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Acta Cryst. (2011). E67, m170    [ doi:10.1107/S1600536810054280 ]

Bis(N,N-diisopropylbutanaminium) bis[di-[mu]-chlorido-bis[dichloridocuprate(II)]]

J. Dai and J. Xu

Abstract top

In the title compound, (C10H24N)2[Cu2Cl6], N,N-diisopropylbutanamine is protonated on the N atom. The CuII atom in the centrosymmetric [Cu2Cl6]2- anion has a distorted tetrahedral geometry. In the crystal, the cations and anions are connected by N-H...Cl and C-H...Cl hydrogen bonds into layers parallel to (100).

Comment top

Salts of amide have attracted more attention as phase transition dielectric materials for its applications in memory storage (Fu et al., 2007, 2008, 2009; Fu & Xiong, 2008). With the purpose of obtaining phase transition crystals of N,N-diisopropylbutyl-1-amine salts, its interactions with various metal ions have been studied and we have elaborated a series of new materials with this organic molecule. In this paper, we describe the crystal structure of the title compound,

The asymmetric unit is composed of half [Cu2Cl6]2- anion and one [C10H24N]+ cation (Fig. 1). The N atom of N,N-diisopropylbutyl-1-amine is protonated, thus indicating one positive charge in the amide N atom. The half [Cu2Cl6]2- anion showing one negative charge makes charge balance. The geometric parameters of the title compound are in a normal range. In the crystal structure, the cations and anions are involved in N—H···Cl and C—H···Cl hydrogen bonds (Table 1), which link the cations and anions into a two-dimensional network (Fig. 2).

Related literature top

For the properties and structures of N,N-diisopropylbutyl-1-amine compounds, see: Fu et al. (2007, 2008, 2009); Fu & Xiong (2008).

Experimental top

The commercial N,N-diisopropylbutyl-1-amine (10 mmol), HCl (2 ml) and CuCl2 (5 mmol) were dissolved in 10 ml water. The solvent was slowly evaporated in air, affording blue block-shaped crystals of the title compound suitable for X-ray analysis.

The dielectric constant of the title compound as a function of temperature indicates that the permittivity is basically temperature-independent, suggesting that this compound should not be a real ferroelectrics or there may be no distinct phase transition occurred within the measured temperature range. Similarly, below the melting point (446–447 K) of the compound, the dielectric constant as a function of temperature also goes smoothly, and there is no dielectric anomaly observed (dielectric constant equaling to 8.9 to 10.6).

Refinement top

H atoms were positioned geometrically and treated as riding, with C—H = 0.98 (CH), 0.97 (CH2) and 0.96 (CH3) Å and N—H = 0.91 Å and with Uiso(H) = 1.2(1.5 for methyl)Ueq(C, N).

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) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. Molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry code: (A) 1-x, 2-y, 1-z.]
[Figure 2] Fig. 2. The crystal packing of the title compound, showing the two-dimensional network. Dashed lines denote hydrogen bonds.
Bis(N,N-diisopropylbutanaminium) bis[di-µ-chlorido-bis[dichloridocuprate(II)]] top
Crystal data top
(C10H24N)2[Cu2Cl6]Z = 1
Mr = 656.40F(000) = 342
Triclinic, P1Dx = 1.388 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.5697 (17) ÅCell parameters from 3588 reflections
b = 10.213 (2) Åθ = 3.4–27.5°
c = 10.384 (2) ŵ = 1.88 mm−1
α = 72.43 (3)°T = 298 K
β = 68.53 (3)°Block, blue
γ = 71.78 (3)°0.30 × 0.05 × 0.05 mm
V = 785.1 (3) Å3
Data collection top
Rigaku Mercury2 CCD
diffractometer		3588 independent reflections
Radiation source: fine-focus sealed tube2728 reflections with I > 2σ(I)
graphiteRint = 0.044
Detector resolution: 13.6612 pixels mm-1θmax = 27.5°, θmin = 3.4°
ω scansh = −11→11
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)		k = −13→13
Tmin = 0.910, Tmax = 1.000l = −13→13
8206 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)] = 0.046Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.107H-atom parameters constrained
S = 1.08 w = 1/[σ2(Fo2) + (0.0342P)2 + 0.4528P]
where P = (Fo2 + 2Fc2)/3
3588 reflections(Δ/σ)max < 0.001
141 parametersΔρmax = 0.45 e Å−3
0 restraintsΔρmin = −0.52 e Å−3
Crystal data top
(C10H24N)2[Cu2Cl6]γ = 71.78 (3)°
Mr = 656.40V = 785.1 (3) Å3
Triclinic, P1Z = 1
a = 8.5697 (17) ÅMo Kα radiation
b = 10.213 (2) ŵ = 1.88 mm−1
c = 10.384 (2) ÅT = 298 K
α = 72.43 (3)°0.30 × 0.05 × 0.05 mm
β = 68.53 (3)°
Data collection top
Rigaku Mercury2 CCD
diffractometer		3588 independent reflections
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)		2728 reflections with I > 2σ(I)
Tmin = 0.910, Tmax = 1.000Rint = 0.044
8206 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.046H-atom parameters constrained
wR(F2) = 0.107Δρmax = 0.45 e Å−3
S = 1.08Δρmin = −0.52 e Å−3
3588 reflectionsAbsolute structure: ?
141 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N10.7275 (3)0.3131 (3)0.7043 (3)0.0374 (6)
H10.71970.40660.66440.045*
C10.5308 (7)0.1423 (5)0.8060 (6)0.0907 (17)
H1A0.42480.12970.80510.136*
H1B0.53000.12670.90210.136*
H1C0.62560.07610.75890.136*
Cu10.55821 (5)0.83754 (4)0.59096 (4)0.03888 (14)
Cl10.30886 (11)1.01180 (9)0.60170 (11)0.0629 (3)
C20.5495 (4)0.2903 (4)0.7304 (4)0.0510 (9)
H2A0.53440.30620.63740.061*
Cl20.50922 (16)0.75177 (13)0.81673 (10)0.0778 (4)
C30.4106 (5)0.3995 (5)0.8062 (5)0.0680 (12)
H3A0.30110.40030.80020.102*
H3B0.43570.49090.76250.102*
H3C0.40690.37660.90380.102*
Cl30.70329 (12)0.64171 (9)0.51116 (9)0.0505 (2)
C40.8746 (6)0.4013 (5)0.8158 (4)0.0663 (12)
H4A0.89940.39220.90150.099*
H4B0.80650.49410.79120.099*
H4C0.98050.38640.74070.099*
C50.7756 (4)0.2922 (4)0.8379 (4)0.0449 (8)
H5A0.66790.31140.91400.054*
C60.8723 (6)0.1434 (4)0.8862 (4)0.0707 (13)
H6A0.88020.13310.97870.106*
H6B0.98600.12610.82090.106*
H6C0.81190.07710.88940.106*
C70.8673 (4)0.2391 (4)0.5948 (3)0.0447 (8)
H7A0.87090.13890.62580.054*
H7B0.97680.25200.59020.054*
C80.8484 (5)0.2876 (4)0.4479 (3)0.0452 (8)
H8A0.83660.38900.41830.054*
H8B0.74460.26700.44940.054*
C91.0015 (5)0.2162 (4)0.3426 (4)0.0565 (10)
H9A1.10460.23750.34170.068*
H9B1.01370.11490.37400.068*
C100.9891 (6)0.2596 (5)0.1937 (4)0.0698 (12)
H10A1.09040.21070.13280.105*
H10B0.97960.35950.16070.105*
H10C0.88930.23640.19290.105*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0384 (15)0.0359 (14)0.0347 (15)−0.0041 (11)−0.0109 (12)−0.0078 (12)
C10.083 (3)0.072 (3)0.124 (5)−0.045 (3)−0.018 (3)−0.016 (3)
Cu10.0400 (2)0.0323 (2)0.0370 (2)−0.00387 (16)−0.00747 (17)−0.00665 (17)
Cl10.0393 (5)0.0424 (5)0.0699 (7)−0.0006 (4)0.0065 (4)0.0027 (4)
C20.043 (2)0.066 (2)0.047 (2)−0.0150 (18)−0.0124 (17)−0.0148 (19)
Cl20.0893 (8)0.0808 (8)0.0353 (5)−0.0012 (6)−0.0073 (5)−0.0061 (5)
C30.040 (2)0.084 (3)0.070 (3)−0.007 (2)−0.009 (2)−0.019 (2)
Cl30.0628 (6)0.0332 (4)0.0488 (5)−0.0008 (4)−0.0151 (4)−0.0118 (4)
C40.073 (3)0.083 (3)0.058 (3)−0.023 (2)−0.031 (2)−0.017 (2)
C50.0412 (19)0.053 (2)0.0355 (19)−0.0014 (16)−0.0136 (15)−0.0097 (16)
C60.084 (3)0.065 (3)0.054 (3)0.011 (2)−0.039 (2)−0.005 (2)
C70.0429 (19)0.0426 (19)0.042 (2)0.0019 (15)−0.0118 (16)−0.0134 (16)
C80.051 (2)0.0408 (19)0.044 (2)−0.0037 (16)−0.0172 (17)−0.0138 (16)
C90.057 (2)0.062 (2)0.046 (2)−0.0047 (19)−0.0102 (18)−0.0212 (19)
C100.081 (3)0.083 (3)0.049 (2)−0.017 (2)−0.012 (2)−0.030 (2)
Geometric parameters (Å, °) top
N1—C71.501 (4)C4—H4B0.9600
N1—C51.525 (4)C4—H4C0.9600
N1—C21.528 (4)C5—C61.518 (5)
N1—H10.9100C5—H5A0.9800
C1—C21.506 (5)C6—H6A0.9600
C1—H1A0.9600C6—H6B0.9600
C1—H1B0.9600C6—H6C0.9600
C1—H1C0.9600C7—C81.508 (4)
Cu1—Cl22.1701 (13)C7—H7A0.9700
Cu1—Cl32.2190 (12)C7—H7B0.9700
Cu1—Cl1i2.2884 (14)C8—C91.511 (5)
Cu1—Cl12.3051 (13)C8—H8A0.9700
Cl1—Cu1i2.2884 (14)C8—H8B0.9700
C2—C31.515 (5)C9—C101.509 (5)
C2—H2A0.9800C9—H9A0.9700
C3—H3A0.9600C9—H9B0.9700
C3—H3B0.9600C10—H10A0.9600
C3—H3C0.9600C10—H10B0.9600
C4—C51.519 (5)C10—H10C0.9600
C4—H4A0.9600
C7—N1—C5113.3 (2)C6—C5—C4111.9 (3)
C7—N1—C2113.5 (3)C6—C5—N1113.9 (3)
C5—N1—C2114.8 (3)C4—C5—N1109.1 (3)
C7—N1—H1104.6C6—C5—H5A107.2
C5—N1—H1104.6C4—C5—H5A107.2
C2—N1—H1104.6N1—C5—H5A107.2
C2—C1—H1A109.5C5—C6—H6A109.5
C2—C1—H1B109.5C5—C6—H6B109.5
H1A—C1—H1B109.5H6A—C6—H6B109.5
C2—C1—H1C109.5C5—C6—H6C109.5
H1A—C1—H1C109.5H6A—C6—H6C109.5
H1B—C1—H1C109.5H6B—C6—H6C109.5
Cl2—Cu1—Cl399.48 (5)N1—C7—C8115.2 (3)
Cl2—Cu1—Cl1i146.21 (6)N1—C7—H7A108.5
Cl3—Cu1—Cl1i96.22 (5)C8—C7—H7A108.5
Cl2—Cu1—Cl197.69 (6)N1—C7—H7B108.5
Cl3—Cu1—Cl1143.17 (5)C8—C7—H7B108.5
Cl1i—Cu1—Cl187.01 (5)H7A—C7—H7B107.5
Cu1i—Cl1—Cu192.99 (5)C7—C8—C9111.6 (3)
C1—C2—C3112.0 (4)C7—C8—H8A109.3
C1—C2—N1113.3 (3)C9—C8—H8A109.3
C3—C2—N1110.3 (3)C7—C8—H8B109.3
C1—C2—H2A107.0C9—C8—H8B109.3
C3—C2—H2A107.0H8A—C8—H8B108.0
N1—C2—H2A107.0C10—C9—C8114.0 (3)
C2—C3—H3A109.5C10—C9—H9A108.8
C2—C3—H3B109.5C8—C9—H9A108.8
H3A—C3—H3B109.5C10—C9—H9B108.8
C2—C3—H3C109.5C8—C9—H9B108.8
H3A—C3—H3C109.5H9A—C9—H9B107.6
H3B—C3—H3C109.5C9—C10—H10A109.5
C5—C4—H4A109.5C9—C10—H10B109.5
C5—C4—H4B109.5H10A—C10—H10B109.5
H4A—C4—H4B109.5C9—C10—H10C109.5
C5—C4—H4C109.5H10A—C10—H10C109.5
H4A—C4—H4C109.5H10B—C10—H10C109.5
H4B—C4—H4C109.5
Cl2—Cu1—Cl1—Cu1i146.38 (6)C2—N1—C5—C692.1 (4)
Cl3—Cu1—Cl1—Cu1i−96.39 (7)C7—N1—C5—C485.3 (4)
Cl1i—Cu1—Cl1—Cu1i0.0C2—N1—C5—C4−142.1 (3)
C7—N1—C2—C170.5 (4)C5—N1—C7—C8−163.7 (3)
C5—N1—C2—C1−62.1 (4)C2—N1—C7—C863.0 (4)
C7—N1—C2—C3−163.1 (3)N1—C7—C8—C9175.3 (3)
C5—N1—C2—C364.3 (4)C7—C8—C9—C10179.4 (3)
C7—N1—C5—C6−40.5 (4)
Symmetry codes: (i) −x+1, −y+2, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···Cl30.912.443.336 (3)168
C2—H2A···Cl3ii0.982.823.668 (5)146
C5—H5A···Cl2iii0.982.643.511 (4)149
C8—H8A···Cl30.972.783.617 (4)144
Symmetry codes: (ii) −x+1, −y+1, −z+1; (iii) −x+1, −y+1, −z+2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···Cl30.912.443.336 (3)168
C2—H2A···Cl3i0.982.823.668 (5)146
C5—H5A···Cl2ii0.982.643.511 (4)149
C8—H8A···Cl30.972.783.617 (4)144
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y+1, −z+2.
Acknowledgements top

This work was supported by a start-up grant from Southeast University, China.

references
References top

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