Monoclinic form of (cyanato-κN){2,2′-[ethane-1,2-diylbis(nitrilo­methyl­idyne)]diphenolato-κ4O,N,N′,O′}manganese(III)

Zhang, D.

doi:10.1107/S1600536810048270

metal-organic compounds

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Volume 66| Part 12| December 2010| Page m1656

https://doi.org/10.1107/S1600536810048270

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Monoclinic form of (cyanato-κN){2,2′-[ethane-1,2-diylbis(nitrilomethylidyne)]diphenolato-κ⁴O,N,N′,O′}manganese(III)

Daopeng Zhang ^a ^*

^aCollege of Chemical Engineering, Shandong University of Technology, Zibo 255049, People's Republic of China
^*Correspondence e-mail: dpzhang73@126.com

(Received 14 November 2010; accepted 19 November 2010; online 24 November 2010)

The title compound, [Mn(C₁₆H₁₄N₂O₂)(NCO)], is a monoclinic polymorph of the previously published orthorhombic form [Lu et al. (2006 ). Inorg. Chem. 45, 3538–3548]. The Mn^III ion is chelated by a tetradentate Schiff base ligand and coordinated by the N atom of a cyanate ligand in a distorted square-pyramidal arrangement. In the crystal, there are short intermolecular Mn⋯O_phenolate distances of 2.752 (3) Å between pairs of inversion-related molecules.

Related literature

For the orthorhombic polymorph of the title compound, see: Lu et al. (2006). For related structures, see: Mikuriya et al. (1992 ); Li et al. (1997 ); Wang et al. (2008 ).

Experimental

Crystal data

[Mn(C₁₆H₁₄N₂O₂)(NCO)]
M_r = 363.25
Monoclinic, P 2₁ /n
a = 9.6399 (16) Å
b = 10.9133 (18) Å
c = 15.198 (3) Å
β = 97.826 (3)°
V = 1584.0 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.85 mm⁻¹
T = 293 K
0.37 × 0.35 × 0.23 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.743, T_max = 0.828
7377 measured reflections
2698 independent reflections
1769 reflections with I > 2σ(I)
R_int = 0.047

Refinement

R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.131
S = 1.01
2698 reflections
217 parameters
H-atom parameters constrained
Δρ_max = 0.53 e Å⁻³
Δρ_min = −0.33 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: https://doi.org/10.1107/S1600536810048270/lh5164sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810048270/lh5164Isup2.hkl

checkCIF report

Comment top

Because of their excellent chelating ability for metal atoms, the tetradentate schiff-base ligands containing N₂O₂ coordination unit have been widely studied in coordination chemistry field. Here, we report a Mn(III) complex based on tetradentate ligand N,N'-bis(salicylidene)-1,2-diphenyl-1,2-ethanediamine.

The molecular structure of the title complex is shown in Figure 1. The Mn^III ion is involved in a distorted square-pyramidal arrangement by a N₃O₂ unit, in which the four basal sites are occupied by two N atoms and two O atoms from the Schiff base ligand, and the apical position is occupied by the N atom of a cyanato ligand. The bond distances can be compared to this those found in the related structures (Lu, et al., 2006; Mikuriya, et al., 1992; Li, et al., 1997; Wang, et al., 2008). The Mn^III ion lies above the basal plane formed by N₂O₂ unit by 0.228 Å. The short intermolecular distance of Mn···O_phenolate 2.752 (3) Å indicates that there exsits weak interaction between the two complexes realted by inversion centers in the crystal.

Related literature top

For the orthorhombic polymorph of the title compound, see: Lu et al. (2006). For related structures, see: Mikuriya et al. (1992); Li et al. (1997); Wang et al. (2008).

Experimental top

The synthesis of the title complex was carried out by mixing Mn(ClO₄)₂.6H₂O (0.1mmol), NaNCO (0.1mmol) and the schiff-base ligand (0.1mmol) in methanol (20ml). The mixture was stirred for about half an hour at room temperature and then filtered and the filtrate allowed to partially evaporate in air for sevral days to produce crystals suitable for X-ray diffraction with a yield about 64%.

Structure description top

For the orthorhombic polymorph of the title compound, see: Lu et al. (2006). For related structures, see: Mikuriya et al. (1992); Li et al. (1997); Wang et al. (2008).

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 the title complex with the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are not shown.

(cyanato-κN){2,2'-[ethane-1,2-diylbis(nitrilomethylidyne)]diphenolato- κ⁴O,N,N',O'}manganese(III) top

Crystal data top

[Mn(C₁₆H₁₄N₂O₂)(NCO)]	F(000) = 744
M_r = 363.25	D_x = 1.523 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1289 reflections
a = 9.6399 (16) Å	θ = 2.6–26.6°
b = 10.9133 (18) Å	µ = 0.85 mm⁻¹
c = 15.198 (3) Å	T = 293 K
β = 97.826 (3)°	Block, dark-brown
V = 1584.0 (5) Å³	0.37 × 0.35 × 0.23 mm
Z = 4

Data collection top

Bruker APEXII CCD area-detector diffractometer	2698 independent reflections
Radiation source: fine-focus sealed tube	1769 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.047
φ and ω scans	θ_max = 24.7°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→11
T_min = 0.743, T_max = 0.828	k = −8→12
7377 measured reflections	l = −17→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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.131	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0695P)²] where P = (F_o² + 2F_c²)/3
2698 reflections	(Δ/σ)_max = 0.001
217 parameters	Δρ_max = 0.53 e Å⁻³
0 restraints	Δρ_min = −0.33 e Å⁻³

Crystal data top

[Mn(C₁₆H₁₄N₂O₂)(NCO)]	V = 1584.0 (5) Å³
M_r = 363.25	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.6399 (16) Å	µ = 0.85 mm⁻¹
b = 10.9133 (18) Å	T = 293 K
c = 15.198 (3) Å	0.37 × 0.35 × 0.23 mm
β = 97.826 (3)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	2698 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1769 reflections with I > 2σ(I)
T_min = 0.743, T_max = 0.828	R_int = 0.047
7377 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	0 restraints
wR(F²) = 0.131	H-atom parameters constrained
S = 1.01	Δρ_max = 0.53 e Å⁻³
2698 reflections	Δρ_min = −0.33 e Å⁻³
217 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	0.10463 (6)	0.63253 (5)	0.52050 (4)	0.0420 (2)
O1	−0.0313 (3)	0.7121 (2)	0.57698 (17)	0.0489 (7)
O2	0.1015 (3)	0.4886 (2)	0.58923 (17)	0.0472 (7)
O3	0.5003 (4)	0.6657 (5)	0.6799 (3)	0.1254 (17)
N1	0.0793 (3)	0.7500 (3)	0.4211 (2)	0.0453 (8)
N2	0.2150 (3)	0.5430 (3)	0.4394 (2)	0.0425 (8)
N3	0.2893 (4)	0.7093 (3)	0.5904 (2)	0.0566 (10)
C1	−0.1070 (4)	0.8699 (4)	0.4711 (3)	0.0476 (10)
C2	−0.1116 (4)	0.8071 (4)	0.5515 (3)	0.0463 (10)
C3	−0.2089 (5)	0.8453 (4)	0.6060 (3)	0.0621 (13)
H3	−0.2123	0.8054	0.6598	0.075*
C4	−0.2991 (5)	0.9395 (4)	0.5824 (4)	0.0715 (14)
H4	−0.3638	0.9619	0.6196	0.086*
C5	−0.2956 (5)	1.0021 (4)	0.5037 (4)	0.0724 (15)
H5	−0.3568	1.0667	0.4879	0.087*
C6	−0.2003 (4)	0.9674 (4)	0.4492 (3)	0.0605 (12)
H6	−0.1974	1.0096	0.3963	0.073*
C7	−0.0106 (4)	0.8380 (4)	0.4105 (3)	0.0530 (11)
H7	−0.0132	0.8849	0.3593	0.064*
C8	0.3143 (4)	0.3997 (3)	0.5504 (3)	0.0415 (9)
C9	0.2170 (4)	0.4207 (4)	0.6109 (3)	0.0423 (9)
C10	0.2394 (4)	0.3634 (4)	0.6929 (3)	0.0503 (10)
H10	0.1770	0.3776	0.7334	0.060*
C11	0.3501 (4)	0.2868 (4)	0.7163 (3)	0.0626 (13)
H11	0.3630	0.2503	0.7721	0.075*
C12	0.4445 (4)	0.2632 (4)	0.6557 (3)	0.0638 (13)
H12	0.5195	0.2103	0.6709	0.077*
C13	0.4252 (4)	0.3189 (4)	0.5740 (3)	0.0524 (11)
H13	0.4872	0.3025	0.5337	0.063*
C14	0.2980 (4)	0.4541 (4)	0.4634 (3)	0.0451 (10)
H14	0.3511	0.4225	0.4220	0.054*
C15	0.1771 (4)	0.7294 (4)	0.3564 (3)	0.0569 (12)
H15A	0.2662	0.7686	0.3763	0.068*
H15B	0.1395	0.7634	0.2992	0.068*
C16	0.1964 (4)	0.5929 (4)	0.3489 (3)	0.0533 (11)
H16A	0.1150	0.5565	0.3141	0.064*
H16B	0.2780	0.5752	0.3201	0.064*
C17	0.3891 (6)	0.6904 (5)	0.6329 (3)	0.0659 (14)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn1	0.0320 (4)	0.0509 (4)	0.0445 (4)	0.0037 (3)	0.0098 (3)	0.0052 (3)
O1	0.0417 (16)	0.0560 (18)	0.0502 (17)	0.0124 (14)	0.0108 (13)	0.0024 (13)
O2	0.0324 (16)	0.0555 (17)	0.0570 (19)	0.0080 (13)	0.0174 (13)	0.0130 (13)
O3	0.051 (2)	0.238 (5)	0.081 (3)	0.023 (3)	−0.012 (2)	−0.046 (3)
N1	0.0299 (18)	0.057 (2)	0.049 (2)	0.0001 (16)	0.0062 (15)	0.0068 (16)
N2	0.0301 (18)	0.057 (2)	0.042 (2)	0.0001 (16)	0.0086 (14)	0.0047 (16)
N3	0.043 (2)	0.065 (3)	0.059 (3)	−0.0037 (19)	0.0009 (19)	−0.0029 (19)
C1	0.034 (2)	0.045 (2)	0.063 (3)	−0.003 (2)	0.0041 (19)	0.001 (2)
C2	0.035 (2)	0.046 (2)	0.057 (3)	−0.001 (2)	0.004 (2)	−0.010 (2)
C3	0.056 (3)	0.063 (3)	0.069 (3)	0.008 (2)	0.015 (2)	−0.007 (2)
C4	0.053 (3)	0.068 (3)	0.095 (4)	0.014 (3)	0.014 (3)	−0.007 (3)
C5	0.052 (3)	0.054 (3)	0.109 (5)	0.015 (2)	0.003 (3)	−0.006 (3)
C6	0.044 (3)	0.056 (3)	0.080 (3)	0.002 (2)	0.001 (2)	0.011 (2)
C7	0.038 (2)	0.060 (3)	0.059 (3)	−0.007 (2)	−0.001 (2)	0.016 (2)
C8	0.028 (2)	0.050 (2)	0.048 (2)	−0.0009 (17)	0.0096 (17)	−0.0012 (19)
C9	0.030 (2)	0.048 (2)	0.049 (3)	−0.0021 (18)	0.0077 (18)	0.0004 (19)
C10	0.034 (2)	0.068 (3)	0.049 (3)	0.000 (2)	0.0102 (18)	0.005 (2)
C11	0.040 (3)	0.087 (4)	0.059 (3)	0.008 (2)	0.004 (2)	0.023 (3)
C12	0.034 (3)	0.080 (3)	0.078 (3)	0.011 (2)	0.008 (2)	0.016 (3)
C13	0.028 (2)	0.065 (3)	0.066 (3)	0.000 (2)	0.013 (2)	0.003 (2)
C14	0.026 (2)	0.059 (3)	0.052 (3)	−0.0040 (19)	0.0122 (18)	−0.006 (2)
C15	0.040 (3)	0.081 (3)	0.051 (3)	0.008 (2)	0.013 (2)	0.022 (2)
C16	0.039 (2)	0.085 (3)	0.037 (2)	0.003 (2)	0.0105 (18)	0.005 (2)
C17	0.048 (3)	0.100 (4)	0.054 (3)	−0.013 (3)	0.021 (3)	−0.029 (3)

Geometric parameters (Å, º) top

Mn1—O1	1.874 (2)	C5—C6	1.371 (6)
Mn1—O2	1.889 (3)	C5—H5	0.9300
Mn1—N1	1.971 (3)	C6—H6	0.9300
Mn1—N2	1.991 (3)	C7—H7	0.9300
Mn1—N3	2.118 (4)	C8—C13	1.394 (5)
O1—C2	1.320 (4)	C8—C9	1.418 (5)
O2—C9	1.340 (4)	C8—C14	1.438 (5)
O3—C17	1.235 (6)	C9—C10	1.386 (5)
N1—C7	1.288 (5)	C10—C11	1.364 (5)
N1—C15	1.469 (5)	C10—H10	0.9300
N2—C14	1.280 (5)	C11—C12	1.403 (6)
N2—C16	1.466 (5)	C11—H11	0.9300
N3—C17	1.102 (6)	C12—C13	1.372 (5)
C1—C6	1.403 (5)	C12—H12	0.9300
C1—C2	1.408 (5)	C13—H13	0.9300
C1—C7	1.437 (6)	C14—H14	0.9300
C2—C3	1.397 (5)	C15—C16	1.508 (6)
C3—C4	1.363 (6)	C15—H15A	0.9700
C3—H3	0.9300	C15—H15B	0.9700
C4—C5	1.382 (7)	C16—H16A	0.9700
C4—H4	0.9300	C16—H16B	0.9700

O1—Mn1—O2	93.85 (11)	N1—C7—C1	125.7 (4)
O1—Mn1—N1	91.64 (12)	N1—C7—H7	117.1
O2—Mn1—N1	162.75 (13)	C1—C7—H7	117.1
O1—Mn1—N2	167.59 (13)	C13—C8—C9	119.1 (4)
O2—Mn1—N2	89.12 (12)	C13—C8—C14	118.8 (3)
N1—Mn1—N2	82.24 (13)	C9—C8—C14	122.0 (3)
O1—Mn1—N3	100.33 (13)	O2—C9—C10	119.5 (3)
O2—Mn1—N3	97.30 (13)	O2—C9—C8	122.1 (3)
N1—Mn1—N3	97.78 (14)	C10—C9—C8	118.3 (4)
N2—Mn1—N3	91.22 (14)	C11—C10—C9	122.1 (4)
C2—O1—Mn1	130.4 (2)	C11—C10—H10	119.0
C9—O2—Mn1	121.3 (2)	C9—C10—H10	119.0
C7—N1—C15	120.9 (3)	C10—C11—C12	119.8 (4)
C7—N1—Mn1	126.2 (3)	C10—C11—H11	120.1
C15—N1—Mn1	112.9 (2)	C12—C11—H11	120.1
C14—N2—C16	122.7 (3)	C13—C12—C11	119.5 (4)
C14—N2—Mn1	124.2 (3)	C13—C12—H12	120.3
C16—N2—Mn1	113.0 (2)	C11—C12—H12	120.3
C17—N3—Mn1	145.7 (4)	C12—C13—C8	121.2 (4)
C6—C1—C2	118.7 (4)	C12—C13—H13	119.4
C6—C1—C7	118.8 (4)	C8—C13—H13	119.4
C2—C1—C7	122.5 (4)	N2—C14—C8	124.2 (3)
O1—C2—C3	118.3 (4)	N2—C14—H14	117.9
O1—C2—C1	123.4 (3)	C8—C14—H14	117.9
C3—C2—C1	118.2 (4)	N1—C15—C16	107.4 (3)
C4—C3—C2	121.6 (5)	N1—C15—H15A	110.2
C4—C3—H3	119.2	C16—C15—H15A	110.2
C2—C3—H3	119.2	N1—C15—H15B	110.2
C3—C4—C5	120.8 (5)	C16—C15—H15B	110.2
C3—C4—H4	119.6	H15A—C15—H15B	108.5
C5—C4—H4	119.6	N2—C16—C15	107.2 (3)
C6—C5—C4	118.9 (4)	N2—C16—H16A	110.3
C6—C5—H5	120.5	C15—C16—H16A	110.3
C4—C5—H5	120.5	N2—C16—H16B	110.3
C5—C6—C1	121.8 (5)	C15—C16—H16B	110.3
C5—C6—H6	119.1	H16A—C16—H16B	108.5
C1—C6—H6	119.1	N3—C17—O3	178.2 (6)

Experimental details

Crystal data
Chemical formula	[Mn(C₁₆H₁₄N₂O₂)(NCO)]
M_r	363.25
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	9.6399 (16), 10.9133 (18), 15.198 (3)
β (°)	97.826 (3)
V (Å³)	1584.0 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.85
Crystal size (mm)	0.37 × 0.35 × 0.23

Data collection
Diffractometer	Bruker APEXII CCD area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.743, 0.828
No. of measured, independent and observed [I > 2σ(I)] reflections	7377, 2698, 1769
R_int	0.047
(sin θ/λ)_max (Å⁻¹)	0.589

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.131, 1.01
No. of reflections	2698
No. of parameters	217
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.53, −0.33

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

Acknowledgements

he author thanks the Doctoral Starting Fund of Shandong University of Technology for support.

References

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