Diaqua­[N,N′-(o-phenylene)bis­(pyridine-2-carbox­amidato)-κ⁴N]manganese(III) perchlorate

In the Mn^III complex of the title compound, [Mn^III(C₁₈H₁₂N₄O₂)(H₂O)₂]ClO₄, the Mn^III atom is coordinated by four N atoms from the bpb²⁻ [1,2-bis­(pyridine-2-carboxamido)benzene] ligand located in the equatorial plane and two O atoms of water mol­ecules at axial positions, yielding a distorted MnN₄O₂ octa­hedral coordination geometry. The bpb²⁻ ligand is nearly planar, with a maximum deviation of 0.2311 (3) Å from the mean plane. The Mn^III complex cation and the perchlorate anion, both of which are located on twofold rotation axes, are connected by O—H...O and C—H...O hydrogen bonds into a three-dimensional supra­molecular network structure.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.034
• wR factor = 0.081
• Data-to-parameter ratio = 13.6

checkCIF/PLATON results

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Alert level C
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for        Cl1

Alert level G
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
PLAT794_ALERT_5_G Check Predicted Bond Valency for Mn1         (3)       3.24

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   1 ALERT level C = Check and explain
   3 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
   0 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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S1. Comment

To date, many iron and chromium coordination complexes containing a large in-plane pyridine carboxamide ligand [bpb^2-: 1,2-bis(pyridine-2-carboxamido)benzenate], such as [Cr^III(bpb)(H₂O)(OH)], [Cr^III(bpb)(H₂O)(N₃)] (Ni et al., 2006), [Cr^V(bpb)(N)] (Che et al., 1988), Na[Fe^III(bpb)(N₃)₂], Na[Fe^III(bpb)(CN)₂] (Dutta et al., 2000) and [Co^III(C₁₂H₈N₂)₂(CN)₂] [Cr^III(bpb)(N₃)₂].H₂O (Ni, 2007), have been synthesized and structural characterized. However, the manganese(III) complexes with the bpb^2- ligand and its derivatives are relative scarce (Lin et al., 2003; Liang et al., 2007; Havranek et al., 1999). Herein, we report a new Mn(III) complex [Mn^III(bpb)(H₂O)₂]ClO₄, (I).

The geometry and labeling scheme for the crystal structure of the title complex is depicted in Figure 1. The title compound comprises of a [Mn^III(bpb)(H₂O)₂]⁺ cation and a ClO₄^- balanced anion. The Mn^III atom is coordinated by four N atoms from the bpb^2- ligand located at the equatorial plane and two trans coordinated water molecule O atoms, yielding a distorted MnN₄O₂ octahedral coordination geometry.

The C—O, C_pyridine—N and C_carboxy—N bond distances of the bpb^2- ligand in the title complex are well agree with those reported for other complexes containing the bpb^2- ligand. The Mn—N_pyridine bond distance [2.0563 (18) Å] are significantly longer than that of Mn—N_amide bond length [1.9293 (18) Å], which is in agreement with the fact that the deprotonated amide group is a very strong σ-donor. The O_water—Mn—O_water bond angle is 158.42 (10)°, which is significantly deviated from 180°. The bpb^2- ligands is nearly planar with the largest deviation value of 0.2311 (3) Å from the mean plane.

There exist affluent hydrogen bonds involving coodinated water molecules, perchlorate anions and carboxamide oxygen atoms and pyridine carbon atoms (Table 1), which link the [Mn^III(bpb)(H₂O)₂]ClO₄ molecules into a three-dimensional supramolecular structure.

Related literature

For iron and chromium monomeric complexes with the in-plane 1,2-bis(pyridine-2-carboxamido)benzene (bpb^2-) ligand, see: Ni et al. (2006); Ni (2007); Che et al. (1988); Dutta et al. (2000). For manganese monomeric compounds with the bpb^2- ligand and its derivatives, see: Liang et al. (2007); Lin et al. (2003); Havranek et al. (1999). For the synthesis of the H₂bpb ligand, see: Barnes et al. (1978).

S2. Experimental

The material H₂bpb was synthesized according to the literature method (Barnes et al., 1978). Solid H₂bpb (320 mg, 1 mmol) was added into a methanol-water (20:1 v/v) solution (50 ml) of Mn^II(ClO₄)₂.6H₂O (360 mg, 1 mmol). Then, solid NaOH (80 mg, 2 mmol) was added into the above mixture. The resulting mixture was refluxed for about 2 d until the solution become dark brown. The mixture was then filtered and the resulting solution was kept at room temperature for about one week, giving rise to block brown crystals of the title compound (yield 50%). Elemental analysis [found(calculated)] for C₁₈H₁₆ClMnN₄O₈: C 42.54 (42.66), H 3.30 (3.18), N 11.52% (11.60%).

S3. Refinement

H atoms of the water molecules were found in a difference Fourier map and refined as riding, with O—H = 0.85 Å, and with U_iso(H) = 1.5U_eq(O). C-bound H atoms were positioned geometrically (C—H = 0.93 Å) and refined as riding, with U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Sheldrick, 1998); software used to prepare material for publication: XP (Sheldrick, 1998).

Figures

	Fig. 1. The molecular structure of the title compound, with the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A packing view of the title compound, viewed approximately down the b axis, showing two-dimensional network supramolecular structure through O—H···O hydrogen bonds. All H atoms bound to C atoms are omitted for clarity.

Diaqua[N,N'-(o-phenylene)bis(pyridine-2-carboxamidato)- κ⁴N]manganese(III) perchlorate

Crystal data

[Mn(C18H12N4O2)(H2O)2]·ClO4	F(000) = 1032
Mr = 506.74	Dx = 1.644 Mg m^−3
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 1987 reflections
a = 9.941 (2) Å	θ = 3.1–26.0°
b = 15.416 (3) Å	µ = 0.83 mm^−1
c = 13.357 (3) Å	T = 293 K
V = 2047.0 (7) Å^3	Block, brown
Z = 4	0.12 × 0.08 × 0.06 mm

Data collection

Bruker APEXII CCD area-detector diffractometer	1987 independent reflections
Radiation source: fine-focus sealed tube	1456 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.087
φ and ω scans	θmax = 26.0°, θmin = 3.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −12→12
Tmin = 0.926, Tmax = 0.954	k = −18→18
13809 measured reflections	l = −15→15

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.081	H-atom parameters not refined
S = 1.02	w = 1/[σ^2(Fo^2) + (0.028P)^2 + 0.6P] where P = (Fo^2 + 2Fc^2)/3
1987 reflections	(Δ/σ)max < 0.001
146 parameters	Δρmax = 0.41 e Å^−3
0 restraints	Δρmin = −0.41 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Mn1	0.0000	0.43209 (3)	0.7500	0.01226 (15)
C1	−0.1402 (2)	0.41304 (16)	0.93572 (16)	0.0158 (5)
C2	−0.2037 (2)	0.37831 (18)	1.01907 (17)	0.0229 (6)
H2	−0.2490	0.4140	1.0639	0.027*
C3	−0.1983 (2)	0.29012 (17)	1.03424 (18)	0.0264 (6)
H3	−0.2391	0.2657	1.0902	0.032*
C4	−0.1322 (2)	0.23801 (17)	0.96636 (17)	0.0246 (6)
H4	−0.1269	0.1784	0.9762	0.030*
C5	−0.0740 (2)	0.27627 (15)	0.88316 (17)	0.0200 (5)
H5	−0.0303	0.2412	0.8367	0.024*
C6	−0.1314 (2)	0.50845 (16)	0.91745 (16)	0.0162 (5)
C7	−0.0379 (2)	0.61090 (15)	0.79440 (16)	0.0149 (5)
C8	−0.0769 (2)	0.68901 (16)	0.83709 (17)	0.0216 (6)
H8	−0.1288	0.6895	0.8950	0.026*
C9	−0.0381 (3)	0.76609 (16)	0.79295 (18)	0.0263 (6)
H9	−0.0639	0.8185	0.8216	0.032*
N1	−0.06538 (18)	0.52651 (12)	0.83139 (12)	0.0139 (4)
N2	−0.07841 (18)	0.36203 (12)	0.86726 (13)	0.0152 (4)
O1	−0.10420 (19)	−0.01530 (13)	0.79040 (13)	0.0386 (5)
O2	0.0547 (2)	0.09200 (15)	0.82695 (18)	0.0689 (8)
O3	−0.17778 (17)	0.56134 (11)	0.97762 (11)	0.0234 (4)
O1W	0.19449 (15)	0.40514 (10)	0.82552 (10)	0.0183 (4)
H1W	0.1914	0.4163	0.8878	0.027*
H2W	0.2651	0.4282	0.8015	0.027*
Cl1	0.0000	0.03896 (6)	0.7500	0.0297 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.0141 (3)	0.0120 (3)	0.0107 (3)	0.000	0.0028 (2)	0.000
C1	0.0112 (11)	0.0252 (14)	0.0111 (12)	−0.0006 (10)	−0.0016 (9)	0.0027 (10)
C2	0.0170 (13)	0.0376 (16)	0.0141 (12)	−0.0032 (11)	0.0036 (10)	0.0033 (11)
C3	0.0206 (13)	0.0396 (17)	0.0191 (13)	−0.0117 (12)	0.0007 (11)	0.0096 (12)
C4	0.0260 (14)	0.0240 (14)	0.0238 (14)	−0.0102 (11)	−0.0067 (11)	0.0091 (12)
C5	0.0209 (13)	0.0202 (14)	0.0188 (13)	−0.0051 (11)	−0.0041 (10)	0.0009 (10)
C6	0.0116 (11)	0.0244 (14)	0.0127 (12)	0.0009 (10)	−0.0023 (9)	−0.0012 (10)
C7	0.0148 (11)	0.0149 (12)	0.0151 (12)	0.0017 (10)	−0.0035 (9)	0.0000 (10)
C8	0.0219 (13)	0.0209 (14)	0.0219 (13)	0.0049 (11)	−0.0020 (11)	−0.0043 (11)
C9	0.0334 (15)	0.0137 (12)	0.0320 (15)	0.0048 (11)	−0.0097 (11)	−0.0050 (11)
N1	0.0156 (10)	0.0162 (11)	0.0098 (10)	−0.0002 (8)	0.0025 (8)	−0.0006 (8)
N2	0.0147 (10)	0.0164 (11)	0.0144 (10)	−0.0017 (8)	−0.0008 (8)	0.0012 (8)
O1	0.0275 (11)	0.0486 (14)	0.0398 (11)	−0.0079 (10)	0.0009 (9)	−0.0066 (10)
O2	0.0526 (15)	0.0466 (15)	0.108 (2)	0.0080 (12)	−0.0470 (14)	−0.0416 (14)
O3	0.0284 (10)	0.0280 (10)	0.0139 (8)	0.0101 (8)	0.0034 (8)	−0.0041 (8)
O1W	0.0178 (9)	0.0267 (10)	0.0103 (8)	0.0004 (7)	0.0011 (6)	−0.0010 (7)
Cl1	0.0223 (5)	0.0172 (4)	0.0495 (6)	0.000	−0.0171 (4)	0.000

Geometric parameters (Å, º)

Mn1—N1^i	1.9295 (18)	C5—H5	0.9300
Mn1—N1	1.9295 (18)	C6—O3	1.234 (3)
Mn1—N2^i	2.0561 (18)	C6—N1	1.353 (3)
Mn1—N2	2.0561 (18)	C7—C8	1.387 (3)
Mn1—O1W^i	2.2200 (15)	C7—C7^i	1.406 (4)
Mn1—O1W	2.2200 (15)	C7—N1	1.418 (3)
C1—N2	1.353 (3)	C8—C9	1.381 (3)
C1—C2	1.387 (3)	C8—H8	0.9300
C1—C6	1.493 (3)	C9—C9^i	1.375 (5)
C2—C3	1.376 (4)	C9—H9	0.9300
C2—H2	0.9300	O1—Cl1	1.4366 (19)
C3—C4	1.378 (3)	O2—Cl1	1.422 (2)
C3—H3	0.9300	O1W—H1W	0.8500
C4—C5	1.385 (3)	O1W—H2W	0.8500
C4—H4	0.9300	Cl1—O2^i	1.422 (2)
C5—N2	1.340 (3)	Cl1—O1^i	1.4366 (19)
N1^i—Mn1—N1	82.06 (11)	C4—C5—H5	118.9
N1^i—Mn1—N2^i	80.76 (8)	O3—C6—N1	126.8 (2)
N1—Mn1—N2^i	162.40 (8)	O3—C6—C1	121.5 (2)
N1^i—Mn1—N2	162.40 (8)	N1—C6—C1	111.70 (19)
N1—Mn1—N2	80.76 (8)	C8—C7—C7^i	119.78 (14)
N2^i—Mn1—N2	116.62 (11)	C8—C7—N1	126.8 (2)
N1^i—Mn1—O1W^i	100.29 (7)	C7^i—C7—N1	113.41 (12)
N1—Mn1—O1W^i	95.96 (7)	C9—C8—C7	119.5 (2)
N2^i—Mn1—O1W^i	83.44 (6)	C9—C8—H8	120.2
N2—Mn1—O1W^i	85.27 (6)	C7—C8—H8	120.2
N1^i—Mn1—O1W	95.96 (7)	C9^i—C9—C8	120.66 (15)
N1—Mn1—O1W	100.29 (7)	C9^i—C9—H9	119.7
N2^i—Mn1—O1W	85.27 (6)	C8—C9—H9	119.7
N2—Mn1—O1W	83.44 (6)	C6—N1—C7	125.33 (19)
O1W^i—Mn1—O1W	158.42 (8)	C6—N1—Mn1	119.14 (16)
N2—C1—C2	121.6 (2)	C7—N1—Mn1	115.53 (14)
N2—C1—C6	115.82 (19)	C5—N2—C1	118.8 (2)
C2—C1—C6	122.5 (2)	C5—N2—Mn1	128.81 (16)
C3—C2—C1	118.8 (2)	C1—N2—Mn1	112.42 (15)
C3—C2—H2	120.6	Mn1—O1W—H1W	112.0
C1—C2—H2	120.6	Mn1—O1W—H2W	117.9
C2—C3—C4	119.9 (2)	H1W—O1W—H2W	108.4
C2—C3—H3	120.1	O2—Cl1—O2^i	109.8 (2)
C4—C3—H3	120.1	O2—Cl1—O1	109.83 (13)
C3—C4—C5	118.6 (2)	O2^i—Cl1—O1	109.31 (12)
C3—C4—H4	120.7	O2—Cl1—O1^i	109.31 (12)
C5—C4—H4	120.7	O2^i—Cl1—O1^i	109.83 (13)
N2—C5—C4	122.3 (2)	O1—Cl1—O1^i	108.78 (17)
N2—C5—H5	118.9

Symmetry code: (i) −x, y, −z+3/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W···O3^ii	0.85	1.84	2.685 (2)	178
O1W—H2W···O1^iii	0.85	1.99	2.812 (2)	163
C2—H2···O2^iv	0.93	2.44	3.195 (2)	139
C5—H5···O2	0.93	2.45	3.205 (2)	138

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