Bis(4-picoline-[kappa]N)gold(I) di­bromido­aurate(I) and bis­(4-picoline-[kappa]N)gold(I) di­chlorido­aurate(I): space-group ambiguity?

Bis(4-picoline-[kappa]N)gold(I) di­bromido­aurate(I), [Au(C₆H₇N)₂][AuBr₂], (I), crystallizes in the monoclinic space group P2₁/n, with two half cations and one general anion in the asymmetric unit. The cations, located on centres of inversion, assemble to form chains parallel to the a axis, but there are no significant contacts between the cations. Cohesion is provided by flanking anions, which are connected to the cations by short Au...Au contacts and C-H...Br hydrogen bonds, and to each other by Br...Br contacts. The corresponding chloride derivative, [Au(C₆H₇N)₂][AuCl₂], (II), is isotypic. A previous structure determination of (II), reported in the space group P with very similar axis lengths to those of (I) [Lin et al. (2008). Inorg. Chem. 47, 2543-2551], might be identical to the structure presented here, except that its [gamma] angle of 88.79 (7)° seems to rule out a monoclinic cell. No phase transformation of (II) could be detected on the basis of data sets recorded at 100, 200 and 295 K.

S1. Comment

Complexes of gold(I) halides with pyridines, picolines and lutidines L are generally of the form (L₂Au)⁺.(AuX₂)^-, whereby the ions are linked by Au···Au contacts to form finite or infinite chains. The pioneering work on these complexes was performed by Strähle and co-workers (see e.g. Adams et al., 1982; Conzelmann et al., 1984). However, the complex (2-picoline)AuCl is molecular (Jones & Ahrens, 1998).

We are interested in amine complexes of gold (Döring & Jones, 2013a, and references therein) and have recently begun to study amine complexes of gold(I) bromide (Döring & Jones, 2013b). We began by determining the structure of the 4-picoline complex of AuBr, (I), which adopts the usual ionic form. A comparison with the structure of the analogous chloro derivative, (II) (Lin et al., 2008), revealed some apparent inconsistencies, which led us to redetermine the latter structure.

Compound (I) crystallizes in space group P2₁/n with Z = 4. The asymmetric unit contains two half cations, in which the Au atoms occupy inversion centres, and a complete anion (Fig. 1). Fig. 2 shows the packing of the various ions. The cations assemble to form chains parallel to the a axis; the cations based on Au1 and Au3 occupy alternate positions, and the N—Au—N vectors are perpendicular to the chain direction. The Au1···Au3 distances within the chain are, at 4.1243 (2) Å, too long to represent significant aurophilic interactions.

The cations centred on Au1 are flanked by the anions via a short contact Au1···Au2 = 3.1796 (2) Å. Further support for the chain is provided by four `weak' hydrogen bonds of C—H···Br type (Table 2) involving the ortho H atoms of the picoline ligands. We have previously drawn attention to the importance of such interactions in the packing of bis(3-bromopyridine)gold(I) dichloroaurate(I) (Freytag & Jones, 2000), and thus in general for other gold complexes with pyridine-type ligands. Fig. 2 also shows the short Br···Br contacts of 3.5098 (7) Å between neighbouring anions. These are the shortest known between AuBr₂^- anions, the previous shortest according to a search of the Cambridge Structural Database (CSD, Version?; Allen, 2002) being 3.677 Å in a tetrathiafulvalene charge-transfer complex (Beno et al., 1990), but they are probably too linear [Au—Br···Br = 173.53 (2) and 170.55 (2)°] to be regarded as significant stabilizing interactions (Pedireddi et al., 1994). Similarly, Au3···Br contacts of 3.6–3.7 Å are also probably too long to be significant, and are not shown in Fig. 2.

The structure of (II), as published by Lin et al. (2008), was reported in space group P1 with cell constants (at room temperature) a = 8.121 (8), b = 9.827 (7) and c = 19.982 (7) Å, α = 89.72 (4), β = 82.21 (4) and γ = 88.79 (7), and Z = 4 (four independent cations with inversion symmetry and two independent anions on general positions). General features of the packing were closely analogous to those of (I). In general, analogous chloro and bromo derivatives may well be isotypic. The general similarity of the cell of (II) to that of (I) is clear, if the complementary angle for β is used, but the value of γ seems to rule out a monoclinic setting for (II). We therefore decided to redetermine the structure of (II) at low temperature.

The structure of (II) at 100 K is shown in Fig. 3. Compounds (I) and (II) are indeed isotypic at 100 K. There are significant shifts in the cell constants, especially β, but the coordinates of (I) can be used as a starting point for the refinement of (II) and vice versa. Details of C—H···Cl hydrogen bonds within the chains are given in Table 3. Further borderline contacts between chains, not observed for the bromo derivative, are given in the Supplementary Materials. Contact distances: Au1···Au2 = 3.1874 (2), Au1···Au3 = 3.9524 (2) and Cl1···Cl2 between anions = 3.4128 (14) Å. A database search revealed no other structures with short Cl···Cl contacts between AuCl₂^- anions. No separate packing diagram is presented because of the close similarity to the packing of (I).

If the structure of (II) is indeed monoclinic at 100 K but triclinic at room temperature, presumably a phase transition must take place somewhere between these two temperatures. We therefore remeasured the structure at 200 and 295 K. However, the monoclinic cell remained essentially unchanged, apart from slight changes in cell constants, especially the β angle [at 200 K, a = 7.9579 (4), b = 9.6670 (5) and c = 19.9987 (9) Å, β = 98.250 (5)° and V = 1522.55 (13) ų; at 295 K, a = 8.0221 (7), b = 9.7523 (6) and c = 19.9889 (19) Å, β = 97.552 (6)° and V = 1550.26 (18) ų], corresponding to the expected increase in cell volume with temperature. In particular, there was no evidence for a significant deviation of α or γ from 90°. Details of these structures are contained in the deposited CIF files.

Finally, we used the deposited structure of (II) (Lin et al., 2008) to calculate structure factors (using the program XPREP, which forms part of the SHELX suite; Sheldrick, 2008). The same program was then used to check for higher symmetry, increasing the angle tolerance to 2°. The program chose a monoclinic cell [space group P2₁/n, same axes, α = 89.72, β = 97.79 and γ = 91.21°, matrix 1 0 0 / 0 1 0 / 0 0 1] with an R(int) value of 0.02, and the intensity data thus transformed could be used to refine our structure of (II) with a simulated R value of essentially zero. It therefore seems possible that the two structures are identical, and that errors in the apparent values for the α and γ angles may have led to the false assumption of triclinic symmetry for (II). Clearly, the crystal quality was only moderate, in view of the reported wR2 value of 0.218. We too were once misled in one such case when the preliminary cell from a poor-quality crystal had an angle just greater than 91°; the program decided on a triclinic cell and, in the pre-CheckCIF era, we carelessly failed to check this assumption, leading to the publication of a structure in an incorrect space group (Ahrens et al., 2000; CSD refcode DUHQUS, later corrected as DUHQUS01, space group C2/c). However, we cannot with total certainty rule out the coexistence of two closely similar structures, one triclinic and one monoclinic. The powder patterns would be almost identical, and the compound is not especially stable, so extensive attempts to interconvert putative polymorphs would probably be unsuccessful.

We contacted the starred author of the previous report but he was unable to comment for health reasons.

Related literature

For related literature, see: Adams et al. (1982); Ahrens et al. (2000); Allen (2002); Beno et al. (1990); Conzelmann et al. (1984); Döring & Jones (2013a, 2013b); Freytag & Jones (2000); Jones & Ahrens (1998); Lin et al. (2008); Pedireddi et al. (1994); Sheldrick (2008).

S2. Experimental

Compounds (I) (II) were obtained by reaction of 4-picoline with (tht)AuX (tht = tetrahydrothiophene and X = Br or Cl) [Please give quantities or mole ratios]. Overlayering the solutions with diethyl ether (X = Br) or petroleum ether (X = Cl) provided single crystals.

S3. Refinement

Methyl groups were refined as idealized rigid groups allowed to rotate but not tip, with C—H = 0.98 Å and H—C—H = 109.5°, and with U_iso(H) = 1.5U_eq(C). Other H atoms were refined using a riding model starting from calculated positions, with aromatic C—H = 0.98 Å and U_iso(H) = 1.2U_eq(C). The methyl H atoms of the room-temperature structure were indistinct.

Computing details

For all compounds, data collection: CrysAlis PRO (Agilent, 2013); cell refinement: CrysAlis PRO (Agilent, 2013); data reduction: CrysAlis PRO (Agilent, 2013); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP (Siemens, 1994); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. The structure of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the ??% probability level. [Please complete] Both cations have been extended by symmetry over the relevant inversion centres Two methyl H atoms on the extreme left are eclipsed. No secondary interactions (see text) are shown.
	Fig. 2. A packing diagram for (I), showing a chain of ions parallel to the a axis. Ortho H atoms are retained. Dashed lines represent various types of interionic contact (see text). C—H···Br hydrogen bonds are numbered according to their order in Table 2.
	Fig. 3. The structure of (II) at 100 K, with the atom-numbering scheme. Displacement ellipsoids are drawn at the ??% probability level. [Please complete] Both cations have been extended by symmetry over the relevant inversion centres No secondary interactions (see text) are shown.

(I) Bis(4-picoline-κN)gold(I) dibromidoaurate(I)

Crystal data

[Au(C6H7N)2][AuBr2]	F(000) = 1312
Mr = 740.01	Dx = 3.103 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 12461 reflections
a = 8.2485 (3) Å	θ = 2.6–30.3°
b = 9.7291 (3) Å	µ = 23.53 mm^−1
c = 19.8055 (6) Å	T = 100 K
β = 94.737 (3)°	Hexagonal tablet, colourless
V = 1583.97 (9) Å^3	0.15 × 0.08 × 0.05 mm
Z = 4

Data collection

Oxford Xcalibur diffractometer with Eos detector	4090 independent reflections
Radiation source: Enhance (Mo) X-ray Source	3452 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.072
Detector resolution: 16.1419 pixels mm^-1	θmax = 28.7°, θmin = 2.3°
ω scans	h = −11→11
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013)	k = −13→13
Tmin = 0.282, Tmax = 1.000	l = −26→26
78671 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)] = 0.025	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.048	H-atom parameters constrained
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0176P)^2 + 2.0928P] where P = (Fo^2 + 2Fc^2)/3
4090 reflections	(Δ/σ)max = 0.001
168 parameters	Δρmax = 1.10 e Å^−3
0 restraints	Δρmin = −1.37 e Å^−3

Special details

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

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

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

	x	y	z	Uiso*/Ueq
Au1	0.0000	0.5000	0.0000	0.01804 (6)
Au2	0.01325 (2)	0.730233 (17)	0.114269 (9)	0.01520 (5)
Au3	0.5000	0.5000	0.0000	0.03044 (8)
Br1	0.30111 (6)	0.73618 (5)	0.11015 (2)	0.02044 (10)
Br2	−0.27195 (6)	0.73941 (5)	0.12396 (2)	0.02214 (11)
N11	0.0267 (5)	0.3507 (4)	0.07140 (19)	0.0168 (8)
C12	0.1275 (6)	0.3670 (5)	0.1275 (2)	0.0197 (10)
H12	0.1904	0.4487	0.1327	0.024*
C13	0.1426 (6)	0.2683 (5)	0.1780 (2)	0.0205 (10)
H13	0.2133	0.2840	0.2176	0.025*
C14	0.0551 (6)	0.1468 (5)	0.1711 (2)	0.0197 (10)
C15	−0.0461 (6)	0.1301 (5)	0.1126 (2)	0.0224 (11)
H15	−0.1077	0.0480	0.1060	0.027*
C16	−0.0588 (6)	0.2317 (5)	0.0636 (2)	0.0211 (10)
H16	−0.1288	0.2179	0.0236	0.025*
C17	0.0678 (7)	0.0406 (5)	0.2258 (3)	0.0325 (13)
H17A	0.0038	−0.0403	0.2109	0.049*
H17B	0.0260	0.0784	0.2668	0.049*
H17C	0.1820	0.0142	0.2356	0.049*
N21	0.5229 (6)	0.3462 (4)	0.0686 (2)	0.0266 (10)
C22	0.4648 (7)	0.2191 (5)	0.0534 (3)	0.0289 (12)
H22	0.4156	0.2013	0.0092	0.035*
C23	0.4752 (6)	0.1142 (5)	0.1008 (2)	0.0244 (11)
H23	0.4331	0.0259	0.0887	0.029*
C24	0.5455 (6)	0.1366 (5)	0.1650 (2)	0.0215 (11)
C25	0.6075 (7)	0.2671 (5)	0.1800 (3)	0.0256 (11)
H25	0.6586	0.2859	0.2238	0.031*
C26	0.5950 (7)	0.3689 (5)	0.1317 (3)	0.0278 (12)
H26	0.6380	0.4574	0.1427	0.033*
C27	0.5548 (7)	0.0271 (5)	0.2185 (3)	0.0288 (12)
H27A	0.4888	−0.0519	0.2025	0.043*
H27B	0.5135	0.0636	0.2599	0.043*
H27C	0.6682	−0.0018	0.2281	0.043*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Au1	0.02986 (15)	0.01182 (11)	0.01237 (12)	−0.00069 (10)	0.00133 (10)	0.00101 (9)
Au2	0.01685 (9)	0.01383 (8)	0.01463 (8)	−0.00144 (7)	−0.00049 (6)	−0.00024 (7)
Au3	0.0595 (2)	0.01621 (13)	0.01688 (14)	0.00243 (13)	0.01097 (13)	0.00097 (10)
Br1	0.0165 (2)	0.0222 (2)	0.0224 (2)	−0.00326 (18)	0.00048 (18)	0.00025 (18)
Br2	0.0165 (2)	0.0252 (3)	0.0244 (3)	−0.00093 (19)	−0.0002 (2)	−0.00162 (19)
N11	0.026 (2)	0.0121 (18)	0.0123 (19)	0.0002 (16)	0.0033 (16)	0.0018 (14)
C12	0.027 (3)	0.012 (2)	0.020 (2)	−0.0009 (19)	0.001 (2)	−0.0011 (18)
C13	0.026 (3)	0.015 (2)	0.019 (2)	−0.0005 (19)	−0.005 (2)	−0.0025 (18)
C14	0.028 (3)	0.018 (2)	0.013 (2)	0.004 (2)	0.002 (2)	−0.0018 (17)
C15	0.031 (3)	0.015 (2)	0.022 (3)	−0.007 (2)	0.003 (2)	−0.0007 (18)
C16	0.027 (3)	0.019 (2)	0.016 (2)	−0.004 (2)	−0.001 (2)	−0.0025 (18)
C17	0.054 (4)	0.019 (3)	0.024 (3)	−0.007 (2)	−0.006 (3)	0.008 (2)
N21	0.049 (3)	0.015 (2)	0.018 (2)	0.0018 (19)	0.012 (2)	0.0013 (16)
C22	0.043 (3)	0.022 (3)	0.022 (3)	−0.001 (2)	0.005 (2)	−0.003 (2)
C23	0.038 (3)	0.014 (2)	0.020 (3)	−0.004 (2)	0.001 (2)	−0.0052 (18)
C24	0.032 (3)	0.014 (2)	0.020 (2)	0.004 (2)	0.007 (2)	0.0033 (18)
C25	0.042 (3)	0.020 (2)	0.015 (2)	0.001 (2)	0.002 (2)	−0.0025 (19)
C26	0.044 (3)	0.022 (3)	0.018 (3)	−0.003 (2)	0.005 (2)	−0.005 (2)
C27	0.042 (3)	0.020 (3)	0.024 (3)	0.000 (2)	0.001 (2)	0.000 (2)

Geometric parameters (Å, º)

Au1—N11	2.027 (4)	C23—C24	1.370 (7)
Au1—N11^i	2.027 (4)	C24—C25	1.391 (7)
Au1—Au2^i	3.1796 (2)	C24—C27	1.500 (6)
Au1—Au2	3.1797 (2)	C25—C26	1.376 (7)
Au2—Br2	2.3777 (5)	C12—H12	0.9500
Au2—Br1	2.3833 (5)	C13—H13	0.9500
Au3—N21	2.019 (4)	C15—H15	0.9500
Au3—N21^ii	2.019 (4)	C16—H16	0.9500
N11—C12	1.341 (6)	C17—H17A	0.9800
N11—C16	1.357 (6)	C17—H17B	0.9800
C12—C13	1.385 (6)	C17—H17C	0.9800
C13—C14	1.385 (6)	C22—H22	0.9500
C14—C15	1.381 (7)	C23—H23	0.9500
C14—C17	1.494 (6)	C25—H25	0.9500
C15—C16	1.383 (6)	C26—H26	0.9500
N21—C22	1.351 (6)	C27—H27A	0.9800
N21—C26	1.356 (6)	C27—H27B	0.9800
C22—C23	1.385 (7)	C27—H27C	0.9800
N11—Au1—N11^i	180.0	N21—C26—C25	121.8 (5)
N11—Au1—Au2^i	89.25 (10)	N11—C12—H12	119.1
N11^i—Au1—Au2^i	90.75 (10)	C13—C12—H12	119.1
N11—Au1—Au2	90.75 (10)	C12—C13—H13	119.8
N11^i—Au1—Au2	89.25 (10)	C14—C13—H13	119.8
Au2^i—Au1—Au2	180.0	C14—C15—H15	119.7
Br2—Au2—Br1	175.569 (18)	C16—C15—H15	119.7
Br2—Au2—Au1	96.191 (13)	N11—C16—H16	119.3
Br1—Au2—Au1	88.194 (13)	C15—C16—H16	119.3
N21—Au3—N21^ii	180.0	C14—C17—H17A	109.5
C12—N11—C16	118.5 (4)	C14—C17—H17B	109.5
C12—N11—Au1	121.1 (3)	H17A—C17—H17B	109.5
C16—N11—Au1	120.4 (3)	C14—C17—H17C	109.5
N11—C12—C13	121.9 (4)	H17A—C17—H17C	109.5
C12—C13—C14	120.4 (4)	H17B—C17—H17C	109.5
C15—C14—C13	117.2 (4)	N21—C22—H22	119.2
C15—C14—C17	121.9 (4)	C23—C22—H22	119.2
C13—C14—C17	120.9 (4)	C24—C23—H23	119.7
C14—C15—C16	120.7 (4)	C22—C23—H23	119.7
N11—C16—C15	121.4 (4)	C26—C25—H25	119.9
C22—N21—C26	118.3 (4)	C24—C25—H25	119.9
C22—N21—Au3	121.1 (4)	N21—C26—H26	119.1
C26—N21—Au3	120.6 (3)	C25—C26—H26	119.1
N21—C22—C23	121.5 (5)	C24—C27—H27A	109.5
C24—C23—C22	120.7 (5)	C24—C27—H27B	109.5
C23—C24—C25	117.6 (4)	H27A—C27—H27B	109.5
C23—C24—C27	122.4 (4)	C24—C27—H27C	109.5
C25—C24—C27	120.0 (5)	H27A—C27—H27C	109.5
C26—C25—C24	120.2 (5)	H27B—C27—H27C	109.5
N11—Au1—Au2—Br2	−91.17 (11)	C17—C14—C15—C16	178.3 (5)
N11^i—Au1—Au2—Br2	88.84 (11)	C12—N11—C16—C15	1.4 (7)
N11—Au1—Au2—Br1	89.47 (11)	Au1—N11—C16—C15	−178.1 (4)
N11^i—Au1—Au2—Br1	−90.53 (11)	C14—C15—C16—N11	−0.3 (8)
Au2^i—Au1—N11—C12	140.7 (4)	C26—N21—C22—C23	1.0 (8)
Au2—Au1—N11—C12	−39.3 (4)	Au3—N21—C22—C23	−177.8 (4)
Au2^i—Au1—N11—C16	−39.8 (3)	N21—C22—C23—C24	−0.1 (8)
Au2—Au1—N11—C16	140.2 (3)	C22—C23—C24—C25	−0.9 (8)
C16—N11—C12—C13	−2.0 (7)	C22—C23—C24—C27	178.1 (5)
Au1—N11—C12—C13	177.5 (4)	C23—C24—C25—C26	1.0 (8)
N11—C12—C13—C14	1.4 (7)	C27—C24—C25—C26	−178.1 (5)
C12—C13—C14—C15	−0.2 (7)	C22—N21—C26—C25	−1.0 (8)
C12—C13—C14—C17	−178.8 (5)	Au3—N21—C26—C25	177.9 (4)
C13—C14—C15—C16	−0.3 (7)	C24—C25—C26—N21	0.0 (8)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12···Br1	0.95	2.99	3.892 (5)	160
C16—H16···Br1^i	0.95	2.94	3.847 (5)	161
C22—H22···Br2^i	0.95	2.86	3.756 (5)	158
C26—H26···Br2^iii	0.95	2.87	3.775 (5)	159

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

(II_100K) Bis(4-picoline-κN)gold(I) dichloridoaurate(I)

Crystal data

[Au(C6H7N)2][AuCl2]	F(000) = 1168
Mr = 651.09	Dx = 2.886 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 7483 reflections
a = 7.9048 (3) Å	θ = 2.6–30.4°
b = 9.5597 (3) Å	µ = 19.90 mm^−1
c = 20.1036 (7) Å	T = 100 K
β = 99.421 (4)°	Block, colourless
V = 1498.68 (9) Å^3	0.10 × 0.05 × 0.02 mm
Z = 4

Data collection

Oxford Xcalibur diffractometer with Eos detector	3726 independent reflections
Radiation source: Enhance (Mo) X-ray Source	3169 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.059
Detector resolution: 16.1419 pixels mm^-1	θmax = 28.3°, θmin = 2.4°
w scans	h = −10→10
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013)	k = −12→12
Tmin = 0.433, Tmax = 1.000	l = −26→26
37223 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.023	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.040	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0129P)^2 + 0.7856P] where P = (Fo^2 + 2Fc^2)/3
3726 reflections	(Δ/σ)max = 0.004
168 parameters	Δρmax = 0.86 e Å^−3
0 restraints	Δρmin = −0.92 e Å^−3

Special details

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

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

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

	x	y	z	Uiso*/Ueq
Au1	0.0000	0.5000	0.0000	0.01521 (6)
Au2	0.01655 (2)	0.725156 (17)	0.117825 (9)	0.01450 (5)
Au3	0.5000	0.5000	0.0000	0.02088 (6)
Cl1	0.29978 (14)	0.72685 (12)	0.11165 (6)	0.0208 (2)
Cl2	−0.26357 (14)	0.73204 (12)	0.12859 (6)	0.0214 (2)
N11	0.0236 (4)	0.3462 (4)	0.06997 (18)	0.0152 (8)
C12	0.1261 (5)	0.3626 (4)	0.1300 (2)	0.0157 (9)
H12	0.1957	0.4439	0.1374	0.019*
C13	0.1332 (6)	0.2651 (4)	0.1809 (2)	0.0178 (10)
H13	0.2053	0.2809	0.2229	0.021*
C14	0.0347 (5)	0.1432 (4)	0.1710 (2)	0.0162 (9)
C15	−0.0651 (5)	0.1255 (5)	0.1086 (2)	0.0180 (10)
H15	−0.1317	0.0429	0.0993	0.022*
C16	−0.0690 (5)	0.2272 (5)	0.0593 (2)	0.0172 (9)
H16	−0.1388	0.2128	0.0167	0.021*
C17	0.0321 (6)	0.0412 (5)	0.2270 (2)	0.0251 (11)
H17A	−0.0789	0.0462	0.2426	0.038*
H17B	0.1239	0.0640	0.2644	0.038*
H17C	0.0496	−0.0535	0.2108	0.038*
N21	0.5169 (5)	0.3414 (4)	0.06687 (19)	0.0203 (8)
C22	0.4513 (6)	0.2142 (5)	0.0486 (2)	0.0210 (10)
H22	0.4015	0.1977	0.0030	0.025*
C23	0.4555 (6)	0.1075 (5)	0.0952 (2)	0.0224 (10)
H23	0.4071	0.0193	0.0812	0.027*
C24	0.5287 (6)	0.1267 (5)	0.1621 (2)	0.0173 (10)
C25	0.5994 (6)	0.2572 (4)	0.1792 (2)	0.0178 (10)
H25	0.6540	0.2747	0.2242	0.021*
C26	0.5910 (6)	0.3616 (5)	0.1317 (2)	0.0206 (10)
H26	0.6388	0.4506	0.1448	0.025*
C27	0.5290 (6)	0.0145 (5)	0.2140 (2)	0.0228 (11)
H27A	0.4111	−0.0040	0.2207	0.034*
H27B	0.5974	0.0451	0.2566	0.034*
H27C	0.5788	−0.0711	0.1985	0.034*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Au1	0.02321 (13)	0.01053 (12)	0.01154 (12)	−0.00073 (9)	0.00179 (10)	0.00109 (9)
Au2	0.01771 (8)	0.01269 (8)	0.01244 (8)	−0.00077 (7)	0.00051 (6)	−0.00074 (7)
Au3	0.03403 (15)	0.01536 (13)	0.01342 (13)	0.00216 (10)	0.00437 (11)	0.00088 (10)
Cl1	0.0170 (5)	0.0239 (6)	0.0207 (6)	−0.0024 (4)	0.0006 (4)	−0.0004 (5)
Cl2	0.0183 (5)	0.0261 (6)	0.0197 (6)	0.0003 (4)	0.0026 (4)	−0.0024 (5)
N11	0.0199 (19)	0.0111 (19)	0.015 (2)	0.0004 (14)	0.0035 (16)	−0.0003 (15)
C12	0.018 (2)	0.010 (2)	0.018 (2)	0.0014 (16)	−0.0005 (19)	−0.0041 (18)
C13	0.024 (2)	0.014 (2)	0.013 (2)	0.0022 (18)	−0.0013 (19)	−0.0024 (19)
C14	0.020 (2)	0.014 (2)	0.016 (2)	0.0028 (17)	0.0065 (19)	0.0021 (19)
C15	0.019 (2)	0.015 (2)	0.021 (3)	−0.0013 (18)	0.005 (2)	0.0010 (19)
C16	0.022 (2)	0.015 (2)	0.014 (2)	−0.0020 (19)	0.0025 (18)	−0.0022 (19)
C17	0.034 (3)	0.018 (2)	0.022 (3)	−0.003 (2)	0.001 (2)	0.004 (2)
N21	0.029 (2)	0.015 (2)	0.017 (2)	0.0011 (16)	0.0029 (17)	−0.0006 (16)
C22	0.030 (3)	0.017 (2)	0.014 (2)	0.001 (2)	−0.001 (2)	−0.005 (2)
C23	0.030 (3)	0.016 (2)	0.021 (3)	−0.003 (2)	0.000 (2)	−0.001 (2)
C24	0.022 (2)	0.016 (2)	0.015 (2)	0.0012 (18)	0.0061 (19)	0.0000 (19)
C25	0.022 (2)	0.018 (3)	0.013 (2)	0.0011 (18)	0.0008 (18)	−0.0024 (18)
C26	0.028 (3)	0.017 (2)	0.018 (3)	−0.0032 (19)	0.007 (2)	−0.006 (2)
C27	0.032 (3)	0.018 (3)	0.017 (3)	0.000 (2)	0.002 (2)	0.003 (2)

Geometric parameters (Å, º)

Au1—N11^i	2.022 (4)	C23—C24	1.385 (6)
Au1—N11	2.022 (4)	C24—C25	1.388 (6)
Au1—Au2	3.1874 (2)	C24—C27	1.496 (6)
Au1—Au2^i	3.1875 (2)	C25—C26	1.376 (6)
Au2—Cl2	2.2608 (11)	C12—H12	0.9500
Au2—Cl1	2.2626 (11)	C13—H13	0.9500
Au3—N21	2.016 (4)	C15—H15	0.9500
Au3—N21^ii	2.016 (4)	C16—H16	0.9500
N11—C12	1.348 (5)	C17—H17A	0.9800
N11—C16	1.351 (5)	C17—H17B	0.9800
C12—C13	1.379 (6)	C17—H17C	0.9800
C13—C14	1.397 (6)	C22—H22	0.9500
C14—C15	1.380 (6)	C23—H23	0.9500
C14—C17	1.492 (6)	C25—H25	0.9500
C15—C16	1.385 (6)	C26—H26	0.9500
N21—C22	1.350 (6)	C27—H27A	0.9800
N21—C26	1.352 (6)	C27—H27B	0.9800
C22—C23	1.382 (6)	C27—H27C	0.9800
N11^i—Au1—N11	180.0	N21—C26—C25	122.0 (4)
N11^i—Au1—Au2	90.79 (10)	N11—C12—H12	119.0
N11—Au1—Au2	89.21 (10)	C13—C12—H12	119.0
N11^i—Au1—Au2^i	89.21 (10)	C12—C13—H13	119.9
N11—Au1—Au2^i	90.79 (10)	C14—C13—H13	119.9
Au2—Au1—Au2^i	180.0	C14—C15—H15	119.8
Cl2—Au2—Cl1	176.89 (4)	C16—C15—H15	119.8
Cl2—Au2—Au1	99.73 (3)	N11—C16—H16	119.0
Cl1—Au2—Au1	83.38 (3)	C15—C16—H16	119.0
N21—Au3—N21^ii	180.0	C14—C17—H17A	109.5
C12—N11—C16	118.1 (4)	C14—C17—H17B	109.5
C12—N11—Au1	120.7 (3)	H17A—C17—H17B	109.5
C16—N11—Au1	121.1 (3)	C14—C17—H17C	109.5
N11—C12—C13	122.1 (4)	H17A—C17—H17C	109.5
C12—C13—C14	120.3 (4)	H17B—C17—H17C	109.5
C15—C14—C13	117.0 (4)	N21—C22—H22	119.5
C15—C14—C17	122.0 (4)	C23—C22—H22	119.5
C13—C14—C17	121.0 (4)	C22—C23—H23	119.3
C14—C15—C16	120.4 (4)	C24—C23—H23	119.3
N11—C16—C15	122.0 (4)	C26—C25—H25	119.7
C22—N21—C26	118.5 (4)	C24—C25—H25	119.7
C22—N21—Au3	121.0 (3)	N21—C26—H26	119.0
C26—N21—Au3	120.4 (3)	C25—C26—H26	119.0
N21—C22—C23	121.0 (4)	C24—C27—H27A	109.5
C22—C23—C24	121.3 (4)	C24—C27—H27B	109.5
C23—C24—C25	116.6 (4)	H27A—C27—H27B	109.5
C23—C24—C27	122.3 (4)	C24—C27—H27C	109.5
C25—C24—C27	121.1 (4)	H27A—C27—H27C	109.5
C26—C25—C24	120.5 (4)	H27B—C27—H27C	109.5
N11^i—Au1—Au2—Cl2	93.66 (10)	C17—C14—C15—C16	175.3 (4)
N11—Au1—Au2—Cl2	−86.34 (10)	C12—N11—C16—C15	2.1 (6)
N11^i—Au1—Au2—Cl1	−86.39 (10)	Au1—N11—C16—C15	−174.7 (3)
N11—Au1—Au2—Cl1	93.61 (10)	C14—C15—C16—N11	0.1 (7)
Au2—Au1—N11—C12	−37.4 (3)	C26—N21—C22—C23	1.7 (7)
Au2^i—Au1—N11—C12	142.5 (3)	Au3—N21—C22—C23	−176.8 (3)
Au2—Au1—N11—C16	139.3 (3)	N21—C22—C23—C24	−0.8 (7)
Au2^i—Au1—N11—C16	−40.7 (3)	C22—C23—C24—C25	−0.9 (7)
C16—N11—C12—C13	−2.8 (6)	C22—C23—C24—C27	177.7 (4)
Au1—N11—C12—C13	174.1 (3)	C23—C24—C25—C26	1.8 (6)
N11—C12—C13—C14	1.2 (6)	C27—C24—C25—C26	−176.9 (4)
C12—C13—C14—C15	1.1 (6)	C22—N21—C26—C25	−0.8 (7)
C12—C13—C14—C17	−176.0 (4)	Au3—N21—C26—C25	177.7 (3)
C13—C14—C15—C16	−1.7 (6)	C24—C25—C26—N21	−1.0 (7)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12···Cl1	0.95	2.90	3.783 (4)	155
C16—H16···Cl1^i	0.95	2.75	3.644 (5)	158
C17—H17B···Cl1^iii	0.98	2.92	3.745 (5)	143
C22—H22···Cl2^i	0.95	2.77	3.664 (5)	156
C25—H25···Cl2^iii	0.95	2.97	3.876 (5)	159
C26—H26···Cl2^iv	0.95	2.83	3.727 (5)	157
C27—H27C···Cl2^v	0.98	2.76	3.721 (5)	165

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

(II_295K) Bis(4-picolino)gold(I) dichloroaurate(I)

Crystal data

[Au(C6H7N)2]·[AuCl2]	F(000) = 1168
Mr = 651.09	Dx = 2.790 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 5451 reflections
a = 8.0221 (7) Å	θ = 2.6–21.9°
b = 9.7523 (6) Å	µ = 19.23 mm^−1
c = 19.9889 (10) Å	T = 295 K
β = 97.552 (6)°	Block, colourless
V = 1550.26 (18) Å^3	0.10 × 0.05 × 0.02 mm
Z = 4

Data collection

Oxford Xcalibur diffractometer with Eos detector	3283 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2251 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.091
Detector resolution: 16.1419 pixels mm^-1	θmax = 26.7°, θmin = 2.3°
ω scans	h = −10→10
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013)	k = −12→12
Tmin = 0.392, Tmax = 1.000	l = −25→25
48444 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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.065	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0217P)^2] where P = (Fo^2 + 2Fc^2)/3
3283 reflections	(Δ/σ)max = 0.001
168 parameters	Δρmax = 0.80 e Å^−3
0 restraints	Δρmin = −0.88 e Å^−3

Special details

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.

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 > 2sigma(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
Au1	0.0000	0.5000	0.0000	0.05325 (14)
Au2	0.00990 (4)	0.72769 (3)	0.118601 (15)	0.05146 (11)
Au3	0.5000	0.5000	0.0000	0.07254 (18)
Cl1	0.2890 (3)	0.7347 (2)	0.11267 (12)	0.0735 (6)
Cl2	−0.2669 (3)	0.7285 (3)	0.12808 (11)	0.0759 (7)
N11	0.0245 (8)	0.3499 (6)	0.0702 (3)	0.0484 (16)
C12	0.1207 (10)	0.3669 (8)	0.1300 (4)	0.053 (2)
H12	0.1822	0.4475	0.1377	0.063*
C13	0.1315 (10)	0.2698 (8)	0.1801 (4)	0.053 (2)
H13	0.1981	0.2861	0.2210	0.064*
C14	0.0444 (10)	0.1483 (8)	0.1701 (4)	0.050 (2)
C15	−0.0490 (10)	0.1316 (8)	0.1087 (4)	0.057 (2)
H15	−0.1081	0.0503	0.0995	0.068*
C16	−0.0584 (10)	0.2315 (8)	0.0600 (4)	0.056 (2)
H16	−0.1242	0.2163	0.0188	0.067*
C17	0.0504 (12)	0.0434 (9)	0.2262 (4)	0.078 (3)
H17A	0.0707	−0.0458	0.2087	0.116*
H17B	−0.0549	0.0432	0.2441	0.116*
H17C	0.1393	0.0664	0.2614	0.116*
N21	0.5204 (9)	0.3433 (7)	0.0662 (3)	0.0651 (19)
C22	0.4577 (12)	0.2167 (9)	0.0492 (4)	0.072 (3)
H22	0.4081	0.2011	0.0051	0.086*
C23	0.4653 (11)	0.1124 (9)	0.0944 (4)	0.067 (2)
H23	0.4223	0.0269	0.0807	0.081*
C24	0.5360 (10)	0.1321 (9)	0.1602 (4)	0.056 (2)
C25	0.6011 (11)	0.2601 (8)	0.1773 (4)	0.059 (2)
H25	0.6518	0.2770	0.2211	0.071*
C26	0.5912 (11)	0.3625 (9)	0.1302 (4)	0.065 (2)
H26	0.6350	0.4483	0.1429	0.078*
C27	0.5443 (12)	0.0179 (8)	0.2125 (4)	0.080 (3)
H27A	0.4354	0.0056	0.2266	0.120*
H27B	0.6240	0.0420	0.2508	0.120*
H27C	0.5788	−0.0658	0.1931	0.120*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Au1	0.0820 (4)	0.0378 (3)	0.0389 (3)	−0.0009 (2)	0.0038 (2)	0.00287 (18)
Au2	0.0680 (2)	0.04282 (19)	0.04147 (18)	−0.00235 (17)	−0.00048 (14)	−0.00302 (14)
Au3	0.1132 (5)	0.0569 (3)	0.0482 (3)	0.0065 (3)	0.0130 (3)	0.0014 (2)
Cl1	0.0663 (14)	0.0821 (17)	0.0696 (14)	−0.0138 (12)	−0.0004 (11)	−0.0026 (12)
Cl2	0.0674 (15)	0.0905 (19)	0.0690 (15)	0.0030 (12)	0.0054 (12)	−0.0093 (12)
N11	0.074 (5)	0.034 (4)	0.037 (4)	0.001 (3)	0.005 (3)	−0.003 (3)
C12	0.077 (6)	0.038 (5)	0.042 (5)	−0.010 (4)	0.003 (4)	−0.005 (4)
C13	0.071 (6)	0.040 (5)	0.045 (5)	0.006 (4)	−0.007 (4)	−0.003 (4)
C14	0.062 (5)	0.043 (5)	0.043 (5)	0.006 (4)	0.001 (4)	−0.003 (4)
C15	0.076 (6)	0.043 (5)	0.048 (5)	−0.019 (4)	−0.005 (4)	0.000 (4)
C16	0.075 (6)	0.052 (5)	0.039 (5)	−0.006 (5)	−0.001 (4)	0.000 (4)
C17	0.102 (8)	0.080 (7)	0.047 (5)	0.001 (6)	−0.009 (5)	−0.002 (5)
N21	0.098 (6)	0.052 (5)	0.045 (4)	0.004 (4)	0.008 (4)	−0.005 (3)
C22	0.096 (7)	0.066 (7)	0.049 (5)	−0.007 (5)	−0.004 (5)	−0.013 (5)
C23	0.092 (7)	0.045 (5)	0.063 (6)	−0.009 (5)	0.003 (5)	0.002 (4)
C24	0.064 (6)	0.058 (6)	0.045 (5)	0.005 (4)	0.009 (4)	0.003 (4)
C25	0.079 (6)	0.047 (6)	0.052 (5)	−0.008 (5)	0.004 (4)	−0.009 (4)
C26	0.093 (7)	0.050 (6)	0.053 (6)	−0.002 (5)	0.013 (5)	−0.010 (4)
C27	0.107 (8)	0.067 (7)	0.064 (6)	0.013 (6)	0.006 (6)	−0.007 (5)

Geometric parameters (Å, º)

Au1—N11^i	2.019 (6)	C13—C14	1.376 (10)
Au1—N11	2.019 (6)	C14—C15	1.362 (9)
Au1—Au2^i	3.2415 (3)	C14—C17	1.514 (10)
Au1—Au2	3.2415 (3)	C15—C16	1.372 (10)
Au2—Cl2	2.254 (2)	N21—C26	1.342 (9)
Au2—Cl1	2.259 (2)	N21—C22	1.359 (10)
Au3—N21	2.015 (7)	C22—C23	1.356 (11)
Au3—N21^ii	2.015 (7)	C23—C24	1.376 (10)
N11—C16	1.335 (9)	C24—C25	1.379 (10)
N11—C12	1.345 (8)	C24—C27	1.523 (11)
C12—C13	1.373 (10)	C25—C26	1.368 (10)
N11^i—Au1—N11	179.999 (1)	C15—C14—C13	116.3 (7)
N11^i—Au1—Au2^i	89.85 (16)	C15—C14—C17	123.2 (7)
N11—Au1—Au2^i	90.15 (16)	C13—C14—C17	120.5 (7)
N11^i—Au1—Au2	90.15 (16)	C14—C15—C16	121.8 (7)
N11—Au1—Au2	89.85 (16)	N11—C16—C15	121.7 (7)
Au2^i—Au1—Au2	180.0	C26—N21—C22	117.5 (7)
Cl2—Au2—Cl1	177.35 (8)	C26—N21—Au3	120.5 (6)
Cl2—Au2—Au1	97.72 (6)	C22—N21—Au3	121.9 (6)
Cl1—Au2—Au1	84.93 (6)	C23—C22—N21	122.1 (8)
N21—Au3—N21^ii	179.999 (1)	C22—C23—C24	120.6 (8)
C16—N11—C12	117.3 (6)	C23—C24—C25	117.3 (8)
C16—N11—Au1	121.3 (5)	C23—C24—C27	122.0 (8)
C12—N11—Au1	121.4 (5)	C25—C24—C27	120.7 (7)
N11—C12—C13	122.5 (7)	C26—C25—C24	120.2 (8)
C12—C13—C14	120.4 (7)	N21—C26—C25	122.2 (8)
N11^i—Au1—Au2—Cl2	92.80 (19)	C17—C14—C15—C16	176.7 (8)
N11—Au1—Au2—Cl2	−87.20 (19)	C12—N11—C16—C15	1.2 (12)
N11^i—Au1—Au2—Cl1	−87.03 (19)	Au1—N11—C16—C15	−176.7 (6)
N11—Au1—Au2—Cl1	92.97 (19)	C14—C15—C16—N11	0.4 (13)
Au2^i—Au1—N11—C16	−38.4 (6)	C26—N21—C22—C23	0.0 (13)
Au2—Au1—N11—C16	141.6 (6)	Au3—N21—C22—C23	−177.3 (7)
Au2^i—Au1—N11—C12	143.8 (6)	N21—C22—C23—C24	0.8 (14)
Au2—Au1—N11—C12	−36.2 (6)	C22—C23—C24—C25	−1.3 (13)
C16—N11—C12—C13	−1.9 (11)	C22—C23—C24—C27	179.1 (8)
Au1—N11—C12—C13	176.0 (6)	C23—C24—C25—C26	1.2 (13)
N11—C12—C13—C14	1.0 (12)	C27—C24—C25—C26	−179.2 (8)
C12—C13—C14—C15	0.6 (12)	C22—N21—C26—C25	−0.1 (13)
C12—C13—C14—C17	−177.5 (8)	Au3—N21—C26—C25	177.2 (7)
C13—C14—C15—C16	−1.3 (12)	C24—C25—C26—N21	−0.5 (13)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12···Cl1	0.93	2.99	3.864 (8)	157
C16—H16···Cl1^i	0.93	2.82	3.710 (8)	160
C17—H17C···Cl1^iii	0.96	3.00	3.798 (9)	142
C22—H22···Cl2^i	0.93	2.84	3.709 (9)	157
C26—H26···Cl2^iv	0.93	2.87	3.748 (9)	158
C27—H27C···Cl2^v	0.96	2.77	3.712 (9)	167

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

(II_200K) Bis(4-picolino)gold(I) dichloroaurate(I)

Crystal data

[Au(C6H7N)2]·[AuCl2]	F(000) = 1168
Mr = 651.09	Dx = 2.840 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 6856 reflections
a = 7.9579 (4) Å	θ = 2.6–26.7°
b = 9.6670 (5) Å	µ = 19.58 mm^−1
c = 19.9987 (9) Å	T = 200 K
β = 98.250 (5)°	Block, colourless
V = 1522.55 (13) Å^3	0.10 × 0.05 × 0.02 mm
Z = 4

Data collection

Oxford Xcalibur diffractometer with Eos detector	3929 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2982 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.088
Detector resolution: 16.1419 pixels mm^-1	θmax = 28.7°, θmin = 2.3°
ω scans	h = −10→10
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013)	k = −13→13
Tmin = 0.412, Tmax = 1.000	l = −27→27
57728 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) = 0.055	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0184P)^2] where P = (Fo^2 + 2Fc^2)/3
3929 reflections	(Δ/σ)max = 0.013
168 parameters	Δρmax = 0.76 e Å^−3
0 restraints	Δρmin = −0.98 e Å^−3

Special details

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.

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 > 2sigma(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
Au1	0.0000	0.5000	0.0000	0.03311 (9)
Au2	0.01229 (3)	0.72619 (2)	0.118343 (11)	0.03148 (7)
Au3	0.5000	0.5000	0.0000	0.04560 (11)
Cl1	0.2937 (2)	0.73117 (17)	0.11232 (8)	0.0444 (4)
Cl2	−0.26575 (19)	0.72982 (18)	0.12844 (8)	0.0458 (4)
N11	0.0240 (6)	0.3469 (5)	0.0704 (2)	0.0310 (11)
C12	0.1225 (7)	0.3640 (6)	0.1300 (3)	0.0343 (14)
H12	0.1880	0.4462	0.1375	0.041*
C13	0.1324 (7)	0.2674 (6)	0.1806 (3)	0.0335 (13)
H13	0.2028	0.2838	0.2224	0.040*
C14	0.0403 (7)	0.1461 (6)	0.1710 (3)	0.0310 (13)
C15	−0.0559 (8)	0.1276 (6)	0.1087 (3)	0.0380 (15)
H15	−0.1181	0.0442	0.0993	0.046*
C16	−0.0628 (7)	0.2291 (6)	0.0595 (3)	0.0327 (13)
H16	−0.1309	0.2145	0.0171	0.039*
C17	0.0427 (9)	0.0414 (7)	0.2266 (3)	0.0489 (17)
H17A	−0.0574	0.0542	0.2493	0.073*
H17B	0.1457	0.0536	0.2593	0.073*
H17C	0.0413	−0.0519	0.2074	0.073*
N21	0.5190 (6)	0.3429 (5)	0.0667 (2)	0.0403 (12)
C22	0.4541 (8)	0.2165 (7)	0.0488 (3)	0.0453 (16)
H22	0.4034	0.2008	0.0035	0.054*
C23	0.4601 (8)	0.1101 (6)	0.0950 (3)	0.0409 (15)
H23	0.4134	0.0225	0.0811	0.049*
C24	0.5332 (7)	0.1295 (6)	0.1612 (3)	0.0350 (14)
C25	0.6015 (8)	0.2587 (6)	0.1781 (3)	0.0386 (15)
H25	0.6552	0.2758	0.2229	0.046*
C26	0.5923 (8)	0.3614 (7)	0.1312 (3)	0.0421 (16)
H26	0.6393	0.4493	0.1444	0.051*
C27	0.5368 (9)	0.0156 (6)	0.2137 (3)	0.0467 (17)
H27A	0.4206	−0.0154	0.2163	0.070*
H27B	0.5880	0.0511	0.2579	0.070*
H27C	0.6040	−0.0624	0.2009	0.070*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Au1	0.0510 (2)	0.02356 (17)	0.02408 (17)	−0.00100 (14)	0.00290 (14)	0.00204 (13)
Au2	0.03985 (13)	0.02709 (12)	0.02623 (11)	−0.00144 (11)	0.00044 (9)	−0.00162 (10)
Au3	0.0726 (3)	0.0346 (2)	0.03005 (19)	0.00465 (18)	0.00897 (18)	0.00138 (15)
Cl1	0.0388 (8)	0.0506 (10)	0.0422 (9)	−0.0081 (7)	0.0002 (7)	−0.0011 (7)
Cl2	0.0401 (8)	0.0557 (11)	0.0409 (9)	0.0009 (7)	0.0033 (7)	−0.0057 (8)
N11	0.043 (3)	0.026 (3)	0.023 (2)	0.002 (2)	0.004 (2)	0.001 (2)
C12	0.047 (4)	0.022 (3)	0.034 (3)	0.000 (3)	0.006 (3)	−0.005 (3)
C13	0.042 (3)	0.028 (3)	0.028 (3)	0.005 (3)	−0.004 (3)	0.000 (2)
C14	0.043 (3)	0.022 (3)	0.028 (3)	0.000 (3)	0.007 (3)	−0.003 (2)
C15	0.050 (4)	0.030 (4)	0.032 (3)	−0.011 (3)	0.001 (3)	−0.001 (3)
C16	0.044 (3)	0.030 (3)	0.023 (3)	−0.006 (3)	0.000 (3)	0.002 (2)
C17	0.062 (4)	0.046 (4)	0.035 (4)	0.001 (3)	−0.003 (3)	0.007 (3)
N21	0.060 (3)	0.029 (3)	0.032 (3)	0.004 (3)	0.009 (3)	−0.003 (2)
C22	0.062 (4)	0.041 (4)	0.032 (3)	−0.006 (3)	0.005 (3)	−0.007 (3)
C23	0.057 (4)	0.031 (4)	0.034 (3)	−0.005 (3)	0.003 (3)	−0.007 (3)
C24	0.039 (3)	0.036 (4)	0.031 (3)	0.002 (3)	0.009 (3)	−0.004 (3)
C25	0.052 (4)	0.034 (4)	0.029 (3)	0.004 (3)	0.005 (3)	−0.005 (3)
C26	0.057 (4)	0.031 (4)	0.038 (4)	−0.005 (3)	0.009 (3)	−0.010 (3)
C27	0.065 (5)	0.029 (4)	0.043 (4)	−0.002 (3)	−0.001 (3)	−0.004 (3)

Geometric parameters (Å, º)

Au1—N11	2.032 (4)	C13—C14	1.381 (7)
Au1—N11^i	2.033 (4)	C14—C15	1.378 (7)
Au1—Au2^i	3.2133 (2)	C14—C17	1.501 (8)
Au1—Au2	3.2134 (2)	C15—C16	1.385 (7)
Au2—Cl2	2.2507 (15)	N21—C26	1.350 (7)
Au2—Cl1	2.2602 (16)	N21—C22	1.355 (7)
Au3—N21	2.012 (5)	C22—C23	1.378 (8)
Au3—N21^ii	2.012 (5)	C23—C24	1.380 (8)
N11—C16	1.334 (7)	C24—C25	1.385 (8)
N11—C12	1.340 (7)	C24—C27	1.520 (8)
C12—C13	1.371 (8)	C25—C26	1.360 (8)
N11—Au1—N11^i	180.0 (3)	C15—C14—C13	116.9 (5)
N11—Au1—Au2^i	90.27 (12)	C15—C14—C17	121.9 (5)
N11^i—Au1—Au2^i	89.73 (12)	C13—C14—C17	121.2 (5)
N11—Au1—Au2	89.73 (12)	C14—C15—C16	120.7 (5)
N11^i—Au1—Au2	90.27 (12)	N11—C16—C15	121.5 (5)
Au2^i—Au1—Au2	180.0	C26—N21—C22	117.9 (5)
Cl2—Au2—Cl1	177.04 (6)	C26—N21—Au3	121.0 (4)
Cl2—Au2—Au1	98.64 (4)	C22—N21—Au3	121.1 (4)
Cl1—Au2—Au1	84.31 (4)	N21—C22—C23	121.5 (6)
N21—Au3—N21^ii	179.998 (1)	C22—C23—C24	120.6 (6)
C16—N11—C12	118.3 (5)	C23—C24—C25	117.0 (6)
C16—N11—Au1	120.9 (4)	C23—C24—C27	121.9 (6)
C12—N11—Au1	120.8 (4)	C25—C24—C27	121.1 (5)
N11—C12—C13	122.5 (5)	C26—C25—C24	120.6 (6)
C12—C13—C14	120.1 (5)	N21—C26—C25	122.4 (6)
N11—Au1—Au2—Cl2	−86.86 (13)	C17—C14—C15—C16	176.6 (6)
N11^i—Au1—Au2—Cl2	93.14 (13)	C12—N11—C16—C15	1.6 (8)
N11—Au1—Au2—Cl1	93.26 (13)	Au1—N11—C16—C15	−175.9 (4)
N11^i—Au1—Au2—Cl1	−86.74 (13)	C14—C15—C16—N11	0.7 (9)
Au2^i—Au1—N11—C16	−39.3 (4)	C26—N21—C22—C23	0.9 (9)
Au2—Au1—N11—C16	140.7 (4)	Au3—N21—C22—C23	−177.2 (5)
Au2^i—Au1—N11—C12	143.3 (4)	N21—C22—C23—C24	−0.1 (10)
Au2—Au1—N11—C12	−36.7 (4)	C22—C23—C24—C25	−1.0 (9)
C16—N11—C12—C13	−2.3 (8)	C22—C23—C24—C27	178.0 (6)
Au1—N11—C12—C13	175.2 (4)	C23—C24—C25—C26	1.4 (9)
N11—C12—C13—C14	0.7 (9)	C27—C24—C25—C26	−177.7 (6)
C12—C13—C14—C15	1.5 (9)	C22—N21—C26—C25	−0.6 (9)
C12—C13—C14—C17	−177.3 (6)	Au3—N21—C26—C25	177.5 (5)
C13—C14—C15—C16	−2.2 (9)	C24—C25—C26—N21	−0.6 (10)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12···Cl1	0.95	2.94	3.836 (6)	157
C16—H16···Cl1^i	0.95	2.77	3.677 (6)	159
C22—H22···Cl2^i	0.95	2.79	3.682 (6)	157
C25—H25···Cl2^iii	0.95	3.01	3.912 (6)	159
C26—H26···Cl2^iv	0.95	2.85	3.739 (7)	157
C27—H27C···Cl2^v	0.98	2.76	3.712 (7)	163

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