Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807050453/is2217sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807050453/is2217Isup2.hkl |
CCDC reference: 667183
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.003 Å
- R factor = 0.034
- wR factor = 0.081
- Data-to-parameter ratio = 13.6
checkCIF/PLATON results
No syntax errors found
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
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 MnII(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%).
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 Uiso(H) = 1.5Ueq(O). C-bound H atoms were positioned geometrically (C—H = 0.93 Å) and refined as riding, with Uiso(H) = 1.2Ueq(C).
To date, many iron and chromium coordination complexes containing a large in-plane pyridine carboxamide ligand [bpb2-: 1,2-bis(pyridine-2-carboxamido)benzenate], such as [CrIII(bpb)(H2O)(OH)], [CrIII(bpb)(H2O)(N3)] (Ni et al., 2006), [CrV(bpb)(N)] (Che et al., 1988), Na[FeIII(bpb)(N3)2], Na[FeIII(bpb)(CN)2] (Dutta et al., 2000) and [CoIII(C12H8N2)2(CN)2] [CrIII(bpb)(N3)2].H2O (Ni, 2007), have been synthesized and structural characterized. However, the manganese(III) complexes with the bpb2- 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 [MnIII(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 [MnIII(bpb)(H2O)2]+ cation and a ClO4- balanced anion. The MnIII atom is coordinated by four N atoms from the bpb2- ligand located at the equatorial plane and two trans coordinated water molecule O atoms, yielding a distorted MnN4O2 octahedral coordination geometry.
The C—O, Cpyridine—N and Ccarboxy—N bond distances of the bpb2- ligand in the title complex are well agree with those reported for other complexes containing the bpb2- ligand. The Mn—Npyridine bond distance [2.0563 (18) Å] are significantly longer than that of Mn—Namide 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 Owater—Mn—Owater bond angle is 158.42 (10)°, which is significantly deviated from 180°. The bpb2- 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 [MnIII(bpb)(H2O)2]ClO4 molecules into a three-dimensional supramolecular structure.
For iron and chromium monomeric complexes with the in-plane 1,2-bis(pyridine-2-carboxamido)benzene (bpb2-) ligand, see: Ni et al. (2006); Ni (2007); Che et al. (1988); Dutta et al. (2000). For manganese monomeric compounds with the bpb2- 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).
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).
[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) Å3 | Block, brown |
Z = 4 | 0.12 × 0.08 × 0.06 mm |
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 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) = 0.081 | H-atom parameters not refined |
S = 1.02 | w = 1/[σ2(Fo2) + (0.028P)2 + 0.6P] where P = (Fo2 + 2Fc2)/3 |
1987 reflections | (Δ/σ)max < 0.001 |
146 parameters | Δρmax = 0.41 e Å−3 |
0 restraints | Δρmin = −0.41 e Å−3 |
[Mn(C18H12N4O2)(H2O)2]·ClO4 | V = 2047.0 (7) Å3 |
Mr = 506.74 | Z = 4 |
Orthorhombic, Pbcn | Mo Kα radiation |
a = 9.941 (2) Å | µ = 0.83 mm−1 |
b = 15.416 (3) Å | T = 293 K |
c = 13.357 (3) Å | 0.12 × 0.08 × 0.06 mm |
Bruker APEXII CCD area-detector diffractometer | 1987 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 1456 reflections with I > 2σ(I) |
Tmin = 0.926, Tmax = 0.954 | Rint = 0.087 |
13809 measured reflections |
R[F2 > 2σ(F2)] = 0.034 | 0 restraints |
wR(F2) = 0.081 | H-atom parameters not refined |
S = 1.02 | Δρmax = 0.41 e Å−3 |
1987 reflections | Δρmin = −0.41 e Å−3 |
146 parameters |
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. |
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) |
U11 | U22 | U33 | U12 | U13 | U23 | |
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 |
Mn1—N1i | 1.9295 (18) | C5—H5 | 0.9300 |
Mn1—N1 | 1.9295 (18) | C6—O3 | 1.234 (3) |
Mn1—N2i | 2.0561 (18) | C6—N1 | 1.353 (3) |
Mn1—N2 | 2.0561 (18) | C7—C8 | 1.387 (3) |
Mn1—O1Wi | 2.2200 (15) | C7—C7i | 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—C9i | 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—O2i | 1.422 (2) |
C5—N2 | 1.340 (3) | Cl1—O1i | 1.4366 (19) |
N1i—Mn1—N1 | 82.06 (11) | C4—C5—H5 | 118.9 |
N1i—Mn1—N2i | 80.76 (8) | O3—C6—N1 | 126.8 (2) |
N1—Mn1—N2i | 162.40 (8) | O3—C6—C1 | 121.5 (2) |
N1i—Mn1—N2 | 162.40 (8) | N1—C6—C1 | 111.70 (19) |
N1—Mn1—N2 | 80.76 (8) | C8—C7—C7i | 119.78 (14) |
N2i—Mn1—N2 | 116.62 (11) | C8—C7—N1 | 126.8 (2) |
N1i—Mn1—O1Wi | 100.29 (7) | C7i—C7—N1 | 113.41 (12) |
N1—Mn1—O1Wi | 95.96 (7) | C9—C8—C7 | 119.5 (2) |
N2i—Mn1—O1Wi | 83.44 (6) | C9—C8—H8 | 120.2 |
N2—Mn1—O1Wi | 85.27 (6) | C7—C8—H8 | 120.2 |
N1i—Mn1—O1W | 95.96 (7) | C9i—C9—C8 | 120.66 (15) |
N1—Mn1—O1W | 100.29 (7) | C9i—C9—H9 | 119.7 |
N2i—Mn1—O1W | 85.27 (6) | C8—C9—H9 | 119.7 |
N2—Mn1—O1W | 83.44 (6) | C6—N1—C7 | 125.33 (19) |
O1Wi—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—O2i | 109.8 (2) |
C4—C3—H3 | 120.1 | O2—Cl1—O1 | 109.83 (13) |
C3—C4—C5 | 118.6 (2) | O2i—Cl1—O1 | 109.31 (12) |
C3—C4—H4 | 120.7 | O2—Cl1—O1i | 109.31 (12) |
C5—C4—H4 | 120.7 | O2i—Cl1—O1i | 109.83 (13) |
N2—C5—C4 | 122.3 (2) | O1—Cl1—O1i | 108.78 (17) |
N2—C5—H5 | 118.9 |
Symmetry code: (i) −x, y, −z+3/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1W···O3ii | 0.85 | 1.84 | 2.685 (2) | 178 |
O1W—H2W···O1iii | 0.85 | 1.99 | 2.812 (2) | 163 |
C2—H2···O2iv | 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. |
Experimental details
Crystal data | |
Chemical formula | [Mn(C18H12N4O2)(H2O)2]·ClO4 |
Mr | 506.74 |
Crystal system, space group | Orthorhombic, Pbcn |
Temperature (K) | 293 |
a, b, c (Å) | 9.941 (2), 15.416 (3), 13.357 (3) |
V (Å3) | 2047.0 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.83 |
Crystal size (mm) | 0.12 × 0.08 × 0.06 |
Data collection | |
Diffractometer | Bruker APEXII CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.926, 0.954 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13809, 1987, 1456 |
Rint | 0.087 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.081, 1.02 |
No. of reflections | 1987 |
No. of parameters | 146 |
H-atom treatment | H-atom parameters not refined |
Δρmax, Δρmin (e Å−3) | 0.41, −0.41 |
Computer programs: APEX2 (Bruker, 2004), SAINT-Plus (Bruker, 2001), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), XP (Sheldrick, 1998).
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1W···O3i | 0.85 | 1.84 | 2.685 (2) | 178 |
O1W—H2W···O1ii | 0.85 | 1.99 | 2.812 (2) | 163 |
C2—H2···O2iii | 0.93 | 2.44 | 3.195 (2) | 139 |
C5—H5···O2 | 0.93 | 2.45 | 3.205 (2) | 138 |
Symmetry codes: (i) −x, −y+1, −z+2; (ii) x+1/2, y+1/2, −z+3/2; (iii) x−1/2, −y+1/2, −z+2. |
To date, many iron and chromium coordination complexes containing a large in-plane pyridine carboxamide ligand [bpb2-: 1,2-bis(pyridine-2-carboxamido)benzenate], such as [CrIII(bpb)(H2O)(OH)], [CrIII(bpb)(H2O)(N3)] (Ni et al., 2006), [CrV(bpb)(N)] (Che et al., 1988), Na[FeIII(bpb)(N3)2], Na[FeIII(bpb)(CN)2] (Dutta et al., 2000) and [CoIII(C12H8N2)2(CN)2] [CrIII(bpb)(N3)2].H2O (Ni, 2007), have been synthesized and structural characterized. However, the manganese(III) complexes with the bpb2- 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 [MnIII(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 [MnIII(bpb)(H2O)2]+ cation and a ClO4- balanced anion. The MnIII atom is coordinated by four N atoms from the bpb2- ligand located at the equatorial plane and two trans coordinated water molecule O atoms, yielding a distorted MnN4O2 octahedral coordination geometry.
The C—O, Cpyridine—N and Ccarboxy—N bond distances of the bpb2- ligand in the title complex are well agree with those reported for other complexes containing the bpb2- ligand. The Mn—Npyridine bond distance [2.0563 (18) Å] are significantly longer than that of Mn—Namide 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 Owater—Mn—Owater bond angle is 158.42 (10)°, which is significantly deviated from 180°. The bpb2- 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 [MnIII(bpb)(H2O)2]ClO4 molecules into a three-dimensional supramolecular structure.