A dinuclear manganese(II) complex with a 4-amino­anti­pyrine-derived Schiff base ligand

Zhao, W.-N.

doi:10.1107/S1600536807032461

A dinuclear manganese(II) complex with a 4-aminoantipyrine-derived Schiff base ligand

In the crystal structure of the centrosymmetric title complex, bis[μ-(E)-1,5-dimethyl-2-phenyl-4-(3-pyridylmethyleneamino)pyrazol-3(2H)-one]bis{dibromido[(E)-1,5-dimethyl-2-phenyl-4-(3-pyridylmethyleneamino)pyrazol-3(2H)-one]manganese(II)}, [Mn₂Br₄(C₁₇H₁₆N₄O)₄], the Mn atom adopts a trigonal–bipyramidal geometry and the ligand adopts two coordination modes, monodentate and bidentate bridging.

Read article Similar articles

Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807032461/wk2058sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807032461/wk2058Isup2.hkl Contains datablock I

CCDC reference: 657549

checkCIF report

Key indicators

Single-crystal X-ray study
T = 298 K
Mean (C-C) = 0.008 Å
R factor = 0.058
wR factor = 0.114
Data-to-parameter ratio = 17.9

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.95
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?
PLAT154_ALERT_1_C The su's on the Cell Angles are Equal  (x 10000)       3000 Deg.
PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          8
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         54
            N5  -MN1 -N1  -C5    168.50  0.80   2.666   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         58
            N5  -MN1 -N1  -C1    -10.80  1.20   2.666   1.555   1.555   1.555

Alert level G
PLAT794_ALERT_5_G Check Predicted Bond Valency for Mn1         (2)       2.13

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   6 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

Comment top

Great effort is currently being devoted to the design and syntheses of metal Schiff base complexes due to their potential applications as functional materials (O'Donnell, 2004). The Schiff bases of 4-aminoantipyrine and their complexes have been extensively investigated because of their biological, clinical and pharmacological applications (Rajendran & Sreeletha, 2002; Raman et al., 2001). However, only a few structurally characterized metal complexes with 4-aminoantipyrine Schiff base derived ligands have been reported, and its coordination chemistry remains largely unexplored (Liang et al., 2004; Liang et al., 2002; Wang et al., 2003). Herein we report the synthesis and crystal structure of a new dinuclear manganese(II) complex with a 4-aminoantipyrine derived Schiff base ligand: Mn₂(L₄)Br₄(L = (E)-1,5-dimethyl-2-phenyl-4-(pyridin-3-ylmethyleneamino)-1,2-dihydropyrazol-3-one) (I).

The ligand L was synthesized as reported previously by the base condensation of 4-aminoantipyrine with pyridine-3-carboxaldehyde (Montalvo-Gonzalez & Arisa-Castolo 2003). The title complex (I) was obtained under solvothermal conditions and characterized by X-ray crystallography. The molecular structure of (I) is shown in Fig. 1. Selected bond distances and bond angles are normal and listed in Table 1. (I) is a dinuclear Mn^II complex arranged around an inversion center. Each Mn atom is coordinated by two pyridine N atoms from two ligands, and one pyrazole O atom from another ligand, and two Br anions in a trigonal-bipyramidal geometry. There are two kinds of coordination modes of ligand L: one is monodentately linked to the Mn center through the N atom of the pyridine group, the other bidentately bridges two Mn centers by pyridine N atom and pyrazole O atom. The dimer Mn₂L₂ ring is formed with Mn···Mn separation of 8.878 (4) Å.

Related literature top

For related literature, see: Liang et al. (2002, 2004); Montalvo-Gonzalez & Arisa-Castolo (2003); O'Donnell (2004); Rajendran & Sreeletha (2002); Raman et al. (2001); Wang et al. (2003).

Experimental top

A 25 ml Teflon-lined stainless steel autoclave was charged with 0.215 g (1 mmol) MnBr₂, 0.260 g (1 mmol) L and 15 ml CH₃OH and heated at 80 °C for 24 h in oven, then cooled to room temperature. Red crystals were obtained in 60% yield based on the initial MnBr₂.

Structure description top

For related literature, see: Liang et al. (2002, 2004); Montalvo-Gonzalez & Arisa-Castolo (2003); O'Donnell (2004); Rajendran & Sreeletha (2002); Raman et al. (2001); Wang et al. (2003).

Computing details top

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT; 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.

Figures top

Fig. 1. The molecular structure of (I), with displacement ellipsoids drawn at the 30% probability level. H atoms were omitted for clarity. (Symmetry codes: (A) -x + 1, -y + 1, -z + 1.)

bis[µ-(E)-1,5-dimethyl-2-phenyl-4-(3-pyridylmethyleneamino)pyrazol-\3(2H)-one]bis{dibromido[(E)-1,5-dimethyl-2-phenyl-4-(3-πyridylmethyleneamino)pyrazol-3(2H)-one]manganese(II)} top

Crystal data top

[Mn₂Br₄(C₁₇H₁₆N₄O)₄]	V = 1699.2 (6) Å³
M_r = 1598.87	Z = 1
Triclinic, P1	F(000) = 806
Hall symbol: -P 1	D_x = 1.563 Mg m⁻³
a = 10.052 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.372 (3) Å	θ = 3.1–27.5°
c = 15.257 (3) Å	µ = 2.78 mm⁻¹
α = 72.68 (3)°	T = 298 K
β = 77.66 (3)°	Block, red
γ = 71.09 (3)°	0.24 × 0.20 × 0.18 mm

Data collection top

Bruker SMART APEX II CCD diffractometer	7658 independent reflections
Radiation source: fine-focus sealed tube	4058 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.073
Detector resolution: 8.40 pixels mm^-1	θ_max = 27.5°, θ_min = 3.1°
ω scans	h = −13→12
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −16→13
T_min = 0.555, T_max = 0.634	l = −19→19
16756 measured reflections

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)] = 0.058	Hydrogen site location: geom, Me from difmap
wR(F²) = 0.114	H-atom parameters constrained
S = 0.99	w = 1/[σ²(F_o²) + (0.0306P)² + 1.9264P] where P = (F_o² + 2F_c²)/3
7658 reflections	(Δ/σ)_max = 0.001
428 parameters	Δρ_max = 0.48 e Å⁻³
0 restraints	Δρ_min = −0.53 e Å⁻³

Crystal data top

[Mn₂Br₄(C₁₇H₁₆N₄O)₄]	γ = 71.09 (3)°
M_r = 1598.87	V = 1699.2 (6) Å³
Triclinic, P1	Z = 1
a = 10.052 (2) Å	Mo Kα radiation
b = 12.372 (3) Å	µ = 2.78 mm⁻¹
c = 15.257 (3) Å	T = 298 K
α = 72.68 (3)°	0.24 × 0.20 × 0.18 mm
β = 77.66 (3)°

Data collection top

Bruker SMART APEX II CCD diffractometer	7658 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	4058 reflections with I > 2σ(I)
T_min = 0.555, T_max = 0.634	R_int = 0.073
16756 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.058	0 restraints
wR(F²) = 0.114	H-atom parameters constrained
S = 0.99	Δρ_max = 0.48 e Å⁻³
7658 reflections	Δρ_min = −0.53 e Å⁻³
428 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
Br1	0.63805 (6)	0.05458 (5)	0.35815 (4)	0.04788 (16)
Br2	0.63104 (6)	0.44060 (5)	0.23134 (4)	0.05393 (18)
Mn1	0.51827 (8)	0.27528 (6)	0.31633 (5)	0.03622 (19)
C1	0.4160 (5)	0.1657 (5)	0.1809 (4)	0.0478 (14)
H1A	0.4031	0.1123	0.2373	0.057*
C2	0.3812 (5)	0.1489 (5)	0.1036 (3)	0.0441 (13)
C3	0.4052 (6)	0.2288 (5)	0.0195 (4)	0.0579 (16)
H3A	0.3857	0.2203	−0.0346	0.069*
C4	0.4569 (6)	0.3189 (5)	0.0165 (4)	0.0592 (16)
H4A	0.4725	0.3725	−0.0394	0.071*
C5	0.4861 (6)	0.3296 (5)	0.0976 (4)	0.0511 (14)
H5A	0.5204	0.3920	0.0951	0.061*
C6	0.3263 (5)	0.0506 (5)	0.1086 (4)	0.0503 (14)
H6A	0.3232	−0.0083	0.1631	0.060*
C7	0.2306 (5)	−0.0400 (5)	0.0312 (3)	0.0444 (13)
C8	0.2039 (6)	−0.1426 (5)	0.1000 (4)	0.0532 (15)
C9	0.1419 (7)	−0.1849 (6)	−0.1123 (4)	0.0653 (17)
H9A	0.1759	−0.1408	−0.1713	0.098*
H9B	0.0449	−0.1813	−0.1116	0.098*
H9C	0.1985	−0.2656	−0.1019	0.098*
C10	0.1982 (6)	−0.0416 (5)	−0.0504 (3)	0.0478 (14)
C11	0.2115 (7)	0.0452 (5)	−0.1417 (4)	0.0659 (17)
H11A	0.2774	0.0057	−0.1856	0.099*
H11B	0.2450	0.1061	−0.1346	0.099*
H11C	0.1205	0.0795	−0.1635	0.099*
C12	0.1099 (6)	−0.3036 (5)	0.0855 (3)	0.0456 (13)
C13	0.1934 (6)	−0.4053 (6)	0.1355 (4)	0.0611 (17)
H13A	0.2790	−0.4059	0.1498	0.073*
C14	0.1494 (7)	−0.5066 (6)	0.1643 (4)	0.0684 (19)
H14A	0.2055	−0.5752	0.1988	0.082*
C15	0.0245 (8)	−0.5076 (6)	0.1429 (4)	0.0716 (19)
H15A	−0.0033	−0.5766	0.1614	0.086*
C16	−0.0588 (7)	−0.4060 (5)	0.0940 (4)	0.0633 (17)
H16A	−0.1443	−0.4059	0.0798	0.076*
C17	−0.0176 (6)	−0.3035 (5)	0.0656 (4)	0.0537 (15)
H17A	−0.0757	−0.2345	0.0331	0.064*
C18	0.5023 (5)	0.7949 (4)	0.4609 (4)	0.0428 (13)
H18A	0.5413	0.8495	0.4687	0.051*
C19	0.5012 (6)	0.7883 (5)	0.3727 (4)	0.0475 (13)
H19A	0.5408	0.8370	0.3221	0.057*
C20	0.4414 (5)	0.7093 (4)	0.3593 (4)	0.0464 (13)
H20A	0.4409	0.7036	0.2999	0.056*
C21	0.3823 (5)	0.6389 (4)	0.4360 (3)	0.0379 (12)
C22	0.3906 (5)	0.6490 (4)	0.5229 (3)	0.0388 (12)
H22A	0.3535	0.6000	0.5746	0.047*
C23	0.3187 (5)	0.5523 (4)	0.4278 (4)	0.0415 (12)
H23A	0.3280	0.5357	0.3709	0.050*
C24	0.1985 (5)	0.4090 (4)	0.4968 (3)	0.0350 (11)
C25	0.2266 (5)	0.3429 (4)	0.4310 (3)	0.0342 (11)
C26	0.1086 (5)	0.3641 (4)	0.5703 (3)	0.0405 (12)
C27	0.0579 (6)	0.3964 (5)	0.6601 (4)	0.0620 (16)
H27A	−0.0420	0.4352	0.6639	0.093*
H27B	0.1074	0.4485	0.6650	0.093*
H27C	0.0755	0.3265	0.7098	0.093*
C28	0.0008 (6)	0.1944 (5)	0.6100 (4)	0.0629 (17)
H28A	0.0684	0.1202	0.6311	0.094*
H28B	−0.0619	0.1841	0.5757	0.094*
H28C	−0.0531	0.2236	0.6624	0.094*
C29	0.1161 (5)	0.1969 (4)	0.4157 (3)	0.0371 (11)
C30	0.2016 (5)	0.0863 (4)	0.4116 (4)	0.0475 (14)
H30A	0.2800	0.0520	0.4437	0.057*
C31	0.1695 (6)	0.0269 (5)	0.3593 (4)	0.0592 (16)
H31A	0.2277	−0.0476	0.3549	0.071*
C32	0.0524 (6)	0.0767 (5)	0.3135 (4)	0.0578 (16)
H32A	0.0318	0.0360	0.2781	0.069*
C33	−0.0341 (6)	0.1856 (5)	0.3195 (4)	0.0664 (18)
H33A	−0.1144	0.2184	0.2893	0.080*
C34	−0.0025 (6)	0.2472 (5)	0.3706 (4)	0.0548 (15)
H34A	−0.0606	0.3218	0.3745	0.066*
N1	0.4672 (4)	0.2542 (4)	0.1794 (3)	0.0422 (10)
N2	0.2830 (4)	0.0471 (4)	0.0375 (3)	0.0460 (11)
N3	0.1569 (5)	−0.2006 (4)	0.0520 (3)	0.0510 (12)
N4	0.1516 (5)	−0.1351 (4)	−0.0398 (3)	0.0498 (12)
N5	0.4485 (4)	0.7247 (3)	0.5364 (3)	0.0376 (10)
N6	0.2502 (4)	0.4994 (3)	0.4991 (3)	0.0408 (10)
N7	0.1511 (4)	0.2608 (3)	0.4669 (3)	0.0390 (10)
N8	0.0750 (4)	0.2783 (4)	0.5509 (3)	0.0434 (10)
O1	0.2122 (5)	−0.1777 (4)	0.1843 (3)	0.0763 (13)
O2	0.3029 (3)	0.3472 (3)	0.3532 (2)	0.0402 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0660 (4)	0.0392 (3)	0.0413 (3)	−0.0147 (3)	−0.0104 (3)	−0.0116 (2)
Br2	0.0723 (4)	0.0535 (3)	0.0454 (3)	−0.0370 (3)	−0.0010 (3)	−0.0092 (3)
Mn1	0.0430 (4)	0.0372 (4)	0.0343 (4)	−0.0177 (4)	−0.0038 (3)	−0.0111 (3)
C1	0.054 (3)	0.048 (3)	0.043 (3)	−0.015 (3)	−0.015 (3)	−0.008 (3)
C2	0.046 (3)	0.053 (3)	0.039 (3)	−0.013 (3)	−0.009 (3)	−0.018 (3)
C3	0.069 (4)	0.073 (4)	0.032 (3)	−0.022 (3)	−0.011 (3)	−0.009 (3)
C4	0.071 (4)	0.069 (4)	0.036 (3)	−0.027 (3)	−0.009 (3)	−0.002 (3)
C5	0.058 (4)	0.052 (3)	0.045 (3)	−0.021 (3)	−0.008 (3)	−0.006 (3)
C6	0.056 (3)	0.061 (4)	0.040 (3)	−0.015 (3)	−0.015 (3)	−0.017 (3)
C7	0.037 (3)	0.063 (4)	0.036 (3)	−0.011 (3)	−0.006 (2)	−0.020 (3)
C8	0.057 (4)	0.078 (4)	0.035 (3)	−0.023 (3)	−0.006 (3)	−0.023 (3)
C9	0.083 (4)	0.086 (5)	0.046 (4)	−0.039 (4)	−0.010 (3)	−0.027 (3)
C10	0.051 (3)	0.056 (3)	0.037 (3)	−0.008 (3)	−0.007 (3)	−0.020 (3)
C11	0.098 (5)	0.063 (4)	0.041 (3)	−0.023 (4)	−0.014 (3)	−0.016 (3)
C12	0.051 (3)	0.056 (3)	0.033 (3)	−0.016 (3)	−0.005 (3)	−0.014 (3)
C13	0.048 (3)	0.086 (5)	0.042 (3)	−0.002 (4)	−0.007 (3)	−0.022 (3)
C14	0.074 (5)	0.062 (4)	0.049 (4)	0.007 (4)	−0.009 (3)	−0.013 (3)
C15	0.096 (5)	0.054 (4)	0.062 (4)	−0.025 (4)	0.000 (4)	−0.014 (3)
C16	0.067 (4)	0.064 (4)	0.069 (4)	−0.024 (3)	−0.013 (3)	−0.022 (3)
C17	0.054 (3)	0.056 (4)	0.052 (3)	−0.010 (3)	−0.017 (3)	−0.012 (3)
C18	0.052 (3)	0.039 (3)	0.047 (3)	−0.019 (3)	−0.013 (3)	−0.013 (2)
C19	0.059 (3)	0.049 (3)	0.038 (3)	−0.022 (3)	−0.009 (3)	−0.006 (2)
C20	0.057 (3)	0.045 (3)	0.039 (3)	−0.013 (3)	−0.011 (3)	−0.011 (2)
C21	0.040 (3)	0.039 (3)	0.042 (3)	−0.013 (2)	−0.009 (2)	−0.015 (2)
C22	0.043 (3)	0.039 (3)	0.040 (3)	−0.015 (2)	−0.010 (2)	−0.012 (2)
C23	0.050 (3)	0.040 (3)	0.042 (3)	−0.015 (3)	−0.014 (3)	−0.014 (2)
C24	0.036 (3)	0.038 (3)	0.035 (3)	−0.013 (2)	−0.008 (2)	−0.011 (2)
C25	0.037 (3)	0.038 (3)	0.033 (3)	−0.014 (2)	−0.006 (2)	−0.011 (2)
C26	0.040 (3)	0.044 (3)	0.039 (3)	−0.012 (2)	−0.002 (2)	−0.016 (2)
C27	0.076 (4)	0.067 (4)	0.047 (3)	−0.021 (3)	0.004 (3)	−0.026 (3)
C28	0.059 (4)	0.061 (4)	0.062 (4)	−0.032 (3)	0.010 (3)	−0.002 (3)
C29	0.040 (3)	0.038 (3)	0.043 (3)	−0.020 (2)	−0.005 (2)	−0.013 (2)
C30	0.048 (3)	0.044 (3)	0.060 (4)	−0.013 (3)	−0.019 (3)	−0.019 (3)
C31	0.065 (4)	0.041 (3)	0.080 (4)	−0.016 (3)	−0.021 (4)	−0.017 (3)
C32	0.079 (4)	0.053 (4)	0.057 (4)	−0.034 (3)	−0.020 (3)	−0.012 (3)
C33	0.065 (4)	0.056 (4)	0.090 (5)	−0.019 (3)	−0.044 (4)	−0.010 (4)
C34	0.051 (3)	0.043 (3)	0.074 (4)	−0.008 (3)	−0.028 (3)	−0.013 (3)
N1	0.047 (3)	0.047 (2)	0.035 (2)	−0.013 (2)	−0.006 (2)	−0.014 (2)
N2	0.045 (3)	0.061 (3)	0.041 (3)	−0.014 (2)	−0.005 (2)	−0.026 (2)
N3	0.057 (3)	0.074 (3)	0.033 (2)	−0.028 (3)	−0.007 (2)	−0.017 (2)
N4	0.062 (3)	0.060 (3)	0.033 (2)	−0.011 (2)	−0.013 (2)	−0.021 (2)
N5	0.045 (2)	0.032 (2)	0.042 (2)	−0.0137 (19)	−0.012 (2)	−0.0093 (18)
N6	0.044 (2)	0.043 (2)	0.044 (3)	−0.016 (2)	−0.009 (2)	−0.017 (2)
N7	0.043 (2)	0.043 (2)	0.038 (2)	−0.017 (2)	−0.003 (2)	−0.0165 (19)
N8	0.051 (3)	0.050 (3)	0.035 (2)	−0.025 (2)	0.004 (2)	−0.012 (2)
O1	0.114 (4)	0.101 (3)	0.035 (2)	−0.056 (3)	−0.019 (2)	−0.013 (2)
O2	0.0418 (19)	0.054 (2)	0.0354 (19)	−0.0218 (17)	−0.0022 (16)	−0.0186 (16)

Geometric parameters (Å, º) top

Br1—Mn1	2.5441 (12)	C17—H17A	0.9300
Br2—Mn1	2.5387 (12)	C18—N5	1.348 (6)
Mn1—O2	2.080 (3)	C18—C19	1.374 (7)
Mn1—N5ⁱ	2.341 (4)	C18—H18A	0.9300
Mn1—N1	2.360 (4)	C19—C20	1.384 (7)
C1—N1	1.345 (6)	C19—H19A	0.9300
C1—C2	1.386 (7)	C20—C21	1.383 (7)
C1—H1A	0.9300	C20—H20A	0.9300
C2—C3	1.395 (7)	C21—C22	1.389 (6)
C2—C6	1.467 (7)	C21—C23	1.459 (6)
C3—C4	1.360 (8)	C22—N5	1.334 (6)
C3—H3A	0.9300	C22—H22A	0.9300
C4—C5	1.384 (7)	C23—N6	1.279 (6)
C4—H4A	0.9300	C23—H23A	0.9300
C5—N1	1.336 (6)	C24—C26	1.380 (7)
C5—H5A	0.9300	C24—N6	1.389 (6)
C6—N2	1.270 (6)	C24—C25	1.405 (7)
C6—H6A	0.9300	C25—O2	1.265 (5)
C7—C10	1.361 (7)	C25—N7	1.378 (6)
C7—N2	1.378 (7)	C26—N8	1.337 (6)
C7—C8	1.446 (8)	C26—C27	1.482 (7)
C8—O1	1.241 (6)	C27—H27A	0.9600
C8—N3	1.399 (7)	C27—H27B	0.9600
C9—N4	1.450 (7)	C27—H27C	0.9600
C9—H9A	0.9600	C28—N8	1.450 (6)
C9—H9B	0.9600	C28—H28A	0.9600
C9—H9C	0.9600	C28—H28B	0.9600
C10—N4	1.339 (7)	C28—H28C	0.9600
C10—C11	1.494 (7)	C29—C30	1.371 (7)
C11—H11A	0.9600	C29—C34	1.378 (6)
C11—H11B	0.9600	C29—N7	1.423 (6)
C11—H11C	0.9600	C30—C31	1.377 (7)
C12—C13	1.374 (7)	C30—H30A	0.9300
C12—C17	1.378 (7)	C31—C32	1.370 (7)
C12—N3	1.418 (7)	C31—H31A	0.9300
C13—C14	1.381 (9)	C32—C33	1.364 (8)
C13—H13A	0.9300	C32—H32A	0.9300
C14—C15	1.368 (9)	C33—C34	1.379 (8)
C14—H14A	0.9300	C33—H33A	0.9300
C15—C16	1.365 (8)	C34—H34A	0.9300
C15—H15A	0.9300	N3—N4	1.395 (5)
C16—C17	1.380 (8)	N5—Mn1ⁱ	2.341 (4)
C16—H16A	0.9300	N7—N8	1.383 (5)

O2—Mn1—N5ⁱ	87.27 (13)	C21—C20—C19	118.5 (5)
O2—Mn1—N1	89.45 (14)	C21—C20—H20A	120.7
N5ⁱ—Mn1—N1	171.60 (15)	C19—C20—H20A	120.7
O2—Mn1—Br2	109.22 (10)	C20—C21—C22	117.9 (5)
N5ⁱ—Mn1—Br2	94.75 (10)	C20—C21—C23	121.9 (5)
N1—Mn1—Br2	93.63 (11)	C22—C21—C23	120.1 (5)
O2—Mn1—Br1	122.63 (10)	N5—C22—C21	123.9 (5)
N5ⁱ—Mn1—Br1	86.76 (10)	N5—C22—H22A	118.1
N1—Mn1—Br1	88.51 (11)	C21—C22—H22A	118.1
Br2—Mn1—Br1	128.13 (4)	N6—C23—C21	119.8 (5)
N1—C1—C2	124.3 (5)	N6—C23—H23A	120.1
N1—C1—H1A	117.9	C21—C23—H23A	120.1
C2—C1—H1A	117.9	C26—C24—N6	121.0 (4)
C1—C2—C3	116.5 (5)	C26—C24—C25	107.5 (4)
C1—C2—C6	122.2 (5)	N6—C24—C25	131.4 (5)
C3—C2—C6	121.3 (5)	O2—C25—N7	121.1 (4)
C4—C3—C2	120.2 (5)	O2—C25—C24	132.7 (5)
C4—C3—H3A	119.9	N7—C25—C24	106.2 (4)
C2—C3—H3A	119.9	N8—C26—C24	109.2 (4)
C3—C4—C5	119.1 (5)	N8—C26—C27	122.4 (5)
C3—C4—H4A	120.4	C24—C26—C27	128.3 (5)
C5—C4—H4A	120.4	C26—C27—H27A	109.5
N1—C5—C4	122.7 (5)	C26—C27—H27B	109.5
N1—C5—H5A	118.6	H27A—C27—H27B	109.5
C4—C5—H5A	118.6	C26—C27—H27C	109.5
N2—C6—C2	119.0 (5)	H27A—C27—H27C	109.5
N2—C6—H6A	120.5	H27B—C27—H27C	109.5
C2—C6—H6A	120.5	N8—C28—H28A	109.5
C10—C7—N2	121.4 (5)	N8—C28—H28B	109.5
C10—C7—C8	107.6 (5)	H28A—C28—H28B	109.5
N2—C7—C8	131.0 (5)	N8—C28—H28C	109.5
O1—C8—N3	123.0 (5)	H28A—C28—H28C	109.5
O1—C8—C7	132.3 (5)	H28B—C28—H28C	109.5
N3—C8—C7	104.7 (4)	C30—C29—C34	121.0 (5)
N4—C9—H9A	109.5	C30—C29—N7	119.4 (4)
N4—C9—H9B	109.5	C34—C29—N7	119.6 (5)
H9A—C9—H9B	109.5	C29—C30—C31	118.9 (5)
N4—C9—H9C	109.5	C29—C30—H30A	120.5
H9A—C9—H9C	109.5	C31—C30—H30A	120.5
H9B—C9—H9C	109.5	C32—C31—C30	120.4 (5)
N4—C10—C7	110.6 (5)	C32—C31—H31A	119.8
N4—C10—C11	122.3 (5)	C30—C31—H31A	119.8
C7—C10—C11	127.2 (6)	C33—C32—C31	120.4 (5)
C10—C11—H11A	109.5	C33—C32—H32A	119.8
C10—C11—H11B	109.5	C31—C32—H32A	119.8
H11A—C11—H11B	109.5	C32—C33—C34	120.0 (5)
C10—C11—H11C	109.5	C32—C33—H33A	120.0
H11A—C11—H11C	109.5	C34—C33—H33A	120.0
H11B—C11—H11C	109.5	C29—C34—C33	119.2 (5)
C13—C12—C17	119.6 (6)	C29—C34—H34A	120.4
C13—C12—N3	120.1 (5)	C33—C34—H34A	120.4
C17—C12—N3	120.2 (5)	C5—N1—C1	117.2 (4)
C12—C13—C14	119.6 (6)	C5—N1—Mn1	121.8 (4)
C12—C13—H13A	120.2	C1—N1—Mn1	121.0 (3)
C14—C13—H13A	120.2	C6—N2—C7	125.6 (5)
C15—C14—C13	120.9 (6)	N4—N3—C8	108.8 (4)
C15—C14—H14A	119.5	N4—N3—C12	121.6 (4)
C13—C14—H14A	119.5	C8—N3—C12	129.4 (4)
C16—C15—C14	119.2 (6)	C10—N4—N3	108.2 (4)
C16—C15—H15A	120.4	C10—N4—C9	127.0 (5)
C14—C15—H15A	120.4	N3—N4—C9	122.0 (5)
C15—C16—C17	120.7 (6)	C22—N5—C18	117.5 (4)
C15—C16—H16A	119.6	C22—N5—Mn1ⁱ	122.6 (3)
C17—C16—H16A	119.6	C18—N5—Mn1ⁱ	119.5 (3)
C12—C17—C16	119.8 (5)	C23—N6—C24	122.0 (4)
C12—C17—H17A	120.1	C25—N7—N8	108.7 (4)
C16—C17—H17A	120.1	C25—N7—C29	125.7 (4)
N5—C18—C19	122.1 (5)	N8—N7—C29	122.4 (4)
N5—C18—H18A	118.9	C26—N8—N7	108.3 (4)
C19—C18—H18A	118.9	C26—N8—C28	129.9 (5)
C18—C19—C20	120.0 (5)	N7—N8—C28	120.4 (5)
C18—C19—H19A	120.0	C25—O2—Mn1	132.0 (3)
C20—C19—H19A	120.0

N1—C1—C2—C3	1.6 (8)	Br2—Mn1—N1—C5	−7.7 (4)
N1—C1—C2—C6	179.7 (5)	Br1—Mn1—N1—C5	−135.8 (4)
C1—C2—C3—C4	−1.5 (8)	O2—Mn1—N1—C1	−77.7 (4)
C6—C2—C3—C4	−179.6 (5)	N5ⁱ—Mn1—N1—C1	−10.8 (12)
C2—C3—C4—C5	0.4 (9)	Br2—Mn1—N1—C1	173.1 (4)
C3—C4—C5—N1	0.8 (9)	Br1—Mn1—N1—C1	44.9 (4)
C1—C2—C6—N2	172.9 (5)	C2—C6—N2—C7	179.1 (5)
C3—C2—C6—N2	−9.1 (8)	C10—C7—N2—C6	−174.2 (5)
C10—C7—C8—O1	−177.1 (6)	C8—C7—N2—C6	3.6 (9)
N2—C7—C8—O1	4.8 (11)	O1—C8—N3—N4	176.4 (5)
C10—C7—C8—N3	0.6 (6)	C7—C8—N3—N4	−1.6 (6)
N2—C7—C8—N3	−177.5 (5)	O1—C8—N3—C12	0.9 (9)
N2—C7—C10—N4	179.0 (4)	C7—C8—N3—C12	−177.1 (5)
C8—C7—C10—N4	0.7 (6)	C13—C12—N3—N4	131.6 (5)
N2—C7—C10—C11	−0.5 (9)	C17—C12—N3—N4	−46.3 (7)
C8—C7—C10—C11	−178.8 (5)	C13—C12—N3—C8	−53.4 (8)
C17—C12—C13—C14	0.7 (8)	C17—C12—N3—C8	128.7 (6)
N3—C12—C13—C14	−177.2 (5)	C7—C10—N4—N3	−1.8 (6)
C12—C13—C14—C15	0.8 (9)	C11—C10—N4—N3	177.8 (5)
C13—C14—C15—C16	−1.4 (10)	C7—C10—N4—C9	−162.7 (5)
C14—C15—C16—C17	0.6 (10)	C11—C10—N4—C9	16.9 (8)
C13—C12—C17—C16	−1.5 (9)	C8—N3—N4—C10	2.1 (6)
N3—C12—C17—C16	176.4 (5)	C12—N3—N4—C10	178.1 (5)
C15—C16—C17—C12	0.9 (9)	C8—N3—N4—C9	164.2 (5)
N5—C18—C19—C20	1.2 (8)	C12—N3—N4—C9	−19.9 (7)
C18—C19—C20—C21	0.6 (8)	C21—C22—N5—C18	−0.2 (7)
C19—C20—C21—C22	−2.1 (7)	C21—C22—N5—Mn1ⁱ	−173.3 (4)
C19—C20—C21—C23	−179.2 (4)	C19—C18—N5—C22	−1.4 (7)
C20—C21—C22—N5	1.9 (7)	C19—C18—N5—Mn1ⁱ	172.0 (4)
C23—C21—C22—N5	179.2 (4)	C21—C23—N6—C24	−174.2 (4)
C20—C21—C23—N6	−171.5 (5)	C26—C24—N6—C23	−171.0 (4)
C22—C21—C23—N6	11.4 (7)	C25—C24—N6—C23	13.1 (7)
C26—C24—C25—O2	−179.0 (5)	O2—C25—N7—N8	−178.5 (4)
N6—C24—C25—O2	−2.6 (8)	C24—C25—N7—N8	1.9 (5)
C26—C24—C25—N7	0.6 (5)	O2—C25—N7—C29	−18.5 (7)
N6—C24—C25—N7	176.9 (4)	C24—C25—N7—C29	161.9 (4)
N6—C24—C26—N8	−179.8 (4)	C30—C29—N7—C25	95.3 (6)
C25—C24—C26—N8	−3.0 (5)	C34—C29—N7—C25	−84.4 (6)
N6—C24—C26—C27	−2.6 (8)	C30—C29—N7—N8	−107.3 (5)
C25—C24—C26—C27	174.2 (5)	C34—C29—N7—N8	72.9 (6)
C34—C29—C30—C31	1.9 (8)	C24—C26—N8—N7	4.2 (5)
N7—C29—C30—C31	−177.8 (5)	C27—C26—N8—N7	−173.2 (4)
C29—C30—C31—C32	−1.3 (9)	C24—C26—N8—C28	170.5 (5)
C30—C31—C32—C33	−0.3 (9)	C27—C26—N8—C28	−6.9 (8)
C31—C32—C33—C34	1.2 (10)	C25—N7—N8—C26	−3.8 (5)
C30—C29—C34—C33	−1.0 (8)	C29—N7—N8—C26	−164.6 (4)
N7—C29—C34—C33	178.8 (5)	C25—N7—N8—C28	−171.7 (4)
C32—C33—C34—C29	−0.6 (9)	C29—N7—N8—C28	27.6 (6)
C4—C5—N1—C1	−0.7 (8)	N7—C25—O2—Mn1	−95.7 (5)
C4—C5—N1—Mn1	180.0 (4)	C24—C25—O2—Mn1	83.8 (6)
C2—C1—N1—C5	−0.5 (8)	N5ⁱ—Mn1—O2—C25	−24.9 (4)
C2—C1—N1—Mn1	178.8 (4)	N1—Mn1—O2—C25	147.3 (4)
O2—Mn1—N1—C5	101.5 (4)	Br2—Mn1—O2—C25	−119.0 (4)
N5ⁱ—Mn1—N1—C5	168.5 (8)	Br1—Mn1—O2—C25	59.4 (4)

Symmetry code: (i) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	[Mn₂Br₄(C₁₇H₁₆N₄O)₄]
M_r	1598.87
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	10.052 (2), 12.372 (3), 15.257 (3)
α, β, γ (°)	72.68 (3), 77.66 (3), 71.09 (3)
V (Å³)	1699.2 (6)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	2.78
Crystal size (mm)	0.24 × 0.20 × 0.18

Data collection
Diffractometer	Bruker SMART APEX II CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.555, 0.634
No. of measured, independent and observed [I > 2σ(I)] reflections	16756, 7658, 4058
R_int	0.073
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.058, 0.114, 0.99
No. of reflections	7658
No. of parameters	428
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.48, −0.53

Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003), SAINT, SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b), SHELXTL.

Selected geometric parameters (Å, º) top

Br1—Mn1	2.5441 (12)	Mn1—N5ⁱ	2.341 (4)
Br2—Mn1	2.5387 (12)	Mn1—N1	2.360 (4)
Mn1—O2	2.080 (3)

O2—Mn1—N5ⁱ	87.27 (13)	N1—Mn1—Br2	93.63 (11)
O2—Mn1—N1	89.45 (14)	O2—Mn1—Br1	122.63 (10)
N5ⁱ—Mn1—N1	171.60 (15)	N5ⁱ—Mn1—Br1	86.76 (10)
O2—Mn1—Br2	109.22 (10)	N1—Mn1—Br1	88.51 (11)
N5ⁱ—Mn1—Br2	94.75 (10)	Br2—Mn1—Br1	128.13 (4)