Two thiourea-containing gold(I) complexes

The crystal structures of two salts of bis­(thio­urea)­gold(I) complexes, namely bis­(thio­urea-κS)­gold(I) chloride, [Au(CH₄N₂S)₂]Cl, (I), and bis­[bis­(thio­urea-κS)­gold(I)] sulfate, [Au(CH₄N₂S)₂]₂SO₄, (II), have been determined. The chloride salt, (I), is isomorphous with the corresponding bromide salt, although there are differences in the bonding. The Au^I ion is located on an inversion centre and coordinated by two symmetry-related thio­urea ligands through the lone pairs on their S atoms [Au—S 2.278 (2) Å and Au—S—C 105.3 (2)°]. The sulfate salt, (II), crystallizes with four independent [Au(CH₄N₂S)₂]⁺ cations per asymmetric unit, all with nearly linear S—Au—S bonding. The cations in (II) have similar conformations to that found for (I). The Au—S distances range from 2.276 (3) to 2.287 (3) Å and the Au—S—C angles from 173.5 (1) to 177.7 (1)°. These data are relevant in interpreting different electrochemical processes where gold–thio­urea species are formed.

Computing details

Data collection: CAD-4 EXPRESS (Enraf-Nonius, 1994) for (I); KappaCCD Server Software (Nonius, 1998) for (II). Cell refinement: CAD-4 EXPRESS for (I); HKL SCALEPACK (Otwinowski & Minor, 1997) for (II). Data reduction: XCAD4 (Harms & Wocadlo, 1995) for (I); HKL DENZO (Otwinowski & Minor, 1997) and SCALEPACK for (II). For both compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP (Johnson, 1965); software used to prepare material for publication: SHELXL97.

(I) Bis(thiourea-κS)gold(I) chloride

Crystal data

[Au(CH4N2S)2]Cl	F(000) = 704
Mr = 384.66	Dx = 2.827 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 23 reflections
a = 8.3991 (10) Å	θ = 8.4–20.7°
b = 15.510 (3) Å	µ = 16.97 mm^−1
c = 7.1584 (10) Å	T = 293 K
β = 104.261 (10)°	Cut fragment, colourless
V = 903.8 (2) Å^3	0.25 × 0.22 × 0.20 mm
Z = 4

Data collection

Enraf-Nonius CAD-4 diffractometer	837 reflections with I > 2σ(I)
Radiation source: Enraf-Nonius FR590 with sealed tube	Rint = 0.026
Graphite monochromator	θmax = 30.0°, θmin = 2.6°
ω/2θ scans	h = −11→11
Absorption correction: ψ scan (North et al., 1968)	k = 0→21
Tmin = 0.703, Tmax = 0.999	l = 0→10
1456 measured reflections	2 standard reflections every 30 min
1313 independent reflections	intensity decay: 2%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.031	H-atom parameters constrained
wR(F^2) = 0.102	w = 1/[σ^2(Fo^2) + (0.05P)^2 + 2.2P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max = 0.001
1313 reflections	Δρmax = 1.19 e Å^−3
49 parameters	Δρmin = −1.28 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0086 (6)

Special details

Experimental. Psi-scans: North A·C·T., Phillips D·C. & Mathews F·S. (1968). Acta. Cryst. A24, 351 Number of psi-scan sets used was 8 Theta correction was applied. Averaged transmission function was used. No Fourier smoothing was applied.

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.

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

	x	y	z	Uiso*/Ueq
Au	0.0000	0.0000	0.0000	0.0543 (2)
Cl	0.0000	0.37248 (16)	0.2500	0.0735 (9)
S	0.1061 (3)	0.13572 (11)	0.0170 (3)	0.0638 (6)
N1	0.3262 (7)	0.0707 (4)	0.3182 (11)	0.0609 (16)
H1A	0.4006	0.0756	0.4243	0.073*
H1B	0.3001	0.0206	0.2687	0.073*
N2	0.2936 (8)	0.2144 (4)	0.3085 (10)	0.0631 (17)
H2A	0.3682	0.2185	0.4147	0.076*
H2B	0.2463	0.2601	0.2532	0.076*
C	0.2527 (8)	0.1395 (4)	0.2319 (10)	0.0448 (13)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Au	0.0697 (3)	0.0387 (2)	0.0549 (3)	0.00474 (17)	0.01620 (18)	−0.00512 (16)
Cl	0.0636 (17)	0.0399 (12)	0.100 (2)	0.000	−0.0126 (15)	0.000
S	0.0960 (16)	0.0407 (9)	0.0518 (9)	−0.0002 (9)	0.0131 (9)	0.0061 (8)
N1	0.054 (3)	0.047 (3)	0.080 (5)	0.015 (3)	0.013 (3)	0.009 (3)
N2	0.062 (4)	0.040 (3)	0.079 (4)	−0.002 (3)	0.002 (3)	0.008 (3)
C	0.042 (3)	0.038 (3)	0.059 (4)	0.001 (2)	0.021 (3)	0.007 (3)

Geometric parameters (Å, º)

Au—S	2.278 (2)	N1—H1B	0.8600
S—C	1.718 (7)	N2—C	1.294 (8)
N1—C	1.309 (8)	N2—H2A	0.8600
N1—H1A	0.8600	N2—H2B	0.8600
S—Au—S^i	180	C—N2—H2B	120
C—S—Au	105.3 (2)	H2A—N2—H2B	120
C—N1—H1A	120	N2—C—N1	119.1 (7)
C—N1—H1B	120	N2—C—S	117.9 (5)
H1A—N1—H1B	120	N1—C—S	123.0 (6)
C—N2—H2A	120
N1—C—S—Au	23.9 (6)	N2—C—S—Au	−157.6 (5)

Symmetry code: (i) −x, −y, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl^ii	0.86	2.41	3.200 (7)	152
N1—H1B···Cl^iii	0.86	2.87	3.489 (6)	131
N2—H2A···Cl^ii	0.86	2.77	3.480 (7)	141
N2—H2A···S^iv	0.86	2.99	3.548 (6)	125
N2—H2B···Cl	0.86	2.70	3.429 (7)	143
N2—H2B···S^v	0.86	3.01	3.536 (6)	121

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

(II) Bis[bis(thiourea-κS)gold(I)] sulfate

Crystal data

[Au(CH4N2S)2]2SO4	Z = 4
Mr = 794.48	F(000) = 1464
Triclinic, P1	Dx = 2.850 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71070 Å
a = 8.0590 (1) Å	Cell parameters from 25866 reflections
b = 11.4980 (2) Å	θ = 3.1–27.4°
c = 20.0690 (4) Å	µ = 16.42 mm^−1
α = 88.8130 (9)°	T = 293 K
β = 85.0540 (11)°	Plate, colourless
γ = 88.2170 (12)°	0.38 × 0.37 × 0.14 mm
V = 1851.52 (5) Å^3

Data collection

Nonius KappaCCD area-detector diffractometer	8386 independent reflections
Radiation source: sealed tube	7569 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.067
CCD scans	θmax = 27.4°, θmin = 3.1°
Absorption correction: gaussian integration (Coppens, 1970)	h = −10→10
Tmin = 0.010, Tmax = 0.131	k = −14→14
18534 measured reflections	l = −25→25

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.139	H-atom parameters constrained
S = 1.08	Calculated w = 1/[σ^2(Fo^2) + (0.077P)^2 + 22.72P] where P = (Fo^2 + 2Fc^2)/3
8386 reflections	(Δ/σ)max = 0.001
415 parameters	Δρmax = 1.49 e Å^−3
0 restraints	Δρmin = −3.03 e Å^−3

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

	x	y	z	Uiso*/Ueq
Au1	1.01064 (5)	0.14266 (3)	0.06587 (19)	0.03105 (11)
S11	0.8719 (4)	0.3096 (2)	0.03797 (15)	0.0475 (7)
C11	0.8783 (12)	0.4073 (8)	0.1017 (5)	0.0309 (19)
N11	0.9021 (11)	0.3761 (8)	0.1639 (4)	0.0367 (19)
H11A	0.9011	0.4280	0.1942	0.044*
H11B	0.9186	0.3039	0.1741	0.044*
N13	0.8528 (11)	0.5193 (7)	0.0863 (5)	0.038 (2)
H13A	0.8519	0.5708	0.1167	0.046*
H13B	0.8373	0.5400	0.0458	0.046*
S12	1.1659 (3)	−0.0234 (2)	0.08211 (15)	0.0384 (6)
C12	1.0469 (12)	−0.1145 (8)	0.1356 (5)	0.0293 (19)
N12	0.9208 (10)	−0.0776 (7)	0.1746 (5)	0.0336 (18)
H12A	0.8669	−0.1255	0.2012	0.040*
H12B	0.8910	−0.0051	0.1739	0.040*
N14	1.0924 (13)	−0.2273 (8)	0.1369 (5)	0.047 (2)
H14A	1.0381	−0.2748	0.1636	0.056*
H14B	1.1761	−0.2523	0.1111	0.056*
Au2	0.46309 (5)	0.64309 (3)	0.06301 (19)	0.03105 (11)
S21	0.2982 (3)	0.4851 (2)	0.07996 (14)	0.0372 (6)
C21	0.3936 (12)	0.3916 (8)	0.1354 (5)	0.0290 (18)
N21	0.4980 (10)	0.4269 (7)	0.1747 (4)	0.0326 (17)
H21A	0.5407	0.3787	0.2024	0.039*
H21B	0.5254	0.4986	0.1735	0.039*
N23	0.3525 (13)	0.2801 (8)	0.1378 (5)	0.045 (2)
H23A	0.3958	0.2326	0.1656	0.054*
H23B	0.2826	0.2556	0.1116	0.054*
S22	0.6177 (4)	0.8024 (2)	0.03516 (15)	0.0456 (7)
C22	0.5805 (12)	0.9040 (8)	0.0993 (5)	0.0300 (19)
N22	0.5300 (11)	0.8727 (7)	0.1595 (4)	0.0342 (18)
H22A	0.5164	0.9237	0.1904	0.041*
H22B	0.5098	0.8009	0.1688	0.041*
N24	0.6125 (12)	1.0125 (8)	0.0832 (5)	0.041 (2)
H24A	0.6000	1.0651	0.1132	0.049*
H24B	0.6461	1.0311	0.0427	0.049*
Au3	0.19825 (6)	0.24665 (4)	0.3959 (2)	0.04073 (12)
S31	0.2925 (5)	0.1080 (2)	0.46792 (15)	0.0473 (7)
C31	0.2949 (13)	0.1765 (9)	0.5431 (6)	0.037 (2)
N31	0.2258 (15)	0.2793 (10)	0.5555 (6)	0.059 (3)
H31A	0.2314	0.3100	0.5939	0.070*
H31B	0.1748	0.3161	0.5252	0.070*
N33	0.3723 (12)	0.1226 (9)	0.5912 (5)	0.041 (2)
H33A	0.3761	0.1552	0.6292	0.049*
H33B	0.4187	0.0551	0.5843	0.049*
S32	0.0965 (4)	0.3800 (3)	0.32271 (18)	0.0530 (8)
C32	0.2449 (13)	0.4832 (9)	0.3092 (5)	0.035 (2)
N32	0.3905 (11)	0.4768 (9)	0.3345 (5)	0.042 (2)
H32A	0.4595	0.5321	0.3270	0.051*
H32B	0.4166	0.4173	0.3585	0.051*
N34	0.2051 (13)	0.5769 (8)	0.2715 (5)	0.046 (2)
H34A	0.2746	0.6319	0.2641	0.055*
H34B	0.1103	0.5816	0.2548	0.055*
Au4	0.2320 (6)	0.75972 (4)	0.39976 (2)	0.0394 (12)
S41	0.3019 (3)	0.8870 (3)	0.31424 (16)	0.0465 (7)
C41	0.1330 (12)	0.9799 (9)	0.3055 (5)	0.0310 (19)
N41	−0.0158 (12)	0.9596 (9)	0.3314 (5)	0.044 (2)
H41A	−0.0966	1.0077	0.3244	0.053*
H41B	−0.0340	0.8980	0.3556	0.053*
N43	0.1632 (13)	1.0741 (9)	0.2682 (5)	0.046 (2)
H43A	0.0833	1.1228	0.2609	0.055*
H43B	0.2628	1.0868	0.2511	0.055*
S42	0.1901 (5)	0.6262 (3)	0.48489 (15)	0.0496 (7)
C42	0.2530 (13)	0.6980 (9)	0.5543 (5)	0.035 (2)
N42	0.2649 (14)	0.8113 (8)	0.5559 (5)	0.050 (3)
H42A	0.2919	0.8435	0.5916	0.060*
H42B	0.2457	0.8533	0.5213	0.060*
N44	0.2818 (12)	0.6328 (8)	0.6066 (5)	0.041 (2)
H44A	0.3089	0.6642	0.6425	0.050*
H44B	0.2737	0.5585	0.6050	0.050*
S1	0.7264 (3)	0.66129 (18)	0.26477 (12)	0.0278 (4)
O11	0.7105 (10)	0.5947 (6)	0.3283 (4)	0.0410 (17)
O12	0.8734 (10)	0.6168 (7)	0.2222 (4)	0.0420 (17)
O13	0.7500 (9)	0.7839 (6)	0.2786 (4)	0.0357 (15)
O14	0.5758 (10)	0.6501 (6)	0.2295 (4)	0.0404 (17)
S2	0.6596 (3)	0.15489 (18)	0.25928 (12)	0.0275 (4)
O21	0.6170 (10)	0.2759 (6)	0.2758 (4)	0.0364 (16)
O22	0.6700 (10)	0.0847 (6)	0.3208 (4)	0.0415 (17)
O23	0.8244 (10)	0.1496 (7)	0.2209 (4)	0.0438 (18)
O24	0.5320 (10)	0.1101 (6)	0.2182 (4)	0.0421 (18)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Au1	0.0353 (2)	0.02701 (18)	0.0310 (2)	−0.00270 (14)	−0.00351 (14)	0.00108 (14)
S11	0.074 (2)	0.0343 (13)	0.0366 (15)	0.0132 (13)	−0.0249 (14)	−0.0032 (11)
C11	0.033 (5)	0.020 (4)	0.040 (5)	−0.002 (3)	−0.003 (4)	0.002 (4)
N11	0.043 (5)	0.035 (4)	0.032 (5)	−0.004 (4)	−0.005 (4)	0.008 (4)
N13	0.038 (5)	0.026 (4)	0.051 (6)	0.002 (3)	−0.010 (4)	0.000 (4)
S12	0.0341 (12)	0.0359 (12)	0.0425 (15)	0.0049 (10)	0.0081 (10)	0.0074 (11)
C12	0.037 (5)	0.024 (4)	0.027 (5)	0.001 (4)	−0.007 (4)	−0.003 (3)
N12	0.037 (4)	0.021 (4)	0.042 (5)	0.000 (3)	0.002 (4)	−0.001 (3)
N14	0.056 (6)	0.026 (4)	0.056 (6)	0.011 (4)	0.009 (5)	−0.003 (4)
Au2	0.0356 (2)	0.02640 (18)	0.0311 (2)	0.00183 (14)	−0.00427 (15)	0.00084 (14)
S21	0.0402 (13)	0.0329 (12)	0.0412 (14)	−0.0041 (10)	−0.0188 (11)	0.0043 (10)
C21	0.032 (5)	0.027 (4)	0.027 (5)	−0.001 (3)	−0.002 (4)	0.000 (4)
N21	0.032 (4)	0.027 (4)	0.040 (5)	0.000 (3)	−0.007 (3)	0.002 (3)
N23	0.053 (6)	0.031 (4)	0.054 (6)	−0.010 (4)	−0.022 (5)	0.004 (4)
S22	0.0619 (18)	0.0353 (13)	0.0373 (15)	−0.0109 (12)	0.0123 (13)	−0.0042 (11)
C22	0.032 (5)	0.029 (4)	0.030 (5)	0.002 (4)	−0.011 (4)	0.005 (4)
N22	0.049 (5)	0.028 (4)	0.026 (4)	−0.004 (3)	−0.003 (4)	−0.003 (3)
N24	0.056 (6)	0.032 (4)	0.036 (5)	−0.007 (4)	−0.009 (4)	0.005 (4)
Au3	0.0503 (2)	0.0412 (2)	0.0323 (2)	−0.00862 (18)	−0.01174 (18)	0.00633 (17)
S31	0.076 (2)	0.0358 (13)	0.0319 (14)	0.0032 (13)	−0.0145 (13)	−0.0006 (11)
C31	0.039 (5)	0.032 (5)	0.041 (6)	−0.005 (4)	−0.010 (4)	0.007 (4)
N31	0.071 (7)	0.059 (7)	0.049 (6)	0.021 (6)	−0.027 (6)	−0.022 (5)
N33	0.043 (5)	0.049 (5)	0.034 (5)	−0.003 (4)	−0.017 (4)	0.007 (4)
S32	0.0419 (15)	0.0626 (19)	0.0573 (19)	−0.0202 (13)	−0.0202 (14)	0.0297 (16)
C32	0.035 (5)	0.035 (5)	0.033 (5)	−0.001 (4)	−0.003 (4)	−0.005 (4)
N32	0.031 (4)	0.043 (5)	0.054 (6)	0.000 (4)	−0.009 (4)	0.003 (4)
N34	0.052 (6)	0.032 (4)	0.054 (6)	−0.002 (4)	−0.003 (5)	0.004 (4)
Au4	0.0487 (2)	0.0395 (2)	0.0306 (2)	0.00233 (17)	−0.00904 (17)	0.00261 (16)
S41	0.0358 (13)	0.0571 (17)	0.0445 (16)	0.0073 (12)	0.0011 (11)	0.0175 (13)
C41	0.032 (5)	0.038 (5)	0.024 (5)	−0.003 (4)	−0.011 (4)	−0.005 (4)
N41	0.041 (5)	0.044 (5)	0.046 (6)	0.006 (4)	−0.006 (4)	0.011 (4)
N43	0.046 (5)	0.040 (5)	0.053 (6)	−0.007 (4)	−0.007 (5)	0.010 (4)
S42	0.082 (2)	0.0357 (13)	0.0343 (15)	−0.0133 (14)	−0.0190 (14)	0.0027 (11)
C42	0.039 (5)	0.032 (5)	0.031 (5)	0.001 (4)	0.001 (4)	0.005 (4)
N42	0.077 (7)	0.035 (5)	0.041 (6)	−0.013 (5)	−0.020 (5)	−0.002 (4)
N44	0.058 (6)	0.031 (4)	0.036 (5)	−0.003 (4)	−0.015 (4)	0.001 (4)
S1	0.0354 (11)	0.0198 (9)	0.0288 (11)	−0.0036 (8)	−0.0055 (9)	0.0017 (8)
O11	0.054 (5)	0.034 (4)	0.036 (4)	−0.007 (3)	−0.007 (3)	0.009 (3)
O12	0.045 (4)	0.036 (4)	0.044 (5)	0.005 (3)	0.003 (3)	−0.004 (3)
O13	0.051 (4)	0.021 (3)	0.037 (4)	−0.010 (3)	−0.004 (3)	−0.001 (3)
O14	0.046 (4)	0.033 (4)	0.046 (4)	−0.005 (3)	−0.022 (3)	−0.002 (3)
S2	0.0366 (11)	0.0196 (9)	0.0266 (11)	0.0020 (8)	−0.0046 (9)	−0.0001 (8)
O21	0.053 (4)	0.023 (3)	0.033 (4)	0.014 (3)	−0.011 (3)	−0.008 (3)
O22	0.058 (5)	0.031 (4)	0.034 (4)	0.001 (3)	−0.005 (3)	0.012 (3)
O23	0.044 (4)	0.035 (4)	0.049 (5)	0.007 (3)	0.010 (4)	0.004 (3)
O24	0.048 (4)	0.031 (4)	0.051 (5)	−0.005 (3)	−0.019 (4)	0.000 (3)

Geometric parameters (Å, º)

Au1—S11	2.276 (3)	C31—N33	1.325 (13)
Au1—S12	2.283 (3)	N31—H31A	0.8600
S11—C11	1.724 (10)	N31—H31B	0.8600
C11—N11	1.320 (13)	N33—H33A	0.8600
C11—N13	1.332 (12)	N33—H33B	0.8600
N11—H11A	0.8600	S32—C32	1.712 (11)
N11—H11B	0.8600	C32—N32	1.318 (13)
N13—H13A	0.8600	C32—N34	1.350 (14)
N13—H13B	0.8600	N32—H32A	0.8600
S12—C12	1.734 (10)	N32—H32B	0.8600
C12—N12	1.294 (13)	N34—H34A	0.8600
C12—N14	1.337 (12)	N34—H34B	0.8600
N12—H12A	0.8600	Au4—S41	2.277 (3)
N12—H12B	0.8600	Au4—S42	2.283 (3)
N14—H14A	0.8600	S41—C41	1.722 (10)
N14—H14B	0.8600	C41—N41	1.291 (14)
Au2—S22	2.280 (3)	C41—N43	1.322 (14)
Au2—S21	2.287 (3)	N41—H41A	0.8600
S21—C21	1.740 (10)	N41—H41B	0.8600
C21—N21	1.283 (13)	N43—H43A	0.8600
C21—N23	1.333 (13)	N43—H43B	0.8600
N21—H21A	0.8600	S42—C42	1.754 (11)
N21—H21B	0.8600	C42—N42	1.309 (14)
N23—H23A	0.8600	C42—N44	1.310 (13)
N23—H23B	0.8600	N42—H42A	0.8600
S22—C22	1.757 (10)	N42—H42B	0.8600
C22—N22	1.289 (13)	N44—H44A	0.8600
C22—N24	1.311 (13)	N44—H44B	0.8600
N22—H22A	0.8600	S1—O13	1.464 (7)
N22—H22B	0.8600	S1—O14	1.467 (7)
N24—H24A	0.8600	S1—O11	1.472 (8)
N24—H24B	0.8600	S1—O12	1.483 (8)
Au3—S32	2.284 (3)	S2—O21	1.460 (6)
Au3—S31	2.286 (3)	S2—O22	1.468 (7)
S31—C31	1.719 (12)	S2—O23	1.477 (8)
C31—N31	1.310 (15)	S2—O24	1.483 (8)
S11—Au1—S12	173.49 (11)	C31—N31—H31B	120.0
C11—S11—Au1	108.7 (3)	H31A—N31—H31B	120.0
N11—C11—N13	119.6 (10)	C31—N33—H33A	120.0
N11—C11—S11	123.5 (7)	C31—N33—H33B	120.0
N13—C11—S11	116.8 (8)	H33A—N33—H33B	120.0
C11—N11—H11A	120.0	C32—S32—Au3	106.1 (4)
C11—N11—H11B	120.0	N32—C32—N34	119.5 (10)
H11A—N11—H11B	120.0	N32—C32—S32	123.8 (9)
C11—N13—H13A	120.0	N34—C32—S32	116.6 (8)
C11—N13—H13B	120.0	C32—N32—H32A	120.0
H13A—N13—H13B	120.0	C32—N32—H32B	120.0
C12—S12—Au1	107.7 (3)	H32A—N32—H32B	120.0
N12—C12—N14	119.6 (9)	C32—N34—H34A	120.0
N12—C12—S12	123.0 (7)	C32—N34—H34B	120.0
N14—C12—S12	117.3 (8)	H34A—N34—H34B	120.0
C12—N12—H12A	120.0	S41—Au4—S42	174.13 (12)
C12—N12—H12B	120.0	C41—S41—Au4	107.9 (4)
H12A—N12—H12B	120.0	N41—C41—N43	120.8 (10)
C12—N14—H14A	120.0	N41—C41—S41	123.6 (8)
C12—N14—H14B	120.0	N43—C41—S41	115.6 (8)
H14A—N14—H14B	120.0	C41—N41—H41A	120.0
S22—Au2—S21	173.97 (11)	C41—N41—H41B	120.0
C21—S21—Au2	106.9 (3)	H41A—N41—H41B	120.0
N21—C21—N23	119.3 (9)	C41—N43—H43A	120.0
N21—C21—S21	122.4 (7)	C41—N43—H43B	120.0
N23—C21—S21	118.3 (8)	H43A—N43—H43B	120.0
C21—N21—H21A	120.0	C42—S42—Au4	103.4 (4)
C21—N21—H21B	120.0	N42—C42—N44	120.7 (10)
H21A—N21—H21B	120.0	N42—C42—S42	122.7 (8)
C21—N23—H23A	120.0	N44—C42—S42	116.5 (8)
C21—N23—H23B	120.0	C42—N42—H42A	120.0
H23A—N23—H23B	120.0	C42—N42—H42B	120.0
C22—S22—Au2	108.4 (3)	H42A—N42—H42B	120.0
N22—C22—N24	121.8 (10)	C42—N44—H44A	120.0
N22—C22—S22	121.7 (7)	C42—N44—H44B	120.0
N24—C22—S22	116.4 (8)	H44A—N44—H44B	120.0
C22—N22—H22A	120.0	O13—S1—O14	109.7 (4)
C22—N22—H22B	120.0	O13—S1—O11	109.2 (4)
H22A—N22—H22B	120.0	O14—S1—O11	109.9 (5)
C22—N24—H24A	120.0	O13—S1—O12	108.8 (4)
C22—N24—H24B	120.0	O14—S1—O12	109.5 (5)
H24A—N24—H24B	120.0	O11—S1—O12	109.7 (5)
S32—Au3—S31	177.70 (12)	O21—S2—O22	110.1 (4)
C31—S31—Au3	105.2 (4)	O21—S2—O23	108.9 (5)
N31—C31—N33	118.2 (11)	O22—S2—O23	108.2 (5)
N31—C31—S31	123.7 (9)	O21—S2—O24	109.0 (4)
N33—C31—S31	118.1 (8)	O22—S2—O24	111.0 (5)
C31—N31—H31A	120.0	O23—S2—O24	109.6 (5)
N11—C11—S11—Au1	−22.9 (10)	N31—C31—S31—Au3	11.2 (12)
N13—C11—S11—Au1	159.0 (7)	N33—C31—S31—Au3	−168.2 (8)
N12—C12—S12—Au1	−20.3 (9)	N32—C32—S32—Au3	3.8 (10)
N14—C12—S12—Au1	161.4 (8)	N34—C32—S32—Au3	−174.5 (8)
N21—C21—S21—Au2	21.9 (9)	N41—C41—S41—Au4	−16.0 (10)
N23—C21—S21—Au2	−159.9 (8)	N43—C41—S41—Au4	166.0 (7)
N22—C22—S22—Au2	24.1 (9)	N42—C42—S42—Au4	19.2 (11)
N24—C22—S22—Au2	−158.2 (7)	N44—C42—S42—Au4	−163.5 (8)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N11—H11A···O12	0.86	2.25	3.021 (12)	149
N11—H11B···O23	0.86	2.12	2.889 (12)	148
N13—H13A···O12	0.86	2.21	2.990 (13)	150
N13—H13B···S21^i	0.86	2.86	3.651 (10)	154
N12—H12A···O13^ii	0.86	2.03	2.879 (11)	168
N12—H12B···O23	0.86	2.07	2.854 (11)	152
N14—H14A···O12^ii	0.86	2.12	2.969 (13)	172
N21—H21A···O21	0.86	2.00	2.850 (11)	172
N21—H21B···O14	0.86	2.16	2.920 (11)	147
N23—H23A···O24	0.86	2.09	2.935 (12)	169
N22—H22A···O24^iii	0.86	2.24	2.997 (11)	147
N22—H22A···S41	0.86	2.93	3.473 (9)	123
N22—H22B···O14	0.86	2.18	2.923 (11)	145
N24—H24A···O24^iii	0.86	2.20	2.965 (13)	148
N24—H24B···S12^iv	0.86	2.82	3.633 (10)	159
N31—H31A···O11^v	0.86	2.02	2.863 (13)	166
N31—H31B···S42^vi	0.86	3.02	3.643 (11)	131
N33—H33A···O13^v	0.86	2.15	2.926 (13)	149
N33—H33A···S41^v	0.86	2.94	3.369 (9)	112
N33—H33B···O22^vii	0.86	2.54	2.949 (11)	110
N32—H32A···O11	0.86	2.17	2.942 (12)	149
N32—H32A···O14	0.86	2.49	3.179 (13)	138
N32—H32B···N44^v	0.86	2.63	3.198 (13)	125
N34—H34A···O14	0.86	2.48	3.167 (13)	137
N34—H34B···O12^viii	0.86	2.10	2.950 (13)	171
N41—H41A···O22^ix	0.86	2.06	2.896 (12)	163
N43—H43A···O23^ix	0.86	2.31	3.061 (13)	146
N43—H43B···O24^iii	0.86	2.24	3.093 (13)	173
N42—H42A···O22^v	0.86	2.01	2.866 (13)	174
N44—H44A···O21^v	0.86	1.94	2.799 (12)	175
N44—H44B···O11^v	0.86	2.20	2.901 (11)	139

Symmetry codes: (i) −x+1, −y+1, −z; (ii) x, y−1, z; (iii) x, y+1, z; (iv) −x+2, −y+1, −z; (v) −x+1, −y+1, −z+1; (vi) −x, −y+1, −z+1; (vii) −x+1, −y, −z+1; (viii) x−1, y, z; (ix) x−1, y+1, z.