cis-(Acetonitrile-κN)aqua­bis­(2,2′-bipyrimidine-κ2N1,N1′)manganese(II) cis-diaqua­bis­(2,2′-bipyrimidine-κ2N1,N1′)manganese(II) tetrakis(perchlorate) dihydrate

Ha, K.

doi:10.1107/S1600536811015388

Volume 67
Part 6
Pages m656-m657
June 2011

Received 14 April 2011
Accepted 24 April 2011
Online 7 May 2011

Key indicators
Single-crystal X-ray study
T = 200 K
Mean (C-C) = 0.010 Å
Disorder in solvent or counterion
R = 0.082
wR = 0.253
Data-to-parameter ratio = 17.0
Details

cis-(Acetonitrile-N)aquabis(2,2'-bipyrimidine-²N¹,N^1')manganese(II) cis-diaquabis(2,2'-bipyrimidine-²N¹,N^1')manganese(II) tetrakis(perchlorate) 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

The asymmetric unit of the title compound, [Mn(CH₃CN)(C₈H₆N₄)₂(H₂O)][Mn(C₈H₆N₄)₂(H₂O)₂](ClO₄)₄·2H₂O, contains two distinct cationic Mn^II complexes, four perchlorate anions and two solvent water molecules. In the two complexes, both Mn^II ions are six-coordinated in a distorted octahedral environment, but one Mn ion has a cis-N₅O coordination geometry defined by four N atoms of the two chelating 2,2'-bipyrimidine (bpym) ligands, one N atom of a coordinating acetonitrile molecule and one O atom of a water ligand, whereas the other Mn ion has a cis-N₄O₂ coordination geometry defined by four N atoms of the two bpym ligands and two O atoms of water ligands. In the crystal structure, the complex molecules, anions and solvent water molecules are linked by intermolecular O-HO and O-HN hydrogen bonds. Three of the four perchlorate anions are disordered over two sets of sites in different ratios.

Related literature

For the crystal structures of mononuclear 2,2'-bipyrimidine Mn(II) complexes, see: Hong et al. (1996); Smith et al. (2001); Ha (2011).

Experimental

Crystal data

[Mn(C₂H₃N)(C₈H₆N₄)₂(H₂O)][Mn(C₈H₆N₄)₂(H₂O)₂](ClO₄)₄·2H₂O
M_r = 1271.49
Triclinic, $[P \overline 1]$
a = 12.0386 (5) Å
b = 13.1878 (6) Å
c = 17.5378 (8) Å
= 111.201 (3)°
= 104.147 (3)°
= 91.419 (2)°
V = 2497.37 (19) Å³
Z = 2
Mo K radiation
= 0.82 mm^-1
T = 200 K
0.24 × 0.21 × 0.13 mm

Data collection

Bruker SMART 1000 CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000) T_min = 0.765, T_max = 0.899
18759 measured reflections
12197 independent reflections
5402 reflections with I > 2(I)
R_int = 0.052

Refinement

R[F² > 2(F²)] = 0.082
wR(F²) = 0.253
S = 1.01
12197 reflections
718 parameters
H-atom parameters constrained
_max = 1.01 e Å^-3
_min = -0.61 e Å^-3

Table 1
Selected geometric parameters (Å, °)

Mn1-N9	2.170 (6)
Mn1-O1	2.182 (4)
Mn1-N4	2.236 (4)
Mn1-N8	2.254 (5)
Mn1-N1	2.259 (5)
Mn1-N5	2.271 (5)
Mn2-O3	2.107 (4)
Mn2-O2	2.174 (4)
Mn2-N13	2.238 (5)
Mn2-N10	2.267 (5)
Mn2-N14	2.269 (5)
Mn2-N17	2.272 (5)

N4-Mn1-N1	73.12 (18)
N8-Mn1-N5	73.27 (18)
N13-Mn2-N10	72.99 (19)
N14-Mn2-N17	72.26 (18)

Table 2
Hydrogen-bond geometry (Å, °)

D-HA	D-H	HA	DA	D-HA
O1-H1AN6ⁱ	0.84	2.49	3.139 (6)	135
O1-H1AN7ⁱ	0.84	2.15	2.923 (6)	152
O1-H1BO21ⁱ	0.84	1.89	2.695 (7)	160
O2-H2AN15ⁱⁱ	0.84	2.59	3.244 (7)	136
O2-H2AN16ⁱⁱ	0.84	2.25	3.012 (7)	151
O2-H2BO11Aⁱⁱⁱ	0.84	2.01	2.809 (10)	158
O3-H3AO20	0.84	1.79	2.614 (6)	166
O3-H3BO4ⁱⁱⁱ	0.84	2.07	2.861 (6)	157
O20-H20AN2^iv	0.84	2.08	2.903 (7)	168
O20-H20AN3^iv	0.84	2.56	3.066 (7)	120
O20-H20BO6	0.84	2.08	2.871 (7)	157
O21-H21AO12^v	0.84	2.43	3.126 (12)	141
O21-H21BO16A^iv	0.84	2.07	2.904 (13)	172
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) -x+1, -y+2, -z; (iii) -x+1, -y+1, -z; (iv) x+1, y, z; (v) -x+1, -y, -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: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97.

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: OM2423 ).

Acknowledgements

This work was supported by the Priority Research Centers Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (2010-0029626).

References

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Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.
Ha, K. (2011). Acta Cryst. E67, m474.
Hong, D. M., Wei, H. H., Gan, L. L., Lee, G. H. & Wang, Y. (1996). Polyhedron, 15, 2335-2340.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.
Smith, J. A., Galán-Mascarós, J.-R., Clérac, R., Sun, J.-S., Ouyang, X. & Dunbar, K. R. (2001). Polyhedron, 20, 1727-1734.
Spek, A. L. (2009). Acta Cryst. D65, 148-155.