Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270108031272/sk3265sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270108031272/sk3265Isup2.hkl |
CCDC reference: 710742
A mixture of MnCl2.4H2O (0.090 g, 0.5 mmol), H2dpdc (0.062 g, 0.5 mmol) and L (0.145 g, 0.5 mmol) were dissolved in 14 ml of distilled water, followed by addition of triethylamine until the pH value of the system was adjusted to about 5.5. The resulting solution was stirred for about 1 h at room temperature, sealed in a 23 ml Teflon-lined stainless steel autoclave and heated at 413 K for 3 days under autogenous pressure. The reaction system was then cooled slowly to room temperature. Pale-yellow block crystals of (I) suitable for single-crystal X-ray diffraction analysis were collected from the final reaction system by filtration, washed several times with distilled water and dried in air at ambient temperature (yield 44% based on Mn). The compound once formed is insoluble in most solvents, including water.
All H atoms were positioned geometrically (C—H = 0.93 Å) and refined as riding, with Uiso(H) = 1.2Ueq(carrier).
Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: PROCESS-AUTO (Rigaku, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL-Plus (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
[Mn2(C14H8O4)2(C18H10N4)] | Z = 2 |
Mr = 872.59 | F(000) = 888 |
Triclinic, P1 | Dx = 1.511 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 11.993 (2) Å | Cell parameters from 12518 reflections |
b = 13.516 (3) Å | θ = 3.0–27.5° |
c = 14.196 (3) Å | µ = 0.72 mm−1 |
α = 62.13 (3)° | T = 293 K |
β = 70.55 (2)° | Block, pale yellow |
γ = 82.24 (3)° | 0.31 × 0.24 × 0.21 mm |
V = 1917.6 (9) Å3 |
Rigaku R-AXIS RAPID diffractometer | 8667 independent reflections |
Radiation source: rotating anode | 5367 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.064 |
Detector resolution: 10.0 pixels mm-1 | θmax = 27.5°, θmin = 3.1° |
ω scan | h = −15→15 |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | k = −17→17 |
Tmin = 0.794, Tmax = 0.856 | l = −18→17 |
18726 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)] = 0.056 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.142 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0616P)2] where P = (Fo2 + 2Fc2)/3 |
8667 reflections | (Δ/σ)max < 0.001 |
541 parameters | Δρmax = 0.49 e Å−3 |
0 restraints | Δρmin = −0.37 e Å−3 |
[Mn2(C14H8O4)2(C18H10N4)] | γ = 82.24 (3)° |
Mr = 872.59 | V = 1917.6 (9) Å3 |
Triclinic, P1 | Z = 2 |
a = 11.993 (2) Å | Mo Kα radiation |
b = 13.516 (3) Å | µ = 0.72 mm−1 |
c = 14.196 (3) Å | T = 293 K |
α = 62.13 (3)° | 0.31 × 0.24 × 0.21 mm |
β = 70.55 (2)° |
Rigaku R-AXIS RAPID diffractometer | 8667 independent reflections |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 5367 reflections with I > 2σ(I) |
Tmin = 0.794, Tmax = 0.856 | Rint = 0.064 |
18726 measured reflections |
R[F2 > 2σ(F2)] = 0.056 | 0 restraints |
wR(F2) = 0.142 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.49 e Å−3 |
8667 reflections | Δρmin = −0.37 e Å−3 |
541 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 | ||
C1 | 0.2115 (4) | 0.9126 (3) | 0.1131 (3) | 0.0519 (11) | |
H1 | 0.1713 | 0.8438 | 0.1545 | 0.062* | |
C2 | 0.3123 (5) | 0.9251 (4) | 0.0251 (4) | 0.0704 (15) | |
H2 | 0.3391 | 0.8657 | 0.0082 | 0.084* | |
C3 | 0.3725 (4) | 1.0262 (3) | −0.0373 (4) | 0.0610 (13) | |
H3 | 0.4404 | 1.0362 | −0.0972 | 0.073* | |
C4 | 0.3305 (4) | 1.1138 (3) | −0.0097 (3) | 0.0408 (9) | |
C5 | 0.3895 (3) | 1.2233 (3) | −0.0724 (3) | 0.0360 (8) | |
C6 | 0.5425 (4) | 1.3394 (3) | −0.2102 (3) | 0.0438 (9) | |
C7 | 0.6465 (4) | 1.3597 (4) | −0.3023 (4) | 0.0549 (11) | |
H7 | 0.6798 | 1.3018 | −0.3197 | 0.066* | |
C8 | 0.6978 (4) | 1.4640 (4) | −0.3652 (4) | 0.0586 (12) | |
H8 | 0.7656 | 1.4776 | −0.4261 | 0.070* | |
C9 | 0.6482 (4) | 1.5509 (4) | −0.3380 (4) | 0.0608 (12) | |
H9 | 0.6845 | 1.6216 | −0.3816 | 0.073* | |
C10 | 0.5489 (4) | 1.5358 (3) | −0.2501 (4) | 0.0558 (11) | |
H10 | 0.5188 | 1.5947 | −0.2331 | 0.067* | |
C11 | 0.4920 (4) | 1.4282 (3) | −0.1848 (3) | 0.0418 (9) | |
C12 | 0.3380 (3) | 1.3124 (3) | −0.0450 (3) | 0.0378 (8) | |
C13 | 0.2292 (3) | 1.2902 (3) | 0.0483 (3) | 0.0375 (8) | |
C14 | 0.1732 (4) | 1.3732 (3) | 0.0803 (4) | 0.0567 (12) | |
H14 | 0.2024 | 1.4466 | 0.0389 | 0.068* | |
C15 | 0.0755 (5) | 1.3446 (3) | 0.1730 (4) | 0.0700 (15) | |
H15 | 0.0389 | 1.3980 | 0.1964 | 0.084* | |
C16 | 0.0318 (4) | 1.2355 (3) | 0.2315 (4) | 0.0593 (12) | |
H16 | −0.0344 | 1.2171 | 0.2945 | 0.071* | |
C17 | 0.1773 (3) | 1.1821 (3) | 0.1111 (3) | 0.0354 (8) | |
C18 | 0.2282 (3) | 1.0937 (3) | 0.0801 (3) | 0.0336 (8) | |
C19 | 0.1722 (3) | 0.8227 (3) | 0.4431 (3) | 0.0347 (8) | |
C20 | 0.2411 (3) | 0.8073 (3) | 0.5195 (3) | 0.0369 (8) | |
C21 | 0.2360 (4) | 0.7028 (3) | 0.6101 (4) | 0.0496 (10) | |
H21 | 0.1981 | 0.6434 | 0.6162 | 0.060* | |
C22 | 0.2860 (5) | 0.6848 (4) | 0.6921 (4) | 0.0699 (15) | |
H22 | 0.2831 | 0.6141 | 0.7518 | 0.084* | |
C23 | 0.3401 (5) | 0.7745 (4) | 0.6825 (5) | 0.0761 (16) | |
H23 | 0.3712 | 0.7648 | 0.7381 | 0.091* | |
C24 | 0.3486 (4) | 0.8780 (3) | 0.5918 (4) | 0.0608 (13) | |
H24 | 0.3871 | 0.9367 | 0.5863 | 0.073* | |
C25 | 0.3009 (3) | 0.8967 (3) | 0.5082 (3) | 0.0386 (9) | |
C26 | 0.3284 (3) | 1.0066 (3) | 0.4047 (3) | 0.0394 (9) | |
C27 | 0.4237 (4) | 1.0080 (4) | 0.3157 (4) | 0.0605 (13) | |
H27 | 0.4609 | 0.9414 | 0.3212 | 0.073* | |
C28 | 0.4643 (5) | 1.1057 (4) | 0.2194 (4) | 0.0704 (15) | |
H28 | 0.5283 | 1.1042 | 0.1610 | 0.084* | |
C29 | 0.4117 (4) | 1.2045 (4) | 0.2089 (3) | 0.0570 (12) | |
H29 | 0.4395 | 1.2704 | 0.1437 | 0.068* | |
C30 | 0.3169 (4) | 1.2062 (3) | 0.2956 (3) | 0.0439 (9) | |
H30 | 0.2803 | 1.2735 | 0.2883 | 0.053* | |
C31 | 0.2751 (3) | 1.1080 (3) | 0.3946 (3) | 0.0347 (8) | |
C32 | 0.1700 (3) | 1.1174 (3) | 0.4848 (3) | 0.0348 (8) | |
C33 | −0.0088 (3) | 0.4637 (3) | 0.6570 (3) | 0.0335 (8) | |
C34 | −0.0368 (4) | 0.3832 (3) | 0.7796 (3) | 0.0392 (9) | |
C35 | −0.1456 (4) | 0.3886 (3) | 0.8525 (3) | 0.0511 (11) | |
H35 | −0.1972 | 0.4449 | 0.8258 | 0.061* | |
C36 | −0.1782 (5) | 0.3113 (4) | 0.9642 (3) | 0.0667 (15) | |
H36 | −0.2513 | 0.3156 | 1.0124 | 0.080* | |
C37 | −0.1011 (6) | 0.2273 (4) | 1.0039 (4) | 0.0760 (17) | |
H37 | −0.1234 | 0.1742 | 1.0787 | 0.091* | |
C38 | 0.0073 (5) | 0.2221 (3) | 0.9336 (4) | 0.0623 (14) | |
H38 | 0.0580 | 0.1653 | 0.9613 | 0.075* | |
C39 | 0.0435 (4) | 0.3014 (3) | 0.8201 (3) | 0.0461 (10) | |
C40 | 0.1657 (4) | 0.2989 (3) | 0.7485 (4) | 0.0489 (11) | |
C41 | 0.2042 (4) | 0.2157 (3) | 0.7143 (4) | 0.0482 (10) | |
C42 | 0.3201 (4) | 0.2147 (4) | 0.6504 (4) | 0.0644 (13) | |
H42 | 0.3443 | 0.1567 | 0.6307 | 0.077* | |
C43 | 0.4002 (5) | 0.2987 (5) | 0.6154 (5) | 0.0793 (16) | |
H43 | 0.4777 | 0.2981 | 0.5720 | 0.095* | |
C44 | 0.3628 (6) | 0.3837 (4) | 0.6463 (5) | 0.0782 (17) | |
H44 | 0.4152 | 0.4419 | 0.6215 | 0.094* | |
C45 | 0.2492 (5) | 0.3831 (4) | 0.7132 (4) | 0.0645 (14) | |
H45 | 0.2269 | 0.4394 | 0.7355 | 0.077* | |
C46 | 0.1165 (4) | 0.1338 (3) | 0.7329 (3) | 0.0415 (9) | |
N1 | 0.1692 (3) | 0.9938 (2) | 0.1415 (2) | 0.0371 (7) | |
N2 | 0.0801 (3) | 1.1554 (2) | 0.2020 (2) | 0.0403 (7) | |
N3 | 0.4899 (3) | 1.2368 (3) | −0.1534 (3) | 0.0452 (8) | |
N4 | 0.3902 (3) | 1.4130 (2) | −0.0999 (3) | 0.0415 (7) | |
O1 | 0.1483 (3) | 0.9199 (2) | 0.3819 (2) | 0.0476 (7) | |
O2 | 0.1375 (2) | 0.7352 (2) | 0.4484 (2) | 0.0472 (7) | |
O3 | 0.1163 (2) | 1.0299 (2) | 0.5649 (2) | 0.0443 (7) | |
O4 | 0.1450 (3) | 1.2154 (2) | 0.4722 (2) | 0.0595 (8) | |
O5 | 0.0516 (2) | 0.42984 (18) | 0.58657 (19) | 0.0354 (6) | |
O6 | −0.0497 (3) | 0.56015 (18) | 0.63170 (19) | 0.0442 (7) | |
O7 | 0.0259 (2) | 0.17585 (18) | 0.6986 (2) | 0.0377 (6) | |
O8 | 0.1325 (3) | 0.0316 (2) | 0.7726 (2) | 0.0574 (8) | |
Mn1 | 0.02386 (5) | 0.97654 (4) | 0.29630 (4) | 0.03096 (15) | |
Mn2 | −0.02680 (5) | 0.68565 (4) | 0.46455 (4) | 0.02955 (14) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.058 (3) | 0.034 (2) | 0.053 (2) | −0.0085 (19) | 0.005 (2) | −0.024 (2) |
C2 | 0.079 (4) | 0.043 (2) | 0.076 (3) | −0.014 (2) | 0.020 (3) | −0.042 (3) |
C3 | 0.064 (3) | 0.046 (2) | 0.060 (3) | −0.009 (2) | 0.016 (2) | −0.034 (2) |
C4 | 0.041 (2) | 0.0358 (18) | 0.038 (2) | −0.0055 (17) | 0.0019 (17) | −0.0181 (17) |
C5 | 0.037 (2) | 0.0328 (18) | 0.0341 (18) | −0.0033 (16) | −0.0041 (16) | −0.0153 (16) |
C6 | 0.036 (2) | 0.043 (2) | 0.046 (2) | −0.0100 (18) | −0.0044 (19) | −0.0182 (19) |
C7 | 0.043 (3) | 0.055 (2) | 0.054 (3) | −0.009 (2) | 0.005 (2) | −0.025 (2) |
C8 | 0.046 (3) | 0.062 (3) | 0.051 (3) | −0.021 (2) | 0.006 (2) | −0.020 (2) |
C9 | 0.050 (3) | 0.052 (3) | 0.058 (3) | −0.021 (2) | 0.001 (2) | −0.013 (2) |
C10 | 0.052 (3) | 0.043 (2) | 0.057 (3) | −0.018 (2) | 0.001 (2) | −0.017 (2) |
C11 | 0.040 (2) | 0.0360 (19) | 0.041 (2) | −0.0078 (17) | −0.0046 (18) | −0.0133 (18) |
C12 | 0.039 (2) | 0.0326 (18) | 0.0347 (19) | −0.0061 (16) | −0.0049 (17) | −0.0121 (16) |
C13 | 0.039 (2) | 0.0292 (17) | 0.0368 (19) | −0.0033 (16) | −0.0016 (17) | −0.0147 (16) |
C14 | 0.059 (3) | 0.0314 (19) | 0.065 (3) | −0.0066 (19) | 0.006 (2) | −0.025 (2) |
C15 | 0.071 (4) | 0.040 (2) | 0.073 (3) | −0.006 (2) | 0.020 (3) | −0.032 (2) |
C16 | 0.056 (3) | 0.048 (2) | 0.060 (3) | −0.004 (2) | 0.013 (2) | −0.033 (2) |
C17 | 0.037 (2) | 0.0290 (17) | 0.0339 (19) | −0.0029 (15) | −0.0033 (17) | −0.0135 (16) |
C18 | 0.037 (2) | 0.0288 (16) | 0.0299 (17) | −0.0048 (15) | −0.0041 (16) | −0.0120 (15) |
C19 | 0.029 (2) | 0.0348 (18) | 0.0368 (19) | −0.0036 (15) | −0.0013 (16) | −0.0181 (17) |
C20 | 0.029 (2) | 0.0353 (18) | 0.048 (2) | 0.0035 (16) | −0.0098 (17) | −0.0219 (18) |
C21 | 0.054 (3) | 0.0318 (19) | 0.064 (3) | 0.0057 (19) | −0.025 (2) | −0.019 (2) |
C22 | 0.089 (4) | 0.038 (2) | 0.085 (4) | 0.010 (3) | −0.055 (3) | −0.014 (2) |
C23 | 0.099 (5) | 0.062 (3) | 0.092 (4) | 0.011 (3) | −0.069 (4) | −0.030 (3) |
C24 | 0.071 (4) | 0.043 (2) | 0.089 (3) | 0.005 (2) | −0.051 (3) | −0.030 (2) |
C25 | 0.033 (2) | 0.0342 (18) | 0.055 (2) | 0.0054 (16) | −0.0142 (19) | −0.0258 (18) |
C26 | 0.034 (2) | 0.0406 (19) | 0.052 (2) | −0.0028 (17) | −0.0078 (18) | −0.0303 (19) |
C27 | 0.050 (3) | 0.053 (3) | 0.077 (3) | −0.004 (2) | 0.006 (2) | −0.044 (3) |
C28 | 0.061 (3) | 0.079 (3) | 0.066 (3) | −0.021 (3) | 0.023 (3) | −0.051 (3) |
C29 | 0.064 (3) | 0.060 (3) | 0.041 (2) | −0.030 (2) | 0.007 (2) | −0.025 (2) |
C30 | 0.051 (3) | 0.0345 (19) | 0.038 (2) | −0.0118 (18) | −0.0032 (19) | −0.0139 (17) |
C31 | 0.035 (2) | 0.0327 (17) | 0.0386 (19) | −0.0023 (15) | −0.0076 (17) | −0.0195 (16) |
C32 | 0.031 (2) | 0.0305 (17) | 0.0392 (19) | 0.0063 (15) | −0.0065 (17) | −0.0171 (16) |
C33 | 0.046 (2) | 0.0228 (16) | 0.0310 (18) | −0.0047 (15) | −0.0146 (17) | −0.0079 (15) |
C34 | 0.063 (3) | 0.0221 (16) | 0.0311 (18) | −0.0014 (17) | −0.0168 (19) | −0.0087 (15) |
C35 | 0.078 (4) | 0.036 (2) | 0.032 (2) | −0.002 (2) | −0.009 (2) | −0.0133 (18) |
C36 | 0.103 (5) | 0.045 (2) | 0.036 (2) | −0.010 (3) | −0.004 (3) | −0.015 (2) |
C37 | 0.130 (6) | 0.054 (3) | 0.033 (2) | −0.021 (3) | −0.019 (3) | −0.009 (2) |
C38 | 0.106 (5) | 0.031 (2) | 0.049 (3) | 0.001 (2) | −0.046 (3) | −0.003 (2) |
C39 | 0.073 (3) | 0.0280 (18) | 0.045 (2) | −0.0029 (19) | −0.032 (2) | −0.0119 (17) |
C40 | 0.065 (3) | 0.0293 (18) | 0.059 (3) | 0.0014 (19) | −0.043 (3) | −0.0097 (19) |
C41 | 0.047 (3) | 0.036 (2) | 0.061 (3) | 0.0004 (19) | −0.029 (2) | −0.013 (2) |
C42 | 0.051 (3) | 0.051 (3) | 0.094 (4) | 0.010 (2) | −0.037 (3) | −0.027 (3) |
C43 | 0.047 (3) | 0.077 (4) | 0.100 (4) | −0.008 (3) | −0.028 (3) | −0.022 (3) |
C44 | 0.073 (4) | 0.047 (3) | 0.107 (4) | −0.015 (3) | −0.053 (4) | −0.008 (3) |
C45 | 0.078 (4) | 0.043 (2) | 0.085 (4) | −0.007 (2) | −0.054 (3) | −0.018 (2) |
C46 | 0.054 (3) | 0.0271 (17) | 0.040 (2) | 0.0005 (17) | −0.017 (2) | −0.0106 (16) |
N1 | 0.040 (2) | 0.0265 (14) | 0.0372 (16) | −0.0057 (13) | 0.0004 (14) | −0.0149 (13) |
N2 | 0.041 (2) | 0.0369 (16) | 0.0363 (16) | −0.0066 (14) | 0.0042 (15) | −0.0199 (15) |
N3 | 0.040 (2) | 0.0405 (17) | 0.0452 (19) | −0.0063 (15) | 0.0015 (16) | −0.0195 (16) |
N4 | 0.043 (2) | 0.0318 (15) | 0.0386 (17) | −0.0086 (14) | −0.0008 (15) | −0.0125 (14) |
O1 | 0.0525 (19) | 0.0403 (15) | 0.0495 (16) | −0.0068 (13) | −0.0221 (15) | −0.0137 (13) |
O2 | 0.0416 (18) | 0.0413 (14) | 0.0688 (19) | −0.0002 (12) | −0.0194 (15) | −0.0311 (15) |
O3 | 0.0435 (18) | 0.0322 (13) | 0.0432 (15) | −0.0061 (12) | 0.0051 (13) | −0.0164 (12) |
O4 | 0.066 (2) | 0.0303 (13) | 0.0498 (17) | 0.0079 (14) | 0.0115 (15) | −0.0134 (13) |
O5 | 0.0457 (17) | 0.0257 (11) | 0.0321 (12) | −0.0003 (11) | −0.0113 (12) | −0.0112 (11) |
O6 | 0.072 (2) | 0.0222 (12) | 0.0296 (13) | 0.0026 (12) | −0.0114 (13) | −0.0078 (11) |
O7 | 0.0451 (17) | 0.0260 (12) | 0.0386 (13) | −0.0052 (11) | −0.0162 (13) | −0.0081 (11) |
O8 | 0.072 (2) | 0.0270 (13) | 0.0668 (19) | 0.0025 (14) | −0.0300 (18) | −0.0104 (13) |
Mn1 | 0.0346 (3) | 0.0224 (2) | 0.0266 (3) | −0.0066 (2) | −0.0010 (2) | −0.0075 (2) |
Mn2 | 0.0325 (3) | 0.0206 (2) | 0.0300 (3) | −0.0013 (2) | −0.0053 (2) | −0.0095 (2) |
C1—N1 | 1.323 (4) | C26—C31 | 1.396 (5) |
C1—C2 | 1.380 (6) | C27—C28 | 1.375 (6) |
C1—H1 | 0.9300 | C27—H27 | 0.9300 |
C2—C3 | 1.371 (6) | C28—C29 | 1.362 (7) |
C2—H2 | 0.9300 | C28—H28 | 0.9300 |
C3—C4 | 1.397 (5) | C29—C30 | 1.376 (6) |
C3—H3 | 0.9300 | C29—H29 | 0.9300 |
C4—C18 | 1.388 (5) | C30—C31 | 1.398 (5) |
C4—C5 | 1.454 (5) | C30—H30 | 0.9300 |
C5—N3 | 1.321 (5) | C31—C32 | 1.510 (5) |
C5—C12 | 1.436 (5) | C32—O3 | 1.252 (4) |
C6—N3 | 1.350 (5) | C32—O4 | 1.258 (4) |
C6—C11 | 1.414 (5) | C33—O6 | 1.256 (4) |
C6—C7 | 1.419 (6) | C33—O5 | 1.261 (4) |
C7—C8 | 1.362 (6) | C33—C34 | 1.504 (5) |
C7—H7 | 0.9300 | C34—C35 | 1.387 (6) |
C8—C9 | 1.402 (6) | C34—C39 | 1.403 (5) |
C8—H8 | 0.9300 | C35—C36 | 1.381 (6) |
C9—C10 | 1.362 (6) | C35—H35 | 0.9300 |
C9—H9 | 0.9300 | C36—C37 | 1.388 (7) |
C10—C11 | 1.424 (5) | C36—H36 | 0.9300 |
C10—H10 | 0.9300 | C37—C38 | 1.367 (8) |
C11—N4 | 1.357 (5) | C37—H37 | 0.9300 |
C12—N4 | 1.328 (4) | C38—C39 | 1.407 (6) |
C12—C13 | 1.459 (5) | C38—H38 | 0.9300 |
C13—C17 | 1.405 (5) | C39—C40 | 1.487 (6) |
C13—C14 | 1.409 (5) | C40—C41 | 1.390 (6) |
C14—C15 | 1.369 (6) | C40—C45 | 1.410 (6) |
C14—H14 | 0.9300 | C41—C42 | 1.387 (7) |
C15—C16 | 1.383 (6) | C41—C46 | 1.502 (5) |
C15—H15 | 0.9300 | C42—C43 | 1.381 (7) |
C16—N2 | 1.332 (4) | C42—H42 | 0.9300 |
C16—H16 | 0.9300 | C43—C44 | 1.382 (7) |
C17—N2 | 1.353 (5) | C43—H43 | 0.9300 |
C17—C18 | 1.452 (4) | C44—C45 | 1.377 (8) |
C18—N1 | 1.353 (4) | C44—H44 | 0.9300 |
C19—O1 | 1.249 (4) | C45—H45 | 0.9300 |
C19—O2 | 1.267 (4) | C46—O8 | 1.239 (4) |
C19—C20 | 1.497 (5) | C46—O7 | 1.292 (5) |
C20—C21 | 1.387 (5) | Mn1—N1 | 2.236 (3) |
C20—C25 | 1.406 (5) | Mn1—N2 | 2.215 (3) |
C21—C22 | 1.389 (6) | Mn1—O1 | 2.078 (3) |
C21—H21 | 0.9300 | Mn2—O2 | 2.072 (3) |
C22—C23 | 1.383 (6) | Mn1—O3i | 2.095 (3) |
C22—H22 | 0.9300 | Mn2—O4i | 2.090 (3) |
C23—C24 | 1.375 (6) | Mn2—O5ii | 2.093 (2) |
C23—H23 | 0.9300 | Mn2—O6 | 2.124 (3) |
C24—C25 | 1.390 (5) | Mn1—O7ii | 2.183 (2) |
C24—H24 | 0.9300 | Mn2—O7ii | 2.191 (3) |
C25—C26 | 1.498 (5) | Mn1—O8ii | 2.422 (3) |
C26—C27 | 1.387 (5) | ||
N1—C1—C2 | 123.2 (4) | C30—C31—C32 | 117.2 (3) |
N1—C1—H1 | 118.4 | O3—C32—O4 | 125.5 (3) |
C2—C1—H1 | 118.4 | O3—C32—C31 | 119.0 (3) |
C3—C2—C1 | 119.3 (4) | O4—C32—C31 | 115.5 (3) |
C3—C2—H2 | 120.4 | O6—C33—O5 | 124.2 (3) |
C1—C2—H2 | 120.4 | O6—C33—C34 | 117.3 (3) |
C2—C3—C4 | 119.1 (4) | O5—C33—C34 | 118.5 (3) |
C2—C3—H3 | 120.4 | C35—C34—C39 | 119.9 (4) |
C4—C3—H3 | 120.4 | C35—C34—C33 | 118.9 (3) |
C18—C4—C3 | 117.7 (3) | C39—C34—C33 | 121.1 (4) |
C18—C4—C5 | 120.3 (3) | C36—C35—C34 | 120.8 (4) |
C3—C4—C5 | 122.1 (4) | C36—C35—H35 | 119.6 |
N3—C5—C12 | 122.3 (3) | C34—C35—H35 | 119.6 |
N3—C5—C4 | 118.1 (3) | C35—C36—C37 | 119.6 (5) |
C12—C5—C4 | 119.6 (3) | C35—C36—H36 | 120.2 |
N3—C6—C11 | 121.6 (4) | C37—C36—H36 | 120.2 |
N3—C6—C7 | 118.7 (3) | C38—C37—C36 | 120.3 (4) |
C11—C6—C7 | 119.6 (4) | C38—C37—H37 | 119.8 |
C8—C7—C6 | 120.1 (4) | C36—C37—H37 | 119.8 |
C8—C7—H7 | 120.0 | C37—C38—C39 | 121.1 (4) |
C6—C7—H7 | 120.0 | C37—C38—H38 | 119.5 |
C7—C8—C9 | 119.8 (4) | C39—C38—H38 | 119.5 |
C7—C8—H8 | 120.1 | C34—C39—C38 | 118.2 (4) |
C9—C8—H8 | 120.1 | C34—C39—C40 | 122.2 (4) |
C10—C9—C8 | 122.6 (4) | C38—C39—C40 | 119.5 (4) |
C10—C9—H9 | 118.7 | C41—C40—C45 | 117.0 (5) |
C8—C9—H9 | 118.7 | C41—C40—C39 | 123.2 (4) |
C9—C10—C11 | 118.6 (4) | C45—C40—C39 | 119.8 (4) |
C9—C10—H10 | 120.7 | C42—C41—C40 | 121.3 (4) |
C11—C10—H10 | 120.7 | C42—C41—C46 | 118.2 (4) |
N4—C11—C6 | 121.4 (3) | C40—C41—C46 | 120.0 (4) |
N4—C11—C10 | 119.3 (3) | C43—C42—C41 | 120.9 (5) |
C6—C11—C10 | 119.3 (4) | C43—C42—H42 | 119.6 |
N4—C12—C5 | 121.2 (3) | C41—C42—H42 | 119.6 |
N4—C12—C13 | 119.6 (3) | C42—C43—C44 | 118.7 (6) |
C5—C12—C13 | 119.2 (3) | C42—C43—H43 | 120.6 |
C17—C13—C14 | 117.5 (3) | C44—C43—H43 | 120.6 |
C17—C13—C12 | 119.9 (3) | C45—C44—C43 | 120.8 (5) |
C14—C13—C12 | 122.6 (3) | C45—C44—H44 | 119.6 |
C15—C14—C13 | 119.4 (4) | C43—C44—H44 | 119.6 |
C15—C14—H14 | 120.3 | C44—C45—C40 | 121.3 (5) |
C13—C14—H14 | 120.3 | C44—C45—H45 | 119.4 |
C14—C15—C16 | 119.2 (4) | C40—C45—H45 | 119.4 |
C14—C15—H15 | 120.4 | O8—C46—O7 | 120.9 (3) |
C16—C15—H15 | 120.4 | O8—C46—C41 | 122.5 (4) |
N2—C16—C15 | 123.2 (4) | O7—C46—C41 | 116.4 (3) |
N2—C16—H16 | 118.4 | O8—C46—Mn1ii | 66.4 (2) |
C15—C16—H16 | 118.4 | O7—C46—Mn1ii | 55.53 (16) |
N2—C17—C13 | 122.4 (3) | C41—C46—Mn1ii | 163.7 (3) |
N2—C17—C18 | 117.4 (3) | C1—N1—C18 | 117.8 (3) |
C13—C17—C18 | 120.3 (3) | C1—N1—Mn1 | 126.2 (3) |
N1—C18—C4 | 123.0 (3) | C18—N1—Mn1 | 115.4 (2) |
N1—C18—C17 | 116.4 (3) | C16—N2—C17 | 118.3 (3) |
C4—C18—C17 | 120.6 (3) | C16—N2—Mn1 | 125.7 (3) |
O1—C19—O2 | 124.1 (3) | C17—N2—Mn1 | 115.8 (2) |
O1—C19—C20 | 118.4 (3) | C5—N3—C6 | 116.7 (3) |
O2—C19—C20 | 117.4 (3) | C12—N4—C11 | 116.9 (3) |
C21—C20—C25 | 119.5 (3) | C19—O1—Mn1 | 130.5 (2) |
C21—C20—C19 | 118.0 (3) | C19—O2—Mn2 | 131.8 (2) |
C25—C20—C19 | 122.3 (3) | C32—O3—Mn1i | 125.1 (2) |
C20—C21—C22 | 121.6 (4) | C32—O4—Mn2i | 145.5 (3) |
C20—C21—H21 | 119.2 | C33—O5—Mn2ii | 136.0 (2) |
C22—C21—H21 | 119.2 | C33—O6—Mn2 | 123.9 (2) |
C23—C22—C21 | 118.3 (4) | C46—O7—Mn1ii | 95.26 (19) |
C23—C22—H22 | 120.8 | C46—O7—Mn2ii | 126.9 (2) |
C21—C22—H22 | 120.8 | Mn1ii—O7—Mn2ii | 107.42 (10) |
C24—C23—C22 | 120.9 (4) | C46—O8—Mn1ii | 85.7 (2) |
C24—C23—H23 | 119.6 | O1—Mn1—O3i | 94.57 (11) |
C22—C23—H23 | 119.6 | O1—Mn1—O7ii | 102.47 (10) |
C23—C24—C25 | 121.3 (4) | O3i—Mn1—O7ii | 96.67 (10) |
C23—C24—H24 | 119.3 | O1—Mn1—N2 | 97.39 (12) |
C25—C24—H24 | 119.3 | O3i—Mn1—N2 | 103.28 (11) |
C24—C25—C20 | 118.3 (4) | O7ii—Mn1—N2 | 150.51 (10) |
C24—C25—C26 | 118.0 (3) | O1—Mn1—N1 | 88.13 (12) |
C20—C25—C26 | 123.3 (3) | O3i—Mn1—N1 | 176.37 (11) |
C27—C26—C31 | 118.0 (4) | O7ii—Mn1—N1 | 85.08 (10) |
C27—C26—C25 | 115.8 (3) | N2—Mn1—N1 | 73.93 (11) |
C31—C26—C25 | 125.9 (3) | O1—Mn1—O8ii | 158.69 (10) |
C28—C27—C26 | 121.5 (4) | O3i—Mn1—O8ii | 83.93 (11) |
C28—C27—H27 | 119.2 | O7ii—Mn1—O8ii | 56.84 (9) |
C26—C27—H27 | 119.2 | N2—Mn1—O8ii | 103.65 (11) |
C29—C28—C27 | 120.6 (4) | N1—Mn1—O8ii | 94.43 (11) |
C29—C28—H28 | 119.7 | O2—Mn2—O4i | 103.87 (12) |
C27—C28—H28 | 119.7 | O2—Mn2—O5ii | 123.95 (10) |
C28—C29—C30 | 119.5 (4) | O4i—Mn2—O5ii | 132.03 (12) |
C28—C29—H29 | 120.3 | O2—Mn2—O6 | 92.53 (12) |
C30—C29—H29 | 120.3 | O4i—Mn2—O6 | 88.76 (11) |
C29—C30—C31 | 120.8 (4) | O5ii—Mn2—O6 | 92.47 (9) |
C29—C30—H30 | 119.6 | O2—Mn2—O7ii | 91.76 (11) |
C31—C30—H30 | 119.6 | O4i—Mn2—O7ii | 83.90 (11) |
C26—C31—C30 | 119.7 (3) | O5ii—Mn2—O7ii | 90.52 (9) |
C26—C31—C32 | 123.1 (3) | O6—Mn2—O7ii | 172.21 (10) |
Symmetry codes: (i) −x, −y+2, −z+1; (ii) −x, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Mn2(C14H8O4)2(C18H10N4)] |
Mr | 872.59 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 11.993 (2), 13.516 (3), 14.196 (3) |
α, β, γ (°) | 62.13 (3), 70.55 (2), 82.24 (3) |
V (Å3) | 1917.6 (9) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.72 |
Crystal size (mm) | 0.31 × 0.24 × 0.21 |
Data collection | |
Diffractometer | Rigaku R-AXIS RAPID diffractometer |
Absorption correction | Multi-scan (ABSCOR; Higashi, 1995) |
Tmin, Tmax | 0.794, 0.856 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 18726, 8667, 5367 |
Rint | 0.064 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.056, 0.142, 1.03 |
No. of reflections | 8667 |
No. of parameters | 541 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.49, −0.37 |
Computer programs: PROCESS-AUTO (Rigaku, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL-Plus (Sheldrick, 2008).
Mn1—N1 | 2.236 (3) | Mn2—O5ii | 2.093 (2) |
Mn1—N2 | 2.215 (3) | Mn2—O6 | 2.124 (3) |
Mn1—O1 | 2.078 (3) | Mn1—O7ii | 2.183 (2) |
Mn2—O2 | 2.072 (3) | Mn2—O7ii | 2.191 (3) |
Mn1—O3i | 2.095 (3) | Mn1—O8ii | 2.422 (3) |
Mn2—O4i | 2.090 (3) | ||
O1—Mn1—O3i | 94.57 (11) | N2—Mn1—O8ii | 103.65 (11) |
O1—Mn1—O7ii | 102.47 (10) | N1—Mn1—O8ii | 94.43 (11) |
O3i—Mn1—O7ii | 96.67 (10) | O2—Mn2—O4i | 103.87 (12) |
O1—Mn1—N2 | 97.39 (12) | O2—Mn2—O5ii | 123.95 (10) |
O3i—Mn1—N2 | 103.28 (11) | O4i—Mn2—O5ii | 132.03 (12) |
O7ii—Mn1—N2 | 150.51 (10) | O2—Mn2—O6 | 92.53 (12) |
O1—Mn1—N1 | 88.13 (12) | O4i—Mn2—O6 | 88.76 (11) |
O3i—Mn1—N1 | 176.37 (11) | O5ii—Mn2—O6 | 92.47 (9) |
O7ii—Mn1—N1 | 85.08 (10) | O2—Mn2—O7ii | 91.76 (11) |
N2—Mn1—N1 | 73.93 (11) | O4i—Mn2—O7ii | 83.90 (11) |
O1—Mn1—O8ii | 158.69 (10) | O5ii—Mn2—O7ii | 90.52 (9) |
O3i—Mn1—O8ii | 83.93 (11) | O6—Mn2—O7ii | 172.21 (10) |
O7ii—Mn1—O8ii | 56.84 (9) |
Symmetry codes: (i) −x, −y+2, −z+1; (ii) −x, −y+1, −z+1. |
The metal–organic coordination architectures formed with transition metal ions and organic ligands have been a promising topic for many years owing to their intriguing structures and potential applications in catalysis, separation, gas storage, molecular recognition, magnetic devices and nonlinear optical materials (Eddaoudi et al., 2001; Batten & Robson, 1998; Yang et al., 2008). In this regard, chain structures have received much attention in coordination chemistry and materials chemistry (Lehn, 1990; Li et al., 2002; Chen & Liu, 2002; Yang, Li et al., 2007). An appropriate flexible bidentate organic acid bridge could be useful in the formation of chains in the presence of secondary ligands, such as 2,2'-bipyridine (bipy) and 1,10-phenanthroline (phen) (Qi et al., 2003). The N atoms from the secondary ligand may occupy two coordination positions of the metal ions. The rest of the coordination positions are available for other carboxylate ligands to allow the formation of a chain.
The use of aromatic carboxylic acids in the syntheses of chain coordination polymers has aroused enormous interest owing to their versatile coordination modes and varieties of structural conformations (Chen & Liu, 2002; Zhang et al., 2003; Fan et al., 2002). So far, aromatic multicarboxylate ligands, such as 1,2-benzenedicarboxylic acid, 1,3-benzenedicarboxylic acid and 1,4-benzenedicarboxylic acid, have been widely used to construct chain structures with interesting properties (Chen & Liu, 2002). In this regard, biphenyl-2,2'-dicarboxylic acid (H2dpdc) is also a good ligand in coordination chemistry because of its strong coordination ability and versatile coordination modes, so much attention has been paid to it in the past decade. On the other hand, the phen molecule, as one type of important organic ligand, has been widely utilized in the construction of chain structure complexes. An important derivative of phen, dipyrido[3,2-a:2',3'-c]-phenazine (L) has been widely used to synthesize various RuII complexes in order to recognize the secondary structure of DNA (Wu et al., 1997). However, chain coordination polymers based on the ligand L have rarely been documented. In the present study, we selected H2dpdc as a linker and L as a secondary chelating ligand, forming a new chain coordination polymer, [Mn2(L)(dpdc)2], (I), based on unusual tetranuclear MnII clusters.
Selected bond lengths and angles for (I) are given in Table 1. As shown in Fig. 1, the asymmetric unit of (I) contains two crystallographically unique MnII atoms, one unique L ligand and two unique dpdc ligands. Atom Mn1 is six-coordinated by four O atoms [O1, O3i, O7ii and O8ii; symmetry codes: (i) -x, -y + 2, -z + 1; (ii) -x, -y + 1, -z + 1] from three different dpdc ligands and two N atoms (N1 and N2) from one L ligand, adopting a distorted octahedral coordination geometry. Atom Mn2 is coordinated in a square-pyramidal fashion by five O atoms (O2, O6, O4i, O5ii, O7ii) from four distinct dpdc ligands. The average Mn—O and Mn—N distances in (I) are comparable to those observed for [Mn(bza)2(ppz)2] [bza is benzoic acid and ppz is 3-(2-pyridyl)pyrazole; Zou et al., 2005]. Two coordination modes for the dpdc ligands have been found: one is bis-bidentate, and the second is bidentate/monodentate–bidentate. In these modes, an unusual tetranuclear MnII cluster is formed, where four MnII atoms are bridged by the carboxylate groups of the dpdc ligands to form a discrete rod (Fig. 2). Each cluster lies across an inversion centre, with the Mn2 atoms in the middle and the Mn1 atoms on the ends of the rod. As such, each tetranuclear metal cluster is surrounded by eight organic ligands: six bridging dpdc and two chelating L ligands. To the best of our knowledge, the rod-like tetranuclear MnII cluster containing the bpy-like chelating ligand L has not been reported so far, although other noncoplanar tetranuclear CdII clusters including bpy-like chelating ligands have been reported (Wang et al., 2007).
In the structure of (I), the tetranuclear MnII carboxylate clusters act as rod-shaped secondary building units, which are connected together by the aromatic backbone of the dicarboxylate ligands, forming a one-dimensional chain structure along the b axis (Fig. 3). These chains are decorated with L ligands alternately on two sides. It is noteworthy that the structure of (I) presented here is clearly different from that reported for [Pb(dpdc)(L)] (Yang, Ma et al., 2007). This reported compound features a helical chain structure based on mononuclear lead(II) centers, which are connected by strong π–π interactions to result in a three-dimensional supramolecular architecture.
Over the past decade, chain structures have received much attention in coordination chemistry and materials chemistry because of their importantance in advanced materials such as optical devices, enantiomer separation, chiral synthesis, ligand exchange and selective catalysis (Chen & Liu, 2002). Consequently, many chain complexes have been generated by self-assembly processes. However, the reported chain complexes constructed by dicarboxylate and heteroaromatic N-donor chelating ligands are mainly based on the mononuclear metal centers. To the best of our knowledge, (I), constructed from the dicarboxylate anion and aphen derivative, is the first one-dimensional chain structure based on tetranuclear MnII clusters.