Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270109030583/sq3203sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109030583/sq3203Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109030583/sq3203IIsup3.hkl |
CCDC references: 765456; 765457
For (I), an aqueous solution (200 µl) containing L-ecgonine hydrochloride (100 µg) was combined with a 0.24% gold(III) chloride (HAuCl4.3H2O) solution in 0.24 M HCl (200 µl) [Please check rephrasing]. Slow evaporation of this mixture to dryness produced very light-yellow parallelepipeds of (I), which were used directly for X-ray analysis. For (II), the same preparation was repeated at a later date and the resulting crystals were used for X-ray analysis. These proved to be anhydrous, most probably because of the lack of humidity in the laboratory where the crystals were allowed to grow.
All N– and C-bound H atoms, and two of the four hydroxy H atoms for (I) and both of the hydroxy H atoms for (II), were found in electron-density difference maps. For (I), three of the four carboxylic acid H atoms were found, but the remaining acid H atom was disordered and not found. For (II), both of the acid H atoms were located. The hydroxy and acid H atoms were constrained to idealized positions, with distances fixed at O—H = 0.84 Å and with Uiso(H) = 1.5Ueq(O). The methyl H atoms were placed in ideally staggered positions, with C—H = 0.98 Å and Uiso(H) = 1.5Ueq(C). The methylene and methine H atoms were placed in geometrically idealized positions and constrained to ride on their parent C atoms, with C—H = 0.99 and 1.00 Å, respectively, and with Uiso(H) = 1.2Ueq(C). In (I), because of the small contribution to the total electron density in the cell, no water H atoms were found in difference maps.
For both compounds, data collection: APEX2 (Bruker, 2006); cell refinement: APEX2 (Bruker, 2006); data reduction: SAINT (Bruker, 2005); 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).
(C9H16NO3)4(H3O)[AuCl4]5·6H2O | F(000) = 4840 |
Mr = 2565.86 | Dx = 2.345 Mg m−3 |
Orthorhombic, P212121 | Cu Kα radiation, λ = 1.54178 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 9389 reflections |
a = 9.2153 (16) Å | θ = 3.0–67.4° |
b = 15.299 (3) Å | µ = 25.82 mm−1 |
c = 51.544 (8) Å | T = 100 K |
V = 7267 (2) Å3 | Parallelepiped, yellow |
Z = 4 | 0.35 × 0.11 × 0.10 mm |
Bruker SMART APEXII CCD area-detector diffractometer | 12355 independent reflections |
Radiation source: fine-focus sealed tube | 12097 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.057 |
ϕ and ω scans | θmax = 68.1°, θmin = 1.7° |
Absorption correction: numerical (SADABS; Sheldrick, 2001) | h = −10→11 |
Tmin = 0.040, Tmax = 0.182 | k = −17→18 |
43458 measured reflections | l = −61→47 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.040 | H-atom parameters constrained |
wR(F2) = 0.099 | w = 1/[σ2(Fo2) + (0.0529P)2 + 20.0246P] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max < 0.001 |
12355 reflections | Δρmax = 3.15 e Å−3 |
761 parameters | Δρmin = −1.94 e Å−3 |
0 restraints | Absolute structure: Flack (1983), 5212 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.031 (10) |
(C9H16NO3)4(H3O)[AuCl4]5·6H2O | V = 7267 (2) Å3 |
Mr = 2565.86 | Z = 4 |
Orthorhombic, P212121 | Cu Kα radiation |
a = 9.2153 (16) Å | µ = 25.82 mm−1 |
b = 15.299 (3) Å | T = 100 K |
c = 51.544 (8) Å | 0.35 × 0.11 × 0.10 mm |
Bruker SMART APEXII CCD area-detector diffractometer | 12355 independent reflections |
Absorption correction: numerical (SADABS; Sheldrick, 2001) | 12097 reflections with I > 2σ(I) |
Tmin = 0.040, Tmax = 0.182 | Rint = 0.057 |
43458 measured reflections |
R[F2 > 2σ(F2)] = 0.040 | H-atom parameters constrained |
wR(F2) = 0.099 | w = 1/[σ2(Fo2) + (0.0529P)2 + 20.0246P] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | Δρmax = 3.15 e Å−3 |
12355 reflections | Δρmin = −1.94 e Å−3 |
761 parameters | Absolute structure: Flack (1983), 5212 Friedel pairs |
0 restraints | Absolute structure parameter: 0.031 (10) |
Experimental. crystal mounted on cryoloop using Paratone-N |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 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. |
x | y | z | Uiso*/Ueq | ||
Au1 | 0.74862 (5) | 0.93435 (3) | 0.715499 (8) | 0.02738 (10) | |
Cl1 | 0.5420 (3) | 0.93399 (18) | 0.69119 (6) | 0.0428 (6) | |
Cl2 | 0.7528 (3) | 0.78521 (14) | 0.71406 (4) | 0.0293 (5) | |
Cl3 | 0.7363 (3) | 1.08209 (16) | 0.71804 (5) | 0.0379 (6) | |
Cl4 | 0.9628 (3) | 0.93526 (17) | 0.73783 (5) | 0.0375 (5) | |
O1A | 0.1554 (8) | 0.8451 (5) | 0.66339 (15) | 0.0371 (17) | |
O2A | −0.0728 (9) | 0.8215 (5) | 0.64890 (16) | 0.0420 (19) | |
O3A | 0.0555 (8) | 0.6494 (5) | 0.63127 (13) | 0.0322 (15) | |
N1A | 0.2677 (9) | 0.7238 (5) | 0.69855 (16) | 0.0246 (17) | |
H1NA | 0.2816 | 0.7672 | 0.6862 | 0.030* | |
C1A | 0.1077 (11) | 0.7106 (6) | 0.70197 (18) | 0.027 (2) | |
H1A | 0.0664 | 0.7570 | 0.7135 | 0.032* | |
C2A | 0.0357 (11) | 0.7137 (6) | 0.67500 (19) | 0.028 (2) | |
H2A | −0.0697 | 0.7008 | 0.6775 | 0.033* | |
C3A | 0.0996 (11) | 0.6393 (6) | 0.65789 (19) | 0.029 (2) | |
H3A | 0.0604 | 0.5824 | 0.6644 | 0.035* | |
C4A | 0.2634 (12) | 0.6351 (7) | 0.65901 (18) | 0.030 (2) | |
H4A1 | 0.3049 | 0.6849 | 0.6492 | 0.037* | |
H4A2 | 0.2972 | 0.5804 | 0.6507 | 0.037* | |
C5A | 0.3166 (12) | 0.6382 (6) | 0.6871 (2) | 0.030 (2) | |
H5A | 0.4245 | 0.6319 | 0.6880 | 0.036* | |
C6A | 0.2402 (12) | 0.5736 (7) | 0.7054 (2) | 0.033 (2) | |
H6A1 | 0.3041 | 0.5581 | 0.7201 | 0.040* | |
H6A2 | 0.2133 | 0.5195 | 0.6960 | 0.040* | |
C7A | 0.1011 (12) | 0.6228 (7) | 0.7152 (2) | 0.035 (2) | |
H7A1 | 0.0120 | 0.5908 | 0.7102 | 0.042* | |
H7A2 | 0.1030 | 0.6295 | 0.7343 | 0.042* | |
C8A | 0.3460 (13) | 0.7509 (8) | 0.72283 (19) | 0.039 (2) | |
H8A1 | 0.3037 | 0.8052 | 0.7295 | 0.059* | |
H8A2 | 0.4489 | 0.7601 | 0.7189 | 0.059* | |
H8A3 | 0.3363 | 0.7049 | 0.7359 | 0.059* | |
C9A | 0.0463 (13) | 0.8008 (6) | 0.66226 (19) | 0.034 (2) | |
Au2 | 0.30570 (5) | 0.92904 (3) | 0.794261 (8) | 0.02713 (10) | |
Cl5 | 0.2768 (3) | 0.78095 (16) | 0.79691 (7) | 0.0480 (7) | |
Cl6 | 0.4922 (3) | 0.9113 (2) | 0.76612 (6) | 0.0509 (8) | |
Cl7 | 0.1160 (3) | 0.94711 (16) | 0.82213 (5) | 0.0345 (5) | |
Cl8 | 0.3296 (3) | 1.07667 (15) | 0.79252 (5) | 0.0379 (6) | |
O1B | 0.9797 (9) | 0.6876 (4) | 0.84537 (15) | 0.0383 (18) | |
O2B | 1.0975 (9) | 0.5593 (5) | 0.84181 (16) | 0.046 (2) | |
O3B | 0.7546 (9) | 0.5194 (4) | 0.84790 (14) | 0.0384 (17) | |
H3B1 | 0.7802 | 0.4671 | 0.8461 | 0.046* | |
N1B | 0.8210 (10) | 0.7324 (6) | 0.80203 (17) | 0.0336 (19) | |
H1NB | 0.8530 | 0.7438 | 0.8188 | 0.040* | |
C1B | 0.8963 (12) | 0.6514 (7) | 0.79179 (18) | 0.034 (2) | |
H1B | 0.9954 | 0.6659 | 0.7852 | 0.041* | |
C2B | 0.9046 (12) | 0.5830 (6) | 0.8140 (2) | 0.032 (2) | |
H2B | 0.9489 | 0.5287 | 0.8067 | 0.038* | |
C3B | 0.7496 (13) | 0.5605 (7) | 0.8233 (2) | 0.038 (3) | |
H3B | 0.7035 | 0.5198 | 0.8105 | 0.046* | |
C4B | 0.6522 (13) | 0.6426 (7) | 0.8264 (2) | 0.039 (3) | |
H4B1 | 0.5498 | 0.6242 | 0.8285 | 0.046* | |
H4B2 | 0.6811 | 0.6747 | 0.8423 | 0.046* | |
C5B | 0.6655 (13) | 0.7032 (7) | 0.8029 (2) | 0.036 (2) | |
H5B | 0.5993 | 0.7546 | 0.8048 | 0.043* | |
C6B | 0.6434 (12) | 0.6602 (7) | 0.7772 (2) | 0.037 (2) | |
H6B1 | 0.6089 | 0.7029 | 0.7641 | 0.044* | |
H6B2 | 0.5719 | 0.6121 | 0.7785 | 0.044* | |
C7B | 0.7974 (14) | 0.6241 (7) | 0.7698 (2) | 0.039 (3) | |
H7B1 | 0.7952 | 0.5597 | 0.7681 | 0.046* | |
H7B2 | 0.8308 | 0.6496 | 0.7532 | 0.046* | |
C8B | 0.8517 (14) | 0.8102 (7) | 0.7852 (2) | 0.042 (3) | |
H8B1 | 0.9533 | 0.8276 | 0.7873 | 0.063* | |
H8B2 | 0.7884 | 0.8587 | 0.7904 | 0.063* | |
H8B3 | 0.8333 | 0.7951 | 0.7671 | 0.063* | |
C9B | 0.9985 (14) | 0.6135 (7) | 0.8352 (2) | 0.038 (2) | |
Au3 | 0.94049 (4) | 0.25918 (2) | 0.956030 (8) | 0.02640 (9) | |
Cl9 | 1.1271 (3) | 0.25901 (18) | 0.92737 (6) | 0.0430 (6) | |
Cl10 | 0.7501 (3) | 0.26223 (16) | 0.98452 (5) | 0.0352 (5) | |
Cl11 | 0.9699 (3) | 0.11302 (15) | 0.96206 (5) | 0.0345 (5) | |
Cl12 | 0.9157 (3) | 0.40534 (14) | 0.94945 (5) | 0.0354 (5) | |
O1C | 0.4233 (9) | 0.3312 (5) | 0.90561 (15) | 0.0399 (18) | |
O2C | 0.5840 (10) | 0.3634 (5) | 0.87540 (17) | 0.049 (2) | |
O3C | 0.5037 (9) | 0.5453 (5) | 0.87533 (16) | 0.0441 (19) | |
N1C | 0.3872 (10) | 0.4437 (6) | 0.94632 (17) | 0.035 (2) | |
H1NC | 0.3450 | 0.4089 | 0.9336 | 0.043* | |
C1C | 0.5536 (13) | 0.4461 (8) | 0.9423 (2) | 0.042 (3) | |
H1C | 0.6022 | 0.3931 | 0.9496 | 0.050* | |
C2C | 0.5787 (14) | 0.4553 (7) | 0.9126 (2) | 0.038 (3) | |
H2C | 0.6856 | 0.4596 | 0.9095 | 0.046* | |
C3C | 0.5077 (13) | 0.5403 (7) | 0.9030 (2) | 0.037 (2) | |
H3C | 0.5678 | 0.5903 | 0.9094 | 0.044* | |
C4C | 0.3571 (14) | 0.5521 (7) | 0.9133 (2) | 0.041 (3) | |
H4C1 | 0.3234 | 0.6118 | 0.9090 | 0.049* | |
H4C2 | 0.2918 | 0.5102 | 0.9044 | 0.049* | |
C5C | 0.3442 (14) | 0.5391 (7) | 0.9419 (2) | 0.037 (3) | |
H5C | 0.2435 | 0.5512 | 0.9482 | 0.044* | |
C6C | 0.4548 (15) | 0.5875 (8) | 0.9574 (2) | 0.049 (3) | |
H6C1 | 0.4201 | 0.5969 | 0.9753 | 0.059* | |
H6C2 | 0.4753 | 0.6451 | 0.9494 | 0.059* | |
C7C | 0.5940 (18) | 0.5290 (9) | 0.9573 (3) | 0.061 (4) | |
H7C1 | 0.6752 | 0.5597 | 0.9486 | 0.073* | |
H7C2 | 0.6235 | 0.5144 | 0.9752 | 0.073* | |
C8C | 0.3478 (16) | 0.4101 (9) | 0.9723 (2) | 0.050 (3) | |
H8C1 | 0.4046 | 0.3574 | 0.9760 | 0.075* | |
H8C2 | 0.2442 | 0.3957 | 0.9726 | 0.075* | |
H8C3 | 0.3685 | 0.4548 | 0.9854 | 0.075* | |
C9C | 0.5216 (13) | 0.3768 (6) | 0.8975 (2) | 0.035 (2) | |
Au4 | 0.63437 (4) | 0.84234 (3) | 0.877377 (7) | 0.02490 (9) | |
Cl13 | 0.4588 (3) | 0.79712 (17) | 0.90533 (5) | 0.0360 (5) | |
Cl14 | 0.7996 (3) | 0.77375 (18) | 0.90306 (6) | 0.0435 (6) | |
Cl15 | 0.4669 (3) | 0.9127 (2) | 0.85256 (6) | 0.0476 (7) | |
Cl16 | 0.8114 (3) | 0.88644 (16) | 0.84947 (5) | 0.0324 (5) | |
O1D | 0.7144 (8) | 0.0187 (4) | 0.90788 (13) | 0.0307 (15) | |
O2D | 0.7544 (8) | 0.1642 (4) | 0.90693 (13) | 0.0309 (15) | |
H2D1 | 0.8146 | 0.1596 | 0.8948 | 0.037* | |
O3D | 0.4181 (8) | 0.1525 (4) | 0.90101 (13) | 0.0322 (15) | |
H3D1 | 0.4201 | 0.2073 | 0.9023 | 0.035* | |
N1D | 0.5444 (9) | −0.0414 (5) | 0.94958 (17) | 0.0303 (19) | |
H1ND | 0.5800 | −0.0499 | 0.9329 | 0.036* | |
C1D | 0.5945 (10) | 0.0475 (6) | 0.95921 (17) | 0.0228 (19) | |
H1D | 0.6959 | 0.0456 | 0.9661 | 0.027* | |
C2D | 0.5793 (10) | 0.1123 (6) | 0.93647 (17) | 0.0242 (19) | |
H2D | 0.6015 | 0.1719 | 0.9434 | 0.029* | |
C3D | 0.4233 (11) | 0.1142 (6) | 0.92633 (18) | 0.027 (2) | |
H3D | 0.3629 | 0.1503 | 0.9384 | 0.033* | |
C4D | 0.3543 (12) | 0.0244 (6) | 0.9238 (2) | 0.036 (2) | |
H4D1 | 0.3965 | −0.0059 | 0.9086 | 0.043* | |
H4D2 | 0.2489 | 0.0312 | 0.9207 | 0.043* | |
C5D | 0.3780 (11) | −0.0318 (6) | 0.94815 (19) | 0.027 (2) | |
H5D | 0.3281 | −0.0897 | 0.9469 | 0.033* | |
C6D | 0.3439 (11) | 0.0148 (7) | 0.9733 (2) | 0.033 (2) | |
H6D1 | 0.3182 | −0.0281 | 0.9870 | 0.039* | |
H6D2 | 0.2612 | 0.0553 | 0.9710 | 0.039* | |
C7D | 0.4810 (11) | 0.0656 (7) | 0.98107 (19) | 0.031 (2) | |
H7D1 | 0.5180 | 0.0451 | 0.9980 | 0.037* | |
H7D2 | 0.4600 | 0.1289 | 0.9823 | 0.037* | |
C8D | 0.5951 (12) | −0.1156 (7) | 0.9664 (2) | 0.035 (2) | |
H8D1 | 0.7008 | −0.1211 | 0.9651 | 0.053* | |
H8D2 | 0.5493 | −0.1701 | 0.9606 | 0.053* | |
H8D3 | 0.5681 | −0.1041 | 0.9845 | 0.053* | |
C9D | 0.6869 (11) | 0.0931 (6) | 0.91624 (18) | 0.027 (2) | |
Au5 | 0.98656 (4) | 0.75277 (2) | 0.966586 (7) | 0.02257 (9) | |
Cl17 | 0.9949 (3) | 0.90185 (14) | 0.96923 (5) | 0.0340 (5) | |
Cl18 | 0.8147 (3) | 0.74489 (16) | 0.99822 (5) | 0.0328 (5) | |
Cl19 | 1.1606 (3) | 0.75605 (16) | 0.93526 (4) | 0.0318 (5) | |
Cl20 | 0.9784 (3) | 0.60447 (14) | 0.96329 (5) | 0.0312 (5) | |
O4 | 0.2397 (9) | 0.1265 (5) | 0.86078 (15) | 0.0400 (18) | |
O5 | 0.4390 (9) | 0.2617 (5) | 0.84436 (15) | 0.0412 (18) | |
O6 | 0.3090 (10) | 0.6638 (7) | 0.85737 (18) | 0.057 (2) | |
O7 | 0.1339 (8) | 0.8204 (5) | 0.87393 (15) | 0.0373 (17) | |
O8 | 0.0181 (9) | 0.9550 (5) | 0.90505 (16) | 0.0404 (18) | |
O9 | −0.0546 (12) | 0.9287 (6) | 0.61145 (17) | 0.058 (2) | |
O10 | 0.1013 (13) | 1.0722 (7) | 0.5986 (2) | 0.075 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Au1 | 0.0269 (2) | 0.02786 (18) | 0.02739 (18) | 0.00195 (16) | 0.00045 (17) | −0.00023 (15) |
Cl1 | 0.0370 (15) | 0.0415 (12) | 0.0501 (14) | 0.0089 (12) | −0.0135 (13) | −0.0073 (12) |
Cl2 | 0.0302 (12) | 0.0264 (10) | 0.0312 (10) | 0.0020 (8) | 0.0017 (11) | −0.0023 (8) |
Cl3 | 0.0409 (15) | 0.0310 (11) | 0.0419 (13) | 0.0035 (10) | 0.0000 (12) | −0.0023 (10) |
Cl4 | 0.0350 (15) | 0.0379 (11) | 0.0396 (12) | −0.0070 (11) | −0.0079 (11) | 0.0079 (11) |
O1A | 0.035 (5) | 0.033 (3) | 0.043 (4) | −0.007 (3) | −0.003 (4) | 0.000 (3) |
O2A | 0.038 (5) | 0.036 (4) | 0.052 (5) | 0.007 (3) | −0.002 (4) | 0.003 (3) |
O3A | 0.019 (4) | 0.056 (4) | 0.022 (3) | −0.001 (3) | 0.003 (3) | −0.006 (3) |
N1A | 0.016 (4) | 0.031 (4) | 0.026 (4) | −0.005 (3) | −0.002 (3) | −0.003 (3) |
C1A | 0.026 (6) | 0.033 (4) | 0.021 (4) | −0.005 (4) | −0.002 (4) | −0.001 (4) |
C2A | 0.019 (5) | 0.036 (5) | 0.027 (5) | 0.001 (4) | −0.003 (4) | −0.003 (4) |
C3A | 0.026 (6) | 0.034 (5) | 0.027 (5) | 0.005 (4) | 0.004 (4) | −0.003 (4) |
C4A | 0.031 (6) | 0.041 (5) | 0.020 (4) | −0.003 (4) | 0.004 (4) | 0.005 (4) |
C5A | 0.023 (5) | 0.031 (5) | 0.037 (5) | 0.000 (4) | −0.004 (5) | 0.001 (4) |
C6A | 0.036 (6) | 0.037 (5) | 0.028 (5) | 0.002 (5) | −0.004 (5) | 0.012 (4) |
C7A | 0.028 (6) | 0.042 (5) | 0.034 (5) | −0.003 (4) | −0.002 (5) | 0.003 (4) |
C8A | 0.036 (6) | 0.052 (6) | 0.029 (5) | −0.013 (5) | −0.001 (5) | −0.006 (5) |
C9A | 0.049 (7) | 0.032 (5) | 0.022 (4) | 0.010 (5) | −0.003 (5) | 0.000 (4) |
Au2 | 0.0236 (2) | 0.02822 (18) | 0.02958 (18) | −0.00388 (15) | 0.00276 (17) | −0.00384 (15) |
Cl5 | 0.0339 (16) | 0.0272 (11) | 0.083 (2) | −0.0020 (10) | 0.0071 (16) | −0.0114 (12) |
Cl6 | 0.0366 (16) | 0.0685 (18) | 0.0478 (15) | −0.0171 (14) | 0.0170 (14) | −0.0243 (14) |
Cl7 | 0.0276 (13) | 0.0403 (12) | 0.0355 (11) | 0.0082 (10) | 0.0062 (11) | 0.0021 (10) |
Cl8 | 0.0351 (15) | 0.0291 (11) | 0.0495 (14) | −0.0051 (10) | −0.0124 (12) | 0.0086 (10) |
O1B | 0.045 (5) | 0.033 (4) | 0.037 (4) | −0.001 (3) | −0.009 (4) | 0.000 (3) |
O2B | 0.044 (5) | 0.054 (5) | 0.042 (4) | 0.011 (4) | −0.005 (4) | −0.004 (4) |
O3B | 0.051 (5) | 0.029 (3) | 0.035 (4) | 0.001 (3) | 0.006 (4) | 0.002 (3) |
N1B | 0.030 (5) | 0.040 (5) | 0.031 (4) | −0.002 (4) | −0.002 (4) | 0.007 (4) |
C1B | 0.029 (6) | 0.051 (6) | 0.022 (4) | −0.004 (5) | 0.014 (4) | 0.000 (4) |
C2B | 0.028 (6) | 0.036 (5) | 0.032 (5) | −0.003 (4) | 0.003 (5) | −0.003 (4) |
C3B | 0.049 (7) | 0.030 (5) | 0.036 (5) | −0.011 (5) | 0.010 (5) | −0.008 (4) |
C4B | 0.032 (6) | 0.043 (6) | 0.041 (6) | 0.000 (5) | −0.005 (5) | 0.002 (5) |
C5B | 0.032 (6) | 0.038 (5) | 0.038 (6) | −0.004 (4) | 0.013 (5) | 0.002 (4) |
C6B | 0.020 (5) | 0.036 (5) | 0.054 (6) | 0.001 (4) | 0.003 (5) | 0.001 (5) |
C7B | 0.049 (7) | 0.038 (5) | 0.029 (5) | −0.003 (5) | 0.005 (5) | 0.000 (4) |
C8B | 0.046 (7) | 0.037 (5) | 0.042 (6) | −0.007 (5) | −0.003 (6) | 0.007 (5) |
C9B | 0.042 (7) | 0.039 (5) | 0.034 (5) | −0.006 (5) | 0.007 (5) | 0.001 (4) |
Au3 | 0.0233 (2) | 0.02463 (17) | 0.03130 (18) | 0.00021 (15) | −0.00206 (17) | 0.00141 (15) |
Cl9 | 0.0322 (14) | 0.0440 (13) | 0.0529 (15) | 0.0072 (12) | 0.0148 (13) | 0.0114 (12) |
Cl10 | 0.0346 (13) | 0.0380 (12) | 0.0329 (11) | −0.0004 (11) | 0.0031 (11) | −0.0028 (10) |
Cl11 | 0.0305 (14) | 0.0279 (10) | 0.0452 (13) | 0.0052 (9) | −0.0019 (11) | 0.0059 (10) |
Cl12 | 0.0414 (15) | 0.0242 (10) | 0.0406 (12) | 0.0022 (9) | −0.0001 (12) | 0.0022 (9) |
O1C | 0.044 (5) | 0.032 (3) | 0.044 (4) | −0.008 (3) | 0.019 (4) | −0.002 (3) |
O2C | 0.060 (6) | 0.038 (4) | 0.050 (5) | 0.000 (4) | 0.027 (5) | −0.002 (4) |
O3C | 0.044 (5) | 0.044 (4) | 0.044 (4) | 0.014 (4) | 0.008 (4) | 0.007 (4) |
N1C | 0.030 (5) | 0.044 (5) | 0.033 (4) | 0.012 (4) | 0.007 (4) | 0.004 (4) |
C1C | 0.025 (6) | 0.050 (6) | 0.051 (7) | 0.005 (5) | −0.014 (6) | 0.000 (5) |
C2C | 0.037 (7) | 0.035 (5) | 0.043 (6) | 0.001 (4) | 0.009 (5) | −0.005 (4) |
C3C | 0.035 (6) | 0.037 (5) | 0.038 (6) | 0.009 (4) | −0.001 (5) | −0.006 (4) |
C4C | 0.044 (7) | 0.038 (5) | 0.041 (6) | 0.011 (5) | 0.008 (6) | −0.005 (5) |
C5C | 0.042 (7) | 0.040 (5) | 0.029 (5) | 0.008 (5) | 0.011 (5) | 0.003 (4) |
C6C | 0.055 (8) | 0.059 (7) | 0.034 (5) | 0.000 (6) | 0.005 (6) | −0.014 (5) |
C7C | 0.067 (10) | 0.067 (8) | 0.048 (7) | 0.001 (7) | 0.006 (7) | −0.016 (7) |
C8C | 0.053 (8) | 0.064 (8) | 0.034 (6) | 0.000 (6) | 0.009 (6) | 0.004 (5) |
C9C | 0.044 (7) | 0.032 (5) | 0.029 (5) | 0.001 (5) | 0.005 (5) | 0.011 (4) |
Au4 | 0.0206 (2) | 0.02911 (17) | 0.02497 (17) | −0.00038 (15) | 0.00067 (16) | −0.00093 (14) |
Cl13 | 0.0272 (14) | 0.0452 (13) | 0.0356 (12) | −0.0038 (10) | 0.0057 (11) | 0.0046 (10) |
Cl14 | 0.0282 (14) | 0.0545 (15) | 0.0478 (14) | 0.0042 (11) | −0.0037 (12) | 0.0211 (12) |
Cl15 | 0.0293 (15) | 0.0736 (19) | 0.0398 (13) | 0.0037 (13) | −0.0048 (12) | 0.0156 (13) |
Cl16 | 0.0260 (12) | 0.0385 (11) | 0.0327 (11) | 0.0013 (10) | 0.0050 (10) | 0.0054 (9) |
O1D | 0.026 (4) | 0.035 (4) | 0.030 (3) | −0.002 (3) | 0.005 (3) | −0.001 (3) |
O2D | 0.029 (4) | 0.032 (3) | 0.031 (3) | −0.007 (3) | 0.002 (3) | 0.002 (3) |
O3D | 0.033 (4) | 0.029 (3) | 0.034 (4) | −0.001 (3) | −0.002 (3) | 0.002 (3) |
N1D | 0.021 (5) | 0.037 (4) | 0.034 (4) | 0.003 (3) | 0.005 (4) | 0.007 (4) |
C1D | 0.012 (5) | 0.031 (4) | 0.025 (4) | −0.004 (3) | −0.002 (4) | 0.005 (4) |
C2D | 0.020 (5) | 0.029 (4) | 0.023 (4) | −0.003 (4) | −0.004 (4) | 0.003 (4) |
C3D | 0.019 (5) | 0.038 (5) | 0.025 (4) | 0.005 (4) | −0.005 (4) | 0.003 (4) |
C4D | 0.024 (6) | 0.030 (5) | 0.052 (6) | 0.001 (4) | −0.011 (5) | 0.005 (5) |
C5D | 0.014 (5) | 0.034 (4) | 0.034 (5) | 0.001 (4) | −0.008 (4) | −0.001 (4) |
C6D | 0.018 (5) | 0.043 (5) | 0.038 (5) | −0.002 (4) | 0.006 (4) | 0.013 (4) |
C7D | 0.021 (5) | 0.039 (5) | 0.033 (5) | −0.006 (4) | 0.008 (4) | −0.006 (4) |
C8D | 0.030 (6) | 0.036 (5) | 0.039 (5) | 0.005 (4) | −0.006 (5) | 0.010 (4) |
C9D | 0.023 (5) | 0.033 (5) | 0.025 (4) | −0.007 (4) | −0.012 (4) | 0.001 (4) |
Au5 | 0.01943 (19) | 0.02306 (17) | 0.02521 (17) | 0.00042 (14) | 0.00062 (15) | 0.00180 (14) |
Cl17 | 0.0395 (15) | 0.0225 (9) | 0.0400 (12) | −0.0008 (9) | 0.0031 (12) | 0.0012 (9) |
Cl18 | 0.0315 (12) | 0.0333 (10) | 0.0335 (10) | 0.0051 (10) | 0.0100 (10) | 0.0062 (9) |
Cl19 | 0.0266 (13) | 0.0368 (11) | 0.0318 (10) | 0.0013 (10) | 0.0077 (10) | 0.0037 (10) |
Cl20 | 0.0354 (14) | 0.0234 (9) | 0.0347 (11) | −0.0003 (9) | 0.0030 (11) | −0.0020 (9) |
O4 | 0.032 (4) | 0.049 (4) | 0.040 (4) | 0.007 (3) | −0.008 (4) | −0.007 (3) |
O5 | 0.047 (5) | 0.039 (4) | 0.038 (4) | 0.006 (4) | −0.002 (4) | 0.000 (3) |
O6 | 0.037 (5) | 0.080 (6) | 0.053 (5) | 0.011 (5) | −0.008 (4) | −0.002 (5) |
O7 | 0.025 (4) | 0.047 (4) | 0.041 (4) | 0.006 (3) | −0.004 (4) | 0.003 (3) |
O8 | 0.032 (4) | 0.042 (4) | 0.047 (4) | 0.001 (3) | −0.004 (4) | −0.001 (3) |
O9 | 0.084 (7) | 0.049 (5) | 0.042 (4) | 0.004 (5) | −0.003 (5) | 0.000 (4) |
O10 | 0.083 (8) | 0.080 (7) | 0.062 (6) | −0.023 (6) | 0.001 (6) | 0.004 (6) |
Au1—Cl3 | 2.267 (2) | Au3—Cl10 | 2.289 (3) |
Au1—Cl1 | 2.279 (3) | O1C—C9C | 1.218 (13) |
Au1—Cl2 | 2.283 (2) | O2C—C9C | 1.295 (13) |
Au1—Cl4 | 2.285 (3) | O3C—C3C | 1.427 (13) |
O1A—C9A | 1.215 (14) | N1C—C8C | 1.479 (13) |
O2A—C9A | 1.334 (14) | N1C—C5C | 1.529 (13) |
O3A—C3A | 1.439 (11) | N1C—C1C | 1.548 (15) |
N1A—C1A | 1.498 (13) | N1C—H1NC | 0.9300 |
N1A—C8A | 1.503 (12) | C1C—C7C | 1.529 (17) |
N1A—C5A | 1.507 (12) | C1C—C2C | 1.555 (15) |
N1A—H1NA | 0.9300 | C1C—H1C | 1.0000 |
C1A—C7A | 1.508 (13) | C2C—C9C | 1.523 (15) |
C1A—C2A | 1.541 (13) | C2C—C3C | 1.539 (15) |
C1A—H1A | 1.0000 | C2C—H2C | 1.0000 |
C2A—C9A | 1.489 (13) | C3C—C4C | 1.498 (16) |
C2A—C3A | 1.554 (12) | C3C—H3C | 1.0000 |
C2A—H2A | 1.0000 | C4C—C5C | 1.494 (14) |
C3A—C4A | 1.513 (15) | C4C—H4C1 | 0.9900 |
C3A—H3A | 1.0000 | C4C—H4C2 | 0.9900 |
C4A—C5A | 1.527 (13) | C5C—C6C | 1.491 (17) |
C4A—H4A1 | 0.9900 | C5C—H5C | 1.0000 |
C4A—H4A2 | 0.9900 | C6C—C7C | 1.56 (2) |
C5A—C6A | 1.537 (13) | C6C—H6C1 | 0.9900 |
C5A—H5A | 1.0000 | C6C—H6C2 | 0.9900 |
C6A—C7A | 1.570 (15) | C7C—H7C1 | 0.9900 |
C6A—H6A1 | 0.9900 | C7C—H7C2 | 0.9900 |
C6A—H6A2 | 0.9900 | C8C—H8C1 | 0.9800 |
C7A—H7A1 | 0.9900 | C8C—H8C2 | 0.9800 |
C7A—H7A2 | 0.9900 | C8C—H8C3 | 0.9800 |
C8A—H8A1 | 0.9800 | Au4—Cl13 | 2.274 (3) |
C8A—H8A2 | 0.9800 | Au4—Cl14 | 2.274 (3) |
C8A—H8A3 | 0.9800 | Au4—Cl15 | 2.276 (3) |
Au2—Cl6 | 2.265 (3) | Au4—Cl16 | 2.277 (3) |
Au2—Cl8 | 2.271 (2) | O1D—C9D | 1.243 (12) |
Au2—Cl7 | 2.279 (3) | O2D—C9D | 1.342 (11) |
Au2—Cl5 | 2.285 (3) | O2D—H2D1 | 0.8387 |
O1B—C9B | 1.261 (13) | O3D—C3D | 1.431 (11) |
O2B—C9B | 1.280 (15) | O3D—H3D1 | 0.8400 |
O3B—C3B | 1.417 (12) | N1D—C8D | 1.504 (12) |
O3B—H3B1 | 0.8400 | N1D—C1D | 1.519 (12) |
N1B—C8B | 1.498 (12) | N1D—C5D | 1.542 (13) |
N1B—C5B | 1.502 (14) | N1D—H1ND | 0.9301 |
N1B—C1B | 1.515 (13) | C1D—C2D | 1.541 (12) |
N1B—H1NB | 0.9301 | C1D—C7D | 1.562 (13) |
C1B—C7B | 1.514 (15) | C1D—H1D | 1.0000 |
C1B—C2B | 1.552 (13) | C2D—C9D | 1.468 (14) |
C1B—H1B | 1.0000 | C2D—C3D | 1.530 (13) |
C2B—C9B | 1.468 (15) | C2D—H2D | 1.0000 |
C2B—C3B | 1.546 (16) | C3D—C4D | 1.520 (14) |
C2B—H2B | 1.0010 | C3D—H3D | 1.0000 |
C3B—C4B | 1.552 (15) | C4D—C5D | 1.538 (13) |
C3B—H3B | 1.0000 | C4D—H4D1 | 0.9900 |
C4B—C5B | 1.533 (14) | C4D—H4D2 | 0.9900 |
C4B—H4B1 | 0.9900 | C5D—C6D | 1.514 (14) |
C4B—H4B2 | 0.9900 | C5D—H5D | 1.0000 |
C5B—C6B | 1.491 (15) | C6D—C7D | 1.537 (14) |
C5B—H5B | 1.0000 | C6D—H6D1 | 0.9900 |
C6B—C7B | 1.570 (16) | C6D—H6D2 | 0.9900 |
C6B—H6B1 | 0.9900 | C7D—H7D1 | 0.9900 |
C6B—H6B2 | 0.9900 | C7D—H7D2 | 0.9900 |
C7B—H7B1 | 0.9900 | C8D—H8D1 | 0.9800 |
C7B—H7B2 | 0.9900 | C8D—H8D2 | 0.9800 |
C8B—H8B1 | 0.9800 | C8D—H8D3 | 0.9800 |
C8B—H8B2 | 0.9800 | Au5—Cl19 | 2.276 (2) |
C8B—H8B3 | 0.9800 | Au5—Cl18 | 2.276 (2) |
Au3—Cl9 | 2.267 (3) | Au5—Cl20 | 2.276 (2) |
Au3—Cl12 | 2.273 (2) | Au5—Cl17 | 2.286 (2) |
Au3—Cl11 | 2.274 (2) | ||
O10···Cl14i | 3.217 (11) | O2C···O5 | 2.600 (12) |
O5···Cl1ii | 3.214 (8) | O3A···O4iv | 2.773 (11) |
Cl9···O1Ciii | 3.150 (8) | O3D···O4 | 2.676 (11) |
Cl15···Au2 | 3.361 (3) | O3C···O3B | 2.739 (11) |
O4···O5 | 2.893 (12) | O6···O2Bv | 2.646 (14) |
O6···O7 | 3.012 (12) | O8···O1Dvi | 2.967 (11) |
O7···O8 | 2.820 (11) | O7···O1Bv | 2.883 (11) |
O9···O10 | 2.707 (15) | O6···O3C | 2.713 (12) |
O2A···O9 | 2.538 (12) | ||
Cl3—Au1—Cl1 | 89.55 (10) | Cl12—Au3—Cl10 | 89.92 (9) |
Cl3—Au1—Cl2 | 177.60 (10) | Cl11—Au3—Cl10 | 91.37 (9) |
Cl1—Au1—Cl2 | 89.65 (10) | C8C—N1C—C5C | 113.7 (9) |
Cl3—Au1—Cl4 | 90.47 (10) | C8C—N1C—C1C | 111.8 (10) |
Cl1—Au1—Cl4 | 176.90 (10) | C5C—N1C—C1C | 102.3 (9) |
Cl2—Au1—Cl4 | 90.45 (9) | C8C—N1C—H1NC | 109.7 |
C1A—N1A—C8A | 114.3 (8) | C5C—N1C—H1NC | 109.5 |
C1A—N1A—C5A | 102.9 (7) | C1C—N1C—H1NC | 109.5 |
C8A—N1A—C5A | 115.0 (8) | C7C—C1C—N1C | 101.2 (10) |
C1A—N1A—H1NA | 108.2 | C7C—C1C—C2C | 112.6 (11) |
C8A—N1A—H1NA | 108.0 | N1C—C1C—C2C | 106.3 (9) |
C5A—N1A—H1NA | 108.0 | C7C—C1C—H1C | 112.0 |
N1A—C1A—C7A | 102.3 (8) | N1C—C1C—H1C | 112.0 |
N1A—C1A—C2A | 108.3 (8) | C2C—C1C—H1C | 112.0 |
C7A—C1A—C2A | 114.7 (8) | C9C—C2C—C3C | 110.8 (10) |
N1A—C1A—H1A | 110.4 | C9C—C2C—C1C | 112.3 (9) |
C7A—C1A—H1A | 110.4 | C3C—C2C—C1C | 109.3 (9) |
C2A—C1A—H1A | 110.4 | C9C—C2C—H2C | 108.1 |
C9A—C2A—C1A | 113.4 (8) | C3C—C2C—H2C | 108.1 |
C9A—C2A—C3A | 112.3 (8) | C1C—C2C—H2C | 108.1 |
C1A—C2A—C3A | 109.1 (8) | O3C—C3C—C4C | 108.9 (10) |
C9A—C2A—H2A | 107.2 | O3C—C3C—C2C | 112.3 (8) |
C1A—C2A—H2A | 107.2 | C4C—C3C—C2C | 112.4 (10) |
C3A—C2A—H2A | 107.2 | O3C—C3C—H3C | 107.7 |
O3A—C3A—C4A | 108.8 (8) | C4C—C3C—H3C | 107.7 |
O3A—C3A—C2A | 110.8 (8) | C2C—C3C—H3C | 107.7 |
C4A—C3A—C2A | 112.8 (9) | C5C—C4C—C3C | 114.1 (10) |
O3A—C3A—H3A | 108.1 | C5C—C4C—H4C1 | 108.7 |
C4A—C3A—H3A | 108.1 | C3C—C4C—H4C1 | 108.7 |
C2A—C3A—H3A | 108.1 | C5C—C4C—H4C2 | 108.7 |
C3A—C4A—C5A | 110.8 (9) | C3C—C4C—H4C2 | 108.7 |
C3A—C4A—H4A1 | 109.5 | H4C1—C4C—H4C2 | 107.6 |
C5A—C4A—H4A1 | 109.5 | C6C—C5C—C4C | 114.0 (11) |
C3A—C4A—H4A2 | 109.5 | C6C—C5C—N1C | 102.6 (10) |
C5A—C4A—H4A2 | 109.5 | C4C—C5C—N1C | 104.6 (8) |
H4A1—C4A—H4A2 | 108.1 | C6C—C5C—H5C | 111.7 |
N1A—C5A—C4A | 107.6 (8) | C4C—C5C—H5C | 111.7 |
N1A—C5A—C6A | 100.4 (8) | N1C—C5C—H5C | 111.7 |
C4A—C5A—C6A | 114.5 (8) | C5C—C6C—C7C | 105.9 (10) |
N1A—C5A—H5A | 111.3 | C5C—C6C—H6C1 | 110.6 |
C4A—C5A—H5A | 111.3 | C7C—C6C—H6C1 | 110.6 |
C6A—C5A—H5A | 111.3 | C5C—C6C—H6C2 | 110.6 |
C5A—C6A—C7A | 105.3 (8) | C7C—C6C—H6C2 | 110.6 |
C5A—C6A—H6A1 | 110.7 | H6C1—C6C—H6C2 | 108.7 |
C7A—C6A—H6A1 | 110.7 | C1C—C7C—C6C | 106.1 (12) |
C5A—C6A—H6A2 | 110.7 | C1C—C7C—H7C1 | 110.5 |
C7A—C6A—H6A2 | 110.7 | C6C—C7C—H7C1 | 110.5 |
H6A1—C6A—H6A2 | 108.8 | C1C—C7C—H7C2 | 110.5 |
C1A—C7A—C6A | 104.4 (8) | C6C—C7C—H7C2 | 110.5 |
C1A—C7A—H7A1 | 110.9 | H7C1—C7C—H7C2 | 108.7 |
C6A—C7A—H7A1 | 110.9 | N1C—C8C—H8C1 | 109.5 |
C1A—C7A—H7A2 | 110.9 | N1C—C8C—H8C2 | 109.5 |
C6A—C7A—H7A2 | 110.9 | H8C1—C8C—H8C2 | 109.5 |
H7A1—C7A—H7A2 | 108.9 | N1C—C8C—H8C3 | 109.5 |
N1A—C8A—H8A1 | 109.5 | H8C1—C8C—H8C3 | 109.5 |
N1A—C8A—H8A2 | 109.5 | H8C2—C8C—H8C3 | 109.5 |
H8A1—C8A—H8A2 | 109.5 | O1C—C9C—O2C | 122.7 (11) |
N1A—C8A—H8A3 | 109.5 | O1C—C9C—C2C | 122.4 (10) |
H8A1—C8A—H8A3 | 109.5 | O2C—C9C—C2C | 114.9 (10) |
H8A2—C8A—H8A3 | 109.5 | Cl13—Au4—Cl14 | 88.12 (10) |
O1A—C9A—O2A | 124.9 (9) | Cl13—Au4—Cl15 | 91.01 (10) |
O1A—C9A—C2A | 122.2 (10) | Cl14—Au4—Cl15 | 178.58 (12) |
O2A—C9A—C2A | 112.8 (10) | Cl13—Au4—Cl16 | 179.46 (10) |
Cl6—Au2—Cl8 | 91.17 (11) | Cl14—Au4—Cl16 | 91.41 (10) |
Cl6—Au2—Cl7 | 179.25 (11) | Cl15—Au4—Cl16 | 89.46 (10) |
Cl8—Au2—Cl7 | 88.78 (10) | C9D—O2D—H2D1 | 120.4 |
Cl6—Au2—Cl5 | 90.44 (11) | C3D—O3D—H3D1 | 109.5 |
Cl8—Au2—Cl5 | 178.38 (12) | C8D—N1D—C1D | 113.1 (8) |
Cl7—Au2—Cl5 | 89.61 (10) | C8D—N1D—C5D | 114.1 (8) |
C3B—O3B—H3B1 | 109.5 | C1D—N1D—C5D | 103.5 (7) |
C8B—N1B—C5B | 115.6 (9) | C8D—N1D—H1ND | 108.6 |
C8B—N1B—C1B | 111.3 (8) | C1D—N1D—H1ND | 108.7 |
C5B—N1B—C1B | 101.7 (8) | C5D—N1D—H1ND | 108.6 |
C8B—N1B—H1NB | 109.2 | N1D—C1D—C2D | 107.4 (7) |
C5B—N1B—H1NB | 109.4 | N1D—C1D—C7D | 101.0 (7) |
C1B—N1B—H1NB | 109.4 | C2D—C1D—C7D | 111.9 (8) |
C7B—C1B—N1B | 102.2 (9) | N1D—C1D—H1D | 112.0 |
C7B—C1B—C2B | 113.4 (9) | C2D—C1D—H1D | 112.0 |
N1B—C1B—C2B | 108.5 (7) | C7D—C1D—H1D | 112.0 |
C7B—C1B—H1B | 110.8 | C9D—C2D—C3D | 113.3 (8) |
N1B—C1B—H1B | 110.8 | C9D—C2D—C1D | 110.5 (8) |
C2B—C1B—H1B | 110.8 | C3D—C2D—C1D | 111.0 (8) |
C9B—C2B—C3B | 112.7 (9) | C9D—C2D—H2D | 107.3 |
C9B—C2B—C1B | 111.3 (9) | C3D—C2D—H2D | 107.3 |
C3B—C2B—C1B | 109.5 (9) | C1D—C2D—H2D | 107.3 |
C9B—C2B—H2B | 107.7 | O3D—C3D—C4D | 106.1 (8) |
C3B—C2B—H2B | 107.9 | O3D—C3D—C2D | 110.6 (8) |
C1B—C2B—H2B | 107.5 | C4D—C3D—C2D | 113.9 (8) |
O3B—C3B—C2B | 110.2 (10) | O3D—C3D—H3D | 108.7 |
O3B—C3B—C4B | 106.5 (8) | C4D—C3D—H3D | 108.7 |
C2B—C3B—C4B | 112.7 (9) | C2D—C3D—H3D | 108.7 |
O3B—C3B—H3B | 109.1 | C3D—C4D—C5D | 112.0 (9) |
C2B—C3B—H3B | 109.1 | C3D—C4D—H4D1 | 109.2 |
C4B—C3B—H3B | 109.1 | C5D—C4D—H4D1 | 109.2 |
C5B—C4B—C3B | 111.1 (9) | C3D—C4D—H4D2 | 109.2 |
C5B—C4B—H4B1 | 109.4 | C5D—C4D—H4D2 | 109.2 |
C3B—C4B—H4B1 | 109.4 | H4D1—C4D—H4D2 | 107.9 |
C5B—C4B—H4B2 | 109.4 | C6D—C5D—C4D | 114.1 (8) |
C3B—C4B—H4B2 | 109.4 | C6D—C5D—N1D | 102.1 (8) |
H4B1—C4B—H4B2 | 108.0 | C4D—C5D—N1D | 103.5 (8) |
C6B—C5B—N1B | 103.7 (9) | C6D—C5D—H5D | 112.1 |
C6B—C5B—C4B | 115.2 (9) | C4D—C5D—H5D | 112.1 |
N1B—C5B—C4B | 106.2 (9) | N1D—C5D—H5D | 112.1 |
C6B—C5B—H5B | 110.5 | C5D—C6D—C7D | 106.8 (8) |
N1B—C5B—H5B | 110.5 | C5D—C6D—H6D1 | 110.4 |
C4B—C5B—H5B | 110.5 | C7D—C6D—H6D1 | 110.4 |
C5B—C6B—C7B | 104.3 (9) | C5D—C6D—H6D2 | 110.4 |
C5B—C6B—H6B1 | 110.9 | C7D—C6D—H6D2 | 110.4 |
C7B—C6B—H6B1 | 110.9 | H6D1—C6D—H6D2 | 108.6 |
C5B—C6B—H6B2 | 110.9 | C6D—C7D—C1D | 105.9 (8) |
C7B—C6B—H6B2 | 110.9 | C6D—C7D—H7D1 | 110.6 |
H6B1—C6B—H6B2 | 108.9 | C1D—C7D—H7D1 | 110.6 |
C1B—C7B—C6B | 105.3 (8) | C6D—C7D—H7D2 | 110.6 |
C1B—C7B—H7B1 | 110.7 | C1D—C7D—H7D2 | 110.6 |
C6B—C7B—H7B1 | 110.7 | H7D1—C7D—H7D2 | 108.7 |
C1B—C7B—H7B2 | 110.7 | N1D—C8D—H8D1 | 109.5 |
C6B—C7B—H7B2 | 110.7 | N1D—C8D—H8D2 | 109.5 |
H7B1—C7B—H7B2 | 108.8 | H8D1—C8D—H8D2 | 109.5 |
N1B—C8B—H8B1 | 109.5 | N1D—C8D—H8D3 | 109.5 |
N1B—C8B—H8B2 | 109.5 | H8D1—C8D—H8D3 | 109.5 |
H8B1—C8B—H8B2 | 109.5 | H8D2—C8D—H8D3 | 109.5 |
N1B—C8B—H8B3 | 109.5 | O1D—C9D—O2D | 121.6 (9) |
H8B1—C8B—H8B3 | 109.5 | O1D—C9D—C2D | 124.5 (9) |
H8B2—C8B—H8B3 | 109.5 | O2D—C9D—C2D | 113.9 (8) |
O1B—C9B—O2B | 124.7 (11) | Cl19—Au5—Cl18 | 178.12 (9) |
O1B—C9B—C2B | 120.9 (11) | Cl19—Au5—Cl20 | 89.55 (9) |
O2B—C9B—C2B | 114.4 (10) | Cl18—Au5—Cl20 | 88.73 (9) |
Cl9—Au3—Cl12 | 88.87 (10) | Cl19—Au5—Cl17 | 89.81 (9) |
Cl9—Au3—Cl11 | 89.85 (10) | Cl18—Au5—Cl17 | 91.92 (9) |
Cl12—Au3—Cl11 | 178.71 (10) | Cl20—Au5—Cl17 | 179.13 (9) |
Cl9—Au3—Cl10 | 178.67 (10) | ||
C8A—N1A—C1A—C7A | −77.0 (10) | C8C—N1C—C1C—C7C | −78.6 (12) |
C5A—N1A—C1A—C7A | 48.4 (9) | C5C—N1C—C1C—C7C | 43.5 (11) |
C8A—N1A—C1A—C2A | 161.5 (8) | C8C—N1C—C1C—C2C | 163.6 (9) |
C5A—N1A—C1A—C2A | −73.1 (9) | C5C—N1C—C1C—C2C | −74.3 (10) |
N1A—C1A—C2A—C9A | −65.5 (11) | C7C—C1C—C2C—C9C | −173.2 (11) |
C7A—C1A—C2A—C9A | −179.0 (9) | N1C—C1C—C2C—C9C | −63.2 (12) |
N1A—C1A—C2A—C3A | 60.5 (10) | C7C—C1C—C2C—C3C | −49.8 (14) |
C7A—C1A—C2A—C3A | −53.0 (11) | N1C—C1C—C2C—C3C | 60.2 (12) |
C9A—C2A—C3A—O3A | −42.9 (12) | C9C—C2C—C3C—O3C | −45.1 (14) |
C1A—C2A—C3A—O3A | −169.5 (8) | C1C—C2C—C3C—O3C | −169.4 (10) |
C9A—C2A—C3A—C4A | 79.4 (11) | C9C—C2C—C3C—C4C | 78.0 (12) |
C1A—C2A—C3A—C4A | −47.2 (11) | C1C—C2C—C3C—C4C | −46.3 (13) |
O3A—C3A—C4A—C5A | 171.5 (7) | O3C—C3C—C4C—C5C | 174.0 (9) |
C2A—C3A—C4A—C5A | 48.1 (11) | C2C—C3C—C4C—C5C | 49.0 (13) |
C1A—N1A—C5A—C4A | 72.7 (9) | C3C—C4C—C5C—C6C | 48.7 (13) |
C8A—N1A—C5A—C4A | −162.3 (8) | C3C—C4C—C5C—N1C | −62.7 (13) |
C1A—N1A—C5A—C6A | −47.3 (9) | C8C—N1C—C5C—C6C | 75.0 (12) |
C8A—N1A—C5A—C6A | 77.6 (10) | C1C—N1C—C5C—C6C | −45.8 (10) |
C3A—C4A—C5A—N1A | −61.2 (10) | C8C—N1C—C5C—C4C | −165.6 (11) |
C3A—C4A—C5A—C6A | 49.4 (12) | C1C—N1C—C5C—C4C | 73.6 (11) |
N1A—C5A—C6A—C7A | 28.3 (10) | C4C—C5C—C6C—C7C | −83.2 (12) |
C4A—C5A—C6A—C7A | −86.6 (10) | N1C—C5C—C6C—C7C | 29.4 (12) |
N1A—C1A—C7A—C6A | −28.8 (9) | N1C—C1C—C7C—C6C | −25.2 (13) |
C2A—C1A—C7A—C6A | 88.1 (10) | C2C—C1C—C7C—C6C | 87.9 (13) |
C5A—C6A—C7A—C1A | 0.1 (11) | C5C—C6C—C7C—C1C | −2.3 (14) |
C1A—C2A—C9A—O1A | 40.1 (14) | C3C—C2C—C9C—O1C | −96.5 (13) |
C3A—C2A—C9A—O1A | −84.1 (12) | C1C—C2C—C9C—O1C | 26.1 (16) |
C1A—C2A—C9A—O2A | −142.7 (9) | C3C—C2C—C9C—O2C | 82.5 (13) |
C3A—C2A—C9A—O2A | 93.1 (11) | C1C—C2C—C9C—O2C | −155.0 (10) |
C8B—N1B—C1B—C7B | −78.8 (10) | C8D—N1D—C1D—C2D | 162.2 (8) |
C5B—N1B—C1B—C7B | 44.9 (9) | C5D—N1D—C1D—C2D | −73.9 (9) |
C8B—N1B—C1B—C2B | 161.2 (9) | C8D—N1D—C1D—C7D | −80.5 (9) |
C5B—N1B—C1B—C2B | −75.1 (10) | C5D—N1D—C1D—C7D | 43.5 (9) |
C7B—C1B—C2B—C9B | −178.5 (9) | N1D—C1D—C2D—C9D | −69.7 (9) |
N1B—C1B—C2B—C9B | −65.7 (12) | C7D—C1D—C2D—C9D | −179.7 (8) |
C7B—C1B—C2B—C3B | −53.2 (11) | N1D—C1D—C2D—C3D | 56.8 (10) |
N1B—C1B—C2B—C3B | 59.5 (11) | C7D—C1D—C2D—C3D | −53.1 (10) |
C9B—C2B—C3B—O3B | −38.5 (12) | C9D—C2D—C3D—O3D | −37.6 (11) |
C1B—C2B—C3B—O3B | −162.9 (8) | C1D—C2D—C3D—O3D | −162.5 (7) |
C9B—C2B—C3B—C4B | 80.3 (12) | C9D—C2D—C3D—C4D | 81.8 (10) |
C1B—C2B—C3B—C4B | −44.1 (12) | C1D—C2D—C3D—C4D | −43.2 (11) |
O3B—C3B—C4B—C5B | 167.4 (9) | O3D—C3D—C4D—C5D | 169.1 (8) |
C2B—C3B—C4B—C5B | 46.4 (13) | C2D—C3D—C4D—C5D | 47.2 (12) |
C8B—N1B—C5B—C6B | 74.2 (11) | C3D—C4D—C5D—C6D | 48.0 (12) |
C1B—N1B—C5B—C6B | −46.5 (10) | C3D—C4D—C5D—N1D | −62.1 (11) |
C8B—N1B—C5B—C4B | −164.1 (9) | C8D—N1D—C5D—C6D | 79.6 (10) |
C1B—N1B—C5B—C4B | 75.3 (10) | C1D—N1D—C5D—C6D | −43.7 (9) |
C3B—C4B—C5B—C6B | 51.6 (13) | C8D—N1D—C5D—C4D | −161.6 (8) |
C3B—C4B—C5B—N1B | −62.5 (11) | C1D—N1D—C5D—C4D | 75.0 (9) |
N1B—C5B—C6B—C7B | 29.0 (10) | C4D—C5D—C6D—C7D | −85.2 (10) |
C4B—C5B—C6B—C7B | −86.5 (11) | N1D—C5D—C6D—C7D | 25.7 (10) |
N1B—C1B—C7B—C6B | −26.7 (10) | C5D—C6D—C7D—C1D | 0.7 (10) |
C2B—C1B—C7B—C6B | 89.8 (10) | N1D—C1D—C7D—C6D | −27.1 (9) |
C5B—C6B—C7B—C1B | −1.2 (11) | C2D—C1D—C7D—C6D | 86.9 (9) |
C3B—C2B—C9B—O1B | −71.3 (13) | C3D—C2D—C9D—O1D | −79.9 (12) |
C1B—C2B—C9B—O1B | 52.1 (14) | C1D—C2D—C9D—O1D | 45.4 (13) |
C3B—C2B—C9B—O2B | 108.9 (11) | C3D—C2D—C9D—O2D | 99.4 (10) |
C1B—C2B—C9B—O2B | −127.7 (10) | C1D—C2D—C9D—O2D | −135.4 (8) |
Symmetry codes: (i) −x+1, y+1/2, −z+3/2; (ii) −x+1, y−1/2, −z+3/2; (iii) x+1, y, z; (iv) −x, y+1/2, −z+3/2; (v) x−1, y, z; (vi) x−1, y+1, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H1NA···O1A | 0.93 | 2.04 | 2.792 (11) | 137 |
N1B—H1NB···O1B | 0.93 | 1.99 | 2.757 (11) | 138 |
N1C—H1NC···O1C | 0.93 | 2.00 | 2.734 (12) | 134 |
N1D—H1ND···O1D | 0.93 | 2.07 | 2.814 (11) | 136 |
O3D—H3D1···O1C | 0.84 | 1.90 | 2.743 (10) | 179 |
O3B—H3B1···O1Aii | 0.84 | 2.02 | 2.852 (10) | 172 |
O2D—H2D1···O3Aii | 0.84 | 1.81 | 2.645 (10) | 180 |
Symmetry code: (ii) −x+1, y−1/2, −z+3/2. |
(C9H16NO3)[AuCl4] | F(000) = 1984 |
Mr = 524.99 | Dx = 2.371 Mg m−3 |
Orthorhombic, P212121 | Cu Kα radiation, λ = 1.54178 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 9469 reflections |
a = 10.0276 (1) Å | θ = 3.7–66.9° |
b = 15.7339 (2) Å | µ = 25.50 mm−1 |
c = 18.6416 (2) Å | T = 100 K |
V = 2941.15 (6) Å3 | Parallelepiped, gold |
Z = 8 | 0.23 × 0.17 × 0.10 mm |
Bruker SMART APEXII CCD area-detector diffractometer | 5121 independent reflections |
Radiation source: fine-focus sealed tube | 5053 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.035 |
ϕ and ω scans | θmax = 67.2°, θmin = 3.7° |
Absorption correction: numerical (SADABS; Sheldrick, 2001) | h = −11→11 |
Tmin = 0.067, Tmax = 0.185 | k = −18→17 |
22091 measured reflections | l = −21→21 |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.018 | w = 1/[σ2(Fo2) + (0.0249P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.047 | (Δ/σ)max < 0.001 |
S = 1.08 | Δρmax = 0.93 e Å−3 |
5121 reflections | Δρmin = −0.69 e Å−3 |
332 parameters | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.000106 (7) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983), with 2199 Friedel pairs |
Secondary atom site location: difference Fourier map | Absolute structure parameter: −0.004 (7) |
(C9H16NO3)[AuCl4] | V = 2941.15 (6) Å3 |
Mr = 524.99 | Z = 8 |
Orthorhombic, P212121 | Cu Kα radiation |
a = 10.0276 (1) Å | µ = 25.50 mm−1 |
b = 15.7339 (2) Å | T = 100 K |
c = 18.6416 (2) Å | 0.23 × 0.17 × 0.10 mm |
Bruker SMART APEXII CCD area-detector diffractometer | 5121 independent reflections |
Absorption correction: numerical (SADABS; Sheldrick, 2001) | 5053 reflections with I > 2σ(I) |
Tmin = 0.067, Tmax = 0.185 | Rint = 0.035 |
22091 measured reflections |
R[F2 > 2σ(F2)] = 0.018 | H-atom parameters constrained |
wR(F2) = 0.047 | Δρmax = 0.93 e Å−3 |
S = 1.08 | Δρmin = −0.69 e Å−3 |
5121 reflections | Absolute structure: Flack (1983), with 2199 Friedel pairs |
332 parameters | Absolute structure parameter: −0.004 (7) |
0 restraints |
Experimental. crystal mounted on cryoloop using Paratone-N |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 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. |
x | y | z | Uiso*/Ueq | ||
Au1 | 0.187321 (15) | 0.505994 (11) | 0.090196 (8) | 0.01499 (6) | |
Cl1 | 0.34843 (9) | 0.50710 (7) | 0.00321 (4) | 0.01889 (19) | |
Cl2 | 0.19401 (10) | 0.36001 (6) | 0.09469 (6) | 0.0236 (2) | |
Cl3 | 0.02630 (9) | 0.50577 (8) | 0.17652 (5) | 0.0244 (2) | |
Cl4 | 0.18470 (11) | 0.65024 (6) | 0.08728 (6) | 0.0228 (2) | |
O1 | 0.4912 (3) | 0.75884 (19) | 0.33650 (15) | 0.0215 (7) | |
O2 | 0.4994 (3) | 0.8345 (2) | 0.43767 (16) | 0.0272 (7) | |
H2 | 0.5809 | 0.8370 | 0.4277 | 0.041* | |
O3 | 0.2823 (3) | 0.92123 (18) | 0.34524 (16) | 0.0223 (7) | |
H3 | 0.2952 | 0.9412 | 0.3865 | 0.033* | |
N1 | 0.2625 (3) | 0.6623 (2) | 0.32007 (17) | 0.0147 (7) | |
H1 | 0.3475 | 0.6796 | 0.3064 | 0.018* | |
C1 | 0.2355 (4) | 0.6914 (3) | 0.3961 (2) | 0.0159 (9) | |
H1B | 0.2779 | 0.6525 | 0.4318 | 0.019* | |
C2 | 0.2891 (4) | 0.7822 (3) | 0.4035 (2) | 0.0160 (9) | |
H2B | 0.2720 | 0.8022 | 0.4536 | 0.019* | |
C3 | 0.2151 (4) | 0.8422 (3) | 0.3508 (2) | 0.0166 (8) | |
H3B | 0.1228 | 0.8524 | 0.3692 | 0.020* | |
C4 | 0.2061 (4) | 0.8043 (3) | 0.2760 (2) | 0.0171 (8) | |
H4A | 0.2948 | 0.8072 | 0.2528 | 0.021* | |
H4B | 0.1432 | 0.8383 | 0.2468 | 0.021* | |
C5 | 0.1593 (4) | 0.7119 (3) | 0.2776 (2) | 0.0157 (9) | |
H5A | 0.1490 | 0.6885 | 0.2280 | 0.019* | |
C6 | 0.0330 (4) | 0.6984 (3) | 0.3219 (2) | 0.0163 (9) | |
H6A | −0.0156 | 0.6472 | 0.3055 | 0.020* | |
H6B | −0.0269 | 0.7482 | 0.3180 | 0.020* | |
C7 | 0.0820 (4) | 0.6870 (3) | 0.4003 (2) | 0.0169 (8) | |
H7A | 0.0467 | 0.7328 | 0.4313 | 0.020* | |
H7B | 0.0528 | 0.6315 | 0.4197 | 0.020* | |
C8 | 0.2514 (4) | 0.5682 (3) | 0.3122 (3) | 0.0234 (10) | |
H8A | 0.3174 | 0.5404 | 0.3431 | 0.035* | |
H8B | 0.2679 | 0.5524 | 0.2621 | 0.035* | |
H8C | 0.1616 | 0.5499 | 0.3261 | 0.035* | |
C9 | 0.4370 (4) | 0.7886 (3) | 0.3887 (2) | 0.0173 (9) | |
Au2 | 0.792368 (15) | 0.510510 (11) | −0.096686 (8) | 0.01529 (6) | |
Cl5 | 0.58515 (10) | 0.53140 (7) | −0.14391 (6) | 0.0281 (2) | |
Cl6 | 0.76093 (11) | 0.36699 (6) | −0.09842 (6) | 0.0257 (2) | |
Cl7 | 0.99890 (10) | 0.49006 (8) | −0.04920 (6) | 0.0310 (2) | |
Cl8 | 0.82924 (10) | 0.65411 (6) | −0.09756 (6) | 0.0217 (2) | |
O1A | 0.4689 (3) | 0.64723 (18) | 0.20930 (15) | 0.0193 (6) | |
O2A | 0.5411 (3) | 0.51678 (18) | 0.22023 (17) | 0.0284 (7) | |
H2A | 0.6078 | 0.4880 | 0.2079 | 0.043* | |
O3A | 0.6462 (3) | 0.54127 (17) | 0.06095 (15) | 0.0192 (6) | |
H3A | 0.5632 | 0.5437 | 0.0552 | 0.029* | |
N1A | 0.6350 (4) | 0.7758 (2) | 0.16987 (18) | 0.0169 (8) | |
H1A | 0.5495 | 0.7540 | 0.1758 | 0.020* | |
C1A | 0.7366 (4) | 0.7113 (3) | 0.1973 (2) | 0.0158 (9) | |
H1C | 0.7436 | 0.7134 | 0.2508 | 0.019* | |
C2A | 0.6950 (4) | 0.6225 (3) | 0.1715 (2) | 0.0156 (8) | |
H2C | 0.7631 | 0.5807 | 0.1886 | 0.019* | |
C3A | 0.6934 (4) | 0.6208 (2) | 0.0877 (2) | 0.0147 (8) | |
H3C | 0.7881 | 0.6267 | 0.0715 | 0.018* | |
C4A | 0.6174 (4) | 0.6958 (3) | 0.0570 (2) | 0.0154 (8) | |
H4A1 | 0.5211 | 0.6893 | 0.0673 | 0.018* | |
H4A2 | 0.6290 | 0.6973 | 0.0043 | 0.018* | |
C5A | 0.6683 (4) | 0.7793 (3) | 0.0898 (2) | 0.0170 (9) | |
H5B | 0.6266 | 0.8298 | 0.0662 | 0.020* | |
C6A | 0.8205 (4) | 0.7862 (3) | 0.0909 (2) | 0.0207 (9) | |
H6A1 | 0.8486 | 0.8465 | 0.0901 | 0.025* | |
H6A2 | 0.8597 | 0.7570 | 0.0488 | 0.025* | |
C7A | 0.8658 (5) | 0.7426 (3) | 0.1619 (2) | 0.0200 (10) | |
H7A1 | 0.9263 | 0.6944 | 0.1517 | 0.024* | |
H7A2 | 0.9126 | 0.7836 | 0.1933 | 0.024* | |
C8A | 0.6444 (5) | 0.8597 (3) | 0.2061 (2) | 0.0219 (9) | |
H8A1 | 0.6286 | 0.8525 | 0.2577 | 0.033* | |
H8A2 | 0.5772 | 0.8982 | 0.1861 | 0.033* | |
H8A3 | 0.7335 | 0.8836 | 0.1985 | 0.033* | |
C9A | 0.5599 (4) | 0.5970 (3) | 0.2022 (2) | 0.0180 (9) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Au1 | 0.01423 (9) | 0.01405 (9) | 0.01670 (8) | −0.00097 (6) | −0.00022 (5) | 0.00066 (7) |
Cl1 | 0.0183 (4) | 0.0180 (5) | 0.0204 (4) | 0.0005 (4) | 0.0034 (3) | 0.0013 (4) |
Cl2 | 0.0219 (5) | 0.0138 (5) | 0.0351 (6) | 0.0001 (4) | 0.0027 (5) | 0.0044 (5) |
Cl3 | 0.0223 (5) | 0.0249 (6) | 0.0261 (4) | −0.0035 (5) | 0.0072 (4) | −0.0020 (5) |
Cl4 | 0.0323 (6) | 0.0146 (5) | 0.0214 (5) | −0.0012 (4) | 0.0051 (5) | −0.0023 (4) |
O1 | 0.0161 (15) | 0.0243 (18) | 0.0241 (16) | −0.0009 (12) | 0.0010 (13) | −0.0065 (13) |
O2 | 0.0215 (16) | 0.036 (2) | 0.0239 (15) | −0.0103 (14) | −0.0002 (13) | −0.0042 (14) |
O3 | 0.0287 (17) | 0.0103 (15) | 0.0278 (16) | −0.0041 (13) | 0.0007 (14) | 0.0014 (12) |
N1 | 0.0142 (17) | 0.0122 (17) | 0.0176 (16) | −0.0025 (13) | 0.0007 (14) | 0.0005 (14) |
C1 | 0.020 (2) | 0.014 (2) | 0.0138 (19) | 0.0007 (16) | −0.0026 (17) | 0.0016 (17) |
C2 | 0.019 (2) | 0.0124 (19) | 0.017 (2) | −0.0042 (16) | −0.0017 (18) | 0.0007 (17) |
C3 | 0.014 (2) | 0.014 (2) | 0.022 (2) | −0.0005 (18) | −0.0019 (17) | 0.0026 (17) |
C4 | 0.013 (2) | 0.021 (2) | 0.0173 (19) | 0.0002 (18) | −0.0028 (17) | 0.0007 (17) |
C5 | 0.017 (2) | 0.018 (2) | 0.0125 (18) | 0.0024 (17) | −0.0019 (17) | 0.0006 (16) |
C6 | 0.015 (2) | 0.012 (2) | 0.022 (2) | −0.0016 (17) | −0.0008 (16) | −0.0019 (17) |
C7 | 0.020 (2) | 0.016 (2) | 0.0150 (19) | −0.0036 (16) | 0.0035 (18) | 0.0010 (18) |
C8 | 0.023 (2) | 0.012 (2) | 0.035 (2) | 0.0007 (17) | 0.0045 (19) | −0.0042 (19) |
C9 | 0.021 (2) | 0.014 (2) | 0.017 (2) | −0.0021 (17) | −0.0038 (17) | 0.0040 (17) |
Au2 | 0.01305 (9) | 0.01716 (9) | 0.01567 (8) | −0.00069 (6) | −0.00083 (6) | −0.00075 (7) |
Cl5 | 0.0175 (5) | 0.0231 (6) | 0.0438 (6) | −0.0053 (4) | −0.0106 (4) | 0.0110 (5) |
Cl6 | 0.0267 (5) | 0.0168 (5) | 0.0337 (5) | −0.0003 (4) | −0.0055 (5) | 0.0013 (5) |
Cl7 | 0.0207 (5) | 0.0338 (7) | 0.0386 (5) | 0.0027 (5) | −0.0126 (4) | −0.0025 (6) |
Cl8 | 0.0214 (5) | 0.0186 (5) | 0.0250 (5) | −0.0039 (4) | 0.0006 (5) | −0.0026 (5) |
O1A | 0.0209 (15) | 0.0143 (15) | 0.0228 (15) | 0.0028 (13) | 0.0048 (12) | 0.0007 (12) |
O2A | 0.0314 (17) | 0.0112 (15) | 0.0426 (17) | 0.0021 (13) | 0.0172 (14) | 0.0081 (15) |
O3A | 0.0201 (15) | 0.0119 (15) | 0.0256 (14) | 0.0002 (12) | −0.0030 (12) | −0.0022 (12) |
N1A | 0.021 (2) | 0.0099 (18) | 0.0193 (18) | −0.0019 (15) | 0.0020 (15) | 0.0002 (14) |
C1A | 0.016 (2) | 0.015 (2) | 0.0163 (19) | −0.0005 (17) | −0.0038 (17) | 0.0017 (17) |
C2A | 0.015 (2) | 0.014 (2) | 0.0187 (19) | 0.0012 (16) | 0.0000 (16) | 0.0031 (16) |
C3A | 0.016 (2) | 0.0102 (19) | 0.0172 (19) | 0.0000 (15) | 0.0007 (16) | −0.0015 (16) |
C4A | 0.016 (2) | 0.013 (2) | 0.0176 (19) | 0.0012 (16) | −0.0013 (16) | 0.0017 (17) |
C5A | 0.023 (2) | 0.013 (2) | 0.015 (2) | 0.0005 (16) | 0.0019 (18) | 0.0040 (17) |
C6A | 0.021 (2) | 0.015 (2) | 0.026 (2) | −0.0039 (16) | 0.001 (2) | 0.0044 (19) |
C7A | 0.017 (2) | 0.013 (2) | 0.030 (2) | −0.0030 (17) | −0.0013 (19) | −0.0009 (19) |
C8A | 0.030 (2) | 0.015 (2) | 0.021 (2) | −0.0008 (19) | 0.0007 (18) | −0.0024 (18) |
C9A | 0.019 (2) | 0.015 (2) | 0.0195 (19) | −0.0030 (18) | 0.0031 (16) | 0.0002 (17) |
Au1—Cl4 | 2.2704 (10) | C4—C5 | 1.528 (6) |
Au1—Cl3 | 2.2796 (9) | C4—H4A | 0.9900 |
Au1—Cl1 | 2.2890 (8) | C4—H4B | 0.9900 |
Au1—Cl2 | 2.2994 (10) | C5—C6 | 1.526 (6) |
Au2—Cl7 | 2.2752 (9) | C5—H5A | 1.0000 |
Au2—Cl6 | 2.2803 (10) | C6—C7 | 1.552 (5) |
Au2—Cl5 | 2.2805 (10) | C6—H6A | 0.9900 |
Au2—Cl8 | 2.2895 (10) | C6—H6B | 0.9900 |
O1—C9 | 1.209 (5) | C7—H7A | 0.9900 |
O2—C9 | 1.322 (5) | C7—H7B | 0.9900 |
O2—H2 | 0.8400 | C8—H8A | 0.9800 |
O3—C3 | 1.419 (5) | C8—H8B | 0.9800 |
O3—H3 | 0.8400 | C8—H8C | 0.9800 |
O1A—C9A | 1.214 (5) | C1A—C2A | 1.535 (5) |
O2A—C9A | 1.320 (5) | C1A—C7A | 1.535 (6) |
O2A—H2A | 0.8400 | C1A—H1C | 1.0000 |
O3A—C3A | 1.428 (4) | C2A—C9A | 1.525 (5) |
O3A—H3A | 0.8400 | C2A—C3A | 1.563 (5) |
N1—C8 | 1.492 (5) | C2A—H2C | 1.0000 |
N1—C1 | 1.514 (5) | C3A—C4A | 1.518 (5) |
N1—C5 | 1.518 (5) | C3A—H3C | 1.0000 |
N1—H1 | 0.9300 | C4A—C5A | 1.536 (5) |
N1A—C8A | 1.486 (5) | C4A—H4A1 | 0.9900 |
N1A—C1A | 1.526 (5) | C4A—H4A2 | 0.9900 |
N1A—C5A | 1.531 (5) | C5A—C6A | 1.530 (6) |
N1A—H1A | 0.9300 | C5A—H5B | 1.0000 |
C1—C2 | 1.532 (6) | C6A—C7A | 1.559 (6) |
C1—C7 | 1.543 (6) | C6A—H6A1 | 0.9900 |
C1—H1B | 1.0000 | C6A—H6A2 | 0.9900 |
C2—C9 | 1.512 (6) | C7A—H7A1 | 0.9900 |
C2—C3 | 1.552 (5) | C7A—H7A2 | 0.9900 |
C2—H2B | 1.0000 | C8A—H8A1 | 0.9800 |
C3—C4 | 1.519 (5) | C8A—H8A2 | 0.9800 |
C3—H3B | 1.0000 | C8A—H8A3 | 0.9800 |
Cl4—Au1—Cl3 | 90.59 (4) | C1—C7—H7A | 110.7 |
Cl4—Au1—Cl1 | 89.06 (4) | C6—C7—H7A | 110.7 |
Cl3—Au1—Cl1 | 179.60 (4) | C1—C7—H7B | 110.7 |
Cl4—Au1—Cl2 | 178.76 (4) | C6—C7—H7B | 110.7 |
Cl3—Au1—Cl2 | 89.62 (4) | H7A—C7—H7B | 108.8 |
Cl1—Au1—Cl2 | 90.73 (4) | N1—C8—H8A | 109.5 |
Cl7—Au2—Cl6 | 89.50 (4) | N1—C8—H8B | 109.5 |
Cl7—Au2—Cl5 | 179.76 (5) | H8A—C8—H8B | 109.5 |
Cl6—Au2—Cl5 | 90.65 (4) | N1—C8—H8C | 109.5 |
Cl7—Au2—Cl8 | 89.73 (4) | H8A—C8—H8C | 109.5 |
Cl6—Au2—Cl8 | 178.18 (4) | H8B—C8—H8C | 109.5 |
Cl5—Au2—Cl8 | 90.12 (4) | O1—C9—O2 | 123.7 (4) |
C9—O2—H2 | 109.5 | O1—C9—C2 | 124.2 (4) |
C3—O3—H3 | 109.5 | O2—C9—C2 | 112.0 (4) |
C9A—O2A—H2A | 109.5 | N1A—C1A—C2A | 108.6 (3) |
C3A—O3A—H3A | 109.5 | N1A—C1A—C7A | 101.9 (3) |
C8—N1—C1 | 112.3 (3) | C2A—C1A—C7A | 112.7 (3) |
C8—N1—C5 | 114.0 (3) | N1A—C1A—H1C | 111.1 |
C1—N1—C5 | 102.2 (3) | C2A—C1A—H1C | 111.1 |
C8—N1—H1 | 109.4 | C7A—C1A—H1C | 111.1 |
C1—N1—H1 | 109.4 | C9A—C2A—C1A | 111.3 (3) |
C5—N1—H1 | 109.4 | C9A—C2A—C3A | 111.2 (3) |
C8A—N1A—C1A | 113.3 (3) | C1A—C2A—C3A | 109.4 (3) |
C8A—N1A—C5A | 113.4 (3) | C9A—C2A—H2C | 108.3 |
C1A—N1A—C5A | 101.8 (3) | C1A—C2A—H2C | 108.3 |
C8A—N1A—H1A | 109.3 | C3A—C2A—H2C | 108.3 |
C1A—N1A—H1A | 109.3 | O3A—C3A—C4A | 112.5 (3) |
C5A—N1A—H1A | 109.3 | O3A—C3A—C2A | 111.6 (3) |
N1—C1—C2 | 107.7 (3) | C4A—C3A—C2A | 111.6 (3) |
N1—C1—C7 | 102.3 (3) | O3A—C3A—H3C | 106.9 |
C2—C1—C7 | 112.8 (3) | C4A—C3A—H3C | 106.9 |
N1—C1—H1B | 111.2 | C2A—C3A—H3C | 106.9 |
C2—C1—H1B | 111.2 | C3A—C4A—C5A | 110.4 (3) |
C7—C1—H1B | 111.2 | C3A—C4A—H4A1 | 109.6 |
C9—C2—C1 | 112.9 (3) | C5A—C4A—H4A1 | 109.6 |
C9—C2—C3 | 108.3 (3) | C3A—C4A—H4A2 | 109.6 |
C1—C2—C3 | 110.0 (3) | C5A—C4A—H4A2 | 109.6 |
C9—C2—H2B | 108.5 | H4A1—C4A—H4A2 | 108.1 |
C1—C2—H2B | 108.5 | N1A—C5A—C6A | 102.0 (3) |
C3—C2—H2B | 108.5 | N1A—C5A—C4A | 106.5 (3) |
O3—C3—C4 | 107.8 (3) | C6A—C5A—C4A | 113.4 (4) |
O3—C3—C2 | 110.6 (3) | N1A—C5A—H5B | 111.5 |
C4—C3—C2 | 111.8 (3) | C6A—C5A—H5B | 111.5 |
O3—C3—H3B | 108.9 | C4A—C5A—H5B | 111.5 |
C4—C3—H3B | 108.9 | C5A—C6A—C7A | 105.7 (3) |
C2—C3—H3B | 108.9 | C5A—C6A—H6A1 | 110.6 |
C3—C4—C5 | 111.9 (3) | C7A—C6A—H6A1 | 110.6 |
C3—C4—H4A | 109.2 | C5A—C6A—H6A2 | 110.6 |
C5—C4—H4A | 109.2 | C7A—C6A—H6A2 | 110.6 |
C3—C4—H4B | 109.2 | H6A1—C6A—H6A2 | 108.7 |
C5—C4—H4B | 109.2 | C1A—C7A—C6A | 105.1 (3) |
H4A—C4—H4B | 107.9 | C1A—C7A—H7A1 | 110.7 |
N1—C5—C6 | 102.2 (3) | C6A—C7A—H7A1 | 110.7 |
N1—C5—C4 | 106.8 (3) | C1A—C7A—H7A2 | 110.7 |
C6—C5—C4 | 113.4 (3) | C6A—C7A—H7A2 | 110.7 |
N1—C5—H5A | 111.3 | H7A1—C7A—H7A2 | 108.8 |
C6—C5—H5A | 111.3 | N1A—C8A—H8A1 | 109.5 |
C4—C5—H5A | 111.3 | N1A—C8A—H8A2 | 109.5 |
C5—C6—C7 | 105.2 (3) | H8A1—C8A—H8A2 | 109.5 |
C5—C6—H6A | 110.7 | N1A—C8A—H8A3 | 109.5 |
C7—C6—H6A | 110.7 | H8A1—C8A—H8A3 | 109.5 |
C5—C6—H6B | 110.7 | H8A2—C8A—H8A3 | 109.5 |
C7—C6—H6B | 110.7 | O1A—C9A—O2A | 119.2 (4) |
H6A—C6—H6B | 108.8 | O1A—C9A—C2A | 122.5 (4) |
C1—C7—C6 | 105.2 (3) | O2A—C9A—C2A | 118.3 (4) |
C8—N1—C1—C2 | 163.4 (3) | C8A—N1A—C1A—C2A | 165.3 (3) |
C5—N1—C1—C2 | −74.0 (4) | C5A—N1A—C1A—C2A | −72.6 (4) |
C8—N1—C1—C7 | −77.6 (4) | C8A—N1A—C1A—C7A | −75.6 (4) |
C5—N1—C1—C7 | 45.0 (4) | C5A—N1A—C1A—C7A | 46.6 (4) |
N1—C1—C2—C9 | −59.5 (4) | N1A—C1A—C2A—C9A | −62.4 (4) |
C7—C1—C2—C9 | −171.6 (4) | C7A—C1A—C2A—C9A | −174.6 (3) |
N1—C1—C2—C3 | 61.5 (4) | N1A—C1A—C2A—C3A | 60.8 (4) |
C7—C1—C2—C3 | −50.6 (4) | C7A—C1A—C2A—C3A | −51.3 (4) |
C9—C2—C3—O3 | −43.2 (5) | C9A—C2A—C3A—O3A | −52.5 (4) |
C1—C2—C3—O3 | −167.0 (3) | C1A—C2A—C3A—O3A | −175.9 (3) |
C9—C2—C3—C4 | 76.9 (4) | C9A—C2A—C3A—C4A | 74.4 (4) |
C1—C2—C3—C4 | −46.9 (4) | C1A—C2A—C3A—C4A | −49.0 (4) |
O3—C3—C4—C5 | 169.2 (3) | O3A—C3A—C4A—C5A | 177.7 (3) |
C2—C3—C4—C5 | 47.4 (5) | C2A—C3A—C4A—C5A | 51.3 (4) |
C8—N1—C5—C6 | 74.9 (4) | C8A—N1A—C5A—C6A | 76.1 (4) |
C1—N1—C5—C6 | −46.5 (4) | C1A—N1A—C5A—C6A | −45.9 (4) |
C8—N1—C5—C4 | −165.7 (3) | C8A—N1A—C5A—C4A | −164.7 (3) |
C1—N1—C5—C4 | 72.9 (4) | C1A—N1A—C5A—C4A | 73.2 (4) |
C3—C4—C5—N1 | −61.4 (4) | C3A—C4A—C5A—N1A | −64.6 (4) |
C3—C4—C5—C6 | 50.5 (5) | C3A—C4A—C5A—C6A | 46.8 (5) |
N1—C5—C6—C7 | 29.4 (4) | N1A—C5A—C6A—C7A | 27.3 (4) |
C4—C5—C6—C7 | −85.3 (4) | C4A—C5A—C6A—C7A | −86.8 (4) |
N1—C1—C7—C6 | −26.3 (4) | N1A—C1A—C7A—C6A | −29.1 (4) |
C2—C1—C7—C6 | 89.1 (4) | C2A—C1A—C7A—C6A | 87.1 (4) |
C5—C6—C7—C1 | −2.0 (4) | C5A—C6A—C7A—C1A | 1.0 (4) |
C1—C2—C9—O1 | 49.5 (5) | C1A—C2A—C9A—O1A | 38.2 (5) |
C3—C2—C9—O1 | −72.5 (5) | C3A—C2A—C9A—O1A | −84.1 (5) |
C1—C2—C9—O2 | −134.0 (4) | C1A—C2A—C9A—O2A | −143.3 (4) |
C3—C2—C9—O2 | 104.1 (4) | C3A—C2A—C9A—O2A | 94.5 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1 | 0.93 | 1.99 | 2.768 (4) | 140 |
N1A—H1A···O1A | 0.93 | 1.97 | 2.721 (5) | 137 |
O3A—H3A···Cl1 | 0.84 | 2.43 | 3.219 (3) | 157 |
O2—H2···Cl2i | 0.84 | 2.32 | 3.159 (3) | 173 |
O3—H3···O3Ai | 0.84 | 1.95 | 2.672 (4) | 144 |
O2A—H2A···O3ii | 0.84 | 1.82 | 2.624 (4) | 161 |
Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) −x+1, y−1/2, −z+1/2. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | (C9H16NO3)4(H3O)[AuCl4]5·6H2O | (C9H16NO3)[AuCl4] |
Mr | 2565.86 | 524.99 |
Crystal system, space group | Orthorhombic, P212121 | Orthorhombic, P212121 |
Temperature (K) | 100 | 100 |
a, b, c (Å) | 9.2153 (16), 15.299 (3), 51.544 (8) | 10.0276 (1), 15.7339 (2), 18.6416 (2) |
V (Å3) | 7267 (2) | 2941.15 (6) |
Z | 4 | 8 |
Radiation type | Cu Kα | Cu Kα |
µ (mm−1) | 25.82 | 25.50 |
Crystal size (mm) | 0.35 × 0.11 × 0.10 | 0.23 × 0.17 × 0.10 |
Data collection | ||
Diffractometer | Bruker SMART APEXII CCD area-detector diffractometer | Bruker SMART APEXII CCD area-detector diffractometer |
Absorption correction | Numerical (SADABS; Sheldrick, 2001) | Numerical (SADABS; Sheldrick, 2001) |
Tmin, Tmax | 0.040, 0.182 | 0.067, 0.185 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 43458, 12355, 12097 | 22091, 5121, 5053 |
Rint | 0.057 | 0.035 |
(sin θ/λ)max (Å−1) | 0.602 | 0.598 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.099, 1.08 | 0.018, 0.047, 1.08 |
No. of reflections | 12355 | 5121 |
No. of parameters | 761 | 332 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
w = 1/[σ2(Fo2) + (0.0529P)2 + 20.0246P] where P = (Fo2 + 2Fc2)/3 | w = 1/[σ2(Fo2) + (0.0249P)2] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 3.15, −1.94 | 0.93, −0.69 |
Absolute structure | Flack (1983), 5212 Friedel pairs | Flack (1983), with 2199 Friedel pairs |
Absolute structure parameter | 0.031 (10) | −0.004 (7) |
Computer programs: APEX2 (Bruker, 2006), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 2008).
O10···Cl14i | 3.217 (11) | O2C···O5 | 2.600 (12) |
O5···Cl1ii | 3.214 (8) | O3A···O4iv | 2.773 (11) |
Cl9···O1Ciii | 3.150 (8) | O3D···O4 | 2.676 (11) |
Cl15···Au2 | 3.361 (3) | O3C···O3B | 2.739 (11) |
O4···O5 | 2.893 (12) | O6···O2Bv | 2.646 (14) |
O6···O7 | 3.012 (12) | O8···O1Dvi | 2.967 (11) |
O7···O8 | 2.820 (11) | O7···O1Bv | 2.883 (11) |
O9···O10 | 2.707 (15) | O6···O3C | 2.713 (12) |
O2A···O9 | 2.538 (12) |
Symmetry codes: (i) −x+1, y+1/2, −z+3/2; (ii) −x+1, y−1/2, −z+3/2; (iii) x+1, y, z; (iv) −x, y+1/2, −z+3/2; (v) x−1, y, z; (vi) x−1, y+1, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H1NA···O1A | 0.93 | 2.04 | 2.792 (11) | 137 |
N1B—H1NB···O1B | 0.93 | 1.99 | 2.757 (11) | 138 |
N1C—H1NC···O1C | 0.93 | 2.00 | 2.734 (12) | 134 |
N1D—H1ND···O1D | 0.93 | 2.07 | 2.814 (11) | 136 |
O3D—H3D1···O1C | 0.84 | 1.90 | 2.743 (10) | 179 |
O3B—H3B1···O1Aii | 0.84 | 2.02 | 2.852 (10) | 172 |
O2D—H2D1···O3Aii | 0.84 | 1.81 | 2.645 (10) | 180 |
Symmetry code: (ii) −x+1, y−1/2, −z+3/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1 | 0.93 | 1.99 | 2.768 (4) | 140 |
N1A—H1A···O1A | 0.93 | 1.97 | 2.721 (5) | 137 |
O3A—H3A···Cl1 | 0.84 | 2.43 | 3.219 (3) | 157 |
O2—H2···Cl2i | 0.84 | 2.32 | 3.159 (3) | 173 |
O3—H3···O3Ai | 0.84 | 1.95 | 2.672 (4) | 144 |
O2A—H2A···O3ii | 0.84 | 1.82 | 2.624 (4) | 161 |
Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) −x+1, y−1/2, −z+1/2. |
L-Ecgonine and L-cocaine are among 22 naturally occurring alkaloids found in the leaves of the coca plant, Erythroxylum coca (Ensing & Hummelen, 1991). L-Ecgonine (C9H15NO3), a nitrogen-bridged bicyclo[3.2.1]octane, is both a precursor and a human metabolite of L-cocaine. It is the hydroxy acid obtained by complete acidic, alkaline or enzymatic hydrolysis of both ester functions in L-cocaine, and can crystallize as the hydrochloride salt (Wood et al., 2008). During in vitro storage of blood, cocaine can undergo selective monohydrolysis via two mechanisms: partial saponification under alkaline conditions to yield benzoylecgonine, or enzymatic hydrolysis catalyzed by pseudocholinesterase to yield methylecgonine (ecgonine methyl ester) (Isenschmid et al., 1989). Both of these breakdown products can degrade further to a common stable product, L-ecgonine (Klingmann et al., 2001), which is consistently observed in post mortem blood specimens and whole-blood specimens of cocaine addicts, thus demonstrating the utility of L-ecgonine as a stable marker for recent cocaine use (Logan, 2001). Because time, temperature, drug concentration and the presence of preservative agents can all affect the stability of cocaine in blood and plasma (Baselt, 1983), L-ecgonine, the fully hydrolyzed degradation product, is a much better marker for cocaine use than either benzoylecgonine or ecgonine methyl ester.
The use of the gold(III) chloride microcrystal test in the identification and differentiation of L-cocaine from its seven stereoisomers (Allen et al., 1981) and similar related structures, i.e. L-ecgonine (Amelink, 1938), has been described by the current authors in a previous paper (Wood et al., 2007).
In studying the three-dimensional structures of several cocaine derivatives, the authors have previously reported those of the gold(III) tetrachloride salt of L-cocaine (Wood et al., 2007) and of the hydrochloride salt of L-ecgonine (Wood et al., 2008). We report here the structures of the gold(III) tetrachloride salt of L-ecgonine, which exists as both the hydrate form, (I), (C9H16NO3)4(H3O)[AuCl4]5.6H2O, and the anhydrous form, (II), (C9H16NO3)[AuCl4].
The asymmetric unit of (I) contains four monopositive N-protonated L-ecgonine cations surrounded by five [AuCl4]- anions. One of the seven water molecules has to be a hydronium ion or one of the hydroxy groups of the cations has to be diprotonated, for charge balance. However, the additional proton was not found and we have no evidence as to whether it is consistently positioned in the structure. Each of the four L-ecgonine cations has its quaternary N-bound H atom intramolecularly hydrogen-bonded to its carboxyl C═O group (Table 2, entries 1–4), as was found in (-)-norcocaine [N···O = 2.306 (2) Å; Zhu et al., 1994], in the tetrachloroaurate(III) salt of L-cocaine [N···O = 2.756 (6) Å; Wood et al., 2007] and in the hydrochloride salt of L-ecgonine [N···O = 2.7608 (17) Å; Wood et al., 2008]. All of the L-ecgonine cations in (I) have ordered carboxyl groups, except for molecule B where C9B—O1B = 1.260 (13) and C9B—O2B = 1.280 (14) Å. As a result of this disorder, the acid H atom of this cation could not be found.
Four of the five [AuCl4]- anions of (I) exhibit square-planar geometry, with mean deviations from the five-atom plane ranging from 0.006 (3) (for the Au3 anion) to 0.013 (2) Å (for the Au4 anion). The fifth anion (containing Au1) has a mean deviation from the plane of 0.048 (3) Å, with the AuIII center 0.0070 (11) Å above the best plane. In this anion, one trans pair of Cl atoms is above the best plane by 0.051 (2) Å and the other pair below the plane by 0.054 (2) Å. In a search of the Cambridge Structural Database (CSD, Version 5.29, update of 2008; Allen, 2002), 106 structures containing the gold(III) tetrachloride anion were found, several containing multiple [AuCl4]- species, for a total of 136 different anions. Of these, 71 are essentially flat, and the rest have varying degrees of bowing of the square-planar arrangement of the [AuCl4]- moiety. Only three show flexing larger than that found in (I): tetra(methylthio)tetrathiafulvalene bis(tetrachloroaurate) (refcode GEHSOB01; Jones, 1989), the gold(III) tetrachloride salt of L-cocaine (refcode SETLOT; Wood et al., 2007) and N-benzyl-N,N-bis(pyridinium-2-ylmethyl)amine chloride tetrachloroaurate(III) (refcode NIBWEB; Cao et al., 2007).
Within the asymmetric unit of (I) there are three close Cl···O distances (Table 1), two of which involve water molecules and are 0.05–0.06 Å less than the relevant van der Waals sum of 3.27 Å [Standard reference?], while the third is proximal to the acid carbonyl of an L-ecgonine cation and is shorter than the van der Waals distance by 0.12 Å. Additionally, a single close contact exists between atom Cl15 of the Au4 anion and Au2 (Table 1), which is slightly longer than the shortest reported Au—Cl···Au contact of 3.281 Å found in the CSD (refcode VIMFUS; Dvorkin et al., 1990). Since this Au4 anion uniquely resides in a cavity surrounded predominantly by O atoms, we speculate that this close contact is influenced by its location.
Intermolecular hydroxy-to-carbonyl hydrogen bonds (Table 2, entries 5 and 6) and the one acid-to-hydroxy hydrogen bond (entry 7) are the only interactions where the H atoms involved in the bonding were reliably found.
Within the structure of (I), a network of water molecules was found. It contains close contacts of various types (see Table 1): acid-to-water (entries 9 and 10), hydroxy-to-water (entries 11 and 12), hydroxy-to-hydroxy (entry 13), water-to-acid (entry 14), water-to-carboxyl (entries 15 and 16) and water-to-hydroxy (entry 17). Although the H atoms involved in these bonds could not be found in difference electron-density maps, the proximity of the donor–acceptor atoms clearly demonstrates that hydrogen bonding exists throughout the structure and forms a network of water molecules which threads its way through the cations and anions.
The cations are all joined into a network by either hydrogen bonds or close contacts, through either their hydroxy or their acid functional groups, to adjacent hydration water molecules. These contacts, plus those between the water molecules, form a two-dimensional layer approximately 3.55 Å thick containing all of the O atoms present in the structure and extending in both the a and b cell directions (Fig. 2). These layers are interleaved with sheets of [AuCl4]- anions, recurring every quarter of the cell along c. Four of the five anions lie within the alternating parallel sheets of [AuCl4]- anions, but the Au4 anion resides within the stratum of O atoms.
The anhydrous salt, (II), of the same toxicologically important marker for cocaine (Fig. 3) shows that the cation and anion are again in close proximity to each other, as was found in (I) and in the gold(III) tetrachloride salt of L-cocaine. Each of the two unique L-ecgonine cations has its quaternary N-bound H atom intramolecularly hydrogen-bonded to its carboxyl C═O group (Table 3).
The two independent [AuCl4]- anions of (II) show a bowing of the square-planar arrangement. The Au1 anion has a mean deviation from the plane of 0.0132 (11) Å, with the AuIII center 0.0082 (4) Å below the best plane. One trans pair of Cl atoms is above the best plane by 0.160 (5) Å and the other below the plane by 0.120 (5) Å. The Au2 anion has a mean deviation from the plane of 0.0174 (13) Å, with the AuIII center 0.0117 (5) Å below the best plane. One trans pair of Cl atoms is above the best plane by 0.212 (6) Å and the other below the plane by 0.152 (6) Å.
There are two close hydrogen-bonded contacts involving Cl atoms, one between the hydroxy atom O3A and atom Cl1, and the other between the acid atom O2 and atom Cl2i [Table 3; symmetry code: (i) x - 1, y + 1/2, -z + 1/2]. There are also two hydrogen bonds involving the hydroxy O atoms, between atoms O3 and O3Ai, and between atoms O2A and O3ii [symmetry code: (ii) -x + 1, y - 1/2, -z + 1/2]. The latter involves the acid H atom in the rare anti configuration.
The powder diffraction pattern of the microcrystals (formed as described by Wood et al., 2007) does not singularly match either the hydrated structure, (I), or the anhydrous structure, (II), of the ecgonine AuIII chloride complex, but has peaks associated with both of them. There are more peaks that are similar to the pure single-crystal generated powder pattern of the anhydrous material, (II), than that of the hydrate, (I). However, we cannot conclusively say that the microcrystal test material is one or the other, or a combination of the two (possibly because of the humidity or lack thereof in the laboratory preparations), or a completely different form.