(Acetylacetonato)bis(1,10′-phenanthroline-N,N′)manganese(II) perchlorate

Zhang, X.-F.; Huang, D.-G.; Ma, C.-B.; Chen, C.-N.; Liu, Q.-T.

doi:10.1107/S1600536802014484

(Acetylacetonato)bis(1,10'-phenanthroline-N,N')manganese(II) perchlorate

X.-F. Zhang, D.-G. Huang, C.-B. Ma, C.-N. Chen and Q.-T. Liu

The crystal structure of the title compound, [Mn(C₅H₇O₂)(C₁₂H₈N₂)₂](ClO₄), contains a monomeric [Mn(phen)₂(acac)]⁺ cation and a perchlorate anion [phen is 1,10'-phenanthroline (C₁₂H₈N₂) and acac is acetylacetonate (C₅H₇O₂)]. The Mn^II ion is coordinated by four N atoms from the phen ligands [Mn-N 2.253 (4)-2.322 (4) Å] and two O atoms of the acac ligand [Mn-O 2.116 (3) and 2.124 (3) Å] in chelating mode, forming a distorted octahedral geometry.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802014484/cv6133sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536802014484/cv6133Isup2.hkl Contains datablock I

CCDC reference: 197445

checkCIF report

Key indicators

Single-crystal X-ray study
T = 293 K
Mean (C-C) = 0.008 Å
R factor = 0.064
wR factor = 0.191
Data-to-parameter ratio = 13.3

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



ABSTM_02  Alert C The ratio of expected to reported Tmax/Tmin(RR') is < 0.90
          Tmin and Tmax reported:      0.593     0.854
          Tmin' and Tmax expected:      0.779     0.854
          RR' =      0.761
          Please check that your absorption correction is appropriate.

General Notes



FORMU_01  There is a discrepancy between the atom counts in the
          _chemical_formula_sum and _chemical_formula_moiety. This is
          usually due to the moiety formula being in the wrong format.
          Atom count from _chemical_formula_sum:   C29 H23 Cl1 Mn1 N4 O6
          Atom count from _chemical_formula_moiety:C29 H23 Cl1 Mn1 N4 O8


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 1 Alert Level C = Please check

Comment top

Considerable attention has been focused on the bioinorganic chemistry of Mn and, in particular, on multinuclear Mn metalloenzymes, such as the tetra-Mn in the oxygen-evolving centre (OEC) of photosystem II (PSII) in green plants (Wieghardt, 1989). It is thought that the coordination environment of the Mn in OEC consists essentially of the ligands with O and N donor atoms, and the binding of water to the Mn site may be important for the oxidation of water for the evolution of dioxygen. In recent years, Mn-phen (phen is 1,10'-phenanthroline) complexes have been extensively studied as model compounds for simulating OEC in PSII (Manchanda et al., 1994). In a reaction system containing phen, Mn(acac)₃ (acac is acetylacetonate) and dicarboxylic acid, we isolated the title complex, [Mn(phen)₂(acac)]ClO₄, (I), which contains three different chelating ligands in the cation. Here, we describe its synthesis and crystal structure.

The crystal structure of the (I) is composed of a monomeric [Mn(phen)₂(acac)]⁺ cation and one perchlorate anion, as illustrated in Fig. 1. It is noted that all three ligands coordinate to the Mn^II ion in chelating mode, leading to a serious distortion from the octahedron, with chelating angles of 73.85 (14) and 72.66 (14)° for N—Mn—N and 85.13 (13)° for O—Mn—O.

In addition to [Mn(phen)₃]²⁺ complexes having three uniform phen chelating ligands (Drew et al., 1989), only two examples of an Mn-phen complex containing three different chelating ligands were found in the literature, namely [Mn(phen)(acac)₂}] (Stephens, 1977) and [Mn(phen)₂{CH₂(COO)₂}] (Wang et al., 2000)

All the atoms in the phen ligands of (I), including the Mn^II ion, form a perfect plane, with the largest deviation from the least-squares plane being 0.0148 Å, and the phen planes are inclined at 83.4° with respect to each other. The acac ligand is also planar and the Mn^II atom lies 0.2 Å from the acac plane.

The Mn—N bond lengths in (I) are in the range 2.253 (4)–2.322 (4) Å, and Mn—O bond lengths are in the range 2.116 (3)–2.124 (3) Å. The phenanthroline exhibits its usual acute N···N bite distances [N1—N2 2.723 (3) and N3—N4 2.720 (3) Å], and the N—Mn—N angles are very close to those found in [Mn(phen)₂Cl₂] (McCann et al., 1998), [Mn(phen)₂(NCS)₂] (Holleman et al., 1994) and [Mn(phen)₂(N₃)₂] (Shen et al., 1999).

The packing diagram for (I) seems to show weak π···π stacking of pairs of phen planes between neighbouring [Mn(phen)₂(acac)]⁺ cations, with the characteristic interplanar distance of 3.6 Å, slightly larger than the sum of the van der Waals radii of the two C atoms.

Experimental top

A mixture of 2,5'-pyridinedicarboxylic acid (0.32 g, 2.5 mmol) and KOH (0.28 g, 5 mmol) was dissolved in MeOH/H₂O (20 ml; 1:1 v/v). To the resulting turbid solution, Mn(acac)₃ (0.70 g, 2.0 mmol) was added and the solution stirred for 30 min at room temperature. After addition of phen (0.4 g, 2 mmol) and NaClO₄·4H₂O (0.28 g, 2.0 mmol) and stirring for 2 h, the reaction solution was filtered. The filtrate was allowed to stand at room temperature for two weeks to deposit orange crystals of (I).

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1994); data reduction: XPREP in SHELXTL (Siemens, 1994); program(s) used to solve structure: SHELXTL; program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures top

Fig. 1. The structure of (I) showing 30% probability displacement ellipsoids. H atoms have been omitted for clarity.

(Acetylacetonato)bis(1,10'-phenanthroline-N,N')manganese(II) perchlorate top

Crystal data top

[Mn(C₅H₇O₂)(C₁₂H₈N₂)₂](ClO₄)	F(000) = 2520
M_r = 613.90	D_x = 1.435 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 33.3452 (4) Å	Cell parameters from 4315 reflections
b = 10.5753 (1) Å	θ = 2.3–25.0°
c = 17.1597 (3) Å	µ = 0.61 mm⁻¹
β = 110.05°	T = 293 K
V = 5684.35 (13) Å³	Block, orange
Z = 8	0.40 × 0.38 × 0.26 mm

Data collection top

Siemens SMART CCD area-detector diffractometer	4933 independent reflections
Radiation source: fine-focus sealed tube	3118 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.035
ω scans	θ_max = 25.0°, θ_min = 2.3°
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	h = −39→33
T_min = 0.593, T_max = 0.854	k = −8→12
10092 measured reflections	l = −16→20

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)] = 0.064	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.191	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.1P)²] where P = (F_o² + 2F_c²)/3
4933 reflections	(Δ/σ)_max < 0.001
370 parameters	Δρ_max = 0.86 e Å⁻³
0 restraints	Δρ_min = −0.53 e Å⁻³

Crystal data top

[Mn(C₅H₇O₂)(C₁₂H₈N₂)₂](ClO₄)	V = 5684.35 (13) Å³
M_r = 613.90	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 33.3452 (4) Å	µ = 0.61 mm⁻¹
b = 10.5753 (1) Å	T = 293 K
c = 17.1597 (3) Å	0.40 × 0.38 × 0.26 mm
β = 110.05°

Data collection top

Siemens SMART CCD area-detector diffractometer	4933 independent reflections
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	3118 reflections with I > 2σ(I)
T_min = 0.593, T_max = 0.854	R_int = 0.035
10092 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.064	0 restraints
wR(F²) = 0.191	H-atom parameters constrained
S = 1.03	Δρ_max = 0.86 e Å⁻³
4933 reflections	Δρ_min = −0.53 e Å⁻³
370 parameters

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 > 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.

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

	x	y	z	U_iso*/U_eq
Mn	0.12791 (2)	0.44179 (6)	0.17500 (4)	0.0490 (3)
Cl	0.11302 (5)	1.06724 (15)	0.46179 (11)	0.0849 (5)
O1	0.16161 (10)	0.3908 (3)	0.30019 (19)	0.0603 (8)
O2	0.09971 (11)	0.5836 (3)	0.2264 (2)	0.0651 (9)
O3	0.0832 (3)	0.9660 (6)	0.4550 (7)	0.219 (4)
O4	0.1405 (3)	1.0208 (8)	0.4286 (6)	0.220 (4)
O5	0.0890 (2)	1.1706 (6)	0.4184 (4)	0.162 (3)
O6	0.1248 (3)	1.0866 (8)	0.5452 (4)	0.215 (4)
N1	0.08214 (12)	0.2793 (4)	0.1600 (2)	0.0570 (10)
N2	0.07962 (12)	0.4578 (3)	0.0440 (2)	0.0509 (9)
N3	0.17660 (12)	0.3290 (4)	0.1328 (2)	0.0534 (10)
N4	0.17730 (12)	0.5814 (4)	0.1637 (2)	0.0545 (10)
C1	0.08273 (17)	0.1955 (5)	0.2182 (3)	0.0698 (14)
H1A	0.1048	0.1996	0.2691	0.084*
C2	0.0518 (2)	0.1020 (5)	0.2064 (4)	0.0811 (17)
H2A	0.0532	0.0457	0.2489	0.097*
C3	0.01916 (19)	0.0938 (5)	0.1315 (4)	0.0752 (16)
H3B	−0.0018	0.0322	0.1229	0.090*
C4	0.01780 (16)	0.1794 (4)	0.0680 (3)	0.0591 (13)
C5	−0.01545 (16)	0.1799 (5)	−0.0120 (4)	0.0693 (15)
H5B	−0.0365	0.1179	−0.0244	0.083*
C6	−0.01669 (16)	0.2674 (5)	−0.0687 (4)	0.0661 (14)
H6B	−0.0387	0.2654	−0.1198	0.079*
C7	0.01513 (14)	0.3645 (5)	−0.0526 (3)	0.0570 (12)
C8	0.01400 (17)	0.4615 (5)	−0.1106 (3)	0.0677 (14)
H8A	−0.0076	0.4633	−0.1622	0.081*
C9	0.04525 (17)	0.5524 (5)	−0.0892 (3)	0.0676 (14)
H9A	0.0449	0.6171	−0.1261	0.081*
C10	0.07748 (16)	0.5471 (5)	−0.0118 (3)	0.0585 (12)
H10A	0.0985	0.6091	0.0015	0.070*
C11	0.04838 (13)	0.3669 (4)	0.0236 (3)	0.0479 (11)
C12	0.05009 (14)	0.2723 (4)	0.0860 (3)	0.0490 (11)
C13	0.17499 (17)	0.2070 (5)	0.1119 (3)	0.0662 (14)
H13A	0.1508	0.1607	0.1087	0.079*
C14	0.2079 (2)	0.1463 (6)	0.0948 (4)	0.0836 (18)
H14A	0.2055	0.0612	0.0801	0.100*
C15	0.2432 (2)	0.2109 (7)	0.0995 (4)	0.0861 (19)
H15A	0.2655	0.1701	0.0889	0.103*
C16	0.24684 (16)	0.3392 (6)	0.1203 (3)	0.0715 (16)
C17	0.28368 (19)	0.4177 (8)	0.1272 (4)	0.090 (2)
H17A	0.3071	0.3822	0.1175	0.108*
C18	0.28450 (19)	0.5403 (8)	0.1471 (4)	0.092 (2)
H18A	0.3088	0.5874	0.1523	0.110*
C19	0.24895 (16)	0.6017 (6)	0.1608 (3)	0.0705 (16)
C20	0.2473 (2)	0.7326 (7)	0.1751 (3)	0.0838 (19)
H20A	0.2708	0.7835	0.1799	0.101*
C21	0.2116 (2)	0.7836 (6)	0.1819 (3)	0.0841 (18)
H21A	0.2100	0.8700	0.1903	0.101*
C22	0.17703 (19)	0.7050 (5)	0.1761 (3)	0.0702 (15)
H22A	0.1526	0.7412	0.1811	0.084*
C23	0.21265 (15)	0.5288 (5)	0.1551 (3)	0.0546 (12)
C24	0.21200 (14)	0.3954 (5)	0.1365 (3)	0.0539 (12)
C25	0.1925 (2)	0.3930 (7)	0.4460 (3)	0.100 (2)
H25A	0.2059	0.3184	0.4345	0.150*
H25B	0.1759	0.3713	0.4800	0.150*
H25C	0.2140	0.4534	0.4746	0.150*
C26	0.16360 (16)	0.4499 (5)	0.3652 (3)	0.0612 (13)
C27	0.14085 (18)	0.5600 (5)	0.3677 (3)	0.0713 (15)
H27A	0.1464	0.5970	0.4195	0.086*
C28	0.11076 (16)	0.6200 (5)	0.3008 (3)	0.0616 (13)
C29	0.0887 (2)	0.7364 (6)	0.3174 (4)	0.096 (2)
H29A	0.0691	0.7682	0.2660	0.144*
H29B	0.1096	0.8000	0.3430	0.144*
H29C	0.0733	0.7149	0.3537	0.144*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn	0.0448 (4)	0.0557 (5)	0.0455 (4)	−0.0041 (3)	0.0143 (3)	−0.0034 (3)
Cl	0.0909 (11)	0.0797 (11)	0.0905 (11)	0.0230 (9)	0.0392 (9)	−0.0065 (8)
O1	0.060 (2)	0.073 (2)	0.0432 (18)	0.0099 (17)	0.0130 (15)	−0.0033 (16)
O2	0.065 (2)	0.068 (2)	0.059 (2)	0.0099 (17)	0.0176 (17)	−0.0074 (17)
O3	0.174 (7)	0.107 (5)	0.417 (14)	−0.015 (4)	0.153 (8)	−0.044 (6)
O4	0.208 (8)	0.229 (8)	0.306 (11)	0.107 (6)	0.193 (8)	0.054 (7)
O5	0.207 (7)	0.144 (5)	0.167 (6)	0.086 (5)	0.108 (5)	0.053 (4)
O6	0.192 (7)	0.276 (9)	0.121 (6)	0.093 (7)	−0.017 (5)	−0.066 (6)
N1	0.058 (2)	0.056 (2)	0.058 (3)	−0.0020 (19)	0.021 (2)	0.003 (2)
N2	0.050 (2)	0.053 (2)	0.050 (2)	0.0006 (18)	0.0186 (18)	−0.0008 (19)
N3	0.051 (2)	0.062 (3)	0.050 (2)	−0.0038 (19)	0.0205 (18)	−0.0032 (19)
N4	0.056 (2)	0.057 (3)	0.048 (2)	−0.0101 (19)	0.0143 (19)	−0.0038 (18)
C1	0.068 (3)	0.070 (4)	0.067 (3)	−0.004 (3)	0.017 (3)	0.013 (3)
C2	0.094 (4)	0.067 (4)	0.086 (4)	−0.010 (3)	0.036 (4)	0.016 (3)
C3	0.075 (4)	0.060 (3)	0.095 (5)	−0.018 (3)	0.036 (4)	−0.004 (3)
C4	0.060 (3)	0.051 (3)	0.072 (3)	−0.001 (2)	0.030 (3)	−0.007 (3)
C5	0.056 (3)	0.069 (4)	0.082 (4)	−0.015 (3)	0.023 (3)	−0.022 (3)
C6	0.050 (3)	0.075 (4)	0.067 (4)	−0.007 (3)	0.013 (3)	−0.015 (3)
C7	0.047 (3)	0.065 (3)	0.055 (3)	0.004 (2)	0.012 (2)	−0.009 (2)
C8	0.063 (3)	0.079 (4)	0.056 (3)	0.010 (3)	0.014 (3)	−0.002 (3)
C9	0.077 (4)	0.071 (3)	0.056 (3)	0.009 (3)	0.024 (3)	0.011 (3)
C10	0.057 (3)	0.059 (3)	0.058 (3)	−0.002 (2)	0.018 (2)	0.004 (3)
C11	0.040 (2)	0.052 (3)	0.052 (3)	0.000 (2)	0.017 (2)	−0.011 (2)
C12	0.046 (3)	0.049 (3)	0.054 (3)	−0.001 (2)	0.020 (2)	−0.009 (2)
C13	0.072 (3)	0.063 (3)	0.070 (3)	−0.002 (3)	0.032 (3)	−0.008 (3)
C14	0.094 (5)	0.076 (4)	0.088 (4)	0.014 (4)	0.040 (4)	−0.011 (3)
C15	0.084 (4)	0.108 (5)	0.076 (4)	0.033 (4)	0.039 (4)	0.007 (4)
C16	0.061 (3)	0.105 (5)	0.053 (3)	0.015 (3)	0.026 (3)	0.015 (3)
C17	0.053 (3)	0.150 (7)	0.077 (4)	0.002 (4)	0.035 (3)	0.015 (4)
C18	0.058 (4)	0.148 (7)	0.068 (4)	−0.030 (4)	0.018 (3)	0.011 (4)
C19	0.057 (3)	0.106 (5)	0.042 (3)	−0.031 (3)	0.010 (2)	0.005 (3)
C20	0.096 (5)	0.096 (5)	0.053 (3)	−0.051 (4)	0.017 (3)	−0.004 (3)
C21	0.110 (5)	0.078 (4)	0.058 (4)	−0.035 (4)	0.020 (4)	−0.004 (3)
C22	0.090 (4)	0.060 (3)	0.061 (3)	−0.017 (3)	0.026 (3)	−0.003 (3)
C23	0.053 (3)	0.074 (3)	0.035 (2)	−0.017 (2)	0.012 (2)	0.002 (2)
C24	0.047 (3)	0.075 (3)	0.041 (2)	0.002 (2)	0.017 (2)	0.004 (2)
C25	0.108 (5)	0.132 (6)	0.048 (3)	0.021 (4)	0.010 (3)	−0.005 (3)
C26	0.055 (3)	0.079 (4)	0.046 (3)	−0.002 (3)	0.014 (2)	−0.003 (3)
C27	0.074 (4)	0.088 (4)	0.056 (3)	−0.008 (3)	0.027 (3)	−0.022 (3)
C28	0.060 (3)	0.063 (3)	0.067 (4)	−0.004 (3)	0.030 (3)	−0.010 (3)
C29	0.116 (5)	0.079 (4)	0.101 (5)	0.007 (4)	0.046 (4)	−0.023 (4)

Geometric parameters (Å, º) top

Mn—O2	2.116 (3)	C9—C10	1.394 (7)
Mn—O1	2.124 (3)	C9—H9A	0.9300
Mn—N1	2.253 (4)	C10—H10A	0.9300
Mn—N4	2.269 (4)	C11—C12	1.453 (6)
Mn—N2	2.279 (4)	C13—C14	1.388 (7)
Mn—N3	2.322 (4)	C13—H13A	0.9300
Cl—O4	1.328 (6)	C14—C15	1.337 (8)
Cl—O6	1.363 (7)	C14—H14A	0.9300
Cl—O5	1.407 (5)	C15—C16	1.398 (8)
Cl—O3	1.438 (7)	C15—H15A	0.9300
O1—C26	1.261 (6)	C16—C24	1.415 (7)
O2—C28	1.262 (6)	C16—C17	1.453 (8)
N1—C1	1.331 (6)	C17—C18	1.339 (9)
N1—C12	1.352 (6)	C17—H17A	0.9300
N2—C10	1.329 (6)	C18—C19	1.440 (9)
N2—C11	1.371 (5)	C18—H18A	0.9300
N3—C24	1.356 (6)	C19—C20	1.409 (8)
N3—C13	1.335 (6)	C19—C23	1.410 (7)
N4—C22	1.325 (6)	C20—C21	1.350 (8)
N4—C23	1.356 (6)	C20—H20A	0.9300
C1—C2	1.393 (7)	C21—C22	1.396 (8)
C1—H1A	0.9300	C21—H21A	0.9300
C2—C3	1.372 (8)	C22—H22A	0.9300
C2—H2A	0.9300	C23—C24	1.445 (7)
C3—C4	1.405 (7)	C25—C26	1.515 (7)
C3—H3B	0.9300	C25—H25A	0.9600
C4—C12	1.411 (6)	C25—H25B	0.9600
C4—C5	1.439 (7)	C25—H25C	0.9600
C5—C6	1.333 (7)	C26—C27	1.398 (7)
C5—H5B	0.9300	C27—C28	1.392 (7)
C6—C7	1.434 (7)	C27—H27A	0.9300
C6—H6B	0.9300	C28—C29	1.511 (7)
C7—C11	1.395 (6)	C29—H29A	0.9600
C7—C8	1.421 (7)	C29—H29B	0.9600
C8—C9	1.372 (7)	C29—H29C	0.9600
C8—H8A	0.9300

O2—Mn—O1	85.13 (13)	C4—C12—C11	119.0 (4)
O2—Mn—N1	101.99 (14)	N3—C13—C14	122.8 (5)
O1—Mn—N1	91.43 (14)	N3—C13—H13A	118.6
O2—Mn—N4	90.79 (14)	C14—C13—H13A	118.6
O1—Mn—N4	95.94 (13)	C15—C14—C13	119.6 (6)
N1—Mn—N4	165.76 (14)	C15—C14—H14A	120.2
O2—Mn—N2	95.38 (13)	C13—C14—H14A	120.2
O1—Mn—N2	165.08 (13)	C14—C15—C16	120.7 (6)
N1—Mn—N2	73.85 (14)	C14—C15—H15A	119.7
N4—Mn—N2	98.96 (13)	C16—C15—H15A	119.7
O2—Mn—N3	162.22 (14)	C15—C16—C24	116.9 (5)
O1—Mn—N3	90.06 (13)	C15—C16—C17	124.9 (6)
N1—Mn—N3	95.22 (14)	C24—C16—C17	118.2 (6)
N4—Mn—N3	72.66 (14)	C18—C17—C16	121.1 (6)
N2—Mn—N3	93.65 (13)	C18—C17—H17A	119.5
C26—O1—Mn	128.2 (3)	C16—C17—H17A	119.5
C28—O2—Mn	128.4 (3)	C17—C18—C19	122.2 (6)
C1—N1—C12	118.1 (4)	C17—C18—H18A	118.9
C1—N1—Mn	125.9 (4)	C19—C18—H18A	118.9
C12—N1—Mn	115.8 (3)	C20—C19—C23	117.8 (6)
C10—N2—C11	117.7 (4)	C20—C19—C18	123.6 (6)
C10—N2—Mn	127.5 (3)	C23—C19—C18	118.5 (6)
C11—N2—Mn	114.7 (3)	C21—C20—C19	119.7 (6)
C24—N3—C13	117.9 (4)	C21—C20—H20A	120.2
C24—N3—Mn	114.2 (3)	C19—C20—H20A	120.2
C13—N3—Mn	127.7 (3)	C20—C21—C22	119.2 (6)
C22—N4—C23	118.4 (4)	C20—C21—H21A	120.4
C22—N4—Mn	125.7 (4)	C22—C21—H21A	120.4
C23—N4—Mn	115.2 (3)	N4—C22—C21	123.2 (6)
N1—C1—C2	122.9 (5)	N4—C22—H22A	118.4
N1—C1—H1A	118.5	C21—C22—H22A	118.4
C2—C1—H1A	118.5	N4—C23—C19	121.7 (5)
C3—C2—C1	119.4 (5)	N4—C23—C24	118.4 (4)
C3—C2—H2A	120.3	C19—C23—C24	119.8 (5)
C1—C2—H2A	120.3	N3—C24—C16	122.2 (5)
C2—C3—C4	119.3 (5)	N3—C24—C23	117.6 (4)
C2—C3—H3B	120.3	C16—C24—C23	120.1 (5)
C4—C3—H3B	120.3	C26—C25—H25A	109.5
C12—C4—C3	117.3 (5)	C26—C25—H25B	109.5
C12—C4—C5	119.1 (5)	H25A—C25—H25B	109.5
C3—C4—C5	123.5 (5)	C26—C25—H25C	109.5
C6—C5—C4	121.3 (5)	H25A—C25—H25C	109.5
C6—C5—H5B	119.3	H25B—C25—H25C	109.5
C4—C5—H5B	119.3	O1—C26—C27	125.1 (5)
C5—C6—C7	121.4 (5)	O1—C26—C25	115.9 (5)
C5—C6—H6B	119.3	C27—C26—C25	119.0 (5)
C7—C6—H6B	119.3	C28—C27—C26	126.8 (5)
C11—C7—C8	117.7 (4)	C28—C27—H27A	116.6
C11—C7—C6	119.5 (5)	C26—C27—H27A	116.6
C8—C7—C6	122.8 (5)	O2—C28—C27	125.0 (5)
C9—C8—C7	118.9 (5)	O2—C28—C29	116.6 (5)
C9—C8—H8A	120.5	C27—C28—C29	118.4 (5)
C7—C8—H8A	120.5	C28—C29—H29A	109.5
C8—C9—C10	119.6 (5)	C28—C29—H29B	109.5
C8—C9—H9A	120.2	H29A—C29—H29B	109.5
C10—C9—H9A	120.2	C28—C29—H29C	109.5
N2—C10—C9	123.2 (5)	H29A—C29—H29C	109.5
N2—C10—H10A	118.4	H29B—C29—H29C	109.5
C9—C10—H10A	118.4	O4—Cl—O6	120.8 (6)
N2—C11—C7	122.9 (4)	O4—Cl—O5	114.3 (4)
N2—C11—C12	117.4 (4)	O6—Cl—O5	110.2 (4)
C7—C11—C12	119.7 (4)	O4—Cl—O3	104.5 (5)
N1—C12—C4	122.8 (4)	O6—Cl—O3	98.0 (6)
N1—C12—C11	118.2 (4)	O5—Cl—O3	106.4 (5)

Experimental details

Crystal data
Chemical formula	[Mn(C₅H₇O₂)(C₁₂H₈N₂)₂](ClO₄)
M_r	613.90
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	33.3452 (4), 10.5753 (1), 17.1597 (3)
β (°)	110.05
V (Å³)	5684.35 (13)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.61
Crystal size (mm)	0.40 × 0.38 × 0.26

Data collection
Diffractometer	Siemens SMART CCD area-detector diffractometer
Absorption correction	Empirical (using intensity measurements) (SADABS; Sheldrick, 1996)
T_min, T_max	0.593, 0.854
No. of measured, independent and observed [I > 2σ(I)] reflections	10092, 4933, 3118
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.064, 0.191, 1.03
No. of reflections	4933
No. of parameters	370
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.86, −0.53

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1994), XPREP in SHELXTL (Siemens, 1994), SHELXTL.

Selected geometric parameters (Å, º) top

Mn—O2	2.116 (3)	Mn—N4	2.269 (4)
Mn—O1	2.124 (3)	Mn—N2	2.279 (4)
Mn—N1	2.253 (4)	Mn—N3	2.322 (4)

O2—Mn—O1	85.13 (13)	N1—Mn—N2	73.85 (14)
O2—Mn—N1	101.99 (14)	N4—Mn—N2	98.96 (13)
O1—Mn—N1	91.43 (14)	O2—Mn—N3	162.22 (14)
O2—Mn—N4	90.79 (14)	O1—Mn—N3	90.06 (13)
O1—Mn—N4	95.94 (13)	N1—Mn—N3	95.22 (14)
N1—Mn—N4	165.76 (14)	N4—Mn—N3	72.66 (14)
O2—Mn—N2	95.38 (13)	N2—Mn—N3	93.65 (13)
O1—Mn—N2	165.08 (13)

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