Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803000813/su6009sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803000813/su6009Isup2.hkl |
CCDC reference: 204654
Equimolar amounts (0.065 mmol each) of 18-crown-6, potassium and tetrachloroaurate(III) were dissolved in methanol. Single crystals of the reduced gold complex with the potassium crown ether complex were grown from diffusion of diethyl ether into the methanolic solution of the mixture. 1H NMR (500 MHz, CDCl3, TMS): δ 3.66 (t, CH2). 13C NMR (125 MHz, CDCl3, TMS): δ 70.4 (CH2). MS (FAB): m/z 303 (18 C6 + K)+.
Crystal decay was determined by remeasuring the first 50 frames of data at the end of data collection and comparing the intensities from the first and last runs. All H atoms were constrained using the AFIX 23 parameter in SHELXL97. Residual peaks > 0.5 e Å−3 were near atom Au1.
Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Fig. 1. The structure of (I), with displacement ellipsoids drawn at the 50% probability level. | |
Fig. 2. The packing diagram for (I). H atoms have been omitted for clarity. |
[K(C12H24O6)][AuCl2] | F(000) = 552 |
Mr = 571.28 | Dx = 2.034 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 8.7583 (4) Å | Cell parameters from 4929 reflections |
b = 7.9237 (4) Å | θ = 3.0–30.5° |
c = 13.8393 (6) Å | µ = 8.42 mm−1 |
β = 103.785 (2)° | T = 100 K |
V = 932.76 (8) Å3 | Prism, colourless |
Z = 2 | 0.31 × 0.16 × 0.11 mm |
Bruker APEX diffractometer | 2800 independent reflections |
Radiation source: fine-focus sealed tube | 2470 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.019 |
ω scans | θmax = 30.5°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996; Blessing, 1995) | h = −11→12 |
Tmin = 0.180, Tmax = 0.458 | k = −10→11 |
7528 measured reflections | l = −19→17 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.017 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.047 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0272P)2 + 0.1888P] where P = (Fo2 + 2Fc2)/3 |
2800 reflections | (Δ/σ)max < 0.001 |
103 parameters | Δρmax = 1.66 e Å−3 |
0 restraints | Δρmin = −1.15 e Å−3 |
[K(C12H24O6)][AuCl2] | V = 932.76 (8) Å3 |
Mr = 571.28 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 8.7583 (4) Å | µ = 8.42 mm−1 |
b = 7.9237 (4) Å | T = 100 K |
c = 13.8393 (6) Å | 0.31 × 0.16 × 0.11 mm |
β = 103.785 (2)° |
Bruker APEX diffractometer | 2800 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996; Blessing, 1995) | 2470 reflections with I > 2σ(I) |
Tmin = 0.180, Tmax = 0.458 | Rint = 0.019 |
7528 measured reflections |
R[F2 > 2σ(F2)] = 0.017 | 0 restraints |
wR(F2) = 0.047 | H-atom parameters constrained |
S = 1.04 | Δρmax = 1.66 e Å−3 |
2800 reflections | Δρmin = −1.15 e Å−3 |
103 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
K1 | 0.5000 | 0.5000 | 0.5000 | 0.01508 (12) | |
Au1 | 0.5000 | 1.0000 | 0.5000 | 0.01592 (4) | |
Cl1 | 0.68346 (5) | 0.83457 (6) | 0.45636 (3) | 0.02577 (9) | |
O1 | 0.21989 (13) | 0.60565 (15) | 0.54438 (9) | 0.0194 (2) | |
C2 | 0.11670 (19) | 0.7040 (2) | 0.47040 (13) | 0.0224 (3) | |
H2A | 0.1581 | 0.8201 | 0.4696 | 0.027* | |
H2B | 0.0114 | 0.7103 | 0.4848 | 0.027* | |
C3 | 0.10560 (19) | 0.6203 (2) | 0.37168 (13) | 0.0224 (3) | |
H3A | 0.0726 | 0.5013 | 0.3745 | 0.027* | |
H3B | 0.0265 | 0.6788 | 0.3194 | 0.027* | |
O4 | 0.25593 (13) | 0.62761 (14) | 0.34885 (8) | 0.0190 (2) | |
C5 | 0.2505 (2) | 0.5690 (2) | 0.25103 (13) | 0.0218 (3) | |
H5A | 0.1803 | 0.6420 | 0.2016 | 0.026* | |
H5B | 0.2089 | 0.4524 | 0.2428 | 0.026* | |
C6 | 0.4136 (2) | 0.5733 (2) | 0.23527 (12) | 0.0221 (3) | |
H6A | 0.4110 | 0.5486 | 0.1648 | 0.026* | |
H6B | 0.4597 | 0.6869 | 0.2514 | 0.026* | |
O7 | 0.50738 (14) | 0.44985 (17) | 0.29831 (9) | 0.0188 (2) | |
C8 | 0.6639 (2) | 0.4462 (2) | 0.28588 (14) | 0.0213 (3) | |
H8A | 0.7113 | 0.5600 | 0.2974 | 0.026* | |
H8B | 0.6637 | 0.4112 | 0.2172 | 0.026* | |
C9 | 0.75772 (19) | 0.3232 (2) | 0.35897 (12) | 0.0208 (3) | |
H9A | 0.7008 | 0.2146 | 0.3556 | 0.025* | |
H9B | 0.8606 | 0.3020 | 0.3434 | 0.025* |
U11 | U22 | U33 | U12 | U13 | U23 | |
K1 | 0.0135 (3) | 0.0188 (3) | 0.0135 (3) | 0.00158 (13) | 0.0043 (2) | 0.00069 (13) |
Au1 | 0.01654 (6) | 0.01508 (6) | 0.01601 (6) | −0.00128 (2) | 0.00365 (4) | −0.00002 (2) |
Cl1 | 0.02336 (18) | 0.02127 (18) | 0.0352 (2) | −0.00012 (16) | 0.01197 (16) | −0.00407 (17) |
O1 | 0.0200 (5) | 0.0181 (5) | 0.0204 (6) | 0.0045 (4) | 0.0057 (4) | −0.0006 (4) |
C2 | 0.0160 (7) | 0.0211 (8) | 0.0312 (9) | 0.0048 (6) | 0.0077 (6) | 0.0052 (7) |
C3 | 0.0137 (7) | 0.0262 (9) | 0.0255 (9) | −0.0013 (6) | 0.0011 (6) | 0.0049 (7) |
O4 | 0.0161 (5) | 0.0229 (6) | 0.0169 (6) | −0.0010 (4) | 0.0018 (4) | −0.0003 (4) |
C5 | 0.0261 (8) | 0.0193 (8) | 0.0167 (8) | −0.0003 (6) | −0.0015 (6) | −0.0014 (6) |
C6 | 0.0305 (9) | 0.0204 (9) | 0.0147 (8) | 0.0009 (7) | 0.0042 (6) | 0.0014 (6) |
O7 | 0.0206 (6) | 0.0195 (6) | 0.0174 (6) | −0.0003 (5) | 0.0064 (5) | 0.0019 (5) |
C8 | 0.0258 (9) | 0.0221 (8) | 0.0195 (8) | −0.0045 (7) | 0.0125 (7) | −0.0028 (7) |
C9 | 0.0200 (7) | 0.0204 (8) | 0.0250 (8) | −0.0010 (6) | 0.0118 (6) | −0.0045 (6) |
K1—O1 | 2.7955 (11) | O1—C2 | 1.4251 (19) |
K1—O4 | 2.7994 (11) | C2—C3 | 1.501 (3) |
K1—O7 | 2.8353 (12) | C3—O4 | 1.427 (2) |
K1—Cl1 | 3.2306 (5) | O4—C5 | 1.421 (2) |
K1—Au1 | 3.9618 (2) | C5—C6 | 1.497 (2) |
Au1—Cl1 | 2.2644 (4) | C6—O7 | 1.432 (2) |
Au1—K1i | 3.9619 (2) | O7—C8 | 1.422 (2) |
O1—C9ii | 1.4214 (19) | C8—C9 | 1.500 (3) |
O1ii—K1—O1 | 180.0 | Cl1—K1—Au1 | 34.856 (8) |
O1—K1—O4 | 60.14 (3) | Au1iii—K1—Au1 | 180.0 |
O1—K1—O4ii | 119.86 (3) | Cl1—Au1—Cl1iv | 180.0 |
O4—K1—O4ii | 180.0 | Cl1—Au1—K1 | 54.627 (11) |
O1—K1—O7 | 119.03 (3) | Cl1iv—Au1—K1 | 125.373 (11) |
O4—K1—O7 | 60.49 (3) | Cl1—Au1—K1i | 125.373 (11) |
O1—K1—O7ii | 60.97 (3) | Cl1iv—Au1—K1i | 54.627 (11) |
O4—K1—O7ii | 119.51 (3) | K1—Au1—K1i | 180.0 |
O7—K1—O7ii | 180.0 | Au1—Cl1—K1 | 90.517 (14) |
O1—K1—Cl1 | 107.27 (3) | C9ii—O1—C2 | 112.39 (13) |
O4—K1—Cl1 | 83.64 (2) | C9ii—O1—K1 | 113.20 (9) |
O4ii—K1—Cl1 | 96.36 (2) | C2—O1—K1 | 116.45 (9) |
O7—K1—Cl1 | 78.58 (3) | O1—C2—C3 | 107.75 (13) |
O1—K1—Cl1ii | 72.73 (3) | O4—C3—C2 | 108.70 (13) |
O4—K1—Cl1ii | 96.36 (2) | C5—O4—C3 | 111.98 (13) |
O7—K1—Cl1ii | 101.42 (3) | C5—O4—K1 | 116.12 (9) |
Cl1—K1—Cl1ii | 180.0 | C3—O4—K1 | 113.62 (9) |
O1—K1—Au1iii | 107.43 (2) | O4—C5—C6 | 108.34 (13) |
O4—K1—Au1iii | 111.17 (2) | O7—C6—C5 | 108.92 (14) |
O7—K1—Au1iii | 81.94 (3) | C8—O7—C6 | 111.69 (13) |
Cl1—K1—Au1iii | 145.144 (8) | C8—O7—K1 | 111.76 (10) |
O1—K1—Au1 | 72.57 (2) | C6—O7—K1 | 111.08 (10) |
O4—K1—Au1 | 68.83 (2) | O7—C8—C9 | 108.71 (14) |
O7—K1—Au1 | 98.06 (3) | O1ii—C9—C8 | 107.91 (13) |
O1ii—K1—Au1—Cl1 | 5.60 (3) | O1ii—K1—O4—C5 | 26.95 (11) |
O1—K1—Au1—Cl1 | −174.40 (3) | O1—K1—O4—C5 | −153.05 (11) |
O4—K1—Au1—Cl1 | −110.37 (3) | O7—K1—O4—C5 | 12.39 (10) |
O4ii—K1—Au1—Cl1 | 69.63 (3) | O7ii—K1—O4—C5 | −167.61 (10) |
O7—K1—Au1—Cl1 | −56.41 (3) | Cl1—K1—O4—C5 | 92.84 (10) |
O7ii—K1—Au1—Cl1 | 123.59 (3) | Cl1ii—K1—O4—C5 | −87.16 (10) |
O1ii—K1—Au1—Cl1iv | −174.40 (3) | Au1iii—K1—O4—C5 | −54.54 (11) |
O1—K1—Au1—Cl1iv | 5.60 (3) | Au1—K1—O4—C5 | 125.46 (11) |
O4—K1—Au1—Cl1iv | 69.63 (3) | O1ii—K1—O4—C3 | 158.97 (10) |
O4ii—K1—Au1—Cl1iv | −110.37 (3) | O1—K1—O4—C3 | −21.03 (10) |
O7—K1—Au1—Cl1iv | 123.59 (3) | O7—K1—O4—C3 | 144.40 (11) |
O7ii—K1—Au1—Cl1iv | −56.41 (3) | O7ii—K1—O4—C3 | −35.60 (11) |
Cl1ii—K1—Au1—Cl1iv | 0.02 (10) | Cl1—K1—O4—C3 | −135.15 (10) |
O1ii—K1—Cl1—Au1 | −174.40 (3) | Cl1ii—K1—O4—C3 | 44.85 (10) |
O1—K1—Cl1—Au1 | 5.60 (3) | Au1iii—K1—O4—C3 | 77.47 (10) |
O4—K1—Cl1—Au1 | 61.59 (3) | Au1—K1—O4—C3 | −102.53 (10) |
O4ii—K1—Cl1—Au1 | −118.41 (3) | C3—O4—C5—C6 | −177.34 (13) |
O7—K1—Cl1—Au1 | 122.70 (3) | K1—O4—C5—C6 | −44.57 (15) |
O7ii—K1—Cl1—Au1 | −57.30 (3) | O4—C5—C6—O7 | 67.51 (17) |
O4—K1—O1—C9ii | −146.63 (11) | C5—C6—O7—C8 | 179.26 (14) |
O4ii—K1—O1—C9ii | 33.37 (11) | C5—C6—O7—K1 | −55.22 (15) |
O7—K1—O1—C9ii | −161.12 (10) | O1ii—K1—O7—C8 | −17.46 (10) |
O7ii—K1—O1—C9ii | 18.88 (10) | O1—K1—O7—C8 | 162.54 (10) |
Cl1—K1—O1—C9ii | −74.83 (10) | O4—K1—O7—C8 | 148.09 (12) |
Cl1ii—K1—O1—C9ii | 105.17 (10) | O4ii—K1—O7—C8 | −31.91 (12) |
Au1iii—K1—O1—C9ii | 108.52 (10) | Cl1—K1—O7—C8 | 58.99 (11) |
Au1—K1—O1—C9ii | −71.48 (10) | Cl1ii—K1—O7—C8 | −121.01 (11) |
O4—K1—O1—C2 | −14.08 (10) | Au1iii—K1—O7—C8 | −91.95 (11) |
O4ii—K1—O1—C2 | 165.92 (10) | Au1—K1—O7—C8 | 88.05 (11) |
O7—K1—O1—C2 | −28.58 (12) | O1ii—K1—O7—C6 | −142.94 (12) |
O7ii—K1—O1—C2 | 151.42 (12) | O1—K1—O7—C6 | 37.06 (12) |
Cl1—K1—O1—C2 | 57.72 (11) | O4—K1—O7—C6 | 22.62 (10) |
Cl1ii—K1—O1—C2 | −122.28 (11) | O4ii—K1—O7—C6 | −157.38 (10) |
Au1iii—K1—O1—C2 | −118.93 (10) | Cl1—K1—O7—C6 | −66.49 (10) |
Au1—K1—O1—C2 | 61.07 (10) | Cl1ii—K1—O7—C6 | 113.51 (10) |
C9ii—O1—C2—C3 | 178.36 (13) | Au1iii—K1—O7—C6 | 142.57 (11) |
K1—O1—C2—C3 | 45.44 (15) | Au1—K1—O7—C6 | −37.43 (11) |
O1—C2—C3—O4 | −65.27 (17) | C6—O7—C8—C9 | 176.08 (14) |
C2—C3—O4—C5 | −172.93 (13) | K1—O7—C8—C9 | 50.94 (15) |
C2—C3—O4—K1 | 53.07 (15) | O7—C8—C9—O1ii | −70.56 (17) |
Symmetry codes: (i) x, y+1, z; (ii) −x+1, −y+1, −z+1; (iii) x, y−1, z; (iv) −x+1, −y+2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [K(C12H24O6)][AuCl2] |
Mr | 571.28 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 100 |
a, b, c (Å) | 8.7583 (4), 7.9237 (4), 13.8393 (6) |
β (°) | 103.785 (2) |
V (Å3) | 932.76 (8) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 8.42 |
Crystal size (mm) | 0.31 × 0.16 × 0.11 |
Data collection | |
Diffractometer | Bruker APEX diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996; Blessing, 1995) |
Tmin, Tmax | 0.180, 0.458 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7528, 2800, 2470 |
Rint | 0.019 |
(sin θ/λ)max (Å−1) | 0.714 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.017, 0.047, 1.04 |
No. of reflections | 2800 |
No. of parameters | 103 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.66, −1.15 |
Computer programs: SMART (Bruker, 1998), SMART, SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL.
Although cations are the dominant species in the coordination chemistry of crown ethers, the counter-anions can also play an important role in the binding mode, cation–anion pairing, and the geometry of the structure (Bajaj & Poonia, 1988). Current interests of a number of researchers are thus also focused on the coordination chemistry of anions (Bianchi et al., 1997). Our interests in this area involve exploring dual host receptors (Kavallieratos et al., 2000; Qian et al., 2001), expanding previous work to anionic metal complexes.
The unique formula unit of (I) is shown in Fig. 1. The linear dichloroaurate(I) and the 18-crown-6 potassium complex form infinite alternating cation/anion layers, separated by 3.9618 (2) Å, along the b axis (Fig. 2).
The crown ether adopts D3 d symmetry as observed in most other complexes of 18-crown-6 (Dunitz et al., 1974). The potassium ion is located at the center of the crown and is coordinated to the six O atoms with an average K···O bond distance of 2.810 Å, which is consistent with previously reported results (2.801 Å; Sieler et al., 1974). The linear dichloroaurate anions sit above and below the plane of the crown ether with one of the Cl atoms closer to the potassium [3.2306 (5) Å] than is the gold [3.9618 (2) Å]. The presence of two chlorides approximately above and below the potassium ion thus completes a pseudo-hexagonal bipyrimidal coordination sphere for the alkali metal ion.