Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807020466/si2014sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807020466/si2014Isup2.hkl |
CCDC reference: 646687
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.008 Å
- R factor = 0.072
- wR factor = 0.138
- Data-to-parameter ratio = 12.0
checkCIF/PLATON results
No syntax errors found
Alert level B RINTA01_ALERT_3_B The value of Rint is greater than 0.15 Rint given 0.170 PLAT020_ALERT_3_B The value of Rint is greater than 0.10 ......... 0.17
Alert level C PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.97 PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 8 PLAT415_ALERT_2_C Short Inter D-H..H-X H7 .. H9 .. 2.13 Ang.
Alert level G PLAT794_ALERT_5_G Check Predicted Bond Valency for Mn1 (2) 2.11
0 ALERT level A = In general: serious problem 2 ALERT level B = Potentially serious problem 4 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 4 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
Related complexes of 4-pyridylacetate and 3-pyridylacetate have been reported (Li et al., 2004; Du et al., 2006; Martin et al., 2007).
A mixture of 3-pyridylacetic acid hydrochloride (0.0174 g, 0.1 mmol), Mn(ClO4)2.6H2O(0.0181 g, 0.05 mmol), NaClO4.6H2O (0.0150 g, 0.07 mmol), NaOH (0.0080 g, 0.2 mmol), THF (5 ml) and water (2.5 ml) was sealed in a 25 ml Teflon-lined stainless-steel reactor and heated to 333 K for 96 h, yielding colourless crystals of (I) suitable for X-ray analysis. Elemental analysis for C14H16MnN2O6, calculated: C 46.29, H 4.44, N 7.71%; found: C 45.09, H 4.97, N 7.15%.
H atoms of the water molecules were located in a difference map. H atoms bonded to C atoms were placed at calulated positions and treated using a riding-model approximation [C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C)].
The molecule of the title complex (I), which is similar to the described for [M(Hpya)2(H2O)2]n (M = Cu, Co, Mn, Ni, Zn, Cd; Hpya = 4-pyridylacetic acid) (Li et al., 2004; Du et al.,
2006) and [M(3-pyridylacetato)2(H2O)2]n (M = Ni, Co) (Martin et al., 2007), is centrosymmetric, so pairs of equivalent ligands lie trans to each other in a slightly distorted octahedral geometry. The MnII center is six-coordinated by two pyridyl nitrogen atoms from two 3-pyridylacetate ligands in the axial positions, two carboxylate oxygen atoms from another two 3-pyridylacetate ligands and two oxygen atoms from two water molecules in the equatorial plane. Each 3-pyridylacetate anion uses its pyridine nitrogen atom and one carboxylate oxygen atom to connect two MnII ions. Four 3-pyridylacetate anionic ligands and four MnII ions form a tetragon with a side length of 8.763 Å and a diagonal measurement of 15.199 * 8.728 Å based on the Mn—Mn distances. The tetragon is further extended into a two-dimensional framework with a rhombic grid through sharing MnII ions, 3-pyridylacetate anionic ligands and intramolecular O—H···O hydrogen bonds with angles at hydrogen of 147 ° (Fig. 1).
Adjacent two-dimensional layers are connected via intermolecular O—H···O and weak C—H···O hydrogen-bonding contacts, resulting in a three-dimensional framework structure with oxygen as a trifurcated acceptor atom (Fig. 2).
Related complexes of 4-pyridylacetate and 3-pyridylacetate have been reported (Li et al., 2004; Du et al., 2006; Martin et al., 2007).
Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL.
[Mn(C7H6NO2)2(H2O)2] | F(000) = 374 |
Mr = 363.23 | Dx = 1.612 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 1227 reflections |
a = 9.260 (2) Å | θ = 2.6–28.0° |
b = 8.7283 (18) Å | µ = 0.92 mm−1 |
c = 9.671 (2) Å | T = 298 K |
β = 106.788 (3)° | Block, colourless |
V = 748.3 (3) Å3 | 0.10 × 0.08 × 0.06 mm |
Z = 2 |
Bruker SMART CCD area-detector diffractometer | 1274 independent reflections |
Radiation source: fine-focus sealed tube | 770 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.170 |
φ and ω scans | θmax = 25.0°, θmin = 2.7° |
Absorption correction: multi-scan (SADABS; Bruker, 1998) | h = −10→7 |
Tmin = 0.914, Tmax = 0.947 | k = −10→10 |
3717 measured reflections | l = −11→11 |
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)] = 0.072 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.138 | H-atom parameters constrained |
S = 0.99 | w = 1/[σ2(Fo2) + (0.0532P)2] where P = (Fo2 + 2Fc2)/3 |
1274 reflections | (Δ/σ)max < 0.001 |
106 parameters | Δρmax = 0.48 e Å−3 |
0 restraints | Δρmin = −0.56 e Å−3 |
[Mn(C7H6NO2)2(H2O)2] | V = 748.3 (3) Å3 |
Mr = 363.23 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.260 (2) Å | µ = 0.92 mm−1 |
b = 8.7283 (18) Å | T = 298 K |
c = 9.671 (2) Å | 0.10 × 0.08 × 0.06 mm |
β = 106.788 (3)° |
Bruker SMART CCD area-detector diffractometer | 1274 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1998) | 770 reflections with I > 2σ(I) |
Tmin = 0.914, Tmax = 0.947 | Rint = 0.170 |
3717 measured reflections |
R[F2 > 2σ(F2)] = 0.072 | 0 restraints |
wR(F2) = 0.138 | H-atom parameters constrained |
S = 0.99 | Δρmax = 0.48 e Å−3 |
1274 reflections | Δρmin = −0.56 e Å−3 |
106 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 | 0.5000 | 0.0000 | 0.0000 | 0.0273 (4) | |
N1 | 0.2917 (5) | 0.0792 (5) | 0.0622 (4) | 0.0297 (11) | |
O1 | 0.0346 (5) | 0.2775 (4) | 0.4250 (4) | 0.0376 (10) | |
O2 | 0.1985 (5) | 0.1665 (4) | 0.6121 (4) | 0.0433 (11) | |
O3 | 0.6360 (4) | 0.0553 (4) | 0.2185 (4) | 0.0375 (10) | |
H8 | 0.7067 | 0.0017 | 0.2725 | 0.056* | |
H9 | 0.6703 | 0.1460 | 0.2219 | 0.056* | |
C1 | 0.1243 (7) | 0.1730 (6) | 0.4810 (6) | 0.0284 (13) | |
C2 | 0.1421 (8) | 0.0417 (6) | 0.3840 (6) | 0.0387 (16) | |
H2A | 0.2328 | −0.0146 | 0.4328 | 0.046* | |
H2B | 0.0574 | −0.0275 | 0.3721 | 0.046* | |
C3 | 0.2762 (7) | 0.0467 (6) | 0.1934 (5) | 0.0283 (14) | |
H3A | 0.3539 | −0.0058 | 0.2588 | 0.034* | |
C4 | 0.1512 (6) | 0.0869 (6) | 0.2364 (5) | 0.0269 (13) | |
C5 | 0.0392 (7) | 0.1676 (6) | 0.1404 (6) | 0.0341 (14) | |
H5 | −0.0462 | 0.1982 | 0.1653 | 0.041* | |
C6 | 0.0546 (7) | 0.2029 (6) | 0.0071 (6) | 0.0376 (15) | |
H6 | −0.0205 | 0.2573 | −0.0594 | 0.045* | |
C7 | 0.1825 (7) | 0.1567 (6) | −0.0273 (6) | 0.0347 (15) | |
H7 | 0.1918 | 0.1816 | −0.1178 | 0.042* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mn1 | 0.0316 (8) | 0.0291 (6) | 0.0210 (6) | −0.0029 (7) | 0.0074 (5) | −0.0003 (6) |
N1 | 0.030 (3) | 0.035 (2) | 0.022 (2) | 0.003 (3) | 0.004 (2) | 0.002 (2) |
O1 | 0.053 (3) | 0.028 (2) | 0.027 (2) | 0.009 (2) | 0.005 (2) | −0.0021 (17) |
O2 | 0.052 (3) | 0.039 (2) | 0.032 (2) | 0.008 (2) | 0.001 (2) | −0.0002 (19) |
O3 | 0.041 (3) | 0.038 (2) | 0.027 (2) | −0.001 (2) | −0.0010 (18) | −0.0040 (16) |
C1 | 0.029 (4) | 0.027 (3) | 0.031 (3) | −0.005 (3) | 0.012 (3) | 0.001 (3) |
C2 | 0.054 (4) | 0.032 (3) | 0.035 (3) | 0.007 (3) | 0.021 (3) | 0.005 (2) |
C3 | 0.034 (4) | 0.029 (3) | 0.021 (3) | 0.004 (3) | 0.007 (3) | 0.002 (2) |
C4 | 0.033 (4) | 0.025 (3) | 0.021 (3) | −0.001 (3) | 0.005 (3) | −0.002 (2) |
C5 | 0.027 (4) | 0.038 (3) | 0.034 (3) | 0.003 (3) | 0.004 (3) | −0.006 (3) |
C6 | 0.039 (4) | 0.033 (3) | 0.033 (3) | 0.014 (3) | −0.002 (3) | 0.001 (3) |
C7 | 0.042 (4) | 0.037 (3) | 0.024 (3) | 0.002 (3) | 0.008 (3) | 0.006 (3) |
Mn1—O1i | 2.129 (3) | C1—C2 | 1.520 (7) |
Mn1—O1ii | 2.129 (3) | C2—C4 | 1.507 (6) |
Mn1—O3 | 2.179 (3) | C2—H2A | 0.9700 |
Mn1—O3iii | 2.179 (3) | C2—H2B | 0.9700 |
Mn1—N1iii | 2.287 (4) | C3—C4 | 1.383 (7) |
Mn1—N1 | 2.287 (4) | C3—H3A | 0.9300 |
N1—C7 | 1.313 (7) | C4—C5 | 1.370 (7) |
N1—C3 | 1.348 (6) | C5—C6 | 1.372 (7) |
O1—C1 | 1.247 (6) | C5—H5 | 0.9300 |
O1—Mn1iv | 2.129 (3) | C6—C7 | 1.380 (8) |
O2—C1 | 1.257 (7) | C6—H6 | 0.9300 |
O3—H8 | 0.8500 | C7—H7 | 0.9300 |
O3—H9 | 0.8500 | ||
O1i—Mn1—O1ii | 180 | O1—C1—C2 | 117.4 (5) |
O1i—Mn1—O3 | 88.47 (14) | O2—C1—C2 | 117.6 (5) |
O1ii—Mn1—O3 | 91.53 (14) | C4—C2—C1 | 115.7 (4) |
O1i—Mn1—O3iii | 91.53 (14) | C4—C2—H2A | 108.4 |
O1ii—Mn1—O3iii | 88.47 (14) | C1—C2—H2A | 108.4 |
O3—Mn1—O3iii | 180 | C4—C2—H2B | 108.4 |
O1i—Mn1—N1iii | 92.02 (15) | C1—C2—H2B | 108.4 |
O1ii—Mn1—N1iii | 87.98 (15) | H2A—C2—H2B | 107.4 |
O3—Mn1—N1iii | 91.54 (15) | N1—C3—C4 | 123.8 (5) |
O3iii—Mn1—N1iii | 88.46 (15) | N1—C3—H3A | 118.1 |
O1i—Mn1—N1 | 87.98 (15) | C4—C3—H3A | 118.1 |
O1ii—Mn1—N1 | 92.02 (15) | C5—C4—C3 | 117.5 (5) |
O3—Mn1—N1 | 88.46 (15) | C5—C4—C2 | 122.5 (5) |
O3iii—Mn1—N1 | 91.54 (15) | C3—C4—C2 | 120.0 (5) |
N1iii—Mn1—N1 | 180 | C4—C5—C6 | 119.2 (5) |
C7—N1—C3 | 117.2 (5) | C4—C5—H5 | 120.4 |
C7—N1—Mn1 | 122.0 (3) | C6—C5—H5 | 120.4 |
C3—N1—Mn1 | 120.8 (4) | C5—C6—C7 | 119.4 (6) |
C1—O1—Mn1iv | 131.8 (3) | C5—C6—H6 | 120.3 |
Mn1—O3—H8 | 126.9 | C7—C6—H6 | 120.3 |
Mn1—O3—H9 | 110.4 | N1—C7—C6 | 122.9 (5) |
H8—O3—H9 | 106.1 | N1—C7—H7 | 118.6 |
O1—C1—O2 | 124.9 (5) | C6—C7—H7 | 118.6 |
O1i—Mn1—N1—C7 | −130.5 (4) | C7—N1—C3—C4 | 1.7 (8) |
O1ii—Mn1—N1—C7 | 49.5 (4) | Mn1—N1—C3—C4 | −177.9 (4) |
O3—Mn1—N1—C7 | 141.0 (4) | N1—C3—C4—C5 | −1.6 (8) |
O3iii—Mn1—N1—C7 | −39.0 (4) | N1—C3—C4—C2 | 178.3 (5) |
O1i—Mn1—N1—C3 | 49.1 (4) | C1—C2—C4—C5 | −58.4 (7) |
O1ii—Mn1—N1—C3 | −130.9 (4) | C1—C2—C4—C3 | 121.7 (6) |
O3—Mn1—N1—C3 | −39.4 (4) | C3—C4—C5—C6 | 0.8 (8) |
O3iii—Mn1—N1—C3 | 140.6 (4) | C2—C4—C5—C6 | −179.1 (5) |
Mn1iv—O1—C1—O2 | 14.6 (8) | C4—C5—C6—C7 | −0.2 (8) |
Mn1iv—O1—C1—C2 | −166.9 (4) | C3—N1—C7—C6 | −1.0 (8) |
O1—C1—C2—C4 | 42.5 (7) | Mn1—N1—C7—C6 | 178.7 (4) |
O2—C1—C2—C4 | −139.0 (5) | C5—C6—C7—N1 | 0.3 (9) |
Symmetry codes: (i) −x+1/2, y−1/2, −z+1/2; (ii) x+1/2, −y+1/2, z−1/2; (iii) −x+1, −y, −z; (iv) −x+1/2, y+1/2, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H9···O2ii | 0.85 | 2.01 | 2.763 (5) | 147 |
O3—H8···O2v | 0.85 | 1.90 | 2.707 (5) | 158 |
C5—H5···O2vi | 0.93 | 2.56 | 3.409 (7) | 152 |
Symmetry codes: (ii) x+1/2, −y+1/2, z−1/2; (v) −x+1, −y, −z+1; (vi) x−1/2, −y+1/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | [Mn(C7H6NO2)2(H2O)2] |
Mr | 363.23 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 298 |
a, b, c (Å) | 9.260 (2), 8.7283 (18), 9.671 (2) |
β (°) | 106.788 (3) |
V (Å3) | 748.3 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.92 |
Crystal size (mm) | 0.10 × 0.08 × 0.06 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 1998) |
Tmin, Tmax | 0.914, 0.947 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3717, 1274, 770 |
Rint | 0.170 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.072, 0.138, 0.99 |
No. of reflections | 1274 |
No. of parameters | 106 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.48, −0.56 |
Computer programs: SMART (Bruker, 1998), SMART, SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1998), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H9···O2i | 0.85 | 2.01 | 2.763 (5) | 147.4 |
O3—H8···O2ii | 0.85 | 1.90 | 2.707 (5) | 158.4 |
C5—H5···O2iii | 0.93 | 2.56 | 3.409 (7) | 152.4 |
Symmetry codes: (i) x+1/2, −y+1/2, z−1/2; (ii) −x+1, −y, −z+1; (iii) x−1/2, −y+1/2, z−1/2. |
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The molecule of the title complex (I), which is similar to the described for [M(Hpya)2(H2O)2]n (M = Cu, Co, Mn, Ni, Zn, Cd; Hpya = 4-pyridylacetic acid) (Li et al., 2004; Du et al.,
2006) and [M(3-pyridylacetato)2(H2O)2]n (M = Ni, Co) (Martin et al., 2007), is centrosymmetric, so pairs of equivalent ligands lie trans to each other in a slightly distorted octahedral geometry. The MnII center is six-coordinated by two pyridyl nitrogen atoms from two 3-pyridylacetate ligands in the axial positions, two carboxylate oxygen atoms from another two 3-pyridylacetate ligands and two oxygen atoms from two water molecules in the equatorial plane. Each 3-pyridylacetate anion uses its pyridine nitrogen atom and one carboxylate oxygen atom to connect two MnII ions. Four 3-pyridylacetate anionic ligands and four MnII ions form a tetragon with a side length of 8.763 Å and a diagonal measurement of 15.199 * 8.728 Å based on the Mn—Mn distances. The tetragon is further extended into a two-dimensional framework with a rhombic grid through sharing MnII ions, 3-pyridylacetate anionic ligands and intramolecular O—H···O hydrogen bonds with angles at hydrogen of 147 ° (Fig. 1).
Adjacent two-dimensional layers are connected via intermolecular O—H···O and weak C—H···O hydrogen-bonding contacts, resulting in a three-dimensional framework structure with oxygen as a trifurcated acceptor atom (Fig. 2).