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Acta Cryst. (2011). E67, m108    [ doi:10.1107/S1600536810052578 ]

Aqua{2-morpholino-N-[1-(2-pyridyl)ethylidene]ethanamine-[kappa]3N,N',N''}bis(thiocyanato-[kappa]N)nickel(II)

N. Suleiman Gwaram, N. A. Ikmal Hisham, H. Khaledi and H. Mohd Ali

Abstract top

In the title compound, [Ni(NCS)2(C13H19N3O)(H2O)], the NiII ion is six-coordinated by the N,N',N''-tridentate Schiff base, the N atoms of two thiocyanate ligands and one water O atom in a distorted octahedral geometry. Intramolecular C-H...N and C-H...O hydrogen bonds occur. In the crystal, O-H...S, O-H...O and C-H...S hydrogen bonds link adjacent molecules into layers parallel to the ac plane.

Comment top

The title mixed-ligand nickel(II) complex was obtained by following a similar synthetic procedure as for its analogous copper(II) complex (Suleiman Gwaram et al., 2011). However, compared to the square-pyramidal environment around the CuII ion, afforded by the tridentate Schiff base and the N atoms of two SCN-, the NiII ion is coordinated by one additional water ligand to have an octahedral geometry. The Ni—N and Ni—O bond lengths in this complex are comparable to those in the similar structures (Chiumia et al., 1999; Zhao et al., 2008). In the crystal, the adjacent molecules are linked together through O—H···S, O—H···O and C—H···S hydrogen bonds into layers parallel to the ac plane. An S···S interaction [3.5276 (7) Å] between S1 and S2 of the symmetry related molecule at -x, y + 1/2, -z + 3/2, connects the layers into a three-dimensional network. Intramolecular C—H···N and C—H···O hydrogen bonding are also observed.

Related literature top

For the structure of the Cu(II) complex with the Schiff base and isothiocyante see: Suleiman Gwaram et al. (2011). For the structures of related Ni(II) complexes, see: Chiumia et al. (1999); Zhao et al. (2008).

Experimental top

A mixture of 2-acetylpyridine (0.20 g, 1.65 mmol) and 4-(2-aminoethyl)morpholine (0.21 g, 1.65 mmol) in ethanol (20 ml) was refluxed for 2 hr followed by addition of a solution of nickel(II) acetate tetrahydrate (0.41 g, 1.65 mmol) and sodium thiocyanate (0.134 g, 1.65 mmol) in a minimum amount of water. The resulting solution was refluxed for 30 min, then left at room temperature. The crystals of the title complex were obtained in a week.

Refinement top

The C-bound H atoms were placed at calculated positions (C—H 0.95–0.99 Å) and were treated as riding on their parent C atoms. The O-bound H atoms were located in a difference Fourier map, and refined with a distance restraint of O—H 0.84 (2). For all H atoms, Uiso(H) values were set to 1.2–1.5 Ueq(carrier atom). An additional rigid-bond type restraint (DELU in SHELXL97) was placed on the displacement parameters of S1 and C14; S2 and C15.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. Displacement ellipsoid plot of the title compound at the 30% probability level. Hydrogen atoms are drawn as spheres of arbitrary radii.
[Figure 2] Fig. 2. Packing view looking down the a axis, showing the intermolecular S···S interactions. H atoms have been omitted for clarity.
Aqua{2-morpholino-N-[1-(2-pyridyl)ethylidene]ethanamine- κ3N,N',N''}bis(thiocyanato-κN)nickel(II) top
Crystal data top
[Ni(NCS)2(C13H19N3O)(H2O)]F(000) = 888
Mr = 426.20Dx = 1.477 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 7183 reflections
a = 7.1881 (1) Åθ = 2.5–30.5°
b = 21.9708 (3) ŵ = 1.25 mm−1
c = 12.1438 (2) ÅT = 100 K
β = 91.412 (1)°Block, brown
V = 1917.27 (5) Å30.35 × 0.32 × 0.22 mm
Z = 4
Data collection top
Bruker APEXII CCD
diffractometer		3474 independent reflections
Radiation source: fine-focus sealed tube3168 reflections with I > 2σ(I)
graphiteRint = 0.023
φ and ω scansθmax = 25.3°, θmin = 2.5°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −8→8
Tmin = 0.669, Tmax = 0.771k = −26→26
14240 measured reflectionsl = −14→14
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.025Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.058H atoms treated by a mixture of independent and constrained refinement
S = 1.09 w = 1/[σ2(Fo2) + (0.0176P)2 + 1.4584P]
where P = (Fo2 + 2Fc2)/3
3474 reflections(Δ/σ)max = 0.002
233 parametersΔρmax = 0.45 e Å−3
4 restraintsΔρmin = −0.36 e Å−3
Crystal data top
[Ni(NCS)2(C13H19N3O)(H2O)]V = 1917.27 (5) Å3
Mr = 426.20Z = 4
Monoclinic, P21/cMo Kα radiation
a = 7.1881 (1) ŵ = 1.25 mm−1
b = 21.9708 (3) ÅT = 100 K
c = 12.1438 (2) Å0.35 × 0.32 × 0.22 mm
β = 91.412 (1)°
Data collection top
Bruker APEXII CCD
diffractometer		3474 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		3168 reflections with I > 2σ(I)
Tmin = 0.669, Tmax = 0.771Rint = 0.023
14240 measured reflectionsθmax = 25.3°
Refinement top
R[F2 > 2σ(F2)] = 0.025H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.058Δρmax = 0.45 e Å−3
S = 1.09Δρmin = −0.36 e Å−3
3474 reflectionsAbsolute structure: ?
233 parametersFlack parameter: ?
4 restraintsRogers parameter: ?
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 > 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) top
xyzUiso*/Ueq
Ni10.37854 (3)0.624396 (10)0.738472 (19)0.01680 (7)
S1−0.10541 (7)0.76958 (3)0.71728 (7)0.04681 (19)
S20.09981 (7)0.42948 (2)0.80865 (5)0.03219 (13)
O10.3805 (2)0.71032 (6)1.05938 (12)0.0317 (3)
O20.49597 (19)0.71103 (6)0.71792 (12)0.0252 (3)
H2A0.6074 (16)0.7214 (11)0.715 (2)0.038*
H2B0.439 (3)0.7350 (9)0.6756 (17)0.038*
N10.3653 (2)0.61959 (7)0.56510 (13)0.0243 (4)
N20.6213 (2)0.58250 (7)0.70457 (13)0.0214 (3)
N30.4992 (2)0.61675 (7)0.90902 (13)0.0200 (3)
N40.1391 (2)0.67219 (7)0.75249 (15)0.0264 (4)
N50.2469 (2)0.54344 (7)0.75822 (14)0.0240 (4)
C10.2343 (3)0.64192 (9)0.49655 (18)0.0331 (5)
H10.12600.65940.52690.040*
C20.2495 (4)0.64071 (11)0.3832 (2)0.0489 (7)
H20.15350.65670.33650.059*
C30.4066 (5)0.61587 (13)0.3399 (2)0.0585 (8)
H30.42080.61470.26230.070*
C40.5442 (4)0.59253 (12)0.40919 (19)0.0466 (6)
H40.65400.57540.38020.056*
C50.5190 (3)0.59464 (9)0.52205 (17)0.0286 (5)
C60.6588 (3)0.57188 (9)0.60449 (17)0.0269 (4)
C70.8288 (3)0.53922 (12)0.5662 (2)0.0447 (6)
H7A0.91500.53270.62890.067*
H7B0.88990.56380.51030.067*
H7C0.79260.49980.53450.067*
C80.7380 (3)0.56378 (9)0.79863 (17)0.0261 (4)
H8A0.84020.59340.81110.031*
H8B0.79320.52330.78470.031*
C90.6158 (3)0.56112 (9)0.89870 (17)0.0254 (4)
H9A0.53380.52500.89290.031*
H9B0.69540.55650.96590.031*
C100.3638 (3)0.60553 (9)0.99758 (16)0.0261 (4)
H10A0.43130.59071.06430.031*
H10B0.27510.57350.97330.031*
C110.2574 (3)0.66251 (9)1.02547 (17)0.0293 (5)
H11A0.18300.67580.96010.035*
H11B0.17050.65351.08540.035*
C120.5056 (3)0.72347 (9)0.97228 (17)0.0275 (4)
H12A0.58900.75730.99480.033*
H12B0.43350.73640.90580.033*
C130.6201 (3)0.66828 (9)0.94552 (16)0.0236 (4)
H13A0.70730.67850.88650.028*
H13B0.69440.65601.01150.028*
C140.0359 (3)0.71183 (9)0.73737 (18)0.0268 (4)
C150.1852 (3)0.49652 (8)0.78008 (15)0.0188 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.01653 (12)0.01553 (12)0.01836 (13)0.00019 (9)0.00068 (9)0.00097 (9)
S10.0204 (3)0.0230 (3)0.0970 (6)0.0010 (2)−0.0003 (3)0.0168 (3)
S20.0322 (3)0.0209 (3)0.0432 (3)−0.0068 (2)−0.0049 (2)0.0085 (2)
O10.0418 (9)0.0285 (8)0.0253 (8)−0.0089 (6)0.0097 (6)−0.0101 (6)
O20.0240 (7)0.0231 (7)0.0282 (8)−0.0048 (6)−0.0048 (6)0.0097 (6)
N10.0283 (9)0.0221 (8)0.0222 (9)−0.0049 (7)−0.0045 (7)0.0000 (7)
N20.0202 (8)0.0219 (8)0.0220 (9)0.0012 (6)0.0013 (7)−0.0016 (7)
N30.0244 (8)0.0183 (8)0.0174 (8)−0.0001 (6)0.0013 (6)0.0001 (6)
N40.0210 (8)0.0222 (8)0.0361 (10)0.0012 (7)0.0013 (7)0.0014 (7)
N50.0227 (8)0.0195 (8)0.0298 (9)−0.0001 (7)0.0009 (7)−0.0015 (7)
C10.0408 (12)0.0251 (10)0.0325 (12)−0.0051 (9)−0.0150 (10)0.0002 (9)
C20.0769 (19)0.0364 (13)0.0320 (14)−0.0005 (13)−0.0256 (13)−0.0015 (11)
C30.098 (2)0.0587 (17)0.0186 (12)−0.0007 (16)−0.0089 (14)−0.0053 (12)
C40.0644 (17)0.0520 (15)0.0236 (12)−0.0010 (13)0.0053 (11)−0.0094 (11)
C50.0353 (11)0.0300 (11)0.0205 (11)−0.0069 (9)0.0023 (9)−0.0044 (9)
C60.0238 (10)0.0304 (11)0.0267 (11)−0.0021 (8)0.0051 (8)−0.0059 (9)
C70.0322 (12)0.0589 (16)0.0437 (15)0.0059 (11)0.0123 (11)−0.0165 (12)
C80.0226 (10)0.0261 (10)0.0293 (11)0.0067 (8)−0.0029 (8)−0.0007 (9)
C90.0309 (11)0.0204 (10)0.0247 (11)0.0060 (8)−0.0048 (9)0.0027 (8)
C100.0356 (11)0.0230 (10)0.0197 (10)−0.0058 (8)0.0039 (9)0.0014 (8)
C110.0346 (11)0.0289 (11)0.0250 (11)−0.0077 (9)0.0099 (9)−0.0057 (9)
C120.0368 (11)0.0235 (10)0.0224 (11)−0.0071 (9)0.0040 (9)−0.0034 (8)
C130.0280 (10)0.0244 (10)0.0184 (10)−0.0052 (8)−0.0022 (8)0.0002 (8)
C140.0186 (9)0.0207 (9)0.0410 (12)−0.0037 (7)0.0000 (9)0.0030 (9)
C150.0192 (9)0.0185 (8)0.0184 (9)0.0004 (7)−0.0026 (7)−0.0015 (7)
Geometric parameters (Å, °) top
Ni1—N12.1079 (16)C3—C41.382 (4)
Ni1—N22.0243 (15)C3—H30.9500
Ni1—N32.2317 (16)C4—C51.388 (3)
Ni1—N42.0270 (16)C4—H40.9500
Ni1—N52.0318 (16)C5—C61.487 (3)
Ni1—O22.0996 (13)C6—C71.501 (3)
S1—C141.640 (2)C7—H7A0.9800
S2—C151.6362 (19)C7—H7B0.9800
O1—C111.428 (2)C7—H7C0.9800
O1—C121.434 (2)C8—C91.518 (3)
O2—H2A0.834 (10)C8—H8A0.9900
O2—H2B0.835 (10)C8—H8B0.9900
N1—C11.335 (3)C9—H9A0.9900
N1—C51.350 (3)C9—H9B0.9900
N2—C61.273 (3)C10—C111.510 (3)
N2—C81.459 (2)C10—H10A0.9900
N3—C131.488 (2)C10—H10B0.9900
N3—C101.488 (2)C11—H11A0.9900
N3—C91.489 (2)C11—H11B0.9900
N4—C141.156 (3)C12—C131.505 (3)
N5—C151.156 (2)C12—H12A0.9900
C1—C21.384 (3)C12—H12B0.9900
C1—H10.9500C13—H13A0.9900
C2—C31.371 (4)C13—H13B0.9900
C2—H20.9500
N2—Ni1—N4172.20 (7)N2—C6—C5115.19 (18)
N2—Ni1—N591.85 (6)N2—C6—C7125.2 (2)
N4—Ni1—N592.56 (6)C5—C6—C7119.60 (19)
N2—Ni1—O292.11 (6)C6—C7—H7A109.5
N4—Ni1—O283.40 (6)C6—C7—H7B109.5
N5—Ni1—O2175.94 (6)H7A—C7—H7B109.5
N2—Ni1—N177.99 (6)C6—C7—H7C109.5
N4—Ni1—N195.30 (7)H7A—C7—H7C109.5
N5—Ni1—N193.69 (6)H7B—C7—H7C109.5
O2—Ni1—N186.28 (6)N2—C8—C9107.73 (15)
N2—Ni1—N380.64 (6)N2—C8—H8A110.2
N4—Ni1—N3105.80 (6)C9—C8—H8A110.2
N5—Ni1—N389.77 (6)N2—C8—H8B110.2
O2—Ni1—N391.75 (5)C9—C8—H8B110.2
N1—Ni1—N3158.45 (6)H8A—C8—H8B108.5
C11—O1—C12109.31 (14)N3—C9—C8111.96 (15)
Ni1—O2—H2A129.9 (17)N3—C9—H9A109.2
Ni1—O2—H2B117.1 (17)C8—C9—H9A109.2
H2A—O2—H2B105 (2)N3—C9—H9B109.2
C1—N1—C5118.65 (19)C8—C9—H9B109.2
C1—N1—Ni1128.17 (15)H9A—C9—H9B107.9
C5—N1—Ni1112.94 (13)N3—C10—C11111.62 (16)
C6—N2—C8124.37 (17)N3—C10—H10A109.3
C6—N2—Ni1118.78 (14)C11—C10—H10A109.3
C8—N2—Ni1116.78 (12)N3—C10—H10B109.3
C13—N3—C10107.34 (14)C11—C10—H10B109.3
C13—N3—C9108.88 (15)H10A—C10—H10B108.0
C10—N3—C9107.71 (14)O1—C11—C10111.17 (17)
C13—N3—Ni1115.45 (11)O1—C11—H11A109.4
C10—N3—Ni1115.92 (12)C10—C11—H11A109.4
C9—N3—Ni1100.97 (11)O1—C11—H11B109.4
C14—N4—Ni1156.93 (16)C10—C11—H11B109.4
C15—N5—Ni1172.08 (16)H11A—C11—H11B108.0
N1—C1—C2122.8 (2)O1—C12—C13110.66 (16)
N1—C1—H1118.6O1—C12—H12A109.5
C2—C1—H1118.6C13—C12—H12A109.5
C3—C2—C1118.4 (2)O1—C12—H12B109.5
C3—C2—H2120.8C13—C12—H12B109.5
C1—C2—H2120.8H12A—C12—H12B108.1
C2—C3—C4119.9 (2)N3—C13—C12111.02 (16)
C2—C3—H3120.1N3—C13—H13A109.4
C4—C3—H3120.1C12—C13—H13A109.4
C3—C4—C5118.7 (2)N3—C13—H13B109.4
C3—C4—H4120.6C12—C13—H13B109.4
C5—C4—H4120.6H13A—C13—H13B108.0
N1—C5—C4121.6 (2)N4—C14—S1178.19 (19)
N1—C5—C6114.94 (17)N5—C15—S2178.78 (18)
C4—C5—C6123.5 (2)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O2—H2A···S1i0.83 (1)2.32 (1)3.1410 (14)168 (2)
O2—H2B···O1ii0.84 (1)1.89 (1)2.7023 (19)163 (2)
C2—H2···S1ii0.952.843.769 (3)167
C11—H11A···N40.992.533.409 (3)147
C12—H12B···O20.992.403.100 (2)127
Symmetry codes: (i) x+1, y, z; (ii) x, −y+3/2, z−1/2.
Table 1
Selected geometric parameters (Å) top
Ni1—N12.1079 (16)Ni1—N42.0270 (16)
Ni1—N22.0243 (15)Ni1—N52.0318 (16)
Ni1—N32.2317 (16)Ni1—O22.0996 (13)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O2—H2A···S1i0.83 (1)2.32 (1)3.1410 (14)168 (2)
O2—H2B···O1ii0.84 (1)1.89 (1)2.7023 (19)163 (2)
C2—H2···S1ii0.952.843.769 (3)167
C11—H11A···N40.992.533.409 (3)147
C12—H12B···O20.992.403.100 (2)127
Symmetry codes: (i) x+1, y, z; (ii) x, −y+3/2, z−1/2.
Acknowledgements top

The authors thank the University of Malaya for funding this study (FRGS grant FP004/2010B).

references
References top

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