Synthesis and crystal structure of di­chlorido­(1,10-phenanthroline-κ2N,N′)gold(III) hexa­fluorido­phosphate

Ferraz de Paiva, R.E.; Nakahata, D.H.; Corbi, P.P.

doi:10.1107/S2056989017008763

research communications

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ISSN: 2056-9890

Volume 73| Part 7| July 2017| Pages 1048-1051

https://doi.org/10.1107/S2056989017008763

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Synthesis and crystal structure of dichlorido(1,10-phenanthroline-κ²N,N′)gold(III) hexafluoridophosphate

Raphael Enoque Ferraz de Paiva,^a ‡ Douglas Hideki Nakahata ^a and Pedro Paulo Corbi ^a ^*

^aInstitute of Chemistry, University of Campinas - UNICAMP, Campinas - SP, Brazil
^*Correspondence e-mail: ppcorbi@iqm.unicamp.br

Edited by M. Weil, Vienna University of Technology, Austria (Received 2 June 2017; accepted 12 June 2017; online 16 June 2017)

A gold(III) salt of composition [AuCl₂(C₁₂H₈N₂)]PF₆ was prepared and characterized by elemental and mass spectrometric analysis (ESI(+)–QTOF–MS), ¹H nuclear magnetic resonance measurements and by single-crystal X-ray diffraction. The square-planar coordination sphere of Au^III comprises the bidentate 1,10-phenanthroline ligand and two chloride ions, with the Au^III ion only slightly shifted from the least-squares plane of the ligating atoms (r.m.s. = 0.018 Å). In contrast to two other previously reported Au^III-phenantroline structures that are stabilized by interactions involving the chlorido ligands, the packing of the title compound does not present these features. Instead, the hexafluoridophosphate counter-ion gives rise to anion⋯π interactions that are a crucial factor for the crystal packing.

Keywords: gold(III); 1,10-phenanthroline ligand; square-planar coordination; anion-π interactions; crystal structure.

CCDC reference: 1555623

1. Chemical context

Au^III is isoelectronic with Pt^II and forms compounds with similar coordination modes and structures. Therefore, the synthesis of Au^III-based compounds has attracted much interest in the field of bioinorganic and medicinal chemistry after the successful application of cis-platin [cis-diamminedichloridoplatinum(II)] for cancer treatment (Siddik, 2003 ). Aromatic N-donors, such as 1,10-phenanthroline, are of interest given their planar structure that synergizes well with the typical square-planar coordination sphere of Au^III, producing potent DNA-intercalating agents (Abbate et al., 2000 ; Zou et al., 2015 ). On the other hand, Au^III compounds differ from Pt^II compounds in terms of their interactions with biomolecules, their stability in biological media or their mechanism of action. A review on cytotoxic properties and mechanisms of Au^III compounds with N-donors has been provided by Zou et al. (2015).

In this context we have prepared the title salt, [AuCl₂(C₁₂H₈N₂)]PF₆, that was characterized by elemental and mass spectrometric analysis (ESI(+)–QTOF–MS), ¹H nuclear magnetic resonance measurements and by single crystal X-ray diffraction.

2. Structural commentary

All atoms in the title salt are on general positions. The Au^III atom has a square-planar coordination environment, with the chlorido ligands in a cis configuration to each other. The Au^III atom deviates from planarity (as determined based on the four coordinating atoms) by 0.018 Å (r.m.s.). The main bond lengths [Au—N1 = 2.032 (2), Au—N2 = 2.036 (2), Au—Cl1 = 2.251 (1) and Au—Cl2 = 2.255 (1) Å] are in the normal ranges for this kind of complexes (see Database survey). The bite angle of the 1,10-phenanthroline ligand is 81.75 (9)°, while the Cl1—Au—Cl2 angle is 89.28 (3)°. Despite the highly symmetrical nature of the hexafluoridophosphate counter-ion, this unit does not show any disorder. The structures of the molecular entities of the [AuCl₂(C₁₂H₈N₂)]PF₆ salt are shown in Fig. 1.

Figure 1
The molecular entities of the title salt [AuCl₂(C₁₂H₈N₂)]PF₆. Displacement ellipsoids are drawn at the 40% probability level. Hydrogen atoms are not labelled for clarity.

3. Supramolecular features

The molecular packing in the crystal is shown in Fig. 2. Despite the square-planar coordination environment around Au^III and the presence of the highly conjugated and planar 1,10-phenanthroline ligand, π–π interactions have little relevance to the stabilization of the crystal. The shortest π-like interaction between the centroids [Cg1⋯Cg2ⁱ; symmetry code: (i) $[{1\over 2}]$ + x, y, $[{1\over 2}]$ − z; Fig. 3] of two neighbouring 1,10-phenanthroline rings are associated with a distance of 4.2521 (15) Å, which is very close to the upper limit of the threshold established by Janiak (2000 ) for a relevant offset π interaction.

Figure 2
Packing of the crystal structure of [AuCl₂(C₁₂H₈N₂)]PF₆ in a view along the c axis. Displacement ellipsoids are drawn at the 40% probability level.

Figure 3
Intermolecular interactions present in the crystal structure. Displacement ellipsoids are drawn at the 40% probability level. Hydrogen atoms were omitted for clarity. [Symmetry codes: (i) $[{1\over 2}]$ + x, y, $[{1\over 2}]$ − z, (ii) x, $[{1\over 2}]$ − y, $[{1\over 2}]$ + z, (iii) − $[{1\over 2}]$ + x, y, $[{1\over 2}]$ − z.]

The interactions between the hexafluoridophosphate counter-ion and the 1,10-phenanthroline ligands constitute the major intermolecular interactions in the crystal and can be divided into two types. The first type corresponds to an anion-donor⋯ π-acceptor interaction (Chifotides & Dunbar, 2013 ), with the shortest contact being C1⋯F5ⁱⁱ, of 3.096 (4) Å [symmetry code: (ii) x, ½ − y, ½ + z; Fig. 3]. The second and unique type of interaction between the PF₆⁻ anion and the π system of the phenanthroline ligand is observed where fluorine atoms point directly to the mid-point of an aromatic C—C bond. The distance between F6ⁱⁱ and the mid-point of C5 and C6 is 2.822 Å. The individual distances are C5⋯F6ⁱⁱ 2.925 (3) and C6⋯F6ⁱⁱⁱ 2.894 (3) Å [symmetry code: (iii) − $[{1\over 2}]$ + x, y, $[{1\over 2}]$ − z].

4. Database survey

A few structures of Au^III-(1,10-phenanthroline) compounds have been reported in the literature with different counter-ions. Abbate et al. (2000) reported the monohydrate chloride structure that crystallizes in the space group type P2₁/n, with Au—N distances of 2.033 (8) and 2.056 (8) Å and Au—Cl distances of 2.266 (3) and 2.263 (3) Å, respectively. The N—Au—N angle is 82.0 (3)° and the Cl—Au—Cl angle 89.5 (1)°. Pitteri et al. (2008 ) determined the structure with a disordered [AuBrCl(CN)₂]⁻ unit as a counter-ion in space group type P $[\overline{1}]$ . The Au—N distances are 2.05 (1) and 2.05 (1) Å, while the Au—Cl distances are 2.290 (5) and 2.299 (5) Å. The title compound has Au—N distances similar to that of the structure reported by Abbate et al. (2000), but slightly shorter than the one by Pitteri et al. (2008). Regarding the Au—Cl distances, [AuCl₂(C₁₂H₈N₂)]PF₆ and the structure reported by Abbate et al. (2000) have shorter ones than that reported by Pitteri et al. (2008). Although the [AuCl₂(C₁₂H₈N₂)]⁺ cations in the three structures exhibit no significant differences, their crystal packings vary greatly as a consequence of the intermolecular interactions with the different counter-ions. The structure reported by Abbate et al. (2000) has the Au^III-(1,10-phenanthroline) units closer in space, with the shortest centroid-to-centroid distance being 3.820 Å, much closer than 4.2521 (15) Å observed in the title compound. Furthermore, the presence of a water molecule and the chloride counter-ion establish a classical hydrogen-bonding network, which is absent in the structure of the title compound. The structure determined by Pitteri et al. (2008) is the only one with an axial Au⋯L interaction, namely Au⋯Br (3.374 Å).

5. Synthesis and crystallization

[AuCl₂(C₁₂H₈N₂)]PF₆ was synthesized by a modification of a literature protocol (Casini et al., 2010 ): K[AuCl₄] (0.25 mmol, 95.0 mg) was dissolved in 3 ml of H₂O/CH₃CN (1:5, v/v), and 1,10-phenanthroline, (0.25 mmol, 45 mg) dissolved in 0.5 ml of CH₃CN was then added to the gold(III)-containing solution. Finally, NH₄PF₆ (0.75 mmol, 124.6 mg) was added to the solution and the mixture was refluxed for 16 h. The obtained solid was isolated by filtration, washed with cold water and dried in vacuo. Elemental Analysis was performed on an Elemental Analyzer CHNS-O 2400 Perkin Elmer. Anal. Calcd. for C₁₂H₈AuCl₂F₆N₂P (593.04 g mol⁻¹): C 24.30%, H 1.36%, N 4.72%. Found: C 24.08%, H 0.70%, N 4.73%. Mass spectra were acquired in a XEVO QTOF–MS instrument (Waters). The sample was dissolved in the smallest possible volume of DMSO and diluted in a 1:1 (v/v) mixture of water and acetonitrile containing 0.1% formic acid. ESI(+)–QTOF–MS (m/z, [AuCl₂(C₁₂H₈N₂)]⁺, 100% relative abundance): 446. 9707 (calculated 446.9730). Crystals suitable for single crystal X-ray analysis were obtained by recrystallization from acetonitrile solution.

6. Solution stability

The stability of the [Au(1,10-phenanthroline)]³⁺ moiety is critical for the biological properties of the compound, including cytotoxicity. The [AuCl₂(C₁₂H₈N₂)]PF₆ salt was dissolved in deuterated dimethylsulfoxide (DMSO-d6) and the solvent replacement was followed by ¹H NMR for 72 h (Fig. 4). ¹H NMR spectra were acquired on a Bruker Avance III 400 MHz. The labile chlorido ligands were replaced, as expected, but the [Au(1,10-phenanthroline)]³⁺ moiety remained stable in the presence of the coordinating solvent (DMSO) throughout the period evaluated.

Figure 4
¹H NMR spectra following the Cl replacement by DMSO-d₆ in the salt [Au(phen)Cl₂]PF₆, where phen = 1,10-phenanthroline. (Top) Spectrum obtained from a freshly dissolved sample and (bottom) 72 h after dissolution. Two populations were identified, [Au(phen)Cl₂]⁺ (symbolized by a black square) and a chloride replacement product, most likely [Au(phen)(dmso-d₆)₂]³⁺ (symbolized by a black dot).

7. Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms were set in calculated positions, with C—H = 0.95 Å and U_iso(H) = 1.2U_eq(C).

Table 1
Experimental details

Crystal data
Chemical formula	[AuCl₂(C₁₂H₈N₂)]PF₆
M_r	593.04
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	150
a, b, c (Å)	12.9983 (7), 15.2709 (10), 15.5153 (10)
V (Å³)	3079.7 (3)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	10.07
Crystal size (mm)	0.15 × 0.13 × 0.05

Data collection
Diffractometer	Bruker APEX CCD detector
Absorption correction	Multi-scan (SADABS; Bruker, 2010 )
T_min, T_max	0.576, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	15573, 3822, 3192
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.019, 0.040, 1.01
No. of reflections	3822
No. of parameters	217
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.08, −0.56
Computer programs: APEX2 and SAINT (Bruker, 2010), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), Mercury (Macrae et al., 2006 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1555623

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989017008763/wm5398sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989017008763/wm5398Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989017008763/wm5398Isup3.mol

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2010); cell refinement: SAINT (Bruker, 2010); data reduction: SAINT (Bruker, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: Mercury (Macrae et al., 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Dichlorido(1,10-phenanthroline-κ²N,N')gold(III) hexafluoridophosphate top

Crystal data top

[AuCl₂(C₁₂H₈N₂)]PF₆	D_x = 2.558 Mg m⁻³
M_r = 593.04	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 119 reflections
a = 12.9983 (7) Å	θ = 3.4–27.3°
b = 15.2709 (10) Å	µ = 10.07 mm⁻¹
c = 15.5153 (10) Å	T = 150 K
V = 3079.7 (3) Å³	Plate, yellow
Z = 8	0.15 × 0.13 × 0.05 mm
F(000) = 2208

Data collection top

Bruker APEX CCD detector diffractometer	3822 independent reflections
Radiation source: fine-focus sealed tube	3192 reflections with I > 2σ(I)
Detector resolution: 8.3333 pixels mm^-1	R_int = 0.027
phi and ω scans	θ_max = 28.3°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2010)	h = −17→15
T_min = 0.576, T_max = 0.746	k = −20→15
15573 measured reflections	l = −15→20

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.019	H-atom parameters constrained
wR(F²) = 0.040	w = 1/[σ²(F_o²) + (0.0194P)²] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max = 0.001
3822 reflections	Δρ_max = 1.08 e Å⁻³
217 parameters	Δρ_min = −0.56 e Å⁻³

Special details top

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Au1	0.44227 (2)	0.09568 (2)	0.04214 (2)	0.01802 (4)
Cl1	0.29239 (6)	0.03883 (5)	−0.00417 (5)	0.03186 (17)
Cl2	0.48300 (6)	0.12866 (5)	−0.09535 (5)	0.02952 (17)
N1	0.57092 (15)	0.15008 (15)	0.09387 (16)	0.0184 (5)
N2	0.41395 (16)	0.06735 (15)	0.16813 (15)	0.0170 (5)
C1	0.6465 (2)	0.1908 (2)	0.0529 (2)	0.0254 (7)
H1	0.6468	0.1921	−0.0083	0.030*
C2	0.7252 (2)	0.2317 (2)	0.0982 (2)	0.0295 (7)
H2	0.7786	0.2608	0.0677	0.035*
C3	0.7262 (2)	0.2303 (2)	0.1863 (2)	0.0270 (7)
H3	0.7794	0.2591	0.2172	0.032*
C4	0.6474 (2)	0.18577 (19)	0.2310 (2)	0.0221 (6)
C5	0.57038 (18)	0.14663 (18)	0.18156 (19)	0.0173 (6)
C6	0.48791 (19)	0.10177 (17)	0.22131 (18)	0.0166 (5)
C7	0.4824 (2)	0.09379 (18)	0.31033 (19)	0.0204 (6)
C8	0.5628 (2)	0.1336 (2)	0.3608 (2)	0.0241 (6)
H8	0.5611	0.1288	0.4218	0.029*
C9	0.6403 (2)	0.1775 (2)	0.3226 (2)	0.0260 (7)
H9	0.6918	0.2036	0.3576	0.031*
C10	0.3993 (2)	0.04620 (19)	0.3444 (2)	0.0230 (6)
H10	0.3929	0.0386	0.4050	0.028*
C11	0.3274 (2)	0.01083 (19)	0.29003 (19)	0.0240 (6)
H11	0.2715	−0.0218	0.3129	0.029*
C12	0.3362 (2)	0.02256 (17)	0.20087 (19)	0.0210 (6)
H12	0.2858	−0.0019	0.1636	0.025*
P1	0.40487 (5)	0.14377 (5)	0.61776 (5)	0.01992 (16)
F1	0.38930 (15)	0.08895 (13)	0.70331 (12)	0.0412 (5)
F2	0.41427 (15)	0.05546 (12)	0.56412 (13)	0.0362 (5)
F3	0.52589 (12)	0.14548 (12)	0.63152 (14)	0.0399 (5)
F4	0.41879 (16)	0.19932 (14)	0.53096 (13)	0.0443 (5)
F5	0.28305 (12)	0.14421 (12)	0.60406 (14)	0.0410 (5)
F6	0.39496 (14)	0.23393 (12)	0.67051 (14)	0.0423 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Au1	0.02348 (6)	0.01722 (6)	0.01336 (6)	0.00051 (4)	−0.00115 (4)	−0.00098 (4)
Cl1	0.0364 (4)	0.0344 (4)	0.0249 (4)	−0.0106 (3)	−0.0115 (3)	0.0001 (4)
Cl2	0.0419 (4)	0.0329 (4)	0.0138 (3)	0.0045 (3)	0.0028 (3)	−0.0002 (3)
N1	0.0192 (11)	0.0202 (12)	0.0159 (12)	0.0014 (9)	0.0006 (9)	−0.0011 (10)
N2	0.0210 (11)	0.0166 (11)	0.0134 (12)	0.0001 (9)	−0.0008 (10)	−0.0012 (10)
C1	0.0246 (14)	0.0276 (16)	0.0239 (17)	0.0031 (12)	0.0071 (13)	0.0020 (13)
C2	0.0211 (14)	0.0331 (18)	0.0342 (19)	−0.0027 (13)	0.0067 (13)	0.0066 (15)
C3	0.0183 (14)	0.0269 (16)	0.0359 (19)	0.0008 (12)	−0.0035 (13)	−0.0017 (14)
C4	0.0189 (13)	0.0219 (15)	0.0256 (16)	0.0023 (11)	−0.0023 (12)	−0.0007 (13)
C5	0.0178 (13)	0.0168 (13)	0.0173 (14)	0.0044 (10)	−0.0005 (11)	−0.0010 (11)
C6	0.0177 (12)	0.0140 (12)	0.0182 (14)	0.0043 (10)	−0.0007 (11)	−0.0005 (12)
C7	0.0236 (13)	0.0192 (13)	0.0184 (15)	0.0051 (11)	−0.0007 (12)	0.0011 (12)
C8	0.0304 (15)	0.0259 (15)	0.0158 (15)	0.0058 (12)	−0.0056 (13)	−0.0020 (13)
C9	0.0252 (15)	0.0277 (16)	0.0250 (17)	0.0017 (12)	−0.0082 (13)	−0.0068 (14)
C10	0.0266 (14)	0.0237 (15)	0.0187 (15)	0.0048 (12)	0.0022 (13)	0.0040 (13)
C11	0.0261 (14)	0.0233 (14)	0.0227 (16)	−0.0014 (12)	0.0034 (13)	0.0020 (13)
C12	0.0208 (13)	0.0178 (13)	0.0244 (16)	−0.0014 (11)	−0.0016 (12)	−0.0007 (12)
P1	0.0199 (3)	0.0183 (4)	0.0216 (4)	−0.0015 (3)	0.0008 (3)	−0.0005 (3)
F1	0.0531 (12)	0.0476 (12)	0.0228 (11)	−0.0131 (10)	−0.0014 (9)	0.0103 (9)
F2	0.0484 (11)	0.0258 (10)	0.0345 (12)	0.0000 (9)	−0.0003 (9)	−0.0105 (9)
F3	0.0205 (8)	0.0374 (11)	0.0619 (15)	−0.0024 (8)	−0.0029 (9)	−0.0005 (11)
F4	0.0583 (12)	0.0407 (12)	0.0340 (13)	−0.0018 (10)	0.0028 (9)	0.0167 (10)
F5	0.0221 (8)	0.0325 (11)	0.0683 (15)	−0.0025 (8)	−0.0081 (9)	0.0000 (10)
F6	0.0387 (10)	0.0321 (11)	0.0560 (14)	−0.0106 (8)	0.0194 (10)	−0.0224 (10)

Geometric parameters (Å, º) top

Au1—N1	2.032 (2)	C6—C7	1.388 (4)
Au1—N2	2.036 (2)	C7—C10	1.406 (4)
Au1—Cl1	2.2506 (7)	C7—C8	1.440 (4)
Au1—Cl2	2.2549 (8)	C8—C9	1.348 (4)
N1—C1	1.325 (3)	C8—H8	0.9500
N1—C5	1.362 (4)	C9—H9	0.9500
N2—C12	1.322 (3)	C10—C11	1.370 (4)
N2—C6	1.372 (3)	C10—H10	0.9500
C1—C2	1.389 (4)	C11—C12	1.400 (4)
C1—H1	0.9500	C11—H11	0.9500
C2—C3	1.368 (4)	C12—H12	0.9500
C2—H2	0.9500	P1—F1	1.582 (2)
C3—C4	1.411 (4)	P1—F3	1.5877 (17)
C3—H3	0.9500	P1—F2	1.589 (2)
C4—C5	1.396 (4)	P1—F5	1.5976 (18)
C4—C9	1.430 (4)	P1—F4	1.602 (2)
C5—C6	1.414 (4)	P1—F6	1.6070 (19)

N1—Au1—N2	81.75 (9)	C10—C7—C8	124.8 (3)
N1—Au1—Cl1	174.84 (7)	C9—C8—C7	120.9 (3)
N2—Au1—Cl1	93.90 (6)	C9—C8—H8	119.5
N1—Au1—Cl2	95.11 (7)	C7—C8—H8	119.5
N2—Au1—Cl2	176.74 (6)	C8—C9—C4	122.0 (3)
Cl1—Au1—Cl2	89.28 (3)	C8—C9—H9	119.0
C1—N1—C5	120.1 (2)	C4—C9—H9	119.0
C1—N1—Au1	127.8 (2)	C11—C10—C7	119.7 (3)
C5—N1—Au1	112.00 (17)	C11—C10—H10	120.1
C12—N2—C6	120.2 (2)	C7—C10—H10	120.1
C12—N2—Au1	128.12 (19)	C10—C11—C12	120.2 (3)
C6—N2—Au1	111.69 (18)	C10—C11—H11	119.9
N1—C1—C2	121.0 (3)	C12—C11—H11	119.9
N1—C1—H1	119.5	N2—C12—C11	120.5 (3)
C2—C1—H1	119.5	N2—C12—H12	119.7
C3—C2—C1	120.4 (3)	C11—C12—H12	119.7
C3—C2—H2	119.8	F1—P1—F3	91.30 (11)
C1—C2—H2	119.8	F1—P1—F2	90.01 (11)
C2—C3—C4	119.5 (3)	F3—P1—F2	90.47 (10)
C2—C3—H3	120.3	F1—P1—F5	89.25 (11)
C4—C3—H3	120.3	F3—P1—F5	178.81 (11)
C5—C4—C3	117.2 (3)	F2—P1—F5	90.58 (11)
C5—C4—C9	117.5 (3)	F1—P1—F4	179.13 (12)
C3—C4—C9	125.3 (3)	F3—P1—F4	89.57 (11)
N1—C5—C4	121.9 (3)	F2—P1—F4	90.02 (11)
N1—C5—C6	117.3 (2)	F5—P1—F4	89.88 (11)
C4—C5—C6	120.8 (3)	F1—P1—F6	90.90 (11)
N2—C6—C7	121.9 (3)	F3—P1—F6	89.82 (10)
N2—C6—C5	117.0 (3)	F2—P1—F6	179.04 (12)
C7—C6—C5	121.0 (3)	F5—P1—F6	89.13 (10)
C6—C7—C10	117.4 (3)	F4—P1—F6	89.06 (12)
C6—C7—C8	117.8 (3)

C5—N1—C1—C2	−1.0 (4)	C4—C5—C6—N2	178.2 (2)
Au1—N1—C1—C2	174.1 (2)	N1—C5—C6—C7	178.8 (2)
N1—C1—C2—C3	0.2 (5)	C4—C5—C6—C7	−1.4 (4)
C1—C2—C3—C4	1.0 (5)	N2—C6—C7—C10	2.1 (4)
C2—C3—C4—C5	−1.4 (4)	C5—C6—C7—C10	−178.4 (2)
C2—C3—C4—C9	178.5 (3)	N2—C6—C7—C8	−178.9 (2)
C1—N1—C5—C4	0.6 (4)	C5—C6—C7—C8	0.7 (4)
Au1—N1—C5—C4	−175.2 (2)	C6—C7—C8—C9	0.4 (4)
C1—N1—C5—C6	−179.7 (2)	C10—C7—C8—C9	179.4 (3)
Au1—N1—C5—C6	4.5 (3)	C7—C8—C9—C4	−0.8 (4)
C3—C4—C5—N1	0.6 (4)	C5—C4—C9—C8	0.1 (4)
C9—C4—C5—N1	−179.3 (3)	C3—C4—C9—C8	−179.8 (3)
C3—C4—C5—C6	−179.1 (2)	C6—C7—C10—C11	−0.7 (4)
C9—C4—C5—C6	1.0 (4)	C8—C7—C10—C11	−179.7 (3)
C12—N2—C6—C7	−2.3 (4)	C7—C10—C11—C12	−0.5 (4)
Au1—N2—C6—C7	177.4 (2)	C6—N2—C12—C11	1.0 (4)
C12—N2—C6—C5	178.2 (2)	Au1—N2—C12—C11	−178.6 (2)
Au1—N2—C6—C5	−2.2 (3)	C10—C11—C12—N2	0.4 (4)
N1—C5—C6—N2	−1.6 (3)

Footnotes

‡Additional correspondence author, e-mail: raphael.enoque@gmail.com.

Acknowledgements

The authors are grateful to Dr Déborah de Alencar Simoni, technician of the Institutional Single Crystal XRD facility – UNICAMP, Brazil, for the data collection and preliminary data refinements.

Funding information

Funding for this research was provided by: Fundação de Amparo à Pesquisa do Estado de São Paulo (grant No. 2015/25114-4 to Pedro Paulo Corbi; grant No. 2015/20882-3 to Douglas Hideki Nakahata); Conselho Nacional de Desenvolvimento Científico e Tecnológico (grant No. 140466/2014-2 to Raphael Enoque Ferraz de Paiva).

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