Synthesis and structure of gold and copper complexes: [Ph 3PhCH2P]+[AuCl4]-, [NH(C2H4OH)3]+[AuCl 4]- ? H2O, and [Ph3EtP] 2 + [Cu2Cl6]2-

Article abstract of DOI:10.1134/S0036023610090135

Triphenylbenzylphosphonium tetrachloroaurate (I) and triethanolammonium tetrachloroaurate hydrate (II) were prepared by reacting tetrachloroauric acid in acetone with triphenylbenzylphosphonium and triethanolammonium, respectively. Triphenylethylphosphonium hexachlorodicuprate (III) was synthesized from triphenylethylphosphonium chloride and copper chloride in acetone. The crystal structures of complexes I to III were determined by single-crystal X-ray diffraction. The phosphorus atoms in complex I have a nearly undistorted tetrahedral coordination (CPC, 108.3°-110.6°; P-C, 1.788-1.793 A?). The coordination of nitrogen atoms in the cations of complex II is a distorted tetrahedron (CNC, 111.7°-112.4°). The square coordination of aurum in I and II is only slightly distorted: the ClAuCl angles are 89.6°-90.3° (I) and 89.5°-90.6° (II) and the Au-Cl distances are 2.256-2.278 A? I) and 2.280-2.285 A? (II). The phosphorus atoms in complex III are tetracoordinated (CPC, 106.34°-111.73°; P-C, 1.790-1.795 A?). The copper atoms in III have a distorted tetrahedral coordination (ClCuCl, 98.48°-144.85°; Cu-Cl, 2.1999-2.3263 A?). The central fragment Cu₂Cl₂ in the anion of complex III is bent relative to the Cu₂ axis (the chlorine atom deviates from the Cu₂Cl plane by 0.27 A?).

Full text of DOI:10.1134/S0036023610090135

ISSN 0036ꢀ0236, Russian Journal of Inorganic Chemistry, 2010, Vol. 55, No. 9, pp. 1415–1420. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © V.V. Sharutin, V.S. Senchurin, O.K. Sharutina, A.P. Pakusina, O.A. Fastovets, 2010, published in Zhurnal Neorganicheskoi Khimii, 2010, Vol. 55, No. 9,
pp. 1499–1505.
COORDINATION COMPOUNDS
Synthesis and Structure of Gold and Copper Complexes:
[Ph3PhCH2P]+[AuCl4]–, [NH(C2H4OH)3]+[AuCl4]– · H2O,
and [Ph3EtP]
+2 [Cu2Cl6]2–
V. V. Sharutin, V. S. Senchurin, O. K. Sharutina, A. P. Pakusina, and O. A. Fastovets
Blagoveshchensk State Pedagogical University, ul. Lenina 104, Blagoveshchensk, 675000 Russia.
Received December 23, 2008
Abstract—Triphenylbenzylphosphonium tetrachloroaurate (I) and triethanolammonium tetrachloroaurate
hydrate (II) were prepared by reacting tetrachloroauric acid in acetone with triphenylbenzylphosphonium
and triethanolammonium, respectively. Triphenylethylphosphonium hexachlorodicuprate (III) was syntheꢀ
sized from triphenylethylphosphonium chloride and copper chloride in acetone. The crystal structures of
complexes
have a nearly undistorted tetrahedral coordination (CPC, 108.3
dination of nitrogen atoms in the cations of complex II is a distorted tetrahedron (CNC, 111.7
square coordination of aurum in and II is only slightly distorted: the ClAuCl angles are 89.6
89.5 –90.6 II), and the Au–Cl distances are 2.256–2.278 Å ( ) and 2.280–2.285 Å (II). The phosphorus
atoms in complex III are tetracoordinated (CPC, 106.34 –111.73 ; P–C, 1.790–1.795 Å). The copper
atoms in III have a distorted tetrahedral coordination (ClCuCl, 98.48 –144.85 ; Cu–Cl, 2.1999–2.3263 Å).
I
to III were determined by singleꢀcrystal Xꢀray diffraction. The phosphorus atoms in complex
–110.6 ; P–C, 1.788–1.793 Å). The coorꢀ
–112.4 ). The
–90.3 ) and
I
°
°
°
°
I
°
°
(I
°
°
(
I
°
°
°
°
The central fragment Cu2Cl2 in the anion of complex III is bent relative to the Cu2 axis (the chlorine atom
deviates from the Cu2Cl plane by 0.27 Å).
DOI: 10.1134/S0036023610090135
Salts containing tetrachloroaurate anion and
IR (
, cm–1): 516, 548, 581, 749, 839, 910, 1001,
ν
ammonium or stibonium cations are described in the 1032, 1058, 1091, 1110, 1214, 1265, 1336, 1349, 1362,
literature [1, 2]. Here, the syntheses and structures of 1381, 1408, 1446, 1479, 1607, 2027, 2751, 2894, 2951,
triphenylbenzylphosphonium tetrachloroaurate (I), 3016.
triethanolammonium tetrachloroaurate hydrate (II),
and triphenylethylphosphonium hexachlorodicuprate
For C6H18O4Cl4NAu anal. calcd. (%): C, 14.20; H,
3.55.
(
III) are described.
Found (%): C, 14.07; H, 3.71.
Synthesis of complex III. To a solution of 0.33 g
(1.00 mmol) of triphenylethylphosphonium chloride
dissolved in acetone, 0.17 g (1.00 mmol) of copper(II)
chloride dihydrate was added. The solution color
changed to claret. The solvent was evaporated, and
0.38 g (82%) of claret crystals of III were obtained;
mp 98°C.
EXPERIMENTAL
Synthesis of complex I. A mixture of 0.50 g
(1.29 mmol) of triphenylbenzylphosphonium chloꢀ
ride and 0.53 g (1.29 mmol) of tetrachloroauric acid
hydrate in 30 mL of acetone was kept at 20
°
С
for 24 h.
IR (
, cm–1): 449, 480, 507, 533, 690, 739, 850,
ν
After removing the solvent, complex
Yield 0.75 g (85%); mp 171°C.
I was formed.
895, 993, 1029, 1114, 1159, 1190, 1315, 1341, 1444,
1484, 1587, 2922, 2989, 3051.
For C40H40P2Cu2Cl6 anal. calcd. (%): C, 52.06; H,
4.34.
IR (
, cm–1): 442, 452, 497, 513, 579, 614, 686,
ν
703, 717, 729, 740, 747, 834, 918, 996, 1110, 1317,
1335, 1399, 1440, 1456, 1483, 1588, 2901, 2942, 3059.
For C25H22PAuCl4 anal. calcd. (%): C, 43.35; H,
3.18.
Found (%): C, 49.90; H, 3.14.
IR spectra of complexes I to III were recorded as
Found (%): C, 42.84; H, 3.04.
KBr pellets on a 1201 IR spectrometer.
Synthesis of complex II. To a solution of 0.27 g
Singleꢀcrystal Xꢀray diffraction studies of I–III
(1.47 mmol) of triethanolammonium hydrochloride were performed using a BrukerꢀNonius X8Apex difꢀ
in 20 mL of acetone, 0.61 g (1.47 mmol) of tetrachloꢀ fractometer (Mo
K
radiation,
λ
= 0.71073 Å, graphite
roauric acid hydrate was added. The mixture was monochromator). Correction for absorption was
stirred for 5 min and kept at 20°C for 24 h. After applied empirically (SADABS) [3]. The structures
removing acetone, 0.40 g (55%) of transparent, yellow III were solved by a direct method and refined by the
crystals of complex were obtained; mp = 169°C. fullꢀmatrix leastꢀsquares method in the anisotropic
α
I–
I
1415

1416
SHARUTIN et al.
Table 1. Crystal data, experimental details, and refinement parameters for complexes I–III
Complex
Parameter
I
II
III
T
, K
296(1)
294(1)
100(2)
Crystal system
Space group
Triclinic
Monoclinic
Monoclinic
P21/ñ
P21/ñ
P
1
a
, Å
, Å
7.7446(4)
9.7620(5)
17.1070(9)
78.590(2)
89.401(2)
85.812(2)
1264.38(11)
2
8.3708(19)
22.887(6)
7.6965(18)
90
12.4451(9)
15.8013(9)
20.8174(11)
90
b
c,
Å
α
, deg
β
,
deg
deg
94.229(19)
90
90.4240(10)
90
γ,
V
Z
, Å3
1470.5(6)
4
4093.6(4)
8
ρcalcd, g/cm3
, mm–1
(000)
1.818
2.290
1.497
μ
6.315
10.729
960
1.537
F
668
1880
Crystal shape (dimensions, mm)
θ range, deg
Prism (0.32
×
0.22
×
0.13)
Prism (0.26
×
0.24
×
0.22)
Prism (0.15
×
0.10 × 0.08)
1.21–31.37
1.78–27.57
1.96–26.00
Reflection index range
–10
–13
–22
≤
≤
≤
h
k
≤
10,
11,
23
–10
–29
0
≤
≤
≤
h
k
≤
10,
0,
–15
–19
–25
≤
≤
≤
h
k
≤
15,
19,
25
≤
≤
≤
l
≤
l
≤
10
l
≤
Reflections measured
14649
3632
int = 0.0392)
17416
Independent reflections
6866 (
Rint = 0.0251)
3386 (R
4034 (
Rint = 0.0192)
Reflections with
I
> 2
σ
(
I
)
4976
2878
154
3821
Refinement variables
GOOF
284
226
1.011
1.072
1.069
R
R
indices on F2
>
2
σ
(
F2
)
R
1 = 0.0214, wR2 = 0.0466
1 = 0.0349, wR2 = 0.0509
–0.499/0.654
R
1 = 0.0329, wR2 = 0.0845
1 = 0.0372, wR2 = 0.0882
–1.992/1.696
R
1 = 0.0258, wR2 = 0.0684
1 = 0.0283, wR2 = 0.0699
–0.326/0.539
indices (all data)
R
R
R
Residual electron density
(min/max), e/Å3
approximation for nonꢀhydrogen atoms (SHELXꢀ97)
[4]. Selected crystal data and refinement parameters
[Ph3PhCH2P]Cl + HAuCl4 ⋅ 4H2O
+
–
for structures
I–III are compiled in Table 1; atomic
[Ph3PhCH2P] [AuCl4] + HCl + 4H2O,
coordinates and thermal parameters are presented in
Table 2; and selected bond lengths and bond angles are
shown in Table 3.
I
NH(C2H4OH)3Cl + HAuCl4 ⋅ 4H2O
+
–
[NH(C2H4OH)3] [AuCl4] ⋅ H2O
II
RESULTS AND DISCUSSION
+
HCl + 3H2O.
Ionic complexes of metals with ammonium, phosꢀ
phonium, stibonium, and bismuthonium cations are
usually synthesized from onium salts and metal halides
[5–11]. Substitution reactions with acids containing
complex anions [2] are virtually not used for this purꢀ
Crystals of compounds
I and II consist of tetraꢀ
chloroaurate anions and [Ph3PhCH2P]+ and
[NH(C2H4OH)3]+ cations, respectively (Figs. 1, 2).
The phosphorus atoms in the cation of complex
a virtually undistorted tetrahedral coordination.
I have
pose. We synthesized complexes
I and II by reacting
triphenylbenzylphosphonium or triethanolammoꢀ
The values of the CPC bond angles lie within the
nium chlorides with tetrachloroauric acid in acetone: range from 108.3(9)° to 110.6(4)°; the P–Calk bond
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 55 No. 9 2010

SYNTHESIS AND STRUCTURE OF GOLD AND COPPER COMPLEXES
1417
Table 2. Atomic coordinates (×104) and equivalent isotropic thermal parameters (×103) for structures I–III
Atom
x
y
z
U
eq, Å2
Atom
Cl(4)
x
y
z
U
eq, Å2
I
8986(2)
5123(6)
7628(6)
3354(7)
4653(5)
4003(7)
5015(9)
6099(7)
7153(8)
3376(7)
2374(8)
8390(6)
1233(1)
8387(2)
7936(2)
7447(2)
8535(2)
8963(3)
8967(3)
8762(2)
8277(3)
8332(3)
7867(3)
6873(2)
III
6629(2)
5201(7)
9065(6)
8231(7)
8727(6)
7369(8)
5847(8)
9769(8)
10501(8)
9873(9)
41(1)
53(1)
45(1)
56(1)
29(1)
40(1)
45(1)
38(1)
41(1)
41(1)
Au(1)
Au(2)
Cl(1)
Cl(2)
Cl(3)
Cl(4)
P(1)
0
0
0
5000
0
36.79(5) O(1)
38.08(5) O(2)
0
–697.8(15) 2328.7(8) 4690.7(7)
–1910.0(12) –321.3(8) 4063.4(5)
–2848.5(9) –417.6(10) 101.0(5)
–234.9(11) 1071.4(9) 1068.7(5)
4979.2(8) 2990.4(6) 2532.4(4)
92.9(4)
70.3(3)
67.3(2)
65.6(2)
O(3)
N(1)
C(1)
C(2)
31.39(13) C(3)
C(11)
C(12)
C(13)
C(14)
C(15)
C(16)
C(21)
C(22)
C(23)
C(24)
C(25)
C(26)
C(31)
C(32)
C(33)
C(34)
C(35)
C(36)
C(40)
C(41)
C(42)
C(43)
C(44)
C(45)
C(46)
4672(4)
4006(4)
2752(4)
2131(4)
2765(3)
4056(3)
4434(3)
3102(4)
2659(5)
3510(5)
4818(4)
5291(4)
4164(3)
3214(3)
2589(4)
2897(4)
3820(4)
4462(3)
7324(3)
7988(3)
8852(3)
9374(4)
9058(4)
8235(4)
7711(4)
2926(3)
3380(3)
4477(4)
5112(3)
4664(3)
3578(2)
1231(2)
682(3)
4133.9(15) 43.7(6)
C(4)
C(5)
C(6)
O(1w)
4797.7(17) 54.0(8)
4713.3(18) 57.1(8)
3977.3(18) 52.0(7)
3305.7(16) 40.0(6)
3381.9(14) 33.6(5)
2559.6(15) 35.3(5)
3040.4(19) 59.9(9)
8936(10) 53(2)
10621(7)
54(1)
P(1)
C(1)
C(2)
5323(1)
5050(1)
4311(1)
3979(2)
4395(2)
5139(2)
5474(2)
4120(1)
3224(2)
2246(2)
2166(2)
3051(2)
4032(2)
5660(1)
5312(2)
5711(2)
6458(2)
6814(2)
6413(1)
6446(1)
6773(2)
4303(1)
3108(1)
4362(1)
3895(1)
3220(1)
–844(1)
19(1)
22(1)
28(1)
35(1)
37(1)
37(1)
29(1)
23(1)
31(1)
39(1)
38(1)
35(1)
28(1)
20(1)
27(1)
33(1)
33(1)
30(1)
24(1)
24(1)
29(1)
21(1)
27(1)
24(1)
30(1)
2225(1) –1226(1)
2200(1) –1729(1)
1430(1) –1984(1)
697(1) –1728(1)
706(1) –1236(1)
–661(4)
–1435(3)
–892(3)
440(3)
3025(2)
2539(2)
2056(2)
83.4(13) C(3)
70.3(10) C(4)
55.3(8)
C(5)
2066.8(17) 44.3(6)
1627.1(14) 33.1(5)
1097.7(15) 42.6(6)
399.4(18) 53.8(8)
231.0(17) 54.2(8)
754.6(17) 48.0(7)
1452.1(15) 39.1(6)
2584.0(15) 36.8(5)
2473.5(15) 35.7(5)
1781.2(16) 43.9(6)
C(6)
1474(1)
3508(1)
3769(1)
3872(1)
3725(1)
3464(1)
3350(1)
–976(1)
–426(1)
–780(1)
–473(1)
178(1)
4091(2)
3536(3)
4397(3)
5783(3)
6349(3)
5520(3)
2995(3)
4436(3)
4980(3)
6332(3)
7143(3)
6596(3)
5249(3)
II
C(7)
C(8)
C(9)
C(10)
C(11)
C(12)
C(13)
C(14)
C(15)
C(16)
C(17)
C(18)
C(19)
C(20)
Cu(1)
Cl(3)
Cl(2)
Cl(1)
529(1)
232(1)
3997(1) –1435(1)
4832(1) –1381(1)
5437(1) –1798(1)
5218(1) –2256(1)
4387(1) –2305(1)
3772(1) –1896(1)
1662(2)
2222(2)
57.7(8)
58.4(8)
2920.2(19) 54.2(8)
3049.1(16) 44.7(6)
3151(1)
4029(1)
–300(1)
–50(1)
Au(1)
Cl(1)
Cl(2)
Cl(3)
9406(1)
6818(2)
11988(2)
9813(2)
278(1)
7396(1)
8135(2)
6653(2)
8184(2)
25(1)
39(1)
41(1)
39(1)
7830(1) –1818(1)
6868(1) –1542(1)
216(1)
351(1)
8542(1)
–910(1)
–674(1)
7905(1) –2899(1)
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 55 No. 9 2010

1418
SHARUTIN et al.
Table 3. Selected bond lengths (d) and bond angles (ω) for structures I–IV
Bond d,
Å
Angle
ω
, deg
I
Au(1)–Cl(1)
2.2562(8)
2.2562(8)
2.2738(8)
2.2738(8)
2.2712(7)
2.2712(7)
2.2782(8)
2.2782(8)
1.789(2)
1.790(2)
1.793(2)
1.820(2)
1.381(4)
1.390(3)
1.379(4)
1.365(4)
1.381(4)
1.390(3)
Cl(1)Au(1)Cl(1)#1
Cl(1)Au(1)Cl(2)
180.00
Au(1)–Cl(1)#1
Au(1)–Cl(2)
Au(1)–Cl(2)#1
Au(2)–Cl(3)
Au(2)–Cl(3)#2
Au(2)–Cl(4)#2
Au(2)–Cl(4)
P(1)–C(16)
89.66(3)
90.34(3)
90.34(3)
89.66(3)
180.0
Cl(1)#1Au(1)Cl(2)
Cl(1)Au(1)Cl(2)#1
Cl(1)#1Au(1)Cl(2)#1
Cl(2)Au(1)Cl(2)#1
Cl(3)Au(2)Cl(3)#2
Cl(3)Au(2)Cl(4)#2
Cl(3)#2Au(2)Cl(4)#2
Cl(3)Au(2)Cl(4)
Cl(3)#2Au(2)Cl(4)
Cl(4)#2Au(2)Cl(4)
C(16)P(1)C(21)
180.0
89.70(3)
90.30(3)
90.30(3)
89.70(3)
180.00(5)
108.95(11)
110.63(11)
109.29(12)
108.93(12)
108.40(12)
110.59(11)
P(1)–C(21)
P(1)–C(31)
P(1)–C(40)
C(11)–C(12)
C(11)–C(16)
C(12)–C(13)
C(13)–C(14)
C(14)–C(15)
C(15)–C(16)
Symmetry codes: #1) 1 –
C(16)P(1)C(31)
C(21)P(1)C(31)
C(16)P(1)C(40)
C(21)P(1)C(40)
C(31)P(1)C(40)
x
, –y, –z + 1; #2) –x, –y, –z.
II
Cl(3)Au(1)Cl(2)
Au(1)–Cl(3)
Au(1)–Cl(2)
Au(1)–Cl(4)
Au(1)–Cl(1)
O(1)–C(2)
O(2)–C(4)
O(3)–C(6)
N(1)–C(3)
N(1)–C(1)
N(1)–C(5)
2.2798(14)
2.2826(15)
2.2847(15)
2.2848(14)
1.423(8)
90.63(5)
179.46(5)
89.76(5)
90.03(5)
179.34(5)
89.58(5)
112.5(4)
112.0(4)
111.8(4)
110.6(5)
Cl(3)Au(1)Cl(4)
Cl(2)Au(1)Cl(4)
Cl(3)Au(1)Cl(1)
Cl(2)Au(1)Cl(1)
Cl(4)Au(1)Cl(1)
C(3)N(1)C(1)
C(3)N(1)C(5)
C(1)N(1)C(5)
C(2)C(1)N(1)
1.434(7)
1.400(9)
1.496(7)
1.505(7)
1.508(7)
III
P(1)–C(13)
P(1)–C(1)
1.7904(17)
1.7936(18)
1.7955(18)
1.7955(18)
2.1999(5)
2.2054(5)
2.3078(5)
2.3263(5)
C(1)P(1)C(7)
106.34(8)
111.73(9)
98.48(2)
144.85(2)
98.34(2)
99.53(2)
138.95(2)
87.46(2)
C(1)P(1)C(19)
P(1)–C(7)
Cl(2)Cu(1)Cl(3)
Cl(2)Cu(1)Cl(1)
Cl(3)Cu(1)Cl(1)
Cl(2)Cu(1)Cl(1)#1
Cl(3)Cu(1)Cl(1)#1
Cl(1)Cu(1)Cl(1)#1
P(1)–C(19)
Cu(1)–Cl(2)
Cu(1)–Cl(3)
Cu(1)–Cl(1)
Cu(1)–Cl(1)#1
Symmetry codes: #1) –x + 1, y, –z – 1/2.
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 55 No. 9 2010

SYNTHESIS AND STRUCTURE OF GOLD AND COPPER COMPLEXES
1419
anions (the sum of the radii of chlorine atoms is 3.6 Å).
Therefore, from two crystallographically independent
[AuCl4]– anions, all four Cl atoms of the Au(2) anion
Cl(2a)
Au(1)
Cl(1a)
Cl(2)
Cl(1)
are involved in formation of
НAlk⋅⋅⋅Cl(4) and
C(13)
C(14)
C(12)
Cl(3)⋅⋅⋅Cl(3') “basic” contacts, and only two chlorine
atoms of the Au(1) anion form
contacts.
НAlk⋅⋅⋅Cl(2) “basic”
C(11)
C(16)
C(21)
C(23)
C(22)
C(26)
C(15)
C(46)
Unlike the nearly ideal tetrahedral coordination of
the [Ph3PhCH2P]+ cation, the coordination of the
ammonium cation in complex II is more distorted
because of different volumes of the ligands (hydrogen
and three ethanol groups) bound to the nitrogen atom.
This is evidenced by an increase in the bond angle
CNC to 111.7(6)°–112.4(8)°. The molecule of water of
crystallization in complex II forms three strong hydroꢀ
gen bonds: two bonds with different ammonium catꢀ
C(45)
C(40)
C(24)
C(25)
P(1)
C(41)
C(44)
C(43)
Cl(4)
C(31)
C(32)
Cl(3)
C(42)
C(35)
C(33)
C(34)
Cl(3b)
Au(2)
ions (Н(2w)⋅⋅⋅O(2) 1.96
Å, О(1w)⋅⋅⋅Н(1) 2.07 Å) (the
sum of the van der Waals radii of H and O is 2.6
Å
Cl(4b)
[12]); and one bond (Н(1w)⋅⋅⋅Cl(4) 2.46 Å) with the
tetrachloroaurate anion.
Fig. 1. Structures of the cation and the anion in complex
(hydrogen atoms are omitted for clarity).
I
In the squareꢀplanar [AuCl4]– anion of complex II
,
the Au–Cl distances (2.280(1)–2.285(1) Å) and the
cisꢀangles ClAuCl (89.58 –90.63 ) vary within small
⋅⋅⋅Cl
°
°
(1.820(2) Å) is longer than the Р–СPh distances
(1.789(2), 1.790(2), 1.793(2) Å). Crystals of complex
contain two crystallographically independent squareꢀ
ranges of values. Crystals of II also contain five
Н
I
“basic” contacts (2.82–2.94 Å) between chlorine
atoms of the [AuCl4]– anions and the hydrogen atoms
planar anions of tetrachloroaurate, in which cisꢀangles of ethanol ligands.
ClAuCl are 89.6(6)°–90.3(4)° and 89.7(0)°–90.3(0)°.
Triphenylethylphosphonium hexachlorodicuprate
III) was synthesized from triphenylethylphosphoꢀ
nium chloride and copper chloride in acetone:
(
The Au–Cl distances vary within ranges of 2.2562(8)–
2.2738(8) Å and 2.2712(7)–2.2782(8) Å, respectively.
Hydrogen atoms of the methylene group of the triphꢀ
enylbenzylphosphonium cation are hydrogenꢀbonded
with chlorine atoms of [AuCl4]– anions: Н(40А)⋅⋅⋅Сl(2)
2[Ph3EtP]Cl + 2CuCl2 ⋅ 4H2O
+
[Ph3EtP] [Cu2Cl6]2– + 4H2O.
2
(2.88(4) Å) and Н(40В)⋅⋅⋅Сl(4) (2.92(4) Å) (the sum of
the van der Waals radii of H and Cl is 3.0 Å [12]). An
III
The phosphorus atoms in the cation of complex III
are tetracoordinated (CPC, 106.34°–111.73°; P–C,
interesting fact is the presence of the “basic” contact
Cl(3)⋅⋅⋅Cl(3') (3.337 Å)
between adjacent [Au(2)Cl4]– 1.790–1.795 Å) (Fig. 3).
Cl(1)
O(1W)
O(2)
Cl(3)
Au(1)
O(1)
C(2)
C(4)
Cl(4)
Cl(2)
C(1)
N(1)
C(3)
O(3)
C(5)
C(6)
Fig. 2. Structures of the cation and the anion in complex II (hydrogen atoms are omitted for clarity).
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 55 No. 9 2010

1420
SHARUTIN et al.
C(5)
C(4)
C(3)
C(6)
C(1)
C(2)
C(18)
C(19)
C(20)
P(1)
C(17)
C(16)
C(13)
C(12)
C(11)
C(8)
C(7)
C(14)
Cl(3)
C(15)
C(9)
C(10)
Cu(1)
Cl(1)
Cl(2)
Fig. 3. Structures of the cation and the anion in complex III (hydrogen atoms are omitted for clarity).
2. V. V. Sharutin, V. S. Senchurin, O. A. Fastovets, et al.,
The copper atoms in the centrosymmetric anion of
III have a distorted tetrahedral coordination (ClCuCl,
98.48°–144.85°; Cu–Cl, 2.1999–2.3263 Å). The
Koord. Khim. 34 (5), 373 (2008).
3. G. M. Sheldrick, SADABS: Program for Empirical Xꢀray
Absorption Correction (BrukerꢀNonius, 1990–2004).
4. G. M. Sheldrick, The SHELXꢀ97 Manual (Univ. of
Göttingen, Göttingen, 1997).
5. V. V. Sharutin, A. P. Pakusina, O. K. Sharutina, et al.,
Cu2Cl2 central fragment of the anion of complex III is
bent relative to the Сu2 axis (the chlorine atom deviꢀ
ates from the CuCl2 plane by 0.27 Å). The CuCl2 terꢀ
minal fragments of the anion are in staggered conforꢀ
mation, whereas such cations in a similar anion of the
Koord. Khim. 30 (8), 578 (2004).
complex Ph3PrP] ) are in eclipsed conꢀ
+ [Cu2Cl6]2– (IV
6. V. V. Sharutin, I. V. Egorova, O. A. Dorofeeva, et al.,
Zh. Neorg. Khim. 49 (11) 1821 (2004) [Russ. J. Inorg.
Chem. 49 (11), 1689 (2004)].
7. V. V. Sharutin, I. V. Egorova, O. K. Sharutina, et al.,
Koord. Khim. 31 (10), 791 (2005).
8. V. V. Sharutin, I. V. Egorova, A. P. Pakusina, et al., Zh.
2
formation [13]. Obviously, the difference observed in
the structures of the anions can be explained only by a
small change in the length of the alkyl radical in comꢀ
plexes III and IV
.
Obshch. Khim. 76 (8), 1393 (2006).
9. V. V. Sharutin, I. V. Egorova, O. K. Sharutina, and
E. A. Boyarkina, Koord. Khim. 34 (6) 468 (2008).
10. V. V. Sharutin, I. V. Egorova, E. A. Boyarkina, and O. K.
Sharutina, Zh. Obshch. Khim. 78 (7), 1083 (2008).
11. V. V. Sharutin, A. P. Pakusina, O. K. Sharutina, et al.,
ACKNOWLEDGMENTS
The authors thank E.V. Peresypkina, L.S. Ivashꢀ
kevich, and G.K. Fukin for the Xꢀray crystallographic
studies of complexes
I, II, and III, respectively.
Koord. Khim. 33 (2), 101 (2007).
REFERENCES
12. S. S. Batsanov, Zh. Neorg. Khim. 36 (12), 3015 (1991).
1. R. W. Buckley, P. C. Healy, and W. A. Loughlin, Aust. 13. D. Gatteschi, J. Goslar, W. Hilczer, et al., Inorg. Chem.
J. Chem. 50 (7), 775 (1997).
35 (5), 1148 (1996).
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 55 No. 9 2010