Bis[2,6-bis-(4,5-dihydro-1H-imidazol-2-yl)pyridine]manganese(II) bis-(per-chlorate) acetonitrile solvate.

In the cation of the title compound, [Mn(C(11)H(13)N(5))(2)](ClO(4))(2)·CH(3)CN, the metal atom is located on a twofold rotation axis and is six-coordinated by six N atoms from two different 2,6-bis-(4,5-dihydro-1H-imidazol-2-yl)pyridine (bip) ligands in a distorted octahedral geometry. The O atoms of the perchlorate anions are disordered with occupancies in the ratio 0.593 (10):0.407 (10). In the crystal, mol-ecules are stabilized by two N-H⋯O hydrogen bonds, forming zigzag chains along the a axis, which are further inter-connected by N-H⋯O hydrogen bonds and π-π inter-actions [centroid-centroid distance = 3.50 (1) Å] into a three-dimensional network.

Related literature

For the network topologies and potential applications of supra­molecular architectures, see: Yaghi et al. (1998 ▶); Hagrman et al. (1999 ▶). The protonation and deprotonation of an imidazole ligand is believed to play an important role in the mechanism of the coordination chemistry, see: Bordo et al. (2001 ▶). Our studies of such complexes involving an n class="Chemical">imidazole ligand indicate that hydrogen bonding involving this group influences the geometry around the metal atom and the crystallization mechanism, see: Ren et al. (2007 ▶, 2009 ▶); Ren, Ye, He et al. (2004 ▶); Ren, Ye, Zhu et al. (2004 ▶). For metal–imidazole bond lengths, see: Stupka et al. (2004 ▶); Hammes et al. (2005 ▶); Haga et al. (1996 ▶); Böca et al. (2005 ▶). For metal–imidazole bond lengths, see: Ren et al. (2009 ▶). For the synthesis of 2,6-bis­(4,5-dihydro-1H-imidazol-2-yl)pyridine, see: Baker et al. (1991 ▶).

Experimental

Crystal data

[Mn(C11H13N5)2](ClO4)2·C2H3N

M = 725.42

Monoclinic,

a = 20.521 (5) Å

b = 12.732 (5) Å

c = 14.602 (6) Å

β = 123.893 (10)°

V = 3167.0 (19) Å3

Z = 4

Mo Kα radiation

μ = 0.65 mm−1

T = 273 K

0.28 × 0.21 × 0.14 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 1998 ▶) T min = 0.837, T max = 0.912

7799 measured reflections

2821 independent reflections

1277 reflections with I > 2σ(I)

R int = 0.056

Refinement

R[F 2 > 2σ(F 2)] = 0.047

wR(F 2) = 0.121

S = 0.79

2821 reflections

246 parameters

94 restraints

H-atom parameters constrained

Δρmax = 0.33 e Å−3

Δρmin = −0.27 e Å−3

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT-Plus (Bruker, 1998 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809029195/tk2501sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809029195/tk2501Isup2.hkl

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

[Mn(C11H13N5)2](ClO4)2·C2H3N	F(000) = 1492
Mr = 725.42	Dx = 1.521 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 20.521 (5) Å	Cell parameters from 668 reflections
b = 12.732 (5) Å	θ = 2.0–25.1°
c = 14.602 (6) Å	µ = 0.65 mm−1
β = 123.893 (10)°	T = 273 K
V = 3167.0 (19) Å3	Block, yellow
Z = 4	0.28 × 0.21 × 0.14 mm

Bruker SMART CCD area-detector diffractometer	2821 independent reflections
Radiation source: fine-focus sealed tube	1277 reflections with I > 2σ(I)
graphite	Rint = 0.056
φ and ω scans	θmax = 25.1°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −22→24
Tmin = 0.837, Tmax = 0.912	k = −11→15
7799 measured reflections	l = −16→17

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.121	H-atom parameters constrained
S = 0.79	w = 1/[σ2(Fo2) + (0.0647P)2] where P = (Fo2 + 2Fc2)/3
2821 reflections	(Δ/σ)max = 0.001
246 parameters	Δρmax = 0.33 e Å−3
94 restraints	Δρmin = −0.27 e Å−3

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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
Mn1	0.5000	0.94417 (7)	0.7500	0.0488 (3)
N1	0.51856 (17)	0.8931 (3)	0.9132 (2)	0.0468 (8)
N2	0.59227 (18)	1.0487 (2)	0.8898 (2)	0.0539 (8)
N3	0.6779 (2)	1.0731 (3)	1.0725 (3)	0.0708 (10)
H3A	0.6979	1.0635	1.1416	0.085*
N4	0.40797 (17)	0.8262 (2)	0.7177 (2)	0.0524 (8)
N5	0.3602 (2)	0.7083 (3)	0.7785 (3)	0.0833 (12)
H5A	0.3581	0.6730	0.8271	0.100*
C1	0.6436 (2)	1.1375 (4)	0.9029 (3)	0.0746 (13)
H1A	0.6130	1.2013	0.8721	0.090*
H1B	0.6693	1.1225	0.8652	0.090*
C2	0.7041 (3)	1.1503 (4)	1.0259 (3)	0.0785 (14)
H2A	0.7566	1.1347	1.0453	0.094*
H2B	0.7032	1.2208	1.0504	0.094*
C3	0.6168 (2)	1.0191 (3)	0.9886 (3)	0.0509 (10)
C4	0.5788 (2)	0.9317 (3)	1.0073 (3)	0.0450 (9)
C5	0.6011 (2)	0.8891 (3)	1.1076 (3)	0.0630 (12)
H5	0.6430	0.9169	1.1733	0.076*
C6	0.5594 (3)	0.8037 (4)	1.1076 (3)	0.0757 (14)
H6	0.5736	0.7730	1.1741	0.091*
C7	0.4970 (2)	0.7637 (4)	1.0097 (3)	0.0678 (13)
H7	0.4689	0.7062	1.0090	0.081*
C8	0.4778 (2)	0.8114 (3)	0.9136 (3)	0.0506 (10)
C9	0.4140 (2)	0.7806 (3)	0.8007 (3)	0.0525 (11)
C10	0.3053 (3)	0.6981 (4)	0.6593 (3)	0.0818 (14)
H10A	0.2523	0.7166	0.6361	0.098*
H10B	0.3054	0.6279	0.6335	0.098*
N6	0.5000	0.3462 (7)	0.7500	0.186 (4)
C12	0.5000	0.5403 (7)	0.7500	0.178 (5)
H12B	0.5294	0.5712	0.7238	0.214*	0.50
H12A	0.5189	0.5583	0.8247	0.214*	0.50
H12C	0.4453	0.5583	0.7073	0.214*	0.50
C13	0.5000	0.4339 (7)	0.7500	0.116 (3)
C11	0.3378 (2)	0.7797 (3)	0.6178 (3)	0.0664 (12)
H11A	0.3520	0.7454	0.5720	0.080*
H11B	0.2991	0.8334	0.5742	0.080*
Cl1	0.32690 (9)	0.52285 (13)	0.39585 (12)	0.1026 (5)
O1	0.3119 (7)	0.5391 (11)	0.4824 (8)	0.147 (6)	0.407 (10)
O2	0.4047 (4)	0.4898 (11)	0.4424 (8)	0.152 (7)	0.407 (10)
O3	0.2745 (6)	0.4409 (11)	0.3284 (13)	0.209 (9)	0.407 (10)
O4	0.3090 (11)	0.6156 (10)	0.3332 (15)	0.264 (11)	0.407 (10)
O1'	0.3558 (5)	0.6031 (6)	0.4718 (7)	0.151 (5)	0.593 (10)
O2'	0.3455 (6)	0.4194 (5)	0.4361 (7)	0.139 (5)	0.593 (10)
O3'	0.2464 (3)	0.5354 (7)	0.3137 (5)	0.139 (4)	0.593 (10)
O4'	0.3628 (7)	0.5401 (8)	0.3310 (10)	0.217 (7)	0.593 (10)

	U11	U22	U33	U12	U13	U23
Mn1	0.0517 (6)	0.0556 (6)	0.0338 (5)	0.000	0.0205 (4)	0.000
N1	0.047 (2)	0.054 (2)	0.0324 (18)	−0.0002 (17)	0.0180 (17)	−0.0028 (15)
N2	0.059 (2)	0.058 (2)	0.0378 (19)	−0.0088 (18)	0.0229 (16)	0.0011 (16)
N3	0.074 (2)	0.084 (3)	0.0357 (19)	−0.030 (2)	0.0196 (19)	−0.0089 (19)
N4	0.051 (2)	0.059 (2)	0.0362 (18)	−0.0072 (17)	0.0177 (17)	−0.0039 (16)
N5	0.091 (3)	0.093 (3)	0.046 (2)	−0.046 (3)	0.027 (2)	−0.007 (2)
C1	0.088 (3)	0.072 (3)	0.054 (3)	−0.023 (3)	0.034 (3)	−0.004 (2)
C2	0.081 (3)	0.091 (4)	0.053 (3)	−0.030 (3)	0.032 (3)	−0.009 (2)
C3	0.049 (3)	0.055 (3)	0.042 (2)	−0.002 (2)	0.022 (2)	−0.004 (2)
C4	0.047 (2)	0.051 (3)	0.034 (2)	0.000 (2)	0.020 (2)	−0.002 (2)
C5	0.065 (3)	0.076 (3)	0.035 (2)	−0.010 (3)	0.019 (2)	−0.003 (2)
C6	0.093 (4)	0.089 (4)	0.039 (3)	−0.014 (3)	0.033 (3)	0.008 (2)
C7	0.080 (3)	0.076 (3)	0.040 (3)	−0.022 (3)	0.029 (2)	−0.001 (2)
C8	0.047 (2)	0.056 (3)	0.043 (2)	−0.005 (2)	0.021 (2)	−0.003 (2)
C9	0.054 (3)	0.055 (3)	0.040 (2)	−0.008 (2)	0.021 (2)	−0.003 (2)
C10	0.081 (3)	0.087 (4)	0.058 (3)	−0.034 (3)	0.027 (3)	−0.015 (3)
N6	0.304 (12)	0.120 (8)	0.196 (9)	0.000	0.179 (9)	0.000
C12	0.163 (10)	0.098 (8)	0.154 (9)	0.000	0.013 (7)	0.000
C13	0.153 (8)	0.094 (8)	0.124 (7)	0.000	0.091 (6)	0.000
C11	0.062 (3)	0.073 (3)	0.044 (2)	−0.018 (2)	0.017 (2)	−0.010 (2)
Cl1	0.0956 (11)	0.0967 (12)	0.0876 (10)	0.0154 (9)	0.0339 (9)	−0.0296 (9)
O1	0.165 (12)	0.155 (13)	0.094 (7)	0.048 (10)	0.056 (8)	−0.039 (7)
O2	0.077 (6)	0.243 (16)	0.111 (10)	0.016 (7)	0.038 (6)	−0.023 (10)
O3	0.105 (9)	0.242 (16)	0.247 (18)	−0.054 (11)	0.079 (11)	−0.189 (15)
O4	0.31 (3)	0.224 (15)	0.27 (2)	0.084 (15)	0.17 (2)	0.105 (15)
O1'	0.134 (7)	0.129 (7)	0.109 (6)	0.003 (5)	0.017 (5)	−0.077 (6)
O2'	0.211 (13)	0.103 (5)	0.137 (7)	0.059 (7)	0.118 (8)	0.025 (5)
O3'	0.110 (5)	0.159 (9)	0.065 (4)	−0.011 (5)	−0.004 (4)	−0.018 (4)
O4'	0.320 (15)	0.167 (10)	0.300 (16)	−0.050 (10)	0.256 (16)	−0.056 (9)

Mn1—N4	2.247 (3)	C5—C6	1.384 (5)
Mn1—N4i	2.247 (3)	C5—H5	0.9300
Mn1—N2	2.283 (3)	C6—C7	1.378 (5)
Mn1—N2i	2.283 (3)	C6—H6	0.9300
Mn1—N1	2.287 (3)	C7—C8	1.370 (5)
Mn1—N1i	2.287 (3)	C7—H7	0.9300
N1—C4	1.328 (4)	C8—C9	1.476 (5)
N1—C8	1.337 (4)	C10—C11	1.530 (5)
N2—C3	1.292 (4)	C10—H10A	0.9700
N2—C1	1.484 (5)	C10—H10B	0.9700
N3—C3	1.354 (5)	N6—C13	1.117 (10)
N3—C2	1.458 (5)	C12—C13	1.3547
N3—H3A	0.8600	C12—H12B	0.9600
N4—C9	1.287 (4)	C12—H12A	0.9600
N4—C11	1.486 (4)	C12—H12C	0.9600
N5—C9	1.332 (4)	C11—H11A	0.9700
N5—C10	1.459 (5)	C11—H11B	0.9700
N5—H5A	0.8600	Cl1—O1'	1.376 (5)
C1—C2	1.519 (5)	Cl1—O2'	1.406 (5)
C1—H1A	0.9700	Cl1—O2	1.407 (6)
C1—H1B	0.9700	Cl1—O3'	1.409 (5)
C2—H2A	0.9700	Cl1—O4	1.411 (7)
C2—H2B	0.9700	Cl1—O3	1.426 (7)
C3—C4	1.468 (5)	Cl1—O1	1.474 (7)
C4—C5	1.379 (5)	Cl1—O4'	1.505 (6)
N4—Mn1—N4i	96.14 (16)	C8—C7—H7	121.0
N4—Mn1—N2	139.28 (11)	C6—C7—H7	121.0
N4i—Mn1—N2	91.20 (11)	N1—C8—C7	121.8 (4)
N4—Mn1—N2i	91.20 (11)	N1—C8—C9	111.6 (3)
N4i—Mn1—N2i	139.28 (11)	C7—C8—C9	126.6 (4)
N2—Mn1—N2i	108.70 (16)	N4—C9—N5	116.9 (3)
N4—Mn1—N1	70.18 (11)	N4—C9—C8	119.4 (4)
N4i—Mn1—N1	87.66 (10)	N5—C9—C8	123.7 (4)
N2—Mn1—N1	70.18 (12)	N5—C10—C11	101.3 (3)
N2i—Mn1—N1	132.10 (10)	N5—C10—H10A	111.3
N4—Mn1—N1i	87.66 (10)	C11—C10—H10A	110.3
N4i—Mn1—N1i	70.18 (11)	N5—C10—H10B	112.2
N2—Mn1—N1i	132.10 (11)	C11—C10—H10B	112.1
N2i—Mn1—N1i	70.18 (11)	H10A—C10—H10B	109.4
N1—Mn1—N1i	146.97 (17)	C13—C12—H12B	114.2
C4—N1—C8	120.4 (3)	C13—C12—H12A	103.9
C4—N1—Mn1	119.4 (2)	H12B—C12—H12A	114.2
C8—N1—Mn1	119.0 (2)	C13—C12—H12C	103.9
C3—N2—C1	105.8 (3)	H12B—C12—H12C	114.2
C3—N2—Mn1	116.2 (3)	H12A—C12—H12C	105.4
C1—N2—Mn1	137.3 (2)	N6—C13—C12	180.000 (6)
C3—N3—C2	108.5 (3)	N4—C11—C10	106.3 (3)
C3—N3—H3A	125.7	N4—C11—H11A	110.9
C2—N3—H3A	125.7	C10—C11—H11A	109.5
C9—N4—C11	106.0 (3)	N4—C11—H11B	110.7
C9—N4—Mn1	118.4 (3)	C10—C11—H11B	111.2
C11—N4—Mn1	135.5 (2)	H11A—C11—H11B	108.3
C9—N5—C10	109.6 (3)	O1'—Cl1—O2'	117.7 (5)
C9—N5—H5A	125.2	O1'—Cl1—O2	88.3 (5)
C10—N5—H5A	125.2	O2'—Cl1—O2	63.0 (5)
N2—C1—C2	106.7 (3)	O1'—Cl1—O3'	112.1 (4)
N2—C1—H1A	110.4	O2'—Cl1—O3'	112.2 (5)
C2—C1—H1A	110.4	O2—Cl1—O3'	157.2 (5)
N2—C1—H1B	110.4	O1'—Cl1—O4	74.9 (8)
C2—C1—H1B	110.4	O2'—Cl1—O4	165.2 (8)
H1A—C1—H1B	108.6	O2—Cl1—O4	112.3 (7)
N3—C2—C1	102.0 (3)	O3'—Cl1—O4	66.1 (7)
N3—C2—H2A	111.4	O1'—Cl1—O3	157.0 (5)
C1—C2—H2A	111.4	O2'—Cl1—O3	61.8 (7)
N3—C2—H2B	111.4	O2—Cl1—O3	109.3 (6)
C1—C2—H2B	111.4	O3'—Cl1—O3	54.5 (6)
H2A—C2—H2B	109.2	O4—Cl1—O3	109.9 (7)
N2—C3—N3	116.7 (4)	O1'—Cl1—O1	53.6 (5)
N2—C3—C4	120.8 (3)	O2'—Cl1—O1	84.9 (6)
N3—C3—C4	122.5 (3)	O2—Cl1—O1	110.6 (6)
N1—C4—C5	121.3 (4)	O3'—Cl1—O1	90.5 (5)
N1—C4—C3	111.9 (3)	O4—Cl1—O1	109.6 (6)
C5—C4—C3	126.8 (4)	O3—Cl1—O1	104.9 (6)
C4—C5—C6	118.1 (4)	O1'—Cl1—O4'	104.9 (5)
C4—C5—H5	121.0	O2'—Cl1—O4'	106.6 (4)
C6—C5—H5	121.0	O2—Cl1—O4'	61.7 (5)
C7—C6—C5	120.4 (4)	O3'—Cl1—O4'	101.6 (5)
C7—C6—H6	119.8	O4—Cl1—O4'	60.8 (7)
C5—C6—H6	119.8	O3—Cl1—O4'	96.7 (6)
C8—C7—C6	118.0 (4)	O1—Cl1—O4'	158.3 (6)

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5A···O2ii	0.86	2.50	3.237 (12)	144
N5—H5A···O3ii	0.86	2.25	2.942 (12)	137
N5—H5A···O2'ii	0.86	2.11	2.965 (8)	176
N3—H3A···O4iii	0.86	2.52	3.26 (2)	144
N3—H3A···O3'iii	0.86	2.16	3.015 (8)	178

Table 1

Selected geometric parameters (Å, °)

Mn1—N4	2.247 (3)
Mn1—N2	2.283 (3)
Mn1—N1	2.287 (3)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N5—H5A⋯O2ii	0.86	2.50	3.237 (12)	144
N5—H5A⋯O3ii	0.86	2.25	2.942 (12)	137
N5—H5A⋯O2′ii	0.86	2.11	2.965 (8)	176
N3—H3A⋯O4iii	0.86	2.52	3.26 (2)	144
N3—H3A⋯O3′iii	0.86	2.16	3.015 (8)	178

Symmetry codes: (ii) ; (iii) .