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Acta Cryst. (2007). E63, m2409-m2410    [ doi:10.1107/S1600536807040780 ]

Dihistaminedisaccharinatonickel(II)

I. Bulut, H. Pasaoglu, G. Kastas and A. Bulut

Abstract top

The title complex, bis[2-(1H-imidazol-4-yl)ethanamine]disaccharinatonickel(II), [Ni(C7H4NO3S)2(C5H9N3)2], has an octahedral coordination around the nickel(II) ion, and the Ni atom lies on a center of symmetry. The histamine ligands and sulfonyl group of the saccharinate ligands show disorder, and the two conformations (A and B, with almost equal occupancy) are inversion isomers. The molecular packing is stabilized by intra- and intermolecular hydrogen bonds between imidazole N atoms and sulfonyl O atoms. In the extended stucture, intermolecular N-H...O hydogen bonds constitute a chain structure parallel to the direction [110].

Comment top

The title compound, (I), is composed of discrete [C24H26N8NiO6S2] molecules. As shown in Figure 1, the nickel atom lies on a center of symmetry and is coordinated by four N atoms of two bidentate histamine ligands and monodentate saccharinato ligands. The geometry around the Ni(II) ion is an elongated octahedron. Related bond distances and angles are given in Table 1. The equatorial plane (N2/N3/N2i/N3i) is formed by N atoms of histamine ligands while the axial positions are occupied by saccharinate N atoms. It is observed that the apical Ni–N bond distance is longer than the basal Ni–N bond distances. The intraligand bond distances are comparable to those observed in the complex [C24H26N8CuO6S2] (Bulut et al., 2007).

Histamine ligand and sulfonyl group of saccharinato ligand show disorder, which is modelled as two different orientations with the occupancy factors of 0.493 (8) for conformer A and 0.507 (8) for conformer B. Both conformers, being inversion isomers, have similiar bond angles and distances. These values are also in good agreement with those found in [C24H26N8CuO6S2] (Bulut et al., 2007).

The molecular packing is stabilized by intra- and inter-molecular hydrogen bonds (Table 2). The neutral complexes are linked by N—H···O hydrogen bonding interactions between the imidazole N atoms of histamine and sacchatinate sulfonyl O atoms. As is seen from Figure 2, imidazol atom N4 acts as a donor atom, via H4a, to atom O2a, producing a chain C(8) (Bernstein et al., 1995) running parallel to the direction [110] and centrosymmetric [R22(16)] rings centered at (n+1/2, n+1/2, 0) (n=zero or integer).

Related literature top

For a related structure, see: Bulut et al. (2007).

For related literature, see: Bernstein et al. (1995).

Experimental top

A solution of histamine (2 mmol, 0.222 g) in water (10 ml) was added dropwise upon stirring to the mixture of sodium saccharinate (2 mmol, 0.412 g) and NiCl2·H2O (1 mmol, 0.238 g) in distilled water (30 ml). The solution was heated to 60°C in a temperature-controlled bath and stirred for 8 h at 60°C and then filtered. The blue filtrates were left about two weaks at room temperature, and then the blue crystals of title complex suitable for x-ray diffraction analyses were collected.

Refinement top

The sulfonyl group of sacharinate ligand and the histamine ligand show disorder, which is modelled as two different orientations (C8A—C11A, C8B—C11B; S1A—S1B; O1A—O2A, O1B—O2B) with occupancy factors of 0.507 (8) and 0. 493 (8). All H atoms except those bonded to N4 atom were placed in geometricaly idealized positions, [N—H = 0.90 Å; C—H = 0.93 − 0.97 Å], and refined as riding atoms.

Computing details top

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA (Stoe & Cie, 2002); data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Macrae et al., 2006); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), with atom labels and 30% probability displacement ellipsoids. H atoms not involved in hydrogen bonding have been omitted for clarity.
[Figure 2] Fig. 2. A view of the complex showing the chain structure parallel to direction [110].
bis[2-(1H-imidazol-4-yl)ethanamine]disaccharinatonickel(II) top
Crystal data top
[Ni(C7H4N1O3S1)2(C5H9N3)2]Z = 1
Mr = 645.36F000 = 334
Triclinic, P1Dx = 1.577 Mg m−3
Hall symbol: -P 1Mo Kα radiation
λ = 0.71073 Å
a = 7.7508 (8) ÅCell parameters from 25242 reflections
b = 8.9840 (9) Åθ = 2.0–28.1º
c = 10.8167 (11) ŵ = 0.92 mm−1
α = 93.728 (8)ºT = 296 K
β = 103.541 (8)ºPrism, grey
γ = 109.994 (8)º0.52 × 0.47 × 0.28 mm
V = 679.40 (13) Å3
Data collection top
Stoe IPDS II
diffractometer		2667 independent reflections
Radiation source: fine-focus sealed tube2420 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.050
T = 296 Kθmax = 26.0º
rotation method scansθmin = 2.0º
Absorption correction: integration
(X-RED32; Stoe & Cie, 2002)		h = −8→9
Tmin = 0.629, Tmax = 0.878k = −11→11
9525 measured reflectionsl = −13→13
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)] = 0.036H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.104  w = 1/[σ2(Fo2) + (0.0852P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.01(Δ/σ)max < 0.001
2667 reflectionsΔρmax = 0.92 e Å−3
255 parametersΔρmin = −0.76 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Ni(C7H4N1O3S1)2(C5H9N3)2]γ = 109.994 (8)º
Mr = 645.36V = 679.40 (13) Å3
Triclinic, P1Z = 1
a = 7.7508 (8) ÅMo Kα
b = 8.9840 (9) ŵ = 0.92 mm−1
c = 10.8167 (11) ÅT = 296 K
α = 93.728 (8)º0.52 × 0.47 × 0.28 mm
β = 103.541 (8)º
Data collection top
Stoe IPDS II
diffractometer		2667 independent reflections
Absorption correction: integration
(X-RED32; Stoe & Cie, 2002)		2420 reflections with I > 2σ(I)
Tmin = 0.629, Tmax = 0.878Rint = 0.050
9525 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.036255 parameters
wR(F2) = 0.104H atoms treated by a mixture of
independent and constrained refinement
S = 1.01Δρmax = 0.92 e Å−3
2667 reflectionsΔρmin = −0.76 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)
Ni10.00000.00000.00000.03453 (14)
S1A−0.0051 (8)0.1787 (6)−0.2688 (4)0.0409 (7)0.493 (8)
O1A0.0482 (13)0.0628 (9)−0.3309 (8)0.0616 (17)0.493 (8)
O2A0.1427 (12)0.3296 (11)−0.2139 (9)0.0681 (18)0.493 (8)
S1B−0.0059 (9)0.2164 (7)−0.2538 (6)0.0552 (10)0.507 (8)
O1B0.0969 (14)0.1302 (12)−0.3034 (11)0.086 (3)0.507 (8)
O2B0.1140 (13)0.3761 (10)−0.1841 (10)0.081 (2)0.507 (8)
O3−0.4308 (2)0.0515 (2)−0.14797 (16)0.0563 (4)
N1−0.1265 (2)0.1088 (2)−0.16691 (16)0.0415 (4)
N2−0.1652 (2)0.0732 (2)0.10049 (17)0.0436 (4)
H2A−0.26470.07900.04120.052*
H2B−0.2134−0.00650.14350.052*
N30.2278 (2)0.21908 (19)0.07337 (16)0.0424 (4)
N40.5050 (3)0.4154 (2)0.1223 (2)0.0558 (5)
H4A0.610 (5)0.466 (4)0.120 (3)0.063 (8)*
C1−0.3102 (3)0.1008 (2)−0.20708 (19)0.0407 (4)
C2−0.3531 (3)0.1607 (2)−0.33201 (19)0.0432 (4)
C3−0.5258 (4)0.1636 (3)−0.4027 (2)0.0565 (6)
H3−0.63570.1240−0.37530.068*
C4−0.5279 (5)0.2278 (4)−0.5159 (3)0.0742 (8)
H4−0.64180.2314−0.56510.089*
C5−0.3669 (6)0.2860 (5)−0.5571 (3)0.0812 (9)
H5−0.37400.3276−0.63380.097*
C6−0.1946 (5)0.2844 (4)−0.4874 (3)0.0709 (7)
H6−0.08470.3246−0.51470.085*
C7−0.1933 (3)0.2200 (3)−0.3749 (2)0.0489 (5)
C8A−0.0828 (13)0.2245 (12)0.1936 (8)0.064 (2)0.507 (8)
H8A10.00660.21440.26900.077*0.507 (8)
H8A2−0.18350.24620.22110.077*0.507 (8)
C9A0.0179 (9)0.3599 (6)0.1310 (6)0.069 (2)0.507 (8)
H9A1−0.06360.35320.04610.083*0.507 (8)
H9A20.03870.46080.18150.083*0.507 (8)
C10A0.2042 (9)0.3590 (7)0.1182 (7)0.0509 (13)0.507 (8)
C11A0.3791 (13)0.4790 (9)0.1533 (8)0.0593 (18)0.507 (8)
H11A0.40810.58370.19110.071*0.507 (8)
C8B−0.1115 (12)0.2479 (9)0.1411 (8)0.0513 (17)0.493 (8)
H8B1−0.20450.26560.18050.062*0.493 (8)
H8B2−0.11060.30210.06640.062*0.493 (8)
C9B0.0827 (7)0.3149 (6)0.2356 (5)0.0582 (16)0.493 (8)
H9B10.10160.41930.27930.070*0.493 (8)
H9B20.08860.24510.29990.070*0.493 (8)
C10B0.2398 (8)0.3316 (6)0.1739 (7)0.0466 (13)0.493 (8)
C11B0.4107 (13)0.4534 (10)0.1985 (9)0.0583 (19)0.493 (8)
H11B0.45380.54660.25800.070*0.493 (8)
C120.4010 (3)0.2674 (3)0.0614 (2)0.0508 (5)
H120.44650.20520.01550.061*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.0241 (2)0.0339 (2)0.0429 (2)0.00635 (14)0.01269 (14)−0.00122 (12)
S1A0.0276 (10)0.0488 (17)0.0456 (8)0.0100 (10)0.0132 (6)0.0131 (9)
O1A0.059 (4)0.082 (4)0.062 (2)0.033 (3)0.036 (2)0.017 (3)
O2A0.038 (3)0.070 (4)0.069 (3)−0.011 (3)0.010 (2)0.009 (3)
S1B0.0346 (11)0.059 (2)0.083 (2)0.0180 (15)0.0297 (13)0.0301 (16)
O1B0.074 (6)0.122 (7)0.118 (7)0.066 (5)0.071 (5)0.069 (5)
O2B0.042 (3)0.069 (5)0.100 (6)−0.010 (3)0.002 (3)0.027 (4)
O30.0347 (8)0.0821 (11)0.0600 (9)0.0226 (8)0.0235 (7)0.0210 (8)
N10.0282 (8)0.0472 (9)0.0481 (9)0.0101 (7)0.0140 (7)0.0094 (7)
N20.0326 (9)0.0499 (9)0.0497 (9)0.0144 (7)0.0167 (7)0.0022 (7)
N30.0310 (9)0.0375 (8)0.0518 (9)0.0061 (7)0.0102 (7)0.0007 (7)
N40.0352 (11)0.0477 (10)0.0655 (12)−0.0025 (9)0.0035 (9)0.0148 (9)
C10.0319 (10)0.0424 (9)0.0465 (10)0.0117 (8)0.0125 (8)0.0027 (7)
C20.0379 (11)0.0458 (10)0.0433 (9)0.0143 (8)0.0101 (8)−0.0004 (8)
C30.0438 (13)0.0724 (14)0.0528 (12)0.0253 (11)0.0088 (10)0.0011 (10)
C40.0726 (19)0.103 (2)0.0531 (13)0.0495 (18)0.0033 (13)0.0105 (13)
C50.096 (2)0.109 (2)0.0520 (14)0.050 (2)0.0213 (15)0.0295 (15)
C60.0681 (19)0.0895 (19)0.0634 (15)0.0288 (16)0.0291 (14)0.0299 (14)
C70.0429 (12)0.0527 (11)0.0488 (11)0.0136 (9)0.0141 (9)0.0090 (9)
C8A0.059 (5)0.079 (5)0.058 (4)0.028 (3)0.025 (4)−0.017 (4)
C9A0.066 (4)0.049 (3)0.092 (4)0.024 (3)0.023 (3)−0.013 (2)
C10A0.049 (3)0.042 (2)0.053 (3)0.011 (2)0.010 (3)−0.006 (2)
C11A0.063 (5)0.036 (3)0.059 (4)0.002 (3)0.008 (4)−0.004 (3)
C8B0.043 (3)0.055 (3)0.058 (4)0.023 (3)0.013 (3)−0.005 (3)
C9B0.050 (3)0.061 (3)0.057 (3)0.020 (2)0.008 (2)−0.014 (2)
C10B0.040 (3)0.040 (2)0.052 (3)0.0142 (19)0.002 (2)−0.001 (2)
C11B0.054 (4)0.037 (3)0.062 (5)0.006 (2)−0.006 (4)0.002 (3)
C120.0336 (11)0.0471 (11)0.0647 (13)0.0067 (9)0.0133 (9)0.0081 (9)
Geometric parameters (Å, °) top
Ni1—N12.2874 (19)C2—C31.387 (3)
Ni1—N22.0944 (19)C3—C41.385 (4)
Ni1—N32.094 (2)C3—H30.9300
S1A—O2A1.421 (9)C4—C51.369 (5)
S1A—O1A1.428 (8)C4—H40.9300
S1A—N11.632 (6)C5—C61.377 (5)
S1A—C71.796 (5)C5—H50.9300
S1B—O1B1.445 (9)C6—C71.379 (3)
S1B—O2B1.453 (9)C6—H60.9300
S1B—N11.613 (6)C8A—C9A1.501 (12)
S1B—C71.725 (6)C8A—H8A10.9700
O3—C11.230 (3)C8A—H8A20.9700
N1—C11.363 (3)C9A—C10A1.485 (9)
N2—C8A1.483 (8)C9A—H9A10.9700
N2—C8B1.486 (8)C9A—H9A20.9700
N2—H2A0.9000C10A—C11A1.360 (10)
N2—H2B0.9000C11A—H11A0.9300
N3—C121.303 (3)C8B—C9B1.501 (10)
N3—C10B1.399 (6)C8B—H8B10.9700
N3—C10A1.403 (6)C8B—H8B20.9700
N4—C11B1.322 (11)C9B—C10B1.490 (8)
N4—C121.325 (3)C9B—H9B10.9700
N4—C11A1.379 (10)C9B—H9B20.9700
N4—H4A0.79 (3)C10B—C11B1.352 (11)
C1—C21.495 (3)C11B—H11B0.9300
C2—C71.373 (3)C12—H120.9300
N3—Ni1—N3i180.00 (7)C4—C3—C2117.3 (3)
N3—Ni1—N290.30 (10)C4—C3—H3121.4
N3i—Ni1—N289.70 (10)C2—C3—H3121.4
N3—Ni1—N2i89.70 (10)C5—C4—C3121.7 (3)
N3i—Ni1—N2i90.30 (10)C5—C4—H4119.1
N2—Ni1—N2i180.00 (8)C3—C4—H4119.1
N3—Ni1—N1i89.27 (9)C4—C5—C6121.4 (3)
N3i—Ni1—N1i90.73 (9)C4—C5—H5119.3
N2—Ni1—N1i93.59 (8)C6—C5—H5119.3
N2i—Ni1—N1i86.41 (8)C5—C6—C7116.6 (3)
N3—Ni1—N190.73 (9)C5—C6—H6121.7
N3i—Ni1—N189.27 (9)C7—C6—H6121.7
N2—Ni1—N186.41 (8)C2—C7—C6122.9 (2)
N2i—Ni1—N193.59 (8)C2—C7—S1B106.1 (3)
N1i—Ni1—N1180.00 (7)C6—C7—S1B130.6 (3)
O2A—S1A—O1A116.3 (5)C2—C7—S1A107.5 (2)
O2A—S1A—N1111.0 (4)C6—C7—S1A129.3 (3)
O1A—S1A—N1113.5 (5)N2—C8A—C9A109.4 (6)
O2A—S1A—C7106.4 (5)N2—C8A—H8A1109.8
O1A—S1A—C7112.2 (5)C9A—C8A—H8A1109.8
N1—S1A—C795.3 (3)N2—C8A—H8A2109.8
O1B—S1B—O2B114.1 (6)C9A—C8A—H8A2109.8
O1B—S1B—N1109.1 (5)H8A1—C8A—H8A2108.2
O2B—S1B—N1111.5 (5)C10A—C9A—C8A113.2 (6)
O1B—S1B—C7110.6 (5)C10A—C9A—H9A1108.9
O2B—S1B—C7111.7 (5)C8A—C9A—H9A1108.9
N1—S1B—C798.8 (3)C10A—C9A—H9A2108.9
C1—N1—S1B108.4 (2)C8A—C9A—H9A2108.9
C1—N1—S1A112.1 (2)H9A1—C9A—H9A2107.8
C1—N1—Ni1127.06 (13)C11A—C10A—N3107.5 (6)
S1B—N1—Ni1124.5 (2)C11A—C10A—C9A129.8 (6)
S1A—N1—Ni1120.0 (2)N3—C10A—C9A122.5 (4)
C8A—N2—Ni1121.5 (4)C10A—C11A—N4106.8 (6)
C8B—N2—Ni1118.1 (3)C10A—C11A—H11A126.6
C8A—N2—H2A106.9N4—C11A—H11A126.6
C8B—N2—H2A86.0N2—C8B—C9B109.7 (5)
Ni1—N2—H2A106.9N2—C8B—H8B1109.7
C8A—N2—H2B106.9C9B—C8B—H8B1109.7
C8B—N2—H2B127.1N2—C8B—H8B2109.7
Ni1—N2—H2B106.9C9B—C8B—H8B2109.7
H2A—N2—H2B106.7H8B1—C8B—H8B2108.2
C12—N3—C10B103.1 (3)C10B—C9B—C8B113.0 (5)
C12—N3—C10A105.0 (3)C10B—C9B—H9B1109.0
C12—N3—Ni1130.02 (15)C8B—C9B—H9B1109.0
C10B—N3—Ni1125.2 (3)C10B—C9B—H9B2109.0
C10A—N3—Ni1123.2 (3)C8B—C9B—H9B2109.0
C11B—N4—C12107.2 (4)H9B1—C9B—H9B2107.8
C12—N4—C11A106.3 (4)C11B—C10B—N3108.2 (6)
C11B—N4—H4A126 (2)C11B—C10B—C9B128.4 (6)
C12—N4—H4A126 (2)N3—C10B—C9B123.4 (4)
C11A—N4—H4A125 (2)N4—C11B—C10B107.3 (7)
O3—C1—N1124.7 (2)N4—C11B—H11B126.4
O3—C1—C2122.09 (19)C10B—C11B—H11B126.4
N1—C1—C2113.15 (17)N3—C12—N4112.3 (2)
C7—C2—C3120.0 (2)N3—C12—H12123.9
C7—C2—C1111.53 (19)N4—C12—H12123.9
C3—C2—C1128.4 (2)
Symmetry codes: (i) −x, −y, −z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···O30.902.092.927 (3)153
N2—H2B···O1Ai0.902.322.936 (10)126
N2—H2B···S1Ai0.902.843.409 (5)122
N4—H4A···O2Aii0.79 (3)2.12 (4)2.801 (9)144 (3)
N4—H4A···O2Bii0.79 (3)2.04 (4)2.794 (9)159 (3)
N2—H2B···O3iii0.902.663.123 (4)113
Symmetry codes: (i) −x, −y, −z; (ii) −x+1, −y+1, −z; (iii) −x−1, −y, −z.
Selected geometric parameters (Å) top
Ni1—N12.2874 (19)Ni1—N32.094 (2)
Ni1—N22.0944 (19)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···O30.902.092.927 (3)153
N2—H2B···O1Ai0.902.322.936 (10)126
N2—H2B···S1Ai0.902.843.409 (5)122
N4—H4A···O2Aii0.79 (3)2.12 (4)2.801 (9)144 (3)
N4—H4A···O2Bii0.79 (3)2.04 (4)2.794 (9)159 (3)
N2—H2B···O3iii0.902.663.123 (4)113
Symmetry codes: (i) −x, −y, −z; (ii) −x+1, −y+1, −z; (iii) −x−1, −y, −z.
Acknowledgements top

The authors thank the Faculty of Arts and Sciences, Ondokuz Mayıs University, Turkey, for the use of the Stoe IPDS II diffractometer (purchased under grant No. F279 of the University Research Fund).

references
References top

Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573.

Bulut, İ., U˛car, İ., Karabulut, B. & Bulut, A. (2007). J. Mol. Struct. 834–836, 276–283.

Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565–?.

Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.

Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453–457.

Sheldrick, G. M. (1990). Acta Cryst. A46, 467–473.

Sheldrick, G. M. (1997). SHELXL97. University of Göttingen, Germany.

Stoe & Cie (2002). X-AREA (Version 1.18) and X-RED32 (Version 1.04). Stoe & Cie, Darmstadt, Germany.