Diazido­bis{2-[3-(dimethyl­amino)propyl­imino­meth­yl]phenol}manganese(III) perchlorate

Yang, G.-B.; Sun, Z.-H.

doi:10.1107/S1600536808023349

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 8| August 2008| Page m1080

doi:10.1107/S1600536808023349

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Diazidobis{2-[3-(dimethylamino)propyliminomethyl]phenol}manganese(III) perchlorate

Gui-Bin Yang ^a ^* and Zhen-Hai Sun ^a

^aSchool of Chemistry and Life Sciences, Harbin University, Harbin 150080, People's Republic of China
^*Correspondence e-mail: ygb_hu@sina.com

(Received 8 May 2008; accepted 24 July 2008; online 31 July 2008)

The title compound, [Mn(N₃)₂(C₁₂H₁₈N₂O)₂]ClO₄, was synthesized from manganese(III) acetate, sodium azide and 2-[3-(dimethylamino)propyliminomethyl]phenol by a hydrothermal reaction. The Mn^III ion is hexacoordinated by two N and two O atoms from two phenolate ligands and two N atoms from two azide ligands. The Mn^III cation lies on an inversion centre and, as a result, the asymmetric unit comprises one half-molecule.

Related literature

For related literature, see: Choudhury et al. (2001 ); Church & Halvorson (1959 ); Chung et al. (1971 ); Okabe & Oya (2000 ); Serre et al. (2005 ); Scapin et al. (1997 ).

Experimental

Crystal data

[Mn(N₃)₂(C₁₂H₁₈N₂O)₂]ClO₄
M_r = 651.02
Monoclinic, C 2/c
a = 16.8115 (17) Å
b = 16.4456 (18) Å
c = 12.9059 (14) Å
β = 121.121 (8)°
V = 3054.6 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.57 mm⁻¹
T = 293 (2) K
0.43 × 0.28 × 0.22 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.790, T_max = 0.884
3388 measured reflections
2842 independent reflections
2216 reflections with I > 2σ(I)
R_int = 0.044

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.144
S = 1.00
2842 reflections
195 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.48 e Å⁻³
Δρ_min = −0.48 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808023349/ez2129sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808023349/ez2129Isup2.hkl

checkCIF report

Comment top

In recent years, Schiff base ligands have been widely used as polydentate ligands that can coordinate to transition or rare earth ions yielding complexes with interesting properties that are useful in materials science (Church & Halvorson, 1959; Chung et al., 1971) and in biological systems (Okabe & Oya, 2000; Serre et al., 2005; Scapin et al., 1997). Herein, we report the synthesis and X-ray crystal structure analysis of the title compound, (I).

The molecular structure of (I) is shown in Fig. 1. The Mn^III cation lies on an inversion centre, as a consequence the asymmetric unit comprises half of the molecule. The Mn^III ion is hexacoordinated by two N and two O atoms from two 2-[3-(dimethylamino)propyliminomethyl]phenolate ligands and two N atoms from two azide ligands.

Related literature top

For related literature, see: Choudhury et al. (2001); Church & Halvorson (1959); Chung et al. (1971); Okabe & Oya (2000); Serre et al. (2005); Scapin et al. (1997).

Experimental top

The title compound was synthesized according to the following two steps:

(i) Synthesis of the ligand: 2-[3-(dimethylamino)propyliminomethyl]phenol was prepared by refluxing 3-dimethylamino-1-propylamine (1.0 mmol) and salicylaldehyde (1.0 mmol) in ethanol (25 ml) for two hours and used without further purification, according to the literature method (see: Choudhury et al., 2001).

(ii) Synthesis of the complex: A solution of sodium azide (0.5 mmol) and sodium perchlorate (0.05 mmol) in 5 ml water was added to the ethanol solution of the ligand (1.0 mmol). Then manganese(III) acetate dihydrate (0.5 mmol) in 3 ml water was added to the above mixture. A yellow mixture was obtained by refluxing for 3 h and was left to stand undisturbed. Upon slow evaporation at room temperature, light yellow prismatic crystals suitable for X-ray diffraction appeared three days later and were separated by filtration.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of (I), drawn with 30% probability displacement ellipsoids for the non-hydrogen atoms.

Diazidobis{2-[3-(dimethylamino)propyliminomethyl]phenol}manganese(III) perchlorate top

Crystal data top

[Mn(N₃)₂(C₁₂H₁₈N₂O)₂]ClO₄	F(000) = 1360
M_r = 651.02	D_x = 1.416 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2842 reflections
a = 16.8115 (17) Å	θ = 1.9–25.5°
b = 16.4456 (18) Å	µ = 0.58 mm⁻¹
c = 12.9059 (14) Å	T = 293 K
β = 121.121 (8)°	Prism, yellow
V = 3054.6 (6) Å³	0.43 × 0.28 × 0.22 mm
Z = 4

Data collection top

Bruker APEXII CCD area-detector diffractometer	2842 independent reflections
Radiation source: fine-focus sealed tube	2216 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.044
ϕ and ω scans	θ_max = 25.5°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −20→1
T_min = 0.790, T_max = 0.884	k = −1→19
3388 measured reflections	l = −13→15

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.144	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ²(F_o²) + (0.0843P)² + 2.1116P] where P = (F_o² + 2F_c²)/3
2842 reflections	(Δ/σ)_max < 0.001
195 parameters	Δρ_max = 0.48 e Å⁻³
0 restraints	Δρ_min = −0.48 e Å⁻³

Crystal data top

[Mn(N₃)₂(C₁₂H₁₈N₂O)₂]ClO₄	V = 3054.6 (6) Å³
M_r = 651.02	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 16.8115 (17) Å	µ = 0.58 mm⁻¹
b = 16.4456 (18) Å	T = 293 K
c = 12.9059 (14) Å	0.43 × 0.28 × 0.22 mm
β = 121.121 (8)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	2842 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	2216 reflections with I > 2σ(I)
T_min = 0.790, T_max = 0.884	R_int = 0.044
3388 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.144	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	Δρ_max = 0.48 e Å⁻³
2842 reflections	Δρ_min = −0.48 e Å⁻³
195 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
Mn1	0.2500	0.2500	0.5000	0.0467 (2)
Cl1	0.0000	0.15323 (8)	0.7500	0.0711 (3)
O1	0.28801 (14)	0.20397 (12)	0.40192 (19)	0.0626 (5)
O2	0.0690 (2)	0.2006 (3)	0.7580 (4)	0.1579 (17)
O3	0.0340 (3)	0.1044 (2)	0.8529 (3)	0.1482 (15)
N1	0.13856 (14)	0.16698 (13)	0.43275 (19)	0.0481 (5)
N2	−0.12645 (16)	0.32706 (14)	0.3901 (2)	0.0576 (6)
N3	0.33339 (17)	0.16169 (15)	0.6490 (2)	0.0603 (6)
N4	0.36786 (18)	0.10586 (17)	0.6266 (2)	0.0649 (6)
N5	0.4004 (3)	0.0528 (2)	0.6034 (4)	0.0980 (10)
C1	0.25785 (18)	0.14208 (15)	0.3267 (2)	0.0497 (6)
C2	0.18274 (18)	0.09312 (16)	0.3069 (2)	0.0523 (6)
C3	0.1561 (2)	0.0279 (2)	0.2252 (3)	0.0730 (9)
H3A	0.1071	−0.0055	0.2123	0.088*
C4	0.2015 (3)	0.0129 (2)	0.1639 (4)	0.0896 (11)
H4A	0.1828	−0.0300	0.1092	0.108*
C5	0.2746 (3)	0.0614 (2)	0.1835 (3)	0.0791 (10)
H5A	0.3050	0.0512	0.1417	0.095*
C6	0.3033 (2)	0.12473 (19)	0.2640 (3)	0.0633 (7)
H6A	0.3534	0.1565	0.2771	0.076*
C7	0.12924 (18)	0.10820 (16)	0.3631 (2)	0.0513 (6)
H7A	0.0826	0.0708	0.3467	0.062*
C8	0.06994 (18)	0.17367 (16)	0.4719 (3)	0.0532 (6)
H8A	0.1022	0.1806	0.5590	0.064*
H8B	0.0336	0.1241	0.4513	0.064*
C9	0.0061 (2)	0.24542 (17)	0.4104 (3)	0.0572 (7)
H9A	−0.0247	0.2389	0.3233	0.069*
H9B	0.0427	0.2949	0.4322	0.069*
C10	−0.0665 (2)	0.25332 (17)	0.4460 (3)	0.0583 (7)
H10A	−0.1053	0.2051	0.4203	0.070*
H10B	−0.0358	0.2570	0.5335	0.070*
C11	−0.0775 (3)	0.4036 (2)	0.4465 (4)	0.0850 (10)
H11A	−0.0216	0.4066	0.4438	0.127*
H11B	−0.0621	0.4052	0.5292	0.127*
H11C	−0.1169	0.4488	0.4033	0.127*
C12	−0.2131 (2)	0.3213 (2)	0.3943 (4)	0.0844 (11)
H12A	−0.2501	0.3691	0.3585	0.127*
H12B	−0.1974	0.3170	0.4770	0.127*
H12C	−0.2477	0.2742	0.3502	0.127*
H1A	0.313 (2)	0.2343 (11)	0.376 (3)	0.080*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn1	0.0433 (3)	0.0501 (3)	0.0527 (3)	−0.0081 (2)	0.0290 (3)	−0.0109 (2)
Cl1	0.0692 (7)	0.0852 (8)	0.0727 (7)	0.000	0.0465 (6)	0.000
O1	0.0654 (12)	0.0654 (12)	0.0774 (13)	−0.0213 (10)	0.0513 (11)	−0.0260 (10)
O2	0.083 (2)	0.220 (4)	0.168 (4)	−0.032 (3)	0.062 (2)	0.055 (3)
O3	0.219 (4)	0.128 (3)	0.087 (2)	−0.018 (3)	0.071 (2)	0.0178 (19)
N1	0.0422 (11)	0.0487 (12)	0.0532 (12)	−0.0003 (9)	0.0244 (9)	0.0002 (10)
N2	0.0499 (12)	0.0601 (14)	0.0690 (14)	0.0035 (11)	0.0352 (11)	−0.0025 (11)
N3	0.0555 (13)	0.0637 (15)	0.0616 (14)	−0.0029 (12)	0.0301 (12)	0.0023 (12)
N4	0.0647 (15)	0.0638 (16)	0.0727 (16)	−0.0071 (13)	0.0401 (14)	0.0059 (13)
N5	0.127 (3)	0.0709 (19)	0.135 (3)	0.0137 (19)	0.096 (3)	0.0101 (19)
C1	0.0521 (14)	0.0471 (13)	0.0497 (14)	0.0050 (11)	0.0262 (12)	−0.0020 (11)
C2	0.0484 (14)	0.0480 (14)	0.0532 (14)	0.0048 (11)	0.0212 (12)	−0.0027 (11)
C3	0.073 (2)	0.0593 (17)	0.079 (2)	−0.0060 (15)	0.0346 (17)	−0.0179 (16)
C4	0.102 (3)	0.079 (2)	0.094 (3)	−0.008 (2)	0.055 (2)	−0.039 (2)
C5	0.095 (3)	0.080 (2)	0.079 (2)	0.006 (2)	0.057 (2)	−0.0181 (18)
C6	0.0683 (18)	0.0650 (17)	0.0686 (18)	0.0052 (15)	0.0438 (15)	−0.0039 (14)
C7	0.0425 (13)	0.0456 (14)	0.0567 (15)	−0.0028 (11)	0.0190 (11)	0.0005 (12)
C8	0.0428 (13)	0.0569 (15)	0.0642 (16)	−0.0031 (12)	0.0307 (12)	0.0028 (13)
C9	0.0483 (15)	0.0666 (18)	0.0628 (17)	0.0030 (13)	0.0329 (13)	0.0054 (13)
C10	0.0521 (16)	0.0656 (18)	0.0652 (17)	0.0022 (13)	0.0359 (14)	0.0042 (13)
C11	0.082 (2)	0.068 (2)	0.114 (3)	−0.0071 (18)	0.056 (2)	−0.019 (2)
C12	0.0615 (19)	0.089 (2)	0.119 (3)	0.0021 (18)	0.059 (2)	−0.008 (2)

Geometric parameters (Å, º) top

Mn1—O1	1.8493 (18)	C3—C4	1.377 (5)
Mn1—O1ⁱ	1.8493 (18)	C3—H3A	0.9300
Mn1—N1ⁱ	2.109 (2)	C4—C5	1.374 (5)
Mn1—N1	2.109 (2)	C4—H4A	0.9300
Mn1—N3ⁱ	2.233 (2)	C5—C6	1.370 (4)
Mn1—N3	2.233 (2)	C5—H5A	0.9300
Cl1—O2	1.357 (3)	C6—H6A	0.9300
Cl1—O2ⁱⁱ	1.357 (3)	C7—H7A	0.9300
Cl1—O3ⁱⁱ	1.397 (3)	C8—C9	1.515 (4)
Cl1—O3	1.397 (3)	C8—H8A	0.9700
O1—C1	1.314 (3)	C8—H8B	0.9700
O1—H1A	0.828 (9)	C9—C10	1.516 (4)
N1—C7	1.273 (3)	C9—H9A	0.9700
N1—C8	1.483 (3)	C9—H9B	0.9700
N2—C11	1.474 (4)	C10—H10A	0.9700
N2—C12	1.489 (4)	C10—H10B	0.9700
N2—C10	1.502 (4)	C11—H11A	0.9600
N3—N4	1.199 (4)	C11—H11B	0.9600
N4—N5	1.149 (4)	C11—H11C	0.9600
C1—C6	1.400 (4)	C12—H12A	0.9600
C1—C2	1.405 (4)	C12—H12B	0.9600
C2—C3	1.405 (4)	C12—H12C	0.9600
C2—C7	1.439 (4)

O1—Mn1—O1ⁱ	180.00 (8)	C5—C4—H4A	120.0
O1—Mn1—N1ⁱ	89.94 (8)	C3—C4—H4A	120.0
O1ⁱ—Mn1—N1ⁱ	90.06 (8)	C6—C5—C4	120.8 (3)
O1—Mn1—N1	90.06 (8)	C6—C5—H5A	119.6
O1ⁱ—Mn1—N1	89.94 (8)	C4—C5—H5A	119.6
N1ⁱ—Mn1—N1	180.00 (13)	C5—C6—C1	120.7 (3)
O1—Mn1—N3ⁱ	87.82 (10)	C5—C6—H6A	119.7
O1ⁱ—Mn1—N3ⁱ	92.18 (10)	C1—C6—H6A	119.7
N1ⁱ—Mn1—N3ⁱ	87.83 (8)	N1—C7—C2	127.3 (2)
N1—Mn1—N3ⁱ	92.17 (8)	N1—C7—H7A	116.4
O1—Mn1—N3	92.18 (10)	C2—C7—H7A	116.4
O1ⁱ—Mn1—N3	87.82 (10)	N1—C8—C9	110.2 (2)
N1ⁱ—Mn1—N3	92.17 (8)	N1—C8—H8A	109.6
N1—Mn1—N3	87.83 (8)	C9—C8—H8A	109.6
N3ⁱ—Mn1—N3	180.0	N1—C8—H8B	109.6
O2—Cl1—O2ⁱⁱ	109.9 (5)	C9—C8—H8B	109.6
O2—Cl1—O3ⁱⁱ	108.4 (3)	H8A—C8—H8B	108.1
O2ⁱⁱ—Cl1—O3ⁱⁱ	110.1 (2)	C8—C9—C10	111.8 (2)
O2—Cl1—O3	110.1 (2)	C8—C9—H9A	109.2
O2ⁱⁱ—Cl1—O3	108.4 (3)	C10—C9—H9A	109.2
O3ⁱⁱ—Cl1—O3	109.8 (3)	C8—C9—H9B	109.3
C1—O1—Mn1	133.21 (18)	C10—C9—H9B	109.3
C1—O1—H1A	104.7 (14)	H9A—C9—H9B	107.9
Mn1—O1—H1A	117.3 (13)	N2—C10—C9	111.7 (2)
C7—N1—C8	117.6 (2)	N2—C10—H10A	109.3
C7—N1—Mn1	122.76 (18)	C9—C10—H10A	109.3
C8—N1—Mn1	119.59 (17)	N2—C10—H10B	109.3
C11—N2—C12	110.1 (3)	C9—C10—H10B	109.3
C11—N2—C10	112.8 (2)	H10A—C10—H10B	107.9
C12—N2—C10	111.0 (3)	N2—C11—H11A	109.5
N4—N3—Mn1	117.2 (2)	N2—C11—H11B	109.5
N5—N4—N3	179.0 (3)	H11A—C11—H11B	109.5
O1—C1—C6	117.9 (3)	N2—C11—H11C	109.5
O1—C1—C2	123.1 (2)	H11A—C11—H11C	109.5
C6—C1—C2	119.0 (3)	H11B—C11—H11C	109.5
C1—C2—C3	118.8 (3)	N2—C12—H12A	109.5
C1—C2—C7	123.1 (2)	N2—C12—H12B	109.5
C3—C2—C7	118.0 (3)	H12A—C12—H12B	109.5
C4—C3—C2	120.7 (3)	N2—C12—H12C	109.5
C4—C3—H3A	119.6	H12A—C12—H12C	109.5
C2—C3—H3A	119.6	H12B—C12—H12C	109.5
C5—C4—C3	119.9 (3)

Symmetry codes: (i) −x+1/2, −y+1/2, −z+1; (ii) −x, y, −z+3/2.

Experimental details

Crystal data
Chemical formula	[Mn(N₃)₂(C₁₂H₁₈N₂O)₂]ClO₄
M_r	651.02
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	16.8115 (17), 16.4456 (18), 12.9059 (14)
β (°)	121.121 (8)
V (Å³)	3054.6 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.58
Crystal size (mm)	0.43 × 0.28 × 0.22

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.790, 0.884
No. of measured, independent and observed [I > 2σ(I)] reflections	3388, 2842, 2216
R_int	0.044
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.144, 1.00
No. of reflections	2842
No. of parameters	195
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.48, −0.48

Computer programs: APEX2 (Bruker, 2004), SAINT-Plus (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

The authors thank Harbin University for financial support.

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