Synthesis and crystal structure of the nickel(II) complex with 2-diphenylphosphinobenzaldehyde 2-quinolinylhydrazone

Article abstract of DOI:10.1134/S1070328414050108

2-Diphenylphosphinobenzaldehyde 2-quinolinylhydrazone (HL) and its nickel(II) complex [Ni(L)(CH₃COO)] were synthesized. The structure of the complex was determined by X-ray diffraction. The nickel ion in the molecule of the complex has a square PNN'O donor environment. Owing to C-H.O intermolecular hydrogen bonds, centrosymmetric dimers are formed in the crystal.

Full text of DOI:10.1134/S1070328414050108

ISSN 1070ꢀ3284, Russian Journal of Coordination Chemistry, 2014, Vol. 40, No. 5, pp. 280–283. © Pleiades Publishing, Ltd., 2014.
Original Russian Text © L.D. Popov, S.I. Levchenkov, I.N. Shcherbakov, Z.A. Starikova, V.V. Lukov, V.A. Kogan, 2014, published in Koordinatsionnaya Khimiya, 2014, Vol. 40,
No. 5, pp. 281–284.
Synthesis and Crystal Structure of the Nickel(II) Complex
with 2ꢀDiphenylphosphinobenzaldehyde 2ꢀQuinolinylhydrazone
†
L. D. Popova, S. I. Levchenkovb, *, I. N. Shcherbakova, Z. A. Starikovac, , V. V. Lukova, and V. A. Kogana
a Southern Federal University, ul. Bolshaya Sadovaya 105/42, RostovꢀonꢀDon, 3440006 Russia
b Southern Research Center, Russian Academy of Sciences, ul. Chekhova 41, RostovꢀonꢀDon, 3440006 Russia
c Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences,
ul. Vavilova 28, Moscow, 117813 Russia
*eꢀmail: physchem@yandex.ru
Received August 28, 2013
Abstract—2ꢀDiphenylphosphinobenzaldehyde 2ꢀquinolinylhydrazone (HL) and its nickel(II) complex
[Ni(L)(CH3COO)] were synthesized. The structure of the complex was determined by Xꢀray diffraction. The
...
nickel ion in the molecule of the complex has a square PNN'O donor environment. Owing to C–H O interꢀ
molecular hydrogen bonds, centrosymmetric dimers are formed in the crystal.
DOI: 10.1134/S1070328414050108
†
INTRODUCTION
Ph
P
Ph
In the last decades, transition metal complexes
with hydrazones of polyfunctional carbonyl comꢀ
pounds have been subjects of vigorous research [1–5].
Depending on several factors, hydrazones can form
monoꢀ, biꢀ, or polynuclear complexes, which find use
in homogeneous catalysis [6], medical and bioinorꢀ
ganic chemistry [8, 9], magnetochemistry [10], and so
on. Of particular interest are polyfunctional hydraꢀ
zone derivatives of 2ꢀdiphenylphosphinobenzaldeꢀ
hyde containing various sets of hard and soft donor
N
N
N
H
(HL)
EXPERIMENTAL
Synthesis of HL A solution of 2ꢀhydrazinoquinoꢀ
line (0.005 mol) in ethanol (10 mL) was added to a hot
atoms. Published data are available for some
3dꢀ and
solution
of
2ꢀdiphenylphosphinobenzaldehyde
4dꢀmetal complexes based on various aroylhydrazones
(0.005 mol) in ethanol (15 mL), and the mixture was
refluxed for 1 h and left overnight. The bright yellow
amorphous precipitate was filtered off, washed with
ethanol, and recrystallized from ethanol. Yield 65%.
mp 110–112°C.
[11–16] and derivatives of 2ꢀdiphenylphosphinobenꢀ
zaldehyde semicarbazones [17, 18], thiosemicarbaꢀ
zones [19–21], and selenosemicarbazones [22]. Comꢀ
pounds of 2ꢀdiphenylphosphinobenzaldehyde hetaꢀ
rylhydrazones are much less studied. Only 2ꢀdiꢀpheꢀ
nylphosphinobenzaldehyde 2ꢀpyridylhydrazone comꢀ
plexes with Cu(I), Ni(II), Fe(II), Pt(II), and Pd(II)
were described in the literature [11, 23, 24].
For C28H22N3P
anal. calcd., %: C, 77.94;
Found, %: C, 77.61;
H, 5.14;
H, 5.26;
N, 9.74.
N, 9.81.
As a continuation of our studies of transition metal
complexes with hetarylhydrazones [25–27], we synꢀ
thesized and structurally characterized nickel(II)
complex with a tridentate PNN'ꢀdonor ligand,
2ꢀdiphenylphosphinobenzaldehyde 2ꢀquinolinylhyꢀ
IR (
ν
, cm–1): 3168
ν
δ
(NH), 1637, 1596 ν(С=N).
, ppm): 6.77–6.81 (m, 1H,
1H NMR (DMSOꢀd6;
CHarom); 7.15–7.26 (m, 6H, CHarom); 7.33–7.37 (m,
7H, CHarom); 7.45–7.64 (m, 4H, CHarom); 7.91 (d,
1H,
J = 9.0 Hz, CHarom); 7.98 br.s. (1H, CHarom); 8.62
(d, 1H, JP = 3.0 Hz, CH=N); 11.30 (s, 1H, NH).
UV/Vis (DMSO;
(31100).
drazone (HL) – [Ni(L)(CH3COO)] (I).
λ, nm (ε
, L cm–1 mol–1)): 358
†
Deceasred.
280

SYNTHESIS AND CRYSTAL STRUCTURE OF THE NICKEL(II) COMPLEX
281
Table 1. Crystallographic data and Xꢀray experiment and Table 2. Selected interatomic distances and bond angles in
structure refinement details for complex
I
the coordination polyhedra of nickel atoms in the molecule
of
I
Parameter
Value
Bond
d
, Å
Bond
d, Å
M
548.20
Ni(1)–N(3)
Ni(1)–O(2)
1.865(3) Ni(1)–N(1)
1.883(3) Ni(1)–P(1)
1.947(3)
Crystal size, mm
Temperature, K
System
0.40
×
0.25 × 0.20
2.1660(12)
120(2)
Monoclinic
21/
Angle
ω
, deg
Angle
ω, deg
Space group
P
n
N(3)Ni(1)O(2) 173.68(13) N(3)Ni(1)P(1) 94.60(11)
N(3)Ni(1)N(1) 83.75(14) O(2)Ni(1)P(1) 82.78(9)
O(2)Ni(1)N(1) 99.93(13) N(1)Ni(1)P(1) 168.73(11)
a
, Å
, Å
10.5427(18)
16.967(3)
14.153(2)
98.342(4)
2504.9(7)
4
b
c
, Å
β
V
Z
, deg
, Å3
Table 3. Characteristics of intermolecular hydrogen bonds
C–H⋅⋅⋅O in the crystal of complex
Distance, Å**
H··· ···A
I*
ρcalcd, g/cm3
, mm–1
(000)
Scan range of
1.454
CHO angle,
deg
C–H···O
μ
0.872
O
C
F
1136
C(2)
–
H(2
H(24
H(5
)···O(1)i
A
)···O(2)
2.20
2.33
2.45
2.46
2.975(5)
3.088(5)
3.317(6)
3.314(5)
3.315(5)
141
138
156
153
θ, deg
1.89–26.00
21496
C(24)
–
A
)···O(2)
The number of measured reflections
The ranges of reflection indices
C(5)–
A
–13
–20
–17
≤
≤
≤
h
k
l
≤
≤
≤
13,
20,
17
C(10)–H(10
A
)···O(1)ii
)···O(1)ii
C(16)–H(16
A
2.48
150
The number of independent reflections
4839
2772
335
i
ii
* Crystallographic positions: 5/2 –
x, –1/2 +
y, 3/2 –
z;
2 –
x,
The number of reflections with I > 2σ(I)
–y, 2 –
z.
** C–H is 0.93 Å.
The number of refined parameters
GOOF (all reflections)
1.012
0.0549
0.1390
CHarom); 7.38 (br.s., 1H, CHarom); 7.45–7.57 (m, 5H,
CHarom); 7.79–7.99 (m, 9H, CHarom); 8.36 (d, 1H,
R1
wR2 (all reflections)
Δρmax Δρmin
Å–3
(I > 2σ(I))
JP = 3.0 Hz, CH=N). UV/Vis (DMSO,
λ, nm (ε,
L cm–1 mol–1)): 355)): 355 (7900), 510 (3300).
/
,
e
0.809/–0.595
The 1H NMR spectra were recorded in DMSOꢀd6
on a Varian Unity 300 spectrometer (300 MHz) in the
pulse FT mode using HMDS as the internal standard.
IR spectra were measured on a Varian Scimitar 1000
FTꢀIR instrument at 400–4000 cm–1 for mineral oil
mulls.
Synthesis of I. A hot solution of nickel(II) acetate
(0.002 mol) in methanol (20 mL) was added to a hot
solution of HL (0.002 mol) in methanol (20 mL). The
mixture was refluxed for 4 h and the precipitate was
washed with hot methanol, dried in vacuum, and
recrystallized from DMSO. Yield 45%.
Xꢀray diffraction analysis of
Bruker SMART 1000 CCD diffractometer (MoKα
= 0.71073 Å, graphite monochromator). The initial
I was performed on a
,
λ
For C30H24N3NiO2P
array of measured reflection intensities was processed
using SAINT [28] and SADABS [29] software. The
structure was solved by the direct method and refined
by the fullꢀmatrix leastꢀsquares method in the anisoꢀ
2
anal. calcd., %: C, 65.73;
H, 4.41;
H, 4.28;
N, 7.66.
N, 7.47.
Found, %:
C, 65.39;
1
IR (
ν
, cm–1): 1628, 1595
ν
(С=N). H NMR tropic approximation for nonꢀhydrogen atoms on
Fhkl
.
(DMSOꢀd6;
δ, ppm): 2.72 (s, 1H, CH3); 6.92 (m, 1H, The hydrogen atoms were placed in geometrically calꢀ
CHarom); 7.13 (br.s., 3H, CHarom); 7.28 (br.s., 1H, culated positions and refined using the riding model
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 40
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2014

282
POPOV et al.
O(1)
Ni(1)
O(2)
x
P(1)
N(1)
N(3)
y
0
N(2)
Fig. 1. General view of the molecule of complex
atoms being represented by atom displacement ellipsoids
with 50% probability.
I with
Fig. 2. Packing of the molecules of complex
(view along the crystallographic axis ).
I in the crystal
z
(
U
iso(H) = nUiso(C), where
n
n = 1.5 for methyl carbons cule has an envelope conformation in which the flap,
the nickel atom, deviates from the mean plane of the
other four atoms by 0.145 Å. The sixꢀmembered cheꢀ
late ring is also somewhat distorted due to folding
along the N(3)–P(1) line, resulting in deviation of the
nickel atom from the plane of other atoms by 0.242 Å.
and = 1.2 for other C atoms). All calculations were
carried out by SHELXTL software [30]. The structure
was analyzed using PLATON program [31].
Xꢀray experiment details and crystallographic data
are summarized in Table 1, selected interatomic disꢀ
tances and bond angles are in Table 2, and parameters
The monodeprotonated hydrazone HL residue in
complex I is nearly planar. This is due to the presence
of C–H···O hydrogen bonds are given in Table 3. The
atom coordinates and thermal factors are deposited
with the Cambridge Crystallographic Data Centre
(no. 950913: deposit@ccdc.cam.ac.uk or http://www.
ccdc.cam.ac.uk/data_request/cif).
of extended chain of conjugated bonds, which is conꢀ
firmed by alternation of short and long carbon–carꢀ
bon and carbon–nitrogen bonds [33]. The dihedral
angle between the mean planes of the benzene and
phthalazine rings is only 1.84°, while that between the
planes of the phenyl rings attached to phosphorus is
84.42°. This type of orientation of phenyl groups is
found in all 2ꢀdiphenylphosphinobenzaldehyde
hydrazone complexes described previously by Xꢀray
diffraction [11–24].
RESULTS AND DISCUSSION
The composition and structure of the isolated comꢀ
pounds were established from data of elemental analyꢀ
sis, IR and 1H NMR spectroscopy, and Xꢀray diffracꢀ
tion (for I). The positions of the ν(NH) absorption
band in the IR spectrum and the NH proton signal in
The molecule of the complex has intramolecular
hydrogen bonds (HBs), C–H···
the O(2) atom (Table 3). The O(1) atom has three
more intermolecular HBs, C–H··· , giving rise to
O [34], which involve
1
the H NMR spectrum of HL suggest that the comꢀ
pound exists as the hydrazone tautomer [11, 24, 27].
The signal of the NH proton is fully suppressed by
addition of D2O, indicating its exchange nature.
The reaction of hydrazone HL with nickel(II) aceꢀ
tate in methanol yields complex I. The complex is diaꢀ
magnetic, which attests to a square environment of the
O
centrosymmetric dimers in the crystal (Fig. 2).
The reaction of hydrazone HL with copper(II) salts
is accompanied by its oxidation, resulting in copper(I)
compounds; however, preparative isolation of the
reaction products failed.
nickel ion [32]. The absence of the NHꢀproton signal
in the H NMR spectrum and the
1
ν(NH) absorption
band in the IR spectrum of the complex points to the
monodeprotonated form of hydrazone HL coordiꢀ
nated to nickel.
REFERENCES
1. Kogan, V.A, Zelentsov, V.V., Larin, G.M., and
Lukov, V.V., Kompleksy perekhodnykh metallov s gidraꢀ
zonami. Fizikoꢀkhimicheskie svoistva i stroenie (Transiꢀ
tion Metal Complexes with Hydrazones. Physicoꢀ
chemical Properties and Structures), Moscow: Nauka,
1990.
The structure of complex
I was determined by
Xꢀray diffraction; the single crystal was obtained by
recrystallization from DMSO. The Ni coordination
polyhedron is a slightly distorted square formed by
P(1), heterocyclic N(1) and azomethine N(3) nitroꢀ
gen atoms, and the O(2) atom of the carboxy group
(Fig. 1). The fiveꢀmembered chelate ring in the moleꢀ
2. Vigato, P.A. and Tamburini, S., Coord. Chem. Rev.
2004, vol. 248, nos. 18–20, p. 1717.
,
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 40
No. 5
2014

SYNTHESIS AND CRYSTAL STRUCTURE OF THE NICKEL(II) COMPLEX
283
3. Kogan, V.A., Levchenkov, S.I., Popov, L.D., and 19. Argay, G., Kalman, A., Parkanyi, L., et al., J. Coord.
Shcherbakov, I.N., Ross. Khim. Zh., 2009, vol. 53, no. 1,
Chem., 2000, vol. 51, no. 1, p. 9.
p. 86.
20. Castineiras, A. and Pedrido, R., Dalton Trans., 2010,
vol. 39, no. 15, p. 3572.
4. Popov, L.D., Morozov, A.N., Shcherbakov, I.N., et al.,
Usp. Khim., 2009, vol. 78, no. 7, p. 697.
21. Castineiras, A. and Pedrido, R., Inorg. Chem., 2008,
vol. 47, no. 13, p. 5534.
5. Stadler, A.ꢀM. and Harrowfield, J., Inorg. Chim. Acta,
2009, vol. 362, no. 12, p. 4298.
6. Gupta, K.C. and Sutar, A.K., Coord. Chem. Rev., 2008,
22. Brceski, I.D., Leovac, V.M., Bogdanovic', G.A., et al.,
Inorg. Chem. Commun., 2004, vol. 7, no. 2, p. 253.
23. Chang, M., Horiki, H., Nakajima, K., et al., Bull.
Chem. Soc. Jpn., 2010, vol. 83, no. 8, p. 905.
24. Chang, M., Kobayashi, A., Nakajima, K., et al., Inorg.
Chem., 2011, vol. 50, no. 17, p. 8308.
25. Popov, L.D., Askalepova, O.I., Kaimakan, E.B., et al.,
Russ. J. Gen. Chem., 2012, vol. 82, no. 7, p. 1233.
26. Levchenkov, S.I., Popov, L.D., Shcherbakov, I.N.,
vol. 252, nos. 12–14, p. 1420.
7. Quiroga, A.G. and Ranninger, C.N., Coord. Chem.
Rev., 2004, vol. 248, nos. 1–2, p. 119.
8. Rollas, S. and Küc,ükgüzel, S.G., Molecules, 2007,
vol. 12, no. 8, p. 1910.
9. Ronconi, L. and Sadler, P.J., Coord. Chem. Rev., 2007,
vol. 251, nos. 13–14, p. 1633.
10. Kogan, V.A., Lukov, V.V., and Shcherbakov, I.N., Russ.
J. Coord. Chem., 2010, vol. 36, no. 6, p. 401.
11. Bacchi, A., Carcelli, M., Costa, M., et al., J. Orgaꢀ
nomet. Chem., 2000, vols. 593–594, no. 1, p. 180.
12. Pelagatti, P., Bacchi, A., Bobbio, C., et al., Dalton
Trans., 2002, no. 8, p. 1820.
et al., Russ. J. Coord. Chem., 2013, vol. 39, no. 7, p. 493.
27. Levchenkov, S.I., Shcherbakov, I.N., Popov, L.D.,
et al., Inorg. Chim. Acta, 2013, vol. 405, p. 169.
28. SMART and SAINT. Release 5.0. Area Detector Sontrol
and Integration Software, Madison (WI, USA): Bruker
AXS, Analytical Xꢀray Instruments, 1998.
29. Sheldrick, G.M., SADABS: A Program for Exploiting the
Redundancy of AreaꢀDetector Xꢀray Data, Göttingen
(Germany): Univ. of Göttingen, 1999.
13. Pelagatti, P., Bacchi, A., Carcelli, M., et al., Eur. J.
Inorg. Chem., 2002, no. 2, p. 439.
14. Pelagatti, P., Bacchi, A., Balordi, M., et al., Eur. J.
Inorg. Chem., 2006, no. 12, p. 2422.
30. Sheldrick, G.M., Acta Crystallogr., Sect. A: Found.
Crystallogr., 2008, vol. 64, no. 1, p. 112.
15. Pelagatti, P., Bacchi, A., Balordi, M., et al., Eur. J.
Inorg. Chem., 2007, no. 1, p. 162.
16. Milenkovic', M., Bacchi, A., Cantoni, G., et al., Inorg.
31. Spek, A.L., J. Appl. Crystallogr., 2003, vol. 36, p. 7.
32. Rakitin, Yu.V. and Kalinnikov, V.T., Sovremennaya
magnetokhimiya (Modern Magnetochemistry), St. Peꢀ
tersburg: Nauka, 1994.
Chim. Acta, 2013, vol. 395, p. 33.
33. Allen, F.H., Kennard, O., Watson, D.G., et al.,
17. Barandov, A. and Abram, U., Z. Anorg. Allg. Chem.
,
J. Chem. Soc., Perkin Trans., 1987, no. 12, p. 2.
2007, vol. 633, nos. 11–12, p. 1897.
34. Steiner, T., Crystallogr. Rev., 2003, vol. 9, nos. 2–3,
18. Novakovic', S.B., Bogdanovic', G.A., Brceski, I.D.,
p. 177.
and Leovac, V.M., Acta Crystallogr., Sect. C: Cryst.
Struct. Commun., 2009, vol. 65, no. 7, p. m263.
Translated by Z. Svitan’ko
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 40
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2014