Acta Cryst.(2004). E60, m887±m889 DOI: 10.1107/S1600536804012851 You, Lin, Zhu and Liu [Ni(C16H24N2O)2](NO3)2
m887
metal-organic papers
Acta Crystallographica Section E Structure Reports Online
ISSN 1600-5368
trans
-Bis{2-[3-(cyclohexylamino)propylimino-methyl]phenolato}nickel(II) dinitrate
Zhong-Lu You,a,bYong-Shan Lin,bHai-Liang Zhua,b* and Wei-Sheng Liua
aDepartment of Chemistry, Fuyang Normal College, Fuyang Anhui 236041, People's Republic of China, andbDepartment of Chem-istry, Lanzhou University, Lanzhou 730000, People's Republic of China
Correspondence e-mail: [email protected]
Key indicators
Single-crystal X-ray study
T= 293 K
Mean(C±C) = 0.006 AÊ
Rfactor = 0.063
wRfactor = 0.148
Data-to-parameter ratio = 16.1
For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.
#2004 International Union of Crystallography Printed in Great Britain ± all rights reserved
The title compound, [Ni(C16H24N2O)2](NO3)2, is a
mono-nuclear nickel(II) compound. The NiIIatom is coordinated by
two N atoms and two O atoms from the Schiff base ligands. The four atoms around the metal are coplanar, constituting a slightly distorted square-planar geometry. The complex is located on an inversion center. All of the nitrate O atoms and all amine N atoms in the Schiff base ligands contribute to hydrogen bonds, leading to the formation of a three-dimensional network.
Comment
Recently, we have reported a few Schiff base complexes (You, Linet al., 2003; You, Quet al., 2003; You, Xionget al., 2004; You, Zhu & Liu, 2004). As an extension of our work on the structural characterization of Schiff base complexes, a mono-nuclear nickel(II) complex, (I), is reported here.
The structure of the title compound, (I) (Fig. 1), consists of a mononuclear [Ni(C16H24N2O)2]2+ cation and two nitrate
anions. The Ni atom, on an inversion center, is in a square-planar geometry and is four-coordinated by two N atoms and two O atoms from the Schiff base ligands. The four
coordi-Received 7 May 2004 Accepted 26 May 2004 Online 29 May 2004
Figure 1
metal-organic papers
m888
You, Lin, Zhu and Liu [Ni(C16H24N2O)2](NO3)2 Acta Cryst.(2004). E60, m887±m889 nating atoms around the central metal are coplanar, forming asquare-planar geometry around the Ni atom. The two trans
angles at the nickel(II) center are 180, by symmetry (Table 1),
and all other angles are close to 90, viz. 87.15 (12) and
92.85 (12), thus indicating a slightly distorted square-planar
geometry. The Ni1ÐO1 bond length [1.827 (3) AÊ] is compar-able to that observed in another Schiff base complex [1.833 (3) AÊ; Zhu et al., 2004]. The Ni1ÐN1 bond distance [1.919 (3) AÊ] is a little longer than the value [1.876 (3) AÊ] observed in the same previously reported complex.
In the crystal structure, all of the nitrate O atoms and all the amine N atoms in the Schiff base ligands contribute to the formation of hydrogen bonds, leading to the formation of a three-dimensional network (Fig. 2 and Table 2). As expected, the cyclohexyl groups in the complex adopt chair conforma-tions to minimize steric effects.
Experimental
N-Cyclohexyl-1,3-diaminopropane and salicylaldehyde were avail-able commercially and were used without further puri®cation. N-Cyclohexyl-1,3-diaminopropane (0.2 mmol, 31.2 mg) and salicyl-aldehyde (0.2 mmol, 24.4 mg) were dissolved in methanol (10 ml). The mixture was stirred for 1 h to obtain a clear orange solution ofL (0.2 mmol), where L is 2-[(3-cyclohexylaminopropylimino)methyl]-phenol. To the solution ofLwas added a solution of Ni(NO3)26H2O (0.1 mmol, 29.1 mg) in methanol (10 ml), with stirring. After keeping the resulting solution in air for 9 d, green block-shaped crystals were formed at the bottom of the vessel on slow evaporation of the
solvents. The crystals were isolated, washed three times with methanol and dried in a vacuum desiccator using anhydrous CaCl2 (yield 70.1%). Analysis found: C 54.6, H 6.9, N 11.9%; calculated for C32H48N6NiO8: C 54.8, H 7.1, N 11.8%.
Crystal data
[Ni(C16H24N2O)2](NO3)2
Mr= 703.47 Monoclinic,P21=c
a= 6.444 (2) AÊ b= 22.946 (5) AÊ c= 11.961 (2) AÊ
= 102.02 (3)
V= 1729.9 (6) AÊ3
Z= 2
Dx= 1.351 Mg mÿ3 MoKradiation Cell parameters from 1144
re¯ections
= 2.5±19.9
= 0.62 mmÿ1
T= 293 (2) K Block, green
0.180.150.13 mm
Data collection
Siemens SMART CCD area-detector diffractometer
'and!scans
Absorption correction: multi-scan (SADABS; Blessing, 1995) Tmin= 0.897,Tmax= 0.924
7948 measured re¯ections
3573 independent re¯ections 1985 re¯ections withI> 2(I) Rint= 0.063
max= 26.5
h=ÿ8!4 k=ÿ28!27 l=ÿ14!15
Re®nement
Re®nement onF2
R[F2> 2(F2)] = 0.063
wR(F2) = 0.148
S= 0.95 3573 re¯ections 222 parameters
H atoms treated by a mixture of independent and constrained re®nement
w= 1/[2(F
o2) + (0.0601P)2] whereP= (Fo2+ 2Fc2)/3 (/)max< 0.001
max= 0.48 e AÊÿ3
min=ÿ0.24 e AÊÿ3
Table 1
Selected geometric parameters (AÊ,).
Ni1ÐO1 1.827 (3) Ni1ÐN1 1.919 (3)
O1iÐNi1ÐO1 180
O1iÐNi1ÐN1 87.15 (12) O1ÐNi1ÐN1N1ÐNi1ÐN1i 18092.85 (12)
Symmetry code: (i) 1ÿx;1ÿy;1ÿz.
Table 2
Hydrogen-bonding geometry (AÊ,).
DÐH A DÐH H A D A DÐH A
N2ÐH2B N3ii 0.932 (10) 2.542 (12) 3.458 (6) 168 (3)
N2ÐH2B O3ii 0.932 (10) 2.36 (2) 3.125 (5) 139 (3)
N2ÐH2B O4ii 0.932 (10) 1.980 (15) 2.887 (5) 164 (3)
N2ÐH2A N3 0.926 (10) 2.558 (15) 3.462 (6) 165 (3) N2ÐH2A O2 0.926 (10) 2.26 (2) 3.105 (5) 150 (3) N2ÐH2A O3 0.926 (10) 2.234 (17) 3.076 (5) 151 (3)
Symmetry codes: (ii)x;3 2ÿy;12z.
All H atoms, except H2A and H2B, were placed in idealized positions and constrained to ride on their parent atoms, with CÐH distances of 0.93±0.98 AÊ, and withUiso(H) = 1.2Ueq(C). Atoms H2A and H2Bwere located in a difference Fourier map and were re®ned isotropically.
Data collection: SMART (Siemens, 1996); cell re®nement: SMART; data reduction:SAINT(Siemens, 1996); program(s) used to solve structure:SHELXS97 (Sheldrick, 1997a); program(s) used to re®ne structure:SHELXL97 (Sheldrick, 1997a); molecular graphics:
Figure 2
SHELXTL(Sheldrick, 1997b); software used to prepare material for publication:SHELXTL.
The authors thank the Education Of®ce of Anhui Province, People's Republic of China, for research grant No. 2004kj300zd.
References
Blessing, R. H. (1995).Acta Cryst.A51, 33±38.
Sheldrick, G. M. (1997a). SHELXL97 and SHELXS97. University of GoÈttingen, Germany.
Sheldrick, G. M. (1997b).SHELXTL.Version 5.1. Bruker AXS Inc., Madison, Wisconsin, USA.
Siemens (1996).SMARTandSAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.
You, Z.-L., Lin, Y.-S., Liu, W.-S., Tan, M.-Y. & Zhu, H.-L. (2003).Acta Cryst. E59, m1025±m1027.
You, Z.-L., Qu, Y., Liu, W.-S., Tan, M.-Y. & Zhu, H.-L. (2003).Acta Cryst.E59, m1038±m1040.
You, Z.-L., Xiong, Z.-D., Liu, W.-S., Tan, M.-Y. & Zhu, H.-L. (2004).Acta Cryst.E60, m79±m81.
You, Z.-L., Zhu, H.-L. & Liu, W.-S. (2004). Acta Cryst. E60, m560± m562.
Zhu, B., Ruang, W. & Zhu, Z. (2004).Acta Cryst.E60, m634±m636.
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Acta Cryst. (2004). E60, m887–m889
supporting information
Acta Cryst. (2004). E60, m887–m889 [https://doi.org/10.1107/S1600536804012851]
trans
-Bis{2-[3-(cyclohexylamino)propyliminomethyl]phenolato}nickel(II)
dinitrate
Zhong-Lu You, Yong-Shan Lin, Hai-Liang Zhu and Wei-Sheng Liu
trans-Bis{2-[3-(Cyclohexylamino)propyliminomethyl]phenolato}nickel(II) dinitrate
Crystal data
[Ni(C16H24N2O)2](NO3)2
Mr = 703.47
Monoclinic, P21/c a = 6.444 (2) Å
b = 22.946 (5) Å
c = 11.961 (2) Å
β = 102.02 (3)°
V = 1729.9 (6) Å3
Z = 2
F(000) = 748
Dx = 1.351 Mg m−3
Mo Kα radiation, λ = 0.71073 Å Cell parameters from 1144 reflections
θ = 2.5–19.9°
µ = 0.62 mm−1
T = 293 K Block, green
0.18 × 0.15 × 0.13 mm
Data collection
Siemens SMART CCD area-detector diffractometer
Radiation source: fine-focus sealed tube Graphite monochromator
φ and ω scans
Absorption correction: multi-scan sadabs, (Blessing, 1995)
Tmin = 0.897, Tmax = 0.924
7948 measured reflections 3573 independent reflections 1985 reflections with I > 2σ(I)
Rint = 0.063
θmax = 26.5°, θmin = 1.8°
h = −8→4
k = −28→27
l = −14→15
Refinement
Refinement on F2 Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.063
wR(F2) = 0.148
S = 0.95 3573 reflections 222 parameters 3 restraints
Primary atom site location: structure-invariant direct methods
Secondary atom site location: difference Fourier map
Hydrogen site location: inferred from neighbouring sites
H atoms treated by a mixture of independent and constrained refinement
w = 1/[σ2(F
o2) + (0.0601P)2] where P = (Fo2 + 2Fc2)/3 (Δ/σ)max < 0.001
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Acta Cryst. (2004). E60, m887–m889 Special details
Experimental. C, H and N elemental analyses were performed on a Perkin-Elmer elemental analyzer.
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x y z Uiso*/Ueq
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Acta Cryst. (2004). E60, m887–m889
C13 0.4350 (8) 0.91869 (17) 0.4896 (5) 0.0883 (16) H13A 0.3119 0.9438 0.4689 0.106* H13B 0.5153 0.9311 0.5635 0.106* C14 0.5700 (9) 0.92435 (18) 0.4022 (4) 0.0930 (17) H14A 0.6189 0.9643 0.4005 0.112* H14B 0.4863 0.9150 0.3272 0.112* C15 0.7582 (8) 0.88403 (18) 0.4298 (4) 0.0835 (14) H15A 0.8486 0.8961 0.5014 0.100* H15B 0.8397 0.8872 0.3705 0.100* C16 0.6934 (6) 0.82061 (16) 0.4397 (3) 0.0604 (11) H16A 0.6205 0.8065 0.3654 0.072* H16B 0.8191 0.7969 0.4649 0.072* H2A 0.389 (5) 0.7438 (17) 0.4528 (13) 0.085 (16)* H2B 0.374 (4) 0.7525 (16) 0.575 (2) 0.073 (13)*
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
Ni1 0.0538 (4) 0.0331 (3) 0.0583 (4) −0.0014 (3) 0.0157 (3) 0.0036 (3) O1 0.083 (2) 0.0426 (15) 0.099 (2) 0.0021 (14) 0.0417 (18) 0.0067 (14) O2 0.144 (4) 0.128 (3) 0.114 (3) −0.003 (2) 0.076 (3) −0.019 (2) O3 0.078 (2) 0.101 (2) 0.089 (2) −0.008 (2) 0.003 (2) 0.0032 (19) O4 0.082 (3) 0.243 (5) 0.077 (3) 0.039 (3) 0.012 (2) 0.026 (3) N1 0.0503 (19) 0.0414 (17) 0.0526 (19) −0.0048 (14) 0.0112 (16) −0.0001 (14) N2 0.057 (2) 0.0416 (18) 0.064 (2) −0.0021 (16) 0.018 (2) 0.0049 (16) N3 0.081 (3) 0.080 (3) 0.069 (3) −0.014 (2) 0.020 (3) −0.010 (2) C1 0.058 (2) 0.048 (2) 0.049 (2) −0.0071 (19) 0.0076 (19) −0.0030 (19) C2 0.057 (2) 0.053 (2) 0.051 (2) −0.0073 (19) 0.016 (2) −0.0006 (19) C3 0.082 (3) 0.051 (2) 0.066 (3) −0.003 (2) 0.022 (3) 0.005 (2) C4 0.088 (3) 0.070 (3) 0.064 (3) −0.023 (3) 0.025 (3) 0.011 (2) C5 0.078 (3) 0.096 (4) 0.076 (3) −0.007 (3) 0.040 (3) −0.001 (3) C6 0.082 (3) 0.067 (3) 0.073 (3) 0.006 (2) 0.028 (3) −0.009 (2) C7 0.063 (3) 0.045 (2) 0.054 (2) 0.0020 (19) 0.009 (2) −0.0046 (18) C8 0.059 (3) 0.0361 (19) 0.058 (2) 0.0033 (17) 0.010 (2) 0.0065 (17) C9 0.074 (3) 0.036 (2) 0.066 (3) −0.0049 (19) 0.000 (2) 0.0067 (18) C10 0.054 (3) 0.051 (2) 0.085 (3) 0.0008 (19) −0.002 (2) 0.005 (2) C11 0.072 (3) 0.0337 (19) 0.060 (3) −0.0069 (18) 0.018 (2) −0.0025 (17) C12 0.088 (4) 0.043 (2) 0.113 (4) 0.006 (2) 0.042 (3) 0.002 (2) C13 0.121 (4) 0.042 (2) 0.107 (4) 0.012 (2) 0.033 (4) 0.000 (3) C14 0.150 (5) 0.036 (2) 0.095 (4) −0.004 (3) 0.030 (4) 0.009 (2) C15 0.105 (4) 0.061 (3) 0.088 (4) −0.022 (3) 0.027 (3) 0.014 (2) C16 0.070 (3) 0.050 (2) 0.064 (3) −0.0047 (19) 0.019 (2) 0.0059 (19)
Geometric parameters (Å, º)
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Acta Cryst. (2004). E60, m887–m889
Ni1—N1i 1.919 (3) C9—C10 1.508 (5) O1—C2 1.305 (4) C9—H9A 0.9700 O2—N3 1.208 (5) C9—H9B 0.9700 O3—N3 1.223 (5) C10—H10A 0.9700 O4—N3 1.228 (5) C10—H10B 0.9700 N1—C7 1.268 (5) C11—C16 1.491 (5) N1—C8 1.492 (4) C11—C12 1.515 (5) N2—C10 1.477 (5) C11—H11 0.9800 N2—C11 1.516 (4) C12—C13 1.522 (5) N2—H2A 0.926 (10) C12—H12A 0.9700 N2—H2B 0.932 (10) C12—H12B 0.9700 C1—C6 1.399 (5) C13—C14 1.498 (6) C1—C2 1.403 (5) C13—H13A 0.9700 C1—C7 1.435 (5) C13—H13B 0.9700 C2—C3 1.402 (5) C14—C15 1.506 (6) C3—C4 1.339 (6) C14—H14A 0.9700 C3—H3 0.9300 C14—H14B 0.9700 C4—C5 1.367 (6) C15—C16 1.525 (5) C4—H4 0.9300 C15—H15A 0.9700 C5—C6 1.376 (6) C15—H15B 0.9700 C5—H5 0.9300 C16—H16A 0.9700 C6—H6 0.9300 C16—H16B 0.9700 C7—H7 0.9300
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Acta Cryst. (2004). E60, m887–m889
C3—C2—C1 118.2 (4) C14—C13—H13A 109.5 C4—C3—C2 121.3 (4) C12—C13—H13A 109.5 C4—C3—H3 119.3 C14—C13—H13B 109.5 C2—C3—H3 119.3 C12—C13—H13B 109.5 C3—C4—C5 122.0 (4) H13A—C13—H13B 108.1 C3—C4—H4 119.0 C13—C14—C15 110.6 (4) C5—C4—H4 119.0 C13—C14—H14A 109.5 C4—C5—C6 118.1 (4) C15—C14—H14A 109.5 C4—C5—H5 120.9 C13—C14—H14B 109.5 C6—C5—H5 120.9 C15—C14—H14B 109.5 C5—C6—C1 122.1 (4) H14A—C14—H14B 108.1 C5—C6—H6 119.0 C14—C15—C16 112.5 (4) C1—C6—H6 119.0 C14—C15—H15A 109.1 N1—C7—C1 127.1 (4) C16—C15—H15A 109.1 N1—C7—H7 116.4 C14—C15—H15B 109.1 C1—C7—H7 116.4 C16—C15—H15B 109.1 N1—C8—C9 109.4 (3) H15A—C15—H15B 107.8 N1—C8—H8A 109.8 C11—C16—C15 110.4 (3) C9—C8—H8A 109.8 C11—C16—H16A 109.6 N1—C8—H8B 109.8 C15—C16—H16A 109.6 C9—C8—H8B 109.8 C11—C16—H16B 109.6 H8A—C8—H8B 108.3 C15—C16—H16B 109.6 C10—C9—C8 115.4 (3) H16A—C16—H16B 108.1
O1i—Ni1—O1—C2 32 (100) C7—C1—C6—C5 178.8 (4) N1—Ni1—O1—C2 −3.7 (4) C8—N1—C7—C1 −177.1 (3) N1i—Ni1—O1—C2 176.3 (4) Ni1—N1—C7—C1 2.0 (5) O1i—Ni1—N1—C7 −179.3 (3) C6—C1—C7—N1 178.9 (4) O1—Ni1—N1—C7 0.7 (3) C2—C1—C7—N1 −2.5 (6) N1i—Ni1—N1—C7 −79 (100) C7—N1—C8—C9 94.6 (4) O1i—Ni1—N1—C8 −0.3 (2) Ni1—N1—C8—C9 −84.6 (3) O1—Ni1—N1—C8 179.7 (2) N1—C8—C9—C10 166.7 (3) N1i—Ni1—N1—C8 100 (100) C11—N2—C10—C9 161.8 (3) Ni1—O1—C2—C3 −177.0 (3) C8—C9—C10—N2 59.0 (5) Ni1—O1—C2—C1 4.1 (6) C10—N2—C11—C16 57.4 (5) C6—C1—C2—O1 178.1 (4) C10—N2—C11—C12 −178.2 (4) C7—C1—C2—O1 −0.5 (6) C16—C11—C12—C13 −54.4 (5) C6—C1—C2—C3 −0.9 (5) N2—C11—C12—C13 −177.8 (4) C7—C1—C2—C3 −179.5 (3) C11—C12—C13—C14 55.8 (5) O1—C2—C3—C4 −178.5 (4) C12—C13—C14—C15 −57.0 (5) C1—C2—C3—C4 0.5 (6) C13—C14—C15—C16 56.4 (5) C2—C3—C4—C5 0.7 (7) C12—C11—C16—C15 52.7 (5) C3—C4—C5—C6 −1.5 (7) N2—C11—C16—C15 174.0 (3) C4—C5—C6—C1 1.0 (7) C14—C15—C16—C11 −53.7 (5) C2—C1—C6—C5 0.1 (6)
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Acta Cryst. (2004). E60, m887–m889 Hydrogen-bond geometry (Å, º)
D—H···A D—H H···A D···A D—H···A
N2—H2B···N3ii 0.93 (1) 2.54 (1) 3.458 (6) 168 (3) N2—H2B···O3ii 0.93 (1) 2.36 (2) 3.125 (5) 139 (3) N2—H2B···O4ii 0.93 (1) 1.98 (2) 2.887 (5) 164 (3) N2—H2A···N3 0.93 (1) 2.56 (2) 3.462 (6) 165 (3) N2—H2A···O2 0.93 (1) 2.26 (2) 3.105 (5) 150 (3) N2—H2A···O3 0.93 (1) 2.23 (2) 3.076 (5) 151 (3)
