PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2010 July 1; 66(Pt 7): m836.
Published online 2010 June 23. doi:  10.1107/S1600536810023500
PMCID: PMC3006861

Diaqua­bromido­copper(II)–18-crown-6–water (1/1/2)

Abstract

In the title compound, [CuBr2(H2O)2]·C12H24O6·2H2O, the CuII atom, which is situated on an inversion centre and has a slightly distorted square-planar geometry, and the two coordinated water mol­ecules are linked to the 18-crown-6 macrocycles by O—H(...)O hydrogen bonds. The water mol­ecule of crystallization further links the metal complex and the crown ether macrocycles into a chain along the c axis.

Related literature

For the ability of 18-crown-6 ether to form complexes with different metal ions, see: Jackson et al. (1981 [triangle]); Otter & Hartshorn (2004 [triangle]). For similar structures, see: Antsyshkina et al. (2004 [triangle]); Liu et al. (2007 [triangle]). For bond-length data, see: Allen et al. (1987 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-0m836-scheme1.jpg

Experimental

Crystal data

  • [CuBr2(H2O)2]·C12H24O6·2H2O
  • M r = 559.73
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-0m836-efi1.jpg
  • a = 7.4418 (5) Å
  • b = 8.1724 (6) Å
  • c = 10.1510 (2) Å
  • α = 75.220 (3)°
  • β = 69.47 (1)°
  • γ = 78.51 (1)°
  • V = 554.90 (6) Å3
  • Z = 1
  • Mo Kα radiation
  • μ = 4.63 mm−1
  • T = 298 K
  • 0.20 × 0.20 × 0.20 mm

Data collection

  • Rigaku SCXmini diffractometer
  • Absorption correction: multi-scan CrystalClear (Rigaku, 2005 [triangle]) T min = 0.397, T max = 0.412
  • 5746 measured reflections
  • 2537 independent reflections
  • 2064 reflections with I > 2σ(I)
  • R int = 0.037

Refinement

  • R[F 2 > 2σ(F 2)] = 0.052
  • wR(F 2) = 0.155
  • S = 1.08
  • 2537 reflections
  • 123 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 1.27 e Å−3
  • Δρmin = −1.55 e Å−3

Data collection: CrystalClear (Rigaku 2005 [triangle]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: PRPKAPPA (Ferguson, 1999 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536810023500/jj2036sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810023500/jj2036Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The author is grateful to the starter fund of Southeast University for financial support to purchase the X-ray diffractometer.

supplementary crystallographic information

Comment

The ability of 18-crown-6 ether (18-C-6) to form complexes with different metal ions has been widely investigated (Jackson et al., 1981; Otter & Hartshorn, 2004). We report here the synthesis and crystal structure of an intermediate in the 18-crown-6 ether-mediated solubilization of copper bromide salts, namely [CuBr2(H2O)2 ].(18-crown-6).2H2O, (I).

The crystal structure of (I) consists of CuBr2(H2O)2 complex, one molecule of 18-crown-6 ether and two water molecule in the crystallographic asymmetric unit (Fig. 1). The structure is similar to that found in [CuCl2(H2O)2].(18-crown-6).2H2O (Antsyshkina et al., 2004; Liu et al., 2007), where the Cu atom is bonded to two Br and two H2O molecules in a square planar coordination. The mean Cu—Br and Cu—O bond lengths are 2.3687 (5) Åand 1.911 (4) Å, respectively. Bond length and angles are in normal ranges (Allen et al., 1987). All O atoms in the crown form O—H···Ocrown hydrogen bonds with adjacent coordinated (O5W) and uncoordinated (O4W) water molecules, with average O···O distances of 2.609 Å. Thus, the hydrogen bonds link the crown ethers and Cu complex into a one-dimensional chain along the c axis (Fig. 2).

Experimental

CuBr2(44.6 mg, 0.2 mmol) and 18-crown-6 (53 mg, 0.2 mmol) were added to 10 ml of THF and 2 ml H2O, and this reaction mixture was stirred at 333 K for 6 h. After filtration, the resulting filtrate was reduced to 5 ml in a small tube, which was loaded into a large vial containing 5 ml of diethyl ether. The large vial was sealed and left undisturbed at room temperature, and colorless crystals of (I) were obtained in 5 d.

Refinement

Water H atoms were located in a difference Fourier map and refined as riding in their as-found relative positions, with Uiso(H) = 1.2Ueq(O). Other H atoms were placed in calculated positions, with C—H = 0.97 Å, and refined in riding mode, with Uiso(H) = 1.2Ueq(C).

Figures

Fig. 1.
The molecular structure of the title compound, with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level, and the H atoms attached to C have been omitted for clarity. Dashed lines indicate O—H···O ...
Fig. 2.
One-dimensional chain of (I) showing the Owater—H···Ocrown hydrogen bonds (dashed lines). H atoms attached to C have been omitted.

Crystal data

[CuBr2(H2O)2]·C12H24O6·2H2OZ = 1
Mr = 559.73F(000) = 283
Triclinic, P1Dx = 1.675 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.4418 (5) ÅCell parameters from 2622 reflections
b = 8.1724 (6) Åθ = 3.0–27.5°
c = 10.1510 (2) ŵ = 4.63 mm1
α = 75.220 (3)°T = 298 K
β = 69.47 (1)°Prism, green
γ = 78.51 (1)°0.20 × 0.20 × 0.20 mm
V = 554.90 (6) Å3

Data collection

Rigaku SCXmini diffractometer2537 independent reflections
Radiation source: fine-focus sealed tube2064 reflections with I > 2σ(I)
graphiteRint = 0.037
Detector resolution: 13.6612 pixels mm-1θmax = 27.5°, θmin = 3.0°
ω scansh = −9→9
Absorption correction: multi-scan CrystalClear (Rigaku, 2005)k = −10→10
Tmin = 0.397, Tmax = 0.412l = −13→13
5746 measured reflections

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.052Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.155H atoms treated by a mixture of independent and constrained refinement
S = 1.08w = 1/[σ2(Fo2) + (0.0755P)2 + 0.8701P] where P = (Fo2 + 2Fc2)/3
2537 reflections(Δ/σ)max < 0.001
123 parametersΔρmax = 1.27 e Å3
0 restraintsΔρmin = −1.55 e Å3

Special details

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)

xyzUiso*/Ueq
Br10.05334 (10)0.20118 (6)0.58028 (6)0.0652 (3)
C10.7159 (11)0.5878 (10)0.2213 (9)0.080 (2)
H1A0.78930.56780.28750.096*
H1B0.58810.64300.26520.096*
C20.6378 (11)0.3049 (11)0.3232 (7)0.082 (2)
H2A0.52370.35350.39030.099*
H2B0.73870.27000.36810.099*
C30.5931 (11)0.1552 (9)0.2897 (7)0.078 (2)
H3A0.70430.11040.21800.094*
H3B0.56240.06640.37550.094*
C40.3741 (11)0.0667 (7)0.2063 (8)0.077 (2)
H4A0.3196−0.01190.29510.092*
H4B0.48510.00530.14650.092*
C50.2298 (10)0.1320 (9)0.1320 (9)0.079 (2)
H5A0.18340.03780.11660.095*
H5B0.12060.19680.19010.095*
C60.1858 (10)0.3000 (10)−0.0843 (10)0.083 (2)
H6A0.07090.3637−0.03040.100*
H6B0.14660.2052−0.10450.100*
Cu10.00000.50000.50000.0335 (2)
O10.7004 (6)0.4308 (6)0.1941 (4)0.0626 (10)
O20.4337 (5)0.2051 (5)0.2370 (4)0.0559 (9)
O30.3148 (5)0.2374 (5)−0.0014 (5)0.0613 (10)
O4W0.3072 (6)0.6708 (6)0.0637 (4)0.0566 (10)
O5W0.1698 (7)0.4741 (5)0.3133 (4)0.0900 (18)
H5WA0.22290.37560.29790.108*
H5WB0.19200.56100.24550.108*
H4WA0.309 (11)0.633 (10)0.011 (8)0.07 (3)*
H4WB0.436 (11)0.688 (9)0.040 (8)0.08 (2)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br10.0949 (5)0.0358 (3)0.0446 (3)−0.0137 (3)0.0039 (3)−0.0051 (2)
C10.085 (5)0.091 (5)0.092 (5)0.007 (4)−0.054 (4)−0.043 (4)
C20.088 (5)0.112 (6)0.044 (3)0.010 (4)−0.035 (3)−0.007 (4)
C30.088 (5)0.066 (4)0.053 (4)0.011 (4)−0.016 (3)0.011 (3)
C40.093 (5)0.037 (3)0.066 (4)−0.015 (3)0.016 (4)−0.006 (3)
C50.066 (4)0.059 (4)0.095 (5)−0.033 (3)0.015 (4)−0.025 (4)
C60.066 (4)0.084 (5)0.132 (7)−0.008 (4)−0.045 (5)−0.057 (5)
Cu10.0319 (4)0.0385 (4)0.0250 (4)−0.0049 (3)−0.0047 (3)−0.0033 (3)
O10.068 (2)0.077 (3)0.048 (2)0.000 (2)−0.023 (2)−0.022 (2)
O20.056 (2)0.0428 (19)0.047 (2)0.0025 (16)0.0013 (17)−0.0033 (16)
O30.049 (2)0.060 (2)0.073 (3)−0.0165 (18)−0.0070 (19)−0.021 (2)
O4W0.054 (2)0.074 (3)0.034 (2)−0.016 (2)−0.0026 (17)−0.0073 (19)
O5W0.109 (4)0.054 (2)0.040 (2)0.029 (2)0.026 (2)0.0074 (18)

Geometric parameters (Å, °)

Br1—Cu12.3687 (5)C4—H4B0.9700
C1—O11.414 (8)C5—O31.413 (8)
C1—C6i1.488 (11)C5—H5A0.9700
C1—H1A0.9700C5—H5B0.9700
C1—H1B0.9700C6—O31.429 (8)
C2—O11.438 (8)C6—C1i1.488 (11)
C2—C31.476 (11)C6—H6A0.9700
C2—H2A0.9700C6—H6B0.9700
C2—H2B0.9700Cu1—O5Wii1.911 (4)
C3—O21.414 (8)Cu1—O5W1.911 (4)
C3—H3A0.9700Cu1—Br1ii2.3687 (5)
C3—H3B0.9700O4W—H4WA0.68 (7)
C4—O21.432 (8)O4W—H4WB0.93 (8)
C4—C51.463 (11)O5W—H5WA0.8500
C4—H4A0.9700O5W—H5WB0.8500
O1—C1—C6i109.7 (6)O3—C5—H5A109.9
O1—C1—H1A109.7C4—C5—H5A109.9
C6i—C1—H1A109.7O3—C5—H5B109.9
O1—C1—H1B109.7C4—C5—H5B109.9
C6i—C1—H1B109.7H5A—C5—H5B108.3
H1A—C1—H1B108.2O3—C6—C1i109.5 (5)
O1—C2—C3110.2 (5)O3—C6—H6A109.8
O1—C2—H2A109.6C1i—C6—H6A109.8
C3—C2—H2A109.6O3—C6—H6B109.8
O1—C2—H2B109.6C1i—C6—H6B109.8
C3—C2—H2B109.6H6A—C6—H6B108.2
H2A—C2—H2B108.1O5Wii—Cu1—O5W180.000 (1)
O2—C3—C2108.9 (5)O5Wii—Cu1—Br1ii89.03 (12)
O2—C3—H3A109.9O5W—Cu1—Br1ii90.97 (12)
C2—C3—H3A109.9O5Wii—Cu1—Br190.97 (12)
O2—C3—H3B109.9O5W—Cu1—Br189.03 (12)
C2—C3—H3B109.9Br1ii—Cu1—Br1180.0
H3A—C3—H3B108.3C1—O1—C2112.9 (6)
O2—C4—C5109.9 (5)C3—O2—C4113.2 (5)
O2—C4—H4A109.7C5—O3—C6112.7 (5)
C5—C4—H4A109.7H4WA—O4W—H4WB103 (8)
O2—C4—H4B109.7Cu1—O5W—H5WA120.0
C5—C4—H4B109.7Cu1—O5W—H5WB120.0
H4A—C4—H4B108.2H5WA—O5W—H5WB120.0
O3—C5—C4109.1 (5)
O1—C2—C3—O2−64.8 (7)C2—C3—O2—C4−177.8 (5)
O2—C4—C5—O363.1 (7)C5—C4—O2—C3−171.2 (5)
C6i—C1—O1—C2169.8 (6)C4—C5—O3—C6177.1 (5)
C3—C2—O1—C1170.5 (6)C1i—C6—O3—C5178.9 (5)

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

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O4W—H4WA···O1i0.68 (7)2.30 (8)2.962 (6)167 (9)
O4W—H4WB···O3i0.93 (8)1.95 (8)2.869 (6)170 (6)
O5W—H5WA···O20.851.922.715 (5)156
O5W—H5WB···O4W0.851.822.609 (6)155

Symmetry codes: (i) −x+1, −y+1, −z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: JJ2036).

References

  • Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.
  • Antsyshkina, A. S., Sadikov, G. G., Koksharova, T. V. & Sergienko, V. S. (2004). Zh. Neorg. Khim.49, 1797–1800.
  • Ferguson, G. (1999). PRPKAPPA University of Guelph, Canada.
  • Jackson, W. G., Sargeson, A. M., Tucker, P. A. & Watson, A. D. (1981). J. Am. Chem. Soc.103, 533–540.
  • Liu, X., Guo, G.-C. & Sun, Y.-Y. (2007). Acta Cryst. E63, m275–m277.
  • Otter, C. A. & Hartshorn, R. M. (2004). J. Chem. Soc. Dalton Trans. pp. 150–156. [PubMed]
  • Rigaku (2005). CrystalClear Rigaku Corporation, Tokyo, Japan.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography