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ISSN: 2056-9890

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

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[Fu, D.-W., Ge, J.-Z., Dai, J., Ye, H.-Y. & Qu, Z.-R. (2009). Inorg. Chem. Commun. 12, 994-997.]); Aminabhavi et al. (1986[Aminabhavi, T. M., Biradar, N. S. & Patil, S. B. (1986). Inorg. Chim. Acta, 125, 125-128.]); Dai & Fu (2008a[Dai, W. & Fu, D.-W. (2008a). Acta Cryst. E64, m1016.],b[Dai, W. & Fu, D.-W. (2008b). Acta Cryst. E64, m1017.]).

[Scheme 1]

Experimental

Crystal data
  • (C2H8N)(C5H12NO)[ZnCl4]

  • Mr = 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[Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.]) Tmin = 0.910, Tmax = 1.000

  • 15010 measured reflections

  • 1851 independent reflections

  • 1655 reflections with I > 2σ(I)

  • Rint = 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

  • Δρmax = 0.38 e Å−3

  • Δρmin = −0.42 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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[Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supporting information


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 ZnCl42- 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.

Refinement top

All H atoms attached to C and N atoms were fixed geometrically and treated as riding with C-H = 0.97 Å(methylene), and C-H = 0.96 Å(methyl) N-H = 0.86 Å, with Uiso(H) = 1.2Ueq(methylene or N) and Uiso(H) = 1.5Ueq(methyl).

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
[Figure 1] Fig. 1. Molecular view of the title compound with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] 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
Mr = 355.42Dx = 1.546 Mg m3
Orthorhombic, PnmaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2nCell parameters from 1851 reflections
a = 20.272 (4) Åθ = 3.4–27.5°
b = 10.220 (2) ŵ = 2.29 mm1
c = 7.3727 (15) ÅT = 298 K
V = 1527.5 (5) Å3Block, colorless
Z = 40.30 × 0.05 × 0.05 mm
Data collection top
Rigaku Mercury2
diffractometer
1851 independent reflections
Radiation source: fine-focus sealed tube1655 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.031
Detector resolution: 13.6612 pixels mm-1θmax = 27.5°, θmin = 3.4°
CCD profile fitting scansh = 2625
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)
k = 1313
Tmin = 0.910, Tmax = 1.000l = 99
15010 measured reflections
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)] = 0.030Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.072H atoms treated by a mixture of independent and constrained refinement
S = 1.14 w = 1/[σ2(Fo2) + (0.0307P)2 + 0.7198P]
where P = (Fo2 + 2Fc2)/3
1851 reflections(Δ/σ)max < 0.001
86 parametersΔρmax = 0.38 e Å3
0 restraintsΔρmin = 0.42 e Å3
Crystal data top
(C2H8N)(C5H12NO)[ZnCl4]V = 1527.5 (5) Å3
Mr = 355.42Z = 4
Orthorhombic, PnmaMo Kα radiation
a = 20.272 (4) ŵ = 2.29 mm1
b = 10.220 (2) ÅT = 298 K
c = 7.3727 (15) Å0.30 × 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)
Tmin = 0.910, Tmax = 1.000Rint = 0.031
15010 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0300 restraints
wR(F2) = 0.072H atoms treated by a mixture of independent and constrained refinement
S = 1.14Δρmax = 0.38 e Å3
1851 reflectionsΔρmin = 0.42 e Å3
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
xyzUiso*/Ueq
Zn10.141654 (15)0.25000.85173 (4)0.03264 (11)
N10.04000 (12)0.25000.6307 (3)0.0340 (5)
H1C0.0015 (17)0.25000.663 (4)0.041*
Cl20.25325 (4)0.25000.84857 (11)0.0495 (2)
O10.09518 (12)0.25000.9876 (3)0.0541 (6)
Cl30.10112 (4)0.25001.13530 (10)0.0585 (3)
Cl10.10455 (3)0.07882 (5)0.68372 (8)0.04847 (16)
C20.06975 (11)0.1302 (2)0.7135 (3)0.0402 (5)
H2A0.04720.05300.66860.048*
H2B0.11590.12400.67950.048*
C10.06386 (13)0.1363 (2)0.9169 (3)0.0507 (6)
H1A0.08390.05900.96950.061*
H1B0.01760.13700.95060.061*
C30.0450 (2)0.25000.4300 (4)0.0532 (9)
H3A0.02400.32670.38210.080*
H3B0.09070.25000.39610.080*
N20.22432 (15)0.25000.4099 (4)0.0492 (7)
H2C0.2277 (19)0.25000.525 (5)0.059*
H2D0.184 (2)0.25000.370 (5)0.059*
C40.25540 (16)0.1297 (3)0.3477 (4)0.0701 (8)
H4A0.23310.05590.39980.105*
H4B0.30080.12890.38440.105*
H4C0.25280.12490.21780.105*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.02909 (17)0.0403 (2)0.02851 (17)0.0000.00062 (12)0.000
N10.0280 (11)0.0368 (13)0.0371 (13)0.0000.0001 (10)0.000
Cl20.0281 (4)0.0729 (6)0.0476 (4)0.0000.0013 (3)0.000
O10.0637 (15)0.0544 (14)0.0441 (13)0.0000.0202 (11)0.000
Cl30.0404 (4)0.1060 (8)0.0291 (4)0.0000.0030 (3)0.000
Cl10.0547 (3)0.0400 (3)0.0508 (3)0.0067 (2)0.0042 (2)0.0089 (2)
C20.0421 (11)0.0304 (10)0.0479 (12)0.0014 (9)0.0017 (9)0.0011 (9)
C10.0591 (14)0.0453 (13)0.0476 (12)0.0025 (11)0.0076 (11)0.0104 (11)
C30.072 (2)0.054 (2)0.0340 (16)0.0000.0016 (16)0.000
N20.0449 (15)0.0621 (18)0.0405 (14)0.0000.0003 (13)0.000
C40.0778 (19)0.0614 (18)0.0712 (18)0.0134 (15)0.0120 (15)0.0059 (15)
Geometric parameters (Å, º) top
Zn1—Cl32.2464 (9)C2—H2B0.9700
Zn1—Cl22.2625 (9)C1—H1A0.9700
Zn1—Cl12.2717 (6)C1—H1B0.9700
Zn1—Cl1i2.2717 (6)C3—H3A0.9597
N1—C31.483 (4)C3—H3B0.9597
N1—C21.495 (2)N2—C41.456 (3)
N1—C2i1.495 (2)N2—C4i1.456 (3)
N1—H1C0.81 (3)N2—H2C0.85 (4)
O1—C11.423 (3)N2—H2D0.86 (4)
O1—C1i1.423 (3)C4—H4A0.9600
C2—C11.505 (3)C4—H4B0.9600
C2—H2A0.9700C4—H4C0.9600
Cl3—Zn1—Cl2112.05 (3)O1—C1—H1A109.4
Cl3—Zn1—Cl1112.73 (2)C2—C1—H1A109.4
Cl2—Zn1—Cl1108.99 (2)O1—C1—H1B109.4
Cl3—Zn1—Cl1i112.73 (2)C2—C1—H1B109.4
Cl2—Zn1—Cl1i108.99 (2)H1A—C1—H1B108.0
Cl1—Zn1—Cl1i100.72 (4)N1—C3—H3A109.7
C3—N1—C2112.33 (16)N1—C3—H3B109.1
C3—N1—C2i112.33 (16)H3A—C3—H3B109.5
C2—N1—C2i109.9 (2)C4—N2—C4i115.3 (3)
C3—N1—H1C111 (2)C4—N2—H2C106.2 (13)
C2—N1—H1C105.6 (12)C4i—N2—H2C106.2 (13)
C2i—N1—H1C105.6 (12)C4—N2—H2D107.4 (12)
C1—O1—C1i109.5 (2)C4i—N2—H2D107.4 (12)
N1—C2—C1109.96 (19)H2C—N2—H2D115 (4)
N1—C2—H2A109.7N2—C4—H4A109.5
C1—C2—H2A109.7N2—C4—H4B109.5
N1—C2—H2B109.7H4A—C4—H4B109.5
C1—C2—H2B109.7N2—C4—H4C109.5
H2A—C2—H2B108.2H4A—C4—H4C109.5
O1—C1—C2111.3 (2)H4B—C4—H4C109.5
C3—N1—C2—C1179.4 (2)C1i—O1—C1—C261.7 (3)
C2i—N1—C2—C153.6 (3)N1—C2—C1—O158.1 (3)
Symmetry code: (i) x, y+1/2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1C···Cl1i0.81 (3)2.78 (3)3.435 (2)139 (1)
N2—H2D···Cl3ii0.86 (4)2.42 (4)3.215 (3)154 (3)
N1—H1C···Cl10.81 (3)2.78 (3)3.435 (2)139 (1)
N2—H2C···Cl20.85 (4)2.44 (4)3.287 (3)172 (4)
Symmetry codes: (i) x, y+1/2, z; (ii) x, y, z1.

Experimental details

Crystal data
Chemical formula(C2H8N)(C5H12NO)[ZnCl4]
Mr355.42
Crystal system, space groupOrthorhombic, Pnma
Temperature (K)298
a, b, c (Å)20.272 (4), 10.220 (2), 7.3727 (15)
V3)1527.5 (5)
Z4
Radiation typeMo Kα
µ (mm1)2.29
Crystal size (mm)0.30 × 0.05 × 0.05
Data collection
DiffractometerRigaku Mercury2
diffractometer
Absorption correctionMulti-scan
(CrystalClear; Rigaku, 2005)
Tmin, Tmax0.910, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections
15010, 1851, 1655
Rint0.031
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.030, 0.072, 1.14
No. of reflections1851
No. of parameters86
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)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···AD—HH···AD···AD—H···A
N1—H1C···Cl1i0.81 (3)2.78 (3)3.435 (2)139.3 (8)
N2—H2D···Cl3ii0.86 (4)2.42 (4)3.215 (3)154 (3)
N1—H1C···Cl10.81 (3)2.78 (3)3.435 (2)139.3 (8)
N2—H2C···Cl20.85 (4)2.44 (4)3.287 (3)172 (4)
Symmetry codes: (i) x, y+1/2, z; (ii) x, y, z1.
 

Acknowledgements

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

References

First citationAminabhavi, T. M., Biradar, N. S. & Patil, S. B. (1986). Inorg. Chim. Acta, 125, 125–128.  CrossRef CAS Web of Science Google Scholar
First citationDai, W. & Fu, D.-W. (2008a). Acta Cryst. E64, m1016.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationDai, W. & Fu, D.-W. (2008b). Acta Cryst. E64, m1017.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationFu, D.-W., Ge, J.-Z., Dai, J., Ye, H.-Y. & Qu, Z.-R. (2009). Inorg. Chem. Commun. 12, 994–997.  Web of Science CSD CrossRef CAS Google Scholar
First citationRigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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