Chlorido{5,5'-dimethyl-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(2))Cl], the Mn(III) center is in a distorted square-pyramidal configuration; the basal plane is formed by the N(2)O(2) donors of the tetra-dentate Schiff base dianion, with the two phenol O atoms and two imine N atoms each mutually cis. The chloride ion occupies the apical coordination site. The dihedral angle between the two outer phenolate rings of the tetra-dentate ligand is 18.24 (9)°. The central benzene ring makes dihedral angles of 13.71 (8) and 30.50 (8)° with the two outer phenolate rings. In the crystal structure, weak C-H⋯Cl inter-actions link the mol-ecules into screw helices along the b direction. These helices are further connected by weak C-H⋯O inter-actions into a three-dimensional network. The crystal structure is further stabilized by C-H⋯π inter-actions involving the central benzene ring.

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. (2008 ▶); Habibi et al. (2007 ▶); Mitra et al. (2006 ▶). For background to applications of manganese complexes, see, for example: Dixit & Srinivasan (1988 ▶); Glatzel et al. (2004 ▶); Lu et al. (2006 ▶); Stallings et al. (1985 ▶).

Experimental

Crystal data

[Mn(C22H18N2O2)Cl]

M = 432.77

Monoclinic,

a = 20.9593 (5) Å

b = 13.5897 (3) Å

c = 14.9316 (3) Å

β = 119.641 (1)°

V = 3696.43 (14) Å3

Z = 8

Mo Kα radiation

μ = 0.88 mm−1

T = 100.0 (1) K

0.56 × 0.20 × 0.19 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.639, T max = 0.852

35769 measured reflections

8109 independent reflections

5992 reflections with I > 2σ(I)

R int = 0.048

Refinement

R[F 2 > 2σ(F 2)] = 0.045

wR(F 2) = 0.126

S = 1.07

8109 reflections

255 parameters

H-atom parameters constrained

Δρmax = 0.75 e Å−3

Δρmin = −0.69 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/S1600536808007459/sj2474sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808007459/sj2474Isup2.hkl

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

[Mn(C22H18N2O2)Cl]	F000 = 1776
Mr = 432.77	Dx = 1.555 Mg m−3
Monoclinic, C2/c	Mo Kα radiation λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 8109 reflections
a = 20.9593 (5) Å	θ = 2.1–35.0º
b = 13.5897 (3) Å	µ = 0.88 mm−1
c = 14.9316 (3) Å	T = 100.0 (1) K
β = 119.641 (1)º	Block, brown
V = 3696.43 (14) Å3	0.56 × 0.20 × 0.19 mm
Z = 8

Bruker SMART APEXII CCD area-detector diffractometer	8109 independent reflections
Radiation source: fine-focus sealed tube	5992 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.048
Detector resolution: 8.33 pixels mm-1	θmax = 35.0º
T = 100.0(1) K	θmin = 2.1º
ω scans	h = −33→28
Absorption correction: multi-scan(SADABS; Bruker, 2005)	k = −21→21
Tmin = 0.639, Tmax = 0.852	l = −23→24
35769 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)] = 0.045	H-atom parameters constrained
wR(F2) = 0.126	w = 1/[σ2(Fo2) + (0.0635P)2 + 1.3131P] where P = (Fo2 + 2Fc2)/3
S = 1.07	(Δ/σ)max = 0.001
8109 reflections	Δρmax = 0.75 e Å−3
255 parameters	Δρmin = −0.69 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

Experimental. The low-temperature data was collected with the Oxford Cyrosystem Cobra low-temperature attachment.

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	0.225261 (11)	0.228215 (15)	0.091917 (16)	0.01606 (6)
Cl1	0.16386 (2)	0.29835 (3)	0.17860 (3)	0.02432 (9)
O1	0.14852 (6)	0.14593 (7)	0.00249 (8)	0.0192 (2)
O2	0.19870 (6)	0.32753 (7)	−0.00984 (8)	0.0185 (2)
N1	0.27984 (6)	0.11876 (9)	0.18852 (9)	0.0168 (2)
N2	0.31816 (6)	0.30016 (9)	0.18058 (9)	0.0167 (2)
C1	0.13609 (8)	0.05345 (10)	0.01522 (11)	0.0174 (3)
C2	0.07011 (8)	0.00997 (11)	−0.05872 (12)	0.0219 (3)
H2A	0.0365	0.0481	−0.1136	0.026*
C3	0.05302 (8)	−0.08722 (11)	−0.05333 (12)	0.0209 (3)
C4	0.10445 (9)	−0.14629 (12)	0.02727 (12)	0.0226 (3)
H4A	0.0941	−0.2121	0.0314	0.027*
C5	0.17011 (8)	−0.10657 (11)	0.10001 (11)	0.0209 (3)
H5A	0.2043	−0.1468	0.1520	0.025*
C6	0.18698 (8)	−0.00631 (10)	0.09789 (10)	0.0168 (2)
C7	0.25658 (8)	0.02818 (11)	0.17669 (10)	0.0173 (2)
H7A	0.2881	−0.0180	0.2237	0.021*
C8	0.35313 (7)	0.14389 (11)	0.26289 (10)	0.0177 (3)
C9	0.40356 (8)	0.08078 (12)	0.33913 (12)	0.0233 (3)
H9A	0.3889	0.0190	0.3489	0.028*
C10	0.47580 (8)	0.11154 (13)	0.40001 (12)	0.0263 (3)
H10A	0.5094	0.0701	0.4512	0.032*
C11	0.49860 (8)	0.20291 (13)	0.38569 (12)	0.0258 (3)
H11A	0.5475	0.2215	0.4251	0.031*
C12	0.44804 (8)	0.26669 (12)	0.31221 (12)	0.0229 (3)
H12A	0.4631	0.3282	0.3024	0.027*
C13	0.37498 (8)	0.23870 (11)	0.25325 (11)	0.0174 (3)
C14	0.32367 (8)	0.39542 (11)	0.17937 (11)	0.0193 (3)
H14A	0.3669	0.4242	0.2297	0.023*
C15	0.26777 (8)	0.45912 (10)	0.10593 (11)	0.0179 (3)
C16	0.27519 (9)	0.56198 (11)	0.12163 (12)	0.0216 (3)
H16A	0.3150	0.5867	0.1811	0.026*
C17	0.22469 (9)	0.62645 (11)	0.05081 (12)	0.0235 (3)
H17A	0.2306	0.6938	0.0630	0.028*
C18	0.16426 (9)	0.59053 (11)	−0.03985 (12)	0.0216 (3)
C19	0.15624 (8)	0.48953 (11)	−0.05583 (11)	0.0196 (3)
H19A	0.1159	0.4657	−0.1152	0.024*
C20	0.20661 (8)	0.42298 (10)	0.01426 (11)	0.0176 (3)
C21	−0.01947 (9)	−0.12957 (13)	−0.13236 (15)	0.0305 (4)
H21A	−0.0443	−0.0835	−0.1878	0.046*
H21B	−0.0491	−0.1423	−0.1011	0.046*
H21C	−0.0114	−0.1899	−0.1587	0.046*
C22	0.10955 (10)	0.65886 (13)	−0.12034 (14)	0.0305 (4)
H22A	0.1032	0.6414	−0.1866	0.046*
H22B	0.1271	0.7253	−0.1040	0.046*
H22C	0.0634	0.6535	−0.1218	0.046*

	U11	U22	U33	U12	U13	U23
Mn1	0.01366 (10)	0.01200 (11)	0.01705 (10)	−0.00147 (7)	0.00341 (7)	0.00028 (7)
Cl1	0.02102 (17)	0.02319 (18)	0.02899 (18)	−0.00435 (13)	0.01255 (14)	−0.00675 (13)
O1	0.0161 (5)	0.0125 (4)	0.0212 (5)	−0.0013 (4)	0.0033 (4)	0.0006 (3)
O2	0.0210 (5)	0.0112 (4)	0.0180 (4)	−0.0003 (4)	0.0057 (4)	−0.0002 (3)
N1	0.0142 (5)	0.0162 (5)	0.0164 (5)	−0.0010 (4)	0.0049 (4)	0.0001 (4)
N2	0.0142 (5)	0.0148 (5)	0.0183 (5)	−0.0012 (4)	0.0058 (4)	−0.0014 (4)
C1	0.0150 (6)	0.0136 (6)	0.0218 (6)	−0.0009 (5)	0.0077 (5)	−0.0011 (5)
C2	0.0139 (6)	0.0168 (7)	0.0271 (7)	−0.0012 (5)	0.0041 (5)	−0.0017 (5)
C3	0.0149 (6)	0.0174 (7)	0.0280 (7)	−0.0028 (5)	0.0087 (5)	−0.0033 (5)
C4	0.0251 (7)	0.0174 (7)	0.0250 (7)	−0.0053 (6)	0.0121 (6)	−0.0018 (5)
C5	0.0231 (7)	0.0147 (6)	0.0214 (6)	−0.0012 (5)	0.0084 (5)	0.0013 (5)
C6	0.0153 (6)	0.0146 (6)	0.0188 (6)	−0.0016 (5)	0.0070 (5)	0.0000 (4)
C7	0.0175 (6)	0.0154 (6)	0.0170 (5)	0.0002 (5)	0.0070 (5)	0.0012 (4)
C8	0.0133 (6)	0.0181 (6)	0.0180 (6)	0.0000 (5)	0.0049 (5)	−0.0002 (5)
C9	0.0166 (6)	0.0227 (7)	0.0230 (6)	0.0002 (5)	0.0041 (5)	0.0039 (5)
C10	0.0166 (7)	0.0282 (8)	0.0242 (7)	0.0023 (6)	0.0025 (5)	0.0038 (6)
C11	0.0142 (6)	0.0295 (8)	0.0264 (7)	−0.0010 (6)	0.0044 (5)	−0.0017 (6)
C12	0.0149 (6)	0.0217 (7)	0.0272 (7)	−0.0028 (5)	0.0067 (5)	−0.0032 (5)
C13	0.0144 (6)	0.0171 (6)	0.0178 (6)	−0.0011 (5)	0.0057 (5)	−0.0022 (5)
C14	0.0181 (6)	0.0172 (6)	0.0205 (6)	−0.0037 (5)	0.0080 (5)	−0.0031 (5)
C15	0.0171 (6)	0.0129 (6)	0.0223 (6)	−0.0023 (5)	0.0087 (5)	−0.0011 (5)
C16	0.0233 (7)	0.0155 (6)	0.0253 (7)	−0.0033 (5)	0.0115 (6)	−0.0026 (5)
C17	0.0280 (8)	0.0132 (6)	0.0308 (7)	−0.0001 (5)	0.0158 (6)	−0.0011 (5)
C18	0.0250 (7)	0.0171 (7)	0.0247 (7)	0.0029 (5)	0.0139 (6)	0.0022 (5)
C19	0.0210 (7)	0.0163 (6)	0.0212 (6)	0.0012 (5)	0.0102 (5)	0.0003 (5)
C20	0.0191 (6)	0.0138 (6)	0.0201 (6)	−0.0016 (5)	0.0097 (5)	−0.0006 (5)
C21	0.0176 (7)	0.0219 (8)	0.0417 (9)	−0.0054 (6)	0.0068 (6)	−0.0063 (7)
C22	0.0371 (9)	0.0193 (7)	0.0317 (8)	0.0082 (7)	0.0143 (7)	0.0026 (6)

Mn1—O1	1.8698 (10)	C9—H9A	0.9300
Mn1—O2	1.8983 (10)	C10—C11	1.385 (2)
Mn1—N2	1.9875 (12)	C10—H10A	0.9300
Mn1—N1	1.9923 (12)	C11—C12	1.388 (2)
Mn1—Cl1	2.4263 (4)	C11—H11A	0.9300
O1—C1	1.3162 (17)	C12—C13	1.390 (2)
O2—C20	1.3344 (17)	C12—H12A	0.9300
N1—C7	1.3034 (18)	C14—C15	1.433 (2)
N1—C8	1.4221 (17)	C14—H14A	0.9300
N2—C14	1.3006 (19)	C15—C16	1.413 (2)
N2—C13	1.4195 (18)	C15—C20	1.4221 (19)
C1—C2	1.4036 (19)	C16—C17	1.378 (2)
C1—C6	1.4208 (19)	C16—H16A	0.9300
C2—C3	1.381 (2)	C17—C18	1.407 (2)
C2—H2A	0.9300	C17—H17A	0.9300
C3—C4	1.404 (2)	C18—C19	1.389 (2)
C3—C21	1.503 (2)	C18—C22	1.503 (2)
C4—C5	1.373 (2)	C19—C20	1.391 (2)
C4—H4A	0.9300	C19—H19A	0.9300
C5—C6	1.412 (2)	C21—H21A	0.9600
C5—H5A	0.9300	C21—H21B	0.9600
C6—C7	1.4263 (19)	C21—H21C	0.9600
C7—H7A	0.9300	C22—H22A	0.9600
C8—C13	1.398 (2)	C22—H22B	0.9600
C8—C9	1.399 (2)	C22—H22C	0.9600
C9—C10	1.390 (2)
O1—Mn1—O2	92.61 (4)	C11—C10—C9	121.08 (14)
O1—Mn1—N2	169.49 (5)	C11—C10—H10A	119.5
O2—Mn1—N2	89.21 (5)	C9—C10—H10A	119.5
O1—Mn1—N1	93.07 (5)	C10—C11—C12	119.67 (14)
O2—Mn1—N1	161.15 (5)	C10—C11—H11A	120.2
N2—Mn1—N1	82.10 (5)	C12—C11—H11A	120.2
O1—Mn1—Cl1	96.89 (4)	C11—C12—C13	120.06 (15)
O2—Mn1—Cl1	97.16 (4)	C11—C12—H12A	120.0
N2—Mn1—Cl1	93.14 (4)	C13—C12—H12A	120.0
N1—Mn1—Cl1	99.97 (4)	C12—C13—C8	120.09 (13)
C1—O1—Mn1	129.03 (9)	C12—C13—N2	124.62 (14)
C20—O2—Mn1	121.82 (9)	C8—C13—N2	115.29 (12)
C7—N1—C8	121.32 (12)	N2—C14—C15	124.56 (13)
C7—N1—Mn1	124.38 (10)	N2—C14—H14A	117.7
C8—N1—Mn1	113.44 (9)	C15—C14—H14A	117.7
C14—N2—C13	123.34 (12)	C16—C15—C20	118.30 (13)
C14—N2—Mn1	123.02 (10)	C16—C15—C14	119.30 (13)
C13—N2—Mn1	113.25 (9)	C20—C15—C14	122.31 (13)
O1—C1—C2	118.48 (13)	C17—C16—C15	121.46 (14)
O1—C1—C6	123.65 (12)	C17—C16—H16A	119.3
C2—C1—C6	117.84 (13)	C15—C16—H16A	119.3
C3—C2—C1	122.67 (14)	C16—C17—C18	120.13 (14)
C3—C2—H2A	118.7	C16—C17—H17A	119.9
C1—C2—H2A	118.7	C18—C17—H17A	119.9
C2—C3—C4	119.04 (13)	C19—C18—C17	118.89 (14)
C2—C3—C21	120.74 (14)	C19—C18—C22	119.57 (14)
C4—C3—C21	120.23 (14)	C17—C18—C22	121.52 (14)
C5—C4—C3	119.82 (14)	C18—C19—C20	122.06 (14)
C5—C4—H4A	120.1	C18—C19—H19A	119.0
C3—C4—H4A	120.1	C20—C19—H19A	119.0
C4—C5—C6	121.72 (14)	O2—C20—C19	118.83 (13)
C4—C5—H5A	119.1	O2—C20—C15	121.86 (13)
C6—C5—H5A	119.1	C19—C20—C15	119.15 (13)
C5—C6—C1	118.84 (12)	C3—C21—H21A	109.5
C5—C6—C7	117.65 (13)	C3—C21—H21B	109.5
C1—C6—C7	123.43 (13)	H21A—C21—H21B	109.5
N1—C7—C6	125.70 (13)	C3—C21—H21C	109.5
N1—C7—H7A	117.2	H21A—C21—H21C	109.5
C6—C7—H7A	117.2	H21B—C21—H21C	109.5
C13—C8—C9	119.63 (13)	C18—C22—H22A	109.5
C13—C8—N1	115.03 (12)	C18—C22—H22B	109.5
C9—C8—N1	125.29 (13)	H22A—C22—H22B	109.5
C10—C9—C8	119.20 (15)	C18—C22—H22C	109.5
C10—C9—H9A	120.4	H22A—C22—H22C	109.5
C8—C9—H9A	120.4	H22B—C22—H22C	109.5
O2—Mn1—O1—C1	170.43 (13)	C5—C6—C7—N1	−177.31 (15)
N2—Mn1—O1—C1	70.7 (3)	C1—C6—C7—N1	6.2 (2)
N1—Mn1—O1—C1	8.41 (13)	C7—N1—C8—C13	167.53 (14)
Cl1—Mn1—O1—C1	−92.03 (12)	Mn1—N1—C8—C13	−2.25 (16)
O1—Mn1—O2—C20	145.34 (11)	C7—N1—C8—C9	−9.7 (2)
N2—Mn1—O2—C20	−45.01 (11)	Mn1—N1—C8—C9	−179.47 (13)
N1—Mn1—O2—C20	−107.23 (17)	C13—C8—C9—C10	−3.8 (2)
Cl1—Mn1—O2—C20	48.06 (11)	N1—C8—C9—C10	173.30 (15)
O1—Mn1—N1—C7	−1.63 (13)	C8—C9—C10—C11	−0.6 (3)
O2—Mn1—N1—C7	−108.98 (16)	C9—C10—C11—C12	2.6 (3)
N2—Mn1—N1—C7	−172.25 (13)	C10—C11—C12—C13	−0.1 (3)
Cl1—Mn1—N1—C7	95.93 (12)	C11—C12—C13—C8	−4.3 (2)
O1—Mn1—N1—C8	167.79 (10)	C11—C12—C13—N2	176.11 (15)
O2—Mn1—N1—C8	60.44 (19)	C9—C8—C13—C12	6.3 (2)
N2—Mn1—N1—C8	−2.83 (10)	N1—C8—C13—C12	−171.13 (14)
Cl1—Mn1—N1—C8	−94.65 (10)	C9—C8—C13—N2	−174.11 (13)
O1—Mn1—N2—C14	131.1 (2)	N1—C8—C13—N2	8.51 (19)
O2—Mn1—N2—C14	31.04 (12)	C14—N2—C13—C12	−18.1 (2)
N1—Mn1—N2—C14	−165.73 (13)	Mn1—N2—C13—C12	168.88 (13)
Cl1—Mn1—N2—C14	−66.09 (12)	C14—N2—C13—C8	162.28 (14)
O1—Mn1—N2—C13	−55.8 (3)	Mn1—N2—C13—C8	−10.73 (16)
O2—Mn1—N2—C13	−155.92 (10)	C13—N2—C14—C15	178.88 (14)
N1—Mn1—N2—C13	7.31 (10)	Mn1—N2—C14—C15	−8.8 (2)
Cl1—Mn1—N2—C13	106.95 (10)	N2—C14—C15—C16	170.29 (15)
Mn1—O1—C1—C2	173.26 (11)	N2—C14—C15—C20	−13.2 (2)
Mn1—O1—C1—C6	−9.1 (2)	C20—C15—C16—C17	0.3 (2)
O1—C1—C2—C3	178.35 (15)	C14—C15—C16—C17	176.93 (15)
C6—C1—C2—C3	0.6 (2)	C15—C16—C17—C18	−0.3 (2)
C1—C2—C3—C4	−2.1 (2)	C16—C17—C18—C19	0.6 (2)
C1—C2—C3—C21	177.86 (16)	C16—C17—C18—C22	−177.92 (16)
C2—C3—C4—C5	1.0 (2)	C17—C18—C19—C20	−0.9 (2)
C21—C3—C4—C5	−179.03 (16)	C22—C18—C19—C20	177.67 (15)
C3—C4—C5—C6	1.7 (2)	Mn1—O2—C20—C19	−146.85 (11)
C4—C5—C6—C1	−3.3 (2)	Mn1—O2—C20—C15	37.70 (18)
C4—C5—C6—C7	−179.96 (15)	C18—C19—C20—O2	−174.69 (14)
O1—C1—C6—C5	−175.56 (14)	C18—C19—C20—C15	0.9 (2)
C2—C1—C6—C5	2.1 (2)	C16—C15—C20—O2	174.89 (14)
O1—C1—C6—C7	0.9 (2)	C14—C15—C20—O2	−1.6 (2)
C2—C1—C6—C7	178.55 (14)	C16—C15—C20—C19	−0.6 (2)
C8—N1—C7—C6	−173.22 (14)	C14—C15—C20—C19	−177.07 (14)
Mn1—N1—C7—C6	−4.6 (2)

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5A···Cl1i	0.93	2.77	3.6508 (16)	158
C7—H7A···Cl1i	0.93	2.81	3.6933 (15)	158
C11—H11A···O1ii	0.93	2.58	3.423 (2)	151
C4—H4A···Cg1iii	0.93	2.83	3.5443 (19)	135

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5A⋯Cl1i	0.93	2.77	3.6508 (16)	158
C7—H7A⋯Cl1i	0.93	2.81	3.6933 (15)	158
C11—H11A⋯O1ii	0.93	2.58	3.423 (2)	151
C4—H4A⋯Cg1iii	0.93	2.83	3.5443 (19)	135

Symmetry codes: (i) ; (ii) ; (iii) . Cg1 is the centroid of the C8–C13 benzene ring.