Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270109030832/sq3200sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109030832/sq3200Isup2.hkl |
CCDC reference: 749718
An aqueous solution (10 ml) of 4,4'-bipy (7.8 mg, 0.05 mmol), 5,5'-H4mdsa (14.4 mg, 0.05 mmol) and Mn(OAc)2.4H2O (12.3 mg, 0.05 mmol) was placed in a Parr Teflon-lined stainless steel vessel (20 ml), which was sealed and heated to 413 K for 72 h and then subsequently cooled to room temperature at a rate of 5 K h-1. Colourless block-shaped crystals of (I) were afforded in 45% yield (9.8 mg, based on 4,4'-bipy). Analysis, calculated for C28H24N3O2: C 77.40, H 5.57, N 9.67%; found: C 77.44, H 5.69, N 9.71%. Thermogravimetric analysis (TGA) was recorded with a Dupont thermal analyser in the temperature range 298–1073 K under nitrogen atmosphere at a heating rate of 10 K min-1.
All H atoms were visible in difference maps. C-bound H atoms were placed at calculated positions, with C—H = 0.93 (for sp2 C atoms) or 0.97 Å (for sp3 C atoms) and refined as riding atoms. O-bound carboxyl H atoms were refined as rigid groups that were allowed to rotate but not tip, with O—H = 0.82 Å. Uiso(H) = 1.2Ueq(C) or 1.5Ueq(O).
Data collection: APEX2 (Bruker, 2003); cell refinement: APEX2 (Bruker, 2003) and SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2005); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
C13H12O2·1.5C10H8N2 | F(000) = 916 |
Mr = 434.50 | Dx = 1.276 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 1921 reflections |
a = 19.606 (2) Å | θ = 2.6–21.5° |
b = 5.7354 (6) Å | µ = 0.08 mm−1 |
c = 25.4316 (18) Å | T = 294 K |
β = 127.755 (5)° | Block, colourless |
V = 2261.0 (4) Å3 | 0.25 × 0.16 × 0.14 mm |
Z = 4 |
Bruker APEXII CCD area-detector diffractometer | 3976 independent reflections |
Radiation source: fine-focus sealed tube | 2727 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.025 |
ϕ and ω scans | θmax = 25.0°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −23→22 |
Tmin = 0.981, Tmax = 0.988 | k = −6→6 |
11614 measured reflections | l = −25→30 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.041 | H-atom parameters constrained |
wR(F2) = 0.120 | w = 1/[σ2(Fo2) + (0.034P)2 + 0.4007P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max < 0.001 |
3976 reflections | Δρmax = 0.18 e Å−3 |
299 parameters | Δρmin = −0.15 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0044 (9) |
C13H12O2·1.5C10H8N2 | V = 2261.0 (4) Å3 |
Mr = 434.50 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 19.606 (2) Å | µ = 0.08 mm−1 |
b = 5.7354 (6) Å | T = 294 K |
c = 25.4316 (18) Å | 0.25 × 0.16 × 0.14 mm |
β = 127.755 (5)° |
Bruker APEXII CCD area-detector diffractometer | 3976 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2727 reflections with I > 2σ(I) |
Tmin = 0.981, Tmax = 0.988 | Rint = 0.025 |
11614 measured reflections |
R[F2 > 2σ(F2)] = 0.041 | 0 restraints |
wR(F2) = 0.120 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.18 e Å−3 |
3976 reflections | Δρmin = −0.15 e Å−3 |
299 parameters |
Experimental. IR (KBr pellet, cm-1): 3398b, 1600vs, 1566 s, 1488w, 1435 s, 1413 s, 1221m, 1069w, 1044w, 996w, 813 s, 734w, 670w, 625m, 505w. |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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 | ||
N1 | 0.11056 (11) | 0.8519 (3) | 0.86394 (9) | 0.0727 (5) | |
O1 | 0.16109 (8) | 0.4496 (2) | 0.84099 (7) | 0.0749 (4) | |
H1 | 0.1541 | 0.5759 | 0.8522 | 0.112* | |
O2 | 0.27022 (8) | 0.9862 (3) | 0.55323 (7) | 0.0886 (5) | |
H2 | 0.3015 | 1.0933 | 0.5583 | 0.133* | |
C1 | 0.34478 (11) | 0.4928 (3) | 0.80898 (9) | 0.0580 (5) | |
C2 | 0.29339 (12) | 0.2992 (3) | 0.79159 (9) | 0.0636 (5) | |
H2A | 0.3001 | 0.1728 | 0.7722 | 0.076* | |
C3 | 0.23241 (13) | 0.2872 (3) | 0.80200 (9) | 0.0635 (5) | |
H3 | 0.1984 | 0.1545 | 0.7893 | 0.076* | |
C4 | 0.22140 (11) | 0.4711 (3) | 0.83116 (9) | 0.0559 (5) | |
C5 | 0.27270 (12) | 0.6659 (3) | 0.84973 (9) | 0.0608 (5) | |
H5 | 0.2666 | 0.7908 | 0.8698 | 0.073* | |
C6 | 0.33302 (12) | 0.6755 (3) | 0.83850 (9) | 0.0634 (5) | |
H6 | 0.3669 | 0.8085 | 0.8511 | 0.076* | |
C7 | 0.40905 (12) | 0.5113 (4) | 0.79462 (10) | 0.0729 (6) | |
H7A | 0.4603 | 0.5911 | 0.8313 | 0.087* | |
H7B | 0.4260 | 0.3556 | 0.7919 | 0.087* | |
C8 | 0.37374 (11) | 0.6403 (3) | 0.73083 (9) | 0.0579 (5) | |
C9 | 0.41147 (11) | 0.8411 (4) | 0.72991 (9) | 0.0624 (5) | |
H9 | 0.4606 | 0.8983 | 0.7697 | 0.075* | |
C10 | 0.37854 (11) | 0.9602 (3) | 0.67170 (9) | 0.0608 (5) | |
H10 | 0.4051 | 1.0962 | 0.6726 | 0.073* | |
C11 | 0.30667 (11) | 0.8778 (4) | 0.61251 (9) | 0.0598 (5) | |
C12 | 0.26806 (13) | 0.6763 (4) | 0.61194 (10) | 0.0719 (6) | |
H12 | 0.2195 | 0.6183 | 0.5720 | 0.086* | |
C13 | 0.30136 (12) | 0.5608 (4) | 0.67043 (10) | 0.0689 (5) | |
H13 | 0.2745 | 0.4254 | 0.6694 | 0.083* | |
N2 | −0.09001 (18) | 1.7374 (4) | 0.92117 (14) | 0.1026 (7) | |
C14 | 0.03104 (11) | 1.2046 (3) | 0.88543 (9) | 0.0568 (5) | |
C15 | 0.11644 (11) | 1.1427 (4) | 0.93340 (10) | 0.0666 (5) | |
H15 | 0.1493 | 1.2187 | 0.9743 | 0.080* | |
C16 | 0.15242 (13) | 0.9692 (4) | 0.92056 (11) | 0.0730 (6) | |
H16 | 0.2099 | 0.9314 | 0.9537 | 0.088* | |
C17 | 0.02891 (14) | 0.9140 (4) | 0.81768 (11) | 0.0789 (6) | |
H17 | −0.0021 | 0.8364 | 0.7771 | 0.095* | |
C18 | −0.01223 (13) | 1.0849 (4) | 0.82604 (10) | 0.0729 (6) | |
H18 | −0.0695 | 1.1205 | 0.7916 | 0.087* | |
C19 | −0.01131 (12) | 1.3883 (4) | 0.89741 (10) | 0.0622 (5) | |
C20 | −0.09922 (14) | 1.3839 (4) | 0.86562 (11) | 0.0823 (7) | |
H20 | −0.1336 | 1.2650 | 0.8360 | 0.099* | |
C21 | −0.13467 (18) | 1.5614 (6) | 0.87907 (15) | 0.0993 (9) | |
H21 | −0.1938 | 1.5575 | 0.8572 | 0.119* | |
C22 | −0.00638 (19) | 1.7353 (4) | 0.95122 (14) | 0.0910 (7) | |
H22 | 0.0268 | 1.8549 | 0.9810 | 0.109* | |
C23 | 0.03511 (15) | 1.5685 (4) | 0.94149 (11) | 0.0728 (6) | |
H23 | 0.0945 | 1.5770 | 0.9646 | 0.087* | |
C24 | 0.47205 (10) | 1.4604 (3) | 0.50883 (8) | 0.0510 (4) | |
N3 | 0.36938 (10) | 1.3029 (3) | 0.54424 (8) | 0.0697 (5) | |
C25 | 0.42120 (13) | 1.2642 (4) | 0.48076 (10) | 0.0734 (6) | |
H25 | 0.4200 | 1.1794 | 0.4491 | 0.088* | |
C26 | 0.37212 (14) | 1.1942 (4) | 0.49982 (11) | 0.0822 (7) | |
H26 | 0.3385 | 1.0609 | 0.4800 | 0.099* | |
C27 | 0.41740 (13) | 1.4927 (4) | 0.57059 (10) | 0.0715 (6) | |
H27 | 0.4166 | 1.5749 | 0.6017 | 0.086* | |
C28 | 0.46844 (12) | 1.5757 (4) | 0.55469 (10) | 0.0656 (5) | |
H28 | 0.5008 | 1.7104 | 0.5750 | 0.079* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0750 (11) | 0.0791 (12) | 0.0753 (12) | 0.0037 (9) | 0.0518 (10) | −0.0023 (10) |
O1 | 0.0818 (9) | 0.0712 (9) | 0.0891 (10) | 0.0017 (7) | 0.0613 (8) | 0.0046 (8) |
O2 | 0.0722 (9) | 0.1162 (13) | 0.0683 (9) | −0.0161 (8) | 0.0384 (8) | 0.0219 (9) |
C1 | 0.0587 (10) | 0.0570 (12) | 0.0537 (10) | 0.0097 (9) | 0.0321 (9) | 0.0158 (9) |
C2 | 0.0785 (12) | 0.0525 (12) | 0.0648 (12) | 0.0080 (10) | 0.0465 (11) | 0.0034 (9) |
C3 | 0.0756 (12) | 0.0476 (11) | 0.0697 (13) | −0.0033 (9) | 0.0457 (11) | 0.0009 (9) |
C4 | 0.0592 (10) | 0.0537 (11) | 0.0539 (10) | 0.0061 (9) | 0.0343 (9) | 0.0100 (9) |
C5 | 0.0703 (11) | 0.0489 (11) | 0.0619 (12) | 0.0041 (9) | 0.0398 (10) | 0.0016 (9) |
C6 | 0.0636 (11) | 0.0522 (12) | 0.0656 (12) | −0.0046 (9) | 0.0350 (10) | 0.0046 (9) |
C7 | 0.0635 (11) | 0.0819 (15) | 0.0742 (13) | 0.0151 (10) | 0.0426 (11) | 0.0215 (11) |
C8 | 0.0522 (10) | 0.0636 (12) | 0.0622 (11) | 0.0065 (9) | 0.0372 (9) | 0.0085 (9) |
C9 | 0.0481 (9) | 0.0730 (13) | 0.0602 (12) | −0.0024 (9) | 0.0302 (9) | 0.0014 (10) |
C10 | 0.0523 (10) | 0.0611 (12) | 0.0715 (13) | −0.0059 (9) | 0.0393 (10) | 0.0037 (10) |
C11 | 0.0524 (10) | 0.0760 (13) | 0.0574 (11) | 0.0011 (9) | 0.0369 (9) | 0.0114 (10) |
C12 | 0.0669 (12) | 0.0837 (15) | 0.0602 (12) | −0.0184 (11) | 0.0364 (10) | −0.0030 (11) |
C13 | 0.0705 (12) | 0.0658 (13) | 0.0716 (13) | −0.0122 (10) | 0.0440 (11) | 0.0031 (11) |
N2 | 0.135 (2) | 0.0843 (16) | 0.136 (2) | 0.0400 (15) | 0.1073 (18) | 0.0356 (15) |
C14 | 0.0576 (10) | 0.0614 (12) | 0.0562 (11) | 0.0030 (9) | 0.0372 (9) | 0.0091 (9) |
C15 | 0.0568 (11) | 0.0718 (13) | 0.0623 (12) | 0.0011 (10) | 0.0320 (10) | −0.0057 (10) |
C16 | 0.0566 (11) | 0.0773 (15) | 0.0775 (14) | 0.0060 (10) | 0.0372 (11) | −0.0004 (12) |
C17 | 0.0810 (14) | 0.0889 (16) | 0.0612 (13) | 0.0037 (12) | 0.0407 (12) | −0.0071 (12) |
C18 | 0.0620 (11) | 0.0886 (15) | 0.0554 (12) | 0.0098 (11) | 0.0294 (10) | 0.0023 (11) |
C19 | 0.0712 (12) | 0.0634 (13) | 0.0667 (12) | 0.0130 (10) | 0.0497 (10) | 0.0173 (10) |
C20 | 0.0724 (13) | 0.0903 (17) | 0.0914 (16) | 0.0205 (12) | 0.0538 (13) | 0.0217 (13) |
C21 | 0.0907 (17) | 0.110 (2) | 0.125 (2) | 0.0419 (17) | 0.0802 (17) | 0.0472 (19) |
C22 | 0.130 (2) | 0.0679 (15) | 0.119 (2) | 0.0184 (15) | 0.0985 (19) | 0.0153 (14) |
C23 | 0.0916 (14) | 0.0616 (13) | 0.0873 (15) | 0.0057 (11) | 0.0660 (13) | 0.0063 (12) |
C24 | 0.0472 (9) | 0.0565 (11) | 0.0427 (9) | −0.0020 (8) | 0.0242 (8) | 0.0025 (8) |
N3 | 0.0637 (10) | 0.0890 (13) | 0.0579 (10) | −0.0096 (9) | 0.0379 (8) | 0.0036 (9) |
C25 | 0.0869 (14) | 0.0837 (15) | 0.0615 (12) | −0.0337 (12) | 0.0514 (11) | −0.0203 (11) |
C26 | 0.0893 (15) | 0.0920 (17) | 0.0702 (14) | −0.0378 (13) | 0.0513 (12) | −0.0163 (12) |
C27 | 0.0718 (12) | 0.0811 (15) | 0.0748 (13) | −0.0022 (11) | 0.0516 (11) | −0.0060 (11) |
C28 | 0.0672 (11) | 0.0642 (12) | 0.0737 (13) | −0.0092 (10) | 0.0475 (10) | −0.0121 (10) |
N1—C16 | 1.324 (3) | N2—C22 | 1.318 (3) |
N1—C17 | 1.330 (3) | N2—C21 | 1.336 (4) |
O1—C4 | 1.356 (2) | C14—C18 | 1.380 (3) |
O1—H1 | 0.8200 | C14—C15 | 1.384 (2) |
O2—C11 | 1.360 (2) | C14—C19 | 1.484 (3) |
O2—H2 | 0.8199 | C15—C16 | 1.370 (3) |
C1—C2 | 1.378 (3) | C15—H15 | 0.9300 |
C1—C6 | 1.388 (3) | C16—H16 | 0.9300 |
C1—C7 | 1.515 (3) | C17—C18 | 1.366 (3) |
C2—C3 | 1.376 (3) | C17—H17 | 0.9300 |
C2—H2A | 0.9300 | C18—H18 | 0.9300 |
C3—C4 | 1.380 (3) | C19—C23 | 1.380 (3) |
C3—H3 | 0.9300 | C19—C20 | 1.385 (3) |
C4—C5 | 1.379 (3) | C20—C21 | 1.389 (3) |
C5—C6 | 1.377 (3) | C20—H20 | 0.9300 |
C5—H5 | 0.9300 | C21—H21 | 0.9300 |
C6—H6 | 0.9300 | C22—C23 | 1.373 (3) |
C7—C8 | 1.511 (3) | C22—H22 | 0.9300 |
C7—H7A | 0.9700 | C23—H23 | 0.9300 |
C7—H7B | 0.9700 | C24—C25 | 1.378 (3) |
C8—C9 | 1.377 (3) | C24—C28 | 1.380 (2) |
C8—C13 | 1.383 (3) | C24—C24i | 1.487 (3) |
C9—C10 | 1.380 (3) | N3—C26 | 1.320 (3) |
C9—H9 | 0.9300 | N3—C27 | 1.322 (3) |
C10—C11 | 1.370 (2) | C25—C26 | 1.376 (3) |
C10—H10 | 0.9300 | C25—H25 | 0.9300 |
C11—C12 | 1.377 (3) | C26—H26 | 0.9300 |
C12—C13 | 1.374 (3) | C27—C28 | 1.374 (3) |
C12—H12 | 0.9300 | C27—H27 | 0.9300 |
C13—H13 | 0.9300 | C28—H28 | 0.9300 |
C16—N1—C17 | 115.79 (18) | C18—C14—C15 | 115.99 (18) |
C4—O1—H1 | 109.5 | C18—C14—C19 | 122.13 (17) |
C11—O2—H2 | 109.5 | C15—C14—C19 | 121.88 (18) |
C2—C1—C6 | 116.81 (17) | C16—C15—C14 | 119.86 (19) |
C2—C1—C7 | 122.11 (19) | C16—C15—H15 | 120.1 |
C6—C1—C7 | 121.05 (18) | C14—C15—H15 | 120.1 |
C3—C2—C1 | 121.97 (18) | N1—C16—C15 | 124.17 (19) |
C3—C2—H2A | 119.0 | N1—C16—H16 | 117.9 |
C1—C2—H2A | 119.0 | C15—C16—H16 | 117.9 |
C2—C3—C4 | 120.36 (18) | N1—C17—C18 | 124.1 (2) |
C2—C3—H3 | 119.8 | N1—C17—H17 | 118.0 |
C4—C3—H3 | 119.8 | C18—C17—H17 | 118.0 |
O1—C4—C5 | 123.13 (17) | C17—C18—C14 | 120.10 (19) |
O1—C4—C3 | 118.05 (17) | C17—C18—H18 | 120.0 |
C5—C4—C3 | 118.81 (17) | C14—C18—H18 | 120.0 |
C6—C5—C4 | 120.03 (18) | C23—C19—C20 | 117.0 (2) |
C6—C5—H5 | 120.0 | C23—C19—C14 | 121.67 (18) |
C4—C5—H5 | 120.0 | C20—C19—C14 | 121.3 (2) |
C5—C6—C1 | 122.00 (18) | C19—C20—C21 | 118.3 (3) |
C5—C6—H6 | 119.0 | C19—C20—H20 | 120.8 |
C1—C6—H6 | 119.0 | C21—C20—H20 | 120.8 |
C8—C7—C1 | 113.02 (15) | N2—C21—C20 | 124.8 (3) |
C8—C7—H7A | 109.0 | N2—C21—H21 | 117.6 |
C1—C7—H7A | 109.0 | C20—C21—H21 | 117.6 |
C8—C7—H7B | 109.0 | N2—C22—C23 | 124.5 (3) |
C1—C7—H7B | 109.0 | N2—C22—H22 | 117.8 |
H7A—C7—H7B | 107.8 | C23—C22—H22 | 117.8 |
C9—C8—C13 | 116.98 (17) | C22—C23—C19 | 120.0 (2) |
C9—C8—C7 | 122.02 (18) | C22—C23—H23 | 120.0 |
C13—C8—C7 | 121.00 (18) | C19—C23—H23 | 120.0 |
C8—C9—C10 | 121.92 (18) | C25—C24—C28 | 115.72 (17) |
C8—C9—H9 | 119.0 | C25—C24—C24i | 121.8 (2) |
C10—C9—H9 | 119.0 | C28—C24—C24i | 122.5 (2) |
C11—C10—C9 | 119.93 (18) | C26—N3—C27 | 115.68 (17) |
C11—C10—H10 | 120.0 | C26—C25—C24 | 119.75 (19) |
C9—C10—H10 | 120.0 | C26—C25—H25 | 120.1 |
O2—C11—C10 | 123.29 (18) | C24—C25—H25 | 120.1 |
O2—C11—C12 | 117.37 (17) | N3—C26—C25 | 124.6 (2) |
C10—C11—C12 | 119.33 (17) | N3—C26—H26 | 117.7 |
C13—C12—C11 | 119.96 (19) | C25—C26—H26 | 117.7 |
C13—C12—H12 | 120.0 | N3—C27—C28 | 123.85 (19) |
C11—C12—H12 | 120.0 | N3—C27—H27 | 118.1 |
C12—C13—C8 | 121.87 (19) | C28—C27—H27 | 118.1 |
C12—C13—H13 | 119.1 | C27—C28—C24 | 120.43 (19) |
C8—C13—H13 | 119.1 | C27—C28—H28 | 119.8 |
C22—N2—C21 | 115.5 (2) | C24—C28—H28 | 119.8 |
C6—C1—C2—C3 | 0.8 (3) | C17—N1—C16—C15 | 0.9 (3) |
C7—C1—C2—C3 | −177.04 (17) | C14—C15—C16—N1 | 0.0 (3) |
C1—C2—C3—C4 | −0.6 (3) | C16—N1—C17—C18 | −0.8 (3) |
C2—C3—C4—O1 | −179.29 (17) | N1—C17—C18—C14 | −0.2 (4) |
C2—C3—C4—C5 | −0.2 (3) | C15—C14—C18—C17 | 1.1 (3) |
O1—C4—C5—C6 | 179.69 (16) | C19—C14—C18—C17 | −178.78 (19) |
C3—C4—C5—C6 | 0.6 (3) | C18—C14—C19—C23 | −152.72 (19) |
C4—C5—C6—C1 | −0.4 (3) | C15—C14—C19—C23 | 27.5 (3) |
C2—C1—C6—C5 | −0.4 (3) | C18—C14—C19—C20 | 28.5 (3) |
C7—C1—C6—C5 | 177.53 (17) | C15—C14—C19—C20 | −151.3 (2) |
C2—C1—C7—C8 | 95.7 (2) | C23—C19—C20—C21 | 1.2 (3) |
C6—C1—C7—C8 | −82.0 (2) | C14—C19—C20—C21 | −179.94 (18) |
C1—C7—C8—C9 | 120.0 (2) | C22—N2—C21—C20 | −0.2 (4) |
C1—C7—C8—C13 | −59.9 (3) | C19—C20—C21—N2 | −0.5 (4) |
C13—C8—C9—C10 | 0.6 (3) | C21—N2—C22—C23 | 0.3 (4) |
C7—C8—C9—C10 | −179.24 (17) | N2—C22—C23—C19 | 0.4 (3) |
C8—C9—C10—C11 | −0.5 (3) | C20—C19—C23—C22 | −1.2 (3) |
C9—C10—C11—O2 | 179.59 (17) | C14—C19—C23—C22 | 179.98 (18) |
C9—C10—C11—C12 | 0.0 (3) | C28—C24—C25—C26 | −0.8 (3) |
O2—C11—C12—C13 | −179.17 (18) | C24i—C24—C25—C26 | 178.4 (2) |
C10—C11—C12—C13 | 0.4 (3) | C27—N3—C26—C25 | 0.7 (3) |
C11—C12—C13—C8 | −0.4 (3) | C24—C25—C26—N3 | 0.1 (4) |
C9—C8—C13—C12 | −0.2 (3) | C26—N3—C27—C28 | −0.7 (3) |
C7—C8—C13—C12 | 179.70 (18) | N3—C27—C28—C24 | 0.0 (3) |
C18—C14—C15—C16 | −1.0 (3) | C25—C24—C28—C27 | 0.8 (3) |
C19—C14—C15—C16 | 178.86 (18) | C24i—C24—C28—C27 | −178.4 (2) |
Symmetry code: (i) −x+1, −y+3, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···N1 | 0.82 | 1.91 | 2.712 (2) | 167 |
O2—H2···N3 | 0.82 | 1.98 | 2.770 (2) | 161 |
C15—H15···O2ii | 0.93 | 2.59 | 3.414 (2) | 149 |
Symmetry code: (ii) x, −y+5/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C13H12O2·1.5C10H8N2 |
Mr | 434.50 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 294 |
a, b, c (Å) | 19.606 (2), 5.7354 (6), 25.4316 (18) |
β (°) | 127.755 (5) |
V (Å3) | 2261.0 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.25 × 0.16 × 0.14 |
Data collection | |
Diffractometer | Bruker APEXII CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.981, 0.988 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11614, 3976, 2727 |
Rint | 0.025 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.120, 1.03 |
No. of reflections | 3976 |
No. of parameters | 299 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.18, −0.15 |
Computer programs: , APEX2 (Bruker, 2003) and SAINT (Bruker, 2001), SAINT (Bruker, 2001), SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2005).
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···N1 | 0.82 | 1.91 | 2.712 (2) | 166.8 |
O2—H2···N3 | 0.82 | 1.98 | 2.770 (2) | 161.0 |
C15—H15···O2i | 0.93 | 2.59 | 3.414 (2) | 148.6 |
Symmetry code: (i) x, −y+5/2, z+1/2. |
Hydrothermal syntheses have been widely used in crystal engineering to produce functional metal–organic coordinate networks such as zeolites, nanomaterials and metal–oxide hydrogen-storage materials (Rowsell & Yaghi, 2005). Many unprecedented in situ metal/organic reactions, including ligand oxidative coupling, hydrolysis and substitution, have been detected during the hydrothermal process (Chen & Tong, 2007). Among these cases, hydrothermal decarboxylations have frequently been reported in the process of discovering novel metal–organic frameworks (Yigit et al., 2006; Sun et al., 2006).
In this work, we chose 5,5'-methylenedisalicylic acid (5,5'-H4mdsa, C15H12O6), bearing both carboxyl and hydroxyl groups, along with 4,4'-bipyridine (4,4'-bipy) and manganese(II) acetate, in an attempt to create a novel inorganic–organic hybrid complex under hydrothermal conditions. Unexpectedly, hydrothermal reaction at 413 K led ultimately to the formation of the title 2:3 binary cocrystal, [(4,4'-H2dhdp)(4,4'-bipy)1.5], (I), in which 4-(4-hydroxybenzyl)phenol (4,4'-H2dhdp, C13H12O2) is generated by concomitant in situ decarboxylation of 5,5'-H4mdsa. Notably, combination of 5,5'-H4mdsa and 4,4'-bipy without MnII ions under the same synthetic conditions did not lead to decarboxylation, rather resulting in an unidentified white precipitate. Due to one of the pyridyl N-atom donors of 4,4'-bipy not forming any hydrogen bonds, this composition is not consistent with the hydrogen-bond donating/accepting ability of the two subunits (equivalent hydroxyl and pyridyl groups). In compound (I), both classical O—H···N and weak C—H···O interactions are involved in constructing an unusual two-dimensional hydrogen-bonded bilayer with a simple mononodal hcb network (Delgado-Friedrichs et al., 2005). Significantly, the decarboxylation of 5,5'-H4mdsa under hydrothermal conditions has not been documented so far, although incomplete decarboxylation catalyzed by MnII ions of other polycarboxylic acids containing N-atom donors has been detected recently (Wu et al., 2007).
The asymmetric unit of (I) contains one and a half 4,4'-bipy moieties and one 4,4'-H2dhdp molecule (Fig. 1). In the 4,4'-H2dhdp component, the dihedral angle between the two phenyl rings is 76.2 (3)°, while the two pyridyl groups in one of the 4,4'-bipy molecules make a dihedral of 27.9 (4)° with each other. The centrosymmetric 4,4'-bipy molecule is connected to two 4,4'-H2dhdp components via O2—H2···N3 interactions between a pyridyl N atom and a hydroxyl H atom, and the other hydroxyl group of the 4,4'-H2dhdp moiety is linked to the other 4,4'-bipy through O1—H1···N1 hydrogen bonds (Fig. 2, Table 1). Such hydrogen bonds lead to a discrete ribbon-like motif with a repeat length of ca 40 Å, which is further extended to a two-dimensional supramolecular architecture via weak C15—H15···O2i interactions [symmetry code: (i) x, -y + 5/2, z + 1/2]. Further topological analysis using the TOPOS package indicates that (I) is an hcb (63) bilayer net (Blatov, 2004, 2006). Additionally, neighbouring two-dimensional arrays stack somewhat offset along the [010] direction, and they are further joined into a three-dimensional supramolecular motif by aromatic π–π interactions between the non-hydrogen-bonded pyridyl groups from adjacent layers, with centre-to-centre and centre-to-face distances of 3.81 (2) and 3.42 (1) Å, respectively.
Thermogravimetric analysis shows that three consecutive weight losses occur in the range 318–598 K, corresponding to the complete decomposition of the hydrogen-bonding network. The first weight loss occurs in the range 318–373 K, corresponding to the removal of the centrosymmetric 4,4'-bipy molecule (calculated 18.0%; observed 17.9%). The second weight loss of 35.8% from 396–476 K corresponds to the loss of the other 4,4'-bipy component (calculated 36.0%). A sharp weight loss of all residual samples then begins at 488 K and stops at 598 K, indicating the decomposition of the 4,4'-H2dhdp moieties.
The 4,4'-H2dhdp molecule has seldom been utilized in the construction of coordination complexes (Son et al., 2005) or molecular cocrystals (Vangala et al., 2005). There are only two examples of its cocrystals, which arise from complementary O—H···N and N—H···O recognition with dianilines. Both cases reveal that the formation of 1:1 diphenol–diamine molecular cocrystals is the usual propensity, since the resulting N—H···O hydrogen bonds are stronger than the O—H···O and N—H···N bonds in the crystal structures of the respective individual components (Vangala et al., 2005). By contrast, in this work an unexpected 2:3 molecular cocrystal of diphenol–diamine is afforded, connected by strong O—H···N hydrogen bonds. It is unusual that one of the pyridyl N-atom donors is `free' and this phenomenon plays a dominant role in controlling the discrete hydrogen-bonding ribbon array with the 2:3 ratio of hydroxyl and pyridyl subunits. This result presents a new challenge in the seemingly predictable crystal engineering of complementary diphenol–diamine systems, and further investigation is warranted.