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

Wang, B.

doi:10.1107/S1600536810023500

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 7| July 2010| Page m836

doi:10.1107/S1600536810023500

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

Bo Wang ^a ^*

^aOrdered Matter Science Research Center, Southeast University, Nanjing 211189, People's Republic of China
^*Correspondence e-mail: wsp1314@126.com

(Received 29 May 2010; accepted 17 June 2010; online 23 June 2010)

In the title compound, [CuBr₂(H₂O)₂]·C₁₂H₂₄O₆·2H₂O, the Cu^II 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 ); Otter & Hartshorn (2004 ). For similar structures, see: Antsyshkina et al. (2004 ); Liu et al. (2007 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

[CuBr₂(H₂O)₂]·C₁₂H₂₄O₆·2H₂O
M_r = 559.73
Triclinic, $[P \overline 1]$
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 ) 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[F² > 2σ(F²)] = 0.052
wR(F²) = 0.155
S = 1.08
2537 reflections
123 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.27 e Å⁻³
Δρ_min = −1.55 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4W—H4WA⋯O1ⁱ	0.68 (7)	2.30 (8)	2.962 (6)	167 (9)
O4W—H4WB⋯O3ⁱ	0.93 (8)	1.95 (8)	2.869 (6)	170 (6)
O5W—H5WA⋯O2	0.85	1.92	2.715 (5)	156
O5W—H5WB⋯O4W	0.85	1.82	2.609 (6)	155
Symmetry code: (i) -x+1, -y+1, -z.

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: PRPKAPPA (Ferguson, 1999 ).

Supporting information

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

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

checkCIF report

Comment top

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···O_crown 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).

Related literature top

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

Experimental top

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.

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: PRPKAPPA (Ferguson, 1999).

Figures top

	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 hydrogen bonds.
	Fig. 2. One-dimensional chain of (I) showing the O_water—H···O_crown hydrogen bonds (dashed lines). H atoms attached to C have been omitted.

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

Crystal data top

[CuBr₂(H₂O)₂]·C₁₂H₂₄O₆·2H₂O	Z = 1
M_r = 559.73	F(000) = 283
Triclinic, P1	D_x = 1.675 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.4418 (5) Å	Cell parameters from 2622 reflections
b = 8.1724 (6) Å	θ = 3.0–27.5°
c = 10.1510 (2) Å	µ = 4.63 mm⁻¹
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 top

Rigaku SCXmini diffractometer	2537 independent reflections
Radiation source: fine-focus sealed tube	2064 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.037
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.0°
ω scans	h = −9→9
Absorption correction: multi-scan CrystalClear (Rigaku, 2005)	k = −10→10
T_min = 0.397, T_max = 0.412	l = −13→13
5746 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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.155	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ²(F_o²) + (0.0755P)² + 0.8701P] where P = (F_o² + 2F_c²)/3
2537 reflections	(Δ/σ)_max < 0.001
123 parameters	Δρ_max = 1.27 e Å⁻³
0 restraints	Δρ_min = −1.55 e Å⁻³

Crystal data top

[CuBr₂(H₂O)₂]·C₁₂H₂₄O₆·2H₂O	γ = 78.51 (1)°
M_r = 559.73	V = 554.90 (6) Å³
Triclinic, P1	Z = 1
a = 7.4418 (5) Å	Mo Kα radiation
b = 8.1724 (6) Å	µ = 4.63 mm⁻¹
c = 10.1510 (2) Å	T = 298 K
α = 75.220 (3)°	0.20 × 0.20 × 0.20 mm
β = 69.47 (1)°

Data collection top

Rigaku SCXmini diffractometer	2537 independent reflections
Absorption correction: multi-scan CrystalClear (Rigaku, 2005)	2064 reflections with I > 2σ(I)
T_min = 0.397, T_max = 0.412	R_int = 0.037
5746 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.052	0 restraints
wR(F²) = 0.155	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	Δρ_max = 1.27 e Å⁻³
2537 reflections	Δρ_min = −1.55 e Å⁻³
123 parameters

Special details top

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

	x	y	z	U_iso*/U_eq
Br1	0.05334 (10)	0.20118 (6)	0.58028 (6)	0.0652 (3)
C1	0.7159 (11)	0.5878 (10)	0.2213 (9)	0.080 (2)
H1A	0.7893	0.5678	0.2875	0.096*
H1B	0.5881	0.6430	0.2652	0.096*
C2	0.6378 (11)	0.3049 (11)	0.3232 (7)	0.082 (2)
H2A	0.5237	0.3535	0.3903	0.099*
H2B	0.7387	0.2700	0.3681	0.099*
C3	0.5931 (11)	0.1552 (9)	0.2897 (7)	0.078 (2)
H3A	0.7043	0.1104	0.2180	0.094*
H3B	0.5624	0.0664	0.3755	0.094*
C4	0.3741 (11)	0.0667 (7)	0.2063 (8)	0.077 (2)
H4A	0.3196	−0.0119	0.2951	0.092*
H4B	0.4851	0.0053	0.1465	0.092*
C5	0.2298 (10)	0.1320 (9)	0.1320 (9)	0.079 (2)
H5A	0.1834	0.0378	0.1166	0.095*
H5B	0.1206	0.1968	0.1901	0.095*
C6	0.1858 (10)	0.3000 (10)	−0.0843 (10)	0.083 (2)
H6A	0.0709	0.3637	−0.0304	0.100*
H6B	0.1466	0.2052	−0.1045	0.100*
Cu1	0.0000	0.5000	0.5000	0.0335 (2)
O1	0.7004 (6)	0.4308 (6)	0.1941 (4)	0.0626 (10)
O2	0.4337 (5)	0.2051 (5)	0.2370 (4)	0.0559 (9)
O3	0.3148 (5)	0.2374 (5)	−0.0014 (5)	0.0613 (10)
O4W	0.3072 (6)	0.6708 (6)	0.0637 (4)	0.0566 (10)
O5W	0.1698 (7)	0.4741 (5)	0.3133 (4)	0.0900 (18)
H5WA	0.2229	0.3756	0.2979	0.108*
H5WB	0.1920	0.5610	0.2455	0.108*
H4WA	0.309 (11)	0.633 (10)	0.011 (8)	0.07 (3)*
H4WB	0.436 (11)	0.688 (9)	0.040 (8)	0.08 (2)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0949 (5)	0.0358 (3)	0.0446 (3)	−0.0137 (3)	0.0039 (3)	−0.0051 (2)
C1	0.085 (5)	0.091 (5)	0.092 (5)	0.007 (4)	−0.054 (4)	−0.043 (4)
C2	0.088 (5)	0.112 (6)	0.044 (3)	0.010 (4)	−0.035 (3)	−0.007 (4)
C3	0.088 (5)	0.066 (4)	0.053 (4)	0.011 (4)	−0.016 (3)	0.011 (3)
C4	0.093 (5)	0.037 (3)	0.066 (4)	−0.015 (3)	0.016 (4)	−0.006 (3)
C5	0.066 (4)	0.059 (4)	0.095 (5)	−0.033 (3)	0.015 (4)	−0.025 (4)
C6	0.066 (4)	0.084 (5)	0.132 (7)	−0.008 (4)	−0.045 (5)	−0.057 (5)
Cu1	0.0319 (4)	0.0385 (4)	0.0250 (4)	−0.0049 (3)	−0.0047 (3)	−0.0033 (3)
O1	0.068 (2)	0.077 (3)	0.048 (2)	0.000 (2)	−0.023 (2)	−0.022 (2)
O2	0.056 (2)	0.0428 (19)	0.047 (2)	0.0025 (16)	0.0013 (17)	−0.0033 (16)
O3	0.049 (2)	0.060 (2)	0.073 (3)	−0.0165 (18)	−0.0070 (19)	−0.021 (2)
O4W	0.054 (2)	0.074 (3)	0.034 (2)	−0.016 (2)	−0.0026 (17)	−0.0073 (19)
O5W	0.109 (4)	0.054 (2)	0.040 (2)	0.029 (2)	0.026 (2)	0.0074 (18)

Geometric parameters (Å, º) top

Br1—Cu1	2.3687 (5)	C4—H4B	0.9700
C1—O1	1.414 (8)	C5—O3	1.413 (8)
C1—C6ⁱ	1.488 (11)	C5—H5A	0.9700
C1—H1A	0.9700	C5—H5B	0.9700
C1—H1B	0.9700	C6—O3	1.429 (8)
C2—O1	1.438 (8)	C6—C1ⁱ	1.488 (11)
C2—C3	1.476 (11)	C6—H6A	0.9700
C2—H2A	0.9700	C6—H6B	0.9700
C2—H2B	0.9700	Cu1—O5Wⁱⁱ	1.911 (4)
C3—O2	1.414 (8)	Cu1—O5W	1.911 (4)
C3—H3A	0.9700	Cu1—Br1ⁱⁱ	2.3687 (5)
C3—H3B	0.9700	O4W—H4WA	0.68 (7)
C4—O2	1.432 (8)	O4W—H4WB	0.93 (8)
C4—C5	1.463 (11)	O5W—H5WA	0.8500
C4—H4A	0.9700	O5W—H5WB	0.8500

O1—C1—C6ⁱ	109.7 (6)	O3—C5—H5A	109.9
O1—C1—H1A	109.7	C4—C5—H5A	109.9
C6ⁱ—C1—H1A	109.7	O3—C5—H5B	109.9
O1—C1—H1B	109.7	C4—C5—H5B	109.9
C6ⁱ—C1—H1B	109.7	H5A—C5—H5B	108.3
H1A—C1—H1B	108.2	O3—C6—C1ⁱ	109.5 (5)
O1—C2—C3	110.2 (5)	O3—C6—H6A	109.8
O1—C2—H2A	109.6	C1ⁱ—C6—H6A	109.8
C3—C2—H2A	109.6	O3—C6—H6B	109.8
O1—C2—H2B	109.6	C1ⁱ—C6—H6B	109.8
C3—C2—H2B	109.6	H6A—C6—H6B	108.2
H2A—C2—H2B	108.1	O5Wⁱⁱ—Cu1—O5W	180.000 (1)
O2—C3—C2	108.9 (5)	O5Wⁱⁱ—Cu1—Br1ⁱⁱ	89.03 (12)
O2—C3—H3A	109.9	O5W—Cu1—Br1ⁱⁱ	90.97 (12)
C2—C3—H3A	109.9	O5Wⁱⁱ—Cu1—Br1	90.97 (12)
O2—C3—H3B	109.9	O5W—Cu1—Br1	89.03 (12)
C2—C3—H3B	109.9	Br1ⁱⁱ—Cu1—Br1	180.0
H3A—C3—H3B	108.3	C1—O1—C2	112.9 (6)
O2—C4—C5	109.9 (5)	C3—O2—C4	113.2 (5)
O2—C4—H4A	109.7	C5—O3—C6	112.7 (5)
C5—C4—H4A	109.7	H4WA—O4W—H4WB	103 (8)
O2—C4—H4B	109.7	Cu1—O5W—H5WA	120.0
C5—C4—H4B	109.7	Cu1—O5W—H5WB	120.0
H4A—C4—H4B	108.2	H5WA—O5W—H5WB	120.0
O3—C5—C4	109.1 (5)

O1—C2—C3—O2	−64.8 (7)	C2—C3—O2—C4	−177.8 (5)
O2—C4—C5—O3	63.1 (7)	C5—C4—O2—C3	−171.2 (5)
C6ⁱ—C1—O1—C2	169.8 (6)	C4—C5—O3—C6	177.1 (5)
C3—C2—O1—C1	170.5 (6)	C1ⁱ—C6—O3—C5	178.9 (5)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4W—H4WA···O1ⁱ	0.68 (7)	2.30 (8)	2.962 (6)	167 (9)
O4W—H4WB···O3ⁱ	0.93 (8)	1.95 (8)	2.869 (6)	170 (6)
O5W—H5WA···O2	0.85	1.92	2.715 (5)	156
O5W—H5WB···O4W	0.85	1.82	2.609 (6)	155

Symmetry code: (i) −x+1, −y+1, −z.

Experimental details

Crystal data
Chemical formula	[CuBr₂(H₂O)₂]·C₁₂H₂₄O₆·2H₂O
M_r	559.73
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	7.4418 (5), 8.1724 (6), 10.1510 (2)
α, β, γ (°)	75.220 (3), 69.47 (1), 78.51 (1)
V (Å³)	554.90 (6)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	4.63
Crystal size (mm)	0.20 × 0.20 × 0.20

Data collection
Diffractometer	Rigaku SCXmini diffractometer
Absorption correction	Multi-scan CrystalClear (Rigaku, 2005)
T_min, T_max	0.397, 0.412
No. of measured, independent and observed [I > 2σ(I)] reflections	5746, 2537, 2064
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.155, 1.08
No. of reflections	2537
No. of parameters	123
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.27, −1.55

Computer programs: CrystalClear (Rigaku 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), PRPKAPPA (Ferguson, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4W—H4WA···O1ⁱ	0.68 (7)	2.30 (8)	2.962 (6)	167 (9)
O4W—H4WB···O3ⁱ	0.93 (8)	1.95 (8)	2.869 (6)	170 (6)
O5W—H5WA···O2	0.85	1.92	2.715 (5)	156.0
O5W—H5WB···O4W	0.85	1.82	2.609 (6)	154.5

Symmetry code: (i) −x+1, −y+1, −z.

Acknowledgements

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

References

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