2
722
GARIFZYANOV et al.
at 25°C using an EKSPERT-001 instrument equipped
with an ES-10603 glass electrode (measurement accuracy
0.001 pH unit; experimental error ±0.005 pH unit)
±
and an ESr-10108 silver chloride electrode. The results
were processed using CPESSP software [4].
The X-ray diffraction data for compound 2 were
acquired at 198(2) K on a Bruker AXS Kappa APEX
Duo diffractometer (CuK radiation, λ 1.54178 Å) using
α
APEX2 [5], SAINT [6], SHELXS97 [7], and SADABS
[8]. Orthorhombic crystal system, space group Pbca;
C H K N O P , M 584.37; unit cell parameters: a =
1
3
10
3
3
11 3
1
8.1114(7), b = 9.3665(4), c = 33.2472(13) Å;
3
3
V 5640.1(4) Å ; Z = 8; d
= 1.376 g/cm ; μ =
calc
–
1
6
.365 mm . Total of 52 285 reflection intensities were
measured, including 5168 independent reflections
Rint = 0.0446) and 5125 reflections with I ≥ 2σ(I);
Structure of the molecule of tripotassium tributyl [nitrilotris-
methylene)]tris(phosphonate) (2) in crystal according to the
X-ray diffraction data.
(
(
2
2
98 variables; R = 0.0575, wR = 0.1687; maximum/
–3
minimum residual electron density 1.183/–0.583 ē/Å .
The crystallographic data for compound 2 were
deposited to the Cambridge Crystallographic Data
Centre (CCDC entry no. 1 489 195).
2
m (12H, CH ), 3.31 d (6H, PCH N, J = 10.9), 4.02–
4
2
2
PH
31
.09 m (12H, OCH ). P NMR spectrum: δ 23.94 ppm.
2
P
Tripotassium tributyl [nitrilotris(methylene)]tris
phosphonate) (2). A mixture of 108 g (0.17 mol) of
(
ACKNOWLEDGMENTS
tris-phosphonate 1 and 71 g of 50% aqueous potassium
This study was funded by the subsidy allocated to
Kazan Federal University for the fulfillment of the
project part of state assignment in the sphere of
research activity.
hydroxide (0.52 mol) in 25 mL of dioxane was heated
3
1
for 6 h at 110°C. When the reaction was complete ( P
NMR), the mixture was cooled, and the white plates
were filtered off and recrystallized from ethanol–
acetone (1 : 2). Yield 57.3 g (51.2%), decomposition
–
1
REFERENCES
point 230°C. IR spectrum, ν, cm : 1215 (P=O), 1046
1
(
0
1
P–O–C). H NMR spectrum (D O), δ, ppm (J, Hz):
2
1
. Davletshina, N.V., Koshkin, S.A., Garifzyanov, A.R.,
Filimonova, M.A., Gainullin, A.Z., and Cherkasov, R.A.,
Russ. J. Gen. Chem., 2015, vol. 85, no. 9, p. 2198. doi
10.1134/S107036321509025X
3
.86 t (9H, CH , J = 7.4), 1.28–1.37 m (6H, CH ),
3 NH 2
.52–1.58 m (6H, CH ), 3.01 d (6H, PCH N, J =
1.1), 3.82–3.87 m (6H, OCH2). C–{ H} NMR
2
2
2
PH
1
3
1
1
spectrum (D O), δ , ppm (J, Hz): 13.1 [(CH ) CH ],
2. Prishchenko, A.A., Livantsov, M.V., Novikova, O.P.,
Livantsova, L.I., and Petrosyan, V.S., Heteroatom Chem.,
2010, vol. 21, no. 6, p. 430. doi 10.1002/hc.20616
2
C
2 3
3
1
8.4 [(CH ) CH CH )], 32.3 d (CH CH CH CH ,
2 2 2 3 2 2 2 3
3
1
JPC = 5.6), 52.5 d (PCH , J = 150.0), 64.6 d
2
PC
2
31
1
[CH (CH ) CH , J = 5.8]. P–{ H} NMR spectrum
3. Irving, H. and Williams, R.J.P., J. Chem. Soc., 1953,
2
2 2
3
PC
p. 3192. doi 10.1039/JR9530003192
(
D O): δP 20.74 ppm. Found, %:
2
K
20.15.
C H K NO P . Calculated, %: K 20.17.
4. Sal’nikov, Yu.I., Glebov, A.N., and Devyatov, Yu.I.,
9
21
3
9
3
Poliyadernye kompleksy
v rastvorakh (Polynuclear
1
13
1
31
1
The H, C–{ H}, and P–{ H} NMR spectra were
Complexes in Solution), Kazan’: Kazan. Gos. Univ., 1989.
recorded on a Bruker AVANCE 400 spectrometer at
5
6
. Bruker. APEX2 Software Suite for Crystallographic
Programs, Madison, USA: Bruker AXS, 2009.
. Bruker. Area Detector Control and Integration Software.
Version 5.x. SMART and SAINT, Madison, USA: Bruker
Analytical X-ray Instruments, 1996.
1
4
00, 100, and 160 MHz, respectively. The H chemical
shifts were measured relative to the residual proton
signals of the deuterated solvents (CDCl , D O). The
3
2
IR spectra were recorded on a Perkin Elmer UATR
Two FT-IR Spectrometer (Spectrum Two). The melting
7
8
. Sheldrick, G.M., Acta Crystallogr., Sect. A, 2008, vol. 64,
p. 112. doi 10.1107/S0108767307043930
. Sheldrick, G.M., SADABS. Program for Absorption
Corrections, Göttingen, Germany: Univ. of Göttingen, 1996.
(
decomposition) points were determined with an
accuracy of ±1°C with a Stuart SMP10 melting point
apparatus. Potentiometic measurements were performed
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 86 No. 12 2016