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

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.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.005 Å
• Disorder in solvent or counterion
• R factor = 0.034
• wR factor = 0.092
• Data-to-parameter ratio = 12.0

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT417_ALERT_2_B Short Inter D-H..H-D       H2     ..  H44     ..       1.89 Ang.

Alert level C
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.79 Ratio
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         S1
PLAT302_ALERT_4_C Anion/Solvent Disorder .........................      50.00 Perc.
PLAT601_ALERT_2_C Structure Contains Solvent Accessible VOIDS of .      42.00 A   3 

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   4 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

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

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).

S2. Experimental

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.

S3. Refinement

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 0.97 Å (methylene) and N—H = 0.86 Å with U_iso(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 U_iso(H) = 1.5Ueq(O). In the last stage of refinement, they were treated as riding on the water O atom.

Computing details

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

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

Crystal data

[Ni(SO4)(C19H17N7)]·2H2O	F(000) = 1096
Mr = 532.18	Dx = 1.589 Mg m^−3
Orthorhombic, Pnnm	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2 2n	Cell parameters from 2104 reflections
a = 15.912 (2) Å	θ = 2.1–25.2°
b = 11.4246 (15) Å	µ = 1.02 mm^−1
c = 12.2370 (16) Å	T = 298 K
V = 2224.5 (5) Å^3	Block, green
Z = 4	0.28 × 0.23 × 0.15 mm

Data collection

Bruker APEXII area-detector diffractometer	2104 independent reflections
Radiation source: fine-focus sealed tube	1719 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.038
ϕ and ω scan	θmax = 25.2°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −18→19
Tmin = 0.764, Tmax = 0.862	k = −10→13
11003 measured reflections	l = −14→14

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.092	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.P)^2 + 1.0521P] where P = (Fo^2 + 2Fc^2)/3
2104 reflections	(Δ/σ)max < 0.001
175 parameters	Δρmax = 0.30 e Å^−3
0 restraints	Δρmin = −0.37 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Ni1	0.18503 (2)	0.06288 (4)	0.5000	0.03885 (16)
S1	0.08564 (5)	0.24842 (8)	0.5000	0.0454 (2)
O2	0.05011 (14)	0.2996 (2)	0.40209 (18)	0.0782 (7)
O3	0.17834 (15)	0.2561 (2)	0.5000	0.0575 (7)
O1	0.06843 (14)	0.1189 (2)	0.5000	0.0506 (6)
N1	0.17888 (12)	−0.0097 (2)	0.35331 (18)	0.0490 (5)
N2	0.31683 (13)	0.04742 (19)	0.30851 (19)	0.0544 (6)
H2	0.3449	0.0721	0.2531	0.065*
N3	0.43009 (13)	0.1129 (2)	0.4028 (2)	0.0560 (6)
N4	0.30740 (17)	0.0560 (2)	0.5000	0.0426 (7)
C1	0.10833 (18)	−0.0686 (3)	0.3268 (3)	0.0676 (8)
H1	0.0637	−0.0684	0.3758	0.081*
C2	0.0999 (2)	−0.1282 (4)	0.2316 (3)	0.0919 (12)
H2A	0.0505	−0.1681	0.2154	0.110*
C3	0.1663 (3)	−0.1282 (4)	0.1595 (3)	0.0961 (13)
H3	0.1622	−0.1684	0.0937	0.115*
C4	0.2380 (2)	−0.0693 (3)	0.1846 (3)	0.0768 (10)
H4	0.2830	−0.0683	0.1361	0.092*
C5	0.24299 (17)	−0.0110 (2)	0.2830 (2)	0.0506 (6)
C6	0.35177 (15)	0.0718 (2)	0.4067 (2)	0.0455 (6)
C7	0.4653 (2)	0.1345 (3)	0.5000	0.0562 (10)
C8	0.5512 (2)	0.1856 (3)	0.5000	0.0656 (12)
C9	0.59136 (18)	0.2092 (3)	0.4015 (4)	0.0821 (11)
H9	0.5649	0.1922	0.3356	0.098*
C10	0.6715 (2)	0.2585 (3)	0.4022 (5)	0.1124 (18)
H10	0.6985	0.2755	0.3367	0.135*
C11	0.7105 (4)	0.2819 (5)	0.5000	0.127 (3)
H11	0.7642	0.3141	0.5000	0.152*
O4	0.4158 (3)	0.0491 (4)	0.1161 (5)	0.0835 (15)	0.58
H41	0.4458	0.1115	0.1204	0.125*	0.58
H43	0.4464	−0.0088	0.1369	0.125*	0.58
O41	0.3923 (4)	0.1150 (6)	0.1133 (6)	0.0748 (17)	0.42
H42	0.3790	0.0943	0.0489	0.112*	0.42
H44	0.3635	0.1736	0.1335	0.112*	0.42

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0269 (2)	0.0473 (3)	0.0424 (3)	0.00399 (17)	0.000	0.000
S1	0.0370 (5)	0.0476 (5)	0.0517 (5)	0.0082 (4)	0.000	0.000
O2	0.0715 (14)	0.0913 (16)	0.0720 (14)	0.0225 (12)	−0.0080 (11)	0.0278 (12)
O3	0.0383 (14)	0.0467 (15)	0.087 (2)	−0.0007 (11)	0.000	0.000
O1	0.0344 (13)	0.0467 (14)	0.0706 (17)	0.0008 (11)	0.000	0.000
N1	0.0419 (12)	0.0513 (13)	0.0538 (13)	−0.0002 (10)	0.0028 (10)	−0.0051 (10)
N2	0.0518 (14)	0.0571 (15)	0.0541 (14)	−0.0098 (10)	0.0143 (11)	0.0008 (10)
N3	0.0359 (12)	0.0479 (13)	0.0843 (17)	0.0003 (10)	0.0097 (11)	0.0012 (12)
N4	0.0348 (15)	0.0403 (16)	0.0528 (18)	0.0031 (12)	0.000	0.000
C1	0.0502 (17)	0.082 (2)	0.070 (2)	−0.0170 (15)	0.0045 (15)	−0.0190 (16)
C2	0.086 (3)	0.114 (3)	0.076 (2)	−0.043 (2)	0.006 (2)	−0.036 (2)
C3	0.124 (3)	0.100 (3)	0.064 (2)	−0.049 (3)	0.015 (2)	−0.032 (2)
C4	0.097 (3)	0.077 (2)	0.0568 (19)	−0.0252 (19)	0.0279 (18)	−0.0147 (16)
C5	0.0556 (16)	0.0442 (14)	0.0522 (16)	−0.0044 (12)	0.0063 (13)	−0.0014 (12)
C6	0.0356 (13)	0.0386 (13)	0.0625 (17)	0.0032 (10)	0.0071 (12)	0.0031 (11)
C7	0.0316 (19)	0.035 (2)	0.102 (3)	0.0035 (15)	0.000	0.000
C8	0.032 (2)	0.040 (2)	0.125 (4)	0.0030 (16)	0.000	0.000
C9	0.0443 (17)	0.0491 (18)	0.153 (4)	0.0024 (13)	0.014 (2)	0.009 (2)
C10	0.050 (2)	0.063 (2)	0.224 (6)	−0.0063 (17)	0.030 (3)	0.017 (3)
C11	0.037 (3)	0.069 (4)	0.274 (11)	−0.007 (3)	0.000	0.000
O4	0.082 (4)	0.071 (3)	0.097 (3)	−0.006 (2)	0.033 (3)	0.000 (3)
O41	0.058 (4)	0.097 (5)	0.070 (4)	−0.004 (4)	0.014 (3)	−0.001 (4)

Geometric parameters (Å, º)

Ni1—N4	1.949 (3)	C2—H2A	0.9300
Ni1—O1	1.963 (2)	C3—C4	1.359 (5)
Ni1—N1	1.980 (2)	C3—H3	0.9300
Ni1—O3	2.210 (3)	C4—C5	1.378 (4)
Ni1—S1	2.6447 (10)	C4—H4	0.9300
S1—O2	1.448 (2)	C7—C8	1.486 (5)
S1—O3	1.478 (2)	C8—C9	1.390 (4)
S1—O1	1.505 (3)	C9—C10	1.395 (4)
N1—C5	1.335 (3)	C9—H9	0.9300
N1—C1	1.349 (3)	C10—C11	1.374 (6)
N2—C6	1.353 (3)	C10—H10	0.9300
N2—C5	1.387 (3)	C11—H11	0.9300
N2—H2	0.8600	O4—H41	0.8594
N3—C6	1.333 (3)	O4—H43	0.8603
N3—C7	1.338 (3)	O4—H42	1.1338
N4—C6	1.354 (3)	O41—H41	0.8568
C1—C2	1.356 (4)	O41—H42	0.8499
C1—H1	0.9300	O41—H44	0.8478
C2—C3	1.377 (5)
N4—Ni1—O1	163.28 (11)	C1—C2—H2A	120.9
N4—Ni1—N1	91.87 (7)	C3—C2—H2A	120.9
O1—Ni1—N1	95.15 (7)	C4—C3—C2	120.0 (3)
N1—Ni1—N1^i	130.12 (14)	C4—C3—H3	120.0
N4—Ni1—O3	95.06 (10)	C2—C3—H3	120.0
O1—Ni1—O3	68.22 (10)	C3—C4—C5	119.0 (3)
N1—Ni1—O3	114.57 (7)	C3—C4—H4	120.5
N4—Ni1—S1	129.03 (8)	C5—C4—H4	120.5
O1—Ni1—S1	34.25 (7)	N1—C5—C4	121.7 (3)
N1—Ni1—S1	107.82 (6)	N1—C5—N2	119.8 (2)
O3—Ni1—S1	33.96 (6)	C4—C5—N2	118.6 (3)
O2^i—S1—O2	111.65 (19)	N3—C6—N2	115.1 (2)
O2—S1—O3	111.45 (11)	N3—C6—N4	124.4 (3)
O2—S1—O1	109.03 (12)	N2—C6—N4	120.5 (2)
O3—S1—O1	103.90 (14)	N3—C7—N3^i	125.5 (3)
O2—S1—Ni1	123.86 (10)	N3—C7—C8	117.25 (17)
O3—S1—Ni1	56.69 (10)	C9^i—C8—C9	120.2 (4)
O1—S1—Ni1	47.21 (9)	C9—C8—C7	119.9 (2)
S1—O3—Ni1	89.35 (12)	C8—C9—C10	119.6 (5)
S1—O1—Ni1	98.53 (12)	C8—C9—H9	120.2
C5—N1—C1	118.4 (2)	C10—C9—H9	120.2
C5—N1—Ni1	123.48 (17)	C11—C10—C9	119.8 (6)
C1—N1—Ni1	117.93 (19)	C11—C10—H10	120.1
C6—N2—C5	130.3 (2)	C9—C10—H10	120.1
C6—N2—H2	114.8	C10^i—C11—C10	121.1 (6)
C5—N2—H2	114.8	C10—C11—H11	119.5
C6—N3—C7	115.1 (3)	H41—O4—H43	107.8
C6^i—N4—C6	114.9 (3)	H41—O4—H42	87.4
C6—N4—Ni1	121.04 (15)	H43—O4—H42	149.1
N1—C1—C2	122.7 (3)	H41—O41—H42	109.1
N1—C1—H1	118.7	H41—O41—H44	123.0
C2—C1—H1	118.7	H42—O41—H44	110.8
C1—C2—C3	118.3 (3)

Symmetry code: (i) x, y, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O4	0.86	2.04	2.833 (6)	153
N2—H2···O41	0.86	1.93	2.782 (7)	170
O4—H41···O2^ii	0.86	1.97	2.757 (6)	153
O41—H42···O41^iii	0.85	2.01	2.774 (14)	149

Symmetry codes: (ii) x+1/2, −y+1/2, −z+1/2; (iii) x, y, −z.