N,N,N′,N′-Tetra­methyl­ethylene­diammonium tetra­chlorido­zincate

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

doi:10.1107/S1600536813029802

metal-organic compounds

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ISSN: 2056-9890

Volume 69| Part 12| December 2013| Page m642

doi:10.1107/S1600536813029802

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N,N,N′,N′-Tetramethylethylenediammonium tetrachloridozincate

Muhammad Akhtar,^a Mohammed Fettouhi,^b Maqsood Ahmed,^c Islam Ullah Khan ^d and Saeed Ahmad ^e ^*

^aDepartment of Chemistry, Quaid-i-Azam University, Islamabad, Pakistan, ^bDepartment of Chemistry, King Fahd University of Petroleum and Minerals, Dhahran 31261, Saudi Arabia, ^cDepartment of Chemistry, Islamia University, Bahawalpur, Pakistan, ^dDepartment of Chemistry, Government College College University, Lahore 54000, Pakistan, and ^eDepartment of Chemistry, University of Engineering and Technology, Lahore 54890, Pakistan
^*Correspondence e-mail: saeed_a786@hotmail.com

(Received 11 September 2013; accepted 30 October 2013; online 6 November 2013)

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 Zn^II 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].

CCDC reference: 969557

Related literature

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

Crystal data

(C₆H₁₈N₂)[ZnCl₄]
M_r = 325.42
Triclinic, $[P \overline 1]$
a = 6.893 (4) Å
b = 8.257 (6) Å
c = 13.33 (1) Å
α = 72.78 (3)°
β = 87.44 (3)°
γ = 69.42 (3)°
V = 676.9 (8) Å³
Z = 2
Mo Kα radiation
μ = 2.57 mm⁻¹
T = 293 K
0.95 × 0.44 × 0.08 mm

Data collection

Bruker SMART APEX area-detector diffractometer
Absorption correction: analytical (SADABS; Sheldrick, 1996 ) T_min = 0.194, T_max = 0.821
9440 measured reflections
2466 independent reflections
1806 reflections with I > 2σ(I)
R_int = 0.041

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.075
S = 1.05
2466 reflections
154 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.54 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2N⋯Cl1	0.91	2.30	3.157 (3)	158
N1—H1N⋯Cl3ⁱ	0.85 (4)	2.44 (4)	3.227 (4)	155 (3)
Symmetry code: (i) x, y, z-1.

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; 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.

Supporting information

CCDC reference: 969557

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536813029802/gk2591sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813029802/gk2591Isup2.hkl

checkCIF report

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.

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

	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.
	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
M_r = 325.42	F(000) = 332
Triclinic, P1	D_x = 1.596 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.893 (4) Å	Cell parameters from 162 reflections
b = 8.257 (6) Å	θ = 3.2–25.6°
c = 13.33 (1) Å	µ = 2.57 mm⁻¹
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 tube	1806 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.041
ω scans	θ_max = 25.6°, θ_min = 3.2°
Absorption correction: analytical (SADABS; Sheldrick, 1996)	h = −8→8
T_min = 0.194, T_max = 0.821	k = −9→9
9440 measured reflections	l = −15→16

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.075	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0336P)² + 0.066P] where P = (F_o² + 2F_c²)/3
2466 reflections	(Δ/σ)_max = 0.001
154 parameters	Δρ_max = 0.40 e Å⁻³
6 restraints	Δρ_min = −0.54 e Å⁻³

Crystal data top

(C₆H₁₈N₂)[ZnCl₄]	γ = 69.42 (3)°
M_r = 325.42	V = 676.9 (8) Å³
Triclinic, P1	Z = 2
a = 6.893 (4) Å	Mo Kα radiation
b = 8.257 (6) Å	µ = 2.57 mm⁻¹
c = 13.33 (1) Å	T = 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)
T_min = 0.194, T_max = 0.821	R_int = 0.041
9440 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	6 restraints
wR(F²) = 0.075	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.40 e Å⁻³
2466 reflections	Δρ_min = −0.54 e Å⁻³
154 parameters

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Zn1	0.08487 (5)	0.89099 (5)	0.74635 (3)	0.03316 (14)
Cl1	0.28956 (12)	0.66541 (11)	0.67979 (6)	0.0410 (2)
Cl2	−0.07173 (14)	0.75755 (15)	0.87904 (8)	0.0654 (3)
Cl3	0.30346 (14)	0.98281 (13)	0.81654 (7)	0.0518 (3)
Cl4	−0.12777 (13)	1.13302 (12)	0.62136 (8)	0.0541 (3)
N2	0.6233 (4)	0.7466 (3)	0.5224 (2)	0.0339 (6)
H2N	0.5080	0.7274	0.5510	0.041*
C1	0.178 (2)	0.727 (2)	0.1182 (13)	0.080 (4)	0.780 (17)
H1A	0.2288	0.6592	0.1898	0.120*	0.780 (17)
H1B	0.0775	0.6846	0.0974	0.120*	0.780 (17)
H1C	0.1146	0.8531	0.1123	0.120*	0.780 (17)
N1	0.3533 (4)	0.7001 (4)	0.0490 (2)	0.0433 (8)	0.50
H1N	0.301 (6)	0.773 (5)	−0.011 (3)	0.067 (13)*
C2	0.4241 (11)	0.5105 (4)	0.0424 (4)	0.0374 (19)	0.780 (17)
H2A	0.3053	0.4832	0.0264	0.045*	0.780 (17)
H2B	0.4901	0.4258	0.1096	0.045*	0.780 (17)
C3	0.5165 (17)	0.756 (2)	0.0811 (17)	0.064 (3)	0.780 (17)
H3A	0.4547	0.8759	0.0881	0.096*	0.780 (17)
H3B	0.6167	0.7563	0.0287	0.096*	0.780 (17)
H3C	0.5841	0.6728	0.1473	0.096*	0.780 (17)
C1'	0.210 (7)	0.655 (7)	0.129 (4)	0.081 (15)	0.220 (17)
H1'1	0.0977	0.7635	0.1299	0.121*	0.220 (17)
H1'2	0.2835	0.5981	0.1972	0.121*	0.220 (17)
H1'3	0.1554	0.5729	0.1124	0.121*	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)
H2'1	0.5918	0.4579	0.1013	0.049*	0.220 (17)
H2'2	0.6407	0.5894	−0.0001	0.049*	0.220 (17)
C3'	0.454 (8)	0.799 (10)	0.092 (7)	0.087 (18)	0.220 (17)
H3'1	0.3489	0.9006	0.1069	0.130*	0.220 (17)
H3'2	0.5422	0.8416	0.0418	0.130*	0.220 (17)
H3'3	0.5349	0.7194	0.1560	0.130*	0.220 (17)
C4	0.7855 (5)	0.6795 (5)	0.6093 (3)	0.0564 (11)
H4A	0.8210	0.5510	0.6401	0.085*
H4B	0.7337	0.7393	0.6619	0.085*
H4C	0.9066	0.7046	0.5823	0.085*
C5	0.6891 (5)	0.6428 (5)	0.4463 (3)	0.0529 (10)
H5A	0.8031	0.6690	0.4101	0.079*
H5B	0.5752	0.6764	0.3963	0.079*
H5C	0.7318	0.5155	0.4829	0.079*
C6	0.5632 (5)	0.9456 (4)	0.4667 (3)	0.0393 (8)
H6A	0.6874	0.9753	0.4499	0.047*
H6B	0.4840	0.9756	0.4012	0.047*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0325 (2)	0.0332 (2)	0.0319 (2)	−0.00986 (16)	0.00269 (15)	−0.00935 (18)
Cl1	0.0448 (5)	0.0389 (5)	0.0395 (5)	−0.0121 (4)	0.0087 (4)	−0.0165 (4)
Cl2	0.0617 (6)	0.0736 (7)	0.0589 (7)	−0.0331 (5)	0.0258 (5)	−0.0092 (6)
Cl3	0.0660 (6)	0.0532 (6)	0.0450 (6)	−0.0335 (5)	−0.0084 (4)	−0.0108 (5)
Cl4	0.0452 (5)	0.0446 (6)	0.0555 (6)	−0.0068 (4)	−0.0114 (4)	0.0002 (5)
N2	0.0295 (13)	0.0262 (15)	0.0493 (18)	−0.0108 (11)	0.0103 (12)	−0.0161 (14)
C1	0.075 (5)	0.091 (8)	0.068 (6)	−0.017 (6)	0.025 (4)	−0.033 (6)
N1	0.0572 (19)	0.0316 (18)	0.0320 (18)	−0.0055 (14)	−0.0015 (15)	−0.0083 (16)
C2	0.041 (3)	0.030 (3)	0.045 (3)	−0.017 (2)	0.004 (3)	−0.012 (2)
C3	0.096 (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)
C4	0.054 (2)	0.049 (2)	0.054 (3)	−0.0059 (18)	−0.0111 (19)	−0.011 (2)
C5	0.050 (2)	0.045 (2)	0.067 (3)	−0.0097 (18)	0.0089 (19)	−0.033 (2)
C6	0.0411 (18)	0.0296 (19)	0.046 (2)	−0.0115 (14)	0.0103 (15)	−0.0118 (17)

Geometric parameters (Å, º) top

Zn1—Cl2	2.2404 (15)	C3—H3C	0.9600
Zn1—Cl3	2.2516 (13)	C1'—H1'1	0.9600
Zn1—Cl4	2.2596 (17)	C1'—H1'2	0.9600
Zn1—Cl1	2.2949 (16)	C1'—H1'3	0.9600
N2—C5	1.472 (4)	C2'—C2'ⁱ	1.50 (5)
N2—C4	1.483 (4)	C2'—H2'1	0.9700
N2—C6	1.500 (4)	C2'—H2'2	0.9700
N2—H2N	0.9100	C3'—H3'1	0.9600
C1—N1	1.481 (2)	C3'—H3'2	0.9600
C1—H1A	0.9600	C3'—H3'3	0.9600
C1—H1B	0.9600	C4—H4A	0.9600
C1—H1C	0.9600	C4—H4B	0.9600
N1—C3	1.480 (2)	C4—H4C	0.9600
N1—C2	1.496 (2)	C5—H5A	0.9600
N1—H1N	0.85 (4)	C5—H5B	0.9600
C2—C2ⁱ	1.511 (13)	C5—H5C	0.9600
C2—H2A	0.9700	C6—C6ⁱⁱ	1.486 (6)
C2—H2B	0.9700	C6—H6A	0.9700
C3—H3A	0.9600	C6—H6B	0.9700
C3—H3B	0.9600

Cl2—Zn1—Cl3	107.45 (6)	C2ⁱ—C2—H2A	109.7
Cl2—Zn1—Cl4	115.80 (6)	N1—C2—H2B	109.7
Cl3—Zn1—Cl4	108.07 (6)	C2ⁱ—C2—H2B	109.7
Cl2—Zn1—Cl1	105.93 (7)	H2A—C2—H2B	108.2
Cl3—Zn1—Cl1	106.21 (6)	H1'1—C1'—H1'2	109.5
Cl4—Zn1—Cl1	112.86 (7)	H1'1—C1'—H1'3	109.5
C5—N2—C4	110.7 (3)	H1'2—C1'—H1'3	109.5
C5—N2—C6	110.0 (3)	C2'ⁱ—C2'—H2'1	109.6
C4—N2—C6	113.4 (3)	C2'ⁱ—C2'—H2'2	109.6
C5—N2—H2N	107.5	H2'1—C2'—H2'2	108.1
C4—N2—H2N	107.5	H3'1—C3'—H3'2	109.5
C6—N2—H2N	107.5	H3'1—C3'—H3'3	109.5
C3—N1—C1	111.3 (11)	H3'2—C3'—H3'3	109.5
C3—N1—C2	115.7 (6)	C6ⁱⁱ—C6—N2	110.7 (3)
C1—N1—C2	108.9 (7)	C6ⁱⁱ—C6—H6A	109.5
C3—N1—H1N	107 (3)	N2—C6—H6A	109.5
C1—N1—H1N	105 (3)	C6ⁱⁱ—C6—H6B	109.5
C2—N1—H1N	108 (3)	N2—C6—H6B	109.5
N1—C2—C2ⁱ	110.0 (5)	H6A—C6—H6B	108.1
N1—C2—H2A	109.7

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···Cl1	0.91	2.30	3.157 (3)	158
N1—H1N···Cl3ⁱⁱⁱ	0.85 (4)	2.44 (4)	3.227 (4)	155 (3)

Symmetry code: (iii) x, y, z−1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···Cl1	0.91	2.30	3.157 (3)	158
N1—H1N···Cl3ⁱ	0.85 (4)	2.44 (4)	3.227 (4)	155 (3)

Symmetry code: (i) x, y, z−1.

Acknowledgements

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

References

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