253 (3)	0.28597 (11)	0.14381 (14)	0.0478 (5)
H19A	−0.0950	0.2488	0.1477	0.057*
H19B	−0.0980	0.3199	0.1181	0.057*
C20	0.1053 (3)	0.27344 (11)	0.07894 (14)	0.0481 (5)
C21	0.2225 (3)	0.32677 (11)	0.07037 (14)	0.0484 (5)
H21A	0.1593	0.3619	0.0406	0.058*
H21B	0.3069	0.3145	0.0292	0.058*
C22	0.3115 (2)	0.34782 (10)	0.16569 (13)	0.0410 (4)
C23	−0.0756 (3)	0.33124 (12)	0.30027 (17)	0.0564 (6)
H23A	−0.1231	0.3683	0.2691	0.085*
H23B	−0.0226	0.3420	0.3626	0.085*
H23C	−0.1638	0.3011	0.3059	0.085*
C24	0.1317 (3)	0.24728 (11)	0.29362 (16)	0.0528 (5)
H24A	0.2090	0.2276	0.2550	0.079*
H24B	0.0443	0.2180	0.3052	0.079*
H24C	0.1919	0.2601	0.3532	0.079*
C25	0.3892 (3)	0.41145 (11)	0.15960 (16)	0.0531 (5)
H25A	0.4477	0.4225	0.2205	0.080*
H25B	0.3019	0.4418	0.1418	0.080*
H25C	0.4679	0.4109	0.1126	0.080*
C26	0.4476 (3)	0.30214 (11)	0.20081 (15)	0.0503 (5)
H26A	0.4891	0.3120	0.2656	0.076*
H26B	0.5388	0.3048	0.1616	0.076*
H26C	0.4021	0.2603	0.1978	0.076*
P1	0.31791 (7)	0.66187 (3)	0.11742 (4)	0.04971 (19)
F1	0.12762 (17)	0.64878 (8)	0.08349 (10)	0.0689 (4)
F2	0.26942 (19)	0.68352 (8)	0.21740 (9)	0.0711 (4)
F3	0.36729 (18)	0.64070 (8)	0.01716 (10)	0.0684 (4)
F4	0.2933 (2)	0.73101 (8)	0.08027 (12)	0.0791 (5)
F5	0.3422 (2)	0.59309 (8)	0.15436 (12)	0.0779 (5)
F6	0.50828 (18)	0.67593 (9)	0.15032 (14)	0.0894 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0421 (9)	0.0538 (10)	0.0367 (8)	−0.0054 (8)	0.0016 (6)	0.0039 (7)
N2	0.0353 (8)	0.0516 (10)	0.0368 (8)	−0.0058 (7)	0.0090 (6)	−0.0013 (7)
N3	0.0424 (9)	0.0584 (11)	0.0461 (9)	0.0065 (8)	0.0001 (7)	−0.0012 (8)
C1	0.0473 (12)	0.0562 (13)	0.0451 (11)	−0.0059 (10)	−0.0007 (9)	0.0066 (9)
C2	0.0442 (11)	0.0710 (15)	0.0504 (12)	−0.0060 (11)	−0.0045 (9)	0.0176 (11)
C3	0.0455 (11)	0.0870 (17)	0.0357 (10)	−0.0154 (12)	−0.0023 (8)	0.0063 (10)
C4	0.0362 (10)	0.0766 (15)	0.0355 (10)	−0.0139 (10)	0.0045 (7)	−0.0009 (9)
C5	0.0339 (9)	0.0609 (12)	0.0328 (9)	−0.0124 (9)	0.0072 (7)	−0.0004 (8)
C6	0.0499 (13)	0.096 (2)	0.0402 (11)	−0.0183 (13)	0.0071 (9)	−0.0095 (12)
C7	0.0503 (13)	0.0810 (18)	0.0552 (13)	−0.0150 (13)	0.0156 (10)	−0.0189 (12)
C8	0.0373 (10)	0.0632 (13)	0.0443 (10)	−0.0117 (10)	0.0137 (8)	−0.0088 (9)
C9	0.0322 (9)	0.0550 (12)	0.0370 (9)	−0.0099 (8)	0.0100 (7)	−0.0033 (8)
C10	0.0454 (12)	0.0581 (13)	0.0584 (13)	−0.0076 (10)	0.0162 (10)	−0.0134 (10)
C11	0.0431 (11)	0.0535 (13)	0.0586 (13)	−0.0008 (10)	0.0120 (9)	−0.0032 (10)
C12	0.0342 (10)	0.0522 (12)	0.0448 (10)	−0.0039 (9)	0.0109 (8)	0.0008 (8)
C13	0.0375 (10)	0.0498 (11)	0.0445 (10)	−0.0020 (9)	0.0096 (8)	0.0038 (8)
C14	0.0565 (13)	0.0515 (13)	0.0521 (12)	0.0101 (10)	0.0091 (10)	0.0045 (9)
C15	0.0517 (13)	0.0637 (15)	0.0564 (13)	0.0114 (11)	0.0027 (10)	0.0156 (11)
C16	0.0497 (12)	0.0620 (14)	0.0471 (11)	0.0015 (10)	−0.0036 (9)	0.0092 (10)
C17	0.0535 (13)	0.0600 (14)	0.0462 (11)	0.0061 (11)	−0.0035 (9)	−0.0014 (10)
O1	0.0653 (11)	0.0733 (12)	0.0578 (10)	0.0019 (9)	0.0047 (8)	−0.0229 (9)
N4	0.0341 (8)	0.0508 (10)	0.0318 (8)	−0.0001 (7)	0.0026 (6)	−0.0015 (7)
C18	0.0368 (10)	0.0564 (12)	0.0391 (9)	−0.0061 (9)	0.0064 (7)	−0.0028 (8)
C19	0.0380 (10)	0.0591 (13)	0.0453 (10)	−0.0022 (9)	0.0001 (8)	−0.0042 (9)
C20	0.0421 (11)	0.0641 (14)	0.0363 (9)	0.0026 (10)	−0.0035 (8)	−0.0064 (9)
C21	0.0423 (11)	0.0690 (14)	0.0339 (9)	0.0046 (10)	0.0045 (8)	−0.0010 (9)
C22	0.0352 (9)	0.0539 (12)	0.0344 (9)	0.0020 (8)	0.0057 (7)	−0.0001 (8)
C23	0.0459 (12)	0.0687 (15)	0.0572 (13)	−0.0076 (11)	0.0179 (10)	−0.0090 (11)
C24	0.0474 (12)	0.0614 (14)	0.0489 (11)	−0.0065 (10)	0.0023 (9)	0.0051 (10)
C25	0.0471 (12)	0.0658 (15)	0.0476 (11)	−0.0072 (10)	0.0104 (9)	0.0034 (10)
C26	0.0389 (10)	0.0661 (14)	0.0459 (11)	0.0069 (10)	0.0042 (8)	0.0020 (10)
P1	0.0365 (3)	0.0671 (4)	0.0442 (3)	0.0052 (2)	−0.0014 (2)	−0.0119 (2)
F1	0.0390 (7)	0.1090 (12)	0.0577 (8)	−0.0025 (7)	0.0008 (6)	−0.0167 (8)
F2	0.0675 (9)	0.0983 (12)	0.0455 (7)	0.0249 (8)	−0.0035 (6)	−0.0166 (7)
F3	0.0576 (8)	0.0953 (11)	0.0545 (8)	−0.0017 (8)	0.0158 (6)	−0.0192 (7)
F4	0.0816 (11)	0.0715 (10)	0.0859 (11)	0.0076 (8)	0.0165 (9)	0.0022 (8)
F5	0.0901 (12)	0.0721 (10)	0.0708 (10)	0.0165 (9)	0.0053 (8)	−0.0017 (8)
F6	0.0399 (8)	0.1147 (14)	0.1095 (14)	0.0029 (8)	−0.0109 (8)	−0.0499 (11)

Geometric parameters (Å, º)

N1—C1	1.330 (3)	N4—C22	1.530 (2)
N1—C5	1.368 (3)	N4—C18	1.532 (3)
N2—C12	1.339 (3)	N4—H4A	0.92 (2)
N2—C9	1.359 (3)	N4—H4B	0.95 (3)
N3—C17	1.339 (3)	C18—C24	1.526 (3)
N3—C13	1.352 (3)	C18—C23	1.529 (3)
C1—C2	1.403 (3)	C18—C19	1.546 (3)
C1—H1	0.9500	C19—C20	1.512 (3)
C2—C3	1.364 (4)	C19—H19A	0.9900
C2—H2	0.9500	C19—H19B	0.9900
C3—C4	1.407 (4)	C20—C21	1.512 (3)
C3—H3	0.9500	C21—C22	1.548 (3)
C4—C5	1.424 (3)	C21—H21A	0.9900
C4—C6	1.438 (4)	C21—H21B	0.9900
C5—C9	1.454 (3)	C22—C25	1.525 (3)
C6—C7	1.350 (4)	C22—C26	1.527 (3)
C6—H6	0.9500	C23—H23A	0.9800
C7—C8	1.432 (3)	C23—H23B	0.9800
C7—H7	0.9500	C23—H23C	0.9800
C8—C10	1.403 (3)	C24—H24A	0.9800
C8—C9	1.422 (3)	C24—H24B	0.9800
C10—C11	1.373 (3)	C24—H24C	0.9800
C10—H10	0.9500	C25—H25A	0.9800
C11—C12	1.418 (3)	C25—H25B	0.9800
C11—H11	0.9500	C25—H25C	0.9800
C12—C13	1.494 (3)	C26—H26A	0.9800
C13—C14	1.398 (3)	C26—H26B	0.9800
C14—C15	1.395 (3)	C26—H26C	0.9800
C14—H14	0.9500	P1—F5	1.5906 (18)
C15—C16	1.367 (4)	P1—F1	1.5912 (14)
C15—H15	0.9500	P1—F6	1.5929 (15)
C16—C17	1.389 (3)	P1—F4	1.5989 (18)
C16—H16	0.9500	P1—F2	1.6049 (14)
C17—H17	0.9500	P1—F3	1.6081 (14)
O1—C20	1.210 (3)
C1—N1—C5	118.10 (18)	C24—C18—C19	110.63 (18)
C12—N2—C9	118.34 (18)	C23—C18—C19	110.92 (18)
C17—N3—C13	117.98 (19)	N4—C18—C19	108.63 (16)
N1—C1—C2	124.0 (2)	C20—C19—C18	111.53 (16)
N1—C1—H1	118.0	C20—C19—H19A	109.3
C2—C1—H1	118.0	C18—C19—H19A	109.3
C3—C2—C1	118.5 (2)	C20—C19—H19B	109.3
C3—C2—H2	120.8	C18—C19—H19B	109.3
C1—C2—H2	120.8	H19A—C19—H19B	108.0
C2—C3—C4	119.9 (2)	O1—C20—C21	123.2 (2)
C2—C3—H3	120.0	O1—C20—C19	123.1 (2)
C4—C3—H3	120.0	C21—C20—C19	113.70 (19)
C3—C4—C5	118.1 (2)	C20—C21—C22	112.91 (17)
C3—C4—C6	122.3 (2)	C20—C21—H21A	109.0
C5—C4—C6	119.6 (2)	C22—C21—H21A	109.0
N1—C5—C4	121.4 (2)	C20—C21—H21B	109.0
N1—C5—C9	119.41 (17)	C22—C21—H21B	109.0
C4—C5—C9	119.24 (19)	H21A—C21—H21B	107.8
C7—C6—C4	121.5 (2)	C25—C22—C26	108.66 (18)
C7—C6—H6	119.3	C25—C22—N4	105.43 (16)
C4—C6—H6	119.3	C26—C22—N4	112.04 (16)
C6—C7—C8	120.5 (2)	C25—C22—C21	111.80 (17)
C6—C7—H7	119.8	C26—C22—C21	110.55 (18)
C8—C7—H7	119.8	N4—C22—C21	108.30 (15)
C10—C8—C9	117.46 (19)	C18—C23—H23A	109.5
C10—C8—C7	121.8 (2)	C18—C23—H23B	109.5
C9—C8—C7	120.7 (2)	H23A—C23—H23B	109.5
N2—C9—C8	122.6 (2)	C18—C23—H23C	109.5
N2—C9—C5	118.91 (18)	H23A—C23—H23C	109.5
C8—C9—C5	118.49 (18)	H23B—C23—H23C	109.5
C11—C10—C8	120.1 (2)	C18—C24—H24A	109.5
C11—C10—H10	119.9	C18—C24—H24B	109.5
C8—C10—H10	119.9	H24A—C24—H24B	109.5
C10—C11—C12	118.8 (2)	C18—C24—H24C	109.5
C10—C11—H11	120.6	H24A—C24—H24C	109.5
C12—C11—H11	120.6	H24B—C24—H24C	109.5
N2—C12—C11	122.60 (19)	C22—C25—H25A	109.5
N2—C12—C13	117.81 (18)	C22—C25—H25B	109.5
C11—C12—C13	119.56 (19)	H25A—C25—H25B	109.5
N3—C13—C14	121.18 (19)	C22—C25—H25C	109.5
N3—C13—C12	117.79 (18)	H25A—C25—H25C	109.5
C14—C13—C12	121.0 (2)	H25B—C25—H25C	109.5
C15—C14—C13	119.4 (2)	C22—C26—H26A	109.5
C15—C14—H14	120.3	C22—C26—H26B	109.5
C13—C14—H14	120.3	H26A—C26—H26B	109.5
C16—C15—C14	119.4 (2)	C22—C26—H26C	109.5
C16—C15—H15	120.3	H26A—C26—H26C	109.5
C14—C15—H15	120.3	H26B—C26—H26C	109.5
C15—C16—C17	118.0 (2)	F5—P1—F1	90.85 (10)
C15—C16—H16	121.0	F5—P1—F6	90.02 (11)
C17—C16—H16	121.0	F1—P1—F6	179.08 (12)
N3—C17—C16	124.1 (2)	F5—P1—F4	179.92 (11)
N3—C17—H17	118.0	F1—P1—F4	89.07 (10)
C16—C17—H17	118.0	F6—P1—F4	90.06 (11)
C22—N4—C18	119.99 (16)	F5—P1—F2	90.47 (9)
C22—N4—H4A	106.8 (14)	F1—P1—F2	90.17 (8)
C18—N4—H4A	113.6 (14)	F6—P1—F2	90.11 (9)
C22—N4—H4B	108.9 (14)	F4—P1—F2	89.51 (9)
C18—N4—H4B	107.1 (14)	F5—P1—F3	89.90 (9)
H4A—N4—H4B	98 (2)	F1—P1—F3	90.11 (8)
C24—C18—C23	109.07 (18)	F6—P1—F3	89.61 (9)
C24—C18—N4	111.96 (17)	F4—P1—F3	90.12 (9)
C23—C18—N4	105.53 (17)	F2—P1—F3	179.53 (10)
C5—N1—C1—C2	0.4 (3)	C10—C11—C12—N2	−2.0 (3)
N1—C1—C2—C3	0.6 (3)	C10—C11—C12—C13	176.04 (19)
C1—C2—C3—C4	−1.2 (3)	C17—N3—C13—C14	0.5 (3)
C2—C3—C4—C5	0.9 (3)	C17—N3—C13—C12	178.55 (19)
C2—C3—C4—C6	−175.9 (2)	N2—C12—C13—N3	−11.5 (3)
C1—N1—C5—C4	−0.8 (3)	C11—C12—C13—N3	170.34 (19)
C1—N1—C5—C9	178.47 (18)	N2—C12—C13—C14	166.55 (19)
C3—C4—C5—N1	0.1 (3)	C11—C12—C13—C14	−11.6 (3)
C6—C4—C5—N1	177.04 (19)	N3—C13—C14—C15	1.0 (3)
C3—C4—C5—C9	−179.11 (18)	C12—C13—C14—C15	−177.0 (2)
C6—C4—C5—C9	−2.2 (3)	C13—C14—C15—C16	−1.1 (4)
C3—C4—C6—C7	177.8 (2)	C14—C15—C16—C17	−0.1 (4)
C5—C4—C6—C7	1.1 (3)	C13—N3—C17—C16	−1.8 (4)
C4—C6—C7—C8	0.2 (4)	C15—C16—C17—N3	1.6 (4)
C6—C7—C8—C10	−179.3 (2)	C22—N4—C18—C24	73.0 (2)
C6—C7—C8—C9	−0.2 (3)	C22—N4—C18—C23	−168.50 (17)
C12—N2—C9—C8	0.4 (3)	C22—N4—C18—C19	−49.5 (2)
C12—N2—C9—C5	−179.63 (16)	C24—C18—C19—C20	−72.8 (2)
C10—C8—C9—N2	−1.9 (3)	C23—C18—C19—C20	166.0 (2)
C7—C8—C9—N2	179.02 (18)	N4—C18—C19—C20	50.5 (2)
C10—C8—C9—C5	178.14 (17)	C18—C19—C20—O1	122.3 (2)
C7—C8—C9—C5	−0.9 (3)	C18—C19—C20—C21	−57.1 (2)
N1—C5—C9—N2	2.9 (3)	O1—C20—C21—C22	−123.2 (2)
C4—C5—C9—N2	−177.83 (17)	C19—C20—C21—C22	56.3 (2)
N1—C5—C9—C8	−177.13 (17)	C18—N4—C22—C25	167.70 (17)
C4—C5—C9—C8	2.1 (3)	C18—N4—C22—C26	−74.3 (2)
C9—C8—C10—C11	1.4 (3)	C18—N4—C22—C21	47.9 (2)
C7—C8—C10—C11	−179.5 (2)	C20—C21—C22—C25	−163.85 (18)
C8—C10—C11—C12	0.4 (3)	C20—C21—C22—C26	75.0 (2)
C9—N2—C12—C11	1.6 (3)	C20—C21—C22—N4	−48.1 (2)
C9—N2—C12—C13	−176.51 (16)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···N1	0.92 (2)	1.98 (2)	2.887 (2)	169 (2)
N4—H4B···N3	0.95 (3)	2.03 (3)	2.965 (3)	170 (2)