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Acta Cryst. (2007). E63, m3025-m3026    [ doi:10.1107/S1600536807056644 ]

{2,6-Bis[1-(phenylimino)ethyl]pyridine}dichloridomanganese(II) dichloromethane hemisolvate

M.-P. Guo, G.-Q. Guo, H.-R. Guo, D.-C. Zhong and W.-Q. Zhou

Abstract top

The title complex, [MnCl2(C21H19N3)]·0.5CH2Cl2 or [MnCl2(Plep)]·0.5CH2Cl2 {Plep is 2,6-bis[1-(phenylimino)ethyl]pyridine, derived from the condensation of 2,6-diacetylpyridine and aniline in methanol} is composed of two crystallographically independent [MnCl2(Plep)] neutral units and a CH2Cl2 solvent molecule. Both complex molecules have similar geometries in which the MnII atom is coordinated by the N atoms of pyridine and the two imine groups of a neutral Schiff base, and by two chloride anions in a distorted trigonal-bipyramidal geometry. The structure of each [MnCl2(Plep)] unit exhibits a pseudo-mirror plane through the metal atom, two chloride anions and the pyridine ring. The crystal packing is stabilized by intermolecular C-H...Cl and C-H...[pi] and interactions.

Comment top

In recent years, many researchers focused on metal complexes based on Schiff base ligands derived from 2,6-diacetylpyridine due to their antimicrobial, cytotoxic, antioxidant, especially their catalytic activities (Reardon et al., 2002; Esteruelas et al., 2003; Pradhan et al.. 2003; Gibson et al.. 2001). The related metal complexes were synthesized from the condensation of 2,6-diacetylpyridine and aniline and were reported last several years (Marganian et al., 1995; Mentes et al., 2001; Trivedi et al.. 2007; Jiang et al.. 2005). Here, we report on the synthesis and crystal structure of analogous Mn(II) complex, (I). The title compound, (I), (Fig. 1) is isostructural with the the analogous nickel(II) complex (Fan et al., 2005). Each Mn(II) atom is coordinated by three N atoms (pyridyl N and two imino N atoms) from Plep Schiff base and two Cl anions, disposed in a distorted trigonal-bipyramid geometry as suggest the bond lengths and three trans angles at Mn(II) (Table 1). The pyridyl N atom and two Cl anions are disposed in the equatorial plane and the aptical position is occupied by two imino N atoms. In each Mn(Plep)Cl2 molecule, the Mn—N(pyridyl) bond is significantly shorter than the Mn—N(imino) bond, with the formal double bond character of the imino bonds N3—C14, N1—C7, N4—C28 and N6—C35 [C=N distances in the range 1.273 (3) to 1.280 (3) Å]. Each of two Mn(II) atoms is coplanar with the N3-ligand plane with the deviations from the plane by 0.0149 Å and 0.0289 Å, respectively. The molecules are held together by intermolecular hydrogen bond C—H···Cl (Table 2a), CH···π (Table 2 b), and p\- p\ interactions (Table 2c) forming a three-dimensional network (Fig. 2). The phenyl ring C4 and pyridyl ring C10 donate H atoms to Cl3 to form C—H···Cli and C—H···Clii hydrogen bonds, respectively [symmetry codes i = −1 + x, y, z; ii = x, y, z]. The Cl3 also accepts H atom from solvent dichloromethane C43 to form C—H···Clii hydrogen bond. Similarly, Cl2 accepts H atoms from C15 and C31 to form C—H···Cliii and C—H···CliV hydrogen bonds [symmetry codes iii = 1 − x, 2 − y, −z; iv = 1 + x, −1 + y, z]. In addition, methyl C29 and C36 atoms donate H atoms to Cl1 to form C—H···Cliv and C—H···Clv hydrogen bonds [symmetry codes v = x, −1 + y, z] (Table 2a, Fig. 2). In addition, the CH···π interaction between methyl group C8 and C11 of the aromatic ring, and p\- p\ interactions between the aromatic rings C22→C27 and C37→ C42 of the Plep (Table 2c, Fig. 2) are pronounced in this crystal structure. To classify these interactions the numerical criteria given in the literature were used (Štefanić et al., 2006; Nishio et al., 2004).

Related literature top

For related literature, see: Babik & Fink (2003); Esteruelas et al. (2003); Fan et al. (2005); Gibson et al. (2001); Jiang et al. (2005); Marganian et al. (1995); Mentes et al. (2001); Nishio (2004); Pradhan et al. (2003); Reardon et al. (2002); Trivedi et al. (2007).

For related literature, see: Štefanić et al. (2006).

Experimental top

The ligand Plep (2,6-bis[(1-phenylimino)ethyl]pyridine) was prepared in high yield from condensation of two equivalents of aniline with one equivalent of 2,6-diacetylpyridine in methanol according to the reported paper (Babik et al., 2003). The title complex was synthesized in good yield by treating MnCl2·4H2O with Plep in a mixture solution. To a solution of Plep (0.5 mmol) in a methanol-dichloromethane mixture (1:1 v/v; 10 ml), a solution of MnCl2·4H2O (0.5 mmol) in methanol (10 ml) was added dropwise at 353 K. After stirring for 2 h, the mixture was allowed to cool to room temperature and filtrated. The resultant filtrate was left to stand to evaporate slowly at room temperature. Red single crystals of (I) suitable for X-ray structure analysis were obtained after a week (yield 72%).

Refinement top

Hydrogen atoms attached to carbon atoms were positioned geometrically and treated as riding, with C—H = 0.95 Å, and Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: SMART (Bruker, 2004); cell refinement: SMART (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL (Sheldrick, 1997b).

Figures top
[Figure 1] Fig. 1. The structure of (I), showing the 30% probability displacement ellipsoids and the atom-labeling scheme (CH2Cl2 molecule was omitted).
[Figure 2] Fig. 2. Three-dimensional network generated by hydrogen bonding (dashed lines) and p\- p\ interactions.
{2,6-Bis[1-(phenylimino)ethyl]pyridine}dichloridomanganese(II) dichloromethane hemisolvate top
Crystal data top
[MnCl2(C21H19N3)]·0.5CH2Cl2V = 2248.6 (9) Å3
Mr = 481.70Z = 4
Triclinic, P1F000 = 984
Hall symbol: -P 1Dx = 1.423 Mg m−3
a = 9.007 (2) ÅMo Kα radiation
λ = 0.71073 Å
b = 12.834 (3) Åθ = 2.1–29.2º
c = 20.139 (5) ŵ = 0.96 mm−1
α = 79.582 (16)ºT = 273 (2) K
β = 79.230 (16)ºBlock, yellow
γ = 86.698 (16)º0.42 × 0.38 × 0.22 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer		11765 independent reflections
Radiation source: fine-focus sealed tube7352 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.034
T = 273(2) Kθmax = 29.2º
phi and ω scansθmin = 2.1º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −12→12
Tmin = 0.678, Tmax = 0.808k = −17→17
25241 measured reflectionsl = −27→27
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.044H-atom parameters constrained
wR(F2) = 0.121  w = 1/[σ2(Fo2) + (0.0593P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max = 0.001
11765 reflectionsΔρmax = 0.41 e Å−3
518 parametersΔρmin = −0.51 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[MnCl2(C21H19N3)]·0.5CH2Cl2γ = 86.698 (16)º
Mr = 481.70V = 2248.6 (9) Å3
Triclinic, P1Z = 4
a = 9.007 (2) ÅMo Kα
b = 12.834 (3) ŵ = 0.96 mm−1
c = 20.139 (5) ÅT = 273 (2) K
α = 79.582 (16)º0.42 × 0.38 × 0.22 mm
β = 79.230 (16)º
Data collection top
Bruker SMART CCD area-detector
diffractometer		11765 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		7352 reflections with I > 2σ(I)
Tmin = 0.678, Tmax = 0.808Rint = 0.034
25241 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.044518 parameters
wR(F2) = 0.121H-atom parameters constrained
S = 1.00Δρmax = 0.41 e Å−3
11765 reflectionsΔρmin = −0.51 e Å−3
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 > 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Mn10.35408 (4)0.98111 (3)0.193164 (17)0.04029 (10)
Mn20.67731 (4)0.39071 (3)0.267042 (17)0.04065 (10)
Cl10.29641 (8)1.11792 (5)0.25620 (3)0.06043 (18)
Cl20.18473 (7)0.94877 (6)0.12561 (3)0.06250 (19)
Cl30.78757 (8)0.47289 (5)0.34005 (3)0.05625 (17)
Cl40.51865 (9)0.49654 (6)0.20323 (4)0.0730 (2)
N10.3060 (2)0.83597 (15)0.27966 (10)0.0459 (5)
N20.5600 (2)0.88241 (14)0.19373 (9)0.0415 (4)
N30.5413 (2)1.06172 (15)0.10978 (9)0.0432 (4)
N40.8875 (2)0.37159 (16)0.18821 (9)0.0469 (5)
N50.7246 (2)0.22045 (14)0.26773 (9)0.0400 (4)
N60.5066 (2)0.29645 (15)0.35063 (9)0.0442 (4)
C10.1026 (3)0.8939 (2)0.36272 (13)0.0524 (6)
H1A0.15680.95400.36140.063*
C2−0.0366 (3)0.8788 (2)0.40499 (13)0.0606 (7)
H2A−0.07490.92800.43300.073*
C3−0.1182 (3)0.7924 (2)0.40592 (15)0.0641 (7)
H3A−0.21150.78230.43480.077*
C4−0.0632 (3)0.7205 (2)0.36453 (16)0.0675 (8)
H4A−0.12010.66220.36480.081*
C50.0767 (3)0.7338 (2)0.32223 (14)0.0618 (7)
H5A0.11330.68490.29380.074*
C60.1615 (3)0.81979 (19)0.32230 (12)0.0468 (6)
C70.4155 (3)0.76982 (18)0.28844 (12)0.0493 (6)
C80.4137 (4)0.6754 (2)0.34480 (15)0.0736 (9)
H8A0.32190.67700.37770.110*
H8B0.49880.67720.36700.110*
H8C0.41910.61160.32580.110*
C90.5596 (3)0.79176 (18)0.23885 (12)0.0452 (5)
C100.6860 (3)0.7250 (2)0.23775 (15)0.0597 (7)
H10A0.68480.66220.26920.072*
C110.8119 (3)0.7522 (2)0.19015 (16)0.0629 (7)
H11A0.89740.70780.18870.075*
C120.8130 (3)0.8461 (2)0.14377 (14)0.0556 (6)
H12A0.89850.86560.11100.067*
C130.6840 (3)0.91029 (18)0.14731 (11)0.0428 (5)
C140.6706 (3)1.01542 (19)0.10174 (11)0.0431 (5)
C150.8071 (3)1.0581 (3)0.05254 (13)0.0656 (8)
H15A0.79161.13240.03690.098*
H15B0.82451.02160.01400.098*
H15C0.89331.04760.07500.098*
C160.5139 (3)1.16236 (18)0.06797 (12)0.0456 (5)
C170.4990 (4)1.1675 (2)0.00081 (14)0.0649 (8)
H17A0.51321.1070−0.01920.078*
C180.4625 (4)1.2638 (3)−0.03660 (16)0.0795 (10)
H18A0.45051.2676−0.08190.095*
C190.4439 (3)1.3538 (2)−0.00793 (18)0.0748 (9)
H19A0.42021.4183−0.03370.090*
C200.4601 (4)1.3486 (2)0.05816 (17)0.0723 (8)
H20A0.44761.40960.07760.087*
C210.4951 (3)1.2528 (2)0.09685 (14)0.0594 (7)
H21A0.50601.24960.14220.071*
C221.0981 (3)0.4912 (2)0.16725 (16)0.0692 (8)
H22A1.13490.45090.20420.083*
C231.1739 (4)0.5794 (3)0.13071 (19)0.0850 (10)
H23A1.26240.59780.14270.102*
C241.1207 (4)0.6395 (3)0.07757 (19)0.0864 (10)
H24A1.17250.69900.05300.104*
C250.9915 (5)0.6126 (3)0.06016 (16)0.0916 (11)
H25A0.95560.65410.02330.110*
C260.9113 (4)0.5241 (3)0.09653 (14)0.0720 (8)
H26A0.82120.50730.08520.086*
C270.9686 (3)0.4623 (2)0.14951 (12)0.0502 (6)
C280.9344 (3)0.27781 (19)0.18030 (11)0.0445 (5)
C291.0691 (3)0.2511 (2)0.13030 (14)0.0658 (8)
H29A1.10440.31420.09920.099*
H29B1.04180.20090.10490.099*
H29C1.14780.22080.15460.099*
C300.8454 (3)0.18943 (19)0.22606 (11)0.0428 (5)
C310.8853 (3)0.0831 (2)0.22799 (12)0.0497 (6)
H31A0.97020.06260.19880.060*
C320.7970 (3)0.0084 (2)0.27390 (13)0.0561 (7)
H32A0.8215−0.06340.27580.067*
C330.6722 (3)0.04079 (19)0.31688 (13)0.0506 (6)
H33A0.6113−0.00850.34810.061*
C340.6392 (3)0.14914 (18)0.31264 (11)0.0426 (5)
C350.5134 (3)0.19527 (19)0.35903 (11)0.0424 (5)
C360.4090 (3)0.1228 (2)0.41136 (13)0.0565 (6)
H36A0.33070.16390.43480.085*
H36B0.46480.08230.44390.085*
H36C0.36470.07570.38900.085*
C370.3959 (3)0.35222 (18)0.39241 (12)0.0441 (5)
C380.4284 (3)0.3792 (2)0.45107 (13)0.0553 (6)
H38A0.51890.35590.46530.066*
C390.3277 (3)0.4405 (2)0.48881 (14)0.0657 (8)
H39A0.35020.45830.52850.079*
C400.1955 (3)0.4750 (2)0.46821 (17)0.0690 (8)
H40A0.12770.51670.49360.083*
C410.1622 (3)0.4480 (2)0.40971 (17)0.0695 (8)
H41A0.07130.47140.39590.083*
C420.2621 (3)0.3866 (2)0.37111 (14)0.0595 (7)
H42A0.23930.36890.33140.071*
Cl60.99171 (12)0.17671 (8)0.38588 (6)0.1018 (3)
Cl50.72467 (12)0.14750 (10)0.49217 (6)0.1190 (4)
C430.8709 (4)0.2322 (3)0.44971 (18)0.0885 (11)
H43A0.92870.24750.48270.106*
H43B0.82800.29850.42910.106*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mn10.03806 (19)0.0390 (2)0.04186 (19)0.00085 (14)−0.00693 (15)−0.00276 (14)
Mn20.0428 (2)0.03747 (19)0.04098 (19)0.00176 (15)−0.00385 (15)−0.00964 (14)
Cl10.0791 (5)0.0531 (4)0.0491 (3)−0.0070 (3)−0.0059 (3)−0.0130 (3)
Cl20.0499 (4)0.0848 (5)0.0605 (4)0.0028 (3)−0.0144 (3)−0.0298 (4)
Cl30.0696 (4)0.0470 (4)0.0574 (4)−0.0032 (3)−0.0213 (3)−0.0121 (3)
Cl40.0699 (5)0.0828 (5)0.0667 (4)0.0132 (4)−0.0267 (4)−0.0038 (4)
N10.0496 (12)0.0384 (11)0.0475 (11)−0.0032 (9)−0.0089 (9)−0.0009 (9)
N20.0405 (10)0.0401 (11)0.0449 (10)0.0007 (8)−0.0101 (9)−0.0076 (8)
N30.0438 (11)0.0404 (11)0.0439 (10)−0.0035 (9)−0.0066 (9)−0.0036 (8)
N40.0459 (11)0.0478 (12)0.0439 (11)0.0017 (9)−0.0027 (9)−0.0064 (9)
N50.0418 (10)0.0401 (10)0.0386 (10)0.0025 (8)−0.0061 (8)−0.0103 (8)
N60.0437 (11)0.0417 (11)0.0468 (11)−0.0028 (9)−0.0026 (9)−0.0120 (9)
C10.0571 (16)0.0448 (14)0.0533 (14)−0.0106 (12)−0.0076 (12)−0.0026 (11)
C20.0630 (17)0.0587 (17)0.0544 (15)−0.0043 (14)0.0007 (13)−0.0056 (13)
C30.0553 (16)0.0644 (19)0.0639 (17)−0.0095 (14)−0.0015 (14)0.0046 (14)
C40.0642 (18)0.0578 (18)0.079 (2)−0.0228 (14)−0.0129 (16)−0.0020 (15)
C50.0661 (18)0.0535 (16)0.0653 (17)−0.0138 (14)−0.0055 (14)−0.0117 (13)
C60.0501 (14)0.0416 (13)0.0456 (13)−0.0081 (11)−0.0105 (11)0.0044 (10)
C70.0605 (16)0.0365 (13)0.0499 (14)−0.0014 (11)−0.0140 (12)−0.0003 (10)
C80.078 (2)0.0533 (17)0.076 (2)0.0044 (15)−0.0087 (16)0.0166 (15)
C90.0509 (14)0.0342 (12)0.0515 (13)0.0019 (10)−0.0148 (11)−0.0054 (10)
C100.0646 (18)0.0428 (15)0.0724 (18)0.0090 (13)−0.0223 (15)−0.0047 (13)
C110.0535 (16)0.0557 (17)0.083 (2)0.0182 (13)−0.0188 (15)−0.0195 (15)
C120.0443 (14)0.0606 (17)0.0638 (16)0.0062 (12)−0.0096 (12)−0.0186 (13)
C130.0419 (13)0.0454 (13)0.0449 (12)0.0016 (10)−0.0126 (10)−0.0139 (10)
C140.0400 (12)0.0535 (14)0.0373 (12)−0.0054 (11)−0.0063 (10)−0.0109 (10)
C150.0464 (15)0.093 (2)0.0502 (15)−0.0072 (14)−0.0017 (12)0.0020 (14)
C160.0402 (12)0.0420 (13)0.0505 (14)−0.0042 (10)−0.0036 (10)−0.0010 (11)
C170.090 (2)0.0509 (16)0.0559 (16)−0.0101 (15)−0.0222 (15)−0.0024 (13)
C180.102 (3)0.071 (2)0.0669 (19)−0.0221 (19)−0.0379 (18)0.0134 (16)
C190.068 (2)0.0527 (18)0.093 (2)−0.0084 (15)−0.0178 (18)0.0203 (17)
C200.082 (2)0.0432 (16)0.081 (2)−0.0026 (15)0.0051 (17)−0.0039 (15)
C210.0735 (19)0.0482 (16)0.0524 (15)−0.0087 (13)−0.0024 (13)−0.0051 (12)
C220.0572 (17)0.0667 (19)0.078 (2)−0.0042 (14)−0.0166 (15)0.0077 (15)
C230.0566 (19)0.074 (2)0.114 (3)−0.0117 (16)−0.0070 (19)0.007 (2)
C240.080 (2)0.071 (2)0.089 (2)−0.0100 (19)0.014 (2)0.0105 (19)
C250.116 (3)0.084 (2)0.0591 (19)−0.001 (2)−0.010 (2)0.0201 (17)
C260.082 (2)0.077 (2)0.0534 (16)−0.0032 (17)−0.0150 (15)0.0025 (15)
C270.0477 (14)0.0513 (15)0.0464 (13)0.0062 (11)0.0013 (11)−0.0076 (11)
C280.0428 (13)0.0506 (15)0.0396 (12)0.0081 (11)−0.0086 (10)−0.0082 (10)
C290.0608 (17)0.0638 (18)0.0624 (17)0.0138 (14)0.0088 (13)−0.0088 (14)
C300.0444 (13)0.0476 (14)0.0389 (12)0.0062 (10)−0.0090 (10)−0.0143 (10)
C310.0551 (15)0.0509 (15)0.0454 (13)0.0126 (12)−0.0108 (11)−0.0167 (11)
C320.0729 (18)0.0424 (14)0.0591 (16)0.0070 (13)−0.0206 (14)−0.0185 (12)
C330.0613 (16)0.0382 (13)0.0538 (14)−0.0039 (11)−0.0111 (12)−0.0101 (11)
C340.0465 (13)0.0430 (13)0.0420 (12)−0.0033 (10)−0.0120 (10)−0.0125 (10)
C350.0411 (12)0.0468 (14)0.0402 (12)−0.0066 (10)−0.0065 (10)−0.0093 (10)
C360.0606 (16)0.0530 (15)0.0531 (15)−0.0113 (13)−0.0036 (12)−0.0053 (12)
C370.0392 (12)0.0433 (13)0.0468 (13)−0.0052 (10)0.0036 (10)−0.0105 (10)
C380.0465 (14)0.0660 (17)0.0536 (15)0.0008 (12)−0.0014 (12)−0.0202 (13)
C390.0591 (18)0.078 (2)0.0592 (16)−0.0128 (15)0.0119 (14)−0.0289 (15)
C400.0517 (17)0.0612 (18)0.086 (2)−0.0069 (14)0.0236 (15)−0.0270 (16)
C410.0387 (14)0.071 (2)0.090 (2)0.0062 (13)0.0023 (14)−0.0081 (17)
C420.0469 (15)0.0693 (18)0.0630 (16)−0.0022 (13)−0.0078 (13)−0.0148 (14)
Cl60.0934 (7)0.0891 (7)0.1316 (8)0.0004 (5)−0.0274 (6)−0.0354 (6)
Cl50.1017 (8)0.1494 (10)0.1039 (7)−0.0284 (7)−0.0426 (6)0.0162 (7)
C430.105 (3)0.065 (2)0.099 (3)0.0036 (19)−0.042 (2)−0.0026 (18)
Geometric parameters (Å, °) top
Mn1—N22.1856 (19)C17—C181.383 (4)
Mn1—N32.291 (2)C17—H17A0.9300
Mn1—N12.3084 (19)C18—C191.371 (5)
Mn1—Cl22.3244 (8)C18—H18A0.9300
Mn1—Cl12.3279 (9)C19—C201.355 (4)
Mn2—N52.2001 (19)C19—H19A0.9300
Mn2—N42.265 (2)C20—C211.385 (4)
Mn2—N62.274 (2)C20—H20A0.9300
Mn2—Cl42.3174 (9)C21—H21A0.9300
Mn2—Cl32.3426 (8)C22—C271.371 (4)
N1—C71.280 (3)C22—C231.374 (4)
N1—C61.423 (3)C22—H22A0.9300
N2—C131.336 (3)C23—C241.349 (4)
N2—C91.340 (3)C23—H23A0.9300
N3—C141.273 (3)C24—C251.357 (5)
N3—C161.444 (3)C24—H24A0.9300
N4—C281.280 (3)C25—C261.395 (5)
N4—C271.433 (3)C25—H25A0.9300
N5—C341.330 (3)C26—C271.373 (4)
N5—C301.333 (3)C26—H26A0.9300
N6—C351.278 (3)C28—C291.491 (3)
N6—C371.427 (3)C28—C301.493 (3)
C1—C21.380 (4)C29—H29A0.9600
C1—C61.382 (4)C29—H29B0.9600
C1—H1A0.9300C29—H29C0.9600
C2—C31.361 (4)C30—C311.386 (3)
C2—H2A0.9300C31—C321.378 (4)
C3—C41.365 (4)C31—H31A0.9300
C3—H3A0.9300C32—C331.378 (4)
C4—C51.383 (4)C32—H32A0.9300
C4—H4A0.9300C33—C341.396 (3)
C5—C61.378 (3)C33—H33A0.9300
C5—H5A0.9300C34—C351.495 (3)
C7—C91.489 (4)C35—C361.495 (3)
C7—C81.502 (3)C36—H36A0.9600
C8—H8A0.9600C36—H36B0.9600
C8—H8B0.9600C36—H36C0.9600
C8—H8C0.9600C37—C381.375 (3)
C9—C101.385 (3)C37—C421.376 (3)
C10—C111.359 (4)C38—C391.377 (4)
C10—H10A0.9300C38—H38A0.9300
C11—C121.384 (4)C39—C401.358 (4)
C11—H11A0.9300C39—H39A0.9300
C12—C131.383 (3)C40—C411.374 (4)
C12—H12A0.9300C40—H40A0.9300
C13—C141.501 (3)C41—C421.383 (4)
C14—C151.490 (3)C41—H41A0.9300
C15—H15A0.9600C42—H42A0.9300
C15—H15B0.9600Cl6—C431.750 (4)
C15—H15C0.9600Cl5—C431.748 (4)
C16—C171.373 (3)C43—H43A0.9700
C16—C211.378 (4)C43—H43B0.9700
N2—Mn1—N371.44 (7)C21—C16—N3119.5 (2)
N2—Mn1—N171.40 (7)C16—C17—C18119.1 (3)
N3—Mn1—N1142.81 (7)C16—C17—H17A120.4
N2—Mn1—Cl2118.40 (5)C18—C17—H17A120.4
N3—Mn1—Cl2100.02 (5)C19—C18—C17120.9 (3)
N1—Mn1—Cl298.81 (6)C19—C18—H18A119.5
N2—Mn1—Cl1123.33 (5)C17—C18—H18A119.5
N3—Mn1—Cl198.45 (6)C20—C19—C18119.7 (3)
N1—Mn1—Cl1100.39 (6)C20—C19—H19A120.1
Cl2—Mn1—Cl1118.26 (3)C18—C19—H19A120.1
N5—Mn2—N471.49 (7)C19—C20—C21120.4 (3)
N5—Mn2—N670.90 (7)C19—C20—H20A119.8
N4—Mn2—N6142.25 (7)C21—C20—H20A119.8
N5—Mn2—Cl4125.72 (5)C16—C21—C20119.8 (3)
N4—Mn2—Cl4103.15 (6)C16—C21—H21A120.1
N6—Mn2—Cl4101.10 (6)C20—C21—H21A120.1
N5—Mn2—Cl3117.98 (5)C27—C22—C23120.4 (3)
N4—Mn2—Cl398.18 (6)C27—C22—H22A119.8
N6—Mn2—Cl396.48 (5)C23—C22—H22A119.8
Cl4—Mn2—Cl3116.25 (3)C24—C23—C22120.5 (3)
C7—N1—C6120.6 (2)C24—C23—H23A119.8
C7—N1—Mn1117.35 (16)C22—C23—H23A119.8
C6—N1—Mn1122.06 (14)C23—C24—C25119.7 (3)
C13—N2—C9120.1 (2)C23—C24—H24A120.1
C13—N2—Mn1119.96 (15)C25—C24—H24A120.1
C9—N2—Mn1119.85 (16)C24—C25—C26121.2 (3)
C14—N3—C16121.0 (2)C24—C25—H25A119.4
C14—N3—Mn1117.94 (15)C26—C25—H25A119.4
C16—N3—Mn1121.07 (14)C27—C26—C25118.4 (3)
C28—N4—C27120.8 (2)C27—C26—H26A120.8
C28—N4—Mn2118.48 (16)C25—C26—H26A120.8
C27—N4—Mn2120.73 (15)C22—C27—C26119.8 (3)
C34—N5—C30120.3 (2)C22—C27—N4120.6 (2)
C34—N5—Mn2120.13 (15)C26—C27—N4119.5 (2)
C30—N5—Mn2119.46 (15)N4—C28—C29125.5 (2)
C35—N6—C37122.1 (2)N4—C28—C30115.9 (2)
C35—N6—Mn2119.02 (16)C29—C28—C30118.6 (2)
C37—N6—Mn2118.89 (14)C28—C29—H29A109.5
C2—C1—C6120.0 (2)C28—C29—H29B109.5
C2—C1—H1A120.0H29A—C29—H29B109.5
C6—C1—H1A120.0C28—C29—H29C109.5
C3—C2—C1120.3 (3)H29A—C29—H29C109.5
C3—C2—H2A119.9H29B—C29—H29C109.5
C1—C2—H2A119.9N5—C30—C31121.4 (2)
C2—C3—C4120.1 (3)N5—C30—C28114.6 (2)
C2—C3—H3A119.9C31—C30—C28123.9 (2)
C4—C3—H3A119.9C32—C31—C30118.9 (2)
C3—C4—C5120.4 (3)C32—C31—H31A120.5
C3—C4—H4A119.8C30—C31—H31A120.5
C5—C4—H4A119.8C33—C32—C31119.5 (2)
C6—C5—C4119.8 (3)C33—C32—H32A120.3
C6—C5—H5A120.1C31—C32—H32A120.3
C4—C5—H5A120.1C32—C33—C34118.7 (2)
C5—C6—C1119.3 (2)C32—C33—H33A120.6
C5—C6—N1121.4 (2)C34—C33—H33A120.6
C1—C6—N1119.3 (2)N5—C34—C33121.2 (2)
N1—C7—C9116.1 (2)N5—C34—C35114.5 (2)
N1—C7—C8126.4 (2)C33—C34—C35124.2 (2)
C9—C7—C8117.5 (2)N6—C35—C34115.4 (2)
C7—C8—H8A109.5N6—C35—C36125.2 (2)
C7—C8—H8B109.5C34—C35—C36119.4 (2)
H8A—C8—H8B109.5C35—C36—H36A109.5
C7—C8—H8C109.5C35—C36—H36B109.5
H8A—C8—H8C109.5H36A—C36—H36B109.5
H8B—C8—H8C109.5C35—C36—H36C109.5
N2—C9—C10120.9 (2)H36A—C36—H36C109.5
N2—C9—C7115.2 (2)H36B—C36—H36C109.5
C10—C9—C7123.9 (2)C38—C37—C42119.9 (2)
C11—C10—C9119.2 (2)C38—C37—N6119.8 (2)
C11—C10—H10A120.4C42—C37—N6120.0 (2)
C9—C10—H10A120.4C37—C38—C39120.4 (3)
C10—C11—C12120.0 (2)C37—C38—H38A119.8
C10—C11—H11A120.0C39—C38—H38A119.8
C12—C11—H11A120.0C40—C39—C38120.2 (3)
C13—C12—C11118.5 (3)C40—C39—H39A119.9
C13—C12—H12A120.7C38—C39—H39A119.9
C11—C12—H12A120.7C39—C40—C41119.7 (3)
N2—C13—C12121.2 (2)C39—C40—H40A120.1
N2—C13—C14114.5 (2)C41—C40—H40A120.1
C12—C13—C14124.3 (2)C40—C41—C42120.9 (3)
N3—C14—C15125.5 (2)C40—C41—H41A119.5
N3—C14—C13116.0 (2)C42—C41—H41A119.5
C15—C14—C13118.6 (2)C37—C42—C41118.9 (3)
C14—C15—H15A109.5C37—C42—H42A120.6
C14—C15—H15B109.5C41—C42—H42A120.6
H15A—C15—H15B109.5Cl5—C43—Cl6111.9 (2)
C14—C15—H15C109.5Cl5—C43—H43A109.2
H15A—C15—H15C109.5Cl6—C43—H43A109.2
H15B—C15—H15C109.5Cl5—C43—H43B109.2
C17—C16—C21120.0 (2)Cl6—C43—H43B109.2
C17—C16—N3120.4 (2)H43A—C43—H43B107.9
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C4—H4A···Cl3i0.932.773.668 (3)163
C10—H10A···Cl30.932.793.675 (3)160
C43—H43B···Cl30.972.663.587 (4)161
C15—H15B···Cl2ii0.962.783.592 (3)142
C31—H31A···Cl2iii0.932.733.629 (3)164
C29—H29C···Cl1iii0.962.753.676 (3)162
C36—H36C···Cl1iv0.962.813.473 (3)127
Symmetry codes: (i) x−1, y, z; (ii) −x+1, −y+2, −z; (iii) x+1, y−1, z; (iv) x, y−1, z.
Selected geometric parameters (Å, °) top
Mn1—N22.1856 (19)Mn2—N52.2001 (19)
Mn1—N32.291 (2)Mn2—N42.265 (2)
Mn1—N12.3084 (19)Mn2—N62.274 (2)
Mn1—Cl22.3244 (8)Mn2—Cl42.3174 (9)
Mn1—Cl12.3279 (9)Mn2—Cl32.3426 (8)
N2—Mn1—N371.44 (7)N5—Mn2—N471.49 (7)
N2—Mn1—N171.40 (7)N5—Mn2—N670.90 (7)
N3—Mn1—N1142.81 (7)N4—Mn2—N6142.25 (7)
N2—Mn1—Cl2118.40 (5)N5—Mn2—Cl4125.72 (5)
N3—Mn1—Cl2100.02 (5)N4—Mn2—Cl4103.15 (6)
N1—Mn1—Cl298.81 (6)N6—Mn2—Cl4101.10 (6)
N2—Mn1—Cl1123.33 (5)N5—Mn2—Cl3117.98 (5)
N3—Mn1—Cl198.45 (6)N4—Mn2—Cl398.18 (6)
N1—Mn1—Cl1100.39 (6)N6—Mn2—Cl396.48 (5)
Cl2—Mn1—Cl1118.26 (3)Cl4—Mn2—Cl3116.25 (3)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C4—H4A···Cl3i0.932.773.668 (3)163
C10—H10A···Cl30.932.793.675 (3)160
C43—H43B···Cl30.972.663.587 (4)161
C15—H15B···Cl2ii0.962.783.592 (3)142
C31—H31A···Cl2iii0.932.733.629 (3)164
C29—H29C···Cl1iii0.962.753.676 (3)162
C36—H36C···Cl1iv0.962.813.473 (3)127
Symmetry codes: (i) x−1, y, z; (ii) −x+1, −y+2, −z; (iii) x+1, y−1, z; (iv) x, y−1, z.
C—H···π interactions (Å, °) top
C—H···CgaH···CgC···CgγbC—H···Cg)
C11—H11A···Cg(C22→C27)2.853.604 (3)10.09139
C32—H32A···Cg(N2→C13)i2.933.473 (3)6.10119
C32—H32A···Cg(C1→C6)ii2.983.620 (3)12.23127
Notes: Cga = centroid of the six-membered ring. γb = angle defined by a line connecting the centroid of the six-membered ring with H atom and the normal to the six-membered ring. Symmetry codes: (i) x,-1 + y,z; (ii) 1 + x,-1 + y,z.
π···π interactions (Å, °) top
π···π contactsCg···CgαaβbCg···Plane
Cg(C22A→C27A)···Cg(C22B→C27B)5.195 (2)0.0047.303.523
Notes: αa = angle between the planes of the two aromatic rings. βb = angle between Cg···Cg line and normal to the plane of the first aromatic ring.
Acknowledgements top

The work was supportd by the National Natural Science Foundation of China (No. 20763008)

references
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