Diaqua­bis­(4-bromo­benzoato-κO)bis­(N,N-diethyl­nicotinamide-κN1)manganese(II)

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

doi:10.1107/S1600536811031412

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 9| September 2011| Pages m1209-m1210

doi:10.1107/S1600536811031412

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Diaquabis(4-bromobenzoato-κO)bis(N,N-diethylnicotinamide-κN¹)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 3 August 2011; accepted 3 August 2011; online 6 August 2011)

In the crystal structure of the title Mn^II complex, [Mn(C₇H₄BrO₂)₂(C₁₀H₁₄N₂O)₂(H₂O)₂], the Mn^II cation is located on an inversion center and coordinated by two diethylnicotinamide (DENA) ligands, two 4-bromobenzoate (PBB) anions and two water molecules in a distorted octahedral geometry. The dihedral angle between the carboxylate group and the adjacent benzene ring is 3.25 (14)°. In the molecule, the pyridine ring and the benzene ring are oriented at a dihedral angle of 77.24 (5)°. In the crystal, intermolecular C—H⋯O hydrogen bonds link the molecules into a two-dimensional network. Weak intermolecular C—H⋯O hydrogen bonds and π–π interactions between the pyridine rings of neighbouring molecules [centroid–centroid distance = 3.537 (1) Å] further consolidate the crystal packing.

Related literature

For literature on 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. (1996 , 2009a ,b ); Hökelek & Necefoğlu (1998 , 2007 ); Necefoğlu et al. (2011 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

[Mn(C₇H₄BrO₂)₂(C₁₀H₁₄N₂O)₂(H₂O)₂]
M_r = 847.46
Triclinic, $[P \overline 1]$
a = 7.2939 (2) Å
b = 8.5130 (2) Å
c = 16.1252 (4) Å
α = 83.970 (3)°
β = 79.529 (3)°
γ = 68.031 (2)°
V = 912.34 (4) Å³
Z = 1
Mo Kα radiation
μ = 2.61 mm⁻¹
T = 100 K
0.35 × 0.25 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.462, T_max = 0.594
16194 measured reflections
4616 independent reflections
4127 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.026
wR(F²) = 0.073
S = 1.09
4616 reflections
233 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H41⋯O2	0.86 (3)	1.82 (3)	2.6606 (18)	165 (3)
O4—H42⋯O3	0.82 (2)	1.92 (3)	2.742 (2)	166 (3)
C6—H6⋯O2ⁱ	0.93	2.30	3.168 (3)	155
C10—H10⋯O2	0.93	2.44	3.353 (2)	168
Symmetry code: (i) x+1, y, z.

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/S1600536811031412/xu5285sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811031412/xu5285Isup2.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 asymmetric unit of the title mononuclear Mn^II complex, (Fig. 1), contains one-half molecule, the Mn^II atom being located on an inversion center. It consists of two N,N-diethylnicotinamide (DENA), two 4-bromobenzoate (PBB) ligands and two coordinated water molecules, all ligands coordinating in a monodentate manner. The crystal structures of similar omplexes of Cu^II, Co^II, Ni^II, Mn^II and Zn^II ions, [Cu(C₇H₅O₂)₂(C₁₀H₁₄N₂O)₂] (Hökelek et al., 1996), [Co(C₆H₆N₂O)₂(C₇H₄NO₄)₂(H₂O)₂] (Hökelek & Necefoğlu, 1998), [Co(C₉H₉O₂)₂(C₁₀H₁₄N₂O)₂(H₂O)₂] (Necefoğlu et al., 2011), [Ni(C₇H₄ClO₂)₂(C₆H₆N₂O)₂(H₂O)₂] (Hökelek et al., 2009a), [Mn(C₉H₁₀NO₂)₂(H₂O)₄].2H₂O (Hökelek & Necefoğlu, 2007) and [Zn(C₇H₄BrO₂)₂(C₆H₆N₂O)₂(H₂O)₂] (Hökelek et al., 2009b) have also been reported. In the copper(II) complex mentioned above the two benzoate ions coordinate to the Cu^II atom as bidentate ligands, while in the other structures all the ligands coordinate in a monodentate manner.

In the title complex, the four symmetry related O atoms (O1, O1', O4 and O4') in the equatorial plane around the Mn^II ion form a slightly distorted square-planar arrangement, while the slightly distorted octahedral coordination is completed by the two N atoms of the DENA ligands (N1 and N1') in the axial positions. The intramolecular O—H···O hydrogen bonds (Table 1, Fig. 1) link the water molecules to the carboxylate oxygens. The near equalities of the C1—O1 [1.266 (2) Å] and C1—O2 [1.256 (2) Å] bonds in the carboxylate groups indicate delocalized bonding arrangements, rather than localized single and double bonds. The Mn—O bond lengths are 2.1542 (12) Å (for benzoate oxygen) and 2.2088 (13) Å (for water oxygen), and the Mn—N bond length is 2.2632 (14) Å, close to standard values (Allen et al., 1987). The Mn atom is displaced out of the mean-plane of the carboxylate group (O1/C1/O2) by 0.9729 (1) Å. The dihedral angle between the planar carboxylate group and the adjacent benzene ring A (C2—C7) is 3.25 (14)°. The benzene A (C2—C7) and the pyridine B (N1/C8—C12) rings are oriented at a dihedral angle of A/B = 77.24 (5)°.

In the crystal, intermolecular O—H···O hydrogen bonds (Table 1, Fig. 2) link the molecules into a two-dimensional network. Weak intermolecular C—H···O hydrogen bonds (Table 1) and π···π interactions between the pyridine rings, Cg2—Cg2ⁱ, of neighbouring molecules [centroid-centroid distance = 3.537 (1) Å; symmetry code: (i) -x, 1 - y, 1 - z; Cg2 is the centroid of the ring B (N1/C8—C12)] further consolidate the crystal packing.

Related literature top

For literature on 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. (1996, 2009a,b); Hökelek & Necefoğlu (1998, 2007); Necefoğlu et al. (2011). For bond-length data, see: Allen et al. (1987).

Experimental top

The title compound was prepared by the reaction of MnSO₄.H₂O (0.85 g, 5 mmol) in H₂O (25 ml) and DENA (1.78 g, 10 mmol) in H₂O (25 ml) with sodium 4-bromobenzoate (2.23 g, 10 mmol) in H₂O (100 ml) at room temperature. The mixture was filtered and set aside to crystallize at ambient temperature for two weeks, 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]. Hydrogen bonds are shown as dashed lines.
	Fig. 2. A view of the crystal packing of the title compound. Only the intermolecular O—H···O hydrogen bonds are shown as dashed lines. [H-atoms not involved in hydrogen bonding have been omitted for clarity].

Diaquabis(4-bromobenzoato-κO)bis(N,N- diethylnicotinamide-κN¹)manganese(II) top

Crystal data top

[Mn(C₇H₄BrO₂)₂(C₁₀H₁₄N₂O)₂(H₂O)₂]	Z = 1
M_r = 847.46	F(000) = 431
Triclinic, P1	D_x = 1.542 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.2939 (2) Å	Cell parameters from 9256 reflections
b = 8.5130 (2) Å	θ = 2.6–28.5°
c = 16.1252 (4) Å	µ = 2.61 mm⁻¹
α = 83.970 (3)°	T = 100 K
β = 79.529 (3)°	Block, colorless
γ = 68.031 (2)°	0.35 × 0.25 × 0.20 mm
V = 912.34 (4) Å³

Data collection top

Bruker Kappa APEXII CCD area-detector diffractometer	4616 independent reflections
Radiation source: fine-focus sealed tube	4127 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
ϕ and ω scans	θ_max = 28.7°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −9→8
T_min = 0.462, T_max = 0.594	k = −11→11
16194 measured reflections	l = −21→21

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)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.073	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ²(F_o²) + (0.0308P)² + 0.6418P] where P = (F_o² + 2F_c²)/3
4616 reflections	(Δ/σ)_max = 0.001
233 parameters	Δρ_max = 0.42 e Å⁻³
2 restraints	Δρ_min = −0.39 e Å⁻³

Crystal data top

[Mn(C₇H₄BrO₂)₂(C₁₀H₁₄N₂O)₂(H₂O)₂]	γ = 68.031 (2)°
M_r = 847.46	V = 912.34 (4) Å³
Triclinic, P1	Z = 1
a = 7.2939 (2) Å	Mo Kα radiation
b = 8.5130 (2) Å	µ = 2.61 mm⁻¹
c = 16.1252 (4) Å	T = 100 K
α = 83.970 (3)°	0.35 × 0.25 × 0.20 mm
β = 79.529 (3)°

Data collection top

Bruker Kappa APEXII CCD area-detector diffractometer	4616 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	4127 reflections with I > 2σ(I)
T_min = 0.462, T_max = 0.594	R_int = 0.029
16194 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.026	2 restraints
wR(F²) = 0.073	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	Δρ_max = 0.42 e Å⁻³
4616 reflections	Δρ_min = −0.39 e Å⁻³
233 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
Br1	−0.75487 (3)	−0.83337 (3)	0.028844 (11)	0.02549 (7)
Mn1	−1.5000	−1.0000	0.5000	0.01072 (8)
O1	−1.38994 (18)	−0.87032 (15)	0.39214 (7)	0.0149 (2)
O2	−1.58179 (18)	−0.86624 (16)	0.29746 (8)	0.0162 (2)
O3	−2.33701 (19)	−0.67456 (16)	0.62449 (8)	0.0180 (3)
O4	−1.73146 (19)	−1.01296 (16)	0.43251 (8)	0.0164 (2)
H41	−1.695 (5)	−0.972 (4)	0.3842 (14)	0.061 (10)*
H42	−1.724 (4)	−1.107 (2)	0.4215 (17)	0.039 (7)*
N1	−1.7301 (2)	−0.75479 (18)	0.55238 (9)	0.0135 (3)
N2	−2.3337 (2)	−0.57656 (18)	0.74841 (9)	0.0154 (3)
C1	−1.4231 (3)	−0.8666 (2)	0.31747 (10)	0.0132 (3)
C2	−1.2580 (3)	−0.8627 (2)	0.24697 (10)	0.0122 (3)
C3	−1.2803 (3)	−0.8670 (2)	0.16323 (11)	0.0156 (3)
H3	−1.3960	−0.8757	0.1511	0.019*
C4	−1.1308 (3)	−0.8583 (2)	0.09777 (11)	0.0167 (3)
H4	−1.1453	−0.8606	0.0418	0.020*
C5	−0.9600 (3)	−0.8463 (2)	0.11768 (11)	0.0159 (3)
C6	−0.9306 (3)	−0.8470 (2)	0.20023 (11)	0.0158 (3)
H6	−0.8128	−0.8420	0.2121	0.019*
C7	−1.0816 (3)	−0.8554 (2)	0.26481 (10)	0.0145 (3)
H7	−1.0647	−0.8561	0.3207	0.017*
C8	−1.7011 (3)	−0.6072 (2)	0.54066 (10)	0.0142 (3)
H8	−1.5813	−0.6055	0.5095	0.017*
C9	−1.8416 (3)	−0.4569 (2)	0.57292 (11)	0.0158 (3)
H9	−1.8164	−0.3567	0.5635	0.019*
C10	−2.0201 (3)	−0.4589 (2)	0.61946 (11)	0.0148 (3)
H10	−2.1162	−0.3603	0.6426	0.018*
C11	−2.0531 (3)	−0.6112 (2)	0.63100 (10)	0.0131 (3)
C12	−1.9050 (3)	−0.7549 (2)	0.59574 (10)	0.0137 (3)
H12	−1.9281	−0.8561	0.6025	0.016*
C13	−2.2514 (3)	−0.6235 (2)	0.66923 (11)	0.0138 (3)
C14	−2.5372 (3)	−0.5766 (2)	0.77833 (12)	0.0203 (4)
H14A	−2.6183	−0.5272	0.7341	0.024*
H14B	−2.5964	−0.5054	0.8266	0.024*
C15	−2.5430 (3)	−0.7523 (2)	0.80336 (13)	0.0261 (4)
H15A	−2.6787	−0.7433	0.8232	0.039*
H15B	−2.4636	−0.8021	0.8474	0.039*
H15C	−2.4902	−0.8223	0.7553	0.039*
C16	−2.2354 (3)	−0.5264 (2)	0.80695 (11)	0.0192 (4)
H16A	−2.3176	−0.4126	0.8246	0.023*
H16B	−2.1082	−0.5237	0.7775	0.023*
C17	−2.1988 (4)	−0.6441 (3)	0.88473 (14)	0.0370 (5)
H17A	−2.1306	−0.6066	0.9195	0.056*
H17B	−2.1182	−0.7572	0.8678	0.056*
H17C	−2.3246	−0.6427	0.9160	0.056*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.02017 (11)	0.04066 (12)	0.01687 (10)	−0.01507 (9)	0.00437 (7)	−0.00377 (8)
Mn1	0.00970 (17)	0.01062 (15)	0.01099 (16)	−0.00281 (13)	−0.00032 (13)	−0.00241 (12)
O1	0.0165 (6)	0.0158 (6)	0.0132 (5)	−0.0070 (5)	−0.0006 (5)	−0.0021 (4)
O2	0.0120 (6)	0.0194 (6)	0.0172 (6)	−0.0056 (5)	−0.0026 (5)	−0.0003 (5)
O3	0.0163 (6)	0.0198 (6)	0.0203 (6)	−0.0083 (5)	−0.0027 (5)	−0.0043 (5)
O4	0.0175 (6)	0.0174 (6)	0.0167 (6)	−0.0085 (5)	−0.0031 (5)	−0.0022 (5)
N1	0.0128 (7)	0.0138 (6)	0.0136 (6)	−0.0042 (5)	−0.0019 (5)	−0.0025 (5)
N2	0.0155 (7)	0.0146 (6)	0.0152 (7)	−0.0055 (6)	0.0013 (6)	−0.0024 (5)
C1	0.0151 (8)	0.0084 (7)	0.0138 (7)	−0.0024 (6)	0.0003 (6)	−0.0022 (5)
C2	0.0121 (8)	0.0104 (7)	0.0130 (7)	−0.0026 (6)	−0.0011 (6)	−0.0021 (6)
C3	0.0140 (8)	0.0174 (8)	0.0158 (8)	−0.0056 (7)	−0.0024 (6)	−0.0022 (6)
C4	0.0183 (9)	0.0187 (8)	0.0124 (7)	−0.0057 (7)	−0.0014 (7)	−0.0030 (6)
C5	0.0142 (8)	0.0176 (8)	0.0151 (8)	−0.0061 (7)	0.0018 (6)	−0.0023 (6)
C6	0.0126 (8)	0.0178 (8)	0.0181 (8)	−0.0065 (7)	−0.0031 (6)	−0.0009 (6)
C7	0.0179 (9)	0.0138 (7)	0.0125 (7)	−0.0062 (7)	−0.0022 (6)	−0.0019 (6)
C8	0.0126 (8)	0.0157 (7)	0.0150 (7)	−0.0063 (6)	−0.0014 (6)	−0.0011 (6)
C9	0.0188 (9)	0.0133 (7)	0.0172 (8)	−0.0076 (7)	−0.0028 (7)	−0.0017 (6)
C10	0.0158 (8)	0.0112 (7)	0.0155 (7)	−0.0026 (6)	−0.0009 (6)	−0.0040 (6)
C11	0.0129 (8)	0.0154 (7)	0.0114 (7)	−0.0053 (6)	−0.0019 (6)	−0.0020 (6)
C12	0.0141 (8)	0.0120 (7)	0.0150 (7)	−0.0048 (6)	−0.0019 (6)	−0.0014 (6)
C13	0.0132 (8)	0.0095 (7)	0.0165 (8)	−0.0021 (6)	−0.0008 (6)	−0.0016 (6)
C14	0.0173 (9)	0.0177 (8)	0.0233 (9)	−0.0068 (7)	0.0066 (7)	−0.0053 (7)
C15	0.0253 (10)	0.0219 (9)	0.0304 (10)	−0.0119 (8)	0.0064 (8)	−0.0034 (8)
C16	0.0248 (10)	0.0197 (8)	0.0146 (8)	−0.0098 (7)	−0.0015 (7)	−0.0034 (6)
C17	0.0505 (15)	0.0392 (12)	0.0281 (11)	−0.0209 (11)	−0.0191 (11)	0.0106 (9)

Geometric parameters (Å, º) top

Br1—C5	1.9009 (17)	C6—H6	0.9300
Mn1—O1	2.1542 (12)	C7—C2	1.393 (2)
Mn1—O1ⁱ	2.1542 (12)	C7—H7	0.9300
Mn1—O4	2.2088 (13)	C8—C9	1.387 (2)
Mn1—O4ⁱ	2.2089 (13)	C8—H8	0.9300
Mn1—N1	2.2632 (14)	C9—H9	0.9300
Mn1—N1ⁱ	2.2632 (14)	C10—C9	1.385 (2)
O1—C1	1.266 (2)	C10—C11	1.393 (2)
O2—C1	1.256 (2)	C10—H10	0.9300
O3—C13	1.238 (2)	C11—C13	1.503 (2)
O4—H41	0.860 (18)	C12—C11	1.386 (2)
O4—H42	0.823 (17)	C12—H12	0.9300
N1—C8	1.339 (2)	C14—C15	1.521 (2)
N1—C12	1.339 (2)	C14—H14A	0.9700
N2—C13	1.341 (2)	C14—H14B	0.9700
N2—C14	1.475 (2)	C15—H15A	0.9600
N2—C16	1.465 (2)	C15—H15B	0.9600
C1—C2	1.506 (2)	C15—H15C	0.9600
C3—C2	1.395 (2)	C16—C17	1.518 (3)
C3—H3	0.9300	C16—H16A	0.9700
C4—C3	1.391 (2)	C16—H16B	0.9700
C4—C5	1.383 (3)	C17—H17A	0.9600
C4—H4	0.9300	C17—H17B	0.9600
C5—C6	1.385 (2)	C17—H17C	0.9600
C6—C7	1.389 (2)

O1ⁱ—Mn1—O1	180.000 (1)	C6—C7—C2	120.84 (15)
O1—Mn1—O4	90.55 (5)	C6—C7—H7	119.6
O1ⁱ—Mn1—O4	89.45 (5)	N1—C8—C9	122.95 (16)
O1—Mn1—O4ⁱ	89.45 (5)	N1—C8—H8	118.5
O1ⁱ—Mn1—O4ⁱ	90.55 (5)	C9—C8—H8	118.5
O4—Mn1—O4ⁱ	180.00 (5)	C8—C9—H9	120.6
O1—Mn1—N1	92.44 (5)	C10—C9—C8	118.76 (15)
O1ⁱ—Mn1—N1	87.56 (5)	C10—C9—H9	120.6
O1—Mn1—N1ⁱ	87.56 (5)	C9—C10—C11	118.77 (15)
O1ⁱ—Mn1—N1ⁱ	92.44 (5)	C9—C10—H10	120.6
O4—Mn1—N1	87.02 (5)	C11—C10—H10	120.6
O4ⁱ—Mn1—N1	92.98 (5)	C10—C11—C13	123.27 (15)
O4—Mn1—N1ⁱ	92.98 (5)	C12—C11—C10	118.50 (15)
O4ⁱ—Mn1—N1ⁱ	87.02 (5)	C12—C11—C13	117.68 (14)
N1—Mn1—N1ⁱ	180.0	N1—C12—C11	123.06 (15)
C1—O1—Mn1	125.95 (11)	N1—C12—H12	118.5
Mn1—O4—H41	98 (2)	C11—C12—H12	118.5
Mn1—O4—H42	118 (2)	O3—C13—N2	121.63 (16)
H42—O4—H41	103 (3)	O3—C13—C11	117.65 (15)
C8—N1—Mn1	122.84 (11)	N2—C13—C11	120.70 (15)
C12—N1—Mn1	119.21 (11)	N2—C14—C15	113.64 (16)
C12—N1—C8	117.93 (15)	N2—C14—H14A	108.8
C13—N2—C14	117.30 (15)	N2—C14—H14B	108.8
C13—N2—C16	124.64 (15)	C15—C14—H14A	108.8
C16—N2—C14	118.06 (14)	C15—C14—H14B	108.8
O1—C1—C2	117.11 (15)	H14A—C14—H14B	107.7
O2—C1—O1	125.40 (15)	C14—C15—H15A	109.5
O2—C1—C2	117.49 (14)	C14—C15—H15B	109.5
C3—C2—C1	120.22 (15)	C14—C15—H15C	109.5
C7—C2—C1	120.33 (15)	H15A—C15—H15B	109.5
C7—C2—C3	119.45 (15)	H15A—C15—H15C	109.5
C2—C3—H3	119.8	H15B—C15—H15C	109.5
C4—C3—C2	120.44 (16)	N2—C16—C17	113.53 (16)
C4—C3—H3	119.8	N2—C16—H16A	108.9
C3—C4—H4	120.7	N2—C16—H16B	108.9
C5—C4—C3	118.55 (16)	C17—C16—H16A	108.9
C5—C4—H4	120.7	C17—C16—H16B	108.9
C4—C5—Br1	119.00 (13)	H16A—C16—H16B	107.7
C4—C5—C6	122.43 (16)	C16—C17—H17A	109.5
C6—C5—Br1	118.55 (13)	C16—C17—H17B	109.5
C5—C6—C7	118.23 (16)	C16—C17—H17C	109.5
C5—C6—H6	120.9	H17A—C17—H17B	109.5
C7—C6—H6	120.9	H17A—C17—H17C	109.5
C2—C7—H7	119.6	H17B—C17—H17C	109.5

O4—Mn1—O1—C1	−18.28 (14)	C14—N2—C16—C17	63.1 (2)
O4ⁱ—Mn1—O1—C1	161.72 (14)	O1—C1—C2—C3	176.80 (15)
N1—Mn1—O1—C1	−105.33 (14)	O1—C1—C2—C7	−3.0 (2)
N1ⁱ—Mn1—O1—C1	74.67 (14)	O2—C1—C2—C3	−3.0 (2)
O1—Mn1—N1—C8	−31.20 (13)	O2—C1—C2—C7	177.19 (14)
O1ⁱ—Mn1—N1—C8	148.80 (13)	C4—C3—C2—C1	178.07 (15)
O1—Mn1—N1—C12	147.52 (12)	C4—C3—C2—C7	−2.1 (2)
O1ⁱ—Mn1—N1—C12	−32.48 (12)	C3—C4—C5—Br1	−179.73 (13)
O4—Mn1—N1—C8	−121.63 (13)	C3—C4—C5—C6	1.7 (3)
O4ⁱ—Mn1—N1—C8	58.37 (13)	C5—C4—C3—C2	0.3 (3)
O4—Mn1—N1—C12	57.09 (13)	Br1—C5—C6—C7	179.61 (13)
O4ⁱ—Mn1—N1—C12	−122.91 (13)	C4—C5—C6—C7	−1.9 (3)
Mn1—O1—C1—O2	33.9 (2)	C5—C6—C7—C2	−0.1 (2)
Mn1—O1—C1—C2	−145.88 (11)	C6—C7—C2—C1	−178.19 (15)
Mn1—N1—C8—C9	−179.79 (13)	C6—C7—C2—C3	2.0 (2)
C12—N1—C8—C9	1.5 (2)	N1—C8—C9—C10	0.1 (3)
Mn1—N1—C12—C11	179.07 (12)	C11—C10—C9—C8	−1.0 (3)
C8—N1—C12—C11	−2.1 (2)	C9—C10—C11—C12	0.4 (2)
C14—N2—C13—O3	−4.2 (2)	C9—C10—C11—C13	−170.84 (16)
C14—N2—C13—C11	174.13 (15)	C10—C11—C13—O3	117.15 (18)
C16—N2—C13—O3	175.47 (16)	C10—C11—C13—N2	−61.2 (2)
C16—N2—C13—C11	−6.2 (2)	C12—C11—C13—O3	−54.2 (2)
C13—N2—C14—C15	78.2 (2)	C12—C11—C13—N2	127.49 (17)
C16—N2—C14—C15	−101.50 (19)	N1—C12—C11—C10	1.2 (3)
C13—N2—C16—C17	−116.6 (2)	N1—C12—C11—C13	172.96 (15)

Symmetry code: (i) −x−3, −y−2, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H41···O2	0.86 (3)	1.82 (3)	2.6606 (18)	165 (3)
O4—H42···O3	0.82 (2)	1.92 (3)	2.742 (2)	166 (3)
C6—H6···O2ⁱⁱ	0.93	2.30	3.168 (3)	155
C10—H10···O2	0.93	2.44	3.353 (2)	168

Symmetry code: (ii) x+1, y, z.

Experimental details

Crystal data
Chemical formula	[Mn(C₇H₄BrO₂)₂(C₁₀H₁₄N₂O)₂(H₂O)₂]
M_r	847.46
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	7.2939 (2), 8.5130 (2), 16.1252 (4)
α, β, γ (°)	83.970 (3), 79.529 (3), 68.031 (2)
V (Å³)	912.34 (4)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	2.61
Crystal size (mm)	0.35 × 0.25 × 0.20

Data collection
Diffractometer	Bruker Kappa APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.462, 0.594
No. of measured, independent and observed [I > 2σ(I)] reflections	16194, 4616, 4127
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.675

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.026, 0.073, 1.09
No. of reflections	4616
No. of parameters	233
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.42, −0.39

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).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H41···O2	0.86 (3)	1.82 (3)	2.6606 (18)	165 (3)
O4—H42···O3	0.82 (2)	1.92 (3)	2.742 (2)	166 (3)
C6—H6···O2ⁱ	0.93	2.30	3.168 (3)	155
C10—H10···O2	0.93	2.44	3.353 (2)	168

Symmetry code: (i) x+1, y, z.

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 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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