Di-μ-nicotinamide-κ2N1:O;κ2O:N1-bis­[aqua­bis­(4-bromo­benzoato)-κO;κ2O,O′-manganese(II)]

Necefoğlu, H.; Özbek, F.E.; Öztürk, V.; Adıgüzel, V.; Hökelek, T.

doi:10.1107/S1600536811028492

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 67| Part 8| August 2011| Pages m1128-m1129

doi:10.1107/S1600536811028492

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Di-μ-nicotinamide-κ²N¹:O;κ²O:N¹-bis[aquabis(4-bromobenzoato)-κO;κ²O,O′-manganese(II)]

Hacali Necefoğlu,^a Füreya Elif Özbek,^a Vijdan Öztürk,^a Vedat Adıgüzel ^a and Tuncer Hökelek ^b ^*

^aKafkas University, Department of Chemistry, 36100 Kars, Turkey, and ^bHacettepe University, Department of Physics, 06800 Beytepe, Ankara, Turkey
^*Correspondence e-mail: merzifon@hacettepe.edu.tr

(Received 14 July 2011; accepted 15 July 2011; online 23 July 2011)

In the centrosymmetric dinuclear title compound, [Mn₂(C₇H₄BrO₂)₄(C₆H₆N₂O)₂(H₂O)₂], the Mn^II atom is coordinated by one N atom from one bridging nicotinamide ligand and one O atom from another symmetry-related bridging nicotinamide ligand, three O atoms from two 4-bromobenzoate ligands and one water molecule in a distorted octahedral geometry. The dihedral angles between the carboxylate groups and the adjacent benzene rings are 10.89 (16) and 8.4 (2)°, while the benzene rings are oriented at a dihedral angle of 6.09 (13)°. Intermolecular O—H⋯O, N—H⋯O and weak C—H⋯O hydrogen bonds link the molecules into a three-dimensional network. π–π interactions, indicated by short centroid–centroid distances [3.845 (2) Å between the benzene rings, 3.650 (2) Å between the pyridine rings and 3.700 (3) Å between the benzene and pyridine rings] further stabilize the structure.

Related literature

For niacin, see: Krishnamachari (1974 ). For information on the nicotinic acid derivative N,N-diethylnicotinamide, see: Bigoli et al. (1972 ). For related structures, see: Hökelek et al. (2009a ,b ); Hökelek et al. (2010a ,b ); Necefoğlu et al. (2011 ); Greenaway et al. (1984 ).

Experimental

Crystal data

[Mn₂(C₇H₄BrO₂)₄(C₆H₆N₂O)₂(H₂O)₂]
M_r = 1190.18
Triclinic, $[P \overline 1]$
a = 7.2213 (2) Å
b = 12.1782 (3) Å
c = 13.4931 (4) Å
α = 110.038 (3)°
β = 91.206 (2)°
γ = 103.653 (2)°
V = 1076.51 (6) Å³
Z = 1
Mo Kα radiation
μ = 4.37 mm⁻¹
T = 294 K
0.29 × 0.22 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.329, T_max = 0.418
18469 measured reflections
5394 independent reflections
4298 reflections with I > 2σ(I)
R_int = 0.039

Refinement

R[F² > 2σ(F²)] = 0.049
wR(F²) = 0.126
S = 1.05
5394 reflections
297 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 2.03 e Å⁻³
Δρ_min = −1.76 e Å⁻³

Table 1
Selected bond lengths (Å)

Mn1—O1	2.316 (2)
Mn1—O2	2.237 (2)
Mn1—O3	2.025 (3)
Mn1—O5	2.217 (2)
Mn1—O6	2.170 (2)
Mn1—N1	2.272 (3)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O2ⁱ	0.85 (3)	2.02 (3)	2.856 (4)	168 (5)
O6—H6A⋯O1ⁱⁱ	0.84 (5)	1.96 (6)	2.771 (4)	162 (5)
O6—H6B⋯O4ⁱⁱ	0.84 (4)	1.83 (4)	2.670 (4)	175 (4)
C17—H17⋯O2ⁱⁱⁱ	0.93	2.27	3.125 (5)	152
Symmetry codes: (i) x-1, y, z; (ii) -x, -y, -z+1; (iii) -x+1, -y+1, -z+1.

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ) and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811028492/xu5272sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811028492/xu5272Isup2.hkl

checkCIF report

Comment top

As a part of our ongoing investigations of transition metal complexes of nicotinamide (NA), one form of niacin (Krishnamachari, 1974), and/or the nicotinic acid derivative N,N-diethylnicotinamide (DENA), an important respiratory stimulant (Bigoli et al., 1972), the title compound was synthesized and its crystal structure is reported herein.

The title compound, (I), consists of dimeric units located around a crystallographic symmetry centre and made up of two Mn cations, four 4-bromobenzoate (PBB) anions, which act in different modes-monodentate, bidentate and bidentate, monodentate, respectively, two nicotinamide (NA) ligands and two water molecules (Fig. 1). Both of the Mn^II centres are six-coordinated, and the two monomeric units are bridged through the two nicotinamide (NA) ligands about an inversion center. The Mn1···Mn1ⁱ [symmetry code: (i) -x, -y, -z] distance is 7.180 (2) Å. In the molecule, one Mn—O bond distance [2.316 (2) Å] is significantly longer than the other four, and the average Mn—O bond length is 2.193 (2) Å (Table 1). The Mn atom is displaced out of the least-squares planes of the carboxylate groups (O1/C1/O2) and (O3/C8/O4) by -0.0925 (5) and -0.5744 (5) Å, respectively.

The dihedral angles between the planar carboxylate groups and the adjacent benzene rings A (C2—C7) and B (C9—C14) are 10.89 (16) and 8.37 (20) °, respectively, while those between rings A, B and C (N1/C15—C19) are A/B = 6.09 (13), A/C = 85.37 (11), B/C = 86.41 (13) °.

In (I), the O1-Mn1-O2 angle is 57.61 (8)°. The corresponding O—M—O (where M is a metal) angles are 57.75 (2)° in [Cu(C₇H₅O₂F)(C₇H₄O₂F)₂(C₆H₆N₂O)₂], (II) (Necefoğlu et al., 2011), 60.32 (4)° in [Co(C₈H₇O₃)₂(C₆H₆N₂O)(H₂O)₂], (III) (Hökelek et al., 2010a), 59.02 (8)° in [Zn(C₈H₈NO₂)₂(C₆H₆N₂O)₂].H₂O, (IV) (Hökelek et al., 2009a), 60.03 (6)° in [Zn(C₉H₁₀NO₂)₂(C₆H₆N₂O)₂(H₂O)₂], (V) (Hökelek et al., 2009b), 57.53 (5)°, 56.19 (5)° and 59.04 (4)° in [Zn(C₈H₇O₃)₂(C₆H₆N₂O)₂], (VI) (Hökelek et al., 2010b) and 55.2 (1)° in [Cu(Asp)₂(py)₂] (where Asp is acetylsalicylate and py is pyridine) [(VII); Greenaway et al., 1984].

In the crystal structure, intermolecular O—H···O, N—H···O and C—H···O hydrogen bonds link the molecules into a three dimensional network (Table 2, Fig. 2), in which they may be effective in the stabilization of the structure. The π–π contacts between the benzene rings, between the pyridine rings and the benzene and pyridine rings Cg1—Cg1ⁱ, Cg3—Cg3ⁱⁱ and Cg1—Cg2ⁱⁱⁱ [symmetry codes: (i) 2 - x, -y, -z; (ii) 3 - x, 1 - y, 1 - z; (iii) 2 - x, -y, 1 - z, where Cg1, Cg2 and Cg3 are the centroids of the rings A (C2—C7), B (C9—C14) and C (N1/C15—C19), respectively] may further stabilize the structure, with centroid-centroid distances of 3.845 (2), 3.650 (2) and 3.700 (3) Å, respectively.

Related literature top

For niacin, see: Krishnamachari (1974). For information on the nicotinic acid derivative N,N-diethylnicotinamide, see: Bigoli et al. (1972). For related structures, see: Hökelek et al. (2009a,b); Hökelek et al. (2010a,b); Necefoğlu et al. (2011); Greenaway et al. (1984).

Experimental top

The title compound was prepared by the reaction of MnSO₄.H₂O (0.85 g, 10 mmol) in H₂O (25 ml) and nicotinamide (1.22 g, 20 mmol) in H₂O (25 ml) with sodium 4-bromobenzoate (2.23 g, 20 mmol) in H₂O (100 ml) at room temperature. The mixture was filtered and set aside to crystallize at ambient temperature for a few days, giving colorless single crystals.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title molecule with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level [symmetry code: (') -x, -y, -z].
	Fig. 2. A view of the crystal packing of the title compound. Hydrogen bonds are shown as dashed lines. [H-atoms not involved in hydrogen bonding have been omitted for clarity].

Di-µ-nicotinamide-κ²N¹:O;κ²O:N¹- bis[aquabis(4-bromobenzoato)-κO;κ²O,O'-manganese(II)] top

Crystal data top

[Mn₂(C₇H₄BrO₂)₄(C₆H₆N₂O)₂(H₂O)₂]	Z = 1
M_r = 1190.18	F(000) = 586
Triclinic, P1	D_x = 1.836 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.2213 (2) Å	Cell parameters from 7870 reflections
b = 12.1782 (3) Å	θ = 2.9–28.1°
c = 13.4931 (4) Å	µ = 4.37 mm⁻¹
α = 110.038 (3)°	T = 294 K
β = 91.206 (2)°	Block, colorless
γ = 103.653 (2)°	0.29 × 0.22 × 0.20 mm
V = 1076.51 (6) Å³

Data collection top

Bruker Kappa APEXII CCD area-detector diffractometer	5394 independent reflections
Radiation source: fine-focus sealed tube	4298 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.039
ϕ and ω scans	θ_max = 28.6°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −9→9
T_min = 0.329, T_max = 0.418	k = −16→16
18469 measured reflections	l = −18→17

Refinement top

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)] = 0.049	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.126	w = 1/[σ²(F_o²) + (0.0463P)² + 2.4514P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
5394 reflections	Δρ_max = 2.03 e Å⁻³
297 parameters	Δρ_min = −1.76 e Å⁻³
4 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0235 (13)

Crystal data top

[Mn₂(C₇H₄BrO₂)₄(C₆H₆N₂O)₂(H₂O)₂]	γ = 103.653 (2)°
M_r = 1190.18	V = 1076.51 (6) Å³
Triclinic, P1	Z = 1
a = 7.2213 (2) Å	Mo Kα radiation
b = 12.1782 (3) Å	µ = 4.37 mm⁻¹
c = 13.4931 (4) Å	T = 294 K
α = 110.038 (3)°	0.29 × 0.22 × 0.20 mm
β = 91.206 (2)°

Data collection top

Bruker Kappa APEXII CCD area-detector diffractometer	5394 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	4298 reflections with I > 2σ(I)
T_min = 0.329, T_max = 0.418	R_int = 0.039
18469 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	4 restraints
wR(F²) = 0.126	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 2.03 e Å⁻³
5394 reflections	Δρ_min = −1.76 e Å⁻³
297 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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

	x	y	z	U_iso*/U_eq
Mn1	0.03281 (7)	0.20681 (4)	0.48986 (4)	0.02469 (14)
Br1	0.08035 (10)	−0.25888 (5)	−0.16236 (4)	0.0704 (2)
Br2	−0.35117 (11)	0.46846 (7)	1.09799 (4)	0.0875 (3)
O1	−0.0971 (3)	0.0349 (2)	0.34227 (19)	0.0305 (5)
O2	0.1724 (3)	0.1626 (2)	0.33974 (19)	0.0294 (5)
O3	−0.1656 (5)	0.1988 (3)	0.5927 (3)	0.0537 (8)
O4	−0.3453 (4)	0.0368 (2)	0.6157 (2)	0.0470 (7)
O5	−0.1222 (3)	0.3095 (2)	0.4261 (2)	0.0320 (5)
O6	0.2150 (4)	0.1154 (2)	0.5439 (2)	0.0326 (5)
H6A	0.174 (7)	0.083 (5)	0.588 (3)	0.068 (17)*
H6B	0.259 (6)	0.066 (3)	0.496 (3)	0.042 (12)*
N1	0.2516 (4)	0.3847 (2)	0.5796 (2)	0.0291 (6)
N2	−0.4244 (4)	0.1935 (3)	0.3759 (3)	0.0369 (7)
H2A	−0.541 (3)	0.187 (4)	0.357 (4)	0.054 (14)*
H2B	−0.394 (7)	0.133 (3)	0.384 (4)	0.053 (13)*
C1	0.0442 (4)	0.0650 (3)	0.2952 (2)	0.0243 (6)
C2	0.0602 (5)	−0.0145 (3)	0.1855 (3)	0.0281 (7)
C3	−0.0629 (5)	−0.1295 (3)	0.1423 (3)	0.0358 (8)
H3	−0.1523	−0.1571	0.1827	0.043*
C4	−0.0537 (6)	−0.2035 (4)	0.0392 (3)	0.0439 (9)
H4	−0.1349	−0.2811	0.0106	0.053*
C5	0.0761 (6)	−0.1610 (4)	−0.0197 (3)	0.0433 (9)
C6	0.2021 (6)	−0.0479 (4)	0.0219 (3)	0.0453 (9)
H6	0.2915	−0.0212	−0.0190	0.054*
C7	0.1942 (5)	0.0256 (3)	0.1250 (3)	0.0354 (8)
H7	0.2789	0.1021	0.1538	0.043*
C8	−0.2679 (5)	0.1464 (3)	0.6458 (3)	0.0318 (7)
C9	−0.2941 (5)	0.2254 (3)	0.7544 (3)	0.0314 (7)
C10	−0.1872 (6)	0.3452 (3)	0.7977 (3)	0.0412 (9)
H10	−0.1026	0.3769	0.7574	0.049*
C11	−0.2037 (7)	0.4181 (4)	0.8993 (4)	0.0515 (11)
H11	−0.1332	0.4986	0.9273	0.062*
C12	−0.3271 (7)	0.3688 (4)	0.9580 (3)	0.0512 (11)
C13	−0.4343 (6)	0.2518 (5)	0.9188 (4)	0.0522 (11)
H13	−0.5171	0.2207	0.9602	0.063*
C14	−0.4181 (6)	0.1794 (4)	0.8158 (3)	0.0425 (9)
H14	−0.4911	0.0995	0.7881	0.051*
C15	0.2168 (5)	0.4876 (3)	0.5798 (3)	0.0291 (7)
H15	0.0945	0.4845	0.5539	0.035*
C16	0.3514 (4)	0.5991 (3)	0.6163 (2)	0.0235 (6)
C17	0.5302 (5)	0.6036 (3)	0.6579 (3)	0.0313 (7)
H17	0.6249	0.6762	0.6834	0.038*
C18	0.5661 (5)	0.4984 (3)	0.6609 (3)	0.0373 (8)
H18	0.6852	0.4998	0.6897	0.045*
C19	0.4250 (5)	0.3911 (3)	0.6212 (3)	0.0325 (7)
H19	0.4515	0.3208	0.6234	0.039*
C20	−0.2925 (4)	0.2957 (3)	0.3966 (3)	0.0252 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn1	0.0273 (2)	0.0187 (2)	0.0281 (3)	0.00505 (17)	0.00231 (18)	0.00905 (18)
Br1	0.1104 (5)	0.0750 (4)	0.0318 (2)	0.0543 (3)	0.0100 (2)	0.0063 (2)
Br2	0.1231 (6)	0.1180 (5)	0.0361 (3)	0.0877 (5)	0.0081 (3)	0.0083 (3)
O1	0.0304 (12)	0.0269 (11)	0.0325 (12)	0.0038 (9)	0.0061 (10)	0.0109 (9)
O2	0.0269 (11)	0.0266 (11)	0.0337 (12)	0.0043 (9)	0.0009 (9)	0.0114 (9)
O3	0.0640 (19)	0.0517 (17)	0.0500 (18)	0.0148 (15)	0.0300 (15)	0.0226 (14)
O4	0.0580 (18)	0.0320 (13)	0.0502 (17)	0.0133 (12)	0.0130 (14)	0.0123 (12)
O5	0.0243 (11)	0.0230 (10)	0.0482 (15)	0.0044 (9)	−0.0054 (10)	0.0138 (10)
O6	0.0429 (14)	0.0239 (11)	0.0354 (14)	0.0116 (10)	0.0044 (11)	0.0141 (10)
N1	0.0297 (14)	0.0208 (12)	0.0361 (15)	0.0041 (10)	−0.0034 (11)	0.0113 (11)
N2	0.0276 (15)	0.0221 (13)	0.060 (2)	0.0016 (11)	−0.0041 (14)	0.0175 (14)
C1	0.0263 (15)	0.0230 (13)	0.0264 (15)	0.0076 (11)	−0.0012 (12)	0.0116 (12)
C2	0.0300 (16)	0.0301 (15)	0.0274 (16)	0.0121 (13)	0.0007 (13)	0.0117 (13)
C3	0.0403 (19)	0.0303 (16)	0.0323 (18)	0.0080 (14)	0.0012 (15)	0.0065 (14)
C4	0.054 (2)	0.0332 (18)	0.038 (2)	0.0134 (17)	−0.0039 (17)	0.0047 (16)
C5	0.060 (2)	0.047 (2)	0.0288 (18)	0.034 (2)	0.0022 (17)	0.0079 (16)
C6	0.050 (2)	0.060 (3)	0.039 (2)	0.027 (2)	0.0165 (18)	0.0250 (19)
C7	0.0354 (18)	0.0396 (18)	0.0342 (19)	0.0113 (15)	0.0048 (14)	0.0157 (15)
C8	0.0300 (16)	0.0357 (17)	0.0366 (18)	0.0163 (14)	0.0073 (14)	0.0161 (14)
C9	0.0319 (17)	0.0359 (17)	0.0351 (18)	0.0183 (14)	0.0065 (14)	0.0171 (14)
C10	0.049 (2)	0.0363 (19)	0.042 (2)	0.0151 (16)	0.0051 (17)	0.0163 (16)
C11	0.070 (3)	0.040 (2)	0.044 (2)	0.025 (2)	−0.003 (2)	0.0081 (18)
C12	0.064 (3)	0.064 (3)	0.033 (2)	0.046 (2)	0.0022 (19)	0.0071 (19)
C13	0.045 (2)	0.079 (3)	0.047 (2)	0.031 (2)	0.0176 (19)	0.030 (2)
C14	0.038 (2)	0.050 (2)	0.045 (2)	0.0143 (17)	0.0127 (17)	0.0219 (18)
C15	0.0259 (15)	0.0221 (14)	0.0378 (18)	0.0033 (12)	−0.0062 (13)	0.0112 (13)
C16	0.0248 (14)	0.0196 (13)	0.0263 (15)	0.0047 (11)	0.0018 (11)	0.0092 (11)
C17	0.0259 (15)	0.0255 (15)	0.0408 (19)	0.0019 (12)	−0.0053 (13)	0.0134 (14)
C18	0.0289 (17)	0.0336 (17)	0.051 (2)	0.0064 (14)	−0.0079 (15)	0.0190 (16)
C19	0.0361 (18)	0.0255 (15)	0.0391 (19)	0.0096 (13)	−0.0021 (14)	0.0148 (14)
C20	0.0262 (15)	0.0196 (13)	0.0278 (15)	0.0053 (11)	0.0008 (12)	0.0064 (11)

Geometric parameters (Å, º) top

Mn1—O1	2.316 (2)	C6—C5	1.377 (6)
Mn1—O2	2.237 (2)	C6—H6	0.9300
Mn1—O3	2.025 (3)	C7—C6	1.384 (6)
Mn1—C1	2.619 (3)	C7—H7	0.9300
Br1—C5	1.891 (4)	C9—C8	1.497 (5)
Br2—C12	1.901 (4)	C9—C10	1.389 (5)
O1—C1	1.260 (4)	C9—C14	1.384 (5)
O2—C1	1.265 (4)	C10—C11	1.380 (6)
O3—C8	1.257 (4)	C10—H10	0.9300
O4—C8	1.235 (4)	C11—H11	0.9300
Mn1—O5	2.217 (2)	C12—C13	1.362 (7)
O5—C20	1.239 (4)	C12—C11	1.373 (7)
Mn1—O6	2.170 (2)	C13—H13	0.9300
O6—H6A	0.845 (19)	C14—C13	1.392 (6)
O6—H6B	0.847 (19)	C14—H14	0.9300
Mn1—N1	2.272 (3)	C15—C16	1.389 (4)
N1—C15	1.334 (4)	C15—H15	0.9300
N1—C19	1.335 (4)	C16—C17	1.378 (4)
N2—H2A	0.853 (19)	C16—C20ⁱ	1.503 (4)
N2—H2B	0.857 (19)	C17—H17	0.9300
C1—C2	1.490 (5)	C18—C17	1.380 (5)
C2—C3	1.386 (5)	C18—H18	0.9300
C2—C7	1.388 (5)	C19—C18	1.379 (5)
C3—C4	1.388 (5)	C19—H19	0.9300
C3—H3	0.9300	C20—N2	1.314 (4)
C4—H4	0.9300	C20—C16ⁱ	1.503 (4)
C5—C4	1.364 (6)

O1—Mn1—C1	28.77 (9)	C4—C5—Br1	119.1 (3)
O2—Mn1—O1	57.61 (8)	C4—C5—C6	121.6 (4)
O2—Mn1—N1	96.47 (10)	C6—C5—Br1	119.3 (3)
O2—Mn1—C1	28.85 (9)	C5—C6—C7	119.3 (4)
O3—Mn1—O1	102.93 (11)	C5—C6—H6	120.3
O3—Mn1—O2	160.32 (12)	C7—C6—H6	120.3
O3—Mn1—O5	89.12 (12)	C2—C7—H7	120.0
O3—Mn1—O6	97.50 (12)	C6—C7—C2	120.1 (4)
O3—Mn1—N1	102.86 (12)	C6—C7—H7	120.0
O3—Mn1—C1	131.68 (12)	O3—C8—C9	116.0 (3)
O5—Mn1—O1	89.54 (9)	O4—C8—O3	125.3 (4)
O5—Mn1—O2	87.89 (9)	O4—C8—C9	118.7 (3)
O5—Mn1—N1	87.93 (9)	C10—C9—C8	120.6 (3)
O5—Mn1—C1	89.17 (9)	C14—C9—C8	120.8 (3)
O6—Mn1—O1	91.37 (9)	C14—C9—C10	118.5 (4)
O6—Mn1—O2	86.68 (9)	C9—C10—H10	119.3
O6—Mn1—O5	172.93 (10)	C11—C10—C9	121.4 (4)
O6—Mn1—N1	88.18 (10)	C11—C10—H10	119.3
O6—Mn1—C1	88.26 (10)	C10—C11—H11	120.9
N1—Mn1—O1	154.04 (10)	C12—C11—C10	118.2 (4)
N1—Mn1—C1	125.32 (10)	C12—C11—H11	120.9
C1—O1—Mn1	89.05 (18)	C11—C12—Br2	118.6 (4)
C1—O2—Mn1	92.58 (19)	C13—C12—Br2	119.1 (4)
C8—O3—Mn1	152.3 (3)	C13—C12—C11	122.3 (4)
C20—O5—Mn1	134.3 (2)	C12—C13—C14	119.0 (4)
Mn1—O6—H6B	116 (3)	C12—C13—H13	120.5
Mn1—O6—H6A	117 (4)	C14—C13—H13	120.5
H6B—O6—H6A	108 (5)	C9—C14—C13	120.5 (4)
C15—N1—Mn1	118.9 (2)	C9—C14—H14	119.7
C15—N1—C19	117.4 (3)	C13—C14—H14	119.7
C19—N1—Mn1	123.1 (2)	N1—C15—C16	124.2 (3)
C20—N2—H2A	121 (3)	N1—C15—H15	117.9
C20—N2—H2B	120 (3)	C16—C15—H15	117.9
H2A—N2—H2B	119 (5)	C15—C16—C20ⁱ	117.2 (3)
O1—C1—Mn1	62.18 (17)	C17—C16—C15	117.5 (3)
O1—C1—O2	120.7 (3)	C17—C16—C20ⁱ	125.2 (3)
O1—C1—C2	119.9 (3)	C16—C17—C18	118.8 (3)
O2—C1—Mn1	58.57 (17)	C16—C17—H17	120.6
O2—C1—C2	119.4 (3)	C18—C17—H17	120.6
C2—C1—Mn1	177.4 (2)	C17—C18—H18	120.1
C3—C2—C1	119.6 (3)	C19—C18—C17	119.9 (3)
C3—C2—C7	119.4 (3)	C19—C18—H18	120.1
C7—C2—C1	121.0 (3)	N1—C19—C18	122.2 (3)
C2—C3—C4	120.4 (4)	N1—C19—H19	118.9
C2—C3—H3	119.8	C18—C19—H19	118.9
C4—C3—H3	119.8	O5—C20—N2	123.2 (3)
C3—C4—H4	120.4	O5—C20—C16ⁱ	118.5 (3)
C5—C4—C3	119.1 (4)	N2—C20—C16ⁱ	118.3 (3)
C5—C4—H4	120.4

O2—Mn1—O1—C1	1.32 (17)	C19—N1—Mn1—O1	−78.8 (4)
O3—Mn1—O1—C1	178.1 (2)	C19—N1—Mn1—O2	−75.9 (3)
O3—Mn1—O2—C1	−10.6 (4)	C19—N1—Mn1—O3	107.9 (3)
O5—Mn1—O1—C1	89.11 (19)	C19—N1—Mn1—O5	−163.5 (3)
O6—Mn1—O1—C1	−83.88 (19)	C19—N1—Mn1—O6	10.6 (3)
N1—Mn1—O1—C1	4.8 (3)	C19—N1—Mn1—C1	−76.0 (3)
O1—Mn1—O2—C1	−1.31 (17)	Mn1—N1—C15—C16	−168.9 (3)
O5—Mn1—O2—C1	−92.11 (18)	C19—N1—C15—C16	2.8 (5)
O6—Mn1—O2—C1	92.42 (18)	Mn1—N1—C19—C18	169.8 (3)
N1—Mn1—O2—C1	−179.79 (18)	C15—N1—C19—C18	−1.5 (6)
O1—Mn1—O3—C8	56.2 (7)	O1—C1—C2—C3	−10.1 (5)
O2—Mn1—O3—C8	64.3 (8)	O2—C1—C2—C3	170.3 (3)
O5—Mn1—O3—C8	145.5 (7)	O1—C1—C2—C7	168.6 (3)
O6—Mn1—O3—C8	−37.0 (7)	O2—C1—C2—C7	−10.9 (5)
N1—Mn1—O3—C8	−126.8 (6)	C1—C2—C3—C4	178.2 (3)
C1—Mn1—O3—C8	57.4 (7)	C7—C2—C3—C4	−0.6 (5)
O1—Mn1—C1—O2	177.7 (3)	C1—C2—C7—C6	−177.6 (3)
O2—Mn1—C1—O1	−177.7 (3)	C3—C2—C7—C6	1.2 (5)
O3—Mn1—C1—O1	−2.5 (3)	C2—C3—C4—C5	−1.0 (6)
O3—Mn1—C1—O2	175.22 (19)	Br1—C5—C4—C3	−177.0 (3)
O5—Mn1—C1—O1	−90.56 (18)	C6—C5—C4—C3	2.0 (6)
O5—Mn1—C1—O2	87.14 (18)	C7—C6—C5—Br1	177.6 (3)
O6—Mn1—C1—O1	96.03 (19)	C7—C6—C5—C4	−1.5 (6)
O6—Mn1—C1—O2	−86.28 (18)	C2—C7—C6—C5	−0.2 (6)
N1—Mn1—C1—O1	−177.43 (17)	C10—C9—C8—O3	−9.3 (5)
N1—Mn1—C1—O2	0.3 (2)	C10—C9—C8—O4	170.2 (3)
Mn1—O1—C1—O2	−2.3 (3)	C14—C9—C8—O3	173.9 (4)
Mn1—O1—C1—C2	178.2 (3)	C14—C9—C8—O4	−6.5 (5)
Mn1—O2—C1—O1	2.4 (3)	C8—C9—C10—C11	−177.4 (4)
Mn1—O2—C1—C2	−178.1 (2)	C14—C9—C10—C11	−0.6 (6)
Mn1—O3—C8—O4	−37.6 (9)	C8—C9—C14—C13	176.7 (4)
Mn1—O3—C8—C9	142.0 (5)	C10—C9—C14—C13	−0.2 (6)
C20—O5—Mn1—O1	55.0 (3)	C9—C10—C11—C12	1.1 (6)
C20—O5—Mn1—O2	112.6 (3)	Br2—C12—C11—C10	−180.0 (3)
C20—O5—Mn1—O3	−47.9 (3)	C13—C12—C11—C10	−0.9 (7)
C20—O5—Mn1—N1	−150.8 (3)	Br2—C12—C13—C14	179.2 (3)
C20—O5—Mn1—C1	83.8 (3)	C11—C12—C13—C14	0.2 (7)
Mn1—O5—C20—N2	−15.3 (5)	C9—C14—C13—C12	0.3 (6)
Mn1—O5—C20—C16ⁱ	164.6 (2)	N1—C15—C16—C17	−2.1 (5)
C15—N1—Mn1—O1	92.4 (3)	N1—C15—C16—C20ⁱ	175.6 (3)
C15—N1—Mn1—O2	95.3 (3)	C15—C16—C17—C18	0.2 (5)
C15—N1—Mn1—O3	−80.9 (3)	C20ⁱ—C16—C17—C18	−177.4 (3)
C15—N1—Mn1—O5	7.7 (3)	C19—C18—C17—C16	1.0 (6)
C15—N1—Mn1—O6	−178.2 (3)	N1—C19—C18—C17	−0.3 (6)
C15—N1—Mn1—C1	95.2 (3)

Symmetry code: (i) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O2ⁱⁱ	0.85 (3)	2.02 (3)	2.856 (4)	168 (5)
O6—H6A···O1ⁱⁱⁱ	0.84 (5)	1.96 (6)	2.771 (4)	162 (5)
O6—H6B···O4ⁱⁱⁱ	0.84 (4)	1.83 (4)	2.670 (4)	175 (4)
C15—H15···O5	0.93	2.40	3.032 (4)	125
C17—H17···O2^iv	0.93	2.27	3.125 (5)	152
C19—H19···O6	0.93	2.53	3.129 (5)	123

Symmetry codes: (ii) x−1, y, z; (iii) −x, −y, −z+1; (iv) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	[Mn₂(C₇H₄BrO₂)₄(C₆H₆N₂O)₂(H₂O)₂]
M_r	1190.18
Crystal system, space group	Triclinic, P1
Temperature (K)	294
a, b, c (Å)	7.2213 (2), 12.1782 (3), 13.4931 (4)
α, β, γ (°)	110.038 (3), 91.206 (2), 103.653 (2)
V (Å³)	1076.51 (6)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	4.37
Crystal size (mm)	0.29 × 0.22 × 0.20

Data collection
Diffractometer	Bruker Kappa APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.329, 0.418
No. of measured, independent and observed [I > 2σ(I)] reflections	18469, 5394, 4298
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.673

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.126, 1.05
No. of reflections	5394
No. of parameters	297
No. of restraints	4
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	2.03, −1.76

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Selected bond lengths (Å) top

Mn1—O1	2.316 (2)	Mn1—O5	2.217 (2)
Mn1—O2	2.237 (2)	Mn1—O6	2.170 (2)
Mn1—O3	2.025 (3)	Mn1—N1	2.272 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O2ⁱ	0.85 (3)	2.02 (3)	2.856 (4)	168 (5)
O6—H6A···O1ⁱⁱ	0.84 (5)	1.96 (6)	2.771 (4)	162 (5)
O6—H6B···O4ⁱⁱ	0.84 (4)	1.83 (4)	2.670 (4)	175 (4)
C17—H17···O2ⁱⁱⁱ	0.93	2.27	3.125 (5)	152

Symmetry codes: (i) x−1, y, z; (ii) −x, −y, −z+1; (iii) −x+1, −y+1, −z+1.

Acknowledgements

The authors are indebted to Anadolu University and the Medicinal Plants and Medicine Research Centre of Anadolu University, Eskişehir, Turkey, for the use of the X-ray diffractometer. This work was supported financially by the Scientific and Technological Research Council of Turkey (grant No. 106 T472).

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