Bis{μ-2,2′-[1,1′-(ethane-1,2-diyldinitrilo)diethyl­idyne]diphenolato-κ5O,N,N′,O′:O}bis­[chloridomanganese(III)]

Thampidas, V.S.; Radhakrishnan, T.; Pike, R.D.

doi:10.1107/S1600536808000226

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 2| February 2008| Page m307

doi:10.1107/S1600536808000226

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Bis{μ-2,2′-[1,1′-(ethane-1,2-diyldinitrilo)diethylidyne]diphenolato-κ⁵O,N,N′,O′:O}bis[chloridomanganese(III)]

V. S. Thampidas,^a ^* T. Radhakrishnan ^b and Robert D. Pike ^c

^aDepartment of Chemistry, SN College, Varkala, Kerala 695 145, India, ^bDepartment of Chemistry, University of Kerala, Thiruvananthapuram, Kerala 695 581, India, and ^cDepartment of Chemistry, College of William and Mary, PO Box 8795, Williamsburg, VA 23187-8795, USA
^*Correspondence e-mail: dasthampi@hotmail.com

(Received 12 December 2007; accepted 3 January 2008; online 9 January 2008)

The title compound, [Mn₂(C₁₈H₁₈N₂O₂)₂Cl₂], was synthesized by the reaction between manganese(II) o-chlorobenzoate and the Schiff base generated in situ by the condensation of ethane-1,2-diamine and o-hydroxyacetophenone. The centrosymmetric dimer contains two Jahn–Teller-distorted manganese(III) ions, each in an octahedral geometry, connected through two phenoxy bridges from two ligands.

Related literature

For related literature, see: Christou (2005 ); Horwitz et al. (1995 ); Jacobsen et al. (1991 ); Larrow & Jacobsen (2004 ); Panja et al. (2003 ); Pecoraro & Butler (1986 ); Saha et al. (2004 ); Triller et al. (2002 ); Vites & Lynam (1998 ); Zhang et al. (1990 ).

Experimental

Crystal data

[Mn₂(C₁₈H₁₈N₂O₂)₂Cl₂]
M_r = 769.47
Triclinic, $[P \overline 1]$
a = 7.8261 (3) Å
b = 9.8046 (3) Å
c = 11.2372 (4) Å
α = 97.207 (2)°
β = 94.701 (2)°
γ = 108.081 (2)°
V = 806.49 (5) Å³
Z = 1
Cu Kα radiation
μ = 8.29 mm⁻¹
T = 100 (2) K
0.28 × 0.14 × 0.14 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SAINT-Plus; Bruker, 2004 ) T_min = 0.205, T_max = 0.390 (expected range = 0.165–0.313)
12822 measured reflections
2781 independent reflections
2733 reflections with I > 2σ(I)
R_int = 0.033

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.088
S = 1.10
2781 reflections
219 parameters
H-atom parameters constrained
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.44 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Mn1—O2	1.8738 (16)
Mn1—O1	1.9191 (16)
Mn1—N1	1.9964 (19)
Mn1—N2	2.0129 (19)
Mn1—Cl1	2.4633 (6)
Mn1—O1ⁱ	2.4720 (16)

O2—Mn1—O1	95.14 (7)
O2—Mn1—N1	170.58 (8)
O1—Mn1—N1	87.86 (7)
O2—Mn1—N2	90.36 (7)
O1—Mn1—N2	163.69 (8)
N1—Mn1—N2	84.44 (8)
O2—Mn1—Cl1	95.48 (5)
O1—Mn1—Cl1	96.66 (5)
N1—Mn1—Cl1	93.03 (6)
N2—Mn1—Cl1	98.09 (6)
O2—Mn1—O1ⁱ	88.58 (6)
O1—Mn1—O1ⁱ	77.02 (7)
N1—Mn1—O1ⁱ	83.39 (7)
N2—Mn1—O1ⁱ	87.80 (7)
Cl1—Mn1—O1ⁱ	172.81 (4)
Mn1—O1—Mn1ⁱ	102.98 (7)
Symmetry code: (i) -x, -y+2, -z.

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT-Plus (Bruker, 2004); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808000226/hy2115sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808000226/hy2115Isup2.hkl

checkCIF report

Comment top

Manganese coordination chemistry, in recent decades, has been in intense research focus in connection with developments in diverse fields as bioinorganic modeling (Triller et al., 2002), asymmetric catalysis (Larrow & Jacobsen, 2004), molecular magnetism (Christou, 2005) etc. Schiff base ligands with nitrogen and oxygen donor atoms seem to stabilize the various oxidation states of manganese better than any other ligand systems, as it is evident from the sheer number of publications in this area (Vites & Lynam, 1998). The penta-coordinate [Mn(salen)Cl] (H₂salen = N,N'-bis(salicylidene)-1,2-diaminoethane) was one of the earliest crystallographically characterized manganese(III) Schiff base complexes (Pecoraro & Butler, 1986). This may be considered as a prototype molecule, that has led to the development of large number of manganese(III) complexes with a square planar MnN₂O₂ core, stabilized by a chiral-salen ligand and a chloride ion in the axial position (Zhang et al., 1990; Jacobsen et al., 1991). In our effort to synthesize dimeric manganese(III) complexes of a salen-like ligand, N,N'-bis(o-hydroxyacetophenonylidene)-1,2-diaminoethane with o-chlorobenzoate as an ancillary ligand, we unexpectedly obtained a dimeric manganese(III) complex stabilized by the Schiff base and two axial chloride ligands. Here we report the crystal structure of the new dichloride dimer (Fig. 1).

In the title compound, the centrosymmetric dimer is crystallographically half independent and consists of two Mn^III atoms, linked by two phenolic O atoms of two ligands. Two Mn—N bonds and two Mn—O bonds complete the equatorial square plane geometry around the Mn^III atom (Table 1). This leaves the two axial positions open for coordination to the Cl atoms, leading to the formation of a rare dichloride dimer. Jahn-Teller distortion elongates the Mn—Cl bond [Mn1—Cl1 = 2.4633 (6) Å] substantially, which is comparable to the Mn—Cl bond length of 2.461 (1)Å in the square pyramidal [Mn(salen)Cl] (Pecoraro & Butler, 1986). But the elongation is not as much as seen in the square pyramidal [Mn(5—Cl-salen)Cl] (Horwitz et al., 1995) and octahedral [Mn(salen)Cl(H₂O)] (Panja et al., 2003), where Mn—Cl distances are 2.572 (1) Å and 2.621 (6) Å, respectively. Jahn-Teller effect is also apparent in the longer Mn—O bond [Mn1—O1 = 2.4720 (16) Å] of the Mn₂(µ-O)₂ diamond core of the dimer. This makes the Mn—O—Mn bridge of the complex considerably weaker than that in the diazide dimer [Mn₂(L)₂(N₃)₂] (H₂L = N,N'-bis(o-hydroxyacetophenonylidene)-1,2-diaminoethane) (Saha et al., 2004), where the corresponding bond length is 2.375 (5) Å. The Mn···Mn separation in the title compound is 3.453 (2) Å, compared to 3.341 (2)Å in [Mn₂(L)₂(N₃)₂].

Related literature top

For related literature, see: Christou (2005); Horwitz et al. (1995); Jacobsen et al. (1991); Larrow & Jacobsen (2004); Panja et al. (2003); Pecoraro & Butler (1986); Saha et al. (2004); Triller et al. (2002); Vites & Lynam (1998); Zhang et al. (1990).

Experimental top

To a solution of Mn(o—Cl—C₆H₄CO₂)₂.2H₂O (1.00 g, 2.49 mmol) and o-hydroxyacetophenone (0.68 g, 4.98 mmol) in methanol (40 ml), ethane-1,2-diamine (0.14 g, 2.49 mmol) was added. The solution was stirred for 20 min, filtered and left to evaporation in an open conical flask. Brown crystals were deposited in 2–3 days. These were collected by filtration, washed with methanol, and dried in air (yield 0.80 g, 80.6% based on Mn).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT-Plus (Bruker, 2004); data reduction: SAINT-Plus (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PRPKAPPA (Ferguson, 1999).

Figures top

Fig. 1. Molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry code: (i) -x, 2 - y, -z.]

Bis{µ-2,2'-[1,1'-(ethane-1,2-diyldinitrilo)diethylidyne]diphenolato- κ⁵O,N,N',O':O}bis[chloridomanganese(III)] top

Crystal data top

[Mn₂(C₁₈H₁₈N₂O₂)₂Cl₂]	Z = 1
M_r = 769.47	F(000) = 396
Triclinic, P1	D_x = 1.584 Mg m⁻³
Hall symbol: -P 1	Cu Kα radiation, λ = 1.54178 Å
a = 7.8261 (3) Å	Cell parameters from 2781 reflections
b = 9.8046 (3) Å	θ = 9.8–71.6°
c = 11.2372 (4) Å	µ = 8.29 mm⁻¹
α = 97.207 (2)°	T = 100 K
β = 94.701 (2)°	Prism, brown
γ = 108.081 (2)°	0.28 × 0.14 × 0.14 mm
V = 806.49 (5) Å³

Data collection top

Bruker SMART APEXII CCD diffractometer	2781 independent reflections
Radiation source: fine-focus sealed tube	2733 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
ϕ and ω scans	θ_max = 67.0°, θ_min = 4.0°
Absorption correction: multi-scan (SAINT-Plus; Bruker, 2004)	h = −9→9
T_min = 0.205, T_max = 0.390	k = −11→11
12822 measured reflections	l = −13→12

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.088	H-atom parameters constrained
S = 1.10	w = 1/[σ²(F_o²) + (0.0396P)² + 1.0982P] where P = (F_o² + 2F_c²)/3
2781 reflections	(Δ/σ)_max = 0.001
219 parameters	Δρ_max = 0.39 e Å⁻³
0 restraints	Δρ_min = −0.44 e Å⁻³

Crystal data top

[Mn₂(C₁₈H₁₈N₂O₂)₂Cl₂]	γ = 108.081 (2)°
M_r = 769.47	V = 806.49 (5) Å³
Triclinic, P1	Z = 1
a = 7.8261 (3) Å	Cu Kα radiation
b = 9.8046 (3) Å	µ = 8.29 mm⁻¹
c = 11.2372 (4) Å	T = 100 K
α = 97.207 (2)°	0.28 × 0.14 × 0.14 mm
β = 94.701 (2)°

Data collection top

Bruker SMART APEXII CCD diffractometer	2781 independent reflections
Absorption correction: multi-scan (SAINT-Plus; Bruker, 2004)	2733 reflections with I > 2σ(I)
T_min = 0.205, T_max = 0.390	R_int = 0.033
12822 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.088	H-atom parameters constrained
S = 1.10	Δρ_max = 0.39 e Å⁻³
2781 reflections	Δρ_min = −0.44 e Å⁻³
219 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Mn1	0.03321 (5)	0.93493 (4)	0.13283 (3)	0.00849 (13)
Cl1	0.23277 (7)	0.82169 (6)	0.23406 (5)	0.01447 (15)
O1	0.1568 (2)	0.96398 (17)	−0.00716 (14)	0.0108 (3)
O2	0.1517 (2)	1.12309 (17)	0.21677 (14)	0.0118 (3)
N1	−0.1287 (3)	0.7452 (2)	0.04014 (18)	0.0107 (4)
N2	−0.1560 (3)	0.9047 (2)	0.24675 (17)	0.0109 (4)
C18	0.1226 (3)	1.1893 (3)	0.3192 (2)	0.0114 (5)
C12	−0.1614 (3)	0.9876 (3)	0.3457 (2)	0.0107 (5)
C5	0.1437 (3)	0.6051 (3)	−0.1622 (2)	0.0137 (5)
H5	0.0687	0.5063	−0.1770	0.016*
C7	−0.0921 (3)	0.6659 (2)	−0.0498 (2)	0.0112 (5)
C8	−0.2364 (3)	0.5291 (3)	−0.1141 (2)	0.0142 (5)
H8A	−0.2528	0.4528	−0.0634	0.021*
H8B	−0.1993	0.4970	−0.1910	0.021*
H8C	−0.3509	0.5488	−0.1297	0.021*
C2	0.3629 (3)	0.8946 (3)	−0.1229 (2)	0.0119 (5)
H2	0.4379	0.9934	−0.1109	0.014*
C1	0.2018 (3)	0.8569 (2)	−0.0705 (2)	0.0102 (4)
C11	−0.3108 (3)	0.9334 (3)	0.4225 (2)	0.0160 (5)
H11A	−0.4250	0.9375	0.3830	0.024*
H11B	−0.2802	0.9946	0.5022	0.024*
H11C	−0.3238	0.8328	0.4321	0.024*
C9	−0.3112 (3)	0.7098 (3)	0.0770 (2)	0.0135 (5)
H9A	−0.3738	0.6036	0.0577	0.016*
H9B	−0.3829	0.7588	0.0323	0.016*
C13	−0.0262 (3)	1.1327 (3)	0.3837 (2)	0.0123 (5)
C14	−0.0442 (3)	1.2227 (3)	0.4882 (2)	0.0158 (5)
H14	−0.1439	1.1874	0.5315	0.019*
C6	0.0872 (3)	0.7094 (3)	−0.0912 (2)	0.0106 (4)
C17	0.2500 (3)	1.3270 (3)	0.3664 (2)	0.0141 (5)
H17	0.3542	1.3622	0.3270	0.017*
C10	−0.2963 (3)	0.7598 (3)	0.2119 (2)	0.0139 (5)
H10A	−0.4146	0.7652	0.2331	0.017*
H10B	−0.2637	0.6889	0.2569	0.017*
C3	0.4149 (3)	0.7907 (3)	−0.1920 (2)	0.0138 (5)
H3	0.5247	0.8183	−0.2269	0.017*
C16	0.2281 (3)	1.4120 (3)	0.4680 (2)	0.0165 (5)
H16	0.3142	1.5054	0.4963	0.020*
C4	0.3054 (3)	0.6445 (3)	−0.2101 (2)	0.0146 (5)
H4	0.3426	0.5726	−0.2555	0.018*
C15	0.0780 (4)	1.3594 (3)	0.5286 (2)	0.0184 (5)
H15	0.0604	1.4177	0.5976	0.022*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn1	0.0089 (2)	0.0085 (2)	0.0068 (2)	0.00102 (14)	0.00293 (13)	0.00013 (14)
Cl1	0.0154 (3)	0.0175 (3)	0.0120 (3)	0.0072 (2)	0.0016 (2)	0.0030 (2)
O1	0.0127 (8)	0.0106 (8)	0.0091 (8)	0.0036 (6)	0.0037 (6)	0.0006 (6)
O2	0.0130 (8)	0.0121 (8)	0.0087 (8)	0.0018 (6)	0.0039 (6)	0.0004 (6)
N1	0.0095 (9)	0.0113 (9)	0.0110 (10)	0.0017 (7)	0.0032 (7)	0.0036 (8)
N2	0.0104 (9)	0.0115 (9)	0.0110 (10)	0.0028 (8)	0.0027 (7)	0.0031 (8)
C18	0.0136 (11)	0.0143 (11)	0.0085 (11)	0.0074 (9)	0.0005 (9)	0.0026 (9)
C12	0.0108 (11)	0.0160 (11)	0.0078 (11)	0.0072 (9)	0.0015 (8)	0.0042 (9)
C5	0.0182 (12)	0.0103 (11)	0.0109 (11)	0.0027 (9)	0.0004 (9)	0.0008 (9)
C7	0.0159 (12)	0.0108 (11)	0.0068 (11)	0.0040 (9)	−0.0004 (9)	0.0029 (9)
C8	0.0142 (12)	0.0132 (11)	0.0129 (12)	0.0017 (9)	0.0029 (9)	0.0004 (9)
C2	0.0119 (11)	0.0135 (11)	0.0089 (11)	0.0027 (9)	−0.0011 (9)	0.0021 (9)
C1	0.0121 (11)	0.0128 (11)	0.0061 (10)	0.0052 (9)	−0.0004 (8)	0.0011 (9)
C11	0.0154 (12)	0.0188 (12)	0.0129 (12)	0.0037 (10)	0.0059 (9)	0.0014 (10)
C9	0.0094 (11)	0.0138 (11)	0.0154 (12)	0.0012 (9)	0.0037 (9)	0.0011 (9)
C13	0.0139 (12)	0.0150 (11)	0.0087 (11)	0.0056 (9)	0.0014 (9)	0.0015 (9)
C14	0.0166 (12)	0.0207 (12)	0.0108 (12)	0.0064 (10)	0.0044 (9)	0.0023 (10)
C6	0.0117 (11)	0.0136 (11)	0.0062 (10)	0.0041 (9)	−0.0009 (8)	0.0015 (9)
C17	0.0143 (12)	0.0150 (11)	0.0121 (11)	0.0029 (9)	0.0028 (9)	0.0029 (9)
C10	0.0119 (11)	0.0134 (11)	0.0148 (12)	0.0005 (9)	0.0057 (9)	0.0039 (9)
C3	0.0117 (11)	0.0199 (12)	0.0096 (11)	0.0049 (9)	0.0027 (9)	0.0009 (9)
C16	0.0194 (13)	0.0137 (11)	0.0135 (12)	0.0028 (10)	0.0005 (9)	−0.0010 (10)
C4	0.0169 (12)	0.0154 (12)	0.0123 (12)	0.0078 (10)	0.0021 (9)	−0.0021 (9)
C15	0.0242 (13)	0.0196 (13)	0.0117 (12)	0.0089 (11)	0.0035 (10)	−0.0021 (10)

Geometric parameters (Å, º) top

Mn1—O2	1.8738 (16)	C8—H8C	0.9800
Mn1—O1	1.9191 (16)	C2—C3	1.385 (3)
Mn1—N1	1.9964 (19)	C2—C1	1.400 (3)
Mn1—N2	2.0129 (19)	C2—H2	0.9500
Mn1—Cl1	2.4633 (6)	C1—C6	1.423 (3)
Mn1—O1ⁱ	2.4720 (16)	C11—H11A	0.9800
O1—C1	1.348 (3)	C11—H11B	0.9800
O1—Mn1ⁱ	2.4720 (16)	C11—H11C	0.9800
O2—C18	1.321 (3)	C9—C10	1.517 (3)
N1—C7	1.302 (3)	C9—H9A	0.9900
N1—C9	1.469 (3)	C9—H9B	0.9900
N2—C12	1.305 (3)	C13—C14	1.422 (3)
N2—C10	1.483 (3)	C14—C15	1.378 (4)
C18—C17	1.413 (3)	C14—H14	0.9500
C18—C13	1.424 (3)	C17—C16	1.382 (3)
C12—C13	1.471 (3)	C17—H17	0.9500
C12—C11	1.513 (3)	C10—H10A	0.9900
C5—C4	1.379 (4)	C10—H10B	0.9900
C5—C6	1.418 (3)	C3—C4	1.402 (3)
C5—H5	0.9500	C3—H3	0.9500
C7—C6	1.467 (3)	C16—C15	1.398 (4)
C7—C8	1.510 (3)	C16—H16	0.9500
C8—H8A	0.9800	C4—H4	0.9500
C8—H8B	0.9800	C15—H15	0.9500

O2—Mn1—O1	95.14 (7)	O1—C1—C2	118.2 (2)
O2—Mn1—N1	170.58 (8)	O1—C1—C6	122.4 (2)
O1—Mn1—N1	87.86 (7)	C2—C1—C6	119.3 (2)
O2—Mn1—N2	90.36 (7)	C12—C11—H11A	109.5
O1—Mn1—N2	163.69 (8)	C12—C11—H11B	109.5
N1—Mn1—N2	84.44 (8)	H11A—C11—H11B	109.5
O2—Mn1—Cl1	95.48 (5)	C12—C11—H11C	109.5
O1—Mn1—Cl1	96.66 (5)	H11A—C11—H11C	109.5
N1—Mn1—Cl1	93.03 (6)	H11B—C11—H11C	109.5
N2—Mn1—Cl1	98.09 (6)	N1—C9—C10	109.25 (19)
O2—Mn1—O1ⁱ	88.58 (6)	N1—C9—H9A	109.8
O1—Mn1—O1ⁱ	77.02 (7)	C10—C9—H9A	109.8
N1—Mn1—O1ⁱ	83.39 (7)	N1—C9—H9B	109.8
N2—Mn1—O1ⁱ	87.80 (7)	C10—C9—H9B	109.8
Cl1—Mn1—O1ⁱ	172.81 (4)	H9A—C9—H9B	108.3
C1—O1—Mn1	121.87 (14)	C14—C13—C18	117.7 (2)
C1—O1—Mn1ⁱ	112.89 (13)	C14—C13—C12	119.4 (2)
Mn1—O1—Mn1ⁱ	102.98 (7)	C18—C13—C12	122.9 (2)
C18—O2—Mn1	130.34 (15)	C15—C14—C13	122.2 (2)
C7—N1—C9	121.6 (2)	C15—C14—H14	118.9
C7—N1—Mn1	127.36 (16)	C13—C14—H14	118.9
C9—N1—Mn1	110.67 (14)	C5—C6—C1	118.3 (2)
C12—N2—C10	119.38 (19)	C5—C6—C7	119.8 (2)
C12—N2—Mn1	129.33 (16)	C1—C6—C7	121.7 (2)
C10—N2—Mn1	111.08 (14)	C16—C17—C18	122.1 (2)
O2—C18—C17	116.5 (2)	C16—C17—H17	118.9
O2—C18—C13	125.0 (2)	C18—C17—H17	118.9
C17—C18—C13	118.5 (2)	N2—C10—C9	109.88 (18)
N2—C12—C13	121.5 (2)	N2—C10—H10A	109.7
N2—C12—C11	119.1 (2)	C9—C10—H10A	109.7
C13—C12—C11	119.4 (2)	N2—C10—H10B	109.7
C4—C5—C6	121.3 (2)	C9—C10—H10B	109.7
C4—C5—H5	119.4	H10A—C10—H10B	108.2
C6—C5—H5	119.4	C2—C3—C4	119.9 (2)
N1—C7—C6	120.7 (2)	C2—C3—H3	120.1
N1—C7—C8	119.9 (2)	C4—C3—H3	120.1
C6—C7—C8	119.4 (2)	C17—C16—C15	119.4 (2)
C7—C8—H8A	109.5	C17—C16—H16	120.3
C7—C8—H8B	109.5	C15—C16—H16	120.3
H8A—C8—H8B	109.5	C5—C4—C3	119.9 (2)
C7—C8—H8C	109.5	C5—C4—H4	120.0
H8A—C8—H8C	109.5	C3—C4—H4	120.0
H8B—C8—H8C	109.5	C14—C15—C16	119.8 (2)
C3—C2—C1	121.3 (2)	C14—C15—H15	120.1
C3—C2—H2	119.4	C16—C15—H15	120.1
C1—C2—H2	119.4

O2—Mn1—O1—C1	144.83 (16)	Mn1—N1—C7—C8	−176.24 (16)
N1—Mn1—O1—C1	−44.12 (17)	Mn1—O1—C1—C2	−145.77 (17)
N2—Mn1—O1—C1	−105.9 (3)	Mn1ⁱ—O1—C1—C2	90.9 (2)
Cl1—Mn1—O1—C1	48.69 (16)	Mn1—O1—C1—C6	37.8 (3)
O1ⁱ—Mn1—O1—C1	−127.83 (18)	Mn1ⁱ—O1—C1—C6	−85.5 (2)
O2—Mn1—O1—Mn1ⁱ	−87.35 (7)	C3—C2—C1—O1	−178.2 (2)
N1—Mn1—O1—Mn1ⁱ	83.71 (7)	C3—C2—C1—C6	−1.7 (3)
N2—Mn1—O1—Mn1ⁱ	21.9 (3)	C7—N1—C9—C10	149.6 (2)
Cl1—Mn1—O1—Mn1ⁱ	176.51 (4)	Mn1—N1—C9—C10	−36.7 (2)
O1ⁱ—Mn1—O1—Mn1ⁱ	0.0	O2—C18—C13—C14	−175.6 (2)
O1—Mn1—O2—C18	172.36 (19)	C17—C18—C13—C14	4.1 (3)
N2—Mn1—O2—C18	7.7 (2)	O2—C18—C13—C12	3.3 (4)
Cl1—Mn1—O2—C18	−90.43 (19)	C17—C18—C13—C12	−177.0 (2)
O1ⁱ—Mn1—O2—C18	95.52 (19)	N2—C12—C13—C14	176.1 (2)
O1—Mn1—N1—C7	25.1 (2)	C11—C12—C13—C14	−3.6 (3)
N2—Mn1—N1—C7	−169.3 (2)	N2—C12—C13—C18	−2.9 (3)
Cl1—Mn1—N1—C7	−71.4 (2)	C11—C12—C13—C18	177.4 (2)
O1ⁱ—Mn1—N1—C7	102.3 (2)	C18—C13—C14—C15	−1.2 (4)
O1—Mn1—N1—C9	−148.16 (15)	C12—C13—C14—C15	179.8 (2)
N2—Mn1—N1—C9	17.44 (15)	C4—C5—C6—C1	0.1 (3)
Cl1—Mn1—N1—C9	115.28 (14)	C4—C5—C6—C7	175.1 (2)
O1ⁱ—Mn1—N1—C9	−70.98 (15)	O1—C1—C6—C5	178.0 (2)
O2—Mn1—N2—C12	−7.3 (2)	C2—C1—C6—C5	1.6 (3)
O1—Mn1—N2—C12	−117.2 (3)	O1—C1—C6—C7	3.1 (3)
N1—Mn1—N2—C12	−179.4 (2)	C2—C1—C6—C7	−173.3 (2)
Cl1—Mn1—N2—C12	88.3 (2)	N1—C7—C6—C5	161.2 (2)
O1ⁱ—Mn1—N2—C12	−95.9 (2)	C8—C7—C6—C5	−20.0 (3)
O2—Mn1—N2—C10	178.04 (15)	N1—C7—C6—C1	−24.0 (3)
O1—Mn1—N2—C10	68.1 (3)	C8—C7—C6—C1	154.8 (2)
N1—Mn1—N2—C10	5.90 (15)	O2—C18—C17—C16	175.2 (2)
Cl1—Mn1—N2—C10	−86.38 (15)	C13—C18—C17—C16	−4.5 (4)
O1ⁱ—Mn1—N2—C10	89.48 (15)	C12—N2—C10—C9	157.5 (2)
Mn1—O2—C18—C17	172.84 (15)	Mn1—N2—C10—C9	−27.3 (2)
Mn1—O2—C18—C13	−7.4 (3)	N1—C9—C10—N2	41.7 (3)
C10—N2—C12—C13	−179.6 (2)	C1—C2—C3—C4	−0.1 (4)
Mn1—N2—C12—C13	6.2 (3)	C18—C17—C16—C15	1.8 (4)
C10—N2—C12—C11	0.2 (3)	C6—C5—C4—C3	−1.9 (4)
Mn1—N2—C12—C11	−174.11 (16)	C2—C3—C4—C5	1.9 (4)
C9—N1—C7—C6	175.2 (2)	C13—C14—C15—C16	−1.5 (4)
Mn1—N1—C7—C6	2.5 (3)	C17—C16—C15—C14	1.2 (4)
C9—N1—C7—C8	−3.6 (3)

Symmetry code: (i) −x, −y+2, −z.

Experimental details

Crystal data
Chemical formula	[Mn₂(C₁₈H₁₈N₂O₂)₂Cl₂]
M_r	769.47
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	7.8261 (3), 9.8046 (3), 11.2372 (4)
α, β, γ (°)	97.207 (2), 94.701 (2), 108.081 (2)
V (Å³)	806.49 (5)
Z	1
Radiation type	Cu Kα
µ (mm⁻¹)	8.29
Crystal size (mm)	0.28 × 0.14 × 0.14

Data collection
Diffractometer	Bruker SMART APEXII CCD diffractometer
Absorption correction	Multi-scan (SAINT-Plus; Bruker, 2004)
T_min, T_max	0.205, 0.390
No. of measured, independent and observed [I > 2σ(I)] reflections	12822, 2781, 2733
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.597

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.088, 1.10
No. of reflections	2781
No. of parameters	219
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.39, −0.44

Computer programs: APEX2 (Bruker, 2004), SAINT-Plus (Bruker, 2004), SHELXS97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), SHELXL97 (Sheldrick, 2008) and PRPKAPPA (Ferguson, 1999).

Selected geometric parameters (Å, º) top

Mn1—O2	1.8738 (16)	Mn1—N2	2.0129 (19)
Mn1—O1	1.9191 (16)	Mn1—Cl1	2.4633 (6)
Mn1—N1	1.9964 (19)	Mn1—O1ⁱ	2.4720 (16)

O2—Mn1—O1	95.14 (7)	N1—Mn1—Cl1	93.03 (6)
O2—Mn1—N1	170.58 (8)	N2—Mn1—Cl1	98.09 (6)
O1—Mn1—N1	87.86 (7)	O2—Mn1—O1ⁱ	88.58 (6)
O2—Mn1—N2	90.36 (7)	O1—Mn1—O1ⁱ	77.02 (7)
O1—Mn1—N2	163.69 (8)	N1—Mn1—O1ⁱ	83.39 (7)
N1—Mn1—N2	84.44 (8)	N2—Mn1—O1ⁱ	87.80 (7)
O2—Mn1—Cl1	95.48 (5)	Cl1—Mn1—O1ⁱ	172.81 (4)
O1—Mn1—Cl1	96.66 (5)	Mn1—O1—Mn1ⁱ	102.98 (7)

Symmetry code: (i) −x, −y+2, −z.

Acknowledgements

The authors acknowledge the authorities of SN College, Varkala, Kerala, India, for access to the college facilities for this research. The authors also acknowledge the NSF (grant No. CHE-0443345) and the College of William and Mary for the purchase of the X-ray equipment.

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