Synthesis, Characterization and Crystal Structure of

32 卷 10 期 2013. 10

结

构化学（JIEGOU HUAXUE） Chinese J. Struct. Chem.

Vol. 32, No. 10 1485─1490

Synthesis, Characterization and Crystal Structure of [Ni(S2P{O}OC6H4CH3-p)(dppv)] ① XIE Bina, b② ZHU Sha-Shac LI Yu-Longa, b ZOU Li-Kea, b LIN Xiaoc HE Lin-Xina ZHANG Xiu-Lana XIE Fengd a

(Institute of Functional Materials, Sichuan University of Science & Engineering, Zigong 643000, China) b

(University Key Laboratory of Green Chemistry of

Sichuan Institutes of Higher Education, Zigong 643000, China) c

(College of Material & Chemical Engineering,

Sichuan University of Science & Engineering, Zigong 643000, China) d

(College of Chemistry & Chemical Engineering,

Neijiang Normal University, Neijiang 641100, China) ABSTRACT

O-(p-tolyl)dithiophosphato nickel complex [Ni(S2P{O}OC6H4CH3-p)(dppv)] has

been synthesized by the treatment of (dppv)NiCl2 (dppv = Ph2PCH=CHPPh2) with (p-CH3C6H4O)2P{S}SH·Et2NH in THF. The new complex was fully characterized by elemental analysis, IR, 1H NMR,

31

P NMR spectroscopies and thermo-gravimetric analysis. The molecular

structure of the complex was established by X-ray crystallography. The crystal crystallizes in monoclinic, space group P21/c with a = 9.2739(5), b = 17.8803(8), c = 20.1879(12) Å, β = 93.269(5)º, V = 3342.1(3) Å3, Z = 4, C33H29NiO2P3S2, Mr = 673.30, Dc = 1.338 g/cm3, F(000) = 1392 and μ(MoKα) = 0.877 mm-1. The final R = 0.0578 and wR = 0.1045 for 4138 observed reflections with I > 2σ(I) and R = 0.1050 and wR = 0.1204 for all data. The Ni centre atom adopts a NiP2S2 square-planar geometry with two phosphorus atoms from the dppv ligand and two sulfur atoms from the O-(p-tolyl)dithiophosphate ligand. The most interesting structural feature of the title complex resides in its 1D helical chain structure constructing via intermolecular C–H···O secondary interactions along the b-axis. The adjacent helical chains running in opposite directions are connected into a 1D double-stranded helical chain and further linked into a 2D supramolecular network by weak C–H···C interaction. Keywords: dithiophosphate, synthesis, dppv, crystal structure

1 INTRODUCTION

place of Pd in Suzuki-type coupling of boronic acids, (diphosphine)NiCl2 (diphosphine = dppe,

Since the discovery of nickel could be used in

dppv, dppf) have received special attention[1-5].

Received 14 March 2013; accepted 27 August 2013 (CCDC 920345) ① The work was supported by Science & Technology Department of Sichuan Province (Nos: 2011JY0052, 2012JY0115, 2010GZ0130), Sichuan University of Science & Engineering (Nos: 2012PY04, 2012PY14, 2011RC06, y2012017), and University Key Laboratory of Green Chemistry of Sichuan Institutes of Higher Education (No. LZJ1103, LZJ1203) ② Corresponding author. E-mail: [email protected]

XIE B. et al.: Synthesis, Characterization and Crystal Structure of [Ni(S2P{O}OC6H4CH3-p)(dppv)]

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Meanwhile, dithiophosphoric acid (RO)2P(S)SH has

CH2Cl2/THF (v/v = 6:1) as eluent. From the main

also been well investigated, largely because of its

red band, complex [Ni(S2P{O}OC6H4CH3-p)(dppv)]

applications as insecticides and inhibitors of hy-

(0.300 g, 89%) was obtained as a red solid. m.p:

[6]

drolysis of the enzyme acetylcholinesterase . To

210～212 ℃. Anal. Calcd. (%) for C33H29NiO2P3S2:

date, a lot of dithiophosphate complexes have been

C, 58.86; H, 4.34. Found (%): C, 58.75; H, 4.40. IR

[7-10]

(p-

(KBr disk): 3052(m), 2938(s), 2828(w), 1616(s),

CH3C6H4O)2PS2H·Et2NH in THF at room tem-

1516(s), 1481(s), 1435(vs), 1206(vs), 1160(vs),

perature, (dppv)NiCl2 (dppv = Ph2PCH=CHPPh2)

1101(vs),

published

.

When

treated

with

affords a new O-(p-tolyl)dithiophosphato nickel complex

[Ni(S2P{O}OC6H4CH3-p)(dppv)].

The

1046(vs),

999(s),

755(vs),

715(vs),

−1 1

691(vs), 530(vs) cm . H NMR (400 MHz, DMSO, TMS): 2.38 (s, 3H, CH3), 6.95, 7.15 (2s, 2H,

synthetic route is very simple and can be used to

CH=CH), 7.51～7.90 (m, 24H, 4C6H5, C6H4) ppm.

synthesize other analogues. We also expect the title

31

complex can be used to synthesize the [NiFe]

73.24 (s) ppm.

[11]

hydrogenases models

.

P NMR (162 MHz, DMSO, 85% H3PO4): 54.03 (s),

2. 3

Structure determination

A red single crystal for X-ray diffraction analysis

2

was grown by slow evaporation of the CH2Cl2/n-

EXPERIMENTAL

hexane solutions at about −10 ℃. The single crystal 2. 1

was mounted on a Rigaku saturn CCD area detector.

Materials and measurements

All solvents were dried using standard procedures

Data were collected at 293(2) K by using a

and

graphite-monochromator with Mo-Kα radiation

(p-CH3C6H4O)2PS2H·Et2NH were prepared accor-

(λ = 0.71073 Å) in the ω-φ scanning mode. A total

and

distillated

under

N2.

Ni(dppv)Cl2 [12-13]

, respectively.

of 14047 reflections were measured in the range of

Some other materials were commercially available.

2.90

A solution of (dppv)NiCl2 (0.263 g, 0.5 mmol) in THF

(20

mL)

was

treated

with

2σ(I) and R = 0.1050 and wR = 0.1204 for all data.

(p-

The solvent molecules are highly disordered in the

CH3C6H4O)2PS2H·Et2NH (0.395 g, 1.0 mmol) to

crystal and the resulting electron density is found to

give a red solution. After stirring at room tem-

be

perature for 1.0 h, volatiles were removed under

scattering contribution was subtracted from the

vacuum and the residue was subjected to TLC using

observed diffraction data using the SQUEEZE

uninterpretable.

Therefore,

their

estimated

2013

Vol. 32

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routine in PLATON

构

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学（JIEGOU HUAXUE）Chinese

[17]

. The solvent-free model was

employed for the final refinement and thus causes 3

four cavities of 69 Å per unit cell.

J. Struct.

Chem.

1487

[9]

ligand, respectively . 3. 2

Crystal structure

The molecular structure of the O-(p-tolyl)dithiophosphato nickel complex [Ni(S2P{O}OC6H4CH3p)(dppv)] was determined by X-ray diffraction

3 RESULTS AND DISCUSSION

analysis. ORTEP diagram of the title complex is 3. 1

shown in Fig. 1 and the selected bond lengths and

Synthesis and characterization (p-

bond angles are listed in Table 1. As can be seen in

CH3C6H4O)2P{S}SH·Et2NH in THF solution at

Fig. 1, the geometry at the Ni centre in complex

room temperature afforded the O-(p-tolyl)dithio-

[Ni(S2P{O}OC6H4CH3-p)(dppv)] is square-planar

phosphato nickel complex [Ni(S2P{O}OC6H4CH3-

with the NiP2S2 chromophore. The nickel atom is

p)(dppv)] in 89% yield. The new complex was fully

coordinated by two phosphorus atoms from one

characterized by elemental analysis and various

dppv ligand and two sulfur atoms from one O-(p-

spectroscopies. For example, the IR spectrum of the

tolyl)dithiophosphato ligand. The crystallographic

title complex shows the bands as follows: 3052 (Ar,

study of the complex [Ni(S2P{O}OC6H4CH3-

v[C-H]), 1616, 1516, 1481 (Ar, v[C=C]), 1046(v[P-

p)(dppv)] revealed that the Ni(1)–P(3) 2.1484(10) Å,

O-(C)]), 999(v[(P)-O-C]), 694(v[P-S]as), and 530

Ni(1)–P(2) 2.1464(11) Å, Ni(1)–S(1) 2.2192(11) Å,

The

treatment

-1

of

(dppv)NiCl2

with

1

(v[P-S]s) cm . The H NMR spectrum of the title

and Ni(1)–S(2) 2.2105(11) Å bond lengths are

complex displayed signals in the range of δ 7.51～

almost the same as the corresponding values of

31

7.90 ppm for the Ph groups. The P NMR spectrum

complex [Ni(S2P{O}OCH2CH3)(dppe)] (Ni(1)–P(3)

in DMSO solution demonstrated two single peaks at

2.1414(6) Å, Ni(1)–P(2) 2.1608(6) Å, Ni(1)–S(1)

δ 54.03 and 73.24 ppm which can be assigned to the

2.2224(6) Å, and Ni(1)–S(2) 2.2124(6) Å)[9].

bidentate dppv ligand and the bidentate RO{O}PS22Table 1.

Selected Bond Lengths (Å) and Bond Angles (°)

Bond

Dist.

Bond

Dist.

Bond

Dist.

Ni(1)–P(3)

2.1484(10)

Ni(1)–S(2)

2.2105(11)

P(1)–O(2)

1.617(3)

Ni(1)–P(2)

2.1464(11)

S(1)–P(1)

2.0273(15)

P(1)–O(1)

1.471(3)

N(1)–S(1)

2.2192(11)

S(2)–P(1)

2.0299(15)

P(2) –C(1)

1.804(4)

Angle

(°)

Angle

(°)

Angle

(°)

P(2)–Ni(1)–P(3)

87.61(4)

P(3)–Ni(1)–S(2)

91.94(4)

S(1)–P(1)–S(2)

99.22(6)

P(2)–Ni(1)–S(1)

91.81(4)

S(2)–Ni(1)–S(1)

88.47(4)

O(1)–P(1)–S(1)

117.64(15)

P(2)–Ni(1)–S(2)

176.26(5)

P(1)–S(1)–Ni(1)

85.89(5)

O(1)–P(1)–O(2)

104.76(15)

P(3)–Ni(1)–S(1)

177.41(4)

P(1)–S(2)–Ni(1)

86.06(5)

O(2)–P(1)–S(1)

108.72(12)

Fig. 1.

ORTEP view of the title complex with 30% probability level ellipsoids


1488

The

selected

bond

P(2)−Ni(1)−P(3)

constructing via intermolecular secondary interac-

87.61(4)°, P(1)−Ni(1)−S(1) 91.81(4)°, S(2)−Ni(1)−

tions along the b-axis, as illustrated in Fig. 2. The

S(1) 88.47(4)°, and P(3)−Ni(1)−S(2) 91.94(4)° for

parameters associated with the intermolecular

the complex [Ni(S2P{O}OC6H4CH3-p)(dppv)] indi-

C–H···O associations are H(20)···O(1)i 2.498 Å,

cated that the coordination geometry around nickel

C(20)···O(1)i 3.356 Å and the angle at H is 153.66°

is slightly distorted from square-planar configuration

for symmetry operation (i): –x, 1/2+y, 1/2–z. The

(sum of the angles is 360.83°), which can be further

hydrogen bonds undoubtedly steer the rotation

illustrated by the torsion angles, Ni(1)–S(1)–

direction of the helix. The adjacent helical chains

P(1)–S(2)

Ni(1)–S(2)–P(1)–S(1)

run in opposite direction and are not entangled

4.75(6)°, only slightly deviating from the desired

together but connected into a 1D double-stranded

value 0° for square-planar geometry. The two

helical chain by weak C–H···C interaction offered

phosphorus atoms from the dppv ligand and two

alternatively by two helical chains[18]. The para-

sulfur atoms from the O-(p-tolyl)dithiophosphato

meters associated with the C–H···C intermolecular

ligand are located on one absolute plane, and the

secondary interactions are H(18)···C(33)ii 2.751 Å,

nickel atom is 0.048 Å deviating from this plane.

C(18)···C(33)ii 3.506 Å and the angle at H is 139.07°

The dihedral angle between the coordination plane

(symmetry operation (ii): –1+x, 3/2–y, –1/2+z).

NiP2S2 and the CH=CH plane of the dppv ligand is

Furthermore, the same C–H···C interactions link the

only 7.51°. The five-membered coordination ring

1D double-stranded helical chains into a 2D

NiP2C2 fragment is essentially planar with the

supramolecular network, as shown in Fig. 2. Due to

maximum deviations of 0.042(5) Å for P(3) atom

left- and right-handed helical chains coexisting in

and 0.042(4) Å for Ni(1) atom, respectively.

the crystal structure, the whole crystal is mesomeric

–4.74(6)°

angels

No. 10

and

The most interesting structural feature of the title

and does not exhibit chirality[19].

complex resides in its 1D helical chain structure

Fig. 2.

3. 3

Views of 1D double-stranded helical chains and 2D supramolecular network (The phenyl rings on the P(2) atoms are omitted for clarity)

TG analysis

NETZSCH STA 409 PC/PG instrument over a

To reveal the thermal stability of the title complex,

temperature range from ambient to about 1000 ℃ at

TG measurement has been carried out on a

a heating rate of 5 ℃·min-1 in the presence of

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J. Struct.

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2-

purified N2 (10 mL·min ) atmosphere. The TG

CH3C6H4O{O}PS2 . The residual mass (22.46%) is

curve (Fig. 3) indicates that there are three stages

consistent with the mass of nickel pyrophosphate

occurring during the weight loss process. The first

(Ni2P2O7, calcd. 21.62% of the initial mass). The last

slight weight loss of 1.77% (up to about 160 ℃) is

stage occurs over a wide temperature range (from

due to moisture removal from the sample. The

410.3 ℃ to temperature > 800 ℃) and results from

second and major weight loss of 75.26% of the

the additional removal of PO3 group. The residual

initial mass in the corresponding temperature range

mass (16.75%) is roughly consistent with the mass

(from 290.3 to 410.3 ℃) corresponds to the

of nickel phosphate (Ni3(PO4)2, calcd. 18.12% of the

decomposition of both ligands, dppv and p-

initial mass).

Weight %

100

80

60

40

20

0 0

200

400

600

800 T e m p e ra tu re

Fig. 3.

1000 o

C

TG curve for the title complex

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