metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890

catena-Poly[[[di­bromidomanganese(II)]-μ-2,2′-bi­pyrimidine-κ4N1,N1′:N3,N3′]dihydrate]

aSchool of Applied Chemical Engineering, The Research Institute of Catalysis, Chonnam National University, Gwangju 500-757, Republic of Korea
*Correspondence e-mail: hakwang@chonnam.ac.kr

(Received 9 November 2011; accepted 21 November 2011; online 30 November 2011)

The asymmetric unit of the title compound, {[MnBr2(C8H6N4)]·2H2O}n, contains one half of a repeat unit of the neutral linear coordination polymer and a solvent water mol­ecule, with the MnII ion on a crystallographic twofold axis. In the polymer, inversion-related MnII ions are bridged by the bis-chelating 2,2′-bipyrimidine (bpym) ligands, thereby forming a chain structure along the c-axis direction, and are six-coordinated in a distorted cis-N4Br2 octa­hedral environment by four N atoms of twofold-related bpym ligands and twofold-related bromide anions. In the crystal, the complex polymers and solvent water mol­ecules are linked by inter­molecular O—H⋯Br and C—H⋯O hydrogen bonds, forming a two-dimensional layered structure extending parallel to the ac plane.

Related literature

For the crystal structure of the chlorido MnII complex polymer [MnCl2(bpym)]n.2nH2O, which is isotypic to the title compound, see: Armentano et al. (2003[Armentano, D., de Munno, G., Guerra, F., Faus, J., Lloret, F. & Julve, M. (2003). Dalton Trans. pp. 4626-4634.]).

[Scheme 1]

Experimental

Crystal data
  • [MnBr2(C8H6N4)]·2H2O

  • Mr = 408.96

  • Monoclinic, C 2/c

  • a = 17.950 (9) Å

  • b = 8.263 (4) Å

  • c = 10.188 (5) Å

  • β = 123.888 (8)°

  • V = 1254.4 (10) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 7.42 mm−1

  • T = 200 K

  • 0.30 × 0.17 × 0.16 mm

Data collection
  • Bruker SMART 1000 CCD diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2000[Bruker (2000). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.668, Tmax = 1.000

  • 4360 measured reflections

  • 1524 independent reflections

  • 1207 reflections with I > 2σ(I)

  • Rint = 0.043

Refinement
  • R[F2 > 2σ(F2)] = 0.033

  • wR(F2) = 0.097

  • S = 1.14

  • 1524 reflections

  • 78 parameters

  • H-atom parameters constrained

  • Δρmax = 0.92 e Å−3

  • Δρmin = −0.76 e Å−3

Table 1
Selected geometric parameters (Å, °)

Mn1—N1 2.300 (3)
Mn1—N2 2.322 (3)
Mn1—Br1 2.6094 (10)
N1—Mn1—N2 71.21 (11)
Br1i—Mn1—Br1 97.93 (5)
Symmetry code: (i) [-x, y, -z+{\script{3\over 2}}].

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
O1—H1A⋯Br1ii 0.84 2.57 3.356 (3) 156
O1—H1B⋯Br1iii 0.84 2.61 3.394 (4) 157
C2—H2⋯O1iv 0.95 2.45 3.364 (5) 161
Symmetry codes: (ii) [-x, y, -z+{\script{1\over 2}}]; (iii) -x, -y+1, -z+1; (iv) [-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1].

Data collection: SMART (Bruker, 2000[Bruker (2000). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2000[Bruker (2000). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]); software used to prepare material for publication: SHELXL97.

Supporting information


Comment top

The title compound, [MnBr2(bpym)]n.2nH2O (bpym = 2,2'-bipyrimidine, C8H6N4), consists of a neutral complex polymer and solvent water molecules. The compound is isomorphous with the chloro analogue [MnCl2(bpym)]n.2nH2O (Armentano et al., 2003).

The asymmetric unit contains one half of a repeat unit of the polymer and a water molecule (Fig. 1). In the polymer, the symmetry related MnII ions are bridged by the bis(chelating) bpym ligands, thereby forming a chain structure along the c axis, and are six-coordinated in a distorted cis-N4Br2 octahedral environment by four N atoms of the two different bpym ligands and two bromide anions. The Br atoms are cis with respect to each other. The main contributions to the distortion are the tight N—Mn—N chelate angle and the Br—Br repelling (<N1—Mn1—N2 = 71.21 (11)° and <Br1—Mn1—Br1a = 97.93 (5)°; symmetry code a: -x, y, 3/2 - z), which result in non-linear trans axes (<N1—Mn1—N1a = 153.49 (16)° and <N2—Mn1—Br1a = 165.13 (7)°). The Mn—N bond lengths are almost equivalent (Table 1). In the crystal structure, the complex polymers and solvent water molecules are linked by intermolecular O—H···Br and C—H···O hydrogen bonds, forming a two-dimensional layer structure extending parallel to ac plane (Fig. 2, Table 2). The chains are stacked along the b axis. The shortest ring centroid-centroid distance is 5.337 (3) Å.

Related literature top

For the crystal structure of the chloro MnII complex polymer [MnCl2(bpym)]n.2nH2O, which is isotypic to the title compound, see: Armentano et al. (2003).

Experimental top

To a solution of MnBr2.4H2O (0.2867 g, 1.000 mmol) in EtOH (30 ml) was added 2,2'-bipyrimidine (0.1584 g, 1.002 mmol) and stirred for 3 h at room temperature. The precipitate was separated by filtration, washed with EtOH and dried at 50 °C, to give a yellow powder (0.3441 g). Crystals suitable for X-ray analysis were obtained by slow evaporation from a methanol solution.

Refinement top

Carbon-bound H atoms were positioned geometrically and allowed to ride on their respective parent atoms [C—H = 0.95 Å and Uiso(H) = 1.2Ueq(C)]. The H atoms of the solvent water molecule were located in a difference Fourier map then allowed to ride on their parent O atom in the final cycles of refinement with O—H = 0.84 Å and Uiso(H) = 1.5 Ueq(O). The highest peak (0.92 e Å-3) and the deepest hole (-0.75 e Å-3) in the difference Fourier map are located 1.26 Å and 0.96 Å from the atoms H1B and Br1, respectively.

Structure description top

The title compound, [MnBr2(bpym)]n.2nH2O (bpym = 2,2'-bipyrimidine, C8H6N4), consists of a neutral complex polymer and solvent water molecules. The compound is isomorphous with the chloro analogue [MnCl2(bpym)]n.2nH2O (Armentano et al., 2003).

The asymmetric unit contains one half of a repeat unit of the polymer and a water molecule (Fig. 1). In the polymer, the symmetry related MnII ions are bridged by the bis(chelating) bpym ligands, thereby forming a chain structure along the c axis, and are six-coordinated in a distorted cis-N4Br2 octahedral environment by four N atoms of the two different bpym ligands and two bromide anions. The Br atoms are cis with respect to each other. The main contributions to the distortion are the tight N—Mn—N chelate angle and the Br—Br repelling (<N1—Mn1—N2 = 71.21 (11)° and <Br1—Mn1—Br1a = 97.93 (5)°; symmetry code a: -x, y, 3/2 - z), which result in non-linear trans axes (<N1—Mn1—N1a = 153.49 (16)° and <N2—Mn1—Br1a = 165.13 (7)°). The Mn—N bond lengths are almost equivalent (Table 1). In the crystal structure, the complex polymers and solvent water molecules are linked by intermolecular O—H···Br and C—H···O hydrogen bonds, forming a two-dimensional layer structure extending parallel to ac plane (Fig. 2, Table 2). The chains are stacked along the b axis. The shortest ring centroid-centroid distance is 5.337 (3) Å.

For the crystal structure of the chloro MnII complex polymer [MnCl2(bpym)]n.2nH2O, which is isotypic to the title compound, see: Armentano et al. (2003).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. A fragment structure of the title compound, with displacement ellipsoids drawn at the 50% probability level for non-H atoms [symmetry codes: (a) -x, y, 3/2 - z, (b) -x, -y, 1 - z, (c) x, -y, -1/2 + z].
[Figure 2] Fig. 2. View of the unit-cell contents of the title compound. Hydrogen-bond interactions are drawn with dashed lines.
catena-Poly[[[dibromidomanganese(II)]-µ-2,2'-bipyrimidine- κ4N1,N1':N3,N3']dihydrate] top
Crystal data top
[MnBr2(C8H6N4)]·2H2OF(000) = 788
Mr = 408.96Dx = 2.165 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 2416 reflections
a = 17.950 (9) Åθ = 2.4–28.3°
b = 8.263 (4) ŵ = 7.42 mm1
c = 10.188 (5) ÅT = 200 K
β = 123.888 (8)°Stick, yellow
V = 1254.4 (10) Å30.30 × 0.17 × 0.16 mm
Z = 4
Data collection top
Bruker SMART 1000 CCD
diffractometer
1524 independent reflections
Radiation source: fine-focus sealed tube1207 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.043
φ and ω scansθmax = 28.3°, θmin = 2.7°
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
h = 2323
Tmin = 0.668, Tmax = 1.000k = 118
4360 measured reflectionsl = 1312
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)] = 0.033Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.097H-atom parameters constrained
S = 1.14 w = 1/[σ2(Fo2) + (0.0395P)2]
where P = (Fo2 + 2Fc2)/3
1524 reflections(Δ/σ)max < 0.001
78 parametersΔρmax = 0.92 e Å3
0 restraintsΔρmin = 0.76 e Å3
Crystal data top
[MnBr2(C8H6N4)]·2H2OV = 1254.4 (10) Å3
Mr = 408.96Z = 4
Monoclinic, C2/cMo Kα radiation
a = 17.950 (9) ŵ = 7.42 mm1
b = 8.263 (4) ÅT = 200 K
c = 10.188 (5) Å0.30 × 0.17 × 0.16 mm
β = 123.888 (8)°
Data collection top
Bruker SMART 1000 CCD
diffractometer
1524 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
1207 reflections with I > 2σ(I)
Tmin = 0.668, Tmax = 1.000Rint = 0.043
4360 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0330 restraints
wR(F2) = 0.097H-atom parameters constrained
S = 1.14Δρmax = 0.92 e Å3
1524 reflectionsΔρmin = 0.76 e Å3
78 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
xyzUiso*/Ueq
Mn10.00000.20755 (10)0.75000.0207 (2)
Br10.11908 (3)0.41487 (5)0.54940 (5)0.03063 (17)
N10.07975 (19)0.1437 (4)0.6421 (3)0.0197 (6)
N20.07926 (19)0.0143 (4)0.5541 (3)0.0200 (6)
C10.1597 (2)0.2064 (5)0.6848 (4)0.0243 (8)
H10.18690.28570.76600.029*
C20.2028 (2)0.1594 (5)0.6146 (4)0.0272 (9)
H20.25980.20250.64780.033*
C30.1606 (2)0.0473 (5)0.5058 (5)0.0254 (8)
H30.18920.01250.55610.030*
C40.0437 (2)0.0356 (4)0.5240 (4)0.0177 (7)
O10.0770 (2)0.2654 (4)0.2093 (4)0.0470 (8)
H1A0.08330.32970.15230.070*
H1B0.07170.33690.26230.070*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mn10.0210 (4)0.0249 (5)0.0165 (4)0.0000.0106 (3)0.000
Br10.0324 (3)0.0312 (3)0.0244 (3)0.00758 (15)0.0134 (2)0.00491 (15)
N10.0224 (15)0.0209 (17)0.0148 (15)0.0028 (12)0.0097 (13)0.0009 (12)
N20.0187 (14)0.0245 (18)0.0166 (15)0.0033 (12)0.0097 (13)0.0003 (12)
C10.0251 (19)0.027 (2)0.0189 (19)0.0074 (15)0.0110 (16)0.0016 (14)
C20.0195 (18)0.039 (3)0.025 (2)0.0068 (16)0.0131 (17)0.0006 (17)
C30.0231 (19)0.032 (2)0.022 (2)0.0018 (16)0.0130 (17)0.0006 (16)
C40.0180 (17)0.0193 (19)0.0172 (17)0.0038 (13)0.0107 (15)0.0028 (13)
O10.058 (2)0.045 (2)0.041 (2)0.0146 (16)0.0301 (18)0.0070 (15)
Geometric parameters (Å, º) top
Mn1—N12.300 (3)C1—C21.371 (5)
Mn1—N1i2.300 (3)C1—H10.9500
Mn1—N22.322 (3)C2—C3ii1.379 (5)
Mn1—N2i2.322 (3)C2—H20.9500
Mn1—Br1i2.6094 (10)C3—C2ii1.379 (5)
Mn1—Br12.6094 (10)C3—H30.9500
N1—C41.340 (5)C4—N2ii1.333 (4)
N1—C11.349 (4)C4—C4ii1.481 (7)
N2—C4ii1.333 (4)O1—H1A0.8400
N2—C31.353 (5)O1—H1B0.8400
N1—Mn1—N1i153.49 (16)C1—N1—Mn1126.2 (2)
N1—Mn1—N271.21 (11)C4ii—N2—C3116.4 (3)
N1i—Mn1—N290.38 (11)C4ii—N2—Mn1117.3 (2)
N1—Mn1—N2i90.38 (11)C3—N2—Mn1126.2 (2)
N1i—Mn1—N2i71.21 (11)N1—C1—C2122.1 (4)
N2—Mn1—N2i93.08 (16)N1—C1—H1119.0
N1—Mn1—Br1i93.93 (8)C2—C1—H1119.0
N1i—Mn1—Br1i103.45 (8)C1—C2—C3ii117.7 (3)
N2—Mn1—Br1i165.13 (7)C1—C2—H2121.2
N2i—Mn1—Br1i86.37 (8)C3ii—C2—H2121.2
N1—Mn1—Br1103.45 (8)N2—C3—C2ii121.5 (3)
N1i—Mn1—Br193.93 (8)N2—C3—H3119.2
N2—Mn1—Br186.37 (8)C2ii—C3—H3119.2
N2i—Mn1—Br1165.13 (7)N2ii—C4—N1126.2 (3)
Br1i—Mn1—Br197.93 (5)N2ii—C4—C4ii116.9 (4)
C4—N1—C1116.1 (3)N1—C4—C4ii116.9 (4)
C4—N1—Mn1117.7 (2)H1A—O1—H1B96.1
N1i—Mn1—N1—C449.5 (3)N1—Mn1—N2—C3177.7 (3)
N2—Mn1—N1—C41.3 (3)N1i—Mn1—N2—C321.8 (3)
N2i—Mn1—N1—C494.4 (3)N2i—Mn1—N2—C393.0 (3)
Br1i—Mn1—N1—C4179.2 (3)Br1i—Mn1—N2—C3179.6 (2)
Br1—Mn1—N1—C480.1 (3)Br1—Mn1—N2—C372.1 (3)
N1i—Mn1—N1—C1131.5 (3)C4—N1—C1—C21.7 (6)
N2—Mn1—N1—C1179.7 (3)Mn1—N1—C1—C2179.2 (3)
N2i—Mn1—N1—C186.5 (3)N1—C1—C2—C3ii1.7 (6)
Br1i—Mn1—N1—C10.2 (3)C4ii—N2—C3—C2ii1.9 (5)
Br1—Mn1—N1—C199.0 (3)Mn1—N2—C3—C2ii178.5 (3)
N1—Mn1—N2—C4ii1.1 (2)C1—N1—C4—N2ii0.2 (6)
N1i—Mn1—N2—C4ii161.7 (3)Mn1—N1—C4—N2ii179.0 (3)
N2i—Mn1—N2—C4ii90.5 (3)C1—N1—C4—C4ii179.5 (4)
Br1i—Mn1—N2—C4ii3.0 (5)Mn1—N1—C4—C4ii1.3 (5)
Br1—Mn1—N2—C4ii104.4 (3)
Symmetry codes: (i) x, y, z+3/2; (ii) x, y, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···Br1iii0.842.573.356 (3)156
O1—H1B···Br1iv0.842.613.394 (4)157
C2—H2···O1v0.952.453.364 (5)161
Symmetry codes: (iii) x, y, z+1/2; (iv) x, y+1, z+1; (v) x+1/2, y+1/2, z+1.

Experimental details

Crystal data
Chemical formula[MnBr2(C8H6N4)]·2H2O
Mr408.96
Crystal system, space groupMonoclinic, C2/c
Temperature (K)200
a, b, c (Å)17.950 (9), 8.263 (4), 10.188 (5)
β (°) 123.888 (8)
V3)1254.4 (10)
Z4
Radiation typeMo Kα
µ (mm1)7.42
Crystal size (mm)0.30 × 0.17 × 0.16
Data collection
DiffractometerBruker SMART 1000 CCD
Absorption correctionMulti-scan
(SADABS; Bruker, 2000)
Tmin, Tmax0.668, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections
4360, 1524, 1207
Rint0.043
(sin θ/λ)max1)0.668
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.033, 0.097, 1.14
No. of reflections1524
No. of parameters78
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.92, 0.76

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Selected geometric parameters (Å, º) top
Mn1—N12.300 (3)Mn1—Br12.6094 (10)
Mn1—N22.322 (3)
N1—Mn1—N271.21 (11)Br1i—Mn1—Br197.93 (5)
Symmetry code: (i) x, y, z+3/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···Br1ii0.842.573.356 (3)156.4
O1—H1B···Br1iii0.842.613.394 (4)156.7
C2—H2···O1iv0.952.453.364 (5)160.9
Symmetry codes: (ii) x, y, z+1/2; (iii) x, y+1, z+1; (iv) x+1/2, y+1/2, z+1.
 

Acknowledgements

This study was supported financially by Chonnam National University, 2010.

References

First citationArmentano, D., de Munno, G., Guerra, F., Faus, J., Lloret, F. & Julve, M. (2003). Dalton Trans. pp. 4626–4634.  Web of Science CSD CrossRef Google Scholar
First citationBruker (2000). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSpek, A. L. (2009). Acta Cryst. D65, 148–155.  Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds