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Di­aqua(1,4,7,10,14-penta­oxa­cyclo­penta­decane)­manganese(II) dibromide, [Mn(C10H20O5)(H2O)2]Br2, prepared in a search for emissive MnII ions in unusual coordination environments, contains the metal ion encircled by the crown ether ligand, with the water mol­ecules in trans axial positions. Hydro­gen bonding between these and the Br- counter-ions forms chains of cations running approximately parallel to a.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536800018110/na6008sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536800018110/na6008Isup2.hkl
Contains datablock I

CCDC reference: 155831

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.004 Å
  • R factor = 0.024
  • wR factor = 0.086
  • Data-to-parameter ratio = 14.8

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry




Comment top

Compounds of Mn2+ and 15-crown-5 were prepared in search of crystals with emissive MnII ions in environments other than tetrahedral or octahedral geometries (Reid et al., 1998, 1999). In one of these, [Mn(H2O)2(15-crown-5)]Br2, (I), the cation was found to have crystallographically imposed twofold rotation symmetry, with the axis passing through O1, Mn and the midpoint of the C5—C5A bond. The cations are arranged in chains approximately parallel to a and held together by hydrogen bonding between the water molecules and the Br- ions.

Experimental top

MnBr2·4H2O (1 mmol) and a slight excess of 15-crown-5 were dissolved in 40 ml of methanol. Vapor diffusion of diethyl ether into this solution at 293 K afforded pale brown columnar crystals of the title compound in 86% yield. Analysis calculated for C10H24Br2MnO7: C 25.5, H 5.1, Br 33.9%; found: C 25.3, H 5.1, Br 33.8%.

Computing details top

Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: PROCESS in MolEN (Fair, 1990); program(s) used to solve structure: SIR (Burla et al., 1989); program(s) used to refine structure: LSFM in MolEN (Fair, 1990); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The hydrogen-bonded cation–anion chain.
Diaqua(1,4,7,10,14-pentaoxacyclopentadecane)manganese(II) dibromide top
Crystal data top
[Mn(C10H20O5)(H2O)2]Br2F(000) = 940
Mr = 471.05Dx = 1.87 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
a = 13.687 (2) ÅCell parameters from 25 reflections
b = 15.856 (1) Åθ = 13–17°
c = 7.7761 (9) ŵ = 5.60 mm1
β = 97.936 (9)°T = 293 K
V = 1671.4 (5) Å3Column, pale brown
Z = 40.50 × 0.40 × 0.30 mm
Data collection top
Enraf-Nonius CAD-4
diffractometer
Rint = 0.018
θ/2θ scansθmax = 26.0°, θmin = 2.0°
Absorption correction: empirical (using intensity measurements)
via ψ scan (North et al., 1968)
h = 016
Tmin = 0.084, Tmax = 0.196k = 019
1780 measured reflectionsl = 99
1644 independent reflections3 standard reflections every 120 min
1362 reflections with I > 2σ(I) intensity decay: <1%
Refinement top
Refinement on FPrimary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.024Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.086H-atom parameters not refined
S = 1.28 w = 4Fo2/[σ2(Fo2) + 0.0016Fo4]
1362 reflections(Δ/σ)max = 0.004
92 parametersΔρmax = 0.25 e Å3
24 restraintsΔρmin = 0.58 e Å3
Crystal data top
[Mn(C10H20O5)(H2O)2]Br2V = 1671.4 (5) Å3
Mr = 471.05Z = 4
Monoclinic, C2/cMo Kα radiation
a = 13.687 (2) ŵ = 5.60 mm1
b = 15.856 (1) ÅT = 293 K
c = 7.7761 (9) Å0.50 × 0.40 × 0.30 mm
β = 97.936 (9)°
Data collection top
Enraf-Nonius CAD-4
diffractometer
1362 reflections with I > 2σ(I)
Absorption correction: empirical (using intensity measurements)
via ψ scan (North et al., 1968)
Rint = 0.018
Tmin = 0.084, Tmax = 0.1963 standard reflections every 120 min
1780 measured reflections intensity decay: <1%
1644 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.02424 restraints
wR(F2) = 0.086H-atom parameters not refined
S = 1.28Δρmax = 0.25 e Å3
1362 reflectionsΔρmin = 0.58 e Å3
92 parameters
Special details top

Experimental. A pale brown columnar crystal was cut to size and mounted on a thin glass fiber with a coat of epoxy cement. General procedures for crystal orientation, unit cell determination and refinement and data collection have been published (Mague & Lloyd, 1988). The C-centered monoclinic cell indicated by the CAD-4 Software was confirmed by the observation of 2/m diffraction symmetry and the appropriate systematic absences in a limited sample of reciprocal space. Additional systematic absences indicated the space group to be either Cc or C2/c. While intensity statistics did not permit a clear choice between these,they tended to favor the latter and this choice was confirmed by the successful refinement. Attempts to refine the structure in Cc resulted in the persistence of substantial shifts in the positional parameters of those atoms related by symmetry in C2/c, again supporting the original choice.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Br0.26553 (2)0.09483 (2)0.50218 (4)0.04203 (8)
Mn0.50000.26507 (3)0.25000.0272 (1)
O10.50000.1287 (2)0.25000.0434 (8)
O20.3859 (1)0.2188 (1)0.0276 (2)0.0374 (5)
O30.4474 (1)0.3788 (1)0.0911 (2)0.0369 (5)
O40.3878 (1)0.2616 (1)0.4169 (3)0.0440 (5)
C10.4321 (2)0.0836 (2)0.1266 (4)0.0459 (8)
C20.4136 (2)0.1368 (2)0.0301 (4)0.0486 (8)
C30.3658 (2)0.2811 (2)0.1066 (4)0.0512 (9)
C40.3558 (2)0.3635 (2)0.0171 (4)0.0486 (8)
C50.4511 (2)0.4539 (2)0.1945 (4)0.0415 (7)
H1w0.35120.30460.43890.0527*
H2w0.35260.21520.42960.0527*
H1a0.37220.07380.17240.0551*
H1b0.45980.03110.09940.0551*
H2a0.47160.14100.08400.0583*
H2b0.36180.11370.11000.0583*
H3a0.30640.26790.17980.0615*
H3b0.41860.28370.17390.0615*
H4a0.34270.40740.10030.0583*
H4b0.30360.36050.05160.0583*
H5a0.44290.50560.12000.0497*
H5b0.39190.45650.26050.0497*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br0.0430 (1)0.0393 (2)0.0443 (2)0.0015 (1)0.0077 (1)0.0032 (1)
Mn0.0248 (2)0.0331 (2)0.0225 (3)0.00000.0003 (2)0.0000
O10.045 (2)0.034 (1)0.047 (2)0.00000.007 (1)0.0000
O20.0374 (9)0.049 (1)0.0245 (9)0.0010 (9)0.0012 (8)0.0048 (8)
O30.0320 (9)0.044 (1)0.033 (1)0.0042 (8)0.0003 (8)0.0021 (8)
O40.041 (1)0.043 (1)0.051 (1)0.0033 (8)0.0213 (9)0.0054 (9)
C10.047 (2)0.039 (1)0.054 (2)0.008 (1)0.010 (1)0.018 (1)
C20.045 (2)0.061 (2)0.039 (2)0.002 (1)0.004 (1)0.019 (1)
C30.047 (2)0.074 (2)0.029 (2)0.003 (2)0.008 (1)0.007 (2)
C40.036 (1)0.062 (2)0.043 (2)0.003 (1)0.010 (1)0.019 (1)
C50.049 (1)0.035 (1)0.043 (1)0.007 (1)0.015 (1)0.004 (1)
Geometric parameters (Å, º) top
Mn—O12.162 (3)O2—C31.436 (4)
Mn—O32.247 (2)O3—C41.431 (4)
Mn—O42.144 (2)O3—C51.434 (3)
O1—C11.432 (3)C1—C21.476 (5)
O2—C21.443 (4)C3—C41.495 (5)
O1—Mn—O3143.34 (5)Mn—O3—C5111.9 (2)
O1—Mn—O488.53 (5)C4—O3—C5115.5 (2)
O3—Mn—O498.71 (8)O1—C1—C2106.8 (3)
Mn—O1—C1120.0 (2)O2—C2—C1106.3 (2)
C2—O2—C3115.2 (3)O2—C3—C4106.5 (3)
Mn—O3—C4112.1 (2)O3—C4—C3107.0 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O4—H1w···Bri0.882.353.216 (2)172
O4—H2w···Br0.892.363.246 (2)173
Symmetry code: (i) x+1/2, y+1/2, z+1.

Experimental details

Crystal data
Chemical formula[Mn(C10H20O5)(H2O)2]Br2
Mr471.05
Crystal system, space groupMonoclinic, C2/c
Temperature (K)293
a, b, c (Å)13.687 (2), 15.856 (1), 7.7761 (9)
β (°) 97.936 (9)
V3)1671.4 (5)
Z4
Radiation typeMo Kα
µ (mm1)5.60
Crystal size (mm)0.50 × 0.40 × 0.30
Data collection
DiffractometerEnraf-Nonius CAD-4
diffractometer
Absorption correctionEmpirical (using intensity measurements)
via ψ scan (North et al., 1968)
Tmin, Tmax0.084, 0.196
No. of measured, independent and
observed [I > 2σ(I)] reflections
1780, 1644, 1362
Rint0.018
(sin θ/λ)max1)0.616
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.024, 0.086, 1.28
No. of reflections1362
No. of parameters92
No. of restraints24
H-atom treatmentH-atom parameters not refined
Δρmax, Δρmin (e Å3)0.25, 0.58

Computer programs: CAD-4 Software (Enraf-Nonius, 1989), CAD-4 Software, PROCESS in MolEN (Fair, 1990), SIR (Burla et al., 1989), LSFM in MolEN (Fair, 1990), SHELXTL (Bruker, 1997), SHELXTL.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O4—H1w···Bri0.882.353.216 (2)172
O4—H2w···Br0.892.363.246 (2)173
Symmetry code: (i) x+1/2, y+1/2, z+1.
 

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