[μ-10,21-Dimethyl-3,6,14,17-tetra­za­tricyclo­[17.3.1.18,12]tetra­cosa-1(23),2,6,8,10,12 (24),13,17,19,21-deca­ene-23,24-diolato-κ4N3,N6,O23,O24:κ4N14,N17,O23,O24]bis­(perchlorato-κO)dimanganese(II)

Liu, J.; Pan, Z.-Q.; Zhou, H.; Li, Y.-Z.

doi:10.1107/S1600536808035551

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 12| December 2008| Page m1506

doi:10.1107/S1600536808035551

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[μ-10,21-Dimethyl-3,6,14,17-tetrazatricyclo[17.3.1.1^8,12]tetracosa-1(23),2,6,8,10,12 (24),13,17,19,21-decaene-23,24-diolato-κ⁴N³,N⁶,O²³,O²⁴:κ⁴N¹⁴,N¹⁷,O²³,O²⁴]bis(perchlorato-κO)dimanganese(II)

Jing Liu,^a Zhi-Quan Pan,^a ^* Hong Zhou ^a and Yi-Zhi Li ^b

^aKey Laboratory for Green Chemical Processes of the Ministry of Education, Wuhan Institute of Technology, Wuhan 430073, People's Republic of China, and ^bState Key Laboratory of Coordination Chemistry, Coordination Chemistry Institute, Nanjing University, Nanjing 210093, People's Republic of China
^*Correspondence e-mail: zhiqpan@163.com

(Received 14 October 2008; accepted 30 October 2008; online 8 November 2008)

In the centrosymmetric and dinuclear title complex, [Mn₂(C₂₂H₂₂N₄O₂)(ClO₄)₂], the two Mn atoms are bridged by two phenolate O atoms of the N₄O₂ macrocycle with an Mn⋯Mn distance of 2.9228 (11) Å. The distorted square–pyramidal N₂O₃ coordination geometry is completed by an O atom derived from a perchlorate anion.

Related literature

For related literature, see: Bai et al. (2007 ); Venegas-Yazigi et al. (2006 ); Jong et al. (2006 ); Ki et al. (2006 ); Tei et al. (2001 ); Brooker & Croucher (1997 ); Chattopadhyay et al. (2007 ). For synthesis, see: Taniguchi (1984 ).

Experimental

Crystal data

[Mn₂(C₂₂H₂₂N₄O₂)(ClO₄)₂]
M_r = 683.22
Triclinic, $[P \overline 1]$
a = 8.3129 (10) Å
b = 8.3759 (11) Å
c = 9.9712 (12) Å
α = 81.484 (2)°
β = 68.520 (3)°
γ = 78.838 (2)°
V = 631.56 (14) Å³
Z = 1
Mo Kα radiation
μ = 1.28 mm⁻¹
T = 291 (2) K
0.31 × 0.21 × 0.15 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.73, T_max = 0.83
3663 measured reflections
2439 independent reflections
1701 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.052
wR(F²) = 0.118
S = 0.99
2439 reflections
182 parameters
H-atom parameters constrained
Δρ_max = 0.56 e Å⁻³
Δρ_min = −0.58 e Å⁻³

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; 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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808035551/tk2317sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808035551/tk2317Isup2.hkl

checkCIF report

Comment top

Schiff base macrocyclic complexes, derived from the cyclocondensation of 2,6-di-formyl-4-phenol and alkylenediamine in the presence of metal ions, have been extensively studied (Ki et al., 2006; Brooker & Croucher, 1997). The properties of the complexes vary with the differences in the macrocyclic structures and in the nature of the metal ions (Tei et al., 2001; Jong et al., 2006; Venegas-Yazigi et al., 2006). Although the same macrocyclic ligand featured in the title complex, (I), exists in the literature (Bai et al., 2007; Chattopadhyay et al., 2007), the dinuclear Mn(II) complex is novel; the structure is reported herein.

The dinuclear and centrosymmetric structure of (I), Fig. 1, is constructed about a Mn₂O₂ core. The macrocyclic ligand is hexadentate forming an N₄O₂ donor set. The Mn ion is coordinated by two endogenous phenolic-O atoms and two azomethine-N atoms that form an approximately square planar geometry. The distorted square pyramidal geometry is completed by a weakly coordinated O atom derived from the perchlorate anion, 2.390 (3) Å. The latter distance is greater than the range of the other Mn-(donor atom) distances, i.e. 1.888 (3) to 1.909 (3) Å. The Mn—Mn distance is 2.9228 (11) Å.

Related literature top

For related literature, see: Bai et al. (2007); Venegas-Yazigi et al. (2006); Jong et al. (2006); Ki et al. (2006); Tei et al. (2001); Brooker & Croucher (1997); Chattopadhyay et al. (2007). For synthesis, see: Taniguchi (1984).

Experimental top

2,6-Di-formyl-4-methylphenol was prepared according to the literature method (Taniguchi, 1984). Ethylenediamine (0.8 mmol, 0.048 g) in absolute methanol (10 ml) was added to a methanol solution (10 ml) containing 2,6-di-formyl-4-methylphenol (0.8 mmol, 0.13 g). The solution was stirred vigorously for 3 h in a ice-bath. Afterwards, a methanol solution (5 ml) of Mn(OAc)₂.4H₂O (0.4 mmol, 0.1 g) was added dropwise over a period of 1 h at room temperature. The mixture was stirred for a further 12 h at ambient temperature. Finally, Mn(ClO₄)₂.6H₂O (0.4 mmol, 0.15 g) dissolved in methanol (5 ml) was added to the mixture and stirred for 8 h at room temperature. The dark-red block-shaped crystals suitable for X-ray diffraction precipitated by slow volatilization over a period of one month.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. A view of (I), showing the labeling of the non-H atoms and 30% probability ellipsoids. H atoms have been omitted for clarity.

[µ-10,21-Dimethyl-3,6,14,17-tetrazatricyclo[17.3.1.1^8,12]tetracosa-1(23),2, 6,8,10,12 (24),13,17,19,21-decaene-23,24-diolato-κ⁴N³,N⁶, O²³,O²⁴:κ⁴N¹⁴,N¹⁷,O²³,O²⁴]bis(perchlorato-κO)dimanganese(II) top

Crystal data top

[Mn₂(C₂₂H₂₂N₄O₂)(ClO₄)₂]	Z = 1
M_r = 683.22	F(000) = 346
Triclinic, P1	D_x = 1.796 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.3129 (10) Å	Cell parameters from 1608 reflections
b = 8.3759 (11) Å	θ = 2.5–25.7°
c = 9.9712 (12) Å	µ = 1.28 mm⁻¹
α = 81.484 (2)°	T = 291 K
β = 68.520 (3)°	Block, red
γ = 78.838 (2)°	0.31 × 0.21 × 0.15 mm
V = 631.56 (14) Å³

Data collection top

Bruker SMART APEX CCD diffractometer	2439 independent reflections
Radiation source: sealed tube	1701 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
ϕ and ω scans	θ_max = 26.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −6→10
T_min = 0.73, T_max = 0.83	k = −9→10
3663 measured reflections	l = −12→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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.118	H-atom parameters constrained
S = 0.99	w = 1/[σ²(F_o²) + (0.0643P)²] where P = (F_o² + 2F_c²)/3
2439 reflections	(Δ/σ)_max < 0.001
182 parameters	Δρ_max = 0.56 e Å⁻³
0 restraints	Δρ_min = −0.58 e Å⁻³

Crystal data top

[Mn₂(C₂₂H₂₂N₄O₂)(ClO₄)₂]	γ = 78.838 (2)°
M_r = 683.22	V = 631.56 (14) Å³
Triclinic, P1	Z = 1
a = 8.3129 (10) Å	Mo Kα radiation
b = 8.3759 (11) Å	µ = 1.28 mm⁻¹
c = 9.9712 (12) Å	T = 291 K
α = 81.484 (2)°	0.31 × 0.21 × 0.15 mm
β = 68.520 (3)°

Data collection top

Bruker SMART APEX CCD diffractometer	2439 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	1701 reflections with I > 2σ(I)
T_min = 0.73, T_max = 0.83	R_int = 0.029
3663 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.052	0 restraints
wR(F²) = 0.118	H-atom parameters constrained
S = 0.99	Δρ_max = 0.56 e Å⁻³
2439 reflections	Δρ_min = −0.58 e Å⁻³
182 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
C1	0.7059 (6)	0.6449 (6)	0.4901 (5)	0.0464 (10)
C2	0.5527 (5)	0.6225 (5)	0.6085 (5)	0.0419 (9)
C3	0.3922 (6)	0.7068 (5)	0.6049 (4)	0.0400 (9)
H3	0.2908	0.6855	0.6806	0.048*
C4	0.3786 (6)	0.8204 (5)	0.4932 (5)	0.0458 (10)
C5	0.5336 (6)	0.8403 (6)	0.3738 (5)	0.0475 (11)
H5	0.5278	0.9107	0.2938	0.057*
C6	0.6944 (6)	0.7556 (5)	0.3752 (5)	0.0413 (9)
C7	0.5468 (6)	0.5007 (6)	0.7344 (5)	0.0476 (10)
H7	0.4369	0.4830	0.7991	0.057*
C8	0.8486 (5)	0.7881 (5)	0.2457 (4)	0.0335 (8)
H8	0.8285	0.8662	0.1746	0.040*
C9	0.8484 (6)	0.2595 (5)	0.9110 (5)	0.0494 (11)
H9A	0.8402	0.3379	0.9766	0.059*
H9B	0.8668	0.1507	0.9574	0.059*
C10	0.6753 (5)	0.2848 (5)	0.8787 (4)	0.0425 (10)
H10A	0.6616	0.1845	0.8492	0.051*
H10B	0.5766	0.3124	0.9655	0.051*
C11	0.2057 (6)	0.9079 (6)	0.4876 (5)	0.0494 (11)
H11A	0.1131	0.8652	0.5667	0.074*
H11B	0.1953	0.8923	0.3978	0.074*
H11C	0.1980	1.0224	0.4946	0.074*
Cl1	0.82655 (13)	0.75907 (13)	0.86577 (11)	0.0428 (3)
Mn1	0.91488 (7)	0.43436 (7)	0.64841 (6)	0.0349 (2)
N1	0.6784 (5)	0.4187 (4)	0.7614 (4)	0.0475 (9)
N2	0.9957 (5)	0.2803 (4)	0.7770 (4)	0.0469 (9)
O1	0.8573 (4)	0.5649 (4)	0.4947 (3)	0.0449 (7)
O2	0.9409 (4)	0.6619 (4)	0.7542 (3)	0.0523 (8)
O3	0.9142 (4)	0.8814 (4)	0.8771 (3)	0.0457 (7)
O4	0.7776 (4)	0.6558 (4)	0.9924 (3)	0.0476 (7)
O5	0.6808 (4)	0.8267 (4)	0.8254 (3)	0.0551 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.036 (2)	0.059 (3)	0.043 (2)	0.0015 (19)	−0.0149 (18)	−0.010 (2)
C2	0.037 (2)	0.039 (2)	0.049 (2)	−0.0074 (17)	−0.0145 (19)	−0.0029 (18)
C3	0.038 (2)	0.044 (2)	0.042 (2)	−0.0069 (17)	−0.0163 (17)	−0.0121 (17)
C4	0.052 (3)	0.041 (2)	0.050 (2)	0.0047 (19)	−0.028 (2)	−0.0122 (19)
C5	0.038 (2)	0.067 (3)	0.041 (2)	0.005 (2)	−0.0200 (19)	−0.014 (2)
C6	0.043 (2)	0.0331 (19)	0.045 (2)	−0.0020 (17)	−0.0115 (18)	−0.0112 (17)
C7	0.039 (2)	0.055 (3)	0.045 (2)	−0.012 (2)	−0.0046 (19)	−0.010 (2)
C8	0.042 (2)	0.0357 (19)	0.0332 (19)	−0.0088 (16)	−0.0277 (17)	0.0084 (15)
C9	0.036 (2)	0.042 (2)	0.058 (3)	0.0016 (18)	−0.009 (2)	0.008 (2)
C10	0.043 (2)	0.049 (3)	0.039 (2)	−0.0161 (19)	−0.0178 (19)	0.0065 (18)
C11	0.048 (3)	0.055 (3)	0.044 (2)	0.002 (2)	−0.016 (2)	−0.010 (2)
Cl1	0.0484 (6)	0.0439 (5)	0.0378 (5)	−0.0173 (4)	−0.0121 (4)	−0.0020 (4)
Mn1	0.0334 (3)	0.0348 (3)	0.0293 (3)	−0.0010 (2)	−0.0074 (2)	0.0043 (2)
N1	0.042 (2)	0.044 (2)	0.051 (2)	−0.0087 (17)	−0.0114 (17)	0.0014 (16)
N2	0.049 (2)	0.045 (2)	0.0361 (18)	0.0054 (17)	−0.0119 (16)	0.0038 (16)
O1	0.0312 (14)	0.0499 (17)	0.0430 (16)	0.0020 (12)	−0.0097 (12)	0.0100 (13)
O2	0.0483 (18)	0.0482 (17)	0.0523 (18)	−0.0217 (14)	0.0020 (15)	−0.0113 (14)
O3	0.0583 (18)	0.0484 (17)	0.0359 (15)	−0.0247 (14)	−0.0123 (13)	−0.0094 (12)
O4	0.0412 (16)	0.0527 (18)	0.0475 (17)	−0.0193 (13)	−0.0142 (13)	0.0133 (14)
O5	0.0497 (18)	0.0483 (18)	0.0445 (17)	0.0108 (14)	−0.0063 (14)	0.0157 (14)

Geometric parameters (Å, º) top

C1—O1	1.321 (5)	C9—H9B	0.9700
C1—C6	1.383 (6)	C10—N1	1.492 (5)
C1—C2	1.406 (6)	C10—H10A	0.9700
C2—C3	1.393 (6)	C10—H10B	0.9700
C2—C7	1.488 (6)	C11—H11A	0.9600
C3—C4	1.376 (6)	C11—H11B	0.9600
C3—H3	0.9300	C11—H11C	0.9600
C4—C5	1.417 (6)	Cl1—O4	1.394 (3)
C4—C11	1.499 (6)	Cl1—O5	1.405 (3)
C5—C6	1.390 (6)	Cl1—O3	1.406 (3)
C5—H5	0.9300	Cl1—O2	1.413 (3)
C6—C8	1.485 (6)	Mn1—N2	1.888 (3)
C7—N1	1.269 (6)	Mn1—N1	1.893 (4)
C7—H7	0.9300	Mn1—O1	1.900 (3)
C8—N2ⁱ	1.262 (5)	Mn1—O1ⁱ	1.909 (3)
C8—H8	0.9300	Mn1—O2	2.391 (3)
C9—N2	1.460 (5)	Mn1—Mn1ⁱ	2.9228 (11)
C9—C10	1.556 (6)	N2—C8ⁱ	1.262 (5)
C9—H9A	0.9700	O1—Mn1ⁱ	1.909 (3)

O1—C1—C6	121.9 (4)	C4—C11—H11B	109.5
O1—C1—C2	119.0 (4)	H11A—C11—H11B	109.5
C6—C1—C2	119.0 (4)	C4—C11—H11C	109.5
C3—C2—C1	119.4 (4)	H11A—C11—H11C	109.5
C3—C2—C7	116.3 (4)	H11B—C11—H11C	109.5
C1—C2—C7	124.0 (4)	O4—Cl1—O5	110.61 (18)
C4—C3—C2	122.3 (4)	O4—Cl1—O3	112.37 (19)
C4—C3—H3	118.8	O5—Cl1—O3	111.3 (2)
C2—C3—H3	118.8	O4—Cl1—O2	107.3 (2)
C3—C4—C5	117.5 (4)	O5—Cl1—O2	106.4 (2)
C3—C4—C11	122.3 (4)	O3—Cl1—O2	108.58 (18)
C5—C4—C11	119.9 (4)	N2—Mn1—N1	91.90 (16)
C6—C5—C4	120.6 (4)	N2—Mn1—O1	170.28 (14)
C6—C5—H5	119.7	N1—Mn1—O1	93.45 (14)
C4—C5—H5	119.7	N2—Mn1—O1ⁱ	93.60 (13)
C1—C6—C5	120.9 (4)	N1—Mn1—O1ⁱ	168.66 (16)
C1—C6—C8	123.0 (4)	O1—Mn1—O1ⁱ	79.78 (13)
C5—C6—C8	116.1 (4)	N2—Mn1—O2	93.10 (15)
N1—C7—C2	125.8 (4)	N1—Mn1—O2	97.47 (14)
N1—C7—H7	117.1	O1—Mn1—O2	94.23 (13)
C2—C7—H7	117.1	O1ⁱ—Mn1—O2	92.12 (12)
N2ⁱ—C8—C6	126.1 (3)	N2—Mn1—Mn1ⁱ	132.98 (11)
N2ⁱ—C8—H8	117.0	N1—Mn1—Mn1ⁱ	132.81 (12)
C6—C8—H8	117.0	O1—Mn1—Mn1ⁱ	40.01 (8)
N2—C9—C10	110.2 (4)	O1ⁱ—Mn1—Mn1ⁱ	39.77 (8)
N2—C9—H9A	109.6	O2—Mn1—Mn1ⁱ	94.14 (8)
C10—C9—H9A	109.6	C7—N1—C10	126.4 (4)
N2—C9—H9B	109.6	C7—N1—Mn1	125.2 (3)
C10—C9—H9B	109.6	C10—N1—Mn1	108.2 (3)
H9A—C9—H9B	108.1	C8ⁱ—N2—C9	125.4 (3)
N1—C10—C9	109.9 (3)	C8ⁱ—N2—Mn1	126.2 (3)
N1—C10—H10A	109.7	C9—N2—Mn1	108.3 (3)
C9—C10—H10A	109.7	C1—O1—Mn1	130.6 (3)
N1—C10—H10B	109.7	C1—O1—Mn1ⁱ	129.0 (3)
C9—C10—H10B	109.7	Mn1—O1—Mn1ⁱ	100.22 (13)
H10A—C10—H10B	108.2	Cl1—O2—Mn1	134.41 (17)
C4—C11—H11A	109.5

Symmetry code: (i) −x+2, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	[Mn₂(C₂₂H₂₂N₄O₂)(ClO₄)₂]
M_r	683.22
Crystal system, space group	Triclinic, P1
Temperature (K)	291
a, b, c (Å)	8.3129 (10), 8.3759 (11), 9.9712 (12)
α, β, γ (°)	81.484 (2), 68.520 (3), 78.838 (2)
V (Å³)	631.56 (14)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	1.28
Crystal size (mm)	0.31 × 0.21 × 0.15

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.73, 0.83
No. of measured, independent and observed [I > 2σ(I)] reflections	3663, 2439, 1701
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.118, 0.99
No. of reflections	2439
No. of parameters	182
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.56, −0.58

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXTL (Sheldrick, 2008).

Acknowledgements

The authors thank the National Science Foundation of China (grant No. 20271039).

References

Bai, J.-L., Zhou, H., Pan, Z.-Q. & Meng, X.-G. (2007). Acta Cryst. E63, m2641. Web of Science CSD CrossRef IUCr Journals Google Scholar
Brooker, S. & Croucher, P. D. (1997). Chem. Commun. pp. 459–460. CSD CrossRef Web of Science Google Scholar
Bruker (2000). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Chattopadhyay, T., Banu, K. S., Banerjee, A., Ribas, J., Majee, A., Nethaji, M. & Das, D. (2007). J. Mol. Struct. 833, 13–22. Web of Science CSD CrossRef CAS Google Scholar
Jong, C. B., Chung, H. H. & Ki, J. K. (2006). Inorg. Chem. Commun. 9, 171–174. Google Scholar
Ki, J. K., Duk, S. J., Duk, S. K., Chi, K. C., Ki, M. P. & Jong, C. B. (2006). Bull. Korean Chem. Soc. 27, 1747–1751. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Taniguchi, S. (1984). Bull. Chem. Soc. Jpn, 57, 2683–2684. CrossRef CAS Web of Science Google Scholar
Tei, L., Blake, A. J., Devillanova, F. A., Garau, A., Lippolis, V., Wilson, C. & Schröder, M. (2001). Chem. Commun. pp. 2582–2583. Web of Science CSD CrossRef Google Scholar
Venegas-Yazigi, D., Cortés, S., Paredes-García, V., Peña, O., Ibañez, A., Baggio, R. & Spodine, E. (2006). Polyhedron, 25, 2072–2082. Web of Science CSD CrossRef CAS Google Scholar

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