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Acta Crystallogr Sect E Struct Rep Online. 2010 May 1; 66(Pt 5): m490–m491.
Published online 2010 April 10. doi:  10.1107/S1600536810011815
PMCID: PMC2979200

Diaqua­bis(4-methyl­benzoato-κO)bis­(nicotinamide-κN 1)manganese(II)

Abstract

In the mononuclear title complex, [Mn(C8H7O2)2(C6H6N2O)2(H2O)2], the MnII ion is located on a crystallographic inversion center. The asymmetric unit contains one 4-methyl­benzoate anion, one nicotinamide (NA) ligand and one coordinated water mol­ecule. The four O atoms in the equatorial plane around the MnII ion form a slightly distorted square-planar arrangement, while the slightly distorted octa­hedral coordination is completed by the two pyridine N atoms of the NA ligands in the axial positions. The dihedral angle between the carboxyl­ate group and the attached benzene ring is 9.01 (7)°, while the pyridine and benzene rings are oriented at a dihedral angle of 42.44 (5)°. In the crystal structure, inter­molecular O—H(...)O, N—H(...)O and C—H(...)O hydrogen bonds, and O—H(...)π and C—H(...)π inter­actions link the mol­ecules into a two-dimensional network parallel to (001).

Related literature

For niacin, see: Krishnamachari (1974 [triangle]), and for the nicotinic acid derivative N,N-diethyl­nicotinamide, see: Bigoli et al. (1972 [triangle]). For related structures, see: Hökelek et al. (1996 [triangle], 2009a [triangle],b [triangle],c [triangle]); Hökelek & Necefoğlu (1998 [triangle]); Necefoğlu et al. (2010 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-0m490-scheme1.jpg

Experimental

Crystal data

  • [Mn(C8H7O2)2(C6H6N2O)2(H2O)2]
  • M r = 605.51
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-0m490-efi1.jpg
  • a = 7.3289 (2) Å
  • b = 10.1768 (3) Å
  • c = 10.6292 (3) Å
  • α = 66.852 (2)°
  • β = 78.232 (4)°
  • γ = 70.206 (3)°
  • V = 683.58 (4) Å3
  • Z = 1
  • Mo Kα radiation
  • μ = 0.54 mm−1
  • T = 100 K
  • 0.38 × 0.25 × 0.19 mm

Data collection

  • Bruker Kappa APEXII CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2005 [triangle]) T min = 0.649, T max = 0.698
  • 11619 measured reflections
  • 3297 independent reflections
  • 3022 reflections with I > 2σ(I)
  • R int = 0.028

Refinement

  • R[F 2 > 2σ(F 2)] = 0.035
  • wR(F 2) = 0.099
  • S = 1.08
  • 3297 reflections
  • 204 parameters
  • 3 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.73 e Å−3
  • Δρmin = −0.38 e Å−3

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

Table 1
Selected bond lengths (Å)
Table 2
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810011815/ci5069sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810011815/ci5069Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

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. 108 T657).

supplementary crystallographic information

Comment

As a part of our ongoing investigation on 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), is a centrosymmetric mononuclear complex, consisting of two nicotinamide (NA) and two 4-methylbenzoate (PMB) ligands and two coordinated water molecules; the MnII ion lies on a centre of symmetry (Fig. 1). The crystal structures of some PMB and/or NA complexes of CuII, CoII, NiII, MnII and ZnII ions, [Cu(C7H5O2)2(C10H14N2O)2], (II) (Hökelek et al., 1996), [Co(C6H6N2O)2(C7H4NO4)2(H2O)2], (III) (Hökelek & Necefoğlu, 1998), [Ni(C7H4ClO2)2(C6H6N2O)2(H2O)2], (IV) (Hökelek et al., 2009a), [Ni(C8H7O2)2(C6H6N2O)2(H2O)2], (V) (Necefoğlu et al., 2010), [Mn(C7H4ClO2)2(C10H14N2O)2(H2O)2], (VI) (Hökelek et al., 2009b) and [Zn(C7H4BrO2)2(C6H6N2O)2(H2O)2], (VII) (Hökelek et al., 2009c) have also been reported. In (II), the two benzoate ions are coordinated to the Cu atom as bidentate ligands, while in other structures all ligands being monodentate.

In the title compound, all ligands are monodentate. The four O atoms (O2, O4, and the symmetry-related atoms, O2', O4') in the equatorial plane around the MnII atom form a slightly distorted square-planar arrangement, while the slightly distorted octahedral coordination is completed by the two N atoms of the NA ligands (N1, N1') in the axial positions (Fig. 1). The near equality of the C1—O1 [1.2466 (19) Å] and C1—O2 [1.2690 (18) Å] bonds in the carboxylate group indicates a delocalized bonding arrangement, rather than localized single and double bonds. The average Mn—O bond length is 2.148 (1) Å (Table 1). The dihedral angle between the planar carboxylate group (O1/O2/C1) and the benzene ring A (C2—C7) is 9.01 (7)°, while that between rings A and B (N1/C9—C13) is 42.44 (5)°.

In the crystal structure, intermolecular O—H···O, N—H···O and C—H···O hydrogen bonds (Table 2) link the molecules into a two-dimensional network parallel to the (001). Weak O—H···π and C—H···π interactions involving the pyridine and benzene rings are also observed (Table 2).

Experimental

The title compound was prepared by the reaction of MnSO4.H2O (0.84 g, 5 mmol) in H2O (10 ml) and NA (1.22 g, 10 mmol) in H2O (10 ml) with sodium 4-methylbenzoate (1.58 g, 10 mmol) in H2O (150 ml). The mixture was filtered and set aside to crystallize at ambient temperature for one month, giving colourless single crystals.

Refinement

H atoms of the NH2 group (H21 and H22) and water molecules (H41 and H42) were located in a difference Fourier map and refined isotropically; the water H atoms were refined with O–H and H···H distance restraints. The remaining H atoms were positioned geometrically with C–H = 0.93 and 0.96 Å, for aromatic and methyl H atoms, respectively, and constrained to ride on their parent atoms, with Uiso(H) = xUeq(C), where x = 1.5 for methyl H and x = 1.2 for aromatic H atoms.

Figures

Fig. 1.
The molecular structure of the title compound, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Primed atoms are generated by the symmetry operator:(') -x, -y, - z.

Crystal data

[Mn(C8H7O2)2(C6H6N2O)2(H2O)2]Z = 1
Mr = 605.51F(000) = 315
Triclinic, P1Dx = 1.471 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.3289 (2) ÅCell parameters from 8087 reflections
b = 10.1768 (3) Åθ = 2.5–28.4°
c = 10.6292 (3) ŵ = 0.54 mm1
α = 66.852 (2)°T = 100 K
β = 78.232 (4)°Block, colourless
γ = 70.206 (3)°0.38 × 0.25 × 0.19 mm
V = 683.58 (4) Å3

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer3297 independent reflections
Radiation source: fine-focus sealed tube3022 reflections with I > 2σ(I)
graphiteRint = 0.028
[var phi] and ω scansθmax = 28.4°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2005)h = −9→9
Tmin = 0.649, Tmax = 0.698k = −11→13
11619 measured reflectionsl = −14→14

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.035Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.099H atoms treated by a mixture of independent and constrained refinement
S = 1.08w = 1/[σ2(Fo2) + (0.058P)2 + 0.3059P] where P = (Fo2 + 2Fc2)/3
3297 reflections(Δ/σ)max = 0.001
204 parametersΔρmax = 0.73 e Å3
3 restraintsΔρmin = −0.38 e Å3

Special details

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 > 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)

xyzUiso*/Ueq
Mn10.00000.00000.00000.01276 (11)
O10.24237 (17)−0.33733 (12)0.25988 (12)0.0207 (2)
O20.16077 (17)−0.08763 (12)0.17238 (12)0.0201 (2)
O30.78404 (16)−0.34130 (13)−0.01469 (13)0.0210 (3)
O40.18323 (19)0.15102 (14)−0.09400 (13)0.0232 (3)
H410.208 (4)0.190 (3)−0.1860 (17)0.064 (9)*
H420.218 (4)0.205 (3)−0.058 (2)0.042 (7)*
N10.21166 (18)−0.15932 (14)−0.10409 (13)0.0143 (3)
N20.84692 (19)−0.50868 (14)−0.11834 (14)0.0167 (3)
H210.810 (3)−0.555 (3)−0.159 (2)0.028 (5)*
H220.958 (4)−0.545 (3)−0.084 (2)0.032 (6)*
C10.2620 (2)−0.21470 (17)0.24423 (15)0.0151 (3)
C20.4196 (2)−0.21314 (16)0.31505 (15)0.0145 (3)
C30.4331 (2)−0.07942 (16)0.31453 (15)0.0164 (3)
H30.34260.00990.27140.020*
C40.5805 (2)−0.07856 (18)0.37770 (16)0.0181 (3)
H40.58710.01150.37670.022*
C50.7191 (2)−0.21079 (19)0.44279 (16)0.0190 (3)
C60.7063 (2)−0.34413 (18)0.44183 (16)0.0203 (3)
H60.7979−0.43330.48390.024*
C70.5589 (2)−0.34546 (17)0.37902 (16)0.0177 (3)
H70.5528−0.43550.37950.021*
C80.8783 (3)−0.2097 (2)0.51214 (18)0.0257 (4)
H8A0.8947−0.11150.47630.039*
H8B0.9977−0.27970.49510.039*
H8C0.8437−0.23710.60920.039*
C90.3975 (2)−0.22336 (16)−0.07444 (15)0.0132 (3)
H90.4418−0.1971−0.01420.016*
C100.5280 (2)−0.32707 (16)−0.12893 (15)0.0134 (3)
C110.4623 (2)−0.36415 (17)−0.22143 (16)0.0170 (3)
H110.5453−0.4328−0.26020.020*
C120.2710 (2)−0.29647 (18)−0.25420 (17)0.0198 (3)
H120.2239−0.3182−0.31640.024*
C130.1508 (2)−0.19621 (17)−0.19343 (16)0.0172 (3)
H130.0221−0.1523−0.21530.021*
C140.7300 (2)−0.39401 (16)−0.08365 (15)0.0142 (3)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Mn10.01065 (17)0.01054 (16)0.01760 (17)0.00071 (11)−0.00334 (11)−0.00758 (12)
O10.0252 (6)0.0149 (5)0.0241 (6)−0.0030 (4)−0.0062 (5)−0.0092 (5)
O20.0216 (6)0.0138 (5)0.0243 (6)0.0035 (4)−0.0106 (5)−0.0092 (4)
O30.0160 (5)0.0184 (5)0.0343 (6)0.0021 (4)−0.0096 (5)−0.0174 (5)
O40.0308 (7)0.0236 (6)0.0233 (6)−0.0146 (5)0.0056 (5)−0.0147 (5)
N10.0126 (6)0.0117 (6)0.0177 (6)−0.0003 (4)−0.0030 (5)−0.0061 (5)
N20.0120 (6)0.0146 (6)0.0258 (7)0.0020 (5)−0.0057 (5)−0.0125 (5)
C10.0149 (7)0.0150 (7)0.0155 (7)0.0004 (5)−0.0019 (5)−0.0091 (6)
C20.0147 (7)0.0137 (7)0.0140 (6)−0.0008 (5)−0.0017 (5)−0.0061 (5)
C30.0175 (7)0.0129 (7)0.0164 (7)−0.0004 (5)−0.0029 (6)−0.0055 (6)
C40.0209 (8)0.0181 (7)0.0173 (7)−0.0059 (6)−0.0014 (6)−0.0080 (6)
C50.0170 (7)0.0245 (8)0.0158 (7)−0.0045 (6)−0.0017 (6)−0.0083 (6)
C60.0182 (7)0.0177 (7)0.0196 (7)0.0026 (6)−0.0066 (6)−0.0053 (6)
C70.0203 (7)0.0124 (7)0.0186 (7)−0.0006 (5)−0.0041 (6)−0.0056 (6)
C80.0199 (8)0.0352 (10)0.0240 (8)−0.0067 (7)−0.0061 (6)−0.0114 (7)
C90.0137 (7)0.0105 (6)0.0160 (6)−0.0017 (5)−0.0027 (5)−0.0060 (5)
C100.0118 (7)0.0101 (6)0.0174 (7)−0.0007 (5)−0.0031 (5)−0.0051 (5)
C110.0146 (7)0.0149 (7)0.0224 (7)0.0015 (5)−0.0042 (6)−0.0110 (6)
C120.0181 (8)0.0194 (7)0.0258 (8)0.0016 (6)−0.0092 (6)−0.0142 (7)
C130.0137 (7)0.0150 (7)0.0229 (7)0.0008 (5)−0.0059 (6)−0.0087 (6)
C140.0127 (7)0.0113 (6)0.0184 (7)−0.0007 (5)−0.0033 (5)−0.0063 (5)

Geometric parameters (Å, °)

Mn1—O22.1036 (11)C4—C31.387 (2)
Mn1—O2i2.1036 (11)C4—C51.396 (2)
Mn1—O42.1924 (12)C4—H40.93
Mn1—O4i2.1924 (12)C5—C81.507 (2)
Mn1—N12.2947 (13)C6—C51.396 (2)
Mn1—N1i2.2947 (13)C6—C71.387 (2)
O1—C11.2466 (19)C6—H60.93
O2—C11.2690 (18)C7—H70.93
O3—C141.2464 (18)C8—H8A0.96
O4—H410.905 (16)C8—H8B0.96
O4—H420.906 (16)C8—H8C0.96
N1—C91.3386 (18)C9—C101.391 (2)
N1—C131.345 (2)C9—H90.93
N2—C141.3283 (19)C11—C101.396 (2)
N2—H210.89 (2)C11—C121.385 (2)
N2—H220.86 (2)C11—H110.93
C1—C21.509 (2)C12—H120.93
C2—C31.395 (2)C13—C121.383 (2)
C2—C71.397 (2)C13—H130.93
C3—H30.93C14—C101.4956 (19)
O2—Mn1—O2i180.00 (4)C3—C4—H4119.5
O2—Mn1—O486.18 (5)C5—C4—H4119.5
O2i—Mn1—O493.82 (5)C4—C5—C8120.94 (15)
O2—Mn1—O4i93.82 (5)C6—C5—C4118.20 (14)
O2i—Mn1—O4i86.18 (5)C6—C5—C8120.86 (15)
O2—Mn1—N1i86.02 (4)C5—C6—H6119.5
O2i—Mn1—N1i93.98 (4)C7—C6—C5120.91 (14)
O2—Mn1—N193.98 (4)C7—C6—H6119.5
O2i—Mn1—N186.02 (4)C2—C7—H7119.6
O4—Mn1—O4i180.00 (5)C6—C7—C2120.74 (14)
O4—Mn1—N1i91.32 (4)C6—C7—H7119.6
O4i—Mn1—N1i88.68 (4)C5—C8—H8A109.5
O4—Mn1—N188.68 (4)C5—C8—H8B109.5
O4i—Mn1—N191.32 (4)C5—C8—H8C109.5
N1i—Mn1—N1180.00 (9)H8A—C8—H8B109.5
C1—O2—Mn1136.86 (10)H8A—C8—H8C109.5
Mn1—O4—H41122.2 (18)H8B—C8—H8C109.5
Mn1—O4—H42129.2 (16)N1—C9—C10123.52 (13)
H42—O4—H41107 (2)N1—C9—H9118.2
C9—N1—Mn1121.52 (10)C10—C9—H9118.2
C9—N1—C13117.56 (13)C9—C10—C11118.15 (13)
C13—N1—Mn1120.88 (10)C9—C10—C14118.12 (13)
C14—N2—H21124.4 (15)C11—C10—C14123.72 (13)
C14—N2—H22113.3 (16)C10—C11—H11120.7
H21—N2—H22121 (2)C12—C11—C10118.59 (14)
O1—C1—O2125.89 (14)C12—C11—H11120.7
O1—C1—C2118.59 (13)C11—C12—H12120.4
O2—C1—C2115.51 (13)C13—C12—C11119.26 (14)
C3—C2—C1120.90 (13)C13—C12—H12120.4
C3—C2—C7118.51 (14)N1—C13—C12122.90 (14)
C7—C2—C1120.56 (13)N1—C13—H13118.6
C2—C3—H3119.7C12—C13—H13118.6
C4—C3—C2120.59 (14)O3—C14—N2121.84 (14)
C4—C3—H3119.7O3—C14—C10119.46 (13)
C3—C4—C5121.05 (14)N2—C14—C10118.71 (13)
O4—Mn1—O2—C1−124.12 (16)O2—C1—C2—C7−169.99 (14)
O4i—Mn1—O2—C155.88 (16)C1—C2—C3—C4−178.83 (14)
N1i—Mn1—O2—C1144.28 (16)C7—C2—C3—C4−0.8 (2)
N1—Mn1—O2—C1−35.72 (16)C1—C2—C7—C6178.70 (15)
O2—Mn1—N1—C9−23.31 (12)C3—C2—C7—C60.6 (2)
O2i—Mn1—N1—C9156.69 (12)C5—C4—C3—C20.2 (2)
O2—Mn1—N1—C13154.04 (12)C3—C4—C5—C60.4 (2)
O2i—Mn1—N1—C13−25.96 (12)C3—C4—C5—C8−179.60 (15)
O4—Mn1—N1—C962.76 (11)C5—C6—C7—C20.0 (2)
O4i—Mn1—N1—C9−117.24 (11)C7—C6—C5—C4−0.6 (2)
O4—Mn1—N1—C13−119.89 (12)C7—C6—C5—C8179.46 (15)
O4i—Mn1—N1—C1360.11 (12)N1—C9—C10—C111.2 (2)
Mn1—O2—C1—O1−26.6 (3)N1—C9—C10—C14−177.98 (13)
Mn1—O2—C1—C2153.01 (12)C12—C11—C10—C9−0.1 (2)
Mn1—N1—C9—C10176.18 (11)C12—C11—C10—C14179.01 (15)
C13—N1—C9—C10−1.3 (2)C10—C11—C12—C13−0.8 (2)
Mn1—N1—C13—C12−177.22 (13)N1—C13—C12—C110.8 (3)
C9—N1—C13—C120.2 (2)O3—C14—C10—C9−9.9 (2)
O1—C1—C2—C3−172.31 (14)O3—C14—C10—C11170.95 (15)
O1—C1—C2—C79.7 (2)N2—C14—C10—C9170.04 (14)
O2—C1—C2—C38.0 (2)N2—C14—C10—C11−9.1 (2)

Symmetry codes: (i) −x, −y, −z.

Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids of the C2-C7 andN1/C9-C13 rings, respectively.
D—H···AD—HH···AD···AD—H···A
N2—H21···O1ii0.88 (3)1.97 (3)2.8456 (19)174 (2)
N2—H22···O3iii0.86 (3)2.09 (3)2.952 (2)172 (3)
O4—H42···O3iv0.90 (3)1.83 (3)2.7071 (19)164 (3)
C11—H11···O1ii0.932.333.200 (2)156
O4—H41···Cg1v0.91 (2)2.33 (2)3.141 (2)149 (3)
C4—H4···Cg2v0.932.803.490 (2)132

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: CI5069).

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