Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104009953/av1183sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104009953/av1183Isup2.hkl |
CCDC reference: 224969
The pH value of an aqueous mixture (10 ml) of Mn(NO3)2·6H2O (0.29 g, 1 mmol), succinic acid (0.12 g, 1 mmol) and 4,4'-bipyridine (0.24 g, 1.5 mmol) was pre-adjusted to about 7 with a 0.1 M NaOH aqueous solution, and the mixture was transferred into a sealed Teflon-lined stainless-steel vessel (20 ml). The vessel was heated at 323 K for 4 d and then cooled to room temperature, to yield pale-yellow crystals of (I). Analysis calculated for C19H18MnN3O5: C 53.91, H 4.29, N 9.93%; C 53.87, H 4.32, N 9.89%. FT–IR (KBr, N, cm−1): 3317 (br, s), 1603 (s), 1535 (versus), 1487 (m), 1452 (m), 1410 (versus), 1387 (versus), 1319 (m), 1237 (w), 1215 (m), 1153 (m), 1086 (w), 1061 (m), 1043 (w), 1005 (w), 989 (w), 872 (w), 814(s), 802 (s), 731 (m), 652 (s), 627 (s), 607 (m), 498 (w), 472 (w).
The water H atoms were located from difference maps and refined with a DFIX restraint of 0.85 (2) Å applied to the two O—H distances. Other H atoms were placed in calculated positions and treated as riding atoms.
Data collection: SMART (Siemens,1996); cell refinement: SAINT (Siemens,1994); data reduction: SHELXTL (Siemens,1994) and SAINT; program(s) used to solve structure: SHELXTL; program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
[Mn(C4H4O4)(C10H8N2)(H2O)]·0.5C10H8N2 | F(000) = 872 |
Mr = 423.30 | Dx = 1.537 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 2349 reflections |
a = 11.7070 (11) Å | θ = 1.8–25.1° |
b = 17.8824 (16) Å | µ = 0.76 mm−1 |
c = 8.8647 (8) Å | T = 293 K |
β = 99.713 (2)° | Prism, pale-yellow |
V = 1829.2 (3) Å3 | 0.30 × 0.24 × 0.10 mm |
Z = 4 |
Siemens SMART CCD area-detector diffractometer | 3178 independent reflections |
Radiation source: fine-focus sealed tube | 2302 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.033 |
ϕ and ω scans | θmax = 25.1°, θmin = 1.8° |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | h = −8→13 |
Tmin = 0.804, Tmax = 0.927 | k = −19→21 |
5491 measured reflections | l = −10→6 |
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)] = 0.054 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.138 | H-atom parameters constrained |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0485P)2 + 3.436P] where P = (Fo2 + 2Fc2)/3 |
3178 reflections | (Δ/σ)max < 0.001 |
261 parameters | Δρmax = 0.30 e Å−3 |
2 restraints | Δρmin = −0.49 e Å−3 |
[Mn(C4H4O4)(C10H8N2)(H2O)]·0.5C10H8N2 | V = 1829.2 (3) Å3 |
Mr = 423.30 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 11.7070 (11) Å | µ = 0.76 mm−1 |
b = 17.8824 (16) Å | T = 293 K |
c = 8.8647 (8) Å | 0.30 × 0.24 × 0.10 mm |
β = 99.713 (2)° |
Siemens SMART CCD area-detector diffractometer | 3178 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 2302 reflections with I > 2σ(I) |
Tmin = 0.804, Tmax = 0.927 | Rint = 0.033 |
5491 measured reflections |
R[F2 > 2σ(F2)] = 0.054 | 2 restraints |
wR(F2) = 0.138 | H-atom parameters constrained |
S = 1.09 | Δρmax = 0.30 e Å−3 |
3178 reflections | Δρmin = −0.49 e Å−3 |
261 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 | ||
Mn | 0.61880 (5) | 0.82992 (3) | 0.20599 (7) | 0.0261 (2) | |
O1 | 0.6146 (3) | 0.95051 (17) | 0.1846 (3) | 0.0429 (8) | |
O2 | 0.6489 (4) | 0.99740 (19) | 0.4181 (4) | 0.0679 (12) | |
O3 | 0.4120 (3) | 1.19403 (16) | 0.0346 (3) | 0.0362 (7) | |
O4 | 0.3876 (3) | 1.20767 (15) | 0.2746 (3) | 0.0330 (7) | |
O5 | 0.6590 (3) | 0.85278 (18) | 0.4500 (3) | 0.0367 (7) | |
H5B | 0.641 (4) | 0.830 (2) | 0.525 (4) | 0.039 (13)* | |
H5C | 0.652 (6) | 0.8998 (13) | 0.459 (8) | 0.11 (3)* | |
N1 | 0.8147 (3) | 0.8276 (2) | 0.1988 (4) | 0.0367 (9) | |
N2 | 1.4227 (3) | 0.8306 (2) | 0.2053 (4) | 0.0322 (8) | |
N3 | 1.0058 (6) | 0.6112 (4) | 0.1706 (8) | 0.116 (3) | |
C1 | 0.8624 (4) | 0.7909 (3) | 0.0939 (7) | 0.0632 (17) | |
H1A | 0.8139 | 0.7646 | 0.0183 | 0.076* | |
C2 | 0.9791 (4) | 0.7900 (3) | 0.0922 (7) | 0.0646 (17) | |
H2A | 1.0076 | 0.7632 | 0.0166 | 0.077* | |
C3 | 1.0548 (4) | 0.8281 (2) | 0.2007 (5) | 0.0337 (10) | |
C4 | 1.0051 (4) | 0.8661 (3) | 0.3071 (6) | 0.0523 (14) | |
H4A | 1.0519 | 0.8929 | 0.3837 | 0.063* | |
C5 | 0.8870 (4) | 0.8651 (3) | 0.3023 (6) | 0.0504 (13) | |
H5A | 0.8565 | 0.8923 | 0.3756 | 0.060* | |
C6 | 1.1820 (3) | 0.8289 (2) | 0.2026 (5) | 0.0329 (10) | |
C7 | 1.2336 (4) | 0.7825 (3) | 0.1086 (6) | 0.0439 (12) | |
H7A | 1.1885 | 0.7496 | 0.0424 | 0.053* | |
C8 | 1.3521 (4) | 0.7851 (3) | 0.1132 (5) | 0.0429 (12) | |
H8A | 1.3845 | 0.7534 | 0.0487 | 0.051* | |
C9 | 1.3733 (4) | 0.8753 (3) | 0.2967 (5) | 0.0397 (11) | |
H9A | 1.4205 | 0.9075 | 0.3622 | 0.048* | |
C10 | 1.2558 (4) | 0.8760 (3) | 0.2985 (5) | 0.0429 (12) | |
H10A | 1.2257 | 0.9082 | 0.3642 | 0.051* | |
C11 | 0.6170 (4) | 1.0031 (2) | 0.2783 (6) | 0.0390 (11) | |
C12 | 0.5766 (4) | 1.0794 (3) | 0.2152 (7) | 0.0514 (13) | |
H12A | 0.6141 | 1.1179 | 0.2831 | 0.062* | |
H12B | 0.5997 | 1.0862 | 0.1160 | 0.062* | |
C13 | 0.4466 (4) | 1.0881 (2) | 0.1986 (5) | 0.0355 (10) | |
H13A | 0.4090 | 1.0567 | 0.1156 | 0.043* | |
H13B | 0.4213 | 1.0719 | 0.2921 | 0.043* | |
C14 | 0.4118 (3) | 1.1682 (2) | 0.1665 (4) | 0.0267 (9) | |
C15 | 1.0991 (7) | 0.5803 (5) | 0.2482 (9) | 0.105 (3) | |
H15A | 1.1686 | 0.5877 | 0.2129 | 0.126* | |
C16 | 1.1018 (6) | 0.5379 (4) | 0.3771 (8) | 0.080 (2) | |
H16A | 1.1720 | 0.5192 | 0.4279 | 0.096* | |
C17 | 1.0012 (5) | 0.5229 (3) | 0.4319 (6) | 0.0510 (13) | |
C18 | 0.9034 (6) | 0.5536 (4) | 0.3492 (8) | 0.082 (2) | |
H18A | 0.8319 | 0.5450 | 0.3787 | 0.099* | |
C19 | 0.9093 (8) | 0.5968 (6) | 0.2240 (10) | 0.120 (3) | |
H19A | 0.8408 | 0.6174 | 0.1726 | 0.144* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mn | 0.0218 (3) | 0.0283 (3) | 0.0290 (3) | 0.0001 (3) | 0.0069 (2) | −0.0011 (3) |
O1 | 0.054 (2) | 0.0301 (17) | 0.0436 (19) | 0.0032 (15) | 0.0067 (16) | 0.0020 (14) |
O2 | 0.115 (3) | 0.038 (2) | 0.047 (2) | 0.009 (2) | 0.003 (2) | −0.0065 (17) |
O3 | 0.0475 (19) | 0.0359 (16) | 0.0269 (16) | 0.0067 (14) | 0.0113 (14) | 0.0002 (13) |
O4 | 0.0455 (18) | 0.0260 (15) | 0.0294 (15) | 0.0027 (13) | 0.0119 (13) | −0.0011 (13) |
O5 | 0.0483 (19) | 0.0337 (18) | 0.0304 (17) | −0.0014 (15) | 0.0134 (15) | 0.0030 (14) |
N1 | 0.0237 (18) | 0.040 (2) | 0.048 (2) | −0.0019 (17) | 0.0093 (17) | −0.0005 (18) |
N2 | 0.0227 (18) | 0.037 (2) | 0.0361 (19) | 0.0002 (16) | 0.0038 (15) | −0.0015 (17) |
N3 | 0.100 (5) | 0.162 (7) | 0.088 (5) | 0.044 (5) | 0.020 (4) | 0.050 (5) |
C1 | 0.027 (3) | 0.067 (4) | 0.095 (5) | −0.004 (2) | 0.008 (3) | −0.043 (3) |
C2 | 0.028 (3) | 0.076 (4) | 0.092 (4) | −0.002 (3) | 0.016 (3) | −0.049 (3) |
C3 | 0.025 (2) | 0.034 (2) | 0.042 (2) | 0.0029 (19) | 0.0058 (19) | 0.003 (2) |
C4 | 0.030 (3) | 0.082 (4) | 0.045 (3) | −0.008 (3) | 0.006 (2) | −0.023 (3) |
C5 | 0.025 (2) | 0.082 (4) | 0.046 (3) | 0.000 (3) | 0.013 (2) | −0.018 (3) |
C6 | 0.025 (2) | 0.034 (2) | 0.040 (2) | 0.0012 (19) | 0.0074 (19) | 0.003 (2) |
C7 | 0.024 (2) | 0.056 (3) | 0.051 (3) | −0.007 (2) | 0.006 (2) | −0.017 (2) |
C8 | 0.032 (3) | 0.053 (3) | 0.045 (3) | −0.001 (2) | 0.010 (2) | −0.016 (2) |
C9 | 0.026 (2) | 0.047 (3) | 0.047 (3) | −0.002 (2) | 0.009 (2) | −0.011 (2) |
C10 | 0.030 (2) | 0.050 (3) | 0.052 (3) | −0.002 (2) | 0.013 (2) | −0.017 (2) |
C11 | 0.033 (3) | 0.032 (3) | 0.052 (3) | 0.003 (2) | 0.007 (2) | 0.002 (2) |
C12 | 0.042 (3) | 0.028 (2) | 0.085 (4) | 0.008 (2) | 0.013 (3) | 0.009 (3) |
C13 | 0.040 (3) | 0.028 (2) | 0.041 (3) | 0.002 (2) | 0.013 (2) | 0.0018 (19) |
C14 | 0.026 (2) | 0.026 (2) | 0.028 (2) | −0.0011 (17) | 0.0075 (17) | 0.0005 (18) |
C15 | 0.078 (5) | 0.139 (8) | 0.103 (6) | 0.031 (5) | 0.031 (5) | 0.045 (6) |
C16 | 0.058 (4) | 0.107 (5) | 0.073 (4) | 0.020 (4) | 0.003 (3) | 0.025 (4) |
C17 | 0.047 (3) | 0.052 (3) | 0.050 (3) | 0.012 (3) | −0.006 (3) | −0.016 (2) |
C18 | 0.057 (4) | 0.106 (6) | 0.079 (5) | 0.024 (4) | 0.000 (3) | 0.024 (4) |
C19 | 0.090 (6) | 0.170 (10) | 0.098 (6) | 0.054 (6) | 0.011 (5) | 0.052 (6) |
Mn—O3i | 2.145 (3) | C5—H5A | 0.9300 |
Mn—O1 | 2.165 (3) | C6—C7 | 1.384 (6) |
Mn—O5 | 2.173 (3) | C6—C10 | 1.390 (6) |
Mn—O4ii | 2.195 (3) | C7—C8 | 1.382 (6) |
Mn—N2iii | 2.295 (3) | C7—H7A | 0.9300 |
Mn—N1 | 2.305 (3) | C8—H8A | 0.9300 |
O1—C11 | 1.252 (5) | C9—C10 | 1.378 (6) |
O2—C11 | 1.236 (6) | C9—H9A | 0.9300 |
O3—C14 | 1.258 (5) | C10—H10A | 0.9300 |
O4—C14 | 1.260 (5) | C11—C12 | 1.520 (6) |
O5—H5B | 0.84 (4) | C12—C13 | 1.512 (6) |
O5—H5C | 0.85 (2) | C12—H12A | 0.9700 |
N1—C5 | 1.322 (6) | C12—H12B | 0.9700 |
N1—C1 | 1.335 (6) | C13—C14 | 1.503 (5) |
N2—C8 | 1.336 (5) | C13—H13A | 0.9700 |
N2—C9 | 1.337 (5) | C13—H13B | 0.9700 |
N3—C15 | 1.311 (9) | C15—C16 | 1.366 (9) |
N3—C19 | 1.321 (10) | C15—H15A | 0.9300 |
C1—C2 | 1.370 (7) | C16—C17 | 1.374 (8) |
C1—H1A | 0.9300 | C16—H16A | 0.9300 |
C2—C3 | 1.373 (7) | C17—C18 | 1.367 (7) |
C2—H2A | 0.9300 | C17—C17iv | 1.463 (11) |
C3—C4 | 1.369 (6) | C18—C19 | 1.363 (10) |
C3—C6 | 1.486 (5) | C18—H18A | 0.9300 |
C4—C5 | 1.377 (6) | C19—H19A | 0.9300 |
C4—H4A | 0.9300 | ||
O3i—Mn—O1 | 96.56 (11) | C7—C6—C3 | 121.7 (4) |
O3i—Mn—O5 | 177.14 (12) | C10—C6—C3 | 122.1 (4) |
O1—Mn—O5 | 84.14 (12) | C8—C7—C6 | 120.1 (4) |
O3i—Mn—O4ii | 82.93 (11) | C8—C7—H7A | 120.0 |
O1—Mn—O4ii | 176.79 (12) | C6—C7—H7A | 120.0 |
O5—Mn—O4ii | 96.53 (11) | N2—C8—C7 | 123.5 (4) |
O3i—Mn—N2iii | 89.90 (12) | N2—C8—H8A | 118.2 |
O1—Mn—N2iii | 89.22 (13) | C7—C8—H8A | 118.2 |
O5—Mn—N2iii | 92.89 (12) | N2—C9—C10 | 123.2 (4) |
O4ii—Mn—N2iii | 87.61 (12) | N2—C9—H9A | 118.4 |
O3i—Mn—N1 | 88.28 (12) | C10—C9—H9A | 118.4 |
O1—Mn—N1 | 91.36 (13) | C9—C10—C6 | 120.4 (4) |
O5—Mn—N1 | 88.93 (13) | C9—C10—H10A | 119.8 |
O4ii—Mn—N1 | 91.79 (12) | C6—C10—H10A | 119.8 |
N2iii—Mn—N1 | 178.14 (13) | O2—C11—O1 | 124.9 (4) |
C11—O1—Mn | 133.8 (3) | O2—C11—C12 | 117.8 (4) |
C14—O3—Mni | 145.5 (3) | O1—C11—C12 | 117.3 (4) |
C14—O4—Mnv | 129.3 (3) | C13—C12—C11 | 111.9 (4) |
Mn—O5—H5B | 131 (3) | C13—C12—H12A | 109.2 |
O3ii—O5—H5B | 52 (3) | C11—C12—H12A | 109.2 |
Mn—O5—H5C | 106 (5) | C13—C12—H12B | 109.2 |
O4vi—O5—H5C | 105 (5) | C11—C12—H12B | 109.2 |
O3ii—O5—H5C | 155 (5) | H12A—C12—H12B | 107.9 |
H5B—O5—H5C | 111 (6) | C14—C13—C12 | 110.6 (3) |
C5—N1—C1 | 116.0 (4) | C14—C13—H13A | 109.5 |
C5—N1—Mn | 119.7 (3) | C12—C13—H13A | 109.5 |
C1—N1—Mn | 124.3 (3) | C14—C13—H13B | 109.5 |
C8—N2—C9 | 116.6 (4) | C12—C13—H13B | 109.5 |
C8—N2—Mnvii | 120.9 (3) | H13A—C13—H13B | 108.1 |
C9—N2—Mnvii | 122.5 (3) | O3—C14—O4 | 122.4 (4) |
C15—N3—C19 | 114.6 (7) | O3—C14—C13 | 118.9 (4) |
N1—C1—C2 | 123.3 (5) | O4—C14—C13 | 118.6 (3) |
N1—C1—H1A | 118.4 | N3—C15—C16 | 124.9 (7) |
C2—C1—H1A | 118.4 | N3—C15—H15A | 117.5 |
C1—C2—C3 | 120.9 (5) | C16—C15—H15A | 117.5 |
C1—C2—H2A | 119.6 | C15—C16—C17 | 120.2 (6) |
C3—C2—H2A | 119.6 | C15—C16—H16A | 119.9 |
C4—C3—C2 | 115.5 (4) | C17—C16—H16A | 119.9 |
C4—C3—C6 | 121.9 (4) | C18—C17—C16 | 115.0 (6) |
C2—C3—C6 | 122.6 (4) | C18—C17—C17iv | 122.4 (7) |
C3—C4—C5 | 120.9 (5) | C16—C17—C17iv | 122.6 (6) |
C3—C4—H4A | 119.6 | C19—C18—C17 | 120.7 (7) |
C5—C4—H4A | 119.6 | C19—C18—H18A | 119.7 |
N1—C5—C4 | 123.4 (4) | C17—C18—H18A | 119.7 |
N1—C5—H5A | 118.3 | N3—C19—C18 | 124.5 (7) |
C4—C5—H5A | 118.3 | N3—C19—H19A | 117.8 |
C7—C6—C10 | 116.2 (4) | C18—C19—H19A | 117.8 |
Symmetry codes: (i) −x+1, −y+2, −z; (ii) −x+1, y−1/2, −z+1/2; (iii) x−1, y, z; (iv) −x+2, −y+1, −z+1; (v) −x+1, y+1/2, −z+1/2; (vi) −x+1, −y+2, −z+1; (vii) x+1, y, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5B···O4vi | 0.84 (4) | 1.98 (2) | 2.807 (4) | 169 (4) |
O5—H5C···O2 | 0.85 (2) | 1.78 (3) | 2.602 (5) | 161 (7) |
Symmetry code: (vi) −x+1, −y+2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Mn(C4H4O4)(C10H8N2)(H2O)]·0.5C10H8N2 |
Mr | 423.30 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 11.7070 (11), 17.8824 (16), 8.8647 (8) |
β (°) | 99.713 (2) |
V (Å3) | 1829.2 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.76 |
Crystal size (mm) | 0.30 × 0.24 × 0.10 |
Data collection | |
Diffractometer | Siemens SMART CCD area-detector diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.804, 0.927 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5491, 3178, 2302 |
Rint | 0.033 |
(sin θ/λ)max (Å−1) | 0.596 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.054, 0.138, 1.09 |
No. of reflections | 3178 |
No. of parameters | 261 |
No. of restraints | 2 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.30, −0.49 |
Computer programs: SMART (Siemens,1996), SAINT (Siemens,1994), SHELXTL (Siemens,1994) and SAINT, SHELXTL.
Mn—O3i | 2.145 (3) | Mn—N2iii | 2.295 (3) |
Mn—O1 | 2.165 (3) | Mn—N1 | 2.305 (3) |
Mn—O5 | 2.173 (3) | C12—C13 | 1.512 (6) |
Mn—O4ii | 2.195 (3) | ||
O3i—Mn—O1 | 96.56 (11) | O5—Mn—N2iii | 92.89 (12) |
O3i—Mn—O5 | 177.14 (12) | O4ii—Mn—N2iii | 87.61 (12) |
O1—Mn—O5 | 84.14 (12) | O3i—Mn—N1 | 88.28 (12) |
O3i—Mn—O4ii | 82.93 (11) | O1—Mn—N1 | 91.36 (13) |
O1—Mn—O4ii | 176.79 (12) | O5—Mn—N1 | 88.93 (13) |
O5—Mn—O4ii | 96.53 (11) | O4ii—Mn—N1 | 91.79 (12) |
O3i—Mn—N2iii | 89.90 (12) | N2iii—Mn—N1 | 178.14 (13) |
O1—Mn—N2iii | 89.22 (13) |
Symmetry codes: (i) −x+1, −y+2, −z; (ii) −x+1, y−1/2, −z+1/2; (iii) x−1, y, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5B···O4iv | 0.84 (4) | 1.98 (2) | 2.807 (4) | 169 (4) |
O5—H5C···O2 | 0.85 (2) | 1.78 (3) | 2.602 (5) | 161 (7) |
Symmetry code: (iv) −x+1, −y+2, −z+1. |
Owing to the great variety of intriguing structural topologies (Zaworotko, 1994) and their potential as functional materials in such fields as separation technology (Biradha & Fujita, 2002) and catalysis (Fujita et al., 1994), as well as in the field of molecular magnetism (Miller and Epstein, 1994), the crystal engineering of extended coordination polymers based on the metal node and the organic spacer has been actively investigated. One strategy that is commonly used to construct such extended frameworks is to select appropriate organic bridging ligands with versatile bonding modes capable of binding more than one metal ion. In this respect, the rigid aromatic dicarboxylates, such as the phthalate isomers, often in combination with other auxiliary ligands, such as 4,4'-bipyridine, have been used extensively in the design of such species because of the rigidity and versatile bonding modes of this type of ligand [Lo et al., 2000; Bourne et al., 2001; Suresh et al., 2001; Ma et al., 2003a].
We and other workers have explored the ability of structurally unsaturated aliphatic α,ω-dicarboxylates, such as maleate and fumarate, to build extended structural frameworks (Shi et al., 2000; Ma et al., 2003b). For comparison, we have also investigated the reaction of the structurally saturated counterpart, i.e. the succinate, with Mn2+ salts under hydrothermal conditions, and obtained the title compound, (I). Complex (I) represents a rare example of a three-dimensional metal–organic open framework with large channels encapsulating organic molecules, based on the combination of the rigid linear ligand and the structurally flexible saturated aliphatic α,ω-dicarboxylate ligand. In this paper, we report the single-crystal structure of (I).
The title compound contains neutral [Mn(succ)(bipy)(H2O)]n polymers and solvate bipy molecules in a molar ratio of 2:1. As shown in Fig. 1, the MnII center is six-coordinated by three carboxylate O atoms of three succ ligands, one water O atom and two pyridyl N atoms of bipy ligands, and displays slightly distorted MnO4N2 octahedral coordination geometry (Table 2), with the three trans angles [176.79 (12), 177.14 (12) and 178.14 (13)°] deviating slightly from the ideal value of 180°. The Mn—Ocarboxy distances [2.145 (3)–2.195 (3) Å] are comparable to those found in other Mn–succinate complexes (McCann et al., 1997; Fleck et al., 2000; Zheng et al., 2002; Xiang et al., 1998; Kim et al., 2001; Liu et al., 2001), and the slightly longer Mn—N distances [2.305 (3) and 2.295 (3) Å] and Mn—Owater distance [2.173 (3) Å] are similar to those found for the reported fumarate manganese(II) complex (Shi et al., 2000).
As shown in Fig. 2, each succ dianion acts as a tridentate bridging ligand, joining three Mn atoms through one bidentate bridging carboxylate group and one unidentate carboxylate group. Every two Mn atoms, at a distance of 5.274 (2) Å, are bridged by the bidentate carboxylate group of one succ ligand to form [Mn(µ-OCO)(H2O)]n zigzag chain, and the neighboring chains are cross-linked via the other, monodentate, end of the same succ ligand, forming [Mn(succ)(H2O)]n corrugated sheets, with syn Mn···Mn and anti Mn···Mn separations by the same succ ligand being 7.392 (2) and 9.435 (2) Å, respectively. Two intra-sheet hydrogen bonds are observed in the crystal structure, as listed in Table 2. The coordinated water molecule donates its one H atom to uncoordinated carboxyl O atom (O2) to form an O5—H5C···O2 hydrogen bond,; the second water H atom is donated to form another hydrogen bond with coordinated carboxyl atom O4 [O5—H5B···O4(-x + 1, −y + 2, −z + 1)].
Finally, the bipy ligands link the neighboring [Mn(succ)(H2O)]n sheets into an infinite three-dimensional framework, exhibiting two kinds of channels parallel to the c direction, with the uncoordinated bipy molecules encapsulated in these channels, as shown in Fig. 3. The Mn···Mn distance through the bipy bridging ligand is 11.707 (2) Å. The two pyridine rings of the uncoordinated bipy molecule are strictly coplanar as a result of the middle of the C17—C17(x − 1, 1 − y, 1 − z) single bond lying on the inversion center, whereas the pyridine rings of the coordinated bipy ligand are slightly twisted, as indicated by the small dihedral angle [9.1 (9)°] between them.