cis-(Acetonitrile-κN)aqua­bis­(2,2′-bipyrimidine-κ2 N 1,N 1′)manganese(II) cis-diaqua­bis­(2,2′-bipyrimidine-κ2 N 1,N 1′)manganese(II) tetrakis(perchlorate) dihydrate

Kwang Ha

doi:10.1107/S1600536811015388

. 2011 May 7;67(Pt 6):m656–m657. doi: 10.1107/S1600536811015388

cis-(Acetonitrile-κN)aquabis(2,2′-bipyrimidine-κ² N ¹,N ^1′)manganese(II) cis-diaquabis(2,2′-bipyrimidine-κ² N ¹,N ^1′)manganese(II) tetrakis(perchlorate) dihydrate

Kwang Ha ^a,^*

PMCID: PMC3120370 PMID: 21754569

Abstract

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—H⋯O and O—H⋯N 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,
a = 12.0386 (5) Å
b = 13.1878 (6) Å
c = 17.5378 (8) Å
α = 111.201 (3)°
β = 104.147 (3)°
γ = 91.419 (2)°
V = 2497.37 (19) Å³
Z = 2
Mo Kα radiation
μ = 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 > 2σ(I)
R _int = 0.052

Refinement

R[F ² > 2σ(F ²)] = 0.082
wR(F ²) = 0.253
S = 1.01
12197 reflections
718 parameters
H-atom parameters constrained
Δρ_max = 1.01 e Å⁻³
Δρ_min = −0.61 e Å⁻³

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 Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811015388/om2423sup1.cif

e-67-0m656-sup1.cif^{(40.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811015388/om2423Isup2.hkl

e-67-0m656-Isup2.hkl^{(596.3KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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)

Open in a new tab

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

Open in a new tab

Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯N6ⁱ	0.84	2.49	3.139 (6)	135
O1—H1A⋯N7ⁱ	0.84	2.15	2.923 (6)	152
O1—H1B⋯O21ⁱ	0.84	1.89	2.695 (7)	160
O2—H2A⋯N15ⁱⁱ	0.84	2.59	3.244 (7)	136
O2—H2A⋯N16ⁱⁱ	0.84	2.25	3.012 (7)	151
O2—H2B⋯O11Aⁱⁱⁱ	0.84	2.01	2.809 (10)	158
O3—H3A⋯O20	0.84	1.79	2.614 (6)	166
O3—H3B⋯O4ⁱⁱⁱ	0.84	2.07	2.861 (6)	157
O20—H20A⋯N2^iv	0.84	2.08	2.903 (7)	168
O20—H20A⋯N3^iv	0.84	2.56	3.066 (7)	120
O20—H20B⋯O6	0.84	2.08	2.871 (7)	157
O21—H21A⋯O12^v	0.84	2.43	3.126 (12)	141
O21—H21B⋯O16A^iv	0.84	2.07	2.904 (13)	172

Open in a new tab

Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) .

Acknowledgments

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).

supplementary crystallographic information

Comment

Mononuclear Mn^II complexes of 2,2'-bipyrimidine (bpym; C₈H₆N₄) ligand, such as [Mn(bpym)₂(H₂O)₂](ClO₄)₂.2H₂O (Hong et al., 1996), [Mn(bpym)₂(H₂O)₂](BF₄)₂.2H₂O (Smith et al., 2001) and [MnBr₂(bpym)₂].CH₃NO₂ (Ha, 2011), have been investigated previously.

The asymmetric unit of the title compound, [Mn(bpym)₂(CH₃CN)(H₂O)][Mn(bpym)₂(H₂O)₂](ClO₄)₄.2H₂O, contains two distinct cationic Mn^II complexes (Fig. 1), four ClO₄ anions and two solvent water molecules. In the two complexes, both the 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 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. The tight N—Mn—N chelating angles (Table 1) contribute the distortion of the octaahedron, which results in non-linear trans axes (<O1—Mn1—N1 = 163.1 (2)°, <N4—Mn1—N8 = 172.3 (2)°, <N5—Mn1—N9 = 165.5 (2)°, <O2—Mn2—N10 = 165.9 (2)°, <O3—Mn2—N14 = 162.0 (2)° and <N13—Mn2—N17 = 161.2 (2)°). The Mn—N(bpym) bond lengths are almost equivalent and slightly longer than the Mn1—N9(CH₃CN) bond (Table 1). On the basis of the Mn—N bonds trans to the N and O atoms, it seems that the N and O atoms have similar trans effects. The dihedral angles between the least-squares planes of the two bpym ligands in the respective complexes are 79.7 (1)° and 70.7 (1)°. In the crystal structure, the complexes, anions and solvent water molecules are linked by intermolecular O—H···O and O—H···N hydrogen bonds (Fig. 2, Table 2). In addition, the complexes display numerous inter- and intramolecular π-π interactions between adjacent pyrimidine rings. The shortest distance between Cg1 (the centroid of ring N14—C30) and Cg2ⁱ (ring N16—C34, symmetry code i: 1 - x, 2 - y, -z) is 3.585 (4) Å, and the dihedral angle between the ring planes is 3.3 (3)°.

Experimental

To a solution of Mn(ClO₄)₂.6H₂O (0.3617 g, 0.999 mmol) in EtOH (20 ml) was added 2,2'-bipyrimidine (0.1586 g, 1.003 mmol) and stirred for 3 h at room temperature. The formed precipitate was separated by filtration, washed with EtOH and dried at 323 K, to give a pale yellow powder (0.2713 g). Crystals suitable for X-ray analysis were obtained by slow evaporation from a CH₃CN solution.