Uranyl complexes with methyl derivatives of alicyclic dioximes

Article abstract of DOI:10.1134/S0036023612070054

A reaction of uranyl dioxalate complexes with methyl derivatives of alicyclic a-dioximes, 3-methyl-1,2-cyclohexanedione dioxime and 3-methyl-1,2-cyclopentanedione dioxime, was studied. The structure of (CN ₃H₆)₄[(UO_2<

Full text of DOI:10.1134/S0036023612070054

ISSN 0036ꢀ0236, Russian Journal of Inorganic Chemistry, 2012, Vol. 57, No. 7, pp. 945–952. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © A.G. Beirakhov, I.M. Orlova, E.G. Il’in, A.S. Kanishcheva, A.V. Churakov, Yu.N. Mikhailov, 2012, published in Zhurnal Neorganicheskoi Khimii, 2012,
Vol. 57, No. 7, pp. 1019–1026.
COORDINATION COMPOUNDS
Uranyl Complexes with Methyl Derivatives of Alicyclic Dioximes
A. G. Beirakhov, I. M. Orlova, E. G. Il’in, A. S. Kanishcheva, A. V. Churakov, and Yu. N. Mikhailov
Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences,
Leninskii pr. 31, Moscow, 119991 Russia
Received December 19, 2011
Abstract—A reaction of uranyl dioxalate complexes with methyl derivatives of alicyclic
3ꢀmethylꢀ1,2ꢀcyclohexanedione dioxime and 3ꢀmethylꢀ1,2ꢀcyclopentanedione dioxime, was studied.
The structure of (CN3H6)4[(UO2)2(C6H8N2O2)(CO3)(C2O4)2] (C6H10N2O2) 2H2O and
NH4(CN3H6)3[(UO2)2(C7H10N2O2)(CO3)(C2O4)2] 2H2O based on binuclear complex anions with carbonꢀ
α
ꢀdioximes,
⋅
⋅
⋅
ate–dioximate fragment was studied by Xꢀray diffraction.
DOI: 10.1134/S0036023612070054
We showed previously that the reaction of uranyl uranyl complexes is cis tetradentate bridging binding.
compounds with ꢀdioximes of different structure led
α
This coordination mode is possible only in the presꢀ
ence of a second bridging ligand: for example, either
carbonate group or (E, Z) isomer of ligand itself can
play such a role in oxalate uranyl complexes with 1,2ꢀ
cyclohexanedione dioxime [1, 2].
to formation of complexes with different modes of
oxime coordination to the central atom owing not
only to conformational (the arrangement of oxime
groups relative to –C–C– bond) but also to isomeric
(the mutual orientation of oxygen atoms of oxime
groups) changes in the ligands. Conformational
changes in the ligands are typical for uranyl complexes
The reaction of dioxalate uranyl compounds with
1,2ꢀcyclohexanedione dioxime leads to the partial
isomerization of the ligand to give a complex with two
bridging dioximate groups in different isomeric
forms: anti isomer with tridentate bridging coordinaꢀ
tion mode and amphi isomer with pentadentate bindꢀ
with
α
ꢀdioximes containing acyclic aliphatic substituꢀ
ents [1], while the geometrical (
E,
Z) isomerism of
α
ꢀ
dioximes was observed only in uranyl complexes with
alicyclic dioximes [2] whose structural feature is the
fixed cis orientation of the oxime groups. Therefore,
the main coordination mode of alicyclic dioximes in ing [2].
3–
Tridentate
chelate bridging
coordination mode
O
(E)
N O
(E)
HO N
O
O
O2
U
UO2
O
O
O
O
N
(Z)
O
N
O
(E)
O
E,ZꢀPentadentate
chelate bridging
coordination mode
Similar reaction in the presence of carbonate ions leads to a complex with double carbonate–dioximate bridge [3].
945

946
BEIRAKHOV et al.
4–
aggregates of thin red lamellar crystals were separated
by filtration and dried on filter in air flow. Yield 1.2 g
(36%).
For (CN3H6)4[(UO2)2(C6H8N2O2)(CO3)(C2O4)2] ·
(C6H10N2O2) · 2H2O anal. calcd. (%): C, 18.90; N,
16.79; UO2, 40.46. Found (%): C, 19.10, 18.60; N,
16.89, 16.27; UO2, 40.63, 40.53.
O
O
O
O
O
O
O
O
O
O
O
O
O
UO2
O2U
N
N
Synthesis of ammonium guanidinium dioxalatoꢀ( ꢀ
µ
3ꢀmethylꢀ1,2ꢀcyclohexanedione
bonatodiuranylate dihydrate (II).
dioximato)ꢀµꢀcarꢀ
One gram of uranyl oxalate trihydrate and 0.22 g of
guanidinium carbonate were stirred under heating in
30 mL of water until complete dissolution. A solution
of 0.2 g of 3ꢀmethylꢀ1,2ꢀcyclohexanedione dioxime in
10 mL of ethanol and 5 g of NH4Cl (molar ratio U :
In this work we have studied the reaction of uranyl
dioxalate complexes with methyl derivatives of alicyꢀ
clic ꢀdioximes, 3ꢀmethylꢀ1,2ꢀcyclohexanedione
α
dioxime
dioxime.
and
3ꢀmethylꢀ1,2ꢀcyclopentanedione
C
2− : C H N O : C 2− = 1 : 1 : 0.5 : 0.5) was added
2O4 O3
7
12
2
2
to the resultant pale yellow solution under stirring and
heating. The orange solution was filtered and allowed
to crystallize in air. After 2–3 h, aggregates of small red
crystals were separated by filtration and dried on filter
in air flow. Yield 0.76 g (54%).
For NH4(CN3H6)3[(UO2)2(C7H10N2O2)(CO3)(C2O4)2] ·
2H2O anal. calcd. (%): C, 15.47; N, 14.43; UO2,
46.37. Found (%): C, 15.83, 15.77; N, 14.86, 14.92;
UO2, 46.65, 46.29.
EXPERIMENTAL
3ꢀMethylꢀ1,2ꢀcyclohexanedione dioxime (3ꢀ
methylꢀ1,2ꢀcyclopentanedione dioxime) was obtained
from the corresponding 1,2ꢀdiketones (Alfa Aesar)
according to the following procedure. A cold aqueous
solutions of NH2OH HCl (14 (15.7) g in 70 mL of
⋅
H2O) and NaOH (8 (9.1) g in 30 mL of H2O) were
mixed. An aqueous solution of diketone (10 g in 100 mL)
was slowly added with stirring under ice cooling.
Xꢀray diffraction study. Experimental data for comꢀ
pounds I and II were collected on a Bruker SMART
Molar ratio NH2OH HCl : NaOH : diketone = 1.27 :
⋅
APEX II automated diffractometer using Mo
K radiaꢀ
α
1.27 : 0.5. The resulting mixture was stirred under
cooling for 4 h and filtered. The precipitate was dried
on filter in air flow and then in vacuum dessicator.
Yield 9.3 (11.4) g, 75 (82)%.
tion (
λ
= 0.71073 Å, graphite monochromator) in the
ω
scan mode. Correction for absorption was made by
measuring the intensities of equivalent reflections [4].
The structures were solved by direct methods and
refined by fullꢀmatrix least squares on F2 for all nonꢀ
hydrogen atoms except for disordered groups in the
Synthesis of guanidinium (3ꢀmethylꢀ1,2ꢀcyclopenꢀ
tanedione dioxime)dioxalatoꢀ(
µ
ꢀ3ꢀmethylꢀ1,2ꢀcycloꢀ
pentanedione
dihydrate (I).
dioximato)ꢀ
µ
ꢀcarbonatodiuranylate
structure of compound
I (SHELXTLꢀPlus [5]). All
hydrogen atoms in both structures were placed in ideal
positions and refined using the riding model. In the
(a) Two grams of uranyl oxalate trihydrate and 1 g of
guanidinium oxalate were stirred under heating in 40
mL of water until complete dissolution. A solution of
0.7 g of 3ꢀmethylꢀ1,2ꢀcyclopentanedione dioxime in
20 mL of ethanol was added to the resultant pale yelꢀ
low solution under stirring and heating (molar ratio
2−
crystal of I, methyl group C(6) in the complex anion is
positionally disordered over the 3ꢀ and 5ꢀpositions of
the fiveꢀmembered ring with a population ratio of
0.6/04. The fiveꢀmembered ring in noncoordinated
organic molecule is conformationally disordered with
a population ratio of 0.7/0.3. Crystallographic data,
experimental details, and structure refining for comꢀ
U :
C
2O4
: C6H10N2O2 = 1 : 2 : 1) and neutralized
(dropwise) with a 25% ammonia solution until pH
~7–8. The yellowꢀorange solution was filtered and
allowed to crystallize in air. A mixture of yellowꢀgreen
crystals with small inclusion of aggregates of thin red
lamellar crystals formed after 3–4 days.
pounds I and II are given in Table 1, atomic coordiꢀ
nates and thermal parameters are presented in Table 2,
bond lengths and bond angles are shown in Table 3.
(b) Two grams of uranyl oxalate trihydrate and 1 g of
guanidinium oxalate were stirred under heating in 40 mL
of water until complete dissolution. A solution of 0.7 g
of 3ꢀmethylꢀ1,2ꢀcyclopentanedione dioxime in 20 mL
of ethanol and 0.44 g of guanidinium carbonate in 10 mL
2−
RESUTS AND DISCUSSION
The main structural units of crystal
ium cation, 3ꢀmethylꢀ1,2ꢀcyclopentanedione
I are guanidinꢀ
dioxime molecule, hydration water molecule, and
complex anion [(UO2)2(C6H8N2O2)(CO3)(C2O4)2]4–
(Fig. 1). The structure of crystal II is composed of
of water (molar ratio U :
C
2− : C H N O : C
=
2O4 O3
6
10
2
2
1 : 2 : 1 : 0.5) was added to the resultant pale yellow complex anion [(UO2)2(C7H10N2O2)(CO3)(C2O4)2]4–
,
solution under stirring and heating. The red solution hydration water molecules, and guanidinium and
was filtered and allowed to crystallize in air. After 2–3 h, ammonium cations (Fig. 2). In the binuclear complex
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 57 No. 7 2012

URANYL COMPLEXES WITH METHYL DERIVATIVES
947
Table 1. Crystallographic data, experimental parameters, and refining for structures of complexes
I
and II
Complex
I
II
Molecular formula
FW
C21H46N16O21U2
1334.74
C15H36N12O19U2
1164.57
Crystal dimensions, mm
Crystal symmetry
0.25
×
0.20
×
0.10
0.08
×
0.06 × 0.04
Triclinic
Orthorhombic
Space group
P
212121
173
P
1
T
, K
293
Unit cell parameters:
a
, Å
, Å
9.2474(6)
9.904(2)
17.400(4)
18.757(5)
90
b
14.8562(10)
16.8917(11)
68.504(1)
77.721(1)
89.793(1)
2102.7(2)
2
c
, Å
, deg
, deg
, deg
α
β
90
γ
90
V
Z
, Å3
3232.2(14)
4
ρcalc, g/cm3
(Mo
), mm–1
2.108
2.393
μ
K
7.787
10.104
2184
α
F(000)
1272
θ
range, deg
2.33–27.00
2.17–27.00
Index range
–11
–18
–21
≤
≤
≤
h
k
l
≤
≤
≤
11
18
21
–7
–21
–23
≤ h
≤ k
≤ l
≤
≤
≤
12
22
23
Total number of reflections
20250
int = 0.0243)
24705
7040 (Rint = 0.0496)
Number of independent reflections
Number of independent reflections
9177 (R
7182
6363
with I >
2σ(I)
Number of refined parameters
549
474
GOOF on F2
1.072
0.604
R1
[I >
2σ(
I)]
R
1 = 0.0328
R1 = 0.0253
wR2 (all data)
wR2 = 0.0902
wR2 = 0.0800
Residual electron density (max/min) e/Å3
2.584/–0.725
1.562/–0.758
anions of compounds
I and II, the composition of the bond distances U–O = 2.299–2.365 Å, U–N =
equatorial plane of uranium atom is the same (5O + 2.413–2.450 Å, OUN angles in threeꢀmembered
metalꢀcontaining rings are of 32.96
°
–33.82 , N–O
°
1N) and supplemented for each uranyl group by the
oxygen atom of bridging carbonato group, the two
oxygen atoms of bidentate chelate oxalato group, the
nitrogen and oxygen atoms of cis tetradentate bridging
dioximate ligand. The U–U distances in the binuclear
bond distances are 1.354–1.392 Å.
It should be noted that the O(1)C(10)O(2) bond
angle in structure in the bridging carbonate group is
126.5(5) , while the other two angles are substantially
smaller: O(1)C(10)O(3) is 116.8(5) and O(2)C(10)O(3)
is 116.6(5) . This duplicates the bond angle distribuꢀ
I
°
moieties (4.8465(4) Å in I and 4.7352(7) Å in II) are
°
comparable with the U–U distances in structurally
similar complexes with methylglyoxime (4.834 Å) [3]
and methylethylglyoxime (4.784 Å) [6]. The geometꢀ
°
tion in carbonate groups not only for structure II but
also for all previously studied uranyl complexes with
rical parameters of oximate groups in structures I and bridged carbonate ligand [3, 6–8]. Both crystal strucꢀ
II have values standard for bidentate coordination: tures have complex threeꢀdimensional networks of
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 57 No. 7 2012

948
BEIRAKHOV et al.
and II
Table 2. Atomic coordinates and thermal parameters in structures
Atom Atom
eq, Å2
C(34A) 0.428(4) –0.0254(14) 0.786(2)
I
x
y
z
U
x
y
z
U
eq, Å2
I
0.121(3)
U(1) 0.82669(2) 0.719998(13) 0.442821(12) 0.03830(7) C(34B) 0.3329(18) –0.0017(10) 0.7622(10) 0.121(3)
U(2) 0.70267(2) 0.726394(15) 0.734188(13) 0.04540(8) C(35) 0.3964(10) 0.0737(8) 0.7901(6) 0.112(3)
0.4060(3) 0.0553(10) C(36A) 0.509(3) 0.1592(16) 0.747(2) 0.121(3)
0.4807(3) 0.0539(10) C(36B) 0.5481(13) 0.0512(11) 0.8050(11) 0.121(3)
O(11) 0.7459(5) 0.8317(3)
O(12) 0.9078(4) 0.6069(3)
O(21) 0.6226(5) 0.8365(3)
O(22) 0.7878(5) 0.6168(3)
C(10) 0.6083(6) 0.6627(4)
O(1) 0.5817(4) 0.6414(3)
O(2) 0.5205(4) 0.6485(3)
O(3) 0.7399(4) 0.7045(3)
C(11) 0.8787(6) 0.7086(4)
C(12) 0.7338(6) 0.6434(4)
O(14) 0.9398(4) 0.7444(3)
O(15) 0.6819(4) 0.6486(3)
O(16) 0.9312(5) 0.7192(3)
O(17) 0.6801(5) 0.5944(3)
C(21) 0.5801(8) 0.7199(5)
C(22) 0.4519(8) 0.6677(6)
O(24) 0.6913(5) 0.7531(3)
O(25) 0.4763(5) 0.6574(4)
O(26) 0.5704(6) 0.7266(4)
O(27) 0.3349(7) 0.6420(5)
N(1) 1.0159(5) 0.8021(3)
N(2) 0.9437(5) 0.8061(3)
O(13) 1.0599(4) 0.8058(3)
O(23) 0.9209(4) 0.8127(3)
C(1) 1.1001(6) 0.8457(4)
C(2) 1.0644(6) 0.8483(4)
C(3) 1.1829(7) 0.9108(6)
C(4) 1.2583(10) 0.9724(7)
C(5) 1.2460(7) 0.9084(6)
C(6) 1.3659(12) 0.8404(8)
0.6932(3) 0.0654(11) O(4)
0.7749(3) 0.0570(10) O(5)
0.6080(4) 0.0469(13)
0.3893(4) 0.5622(3)
0.0642(5) 0.6827(3)
II
0.57676(2) 0.775287(13) 0.762228(13) 0.01874(7)
0.32569(3) 0.935898(15) 0.917017(14) 0.02339(7)
0.4155(3) 0.0600(10)
0.8508(3) 0.0790(14)
0.5466(3) 0.0495(9) U(1)
0.6802(3) 0.0555(10) U(2)
0.5952(2) 0.0508(10) O(11)
0.2471(4) 0.0486(13) O(12)
0.2982(4) 0.0445(12) O(21)
0.2909(2) 0.0541(10) O(22)
0.3728(2) 0.0507(9) C(10)
0.1691(2) 0.0580(11) O(1)
0.2665(3) 0.0572(10) O(2)
0.9339(4) 0.0663(18) O(3)
0.5228(5) 0.6841(3)
0.6307(5) 0.8669(3)
0.2442(5) 0.8595(3)
0.4064(5) 1.0146(3)
0.3186(7) 0.8469(5)
0.3386(5) 0.8080(3)
0.2217(5) 0.8896(3)
0.4167(5) 0.8434(3)
0.6922(6) 0.8056(3)
0.5452(6) 0.8972(4)
0.7754(5) 0.7664(3)
0.4757(5) 0.9432(3)
0.7429(7) 0.8258(4)
0.8871(8) 0.8066(6)
0.9292(9) 0.8167(5)
0.8728(8) 0.8903(5)
0.7170(8) 0.8887(5)
0.6607(8) 0.8726(4)
0.6659(10) 0.8328(6)
0.7400(7) 0.7029(4)
0.5978(8) 0.7086(4)
0.7553(5) 0.7184(3)
0.5120(5) 0.7309(3)
0.8311(6) 0.6828(3)
0.5674(6) 0.6965(3)
0.1195(8) 1.0461(4)
0.0454(8) 1.0331(4)
0.2372(6) 1.0186(3)
0.1120(5) 0.9946(3)
0.0619(6) 1.0825(3)
0.7956(3) 0.0254(10)
0.7273(3) 0.0257(11)
0.9623(3) 0.0313(12)
0.8735(3) 0.0324(12)
0.7860(4) 0.0296(16)
0.7291(3) 0.0331(12)
0.8006(3) 0.0341(13)
0.8344(3) 0.0301(11)
0.8743(3) 0.0213(12)
0.9651(3) 0.0283(13)
0.8268(3) 0.0234(10)
1.0103(3) 0.0348(13)
0.9341(4) 0.0243(14)
0.9505(4) 0.0369(19)
1.0271(4) 0.0347(17)
1.0555(5) 0.0374(19)
1.0562(4) 0.0317(17)
0.9835(4) 0.0276(15)
1.1099(5) 0.049(2)
0.6267(4) 0.0285(16)
0.5997(4) 0.0254(15)
0.6927(3) 0.0254(10)
0.6475(3) 0.0274(11)
0.5855(3) 0.0359(12)
0.5380(3) 0.0355(12)
1.0064(4) 0.0293(17)
0.9354(4) 0.0305(17)
1.0089(3) 0.0339(12)
0.8904(3) 0.0301(11)
1.0535(3) 0.0396(13)
0.9257(3) 0.0377(12)
0.7194(4) 0.0336(18)
0.7048(5) 0.057(2)
0.7583(4) 0.0355(15)
0.6947(4) 0.0387(17)
0.5476(5) 0.0392(18)
0.5785(4) 0.0438(18)
0.4806(4) 0.0458(19)
0.5865(5) 0.056(2)
0.8173(4) 0.0338(17)
0.8657(4) 0.0411(18)
0.8359(5) 0.052(2)
0.7508(4) 0.0444(18)
0.6475(4) 0.0413(13)
0.7399(3) 0.0402(14)
0.5623(3) 0.0367(15)
0.9180(5) 0.082(2)
N(1)
0.8676(3) 0.0641(12) N(2)
0.8459(3) 0.0765(14) O(13)
1.0060(3) 0.0846(15) O(23)
0.9733(4) 0.110(2)
C(1)
0.4765(3) 0.0452(10) C(2)
0.6491(3) 0.0435(10) C(3)
0.3930(2) 0.0550(10) C(4)
0.7293(2) 0.0542(10) C(5)
0.5047(4) 0.0524(14) C(6)
0.5923(4) 0.0484(13) C(7)
0.6011(5) 0.079(2)
0.5087(6) 0.112(3)
0.4553(5) 0.080(2)
0.4609(12) 0.114(6)
C(11)
C(12)
O(14)
O(15)
O(16)
C(7) 1.302(2)
0.8503(14) 0.6357(15) 0.107(7)
C(71) 0.1216(8) 0.0036(5)
N(71) 0.1714(7) 0.0857(4)
N(72) 0.0975(8) –0.0746(4)
N(73) 0.0927(6) –0.0004(4)
C(41) 0.8085(7) 0.5635(5)
N(41) 0.8951(7) 0.6394(4)
0.1782(4) 0.0648(17) O(17)
0.1128(4) 0.0819(19) C(21)
0.1620(4) 0.092(2)
C(22)
0.2578(3) 0.0695(15) O(24)
0.0539(4) 0.0580(15) O(25)
0.0452(4) 0.088(2)
O(26)
N(42) 0.8190(6) 0.5377(4) –0.0132(3) 0.0690(16) O(27) –0.0701(6) 1.0576(3)
N(43) 0.7206(6) 0.5144(4)
C(51) 0.1555(6) 0.5907(4)
N(51) 0.2577(6) 0.5939(4)
N(52) 0.0199(6) 0.5601(4)
N(53) 0.1953(6) 0.6209(4)
C(61) 0.2997(7) 0.6459(5)
N(61) 0.2372(6) 0.6805(5)
N(62) 0.4264(6) 0.6081(4)
N(63) 0.2356(6) 0.6489(5)
N(3) 0.2938(9) 0.0985(5)
N(4) 0.1385(7) –0.0814(4)
O(7) 0.3815(8) 0.1874(5)
O(8) 0.0682(7) –0.1699(4)
C(31) 0.3069(10) 0.0468(6)
C(32) 0.2252(9) –0.0464(5)
C(33) 0.2611(12) –0.0853(6)
0.1285(3) 0.0621(13) C(31)
0.6371(4) 0.0483(13) N(31)
0.5688(3) 0.0644(14) N(32)
0.6471(4) 0.0704(15) N(33)
0.6936(3) 0.0626(14) C(41)
0.2034(4) 0.0604(16) N(41)
0.1367(4) 0.0880(19) N(42)
0.1935(4) 0.0729(16) N(43)
0.2797(4) 0.0768(17) C(51)
0.2910(9) 0.5512(4)
0.1965(9) 0.5001(4)
0.3972(7) 0.5320(4)
0.2785(8) 0.6204(4)
0.8280(10) 0.9020(5)
0.7130(7) 0.8872(4)
0.8318(8) 0.9165(5)
0.9417(9) 0.8992(5)
0.8092(8) 0.5520(5)
0.7875(8) 0.6050(4)
0.7984(9) 0.4793(4)
0.8385(8) 0.5704(4)
0.0750(6) 0.7215(3)
0.9713(5) 0.8449(4)
0.2870(6) 0.7775(4)
0.9303(4) 0.099(2)
0.9869(4) 0.0779(17) N(52)
0.8859(5) 0.127(2) N(53)
1.0000(3) 0.1030(19) O(4)
0.8833(5) 0.085(2) O(5)
0.9135(5) 0.0707(19) N(3)
0.8419(5) 0.100(3) C(34A)
N(51)
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 57 No. 7 2012

URANYL COMPLEXES WITH METHYL DERIVATIVES
949
Table 3. The main bond lengths (
d
) and bond angles ( ) in structures I and II
ω
I
I
I
I
Bond
d, Å
Bond
d, Å
Bond
d, Å
Bond
d, Å
U(1)–O(11)
U(1)–O(12)
U(1)–O(13)
U(1)–N(1)
U(1)–O(15)
U(1)–O(14)
U(1)–O(3)
U(1)–O(1)
U(2)–O(21)
U(2)–O(22)
U(2)–O(23)
U(2)–O(24)
U(2)–N(2)
U(2)–O(25)
U(2)–O(3)
U(2)–O(2)
C(10)–O(1)
1.770(4) C(10)–O(2)
1.790(4) C(10)–O(3)
2.333(4) C(11)–O(16)
2.413(4) C(11)–O(14)
2.432(4) C(11)–C(12)
2.447(4) C(12)–O(17)
2.452(3) C(12)–O(15)
2.529(4) C(21)–O(26)
1.755(5) C(21)–O(24)
1.774(4) C(21)–C(22)
2.365(4) C(22)–O(27)
2.409(4) C(22)–O(25)
2.418(4) N(1)–C(1)
2.431(4) N(1)–O(13)
2.439(3) N(2)–C(2)
2.540(4) N(2)–O(23)
1.258(6) C(1)–C(2)
1.258(7) C(1)–C(5)
1.307(6) C(2)–C(3)
1.256(6) C(3)–C(7)
1.271(6) C(3)–C(4)
1.544(8) C(4)–C(5)
1.210(6) C(5)–C(6)
1.280(6) C(71)–N(73)
1.243(7) C(71)–N(71)
1.289(7) C(71)–N(72)
1.541(10) C(41)–N(43)
1.225(8) C(41)–N(42)
1.254(8) C(41)–N(41)
1.280(7) C(51)–N(52)
1.364(6) C(51)–N(53)
1.291(6) C(51)–N(51)
1.366(5) C(61)–N(62)
1.460(8) C(61)–N(61)
1.531(8) C(61)–N(63)
1.506(7) N(3)–C(31)
1.494(5) N(3)–O(7)
1.501(11) N(4)–C(32)
1.550(11) N(4)–O(8)
1.493(5) C(31)–C(32)
1.292(8) C(31)–C(35)
1.310(8) C(32)–C(33)
1.318(8) C(33)–C(34B)
1.295(7) C(33)–C(34A)
1.307(7) C(34A)–C(35)
1.330(8) C(34B)–C(35)
1.291(7) C(35)–C(36B)
1.308(7) C(35)–C(36A)
1.312(7)
1.315(8)
1.281(9)
1.410(8)
1.249(8)
1.389(7)
1.440(10)
1.520(11)
1.497(10)
1.481(15)
1.69(4)
1.526(13)
1.527(13)
1.493(5)
1.498(5)
1.302(8)
1.311(8)
Angle
ω
, deg
Angle
ω
, deg
Angle
ω
, deg
Angle
ω
, deg
O(11)U(1)O(12) 179.62(19) O(23)U(2)O(24) 68.07(13) O(14)C(11)C(12) 115.4(5) C(6)C(5)C(4)
O(11)U(1)O(13) 88.86(17) O(21)U(2)N(2) 89.61(18) O(17)C(12)O(15) 126.6(5) C(1)C(5)C(4)
O(12)U(1)O(13) 91.33(17) O(22)U(2)N(2) 89.09(17) O(17)C(12)C(11) 120.0(5) N(73)C(71)N(71)
O(11)U(1)N(1) 88.42(17) O(23)U(2)N(2) 33.16(13) O(15)C(12)C(11) 113.4(4) N(73)C(71)N(72)
O(12)U(1)N(1) 91.55(17) O(24)U(2)N(2) 101.22(14) C(11)O(14)U(1) 122.2(3) N(71)C(71)N(72)
111.1(9)
103.4(5)
120.6(6)
120.0(6)
119.3(6)
121.3(6)
120.1(6)
118.6(6)
121.4(6)
120.7(6)
117.9(5)
119.2(6)
120.1(6)
120.6(6)
111.1(7)
111.5(6)
121.7(7)
127.6(7)
110.6(7)
121.9(6)
130.0(7)
108.0(6)
O(13)U(1)N(1) 33.34(13) O(21)U(2)O(25) 90.5(2)
C(12)O(15)U(1) 122.9(3) N(43)C(41)N(42)
O(11)U(1)O(15) 91.89(16) O(22)U(2)O(25) 90.62(19) O(26)C(21)O(24) 125.9(6) N(43)C(41)N(41)
O(12)U(1)O(15) 88.23(16) O(23)U(2)O(25) 133.34(14) O(26)C(21)C(22) 120.0(6) N(42)C(41)N(41)
O(13)U(1)O(15) 131.82(13) O(24)U(2)O(25) 65.29(14) O(24)C(21)C(22) 114.1(5) N(52)C(51)N(53)
N(1)U(1)O(15) 165.15(14) N(2)U(2)O(25) 166.49(15) O(27)C(22)O(25) 124.9(7) N(52)C(51)N(51)
O(11)U(1)O(14) 89.39(17) O(21)U(2)O(3) 92.21(17) O(27)C(22)C(21) 119.5(6) N(53)C(51)N(51)
O(12)U(1)O(14) 90.99(17) O(22)U(2)O(3) 87.89(16) O(25)C(22)C(21) 115.5(6) N(62)C(61)N(61)
O(13)U(1)O(14) 67.23(12) O(23)U(2)O(3) 106.47(12) C(21)O(24)U(2) 122.6(4) N(62)C(61)N(63)
N(1)U(1)O(14) 100.56(13) O(24)U(2)O(3) 174.43(12) C(22)O(25)U(2) 122.3(4) N(61)C(61)N(63)
O(15)U(1)O(14) 64.60(12) N(2)U(2)O(3)
73.35(13) C(1)N(1)O(13) 118.6(4) C(31)N(3)O(7)
O(11)U(1)O(3) 90.93(17) O(25)U(2)O(3) 120.13(13) C(1)N(1)U(1)
O(12)U(1)O(3) 88.70(16) O(21)U(2)O(2) 88.51(18) O(13)N(1)U(1)
170.9(4) C(32)N(4)O(8)
70.1(2) N(3)C(31)C(32)
O(13)U(1)O(3) 106.23(12) O(22)U(2)O(2) 92.64(17) C(2)N(2)O(23) 118.2(4) N(3)C(31)C(35)
N(1)U(1)O(3)
72.91(13) O(23)U(2)O(2) 158.26(13) C(2)N(2)U(2)
170.1(4) C(32)C(31)C(35)
71.3(2) N(4)C(32)C(31)
76.6(2) N(4)C(32)C(33)
75.6(2) C(31)C(32)C(33)
O(15)U(1)O(3) 121.92(12) O(24)U(2)O(2) 133.55(13) O(23)N(2)U(2)
O(14)U(1)O(3) 173.45(11) N(2)U(2)O(2) 125.13(13) N(1)O(13)U(1)
O(11)U(1)O(1) 89.89(17) O(25)U(2)O(2) 68.37(14) N(2)O(23)U(2)
O(12)U(1)O(1) 89.82(16) O(3)U(2)O(2)
51.96(12) N(1)C(1)C(2)
123.8(5) C(34B)C(33)C(32) 105.7(8)
128.7(5) C(32)C(33)C(34A) 101.2(11)
O(13)U(1)O(1) 158.17(12) O(1)C(10)O(2) 126.5(5)
N(1)U(1)O(1) 124.85(13) O(1)C(10)O(3) 116.8(5)
O(15)U(1)O(1) 70.00(12) O(2)C(10)O(3) 116.6(5)
O(14)U(1)O(1) 134.55(12) C(10)O(1)U(1)
O(3)U(1)O(1) 52.00(11) C(10)O(2)U(2)
O(21)U(2)O(22) 178.61(18) C(10)O(3)U(2)
O(21)U(2)O(23) 89.87(17) C(10)O(3)U(1)
O(22)U(2)O(23) 88.77(17) U(2)O(3)U(1) 164.50(17) C(4)C(3)C(2)
N(1)C(1)C(5)
C(2)C(1)C(5)
N(2)C(2)C(1)
N(2)C(2)C(3)
C(1)C(2)C(3)
C(7)C(3)C(4)
C(7)C(3)C(2)
107.4(5) C(35)C(34A)C(33)
98.5(16)
122.8(5) C(33)C(34B)C(35) 108.3(10)
127.6(5) C(36B)C(35)C(31) 101.1(9)
109.5(5) C(36A)C(35)C(31) 121.9(15)
103.8(11) C(36A)C(35)C(34A) 122(2)
110.1(11) C(31)C(35)C(34A) 102.4(15)
104.5(5) C(36B)C(35)C(34B) 110.3(11)
104.9(6) C(36A)C(35)C(34B) 135.8(16)
106.5(7) C(31)C(35)C(34B) 102.3(9)
94.3(3)
94.0(3)
97.4(3)
96.6(3)
O(21)U(2)O(24) 88.96(18) O(16)C(11)O(14) 124.8(5)
O(22)U(2)O(24) 90.82(17) O(16)C(11)C(12) 119.7(5)
C(3)C(4)C(5)
C(6)C(5)C(1)
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 57 No. 7 2012

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BEIRAKHOV et al.
Table 3. (Contd.)
II
II
II
II
Bond
d
, Å
Bond
d
, Å
Bond
d
, Å
Bond
d, Å
U(1)–O(11)
U(1)–O(12)
U(1)–O(13)
U(1)–O(15)
U(1)–O(3)
U(1)–O(14)
U(1)–N(1)
U(1)–O(1)
U(1)–C(10)
U(2)–O(21)
U(2)–O(22)
U(2)–O(23)
U(2)–O(25)
1.788(5) U(2)–O(3)
1.804(5) U(2)–O(24)
2.315(5) U(2)–N(2)
2.375(5) U(2)–O(2)
2.397(5) U(2)–C(10)
2.410(5) C(10)–O(2)
2.450(6) C(10)–O(1)
2.505(5) C(10)–O(3)
2.879(8) N(1)–C(1)
1.773(5) N(1)–O(13)
1.783(5) N(2)–C(6)
2.299(5) N(2)–O(23)
2.402(5) C(1)–C(6)
2.410(5) C(1)–C(2)
2.410(6) C(2)–C(3)
2.447(6) C(3)–C(4)
2.545(5) C(4)–C(5)
2.907(7) C(5)–C(7)
1.244(9) C(5)–C(6)
1.278(9) C(11)–O(16)
1.331(9) C(11)–O(14)
1.279(9) C(11)–C(12)
1.392(7) C(12)–O(17)
1.270(10) C(12)–O(15)
1.354(8) C(21)–O(26)
1.477(10) C(21)–O(24)
1.499(10) C(21)–C(22)
1.507(10) C(22)–O(27)
1.537(11)
1.235(9)
1.264(9)
1.296(10)
1.320(11)
1.322(11)
1.282(11)
1.304(12)
1.342(12)
1.311(11)
1.317(11)
1.319(11)
1.494(12) C(22)–O(25)
1.543(12) C(31)–N(33)
1.488(12) C(31)–N(31)
1.500(10) C(31)–N(32)
1.239(9) C(41)–N(42)
1.277(9) C(41)–N(41)
1.500(10) C(41)–N(43)
1.213(9) C(51)–N(51)
1.295(9) C(51)–N(52)
1.227(9) C(51)–N(53)
1.261(10)
Angle
ω
, deg
Angle
ω
, deg
Angle
ω
, deg
Angle
ω
, deg
O(11)U(1)O(12) 179.2(2)
O(11)U(1)O(13) 90.6(2)
O(12)U(1)O(13) 89.9(2)
O(11)U(1)O(15) 87.0(2)
O(12)U(1)O(15) 92.2(2)
O(13)U(1)O(15) 132.97(16) O(22)U(2)O(23) 90.9(2)
O(11)U(1)O(3) 92.5(2)
O(12)U(1)O(3) 88.0(2)
O(14)U(1)C(10) 155.95(19) O(23)U(2)C(10) 133.5(2)
N(1)U(1)C(10) 100.88(19) O(25)U(2)C(10) 91.66(19) C(3)C(4)C(5)
O(1)U(1)C(10) 26.31(18) O(3)U(2)C(10) 26.99(19) C(7)C(5)C(6)
C(4)C(3)C(2)
109.7(7)
111.2(7)
111.5(7)
111.0(7)
111.5(7)
120.8(7)
121.3(7)
117.9(6)
O(21)U(2)O(22) 178.3(2)
O(21)U(2)O(23) 88.3(2)
O(24)U(2)C(10) 156.1(2)
N(2)U(2)C(10) 100.7(2)
C(7)C(5)C(4)
C(6)C(5)C(4)
O(2)U(2)C(10) 25.29(19) N(2)C(6)C(1)
O(21)U(2)O(25) 91.0(2)
O(22)U(2)O(25) 88.5(2)
O(2)C(10)O(1) 128.3(7)
O(2)C(10)O(3) 116.1(6)
N(2)C(6)C(5)
C(1)C(6)C(5)
O(13)U(1)O(3) 107.45(17) O(23)U(2)O(25) 134.77(18) O(1)C(10)O(3) 115.5(7)
O(16)C(11)O(14) 125.3(7)
O(16)C(11)C(12) 119.5(7)
O(14)C(11)C(12) 115.2(6)
O(17)C(12)O(15) 123.4(7)
O(17)C(12)C(11) 122.9(7)
O(15)C(12)C(11) 113.7(6)
C(11)O(14)U(1) 121.6(4)
C(12)O(15)U(1) 123.2(4)
O(26)C(21)O(24) 126.8(8)
O(26)C(21)C(22) 118.5(7)
O(24)C(21)C(22) 114.7(7)
O(27)C(22)O(25) 124.6(8)
O(27)C(22)C(21) 121.3(7)
O(25)C(22)C(21) 114.1(7)
C(21)O(24)U(2) 122.4(5)
C(22)O(25)U(2) 123.1(5)
N(33)C(31)N(31) 118.9(8)
N(33)C(31)N(32) 120.5(8)
N(31)C(31)N(32) 120.6(7)
N(42)C(41)N(41) 120.0(9)
N(42)C(41)N(43) 121.0(9)
N(41)C(41)N(43) 118.9(8)
N(51)C(51)N(52) 118.6(8)
N(51)C(51)N(53) 121.3(8)
N(52)C(51)N(53) 120.1(8)
O(15)U(1)O(3) 119.58(17) O(21)U(2)O(3)
88.7(2)
92.9(2)
O(2)C(10)U(1) 167.8(5)
O(1)C(10)U(1) 60.3(4)
O(11)U(1)O(14) 92.5(2)
O(12)U(1)O(14) 87.1(2)
O(22)U(2)O(3)
O(23)U(2)O(3) 106.55(19) O(3)C(10)U(1) 55.7(3)
O(13)U(1)O(14) 68.40(16) O(25)U(2)O(3) 118.65(18) O(2)C(10)U(2) 60.9(4)
O(15)U(1)O(14) 64.80(16) O(21)U(2)O(24) 86.5(2)
O(3)U(1)O(14) 173.53(18) O(22)U(2)O(24) 91.8(2)
O(1)C(10)U(2) 169.7(5)
O(3)C(10)U(2) 55.2(3)
O(11)U(1)N(1) 91.7(2)
O(12)U(1)N(1) 89.0(2)
O(23)U(2)O(24) 70.00(18) U(1)C(10)U(2) 109.9(2)
O(25)U(2)O(24) 64.83(18) C(10)O(1)U(1) 93.4(4)
O(13)U(1)N(1) 33.82(17) O(3)U(2)O(24) 174.18(18) C(10)O(2)U(2) 93.8(4)
O(15)U(1)N(1) 166.76(17) O(21)U(2)N(2)
O(3)U(1)N(1) 73.63(18) O(22)U(2)N(2) 88.9(2)
91.2(2)
C(10)O(3)U(1) 96.9(4)
C(10)O(3)U(2) 97.8(4)
O(14)U(1)N(1) 102.13(17) O(23)U(2)N(2) 32.96(19) U(1)O(3)U(2) 160.1(3)
O(11)U(1)O(1) 90.4(2)
O(12)U(1)O(1) 89.3(2)
O(25)U(2)N(2) 167.40(19) C(1)N(1)O(13) 117.6(5)
O(3)U(2)N(2) 73.81(19) C(1)N(1)U(1) 174.4(5)
O(13)U(1)O(1) 160.93(17) O(24)U(2)N(2) 102.9(2)
O(13)N(1)U(1) 67.8(3)
C(6)N(2)O(23) 119.2(6)
C(6)N(2)U(2) 173.4(6)
O(15)U(1)O(1) 66.09(17) O(21)U(2)O(2)
O(3)U(1)O(1) 53.48(17) O(22)U(2)O(2)
89.4(2)
91.8(2)
O(14)U(1)O(1) 130.55(16) O(23)U(2)O(2) 158.75(18) O(23)N(2)U(2) 67.5(3)
N(1)U(1)O(1) 127.12(18) O(25)U(2)O(2)
66.39(17) N(1)O(13)U(1) 78.4(3)
52.26(17) N(2)O(23)U(2) 79.6(4)
O(11)U(1)C(10) 93.7(2)
O(12)U(1)C(10) 86.4(2)
O(3)U(2)O(2)
O(24)U(2)O(2) 130.94(19) N(1)C(1)C(6) 119.0(6)
126.03(19) N(1)C(1)C(2) 119.5(7)
O(13)U(1)C(10) 134.66(18) N(2)U(2)O(2)
O(15)U(1)C(10) 92.35(19) O(21)U(2)C(10) 89.7(2)
O(3)U(1)C(10) 27.33(19) O(22)U(2)C(10) 91.9(2)
C(6)C(1)C(2)
C(1)C(2)C(3)
121.3(7)
115.6(7)
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 57 No. 7 2012

URANYL COMPLEXES WITH METHYL DERIVATIVES
951
N(72)
N(71)
C(71)
N(73)
N(42)
C(41)
N(43)
N(41)
N(61)
C(61)
N(62)
O(17)
O(16)
N(63)
C(11)
O(14)
C(12)
O(15)
O(4)
O(11)
O(13)
U(1)
N(51)
N(53)
O(1)
N(52)
O(12)
C(34B)
C(33)
C(51)
C(5)
N(1)
C(1)
C(10)
C(35)
C(6)
C(4)
O(3)
C(36B)
O(7)
C(32)
O(2)
N(2)
O(21)
O(8)
C(31)
N(3)
C(2)
C(3)
U(2)
N(4)
O(5)
O(25)
O(22)
O(23)
C(22)
O(27)
O(24)
C(21)
O(26)
Fig. 1. Crystallographically independent units in the structure of compound
I. Minor components of disordering are omitted.
O(27)
O(17)
O(25)
O(2)
C(22)
O(1)
C(12)
O(15)
C(10)
O(3)
O(22)
O(12)
O(16)
C(21)
C(11)
O(26)
U(2)
U(1)
O(24)
O(14)
O(21)
O(11)
N(1)
N(2)
O(23)
O(13)
C(6)
C(1)
C(5)
C(2)
C(7)
C(3)
C(4)
4–
Fig. 2. The structure of complex anion [(UO ) (C H N O )(CO )(C O ) ] in compound II
.
2 2
7
10
2
2
3
2 4 2
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 57 No. 7 2012

952
BEIRAKHOV et al.
hydrogen bonds, which involve almost all atoms of the H2O [3] and methylethylglyoxime (CN3H6)4[(UO2)2(CO3)
complexes, including the oxygen atoms of the uranyl (C2O4)2(C5H8N2O2)] 1.5H2O [6] are obtained by the
⋅
groups.
same way but in much larger yield. In the case of 1,2ꢀcycloꢀ
hexanedione dioxime, as noted above, a partial isomerꢀ
ization of the ligand takes place to form the binuclear
complex (CN3H6)3[(UO2)2(C6H9N2O2)(C6H8N2O2)
(C2O4)2] 2H2O [2], while complex II was obtained
only by the addition of carbonate ions to the solution.
The structure of complex anions
terized by the presence of double carbonate–dioxiꢀ
mate bridging moiety
I
and II is characꢀ
⋅
O
O
O
REFERENCES
UO2
O2U
1. A. G. Beirakhov, I. M. Orlova, Yu. N. Mikhailov, et al.,
O
N
N O
Dokl. Ross. Akad. Nauk 381, 60 (2001).
2. A. G. Beirakhov, I. M. Orlova, E. G. Il’in, et al.,
Zh. Neorg. Khim. 53, 2029 (2008).
3. A. G. Beirakhov, I. M. Orlova, Yu. E. Gorbunova, et al.,
H3C
,
Zh. Neorg. Khim. 44, 1492 (1999).
which is observed in all previously isolated uranyl
complexes with cisꢀbridged binding of ꢀdioximes [3,
6–8]. It should be noted that, when uranyl oxalate
complexes were reacted with methyl derivatives of aliꢀ
cyclic dioximes without direct introduction of carbonꢀ
4. G. M. Sheldrick, SADABS. Program for Scaling and
Correction of Area Detector Data (Univ. of Göttingen,
Göttingen, 1997).
α
5. G. M. Sheldrick, Acta Crystallogr., Sect. A 64, 112
(2008).
ate ions into reaction solution, only complex I was isoꢀ
6. A. G. Beirakhov, I. M. Orlova, E. G. Il’in, et al.,
Zh. Neorg. Khim. 55, 1639 (2010).
7. A. G. Beirakhov, I. M. Orlova, Z. R. Ashurov, et al.,
Zh. Neorg. Khim. 36, 647 (1991).
8. P. G. Allen, J. J. Bucher, D. L. Clark, et al., Inorg.
lated in low yield. In our opinion, the absorption of
carbon dioxide from air upon crystallization is one of
the possible sources of carbonate ions in solutions.
Mixed carbonate–oxalate complexes with methylglyꢀ
oxime (C2H10N2)2[(UO2)2(CO3)(C2O4)2(C3H4N2O2)]
⋅
Chem. 34, 4797 (1995).
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 57 No. 7 2012