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The title compound, (C10H21N3)[CuCl4], is composed of one 1-[2-(di­ethyl­aza­nium­yl)eth­yl]-3-methyl­imidazolium dication and a tetra­chlorido­cuprate(II) dianion. The anion adopts a distorted tetra­hedral geometry. Bifurcated interionic N—H...Cl hydrogen bonds and several C—H...Cl contacts are observed, leading to a layer-like arrangement of the components parallel to (100).

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2056989015006799/ff2135sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2056989015006799/ff2135Isup2.hkl
Contains datablock I

mol

MDL mol file https://doi.org/10.1107/S2056989015006799/ff2135Isup3.mol
Supplementary material

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S2056989015006799/ff2135Isup4.cml
Supplementary material

CCDC reference: 1057934

Key indicators

  • Single-crystal X-ray study
  • T = 173 K
  • Mean [sigma](C-C) = 0.004 Å
  • R factor = 0.032
  • wR factor = 0.056
  • Data-to-parameter ratio = 18.0

checkCIF/PLATON results

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Alert level C PLAT125_ALERT_4_C No '_symmetry_space_group_name_Hall' Given ..... Please Do ! PLAT480_ALERT_4_C Long H...A H-Bond Reported H4 .. CL2 .. 2.84 Ang. PLAT906_ALERT_3_C Large K value in the Analysis of Variance ...... 6.494 Check
Alert level G PLAT005_ALERT_5_G No _iucr_refine_instructions_details in the CIF Please Do ! PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms .............. 1 Report PLAT152_ALERT_1_G The Supplied and Calc. Volume s.u. Differ by ... 2 Units PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Th(Min) ... 3 Report PLAT961_ALERT_5_G Dataset Contains no Negative Intensities ....... Please Check
0 ALERT level A = Most likely a serious problem - resolve or explain 0 ALERT level B = A potentially serious problem, consider carefully 3 ALERT level C = Check. Ensure it is not caused by an omission or oversight 5 ALERT level G = General information/check it is not something unexpected 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 3 ALERT type 5 Informative message, check

Comment top

1-[2-(Diethylazaniumyl)ethyl]-3-methylimidazolium ions in deprotonated form can act as bidentate ligands (Laus et al., 2012). In this work, it is shown that they are also capable of coordinating in protonated form. The structure of the ion pair of 3-(2-(diethylammonio)ethyl-1- methylimidazolium tetrachlorocuprate (II) is shown in Figure 1. The anion adopts a distorted tetrahedral geometry. The Cl—Cu—Cl angles range from 97° to 134°. The heterocyclic rings of the cation are oriented parallel to the (3 7 2) and (3 7 2) planes with an interplanar angle of 32.5°. The side chain is twisted out of the heterocyclic ring plane. In the crystal structure, the cations and anions are linked by N—H···Cl and C—H···Cl hydrogen bonds (Figure 2).

Related literature top

For structures of related tetrachloridocuprates(II), see: Russell & Wallwork (1969); Główka & Gilli (1989); Choi et al. (2002); Sun & Qu (2005); Elangovan et al. (2007a); Elangovan et al. (2007b); Strasser et al. (2007). For details of the synthesis, see: Laus et al. (2012); Håkansson & Jagner (1990).

Experimental top

The title compound, (C10H21N3)CuCl4, was obtained from the reaction of bis-(1-(2-(diethylamino)ethyl)-3-methylimidazolin-2-ylidene) di-silver(I) bis(bis(triflimide)) (Laus et al., 2012) and carbonyl chlorocopper(I) (Håkansson & Jagner, 1990) in methanol under ambient conditions. This unconventional synthesis involves redox, protonation and complexation steps. Yellow-green single crystals were obtained from MeOH in modest yield. Melting point 118–120 °C.

Refinement top

All hydrogen atoms were positioned geometrically and constrained to ride on their parent atoms with Uiso(H) = 1.2–1.5Ueq(parent atom).

Structure description top

1-[2-(Diethylazaniumyl)ethyl]-3-methylimidazolium ions in deprotonated form can act as bidentate ligands (Laus et al., 2012). In this work, it is shown that they are also capable of coordinating in protonated form. The structure of the ion pair of 3-(2-(diethylammonio)ethyl-1- methylimidazolium tetrachlorocuprate (II) is shown in Figure 1. The anion adopts a distorted tetrahedral geometry. The Cl—Cu—Cl angles range from 97° to 134°. The heterocyclic rings of the cation are oriented parallel to the (3 7 2) and (3 7 2) planes with an interplanar angle of 32.5°. The side chain is twisted out of the heterocyclic ring plane. In the crystal structure, the cations and anions are linked by N—H···Cl and C—H···Cl hydrogen bonds (Figure 2).

For structures of related tetrachloridocuprates(II), see: Russell & Wallwork (1969); Główka & Gilli (1989); Choi et al. (2002); Sun & Qu (2005); Elangovan et al. (2007a); Elangovan et al. (2007b); Strasser et al. (2007). For details of the synthesis, see: Laus et al. (2012); Håkansson & Jagner (1990).

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell refinement: CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis PRO (Oxford Diffraction, 2010); program(s) used to solve structure: SIR2002 (Burla et al., 2003); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. Ion pair of the title compound, with atom labels and 50% probability displacement ellipsoids for non-H atoms.
[Figure 2] Fig. 2. Interionic contacts in the crystal structure of the title compound. Symmetry codes: (i) x, -1 + y, z; (ii) –x, -1/2 + y, 3/2–z; (iii) x, 1/2–y, 1/2 + z.
1-[2-(Diethylazaniumyl)ethyl]-3-methylimidazolium tetrachloridocuprate(II) top
Crystal data top
(C10H21N3)[CuCl4]F(000) = 796
Mr = 388.64Dx = 1.607 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 17.0041 (8) ÅCell parameters from 4805 reflections
b = 7.1161 (6) Åθ = 3.1–28.5°
c = 14.4143 (7) ŵ = 2.01 mm1
β = 112.956 (6)°T = 173 K
V = 1606.04 (17) Å3Fragment, yellow
Z = 40.20 × 0.16 × 0.12 mm
Data collection top
Oxford Diffraction Gemini-R Ultra
diffractometer
2991 independent reflections
Graphite monochromator2361 reflections with I > 2σ(I)
Detector resolution: 10.3822 pixels mm-1Rint = 0.045
ω (1° width) scansθmax = 25.5°, θmin = 3.1°
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2010)
h = 2020
Tmin = 0.875, Tmax = 1k = 68
10390 measured reflectionsl = 1717
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)] = 0.032Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.056H-atom parameters constrained
S = 0.98 w = 1/[σ2(Fo2) + (0.0234P)2]
where P = (Fo2 + 2Fc2)/3
2991 reflections(Δ/σ)max = 0.001
166 parametersΔρmax = 0.34 e Å3
0 restraintsΔρmin = 0.34 e Å3
Crystal data top
(C10H21N3)[CuCl4]V = 1606.04 (17) Å3
Mr = 388.64Z = 4
Monoclinic, P21/cMo Kα radiation
a = 17.0041 (8) ŵ = 2.01 mm1
b = 7.1161 (6) ÅT = 173 K
c = 14.4143 (7) Å0.20 × 0.16 × 0.12 mm
β = 112.956 (6)°
Data collection top
Oxford Diffraction Gemini-R Ultra
diffractometer
2991 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2010)
2361 reflections with I > 2σ(I)
Tmin = 0.875, Tmax = 1Rint = 0.045
10390 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0320 restraints
wR(F2) = 0.056H-atom parameters constrained
S = 0.98Δρmax = 0.34 e Å3
2991 reflectionsΔρmin = 0.34 e Å3
166 parameters
Special details top

Experimental. Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cu10.24089 (2)0.54432 (5)0.77447 (2)0.01040 (9)
Cl10.33356 (4)0.30011 (9)0.81388 (5)0.01280 (16)
Cl20.12793 (4)0.62361 (10)0.63485 (5)0.01575 (16)
Cl30.17620 (4)0.47770 (9)0.87973 (4)0.01224 (15)
Cl40.33226 (4)0.76469 (10)0.76985 (6)0.02164 (18)
N30.34210 (13)0.2088 (3)1.03033 (15)0.0089 (5)
H3N0.31910.24610.96320.011*
N20.16575 (13)0.0096 (3)0.88310 (15)0.0089 (5)
N10.08640 (14)0.0672 (3)0.73070 (15)0.0118 (5)
C90.35838 (17)0.3852 (4)1.09319 (19)0.0130 (6)
H9A0.38120.35031.16540.016*
H9B0.30360.45191.07770.016*
C20.16480 (17)0.0163 (4)0.79170 (19)0.0125 (6)
H20.21210.00120.77290.015*
C80.46893 (17)0.0322 (4)1.15266 (19)0.0164 (6)
H8A0.48920.14041.19780.025*
H8B0.51780.04521.15640.025*
H8C0.43010.04291.17310.025*
C60.27576 (16)0.0917 (4)1.04753 (19)0.0105 (6)
H6A0.22830.17481.04510.013*
H6B0.30120.03731.11610.013*
C50.23917 (16)0.0678 (4)0.97205 (19)0.0124 (6)
H5A0.28420.11560.95080.015*
H5B0.22190.17211.00550.015*
C70.42237 (16)0.1000 (4)1.04603 (19)0.0132 (6)
H7A0.46130.18091.02730.016*
H7B0.40740.00981.00030.016*
C100.42071 (19)0.5163 (4)1.0745 (2)0.0193 (7)
H10A0.47790.46041.10170.029*
H10B0.42180.63691.10790.029*
H10C0.40280.53671.00190.029*
C10.05856 (19)0.1108 (4)0.62341 (19)0.0215 (7)
H1A0.06680.24510.61510.032*
H1B0.0020.07930.58870.032*
H1C0.09220.03730.59460.032*
C30.03637 (17)0.0745 (4)0.78593 (19)0.0138 (6)
H30.02240.10720.76120.017*
C40.08539 (16)0.0273 (4)0.8808 (2)0.0134 (6)
H40.06820.02060.93590.016*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.01055 (17)0.00944 (18)0.01216 (18)0.00016 (15)0.00545 (14)0.00046 (14)
Cl10.0154 (4)0.0136 (4)0.0110 (3)0.0043 (3)0.0068 (3)0.0018 (3)
Cl20.0162 (4)0.0190 (4)0.0114 (3)0.0037 (3)0.0048 (3)0.0018 (3)
Cl30.0113 (3)0.0140 (4)0.0119 (3)0.0003 (3)0.0051 (3)0.0012 (3)
Cl40.0185 (4)0.0115 (4)0.0420 (5)0.0021 (3)0.0196 (4)0.0007 (3)
N30.0081 (12)0.0116 (12)0.0062 (11)0.0000 (10)0.0020 (10)0.0009 (9)
N20.0094 (12)0.0063 (13)0.0093 (11)0.0013 (9)0.0017 (10)0.0026 (9)
N10.0130 (12)0.0092 (13)0.0098 (12)0.0028 (10)0.0007 (10)0.0026 (9)
C90.0158 (15)0.0119 (15)0.0110 (14)0.0007 (12)0.0049 (12)0.0017 (11)
C20.0153 (15)0.0090 (15)0.0138 (15)0.0033 (12)0.0063 (13)0.0046 (11)
C80.0107 (14)0.0169 (16)0.0182 (15)0.0005 (13)0.0020 (12)0.0005 (13)
C60.0070 (14)0.0142 (16)0.0101 (14)0.0004 (11)0.0029 (12)0.0007 (11)
C50.0095 (14)0.0109 (16)0.0163 (15)0.0002 (12)0.0045 (12)0.0023 (12)
C70.0092 (14)0.0142 (16)0.0184 (15)0.0006 (12)0.0079 (12)0.0011 (12)
C100.0273 (17)0.0147 (17)0.0151 (15)0.0083 (13)0.0075 (13)0.0039 (12)
C10.0277 (18)0.0217 (18)0.0119 (15)0.0021 (14)0.0044 (14)0.0009 (13)
C30.0098 (14)0.0136 (17)0.0179 (15)0.0019 (12)0.0055 (13)0.0039 (12)
C40.0106 (14)0.0146 (15)0.0165 (15)0.0034 (12)0.0070 (13)0.0037 (12)
Geometric parameters (Å, º) top
Cu1—Cl42.2267 (7)C8—H8A0.98
Cu1—Cl32.2447 (6)C8—H8B0.98
Cu1—Cl22.2456 (8)C8—H8C0.98
Cu1—Cl12.2644 (7)C6—C51.527 (4)
N3—C61.499 (3)C6—H6A0.99
N3—C71.507 (3)C6—H6B0.99
N3—C91.509 (3)C5—H5A0.99
N3—H3N0.93C5—H5B0.99
N2—C21.324 (3)C7—H7A0.99
N2—C41.379 (3)C7—H7B0.99
N2—C51.458 (3)C10—H10A0.98
N1—C21.329 (3)C10—H10B0.98
N1—C31.374 (3)C10—H10C0.98
N1—C11.463 (3)C1—H1A0.98
C9—C101.513 (4)C1—H1B0.98
C9—H9A0.99C1—H1C0.98
C9—H9B0.99C3—C41.337 (4)
C2—H20.95C3—H30.95
C8—C71.508 (4)C4—H40.95
Cl4—Cu1—Cl3134.47 (3)C5—C6—H6A108.6
Cl4—Cu1—Cl299.16 (3)N3—C6—H6B108.6
Cl3—Cu1—Cl2100.69 (3)C5—C6—H6B108.6
Cl4—Cu1—Cl197.04 (3)H6A—C6—H6B107.5
Cl3—Cu1—Cl198.33 (3)N2—C5—C6112.7 (2)
Cl2—Cu1—Cl1133.31 (3)N2—C5—H5A109
C6—N3—C7112.7 (2)C6—C5—H5A109
C6—N3—C9109.68 (18)N2—C5—H5B109
C7—N3—C9113.2 (2)C6—C5—H5B109
C6—N3—H3N107H5A—C5—H5B107.8
C7—N3—H3N107N3—C7—C8113.7 (2)
C9—N3—H3N107N3—C7—H7A108.8
C2—N2—C4108.8 (2)C8—C7—H7A108.8
C2—N2—C5126.0 (2)N3—C7—H7B108.8
C4—N2—C5125.19 (19)C8—C7—H7B108.8
C2—N1—C3108.4 (2)H7A—C7—H7B107.7
C2—N1—C1125.8 (2)C9—C10—H10A109.5
C3—N1—C1125.9 (2)C9—C10—H10B109.5
N3—C9—C10112.5 (2)H10A—C10—H10B109.5
N3—C9—H9A109.1C9—C10—H10C109.5
C10—C9—H9A109.1H10A—C10—H10C109.5
N3—C9—H9B109.1H10B—C10—H10C109.5
C10—C9—H9B109.1N1—C1—H1A109.5
H9A—C9—H9B107.8N1—C1—H1B109.5
N2—C2—N1108.4 (2)H1A—C1—H1B109.5
N2—C2—H2125.8N1—C1—H1C109.5
N1—C2—H2125.8H1A—C1—H1C109.5
C7—C8—H8A109.5H1B—C1—H1C109.5
C7—C8—H8B109.5C4—C3—N1107.6 (2)
H8A—C8—H8B109.5C4—C3—H3126.2
C7—C8—H8C109.5N1—C3—H3126.2
H8A—C8—H8C109.5C3—C4—N2106.8 (2)
H8B—C8—H8C109.5C3—C4—H4126.6
N3—C6—C5114.8 (2)N2—C4—H4126.6
N3—C6—H6A108.6
C6—N3—C9—C10176.3 (2)C4—N2—C5—C672.8 (3)
C7—N3—C9—C1056.9 (3)N3—C6—C5—N288.4 (3)
C4—N2—C2—N10.5 (3)C6—N3—C7—C863.9 (3)
C5—N2—C2—N1179.5 (2)C9—N3—C7—C861.3 (3)
C3—N1—C2—N20.4 (3)C2—N1—C3—C40.1 (3)
C1—N1—C2—N2179.5 (2)C1—N1—C3—C4179.2 (2)
C7—N3—C6—C565.8 (3)N1—C3—C4—N20.2 (3)
C9—N3—C6—C5167.1 (2)C2—N2—C4—C30.4 (3)
C2—N2—C5—C6107.2 (3)C5—N2—C4—C3179.5 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H3N···Cl10.932.293.134 (2)150
N3—H3N···Cl30.932.793.399 (2)124
C2—H2···Cl4i0.952.663.480 (3)145
C3—H3···Cl2ii0.952.753.423 (3)128
C3—H3···Cl3ii0.952.773.537 (3)138
C4—H4···Cl2iii0.952.843.608 (3)139
C9—H9A···Cl1iii0.992.783.617 (3)143
Symmetry codes: (i) x, y1, z; (ii) x, y1/2, z+3/2; (iii) x, y+1/2, z+1/2.
Selected bond lengths (Å) top
Cu1—Cl42.2267 (7)Cu1—Cl22.2456 (8)
Cu1—Cl32.2447 (6)Cu1—Cl12.2644 (7)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H3N···Cl10.932.293.134 (2)150
N3—H3N···Cl30.932.793.399 (2)124
C2—H2···Cl4i0.952.663.480 (3)145
C3—H3···Cl2ii0.952.753.423 (3)128
C3—H3···Cl3ii0.952.773.537 (3)138
C4—H4···Cl2iii0.952.843.608 (3)139
C9—H9A···Cl1iii0.992.783.617 (3)143
Symmetry codes: (i) x, y1, z; (ii) x, y1/2, z+3/2; (iii) x, y+1/2, z+1/2.
 

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