supplementary materials


gk2591 scheme

Acta Cryst. (2013). E69, m642    [ doi:10.1107/S1600536813029802 ]

N,N,N',N'-Tetra­methyl­ethylene­diammonium tetra­chlorido­zincate

M. Akhtar, M. Fettouhi, M. Ahmed, I. U. Khan and S. Ahmad

Abstract top

The asymmetric unit of the title compound, (C6H18N2)[ZnCl4], consists of one tetra­chlorido­zincate anion and two half-N,N,N'N'-tetra­methyl­ethylenedi­ammonium cations. Each of the two di­ammonium cations is located about an inversion center and one of them is disordered over two sets of sites in a 0.780 (17):0.220 (17) ratio. The ZnII atom has a slightly distorted tetra­hedral coordination environment. The cations and anions are connected via N-H...Cl hydrogen bonds into chains extending along [0-11].

Comment top

The organic-inorganic hybrid salts consisting of organic cation and polyhalometal counter anions have received considerable attention because of their potential applications in analytical, material and supramolecular chemistry (Al-Ktaifani et al., 2011). In this work, we report the crystal structure of one such compound. The title compound was obtained unexpectedly during an attempt to synthesize a mixed-ligand zinc(II) complex of N,N,N'N'-tetramethylethylenediamine and 2-mercaptosuccinic acid. The crystal structure of the title hybrid material is shown in Fig. 1. The structure is ionic and the asymmetric unit consists of one tetrachloridozincate anion and two halves of tetramethylethylenediammonium cations, located on inversion centers. The Zn atom, coordinated by four chloride anions, shows a distorted tetrahedral environment (Fig. 1). The bond angles around zinc vary from 105.93 (7)° to 115.80 (7)°. The compound is isostructural with its cobalt analogue (Baughman et al., 2011). In the crystal,the cations and anions are linked by N—H···Cl hydrogen bonds into chains propagating along the [011] direction (Fig. 2).

Related literature top

For background to organic–inorganic hybrid materials, see: Al-Ktaifani & Rukiah (2011). For the isotypic tetrachloridocobaltate(II) salt, see: Baughman et al. (2011). For other related structures and discussion of geometrical features, see: Yin & Wu (2010); Zhao & Qu (2010).

Experimental top

The title complex was prepared by adding 0.12 g (1.0 mmol) of N,N,N'N'-tetramethylethylenediamine in 10 ml methanol to an aqueous solution (5 ml) of 0.14 g (1.0 mmol) zinc chloride. The slightly turbid solution was stirred for 15 minutes. Then a solution of 0.16 g (1.0 mmol) 2-mercaptosuccinic acid in 15 ml was added. The mixture was stirred for 30 minutes along with heating. The white mixture obtained was filtered and the filtrate was kept at room temperature for crystallization. As a result, white crystalline product was obtained, that was washed with methanol.

Refinement top

The H1N atom of one of the symmetry independent cations was located on a difference Fourier map and freely refined. All other H atoms were placed in calculated positions with a C—H distance of 0.96 Å (Uiso(H) = 1.5Ueq(C)) for methyl groups, 0.97 Å (Uiso(H) = 1.2Ueq(C)) for methylene groups and N—H distance of 0.91 Å (Uiso(H) = 1.2Ueq(H)) for the other NH group. One of the diammonium cations the atoms C1, C2 and C3 are disordered over two positions, with the occupancy of the major position of 0.780 (17). During the refinement process restraints were imposed on C—N bond distances in the disordered cation.

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: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. Molecular structure of the title compound showing the atomic numbering scheme [symmetry codes: (i) 1 - x,2 - y,1 - z; (ii) 1 - x,1 - y,1 - z; (iii) x,y,1 + z]. Displacement ellipsoids are drawn at the 30% probability level. For clarity, only N-H group H atoms are shown.
[Figure 2] Fig. 2. Packing diagram of the title compound showing the hydrogen-bonding interactions.
N,N,N',N'-Tetramethylethylenediammonium tetrachloridozincate top
Crystal data top
(C6H18N2)[ZnCl4]Z = 2
Mr = 325.42F(000) = 332
Triclinic, P1Dx = 1.596 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 6.893 (4) ÅCell parameters from 162 reflections
b = 8.257 (6) Åθ = 3.2–25.6°
c = 13.33 (1) ŵ = 2.57 mm1
α = 72.78 (3)°T = 293 K
β = 87.44 (3)°Needle, colorless
γ = 69.42 (3)°0.95 × 0.44 × 0.08 mm
V = 676.9 (8) Å3
Data collection top
Bruker SMART APEX area-detector
diffractometer
2466 independent reflections
Radiation source: fine-focus sealed tube1806 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.041
ω scansθmax = 25.6°, θmin = 3.2°
Absorption correction: analytical
(SADABS; Sheldrick, 1996)
h = 88
Tmin = 0.194, Tmax = 0.821k = 99
9440 measured reflectionsl = 1516
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)] = 0.031Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.075H atoms treated by a mixture of independent and constrained refinement
S = 1.05 w = 1/[σ2(Fo2) + (0.0336P)2 + 0.066P]
where P = (Fo2 + 2Fc2)/3
2466 reflections(Δ/σ)max = 0.001
154 parametersΔρmax = 0.40 e Å3
6 restraintsΔρmin = 0.54 e Å3
Crystal data top
(C6H18N2)[ZnCl4]γ = 69.42 (3)°
Mr = 325.42V = 676.9 (8) Å3
Triclinic, P1Z = 2
a = 6.893 (4) ÅMo Kα radiation
b = 8.257 (6) ŵ = 2.57 mm1
c = 13.33 (1) ÅT = 293 K
α = 72.78 (3)°0.95 × 0.44 × 0.08 mm
β = 87.44 (3)°
Data collection top
Bruker SMART APEX area-detector
diffractometer
2466 independent reflections
Absorption correction: analytical
(SADABS; Sheldrick, 1996)
1806 reflections with I > 2σ(I)
Tmin = 0.194, Tmax = 0.821Rint = 0.041
9440 measured reflectionsθmax = 25.6°
Refinement top
R[F2 > 2σ(F2)] = 0.031H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.075Δρmax = 0.40 e Å3
S = 1.05Δρmin = 0.54 e Å3
2466 reflectionsAbsolute structure: ?
154 parametersAbsolute structure parameter: ?
6 restraintsRogers parameter: ?
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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*/UeqOcc. (<1)
Zn10.08487 (5)0.89099 (5)0.74635 (3)0.03316 (14)
Cl10.28956 (12)0.66541 (11)0.67979 (6)0.0410 (2)
Cl20.07173 (14)0.75755 (15)0.87904 (8)0.0654 (3)
Cl30.30346 (14)0.98281 (13)0.81654 (7)0.0518 (3)
Cl40.12777 (13)1.13302 (12)0.62136 (8)0.0541 (3)
N20.6233 (4)0.7466 (3)0.5224 (2)0.0339 (6)
H2N0.50800.72740.55100.041*
C10.178 (2)0.727 (2)0.1182 (13)0.080 (4)0.780 (17)
H1A0.22880.65920.18980.120*0.780 (17)
H1B0.07750.68460.09740.120*0.780 (17)
H1C0.11460.85310.11230.120*0.780 (17)
N10.3533 (4)0.7001 (4)0.0490 (2)0.0433 (8)0.50
H1N0.301 (6)0.773 (5)0.011 (3)0.067 (13)*
C20.4241 (11)0.5105 (4)0.0424 (4)0.0374 (19)0.780 (17)
H2A0.30530.48320.02640.045*0.780 (17)
H2B0.49010.42580.10960.045*0.780 (17)
C30.5165 (17)0.756 (2)0.0811 (17)0.064 (3)0.780 (17)
H3A0.45470.87590.08810.096*0.780 (17)
H3B0.61670.75630.02870.096*0.780 (17)
H3C0.58410.67280.14730.096*0.780 (17)
C1'0.210 (7)0.655 (7)0.129 (4)0.081 (15)0.220 (17)
H1'10.09770.76350.12990.121*0.220 (17)
H1'20.28350.59810.19720.121*0.220 (17)
H1'30.15540.57290.11240.121*0.220 (17)
N1'0.3533 (4)0.7001 (4)0.0490 (2)0.0433 (8)0.50
C2'0.534 (3)0.545 (2)0.0335 (14)0.041 (7)0.220 (17)
H2'10.59180.45790.10130.049*0.220 (17)
H2'20.64070.58940.00010.049*0.220 (17)
C3'0.454 (8)0.799 (10)0.092 (7)0.087 (18)0.220 (17)
H3'10.34890.90060.10690.130*0.220 (17)
H3'20.54220.84160.04180.130*0.220 (17)
H3'30.53490.71940.15600.130*0.220 (17)
C40.7855 (5)0.6795 (5)0.6093 (3)0.0564 (11)
H4A0.82100.55100.64010.085*
H4B0.73370.73930.66190.085*
H4C0.90660.70460.58230.085*
C50.6891 (5)0.6428 (5)0.4463 (3)0.0529 (10)
H5A0.80310.66900.41010.079*
H5B0.57520.67640.39630.079*
H5C0.73180.51550.48290.079*
C60.5632 (5)0.9456 (4)0.4667 (3)0.0393 (8)
H6A0.68740.97530.44990.047*
H6B0.48400.97560.40120.047*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.0325 (2)0.0332 (2)0.0319 (2)0.00986 (16)0.00269 (15)0.00935 (18)
Cl10.0448 (5)0.0389 (5)0.0395 (5)0.0121 (4)0.0087 (4)0.0165 (4)
Cl20.0617 (6)0.0736 (7)0.0589 (7)0.0331 (5)0.0258 (5)0.0092 (6)
Cl30.0660 (6)0.0532 (6)0.0450 (6)0.0335 (5)0.0084 (4)0.0108 (5)
Cl40.0452 (5)0.0446 (6)0.0555 (6)0.0068 (4)0.0114 (4)0.0002 (5)
N20.0295 (13)0.0262 (15)0.0493 (18)0.0108 (11)0.0103 (12)0.0161 (14)
C10.075 (5)0.091 (8)0.068 (6)0.017 (6)0.025 (4)0.033 (6)
N10.0572 (19)0.0316 (18)0.0320 (18)0.0055 (14)0.0015 (15)0.0083 (16)
C20.041 (3)0.030 (3)0.045 (3)0.017 (2)0.004 (3)0.012 (2)
C30.096 (8)0.055 (5)0.054 (6)0.042 (6)0.003 (6)0.016 (4)
C1'0.06 (2)0.13 (5)0.08 (3)0.05 (2)0.025 (19)0.06 (3)
N1'0.0572 (19)0.0316 (18)0.0320 (18)0.0055 (14)0.0015 (15)0.0083 (16)
C2'0.059 (13)0.029 (10)0.039 (12)0.015 (9)0.018 (10)0.014 (9)
C3'0.08 (2)0.12 (5)0.08 (3)0.07 (3)0.01 (3)0.02 (3)
C40.054 (2)0.049 (2)0.054 (3)0.0059 (18)0.0111 (19)0.011 (2)
C50.050 (2)0.045 (2)0.067 (3)0.0097 (18)0.0089 (19)0.033 (2)
C60.0411 (18)0.0296 (19)0.046 (2)0.0115 (14)0.0103 (15)0.0118 (17)
Geometric parameters (Å, º) top
Zn1—Cl22.2404 (15)C3—H3C0.9600
Zn1—Cl32.2516 (13)C1'—H1'10.9600
Zn1—Cl42.2596 (17)C1'—H1'20.9600
Zn1—Cl12.2949 (16)C1'—H1'30.9600
N2—C51.472 (4)C2'—C2'i1.50 (5)
N2—C41.483 (4)C2'—H2'10.9700
N2—C61.500 (4)C2'—H2'20.9700
N2—H2N0.9100C3'—H3'10.9600
C1—N11.481 (2)C3'—H3'20.9600
C1—H1A0.9600C3'—H3'30.9600
C1—H1B0.9600C4—H4A0.9600
C1—H1C0.9600C4—H4B0.9600
N1—C31.480 (2)C4—H4C0.9600
N1—C21.496 (2)C5—H5A0.9600
N1—H1N0.85 (4)C5—H5B0.9600
C2—C2i1.511 (13)C5—H5C0.9600
C2—H2A0.9700C6—C6ii1.486 (6)
C2—H2B0.9700C6—H6A0.9700
C3—H3A0.9600C6—H6B0.9700
C3—H3B0.9600
Cl2—Zn1—Cl3107.45 (6)C2i—C2—H2A109.7
Cl2—Zn1—Cl4115.80 (6)N1—C2—H2B109.7
Cl3—Zn1—Cl4108.07 (6)C2i—C2—H2B109.7
Cl2—Zn1—Cl1105.93 (7)H2A—C2—H2B108.2
Cl3—Zn1—Cl1106.21 (6)H1'1—C1'—H1'2109.5
Cl4—Zn1—Cl1112.86 (7)H1'1—C1'—H1'3109.5
C5—N2—C4110.7 (3)H1'2—C1'—H1'3109.5
C5—N2—C6110.0 (3)C2'i—C2'—H2'1109.6
C4—N2—C6113.4 (3)C2'i—C2'—H2'2109.6
C5—N2—H2N107.5H2'1—C2'—H2'2108.1
C4—N2—H2N107.5H3'1—C3'—H3'2109.5
C6—N2—H2N107.5H3'1—C3'—H3'3109.5
C3—N1—C1111.3 (11)H3'2—C3'—H3'3109.5
C3—N1—C2115.7 (6)C6ii—C6—N2110.7 (3)
C1—N1—C2108.9 (7)C6ii—C6—H6A109.5
C3—N1—H1N107 (3)N2—C6—H6A109.5
C1—N1—H1N105 (3)C6ii—C6—H6B109.5
C2—N1—H1N108 (3)N2—C6—H6B109.5
N1—C2—C2i110.0 (5)H6A—C6—H6B108.1
N1—C2—H2A109.7
Symmetry codes: (i) x+1, y+1, z; (ii) x+1, y+2, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2N···Cl10.912.303.157 (3)158
N1—H1N···Cl3iii0.85 (4)2.44 (4)3.227 (4)155 (3)
Symmetry code: (iii) x, y, z1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2N···Cl10.912.303.157 (3)158
N1—H1N···Cl3i0.85 (4)2.44 (4)3.227 (4)155 (3)
Symmetry code: (i) x, y, z1.
Acknowledgements top

The authors gratefully acknowledge Government College University Lahore, Pakistan, for providing the X-ray facility.

references
References top

Al-Ktaifani, M. M. & Rukiah, M. K. (2011). Chem. Pap. 65, 469–476.

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