Dimethyl­ammonium bis­(4-methyl­morpholin-4-ium) tetra­chloridozincate

Zhang, Y.; Wang, Y.

doi:10.1107/S1600536811025049

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 7| July 2011| Page m1009

doi:10.1107/S1600536811025049

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Dimethylammonium bis(4-methylmorpholin-4-ium) tetrachloridozincate

Yan-wei Zhang ^a and Yan-fei Wang ^a ^*

^aDepartment of Chemical & Environmental Engineering, Anyang Institute of Technology, Anyang 455000, People's Republic of China
^*Correspondence e-mail: ayitzhang@yahoo.com.cn

(Received 8 June 2011; accepted 25 June 2011; online 30 June 2011)

The title compound, (C₂H₈N)(C₅H₁₂NO)[ZnCl₄], was synthesized by hydrothermal reaction of ZnCl₂ with 4-methylmorpholine in a dimethylformamide solution. The asymmetric unit is composed of half a [ZnCl₄]²⁻ anion, half a 4-methylmorpholin-4-ium cation and half a dimethylammonium cation, all located on mirror planes parallel to ac. All the amine H atoms are involved in intermolecular N—H⋯Cl hydrogen bonds, building up an infinite chain parallel to the c axis.

Related literature

For properties of amino compounds, see: Fu et al. (2009 ); Aminabhavi et al. (1986 ); Dai & Fu (2008a ,b ).

Experimental

Crystal data

(C₂H₈N)(C₅H₁₂NO)[ZnCl₄]
M_r = 355.42
Orthorhombic, P n m a
a = 20.272 (4) Å
b = 10.220 (2) Å
c = 7.3727 (15) Å
V = 1527.5 (5) Å³
Z = 4
Mo Kα radiation
μ = 2.29 mm⁻¹
T = 298 K
0.30 × 0.05 × 0.05 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.910, T_max = 1.000
15010 measured reflections
1851 independent reflections
1655 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.072
S = 1.14
1851 reflections
86 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.42 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1C⋯Cl1ⁱ	0.81 (3)	2.78 (3)	3.435 (2)	139 (1)
N2—H2D⋯Cl3ⁱⁱ	0.86 (4)	2.42 (4)	3.215 (3)	154 (3)
N1—H1C⋯Cl1	0.81 (3)	2.78 (3)	3.435 (2)	139 (1)
N2—H2C⋯Cl2	0.85 (4)	2.44 (4)	3.287 (3)	172 (4)
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z]$ ; (ii) x, y, z-1.

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811025049/zk2013sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811025049/zk2013Isup2.hkl

checkCIF report

Comment top

The amino derivatives have found wide range of applications in material science, such as magnetic, fluorescent and dielectric behaviors. And there has been an increased interest in the preparation of amino coordination compound (Aminabhavi et al., 1986; Dai & Fu 2008a; Dai & Fu 2008b; Fu, et al. 2009). We report here the crystal structure of the title compound, Bis-(4-methylmorpholin-4-ium) (dimethylammonium) tetrachloride Zinc(II).

The asymmetric unit is composed of half ZnCl₄^2- anion, half 4-methylmorpholin-4-ium cation and half dimethylammonium cation (Fig.1). The molecules are located in the ac mirror. The geometric parameters of the title compound are in the normal range.

In the crystal structure, all the H atoms of amine groups are involved in intermolecular N—H···Cl hydrogen bonds building up an infinite one-dimensional chain parallel to the c-axis (Table 1 and Fig.2).

Related literature top

For properties of amino compounds, see: Fu et al. (2009); Aminabhavi et al. (1986); Dai & Fu (2008a,b).

Experimental top

A mixture of 4-methylmorpholine (0.4 mmol), ZnCl₂ (0.4 mmol) and DMF/distilled water (10ml,1:1) sealed in a Teflon-lined stainless steel vessel, was maintained at 100 °C. The dimethylamine was generated through the decomposition of DMF. Colorless block crystals suitable for X-ray analysis were obtained after 3 days (yield 31%, based on 4-methylmorpholine). elemental analysis: calcd. C 23.63, H 5.63, N 7.88; found C 23.49, H 5.51, N 7.75.

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular view of the title compound with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The crystal packing of the title compound viewed along the b axis showing the one-dimensionnal hydrogen bondings chain (dashed line). Hydrogen atoms not involved in hydrogen bonding have been omitted for clarity.

Dimethylammonium bis(4-methylmorpholin-4-ium) tetrachloridozincate top

Crystal data top

(C₂H₈N)(C₅H₁₂NO)[ZnCl₄]	F(000) = 728
M_r = 355.42	D_x = 1.546 Mg m⁻³
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 1851 reflections
a = 20.272 (4) Å	θ = 3.4–27.5°
b = 10.220 (2) Å	µ = 2.29 mm⁻¹
c = 7.3727 (15) Å	T = 298 K
V = 1527.5 (5) Å³	Block, colorless
Z = 4	0.30 × 0.05 × 0.05 mm

Data collection top

Rigaku Mercury2 diffractometer	1851 independent reflections
Radiation source: fine-focus sealed tube	1655 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.4°
CCD profile fitting scans	h = −26→25
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −13→13
T_min = 0.910, T_max = 1.000	l = −9→9
15010 measured reflections

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.072	H atoms treated by a mixture of independent and constrained refinement
S = 1.14	w = 1/[σ²(F_o²) + (0.0307P)² + 0.7198P] where P = (F_o² + 2F_c²)/3
1851 reflections	(Δ/σ)_max < 0.001
86 parameters	Δρ_max = 0.38 e Å⁻³
0 restraints	Δρ_min = −0.42 e Å⁻³

Crystal data top

(C₂H₈N)(C₅H₁₂NO)[ZnCl₄]	V = 1527.5 (5) Å³
M_r = 355.42	Z = 4
Orthorhombic, Pnma	Mo Kα radiation
a = 20.272 (4) Å	µ = 2.29 mm⁻¹
b = 10.220 (2) Å	T = 298 K
c = 7.3727 (15) Å	0.30 × 0.05 × 0.05 mm

Data collection top

Rigaku Mercury2 diffractometer	1851 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1655 reflections with I > 2σ(I)
T_min = 0.910, T_max = 1.000	R_int = 0.031
15010 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	0 restraints
wR(F²) = 0.072	H atoms treated by a mixture of independent and constrained refinement
S = 1.14	Δρ_max = 0.38 e Å⁻³
1851 reflections	Δρ_min = −0.42 e Å⁻³
86 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 > 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

	x	y	z	U_iso*/U_eq
Zn1	0.141654 (15)	0.2500	0.85173 (4)	0.03264 (11)
N1	−0.04000 (12)	0.2500	0.6307 (3)	0.0340 (5)
H1C	−0.0015 (17)	0.2500	0.663 (4)	0.041*
Cl2	0.25325 (4)	0.2500	0.84857 (11)	0.0495 (2)
O1	−0.09518 (12)	0.2500	0.9876 (3)	0.0541 (6)
Cl3	0.10112 (4)	0.2500	1.13530 (10)	0.0585 (3)
Cl1	0.10455 (3)	0.07882 (5)	0.68372 (8)	0.04847 (16)
C2	−0.06975 (11)	0.1302 (2)	0.7135 (3)	0.0402 (5)
H2A	−0.0472	0.0530	0.6686	0.048*
H2B	−0.1159	0.1240	0.6795	0.048*
C1	−0.06386 (13)	0.1363 (2)	0.9169 (3)	0.0507 (6)
H1A	−0.0839	0.0590	0.9695	0.061*
H1B	−0.0176	0.1370	0.9506	0.061*
C3	−0.0450 (2)	0.2500	0.4300 (4)	0.0532 (9)
H3A	−0.0240	0.3267	0.3821	0.080*
H3B	−0.0907	0.2500	0.3961	0.080*
N2	0.22432 (15)	0.2500	0.4099 (4)	0.0492 (7)
H2C	0.2277 (19)	0.2500	0.525 (5)	0.059*
H2D	0.184 (2)	0.2500	0.370 (5)	0.059*
C4	0.25540 (16)	0.1297 (3)	0.3477 (4)	0.0701 (8)
H4A	0.2331	0.0559	0.3998	0.105*
H4B	0.3008	0.1289	0.3844	0.105*
H4C	0.2528	0.1249	0.2178	0.105*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.02909 (17)	0.0403 (2)	0.02851 (17)	0.000	−0.00062 (12)	0.000
N1	0.0280 (11)	0.0368 (13)	0.0371 (13)	0.000	0.0001 (10)	0.000
Cl2	0.0281 (4)	0.0729 (6)	0.0476 (4)	0.000	−0.0013 (3)	0.000
O1	0.0637 (15)	0.0544 (14)	0.0441 (13)	0.000	0.0202 (11)	0.000
Cl3	0.0404 (4)	0.1060 (8)	0.0291 (4)	0.000	0.0030 (3)	0.000
Cl1	0.0547 (3)	0.0400 (3)	0.0508 (3)	−0.0067 (2)	−0.0042 (2)	−0.0089 (2)
C2	0.0421 (11)	0.0304 (10)	0.0479 (12)	−0.0014 (9)	0.0017 (9)	0.0011 (9)
C1	0.0591 (14)	0.0453 (13)	0.0476 (12)	0.0025 (11)	0.0076 (11)	0.0104 (11)
C3	0.072 (2)	0.054 (2)	0.0340 (16)	0.000	0.0016 (16)	0.000
N2	0.0449 (15)	0.0621 (18)	0.0405 (14)	0.000	0.0003 (13)	0.000
C4	0.0778 (19)	0.0614 (18)	0.0712 (18)	0.0134 (15)	−0.0120 (15)	−0.0059 (15)

Geometric parameters (Å, º) top

Zn1—Cl3	2.2464 (9)	C2—H2B	0.9700
Zn1—Cl2	2.2625 (9)	C1—H1A	0.9700
Zn1—Cl1	2.2717 (6)	C1—H1B	0.9700
Zn1—Cl1ⁱ	2.2717 (6)	C3—H3A	0.9597
N1—C3	1.483 (4)	C3—H3B	0.9597
N1—C2	1.495 (2)	N2—C4	1.456 (3)
N1—C2ⁱ	1.495 (2)	N2—C4ⁱ	1.456 (3)
N1—H1C	0.81 (3)	N2—H2C	0.85 (4)
O1—C1	1.423 (3)	N2—H2D	0.86 (4)
O1—C1ⁱ	1.423 (3)	C4—H4A	0.9600
C2—C1	1.505 (3)	C4—H4B	0.9600
C2—H2A	0.9700	C4—H4C	0.9600

Cl3—Zn1—Cl2	112.05 (3)	O1—C1—H1A	109.4
Cl3—Zn1—Cl1	112.73 (2)	C2—C1—H1A	109.4
Cl2—Zn1—Cl1	108.99 (2)	O1—C1—H1B	109.4
Cl3—Zn1—Cl1ⁱ	112.73 (2)	C2—C1—H1B	109.4
Cl2—Zn1—Cl1ⁱ	108.99 (2)	H1A—C1—H1B	108.0
Cl1—Zn1—Cl1ⁱ	100.72 (4)	N1—C3—H3A	109.7
C3—N1—C2	112.33 (16)	N1—C3—H3B	109.1
C3—N1—C2ⁱ	112.33 (16)	H3A—C3—H3B	109.5
C2—N1—C2ⁱ	109.9 (2)	C4—N2—C4ⁱ	115.3 (3)
C3—N1—H1C	111 (2)	C4—N2—H2C	106.2 (13)
C2—N1—H1C	105.6 (12)	C4ⁱ—N2—H2C	106.2 (13)
C2ⁱ—N1—H1C	105.6 (12)	C4—N2—H2D	107.4 (12)
C1—O1—C1ⁱ	109.5 (2)	C4ⁱ—N2—H2D	107.4 (12)
N1—C2—C1	109.96 (19)	H2C—N2—H2D	115 (4)
N1—C2—H2A	109.7	N2—C4—H4A	109.5
C1—C2—H2A	109.7	N2—C4—H4B	109.5
N1—C2—H2B	109.7	H4A—C4—H4B	109.5
C1—C2—H2B	109.7	N2—C4—H4C	109.5
H2A—C2—H2B	108.2	H4A—C4—H4C	109.5
O1—C1—C2	111.3 (2)	H4B—C4—H4C	109.5

C3—N1—C2—C1	−179.4 (2)	C1ⁱ—O1—C1—C2	−61.7 (3)
C2ⁱ—N1—C2—C1	−53.6 (3)	N1—C2—C1—O1	58.1 (3)

Symmetry code: (i) x, −y+1/2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···Cl1ⁱ	0.81 (3)	2.78 (3)	3.435 (2)	139 (1)
N2—H2D···Cl3ⁱⁱ	0.86 (4)	2.42 (4)	3.215 (3)	154 (3)
N1—H1C···Cl1	0.81 (3)	2.78 (3)	3.435 (2)	139 (1)
N2—H2C···Cl2	0.85 (4)	2.44 (4)	3.287 (3)	172 (4)

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

Experimental details

Crystal data
Chemical formula	(C₂H₈N)(C₅H₁₂NO)[ZnCl₄]
M_r	355.42
Crystal system, space group	Orthorhombic, Pnma
Temperature (K)	298
a, b, c (Å)	20.272 (4), 10.220 (2), 7.3727 (15)
V (Å³)	1527.5 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.29
Crystal size (mm)	0.30 × 0.05 × 0.05

Data collection
Diffractometer	Rigaku Mercury2 diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.910, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	15010, 1851, 1655
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.072, 1.14
No. of reflections	1851
No. of parameters	86
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.42

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···Cl1ⁱ	0.81 (3)	2.78 (3)	3.435 (2)	139.3 (8)
N2—H2D···Cl3ⁱⁱ	0.86 (4)	2.42 (4)	3.215 (3)	154 (3)
N1—H1C···Cl1	0.81 (3)	2.78 (3)	3.435 (2)	139.3 (8)
N2—H2C···Cl2	0.85 (4)	2.44 (4)	3.287 (3)	172 (4)

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

Acknowledgements

This work was supported by the start-up fund of Anyang Institute of Technology.

References

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