catena-Poly[[[aqua­manganese(III)]-μ-(E)-5-bromo-N-[2-(5-bromo-2-oxidobenzyl­idene­amino)-4-nitro­phen­yl]-2-oxidobenzamidato] N,N-dimethyl­fomamide monosolvate]

Farag, A.M.; Guan, T.S.; Osman, H.; Hemamalini, M.; Fun, H.-K.

doi:10.1107/S1600536812008501

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 68| Part 4| April 2012| Pages m365-m366

doi:10.1107/S1600536812008501

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catena-Poly[[[aquamanganese(III)]-μ-(E)-5-bromo-N-[2-(5-bromo-2-oxidobenzylideneamino)-4-nitrophenyl]-2-oxidobenzamidato] N,N-dimethylfomamide monosolvate]

Abeer Mohamed Farag,^a Teoh Siang Guan,^a Hasnah Osman,^a Madhukar Hemamalini ^b and Hoong-Kun Fun ^b ^*‡

^aSchool of Chemical Sciences, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, and ^bX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia
^*Correspondence e-mail: hkfun@usm.my

(Received 21 February 2012; accepted 25 February 2012; online 3 March 2012)

The asymmetric unit of the title complex, {[Mn(C₂₀H₁₀Br₂N₃O₅)(H₂O)]·(CH₃)₂NCHO}_n, consists of one Mn^III ion, one (E)-5-bromo-N-[2-(5-bromo-2-oxidobenzylideneamino)-4-nitrophenyl]-2-oxidobenzamidate ligand (Schiff base), one water molecule and an N,N-dimethylformamide molecule. The coordination geometry around the Mn^III ion is a distorted octahedron, being surrounded by two O and two N atoms from the Schiff base, which are positioned in the equatorial plane. The water molecule and the O atom of the carbonyl group from the adjacent Mn^III complex are situated at the axial positions, leading to a polymeric chain along the c axis. In the crystal, the complex and N,N-dimethylformamide molecules are connected via O—H⋯O, C—H⋯O and C—H⋯Br hydrogen bonds, forming a three-dimensional network.

Related literature

For details of the coordination chemistry and biological importance of manganese, see: Maneiro et al. (2003 ); Chandra et al. (2009 ); Chrisianson & Cox (1999 ); Ni et al. (2009 ); Zhang et al. (2005 ); Huh & Lee (2008 ); Pastoriza-Santos & Liz-Marzań (2009 ). For related structures, see: Su & Xu (2005 ); Ma et al. (2004 ). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ).

Experimental

Crystal data

[Mn(C₂₀H₁₀Br₂N₃O₅)(H₂O)]·C₃H₇NO
M_r = 678.18
Monoclinic, P 2₁ /c
a = 11.0746 (6) Å
b = 24.9781 (13) Å
c = 9.5563 (5) Å
β = 114.658 (1)°
V = 2402.4 (2) Å³
Z = 4
Mo Kα radiation
μ = 3.93 mm⁻¹
T = 100 K
0.52 × 0.17 × 0.11 mm

Data collection

Bruker APEXII DUO CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.234, T_max = 0.672
27005 measured reflections
8188 independent reflections
6617 reflections with I > 2σ(I)
R_int = 0.032

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.085
S = 1.02
8188 reflections
344 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.85 e Å⁻³
Δρ_min = −0.62 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1W2⋯O5ⁱ	0.73 (4)	2.03 (4)	2.736 (2)	163 (4)
O1W—H2W2⋯O1ⁱⁱ	0.77 (3)	2.55 (3)	3.178 (2)	140 (3)
O1W—H2W2⋯O2ⁱⁱ	0.77 (3)	2.19 (3)	2.890 (2)	153 (3)
C2—H2⋯O5ⁱⁱⁱ	0.93	2.42	3.351 (2)	175
C5—H5⋯O4^iv	0.93	2.49	3.395 (3)	166
C7—H7⋯O3^iv	0.93	2.60	3.509 (2)	167
C18—H18⋯Br2^v	0.93	2.83	3.449 (2)	125
C23—H23A⋯O5^vi	0.96	2.40	3.350 (3)	170
Symmetry codes: (i) $[x-1, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) x-1, y, z-1; (iv) -x+1, -y+1, -z+3; (v) $[-x, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (vi) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I, an. DOI: 10.1107/S1600536812008501/is5080sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812008501/is5080Isup2.hkl

checkCIF report

Comment top

In recent years, the coordination chemistry of manganese has been intensively studied due to its presence in the active sites of some enzymes that participate in the chemistry of reactive oxygen species, such as the participation of Mn(II) complexes in peroxidase activity (Maneiro et al., 2003), antipathogenic activity (Chandra et al., 2009) and as essential cofactors in metalloenzymes (Chrisianson & Cox, 1999). X-Ray crystallography has shown a quasi- two-coordinate strongly bent geometry with Mn, which has an almost linear geometry with a wide N—Mn—N angle of 176.1° (Ni et al., 2009). Octahedral coordination is completed by N₄O₂ ligands (Zhang et al., 2005). The reaction system (solvent composition and reaction temperature) may cause dramatic changes in the structures. The preparation of the polymer results in the introduction of guest molecules such as DMF into its empty channels by the use of mixed solvents DMF-EtOH-H₂O under hydro(solvo)thermal conditions (Huh & Lee, 2008). The mechanism of oxidation by DMF have been proposed by Pastoriza-Santos & Liz-Marzań (2009). Due to these interesting features, the title compound was synthesized and its crystal structure presented here.

The asymmetric unit of the title polymeric complex, consisting of one Mn (III) ion, one (E)-5-bromo-N-(2- (5-bromo-2-hydroxybenzylideneamino)-4-nitrophenyl)-2-hydroxybenzamide (Schiff base), one water molecule and a dimethylformamide solvate molecule is shown in Fig. 1. The coordination geometry around Mn (III) is a distorted octahedron, with the Mn (III) ion being surrounded by two O and two N atoms from the Schiff base which are positioned in the equatorial plane. The water molecule and an atom from a carbonyl group are situated in the axial positions. The carbonyl groups bridge the Mn (III) ions, leading to polymeric chains along the c-axis (Fig. 2). The bond lengths are Mn1—O2 = 1.8557 (13); Mn1—O1 = 1.8875 (13); Mn1—N2 = 1.9750 (15); Mn1—N1 = 1.9782 (15); Mn1—O1W =2.2431(15; Mn1—O6 = 2.3448 (14) Å. All bond lengths are in agreement with those in the related structures (Su & Xu, 2005; Ma et al., 2004). In the crystal, (Fig. 3), the complexes are connected with the solvent molecules via O—H···O, C—H···O and C—H···Br hydrogen bonds (Table 1) to form a three-dimensional network.

Related literature top

For details of the coordination chemistry and biological importance of manganese, see: Maneiro et al. (2003); Chandra et al. (2009); Chrisianson & Cox (1999); Ni et al. (2009); Zhang et al. (2005); Huh & Lee (2008); Pastoriza-Santos & Liz-Marzań (2009). For related structures, see: Su & Xu (2005); Ma et al. (2004). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986).

Experimental top

To the solution of 4-nitrobenzene-1,2-diamine (0.306 g, 2 mmol) in ethanol (30 mL) was added 5-bromo-2-hydroxybenzaldehyde (0.804 g, 4 mmol), after which the colour of solution became orange. The mixture was refluxed with stirring for three hours. On adding manganese(II) chloride (0.395 g, 2 mmol), followed by triethylamine (500 mL, 3.6 mmol), a brown precipitate was formed. The mixture was stirred with reflux for three hours. The precipitate, obtained by filtration, was washed by ethanol (5 mL) and dried, affording the title compound (87.33 % yield). Brown block-shaped single crystals suitable for X-ray structure determination were obtained from DMF: ethanol mixture (2:8) with decomposition pt. >340 °C. IR spectroscopy (KBr): ν = 3370 (-OH), 1612 (C═N), 1335 (NO₂), 639 (M–N), 480 (M–O) cm^-1. Anal. Calcd (found) for [C₂₀H₁₅Br₂N₃O₆Mn].C₃H₇NO: C 39.50 (39.55), H 2.49 (2.11), N 6.91 (6.55), Mn 9.03 (8.66). MASS Calcd (found) m/z: [605.87 - 2H₂O]⁺ = 569.87 (571.9).

Structure description top

For details of the coordination chemistry and biological importance of manganese, see: Maneiro et al. (2003); Chandra et al. (2009); Chrisianson & Cox (1999); Ni et al. (2009); Zhang et al. (2005); Huh & Lee (2008); Pastoriza-Santos & Liz-Marzań (2009). For related structures, see: Su & Xu (2005); Ma et al. (2004). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986).

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The asymmetric unit of the title compound, showing 30% probability displacement ellipsoids and the atom-numbering scheme.
	Fig. 2. : The polymeric chain of the title compound along the c-axis. H atoms and solvent molecules omitted for clarity.
	Fig. 3. The crystal packing of the title compound, showing a 3D molecular network.

catena-Poly[[[aquamanganese(III)]-µ-(E)-5-bromo- N-[2-(5-bromo-2-oxidobenzylideneamino)-4-nitrophenyl]- 2-oxidobenzamidato] N,N-dimethylfomamide monosolvate] top

Crystal data top

[Mn(C₂₀H₁₀Br₂N₃O₅)(H₂O)]·C₃H₇NO	F(000) = 1344
M_r = 678.18	D_x = 1.875 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 7902 reflections
a = 11.0746 (6) Å	θ = 3.2–31.8°
b = 24.9781 (13) Å	µ = 3.93 mm⁻¹
c = 9.5563 (5) Å	T = 100 K
β = 114.658 (1)°	Block, brown
V = 2402.4 (2) Å³	0.52 × 0.17 × 0.11 mm
Z = 4

Data collection top

Bruker APEXII DUO CCD area-detector diffractometer	8188 independent reflections
Radiation source: fine-focus sealed tube	6617 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
φ and ω scans	θ_max = 31.8°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −16→16
T_min = 0.234, T_max = 0.672	k = −36→37
27005 measured reflections	l = −14→14

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.085	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.041P)² + 1.7977P] where P = (F_o² + 2F_c²)/3
8188 reflections	(Δ/σ)_max = 0.003
344 parameters	Δρ_max = 1.85 e Å⁻³
0 restraints	Δρ_min = −0.62 e Å⁻³

Crystal data top

[Mn(C₂₀H₁₀Br₂N₃O₅)(H₂O)]·C₃H₇NO	V = 2402.4 (2) Å³
M_r = 678.18	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.0746 (6) Å	µ = 3.93 mm⁻¹
b = 24.9781 (13) Å	T = 100 K
c = 9.5563 (5) Å	0.52 × 0.17 × 0.11 mm
β = 114.658 (1)°

Data collection top

Bruker APEXII DUO CCD area-detector diffractometer	8188 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	6617 reflections with I > 2σ(I)
T_min = 0.234, T_max = 0.672	R_int = 0.032
27005 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.085	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 1.85 e Å⁻³
8188 reflections	Δρ_min = −0.62 e Å⁻³
344 parameters

Special details top

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1)K.

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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	0.32207 (3)	0.285186 (10)	1.10714 (3)	0.01283 (6)
Br1	0.39872 (2)	−0.002567 (8)	1.29527 (2)	0.02540 (6)
Br2	0.00337 (3)	0.540295 (9)	0.75613 (3)	0.03831 (8)
O1	0.19454 (14)	0.31410 (5)	0.92195 (14)	0.0161 (2)
O2	0.28189 (14)	0.21775 (5)	1.01810 (15)	0.0162 (3)
O3	0.65113 (16)	0.47920 (6)	1.64497 (17)	0.0250 (3)
O4	0.76182 (19)	0.42584 (7)	1.83364 (18)	0.0345 (4)
N1	0.37015 (15)	0.35574 (6)	1.20959 (17)	0.0132 (3)
N2	0.44814 (15)	0.25853 (6)	1.31031 (17)	0.0130 (3)
N3	0.68440 (17)	0.43404 (7)	1.69974 (19)	0.0196 (3)
C1	0.15509 (18)	0.36422 (7)	0.8920 (2)	0.0155 (3)
C2	0.0566 (2)	0.37633 (8)	0.7440 (2)	0.0207 (4)
H2	0.0211	0.3490	0.6722	0.025*
C3	0.0124 (2)	0.42798 (8)	0.7046 (2)	0.0239 (4)
H3	−0.0516	0.4355	0.6063	0.029*
C4	0.0636 (2)	0.46918 (8)	0.8124 (3)	0.0240 (4)
C5	0.1582 (2)	0.45925 (8)	0.9576 (2)	0.0212 (4)
H5	0.1906	0.4870	1.0283	0.025*
C6	0.20647 (19)	0.40668 (7)	0.9997 (2)	0.0163 (3)
C7	0.30926 (19)	0.40035 (7)	1.1515 (2)	0.0154 (3)
H7	0.3347	0.4306	1.2137	0.019*
C8	0.47310 (18)	0.35266 (7)	1.36140 (19)	0.0130 (3)
C9	0.53061 (18)	0.39672 (7)	1.4535 (2)	0.0149 (3)
H9	0.5039	0.4313	1.4178	0.018*
C10	0.62842 (19)	0.38799 (7)	1.5994 (2)	0.0157 (3)
C11	0.6734 (2)	0.33696 (8)	1.6552 (2)	0.0177 (3)
H11	0.7412	0.3324	1.7530	0.021*
C12	0.6157 (2)	0.29309 (7)	1.5628 (2)	0.0169 (3)
H12	0.6452	0.2588	1.5986	0.020*
C13	0.51269 (18)	0.30003 (7)	1.4150 (2)	0.0135 (3)
C14	0.44056 (18)	0.20846 (7)	1.3632 (2)	0.0141 (3)
C15	0.38604 (18)	0.16400 (7)	1.2496 (2)	0.0142 (3)
C16	0.41170 (19)	0.11188 (7)	1.3105 (2)	0.0162 (3)
H16	0.4619	0.1069	1.4155	0.019*
C17	0.3626 (2)	0.06804 (7)	1.2151 (2)	0.0177 (3)
C18	0.2833 (2)	0.07434 (7)	1.0590 (2)	0.0182 (3)
H18	0.2489	0.0446	0.9964	0.022*
C19	0.25639 (19)	0.12505 (7)	0.9983 (2)	0.0166 (3)
H19	0.2018	0.1294	0.8943	0.020*
C20	0.30947 (18)	0.17067 (7)	1.0900 (2)	0.0138 (3)
O6	0.47681 (14)	0.19817 (5)	1.50376 (15)	0.0162 (3)
O1W	0.15751 (15)	0.28059 (7)	1.18541 (18)	0.0203 (3)
O5	0.94801 (16)	0.27762 (6)	1.48344 (18)	0.0259 (3)
N4	0.84158 (18)	0.32089 (7)	1.2543 (2)	0.0202 (3)
C21	0.9247 (2)	0.28447 (8)	1.3460 (3)	0.0232 (4)
H21	0.9687	0.2625	1.3039	0.028*
C22	0.7663 (2)	0.35587 (9)	1.3091 (3)	0.0269 (4)
H22A	0.7843	0.3468	1.4135	0.040*
H22B	0.6731	0.3516	1.2455	0.040*
H22C	0.7915	0.3924	1.3044	0.040*
C23	0.8221 (2)	0.32762 (9)	1.0947 (2)	0.0250 (4)
H23A	0.8686	0.2998	1.0680	0.037*
H23B	0.8558	0.3619	1.0826	0.037*
H23C	0.7290	0.3255	1.0285	0.037*
H1W2	0.110 (4)	0.2602 (15)	1.142 (4)	0.051 (11)*
H2W2	0.180 (3)	0.2712 (12)	1.269 (4)	0.034 (8)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn1	0.01673 (13)	0.01111 (12)	0.00881 (11)	−0.00105 (9)	0.00349 (10)	−0.00144 (9)
Br1	0.03687 (12)	0.01250 (9)	0.02373 (10)	0.00229 (8)	0.00957 (9)	0.00146 (7)
Br2	0.03147 (13)	0.01713 (10)	0.04152 (14)	0.00359 (8)	−0.00934 (10)	0.00522 (9)
O1	0.0204 (6)	0.0140 (6)	0.0106 (5)	−0.0001 (5)	0.0030 (5)	−0.0002 (4)
O2	0.0241 (7)	0.0107 (6)	0.0119 (5)	−0.0022 (5)	0.0057 (5)	−0.0014 (4)
O3	0.0333 (8)	0.0129 (6)	0.0223 (7)	−0.0034 (6)	0.0050 (6)	−0.0013 (5)
O4	0.0465 (10)	0.0217 (7)	0.0162 (7)	−0.0040 (7)	−0.0059 (7)	−0.0030 (6)
N1	0.0153 (7)	0.0128 (6)	0.0105 (6)	−0.0011 (5)	0.0043 (5)	−0.0012 (5)
N2	0.0158 (7)	0.0113 (6)	0.0106 (6)	−0.0006 (5)	0.0044 (5)	−0.0018 (5)
N3	0.0230 (8)	0.0168 (7)	0.0161 (7)	−0.0034 (6)	0.0052 (6)	−0.0032 (6)
C1	0.0163 (8)	0.0155 (8)	0.0132 (7)	−0.0015 (6)	0.0047 (6)	−0.0003 (6)
C2	0.0209 (9)	0.0195 (9)	0.0151 (8)	−0.0017 (7)	0.0011 (7)	0.0001 (7)
C3	0.0203 (9)	0.0212 (9)	0.0204 (9)	0.0007 (7)	−0.0013 (8)	0.0041 (7)
C4	0.0218 (10)	0.0160 (8)	0.0261 (10)	0.0017 (7)	0.0019 (8)	0.0038 (7)
C5	0.0193 (9)	0.0146 (8)	0.0222 (9)	0.0002 (7)	0.0014 (7)	−0.0002 (7)
C6	0.0172 (8)	0.0150 (8)	0.0137 (8)	−0.0003 (6)	0.0034 (7)	−0.0005 (6)
C7	0.0170 (8)	0.0136 (7)	0.0143 (8)	0.0000 (6)	0.0050 (7)	−0.0012 (6)
C8	0.0138 (8)	0.0128 (7)	0.0107 (7)	−0.0004 (6)	0.0036 (6)	−0.0010 (6)
C9	0.0164 (8)	0.0137 (7)	0.0142 (7)	−0.0011 (6)	0.0059 (6)	−0.0014 (6)
C10	0.0186 (8)	0.0141 (8)	0.0129 (7)	−0.0038 (6)	0.0050 (7)	−0.0043 (6)
C11	0.0195 (9)	0.0167 (8)	0.0125 (7)	−0.0011 (7)	0.0024 (7)	−0.0011 (6)
C12	0.0203 (9)	0.0137 (8)	0.0138 (8)	−0.0010 (7)	0.0044 (7)	−0.0011 (6)
C13	0.0156 (8)	0.0133 (7)	0.0115 (7)	−0.0011 (6)	0.0058 (6)	−0.0019 (6)
C14	0.0150 (8)	0.0129 (7)	0.0134 (7)	−0.0003 (6)	0.0049 (6)	−0.0007 (6)
C15	0.0176 (8)	0.0135 (7)	0.0115 (7)	−0.0009 (6)	0.0059 (6)	−0.0008 (6)
C16	0.0193 (9)	0.0133 (8)	0.0152 (8)	0.0003 (6)	0.0063 (7)	0.0003 (6)
C17	0.0215 (9)	0.0113 (7)	0.0210 (9)	0.0007 (7)	0.0096 (7)	0.0009 (6)
C18	0.0222 (9)	0.0134 (8)	0.0180 (8)	−0.0036 (7)	0.0075 (7)	−0.0040 (6)
C19	0.0205 (9)	0.0150 (8)	0.0126 (7)	−0.0029 (7)	0.0052 (7)	−0.0030 (6)
C20	0.0165 (8)	0.0125 (7)	0.0134 (7)	−0.0007 (6)	0.0073 (6)	−0.0014 (6)
O6	0.0196 (6)	0.0164 (6)	0.0120 (6)	0.0000 (5)	0.0058 (5)	0.0006 (5)
O1W	0.0181 (7)	0.0288 (8)	0.0123 (6)	−0.0024 (6)	0.0046 (5)	0.0010 (6)
O5	0.0249 (8)	0.0265 (8)	0.0253 (7)	0.0055 (6)	0.0093 (6)	0.0059 (6)
N4	0.0217 (8)	0.0207 (8)	0.0197 (8)	0.0021 (6)	0.0099 (7)	0.0001 (6)
C21	0.0229 (10)	0.0222 (9)	0.0262 (10)	0.0029 (8)	0.0120 (8)	0.0009 (8)
C22	0.0294 (11)	0.0281 (10)	0.0262 (10)	0.0088 (9)	0.0146 (9)	0.0024 (8)
C23	0.0290 (11)	0.0268 (10)	0.0200 (9)	0.0002 (8)	0.0110 (8)	0.0002 (8)

Geometric parameters (Å, º) top

Mn1—O2	1.8557 (13)	C9—H9	0.9300
Mn1—O1	1.8875 (13)	C10—C11	1.391 (3)
Mn1—N2	1.9750 (15)	C11—C12	1.385 (3)
Mn1—N1	1.9782 (15)	C11—H11	0.9300
Mn1—O1W	2.2431 (15)	C12—C13	1.408 (3)
Mn1—O6ⁱ	2.3448 (14)	C12—H12	0.9300
Br1—C17	1.8977 (18)	C14—O6	1.258 (2)
Br2—C4	1.895 (2)	C14—C15	1.493 (2)
O1—C1	1.317 (2)	C15—C16	1.406 (2)
O2—C20	1.331 (2)	C15—C20	1.412 (2)
O3—N3	1.233 (2)	C16—C17	1.383 (3)
O4—N3	1.224 (2)	C16—H16	0.9300
N1—C7	1.301 (2)	C17—C18	1.389 (3)
N1—C8	1.425 (2)	C18—C19	1.373 (3)
N2—C14	1.365 (2)	C18—H18	0.9300
N2—C13	1.410 (2)	C19—C20	1.407 (2)
N3—C10	1.460 (2)	C19—H19	0.9300
C1—C2	1.412 (3)	O6—Mn1ⁱⁱ	2.3448 (14)
C1—C6	1.421 (3)	O1W—H1W2	0.72 (4)
C2—C3	1.375 (3)	O1W—H2W2	0.77 (3)
C2—H2	0.9300	O5—C21	1.240 (3)
C3—C4	1.398 (3)	N4—C21	1.331 (3)
C3—H3	0.9300	N4—C22	1.448 (3)
C4—C5	1.368 (3)	N4—C23	1.458 (3)
C5—C6	1.412 (3)	C21—H21	0.9300
C5—H5	0.9300	C22—H22A	0.9600
C6—C7	1.430 (3)	C22—H22B	0.9600
C7—H7	0.9300	C22—H22C	0.9600
C8—C9	1.387 (2)	C23—H23A	0.9600
C8—C13	1.413 (2)	C23—H23B	0.9600
C9—C10	1.380 (3)	C23—H23C	0.9600

O2—Mn1—O1	88.57 (6)	C9—C10—N3	118.59 (16)
O2—Mn1—N2	94.63 (6)	C11—C10—N3	118.96 (16)
O1—Mn1—N2	175.06 (6)	C12—C11—C10	118.98 (17)
O2—Mn1—N1	177.72 (6)	C12—C11—H11	120.5
O1—Mn1—N1	93.71 (6)	C10—C11—H11	120.5
N2—Mn1—N1	83.10 (6)	C11—C12—C13	120.50 (17)
O2—Mn1—O1W	91.93 (6)	C11—C12—H12	119.8
O1—Mn1—O1W	86.45 (6)	C13—C12—H12	119.8
N2—Mn1—O1W	89.68 (6)	C12—C13—N2	125.44 (16)
N1—Mn1—O1W	88.22 (6)	C12—C13—C8	118.51 (16)
O2—Mn1—O6ⁱ	92.60 (5)	N2—C13—C8	115.98 (15)
O1—Mn1—O6ⁱ	85.96 (5)	O6—C14—N2	122.76 (16)
N2—Mn1—O6ⁱ	97.63 (6)	O6—C14—C15	118.47 (16)
N1—Mn1—O6ⁱ	87.56 (6)	N2—C14—C15	118.77 (15)
O1W—Mn1—O6ⁱ	171.06 (5)	C16—C15—C20	118.88 (16)
C1—O1—Mn1	128.16 (12)	C16—C15—C14	115.91 (15)
C20—O2—Mn1	127.29 (11)	C20—C15—C14	125.18 (16)
C7—N1—C8	122.21 (15)	C17—C16—C15	120.29 (17)
C7—N1—Mn1	124.56 (13)	C17—C16—H16	119.9
C8—N1—Mn1	113.05 (11)	C15—C16—H16	119.9
C14—N2—C13	120.16 (15)	C16—C17—C18	121.12 (17)
C14—N2—Mn1	123.06 (12)	C16—C17—Br1	120.75 (15)
C13—N2—Mn1	113.00 (11)	C18—C17—Br1	118.11 (14)
O4—N3—O3	123.46 (17)	C19—C18—C17	119.14 (17)
O4—N3—C10	118.37 (17)	C19—C18—H18	120.4
O3—N3—C10	118.17 (16)	C17—C18—H18	120.4
O1—C1—C2	117.94 (16)	C18—C19—C20	121.56 (17)
O1—C1—C6	123.76 (16)	C18—C19—H19	119.2
C2—C1—C6	118.30 (17)	C20—C19—H19	119.2
C3—C2—C1	120.85 (18)	O2—C20—C19	116.61 (16)
C3—C2—H2	119.6	O2—C20—C15	124.49 (16)
C1—C2—H2	119.6	C19—C20—C15	118.89 (16)
C2—C3—C4	120.02 (19)	C14—O6—Mn1ⁱⁱ	116.75 (12)
C2—C3—H3	120.0	Mn1—O1W—H1W2	110 (3)
C4—C3—H3	120.0	Mn1—O1W—H2W2	114 (2)
C5—C4—C3	121.17 (19)	H1W2—O1W—H2W2	103 (3)
C5—C4—Br2	119.20 (16)	C21—N4—C22	121.24 (18)
C3—C4—Br2	119.63 (16)	C21—N4—C23	121.86 (18)
C4—C5—C6	119.77 (18)	C22—N4—C23	116.90 (17)
C4—C5—H5	120.1	O5—C21—N4	125.0 (2)
C6—C5—H5	120.1	O5—C21—H21	117.5
C5—C6—C1	119.88 (17)	N4—C21—H21	117.5
C5—C6—C7	116.01 (16)	N4—C22—H22A	109.5
C1—C6—C7	124.10 (17)	N4—C22—H22B	109.5
N1—C7—C6	125.38 (17)	H22A—C22—H22B	109.5
N1—C7—H7	117.3	N4—C22—H22C	109.5
C6—C7—H7	117.3	H22A—C22—H22C	109.5
C9—C8—C13	121.17 (16)	H22B—C22—H22C	109.5
C9—C8—N1	124.31 (16)	N4—C23—H23A	109.5
C13—C8—N1	114.51 (15)	N4—C23—H23B	109.5
C10—C9—C8	118.35 (17)	H23A—C23—H23B	109.5
C10—C9—H9	120.8	N4—C23—H23C	109.5
C8—C9—H9	120.8	H23A—C23—H23C	109.5
C9—C10—C11	122.43 (16)	H23B—C23—H23C	109.5

O2—Mn1—O1—C1	175.97 (16)	N1—C8—C9—C10	179.15 (17)
N1—Mn1—O1—C1	−4.03 (16)	C8—C9—C10—C11	1.8 (3)
O1W—Mn1—O1—C1	83.95 (16)	C8—C9—C10—N3	−176.83 (16)
O6ⁱ—Mn1—O1—C1	−91.32 (15)	O4—N3—C10—C9	173.19 (19)
O1—Mn1—O2—C20	−162.27 (15)	O3—N3—C10—C9	−6.8 (3)
N2—Mn1—O2—C20	13.96 (16)	O4—N3—C10—C11	−5.5 (3)
O1W—Mn1—O2—C20	−75.87 (15)	O3—N3—C10—C11	174.50 (18)
O6ⁱ—Mn1—O2—C20	111.84 (15)	C9—C10—C11—C12	−1.8 (3)
O1—Mn1—N1—C7	6.45 (16)	N3—C10—C11—C12	176.82 (17)
N2—Mn1—N1—C7	−169.77 (16)	C10—C11—C12—C13	−0.3 (3)
O1W—Mn1—N1—C7	−79.88 (15)	C11—C12—C13—N2	178.99 (18)
O6ⁱ—Mn1—N1—C7	92.24 (15)	C11—C12—C13—C8	2.2 (3)
O1—Mn1—N1—C8	−178.30 (12)	C14—N2—C13—C12	27.2 (3)
N2—Mn1—N1—C8	5.48 (12)	Mn1—N2—C13—C12	−174.01 (15)
O1W—Mn1—N1—C8	95.38 (12)	C14—N2—C13—C8	−155.88 (16)
O6ⁱ—Mn1—N1—C8	−92.51 (12)	Mn1—N2—C13—C8	2.9 (2)
O2—Mn1—N2—C14	−26.70 (15)	C9—C8—C13—C12	−2.2 (3)
N1—Mn1—N2—C14	153.46 (15)	N1—C8—C13—C12	178.80 (16)
O1W—Mn1—N2—C14	65.22 (14)	C9—C8—C13—N2	−179.31 (16)
O6ⁱ—Mn1—N2—C14	−119.95 (14)	N1—C8—C13—N2	1.7 (2)
O2—Mn1—N2—C13	175.27 (12)	C13—N2—C14—O6	7.6 (3)
N1—Mn1—N2—C13	−4.57 (12)	Mn1—N2—C14—O6	−148.89 (15)
O1W—Mn1—N2—C13	−92.82 (13)	C13—N2—C14—C15	−172.84 (16)
O6ⁱ—Mn1—N2—C13	82.02 (12)	Mn1—N2—C14—C15	30.6 (2)
Mn1—O1—C1—C2	−179.45 (14)	O6—C14—C15—C16	−16.2 (3)
Mn1—O1—C1—C6	0.9 (3)	N2—C14—C15—C16	164.22 (16)
O1—C1—C2—C3	−179.07 (19)	O6—C14—C15—C20	162.02 (18)
C6—C1—C2—C3	0.6 (3)	N2—C14—C15—C20	−17.5 (3)
C1—C2—C3—C4	−0.9 (3)	C20—C15—C16—C17	0.1 (3)
C2—C3—C4—C5	0.3 (4)	C14—C15—C16—C17	178.44 (17)
C2—C3—C4—Br2	179.33 (17)	C15—C16—C17—C18	−2.4 (3)
C3—C4—C5—C6	0.7 (3)	C15—C16—C17—Br1	179.05 (14)
Br2—C4—C5—C6	−178.36 (16)	C16—C17—C18—C19	1.7 (3)
C4—C5—C6—C1	−1.0 (3)	Br1—C17—C18—C19	−179.70 (15)
C4—C5—C6—C7	177.4 (2)	C17—C18—C19—C20	1.3 (3)
O1—C1—C6—C5	−179.99 (18)	Mn1—O2—C20—C19	173.51 (13)
C2—C1—C6—C5	0.4 (3)	Mn1—O2—C20—C15	−5.8 (3)
O1—C1—C6—C7	1.8 (3)	C18—C19—C20—O2	177.07 (17)
C2—C1—C6—C7	−177.89 (18)	C18—C19—C20—C15	−3.6 (3)
C8—N1—C7—C6	179.15 (17)	C16—C15—C20—O2	−177.88 (17)
Mn1—N1—C7—C6	−6.0 (3)	C14—C15—C20—O2	3.9 (3)
C5—C6—C7—N1	−177.16 (19)	C16—C15—C20—C19	2.8 (3)
C1—C6—C7—N1	1.2 (3)	C14—C15—C20—C19	−175.36 (17)
C7—N1—C8—C9	−9.0 (3)	N2—C14—O6—Mn1ⁱⁱ	83.77 (19)
Mn1—N1—C8—C9	175.61 (14)	C15—C14—O6—Mn1ⁱⁱ	−95.75 (17)
C7—N1—C8—C13	169.94 (17)	C22—N4—C21—O5	−1.6 (3)
Mn1—N1—C8—C13	−5.44 (19)	C23—N4—C21—O5	178.2 (2)
C13—C8—C9—C10	0.3 (3)

Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) x, −y+1/2, z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W2···O5ⁱⁱⁱ	0.73 (4)	2.03 (4)	2.736 (2)	163 (4)
O1W—H2W2···O1ⁱⁱ	0.77 (3)	2.55 (3)	3.178 (2)	140 (3)
O1W—H2W2···O2ⁱⁱ	0.77 (3)	2.19 (3)	2.890 (2)	153 (3)
C2—H2···O5^iv	0.93	2.42	3.351 (2)	175
C5—H5···O4^v	0.93	2.49	3.395 (3)	166
C7—H7···O3^v	0.93	2.60	3.509 (2)	167
C18—H18···Br2^vi	0.93	2.83	3.449 (2)	125
C23—H23A···O5ⁱ	0.96	2.40	3.350 (3)	170

Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) x, −y+1/2, z+1/2; (iii) x−1, −y+1/2, z−1/2; (iv) x−1, y, z−1; (v) −x+1, −y+1, −z+3; (vi) −x, y−1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	[Mn(C₂₀H₁₀Br₂N₃O₅)(H₂O)]·C₃H₇NO
M_r	678.18
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	11.0746 (6), 24.9781 (13), 9.5563 (5)
β (°)	114.658 (1)
V (Å³)	2402.4 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.93
Crystal size (mm)	0.52 × 0.17 × 0.11

Data collection
Diffractometer	Bruker APEXII DUO CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.234, 0.672
No. of measured, independent and observed [I > 2σ(I)] reflections	27005, 8188, 6617
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.742

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.085, 1.02
No. of reflections	8188
No. of parameters	344
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.85, −0.62

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W2···O5ⁱ	0.73 (4)	2.03 (4)	2.736 (2)	163 (4)
O1W—H2W2···O1ⁱⁱ	0.77 (3)	2.55 (3)	3.178 (2)	140 (3)
O1W—H2W2···O2ⁱⁱ	0.77 (3)	2.19 (3)	2.890 (2)	153 (3)
C2—H2···O5ⁱⁱⁱ	0.93	2.42	3.351 (2)	175
C5—H5···O4^iv	0.93	2.49	3.395 (3)	166
C7—H7···O3^iv	0.93	2.60	3.509 (2)	167
C18—H18···Br2^v	0.93	2.83	3.449 (2)	125
C23—H23A···O5^vi	0.96	2.40	3.350 (3)	170

Symmetry codes: (i) x−1, −y+1/2, z−1/2; (ii) x, −y+1/2, z+1/2; (iii) x−1, y, z−1; (iv) −x+1, −y+1, −z+3; (v) −x, y−1/2, −z+3/2; (vi) x, −y+1/2, z−1/2.

Footnotes

‡Thomson Reuters ResearcherID: A-3561-2009.

Acknowledgements

AMF, TSG and HO thank the Malaysian Government and Universiti Sains Malaysia (USM) for the RU research grant (1001/PKIMIA/815002). AMF thanks Naser Taha and Hema for their help. HKF and MH thanks the Malaysian Government and USM for the Research University Grant No. 1001/PFIZIK/811160. MH also thanks USM for a post-doctoral research fellowship.

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