[μ-N,N′-Bis(2-pyridylmethyl­ene)ethane-1,2-diamine]bis­{aqua­[N,N′-bis­(2-pyridyl­methyl­ene)ethane-1,2-diamine]manganese(II)} tetra­kis(perchlorate)

Ha, K.

doi:10.1107/S1600536810003764

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 3| March 2010| Page m255

doi:10.1107/S1600536810003764

Open

access

[μ-N,N′-Bis(2-pyridylmethylene)ethane-1,2-diamine]bis{aqua[N,N′-bis(2-pyridylmethylene)ethane-1,2-diamine]manganese(II)} tetrakis(perchlorate)

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 28 January 2010; accepted 30 January 2010; online 6 February 2010)

The cation of the salt, [Mn₂(C₁₄H₁₄N₄)₃(H₂O)₂](ClO₄)₄, lies on a center of inversion, the center lying midway along the ethylene chain of the bridging N,N′-bis(2-pyridylmethylene)ethane-1,2-diamine ligand. The Mn atom is chelated by two atoms N atoms of this bridging ligand, and is also coordinated by four N atoms of another ligand. The Mn atom is seven-coordinated in a pentagonal-bipyramidal environment. The crystal structure displays intermolecular π–π interactions between adjacent pyridine rings, with a shortest centroid–centroid distance of 3.784 (3) Å. The perchlorate is linked to the dinuclear cation by O—H⋯O hydrogen bonds.

Related literature

For the crystal structures of Mn(II), Ag(I), Cu(II) and Pd(II) complexes with related ligands, see: Baar et al. (2001 ); Bowyer et al. (1998 ); Hwang & Ha (2009 ); Nguyen & Jeong (2006 ); Schoumacker et al. (2003 ).

Experimental

Crystal data

[Mn₂(C₁₄H₁₄N₄)₃(H₂O)₂](ClO₄)₄
M_r = 1258.59
Monoclinic, P 2₁ /c
a = 11.3698 (6) Å
b = 19.026 (1) Å
c = 12.8628 (7) Å
β = 110.218 (1)°
V = 2611.1 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.77 mm⁻¹
T = 200 K
0.24 × 0.18 × 0.12 mm

Data collection

Bruker SMART 1000 CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.873, T_max = 1.000
19343 measured reflections
6468 independent reflections
3281 reflections with I > 2σ(I)
R_int = 0.080

Refinement

R[F² > 2σ(F²)] = 0.062
wR(F²) = 0.178
S = 1.04
6468 reflections
360 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.82 e Å⁻³
Δρ_min = −0.84 e Å⁻³

Table 1
Selected bond lengths (Å)

Mn1—O1	2.215 (3)
Mn1—N6	2.257 (3)
Mn1—N3	2.278 (3)
Mn1—N2	2.278 (4)
Mn1—N5	2.280 (3)
Mn1—N1	2.504 (3)
Mn1—N4	2.639 (4)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯O3ⁱ	0.84 (1)	1.95 (1)	2.787 (5)	177 (6)
O1—H1B⋯O7ⁱⁱ	0.84 (1)	1.92 (2)	2.721 (6)	159 (6)
Symmetry codes: (i) x+1, y, z; (ii) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810003764/ng2727sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810003764/ng2727Isup2.hkl

checkCIF report

Comment top

The title compound, [Mn₂(C₁₄H₁₄N₄)₂(H₂O)₂(µ-C₁₄H₁₄N₄)](ClO₄)₄, consists of a structurally centrosymmetric dinuclear Mn^II complex and four perchlorate anions, and the asymmetric unit contains one half of the formula unit (Fig. 1). In the cationic complex, the two Mn^II ions are bridged by the symmetry-related tetradentate N,N'-bis(2-pyridylmethylene)ethane-1,2-diamine ligand, thus each Mn ion is seven-coordinated by six N atoms from the two tetradentate ligands and one O atom of the water molecule in an approximately pentagonal-bipyramidal environment, in which the five N1–N5 atoms form the pentagonal plane with O1 and N6 atoms at the apices. The six Mn—N bond lengths are considerably different and lie in the range of 2.257 (3)–2.639 (4) Å (Table 1). The N—Mn1—N chelating angles lie in the range of 66.69 (12)°–74.08 (12)° and the apical O1—Mn1—N6 bond angle is 159.64 (13)°. The crystal structure displays intermolecular π-π interactions between adjacent pyridine rings, with a shortest centroid-centroid distance of 3.784 (3) Å. The component ions interact by means of intermolecular O—H···O hydrogen bonds (Fig. 2 and Table 2).

Related literature top

For the crystal structures of Mn(II), Ag(I), Cu(II) and Pd(II) complexes with related ligands, see: Baar et al. (2001); Bowyer et al. (1998); Hwang & Ha (2009); Nguyen & Jeong (2006); Schoumacker et al. (2003).

Experimental top

To a solution of N,N'-bis(2-pyridylmethylene)ethane-1,2-diamine (0.66 g, 2.77 mmol) in EtOH (30 ml) was added Mn(ClO₄)₂.6H₂O (1.00 g, 2.76 mmol) and stirred for 1 h at room temparature. The formed precipitate was separated by filtration and washed with acetone and dried under vacuum, to give a yellow powder (0.63 g). Crystals suitable for X-ray analysis were obtained by slow evaporation from a CH₃CN solution. IR (KBr): 3394 cm^-1 (broad).

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: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The asymmetric structure of the title compound, with displacement ellipsoids drawn at the 30% probability level for non-H atoms.
	Fig. 2. View of the unit-cell contents of the title compound. Hydrogen-bond interactions are drawn with dashed lines.

[µ-N,N'-Bis(2-pyridylmethylene)ethane-1,2- diamine]bis{aqua[N,N'-bis(2-pyridylmethylene)ethane-1,2- diamine]manganese(II)} tetrakis(perchlorate) top

Crystal data top

[Mn₂(C₁₄H₁₄N₄)₃(H₂O)₂](ClO₄)₄	F(000) = 1288
M_r = 1258.59	D_x = 1.601 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3474 reflections
a = 11.3698 (6) Å	θ = 2.2–23.2°
b = 19.026 (1) Å	µ = 0.77 mm⁻¹
c = 12.8628 (7) Å	T = 200 K
β = 110.218 (1)°	Block, yellow
V = 2611.1 (2) Å³	0.24 × 0.18 × 0.12 mm
Z = 2

Data collection top

Bruker SMART 1000 CCD diffractometer	6468 independent reflections
Radiation source: fine-focus sealed tube	3281 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.080
ϕ and ω scans	θ_max = 28.3°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −15→15
T_min = 0.873, T_max = 1.000	k = −25→22
19343 measured reflections	l = −12→17

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)] = 0.062	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.178	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0701P)²] where P = (F_o² + 2F_c²)/3
6468 reflections	(Δ/σ)_max < 0.001
360 parameters	Δρ_max = 0.82 e Å⁻³
2 restraints	Δρ_min = −0.84 e Å⁻³

Crystal data top

[Mn₂(C₁₄H₁₄N₄)₃(H₂O)₂](ClO₄)₄	V = 2611.1 (2) Å³
M_r = 1258.59	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.3698 (6) Å	µ = 0.77 mm⁻¹
b = 19.026 (1) Å	T = 200 K
c = 12.8628 (7) Å	0.24 × 0.18 × 0.12 mm
β = 110.218 (1)°

Data collection top

Bruker SMART 1000 CCD diffractometer	6468 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	3281 reflections with I > 2σ(I)
T_min = 0.873, T_max = 1.000	R_int = 0.080
19343 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.062	2 restraints
wR(F²) = 0.178	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.82 e Å⁻³
6468 reflections	Δρ_min = −0.84 e Å⁻³
360 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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	0.71734 (6)	0.12570 (3)	0.16693 (5)	0.0293 (2)
O1	0.8064 (3)	0.21764 (17)	0.2697 (3)	0.0391 (8)
H1A	0.8820 (18)	0.224 (3)	0.277 (5)	0.07 (2)*
H1B	0.772 (4)	0.2559 (15)	0.245 (4)	0.07 (2)*
N1	0.9113 (3)	0.07794 (18)	0.1423 (3)	0.0329 (8)
N2	0.7713 (3)	0.18591 (17)	0.0370 (3)	0.0356 (9)
N3	0.5461 (3)	0.18634 (17)	0.0586 (3)	0.0339 (9)
N4	0.5358 (3)	0.13162 (17)	0.2506 (3)	0.0354 (9)
N5	0.7905 (3)	0.06251 (17)	0.3271 (3)	0.0292 (8)
N6	0.6439 (3)	0.01543 (17)	0.1226 (3)	0.0286 (8)
C1	0.9807 (4)	0.0233 (2)	0.1909 (4)	0.0377 (11)
H1	0.9533	−0.0042	0.2399	0.045*
C2	1.0901 (4)	0.0035 (2)	0.1753 (4)	0.0398 (11)
H2	1.1366	−0.0360	0.2130	0.048*
C3	1.1302 (4)	0.0422 (2)	0.1039 (4)	0.0403 (11)
H3	1.2059	0.0306	0.0921	0.048*
C4	1.0579 (4)	0.0986 (2)	0.0496 (4)	0.0395 (11)
H4	1.0819	0.1256	−0.0019	0.047*
C5	0.9507 (4)	0.1147 (2)	0.0714 (4)	0.0317 (10)
C6	0.8697 (4)	0.1738 (2)	0.0151 (4)	0.0370 (11)
H6	0.8909	0.2022	−0.0366	0.044*
C7	0.6868 (4)	0.2436 (2)	−0.0174 (4)	0.0446 (12)
H7A	0.7010	0.2579	−0.0861	0.054*
H7B	0.7013	0.2848	0.0325	0.054*
C8	0.5549 (5)	0.2163 (2)	−0.0439 (4)	0.0466 (13)
H8A	0.4937	0.2550	−0.0709	0.056*
H8B	0.5365	0.1798	−0.1022	0.056*
C9	0.4538 (4)	0.2018 (2)	0.0877 (4)	0.0375 (11)
H9	0.3927	0.2339	0.0442	0.045*
C10	0.4393 (4)	0.1714 (2)	0.1861 (4)	0.0332 (10)
C11	0.3316 (4)	0.1822 (2)	0.2109 (4)	0.0420 (12)
H11	0.2674	0.2122	0.1658	0.050*
C12	0.3181 (4)	0.1489 (3)	0.3016 (5)	0.0460 (13)
H12	0.2442	0.1551	0.3193	0.055*
C13	0.4139 (4)	0.1066 (2)	0.3659 (4)	0.0432 (12)
H13	0.4071	0.0818	0.4277	0.052*
C14	0.5207 (4)	0.1013 (2)	0.3373 (4)	0.0395 (11)
H14	0.5881	0.0737	0.3837	0.047*
C15	0.8513 (4)	0.0865 (2)	0.4293 (4)	0.0337 (10)
H15	0.8819	0.1334	0.4378	0.040*
C16	0.8714 (4)	0.0463 (3)	0.5229 (4)	0.0474 (13)
H16	0.9131	0.0654	0.5944	0.057*
C17	0.8300 (5)	−0.0219 (3)	0.5110 (4)	0.0552 (14)
H17	0.8423	−0.0507	0.5743	0.066*
C18	0.7702 (4)	−0.0484 (2)	0.4056 (4)	0.0438 (12)
H18	0.7442	−0.0962	0.3955	0.053*
C19	0.7489 (4)	−0.0046 (2)	0.3157 (4)	0.0309 (10)
C20	0.6763 (4)	−0.0278 (2)	0.2030 (4)	0.0315 (10)
H20	0.6530	−0.0758	0.1899	0.038*
C21	0.5679 (4)	−0.0107 (2)	0.0132 (3)	0.0328 (10)
H21A	0.5740	−0.0626	0.0116	0.039*
H21B	0.5996	0.0088	−0.0435	0.039*
Cl1	0.08812 (12)	0.30361 (7)	0.26378 (13)	0.0569 (4)
O2	−0.0050 (5)	0.3509 (2)	0.2687 (4)	0.0965 (16)
O3	0.0551 (3)	0.2349 (2)	0.2846 (5)	0.0951 (17)
O4	0.2057 (4)	0.3200 (3)	0.3388 (5)	0.129 (2)
O5	0.0906 (5)	0.3027 (3)	0.1535 (5)	0.128 (2)
Cl2	0.59876 (11)	0.10876 (6)	0.70262 (10)	0.0395 (3)
O6	0.4879 (4)	0.1474 (3)	0.6685 (5)	0.118 (2)
O7	0.6953 (6)	0.1538 (3)	0.7445 (6)	0.160 (3)
O8	0.6025 (5)	0.0622 (2)	0.7867 (4)	0.115 (2)
O9	0.6180 (7)	0.0730 (3)	0.6164 (4)	0.153 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn1	0.0341 (4)	0.0249 (3)	0.0255 (4)	−0.0003 (3)	0.0060 (3)	0.0016 (3)
O1	0.046 (2)	0.0335 (19)	0.038 (2)	−0.0055 (16)	0.0145 (17)	−0.0053 (15)
N1	0.035 (2)	0.036 (2)	0.026 (2)	0.0007 (16)	0.0077 (16)	0.0027 (16)
N2	0.045 (2)	0.031 (2)	0.031 (2)	0.0033 (17)	0.0137 (18)	0.0018 (15)
N3	0.036 (2)	0.030 (2)	0.032 (2)	0.0051 (16)	0.0068 (17)	0.0027 (15)
N4	0.033 (2)	0.032 (2)	0.037 (2)	0.0020 (16)	0.0070 (17)	−0.0012 (17)
N5	0.0282 (18)	0.0297 (19)	0.027 (2)	0.0031 (15)	0.0061 (15)	0.0006 (15)
N6	0.0263 (18)	0.0294 (19)	0.028 (2)	−0.0009 (15)	0.0069 (15)	−0.0027 (15)
C1	0.039 (3)	0.040 (3)	0.034 (3)	0.002 (2)	0.012 (2)	0.004 (2)
C2	0.033 (2)	0.042 (3)	0.042 (3)	0.004 (2)	0.011 (2)	−0.001 (2)
C3	0.030 (2)	0.048 (3)	0.045 (3)	−0.006 (2)	0.015 (2)	−0.011 (2)
C4	0.037 (3)	0.049 (3)	0.035 (3)	−0.009 (2)	0.015 (2)	−0.009 (2)
C5	0.032 (2)	0.035 (2)	0.027 (2)	−0.0035 (19)	0.0090 (19)	−0.0028 (18)
C6	0.043 (3)	0.037 (3)	0.030 (3)	−0.004 (2)	0.012 (2)	0.0022 (19)
C7	0.064 (3)	0.033 (3)	0.040 (3)	0.011 (2)	0.022 (3)	0.016 (2)
C8	0.053 (3)	0.045 (3)	0.037 (3)	0.014 (2)	0.010 (2)	0.014 (2)
C9	0.034 (2)	0.026 (2)	0.044 (3)	0.0029 (19)	0.003 (2)	−0.003 (2)
C10	0.029 (2)	0.028 (2)	0.037 (3)	−0.0018 (18)	0.005 (2)	−0.0100 (19)
C11	0.034 (3)	0.032 (3)	0.056 (3)	0.003 (2)	0.011 (2)	−0.006 (2)
C12	0.031 (2)	0.048 (3)	0.060 (4)	−0.005 (2)	0.017 (2)	−0.016 (3)
C13	0.040 (3)	0.042 (3)	0.051 (3)	−0.009 (2)	0.019 (2)	−0.005 (2)
C14	0.035 (2)	0.042 (3)	0.041 (3)	−0.001 (2)	0.012 (2)	0.001 (2)
C15	0.031 (2)	0.043 (3)	0.025 (2)	−0.0028 (19)	0.0078 (19)	−0.0011 (19)
C16	0.042 (3)	0.066 (4)	0.030 (3)	−0.005 (3)	0.008 (2)	0.002 (2)
C17	0.050 (3)	0.075 (4)	0.032 (3)	−0.005 (3)	0.004 (2)	0.022 (3)
C18	0.045 (3)	0.044 (3)	0.040 (3)	−0.004 (2)	0.011 (2)	0.014 (2)
C19	0.025 (2)	0.033 (2)	0.034 (3)	0.0033 (18)	0.0093 (19)	0.0007 (18)
C20	0.028 (2)	0.025 (2)	0.042 (3)	0.0006 (17)	0.014 (2)	−0.0002 (19)
C21	0.036 (2)	0.033 (2)	0.027 (2)	−0.0004 (19)	0.008 (2)	−0.0072 (18)
Cl1	0.0494 (8)	0.0436 (8)	0.0833 (11)	0.0007 (6)	0.0301 (8)	−0.0063 (7)
O2	0.112 (4)	0.066 (3)	0.127 (4)	0.047 (3)	0.060 (3)	0.009 (3)
O3	0.051 (2)	0.049 (3)	0.179 (5)	0.0034 (19)	0.032 (3)	0.017 (3)
O4	0.069 (3)	0.104 (4)	0.175 (6)	−0.042 (3)	−0.006 (3)	−0.006 (4)
O5	0.146 (5)	0.158 (5)	0.107 (5)	0.044 (4)	0.078 (4)	0.011 (4)
Cl2	0.0421 (7)	0.0335 (6)	0.0423 (7)	−0.0021 (5)	0.0139 (5)	0.0033 (5)
O6	0.063 (3)	0.126 (4)	0.161 (6)	0.037 (3)	0.036 (3)	0.055 (4)
O7	0.127 (5)	0.116 (4)	0.208 (7)	−0.086 (4)	0.022 (5)	0.007 (4)
O8	0.174 (5)	0.092 (3)	0.122 (4)	0.061 (3)	0.106 (4)	0.072 (3)
O9	0.262 (8)	0.137 (5)	0.064 (4)	0.096 (5)	0.062 (4)	−0.001 (3)

Geometric parameters (Å, º) top

Mn1—O1	2.215 (3)	C8—H8A	0.9900
Mn1—N6	2.257 (3)	C8—H8B	0.9900
Mn1—N3	2.278 (3)	C9—C10	1.452 (6)
Mn1—N2	2.278 (4)	C9—H9	0.9500
Mn1—N5	2.280 (3)	C10—C11	1.382 (6)
Mn1—N1	2.504 (3)	C11—C12	1.383 (7)
Mn1—N4	2.639 (4)	C11—H11	0.9500
O1—H1A	0.840 (10)	C12—C13	1.377 (7)
O1—H1B	0.837 (10)	C12—H12	0.9500
N1—C1	1.325 (5)	C13—C14	1.390 (6)
N1—C5	1.343 (5)	C13—H13	0.9500
N2—C6	1.266 (5)	C14—H14	0.9500
N2—C7	1.467 (5)	C15—C16	1.378 (6)
N3—C9	1.264 (5)	C15—H15	0.9500
N3—C8	1.471 (6)	C16—C17	1.370 (7)
N4—C14	1.318 (6)	C16—H16	0.9500
N4—C10	1.355 (5)	C17—C18	1.384 (7)
N5—C15	1.337 (5)	C17—H17	0.9500
N5—C19	1.352 (5)	C18—C19	1.379 (6)
N6—C20	1.272 (5)	C18—H18	0.9500
N6—C21	1.461 (5)	C19—C20	1.466 (6)
C1—C2	1.379 (6)	C20—H20	0.9500
C1—H1	0.9500	C21—C21ⁱ	1.517 (8)
C2—C3	1.372 (6)	C21—H21A	0.9900
C2—H2	0.9500	C21—H21B	0.9900
C3—C4	1.385 (6)	Cl1—O4	1.387 (5)
C3—H3	0.9500	Cl1—O2	1.408 (4)
C4—C5	1.376 (6)	Cl1—O3	1.411 (4)
C4—H4	0.9500	Cl1—O5	1.429 (6)
C5—C6	1.476 (6)	Cl2—O7	1.349 (5)
C6—H6	0.9500	Cl2—O9	1.381 (5)
C7—C8	1.511 (6)	Cl2—O8	1.387 (4)
C7—H7A	0.9900	Cl2—O6	1.393 (4)
C7—H7B	0.9900

O1—Mn1—N6	159.64 (13)	N2—C7—H7B	110.4
O1—Mn1—N3	94.76 (13)	C8—C7—H7B	110.4
N6—Mn1—N3	98.80 (12)	H7A—C7—H7B	108.6
O1—Mn1—N2	81.80 (12)	N3—C8—C7	107.5 (4)
N6—Mn1—N2	116.87 (13)	N3—C8—H8A	110.2
N3—Mn1—N2	71.73 (13)	C7—C8—H8A	110.2
O1—Mn1—N5	85.88 (12)	N3—C8—H8B	110.2
N6—Mn1—N5	74.08 (12)	C7—C8—H8B	110.2
N3—Mn1—N5	141.99 (13)	H8A—C8—H8B	108.5
N2—Mn1—N5	145.21 (13)	N3—C9—C10	121.5 (4)
O1—Mn1—N1	96.96 (12)	N3—C9—H9	119.3
N6—Mn1—N1	84.01 (11)	C10—C9—H9	119.3
N3—Mn1—N1	135.25 (13)	N4—C10—C11	122.4 (4)
N2—Mn1—N1	67.51 (12)	N4—C10—C9	116.3 (4)
N5—Mn1—N1	81.98 (12)	C11—C10—C9	121.3 (4)
O1—Mn1—N4	89.06 (12)	C10—C11—C12	119.5 (4)
N6—Mn1—N4	82.51 (11)	C10—C11—H11	120.2
N3—Mn1—N4	66.69 (12)	C12—C11—H11	120.2
N2—Mn1—N4	136.42 (12)	C13—C12—C11	118.6 (4)
N5—Mn1—N4	75.33 (11)	C13—C12—H12	120.7
N1—Mn1—N4	156.05 (11)	C11—C12—H12	120.7
Mn1—O1—H1A	114 (4)	C12—C13—C14	117.8 (5)
Mn1—O1—H1B	114 (4)	C12—C13—H13	121.1
H1A—O1—H1B	105 (5)	C14—C13—H13	121.1
C1—N1—C5	116.4 (4)	N4—C14—C13	125.0 (4)
C1—N1—Mn1	129.2 (3)	N4—C14—H14	117.5
C5—N1—Mn1	114.3 (3)	C13—C14—H14	117.5
C6—N2—C7	120.9 (4)	N5—C15—C16	122.9 (4)
C6—N2—Mn1	123.7 (3)	N5—C15—H15	118.5
C7—N2—Mn1	115.3 (3)	C16—C15—H15	118.5
C9—N3—C8	119.7 (4)	C17—C16—C15	118.8 (5)
C9—N3—Mn1	123.9 (3)	C17—C16—H16	120.6
C8—N3—Mn1	115.9 (3)	C15—C16—H16	120.6
C14—N4—C10	116.6 (4)	C16—C17—C18	119.2 (5)
C14—N4—Mn1	132.4 (3)	C16—C17—H17	120.4
C10—N4—Mn1	110.9 (3)	C18—C17—H17	120.4
C15—N5—C19	118.1 (4)	C19—C18—C17	119.1 (4)
C15—N5—Mn1	127.7 (3)	C19—C18—H18	120.5
C19—N5—Mn1	113.3 (3)	C17—C18—H18	120.5
C20—N6—C21	118.2 (4)	N5—C19—C18	121.8 (4)
C20—N6—Mn1	114.7 (3)	N5—C19—C20	116.6 (4)
C21—N6—Mn1	127.1 (3)	C18—C19—C20	121.6 (4)
N1—C1—C2	124.4 (4)	N6—C20—C19	121.0 (4)
N1—C1—H1	117.8	N6—C20—H20	119.5
C2—C1—H1	117.8	C19—C20—H20	119.5
C3—C2—C1	118.5 (4)	N6—C21—C21ⁱ	110.0 (4)
C3—C2—H2	120.8	N6—C21—H21A	109.7
C1—C2—H2	120.8	C21ⁱ—C21—H21A	109.7
C2—C3—C4	118.5 (4)	N6—C21—H21B	109.7
C2—C3—H3	120.8	C21ⁱ—C21—H21B	109.7
C4—C3—H3	120.8	H21A—C21—H21B	108.2
C5—C4—C3	118.9 (4)	O4—Cl1—O2	112.6 (3)
C5—C4—H4	120.6	O4—Cl1—O3	109.4 (3)
C3—C4—H4	120.6	O2—Cl1—O3	109.3 (3)
N1—C5—C4	123.3 (4)	O4—Cl1—O5	110.4 (4)
N1—C5—C6	115.6 (4)	O2—Cl1—O5	109.0 (3)
C4—C5—C6	121.1 (4)	O3—Cl1—O5	106.0 (3)
N2—C6—C5	118.6 (4)	O7—Cl2—O9	107.5 (5)
N2—C6—H6	120.7	O7—Cl2—O8	107.0 (4)
C5—C6—H6	120.7	O9—Cl2—O8	110.0 (3)
N2—C7—C8	106.6 (4)	O7—Cl2—O6	108.3 (4)
N2—C7—H7A	110.4	O9—Cl2—O6	112.6 (4)
C8—C7—H7A	110.4	O8—Cl2—O6	111.3 (3)

O1—Mn1—N1—C1	104.0 (4)	N2—Mn1—N6—C20	144.2 (3)
N6—Mn1—N1—C1	−55.5 (4)	N5—Mn1—N6—C20	−0.2 (3)
N3—Mn1—N1—C1	−152.0 (3)	N1—Mn1—N6—C20	83.1 (3)
N2—Mn1—N1—C1	−177.9 (4)	N4—Mn1—N6—C20	−77.0 (3)
N5—Mn1—N1—C1	19.2 (4)	O1—Mn1—N6—C21	171.0 (3)
N4—Mn1—N1—C1	0.5 (5)	N3—Mn1—N6—C21	39.8 (3)
O1—Mn1—N1—C5	−74.2 (3)	N2—Mn1—N6—C21	−34.1 (3)
N6—Mn1—N1—C5	126.3 (3)	N5—Mn1—N6—C21	−178.5 (3)
N3—Mn1—N1—C5	29.8 (4)	N1—Mn1—N6—C21	−95.2 (3)
N2—Mn1—N1—C5	3.9 (3)	N4—Mn1—N6—C21	104.7 (3)
N5—Mn1—N1—C5	−159.0 (3)	C5—N1—C1—C2	1.6 (6)
N4—Mn1—N1—C5	−177.7 (3)	Mn1—N1—C1—C2	−176.6 (3)
O1—Mn1—N2—C6	96.9 (4)	N1—C1—C2—C3	−0.6 (7)
N6—Mn1—N2—C6	−74.5 (4)	C1—C2—C3—C4	−1.1 (7)
N3—Mn1—N2—C6	−165.3 (4)	C2—C3—C4—C5	1.7 (6)
N5—Mn1—N2—C6	26.4 (5)	C1—N1—C5—C4	−0.9 (6)
N1—Mn1—N2—C6	−4.2 (3)	Mn1—N1—C5—C4	177.6 (3)
N4—Mn1—N2—C6	176.8 (3)	C1—N1—C5—C6	177.9 (4)
O1—Mn1—N2—C7	−80.0 (3)	Mn1—N1—C5—C6	−3.7 (5)
N6—Mn1—N2—C7	108.6 (3)	C3—C4—C5—N1	−0.8 (7)
N3—Mn1—N2—C7	17.9 (3)	C3—C4—C5—C6	−179.4 (4)
N5—Mn1—N2—C7	−150.4 (3)	C7—N2—C6—C5	−179.4 (4)
N1—Mn1—N2—C7	179.0 (3)	Mn1—N2—C6—C5	3.9 (6)
N4—Mn1—N2—C7	−0.1 (4)	N1—C5—C6—N2	0.3 (6)
O1—Mn1—N3—C9	−79.5 (3)	C4—C5—C6—N2	179.1 (4)
N6—Mn1—N3—C9	85.3 (3)	C6—N2—C7—C8	139.5 (4)
N2—Mn1—N3—C9	−159.2 (4)	Mn1—N2—C7—C8	−43.6 (4)
N5—Mn1—N3—C9	10.0 (4)	C9—N3—C8—C7	133.0 (4)
N1—Mn1—N3—C9	175.7 (3)	Mn1—N3—C8—C7	−39.0 (4)
N4—Mn1—N3—C9	7.5 (3)	N2—C7—C8—N3	51.7 (5)
O1—Mn1—N3—C8	92.2 (3)	C8—N3—C9—C10	177.8 (4)
N6—Mn1—N3—C8	−103.0 (3)	Mn1—N3—C9—C10	−10.9 (6)
N2—Mn1—N3—C8	12.5 (3)	C14—N4—C10—C11	2.1 (6)
N5—Mn1—N3—C8	−178.4 (3)	Mn1—N4—C10—C11	179.1 (3)
N1—Mn1—N3—C8	−12.7 (4)	C14—N4—C10—C9	−177.0 (4)
N4—Mn1—N3—C8	179.1 (3)	Mn1—N4—C10—C9	0.1 (4)
O1—Mn1—N4—C14	−91.4 (4)	N3—C9—C10—N4	6.4 (6)
N6—Mn1—N4—C14	70.0 (4)	N3—C9—C10—C11	−172.6 (4)
N3—Mn1—N4—C14	173.0 (4)	N4—C10—C11—C12	−3.0 (7)
N2—Mn1—N4—C14	−168.5 (4)	C9—C10—C11—C12	176.0 (4)
N5—Mn1—N4—C14	−5.4 (4)	C10—C11—C12—C13	0.9 (7)
N1—Mn1—N4—C14	13.7 (6)	C11—C12—C13—C14	1.8 (7)
O1—Mn1—N4—C10	92.2 (3)	C10—N4—C14—C13	0.8 (7)
N6—Mn1—N4—C10	−106.4 (3)	Mn1—N4—C14—C13	−175.4 (3)
N3—Mn1—N4—C10	−3.4 (3)	C12—C13—C14—N4	−2.8 (7)
N2—Mn1—N4—C10	15.2 (3)	C19—N5—C15—C16	−1.0 (6)
N5—Mn1—N4—C10	178.2 (3)	Mn1—N5—C15—C16	167.8 (3)
N1—Mn1—N4—C10	−162.6 (3)	N5—C15—C16—C17	1.6 (7)
O1—Mn1—N5—C15	3.9 (3)	C15—C16—C17—C18	0.4 (7)
N6—Mn1—N5—C15	−172.5 (4)	C16—C17—C18—C19	−2.8 (7)
N3—Mn1—N5—C15	−88.6 (4)	C15—N5—C19—C18	−1.6 (6)
N2—Mn1—N5—C15	73.1 (4)	Mn1—N5—C19—C18	−171.9 (3)
N1—Mn1—N5—C15	101.5 (3)	C15—N5—C19—C20	176.5 (4)
N4—Mn1—N5—C15	−86.2 (3)	Mn1—N5—C19—C20	6.1 (4)
O1—Mn1—N5—C19	173.0 (3)	C17—C18—C19—N5	3.5 (7)
N6—Mn1—N5—C19	−3.3 (3)	C17—C18—C19—C20	−174.5 (4)
N3—Mn1—N5—C19	80.6 (3)	C21—N6—C20—C19	−177.9 (4)
N2—Mn1—N5—C19	−117.7 (3)	Mn1—N6—C20—C19	3.6 (5)
N1—Mn1—N5—C19	−89.3 (3)	N5—C19—C20—N6	−6.9 (6)
N4—Mn1—N5—C19	82.9 (3)	C18—C19—C20—N6	171.2 (4)
O1—Mn1—N6—C20	−10.7 (5)	C20—N6—C21—C21ⁱ	102.6 (5)
N3—Mn1—N6—C20	−141.9 (3)	Mn1—N6—C21—C21ⁱ	−79.2 (5)

Symmetry code: (i) −x+1, −y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O3ⁱⁱ	0.84 (1)	1.95 (1)	2.787 (5)	177 (6)
O1—H1B···O7ⁱⁱⁱ	0.84 (1)	1.92 (2)	2.721 (6)	159 (6)

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

Experimental details

Crystal data
Chemical formula	[Mn₂(C₁₄H₁₄N₄)₃(H₂O)₂](ClO₄)₄
M_r	1258.59
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	200
a, b, c (Å)	11.3698 (6), 19.026 (1), 12.8628 (7)
β (°)	110.218 (1)
V (Å³)	2611.1 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.77
Crystal size (mm)	0.24 × 0.18 × 0.12

Data collection
Diffractometer	Bruker SMART 1000 CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.873, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	19343, 6468, 3281
R_int	0.080
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.062, 0.178, 1.04
No. of reflections	6468
No. of parameters	360
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.82, −0.84

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009).

Selected bond lengths (Å) top

Mn1—O1	2.215 (3)	Mn1—N5	2.280 (3)
Mn1—N6	2.257 (3)	Mn1—N1	2.504 (3)
Mn1—N3	2.278 (3)	Mn1—N4	2.639 (4)
Mn1—N2	2.278 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O3ⁱ	0.840 (10)	1.947 (12)	2.787 (5)	177 (6)
O1—H1B···O7ⁱⁱ	0.837 (10)	1.92 (2)	2.721 (6)	159 (6)

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

Acknowledgements

This research was supported by the Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (2009–0074570).

References

Baar, C. R., Jennings, M. C. & Puddephatt, R. J. (2001). Organometallics, 20, 3459–3465. Web of Science CSD CrossRef CAS Google Scholar
Bowyer, P. K., Porter, K. A., Rae, A. D., Willis, A. C. & Wild, S. B. (1998). Chem. Commun. pp. 1153–1154. Web of Science CSD CrossRef Google Scholar
Bruker (2000). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Hwang, I.-C. & Ha, K. (2009). Acta Cryst. E65, m64–m65. Web of Science CSD CrossRef IUCr Journals Google Scholar
Nguyen, Q. T. & Jeong, J. H. (2006). Polyhedron, 25, 1787–1790. Web of Science CSD CrossRef CAS Google Scholar
Schoumacker, S., Hamelin, O., Pécaut, J. & Fontecave, M. (2003). Inorg. Chem. 42, 8110–8116. Web of Science CSD CrossRef PubMed CAS 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

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.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 3| March 2010| Page m255

doi:10.1107/S1600536810003764

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

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

[μ-N,N′-Bis(2-pyridylmethyl­ene)ethane-1,2-di­amine]bis­­{aqua­[N,N′-bis­­(2-pyridyl­methyl­ene)ethane-1,2-di­amine]manganese(II)} tetra­kis(perchlorate)

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

[μ-N,N′-Bis(2-pyridylmethylene)ethane-1,2-diamine]bis{aqua[N,N′-bis(2-pyridylmethylene)ethane-1,2-diamine]manganese(II)} tetrakis(perchlorate)