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metal-organic compounds
Diazidobis{2-[3-(dimethylamino)propyliminomethyl]phenol}manganese(III) perchlorate
aSchool of Chemistry and Life Sciences, Harbin University, Harbin 150080, People's Republic of China
*Correspondence e-mail: ygb_hu@sina.com
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 MnIII ion is hexacoordinated by two N and two O atoms from two phenolate ligands and two N atoms from two azide ligands. The MnIII cation lies on an inversion centre and, as a result, the 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
|
Data collection: APEX2 (Bruker, 2004); cell 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
10.1107/S1600536808023349/ez2129sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536808023349/ez2129Isup2.hkl
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.
The H atom on O1 was located from a difference density map and was refined with a distance restraint of d(O—H) = 0.82 (2) Å. All other H atoms were placed in calculated positions with C—H = 0.93 Å and N—H = 0.86 Å and refined as riding with Uiso(H) = 1.2Ueq(carrier).
Data collection: APEX2 (Bruker, 2004); cell
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). ![]() | Fig. 1. The molecular structure of (I), drawn with 30% probability displacement ellipsoids for the non-hydrogen atoms. |
[Mn(N3)2(C12H18N2O)2]ClO4 | F(000) = 1360 |
Mr = 651.02 | Dx = 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 |
Bruker APEXII CCD area-detector diffractometer | 2842 independent reflections |
Radiation source: fine-focus sealed tube | 2216 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.044 |
ϕ and ω scans | θmax = 25.5°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | h = −20→1 |
Tmin = 0.790, Tmax = 0.884 | k = −1→19 |
3388 measured reflections | l = −13→15 |
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(Fo2) + (0.0843P)2 + 2.1116P] where P = (Fo2 + 2Fc2)/3 |
2842 reflections | (Δ/σ)max < 0.001 |
195 parameters | Δρmax = 0.48 e Å−3 |
0 restraints | Δρmin = −0.48 e Å−3 |
[Mn(N3)2(C12H18N2O)2]ClO4 | V = 3054.6 (6) Å3 |
Mr = 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)° |
Bruker APEXII CCD area-detector diffractometer | 2842 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | 2216 reflections with I > 2σ(I) |
Tmin = 0.790, Tmax = 0.884 | Rint = 0.044 |
3388 measured reflections |
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 | Δρmax = 0.48 e Å−3 |
2842 reflections | Δρmin = −0.48 e Å−3 |
195 parameters |
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 | ||
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* |
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) |
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 |
Mr | 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) |
Tmin, Tmax | 0.790, 0.884 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3388, 2842, 2216 |
Rint | 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 |
Δρmax, Δρmin (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.
References
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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.
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 MnIII cation lies on an inversion centre, as a consequence the asymmetric unit comprises half of the molecule. The MnIII 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.