Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802019979/ob6183sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802019979/ob6183Isup2.hkl |
CCDC reference: 202274
Mn(O2CPh)2·2H2O (0.63 g, 2 mmol) was added in the mixed solution of 2,5-pyridinedicarboxylic acid (0.33 g, 2 mmol) and KOH (0.23 g, 4 mmol) in 30 ml of CH3OH/H2O (v/v 1:2) and the resulting solution stirred for 30 min at room temperature. Then phenanthroline (0.40 g, 2 mmol) and NaClO4·H2O (0.28 g, 2 mmol) were added and the resulting solution was stirred at room temperature for 12 h. After filtration, the collected precipitate was dissolved in 15 ml of dmf/CH2Cl2 (v/v 1:1), the resulting filtrate was kept at room temperature for several weeks and yellow crystals of (I) were obtained.
H atoms bonded to carbon were placed at calculated positions, with isotropic displacement parameters, riding on their carrier atoms. Water H atoms were located from difference maps. The O—H bond lengths are 0.838 (19) and 0.85 (2) Å.
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1994); data reduction: XPREP in SHELXTL (Siemens, 1994); program(s) used to solve structure: SHELXTL; program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.
[Mn(C7H5O2)(C12H8N2)2(H2O)](ClO4)·C3H7NO | F(000) = 1500 |
Mr = 727.02 | Dx = 1.476 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 12.1787 (4) Å | Cell parameters from 5235 reflections |
b = 16.0320 (5) Å | θ = 1.8–25.0° |
c = 17.3628 (5) Å | µ = 0.55 mm−1 |
β = 105.223 (1)° | T = 293 K |
V = 3271.11 (18) Å3 | Block, yellow |
Z = 4 | 0.34 × 0.28 × 0.16 mm |
Siemens SMART CCD diffractometer | 5671 independent reflections |
Radiation source: fine-focus sealed tube | 4440 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.030 |
ω scans | θmax = 25.0°, θmin = 1.8° |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | h = −14→13 |
Tmin = 0.700, Tmax = 0.916 | k = −18→17 |
9876 measured reflections | l = −20→10 |
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)] = 0.061 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.153 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.13 | w = 1/[σ2(Fo2) + (0.0479P)2 + 5.0132P] where P = (Fo2 + 2Fc2)/3 |
5671 reflections | (Δ/σ)max = 0.001 |
450 parameters | Δρmax = 0.34 e Å−3 |
2 restraints | Δρmin = −0.43 e Å−3 |
[Mn(C7H5O2)(C12H8N2)2(H2O)](ClO4)·C3H7NO | V = 3271.11 (18) Å3 |
Mr = 727.02 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 12.1787 (4) Å | µ = 0.55 mm−1 |
b = 16.0320 (5) Å | T = 293 K |
c = 17.3628 (5) Å | 0.34 × 0.28 × 0.16 mm |
β = 105.223 (1)° |
Siemens SMART CCD diffractometer | 5671 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 4440 reflections with I > 2σ(I) |
Tmin = 0.700, Tmax = 0.916 | Rint = 0.030 |
9876 measured reflections |
R[F2 > 2σ(F2)] = 0.061 | 2 restraints |
wR(F2) = 0.153 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.13 | Δρmax = 0.34 e Å−3 |
5671 reflections | Δρmin = −0.43 e Å−3 |
450 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 | 0.96327 (5) | 0.77488 (3) | 0.17492 (3) | 0.04156 (18) | |
Cl | 0.50925 (11) | 0.34733 (8) | 0.58597 (7) | 0.0712 (3) | |
O1 | 0.8408 (2) | 0.67976 (16) | 0.17162 (17) | 0.0523 (7) | |
O2 | 0.9287 (3) | 0.5625 (2) | 0.1542 (2) | 0.0795 (10) | |
O3 | 1.0871 (3) | 0.6760 (2) | 0.1896 (2) | 0.0593 (8) | |
H3D | 1.144 (3) | 0.673 (3) | 0.172 (3) | 0.070 (15)* | |
H3C | 1.040 (4) | 0.637 (3) | 0.175 (4) | 0.11 (2)* | |
O4 | 0.4728 (4) | 0.2635 (3) | 0.5670 (3) | 0.1173 (16) | |
O5 | 0.6263 (4) | 0.3496 (4) | 0.5947 (3) | 0.148 (2) | |
O6 | 0.4499 (5) | 0.3975 (3) | 0.5249 (3) | 0.1333 (19) | |
O7 | 0.4848 (4) | 0.3739 (3) | 0.6585 (2) | 0.1053 (14) | |
O8 | 0.7226 (3) | 0.1873 (2) | 0.3603 (2) | 0.0768 (10) | |
N1 | 0.9020 (3) | 0.7959 (2) | 0.04104 (18) | 0.0484 (8) | |
N2 | 1.0871 (3) | 0.8671 (2) | 0.1400 (2) | 0.0508 (8) | |
N3 | 0.8408 (3) | 0.87014 (19) | 0.20083 (19) | 0.0450 (7) | |
N4 | 1.0261 (3) | 0.8067 (2) | 0.30689 (18) | 0.0459 (8) | |
N5 | 0.5679 (3) | 0.2701 (3) | 0.3219 (2) | 0.0667 (10) | |
C1 | 0.8418 (3) | 0.6028 (2) | 0.1556 (2) | 0.0467 (9) | |
C2 | 0.7299 (3) | 0.5572 (2) | 0.1369 (2) | 0.0447 (9) | |
C3 | 0.6337 (4) | 0.5948 (3) | 0.1492 (3) | 0.0683 (13) | |
H3B | 0.6372 | 0.6492 | 0.1684 | 0.082* | |
C4 | 0.5320 (4) | 0.5509 (4) | 0.1328 (4) | 0.0888 (18) | |
H4A | 0.4675 | 0.5760 | 0.1415 | 0.107* | |
C5 | 0.5252 (4) | 0.4712 (4) | 0.1038 (4) | 0.0817 (16) | |
H5A | 0.4564 | 0.4425 | 0.0923 | 0.098* | |
C6 | 0.6207 (4) | 0.4339 (3) | 0.0918 (3) | 0.0741 (14) | |
H6A | 0.6167 | 0.3795 | 0.0727 | 0.089* | |
C7 | 0.7223 (4) | 0.4763 (3) | 0.1079 (3) | 0.0580 (11) | |
H7A | 0.7864 | 0.4504 | 0.0993 | 0.070* | |
C8 | 0.8086 (4) | 0.7628 (3) | −0.0074 (2) | 0.0584 (11) | |
H8A | 0.7623 | 0.7298 | 0.0149 | 0.070* | |
C9 | 0.7770 (4) | 0.7752 (4) | −0.0895 (3) | 0.0735 (15) | |
H9A | 0.7110 | 0.7508 | −0.1208 | 0.088* | |
C10 | 0.8424 (5) | 0.8228 (3) | −0.1233 (3) | 0.0737 (15) | |
H10A | 0.8221 | 0.8314 | −0.1782 | 0.088* | |
C11 | 0.9418 (4) | 0.8594 (3) | −0.0753 (3) | 0.0626 (13) | |
C12 | 1.0177 (6) | 0.9086 (3) | −0.1058 (3) | 0.0822 (17) | |
H12A | 1.0016 | 0.9184 | −0.1604 | 0.099* | |
C13 | 1.1121 (6) | 0.9411 (3) | −0.0573 (4) | 0.0838 (18) | |
H13A | 1.1606 | 0.9724 | −0.0793 | 0.101* | |
C14 | 1.1410 (4) | 0.9291 (3) | 0.0279 (3) | 0.0647 (13) | |
C15 | 1.2357 (5) | 0.9651 (3) | 0.0816 (4) | 0.0826 (17) | |
H15A | 1.2867 | 0.9970 | 0.0626 | 0.099* | |
C16 | 1.2530 (4) | 0.9533 (3) | 0.1611 (4) | 0.0814 (16) | |
H16A | 1.3141 | 0.9785 | 0.1972 | 0.098* | |
C17 | 1.1772 (4) | 0.9025 (3) | 0.1881 (3) | 0.0647 (12) | |
H17A | 1.1911 | 0.8932 | 0.2427 | 0.078* | |
C18 | 1.0680 (3) | 0.8810 (2) | 0.0606 (2) | 0.0470 (9) | |
C19 | 0.9685 (4) | 0.8444 (2) | 0.0078 (2) | 0.0490 (10) | |
C20 | 0.7504 (3) | 0.9016 (3) | 0.1484 (3) | 0.0525 (10) | |
H20A | 0.7345 | 0.8830 | 0.0959 | 0.063* | |
C21 | 0.6786 (4) | 0.9604 (3) | 0.1676 (3) | 0.0651 (12) | |
H21A | 0.6174 | 0.9816 | 0.1286 | 0.078* | |
C22 | 0.6994 (4) | 0.9864 (3) | 0.2445 (3) | 0.0692 (13) | |
H22A | 0.6532 | 1.0269 | 0.2582 | 0.083* | |
C23 | 0.7902 (4) | 0.9527 (3) | 0.3033 (3) | 0.0607 (12) | |
C24 | 0.8134 (5) | 0.9716 (3) | 0.3865 (3) | 0.0750 (15) | |
H24A | 0.7669 | 1.0093 | 0.4038 | 0.090* | |
C25 | 0.9007 (5) | 0.9361 (3) | 0.4401 (3) | 0.0720 (15) | |
H25A | 0.9115 | 0.9478 | 0.4941 | 0.086* | |
C26 | 0.9774 (4) | 0.8806 (3) | 0.4160 (3) | 0.0597 (12) | |
C27 | 1.0722 (5) | 0.8440 (3) | 0.4684 (3) | 0.0701 (15) | |
H27A | 1.0881 | 0.8553 | 0.5228 | 0.084* | |
C28 | 1.1416 (4) | 0.7919 (3) | 0.4407 (3) | 0.0664 (13) | |
H28A | 1.2055 | 0.7687 | 0.4757 | 0.080* | |
C29 | 1.1156 (4) | 0.7738 (3) | 0.3591 (2) | 0.0553 (10) | |
H29A | 1.1625 | 0.7374 | 0.3407 | 0.066* | |
C30 | 0.9581 (3) | 0.8596 (2) | 0.3348 (2) | 0.0470 (9) | |
C31 | 0.8611 (3) | 0.8951 (2) | 0.2780 (2) | 0.0457 (9) | |
C32 | 0.4883 (6) | 0.3134 (4) | 0.2582 (4) | 0.105 (2) | |
H32A | 0.5054 | 0.3014 | 0.2084 | 0.158* | |
H32B | 0.4941 | 0.3723 | 0.2681 | 0.158* | |
H32C | 0.4123 | 0.2951 | 0.2557 | 0.158* | |
C33 | 0.5557 (5) | 0.2810 (4) | 0.4019 (3) | 0.0894 (18) | |
H33A | 0.6133 | 0.2493 | 0.4387 | 0.134* | |
H33B | 0.4819 | 0.2620 | 0.4041 | 0.134* | |
H33C | 0.5639 | 0.3390 | 0.4161 | 0.134* | |
C34 | 0.6520 (4) | 0.2256 (3) | 0.3092 (3) | 0.0671 (12) | |
H34B | 0.6585 | 0.2229 | 0.2571 | 0.081* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mn | 0.0446 (3) | 0.0427 (3) | 0.0394 (3) | −0.0010 (3) | 0.0148 (2) | −0.0009 (2) |
Cl | 0.0679 (7) | 0.0773 (8) | 0.0662 (7) | −0.0065 (6) | 0.0136 (6) | −0.0104 (6) |
O1 | 0.0528 (16) | 0.0425 (16) | 0.0677 (18) | −0.0043 (12) | 0.0266 (14) | −0.0051 (13) |
O2 | 0.0518 (18) | 0.0551 (19) | 0.137 (3) | 0.0006 (15) | 0.0350 (19) | −0.020 (2) |
O3 | 0.0461 (17) | 0.0584 (19) | 0.078 (2) | 0.0027 (15) | 0.0252 (16) | −0.0035 (16) |
O4 | 0.149 (4) | 0.086 (3) | 0.134 (4) | −0.024 (3) | 0.066 (3) | −0.028 (3) |
O5 | 0.067 (3) | 0.206 (6) | 0.178 (5) | −0.025 (3) | 0.043 (3) | −0.087 (4) |
O6 | 0.182 (5) | 0.126 (4) | 0.087 (3) | 0.056 (4) | 0.026 (3) | 0.033 (3) |
O7 | 0.111 (3) | 0.129 (4) | 0.080 (3) | −0.002 (3) | 0.032 (2) | −0.037 (2) |
O8 | 0.0557 (19) | 0.095 (3) | 0.082 (2) | 0.0158 (18) | 0.0231 (18) | 0.016 (2) |
N1 | 0.0500 (19) | 0.056 (2) | 0.0406 (17) | 0.0060 (16) | 0.0150 (15) | −0.0020 (15) |
N2 | 0.0512 (19) | 0.0488 (19) | 0.053 (2) | −0.0025 (16) | 0.0147 (16) | 0.0004 (16) |
N3 | 0.0456 (18) | 0.0410 (17) | 0.0516 (19) | −0.0041 (14) | 0.0185 (15) | 0.0004 (15) |
N4 | 0.054 (2) | 0.0471 (18) | 0.0380 (17) | −0.0088 (15) | 0.0151 (15) | 0.0022 (14) |
N5 | 0.058 (2) | 0.079 (3) | 0.061 (2) | 0.016 (2) | 0.0135 (19) | −0.010 (2) |
C1 | 0.051 (2) | 0.043 (2) | 0.049 (2) | −0.0019 (18) | 0.0186 (18) | 0.0004 (18) |
C2 | 0.046 (2) | 0.041 (2) | 0.048 (2) | 0.0024 (17) | 0.0136 (18) | 0.0043 (17) |
C3 | 0.060 (3) | 0.049 (3) | 0.104 (4) | 0.001 (2) | 0.037 (3) | −0.006 (3) |
C4 | 0.053 (3) | 0.082 (4) | 0.137 (5) | −0.001 (3) | 0.036 (3) | 0.000 (4) |
C5 | 0.059 (3) | 0.073 (4) | 0.110 (4) | −0.016 (3) | 0.016 (3) | 0.008 (3) |
C6 | 0.075 (3) | 0.052 (3) | 0.090 (4) | −0.015 (2) | 0.012 (3) | −0.009 (3) |
C7 | 0.061 (3) | 0.046 (2) | 0.069 (3) | −0.001 (2) | 0.019 (2) | −0.006 (2) |
C8 | 0.049 (2) | 0.076 (3) | 0.048 (2) | 0.007 (2) | 0.010 (2) | −0.010 (2) |
C9 | 0.067 (3) | 0.095 (4) | 0.051 (3) | 0.026 (3) | 0.003 (2) | −0.018 (3) |
C10 | 0.091 (4) | 0.086 (4) | 0.039 (2) | 0.038 (3) | 0.008 (3) | −0.003 (2) |
C11 | 0.092 (3) | 0.058 (3) | 0.047 (2) | 0.036 (3) | 0.034 (3) | 0.012 (2) |
C12 | 0.131 (5) | 0.065 (3) | 0.067 (3) | 0.028 (3) | 0.055 (4) | 0.021 (3) |
C13 | 0.128 (5) | 0.054 (3) | 0.099 (4) | 0.011 (3) | 0.082 (4) | 0.023 (3) |
C14 | 0.078 (3) | 0.041 (2) | 0.092 (4) | 0.003 (2) | 0.051 (3) | 0.007 (2) |
C15 | 0.087 (4) | 0.048 (3) | 0.134 (5) | −0.007 (3) | 0.068 (4) | 0.004 (3) |
C16 | 0.066 (3) | 0.058 (3) | 0.125 (5) | −0.018 (2) | 0.033 (3) | −0.008 (3) |
C17 | 0.062 (3) | 0.059 (3) | 0.071 (3) | −0.009 (2) | 0.015 (2) | −0.003 (2) |
C18 | 0.058 (2) | 0.0346 (19) | 0.057 (2) | 0.0108 (17) | 0.031 (2) | 0.0049 (17) |
C19 | 0.063 (3) | 0.043 (2) | 0.046 (2) | 0.0185 (19) | 0.023 (2) | 0.0057 (18) |
C20 | 0.054 (2) | 0.051 (2) | 0.057 (2) | 0.0025 (19) | 0.021 (2) | 0.004 (2) |
C21 | 0.058 (3) | 0.053 (3) | 0.087 (4) | 0.003 (2) | 0.024 (3) | 0.004 (2) |
C22 | 0.058 (3) | 0.052 (3) | 0.107 (4) | −0.001 (2) | 0.037 (3) | −0.014 (3) |
C23 | 0.066 (3) | 0.050 (2) | 0.078 (3) | −0.020 (2) | 0.039 (3) | −0.023 (2) |
C24 | 0.086 (4) | 0.070 (3) | 0.085 (4) | −0.027 (3) | 0.049 (3) | −0.038 (3) |
C25 | 0.096 (4) | 0.077 (3) | 0.058 (3) | −0.041 (3) | 0.046 (3) | −0.031 (3) |
C26 | 0.081 (3) | 0.059 (3) | 0.045 (2) | −0.033 (2) | 0.027 (2) | −0.011 (2) |
C27 | 0.098 (4) | 0.070 (3) | 0.043 (2) | −0.044 (3) | 0.020 (3) | −0.007 (2) |
C28 | 0.073 (3) | 0.063 (3) | 0.052 (3) | −0.028 (2) | −0.004 (2) | 0.014 (2) |
C29 | 0.058 (3) | 0.056 (3) | 0.048 (2) | −0.012 (2) | 0.007 (2) | 0.009 (2) |
C30 | 0.060 (2) | 0.045 (2) | 0.043 (2) | −0.0215 (19) | 0.0256 (19) | −0.0060 (17) |
C31 | 0.053 (2) | 0.038 (2) | 0.054 (2) | −0.0118 (17) | 0.027 (2) | −0.0084 (17) |
C32 | 0.101 (5) | 0.119 (5) | 0.085 (4) | 0.043 (4) | 0.005 (3) | −0.003 (4) |
C33 | 0.073 (3) | 0.124 (5) | 0.076 (3) | 0.012 (3) | 0.028 (3) | −0.024 (3) |
C34 | 0.061 (3) | 0.081 (3) | 0.063 (3) | −0.001 (3) | 0.022 (2) | −0.005 (3) |
Mn—O1 | 2.124 (3) | C10—H10A | 0.9300 |
Mn—O3 | 2.156 (3) | C11—C19 | 1.414 (6) |
Mn—N3 | 2.261 (3) | C11—C12 | 1.419 (7) |
Mn—N1 | 2.272 (3) | C12—C13 | 1.340 (8) |
Mn—N4 | 2.275 (3) | C12—H12A | 0.9300 |
Mn—N2 | 2.303 (3) | C13—C14 | 1.440 (7) |
Cl—O6 | 1.376 (4) | C13—H13A | 0.9300 |
Cl—O5 | 1.395 (4) | C14—C15 | 1.403 (8) |
Cl—O4 | 1.426 (4) | C14—C18 | 1.405 (6) |
Cl—O7 | 1.433 (4) | C15—C16 | 1.354 (8) |
O1—C1 | 1.266 (5) | C15—H15A | 0.9300 |
O2—C1 | 1.245 (5) | C16—C17 | 1.400 (7) |
O3—H3D | 0.838 (19) | C16—H16A | 0.9300 |
O3—H3C | 0.85 (2) | C17—H17A | 0.9300 |
O8—C34 | 1.226 (6) | C18—C19 | 1.438 (6) |
N1—C8 | 1.334 (5) | C20—C21 | 1.384 (6) |
N1—C19 | 1.357 (5) | C20—H20A | 0.9300 |
N2—C17 | 1.320 (5) | C21—C22 | 1.357 (7) |
N2—C18 | 1.355 (5) | C21—H21A | 0.9300 |
N3—C20 | 1.330 (5) | C22—C23 | 1.402 (7) |
N3—C31 | 1.357 (5) | C22—H22A | 0.9300 |
N4—C29 | 1.331 (5) | C23—C31 | 1.412 (6) |
N4—C30 | 1.360 (5) | C23—C24 | 1.428 (7) |
N5—C34 | 1.313 (6) | C24—C25 | 1.343 (7) |
N5—C32 | 1.443 (6) | C24—H24A | 0.9300 |
N5—C33 | 1.446 (6) | C25—C26 | 1.431 (7) |
C1—C2 | 1.504 (5) | C25—H25A | 0.9300 |
C2—C3 | 1.383 (6) | C26—C27 | 1.398 (7) |
C2—C7 | 1.386 (6) | C26—C30 | 1.407 (5) |
C3—C4 | 1.388 (7) | C27—C28 | 1.361 (7) |
C3—H3B | 0.9300 | C27—H27A | 0.9300 |
C4—C5 | 1.368 (8) | C28—C29 | 1.399 (6) |
C4—H4A | 0.9300 | C28—H28A | 0.9300 |
C5—C6 | 1.371 (7) | C29—H29A | 0.9300 |
C5—H5A | 0.9300 | C30—C31 | 1.443 (6) |
C6—C7 | 1.374 (6) | C32—H32A | 0.9600 |
C6—H6A | 0.9300 | C32—H32B | 0.9600 |
C7—H7A | 0.9300 | C32—H32C | 0.9600 |
C8—C9 | 1.390 (6) | C33—H33A | 0.9600 |
C8—H8A | 0.9300 | C33—H33B | 0.9600 |
C9—C10 | 1.344 (8) | C33—H33C | 0.9600 |
C9—H9A | 0.9300 | C34—H34B | 0.9300 |
C10—C11 | 1.405 (7) | ||
O1—Mn—O3 | 86.56 (12) | C13—C12—H12A | 119.4 |
O1—Mn—N3 | 89.71 (11) | C11—C12—H12A | 119.4 |
O3—Mn—N3 | 161.90 (12) | C12—C13—C14 | 122.1 (5) |
O1—Mn—N1 | 92.24 (12) | C12—C13—H13A | 119.0 |
O3—Mn—N1 | 105.13 (12) | C14—C13—H13A | 119.0 |
N3—Mn—N1 | 92.70 (12) | C15—C14—C18 | 117.0 (5) |
O1—Mn—N4 | 103.67 (11) | C15—C14—C13 | 124.4 (5) |
O3—Mn—N4 | 90.36 (13) | C18—C14—C13 | 118.6 (5) |
N3—Mn—N4 | 73.32 (12) | C16—C15—C14 | 120.0 (5) |
N1—Mn—N4 | 158.51 (12) | C16—C15—H15A | 120.0 |
O1—Mn—N2 | 163.23 (11) | C14—C15—H15A | 120.0 |
O3—Mn—N2 | 90.95 (12) | C15—C16—C17 | 118.9 (5) |
N3—Mn—N2 | 97.51 (11) | C15—C16—H16A | 120.6 |
N1—Mn—N2 | 72.40 (12) | C17—C16—H16A | 120.6 |
N4—Mn—N2 | 92.92 (11) | N2—C17—C16 | 123.4 (5) |
O6—Cl—O5 | 112.6 (4) | N2—C17—H17A | 118.3 |
O6—Cl—O4 | 107.7 (3) | C16—C17—H17A | 118.3 |
O5—Cl—O4 | 107.3 (3) | N2—C18—C14 | 122.9 (4) |
O6—Cl—O7 | 108.4 (3) | N2—C18—C19 | 118.2 (3) |
O5—Cl—O7 | 109.9 (3) | C14—C18—C19 | 118.9 (4) |
O4—Cl—O7 | 111.1 (3) | N1—C19—C11 | 121.9 (4) |
C1—O1—Mn | 131.2 (3) | N1—C19—C18 | 117.4 (3) |
Mn—O3—H3D | 129 (3) | C11—C19—C18 | 120.7 (4) |
Mn—O3—H3C | 97 (4) | N3—C20—C21 | 123.7 (4) |
H3D—O3—H3C | 114 (5) | N3—C20—H20A | 118.2 |
C8—N1—C19 | 117.7 (4) | C21—C20—H20A | 118.2 |
C8—N1—Mn | 125.6 (3) | C22—C21—C20 | 118.7 (5) |
C19—N1—Mn | 116.6 (3) | C22—C21—H21A | 120.7 |
C17—N2—C18 | 117.7 (4) | C20—C21—H21A | 120.7 |
C17—N2—Mn | 127.0 (3) | C21—C22—C23 | 120.4 (4) |
C18—N2—Mn | 115.1 (3) | C21—C22—H22A | 119.8 |
C20—N3—C31 | 117.9 (3) | C23—C22—H22A | 119.8 |
C20—N3—Mn | 126.2 (3) | C22—C23—C31 | 117.0 (4) |
C31—N3—Mn | 115.9 (3) | C22—C23—C24 | 124.3 (5) |
C29—N4—C30 | 118.1 (3) | C31—C23—C24 | 118.6 (5) |
C29—N4—Mn | 126.6 (3) | C25—C24—C23 | 121.5 (5) |
C30—N4—Mn | 115.1 (3) | C25—C24—H24A | 119.3 |
C34—N5—C32 | 121.9 (4) | C23—C24—H24A | 119.3 |
C34—N5—C33 | 120.5 (4) | C24—C25—C26 | 121.3 (4) |
C32—N5—C33 | 117.4 (4) | C24—C25—H25A | 119.4 |
O2—C1—O1 | 124.5 (4) | C26—C25—H25A | 119.4 |
O2—C1—C2 | 118.1 (4) | C27—C26—C30 | 116.4 (4) |
O1—C1—C2 | 117.4 (3) | C27—C26—C25 | 124.1 (4) |
C3—C2—C7 | 119.0 (4) | C30—C26—C25 | 119.5 (5) |
C3—C2—C1 | 120.7 (4) | C28—C27—C26 | 120.6 (4) |
C7—C2—C1 | 120.2 (4) | C28—C27—H27A | 119.7 |
C2—C3—C4 | 119.5 (4) | C26—C27—H27A | 119.7 |
C2—C3—H3B | 120.2 | C27—C28—C29 | 119.3 (5) |
C4—C3—H3B | 120.2 | C27—C28—H28A | 120.4 |
C5—C4—C3 | 121.0 (5) | C29—C28—H28A | 120.4 |
C5—C4—H4A | 119.5 | N4—C29—C28 | 122.3 (5) |
C3—C4—H4A | 119.5 | N4—C29—H29A | 118.8 |
C4—C5—C6 | 119.4 (5) | C28—C29—H29A | 118.8 |
C4—C5—H5A | 120.3 | N4—C30—C26 | 123.3 (4) |
C6—C5—H5A | 120.3 | N4—C30—C31 | 117.9 (3) |
C5—C6—C7 | 120.6 (5) | C26—C30—C31 | 118.8 (4) |
C5—C6—H6A | 119.7 | N3—C31—C23 | 122.2 (4) |
C7—C6—H6A | 119.7 | N3—C31—C30 | 117.6 (3) |
C6—C7—C2 | 120.5 (4) | C23—C31—C30 | 120.2 (4) |
C6—C7—H7A | 119.8 | N5—C32—H32A | 109.5 |
C2—C7—H7A | 119.8 | N5—C32—H32B | 109.5 |
N1—C8—C9 | 123.4 (5) | H32A—C32—H32B | 109.5 |
N1—C8—H8A | 118.3 | N5—C32—H32C | 109.5 |
C9—C8—H8A | 118.3 | H32A—C32—H32C | 109.5 |
C10—C9—C8 | 119.5 (5) | H32B—C32—H32C | 109.5 |
C10—C9—H9A | 120.3 | N5—C33—H33A | 109.5 |
C8—C9—H9A | 120.3 | N5—C33—H33B | 109.5 |
C9—C10—C11 | 119.7 (4) | H33A—C33—H33B | 109.5 |
C9—C10—H10A | 120.2 | N5—C33—H33C | 109.5 |
C11—C10—H10A | 120.2 | H33A—C33—H33C | 109.5 |
C10—C11—C19 | 117.8 (5) | H33B—C33—H33C | 109.5 |
C10—C11—C12 | 123.7 (5) | O8—C34—N5 | 125.5 (5) |
C19—C11—C12 | 118.5 (5) | O8—C34—H34B | 117.3 |
C13—C12—C11 | 121.2 (5) | N5—C34—H34B | 117.3 |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3D···O8i | 0.84 (2) | 1.86 (2) | 2.684 (4) | 168 (5) |
Symmetry code: (i) −x+2, y+1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Mn(C7H5O2)(C12H8N2)2(H2O)](ClO4)·C3H7NO |
Mr | 727.02 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 12.1787 (4), 16.0320 (5), 17.3628 (5) |
β (°) | 105.223 (1) |
V (Å3) | 3271.11 (18) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.55 |
Crystal size (mm) | 0.34 × 0.28 × 0.16 |
Data collection | |
Diffractometer | Siemens SMART CCD diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.700, 0.916 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9876, 5671, 4440 |
Rint | 0.030 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.061, 0.153, 1.13 |
No. of reflections | 5671 |
No. of parameters | 450 |
No. of restraints | 2 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.34, −0.43 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1994), XPREP in SHELXTL (Siemens, 1994), SHELXTL (Bruker, 1997).
Mn—O1 | 2.124 (3) | Mn—N1 | 2.272 (3) |
Mn—O3 | 2.156 (3) | Mn—N4 | 2.275 (3) |
Mn—N3 | 2.261 (3) | Mn—N2 | 2.303 (3) |
O1—Mn—O3 | 86.56 (12) | N3—Mn—N4 | 73.32 (12) |
O1—Mn—N3 | 89.71 (11) | N1—Mn—N4 | 158.51 (12) |
O3—Mn—N3 | 161.90 (12) | O1—Mn—N2 | 163.23 (11) |
O1—Mn—N1 | 92.24 (12) | O3—Mn—N2 | 90.95 (12) |
O3—Mn—N1 | 105.13 (12) | N3—Mn—N2 | 97.51 (11) |
N3—Mn—N1 | 92.70 (12) | N1—Mn—N2 | 72.40 (12) |
O1—Mn—N4 | 103.67 (11) | N4—Mn—N2 | 92.92 (11) |
O3—Mn—N4 | 90.36 (13) |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3D···O8i | 0.838 (19) | 1.86 (2) | 2.684 (4) | 168 (5) |
Symmetry code: (i) −x+2, y+1/2, −z+1/2. |
One of the most important processes in nature occurs in the oxygen evolving complex (OEC) of photosystem II in green plants (Wieghardt, 1989). Manganese ions are the essential components in the active center of the PSII. The coordination sphere of the manganese is believed to be composed of O and N donors from available amino acid side chains (Wieghardt, 1989). In recent years, we have used phen and carboxylic acids to synthesize a series of manganese–phen–carboxylic acid complexes, of which there are some mononuclear complexes, such as {[Mn(phen)2(OAc)(H2O)]ClO4}2·H2O (Zhang, Huang et al., 2002) and [Mn(phen)2(ClCH2COO)(H2O)]ClO4 (Zhang, Chen et al., 2002). In this paper, we report the synthesis and crystal structure of a similar mononuclear manganese compound, viz. [Mn(PhCOO)(phen)2(H2O)]ClO4.dmf, (I).
The crystal structure of (I) consists of a discrete [Mn(PhCOO)(phen)2(H2O)]+ cation, a perchlorate anion and a dmf solvate molecule. As illustrated in Fig. 1, the MnII atom is located in a distorted octahedral environment, with three trans angles in the range 158.51 (12)–163.23 (11)°. It is coordinated by four N atoms from a pair of cis-related chelating phenanthroline ligands and two O atoms from a monodentate benzoate ligand [Mn—O1 = 2.124 (3) Å] and a water molecule [Mn—O3 = 2.156 (3) Å]. The best plane is formed by atoms O1, N1, N2 and N4, with the largest deviation from the mean plane being 0.176 Å, and the Mn atom is 0.0826 (13) Å out of this plane. The axial positions are occupied by the fourth phen N atom and a water O atom.
Each phenanthroline molecule forms a perfect plane, with mean deviations of 0.028 and 0.039 Å, and the planes are inclined at 76.45 (8)° with respect to one another. The Mn—N bond lengths are in the range 2.261 (3)–2.303 (3) Å, while the Mn—O bond lengths are 2.124 (3) and 2.156 (3) Å. It should be noted that the Mn—N bond lengths trans to benzoate and aqua O atoms are 2.303 (3) and 2.261 (3) Å, respectively, showing the stronger trans influence of benzoate over water. The phenanthroline ligands exhibit the usual acute N···N bite distances [N1···N2 2.7019 (13) Å and N3···N4 2.7092 (16) Å] and N—Mn—N angles [N1—Mn1—N2 72.40 (12)° and N3—Mn1—N4 73.32 (12)°]. These values are close to those observed in {[Mn(phen)2(OAc)(H2O)]ClO4}2·H2O (Zhang, Huang et al., 2002) and [Mn(phen)2(ClCH2COO)(H2O)]ClO4 (Zhang, Chen et al., 2002). In addition, a strong hydrogen-bonding interaction is observed between the ligated water molecule and the dmf solvate molecule (Table 2).