Z. Kristallogr. NCS 229 (2014) 449-451 / DOI 10.1515/ncrs-2014-9016
449
© 2014 by Walter de Gruyter Berlin/Boston
Crystal structure of diaqua-(2,4-dihydroxybenzoato-"2O,O')-(2,9dimethyl-1,10-phenanthroline-"2N,N') nickel(II) 2,4-dihydroxybenzoate,
C28H26N2NiO10
Libing GuoI, II and Shuxia Zhang*, I
I
II
School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang 453007, Henan Province, P. R.China
Institute of Chemistry Henan Academy of Sciences, Zhengzhou 450002, Henan Province, P. R. China
Received August 16, 2014, accepted October 06, 2014, available online October 10, 2014, CCDC no. 1267/4196
Abstract
C28H26N2NiO10, monoclinic, P21/n (no. 14), a = 9.4921(9) Å,
b = 24.194(2) Å, c = 11.526(1) Å, $ = 98.607(1)°,
V = 2617.1 Å3, Z = 4, Rgt(F) = 0.0308, wRref(F2) = 0.0822,
T = 296 K.
Table 1. Data collection and handling.
Crystal:
Wavelength:
#:
Diffractometer, scan mode:
2"max:
N(hkl)measured, N(hkl)unique:
Criterion for Iobs, N(hkl)gt:
N(param)refined:
Programs:
blue blocks, size 0.20%0.32%0.36 mm
Mo K# radiation (0.71073 Å)
8.06 cm$1
CCD area detector, ' and &
51°
18917, 4875
Iobs > 2 !(Iobs), 4008
378
SHELX [14]
Source of material
To a solution of 2,9-dimethyl-1,10-phenanthroline hemihydrate
(0.5 mmol), 2,4-hydroxybenzoate (0.5 mmol) and sodium hydroxide (0.5 mmol) in water/ethanol(v:v=2:1, 15 ml) was added a
solution of Ni(NO3)2!6H2O (0.5 mmol) in distilled water (5 ml).
The resulting solution was refluxed for 10 h at 333 K and filtrated.
Blue single crystals of the title compound were obtained by slow
evaporation of the filtrate over four weeks.
Discussion
In recent years, 2,9-dimethyl-phenanthroline (dmphen), as a
usual derivative of 1,10-phenanthroline, has been widely employed in many aspects of coordinational chemistry [1–5],
supermolecular chemistry [6–7] and bioinorganic chemistry [8].
Combined with other aromatic coordinating ligands, dmphen has
_____________
* Correspondence author (e-mail: [email protected])
been used to enhance the characters of their metal complexs [1].
In our previous investigations [3–5], we reported a set of coordination compounds composed of dmphen and hydroxybenzoic
acid. Herein, we present the synthesis and crystal structure of the
title compounds. The experimental crystal parameters are summarized in Table1. As shown in the figure, the asymmetric unit in
the title compound contains one mo non u c l e a r
[Ni(H2O)2(dmphen)(DHB)] (DHB=2,4-dihydroxybenzoic acid),
and one uncoordinated 2,4-dihydroxybenzoate anion. The central
Ni(II) ion adopts a six-coordinated octahedral geometry surrounded by two nitrogen atoms of one bidentate dmphen ligand,
four oxygen atoms from two water molecules and one
deprotonated DHB. The two water molecules occupy the apical
position, and two oxygen atoms of DHB, two nitrogen atoms and
one metal Ni(II) ion form the equatorial plane. The four nonequivalent Ni–O bond lengths are in the ranges of 2.063 - 2.165
Å, and the two Ni–N bond lengths are 2.0608(16) and 2.0756(16)
Å, respectively. Obviously, due to the hindrance effect of two
methyl groups of the dmphen ligand, this compound cannot accommodate two benzoate moieties at the same time as found in
other compounds [9–10], and the water molecules often participate in the coordination [11–12]. Closely related Ni(II) complexes have been reported by Xuan et al. [12–13]. In this crystal
structure, an extensive series of classic O–H!!!O hydrogen bonds,
involving water molecules, the coordinated and uncoordinated
DHB anions, leads to a three-dimensional structure with the O!!!O
distances in the range of 2.531 - 2.872 Å. Additionally, this crystal is further stablizing by the weak %!!!% interactions. Three types
of aromatic %!!!% stacking between dmphen and benzene ligands
are observed in this case. Their centroid-centroid distances lie in
the range of 3.612-3.673 Å. This combination of O–H!!!O hydrogen bonds and %!!!% stacking interactions builds a complex network.
Table 2. Atomic coordinates and displacement parameters (in Å2).
Atom
Site
x
y
H(3)
H(4)
H(7)
H(8)
H(1W)
H(2W)
H(3W)
H(4W)
H(2)
H(3A)
H(5)
H(6)
4e
4e
4e
4e
4e
4e
4e
4e
4e
4e
4e
4e
0.7807
1.1078
0.8058
0.4324
0.3986
0.3686
0.8349
0.7609
0.3664
0.2361
0.1708
0.2011
0.1435
$0.0165
0.2944
0.3130
0.0498
0.1065
0.1026
0.1025
$0.0724
$0.0122
0.0871
0.1780
z
0.4217
0.1711
$0.0695
0.3035
0.5115
0.5089
0.7635
0.8552
0.8972
0.9901
1.0292
0.9984
Uiso
0.098
0.080
0.070
0.067
0.059
0.059
0.049
0.049
0.046
0.049
0.056
0.057
Unauthenticated
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450
C28H26N2NiO10
Table 2. continued.
Table 2. continued.
Atom
Site
x
y
H(8A)
H(9A)
H(13A)
H(13B)
H(13C)
H(14A)
H(14B)
4e
4e
4e
4e
4e
4e
4e
0.3196
0.4644
0.5005
0.5522
0.6412
0.7043
0.6128
0.2544
0.2795
$0.0606
$0.0902
$0.0414
0.2053
0.2590
z
Uiso
Atom
Site
x
y
0.8985
0.7670
0.6667
0.7864
0.7453
0.6552
0.6289
0.052
0.051
0.061
0.061
0.061
0.071
0.071
H(14C)
H(17)
H(19)
H(20)
H(24)
H(26)
H(27)
4e
4e
4e
4e
4e
4e
4e
0.5704
0.9946
0.9740
0.8317
0.6164
0.4794
0.6037
0.2048
0.1073
$0.0551
$0.0369
0.3613
0.2241
0.1714
z
Uiso
0.5574
0.2334
0.2998
0.4399
0.1042
0.2488
0.1331
0.071
0.055
0.042
0.039
0.044
0.048
0.048
Table 3. Atomic coordinates and displacement parameters (in Å2).
Atom
Site
x
Ni(1)
O(1)
O(2)
O(3)
O(4)
O(5)
O(6)
O(7)
O(8)
O(9)
O(10)
N(1)
N(2)
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
C(8)
C(9)
C(10)
C(11)
C(12)
C(13)
C(14)
C(15)
C(16)
C(17)
C(18)
C(19)
C(20)
C(21)
C(22)
C(23)
C(24)
C(25)
C(26)
C(27)
C(28)
4e
4e
4e
4e
4e
4e
4e
4e
4e
4e
4e
4e
4e
4e
4e
4e
4e
4e
4e
4e
4e
4e
4e
4e
4e
4e
4e
4e
4e
4e
4e
4e
4e
4e
4e
4e
4e
4e
4e
4e
4e
0.58590(3)
0.7136(2)
0.6805(2)
0.8392(2)
1.0857(2)
0.8377(2)
0.7477(2)
0.7683(2)
0.4657(2)
0.4111(2)
0.7744(2)
0.4758(2)
0.5019(2)
0.4635(2)
0.3734(2)
0.2965(2)
0.3085(2)
0.2328(3)
0.2502(3)
0.3425(2)
0.3643(3)
0.4503(3)
0.5183(2)
0.4154(2)
0.3997(2)
0.5468(3)
0.6096(3)
0.8237(2)
0.8740(3)
0.9617(3)
0.9996(2)
0.9497(2)
0.8639(2)
0.7357(2)
0.6873(2)
0.6906(2)
0.6145(2)
0.5357(2)
0.5319(2)
0.6068(2)
0.7622(2)
y
0.08002(1)
0.10693(6)
0.01882(5)
0.14224(6)
0.01622(7)
0.22235(7)
0.14619(6)
0.31738(6)
0.33172(6)
0.08080(6)
0.08536(5)
0.03870(6)
0.14823(6)
$0.01543(8)
$0.03465(9)
0.0010(1)
0.05817(9)
0.0984(1)
0.1524(1)
0.17144(9)
0.22744(9)
0.24228(9)
0.20230(8)
0.13315(9)
0.07515(8)
$0.05547(9)
0.21937(9)
0.04606(8)
0.08918(9)
0.07837(9)
0.02466(9)
$0.01890(9)
$0.00770(9)
0.05687(8)
0.23315(8)
0.29106(9)
0.32298(9)
0.29844(9)
0.24102(9)
0.20965(9)
0.19752(9)
z
0.66982(2)
0.5446(1)
0.5681(1)
0.3762(2)
0.1718(2)
$0.0954(2)
$0.0248(1)
$0.0317(1)
0.2548(1)
0.5397(1)
0.7925(1)
0.7861(1)
0.7418(1)
0.8069(2)
0.8841(2)
0.9399(2)
0.9216(2)
0.9785(2)
0.9596(2)
0.8812(2)
0.8594(2)
0.7813(2)
0.7217(2)
0.8214(2)
0.8436(2)
0.7459(2)
0.6328(2)
0.4226(2)
0.3592(2)
0.2752(2)
0.2543(2)
0.3152(2)
0.3984(2)
0.5148(2)
0.0483(2)
0.0421(2)
0.1104(2)
0.1878(2)
0.1967(2)
0.1272(2)
$0.0277(2)
U11
U22
U33
0.0326(2)
0.0485(9)
0.0376(8)
0.103(2)
0.069(1)
0.063(1)
0.072(1)
0.062(1)
0.055(1)
0.0466(9)
0.0358(8)
0.0324(9)
0.0334(9)
0.039(1)
0.050(1)
0.045(1)
0.038(1)
0.051(1)
0.058(2)
0.041(1)
0.055(2)
0.053(1)
0.040(1)
0.031(1)
0.030(1)
0.056(1)
0.058(2)
0.030(1)
0.052(1)
0.060(2)
0.040(1)
0.037(1)
0.036(1)
0.032(1)
0.038(1)
0.036(1)
0.046(1)
0.035(1)
0.049(1)
0.053(1)
0.042(1)
0.0203(1)
0.0258(8)
0.0259(7)
0.0261(9)
0.046(1)
0.043(1)
0.0319(9)
0.0344(9)
0.0344(9)
0.0283(8)
0.0282(8)
0.0231(8)
0.0216(8)
0.024(1)
0.030(1)
0.044(1)
0.041(1)
0.055(2)
0.047(2)
0.035(1)
0.032(1)
0.021(1)
0.024(1)
0.028(1)
0.029(1)
0.025(1)
0.027(1)
0.029(1)
0.026(1)
0.034(1)
0.039(1)
0.031(1)
0.027(1)
0.028(1)
0.028(1)
0.033(1)
0.024(1)
0.033(1)
0.032(1)
0.027(1)
0.038(1)
0.0293(2)
0.0421(9)
0.0339(8)
0.082(1)
0.056(1)
0.053(1)
0.046(1)
0.051(1)
0.052(1)
0.0423(9)
0.0363(8)
0.0271(9)
0.0306(9)
0.029(1)
0.038(1)
0.037(1)
0.030(1)
0.042(1)
0.043(1)
0.034(1)
0.044(1)
0.051(1)
0.039(1)
0.028(1)
0.024(1)
0.044(1)
0.063(2)
0.029(1)
0.044(1)
0.051(1)
0.035(1)
0.040(1)
0.038(1)
0.030(1)
0.032(1)
0.031(1)
0.043(1)
0.034(1)
0.044(1)
0.043(1)
0.033(1)
Acknowledgments. Financial support from the National Natural Science
Foundation of Henan Educational Committee (2011 A150018) is gratefully
acknowledged.
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2. Zhai, C. P.; Yan, F. M.; Zhao P. Z.: Diaqua(2,9-dimethyl-1,10phenanthroline-"2N,N')(4-hydroxybenzoato-"2O,O') cobalt (II) nitrate
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U12
0.0001(1)
$0.0030(7)
$0.0023(6)
0.0058(9)
0.0102(9)
$0.0083(8)
$0.0023(8)
$0.0093(8)
0.0098(8)
0.0034(7)
$0.0026(6)
$0.0002(7)
0.0011(7)
$0.0027(9)
$0.006(1)
$0.007(1)
0.001(1)
0.005(1)
0.014(1)
0.008(1)
0.012(1)
0.003(1)
0.0001(9)
0.0039(9)
0.0011(8)
$0.000(1)
$0.000(1)
$0.0020(9)
0.000(1)
$0.001(1)
0.003(1)
0.0035(9)
$0.0013(9)
$0.0010(9)
$0.0037(9)
$0.0052(9)
$0.002(1)
0.0049(9)
$0.005(1)
$0.003(1)
$0.004(1)
U13
0.0136(1)
0.0224(7)
0.0167(6)
0.060(1)
0.0447(9)
0.0344(9)
0.0265(9)
0.0331(9)
0.0304(8)
0.0017(7)
0.0154(6)
0.0085(7)
0.0086(7)
0.0058(9)
0.013(1)
0.018(1)
0.0104(9)
0.028(1)
0.026(1)
0.008(1)
0.011(1)
0.004(1)
0.006(1)
0.0064(8)
0.0070(8)
0.019(1)
0.024(1)
0.0100(8)
0.021(1)
0.033(1)
0.018(1)
0.017(1)
0.0159(9)
0.0088(9)
0.0090(9)
0.0106(9)
0.013(1)
0.0120(9)
0.025(1)
0.020(1)
0.011(1)
U23
$0.0011(1)
$0.0050(6)
$0.0016(6)
0.0072(9)
0.0082(8)
$0.0089(8)
$0.0086(7)
$0.0019(8)
0.0040(7)
$0.0032(7)
$0.0058(6)
$0.0001(7)
$0.0009(7)
0.0029(8)
0.006(1)
0.009(1)
0.001(1)
0.000(1)
$0.007(1)
$0.0057(9)
$0.010(1)
$0.004(1)
0.0019(9)
$0.0018(8)
0.0004(8)
0.002(1)
0.008(1)
0.0008(9)
0.0011(9)
0.009(1)
0.002(1)
0.0002(9)
0.0010(9)
$0.0025(9)
$0.0051(9)
0.0002(9)
0.0009(9)
$0.0005(9)
0.001(1)
$0.002(1)
$0.006(1)
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C28H26N2NiO10
8. Kashanian, S.; Khodaei, M. M.; Roshanfekr, H.: DNA interaction of
[Cu(dmp)(phen-dion)] (dmp=4,7 and 2,9 dimethyl phenanthroline, phendion=1,10-phenanthroline-5,6-dion) complexes and DNA-based electrochemical biosensor using chitosan-carbon nanotubes composite film.
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