Chlorido{5,5'-dimeth-oxy-2,2'-[1,2-phenyl-enebis(nitrilo-methyl-idyne)]diphenolato-κO,N,N',O'}manganese(III).

In the title complex, [Mn(C(22)H(18)N(2)O(4))Cl], the Mn(III) centre is in a distorted square-pyramidal configuration, with the basal plane formed by the N(2)O(2) donors of the tetra-dentate Schiff base dianion; the two phenolate O atoms and the two imine N atoms are each mutually cis. The chloride ion occupies the apical position. The dihedral angle between the two outer phenolate rings of the tetra-dentate Schiff base ligand is 16.44 (9)°. The central benzene ring makes dihedral angles of 10.64 (9) and 25.17 (10)° with the two outer phenolate rings. In the crystal structure, weak C-H⋯O and C-H⋯Cl inter-actions link the mol-ecules into wave-like face-to-face double layers along the c direction. A π-π inter-action involving the two outer phenolate rings is observed, the centroid-centroid distance being 3.743 (11) Å.

Related literature

For values of bond lengths, see: Allen et al. (1987 ▶). For details of ring conformations, see: Cremer & Pople (1975 ▶). For related structures, see, for example: Eltayeb et al. (2008a ▶,b ▶); Habibi et al. (2007 ▶); Mitra et al. (2006 ▶). For the background to applications of manganese complexes, see, for example: Dixit & Srinivasan (1988 ▶); Glatzel et al. (2004 ▶); Lu et al. (2006 ▶).

Experimental

Crystal data

[Mn(C22H18N2O4)Cl]

M = 464.77

Orthorhombic,

a = 13.7282 (2) Å

b = 15.0250 (2) Å

c = 19.2094 (3) Å

V = 3962.25 (10) Å3

Z = 8

Mo Kα radiation

μ = 0.83 mm−1

T = 296 (2) K

0.44 × 0.42 × 0.11 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (; Bruker, 2005 ▶) T min = 0.708, T max = 0.915

28689 measured reflections

5780 independent reflections

4072 reflections with I > 2σ(I)

R int = 0.032

Refinement

R[F 2 > 2σ(F 2)] = 0.038

wR(F 2) = 0.095

S = 1.05

5780 reflections

273 parameters

H-atom parameters constrained

Δρmax = 0.30 e Å−3

Δρmin = −0.34 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: APEX2; data reduction: SAINT (Bruker, 2005 ▶); 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 and PLATON (Spek, 2003 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808009835/is2286sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808009835/is2286Isup2.hkl

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

[Mn(C22H18N2O4)Cl]	F000 = 1904
Mr = 464.77	Dx = 1.558 Mg m−3
Orthorhombic, Pbca	Mo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 5780 reflections
a = 13.7282 (2) Å	θ = 2.1–30.0º
b = 15.0250 (2) Å	µ = 0.83 mm−1
c = 19.2094 (3) Å	T = 296 (2) K
V = 3962.25 (10) Å3	Block, brown
Z = 8	0.44 × 0.42 × 0.11 mm

Bruker SMART APEXII CCD area-detector diffractometer	5780 independent reflections
Radiation source: fine-focus sealed tube	4072 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.032
Detector resolution: 8.33 pixels mm-1	θmax = 30.0º
T = 296(2) K	θmin = 2.1º
ω scans	h = −19→14
Absorption correction: multi-scan(SADABS; Bruker, 2005)	k = −21→16
Tmin = 0.708, Tmax = 0.915	l = −27→20
28689 measured reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.038	H-atom parameters constrained
wR(F2) = 0.095	w = 1/[σ2(Fo2) + (0.0397P)2 + 1.0383P] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max = 0.001
5780 reflections	Δρmax = 0.30 e Å−3
273 parameters	Δρmin = −0.34 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	0.475763 (18)	0.111700 (17)	0.483521 (14)	0.02817 (9)
Cl1	0.54204 (4)	0.24455 (3)	0.42743 (3)	0.04223 (13)
O1	0.40677 (8)	0.07486 (8)	0.40518 (6)	0.0327 (3)
O2	0.58304 (8)	0.03537 (8)	0.46327 (6)	0.0303 (3)
O3	0.16571 (10)	0.03819 (11)	0.23875 (7)	0.0550 (4)
O4	0.92194 (10)	0.01474 (11)	0.41480 (9)	0.0595 (4)
N1	0.35851 (10)	0.16427 (9)	0.52796 (7)	0.0289 (3)
N2	0.53358 (11)	0.14005 (9)	0.57575 (8)	0.0314 (3)
C1	0.31581 (12)	0.09053 (11)	0.38763 (9)	0.0285 (4)
C2	0.28302 (13)	0.05942 (12)	0.32363 (9)	0.0357 (4)
H2A	0.3262	0.0298	0.2944	0.043*
C3	0.18761 (13)	0.07159 (13)	0.30249 (10)	0.0362 (4)
C4	0.12079 (14)	0.11447 (12)	0.34578 (10)	0.0385 (4)
H4A	0.0565	0.1224	0.3318	0.046*
C5	0.15161 (13)	0.14455 (12)	0.40900 (10)	0.0366 (4)
H5A	0.1068	0.1720	0.4383	0.044*
C6	0.24892 (12)	0.13560 (11)	0.43162 (9)	0.0296 (4)
C7	0.27287 (13)	0.16752 (11)	0.49861 (10)	0.0326 (4)
H7A	0.2228	0.1933	0.5243	0.039*
C8	0.37358 (13)	0.19174 (11)	0.59834 (9)	0.0334 (4)
C9	0.30344 (16)	0.23117 (14)	0.64048 (11)	0.0485 (5)
H9A	0.2425	0.2453	0.6225	0.058*
C10	0.32499 (18)	0.24912 (16)	0.70897 (13)	0.0598 (6)
H10A	0.2781	0.2755	0.7372	0.072*
C11	0.41567 (18)	0.22843 (16)	0.73660 (11)	0.0576 (6)
H11A	0.4288	0.2396	0.7833	0.069*
C12	0.48587 (16)	0.19152 (14)	0.69479 (10)	0.0465 (5)
H12A	0.5468	0.1779	0.7131	0.056*
C13	0.46582 (13)	0.17445 (12)	0.62465 (9)	0.0343 (4)
C14	0.62697 (13)	0.13753 (12)	0.58689 (10)	0.0358 (4)
H14A	0.6489	0.1586	0.6296	0.043*
C15	0.69814 (13)	0.10568 (11)	0.53996 (10)	0.0342 (4)
C16	0.79809 (14)	0.11969 (13)	0.55549 (12)	0.0447 (5)
H16A	0.8148	0.1502	0.5959	0.054*
C17	0.86974 (15)	0.08976 (15)	0.51298 (13)	0.0503 (6)
H17A	0.9347	0.1003	0.5238	0.060*
C18	0.84519 (13)	0.04321 (13)	0.45301 (12)	0.0424 (5)
C19	0.74893 (13)	0.02738 (12)	0.43567 (10)	0.0355 (4)
H19A	0.7339	−0.0033	0.3950	0.043*
C20	0.67467 (12)	0.05740 (11)	0.47896 (9)	0.0305 (4)
C21	0.07328 (15)	0.05817 (18)	0.20853 (11)	0.0587 (6)
H21A	0.0689	0.0310	0.1634	0.088*
H21B	0.0664	0.1215	0.2040	0.088*
H21C	0.0224	0.0355	0.2379	0.088*
C22	0.90345 (17)	−0.03830 (18)	0.35536 (13)	0.0632 (7)
H22A	0.9641	−0.0547	0.3340	0.095*
H22B	0.8648	−0.0052	0.3228	0.095*
H22C	0.8689	−0.0911	0.3690	0.095*

	U11	U22	U33	U12	U13	U23
Mn1	0.02087 (14)	0.03480 (14)	0.02885 (16)	0.00122 (10)	−0.00199 (11)	−0.00309 (10)
Cl1	0.0391 (3)	0.0402 (2)	0.0474 (3)	−0.00523 (19)	0.0018 (2)	0.0043 (2)
O1	0.0219 (6)	0.0452 (7)	0.0310 (7)	0.0052 (5)	−0.0026 (5)	−0.0052 (5)
O2	0.0183 (6)	0.0373 (6)	0.0352 (6)	0.0003 (5)	−0.0030 (5)	−0.0029 (5)
O3	0.0381 (8)	0.0883 (11)	0.0387 (8)	0.0124 (7)	−0.0166 (7)	−0.0130 (8)
O4	0.0255 (7)	0.0776 (11)	0.0754 (11)	0.0040 (7)	0.0088 (8)	0.0008 (9)
N1	0.0264 (7)	0.0297 (7)	0.0308 (8)	0.0000 (6)	0.0008 (6)	−0.0033 (6)
N2	0.0294 (8)	0.0345 (7)	0.0302 (8)	−0.0012 (6)	−0.0048 (7)	−0.0023 (6)
C1	0.0217 (8)	0.0319 (8)	0.0318 (9)	0.0001 (6)	−0.0006 (7)	0.0054 (7)
C2	0.0278 (9)	0.0495 (10)	0.0298 (10)	0.0055 (8)	−0.0011 (8)	−0.0024 (8)
C3	0.0308 (10)	0.0455 (10)	0.0324 (10)	−0.0005 (8)	−0.0061 (8)	0.0048 (8)
C4	0.0233 (9)	0.0491 (10)	0.0430 (11)	0.0036 (8)	−0.0066 (9)	0.0046 (9)
C5	0.0267 (9)	0.0444 (10)	0.0387 (11)	0.0080 (8)	−0.0006 (9)	−0.0007 (8)
C6	0.0253 (8)	0.0324 (8)	0.0310 (9)	0.0020 (7)	−0.0006 (8)	0.0013 (7)
C7	0.0262 (9)	0.0336 (8)	0.0379 (10)	0.0042 (7)	0.0033 (8)	−0.0014 (8)
C8	0.0338 (10)	0.0331 (9)	0.0331 (10)	−0.0020 (7)	0.0019 (8)	−0.0047 (7)
C9	0.0397 (11)	0.0594 (13)	0.0465 (13)	0.0036 (9)	0.0013 (10)	−0.0176 (10)
C10	0.0554 (15)	0.0755 (16)	0.0484 (14)	−0.0009 (12)	0.0121 (12)	−0.0266 (12)
C11	0.0626 (16)	0.0738 (15)	0.0363 (12)	−0.0106 (12)	0.0022 (12)	−0.0169 (11)
C12	0.0448 (12)	0.0584 (13)	0.0362 (11)	−0.0074 (10)	−0.0051 (10)	−0.0033 (9)
C13	0.0373 (10)	0.0343 (9)	0.0313 (9)	−0.0044 (8)	0.0010 (8)	−0.0042 (7)
C14	0.0341 (10)	0.0373 (9)	0.0359 (10)	−0.0020 (8)	−0.0118 (9)	−0.0014 (8)
C15	0.0260 (9)	0.0346 (9)	0.0422 (11)	−0.0019 (7)	−0.0083 (9)	0.0026 (8)
C16	0.0305 (10)	0.0445 (11)	0.0591 (14)	−0.0024 (8)	−0.0141 (10)	−0.0031 (10)
C17	0.0227 (10)	0.0528 (12)	0.0754 (17)	−0.0043 (9)	−0.0106 (11)	0.0021 (11)
C18	0.0241 (9)	0.0454 (10)	0.0578 (13)	0.0013 (8)	0.0033 (10)	0.0115 (10)
C19	0.0259 (9)	0.0415 (10)	0.0392 (10)	0.0013 (7)	−0.0007 (8)	0.0066 (8)
C20	0.0217 (8)	0.0321 (8)	0.0376 (10)	−0.0003 (7)	−0.0031 (8)	0.0072 (7)
C21	0.0392 (12)	0.0960 (18)	0.0410 (12)	0.0053 (12)	−0.0151 (11)	−0.0007 (12)
C22	0.0440 (13)	0.0847 (17)	0.0609 (15)	0.0148 (12)	0.0144 (12)	0.0119 (14)

Mn1—O1	1.8623 (12)	C8—C9	1.390 (3)
Mn1—O2	1.9067 (11)	C9—C10	1.375 (3)
Mn1—N1	1.9859 (14)	C9—H9A	0.9300
Mn1—N2	1.9876 (14)	C10—C11	1.389 (3)
Mn1—Cl1	2.4440 (5)	C10—H10A	0.9300
O1—C1	1.3147 (19)	C11—C12	1.372 (3)
O2—C20	1.335 (2)	C11—H11A	0.9300
O3—C3	1.357 (2)	C12—C13	1.399 (3)
O3—C21	1.427 (2)	C12—H12A	0.9300
O4—C18	1.353 (2)	C14—C15	1.413 (3)
O4—C22	1.415 (3)	C14—H14A	0.9300
N1—C7	1.305 (2)	C15—C20	1.415 (3)
N1—C8	1.429 (2)	C15—C16	1.420 (3)
N2—C14	1.300 (2)	C16—C17	1.355 (3)
N2—C13	1.419 (2)	C16—H16A	0.9300
C1—C2	1.390 (2)	C17—C18	1.389 (3)
C1—C6	1.420 (2)	C17—H17A	0.9300
C2—C3	1.383 (2)	C18—C19	1.383 (3)
C2—H2A	0.9300	C19—C20	1.391 (3)
C3—C4	1.396 (3)	C19—H19A	0.9300
C4—C5	1.363 (3)	C21—H21A	0.9600
C4—H4A	0.9300	C21—H21B	0.9600
C5—C6	1.411 (2)	C21—H21C	0.9600
C5—H5A	0.9300	C22—H22A	0.9600
C6—C7	1.412 (2)	C22—H22B	0.9600
C7—H7A	0.9300	C22—H22C	0.9600
C8—C13	1.388 (3)
O1—Mn1—O2	92.82 (5)	C8—C9—H9A	120.3
O1—Mn1—N1	93.06 (5)	C9—C10—C11	121.0 (2)
O2—Mn1—N1	162.37 (6)	C9—C10—H10A	119.5
O1—Mn1—N2	170.79 (6)	C11—C10—H10A	119.5
O2—Mn1—N2	90.13 (6)	C12—C11—C10	119.8 (2)
N1—Mn1—N2	81.68 (6)	C12—C11—H11A	120.1
O1—Mn1—Cl1	94.35 (4)	C10—C11—H11A	120.1
O2—Mn1—Cl1	96.53 (4)	C11—C12—C13	120.0 (2)
N1—Mn1—Cl1	99.58 (4)	C11—C12—H12A	120.0
N2—Mn1—Cl1	93.97 (4)	C13—C12—H12A	120.0
C1—O1—Mn1	129.57 (11)	C8—C13—C12	119.73 (18)
C20—O2—Mn1	122.17 (11)	C8—C13—N2	115.17 (16)
C3—O3—C21	119.09 (16)	C12—C13—N2	125.11 (17)
C18—O4—C22	118.41 (17)	N2—C14—C15	125.93 (17)
C7—N1—C8	121.91 (15)	N2—C14—H14A	117.0
C7—N1—Mn1	124.02 (12)	C15—C14—H14A	117.0
C8—N1—Mn1	113.85 (11)	C14—C15—C20	122.99 (16)
C14—N2—C13	123.23 (16)	C14—C15—C16	118.94 (18)
C14—N2—Mn1	122.28 (13)	C20—C15—C16	118.03 (18)
C13—N2—Mn1	113.96 (11)	C17—C16—C15	121.7 (2)
O1—C1—C2	118.30 (16)	C17—C16—H16A	119.1
O1—C1—C6	123.17 (16)	C15—C16—H16A	119.1
C2—C1—C6	118.50 (15)	C16—C17—C18	119.38 (18)
C3—C2—C1	121.45 (17)	C16—C17—H17A	120.3
C3—C2—H2A	119.3	C18—C17—H17A	120.3
C1—C2—H2A	119.3	O4—C18—C19	124.0 (2)
O3—C3—C2	115.20 (17)	O4—C18—C17	114.83 (17)
O3—C3—C4	124.24 (16)	C19—C18—C17	121.19 (19)
C2—C3—C4	120.56 (18)	C18—C19—C20	120.04 (18)
C5—C4—C3	118.68 (17)	C18—C19—H19A	120.0
C5—C4—H4A	120.7	C20—C19—H19A	120.0
C3—C4—H4A	120.7	O2—C20—C19	118.37 (16)
C4—C5—C6	122.45 (17)	O2—C20—C15	121.90 (16)
C4—C5—H5A	118.8	C19—C20—C15	119.63 (16)
C6—C5—H5A	118.8	O3—C21—H21A	109.5
C5—C6—C7	117.95 (16)	O3—C21—H21B	109.5
C5—C6—C1	118.32 (16)	H21A—C21—H21B	109.5
C7—C6—C1	123.62 (16)	O3—C21—H21C	109.5
N1—C7—C6	126.21 (16)	H21A—C21—H21C	109.5
N1—C7—H7A	116.9	H21B—C21—H21C	109.5
C6—C7—H7A	116.9	O4—C22—H22A	109.5
C13—C8—C9	119.98 (17)	O4—C22—H22B	109.5
C13—C8—N1	115.00 (16)	H22A—C22—H22B	109.5
C9—C8—N1	125.01 (17)	O4—C22—H22C	109.5
C10—C9—C8	119.4 (2)	H22A—C22—H22C	109.5
C10—C9—H9A	120.3	H22B—C22—H22C	109.5
O2—Mn1—O1—C1	169.80 (14)	C1—C6—C7—N1	3.4 (3)
N1—Mn1—O1—C1	6.44 (15)	C7—N1—C8—C13	172.65 (16)
Cl1—Mn1—O1—C1	−93.42 (14)	Mn1—N1—C8—C13	−2.17 (19)
O1—Mn1—O2—C20	147.01 (13)	C7—N1—C8—C9	−5.9 (3)
N1—Mn1—O2—C20	−103.7 (2)	Mn1—N1—C8—C9	179.32 (16)
N2—Mn1—O2—C20	−41.71 (13)	C13—C8—C9—C10	−2.8 (3)
Cl1—Mn1—O2—C20	52.30 (12)	N1—C8—C9—C10	175.59 (19)
O1—Mn1—N1—C7	−3.45 (15)	C8—C9—C10—C11	0.0 (4)
O2—Mn1—N1—C7	−112.8 (2)	C9—C10—C11—C12	1.6 (4)
N2—Mn1—N1—C7	−175.86 (15)	C10—C11—C12—C13	−0.3 (3)
Cl1—Mn1—N1—C7	91.49 (14)	C9—C8—C13—C12	4.1 (3)
O1—Mn1—N1—C8	171.25 (11)	N1—C8—C13—C12	−174.47 (16)
O2—Mn1—N1—C8	61.9 (2)	C9—C8—C13—N2	−175.66 (17)
N2—Mn1—N1—C8	−1.16 (11)	N1—C8—C13—N2	5.8 (2)
Cl1—Mn1—N1—C8	−93.82 (11)	C11—C12—C13—C8	−2.5 (3)
O2—Mn1—N2—C14	27.96 (14)	C11—C12—C13—N2	177.22 (19)
N1—Mn1—N2—C14	−167.72 (15)	C14—N2—C13—C8	165.17 (17)
Cl1—Mn1—N2—C14	−68.60 (14)	Mn1—N2—C13—C8	−6.68 (19)
O2—Mn1—N2—C13	−160.11 (12)	C14—N2—C13—C12	−14.6 (3)
N1—Mn1—N2—C13	4.21 (12)	Mn1—N2—C13—C12	173.56 (15)
Cl1—Mn1—N2—C13	103.33 (11)	C13—N2—C14—C15	−178.81 (17)
Mn1—O1—C1—C2	176.24 (12)	Mn1—N2—C14—C15	−7.6 (3)
Mn1—O1—C1—C6	−5.5 (2)	N2—C14—C15—C20	−11.7 (3)
O1—C1—C2—C3	178.41 (17)	N2—C14—C15—C16	170.58 (18)
C6—C1—C2—C3	0.0 (3)	C14—C15—C16—C17	179.18 (19)
C21—O3—C3—C2	−171.43 (18)	C20—C15—C16—C17	1.3 (3)
C21—O3—C3—C4	9.4 (3)	C15—C16—C17—C18	−0.8 (3)
C1—C2—C3—O3	179.73 (17)	C22—O4—C18—C19	−3.4 (3)
C1—C2—C3—C4	−1.1 (3)	C22—O4—C18—C17	175.86 (19)
O3—C3—C4—C5	179.50 (18)	C16—C17—C18—O4	−178.80 (19)
C2—C3—C4—C5	0.4 (3)	C16—C17—C18—C19	0.4 (3)
C3—C4—C5—C6	1.4 (3)	O4—C18—C19—C20	178.47 (17)
C4—C5—C6—C7	−178.81 (17)	C17—C18—C19—C20	−0.7 (3)
C4—C5—C6—C1	−2.4 (3)	Mn1—O2—C20—C19	−147.80 (13)
O1—C1—C6—C5	−176.64 (16)	Mn1—O2—C20—C15	35.8 (2)
C2—C1—C6—C5	1.7 (2)	C18—C19—C20—O2	−175.20 (16)
O1—C1—C6—C7	−0.5 (3)	C18—C19—C20—C15	1.3 (3)
C2—C1—C6—C7	177.84 (16)	C14—C15—C20—O2	−3.0 (3)
C8—N1—C7—C6	−174.68 (16)	C16—C15—C20—O2	174.78 (16)
Mn1—N1—C7—C6	−0.4 (2)	C14—C15—C20—C19	−179.30 (16)
C5—C6—C7—N1	179.55 (17)	C16—C15—C20—C19	−1.6 (3)

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7A···Cl1i	0.93	2.81	3.7156 (19)	165
C21—H21A···O2ii	0.96	2.44	3.321 (2)	152

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7A⋯Cl1i	0.93	2.81	3.7156 (19)	165
C21—H21A⋯O2ii	0.96	2.44	3.321 (2)	152

Symmetry codes: (i) ; (ii) .