Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807020533/ci2374sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807020533/ci2374Isup2.hkl |
CCDC reference: 646658
Key indicators
- Single-crystal X-ray study
- T = 295 K
- Mean (C-C) = 0.002 Å
- R factor = 0.027
- wR factor = 0.071
- Data-to-parameter ratio = 14.6
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT154_ALERT_1_C The su's on the Cell Angles are Equal (x 10000) 3000 Deg. PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Mn1 - O2W .. 6.26 su PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........ 4
Alert level G PLAT794_ALERT_5_G Check Predicted Bond Valency for Mn1 (2) 2.08 PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 6
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 2 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 1 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
For general background, see: Edwards et al. (1977). Complexes with 4-OPA- exist as either mononuclear with the ligands as counter-anions (Gao et al., 2004; Zhang et al., 2004a,b; Zhao et al., 2004; Zhang et al., 2005) or as polymers with the metal ions bridged by the 4-OPA- ligands (Zhang et al., 2006).
The title complex was prepared by the addition of MnCl2.4H2O (3.96 g, 20 mmol) to a solution of (4-oxo-4H-pyridin-1-yl)acetic acid (5.84 g, 40 mmol) in H2O-DMF (1:1 v/v), and the pH was adjusted to 7 with 0.2 M NaOH solution. Colourless single crystals of (I) were obtained from the filtered solution, after slow evaporation at room temperature for a week. Analysis calculated for C14H20MnN2O10: C 38.99, H 4.67, N 6.49%; found: C 38.77, H 4.54, N 6.66%.
H atoms of water molecules were located in Fourier difference maps and refined with the restraints O—H = 0.85 (1) Å and H···H = 1.39 (1) Å, and with Uiso(H) = 1.5Ueq(O). C-bound H atoms were placed in calculated positions, with C—H = 0.93 or 0.97 Å and Uiso(H) = 1.2Ueq(C), and were included in the refinement in the riding-model approximation.
(4-Oxo-4H-pyrindin-1-yl)acetic acid (4-OPA-), an important medical intermediate (Edwards et al., 1977), is a potential multidentate ligand with versatile binding ability. Recent studies in our laboratory have demontrated that the complexes containing 4-OPA- ligands exhibit two type structures: mononuclear in which the 4-OPA- ligands exist as counter anions (Gao et al., 2004; Zhang et al., 2004a,b; Zhao et al., 2004; Zhang et al., 2005) and polymer with the adjacent metal ions bridged by carbonyl and carboxylate groups of 4-OPA- ligand (Zhang et al., 2006).
As illustrated in Fig. 1, the title complex has a mononuclear structure, in which the (4-oxo-4H-pyridin-1-yl)acetate ligands are coordinated to the MnII atom through the carbonyl O atoms in a monodentate fashion. The MnII atom is located on an inversion center and is coordinated by two carbonyl O atoms and four water molecules, forming an octahedral coordination geometry. The Mn—Ocarbonyl bond distance is 2.1960 (11) Å, and the Mn—Ow distances are 2.1557 (14) and 2.1952 (12) Å.
The planes of the carboxylate group (O1/O2/C1/C2) and pyridine ring (N1/C3—C7) form a dihedral angle of 67.27 (9)°. The C—O bond lengths [O1—C1 = 1.2566 (18) Å and O2—C1 = 1.2366 (19) Å] suggest delocalization of π-electron density over the carboxylate group.
The coordinated water molecules form intermolecular O—H···O hydrogen bonds with uncoordinated carboxylate groups of adjacent molecules, connecting the mononuclear units into a two-dimensional network parallel to the (0 1 1) plane. The O···O distances of the hydrogen bonds lie in the range 2.6557 (17)–2.7677 (17) Å and the O—H···O angles range from 169.5 (19) to 178 (2)° (Table 1). The adjacent networks are cross-linked via weak π-π stacking interactions between the pyridine rings of the molecules at (x, y, z) and (1 - x, 1 - y, -z), with a centroid···centroid distance of 3.758 (3) Å (Fig. 2).
For general background, see: Edwards et al. (1977). Complexes with 4-OPA- exist as either mononuclear with the ligands as counter-anions (Gao et al., 2004; Zhang et al., 2004a,b; Zhao et al., 2004; Zhang et al., 2005) or as polymers with the metal ions bridged by the 4-OPA- ligands (Zhang et al., 2006).
Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.
[Mn(C7H6NO3)2(H2O)4] | Z = 1 |
Mr = 431.26 | F(000) = 223 |
Triclinic, P1 | Dx = 1.626 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 5.4191 (11) Å | Cell parameters from 4131 reflections |
b = 9.0498 (18) Å | θ = 3.9–27.5° |
c = 10.044 (2) Å | µ = 0.81 mm−1 |
α = 108.16 (3)° | T = 295 K |
β = 99.32 (3)° | Prism, colourless |
γ = 103.38 (3)° | 0.36 × 0.28 × 0.18 mm |
V = 440.5 (2) Å3 |
Rigaku R-AXIS RAPID diffractometer | 1981 independent reflections |
Radiation source: fine-focus sealed tube | 1844 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.014 |
Detector resolution: 10.000 pixels mm-1 | θmax = 27.5°, θmin = 3.9° |
ω scans | h = −6→7 |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | k = −11→11 |
Tmin = 0.760, Tmax = 0.868 | l = −13→13 |
4337 measured reflections |
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)] = 0.027 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.071 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0396P)2 + 0.1219P] where P = (Fo2 + 2Fc2)/3 |
1981 reflections | (Δ/σ)max = 0.001 |
136 parameters | Δρmax = 0.33 e Å−3 |
6 restraints | Δρmin = −0.18 e Å−3 |
[Mn(C7H6NO3)2(H2O)4] | γ = 103.38 (3)° |
Mr = 431.26 | V = 440.5 (2) Å3 |
Triclinic, P1 | Z = 1 |
a = 5.4191 (11) Å | Mo Kα radiation |
b = 9.0498 (18) Å | µ = 0.81 mm−1 |
c = 10.044 (2) Å | T = 295 K |
α = 108.16 (3)° | 0.36 × 0.28 × 0.18 mm |
β = 99.32 (3)° |
Rigaku R-AXIS RAPID diffractometer | 1981 independent reflections |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 1844 reflections with I > 2σ(I) |
Tmin = 0.760, Tmax = 0.868 | Rint = 0.014 |
4337 measured reflections |
R[F2 > 2σ(F2)] = 0.027 | 6 restraints |
wR(F2) = 0.071 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.08 | Δρmax = 0.33 e Å−3 |
1981 reflections | Δρmin = −0.18 e Å−3 |
136 parameters |
x | y | z | Uiso*/Ueq | ||
Mn1 | 0.5000 | 0.5000 | 0.5000 | 0.02410 (10) | |
O1W | 0.7476 (2) | 0.74902 (12) | 0.58032 (12) | 0.0342 (2) | |
H1W1 | 0.693 (3) | 0.8273 (18) | 0.624 (2) | 0.051* | |
H1W2 | 0.894 (3) | 0.789 (2) | 0.566 (2) | 0.051* | |
O1 | 0.2242 (2) | −0.11738 (13) | −0.45608 (12) | 0.0373 (3) | |
O2W | 0.79418 (19) | 0.41863 (13) | 0.61161 (11) | 0.0320 (2) | |
H2W1 | 0.775 (3) | 0.3193 (12) | 0.5618 (19) | 0.048* | |
H2W2 | 0.955 (2) | 0.4702 (19) | 0.634 (2) | 0.048* | |
O2 | 0.5889 (2) | −0.00381 (14) | −0.27545 (12) | 0.0402 (3) | |
O3 | 0.66629 (19) | 0.44717 (13) | 0.31126 (10) | 0.0324 (2) | |
N1 | 0.3688 (2) | 0.22273 (14) | −0.12628 (12) | 0.0257 (2) | |
C1 | 0.3723 (3) | −0.00777 (17) | −0.34111 (14) | 0.0272 (3) | |
C2 | 0.2691 (3) | 0.13736 (17) | −0.28357 (14) | 0.0298 (3) | |
H2A | 0.3194 | 0.2135 | −0.3313 | 0.036* | |
H2B | 0.0790 | 0.0990 | −0.3076 | 0.036* | |
C3 | 0.2162 (3) | 0.20104 (18) | −0.03597 (15) | 0.0303 (3) | |
H3 | 0.0439 | 0.1340 | −0.0750 | 0.036* | |
C4 | 0.3070 (3) | 0.27423 (19) | 0.11032 (16) | 0.0317 (3) | |
H4 | 0.1955 | 0.2578 | 0.1691 | 0.038* | |
C5 | 0.5707 (3) | 0.37566 (17) | 0.17470 (15) | 0.0256 (3) | |
C6 | 0.7223 (3) | 0.39426 (18) | 0.07528 (15) | 0.0309 (3) | |
H6 | 0.8961 | 0.4594 | 0.1103 | 0.037* | |
C7 | 0.6192 (3) | 0.31899 (18) | −0.07022 (16) | 0.0309 (3) | |
H7 | 0.7240 | 0.3343 | −0.1325 | 0.037* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mn1 | 0.01991 (15) | 0.02699 (16) | 0.01976 (15) | 0.00453 (11) | 0.00473 (11) | 0.00294 (11) |
O1W | 0.0286 (5) | 0.0281 (5) | 0.0383 (6) | 0.0039 (4) | 0.0135 (5) | 0.0030 (4) |
O1 | 0.0295 (5) | 0.0329 (5) | 0.0332 (5) | 0.0051 (4) | 0.0037 (4) | −0.0046 (4) |
O2W | 0.0236 (5) | 0.0325 (5) | 0.0299 (5) | 0.0075 (4) | 0.0013 (4) | 0.0014 (4) |
O2 | 0.0326 (6) | 0.0417 (6) | 0.0354 (6) | 0.0156 (5) | 0.0009 (5) | 0.0001 (5) |
O3 | 0.0234 (5) | 0.0426 (6) | 0.0204 (5) | 0.0052 (4) | 0.0042 (4) | 0.0009 (4) |
N1 | 0.0252 (5) | 0.0257 (5) | 0.0205 (5) | 0.0067 (4) | 0.0022 (4) | 0.0030 (4) |
C1 | 0.0269 (7) | 0.0278 (7) | 0.0230 (6) | 0.0051 (5) | 0.0079 (5) | 0.0055 (5) |
C2 | 0.0329 (7) | 0.0300 (7) | 0.0200 (6) | 0.0100 (6) | 0.0002 (5) | 0.0034 (5) |
C3 | 0.0210 (6) | 0.0340 (7) | 0.0276 (7) | 0.0033 (5) | 0.0023 (5) | 0.0058 (6) |
C4 | 0.0237 (6) | 0.0397 (8) | 0.0259 (7) | 0.0038 (6) | 0.0069 (5) | 0.0080 (6) |
C5 | 0.0228 (6) | 0.0277 (6) | 0.0223 (6) | 0.0083 (5) | 0.0045 (5) | 0.0039 (5) |
C6 | 0.0217 (6) | 0.0342 (7) | 0.0256 (7) | 0.0006 (5) | 0.0053 (5) | 0.0020 (6) |
C7 | 0.0269 (7) | 0.0340 (7) | 0.0262 (7) | 0.0036 (5) | 0.0095 (6) | 0.0061 (6) |
Mn1—O1W | 2.1557 (14) | O2W—H2W2 | 0.845 (9) |
Mn1—O2W | 2.1952 (12) | N1—C7 | 1.3481 (19) |
Mn1—O3 | 2.1960 (11) | N1—C3 | 1.3506 (19) |
O1—C1 | 1.2566 (18) | N1—C2 | 1.4677 (17) |
O2—C1 | 1.2366 (19) | C1—C2 | 1.531 (2) |
O3—C5 | 1.2767 (17) | C2—H2A | 0.97 |
C3—C4 | 1.359 (2) | C2—H2B | 0.97 |
C6—C7 | 1.360 (2) | C3—H3 | 0.93 |
Mn1—O1Wi | 2.1557 (14) | C4—C5 | 1.423 (2) |
Mn1—O2Wi | 2.1952 (12) | C4—H4 | 0.93 |
Mn1—O3i | 2.1960 (11) | C5—C6 | 1.417 (2) |
O1W—H1W1 | 0.853 (9) | C6—H6 | 0.93 |
O1W—H1W2 | 0.848 (9) | C7—H7 | 0.93 |
O2W—H2W1 | 0.854 (9) | ||
O1W—Mn1—O2W | 93.31 (5) | C3—N1—C2 | 120.87 (12) |
O1W—Mn1—O2Wi | 86.69 (5) | O2—C1—O1 | 127.28 (14) |
O1W—Mn1—O3 | 89.68 (5) | O2—C1—C2 | 118.63 (12) |
O2W—Mn1—O3 | 89.39 (4) | O1—C1—C2 | 114.04 (13) |
O1W—Mn1—O3i | 90.32 (5) | N1—C2—H2A | 109.0 |
O2W—Mn1—O3i | 90.61 (4) | C1—C2—H2A | 109.0 |
N1—C2—C1 | 112.72 (12) | N1—C2—H2B | 109.0 |
O1Wi—Mn1—O1W | 180 | C1—C2—H2B | 109.0 |
O1Wi—Mn1—O2W | 86.69 (5) | H2A—C2—H2B | 107.8 |
O1Wi—Mn1—O2Wi | 93.31 (5) | N1—C3—C4 | 121.97 (13) |
O2W—Mn1—O2Wi | 180 | N1—C3—H3 | 119.0 |
O1Wi—Mn1—O3 | 90.32 (5) | C4—C3—H3 | 119.0 |
O2Wi—Mn1—O3 | 90.61 (4) | C3—C4—C5 | 120.86 (13) |
O1Wi—Mn1—O3i | 89.68 (5) | C3—C4—H4 | 119.6 |
O2Wi—Mn1—O3i | 89.39 (4) | C5—C4—H4 | 119.6 |
O3—Mn1—O3i | 180.0 | O3—C5—C6 | 121.59 (12) |
Mn1—O1W—H1W1 | 121.0 (13) | O3—C5—C4 | 123.50 (13) |
Mn1—O1W—H1W2 | 130.2 (12) | C6—C5—C4 | 114.91 (12) |
H1W1—O1W—H1W2 | 108.3 (13) | C7—C6—C5 | 121.46 (13) |
Mn1—O2W—H2W1 | 108.5 (13) | C7—C6—H6 | 119.3 |
Mn1—O2W—H2W2 | 120.6 (14) | C5—C6—H6 | 119.3 |
H2W1—O2W—H2W2 | 107.7 (13) | N1—C7—C6 | 121.54 (13) |
C5—O3—Mn1 | 134.77 (9) | N1—C7—H7 | 119.2 |
C7—N1—C3 | 119.26 (12) | C6—C7—H7 | 119.2 |
C7—N1—C2 | 119.81 (12) | ||
O1Wi—Mn1—O3—C5 | 47.96 (14) | N1—C3—C4—C5 | −1.0 (2) |
O1W—Mn1—O3—C5 | −132.04 (14) | Mn1—O3—C5—C6 | 164.14 (11) |
O2W—Mn1—O3—C5 | 134.65 (14) | Mn1—O3—C5—C4 | −15.0 (2) |
O2Wi—Mn1—O3—C5 | −45.35 (14) | C3—C4—C5—O3 | −179.92 (14) |
C7—N1—C2—C1 | 74.23 (17) | C3—C4—C5—C6 | 0.9 (2) |
C3—N1—C2—C1 | −103.03 (15) | O3—C5—C6—C7 | −179.46 (14) |
O2—C1—C2—N1 | −28.52 (19) | C4—C5—C6—C7 | −0.3 (2) |
O1—C1—C2—N1 | 153.79 (13) | C3—N1—C7—C6 | 0.3 (2) |
C7—N1—C3—C4 | 0.4 (2) | C2—N1—C7—C6 | −177.01 (14) |
C2—N1—C3—C4 | 177.64 (14) | C5—C6—C7—N1 | −0.3 (2) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1W1···O2ii | 0.85 (1) | 1.82 (1) | 2.6674 (17) | 178 (2) |
O1W—H1W2···O1iii | 0.85 (1) | 1.87 (1) | 2.7208 (17) | 177 (2) |
O2W—H2W1···O1iv | 0.85 (1) | 1.81 (1) | 2.6557 (17) | 173 (2) |
O2W—H2W2···O3v | 0.84 (1) | 1.93 (1) | 2.7677 (17) | 169 (2) |
Symmetry codes: (ii) x, y+1, z+1; (iii) x+1, y+1, z+1; (iv) −x+1, −y, −z; (v) −x+2, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Mn(C7H6NO3)2(H2O)4] |
Mr | 431.26 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 295 |
a, b, c (Å) | 5.4191 (11), 9.0498 (18), 10.044 (2) |
α, β, γ (°) | 108.16 (3), 99.32 (3), 103.38 (3) |
V (Å3) | 440.5 (2) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 0.81 |
Crystal size (mm) | 0.36 × 0.28 × 0.18 |
Data collection | |
Diffractometer | Rigaku R-AXIS RAPID |
Absorption correction | Multi-scan (ABSCOR; Higashi, 1995) |
Tmin, Tmax | 0.760, 0.868 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4337, 1981, 1844 |
Rint | 0.014 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.027, 0.071, 1.08 |
No. of reflections | 1981 |
No. of parameters | 136 |
No. of restraints | 6 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.33, −0.18 |
Computer programs: RAPID-AUTO (Rigaku, 1998), RAPID-AUTO, CrystalStructure (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976), SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1W1···O2i | 0.85 (1) | 1.82 (1) | 2.6674 (17) | 178 (2) |
O1W—H1W2···O1ii | 0.85 (1) | 1.87 (1) | 2.7208 (17) | 177 (2) |
O2W—H2W1···O1iii | 0.85 (1) | 1.81 (1) | 2.6557 (17) | 173 (2) |
O2W—H2W2···O3iv | 0.84 (1) | 1.93 (1) | 2.7677 (17) | 169 (2) |
Symmetry codes: (i) x, y+1, z+1; (ii) x+1, y+1, z+1; (iii) −x+1, −y, −z; (iv) −x+2, −y+1, −z+1. |
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(4-Oxo-4H-pyrindin-1-yl)acetic acid (4-OPA-), an important medical intermediate (Edwards et al., 1977), is a potential multidentate ligand with versatile binding ability. Recent studies in our laboratory have demontrated that the complexes containing 4-OPA- ligands exhibit two type structures: mononuclear in which the 4-OPA- ligands exist as counter anions (Gao et al., 2004; Zhang et al., 2004a,b; Zhao et al., 2004; Zhang et al., 2005) and polymer with the adjacent metal ions bridged by carbonyl and carboxylate groups of 4-OPA- ligand (Zhang et al., 2006).
As illustrated in Fig. 1, the title complex has a mononuclear structure, in which the (4-oxo-4H-pyridin-1-yl)acetate ligands are coordinated to the MnII atom through the carbonyl O atoms in a monodentate fashion. The MnII atom is located on an inversion center and is coordinated by two carbonyl O atoms and four water molecules, forming an octahedral coordination geometry. The Mn—Ocarbonyl bond distance is 2.1960 (11) Å, and the Mn—Ow distances are 2.1557 (14) and 2.1952 (12) Å.
The planes of the carboxylate group (O1/O2/C1/C2) and pyridine ring (N1/C3—C7) form a dihedral angle of 67.27 (9)°. The C—O bond lengths [O1—C1 = 1.2566 (18) Å and O2—C1 = 1.2366 (19) Å] suggest delocalization of π-electron density over the carboxylate group.
The coordinated water molecules form intermolecular O—H···O hydrogen bonds with uncoordinated carboxylate groups of adjacent molecules, connecting the mononuclear units into a two-dimensional network parallel to the (0 1 1) plane. The O···O distances of the hydrogen bonds lie in the range 2.6557 (17)–2.7677 (17) Å and the O—H···O angles range from 169.5 (19) to 178 (2)° (Table 1). The adjacent networks are cross-linked via weak π-π stacking interactions between the pyridine rings of the molecules at (x, y, z) and (1 - x, 1 - y, -z), with a centroid···centroid distance of 3.758 (3) Å (Fig. 2).