catena-Poly[[aqua(4,4′-bipyridine-κN)manganese(II)]-μ-imidazole-4,5-dicarboxylato-κ4N3,O4:O4′,O5]
Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807054141/nc2070sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807054141/nc2070Isup2.hkl |
CCDC reference: 672571
A mixture of MnCl2 (0.5 mmol), imidazole-4,5-dicarboxylic acid (0.5 mmol), 4,4'-bipyridine (0.8 mmol), and water (10 ml) was stirred for 20 min and then transferred into a 23 ml Teflon reactor. The reactor was kept at 433 K for 120 h under autogenous pressure. Single crystals of (I) were obtained after cooling to room temperature.
H atoms were placed in calculated positions with C—H = 0.93 Å and N—H = 0.86 Å, and refined in riding mode with Uiso(H) = 1.2Ueq(C,N). The H atoms of the water molecule were located in difference map, their bond lengths were set to 0.85 Å and afterwards they were refined using a riding model with Uiso(H) = 1.5Ueq(O).
Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-Plus (Sheldrick, 1990); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997.
Fig. 1. Crystal structure of (I) with labeling and displacement ellipsoids drawn at the 50% probability level. |
[Mn(C5H2N2O4)(C10H8N2)(H2O)] | F(000) = 780 |
Mr = 383.23 | Dx = 1.626 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 14768 reflections |
a = 14.051 (3) Å | θ = 3.0–27.5° |
b = 8.2084 (16) Å | µ = 0.88 mm−1 |
c = 13.979 (3) Å | T = 298 K |
β = 103.80 (3)° | Block, colorless |
V = 1565.8 (5) Å3 | 0.24 × 0.18 × 0.17 mm |
Z = 4 |
Bruker APEX CCD area-detector diffractometer | 3585 independent reflections |
Radiation source: fine-focus sealed tube | 3170 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.025 |
ω scans | θmax = 27.5°, θmin = 3.0° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −18→18 |
Tmin = 0.817, Tmax = 0.865 | k = −10→10 |
14768 measured reflections | l = −18→17 |
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)] = 0.028 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.074 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0398P)2 + 0.4434P] where P = (Fo2 + 2Fc2)/3 |
3585 reflections | (Δ/σ)max = 0.001 |
228 parameters | Δρmax = 0.30 e Å−3 |
0 restraints | Δρmin = −0.25 e Å−3 |
[Mn(C5H2N2O4)(C10H8N2)(H2O)] | V = 1565.8 (5) Å3 |
Mr = 383.23 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 14.051 (3) Å | µ = 0.88 mm−1 |
b = 8.2084 (16) Å | T = 298 K |
c = 13.979 (3) Å | 0.24 × 0.18 × 0.17 mm |
β = 103.80 (3)° |
Bruker APEX CCD area-detector diffractometer | 3585 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 3170 reflections with I > 2σ(I) |
Tmin = 0.817, Tmax = 0.865 | Rint = 0.025 |
14768 measured reflections |
R[F2 > 2σ(F2)] = 0.028 | 0 restraints |
wR(F2) = 0.074 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.30 e Å−3 |
3585 reflections | Δρmin = −0.25 e Å−3 |
228 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 | 0.655818 (15) | 0.01342 (3) | 0.319366 (15) | 0.01988 (8) | |
C1 | 0.54650 (12) | 0.1764 (2) | 0.48789 (11) | 0.0298 (3) | |
H1A | 0.5925 | 0.1506 | 0.5456 | 0.036* | |
C2 | 0.47557 (10) | 0.21157 (17) | 0.33523 (10) | 0.0205 (3) | |
C3 | 0.41124 (11) | 0.26685 (17) | 0.38842 (10) | 0.0218 (3) | |
C4 | 0.47212 (10) | 0.20023 (17) | 0.22797 (10) | 0.0211 (3) | |
C5 | 0.30854 (11) | 0.33264 (18) | 0.36474 (11) | 0.0240 (3) | |
C6 | 0.84725 (13) | 0.2004 (2) | 0.31644 (14) | 0.0353 (4) | |
H6A | 0.8634 | 0.0935 | 0.3049 | 0.042* | |
C7 | 0.92054 (13) | 0.3157 (2) | 0.33212 (14) | 0.0349 (4) | |
H7A | 0.9844 | 0.2855 | 0.3322 | 0.042* | |
C8 | 0.89897 (12) | 0.47683 (18) | 0.34779 (12) | 0.0280 (3) | |
C9 | 0.80176 (14) | 0.5129 (2) | 0.34472 (18) | 0.0451 (5) | |
H9A | 0.7829 | 0.6197 | 0.3523 | 0.054* | |
C10 | 0.73332 (13) | 0.3891 (2) | 0.33030 (17) | 0.0432 (5) | |
H10A | 0.6689 | 0.4156 | 0.3299 | 0.052* | |
C11 | 1.14620 (13) | 0.6796 (2) | 0.42065 (14) | 0.0407 (4) | |
H11A | 1.2117 | 0.6482 | 0.4351 | 0.049* | |
C12 | 1.07570 (13) | 0.5603 (2) | 0.39433 (14) | 0.0383 (4) | |
H12A | 1.0941 | 0.4518 | 0.3922 | 0.046* | |
C13 | 0.97745 (12) | 0.60229 (19) | 0.37104 (12) | 0.0292 (3) | |
C14 | 0.95562 (14) | 0.7667 (2) | 0.37459 (17) | 0.0446 (5) | |
H14A | 0.8909 | 0.8023 | 0.3585 | 0.054* | |
C15 | 1.03154 (15) | 0.8763 (2) | 0.40235 (17) | 0.0497 (5) | |
H15A | 1.0156 | 0.9860 | 0.4043 | 0.060* | |
N1 | 0.55941 (9) | 0.15294 (16) | 0.39850 (9) | 0.0250 (3) | |
N2 | 0.45860 (10) | 0.24189 (17) | 0.48485 (9) | 0.0277 (3) | |
H2A | 0.4357 | 0.2645 | 0.5351 | 0.033* | |
N3 | 0.75455 (10) | 0.23313 (16) | 0.31690 (10) | 0.0302 (3) | |
N4 | 1.12591 (11) | 0.83635 (19) | 0.42656 (12) | 0.0411 (4) | |
O1 | 0.40748 (8) | 0.27583 (13) | 0.16630 (7) | 0.0267 (2) | |
O2 | 0.53640 (9) | 0.11390 (15) | 0.20466 (7) | 0.0329 (3) | |
O3 | 0.27564 (8) | 0.39872 (14) | 0.28237 (8) | 0.0289 (2) | |
O4 | 0.26300 (9) | 0.31810 (17) | 0.43017 (9) | 0.0432 (3) | |
O1W | 0.75594 (8) | −0.06111 (14) | 0.45556 (8) | 0.0335 (3) | |
H1 | 0.7967 | 0.0042 | 0.4908 | 0.050* | |
H2 | 0.7548 | −0.1473 | 0.4890 | 0.050* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mn1 | 0.01936 (12) | 0.02130 (12) | 0.01915 (11) | 0.00103 (8) | 0.00493 (8) | −0.00106 (8) |
C1 | 0.0283 (8) | 0.0426 (9) | 0.0173 (6) | 0.0069 (7) | 0.0032 (6) | 0.0028 (6) |
C2 | 0.0214 (7) | 0.0234 (6) | 0.0165 (6) | 0.0028 (5) | 0.0045 (5) | 0.0016 (5) |
C3 | 0.0250 (7) | 0.0238 (7) | 0.0175 (6) | 0.0029 (6) | 0.0071 (5) | 0.0026 (5) |
C4 | 0.0232 (7) | 0.0232 (6) | 0.0172 (6) | 0.0005 (6) | 0.0054 (5) | −0.0007 (5) |
C5 | 0.0251 (7) | 0.0238 (7) | 0.0258 (7) | 0.0045 (6) | 0.0115 (6) | 0.0046 (6) |
C6 | 0.0365 (9) | 0.0250 (7) | 0.0482 (10) | −0.0016 (7) | 0.0178 (8) | −0.0051 (7) |
C7 | 0.0284 (8) | 0.0289 (8) | 0.0512 (10) | −0.0011 (7) | 0.0171 (7) | −0.0053 (7) |
C8 | 0.0280 (8) | 0.0244 (7) | 0.0313 (8) | −0.0023 (6) | 0.0066 (6) | 0.0003 (6) |
C9 | 0.0313 (9) | 0.0234 (8) | 0.0796 (15) | 0.0017 (7) | 0.0110 (9) | −0.0024 (8) |
C10 | 0.0252 (8) | 0.0297 (8) | 0.0738 (13) | 0.0008 (7) | 0.0100 (8) | −0.0002 (9) |
C11 | 0.0272 (8) | 0.0425 (10) | 0.0492 (10) | −0.0043 (7) | 0.0030 (8) | −0.0037 (8) |
C12 | 0.0318 (9) | 0.0300 (8) | 0.0515 (10) | −0.0002 (7) | 0.0068 (8) | −0.0035 (8) |
C13 | 0.0291 (8) | 0.0259 (7) | 0.0318 (8) | −0.0026 (6) | 0.0061 (6) | −0.0022 (6) |
C14 | 0.0314 (9) | 0.0280 (8) | 0.0699 (13) | −0.0004 (7) | 0.0030 (9) | −0.0051 (9) |
C15 | 0.0438 (11) | 0.0262 (8) | 0.0734 (14) | −0.0043 (8) | 0.0023 (10) | −0.0076 (9) |
N1 | 0.0230 (6) | 0.0341 (7) | 0.0177 (5) | 0.0055 (5) | 0.0043 (5) | 0.0017 (5) |
N2 | 0.0314 (7) | 0.0376 (7) | 0.0157 (5) | 0.0069 (6) | 0.0087 (5) | 0.0009 (5) |
N3 | 0.0291 (7) | 0.0265 (6) | 0.0355 (7) | −0.0035 (5) | 0.0084 (6) | 0.0009 (6) |
N4 | 0.0371 (8) | 0.0382 (8) | 0.0434 (8) | −0.0112 (7) | 0.0003 (7) | −0.0048 (7) |
O1 | 0.0304 (6) | 0.0332 (6) | 0.0159 (4) | 0.0109 (5) | 0.0044 (4) | 0.0028 (4) |
O2 | 0.0347 (6) | 0.0458 (7) | 0.0185 (5) | 0.0190 (5) | 0.0069 (4) | 0.0000 (5) |
O3 | 0.0235 (5) | 0.0364 (6) | 0.0282 (5) | 0.0051 (5) | 0.0090 (4) | 0.0116 (5) |
O4 | 0.0412 (7) | 0.0554 (8) | 0.0424 (7) | 0.0229 (6) | 0.0284 (6) | 0.0240 (6) |
O1W | 0.0351 (6) | 0.0305 (6) | 0.0281 (5) | −0.0091 (5) | −0.0060 (5) | 0.0048 (5) |
Mn1—O3i | 2.1190 (11) | C7—H7A | 0.9300 |
Mn1—O1W | 2.1680 (13) | C8—C9 | 1.388 (2) |
Mn1—O1i | 2.1725 (11) | C8—C13 | 1.487 (2) |
Mn1—O2 | 2.1870 (13) | C9—C10 | 1.380 (3) |
Mn1—N1 | 2.2550 (13) | C9—H9A | 0.9300 |
Mn1—N3 | 2.2805 (14) | C10—N3 | 1.338 (2) |
C1—N1 | 1.3190 (19) | C10—H10A | 0.9300 |
C1—N2 | 1.338 (2) | C11—N4 | 1.325 (3) |
C1—H1A | 0.9300 | C11—C12 | 1.379 (3) |
C2—C3 | 1.3772 (19) | C11—H11A | 0.9300 |
C2—N1 | 1.3800 (18) | C12—C13 | 1.384 (2) |
C2—C4 | 1.4915 (18) | C12—H12A | 0.9300 |
C3—N2 | 1.3689 (18) | C13—C14 | 1.387 (2) |
C3—C5 | 1.502 (2) | C14—C15 | 1.379 (3) |
C4—O2 | 1.2509 (18) | C14—H14A | 0.9300 |
C4—O1 | 1.2567 (18) | C15—N4 | 1.329 (3) |
C5—O4 | 1.2409 (18) | C15—H15A | 0.9300 |
C5—O3 | 1.2569 (18) | N2—H2A | 0.8600 |
C6—N3 | 1.331 (2) | O1—Mn1ii | 2.1725 (11) |
C6—C7 | 1.377 (2) | O3—Mn1ii | 2.1190 (11) |
C6—H6A | 0.9300 | O1W—H1 | 0.8499 |
C7—C8 | 1.386 (2) | O1W—H2 | 0.8500 |
O3i—Mn1—O1W | 99.23 (5) | C9—C8—C13 | 122.15 (15) |
O3i—Mn1—O1i | 85.68 (4) | C10—C9—C8 | 119.60 (16) |
O1W—Mn1—O1i | 81.94 (4) | C10—C9—H9A | 120.2 |
O3i—Mn1—O2 | 93.87 (4) | C8—C9—H9A | 120.2 |
O1W—Mn1—O2 | 166.88 (5) | N3—C10—C9 | 123.64 (17) |
O1i—Mn1—O2 | 98.44 (5) | N3—C10—H10A | 118.2 |
O3i—Mn1—N1 | 167.76 (4) | C9—C10—H10A | 118.2 |
O1W—Mn1—N1 | 93.00 (5) | N4—C11—C12 | 123.70 (17) |
O1i—Mn1—N1 | 95.95 (5) | N4—C11—H11A | 118.2 |
O2—Mn1—N1 | 73.89 (4) | C12—C11—H11A | 118.2 |
O3i—Mn1—N3 | 88.03 (5) | C11—C12—C13 | 119.90 (17) |
O1W—Mn1—N3 | 88.10 (5) | C11—C12—H12A | 120.0 |
O1i—Mn1—N3 | 167.21 (5) | C13—C12—H12A | 120.0 |
O2—Mn1—N3 | 93.08 (5) | C12—C13—C14 | 116.77 (16) |
N1—Mn1—N3 | 92.56 (5) | C12—C13—C8 | 121.66 (15) |
N1—C1—N2 | 111.28 (13) | C14—C13—C8 | 121.52 (15) |
N1—C1—H1A | 124.4 | C15—C14—C13 | 118.82 (17) |
N2—C1—H1A | 124.4 | C15—C14—H14A | 120.6 |
C3—C2—N1 | 109.80 (12) | C13—C14—H14A | 120.6 |
C3—C2—C4 | 134.05 (13) | N4—C15—C14 | 124.66 (18) |
N1—C2—C4 | 116.14 (12) | N4—C15—H15A | 117.7 |
N2—C3—C2 | 104.77 (12) | C14—C15—H15A | 117.7 |
N2—C3—C5 | 119.12 (13) | C1—N1—C2 | 105.49 (12) |
C2—C3—C5 | 136.00 (13) | C1—N1—Mn1 | 140.65 (11) |
O2—C4—O1 | 123.34 (13) | C2—N1—Mn1 | 112.55 (9) |
O2—C4—C2 | 116.41 (12) | C1—N2—C3 | 108.64 (12) |
O1—C4—C2 | 120.24 (13) | C1—N2—H2A | 125.7 |
O4—C5—O3 | 125.12 (14) | C3—N2—H2A | 125.7 |
O4—C5—C3 | 116.12 (13) | C6—N3—C10 | 116.42 (14) |
O3—C5—C3 | 118.76 (13) | C6—N3—Mn1 | 116.08 (11) |
N3—C6—C7 | 123.76 (15) | C10—N3—Mn1 | 126.72 (12) |
N3—C6—H6A | 118.1 | C11—N4—C15 | 116.11 (16) |
C7—C6—H6A | 118.1 | C4—O1—Mn1ii | 128.66 (9) |
C6—C7—C8 | 119.84 (16) | C4—O2—Mn1 | 119.87 (9) |
C6—C7—H7A | 120.1 | C5—O3—Mn1ii | 132.84 (10) |
C8—C7—H7A | 120.1 | Mn1—O1W—H1 | 122.5 |
C7—C8—C9 | 116.69 (15) | Mn1—O1W—H2 | 128.7 |
C7—C8—C13 | 121.11 (15) | H1—O1W—H2 | 107.7 |
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) −x+1, y+1/2, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O1iii | 0.86 | 1.99 | 2.8002 (17) | 156 |
N2—H2A···O2iii | 0.86 | 2.65 | 3.2305 (18) | 126 |
O1W—H1···N4iv | 0.85 | 1.91 | 2.7513 (19) | 173 |
O1W—H2···O4v | 0.85 | 1.85 | 2.6972 (17) | 171 |
Symmetry codes: (iii) x, −y+1/2, z+1/2; (iv) −x+2, −y+1, −z+1; (v) −x+1, −y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Mn(C5H2N2O4)(C10H8N2)(H2O)] |
Mr | 383.23 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 298 |
a, b, c (Å) | 14.051 (3), 8.2084 (16), 13.979 (3) |
β (°) | 103.80 (3) |
V (Å3) | 1565.8 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.88 |
Crystal size (mm) | 0.24 × 0.18 × 0.17 |
Data collection | |
Diffractometer | Bruker APEX CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.817, 0.865 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14768, 3585, 3170 |
Rint | 0.025 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.028, 0.074, 1.08 |
No. of reflections | 3585 |
No. of parameters | 228 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.30, −0.25 |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL-Plus (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997.
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O1i | 0.86 | 1.99 | 2.8002 (17) | 155.6 |
N2—H2A···O2i | 0.86 | 2.65 | 3.2305 (18) | 126.0 |
O1W—H1···N4ii | 0.85 | 1.91 | 2.7513 (19) | 172.8 |
O1W—H2···O4iii | 0.85 | 1.85 | 2.6972 (17) | 170.7 |
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) −x+2, −y+1, −z+1; (iii) −x+1, −y, −z+1. |
Investigations on metal carboxylate coordination polymers have become of increasing interest in the past few years Wang et al. 2005; Hao et al. 2005). As a part of our ongoing investigations in this field we report here the crystal structure of the title compound. In the crystal structure of the title compound the Mn atoms are coordinated by one oxygen atom of a water molecule, one nitrogen atom of a 4,4'-bipyridine ligand, one N and one O atom of an imidazole-4,5-dicarboxylate anion and one carboxylate group of a symmetry related imidazole-4,5-dicarboxylate anion within a distorted octahedral coordination geometry (Figure 1). The manganese atoms are linked by the anions into chains that elongate in the direction of the crystallographic b axis. These chains are further connected by N—H···O, O—H···N and O—H···O hydrogen bonding into a three-dimensional network (Tab. 1).