[N,N-Bis(2-amino­eth­yl)ethane-1,2-diamine](ethane-1,2-diamine)­nickel(II) thio­sulfate trihydrate

Seidlhofer, B.; Näther, C.; Bensch, W.

doi:10.1107/S1600536812001651

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 2| February 2012| Pages m167-m168

doi:10.1107/S1600536812001651

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[N,N-Bis(2-aminoethyl)ethane-1,2-diamine](ethane-1,2-diamine)nickel(II) thiosulfate trihydrate

Beatrix Seidlhofer,^a Christian Näther ^a ^* and Wolfgang Bensch ^a

^aInstitut für Anorganische Chemie, Christian-Albrechts-Universität Kiel, Max-Eyth-Strasse 2, 24118 Kiel, Germany
^*Correspondence e-mail: cnaether@ac.uni-kiel.de

(Received 5 January 2012; accepted 13 January 2012; online 18 January 2012)

The title compound, [Ni(C₂H₈N₂)(C₆H₁₈N₄)]S₂O₃·3H₂O, was accidentally synthesized under solvothermal conditions applying [Ni(en)₃]Cl₂ (en is ethane-1,2-diamine) as the Ni source. The asymmetric unit consists of one discrete [Ni(tren)(en)]²⁺ complex [tren is N,N-bis(2-aminoethyl)ethane-1,2-diamine] in which the Ni²⁺ cation is sixfold coordinated within a slightly distorted octahedron, one thiosulfate anion and three water molecules. In the crystal, the complex cations, anions and water molecules are linked by an intricate hydrogen-bonding network. One C atom of the tren ligand, as well as one O atom of a water molecule, are disordered over two sites and were refined using a split model (occupancy ratios = 0.85:15 and 0.60:0.40, respectively).

Related literature

For background of this work, see: Lühmann et al. (2011 ); Seidlhofer et al. (2011 ). For related thiosulfate crystal structures, see: Nardelli & Coghi (1958 ); Varand et al. (1967 ); Freire et al. (2000 ); Díaz de Vivar et al. (2007 ).

Experimental

Crystal data

[Ni(C₂H₈N₂)(C₆H₁₈N₄)]S₂O₃·3H₂O
M_r = 431.23
Monoclinic, P 2₁ /n
a = 10.890 (2) Å
b = 10.0494 (17) Å
c = 16.689 (3) Å
β = 96.68 (2)°
V = 1813.9 (6) Å³
Z = 4
Mo Kα radiation
μ = 1.34 mm⁻¹
T = 170 K
0.16 × 0.11 × 0.06 mm

Data collection

Stoe IPDS-1 diffractometer
Absorption correction: numerical (X-SHAPE; Stoe & Cie, 1998 ) T_min = 0.559, T_max = 0.748
23884 measured reflections
4358 independent reflections
3924 reflections with I > 2σ(I)
R_int = 0.065

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.099
S = 1.05
4358 reflections
216 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 0.55 e Å⁻³
Δρ_min = −0.77 e Å⁻³

Table 1
Selected bond lengths (Å)

Ni1—N5	2.0865 (16)
Ni1—N4	2.1099 (15)
Ni1—N1	2.1124 (16)
Ni1—N2	2.1364 (15)
Ni1—N3	2.1491 (16)
Ni1—N6	2.1634 (15)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1N2⋯O3ⁱ	0.92	2.47	3.324 (2)	155
N2—H2N2⋯O2ⁱⁱ	0.92	2.25	3.084 (2)	150
N3—H1N3⋯S2ⁱⁱⁱ	0.92	2.68	3.5921 (18)	169
N4—H1N4⋯O2ⁱⁱ	0.92	2.09	2.971 (2)	161
N4—H2N4⋯O2ⁱⁱⁱ	0.92	2.25	3.151 (2)	165
N4—H2N4⋯S2ⁱⁱⁱ	0.92	3.21	3.8838 (17)	131
N5—H1N5⋯O1ⁱⁱⁱ	0.92	2.40	3.244 (2)	153
N5—H1N5⋯O2ⁱⁱⁱ	0.92	2.48	3.289 (2)	147
N5—H2N5⋯O4ⁱⁱ	0.92	2.09	2.997 (3)	168
N6—H1N6⋯O3ⁱ	0.92	2.30	3.062 (2)	140
N6—H2N6⋯O1	0.92	2.44	3.307 (2)	158
N6—H2N6⋯S2	0.92	2.89	3.6214 (17)	137
O4—H2O4⋯S2	0.84	2.56	3.390 (2)	171
O5—H1O5⋯O3	0.84	2.02	2.858 (3)	179
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (iii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: IPDS Program Package (Stoe & Cie, 1998); cell refinement: IPDS Program Package; data reduction: IPDS Program Package; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2006 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812001651/wm2582sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812001651/wm2582Isup2.hkl

checkCIF report

Comment top

The structure of the title compound was determined within a project on the synthesis, structure determination and investigation of the properties of new thioantimonates (Seidlhofer et al., 2011; Lühmann et al., 2011). The crystals were obtained accidentally by the reaction of [Ni(en)₃]Cl₂ with Sb and S in tris(2-aminoethyl)amine.

The structure consists of a discrete [Ni(tren)(en)]²⁺ complex, a thiosulfate anion and three water molecules. The Ni²⁺ cation is octahedrally coordinated by four N atoms from one tris(2-aminoethyl)amine and two N atoms from one ethylenediamine ligand (Fig. 1). The Ni—N bond lengths are between 2.0865 (16) and 2.1634 (15) Å and the N—Ni—N angles range from 82.39 (6) to 175.52 (6) °. In the crystal structure the cations, anions and water molecules are connected by a complex hydrogen-bonded network into a three-dimensional structure (Tab. 1 and Fig. 2). It is noted that only a few isolated thiosulfate nickel complexes are known up to date (Nardelli & Coghi, 1958; Varand et al., 1967; Freire et al., 2000; Díaz de Vivar et al., 2007).

Related literature top

For background of this work, see: Lühmann et al. (2011); Seidlhofer et al. (2011). For related thiosulfate crystal structures, see: Nardelli & Coghi (1958); Varand et al. (1967); Freire et al. (2000); Díaz de Vivar et al. (2007).

Experimental top

The title compound was synthesized by heating [Ni(en)₃]Cl₂ (1.4 mmol), Sb (1.4 mmol) and S (4 mmol) in 50% tris(2-aminoethyl)amine (6.6 ml) for 8 d at 413 K. The reaction mixture was cooled down, filtered off and washed with water, ethanol and acetone. The pink crystals are unstable in air. Yield: 17% based on Ni. Elemental analysis found: C 23.75%, H 7.76%, N 19.90%; calc.: C 22.28%, H 7.48%, N 19.49%.

Computing details top

Data collection: IPDS Program Package (Stoe & Cie, 1998); cell refinement: IPDS Program Package (Stoe & Cie, 1998); data reduction: IPDS Program Package (Stoe & Cie, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular parts of the crystal structure of the title compound with atom labelling and displacement ellipsoids drawn at the 50% probability level. The disorder of the O6 and C6 atoms is shown with bonds as open lines.
	Fig. 2. Crystal structure of the title compound with view along the b axis. Hydrogen bonding is shown as dashed lines; disordered atoms are not shown for clarity. Colour code: Ni: orange; N: blue; O: red; C: black; H white.

[N,N-Bis(2-aminoethyl)ethane-1,2-diamine](ethane-1,2- diamine)nickel(II) thiosulfate trihydrate top

Crystal data top

[Ni(C₂H₈N₂)(C₆H₁₈N₄)]S₂O₃·3H₂O	F(000) = 920
M_r = 431.23	D_x = 1.579 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 4358 reflections
a = 10.890 (2) Å	θ = 2.4–28.1°
b = 10.0494 (17) Å	µ = 1.34 mm⁻¹
c = 16.689 (3) Å	T = 170 K
β = 96.68 (2)°	Parallelepiped, pink
V = 1813.9 (6) Å³	0.16 × 0.11 × 0.06 mm
Z = 4

Data collection top

Stoe IPDS-1 diffractometer	4358 independent reflections
Radiation source: fine-focus sealed tube	3924 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.065
ϕ scans	θ_max = 28.1°, θ_min = 2.4°
Absorption correction: numerical (X-SHAPE; Stoe & Cie, 1998)	h = −14→14
T_min = 0.559, T_max = 0.748	k = −13→13
23884 measured reflections	l = −22→22

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.037	H-atom parameters constrained
wR(F²) = 0.099	w = 1/[σ²(F_o²) + (0.0672P)² + 0.6394P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
4358 reflections	Δρ_max = 0.55 e Å⁻³
216 parameters	Δρ_min = −0.77 e Å⁻³
2 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0202 (16)

Crystal data top

[Ni(C₂H₈N₂)(C₆H₁₈N₄)]S₂O₃·3H₂O	V = 1813.9 (6) Å³
M_r = 431.23	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 10.890 (2) Å	µ = 1.34 mm⁻¹
b = 10.0494 (17) Å	T = 170 K
c = 16.689 (3) Å	0.16 × 0.11 × 0.06 mm
β = 96.68 (2)°

Data collection top

Stoe IPDS-1 diffractometer	4358 independent reflections
Absorption correction: numerical (X-SHAPE; Stoe & Cie, 1998)	3924 reflections with I > 2σ(I)
T_min = 0.559, T_max = 0.748	R_int = 0.065
23884 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	2 restraints
wR(F²) = 0.099	H-atom parameters constrained
S = 1.05	Δρ_max = 0.55 e Å⁻³
4358 reflections	Δρ_min = −0.77 e Å⁻³
216 parameters

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Ni1	0.825612 (19)	0.70992 (2)	0.095341 (12)	0.00955 (10)
N1	0.66319 (15)	0.77843 (15)	0.02610 (9)	0.0145 (3)
C1	0.68958 (19)	0.91729 (19)	0.00384 (13)	0.0231 (4)
H1A	0.6888	0.9758	0.0515	0.028*
H1B	0.6249	0.9488	−0.0385	0.028*
C2	0.8153 (2)	0.9243 (2)	−0.02702 (13)	0.0260 (4)
H2A	0.8116	0.8783	−0.0797	0.031*
H2B	0.8374	1.0185	−0.0351	0.031*
N2	0.91090 (15)	0.86132 (16)	0.03095 (10)	0.0168 (3)
H1N2	0.9468	0.9241	0.0664	0.020*
H2N2	0.9716	0.8247	0.0039	0.020*
C3	0.56558 (18)	0.7694 (2)	0.08050 (12)	0.0200 (4)
H3A	0.4838	0.7849	0.0493	0.024*
H3B	0.5790	0.8390	0.1226	0.024*
C4	0.56718 (18)	0.6330 (2)	0.12019 (12)	0.0216 (4)
H4A	0.5119	0.6334	0.1633	0.026*
H4B	0.5362	0.5654	0.0797	0.026*
N3	0.69498 (15)	0.59804 (16)	0.15526 (9)	0.0170 (3)
H1N3	0.7082	0.5084	0.1490	0.020*
H2N3	0.7052	0.6171	0.2095	0.020*
C5	0.63530 (14)	0.69377 (15)	−0.04694 (9)	0.0204 (4)
H5A	0.6615	0.7413	−0.0941	0.024*
H5B	0.5448	0.6800	−0.0571	0.024*
C6	0.69987 (14)	0.55683 (15)	−0.03937 (9)	0.0174 (4)	0.85
H6A	0.6530	0.4959	−0.0076	0.021*	0.85
H6B	0.7018	0.5177	−0.0937	0.021*	0.85
C6'	0.7426 (12)	0.6239 (15)	−0.0703 (8)	0.029 (3)*	0.15
H6C	0.7902	0.6853	−0.1013	0.034*	0.15
H6D	0.7142	0.5488	−0.1061	0.034*	0.15
N4	0.82558 (15)	0.57175 (15)	0.00015 (9)	0.0151 (3)
H1N4	0.8765	0.6013	−0.0364	0.018*
H2N4	0.8548	0.4909	0.0200	0.018*
N5	0.98383 (15)	0.62798 (15)	0.15913 (9)	0.0155 (3)
H1N5	0.9769	0.5368	0.1607	0.019*
H2N5	1.0523	0.6490	0.1341	0.019*
C7	0.99714 (19)	0.6825 (2)	0.24186 (11)	0.0197 (4)
H7A	1.0827	0.6690	0.2678	0.024*
H7B	0.9399	0.6364	0.2746	0.024*
C8	0.96731 (18)	0.8296 (2)	0.23676 (11)	0.0183 (4)
H8A	0.9727	0.8678	0.2917	0.022*
H8B	1.0280	0.8761	0.2069	0.022*
N6	0.84107 (15)	0.84901 (15)	0.19495 (9)	0.0139 (3)
H1N6	0.8306	0.9350	0.1765	0.017*
H2N6	0.7826	0.8313	0.2291	0.017*
S1	0.59787 (4)	0.75756 (4)	0.35625 (3)	0.01400 (12)
S2	0.77905 (5)	0.75258 (6)	0.39543 (3)	0.02618 (14)
O1	0.58163 (15)	0.83268 (16)	0.27970 (9)	0.0263 (3)
O2	0.53275 (14)	0.82554 (16)	0.41669 (9)	0.0241 (3)
O3	0.55239 (16)	0.62002 (14)	0.34450 (11)	0.0307 (4)
O4	0.70135 (19)	0.76209 (19)	0.58623 (12)	0.0412 (5)
H1O4	0.7540	0.7212	0.6179	0.062*
H2O4	0.7245	0.7692	0.5401	0.062*
O5	0.31217 (17)	0.58765 (18)	0.25772 (12)	0.0389 (4)
H1O5	0.3829	0.5982	0.2828	0.058*
H2O5	0.2956	0.6611	0.2350	0.058*
O6	0.3335 (2)	0.8638 (3)	0.21164 (18)	0.0350 (9)	0.60
H1O6	0.2996	0.9412	0.2226	0.053*
H2O6	0.4147	0.8758	0.2313	0.053*
O6'	0.3485 (2)	0.9043 (3)	0.19116 (18)	0.0382 (16)	0.40

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.00967 (15)	0.00919 (14)	0.00982 (14)	−0.00134 (7)	0.00127 (8)	−0.00001 (7)
N1	0.0134 (8)	0.0142 (7)	0.0157 (7)	0.0003 (5)	0.0006 (6)	0.0004 (5)
C1	0.0239 (10)	0.0156 (8)	0.0283 (10)	0.0034 (7)	−0.0032 (8)	0.0080 (7)
C2	0.0295 (11)	0.0240 (10)	0.0241 (10)	−0.0055 (8)	0.0023 (8)	0.0131 (8)
N2	0.0172 (8)	0.0159 (7)	0.0185 (7)	−0.0036 (6)	0.0073 (6)	0.0010 (6)
C3	0.0108 (9)	0.0257 (9)	0.0238 (9)	0.0023 (7)	0.0029 (7)	−0.0019 (7)
C4	0.0149 (9)	0.0245 (9)	0.0269 (10)	−0.0074 (7)	0.0090 (7)	−0.0023 (7)
N3	0.0198 (8)	0.0151 (7)	0.0169 (7)	−0.0048 (6)	0.0056 (6)	0.0011 (5)
C5	0.0203 (10)	0.0245 (9)	0.0146 (8)	−0.0002 (7)	−0.0051 (7)	−0.0023 (7)
C6	0.0174 (10)	0.0182 (10)	0.0157 (9)	−0.0038 (8)	−0.0015 (7)	−0.0061 (8)
N4	0.0177 (8)	0.0131 (7)	0.0152 (7)	−0.0003 (6)	0.0041 (5)	−0.0034 (5)
N5	0.0153 (7)	0.0126 (7)	0.0180 (7)	0.0011 (6)	−0.0007 (6)	−0.0018 (5)
C7	0.0206 (10)	0.0228 (9)	0.0144 (8)	0.0027 (8)	−0.0033 (7)	−0.0017 (7)
C8	0.0179 (9)	0.0190 (8)	0.0167 (8)	−0.0012 (7)	−0.0038 (7)	−0.0056 (7)
N6	0.0170 (7)	0.0118 (6)	0.0130 (7)	−0.0006 (5)	0.0023 (5)	−0.0023 (5)
S1	0.0159 (2)	0.0109 (2)	0.0162 (2)	0.00063 (15)	0.00616 (16)	−0.00066 (15)
S2	0.0154 (3)	0.0291 (3)	0.0348 (3)	0.0045 (2)	0.0061 (2)	0.0132 (2)
O1	0.0286 (8)	0.0301 (8)	0.0198 (7)	0.0012 (6)	0.0007 (6)	0.0067 (6)
O2	0.0212 (7)	0.0251 (7)	0.0287 (7)	0.0008 (6)	0.0141 (6)	−0.0079 (6)
O3	0.0346 (9)	0.0130 (6)	0.0446 (10)	−0.0050 (6)	0.0046 (7)	−0.0052 (6)
O4	0.0467 (12)	0.0387 (9)	0.0426 (10)	0.0195 (9)	0.0234 (9)	0.0145 (8)
O5	0.0305 (9)	0.0374 (9)	0.0483 (10)	0.0004 (7)	0.0025 (8)	0.0186 (8)
O6	0.0327 (18)	0.0252 (14)	0.0431 (18)	−0.0002 (12)	−0.0129 (14)	−0.0037 (14)
O6'	0.024 (2)	0.050 (3)	0.038 (3)	0.008 (2)	−0.0087 (19)	−0.028 (3)

Geometric parameters (Å, º) top

Ni1—N5	2.0865 (16)	C6—H6A	0.9900
Ni1—N4	2.1099 (15)	C6—H6B	0.9900
Ni1—N1	2.1124 (16)	C6'—N4	1.492 (12)
Ni1—N2	2.1364 (15)	C6'—H6C	0.9900
Ni1—N3	2.1491 (16)	C6'—H6D	0.9900
Ni1—N6	2.1634 (15)	N4—H1N4	0.9200
N1—C3	1.479 (2)	N4—H2N4	0.9200
N1—C1	1.481 (2)	N5—C7	1.477 (2)
N1—C5	1.489 (2)	N5—H1N5	0.9200
C1—C2	1.519 (3)	N5—H2N5	0.9200
C1—H1A	0.9900	C7—C8	1.514 (3)
C1—H1B	0.9900	C7—H7A	0.9900
C2—N2	1.479 (3)	C7—H7B	0.9900
C2—H2A	0.9900	C8—N6	1.480 (2)
C2—H2B	0.9900	C8—H8A	0.9900
N2—H1N2	0.9200	C8—H8B	0.9900
N2—H2N2	0.9200	N6—H1N6	0.9200
C3—C4	1.521 (3)	N6—H2N6	0.9200
C3—H3A	0.9900	S1—O2	1.4675 (14)
C3—H3B	0.9900	S1—O3	1.4736 (15)
C4—N3	1.488 (3)	S1—O1	1.4767 (15)
C4—H4A	0.9900	S1—S2	2.0058 (8)
C4—H4B	0.9900	O4—H1O4	0.8401
N3—H1N3	0.9200	O4—H2O4	0.8400
N3—H2N3	0.9200	O5—H1O5	0.8400
C5—C6'	1.454 (12)	O5—H2O5	0.8401
C5—C6	1.5439	O6—H1O6	0.8898
C5—H5A	0.9900	O6—H2O6	0.9142
C5—H5B	0.9900	O6'—H1O6	0.8737
C6—N4	1.457 (2)	O6'—H2O6	0.9683

N5—Ni1—N4	92.99 (6)	C6—C5—H5A	108.9
N5—Ni1—N1	175.52 (6)	C6'—C5—H5B	134.5
N4—Ni1—N1	82.86 (6)	N1—C5—H5B	108.9
N5—Ni1—N2	98.99 (6)	C6—C5—H5B	108.9
N4—Ni1—N2	92.98 (6)	H5A—C5—H5B	107.7
N1—Ni1—N2	83.00 (6)	N4—C6—C5	109.90 (8)
N5—Ni1—N3	96.21 (6)	N4—C6—H6A	109.7
N4—Ni1—N3	93.66 (6)	C5—C6—H6A	109.7
N1—Ni1—N3	82.39 (6)	N4—C6—H6B	109.7
N2—Ni1—N3	163.06 (6)	C5—C6—H6B	109.7
N5—Ni1—N6	82.94 (6)	H6A—C6—H6B	108.2
N4—Ni1—N6	175.51 (6)	C5—C6'—N4	113.0 (9)
N1—Ni1—N6	101.25 (6)	C5—C6'—H6C	109.0
N2—Ni1—N6	85.81 (6)	N4—C6'—H6C	109.0
N3—Ni1—N6	88.69 (6)	C5—C6'—H6D	109.0
C3—N1—C1	112.73 (16)	N4—C6'—H6D	109.0
C3—N1—C5	112.01 (14)	H6C—C6'—H6D	107.8
C1—N1—C5	111.11 (14)	C6—N4—Ni1	109.06 (10)
C3—N1—Ni1	105.07 (11)	C6'—N4—Ni1	108.0 (5)
C1—N1—Ni1	105.65 (11)	C6—N4—H1N4	109.9
C5—N1—Ni1	109.87 (11)	Ni1—N4—H1N4	109.9
N1—C1—C2	109.73 (16)	C6—N4—H2N4	109.9
N1—C1—H1A	109.7	C6'—N4—H2N4	138.3
C2—C1—H1A	109.7	Ni1—N4—H2N4	109.9
N1—C1—H1B	109.7	H1N4—N4—H2N4	108.3
C2—C1—H1B	109.7	C7—N5—Ni1	108.42 (12)
H1A—C1—H1B	108.2	C7—N5—H1N5	110.0
N2—C2—C1	110.62 (16)	Ni1—N5—H1N5	110.0
N2—C2—H2A	109.5	C7—N5—H2N5	110.0
C1—C2—H2A	109.5	Ni1—N5—H2N5	110.0
N2—C2—H2B	109.5	H1N5—N5—H2N5	108.4
C1—C2—H2B	109.5	N5—C7—C8	108.22 (15)
H2A—C2—H2B	108.1	N5—C7—H7A	110.1
C2—N2—Ni1	108.64 (12)	C8—C7—H7A	110.1
C2—N2—H1N2	110.0	N5—C7—H7B	110.1
Ni1—N2—H1N2	110.0	C8—C7—H7B	110.1
C2—N2—H2N2	110.0	H7A—C7—H7B	108.4
Ni1—N2—H2N2	110.0	N6—C8—C7	109.67 (15)
H1N2—N2—H2N2	108.3	N6—C8—H8A	109.7
N1—C3—C4	110.49 (16)	C7—C8—H8A	109.7
N1—C3—H3A	109.6	N6—C8—H8B	109.7
C4—C3—H3A	109.6	C7—C8—H8B	109.7
N1—C3—H3B	109.6	H8A—C8—H8B	108.2
C4—C3—H3B	109.6	C8—N6—Ni1	105.19 (11)
H3A—C3—H3B	108.1	C8—N6—H1N6	110.7
N3—C4—C3	110.30 (15)	Ni1—N6—H1N6	110.7
N3—C4—H4A	109.6	C8—N6—H2N6	110.7
C3—C4—H4A	109.6	Ni1—N6—H2N6	110.7
N3—C4—H4B	109.6	H1N6—N6—H2N6	108.8
C3—C4—H4B	109.6	O2—S1—O3	110.26 (10)
H4A—C4—H4B	108.1	O2—S1—O1	109.74 (10)
C4—N3—Ni1	109.44 (11)	O3—S1—O1	111.09 (10)
C4—N3—H1N3	109.8	O2—S1—S2	108.85 (7)
Ni1—N3—H1N3	109.8	O3—S1—S2	108.82 (8)
C4—N3—H2N3	109.8	O1—S1—S2	108.01 (7)
Ni1—N3—H2N3	109.8	H1O4—O4—H2O4	111.2
H1N3—N3—H2N3	108.2	H1O5—O5—H2O5	104.5
C6'—C5—N1	113.6 (6)	H1O6—O6—H2O6	102.6
N1—C5—C6	113.25 (8)	H1O6—O6'—H2O6	99.6
N1—C5—H5A	108.9

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1N2···O3ⁱ	0.92	2.47	3.324 (2)	155
N2—H2N2···O2ⁱⁱ	0.92	2.25	3.084 (2)	150
N3—H1N3···S2ⁱⁱⁱ	0.92	2.68	3.5921 (18)	169
N4—H1N4···O2ⁱⁱ	0.92	2.09	2.971 (2)	161
N4—H2N4···O2ⁱⁱⁱ	0.92	2.25	3.151 (2)	165
N4—H2N4···S2ⁱⁱⁱ	0.92	3.21	3.8838 (17)	131
N5—H1N5···O1ⁱⁱⁱ	0.92	2.40	3.244 (2)	153
N5—H1N5···O2ⁱⁱⁱ	0.92	2.48	3.289 (2)	147
N5—H2N5···O4ⁱⁱ	0.92	2.09	2.997 (3)	168
N6—H1N6···O3ⁱ	0.92	2.30	3.062 (2)	140
N6—H2N6···O1	0.92	2.44	3.307 (2)	158
N6—H2N6···S2	0.92	2.89	3.6214 (17)	137
O4—H2O4···S2	0.84	2.56	3.390 (2)	171
O5—H1O5···O3	0.84	2.02	2.858 (3)	179

Symmetry codes: (i) −x+3/2, y+1/2, −z+1/2; (ii) x+1/2, −y+3/2, z−1/2; (iii) −x+3/2, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	[Ni(C₂H₈N₂)(C₆H₁₈N₄)]S₂O₃·3H₂O
M_r	431.23
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	170
a, b, c (Å)	10.890 (2), 10.0494 (17), 16.689 (3)
β (°)	96.68 (2)
V (Å³)	1813.9 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.34
Crystal size (mm)	0.16 × 0.11 × 0.06

Data collection
Diffractometer	Stoe IPDS1 diffractometer
Absorption correction	Numerical (X-SHAPE; Stoe & Cie, 1998)
T_min, T_max	0.559, 0.748
No. of measured, independent and observed [I > 2σ(I)] reflections	23884, 4358, 3924
R_int	0.065
(sin θ/λ)_max (Å⁻¹)	0.662

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.099, 1.05
No. of reflections	4358
No. of parameters	216
No. of restraints	2
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.55, −0.77

Computer programs: IPDS Program Package (Stoe & Cie, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2006), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Ni1—N5	2.0865 (16)	Ni1—N2	2.1364 (15)
Ni1—N4	2.1099 (15)	Ni1—N3	2.1491 (16)
Ni1—N1	2.1124 (16)	Ni1—N6	2.1634 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1N2···O3ⁱ	0.92	2.47	3.324 (2)	155.0
N2—H2N2···O2ⁱⁱ	0.92	2.25	3.084 (2)	150.4
N3—H1N3···S2ⁱⁱⁱ	0.92	2.68	3.5921 (18)	169.4
N4—H1N4···O2ⁱⁱ	0.92	2.09	2.971 (2)	160.5
N4—H2N4···O2ⁱⁱⁱ	0.92	2.25	3.151 (2)	165.1
N4—H2N4···S2ⁱⁱⁱ	0.92	3.21	3.8838 (17)	131.3
N5—H1N5···O1ⁱⁱⁱ	0.92	2.40	3.244 (2)	152.9
N5—H1N5···O2ⁱⁱⁱ	0.92	2.48	3.289 (2)	146.7
N5—H2N5···O4ⁱⁱ	0.92	2.09	2.997 (3)	167.7
N6—H1N6···O3ⁱ	0.92	2.30	3.062 (2)	139.5
N6—H2N6···O1	0.92	2.44	3.307 (2)	158.1
N6—H2N6···S2	0.92	2.89	3.6214 (17)	137.4
O4—H2O4···S2	0.84	2.56	3.390 (2)	170.5
O5—H1O5···O3	0.84	2.02	2.858 (3)	178.7

Symmetry codes: (i) −x+3/2, y+1/2, −z+1/2; (ii) x+1/2, −y+3/2, z−1/2; (iii) −x+3/2, y−1/2, −z+1/2.

Acknowledgements

Financial support by the State Schleswig-Holstein and the Deutsche Forschungsgemeinschaft is gratefully acknowledged.

References

Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Díaz de Vivar, M. E., Baggio, S., Garland, M. T. & Baggio, R. (2007). Acta Cryst. C63, m153–m156. CSD CrossRef IUCr Journals Google Scholar
Freire, E., Baggio, S., Mombru, A. & Baggio, R. (2000). Acta Cryst. C56, 541–543. CSD CrossRef CAS IUCr Journals Google Scholar
Lühmann, H., Näther, C. & Bensch, W. (2011). Z. Anorg. Allg. Chem. 637, 1007–1012. Google Scholar
Nardelli, M. & Coghi, L. (1958). Ric. Sci. 28, 609–610. CAS Google Scholar
Seidlhofer, B., Djamil, J., Näther, C. & Bensch, W. (2011). Cryst. Growth Des. 11, 5554–5560. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Stoe & Cie (1998). X-SHAPE and IPDS Program Package. Stoe & Cie, Darmstadt, Germany. Google Scholar
Varand, V. L., Podberezskaya, N. V., Shulman, V. M., Bakakin, V. V. & Ruchkin, E. D. (1967). Izv. Sib. Otd. Akad. Nauk SSSR Ser. Khim. Nauk, 5, 44–47. Google Scholar

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Volume 68| Part 2| February 2012| Pages m167-m168

doi:10.1107/S1600536812001651

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metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

[N,N-Bis(2-amino­eth­yl)ethane-1,2-di­amine](ethane-1,2-di­amine)­nickel(II) thio­sulfate trihydrate

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Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

[N,N-Bis(2-aminoethyl)ethane-1,2-diamine](ethane-1,2-diamine)nickel(II) thiosulfate trihydrate