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

Ha, K.

doi:10.1107/S1600536811049919

metal-organic compounds

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Volume 67| Part 12| December 2011| Page m1848

https://doi.org/10.1107/S1600536811049919

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catena-Poly[[[dibromidomanganese(II)]-μ-2,2′-bipyrimidine-κ⁴N¹,N^1′:N³,N^3′]dihydrate]

Kwang Ha ^a ^*

^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 Mn^II ion on a crystallographic twofold axis. In the polymer, inversion-related Mn^II 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 Mn^II complex polymer [MnCl₂(bpym)]_n.2nH₂O, which is isotypic to the title compound, see: Armentano et al. (2003 ).

Experimental

Crystal data

[MnBr₂(C₈H₆N₄)]·2H₂O
M_r = 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 ) T_min = 0.668, T_max = 1.000
4360 measured reflections
1524 independent reflections
1207 reflections with I > 2σ(I)
R_int = 0.043

Refinement

R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.097
S = 1.14
1524 reflections
78 parameters
H-atom parameters constrained
Δρ_max = 0.92 e Å⁻³
Δρ_min = −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	D⋯A	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⋯O1^iv	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); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; 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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536811049919/pk2362sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811049919/pk2362Isup2.hkl

checkCIF report

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 Mn^II 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—Br1^a = 97.93 (5)°; symmetry code a: -x, y, 3/2 - z), which result in non-linear trans axes (<N1—Mn1—N1^a = 153.49 (16)° and <N2—Mn1—Br1^a = 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 Mn^II 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.

Structure description top

For the crystal structure of the chloro Mn^II 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

	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].
	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,N^1':N³,N^3']dihydrate] top

Crystal data top

[MnBr₂(C₈H₆N₄)]·2H₂O	F(000) = 788
M_r = 408.96	D_x = 2.165 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2416 reflections
a = 17.950 (9) Å	θ = 2.4–28.3°
b = 8.263 (4) Å	µ = 7.42 mm⁻¹
c = 10.188 (5) Å	T = 200 K
β = 123.888 (8)°	Stick, yellow
V = 1254.4 (10) Å³	0.30 × 0.17 × 0.16 mm
Z = 4

Data collection top

Bruker SMART 1000 CCD diffractometer	1524 independent reflections
Radiation source: fine-focus sealed tube	1207 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.043
φ and ω scans	θ_max = 28.3°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −23→23
T_min = 0.668, T_max = 1.000	k = −11→8
4360 measured reflections	l = −13→12

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.097	H-atom parameters constrained
S = 1.14	w = 1/[σ²(F_o²) + (0.0395P)²] where P = (F_o² + 2F_c²)/3
1524 reflections	(Δ/σ)_max < 0.001
78 parameters	Δρ_max = 0.92 e Å⁻³
0 restraints	Δρ_min = −0.76 e Å⁻³

Crystal data top

[MnBr₂(C₈H₆N₄)]·2H₂O	V = 1254.4 (10) Å³
M_r = 408.96	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 17.950 (9) Å	µ = 7.42 mm⁻¹
b = 8.263 (4) Å	T = 200 K
c = 10.188 (5) Å	0.30 × 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)
T_min = 0.668, T_max = 1.000	R_int = 0.043
4360 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	0 restraints
wR(F²) = 0.097	H-atom parameters constrained
S = 1.14	Δρ_max = 0.92 e Å⁻³
1524 reflections	Δρ_min = −0.76 e Å⁻³
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

	x	y	z	U_iso*/U_eq
Mn1	0.0000	0.20755 (10)	0.7500	0.0207 (2)
Br1	−0.11908 (3)	0.41487 (5)	0.54940 (5)	0.03063 (17)
N1	0.07975 (19)	0.1437 (4)	0.6421 (3)	0.0197 (6)
N2	−0.07926 (19)	0.0143 (4)	0.5541 (3)	0.0200 (6)
C1	0.1597 (2)	0.2064 (5)	0.6848 (4)	0.0243 (8)
H1	0.1869	0.2857	0.7660	0.029*
C2	0.2028 (2)	0.1594 (5)	0.6146 (4)	0.0272 (9)
H2	0.2598	0.2025	0.6478	0.033*
C3	−0.1606 (2)	−0.0473 (5)	0.5058 (5)	0.0254 (8)
H3	−0.1892	−0.0125	0.5561	0.030*
C4	0.0437 (2)	0.0356 (4)	0.5240 (4)	0.0177 (7)
O1	0.0770 (2)	0.2654 (4)	0.2093 (4)	0.0470 (8)
H1A	0.0833	0.3297	0.1523	0.070*
H1B	0.0717	0.3369	0.2623	0.070*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn1	0.0210 (4)	0.0249 (5)	0.0165 (4)	0.000	0.0106 (3)	0.000
Br1	0.0324 (3)	0.0312 (3)	0.0244 (3)	0.00758 (15)	0.0134 (2)	0.00491 (15)
N1	0.0224 (15)	0.0209 (17)	0.0148 (15)	−0.0028 (12)	0.0097 (13)	−0.0009 (12)
N2	0.0187 (14)	0.0245 (18)	0.0166 (15)	−0.0033 (12)	0.0097 (13)	−0.0003 (12)
C1	0.0251 (19)	0.027 (2)	0.0189 (19)	−0.0074 (15)	0.0110 (16)	−0.0016 (14)
C2	0.0195 (18)	0.039 (3)	0.025 (2)	−0.0068 (16)	0.0131 (17)	−0.0006 (17)
C3	0.0231 (19)	0.032 (2)	0.022 (2)	−0.0018 (16)	0.0130 (17)	0.0006 (16)
C4	0.0180 (17)	0.0193 (19)	0.0172 (17)	0.0038 (13)	0.0107 (15)	0.0028 (13)
O1	0.058 (2)	0.045 (2)	0.041 (2)	−0.0146 (16)	0.0301 (18)	−0.0070 (15)

Geometric parameters (Å, º) top

Mn1—N1	2.300 (3)	C1—C2	1.371 (5)
Mn1—N1ⁱ	2.300 (3)	C1—H1	0.9500
Mn1—N2	2.322 (3)	C2—C3ⁱⁱ	1.379 (5)
Mn1—N2ⁱ	2.322 (3)	C2—H2	0.9500
Mn1—Br1ⁱ	2.6094 (10)	C3—C2ⁱⁱ	1.379 (5)
Mn1—Br1	2.6094 (10)	C3—H3	0.9500
N1—C4	1.340 (5)	C4—N2ⁱⁱ	1.333 (4)
N1—C1	1.349 (4)	C4—C4ⁱⁱ	1.481 (7)
N2—C4ⁱⁱ	1.333 (4)	O1—H1A	0.8400
N2—C3	1.353 (5)	O1—H1B	0.8400

N1—Mn1—N1ⁱ	153.49 (16)	C1—N1—Mn1	126.2 (2)
N1—Mn1—N2	71.21 (11)	C4ⁱⁱ—N2—C3	116.4 (3)
N1ⁱ—Mn1—N2	90.38 (11)	C4ⁱⁱ—N2—Mn1	117.3 (2)
N1—Mn1—N2ⁱ	90.38 (11)	C3—N2—Mn1	126.2 (2)
N1ⁱ—Mn1—N2ⁱ	71.21 (11)	N1—C1—C2	122.1 (4)
N2—Mn1—N2ⁱ	93.08 (16)	N1—C1—H1	119.0
N1—Mn1—Br1ⁱ	93.93 (8)	C2—C1—H1	119.0
N1ⁱ—Mn1—Br1ⁱ	103.45 (8)	C1—C2—C3ⁱⁱ	117.7 (3)
N2—Mn1—Br1ⁱ	165.13 (7)	C1—C2—H2	121.2
N2ⁱ—Mn1—Br1ⁱ	86.37 (8)	C3ⁱⁱ—C2—H2	121.2
N1—Mn1—Br1	103.45 (8)	N2—C3—C2ⁱⁱ	121.5 (3)
N1ⁱ—Mn1—Br1	93.93 (8)	N2—C3—H3	119.2
N2—Mn1—Br1	86.37 (8)	C2ⁱⁱ—C3—H3	119.2
N2ⁱ—Mn1—Br1	165.13 (7)	N2ⁱⁱ—C4—N1	126.2 (3)
Br1ⁱ—Mn1—Br1	97.93 (5)	N2ⁱⁱ—C4—C4ⁱⁱ	116.9 (4)
C4—N1—C1	116.1 (3)	N1—C4—C4ⁱⁱ	116.9 (4)
C4—N1—Mn1	117.7 (2)	H1A—O1—H1B	96.1

N1ⁱ—Mn1—N1—C4	49.5 (3)	N1—Mn1—N2—C3	−177.7 (3)
N2—Mn1—N1—C4	1.3 (3)	N1ⁱ—Mn1—N2—C3	21.8 (3)
N2ⁱ—Mn1—N1—C4	94.4 (3)	N2ⁱ—Mn1—N2—C3	93.0 (3)
Br1ⁱ—Mn1—N1—C4	−179.2 (3)	Br1ⁱ—Mn1—N2—C3	−179.6 (2)
Br1—Mn1—N1—C4	−80.1 (3)	Br1—Mn1—N2—C3	−72.1 (3)
N1ⁱ—Mn1—N1—C1	−131.5 (3)	C4—N1—C1—C2	−1.7 (6)
N2—Mn1—N1—C1	−179.7 (3)	Mn1—N1—C1—C2	179.2 (3)
N2ⁱ—Mn1—N1—C1	−86.5 (3)	N1—C1—C2—C3ⁱⁱ	1.7 (6)
Br1ⁱ—Mn1—N1—C1	−0.2 (3)	C4ⁱⁱ—N2—C3—C2ⁱⁱ	1.9 (5)
Br1—Mn1—N1—C1	99.0 (3)	Mn1—N2—C3—C2ⁱⁱ	178.5 (3)
N1—Mn1—N2—C4ⁱⁱ	−1.1 (2)	C1—N1—C4—N2ⁱⁱ	−0.2 (6)
N1ⁱ—Mn1—N2—C4ⁱⁱ	−161.7 (3)	Mn1—N1—C4—N2ⁱⁱ	179.0 (3)
N2ⁱ—Mn1—N2—C4ⁱⁱ	−90.5 (3)	C1—N1—C4—C4ⁱⁱ	179.5 (4)
Br1ⁱ—Mn1—N2—C4ⁱⁱ	−3.0 (5)	Mn1—N1—C4—C4ⁱⁱ	−1.3 (5)
Br1—Mn1—N2—C4ⁱⁱ	104.4 (3)

Symmetry codes: (i) −x, y, −z+3/2; (ii) −x, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···Br1ⁱⁱⁱ	0.84	2.57	3.356 (3)	156
O1—H1B···Br1^iv	0.84	2.61	3.394 (4)	157
C2—H2···O1^v	0.95	2.45	3.364 (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
M_r	408.96
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	200
a, b, c (Å)	17.950 (9), 8.263 (4), 10.188 (5)
β (°)	123.888 (8)
V (Å³)	1254.4 (10)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	7.42
Crystal size (mm)	0.30 × 0.17 × 0.16

Data collection
Diffractometer	Bruker SMART 1000 CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.668, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	4360, 1524, 1207
R_int	0.043
(sin θ/λ)_max (Å⁻¹)	0.668

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.097, 1.14
No. of reflections	1524
No. of parameters	78
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	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—N1	2.300 (3)	Mn1—Br1	2.6094 (10)
Mn1—N2	2.322 (3)

N1—Mn1—N2	71.21 (11)	Br1ⁱ—Mn1—Br1	97.93 (5)

Symmetry code: (i) −x, y, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···Br1ⁱⁱ	0.84	2.57	3.356 (3)	156.4
O1—H1B···Br1ⁱⁱⁱ	0.84	2.61	3.394 (4)	156.7
C2—H2···O1^iv	0.95	2.45	3.364 (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

Armentano, 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
Bruker (2000). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar

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