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Acta Cryst. (2007). E63, m2996-m2997    [ doi:10.1107/S1600536807056772 ]

[6-Phenyl-2,4-bis(2-pyridylamino)-1,3,5-triazine]sulfatonickel(II) dihydrate

F.-M. Wang

Abstract top

The title complex, [Ni(SO4)(C19H17N7)]·2H2O or [Ni(SO4)(dpdapt)]·2H2O [dpdapt is 6-phenyl-2,4-bis(2-pyridylamino)-1,3,5-triazine], has a distorted trigonal-bipyramidal coordination where the equatorial plane contains the N atoms of the pyridine rings and one of the O atoms of the sulfate group, while the axial positions are occupied by the other O atom and the N atom of the triazine ring of the dpdapt ligand. The complex lies across a mirror plane. The H atoms of the NH group of the dpdapt ligand and of the solvent water molecule are involved in hydrogen bonds, which form an infinite two-dimensional corrugated sheet parallel to the ac plane. The water molecule is disordered over two positions; the site occupancy factors are 0.58 and 0.42.

Comment top

Transition metal complexes with polypyridylamine ligands, possessing diverse structures and special optical and electromagnetic properties (Xu et al., 2004), have aroused great interest among researchers, tri-pyridyldiamine ligand usually exhibits donor as well as acceptor properties and can be used as a popular chelating ligand (Jing et al., 2000; Nathan, et al., 2003; Wang et al.,2006). In recent years great efforts have been taken to synthesize and characterize metal chain complexes which can be used to study the metal-metal interactions (Yang et al., 1997; Cotton et al., 1998). Also, metal string complexes with their potential application as new nano-materials such as molecular metal wires have attracted much attention and been investigated in great hard (Peng et al., 2000; Wang et al.,1999). By now a series of polynuclear metal chain complexes have been successfully synthesized and characterized (Sheu et al.,1996; Shieh et al., 1997; Chang et al., 1999). Herein we report the synthesis and crystal structure of the title complex.

The Ni1 atom in the title complex has a distorted trigonal bipyramidal coordination where the equatorial plane contains the N atoms of the peripheral pyridine rings and one of the O atom of the sulfate whereas the axial positions are occupied by the other O atom and the N atom of the central pyridine ring of the dpdapt ligand (Fig. 1). The complex lies around a mirror plane. The dihedral angle between the two pyridyl ring planes of the dpdapt ligand is 39.2°. The H atoms of one NH group of the dpdapt ligand and the solvent water molecule are involved in hydrogen bonds which form an infinite two-dimensional corrugated sheet parallel to the ac-plane (Table 1).

Related literature top

For related literature, see: Chang et al. (1999); Cotton et al. (1998); Jing et al. (2000); Nathan & Traina (2003); Peng et al. (2000); Sheu et al. (1996); Shieh et al. (1997); Wang et al. (1999, 2006); Xu et al. (2004); Yang et al. (1997).

Experimental top

Dpdapt (0.022 g, 0.0098 mmol), NiSO4 (0.015 g, 0.0085 mmol). were added in a mixed solvent of acetonitrile, the mixture was heated for eight hours under reflux. During the process stirring and influx were required. The resultant was then filtered to give a pure solution which was infiltrated by diethyl ether freely in a closed vessel, two weeks later some single crystals of the size suitable for X-Ray diffraction analysis.

Refinement top

All H atoms attached to C atoms and N atom were fixed geometrically and treated as riding with C—H = 0.93 Å (aromatic) or 0.97Å (methylene) and N—H = 0.86Å with Uiso(H) = 1.2Ueq (C or N).

The water molecule is disordered over two positions with occupancy factor ratio of 0.58/0.42. H atoms of water molecule were located in difference Fourier maps and included in the subsequent refinement using restraints (O—H= 0.85 (1) Å and H···H= 1.39 (2) Å) with Uiso(H) = 1.5Ueq(O). In the last stage of refinement, they were treated as riding on the water O atom.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. Molecular view of I with the atom-labelling-scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are represented as small sphers of arbitrary radii. Disordered water molecule has been omitted for clarity [symmetry code (i): x, y, 1 − z]
[6-Phenyl-2,4-bis(2-pyridylamino)-1,3,5-triazine]sulfatonickel(II) dihydrate top
Crystal data top
[Ni(SO4)(C19H17N7)]·2H2OF000 = 1096
Mr = 532.18Dx = 1.589 Mg m−3
Orthorhombic, PnnmMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2 2nCell parameters from 2104 reflections
a = 15.912 (2) Åθ = 2.1–25.2º
b = 11.4246 (15) ŵ = 1.02 mm−1
c = 12.2370 (16) ÅT = 298 (2) K
V = 2224.5 (5) Å3Block, green
Z = 40.28 × 0.23 × 0.15 mm
Data collection top
Bruker APEXII area-detector
diffractometer		2104 independent reflections
Radiation source: fine-focus sealed tube1719 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.038
T = 298(2) Kθmax = 25.2º
φ and ω scanθmin = 2.1º
Absorption correction: multi-scan
(SADABS; Bruker, 2004)		h = −18→19
Tmin = 0.764, Tmax = 0.862k = −10→13
11003 measured reflectionsl = −14→14
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.034H-atom parameters constrained
wR(F2) = 0.092  w = 1/[σ2(Fo2) + (0.P)2 + 1.0521P]
where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max < 0.001
2104 reflectionsΔρmax = 0.30 e Å−3
175 parametersΔρmin = −0.37 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Ni(SO4)(C19H17N7)]·2H2OV = 2224.5 (5) Å3
Mr = 532.18Z = 4
Orthorhombic, PnnmMo Kα
a = 15.912 (2) ŵ = 1.02 mm−1
b = 11.4246 (15) ÅT = 298 (2) K
c = 12.2370 (16) Å0.28 × 0.23 × 0.15 mm
Data collection top
Bruker APEXII area-detector
diffractometer		2104 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2004)		1719 reflections with I > 2σ(I)
Tmin = 0.764, Tmax = 0.862Rint = 0.038
11003 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.034175 parameters
wR(F2) = 0.092H-atom parameters constrained
S = 1.07Δρmax = 0.30 e Å−3
2104 reflectionsΔρmin = −0.37 e Å−3
Special details top

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 > 2sigma(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) top
xyzUiso*/UeqOcc. (<1)
Ni10.18503 (2)0.06288 (4)0.50000.03885 (16)
S10.08564 (5)0.24842 (8)0.50000.0454 (2)
O20.05011 (14)0.2996 (2)0.40209 (18)0.0782 (7)
O30.17834 (15)0.2561 (2)0.50000.0575 (7)
O10.06843 (14)0.1189 (2)0.50000.0506 (6)
N10.17888 (12)−0.0097 (2)0.35331 (18)0.0490 (5)
N20.31683 (13)0.04742 (19)0.30851 (19)0.0544 (6)
H20.34490.07210.25310.065*
N30.43009 (13)0.1129 (2)0.4028 (2)0.0560 (6)
N40.30740 (17)0.0560 (2)0.50000.0426 (7)
C10.10833 (18)−0.0686 (3)0.3268 (3)0.0676 (8)
H10.0637−0.06840.37580.081*
C20.0999 (2)−0.1282 (4)0.2316 (3)0.0919 (12)
H2A0.0505−0.16810.21540.110*
C30.1663 (3)−0.1282 (4)0.1595 (3)0.0961 (13)
H30.1622−0.16840.09370.115*
C40.2380 (2)−0.0693 (3)0.1846 (3)0.0768 (10)
H40.2830−0.06830.13610.092*
C50.24299 (17)−0.0110 (2)0.2830 (2)0.0506 (6)
C60.35177 (15)0.0718 (2)0.4067 (2)0.0455 (6)
C70.4653 (2)0.1345 (3)0.50000.0562 (10)
C80.5512 (2)0.1856 (3)0.50000.0656 (12)
C90.59136 (18)0.2092 (3)0.4015 (4)0.0821 (11)
H90.56490.19220.33560.098*
C100.6715 (2)0.2585 (3)0.4022 (5)0.1124 (18)
H100.69850.27550.33670.135*
C110.7105 (4)0.2819 (5)0.50000.127 (3)
H110.76420.31410.50000.152*
O40.4158 (3)0.0491 (4)0.1161 (5)0.0835 (15)0.58
H410.44580.11150.12040.125*0.58
H430.4464−0.00880.13690.125*0.58
O410.3923 (4)0.1150 (6)0.1133 (6)0.0748 (17)0.42
H420.37900.09430.04890.112*0.42
H440.36350.17360.13350.112*0.42
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.0269 (2)0.0473 (3)0.0424 (3)0.00399 (17)0.0000.000
S10.0370 (5)0.0476 (5)0.0517 (5)0.0082 (4)0.0000.000
O20.0715 (14)0.0913 (16)0.0720 (14)0.0225 (12)−0.0080 (11)0.0278 (12)
O30.0383 (14)0.0467 (15)0.087 (2)−0.0007 (11)0.0000.000
O10.0344 (13)0.0467 (14)0.0706 (17)0.0008 (11)0.0000.000
N10.0419 (12)0.0513 (13)0.0538 (13)−0.0002 (10)0.0028 (10)−0.0051 (10)
N20.0518 (14)0.0571 (15)0.0541 (14)−0.0098 (10)0.0143 (11)0.0008 (10)
N30.0359 (12)0.0479 (13)0.0843 (17)0.0003 (10)0.0097 (11)0.0012 (12)
N40.0348 (15)0.0403 (16)0.0528 (18)0.0031 (12)0.0000.000
C10.0502 (17)0.082 (2)0.070 (2)−0.0170 (15)0.0045 (15)−0.0190 (16)
C20.086 (3)0.114 (3)0.076 (2)−0.043 (2)0.006 (2)−0.036 (2)
C30.124 (3)0.100 (3)0.064 (2)−0.049 (3)0.015 (2)−0.032 (2)
C40.097 (3)0.077 (2)0.0568 (19)−0.0252 (19)0.0279 (18)−0.0147 (16)
C50.0556 (16)0.0442 (14)0.0522 (16)−0.0044 (12)0.0063 (13)−0.0014 (12)
C60.0356 (13)0.0386 (13)0.0625 (17)0.0032 (10)0.0071 (12)0.0031 (11)
C70.0316 (19)0.035 (2)0.102 (3)0.0035 (15)0.0000.000
C80.032 (2)0.040 (2)0.125 (4)0.0030 (16)0.0000.000
C90.0443 (17)0.0491 (18)0.153 (4)0.0024 (13)0.014 (2)0.009 (2)
C100.050 (2)0.063 (2)0.224 (6)−0.0063 (17)0.030 (3)0.017 (3)
C110.037 (3)0.069 (4)0.274 (11)−0.007 (3)0.0000.000
O40.082 (4)0.071 (3)0.097 (3)−0.006 (2)0.033 (3)0.000 (3)
O410.058 (4)0.097 (5)0.070 (4)−0.004 (4)0.014 (3)−0.001 (4)
Geometric parameters (Å, °) top
Ni1—N41.949 (3)C2—H2A0.9300
Ni1—O11.963 (2)C3—C41.359 (5)
Ni1—N11.980 (2)C3—H30.9300
Ni1—O32.210 (3)C4—C51.378 (4)
Ni1—S12.6447 (10)C4—H40.9300
S1—O21.448 (2)C7—C81.486 (5)
S1—O31.478 (2)C8—C91.390 (4)
S1—O11.505 (3)C9—C101.395 (4)
N1—C51.335 (3)C9—H90.9300
N1—C11.349 (3)C10—C111.374 (6)
N2—C61.353 (3)C10—H100.9300
N2—C51.387 (3)C11—H110.9300
N2—H20.8600O4—H410.8594
N3—C61.333 (3)O4—H430.8603
N3—C71.338 (3)O4—H421.1338
N4—C61.354 (3)O41—H410.8568
C1—C21.356 (4)O41—H420.8499
C1—H10.9300O41—H440.8478
C2—C31.377 (5)
N4—Ni1—O1163.28 (11)C1—C2—H2A120.9
N4—Ni1—N191.87 (7)C3—C2—H2A120.9
O1—Ni1—N195.15 (7)C4—C3—C2120.0 (3)
N1—Ni1—N1i130.12 (14)C4—C3—H3120.0
N4—Ni1—O395.06 (10)C2—C3—H3120.0
O1—Ni1—O368.22 (10)C3—C4—C5119.0 (3)
N1—Ni1—O3114.57 (7)C3—C4—H4120.5
N4—Ni1—S1129.03 (8)C5—C4—H4120.5
O1—Ni1—S134.25 (7)N1—C5—C4121.7 (3)
N1—Ni1—S1107.82 (6)N1—C5—N2119.8 (2)
O3—Ni1—S133.96 (6)C4—C5—N2118.6 (3)
O2i—S1—O2111.65 (19)N3—C6—N2115.1 (2)
O2—S1—O3111.45 (11)N3—C6—N4124.4 (3)
O2—S1—O1109.03 (12)N2—C6—N4120.5 (2)
O3—S1—O1103.90 (14)N3—C7—N3i125.5 (3)
O2—S1—Ni1123.86 (10)N3—C7—C8117.25 (17)
O3—S1—Ni156.69 (10)C9i—C8—C9120.2 (4)
O1—S1—Ni147.21 (9)C9—C8—C7119.9 (2)
S1—O3—Ni189.35 (12)C8—C9—C10119.6 (5)
S1—O1—Ni198.53 (12)C8—C9—H9120.2
C5—N1—C1118.4 (2)C10—C9—H9120.2
C5—N1—Ni1123.48 (17)C11—C10—C9119.8 (6)
C1—N1—Ni1117.93 (19)C11—C10—H10120.1
C6—N2—C5130.3 (2)C9—C10—H10120.1
C6—N2—H2114.8C10i—C11—C10121.1 (6)
C5—N2—H2114.8C10—C11—H11119.5
C6—N3—C7115.1 (3)H41—O4—H43107.8
C6i—N4—C6114.9 (3)H41—O4—H4287.4
C6—N4—Ni1121.04 (15)H43—O4—H42149.1
N1—C1—C2122.7 (3)H41—O41—H42109.1
N1—C1—H1118.7H41—O41—H44123.0
C2—C1—H1118.7H42—O41—H44110.8
C1—C2—C3118.3 (3)
Symmetry codes: (i) x, y, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2···O40.862.042.833 (6)153
N2—H2···O410.861.932.782 (7)170
O4—H41···O2ii0.861.972.757 (6)153
O41—H42···O41iii0.852.012.774 (14)149
Symmetry codes: (ii) x+1/2, −y+1/2, −z+1/2; (iii) x, y, −z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2···O40.862.042.833 (6)153
N2—H2···O410.861.932.782 (7)170
O4—H41···O2i0.861.972.757 (6)153
O41—H42···O41ii0.852.012.774 (14)149
Symmetry codes: (i) x+1/2, −y+1/2, −z+1/2; (ii) x, y, −z.
Acknowledgements top

The authors are grateful to Weinan Teachers' University for financial support.

references
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