Syntheses and crystal structures of new aurate salts of adenine or guanine nucleobases

Two new gold(III) com­plexes with adenine or guanine nitro­genous bases as counter-cations were synthesized. These are 6-amino-7H-purine-1,9-diium tetra­chlorido­gold(III) chloride monohydrate, (C₅H₇N₅)[AuCl₄]Cl·H₂O, 1, and 2-amino-6-oxo-6,7-di­hydro-1H-purin-9-ium tetra­chlorido­gold(III) hemihydrate, (C₅H₆N₅O)[AuCl₄]·0.5H₂O, 2. Their crystal structures were studied using single-crystal X-ray diffraction and FT–IR spectroscopic techniques. The arrangement of species in the studied crystal structures implies π-stacking inter­actions, as well as concomitant C—H...π inter­actions, hydrogen bonds and other types of noncovalent inter­actions, which were studied qualitatively and qu­anti­tatively using the method of mol­ecular Voronoi–Dirichlet polyhedra. The variation of the nitro­genous base from adenine to guanine results in evident differences in the packing of the species in the crystals of 1 and 2. The splitting and shifting of bands in the FT–IR spectra of the title com­pounds reveals several features representative of noncovalent inter­actions in their crystal structures.

Computing details

For both structures, data collection: APEX2 (Bruker, 2012); cell refinement: SAINT-Plus (Bruker, 2012); data reduction: SAINT-Plus (Bruker, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015); molecular graphics: Mercury (Macrae et al., 2020) and VESTA 3 (Momma & Izumi, 2011).; software used to prepare material for publication: SHELXL2018 (Sheldrick, 2015).

6-Amino-7H-purine-1,9-diium tetrachloridogold(III) chloride monohydrate (Ad)

Crystal data

(C5H7N5)[AuCl4]Cl·H2O	Dx = 2.619 Mg m^−3
Mr = 529.39	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pna21	Cell parameters from 9853 reflections
a = 15.7712 (10) Å	θ = 3.1–30.0°
b = 13.0392 (8) Å	µ = 11.94 mm^−1
c = 13.0556 (8) Å	T = 100 K
V = 2684.8 (3) Å^3	Fragment, yellow
Z = 8	0.30 × 0.28 × 0.20 mm
F(000) = 1968

Data collection

Bruker Kappa APEXII area-detector diffractometer	7427 reflections with I > 2σ(I)
ω and φ scans	Rint = 0.045
Absorption correction: multi-scan (SADABS; Bruker, 2008)	θmax = 30.0°, θmin = 4.2°
Tmin = 0.134, Tmax = 0.199	h = −22→22
60700 measured reflections	k = −18→18
7787 independent reflections	l = −18→18

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.020	w = 1/[σ^2(Fo^2) + 5.3033P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.038	(Δ/σ)max = 0.003
S = 1.05	Δρmax = 0.77 e Å^−3
7787 reflections	Δρmin = −0.74 e Å^−3
350 parameters	Absolute structure: Refined as an inversion twin.
17 restraints	Absolute structure parameter: 0.369 (7)

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. Refined as a 2-component inversion twin.

Single crystals of compounds 1 and 2 suitable for X-ray crystallographic analysis were obtained by slow evaporation of saturated solutions in H₂O and studied at nitrogen temperature (100 K). The intensities of reflections for 1 and 2 were measured with a four-circle diffractometer Bruker KAPPA APEX II with area CCD detector. The unit cell parameters were refined over the whole dataset by using SAINT-Plus software (Bruker, 2012). Absorption correction was made using SADABS program (Bruker, 2008). The structures were solved by direct method and were refined by the full-matrix least-squares method on F² over the whole dataset in the anisotropic approximation for all nonhydrogen atoms using SHELXS97 (Sheldrick, 2008) and SHELXL2014 (Sheldrick, 2015).

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

	x	y	z	Uiso*/Ueq
Au1	0.42408 (2)	0.07548 (2)	0.72930 (2)	0.01264 (4)
Au2	0.66514 (2)	0.41105 (2)	0.72194 (2)	0.01228 (4)
Cl1	0.51685 (7)	0.21062 (8)	0.7258 (2)	0.0204 (2)
Cl2	0.42762 (17)	0.07922 (19)	0.9028 (3)	0.0229 (6)
Cl3	0.33388 (6)	−0.06230 (8)	0.7318 (2)	0.0173 (3)
Cl4	0.42345 (17)	0.07083 (19)	0.5535 (3)	0.0241 (6)
Cl5	0.75611 (7)	0.27575 (7)	0.7238 (2)	0.0189 (2)
Cl6	0.66912 (16)	0.41380 (18)	0.8954 (3)	0.0223 (6)
Cl7	0.57216 (7)	0.54601 (9)	0.7201 (2)	0.0224 (3)
Cl8	0.65865 (18)	0.4024 (2)	0.5459 (3)	0.0262 (6)
Cl9	0.14012 (8)	0.15228 (8)	1.23258 (16)	0.0205 (2)
Cl10	0.41936 (7)	0.10776 (9)	0.22012 (18)	0.0223 (2)
O1W	0.5386 (4)	0.2296 (5)	1.0710 (4)	0.0155 (12)
H1A	0.559 (5)	0.267 (5)	1.120 (4)	0.023*
H1B	0.505 (4)	0.189 (4)	1.103 (5)	0.023*
O2W	0.5375 (4)	0.2159 (6)	0.3821 (4)	0.0169 (11)
H2A	0.563 (5)	0.250 (5)	0.336 (5)	0.025*
H2B	0.527 (4)	0.159 (3)	0.355 (5)	0.025*
N11	0.2781 (7)	0.2404 (8)	1.0871 (6)	0.0299 (19)
H11A	0.236 (4)	0.225 (7)	1.127 (5)	0.036*
H11B	0.330 (3)	0.226 (8)	1.100 (7)	0.036*
N12	0.1902 (4)	0.3429 (5)	0.9757 (5)	0.0194 (13)
H12B	0.148 (3)	0.314 (5)	1.006 (6)	0.023*
N13	0.2375 (6)	0.4499 (6)	0.8439 (5)	0.0241 (17)
N14	0.3921 (5)	0.4443 (6)	0.8367 (5)	0.0255 (16)
H14A	0.399 (5)	0.486 (5)	0.785 (4)	0.031*
N15	0.4201 (4)	0.3378 (5)	0.9613 (5)	0.0224 (15)
H15B	0.435 (5)	0.281 (4)	0.993 (6)	0.027*
N21	0.2980 (6)	0.2361 (9)	0.3632 (7)	0.028 (2)
H21A	0.336 (4)	0.207 (7)	0.323 (5)	0.033*
H21B	0.246 (3)	0.220 (8)	0.352 (7)	0.033*
N22	0.4007 (4)	0.3138 (5)	0.4717 (5)	0.0187 (14)
H22B	0.449 (3)	0.296 (5)	0.441 (5)	0.022*
N23	0.3700 (5)	0.4271 (6)	0.6079 (5)	0.0252 (16)
N24	0.2208 (6)	0.4563 (6)	0.6184 (5)	0.0217 (15)
H24A	0.217 (4)	0.496 (4)	0.671 (4)	0.026*
N25	0.1717 (4)	0.3602 (5)	0.4947 (5)	0.0188 (13)
H25B	0.136 (4)	0.333 (5)	0.451 (5)	0.023*
C11	0.2679 (4)	0.3063 (4)	1.0097 (4)	0.0153 (10)
C12	0.1786 (5)	0.4091 (6)	0.8984 (5)	0.0199 (14)
H12A	0.121835	0.427452	0.882529	0.024*
C13	0.3167 (6)	0.4159 (6)	0.8760 (5)	0.0207 (16)
C14	0.3349 (4)	0.3477 (4)	0.9526 (4)	0.0173 (11)
C15	0.4539 (5)	0.3969 (5)	0.8893 (5)	0.0214 (14)
H15A	0.512920	0.404457	0.876806	0.026*
C21	0.3180 (4)	0.2981 (4)	0.4391 (4)	0.0158 (11)
C22	0.4215 (5)	0.3739 (6)	0.5514 (6)	0.0230 (15)
H22A	0.480057	0.377967	0.568083	0.028*
C23	0.2895 (5)	0.4139 (6)	0.5758 (6)	0.0149 (16)
C24	0.2589 (3)	0.3543 (4)	0.4966 (4)	0.0124 (10)
C25	0.1488 (5)	0.4232 (5)	0.5699 (5)	0.0165 (14)
H25A	0.092332	0.441931	0.586944	0.020*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Au1	0.00994 (7)	0.00963 (7)	0.01835 (8)	−0.00058 (5)	−0.00050 (12)	−0.00030 (12)
Au2	0.01002 (7)	0.00978 (7)	0.01704 (8)	−0.00116 (5)	0.00054 (11)	0.00084 (12)
Cl1	0.0190 (5)	0.0158 (4)	0.0263 (6)	−0.0071 (4)	−0.0002 (9)	−0.0010 (10)
Cl2	0.0265 (13)	0.0231 (12)	0.0190 (12)	−0.0073 (8)	−0.0037 (8)	0.0040 (7)
Cl3	0.0134 (5)	0.0117 (4)	0.0269 (8)	−0.0021 (3)	−0.0013 (9)	0.0003 (7)
Cl4	0.0282 (13)	0.0246 (12)	0.0196 (12)	−0.0073 (9)	0.0024 (8)	−0.0056 (8)
Cl5	0.0182 (5)	0.0111 (4)	0.0275 (6)	0.0020 (4)	−0.0007 (9)	0.0009 (9)
Cl6	0.0295 (11)	0.0200 (10)	0.0173 (11)	0.0035 (7)	−0.0059 (7)	−0.0046 (6)
Cl7	0.0196 (5)	0.0187 (5)	0.0289 (8)	0.0073 (4)	0.0053 (10)	0.0036 (9)
Cl8	0.0379 (13)	0.0238 (11)	0.0168 (11)	0.0018 (8)	0.0061 (8)	0.0046 (8)
Cl9	0.0231 (5)	0.0141 (4)	0.0242 (7)	0.0017 (4)	−0.0009 (8)	0.0007 (7)
Cl10	0.0170 (5)	0.0217 (5)	0.0281 (7)	−0.0064 (4)	0.0025 (10)	−0.0046 (8)
O1W	0.016 (3)	0.017 (3)	0.014 (2)	−0.001 (2)	−0.0003 (18)	−0.0011 (18)
O2W	0.014 (3)	0.017 (3)	0.020 (3)	−0.002 (2)	−0.0012 (19)	−0.002 (2)
N11	0.046 (5)	0.024 (4)	0.020 (3)	−0.005 (4)	0.007 (3)	0.010 (3)
N12	0.016 (3)	0.018 (3)	0.024 (3)	−0.007 (2)	0.008 (2)	−0.006 (2)
N13	0.038 (4)	0.015 (3)	0.019 (3)	−0.008 (3)	0.015 (3)	−0.005 (2)
N14	0.034 (4)	0.028 (4)	0.015 (3)	0.014 (3)	−0.004 (2)	0.001 (2)
N15	0.023 (3)	0.022 (3)	0.022 (3)	0.008 (3)	−0.012 (2)	−0.002 (2)
N21	0.042 (5)	0.027 (4)	0.015 (3)	−0.004 (3)	−0.005 (3)	−0.008 (3)
N22	0.019 (3)	0.018 (3)	0.020 (3)	0.009 (2)	0.007 (2)	0.005 (2)
N23	0.038 (4)	0.022 (3)	0.016 (3)	0.014 (3)	0.003 (3)	0.002 (2)
N24	0.033 (4)	0.015 (3)	0.017 (3)	0.004 (3)	−0.009 (2)	−0.003 (2)
N25	0.015 (3)	0.016 (3)	0.024 (3)	0.000 (2)	−0.004 (2)	0.005 (2)
C11	0.015 (3)	0.014 (3)	0.017 (3)	0.001 (2)	0.000 (2)	−0.002 (2)
C12	0.024 (4)	0.017 (3)	0.019 (3)	0.000 (3)	−0.003 (3)	−0.008 (2)
C13	0.031 (4)	0.018 (3)	0.013 (3)	0.004 (3)	0.000 (3)	−0.001 (2)
C14	0.018 (3)	0.012 (2)	0.021 (3)	0.000 (2)	0.002 (2)	−0.002 (2)
C15	0.026 (4)	0.023 (3)	0.016 (3)	0.006 (3)	−0.006 (3)	0.001 (2)
C21	0.014 (3)	0.014 (3)	0.020 (3)	−0.001 (2)	−0.002 (2)	0.002 (2)
C22	0.017 (3)	0.024 (4)	0.028 (4)	0.005 (3)	0.004 (3)	0.008 (3)
C23	0.027 (4)	0.008 (3)	0.009 (3)	0.008 (3)	0.002 (2)	0.001 (2)
C24	0.011 (2)	0.011 (2)	0.016 (3)	−0.0004 (19)	0.001 (2)	−0.0002 (19)
C25	0.021 (4)	0.014 (3)	0.015 (3)	−0.002 (3)	−0.004 (2)	0.002 (2)

Geometric parameters (Å, º)

Au1—Cl2	2.266 (4)	N15—C14	1.354 (8)
Au1—Cl1	2.2908 (10)	N15—H15B	0.88 (3)
Au1—Cl3	2.2918 (10)	N21—C21	1.318 (11)
Au1—Cl4	2.296 (4)	N21—H21A	0.88 (3)
Au2—Cl6	2.266 (4)	N21—H21B	0.87 (3)
Au2—Cl5	2.2741 (10)	N22—C22	1.344 (10)
Au2—Cl7	2.2909 (11)	N22—C21	1.386 (9)
Au2—Cl8	2.303 (4)	N22—H22B	0.89 (3)
O1W—H1A	0.86 (3)	N23—C22	1.298 (10)
O1W—H1B	0.85 (3)	N23—C23	1.348 (10)
O2W—H2A	0.85 (3)	N24—C23	1.337 (10)
O2W—H2B	0.84 (3)	N24—C25	1.370 (11)
N11—C11	1.336 (10)	N24—H24A	0.85 (3)
N11—H11A	0.87 (3)	N25—C25	1.330 (9)
N11—H11B	0.86 (3)	N25—C24	1.378 (8)
N12—C12	1.340 (9)	N25—H25B	0.88 (3)
N12—C11	1.388 (9)	C11—C14	1.402 (8)
N12—H12B	0.86 (3)	C12—H12A	0.9500
N13—C12	1.285 (11)	C13—C14	1.368 (10)
N13—C13	1.391 (12)	C15—H15A	0.9500
N14—C15	1.343 (10)	C21—C24	1.403 (8)
N14—C13	1.347 (11)	C22—H22A	0.9500
N14—H14A	0.88 (3)	C23—C24	1.380 (9)
N15—C15	1.328 (9)	C25—H25A	0.9500
Cl2—Au1—Cl1	89.29 (9)	C23—N24—H24A	129 (5)
Cl2—Au1—Cl3	91.04 (9)	C25—N24—H24A	120 (5)
Cl1—Au1—Cl3	178.63 (5)	C25—N25—C24	107.0 (6)
Cl2—Au1—Cl4	178.81 (5)	C25—N25—H25B	124 (5)
Cl1—Au1—Cl4	90.18 (9)	C24—N25—H25B	129 (5)
Cl3—Au1—Cl4	89.46 (9)	N11—C11—N12	124.7 (7)
Cl6—Au2—Cl5	89.09 (9)	N11—C11—C14	124.0 (7)
Cl6—Au2—Cl7	90.93 (10)	N12—C11—C14	111.3 (5)
Cl5—Au2—Cl7	179.32 (4)	N13—C12—N12	125.8 (8)
Cl6—Au2—Cl8	177.87 (7)	N13—C12—H12A	117.1
Cl5—Au2—Cl8	90.04 (9)	N12—C12—H12A	117.1
Cl7—Au2—Cl8	89.92 (10)	N14—C13—C14	105.8 (7)
H1A—O1W—H1B	103 (4)	N14—C13—N13	126.2 (7)
H2A—O2W—H2B	105 (4)	C14—C13—N13	128.0 (8)
C11—N11—H11A	121 (6)	N15—C14—C13	109.4 (7)
C11—N11—H11B	114 (7)	N15—C14—C11	131.8 (6)
H11A—N11—H11B	124 (9)	C13—C14—C11	118.7 (6)
C12—N12—C11	125.7 (6)	N15—C15—N14	109.7 (7)
C12—N12—H12B	121 (5)	N15—C15—H15A	125.1
C11—N12—H12B	113 (5)	N14—C15—H15A	125.1
C12—N13—C13	110.5 (7)	N21—C21—N22	123.2 (7)
C15—N14—C13	108.6 (7)	N21—C21—C24	124.3 (6)
C15—N14—H14A	126 (5)	N22—C21—C24	112.5 (5)
C13—N14—H14A	125 (5)	N23—C22—N22	126.7 (7)
C15—N15—C14	106.5 (6)	N23—C22—H22A	116.6
C15—N15—H15B	135 (5)	N22—C22—H22A	116.6
C14—N15—H15B	113 (5)	N24—C23—N23	125.6 (7)
C21—N21—H21A	123 (6)	N24—C23—C24	105.2 (6)
C21—N21—H21B	121 (7)	N23—C23—C24	129.3 (6)
H21A—N21—H21B	116 (9)	N25—C24—C23	109.3 (5)
C22—N22—C21	123.7 (6)	N25—C24—C21	133.0 (6)
C22—N22—H22B	107 (5)	C23—C24—C21	117.6 (5)
C21—N22—H22B	129 (5)	N25—C25—N24	108.1 (7)
C22—N23—C23	110.2 (7)	N25—C25—H25A	126.0
C23—N24—C25	110.4 (7)	N24—C25—H25A	126.0
C12—N12—C11—N11	179.9 (8)	C22—N22—C21—N21	−177.5 (8)
C12—N12—C11—C14	0.2 (9)	C22—N22—C21—C24	1.7 (9)
C13—N13—C12—N12	0.0 (11)	C23—N23—C22—N22	0.2 (11)
C11—N12—C12—N13	−0.6 (12)	C21—N22—C22—N23	−1.4 (12)
C15—N14—C13—C14	−1.5 (9)	C25—N24—C23—N23	−177.2 (7)
C15—N14—C13—N13	178.7 (8)	C25—N24—C23—C24	1.4 (9)
C12—N13—C13—N14	−179.1 (8)	C22—N23—C23—N24	178.8 (7)
C12—N13—C13—C14	1.1 (11)	C22—N23—C23—C24	0.5 (11)
C15—N15—C14—C13	−1.6 (8)	C25—N25—C24—C23	0.9 (7)
C15—N15—C14—C11	−177.8 (6)	C25—N25—C24—C21	177.5 (6)
N14—C13—C14—N15	1.9 (8)	N24—C23—C24—N25	−1.4 (8)
N13—C13—C14—N15	−178.3 (7)	N23—C23—C24—N25	177.1 (8)
N14—C13—C14—C11	178.7 (6)	N24—C23—C24—C21	−178.6 (6)
N13—C13—C14—C11	−1.5 (11)	N23—C23—C24—C21	0.0 (11)
N11—C11—C14—N15	−3.1 (11)	N21—C21—C24—N25	1.9 (11)
N12—C11—C14—N15	176.6 (7)	N22—C21—C24—N25	−177.4 (7)
N11—C11—C14—C13	−178.9 (8)	N21—C21—C24—C23	178.2 (8)
N12—C11—C14—C13	0.7 (8)	N22—C21—C24—C23	−1.0 (8)
C14—N15—C15—N14	0.7 (8)	C24—N25—C25—N24	0.0 (8)
C13—N14—C15—N15	0.5 (9)	C23—N24—C25—N25	−0.9 (9)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1A···Cl9^i	0.86 (3)	2.22 (3)	3.063 (7)	166 (8)
O1W—H1B···Cl10^ii	0.85 (3)	2.30 (3)	3.139 (7)	166 (6)
O2W—H2A···Cl9^iii	0.85 (3)	2.22 (3)	3.064 (7)	173 (8)
O2W—H2B···Cl10	0.84 (3)	2.53 (6)	3.151 (7)	132 (6)
N11—H11A···Cl9	0.87 (3)	2.25 (4)	3.109 (9)	167 (9)
N11—H11B···Cl10^ii	0.86 (3)	2.61 (7)	3.312 (10)	140 (8)
N12—H12B···O1W^iv	0.86 (3)	2.00 (3)	2.856 (9)	170 (7)
N14—H14A···Cl7	0.88 (3)	2.96 (7)	3.484 (8)	120 (6)
N14—H14A···Cl9^v	0.88 (3)	2.35 (5)	3.076 (8)	140 (6)
N14—H14A···N23	0.88 (3)	2.48 (6)	3.016 (7)	120 (6)
N15—H15B···O1W	0.88 (3)	2.04 (5)	2.745 (9)	137 (6)
N21—H21A···Cl10	0.88 (3)	2.28 (3)	3.155 (10)	170 (8)
N21—H21B···Cl9^vi	0.87 (3)	2.44 (6)	3.210 (9)	148 (8)
N22—H22B···O2W	0.89 (3)	1.91 (4)	2.766 (9)	162 (7)
N24—H24A···Cl10^vii	0.85 (3)	2.68 (6)	3.248 (8)	125 (6)
N24—H24A···N13	0.85 (3)	2.36 (6)	2.957 (7)	127 (6)
N25—H25B···O2W^iv	0.88 (3)	1.90 (3)	2.762 (9)	165 (7)

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

2-Amino-6-oxo-6,7-dihydro-1H-purin-9-ium tetrachloridogold(III) hemihydrate (HGuAu)

Crystal data

(C5H6N5O)[AuCl4]·0.5H2O	Z = 4
Mr = 499.92	F(000) = 924
Triclinic, P1	Dx = 2.778 Mg m^−3
a = 8.1408 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.9063 (4) Å	Cell parameters from 9858 reflections
c = 12.4678 (4) Å	θ = 2.9–35.3°
α = 84.918 (2)°	µ = 13.19 mm^−1
β = 84.475 (2)°	T = 100 K
γ = 85.649 (1)°	Fragment, yellow
V = 1195.36 (6) Å^3	0.36 × 0.24 × 0.20 mm

Data collection

Bruker Kappa APEXII area-detector diffractometer	9184 reflections with I > 2σ(I)
ω and φ scans	Rint = 0.052
Absorption correction: multi-scan (SADABS; Bruker, 2008)	θmax = 35.0°, θmin = 4.1°
Tmin = 0.098, Tmax = 0.178	h = −13→13
39106 measured reflections	k = −19→19
10495 independent reflections	l = −18→20

Refinement

Refinement on F^2	13 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.027	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.066	w = 1/[σ^2(Fo^2) + (0.0247P)^2 + 0.1971P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.003
10495 reflections	Δρmax = 2.36 e Å^−3
334 parameters	Δρmin = −3.73 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. Single crystals of compounds 1 and 2 suitable for X-ray crystallographic analysis were obtained by slow evaporation of saturated solutions in H₂O and studied at nitrogen temperature (100 K). The intensities of reflections for 1 and 2 were measured with a four-circle diffractometer Bruker KAPPA APEX II with area CCD detector. The unit cell parameters were refined over the whole dataset by using SAINT-Plus software (Bruker, 2012). Absorption correction was made using SADABS program (Bruker, 2008). The structures were solved by direct method and were refined by the full-matrix least-squares method on F² over the whole dataset in the anisotropic approximation for all nonhydrogen atoms using SHELXS97 (Sheldrick, 2008) and SHELXL2014 (Sheldrick, 2015).

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

	x	y	z	Uiso*/Ueq
Au1	0.12774 (2)	0.13682 (2)	0.48622 (2)	0.00959 (3)
Au2	0.48231 (2)	0.75048 (2)	0.01255 (2)	0.00914 (3)
Cl1	−0.05064 (9)	0.18590 (6)	0.63012 (6)	0.01706 (13)
Cl2	0.03630 (9)	0.29452 (6)	0.38464 (6)	0.01504 (12)
Cl3	0.30987 (8)	0.08884 (6)	0.34522 (6)	0.01522 (12)
Cl4	0.22276 (9)	−0.01798 (6)	0.58943 (6)	0.01597 (12)
Cl5	0.31180 (8)	0.81101 (6)	0.15607 (6)	0.01449 (11)
Cl6	0.41225 (8)	0.91431 (5)	−0.08714 (5)	0.01345 (11)
Cl7	0.64948 (9)	0.69374 (6)	−0.13226 (6)	0.01515 (12)
Cl8	0.56072 (9)	0.58744 (6)	0.11203 (6)	0.01559 (12)
O11	0.1170 (3)	0.44120 (17)	0.68403 (17)	0.0173 (4)
O21	0.7497 (3)	0.83893 (17)	0.15992 (17)	0.0157 (4)
O1W	0.6663 (3)	0.2478 (2)	0.28312 (18)	0.0190 (4)
H1A	0.672 (5)	0.3174 (16)	0.273 (3)	0.029*
H1B	0.594 (4)	0.228 (3)	0.248 (3)	0.029*
N11	0.2913 (3)	0.5778 (2)	0.3389 (2)	0.0158 (5)
H11A	0.358 (4)	0.573 (3)	0.281 (2)	0.019*
H11B	0.210 (3)	0.630 (2)	0.345 (3)	0.019*
N12	0.2122 (3)	0.50429 (19)	0.51238 (18)	0.0114 (4)
H12A	0.150 (4)	0.566 (2)	0.519 (3)	0.014*
N13	0.4340 (3)	0.41643 (19)	0.4046 (2)	0.0126 (4)
N14	0.3906 (3)	0.24492 (19)	0.65180 (19)	0.0117 (4)
H14A	0.332 (4)	0.224 (3)	0.7144 (19)	0.014*
N15	0.5468 (3)	0.24654 (19)	0.49946 (19)	0.0121 (4)
H15B	0.627 (3)	0.227 (3)	0.451 (2)	0.015*
N21	1.1263 (3)	0.5401 (2)	0.0942 (2)	0.0176 (5)
H21A	1.193 (4)	0.507 (3)	0.048 (3)	0.021*
H21B	1.082 (5)	0.512 (3)	0.156 (2)	0.021*
N22	0.9391 (3)	0.69180 (19)	0.1222 (2)	0.0136 (4)
H22A	0.920 (5)	0.650 (3)	0.1844 (19)	0.016*
N23	1.1137 (3)	0.68313 (19)	−0.0426 (2)	0.0131 (4)
N24	0.8678 (3)	0.93946 (18)	−0.06931 (19)	0.0115 (4)
H24A	0.793 (3)	0.992 (2)	−0.052 (3)	0.014*
N25	1.0572 (3)	0.8460 (2)	−0.16686 (19)	0.0137 (4)
H25B	1.135 (4)	0.835 (3)	−0.222 (2)	0.016*
C11	0.3151 (3)	0.4966 (2)	0.4181 (2)	0.0111 (4)
C12	0.2149 (3)	0.4283 (2)	0.6037 (2)	0.0109 (4)
C13	0.3394 (3)	0.3394 (2)	0.5874 (2)	0.0104 (4)
C14	0.4391 (3)	0.3403 (2)	0.4912 (2)	0.0099 (4)
C15	0.5137 (3)	0.1906 (2)	0.5971 (2)	0.0125 (4)
H15A	0.570649	0.122285	0.622670	0.015*
C21	1.0606 (3)	0.6398 (2)	0.0551 (2)	0.0125 (4)
C22	0.8583 (3)	0.7958 (2)	0.0969 (2)	0.0115 (4)
C23	0.9150 (3)	0.8425 (2)	−0.0077 (2)	0.0103 (4)
C24	1.0351 (3)	0.7834 (2)	−0.0688 (2)	0.0111 (4)
C25	0.9558 (3)	0.9394 (2)	−0.1643 (2)	0.0144 (5)
H25A	0.948061	0.997021	−0.221797	0.017*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Au1	0.00965 (4)	0.00832 (4)	0.01038 (5)	0.00044 (3)	−0.00084 (3)	0.00055 (3)
Au2	0.00924 (4)	0.00878 (4)	0.00888 (5)	0.00051 (3)	−0.00096 (3)	0.00131 (3)
Cl1	0.0187 (3)	0.0154 (3)	0.0149 (3)	0.0041 (2)	0.0039 (2)	0.0008 (2)
Cl2	0.0182 (3)	0.0114 (3)	0.0145 (3)	0.0039 (2)	−0.0022 (2)	0.0010 (2)
Cl3	0.0162 (3)	0.0137 (3)	0.0139 (3)	0.0029 (2)	0.0027 (2)	0.0018 (2)
Cl4	0.0184 (3)	0.0126 (3)	0.0148 (3)	0.0043 (2)	0.0009 (2)	0.0035 (2)
Cl5	0.0159 (3)	0.0160 (3)	0.0103 (3)	0.0029 (2)	0.0009 (2)	0.0005 (2)
Cl6	0.0169 (3)	0.0101 (2)	0.0123 (3)	0.0023 (2)	−0.0013 (2)	0.0020 (2)
Cl7	0.0168 (3)	0.0138 (3)	0.0129 (3)	0.0040 (2)	0.0021 (2)	0.0011 (2)
Cl8	0.0173 (3)	0.0124 (3)	0.0152 (3)	0.0026 (2)	−0.0001 (2)	0.0046 (2)
O11	0.0188 (9)	0.0151 (9)	0.0142 (9)	0.0078 (7)	0.0051 (7)	0.0054 (7)
O21	0.0168 (9)	0.0157 (9)	0.0120 (9)	0.0045 (7)	0.0047 (7)	0.0021 (7)
O1W	0.0210 (10)	0.0234 (10)	0.0116 (10)	0.0066 (8)	−0.0013 (8)	−0.0023 (8)
N11	0.0186 (11)	0.0145 (10)	0.0118 (11)	0.0034 (8)	0.0004 (9)	0.0064 (8)
N12	0.0122 (9)	0.0120 (9)	0.0086 (9)	0.0027 (7)	0.0006 (7)	0.0029 (8)
N13	0.0133 (9)	0.0118 (9)	0.0116 (10)	0.0014 (7)	−0.0001 (8)	0.0013 (8)
N14	0.0129 (9)	0.0107 (9)	0.0102 (10)	0.0024 (7)	0.0011 (7)	0.0018 (8)
N15	0.0119 (9)	0.0129 (9)	0.0100 (10)	0.0036 (7)	0.0020 (7)	0.0005 (8)
N21	0.0186 (11)	0.0116 (10)	0.0205 (13)	0.0048 (8)	0.0001 (9)	0.0030 (9)
N22	0.0135 (9)	0.0123 (9)	0.0127 (11)	0.0016 (7)	0.0008 (8)	0.0070 (8)
N23	0.0132 (9)	0.0118 (9)	0.0137 (11)	0.0016 (7)	−0.0014 (8)	0.0008 (8)
N24	0.0127 (9)	0.0100 (9)	0.0105 (10)	0.0026 (7)	0.0003 (7)	0.0019 (7)
N25	0.0137 (10)	0.0187 (10)	0.0068 (10)	0.0024 (8)	0.0019 (7)	0.0032 (8)
C11	0.0125 (10)	0.0119 (10)	0.0084 (11)	−0.0016 (8)	−0.0019 (8)	0.0038 (8)
C12	0.0110 (10)	0.0117 (10)	0.0092 (11)	0.0007 (8)	0.0000 (8)	0.0013 (8)
C13	0.0124 (10)	0.0087 (9)	0.0092 (11)	0.0018 (8)	0.0005 (8)	0.0019 (8)
C14	0.0105 (9)	0.0105 (10)	0.0084 (11)	0.0009 (7)	−0.0011 (8)	0.0004 (8)
C15	0.0130 (10)	0.0119 (10)	0.0119 (12)	0.0023 (8)	−0.0007 (9)	0.0001 (9)
C21	0.0101 (10)	0.0116 (10)	0.0154 (12)	0.0024 (8)	−0.0031 (9)	0.0011 (9)
C22	0.0122 (10)	0.0124 (10)	0.0093 (11)	−0.0012 (8)	−0.0004 (8)	0.0030 (9)
C23	0.0114 (10)	0.0083 (10)	0.0102 (11)	0.0020 (8)	0.0007 (8)	0.0006 (8)
C24	0.0099 (10)	0.0117 (10)	0.0112 (11)	−0.0007 (8)	0.0007 (8)	0.0009 (9)
C25	0.0157 (11)	0.0156 (11)	0.0112 (12)	−0.0004 (9)	−0.0013 (9)	0.0026 (9)

Geometric parameters (Å, º)

Au1—Cl3	2.2721 (7)	N15—C15	1.349 (3)
Au1—Cl4	2.2817 (7)	N15—C14	1.369 (3)
Au1—Cl1	2.2858 (7)	N15—H15B	0.875 (18)
Au1—Cl2	2.2872 (7)	N21—C21	1.336 (3)
Au2—Cl7	2.2741 (7)	N21—H21A	0.857 (18)
Au2—Cl6	2.2831 (6)	N21—H21B	0.868 (18)
Au2—Cl5	2.2905 (7)	N22—C21	1.379 (4)
Au2—Cl8	2.2918 (7)	N22—C22	1.383 (3)
O11—C12	1.232 (3)	N22—H22A	0.888 (18)
O21—C22	1.238 (3)	N23—C21	1.326 (4)
O1W—H1A	0.831 (17)	N23—C24	1.340 (3)
O1W—H1B	0.827 (18)	N24—C25	1.324 (3)
N11—C11	1.336 (3)	N24—C23	1.380 (3)
N11—H11A	0.862 (18)	N24—H24A	0.868 (18)
N11—H11B	0.872 (18)	N25—C25	1.335 (4)
N12—C11	1.382 (3)	N25—C24	1.377 (3)
N12—C12	1.391 (3)	N25—H25B	0.898 (18)
N12—H12A	0.868 (18)	C12—C13	1.422 (4)
N13—C11	1.317 (3)	C13—C14	1.382 (3)
N13—C14	1.348 (3)	C15—H15A	0.9500
N14—C15	1.318 (3)	C22—C23	1.421 (4)
N14—C13	1.385 (3)	C23—C24	1.370 (3)
N14—H14A	0.901 (18)	C25—H25A	0.9500
Cl3—Au1—Cl4	90.32 (2)	C23—N24—H24A	128 (2)
Cl3—Au1—Cl1	178.72 (3)	C25—N25—C24	108.7 (2)
Cl4—Au1—Cl1	89.20 (3)	C25—N25—H25B	122 (2)
Cl3—Au1—Cl2	89.88 (3)	C24—N25—H25B	129 (3)
Cl4—Au1—Cl2	178.67 (2)	N13—C11—N11	120.0 (2)
Cl1—Au1—Cl2	90.58 (3)	N13—C11—N12	123.5 (2)
Cl7—Au2—Cl6	89.13 (2)	N11—C11—N12	116.5 (2)
Cl7—Au2—Cl5	178.74 (2)	O11—C12—N12	121.2 (2)
Cl6—Au2—Cl5	89.62 (2)	O11—C12—C13	128.1 (2)
Cl7—Au2—Cl8	90.05 (3)	N12—C12—C13	110.7 (2)
Cl6—Au2—Cl8	178.28 (2)	C14—C13—N14	107.4 (2)
Cl5—Au2—Cl8	91.20 (2)	C14—C13—C12	119.6 (2)
H1A—O1W—H1B	110 (3)	N14—C13—C12	133.1 (2)
C11—N11—H11A	115 (3)	N13—C14—N15	125.5 (2)
C11—N11—H11B	122 (2)	N13—C14—C13	128.1 (2)
H11A—N11—H11B	123 (4)	N15—C14—C13	106.4 (2)
C11—N12—C12	125.7 (2)	N14—C15—N15	109.7 (2)
C11—N12—H12A	117 (2)	N14—C15—H15A	125.1
C12—N12—H12A	117 (2)	N15—C15—H15A	125.1
C11—N13—C14	112.4 (2)	N23—C21—N21	120.0 (2)
C15—N14—C13	108.0 (2)	N23—C21—N22	124.1 (2)
C15—N14—H14A	130 (2)	N21—C21—N22	116.0 (2)
C13—N14—H14A	121 (2)	O21—C22—N22	122.1 (2)
C15—N15—C14	108.5 (2)	O21—C22—C23	126.3 (2)
C15—N15—H15B	125 (2)	N22—C22—C23	111.6 (2)
C14—N15—H15B	127 (2)	C24—C23—N24	107.6 (2)
C21—N21—H21A	114 (3)	C24—C23—C22	119.5 (2)
C21—N21—H21B	117 (3)	N24—C23—C22	132.9 (2)
H21A—N21—H21B	128 (4)	N23—C24—C23	128.2 (2)
C21—N22—C22	124.5 (2)	N23—C24—N25	125.5 (2)
C21—N22—H22A	111 (2)	C23—C24—N25	106.2 (2)
C22—N22—H22A	124 (2)	N24—C25—N25	109.5 (2)
C21—N23—C24	112.1 (2)	N24—C25—H25A	125.3
C25—N24—C23	108.1 (2)	N25—C25—H25A	125.3
C25—N24—H24A	124 (2)
C14—N13—C11—N11	−178.8 (2)	C24—N23—C21—N21	−179.8 (2)
C14—N13—C11—N12	2.7 (4)	C24—N23—C21—N22	−0.1 (4)
C12—N12—C11—N13	−2.2 (4)	C22—N22—C21—N23	−0.6 (4)
C12—N12—C11—N11	179.2 (3)	C22—N22—C21—N21	179.0 (3)
C11—N12—C12—O11	−179.3 (3)	C21—N22—C22—O21	179.8 (3)
C11—N12—C12—C13	−0.1 (4)	C21—N22—C22—C23	0.5 (4)
C15—N14—C13—C14	−0.6 (3)	C25—N24—C23—C24	0.0 (3)
C15—N14—C13—C12	−179.3 (3)	C25—N24—C23—C22	−176.6 (3)
O11—C12—C13—C14	−179.3 (3)	O21—C22—C23—C24	−179.0 (3)
N12—C12—C13—C14	1.6 (3)	N22—C22—C23—C24	0.3 (4)
O11—C12—C13—N14	−0.7 (5)	O21—C22—C23—N24	−2.8 (5)
N12—C12—C13—N14	−179.8 (3)	N22—C22—C23—N24	176.5 (3)
C11—N13—C14—N15	178.5 (2)	C21—N23—C24—C23	1.0 (4)
C11—N13—C14—C13	−1.1 (4)	C21—N23—C24—N25	−176.4 (3)
C15—N15—C14—N13	−179.6 (2)	N24—C23—C24—N23	−178.3 (3)
C15—N15—C14—C13	0.1 (3)	C22—C23—C24—N23	−1.1 (4)
N14—C13—C14—N13	179.9 (3)	N24—C23—C24—N25	−0.4 (3)
C12—C13—C14—N13	−1.1 (4)	C22—C23—C24—N25	176.7 (2)
N14—C13—C14—N15	0.3 (3)	C25—N25—C24—N23	178.6 (3)
C12—C13—C14—N15	179.2 (2)	C25—N25—C24—C23	0.7 (3)
C13—N14—C15—N15	0.7 (3)	C23—N24—C25—N25	0.4 (3)
C14—N15—C15—N14	−0.5 (3)	C24—N25—C25—N24	−0.7 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1B···Cl6^i	0.83 (2)	2.74 (3)	3.381 (2)	135 (3)
O1W—H1B···Cl7^i	0.83 (2)	2.63 (3)	3.325 (2)	142 (3)
N11—H11A···Cl8	0.86 (2)	2.55 (2)	3.407 (3)	172 (3)
N11—H11B···Cl1^ii	0.87 (2)	2.49 (2)	3.334 (3)	162 (3)
N12—H12A···Cl2^ii	0.87 (2)	2.47 (2)	3.285 (2)	156 (3)
N14—H14A···O21^iii	0.90 (2)	1.77 (2)	2.656 (3)	168 (4)
N15—H15B···Cl4^iv	0.88 (2)	2.76 (3)	3.393 (2)	131 (3)
N15—H15B···O1W	0.88 (2)	2.09 (3)	2.777 (3)	135 (3)
N21—H21A···Cl7^v	0.86 (2)	2.79 (4)	3.236 (3)	114 (3)
N21—H21A···Cl8^v	0.86 (2)	2.92 (2)	3.775 (3)	174 (3)
N21—H21B···O11^iii	0.87 (2)	2.52 (3)	3.257 (3)	143 (3)
N22—H22A···O11^iii	0.89 (2)	1.90 (2)	2.788 (3)	178 (4)
N24—H24A···Cl5^vi	0.87 (2)	2.70 (3)	3.348 (2)	132 (3)
N24—H24A···Cl6^vi	0.87 (2)	2.55 (2)	3.343 (2)	152 (3)
N25—H25B···Cl4^vii	0.90 (2)	2.87 (3)	3.513 (2)	130 (3)
N25—H25B···O1W^v	0.90 (2)	1.96 (3)	2.774 (3)	150 (3)

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