Monoclinic form of (cyanato-κN){2,2'-[ethane-1,2-diylbis(nitrilo-methyl-idyne)]diphenolato-κO,N,N',O'}manganese(III).

The title compound, [Mn(C(16)H(14)N(2)O(2))(NCO)], is a monoclinic polymorph of the previously published ortho-rhom-bic form [Lu et al. (2006 ▶). Inorg. Chem.45, 3538-3548]. The Mn(III) ion is chelated by a tetra-dentate 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 inter-molecular Mn⋯O(phenolate) distances of 2.752 (3) Å between pairs of inversion-related mol-ecules.

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 = 363.25

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.048

wR(F 2) = 0.131

S = 1.01

2698 reflections

217 parameters

H-atom parameters constrained

Δρmax = 0.53 e Å−3

Δρmin = −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.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810048270/lh5164sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810048270/lh5164Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Mn(C16H14N2O2)(NCO)]	F(000) = 744
Mr = 363.25	Dx = 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

Bruker APEXII CCD area-detector diffractometer	2698 independent reflections
Radiation source: fine-focus sealed tube	1769 reflections with I > 2σ(I)
graphite	Rint = 0.047
φ and ω scans	θmax = 24.7°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→11
Tmin = 0.743, Tmax = 0.828	k = −8→12
7377 measured reflections	l = −17→17

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(Fo2) + (0.0695P)2] where P = (Fo2 + 2Fc2)/3
2698 reflections	(Δ/σ)max = 0.001
217 parameters	Δρmax = 0.53 e Å−3
0 restraints	Δρmin = −0.33 e Å−3

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	0.10463 (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)

	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)

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)