catena-Poly[[(6,7,9,10,17,18,20,21-octa­hydro-5,8,11,16,19,22-hexa­oxadibenzo[a,j]cyclo­octa­decene)barium]-di-μ-thio­cyanato-[thio­cyanato­diaurate(I)(Au—Au)]-μ-thio­cyanato]

Stroud, T.L.; Coker, N.L.; Krause, J.A.

doi:10.1107/S1600536809045218

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 12| December 2009| Pages m1509-m1510

doi:10.1107/S1600536809045218

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catena-Poly[[(6,7,9,10,17,18,20,21-octahydro-5,8,11,16,19,22-hexaoxadibenzo[a,j]cyclooctadecene)barium]-di-μ-thiocyanato-[thiocyanatodiaurate(I)(Au—Au)]-μ-thiocyanato]

Tonia L. Stroud,^a Nathan L. Coker ^a ^* and Jeanette A. Krause ^b

^aDepartment of Physical Sciences, Morehead State University, Morehead, KY 40351, USA, and ^bDepartment of Chemistry, University of Cincinnati, Cincinnati, OH 45221-0172, USA
^*Correspondence e-mail: jeanette.krause@uc.edu

(Received 14 September 2009; accepted 28 October 2009; online 4 November 2009)

In the title compound, [Au₂Ba(NCS)₄(C₂₀H₂₄O₆)]_n, the dithiocyanatoaurate(I) anion adopts a dimeric structure with an Au⋯Au distance of 3.1109 (10) Å; both Au^I atoms are also bonded to two S atoms. The Ba^II ion adopts an irregular BaN₃O₆ geometry, arising from the crown ether and three adjacent thiocyanate N atoms; the extended structure of the complex can be described as a one-dimensional coordination polymer generated by the Ba⋯N interactions (two on the endo side and one on the exo side of the crown ether) running parallel to the b axis, with an antiparallel arrangement of ribbons in the unit cell.

Related literature

For further information on gold chemistry, see: Arvapally et al. (2007 ); Beavers et al. (2009 ); Chen et al. (2005 ); Coker (2003 ); Coker et al. (2004a ,b , 2006 ); Mohamed et al. (2003 ); Olmstead et al. (2005 ); Pathaneni & Desiraju (1993 ); Schwerdtferger et al. (1990 ). For further information on barium macrocycles, see: Bordunov et al. (1996 ); Bradshaw & Izatt (1997 ); Felton et al. (2008 ); Henke & Atwood (1998 ); Masci & Thuery (2006 ); Metz et al. (1973 ). For a description of the Cambridge Structural Database, see: Allen (2002 ).

Experimental

Crystal data

[Au₂Ba(NCS)₄(C₂₀H₂₄O₆)]
M_r = 1123.98
Monoclinic, P 2₁ /c
a = 17.5491 (8) Å
b = 12.6183 (4) Å
c = 15.6584 (6) Å
β = 110.598 (2)°
V = 3245.7 (2) Å³
Z = 4
Cu Kα radiation
μ = 28.76 mm⁻¹
T = 150 K
0.14 × 0.08 × 0.01 mm

Data collection

Bruker SMART6000 CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ) T_min = 0.118, T_max = 0.752
14223 measured reflections
4110 independent reflections
2905 reflections with I > 2σ(I)
R_int = 0.069
θ_max = 56.9°

Refinement

R[F² > 2σ(F²)] = 0.053
wR(F²) = 0.128
S = 0.98
4110 reflections
358 parameters
H-atom parameters constrained
Δρ_max = 1.66 e Å⁻³
Δρ_min = −0.85 e Å⁻³

Table 1
Selected bond lengths (Å)

Au1—S2	2.297 (4)
Au1—S1	2.305 (4)
Au2—S4	2.288 (4)
Au2—S3	2.305 (4)
Ba—N1	2.834 (14)
Ba—N2ⁱ	2.877 (13)
Ba—N3	2.774 (14)
Ba—O7	2.840 (9)
Ba—O17	2.845 (9)
Ba—O19	2.921 (12)
Ba—O9	2.927 (12)
Ba—O15	2.940 (11)
Ba—O5	2.988 (10)
Symmetry code: (i) x, y+1, z.

Data collection: SMART (Bruker, 2003 ); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809045218/hb5102sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809045218/hb5102Isup2.hkl

checkCIF report

Comment top

The present work stems from our interest in developing gold(I)-thiocyanate complexes with interesting gold bonding motifs and luminescent properties (Coker et al., 2004a, Arvapally et al.,2007). We have shown that alkali (K⁺, Rb⁺ and Cs⁺) salts of bis(thiocyanato)aurate(I) (Coker et al., 2004a) crystallize as linear one-dimensional polymeric chains with Au—Au distances in the 3.0065 (5)–3.2654 (2) Å range. Bis(thiocyanato)aurate(I) complexes with NH₄⁺ (Coker et al., 2006) and Me₄N⁺ (Coker et al., 2004a) adopt a similar linear or nearly linear motif, respectively, with alternating sets of Au—Au distances (NH₄⁺: 3.1794 (2), 3.2654 (2) Å; Me₄N⁺: 3.1409 (3), 3.1723 (3) Å). In sharp contrast, the anion in [(n-Bu)₄N]bis(thiocyanato)aurate(I) (Coker et al., 2004a) crystallizes as a dimer (Au—Au = 3.0700 (8) Å) while the anion in [Ph₄As]bis(thiocyanato)aurate(I) (Schwerdtferger et al., 1990) and [Ph₄P]bis(thiocyanato)aurate(I) (Coker, 2003) exist as monomers.

To further explore the influence of the cation on the motif adopted by the bis(thiocyanato)aurate(I) anion, we synthesized and characterized the (1,4,7,10,13,16-hexaoxacyclooctadecane)-potassium dithiocyanatoaurate(I) [1,4,7,10,13,16-hexaoxacyclooctadecane = 18-crown-6] (Coker et al., 2004b) and (18-crown-6)-caesium dithiocyanatoaurate(I) (Coker, 2003) complexes. The geometry of the [Au(SCN)₂]^- anion in these complexes is monomeric and analogous to the Ph₄P⁺ and Ph₄As⁺ salts. The extended structure can be described as a zigzag polymeric chain formed by the coordination of the N atoms of the thiocyanate via a single intermolecular interaction to the vacant coordination site on the K or Cs atoms. To extend our bonding motif investigation, complexes utilizing 6,7,9,10,17,18,20,21-octahydro-5,8,11,16,19,22-hexaoxa- dibenzo[a,j]cyclooctadecene (dbz-18-crown-6) with alkali or alkaline earth cations were studied. In the present work, the structure of the title complex, (I), is reported.

The geometry of the anion in (I) (Fig. 1) is a dimer with a Au—Au bond distance of 3.1109 (10) Å and Au—S distances falling in the 2.299 (4)–2.305 (4) Å range. The Au—Au bond distance observed in (I) is less than the sum of the van der Waals radii of 3.32 Å for a gold-gold interaction (Bondi, 1964). A Cambridge Structural Database (CSD) analysis of gold-gold interactions reported by Pathaneni & Desiraju (1993) found that distances in the range 2.6–3.4 Å can be considered to have Au—Au bonding character. Furthermore, the Au—Au and Au—S bond distances in (I) are comparable to those in the related crown complex [CH₃CN-(dbz-18-crown-6-Na)]₂[Au(SCN)₂]₂.dbz-18-crown-6.CH₃CN (Au—Au = 3.0661 (4) Å, Au—S = 2.291 (2)–2.303 (2) Å (Coker, 2003). The metallomacrocyclic gold(I) thiolate cluster, [Au₉(µ-dppm)₄(µ-p-tc)₆](PF₆)₃ (dppm = bis(diphenylphosphine)methane and p-tc = p-thiocresolate), is reported to have four distinct gold environments. These environments consist of (a) Au—Au phosphine bridged single bonds (3.0084 (6)–3.1439 (6) Å, (b) Au—Au sulfiur bridged single bonds (2.9950 (7)–3.1632 (6) Å, (c) Au—Au non-bridged single bonds (3.0135 (7)–3.1825 (7) Å and (d) sulfur bridged Au···Au nonbonded interactions (3.7155 (8)–3.9571 (7) Å (Chen et al., 2005). In the same vein, the PMe₃ analog of the antiarthritic gold drug Auranofin, [(Me₃PAu)₂(µ-TATG)]NO₃ (TATG = 2,3,4,6-tetraacetyl-1-thio-D-glucopyranosato) (Mohamed et al., 2003) forms a tetranuclear gold cluster with Au—Au and Au—S distances in the 3.106 (7)–3.144 (12) Å and 2.334 (3)–2.355 (3) Å range, respectively. A CSD survey (Cambridge Structural Database v5.30) (Allen, 2002) of metal-thiocyanate complexes reveals an average M—S distance of 2.39 Å (M = Pt, Pd, Ag or Au), the Au—S distances in (I) are consistent with this observation.

Alkali and alkaline earth cations have a preferred tendency to bind in a way that high coordination numbers are achieved. This characteristic makes them useful in applications where coordination- flexible ligating agents are a necessity (e.g. sequestration) (Bradshaw & Izatt, 1997). The nine-coordinate Ba atom in (I) is bound to the six oxygen atoms of the dbz-18-crown-6 (Ba—O distances range: 2.940 (9)–2.988 (10) Å) and sits 0.769 (5) Å out of the plane generated by these atoms. The remainder of the coordination sites consists of two endo side and one exo side Ba···N interaction (2.774 (14)–2.877 (13) Å). The fourth thiocyanate moiety (N4) remains uncoordinated, the nearest nonbonded distance to Ba is 4.728 (15) Å. Thus the extended structure of (I) (Fig. 2) can be described as a one-dimensional coordination polymer generated by Ba···N intermolecular interactions running parallel to the b axis, with an overall antiparallel arrangement of ribbons in the unit cell.

In contrast, [poly[triaquatetra-µ-cyanido-tetracyanidobis(1,4,10,13- tetraoxa-7,16-diazacyclo-octadecane)dibarium(II)tetragold(I) crystallizes as a coordination polymer with the [Au(CN)₂]^- anion in monomer, dimer and trimer environments while the barium atoms are bound to the diaza-18-crown-6 and solvent water molecules in nine and ten-coordinate geometries (Beavers et al., 2009). Reported Ba···O and Ba···N distances for this gold-cyanato complex are 2.761 (2)–2.929 (2) Å and 2.867 (3)–2.959 (3) Å, respectively. In the case of catena-poly[[diaqua(1,4,7,10,13,16-hexaoxa-cyclooctadecane)- barium(II)]-µ-cyano-[dicyano-platinum(II)]-µ-cyano], the extended structure is an alternating chain of [18-crown-6-Ba]²⁺ and [Pt(CN)₄]^2- ions bound through the N-atom of the cyano group to the Ba²⁺ ion (ten-coordinate geometry about Ba, Ba···N = 2.901 (2) Å and the average Ba—O_crown and Ba—O_water distances are reported as 2.858 (17) Å and 2.883 (13) Å) (Olmstead et al., 2005). The Ba···O and Ba···N bonds in (I) are also consistent with those observed in structures such as M(TMTH₂)₂.nH₂O (M = Ca, Sr, Ba and TMT=2,4,6-trimercaptotriazine) (Henke & Atwood, 1998) and Ba-containing macroethers, cryptands or lariat ethers, e.g. aqua-(7,16-bis((5-chloro-8-hydroxy-2-quinolinyl)methyl)-1,4,10,13- tetra-oxa-7,16-diazacyclo-octadecane)-barium dibromide (Bordunov et al., 1996), aqua-thiocyanato-crypt(222)-barium thiocyanate (Metz et al., 1973), bis(triethylammonium)diaqua- [2.2.2-crypt]-barium bis((p-tert-butyl-[3.1.3]tetrahomodioxa- calix[4[arene)-dioxo-uranium) pentahydrate (Masci & Thuery, 2006) and (8-propyl-18,21,26,29-tetraoxa-1,7,9,15,32,35-hexaazapenta-cyclo (13.8.8.4^3,13.0^6,34.0^10,33)pentatriaconta-3,5,10,12,32,34- hexaene)-bis(perchlorato)-barium (Felton et al., 2008.

Related literature top

For further information on gold chemistry, see: Arvapally et al. (2007); Beavers et al. (2009); Chen et al. (2005); Coker (2003); Coker et al. (2004a,b, 2006); Mohamed et al. (2003); Olmstead et al. (2005); Pathaneni & Desiraju (1993); Schwerdtferger et al. (1990). For further information on barium macrocycles, see: Bordunov et al. (1996); Bradshaw & Izatt (1997); Felton et al. (2008); Henke & Atwood (1998); Masci & Thuery (2006); Metz et al. (1973). For a description of the Cambridge Structural Database, see: Allen (2002).

Experimental top

Reaction of barium hydroxide (1 equiv) with ammonium thiocyanate (2 eqiv) in water results in the formation of barium thiocyanate with the release of ammonia gas.

Barium bis(thiocyanato)aurate(I) was prepared following the method described by Coker et al., (2004a). (I) was prepared by the analogous method described for (18-crown-6-K)dithiocyanatoaurate(I) (Coker et al., 2004b). Diffraction quality crystals were obtained from slow diffusion of acetonitrile-diethyl ether solution at -4 °C.

Computing details top

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. : Structure of (I) showing 50% probability ellipsoids. H-atoms omitted for clarity.
	Fig. 2. : The one-dimensional polymer chain runs parallel to the b axis, with an antiparallel arrangement of ribbons in the unit cell. H-atoms omitted for clarity.

catena-Poly[[(6,7,9,10,17,18,20,21-octahydro-5,8,11,16,19,22- hexaoxadibenzo[a,j]cyclooctadecene)barium]-di-µ-thiocyanato- [thiocyanatodiaurate(I)(Au—Au)]-µ-thiocyanato] top

Crystal data top

[Au₂Ba(NCS)₄(C₂₀H₂₄O₆)]	F(000) = 2088
M_r = 1123.98	D_x = 2.300 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2ybc	Cell parameters from 4482 reflections
a = 17.5491 (8) Å	θ = 4.4–56.9°
b = 12.6183 (4) Å	µ = 28.76 mm⁻¹
c = 15.6584 (6) Å	T = 150 K
β = 110.598 (2)°	Plate, pale pink
V = 3245.7 (2) Å³	0.14 × 0.08 × 0.01 mm
Z = 4

Data collection top

Bruker SMART6000 CCD diffractometer	4110 independent reflections
Radiation source: fine-focus sealed tube	2905 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.069
Detector resolution: 0.92 pixels mm^-1	θ_max = 56.9°, θ_min = 2.7°
ω scans	h = −16→17
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −11→13
T_min = 0.118, T_max = 0.752	l = −16→17
14223 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.128	H-atom parameters constrained
S = 0.98	w = 1/[σ²(F_o²) + (0.0766P)²] where P = (F_o² + 2F_c²)/3
4110 reflections	(Δ/σ)_max < 0.001
358 parameters	Δρ_max = 1.66 e Å⁻³
0 restraints	Δρ_min = −0.85 e Å⁻³

Crystal data top

[Au₂Ba(NCS)₄(C₂₀H₂₄O₆)]	V = 3245.7 (2) Å³
M_r = 1123.98	Z = 4
Monoclinic, P2₁/c	Cu Kα radiation
a = 17.5491 (8) Å	µ = 28.76 mm⁻¹
b = 12.6183 (4) Å	T = 150 K
c = 15.6584 (6) Å	0.14 × 0.08 × 0.01 mm
β = 110.598 (2)°

Data collection top

Bruker SMART6000 CCD diffractometer	4110 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	2905 reflections with I > 2σ(I)
T_min = 0.118, T_max = 0.752	R_int = 0.069
14223 measured reflections	θ_max = 56.9°

Refinement top

R[F² > 2σ(F²)] = 0.053	0 restraints
wR(F²) = 0.128	H-atom parameters constrained
S = 0.98	Δρ_max = 1.66 e Å⁻³
4110 reflections	Δρ_min = −0.85 e Å⁻³
358 parameters

Special details top

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

The final unit cell is obtained from the refinement of the XYZ weighted centroids of reflections above 20 σ(I). Note that the absorption correction parameters Tmin and Tmax also reflect beam corrections, etc. As a result, the numerical values for Tmin and Tmax may differ from expected values based solely absorption effects and crystal size.

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.

The anisotropic displacement parameters for C7 and C20 were constrained to be equivalent to C6 and C5, respectively.

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

	x	y	z	U_iso*/U_eq
Au1	0.34634 (4)	0.40337 (5)	0.26591 (4)	0.0408 (2)
Au2	0.17476 (4)	0.43183 (5)	0.27917 (5)	0.0453 (3)
S1	0.4056 (2)	0.5186 (3)	0.3851 (2)	0.0433 (11)
S2	0.3048 (3)	0.2863 (3)	0.1460 (3)	0.0584 (13)
S3	0.1241 (3)	0.5265 (4)	0.1450 (3)	0.0635 (14)
S4	0.2067 (3)	0.3454 (3)	0.4158 (3)	0.0490 (11)
C1	0.3550 (10)	0.6284 (13)	0.3434 (10)	0.041 (4)
C2	0.2600 (10)	0.1899 (13)	0.1840 (11)	0.047 (4)
C3	0.1250 (9)	0.6475 (14)	0.1921 (11)	0.047 (4)
C4	0.2867 (11)	0.2679 (14)	0.4179 (11)	0.048 (5)
N1	0.3197 (8)	0.7081 (11)	0.3177 (9)	0.051 (4)
N2	0.2288 (8)	0.1179 (10)	0.2044 (9)	0.047 (4)
N3	0.1230 (9)	0.7317 (11)	0.2215 (10)	0.060 (4)
N4	0.3382 (9)	0.2131 (12)	0.4199 (10)	0.058 (4)
Ba	0.23237 (6)	0.89893 (6)	0.25677 (6)	0.0322 (3)
O5	0.1978 (8)	0.9218 (9)	0.0567 (7)	0.066 (4)
O7	0.3582 (6)	0.9286 (7)	0.1843 (6)	0.036 (2)
O9	0.3953 (7)	0.9610 (9)	0.3779 (7)	0.064 (3)
O15	0.2715 (8)	0.9925 (10)	0.4392 (8)	0.065 (3)
O17	0.1095 (6)	0.9937 (7)	0.3111 (6)	0.039 (3)
O19	0.0748 (7)	0.9545 (9)	0.1208 (7)	0.064 (3)
C5	0.1207 (10)	0.8637 (12)	0.0123 (9)	0.037 (3)
C6	0.2689 (9)	0.8954 (11)	0.0301 (9)	0.036 (3)
H6A	0.2800	0.8184	0.0371	0.043*
H6B	0.2573	0.9146	−0.0346	0.043*
C7	0.3402 (9)	0.9553 (11)	0.0894 (8)	0.036 (3)
H7B	0.3880	0.9389	0.0721	0.043*
H7A	0.3292	1.0322	0.0806	0.043*
C8	0.4339 (9)	0.9751 (12)	0.2431 (9)	0.041 (4)
H8A	0.4274	1.0527	0.2464	0.049*
H8B	0.4773	0.9614	0.2177	0.049*
C9	0.4576 (9)	0.9277 (12)	0.3375 (9)	0.040 (4)
H9A	0.4594	0.8495	0.3339	0.048*
H9B	0.5122	0.9532	0.3761	0.048*
C10	0.4040 (10)	0.9142 (11)	0.4657 (9)	0.038 (4)
C11	0.4680 (10)	0.8473 (11)	0.5139 (10)	0.040 (4)
H11	0.5101	0.8316	0.4908	0.048*
C12	0.4694 (11)	0.8042 (12)	0.5956 (10)	0.047 (4)
H12	0.5129	0.7589	0.6291	0.057*
C13	0.4087 (11)	0.8263 (12)	0.6286 (11)	0.044 (4)
H13	0.4112	0.7978	0.6857	0.053*
C14	0.3448 (10)	0.8886 (11)	0.5806 (10)	0.040 (4)
H14	0.3029	0.9013	0.6046	0.049*
C15	0.3385 (11)	0.9342 (11)	0.4980 (10)	0.037 (4)
C16	0.2001 (10)	1.0007 (13)	0.4669 (11)	0.050 (5)
H16B	0.2145	1.0419	0.5242	0.061*
H16A	0.1833	0.9289	0.4787	0.061*
C17	0.1299 (11)	1.0539 (13)	0.3941 (12)	0.056 (5)
H17A	0.0822	1.0578	0.4139	0.067*
H17B	0.1453	1.1270	0.3838	0.067*
C18	0.0412 (10)	1.0419 (12)	0.2411 (10)	0.048 (5)
H18B	0.0578	1.1098	0.2212	0.058*
H18A	−0.0032	1.0562	0.2647	0.058*
C19	0.0129 (9)	0.9649 (13)	0.1622 (10)	0.042 (4)
H19B	0.0023	0.8948	0.1843	0.050*
H19A	−0.0384	0.9906	0.1162	0.050*
C20	0.0582 (10)	0.8804 (11)	0.0468 (9)	0.037 (3)
C21	−0.0125 (10)	0.8211 (12)	0.0105 (10)	0.045 (4)
H21	−0.0565	0.8328	0.0313	0.054*
C22	−0.0195 (10)	0.7466 (12)	−0.0542 (11)	0.054 (5)
H22	−0.0671	0.7039	−0.0758	0.064*
C23	0.0427 (12)	0.7322 (13)	−0.0892 (11)	0.051 (5)
H23	0.0359	0.6824	−0.1368	0.061*
C24	0.1134 (10)	0.7894 (12)	−0.0554 (10)	0.040 (4)
H24	0.1565	0.7784	−0.0779	0.049*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Au1	0.0510 (5)	0.0316 (4)	0.0483 (4)	0.0031 (3)	0.0280 (4)	0.0028 (3)
Au2	0.0490 (5)	0.0377 (4)	0.0535 (4)	0.0027 (4)	0.0235 (4)	0.0008 (3)
S1	0.044 (3)	0.043 (2)	0.042 (2)	0.010 (2)	0.015 (2)	−0.0041 (19)
S2	0.099 (4)	0.039 (2)	0.053 (2)	−0.007 (2)	0.046 (3)	−0.005 (2)
S3	0.079 (4)	0.069 (3)	0.049 (2)	0.022 (3)	0.030 (3)	0.008 (2)
S4	0.063 (3)	0.039 (2)	0.054 (2)	0.009 (2)	0.033 (2)	0.009 (2)
C1	0.037 (11)	0.042 (9)	0.048 (9)	−0.002 (9)	0.021 (9)	−0.004 (8)
C2	0.045 (12)	0.044 (10)	0.056 (10)	0.011 (9)	0.022 (10)	−0.010 (9)
C3	0.031 (11)	0.056 (11)	0.056 (10)	−0.002 (9)	0.018 (9)	0.034 (10)
C4	0.059 (14)	0.051 (11)	0.048 (10)	−0.022 (10)	0.035 (11)	−0.014 (9)
N1	0.040 (10)	0.050 (9)	0.059 (8)	0.000 (8)	0.012 (8)	−0.014 (7)
N2	0.060 (11)	0.028 (7)	0.053 (8)	−0.008 (7)	0.018 (8)	−0.006 (6)
N3	0.065 (11)	0.035 (8)	0.079 (10)	−0.007 (8)	0.024 (9)	0.017 (8)
N4	0.064 (12)	0.059 (10)	0.064 (9)	0.006 (9)	0.037 (9)	0.008 (8)
Ba	0.0354 (6)	0.0300 (5)	0.0345 (5)	0.0007 (4)	0.0166 (4)	0.0001 (4)
O5	0.074 (10)	0.077 (9)	0.045 (6)	−0.001 (7)	0.021 (7)	−0.001 (6)
O7	0.030 (6)	0.039 (6)	0.041 (5)	−0.004 (5)	0.013 (5)	−0.003 (5)
O9	0.073 (9)	0.063 (8)	0.064 (7)	−0.001 (7)	0.033 (7)	0.007 (6)
O15	0.057 (9)	0.081 (9)	0.065 (7)	0.004 (7)	0.031 (7)	−0.004 (7)
O17	0.050 (7)	0.032 (5)	0.046 (6)	0.006 (5)	0.029 (6)	−0.011 (5)
O19	0.069 (9)	0.073 (8)	0.060 (7)	0.000 (7)	0.035 (7)	−0.007 (7)
C5	0.039 (9)	0.042 (6)	0.028 (6)	0.009 (6)	0.010 (5)	0.011 (5)
C6	0.040 (8)	0.042 (6)	0.036 (6)	0.007 (5)	0.028 (5)	0.003 (5)
C7	0.040 (8)	0.042 (6)	0.036 (6)	0.007 (5)	0.028 (5)	0.003 (5)
C8	0.047 (12)	0.041 (9)	0.046 (9)	−0.018 (8)	0.030 (9)	−0.005 (8)
C9	0.023 (10)	0.053 (10)	0.047 (9)	−0.018 (8)	0.018 (8)	−0.012 (8)
C10	0.041 (11)	0.040 (9)	0.032 (8)	−0.009 (8)	0.011 (8)	−0.006 (8)
C11	0.039 (11)	0.028 (8)	0.048 (9)	−0.007 (8)	0.008 (9)	−0.008 (8)
C12	0.049 (12)	0.036 (9)	0.043 (9)	0.008 (8)	0.000 (9)	0.011 (8)
C13	0.044 (12)	0.042 (10)	0.043 (9)	−0.011 (9)	0.010 (10)	0.004 (8)
C14	0.044 (12)	0.038 (9)	0.044 (9)	−0.018 (9)	0.020 (9)	−0.014 (8)
C15	0.048 (12)	0.027 (8)	0.043 (9)	−0.010 (8)	0.025 (9)	−0.013 (7)
C16	0.063 (14)	0.047 (10)	0.058 (11)	−0.012 (10)	0.043 (11)	−0.033 (9)
C17	0.051 (13)	0.043 (10)	0.094 (14)	−0.001 (9)	0.050 (12)	−0.020 (10)
C18	0.055 (12)	0.033 (9)	0.053 (10)	0.029 (8)	0.014 (9)	0.010 (8)
C19	0.036 (11)	0.058 (10)	0.043 (9)	0.008 (8)	0.028 (9)	0.011 (8)
C20	0.039 (9)	0.042 (6)	0.028 (6)	0.009 (6)	0.010 (5)	0.011 (5)
C21	0.030 (11)	0.038 (9)	0.052 (9)	−0.003 (8)	−0.003 (9)	0.000 (8)
C22	0.023 (11)	0.036 (10)	0.075 (12)	−0.003 (8)	−0.016 (10)	0.000 (9)
C23	0.050 (13)	0.046 (10)	0.048 (10)	0.026 (10)	0.006 (10)	0.013 (9)
C24	0.028 (11)	0.045 (9)	0.046 (9)	0.009 (8)	0.010 (9)	−0.001 (8)

Geometric parameters (Å, º) top

Au1—S2	2.297 (4)	C6—H6A	0.9900
Au1—S1	2.305 (4)	C6—H6B	0.9900
Au1—Au2	3.1109 (10)	C7—H7B	0.9900
Au2—S4	2.288 (4)	C7—H7A	0.9900
Au2—S3	2.305 (4)	C8—C9	1.510 (18)
S1—C1	1.651 (17)	C8—H8A	0.9900
S2—C2	1.668 (19)	C8—H8B	0.9900
S3—C3	1.69 (2)	C9—H9A	0.9900
S4—C4	1.70 (2)	C9—H9B	0.9900
C1—N1	1.176 (18)	C10—C11	1.39 (2)
C2—N2	1.162 (19)	C10—C15	1.43 (2)
C3—N3	1.16 (2)	C11—C12	1.38 (2)
C4—N4	1.131 (19)	C11—H11	0.9500
N2—Baⁱ	2.877 (13)	C12—C13	1.37 (2)
Ba—N1	2.834 (14)	C12—H12	0.9500
Ba—N2ⁱⁱ	2.877 (13)	C13—C14	1.36 (2)
Ba—N3	2.774 (14)	C13—H13	0.9500
Ba—O7	2.840 (9)	C14—C15	1.38 (2)
Ba—O17	2.845 (9)	C14—H14	0.9500
Ba—O19	2.921 (12)	C16—C17	1.51 (2)
Ba—O9	2.927 (12)	C16—H16B	0.9900
Ba—O15	2.940 (11)	C16—H16A	0.9900
Ba—O5	2.988 (10)	C17—H17A	0.9900
O5—C5	1.479 (18)	C17—H17B	0.9900
O5—C6	1.486 (17)	C18—C19	1.51 (2)
O7—C7	1.446 (15)	C18—H18B	0.9900
O7—C8	1.447 (16)	C18—H18A	0.9900
O9—C10	1.454 (17)	C19—H19B	0.9900
O9—C9	1.504 (18)	C19—H19A	0.9900
O15—C15	1.418 (18)	C20—C21	1.39 (2)
O15—C16	1.467 (18)	C21—C22	1.35 (2)
O17—C17	1.438 (17)	C21—H21	0.9500
O17—C18	1.443 (16)	C22—C23	1.39 (2)
O19—C20	1.436 (18)	C22—H22	0.9500
O19—C19	1.453 (17)	C23—C24	1.37 (2)
C5—C24	1.388 (19)	C23—H23	0.9500
C5—C20	1.40 (2)	C24—H24	0.9500
C6—C7	1.477 (19)

S2—Au1—S1	172.10 (16)	O5—C6—H6B	110.0
S2—Au1—Au2	95.32 (13)	H6A—C6—H6B	108.4
S1—Au1—Au2	92.58 (10)	O7—C7—C6	111.0 (11)
S4—Au2—S3	171.03 (16)	O7—C7—H7B	109.4
S4—Au2—Au1	94.73 (11)	C6—C7—H7B	109.4
S3—Au2—Au1	94.10 (12)	O7—C7—H7A	109.4
C1—S1—Au1	100.5 (5)	C6—C7—H7A	109.4
C2—S2—Au1	103.4 (5)	H7B—C7—H7A	108.0
C3—S3—Au2	97.5 (5)	O7—C8—C9	109.7 (11)
C4—S4—Au2	102.8 (6)	O7—C8—H8A	109.7
N1—C1—S1	177.0 (14)	C9—C8—H8A	109.7
N2—C2—S2	174.5 (14)	O7—C8—H8B	109.7
N3—C3—S3	177.4 (16)	C9—C8—H8B	109.7
N4—C4—S4	177.4 (16)	H8A—C8—H8B	108.2
C1—N1—Ba	179.0 (13)	O9—C9—C8	108.1 (12)
C2—N2—Baⁱ	149.7 (12)	O9—C9—H9A	110.1
C3—N3—Ba	131.2 (13)	C8—C9—H9A	110.1
N3—Ba—N1	71.0 (4)	O9—C9—H9B	110.1
N3—Ba—O7	127.0 (4)	C8—C9—H9B	110.1
N1—Ba—O7	80.9 (3)	H9A—C9—H9B	108.4
N3—Ba—O17	80.5 (4)	C11—C10—C15	120.6 (14)
N1—Ba—O17	129.3 (3)	C11—C10—O9	123.7 (14)
O7—Ba—O17	147.3 (3)	C15—C10—O9	115.6 (13)
N3—Ba—N2ⁱⁱ	136.9 (4)	C12—C11—C10	119.2 (15)
N1—Ba—N2ⁱⁱ	150.2 (4)	C12—C11—H11	120.4
O7—Ba—N2ⁱⁱ	72.6 (3)	C10—C11—H11	120.4
O17—Ba—N2ⁱⁱ	74.8 (3)	C13—C12—C11	120.5 (15)
N3—Ba—O19	68.0 (4)	C13—C12—H12	119.8
N1—Ba—O19	135.3 (3)	C11—C12—H12	119.8
O7—Ba—O19	110.3 (3)	C14—C13—C12	120.7 (15)
O17—Ba—O19	59.6 (3)	C14—C13—H13	119.6
N2ⁱⁱ—Ba—O19	69.0 (4)	C12—C13—H13	119.6
N3—Ba—O9	141.5 (4)	C13—C14—C15	122.4 (16)
N1—Ba—O9	73.8 (3)	C13—C14—H14	118.8
O7—Ba—O9	60.3 (3)	C15—C14—H14	118.8
O17—Ba—O9	111.3 (3)	C14—C15—O15	126.7 (15)
N2ⁱⁱ—Ba—O9	81.1 (3)	C14—C15—C10	116.6 (15)
O19—Ba—O9	150.1 (3)	O15—C15—C10	116.6 (13)
N3—Ba—O15	114.1 (4)	O15—C16—C17	111.3 (13)
N1—Ba—O15	95.8 (4)	O15—C16—H16B	109.4
O7—Ba—O15	112.7 (3)	C17—C16—H16B	109.4
O17—Ba—O15	58.9 (3)	O15—C16—H16A	109.4
N2ⁱⁱ—Ba—O15	82.3 (3)	C17—C16—H16A	109.4
O19—Ba—O15	116.7 (3)	H16B—C16—H16A	108.0
O9—Ba—O15	54.7 (3)	O17—C17—C16	108.9 (12)
N3—Ba—O5	89.6 (4)	O17—C17—H17A	109.9
N1—Ba—O5	108.7 (4)	C16—C17—H17A	109.9
O7—Ba—O5	57.9 (3)	O17—C17—H17B	109.9
O17—Ba—O5	112.1 (3)	C16—C17—H17B	109.9
N2ⁱⁱ—Ba—O5	68.4 (3)	H17A—C17—H17B	108.3
O19—Ba—O5	54.6 (3)	O17—C18—C19	107.2 (11)
O9—Ba—O5	116.4 (3)	O17—C18—H18B	110.3
O15—Ba—O5	150.7 (3)	C19—C18—H18B	110.3
C5—O5—C6	118.4 (11)	O17—C18—H18A	110.3
C5—O5—Ba	105.1 (8)	C19—C18—H18A	110.3
C6—O5—Ba	113.0 (8)	H18B—C18—H18A	108.5
C7—O7—C8	112.3 (10)	O19—C19—C18	109.9 (13)
C7—O7—Ba	121.4 (8)	O19—C19—H19B	109.7
C8—O7—Ba	117.9 (7)	C18—C19—H19B	109.7
C10—O9—C9	115.7 (12)	O19—C19—H19A	109.7
C10—O9—Ba	105.0 (8)	C18—C19—H19A	109.7
C9—O9—Ba	110.0 (8)	H19B—C19—H19A	108.2
C15—O15—C16	116.4 (12)	C21—C20—C5	118.0 (14)
C15—O15—Ba	106.3 (8)	C21—C20—O19	125.5 (14)
C16—O15—Ba	112.6 (8)	C5—C20—O19	116.4 (14)
C17—O17—C18	109.8 (11)	C22—C21—C20	120.9 (16)
C17—O17—Ba	121.3 (9)	C22—C21—H21	119.6
C18—O17—Ba	117.7 (8)	C20—C21—H21	119.6
C20—O19—C19	116.6 (12)	C21—C22—C23	120.4 (16)
C20—O19—Ba	107.6 (8)	C21—C22—H22	119.8
C19—O19—Ba	111.1 (8)	C23—C22—H22	119.8
C24—C5—C20	121.6 (15)	C24—C23—C22	120.5 (16)
C24—C5—O5	121.1 (14)	C24—C23—H23	119.7
C20—C5—O5	117.1 (13)	C22—C23—H23	119.7
C7—C6—O5	108.6 (11)	C23—C24—C5	118.5 (16)
C7—C6—H6A	110.0	C23—C24—H24	120.7
O5—C6—H6A	110.0	C5—C24—H24	120.7
C7—C6—H6B	110.0

S2—Au1—Au2—S4	110.83 (15)	C10—C11—C12—C13	0 (2)
S1—Au1—Au2—S4	−69.26 (14)	C11—C12—C13—C14	2 (2)
S2—Au1—Au2—S3	−70.74 (16)	C12—C13—C14—C15	−1 (2)
S1—Au1—Au2—S3	109.17 (16)	C13—C14—C15—O15	174.1 (13)
S2—Au1—S1—C1	118.4 (11)	C13—C14—C15—C10	−1 (2)
Au2—Au1—S1—C1	−60.9 (6)	C16—O15—C15—C14	−3 (2)
S1—Au1—S2—C2	125.3 (11)	C16—O15—C15—C10	172.1 (12)
Au2—Au1—S2—C2	−55.4 (6)	C11—C10—C15—C14	3 (2)
S4—Au2—S3—C3	64.5 (13)	O9—C10—C15—C14	178.7 (12)
Au1—Au2—S3—C3	−105.4 (6)	C11—C10—C15—O15	−172.5 (12)
S3—Au2—S4—C4	167.1 (11)	O9—C10—C15—O15	3.0 (18)
Au1—Au2—S4—C4	−23.0 (6)	C15—O15—C16—C17	−173.8 (12)
Au1—S1—C1—N1	154 (30)	C18—O17—C17—C16	178.7 (13)
Au1—S2—C2—N2	−168 (17)	O15—C16—C17—O17	58.9 (16)
Au2—S3—C3—N3	−148 (35)	C17—O17—C18—C19	−169.6 (12)
Au2—S4—C4—N4	−125 (37)	C20—O19—C19—C18	177.5 (11)
S1—C1—N1—Ba	−68 (93)	O17—C18—C19—O19	−67.0 (15)
S2—C2—N2—Baⁱ	61 (18)	C24—C5—C20—C21	−1 (2)
S3—C3—N3—Ba	−115 (35)	O5—C5—C20—C21	−175.5 (12)
C6—O5—C5—C24	−2.7 (18)	C24—C5—C20—O19	176.2 (12)
C6—O5—C5—C20	172.0 (12)	O5—C5—C20—O19	1.4 (18)
C5—O5—C6—C7	−174.4 (11)	C19—O19—C20—C21	2 (2)
C8—O7—C7—C6	172.3 (11)	C19—O19—C20—C5	−174.6 (12)
O5—C6—C7—O7	59.6 (14)	C5—C20—C21—C22	2 (2)
C7—O7—C8—C9	−169.0 (11)	O19—C20—C21—C22	−174.3 (13)
C10—O9—C9—C8	174.3 (11)	C20—C21—C22—C23	−4 (2)
O7—C8—C9—O9	−66.0 (14)	C21—C22—C23—C24	3 (2)
C9—O9—C10—C11	3.7 (19)	C22—C23—C24—C5	−2 (2)
C9—O9—C10—C15	−171.6 (12)	C20—C5—C24—C23	1 (2)
C15—C10—C11—C12	−3 (2)	O5—C5—C24—C23	175.1 (12)
O9—C10—C11—C12	−178.0 (13)

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

Experimental details

Crystal data
Chemical formula	[Au₂Ba(NCS)₄(C₂₀H₂₄O₆)]
M_r	1123.98
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	150
a, b, c (Å)	17.5491 (8), 12.6183 (4), 15.6584 (6)
β (°)	110.598 (2)
V (Å³)	3245.7 (2)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	28.76
Crystal size (mm)	0.14 × 0.08 × 0.01

Data collection
Diffractometer	Bruker SMART6000 CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003)
T_min, T_max	0.118, 0.752
No. of measured, independent and observed [I > 2σ(I)] reflections	14223, 4110, 2905
R_int	0.069
θ_max (°)	56.9
(sin θ/λ)_max (Å⁻¹)	0.543

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.128, 0.98
No. of reflections	4110
No. of parameters	358
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.66, −0.85

Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Au1—S2	2.297 (4)	Ba—O7	2.840 (9)
Au1—S1	2.305 (4)	Ba—O17	2.845 (9)
Au2—S4	2.288 (4)	Ba—O19	2.921 (12)
Au2—S3	2.305 (4)	Ba—O9	2.927 (12)
Ba—N1	2.834 (14)	Ba—O15	2.940 (11)
Ba—N2ⁱ	2.877 (13)	Ba—O5	2.988 (10)
Ba—N3	2.774 (14)

Symmetry code: (i) x, y+1, z.

Acknowledgements

Funding for the SMART6000 diffractometer through NSF–MRI grant CHE-0215950 is gratefully acknowledged.

References

Allen, F. H. (2002). Acta Cryst. B58, 380–388. Web of Science CrossRef CAS IUCr Journals Google Scholar
Arvapally, R. K., Sinha, P., Hettiarachchi, S. R., Coker, N. L., Bedel, C. E., Patterson, H. H., Elder, R. C., Wilson, A. K. & Omary, M. A. (2007). J. Phys. Chem. 111, 10689–10699. CAS Google Scholar
Beavers, C. M., Paw, U. L. & Olmstead, M. M. (2009). Acta Cryst. E65, m300–m301. Web of Science CSD CrossRef IUCr Journals Google Scholar
Bordunov, A. V., Bradshaw, J. S., Zhang, X. X., Dalley, N. K., Kou, X. & Izatt, R. M. (1996). Inorg. Chem. 35, 7229–7240. CSD CrossRef PubMed CAS Web of Science Google Scholar
Bradshaw, J. S. & Izatt, R. M. (1997). Acc. Chem. Res. 30, 338–345. CrossRef CAS Web of Science Google Scholar
Bruker (2003). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Chen, J., Mohamed, A. A., Abdou, H. E., Krause Bauer, J. A., Fackler, J. P. Jr, Bruce, A. E. & Bruce, M. R. M. (2005). Chem. Commun. pp. 1575–1577. Web of Science CrossRef Google Scholar
Coker, N. L. (2003). PhD dissertation, University of Cincinnati, USA. Google Scholar
Coker, N. L., Bedel, C. E., Krause, J. A. & Elder, R. C. (2006). Acta Cryst. E62, m319–m321. Web of Science CSD CrossRef IUCr Journals Google Scholar
Coker, N. L., Krause Bauer, J. A. & Elder, R. C. (2004a). J. Am. Chem. Soc. 126, 12–13. Web of Science CrossRef PubMed CAS Google Scholar
Coker, N. L., Krause Bauer, J. A. & Elder, R. C. (2004b). Acta Cryst. E60, m814–m816. Web of Science CSD CrossRef IUCr Journals Google Scholar
Felton, C. E., Harding, L. P., Jones, J. E., Kariuki, B. M., Pope, S. J. A. & Rice, C. R. (2008). Chem. Commun. pp. 6185–6187. Web of Science CSD CrossRef Google Scholar
Henke, K. & Atwood, D. A. (1998). Inorg. Chem. 37, 224–227. Web of Science CSD CrossRef CAS Google Scholar
Masci, B. & Thuery, P. (2006). CrystEngComm, 8, 764–772. Web of Science CSD CrossRef CAS Google Scholar
Metz, B., Moras, D. & Weiss, R. (1973). Acta Cryst. B29, 1382–1387. CSD CrossRef CAS IUCr Journals Web of Science Google Scholar
Mohamed, A. A., Chen, J., Bruce, A. E., Bruce, M. R. M., Krause Bauer, J. A. & Hill, D. T. (2003). Inorg. Chem. 42, 2203–2205. Web of Science CSD CrossRef PubMed CAS Google Scholar
Olmstead, M. M., Lee, M. A. & Stork, J. R. (2005). Acta Cryst. E61, m1048–m1050. Web of Science CSD CrossRef IUCr Journals Google Scholar
Pathaneni, S. S. & Desiraju, G. R. (1993). J. Chem. Soc. Dalton Trans. pp. 319–322. CrossRef Web of Science Google Scholar
Schwerdtferger, P., Boyd, P., Burrell, A., Robinson, W. & Taylor, M. (1990). Inorg. Chem. 29, 3593–3607. Google Scholar
Sheldrick, G. M. (2003). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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