Two polymorphs of chlorido(cyclo­hexyl­diphenyl­phosphine)gold(I)

The title compound, [AuCl(C₁₈H₂₁P)], a monomeric two-coordinate gold(I) complex, has been characterized at 100 K as two distinct monoclinic polymorphs, one from a single crystal, (Is), and one from a pseudo-merohedrally twinned crystal, (It). The mol­ecular structures in the two monoclinic [P2₁/n for (Is) and P2₁/c for (It)] polymorphs are similar; however, the packing arrangements in the two lattices differ considerably. The structure of (It) is pseudo-merohedrally twinned by a twofold rotation about the a* axis.

S1. Comment

Recently, there has been a significant increase in the amount of research focused on the synthesis, characterization and theoretical analysis of gold clusters and nanoparticles, as their potential applications encompass ever-increasing areas of modern technology and scientific advances, ranging from biological luminophores to the components of plasmonic devices and catalysis. Their ability to guide, enhance, emit and modify optical fields put them on the center stage for such applications as photonic crystals, bio-sensors and optical materials (Pyykkö, 2004, 2005; Andres et al., 1996). In our pursuit to synthesize small, luminescent gold clusters, we treated a preformed gold–phosphine cluster, [Au₆(PPh₂Cy)₆](NO₃)₂ (Briant et al., 1986), with either n-butylamine or i-propylamine in various ratios in acetonitrile. The process yielded an unstable luminescent gold-containing product, the crystallization of which from its CH₂Cl₂ solution by layering with pentane resulted in the reaction of this luminescent gold species with CH₂Cl₂ yielding the title compound, (I), in high yield.

Compound (I) has been characterized at 100 K as two distinct monoclinic polymorphs, one from a single crystal, (Is), and one from a pseudo-merohedrally twinned crystal, (It). The structures of (Is) and (It) are shown in Figs. 1 and 2, and their overlap in Fig. 3.

The space groups are P2₁/n and P2₁/c for (Is) and (It); both contain one molecule in the asymmetric unit. The non-conventional setting for (Is) was chosen based on the proximity of the β-angle value to 90°. A Cambridge Structural Database (CSD, September 2009 release; Allen, 2002) search revealed four other P2₁/c–P2₁/c (or P2₁/n) monoclinic polymorphic pairs for phosphine–gold complexes: chloro(trimesitylphosphine)gold(I), P2₁/c (Alyea et al., 1993) and P2₁/c (Bott et al., 2000), both at RT [room temperature?]; [OPh₂PC(PPh₂AuPPh₂)₂CPPh₂ (O)].4CH₂Cl₂, P2₁/c and P2₁/n, both at 173 [K?] (Fernandez et al., 1993); tris[(2-cyanoethyl)phospine]gold(I), P2₁/c and P2₁/c, both at RT (Fackler et al., 1994); and (tricyclohexylphospine)gold(I) 2-mercaptobenzoate, form I P1 at RT (Cookson & Tiekink,1992), form II P2₁/n at 173 K, form III P2₁/n at 173 K, form IV P1 at 173 K, all by Smyth et al. (2001).

There are no aurophilic interactions in either structure of (I). The overall packing is based on a ball motif, because the smallest box circumscribing the molecule is approximately isometric, measuring 10.51 x 11.03 x 10.98 Å for (Is), and 10.56 x 10.96 x 11.86 Å for (It). Interestingly, the volumes of these boxes, 1272.0 ų for (Is) and 1373.6 ų for (It), differ by over 100 Å. Crystal packing in the two lattices is dissimilar (Fig. 4). The packing patterns were examined with a matching routine of the program Mercury (Bruno et al., 2002), which was able to superimpose five molecules out of 20 from the two structures with an r.m.s. of 0.843 Å. The matching pattern of the theoretically computed powder spectra had an r.m.s. of 0.921. Thus, the two polymorphs are indeed distinct.

Unfortunately, it was not possible to establish which polymorph is more stable based on the crystals' density or melting-point measurements. The polymorph densities differ by only 0.005 Mg m^-3, and crystals of (Is) and (It) melted within 0.5° of each other between 485 and 486 K. The unavailability of crystals of (It) did not allow for additional, possibly more conclusive melting-point measurements. We did compare the theoretically computed energies corresponding to the observed molecular conformations in (Is) and (It). The geometries of the complexes were optimized with Gaussian03 (Frisch et al., 2004) using the hybrid DFT PBE1PBE functional of TZVP triple-zeta quality with a polarization basis set on all non-metallic atoms and the SDD basis set with a relativistically corrected Effective Core potential on gold. Our preliminary results suggest that (Is) is the more stable conformer, probably due to stronger Au···H agostic interactions.

The molecular geometries of (Is) and (It) are typical, with bond distances and angles falling in the usual ranges. The P atom is in an equatorial position relative to the cyclohexyl ring. The two structures can be overlaid (Fig. 3), with an r.m.s. of 0.323 Å computed based on all non-H atoms. Herein we compare the selected molecular parameters for (Is), (It), the molecular geometry of (I) optimized with Gaussian03, (I-g), and the average parameters for high-quality crystal structures of phosphine–gold complexes containing a Cl—Au—PC₃ unit as reported to the CSD (II). The Au—Cl and Au—P bond distances and Cl—Au—P angle are 2.2885 (5), 2.2403 (5) Å and 177.668 (19)° in (Is); 2.2915 (14), 2.2335 (13) Å and 176.41 (5)° in (It); 2.2994, 2.2730 Å and 179.44° in (I-g); and 2.288 (11) Å, 2.231 (10) Å and 176 (2) for (II). The overall geometry of (I-g) compares well with those of (Is) and (It); however, the bond distances about the Au atom in (I-g) are slightly longer than in the experimentally established geometries. The results of the CSD search did not reveal any mutual dependence between the Au—Cl and Au—P bonds. Thus, the data probably indicate that the two polymorphs are `conformational', and their existence is due to packing differences induced by different torsion angles, rather than by any change in covalent distances and angles.

The structure of (It) was pseudo-merohedrally twinned, likely due to the proximity of the β angle to 120° and similarity of the a and c axial lengths. We have recently reported a case of a non-merohedrally twinned crystal of nonactin (Guzei et al., 2009) and treated the twinning in (It) according to the procedure described therein. In the case of (It) the twin law (1 0 1 0 - 1 0 0 0 - 1) corresponded to a 180° rotation about the a* axis in reciprocal space. The contribution of the minor twin component was calculated to be 17.14 (9)%.

We have discovered and structurally characterized two polymorphs of a monomeric two-coordinate gold(I) complex Au(PPh₂Cy)Cl, one of which is pseudo-merohedrally twinned.

Related literature

For related literature, see: Allen (2002); Alyea et al. (1993); Andres et al. (1996); Bott et al. (2000); Briant et al. (1986); Bruno et al. (2002); Cookson & Tiekink (1992); Fackler et al. (1994); Fernandez et al. (1993); Frisch et al. (2004); Guzei (2007); Guzei et al. (2009); Pyykkö (2004, 2005); Smyth et al. (2001).

S2. Experimental

n-Butylamine (99.5%) were purchased from Aldrich. Ethanol, methanol, tetrahydrofuran, dichloromethane and pentane were purchased from Acros. Cyclohexyldiphenylphosphine (98%, PCyPPh₂) was purchased from Strem chemicals. NaBH₄ (98%) was purchased from Alfa Aesar. All the chemicals were used as received without further purification. The [Au₆(PCyPh₂)₆](NO₃)₂ cluster was prepared by reduction of Au(PCyPh₂)NO₃ with NaBH₄ in ethanol, as described by Briant et al. (1986). [Au₆(PCyPh₂)₆](NO₃)₂ (0.0175 g) was dispersed in dichloromethane (10 ml) to form a transparent yellow–brown solution. n-Butylamine (0.05 ml) was added to the above solution and stirred at room temperature for 5–7 d. Over time, the yellow–brown color of the original [Au₆(PCyPh₂)₆](NO₃)₂ cluster gradually disappeared producing a luminescent pale-yellow solution. The resulting solution was centrifuged and the supernatant was isolated in a flask and the solvent removed under vacuum to yield a light-yellow–brown precipitate. The precipitate was washed with hexane (twice) to remove excess amine and was then crystallized from dichloromethane by slow diffusion of pentane into the solution. One crystallization batch produced (Is), whereas a repetition of the reaction and crystallization produced (It).

S3. Refinement

All H atoms were placed in idealized locations with C—H distances of 0.95 Å for aromatic C atoms, 0.99 Å for secondary C atoms and 1.00 Å for the tertiary C atom, and refined as riding with thermal displacement coefficients U_iso(H) set to 1.2U_eq (bearing C atom).

The outlier reflections were omitted based on the statistics test described in Prince & Nicholson (1983) and Rollett (1988), and implemented in the program FCF_filter (Guzei, 2007). The number of omitted outliers is 4 for (Is) and 47 for (It).

Computing details

For both compounds, data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008), OLEX2 (Dolomanov et al., 2009); molecular graphics: SHELXTL (Sheldrick, 2008). Software used to prepare material for publication: SHELXTL (Sheldrick, 2008)' for (Is); SHELXTL (Sheldrick, 2008) for (It).

Figures

	Fig. 1. Molecular structure of (Is). The thermal ellipsoids are shown at the 50% probability level.
	Fig. 2. Molecular structure of (It). The thermal ellipsoids are shown at the 50% probability level.
	Fig. 3. An overlay of structure (Is), green, and (It).
	Fig. 4. A partial overlay of the lattices of (Is), black molecules, and (It), orange molecules, viewed along the c axis of (Is). An attempt to overlay 15 molecules resulted in a more or less successful overlay of five molecules (best seen near the origin). The diagram contains more than 15 molecules to emphasize the differences in packing.

(Is) chlorido(cyclohexyldiphenylphosphine)gold(I)

Crystal data

[AuCl(C18H21P)]	F(000) = 960
Mr = 500.73	Dx = 1.931 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 9926 reflections
a = 9.0059 (4) Å	θ = 3.7–30.6°
b = 17.2762 (7) Å	µ = 8.78 mm^−1
c = 11.0719 (4) Å	T = 100 K
β = 91.610 (2)°	Block, colourless
V = 1721.97 (12) Å^3	0.39 × 0.36 × 0.34 mm
Z = 4

Data collection

Bruker SMART APEXII area detector diffractometer	5263 independent reflections
Radiation source: microfocus sealed X-ray tube, Incoatec Iµs	4832 reflections with I > 2σ(I)
Mirror optics monochromator	Rint = 0.032
0.60° ω and 0.6° ϕ scans	θmax = 30.6°, θmin = 3.7°
Absorption correction: analytical (SADABS; Bruker, 2009)	h = −12→12
Tmin = 0.131, Tmax = 0.154	k = −24→24
28496 measured reflections	l = −15→15

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.017	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.037	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0087P)^2 + 1.6386P] where P = (Fo^2 + 2Fc^2)/3
5263 reflections	(Δ/σ)max = 0.001
190 parameters	Δρmax = 1.13 e Å^−3
0 restraints	Δρmin = −1.01 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	0.135506 (8)	0.137210 (4)	0.162402 (6)	0.01344 (3)
Cl1	0.25743 (6)	0.09305 (3)	−0.00258 (4)	0.02139 (10)
P1	0.01962 (6)	0.18529 (3)	0.32235 (4)	0.01262 (9)
C1	−0.1801 (2)	0.17190 (11)	0.30942 (17)	0.0139 (4)
C2	−0.2412 (3)	0.12995 (12)	0.21214 (19)	0.0179 (4)
H2	−0.1787	0.1110	0.1511	0.021*
C3	−0.3928 (3)	0.11584 (13)	0.2045 (2)	0.0209 (4)
H3	−0.4339	0.0872	0.1384	0.025*
C4	−0.4841 (3)	0.14344 (13)	0.2931 (2)	0.0221 (4)
H4	−0.5877	0.1330	0.2885	0.027*
C5	−0.4248 (3)	0.18636 (15)	0.3887 (2)	0.0241 (5)
H5	−0.4882	0.2062	0.4484	0.029*
C6	−0.2734 (2)	0.20037 (13)	0.39738 (19)	0.0191 (4)
H6	−0.2331	0.2294	0.4634	0.023*
C7	0.0752 (2)	0.14114 (11)	0.46518 (17)	0.0132 (3)
C8	0.1445 (2)	0.06901 (12)	0.46443 (19)	0.0173 (4)
H8	0.1653	0.0449	0.3896	0.021*
C9	0.1834 (3)	0.03195 (12)	0.5723 (2)	0.0207 (4)
H9	0.2311	−0.0171	0.5712	0.025*
C10	0.1524 (2)	0.06681 (13)	0.68155 (19)	0.0205 (4)
H10	0.1770	0.0411	0.7553	0.025*
C11	0.0854 (3)	0.13903 (13)	0.68351 (19)	0.0204 (4)
H11	0.0659	0.1631	0.7586	0.025*
C12	0.0467 (2)	0.17637 (12)	0.57590 (18)	0.0174 (4)
H12	0.0008	0.2259	0.5776	0.021*
C13	0.0531 (2)	0.28916 (11)	0.33926 (18)	0.0147 (4)
H13	−0.0090	0.3093	0.4058	0.018*
C14	0.2175 (2)	0.30428 (12)	0.37172 (19)	0.0177 (4)
H14B	0.2429	0.2801	0.4507	0.021*
H14A	0.2802	0.2802	0.3101	0.021*
C15	0.2499 (3)	0.39112 (12)	0.3783 (2)	0.0214 (4)
H15B	0.1962	0.4140	0.4464	0.026*
H15A	0.3576	0.3992	0.3939	0.026*
C16	0.2028 (3)	0.43209 (13)	0.2616 (2)	0.0234 (5)
H16B	0.2193	0.4885	0.2709	0.028*
H16A	0.2649	0.4136	0.1951	0.028*
C17	0.0400 (3)	0.41725 (12)	0.2292 (2)	0.0230 (4)
H17A	0.0146	0.4419	0.1506	0.028*
H17B	−0.0228	0.4409	0.2912	0.028*
C18	0.0074 (3)	0.33047 (12)	0.2213 (2)	0.0196 (4)
H18B	0.0623	0.3078	0.1536	0.024*
H18A	−0.1001	0.3225	0.2045	0.024*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Au1	0.01575 (4)	0.01372 (4)	0.01096 (4)	0.00111 (3)	0.00204 (2)	−0.00015 (3)
Cl1	0.0275 (3)	0.0227 (2)	0.0144 (2)	0.0020 (2)	0.00741 (18)	−0.00141 (18)
P1	0.0141 (2)	0.0119 (2)	0.0120 (2)	0.00018 (18)	0.00155 (17)	−0.00024 (17)
C1	0.0154 (9)	0.0118 (8)	0.0144 (9)	0.0000 (7)	−0.0003 (7)	0.0025 (7)
C2	0.0208 (11)	0.0179 (10)	0.0150 (9)	0.0005 (8)	0.0005 (7)	−0.0010 (7)
C3	0.0207 (11)	0.0203 (10)	0.0214 (10)	−0.0036 (8)	−0.0047 (8)	−0.0003 (8)
C4	0.0144 (10)	0.0291 (11)	0.0228 (10)	−0.0022 (8)	−0.0017 (8)	0.0052 (9)
C5	0.0168 (11)	0.0367 (13)	0.0191 (10)	0.0034 (9)	0.0042 (8)	−0.0012 (9)
C6	0.0176 (10)	0.0241 (10)	0.0157 (9)	−0.0002 (8)	−0.0002 (7)	−0.0027 (8)
C7	0.0123 (9)	0.0142 (9)	0.0132 (8)	−0.0010 (7)	0.0013 (7)	0.0005 (7)
C8	0.0219 (11)	0.0144 (9)	0.0158 (9)	0.0012 (7)	0.0008 (8)	−0.0015 (7)
C9	0.0243 (11)	0.0159 (9)	0.0218 (10)	0.0022 (8)	−0.0031 (8)	0.0016 (8)
C10	0.0215 (11)	0.0225 (10)	0.0171 (10)	−0.0044 (8)	−0.0037 (8)	0.0040 (8)
C11	0.0201 (11)	0.0272 (11)	0.0142 (9)	−0.0023 (9)	0.0012 (8)	−0.0030 (8)
C12	0.0176 (10)	0.0186 (10)	0.0162 (9)	0.0011 (8)	0.0017 (7)	−0.0026 (7)
C13	0.0150 (10)	0.0128 (8)	0.0163 (9)	0.0011 (7)	0.0028 (7)	0.0000 (7)
C14	0.0189 (10)	0.0158 (9)	0.0185 (9)	−0.0024 (7)	0.0012 (8)	0.0003 (7)
C15	0.0266 (12)	0.0168 (10)	0.0208 (10)	−0.0062 (8)	0.0016 (8)	−0.0018 (8)
C16	0.0329 (13)	0.0152 (10)	0.0225 (11)	−0.0052 (9)	0.0079 (9)	0.0014 (8)
C17	0.0263 (12)	0.0155 (10)	0.0275 (11)	0.0021 (8)	0.0056 (9)	0.0054 (8)
C18	0.0217 (11)	0.0146 (9)	0.0224 (10)	0.0002 (8)	−0.0004 (8)	0.0047 (8)

Geometric parameters (Å, º)

Au1—P1	2.2403 (5)	C10—C11	1.386 (3)
Au1—Cl1	2.2885 (5)	C10—H10	0.9500
P1—C7	1.814 (2)	C11—C12	1.391 (3)
P1—C1	1.815 (2)	C11—H11	0.9500
P1—C13	1.828 (2)	C12—H12	0.9500
C1—C6	1.394 (3)	C13—C18	1.535 (3)
C1—C2	1.398 (3)	C13—C14	1.536 (3)
C2—C3	1.387 (3)	C13—H13	1.0000
C2—H2	0.9500	C14—C15	1.530 (3)
C3—C4	1.382 (3)	C14—H14B	0.9900
C3—H3	0.9500	C14—H14A	0.9900
C4—C5	1.387 (3)	C15—C16	1.523 (3)
C4—H4	0.9500	C15—H15B	0.9900
C5—C6	1.385 (3)	C15—H15A	0.9900
C5—H5	0.9500	C16—C17	1.522 (3)
C6—H6	0.9500	C16—H16B	0.9900
C7—C8	1.394 (3)	C16—H16A	0.9900
C7—C12	1.399 (3)	C17—C18	1.530 (3)
C8—C9	1.392 (3)	C17—H17A	0.9900
C8—H8	0.9500	C17—H17B	0.9900
C9—C10	1.386 (3)	C18—H18B	0.9900
C9—H9	0.9500	C18—H18A	0.9900
P1—Au1—Cl1	177.668 (19)	C11—C12—C7	120.1 (2)
C7—P1—C1	105.30 (9)	C11—C12—H12	120.0
C7—P1—C13	106.42 (9)	C7—C12—H12	120.0
C1—P1—C13	107.05 (9)	C18—C13—C14	110.72 (17)
C7—P1—Au1	114.21 (7)	C18—C13—P1	109.25 (14)
C1—P1—Au1	111.90 (7)	C14—C13—P1	110.24 (13)
C13—P1—Au1	111.45 (7)	C18—C13—H13	108.9
C6—C1—C2	119.29 (19)	C14—C13—H13	108.9
C6—C1—P1	121.03 (15)	P1—C13—H13	108.9
C2—C1—P1	119.64 (16)	C15—C14—C13	111.07 (17)
C3—C2—C1	120.2 (2)	C15—C14—H14B	109.4
C3—C2—H2	119.9	C13—C14—H14B	109.4
C1—C2—H2	119.9	C15—C14—H14A	109.4
C4—C3—C2	120.0 (2)	C13—C14—H14A	109.4
C4—C3—H3	120.0	H14B—C14—H14A	108.0
C2—C3—H3	120.0	C16—C15—C14	111.53 (17)
C3—C4—C5	120.1 (2)	C16—C15—H15B	109.3
C3—C4—H4	119.9	C14—C15—H15B	109.3
C5—C4—H4	119.9	C16—C15—H15A	109.3
C4—C5—C6	120.2 (2)	C14—C15—H15A	109.3
C4—C5—H5	119.9	H15B—C15—H15A	108.0
C6—C5—H5	119.9	C17—C16—C15	111.42 (18)
C5—C6—C1	120.1 (2)	C17—C16—H16B	109.3
C5—C6—H6	120.0	C15—C16—H16B	109.3
C1—C6—H6	120.0	C17—C16—H16A	109.3
C8—C7—C12	119.17 (18)	C15—C16—H16A	109.3
C8—C7—P1	118.91 (15)	H16B—C16—H16A	108.0
C12—C7—P1	121.89 (15)	C16—C17—C18	111.16 (18)
C9—C8—C7	120.55 (19)	C16—C17—H17A	109.4
C9—C8—H8	119.7	C18—C17—H17A	109.4
C7—C8—H8	119.7	C16—C17—H17B	109.4
C10—C9—C8	119.8 (2)	C18—C17—H17B	109.4
C10—C9—H9	120.1	H17A—C17—H17B	108.0
C8—C9—H9	120.1	C17—C18—C13	111.12 (18)
C9—C10—C11	120.2 (2)	C17—C18—H18B	109.4
C9—C10—H10	119.9	C13—C18—H18B	109.4
C11—C10—H10	119.9	C17—C18—H18A	109.4
C10—C11—C12	120.2 (2)	C13—C18—H18A	109.4
C10—C11—H11	119.9	H18B—C18—H18A	108.0
C12—C11—H11	119.9
C7—P1—C1—C6	57.84 (19)	P1—C7—C8—C9	−177.45 (17)
C13—P1—C1—C6	−55.15 (19)	C7—C8—C9—C10	0.4 (3)
Au1—P1—C1—C6	−177.53 (15)	C8—C9—C10—C11	−1.3 (3)
C7—P1—C1—C2	−119.78 (17)	C9—C10—C11—C12	1.1 (3)
C13—P1—C1—C2	127.24 (16)	C10—C11—C12—C7	0.0 (3)
Au1—P1—C1—C2	4.85 (18)	C8—C7—C12—C11	−0.9 (3)
C6—C1—C2—C3	−1.0 (3)	P1—C7—C12—C11	177.21 (17)
P1—C1—C2—C3	176.64 (16)	C7—P1—C13—C18	−179.68 (14)
C1—C2—C3—C4	0.2 (3)	C1—P1—C13—C18	−67.45 (16)
C2—C3—C4—C5	1.1 (3)	Au1—P1—C13—C18	55.21 (15)
C3—C4—C5—C6	−1.4 (4)	C7—P1—C13—C14	58.44 (16)
C4—C5—C6—C1	0.5 (3)	C1—P1—C13—C14	170.66 (14)
C2—C1—C6—C5	0.7 (3)	Au1—P1—C13—C14	−66.67 (14)
P1—C1—C6—C5	−176.95 (17)	C18—C13—C14—C15	55.3 (2)
C1—P1—C7—C8	103.74 (18)	P1—C13—C14—C15	176.34 (14)
C13—P1—C7—C8	−142.83 (17)	C13—C14—C15—C16	−55.2 (2)
Au1—P1—C7—C8	−19.42 (19)	C14—C15—C16—C17	55.4 (3)
C1—P1—C7—C12	−74.36 (19)	C15—C16—C17—C18	−55.6 (2)
C13—P1—C7—C12	39.1 (2)	C16—C17—C18—C13	56.0 (2)
Au1—P1—C7—C12	162.48 (15)	C14—C13—C18—C17	−55.8 (2)
C12—C7—C8—C9	0.7 (3)	P1—C13—C18—C17	−177.43 (15)

(It) chlorido(cyclohexyldiphenylphosphine)gold(I)

Crystal data

[AuCl(C18H21P)]	F(000) = 960
Mr = 500.73	Dx = 1.936 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 999 reflections
a = 13.1440 (9) Å	θ = 1.8–28.3°
b = 11.4900 (8) Å	µ = 8.80 mm^−1
c = 13.1056 (9) Å	T = 100 K
β = 119.786 (2)°	Block, colourless
V = 1717.8 (2) Å^3	0.33 × 0.32 × 0.27 mm
Z = 4

Data collection

Bruker SMART APEXII area detector diffractometer	4184 independent reflections
Radiation source: microfocus sealed X-ray tube, Incoatec Iµs	4157 reflections with I > 2σ(I)
Mirror optics monochromator	Rint = 0.053
0.60° ω and 0.6° ϕ scans	θmax = 28.3°, θmin = 1.8°
Absorption correction: analytical (SADABS; Bruker, 2009)	h = −17→17
Tmin = 0.161, Tmax = 0.197	k = −15→15
32548 measured reflections	l = −17→17

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) = 0.088	H-atom parameters constrained
S = 1.09	w = 1/[σ^2(Fo^2) + (0.0488P)^2 + 9.2374P] where P = (Fo^2 + 2Fc^2)/3
4184 reflections	(Δ/σ)max = 0.001
191 parameters	Δρmax = 2.20 e Å^−3
0 restraints	Δρmin = −1.96 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	0.23988 (2)	0.607900 (14)	0.08370 (2)	0.01543 (8)
Cl1	0.25992 (15)	0.43969 (12)	0.18598 (14)	0.0268 (3)
P1	0.23076 (12)	0.76904 (11)	−0.01586 (11)	0.0131 (2)
C1	0.1031 (5)	0.7770 (5)	−0.1623 (5)	0.0153 (10)
C2	0.0149 (5)	0.6946 (5)	−0.1981 (6)	0.0213 (11)
H2	0.0198	0.6345	−0.1460	0.026*
C3	−0.0825 (5)	0.7010 (6)	−0.3129 (6)	0.0248 (12)
H3	−0.1436	0.6450	−0.3384	0.030*
C4	−0.0892 (5)	0.7889 (6)	−0.3886 (6)	0.0223 (12)
H4	−0.1544	0.7928	−0.4661	0.027*
C5	0.0000 (5)	0.8713 (5)	−0.3508 (6)	0.0193 (11)
H5	−0.0048	0.9317	−0.4026	0.023*
C6	0.0959 (5)	0.8660 (5)	−0.2379 (5)	0.0176 (10)
H6	0.1563	0.9226	−0.2123	0.021*
C7	0.2237 (5)	0.9037 (4)	0.0549 (5)	0.0150 (10)
C8	0.2969 (5)	0.9989 (5)	0.0711 (5)	0.0193 (11)
H8	0.3534	0.9948	0.0461	0.023*
C9	0.2863 (7)	1.0992 (5)	0.1242 (6)	0.0244 (13)
H9	0.3364	1.1636	0.1365	0.029*
C10	0.2028 (7)	1.1059 (5)	0.1592 (6)	0.0242 (14)
H10	0.1957	1.1748	0.1951	0.029*
C11	0.1293 (5)	1.0114 (6)	0.1416 (5)	0.0228 (12)
H11	0.0714	1.0162	0.1646	0.027*
C12	0.1411 (5)	0.9103 (5)	0.0903 (5)	0.0177 (11)
H12	0.0920	0.8453	0.0796	0.021*
C13	0.3576 (4)	0.7763 (5)	−0.0381 (5)	0.0142 (10)
H13	0.3557	0.8522	−0.0764	0.017*
C14	0.3472 (5)	0.6764 (5)	−0.1218 (5)	0.0199 (11)
H14A	0.3386	0.6015	−0.0895	0.024*
H14B	0.2760	0.6883	−0.1992	0.024*
C15	0.4539 (5)	0.6702 (6)	−0.1383 (6)	0.0245 (12)
H15A	0.4470	0.6010	−0.1864	0.029*
H15B	0.4557	0.7400	−0.1816	0.029*
C16	0.5679 (5)	0.6629 (5)	−0.0218 (6)	0.0231 (12)
H16B	0.6350	0.6642	−0.0363	0.028*
H16A	0.5705	0.5887	0.0178	0.028*
C17	0.5782 (5)	0.7645 (5)	0.0574 (6)	0.0219 (11)
H17B	0.5817	0.8384	0.0204	0.026*
H17A	0.6517	0.7570	0.1337	0.026*
C18	0.4735 (5)	0.7678 (5)	0.0787 (5)	0.0180 (10)
H18B	0.4812	0.8357	0.1286	0.022*
H18A	0.4733	0.6965	0.1210	0.022*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Au1	0.02043 (11)	0.01226 (11)	0.01618 (12)	0.00181 (7)	0.01105 (10)	0.00332 (6)
Cl1	0.0451 (9)	0.0155 (6)	0.0309 (7)	0.0084 (6)	0.0271 (7)	0.0095 (5)
P1	0.0144 (6)	0.0124 (6)	0.0130 (6)	−0.0002 (5)	0.0072 (5)	0.0013 (4)
C1	0.014 (2)	0.016 (2)	0.015 (2)	−0.0002 (18)	0.007 (2)	−0.0017 (19)
C2	0.019 (3)	0.019 (3)	0.025 (3)	−0.002 (2)	0.010 (2)	0.004 (2)
C3	0.015 (2)	0.022 (3)	0.031 (3)	−0.005 (2)	0.007 (2)	0.000 (2)
C4	0.015 (2)	0.023 (3)	0.022 (3)	0.002 (2)	0.004 (2)	−0.004 (2)
C5	0.021 (3)	0.016 (2)	0.020 (3)	0.004 (2)	0.010 (2)	0.002 (2)
C6	0.019 (2)	0.013 (2)	0.019 (3)	0.000 (2)	0.008 (2)	0.001 (2)
C7	0.021 (3)	0.012 (2)	0.016 (3)	0.0052 (18)	0.013 (2)	0.0010 (17)
C8	0.020 (3)	0.016 (2)	0.026 (3)	0.002 (2)	0.015 (2)	0.001 (2)
C9	0.032 (3)	0.015 (3)	0.024 (3)	−0.001 (2)	0.012 (3)	−0.002 (2)
C10	0.029 (3)	0.021 (3)	0.021 (3)	0.003 (2)	0.011 (3)	−0.004 (2)
C11	0.023 (3)	0.027 (3)	0.019 (3)	0.008 (2)	0.011 (2)	0.001 (2)
C12	0.018 (2)	0.020 (2)	0.015 (3)	0.002 (2)	0.008 (2)	0.002 (2)
C13	0.015 (2)	0.016 (2)	0.011 (2)	0.0019 (18)	0.0061 (19)	−0.0002 (18)
C14	0.018 (2)	0.025 (3)	0.016 (2)	−0.001 (2)	0.008 (2)	−0.006 (2)
C15	0.022 (3)	0.032 (3)	0.020 (3)	0.002 (2)	0.011 (2)	−0.008 (2)
C16	0.018 (3)	0.021 (3)	0.030 (3)	0.001 (2)	0.012 (2)	−0.004 (2)
C17	0.018 (3)	0.022 (3)	0.025 (3)	−0.002 (2)	0.011 (2)	−0.002 (2)
C18	0.017 (3)	0.022 (3)	0.014 (2)	−0.002 (2)	0.006 (2)	−0.001 (2)

Geometric parameters (Å, º)

Au1—P1	2.2337 (12)	C10—C11	1.394 (9)
Au1—Cl1	2.2915 (13)	C10—H10	0.9500
P1—C1	1.819 (6)	C11—C12	1.389 (8)
P1—C7	1.829 (5)	C11—H11	0.9500
P1—C13	1.832 (5)	C12—H12	0.9500
C1—C2	1.386 (8)	C13—C18	1.535 (7)
C1—C6	1.394 (8)	C13—C14	1.547 (7)
C2—C3	1.413 (9)	C13—H13	1.0000
C2—H2	0.9500	C14—C15	1.523 (8)
C3—C4	1.388 (9)	C14—H14A	0.9900
C3—H3	0.9500	C14—H14B	0.9900
C4—C5	1.393 (9)	C15—C16	1.520 (9)
C4—H4	0.9500	C15—H15A	0.9900
C5—C6	1.389 (8)	C15—H15B	0.9900
C5—H5	0.9500	C16—C17	1.524 (9)
C6—H6	0.9500	C16—H16B	0.9900
C7—C12	1.379 (8)	C16—H16A	0.9900
C7—C8	1.401 (8)	C17—C18	1.534 (8)
C8—C9	1.389 (8)	C17—H17B	0.9900
C8—H8	0.9500	C17—H17A	0.9900
C9—C10	1.385 (10)	C18—H18B	0.9900
C9—H9	0.9500	C18—H18A	0.9900
P1—Au1—Cl1	176.41 (5)	C7—C12—C11	120.3 (6)
C1—P1—C7	103.9 (3)	C7—C12—H12	119.9
C1—P1—C13	105.4 (2)	C11—C12—H12	119.9
C7—P1—C13	108.7 (3)	C18—C13—C14	110.8 (4)
C1—P1—Au1	114.31 (18)	C18—C13—P1	111.6 (4)
C7—P1—Au1	113.98 (18)	C14—C13—P1	108.2 (4)
C13—P1—Au1	110.00 (17)	C18—C13—H13	108.7
C2—C1—C6	120.7 (5)	C14—C13—H13	108.7
C2—C1—P1	120.1 (4)	P1—C13—H13	108.7
C6—C1—P1	119.2 (4)	C15—C14—C13	111.9 (5)
C1—C2—C3	119.2 (5)	C15—C14—H14A	109.2
C1—C2—H2	120.4	C13—C14—H14A	109.2
C3—C2—H2	120.4	C15—C14—H14B	109.2
C4—C3—C2	120.1 (6)	C13—C14—H14B	109.2
C4—C3—H3	120.0	H14A—C14—H14B	107.9
C2—C3—H3	120.0	C16—C15—C14	112.2 (5)
C3—C4—C5	119.9 (6)	C16—C15—H15A	109.2
C3—C4—H4	120.1	C14—C15—H15A	109.2
C5—C4—H4	120.1	C16—C15—H15B	109.2
C6—C5—C4	120.4 (6)	C14—C15—H15B	109.2
C6—C5—H5	119.8	H15A—C15—H15B	107.9
C4—C5—H5	119.8	C15—C16—C17	110.6 (5)
C5—C6—C1	119.7 (5)	C15—C16—H16B	109.5
C5—C6—H6	120.2	C17—C16—H16B	109.5
C1—C6—H6	120.2	C15—C16—H16A	109.5
C12—C7—C8	120.1 (5)	C17—C16—H16A	109.5
C12—C7—P1	117.6 (4)	H16B—C16—H16A	108.1
C8—C7—P1	122.2 (4)	C16—C17—C18	111.1 (5)
C9—C8—C7	119.5 (5)	C16—C17—H17B	109.4
C9—C8—H8	120.3	C18—C17—H17B	109.4
C7—C8—H8	120.3	C16—C17—H17A	109.4
C10—C9—C8	120.3 (6)	C18—C17—H17A	109.4
C10—C9—H9	119.8	H17B—C17—H17A	108.0
C8—C9—H9	119.8	C17—C18—C13	110.8 (5)
C9—C10—C11	120.0 (5)	C17—C18—H18B	109.5
C9—C10—H10	120.0	C13—C18—H18B	109.5
C11—C10—H10	120.0	C17—C18—H18A	109.5
C12—C11—C10	119.8 (6)	C13—C18—H18A	109.5
C12—C11—H11	120.1	H18B—C18—H18A	108.1
C10—C11—H11	120.1
C7—P1—C1—C2	−117.3 (5)	P1—C7—C8—C9	179.2 (5)
C13—P1—C1—C2	128.4 (5)	C7—C8—C9—C10	−1.0 (10)
Au1—P1—C1—C2	7.5 (5)	C8—C9—C10—C11	0.2 (11)
C7—P1—C1—C6	63.4 (5)	C9—C10—C11—C12	0.8 (10)
C13—P1—C1—C6	−50.9 (5)	C8—C7—C12—C11	0.4 (9)
Au1—P1—C1—C6	−171.8 (4)	P1—C7—C12—C11	−178.2 (5)
C6—C1—C2—C3	0.5 (9)	C10—C11—C12—C7	−1.2 (9)
P1—C1—C2—C3	−178.8 (5)	C1—P1—C13—C18	−178.8 (4)
C1—C2—C3—C4	0.1 (10)	C7—P1—C13—C18	70.4 (4)
C2—C3—C4—C5	−0.5 (10)	Au1—P1—C13—C18	−55.1 (4)
C3—C4—C5—C6	0.3 (9)	C1—P1—C13—C14	−56.6 (4)
C4—C5—C6—C1	0.3 (9)	C7—P1—C13—C14	−167.5 (4)
C2—C1—C6—C5	−0.7 (9)	Au1—P1—C13—C14	67.1 (4)
P1—C1—C6—C5	178.6 (4)	C18—C13—C14—C15	−53.1 (6)
C1—P1—C7—C12	74.7 (5)	P1—C13—C14—C15	−175.8 (4)
C13—P1—C7—C12	−173.4 (4)	C13—C14—C15—C16	53.7 (7)
Au1—P1—C7—C12	−50.3 (5)	C14—C15—C16—C17	−55.6 (7)
C1—P1—C7—C8	−103.9 (5)	C15—C16—C17—C18	57.4 (7)
C13—P1—C7—C8	8.0 (6)	C16—C17—C18—C13	−57.6 (6)
Au1—P1—C7—C8	131.1 (4)	C14—C13—C18—C17	55.0 (6)
C12—C7—C8—C9	0.6 (9)	P1—C13—C18—C17	175.6 (4)