Literature DB >> 22346844

[N,N-Bis(2-amino-eth-yl)ethane-1,2-diamine](ethane-1,2-diamine)-nickel(II) thio-sulfate trihydrate.

Beatrix Seidlhofer1, Christian Näther, Wolfgang Bensch.   

Abstract

The title compound, [Ni(C(2)n class="Species">H(8)N(2))(C(6)H(18)N(4))]S(2)O(3)·3H(2)O, was accidentally synthesized under solvothermal conditions applying [Ni(en)(3)]Cl(2) (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-amino-eth-yl)ethane-1,2-diamine] in which the Ni(2+) cation is sixfold coord-inated within a slightly distorted octa-hedron, one thio-sulfate anion and three water mol-ecules. In the crystal, the complex cations, anions and water mol-ecules are linked by an intricate hydrogen-bonding network. One C atom of the tren ligand, as well as one O atom of a water mol-ecule, are disordered over two sites and were refined using a split model (occupancy ratios = 0.85:15 and 0.60:0.40, respectively).

Entities:  

Year:  2012        PMID： 22346844      PMCID： PMC3274897          DOI： 10.1107/S1600536812001651

Source DB:  PubMed          Journal:  Acta Crystallogr Sect E Struct Rep Online        ISSN： 1600-5368


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(C2n class="Species">H8N2)(C6H18N4)]S2O3·3H2O M = 431.23 Monoclinic, 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[F 2 > 2σ(F 2)] = 0.037 wR(F 2) = 0.099 S = 1.05 4358 reflections 216 parameters 2 restraints H-atom parameters constrained Δρmax = 0.55 e Å−3 Δρmin = −0.77 e Å−3 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. Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812001651/wm2582sup1.cif Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812001651/wm2582Isup2.hkl Additional supplementary materials: crystallographic information; 3D view; checkCIF report
[Ni(C2H8N2)(C6H18N4)]S2O3·3H2OF(000) = 920
Mr = 431.23Dx = 1.579 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 4358 reflections
a = 10.890 (2) Åθ = 2.4–28.1°
b = 10.0494 (17) ŵ = 1.34 mm−1
c = 16.689 (3) ÅT = 170 K
β = 96.68 (2)°Parallelepiped, pink
V = 1813.9 (6) Å30.16 × 0.11 × 0.06 mm
Z = 4
Stoe IPDS-1 diffractometer4358 independent reflections
Radiation source: fine-focus sealed tube3924 reflections with I > 2σ(I)
graphiteRint = 0.065
φ scansθmax = 28.1°, θmin = 2.4°
Absorption correction: numerical (X-SHAPE; Stoe & Cie, 1998)h = −14→14
Tmin = 0.559, Tmax = 0.748k = −13→13
23884 measured reflectionsl = −22→22
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.037H-atom parameters constrained
wR(F2) = 0.099w = 1/[σ2(Fo2) + (0.0672P)2 + 0.6394P] where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max = 0.001
4358 reflectionsΔρmax = 0.55 e Å−3
216 parametersΔρmin = −0.77 e Å−3
2 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0202 (16)
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.
xyzUiso*/UeqOcc. (<1)
Ni10.825612 (19)0.70992 (2)0.095341 (12)0.00955 (10)
N10.66319 (15)0.77843 (15)0.02610 (9)0.0145 (3)
C10.68958 (19)0.91729 (19)0.00384 (13)0.0231 (4)
H1A0.68880.97580.05150.028*
H1B0.62490.9488−0.03850.028*
C20.8153 (2)0.9243 (2)−0.02702 (13)0.0260 (4)
H2A0.81160.8783−0.07970.031*
H2B0.83741.0185−0.03510.031*
N20.91090 (15)0.86132 (16)0.03095 (10)0.0168 (3)
H1N20.94680.92410.06640.020*
H2N20.97160.82470.00390.020*
C30.56558 (18)0.7694 (2)0.08050 (12)0.0200 (4)
H3A0.48380.78490.04930.024*
H3B0.57900.83900.12260.024*
C40.56718 (18)0.6330 (2)0.12019 (12)0.0216 (4)
H4A0.51190.63340.16330.026*
H4B0.53620.56540.07970.026*
N30.69498 (15)0.59804 (16)0.15526 (9)0.0170 (3)
H1N30.70820.50840.14900.020*
H2N30.70520.61710.20950.020*
C50.63530 (14)0.69377 (15)−0.04694 (9)0.0204 (4)
H5A0.66150.7413−0.09410.024*
H5B0.54480.6800−0.05710.024*
C60.69987 (14)0.55683 (15)−0.03937 (9)0.0174 (4)0.85
H6A0.65300.4959−0.00760.021*0.85
H6B0.70180.5177−0.09370.021*0.85
C6'0.7426 (12)0.6239 (15)−0.0703 (8)0.029 (3)*0.15
H6C0.79020.6853−0.10130.034*0.15
H6D0.71420.5488−0.10610.034*0.15
N40.82558 (15)0.57175 (15)0.00015 (9)0.0151 (3)
H1N40.87650.6013−0.03640.018*
H2N40.85480.49090.02000.018*
N50.98383 (15)0.62798 (15)0.15913 (9)0.0155 (3)
H1N50.97690.53680.16070.019*
H2N51.05230.64900.13410.019*
C70.99714 (19)0.6825 (2)0.24186 (11)0.0197 (4)
H7A1.08270.66900.26780.024*
H7B0.93990.63640.27460.024*
C80.96731 (18)0.8296 (2)0.23676 (11)0.0183 (4)
H8A0.97270.86780.29170.022*
H8B1.02800.87610.20690.022*
N60.84107 (15)0.84901 (15)0.19495 (9)0.0139 (3)
H1N60.83060.93500.17650.017*
H2N60.78260.83130.22910.017*
S10.59787 (4)0.75756 (4)0.35625 (3)0.01400 (12)
S20.77905 (5)0.75258 (6)0.39543 (3)0.02618 (14)
O10.58163 (15)0.83268 (16)0.27970 (9)0.0263 (3)
O20.53275 (14)0.82554 (16)0.41669 (9)0.0241 (3)
O30.55239 (16)0.62002 (14)0.34450 (11)0.0307 (4)
O40.70135 (19)0.76209 (19)0.58623 (12)0.0412 (5)
H1O40.75400.72120.61790.062*
H2O40.72450.76920.54010.062*
O50.31217 (17)0.58765 (18)0.25772 (12)0.0389 (4)
H1O50.38290.59820.28280.058*
H2O50.29560.66110.23500.058*
O60.3335 (2)0.8638 (3)0.21164 (18)0.0350 (9)0.60
H1O60.29960.94120.22260.053*
H2O60.41470.87580.23130.053*
O6'0.3485 (2)0.9043 (3)0.19116 (18)0.0382 (16)0.40
U11U22U33U12U13U23
Ni10.00967 (15)0.00919 (14)0.00982 (14)−0.00134 (7)0.00127 (8)−0.00001 (7)
N10.0134 (8)0.0142 (7)0.0157 (7)0.0003 (5)0.0006 (6)0.0004 (5)
C10.0239 (10)0.0156 (8)0.0283 (10)0.0034 (7)−0.0032 (8)0.0080 (7)
C20.0295 (11)0.0240 (10)0.0241 (10)−0.0055 (8)0.0023 (8)0.0131 (8)
N20.0172 (8)0.0159 (7)0.0185 (7)−0.0036 (6)0.0073 (6)0.0010 (6)
C30.0108 (9)0.0257 (9)0.0238 (9)0.0023 (7)0.0029 (7)−0.0019 (7)
C40.0149 (9)0.0245 (9)0.0269 (10)−0.0074 (7)0.0090 (7)−0.0023 (7)
N30.0198 (8)0.0151 (7)0.0169 (7)−0.0048 (6)0.0056 (6)0.0011 (5)
C50.0203 (10)0.0245 (9)0.0146 (8)−0.0002 (7)−0.0051 (7)−0.0023 (7)
C60.0174 (10)0.0182 (10)0.0157 (9)−0.0038 (8)−0.0015 (7)−0.0061 (8)
N40.0177 (8)0.0131 (7)0.0152 (7)−0.0003 (6)0.0041 (5)−0.0034 (5)
N50.0153 (7)0.0126 (7)0.0180 (7)0.0011 (6)−0.0007 (6)−0.0018 (5)
C70.0206 (10)0.0228 (9)0.0144 (8)0.0027 (8)−0.0033 (7)−0.0017 (7)
C80.0179 (9)0.0190 (8)0.0167 (8)−0.0012 (7)−0.0038 (7)−0.0056 (7)
N60.0170 (7)0.0118 (6)0.0130 (7)−0.0006 (5)0.0023 (5)−0.0023 (5)
S10.0159 (2)0.0109 (2)0.0162 (2)0.00063 (15)0.00616 (16)−0.00066 (15)
S20.0154 (3)0.0291 (3)0.0348 (3)0.0045 (2)0.0061 (2)0.0132 (2)
O10.0286 (8)0.0301 (8)0.0198 (7)0.0012 (6)0.0007 (6)0.0067 (6)
O20.0212 (7)0.0251 (7)0.0287 (7)0.0008 (6)0.0141 (6)−0.0079 (6)
O30.0346 (9)0.0130 (6)0.0446 (10)−0.0050 (6)0.0046 (7)−0.0052 (6)
O40.0467 (12)0.0387 (9)0.0426 (10)0.0195 (9)0.0234 (9)0.0145 (8)
O50.0305 (9)0.0374 (9)0.0483 (10)0.0004 (7)0.0025 (8)0.0186 (8)
O60.0327 (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)
Ni1—N52.0865 (16)C6—H6A0.9900
Ni1—N42.1099 (15)C6—H6B0.9900
Ni1—N12.1124 (16)C6'—N41.492 (12)
Ni1—N22.1364 (15)C6'—H6C0.9900
Ni1—N32.1491 (16)C6'—H6D0.9900
Ni1—N62.1634 (15)N4—H1N40.9200
N1—C31.479 (2)N4—H2N40.9200
N1—C11.481 (2)N5—C71.477 (2)
N1—C51.489 (2)N5—H1N50.9200
C1—C21.519 (3)N5—H2N50.9200
C1—H1A0.9900C7—C81.514 (3)
C1—H1B0.9900C7—H7A0.9900
C2—N21.479 (3)C7—H7B0.9900
C2—H2A0.9900C8—N61.480 (2)
C2—H2B0.9900C8—H8A0.9900
N2—H1N20.9200C8—H8B0.9900
N2—H2N20.9200N6—H1N60.9200
C3—C41.521 (3)N6—H2N60.9200
C3—H3A0.9900S1—O21.4675 (14)
C3—H3B0.9900S1—O31.4736 (15)
C4—N31.488 (3)S1—O11.4767 (15)
C4—H4A0.9900S1—S22.0058 (8)
C4—H4B0.9900O4—H1O40.8401
N3—H1N30.9200O4—H2O40.8400
N3—H2N30.9200O5—H1O50.8400
C5—C6'1.454 (12)O5—H2O50.8401
C5—C61.5439O6—H1O60.8898
C5—H5A0.9900O6—H2O60.9142
C5—H5B0.9900O6'—H1O60.8737
C6—N41.457 (2)O6'—H2O60.9683
N5—Ni1—N492.99 (6)C6—C5—H5A108.9
N5—Ni1—N1175.52 (6)C6'—C5—H5B134.5
N4—Ni1—N182.86 (6)N1—C5—H5B108.9
N5—Ni1—N298.99 (6)C6—C5—H5B108.9
N4—Ni1—N292.98 (6)H5A—C5—H5B107.7
N1—Ni1—N283.00 (6)N4—C6—C5109.90 (8)
N5—Ni1—N396.21 (6)N4—C6—H6A109.7
N4—Ni1—N393.66 (6)C5—C6—H6A109.7
N1—Ni1—N382.39 (6)N4—C6—H6B109.7
N2—Ni1—N3163.06 (6)C5—C6—H6B109.7
N5—Ni1—N682.94 (6)H6A—C6—H6B108.2
N4—Ni1—N6175.51 (6)C5—C6'—N4113.0 (9)
N1—Ni1—N6101.25 (6)C5—C6'—H6C109.0
N2—Ni1—N685.81 (6)N4—C6'—H6C109.0
N3—Ni1—N688.69 (6)C5—C6'—H6D109.0
C3—N1—C1112.73 (16)N4—C6'—H6D109.0
C3—N1—C5112.01 (14)H6C—C6'—H6D107.8
C1—N1—C5111.11 (14)C6—N4—Ni1109.06 (10)
C3—N1—Ni1105.07 (11)C6'—N4—Ni1108.0 (5)
C1—N1—Ni1105.65 (11)C6—N4—H1N4109.9
C5—N1—Ni1109.87 (11)Ni1—N4—H1N4109.9
N1—C1—C2109.73 (16)C6—N4—H2N4109.9
N1—C1—H1A109.7C6'—N4—H2N4138.3
C2—C1—H1A109.7Ni1—N4—H2N4109.9
N1—C1—H1B109.7H1N4—N4—H2N4108.3
C2—C1—H1B109.7C7—N5—Ni1108.42 (12)
H1A—C1—H1B108.2C7—N5—H1N5110.0
N2—C2—C1110.62 (16)Ni1—N5—H1N5110.0
N2—C2—H2A109.5C7—N5—H2N5110.0
C1—C2—H2A109.5Ni1—N5—H2N5110.0
N2—C2—H2B109.5H1N5—N5—H2N5108.4
C1—C2—H2B109.5N5—C7—C8108.22 (15)
H2A—C2—H2B108.1N5—C7—H7A110.1
C2—N2—Ni1108.64 (12)C8—C7—H7A110.1
C2—N2—H1N2110.0N5—C7—H7B110.1
Ni1—N2—H1N2110.0C8—C7—H7B110.1
C2—N2—H2N2110.0H7A—C7—H7B108.4
Ni1—N2—H2N2110.0N6—C8—C7109.67 (15)
H1N2—N2—H2N2108.3N6—C8—H8A109.7
N1—C3—C4110.49 (16)C7—C8—H8A109.7
N1—C3—H3A109.6N6—C8—H8B109.7
C4—C3—H3A109.6C7—C8—H8B109.7
N1—C3—H3B109.6H8A—C8—H8B108.2
C4—C3—H3B109.6C8—N6—Ni1105.19 (11)
H3A—C3—H3B108.1C8—N6—H1N6110.7
N3—C4—C3110.30 (15)Ni1—N6—H1N6110.7
N3—C4—H4A109.6C8—N6—H2N6110.7
C3—C4—H4A109.6Ni1—N6—H2N6110.7
N3—C4—H4B109.6H1N6—N6—H2N6108.8
C3—C4—H4B109.6O2—S1—O3110.26 (10)
H4A—C4—H4B108.1O2—S1—O1109.74 (10)
C4—N3—Ni1109.44 (11)O3—S1—O1111.09 (10)
C4—N3—H1N3109.8O2—S1—S2108.85 (7)
Ni1—N3—H1N3109.8O3—S1—S2108.82 (8)
C4—N3—H2N3109.8O1—S1—S2108.01 (7)
Ni1—N3—H2N3109.8H1O4—O4—H2O4111.2
H1N3—N3—H2N3108.2H1O5—O5—H2O5104.5
C6'—C5—N1113.6 (6)H1O6—O6—H2O6102.6
N1—C5—C6113.25 (8)H1O6—O6'—H2O699.6
N1—C5—H5A108.9
D—H···AD—HH···AD···AD—H···A
N2—H1N2···O3i0.922.473.324 (2)155.
N2—H2N2···O2ii0.922.253.084 (2)150.
N3—H1N3···S2iii0.922.683.5921 (18)169.
N4—H1N4···O2ii0.922.092.971 (2)161.
N4—H2N4···O2iii0.922.253.151 (2)165.
N4—H2N4···S2iii0.923.213.8838 (17)131.
N5—H1N5···O1iii0.922.403.244 (2)153.
N5—H1N5···O2iii0.922.483.289 (2)147.
N5—H2N5···O4ii0.922.092.997 (3)168.
N6—H1N6···O3i0.922.303.062 (2)140.
N6—H2N6···O10.922.443.307 (2)158.
N6—H2N6···S20.922.893.6214 (17)137.
O4—H2O4···S20.842.563.390 (2)171.
O5—H1O5···O30.842.022.858 (3)179.
Table 1

Selected bond lengths (Å)

Ni1—N52.0865 (16)
Ni1—N42.1099 (15)
Ni1—N12.1124 (16)
Ni1—N22.1364 (15)
Ni1—N32.1491 (16)
Ni1—N62.1634 (15)
Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯AD—HH⋯AD⋯AD—H⋯A
N2—H1N2⋯O3i0.922.473.324 (2)155
N2—H2N2⋯O2ii0.922.253.084 (2)150
N3—H1N3⋯S2iii0.922.683.5921 (18)169
N4—H1N4⋯O2ii0.922.092.971 (2)161
N4—H2N4⋯O2iii0.922.253.151 (2)165
N4—H2N4⋯S2iii0.923.213.8838 (17)131
N5—H1N5⋯O1iii0.922.403.244 (2)153
N5—H1N5⋯O2iii0.922.483.289 (2)147
N5—H2N5⋯O4ii0.922.092.997 (3)168
N6—H1N6⋯O3i0.922.303.062 (2)140
N6—H2N6⋯O10.922.443.307 (2)158
N6—H2N6⋯S20.922.893.6214 (17)137
O4—H2O4⋯S20.842.563.390 (2)171
O5—H1O5⋯O30.842.022.858 (3)179

Symmetry codes: (i) ; (ii) ; (iii) .

  3 in total

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Authors: 
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