Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807054517/bt2573sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807054517/bt2573Isup2.hkl |
CCDC reference: 672687
Key indicators
- Single-crystal X-ray study
- T = 294 K
- Mean (C-C) = 0.006 Å
- R factor = 0.059
- wR factor = 0.178
- Data-to-parameter ratio = 18.7
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT026_ALERT_3_C Ratio Observed / Unique Reflections too Low .... 46 Perc. PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given ....... ? PLAT230_ALERT_2_C Hirshfeld Test Diff for N1 - C7 .. 5.11 su PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for N5 PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for C21 PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety C19 PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........ 2 PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 2 C3 H7 N O
Alert level G PLAT794_ALERT_5_G Check Predicted Bond Valency for Mn1 (3) 3.28
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 8 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 6 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
The title complex was prepared in a manner similar to the literature by the reaction of manganese(III) acetate and H2bmpb in DMF in the presence of triethylamine (Ray et al., 1993). Single crystals suitable for X-ray analysis were obtained by slow diffusion of diethyl ether into a DMF solution of the complex. Selected IR data (KBr, cm-1): 2950 (m), 1630 (amide I band, s), 1600(amide II band, s), 1480 (s), 1350 (s), 1165(s), 1020 (m), 850 (m). Analysis calculated for C23H25ClMnN5O4: C 52.53, H 4.79, Cl 6.74, N 13.32, %; found:C 52.87, H 4.32, Cl 6.78 N 12.58%. MS (FAB): 399 ([Mn(bmpb)]+).
All H atoms were fixed geometrically and treated as riding on their parent atoms with O—H =0.86 Å, Caromatic—H = 0.93 Å and Cmethyl—H = 0.96 Å with Uiso(H)= 1.2Ueq(C,O) or Uiso(H) = 1.5Ueq(Cmethyl).
Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL (Bruker, 1997).
Fig. 1. A view of anion of the title complex with displacement ellipsoids drawn at the 30% propability level. The dashed line depicts an intermolecular hydrogen bond. |
[Mn(C20H16N4O2)Cl(H2O)]·C3H7NO | F(000) = 1088 |
Mr = 525.87 | Dx = 1.392 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 11.7182 (15) Å | Cell parameters from 4879 reflections |
b = 15.503 (2) Å | θ = 1–27.5° |
c = 14.0158 (19) Å | µ = 0.67 mm−1 |
β = 99.892 (3)° | T = 294 K |
V = 2508.4 (6) Å3 | Prism, black |
Z = 4 | 0.24 × 0.16 × 0.12 mm |
Bruker CCD area-detector diffractometer | 5805 independent reflections |
Radiation source: fine-focus sealed tube | 2687 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.087 |
phi and ω scans | θmax = 27.6°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −12→15 |
Tmin = 0.856, Tmax = 0.924 | k = −20→17 |
16639 measured reflections | l = −18→17 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.059 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.178 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.075P)2] where P = (Fo2 + 2Fc2)/3 |
5805 reflections | (Δ/σ)max < 0.001 |
310 parameters | Δρmax = 0.57 e Å−3 |
0 restraints | Δρmin = −0.41 e Å−3 |
[Mn(C20H16N4O2)Cl(H2O)]·C3H7NO | V = 2508.4 (6) Å3 |
Mr = 525.87 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 11.7182 (15) Å | µ = 0.67 mm−1 |
b = 15.503 (2) Å | T = 294 K |
c = 14.0158 (19) Å | 0.24 × 0.16 × 0.12 mm |
β = 99.892 (3)° |
Bruker CCD area-detector diffractometer | 5805 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2687 reflections with I > 2σ(I) |
Tmin = 0.856, Tmax = 0.924 | Rint = 0.087 |
16639 measured reflections |
R[F2 > 2σ(F2)] = 0.059 | 0 restraints |
wR(F2) = 0.178 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.57 e Å−3 |
5805 reflections | Δρmin = −0.41 e Å−3 |
310 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
Mn1 | 0.29430 (4) | 0.02350 (4) | 0.62328 (4) | 0.04348 (16) | |
Cl1 | 0.42626 (8) | 0.13481 (7) | 0.57974 (8) | 0.0620 (3) | |
O1 | −0.0071 (2) | 0.13130 (16) | 0.49219 (18) | 0.0549 (7) | |
O1W | 0.2130 (2) | −0.10901 (18) | 0.6296 (2) | 0.0699 (9) | |
H1WA | 0.1476 | −0.1260 | 0.5981 | 0.084* | |
H1WB | 0.2234 | −0.1360 | 0.6841 | 0.084* | |
O2 | 0.3918 (3) | 0.0425 (2) | 0.9130 (2) | 0.0834 (10) | |
N1 | 0.1508 (2) | 0.08875 (18) | 0.6048 (2) | 0.0427 (7) | |
N2 | 0.2379 (2) | 0.00161 (18) | 0.4774 (2) | 0.0452 (8) | |
N3 | 0.4375 (2) | −0.04517 (18) | 0.6902 (2) | 0.0453 (8) | |
N4 | 0.2958 (2) | 0.05783 (19) | 0.7554 (2) | 0.0463 (8) | |
C1 | 0.1261 (3) | 0.1318 (2) | 0.6878 (3) | 0.0433 (9) | |
C2 | 0.2085 (3) | 0.1156 (2) | 0.7712 (3) | 0.0463 (9) | |
C3 | 0.1998 (3) | 0.1578 (3) | 0.8564 (3) | 0.0620 (12) | |
H3A | 0.2556 | 0.1493 | 0.9113 | 0.074* | |
C4 | 0.1080 (4) | 0.2124 (3) | 0.8596 (3) | 0.0701 (13) | |
H4A | 0.1017 | 0.2399 | 0.9174 | 0.084* | |
C5 | 0.0266 (4) | 0.2269 (3) | 0.7800 (3) | 0.0668 (13) | |
H5A | −0.0346 | 0.2641 | 0.7841 | 0.080* | |
C6 | 0.0334 (3) | 0.1872 (2) | 0.6927 (3) | 0.0533 (11) | |
H6A | −0.0228 | 0.1973 | 0.6383 | 0.064* | |
C7 | 0.0855 (3) | 0.0923 (2) | 0.5156 (3) | 0.0440 (9) | |
C8 | 0.1376 (3) | 0.0425 (2) | 0.4426 (3) | 0.0435 (9) | |
C9 | 0.0869 (3) | 0.0375 (2) | 0.3471 (3) | 0.0537 (11) | |
H9A | 0.0173 | 0.0660 | 0.3259 | 0.064* | |
C10 | 0.1382 (4) | −0.0096 (3) | 0.2818 (3) | 0.0567 (11) | |
C11 | 0.2401 (4) | −0.0520 (3) | 0.3179 (3) | 0.0646 (12) | |
H11A | 0.2769 | −0.0853 | 0.2769 | 0.078* | |
C12 | 0.2873 (3) | −0.0450 (3) | 0.4147 (3) | 0.0582 (11) | |
H12A | 0.3563 | −0.0737 | 0.4376 | 0.070* | |
C13 | 0.3800 (3) | 0.0274 (3) | 0.8262 (3) | 0.0517 (10) | |
C14 | 0.4618 (3) | −0.0318 (2) | 0.7858 (3) | 0.0455 (9) | |
C15 | 0.5545 (3) | −0.0706 (2) | 0.8444 (3) | 0.0500 (10) | |
H15A | 0.5691 | −0.0596 | 0.9106 | 0.060* | |
C16 | 0.6255 (3) | −0.1261 (2) | 0.8037 (3) | 0.0507 (10) | |
C17 | 0.5988 (3) | −0.1395 (3) | 0.7056 (3) | 0.0585 (11) | |
H17A | 0.6440 | −0.1767 | 0.6757 | 0.070* | |
C18 | 0.5048 (3) | −0.0981 (3) | 0.6506 (3) | 0.0573 (11) | |
H18A | 0.4887 | −0.1077 | 0.5841 | 0.069* | |
C19 | 0.0836 (4) | −0.0150 (3) | 0.1775 (3) | 0.0816 (15) | |
H19A | 0.0764 | 0.0419 | 0.1500 | 0.122* | |
H19B | 0.0082 | −0.0407 | 0.1721 | 0.122* | |
H19C | 0.1311 | −0.0497 | 0.1432 | 0.122* | |
C20 | 0.7271 (3) | −0.1707 (3) | 0.8662 (3) | 0.0672 (13) | |
H20A | 0.7838 | −0.1859 | 0.8271 | 0.101* | |
H20B | 0.7005 | −0.2220 | 0.8939 | 0.101* | |
H20C | 0.7614 | −0.1325 | 0.9170 | 0.101* | |
O3 | 0.2566 (4) | −0.2053 (4) | 0.7859 (4) | 0.215 (3) | |
N5 | 0.2985 (4) | −0.1807 (3) | 0.9457 (5) | 0.1136 (19) | |
C21 | 0.3201 (5) | −0.2117 (4) | 0.8616 (5) | 0.113 (2) | |
H21A | 0.3899 | −0.2403 | 0.8622 | 0.135* | |
C22 | 0.1947 (7) | −0.1350 (6) | 0.9424 (6) | 0.187 (4) | |
H22A | 0.1688 | −0.1142 | 0.8778 | 0.281* | |
H22B | 0.2072 | −0.0871 | 0.9864 | 0.281* | |
H22C | 0.1370 | −0.1725 | 0.9608 | 0.281* | |
C23 | 0.3818 (6) | −0.1888 (5) | 1.0310 (5) | 0.157 (3) | |
H23A | 0.4456 | −0.2229 | 1.0177 | 0.236* | |
H23B | 0.3472 | −0.2165 | 1.0803 | 0.236* | |
H23C | 0.4090 | −0.1327 | 1.0529 | 0.236* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mn1 | 0.0350 (3) | 0.0512 (3) | 0.0443 (3) | 0.0053 (3) | 0.0072 (2) | −0.0028 (3) |
Cl1 | 0.0529 (5) | 0.0601 (6) | 0.0785 (7) | −0.0063 (5) | 0.0268 (5) | −0.0082 (5) |
O1 | 0.0447 (14) | 0.0578 (17) | 0.0600 (17) | 0.0097 (13) | 0.0026 (13) | 0.0087 (13) |
O1W | 0.0550 (16) | 0.0710 (19) | 0.075 (2) | −0.0168 (14) | −0.0118 (14) | 0.0187 (16) |
O2 | 0.0782 (19) | 0.115 (3) | 0.0513 (19) | 0.0413 (18) | −0.0050 (15) | −0.0195 (17) |
N1 | 0.0363 (15) | 0.0497 (18) | 0.0422 (17) | −0.0003 (14) | 0.0071 (13) | −0.0009 (14) |
N2 | 0.0398 (16) | 0.0475 (18) | 0.0481 (18) | −0.0007 (14) | 0.0066 (14) | −0.0016 (14) |
N3 | 0.0397 (16) | 0.0483 (19) | 0.0474 (19) | 0.0026 (14) | 0.0060 (14) | −0.0056 (14) |
N4 | 0.0363 (15) | 0.0553 (19) | 0.0471 (18) | 0.0079 (14) | 0.0064 (14) | −0.0022 (15) |
C1 | 0.0381 (18) | 0.040 (2) | 0.053 (2) | −0.0005 (16) | 0.0104 (17) | −0.0022 (17) |
C2 | 0.0423 (19) | 0.041 (2) | 0.058 (2) | 0.0059 (17) | 0.0147 (18) | −0.0037 (18) |
C3 | 0.063 (2) | 0.063 (3) | 0.060 (3) | 0.011 (2) | 0.010 (2) | −0.009 (2) |
C4 | 0.070 (3) | 0.067 (3) | 0.074 (3) | 0.018 (2) | 0.015 (2) | −0.021 (2) |
C5 | 0.055 (2) | 0.053 (3) | 0.095 (3) | 0.014 (2) | 0.020 (2) | −0.009 (2) |
C6 | 0.042 (2) | 0.049 (2) | 0.070 (3) | 0.0067 (18) | 0.0124 (19) | 0.003 (2) |
C7 | 0.0376 (19) | 0.037 (2) | 0.058 (2) | −0.0066 (16) | 0.0102 (18) | 0.0058 (18) |
C8 | 0.0390 (19) | 0.041 (2) | 0.050 (2) | −0.0031 (16) | 0.0071 (17) | 0.0077 (17) |
C9 | 0.053 (2) | 0.055 (3) | 0.052 (2) | −0.0071 (19) | 0.0039 (19) | 0.010 (2) |
C10 | 0.065 (3) | 0.057 (2) | 0.047 (2) | −0.019 (2) | 0.007 (2) | 0.000 (2) |
C11 | 0.071 (3) | 0.070 (3) | 0.056 (3) | −0.009 (2) | 0.019 (2) | −0.009 (2) |
C12 | 0.054 (2) | 0.065 (3) | 0.058 (3) | 0.007 (2) | 0.013 (2) | −0.007 (2) |
C13 | 0.046 (2) | 0.063 (3) | 0.045 (2) | 0.007 (2) | 0.0024 (18) | −0.008 (2) |
C14 | 0.0376 (18) | 0.046 (2) | 0.052 (2) | 0.0015 (17) | 0.0057 (17) | −0.0040 (18) |
C15 | 0.045 (2) | 0.055 (2) | 0.048 (2) | −0.0004 (19) | 0.0014 (18) | −0.0031 (19) |
C16 | 0.0375 (19) | 0.047 (2) | 0.068 (3) | 0.0014 (18) | 0.0089 (18) | 0.006 (2) |
C17 | 0.048 (2) | 0.060 (3) | 0.070 (3) | 0.011 (2) | 0.015 (2) | −0.007 (2) |
C18 | 0.051 (2) | 0.066 (3) | 0.055 (2) | 0.008 (2) | 0.0115 (19) | −0.009 (2) |
C19 | 0.105 (4) | 0.090 (3) | 0.049 (3) | −0.020 (3) | 0.010 (3) | −0.001 (2) |
C20 | 0.056 (2) | 0.069 (3) | 0.076 (3) | 0.013 (2) | 0.008 (2) | 0.008 (2) |
O3 | 0.173 (4) | 0.262 (6) | 0.166 (4) | −0.105 (4) | −0.094 (3) | 0.137 (4) |
N5 | 0.078 (3) | 0.081 (3) | 0.176 (6) | 0.003 (3) | 0.006 (3) | −0.001 (3) |
C21 | 0.080 (4) | 0.098 (4) | 0.154 (6) | −0.018 (3) | 0.004 (4) | 0.052 (4) |
C22 | 0.166 (7) | 0.259 (11) | 0.134 | −0.005 (8) | 0.017 (6) | −0.035 (7) |
C23 | 0.176 (7) | 0.166 (7) | 0.111 (6) | −0.031 (6) | −0.026 (5) | 0.007 (5) |
Mn1—N4 | 1.923 (3) | C10—C11 | 1.382 (6) |
Mn1—N1 | 1.941 (3) | C10—C19 | 1.495 (5) |
Mn1—N2 | 2.066 (3) | C11—C12 | 1.380 (5) |
Mn1—N3 | 2.071 (3) | C11—H11A | 0.9300 |
Mn1—O1W | 2.273 (3) | C12—H12A | 0.9300 |
Mn1—Cl1 | 2.4628 (12) | C13—C14 | 1.506 (5) |
O1—C7 | 1.237 (4) | C14—C15 | 1.382 (5) |
O1W—H1WA | 0.8582 | C15—C16 | 1.386 (5) |
O1W—H1WB | 0.8600 | C15—H15A | 0.9300 |
O2—C13 | 1.223 (5) | C16—C17 | 1.373 (6) |
N1—C7 | 1.351 (4) | C16—C20 | 1.519 (5) |
N1—C1 | 1.413 (4) | C17—C18 | 1.389 (5) |
N2—C12 | 1.343 (5) | C17—H17A | 0.9300 |
N2—C8 | 1.350 (4) | C18—H18A | 0.9300 |
N3—C18 | 1.324 (5) | C19—H19A | 0.9600 |
N3—C14 | 1.337 (5) | C19—H19B | 0.9600 |
N4—C13 | 1.358 (4) | C19—H19C | 0.9600 |
N4—C2 | 1.405 (4) | C20—H20A | 0.9600 |
C1—C6 | 1.396 (5) | C20—H20B | 0.9600 |
C1—C2 | 1.405 (5) | C20—H20C | 0.9600 |
C2—C3 | 1.380 (5) | O3—C21 | 1.190 (7) |
C3—C4 | 1.376 (5) | N5—C21 | 1.336 (8) |
C3—H3A | 0.9300 | N5—C22 | 1.401 (9) |
C4—C5 | 1.356 (6) | N5—C23 | 1.413 (7) |
C4—H4A | 0.9300 | C21—H21A | 0.9300 |
C5—C6 | 1.384 (6) | C22—H22A | 0.9600 |
C5—H5A | 0.9300 | C22—H22B | 0.9600 |
C6—H6A | 0.9300 | C22—H22C | 0.9600 |
C7—C8 | 1.492 (5) | C23—H23A | 0.9600 |
C8—C9 | 1.371 (5) | C23—H23B | 0.9600 |
C9—C10 | 1.386 (6) | C23—H23C | 0.9600 |
C9—H9A | 0.9300 | ||
N4—Mn1—N1 | 81.29 (12) | C11—C10—C9 | 117.1 (4) |
N4—Mn1—N2 | 161.16 (12) | C11—C10—C19 | 121.9 (4) |
N1—Mn1—N2 | 80.28 (12) | C9—C10—C19 | 121.0 (4) |
N4—Mn1—N3 | 80.40 (12) | C12—C11—C10 | 119.8 (4) |
N1—Mn1—N3 | 160.75 (12) | C12—C11—H11A | 120.1 |
N2—Mn1—N3 | 117.43 (12) | C10—C11—H11A | 120.1 |
N4—Mn1—O1W | 98.45 (12) | N2—C12—C11 | 122.8 (4) |
N1—Mn1—O1W | 96.71 (11) | N2—C12—H12A | 118.6 |
N2—Mn1—O1W | 79.93 (11) | C11—C12—H12A | 118.6 |
N3—Mn1—O1W | 80.21 (10) | O2—C13—N4 | 127.2 (4) |
N4—Mn1—Cl1 | 98.18 (9) | O2—C13—C14 | 121.3 (3) |
N1—Mn1—Cl1 | 99.69 (9) | N4—C13—C14 | 111.5 (3) |
N2—Mn1—Cl1 | 88.73 (9) | N3—C14—C15 | 122.5 (3) |
N3—Mn1—Cl1 | 88.75 (9) | N3—C14—C13 | 115.6 (3) |
O1W—Mn1—Cl1 | 158.17 (9) | C15—C14—C13 | 121.9 (3) |
Mn1—O1W—H1WA | 126.9 | C14—C15—C16 | 119.5 (4) |
Mn1—O1W—H1WB | 118.6 | C14—C15—H15A | 120.3 |
H1WA—O1W—H1WB | 106.6 | C16—C15—H15A | 120.3 |
C7—N1—C1 | 125.5 (3) | C17—C16—C15 | 117.2 (3) |
C7—N1—Mn1 | 118.9 (2) | C17—C16—C20 | 122.0 (4) |
C1—N1—Mn1 | 115.6 (2) | C15—C16—C20 | 120.8 (4) |
C12—N2—C8 | 117.6 (3) | C16—C17—C18 | 120.5 (4) |
C12—N2—Mn1 | 129.4 (3) | C16—C17—H17A | 119.7 |
C8—N2—Mn1 | 113.0 (2) | C18—C17—H17A | 119.7 |
C18—N3—C14 | 118.5 (3) | N3—C18—C17 | 121.8 (4) |
C18—N3—Mn1 | 128.5 (3) | N3—C18—H18A | 119.1 |
C14—N3—Mn1 | 113.0 (2) | C17—C18—H18A | 119.1 |
C13—N4—C2 | 124.3 (3) | C10—C19—H19A | 109.5 |
C13—N4—Mn1 | 119.5 (2) | C10—C19—H19B | 109.5 |
C2—N4—Mn1 | 116.2 (2) | H19A—C19—H19B | 109.5 |
C6—C1—C2 | 119.9 (3) | C10—C19—H19C | 109.5 |
C6—C1—N1 | 127.0 (3) | H19A—C19—H19C | 109.5 |
C2—C1—N1 | 113.0 (3) | H19B—C19—H19C | 109.5 |
C3—C2—C1 | 119.5 (3) | C16—C20—H20A | 109.5 |
C3—C2—N4 | 127.0 (3) | C16—C20—H20B | 109.5 |
C1—C2—N4 | 113.5 (3) | H20A—C20—H20B | 109.5 |
C4—C3—C2 | 119.6 (4) | C16—C20—H20C | 109.5 |
C4—C3—H3A | 120.2 | H20A—C20—H20C | 109.5 |
C2—C3—H3A | 120.2 | H20B—C20—H20C | 109.5 |
C5—C4—C3 | 121.2 (4) | C21—N5—C22 | 116.6 (6) |
C5—C4—H4A | 119.4 | C21—N5—C23 | 120.4 (6) |
C3—C4—H4A | 119.4 | C22—N5—C23 | 122.8 (7) |
C4—C5—C6 | 120.9 (4) | O3—C21—N5 | 124.9 (7) |
C4—C5—H5A | 119.5 | O3—C21—H21A | 117.5 |
C6—C5—H5A | 119.5 | N5—C21—H21A | 117.5 |
C5—C6—C1 | 118.7 (4) | N5—C22—H22A | 109.5 |
C5—C6—H6A | 120.6 | N5—C22—H22B | 109.5 |
C1—C6—H6A | 120.6 | H22A—C22—H22B | 109.5 |
O1—C7—N1 | 126.6 (3) | N5—C22—H22C | 109.5 |
O1—C7—C8 | 121.0 (3) | H22A—C22—H22C | 109.5 |
N1—C7—C8 | 112.4 (3) | H22B—C22—H22C | 109.5 |
N2—C8—C9 | 122.0 (3) | N5—C23—H23A | 109.5 |
N2—C8—C7 | 115.3 (3) | N5—C23—H23B | 109.5 |
C9—C8—C7 | 122.6 (3) | H23A—C23—H23B | 109.5 |
C8—C9—C10 | 120.7 (4) | N5—C23—H23C | 109.5 |
C8—C9—H9A | 119.7 | H23A—C23—H23C | 109.5 |
C10—C9—H9A | 119.7 | H23B—C23—H23C | 109.5 |
N4—Mn1—N1—C7 | −177.1 (3) | C1—C2—C3—C4 | 2.6 (6) |
N2—Mn1—N1—C7 | −1.0 (2) | N4—C2—C3—C4 | −179.9 (4) |
N3—Mn1—N1—C7 | −159.0 (3) | C2—C3—C4—C5 | −1.2 (7) |
O1W—Mn1—N1—C7 | −79.5 (3) | C3—C4—C5—C6 | −0.1 (7) |
Cl1—Mn1—N1—C7 | 86.0 (2) | C4—C5—C6—C1 | −0.2 (6) |
N4—Mn1—N1—C1 | 5.2 (2) | C2—C1—C6—C5 | 1.6 (5) |
N2—Mn1—N1—C1 | −178.7 (3) | N1—C1—C6—C5 | −176.8 (4) |
N3—Mn1—N1—C1 | 23.3 (5) | C1—N1—C7—O1 | −2.1 (6) |
O1W—Mn1—N1—C1 | 102.7 (2) | Mn1—N1—C7—O1 | −179.6 (3) |
Cl1—Mn1—N1—C1 | −91.7 (2) | C1—N1—C7—C8 | 177.7 (3) |
N4—Mn1—N2—C12 | −167.7 (4) | Mn1—N1—C7—C8 | 0.2 (4) |
N1—Mn1—N2—C12 | −179.7 (3) | C12—N2—C8—C9 | 0.0 (5) |
N3—Mn1—N2—C12 | −7.7 (4) | Mn1—N2—C8—C9 | 178.8 (3) |
O1W—Mn1—N2—C12 | −81.0 (3) | C12—N2—C8—C7 | 179.2 (3) |
Cl1—Mn1—N2—C12 | 80.2 (3) | Mn1—N2—C8—C7 | −2.0 (4) |
N4—Mn1—N2—C8 | 13.6 (5) | O1—C7—C8—N2 | −179.0 (3) |
N1—Mn1—N2—C8 | 1.6 (2) | N1—C7—C8—N2 | 1.2 (4) |
N3—Mn1—N2—C8 | 173.7 (2) | O1—C7—C8—C9 | 0.2 (5) |
O1W—Mn1—N2—C8 | 100.3 (2) | N1—C7—C8—C9 | −179.5 (3) |
Cl1—Mn1—N2—C8 | −98.4 (2) | N2—C8—C9—C10 | −0.8 (5) |
N4—Mn1—N3—C18 | 178.9 (3) | C7—C8—C9—C10 | −179.9 (3) |
N1—Mn1—N3—C18 | 160.8 (3) | C8—C9—C10—C11 | 1.4 (6) |
N2—Mn1—N3—C18 | 5.3 (4) | C8—C9—C10—C19 | −179.7 (4) |
O1W—Mn1—N3—C18 | 78.5 (3) | C9—C10—C11—C12 | −1.2 (6) |
Cl1—Mn1—N3—C18 | −82.6 (3) | C19—C10—C11—C12 | 179.9 (4) |
N4—Mn1—N3—C14 | −1.4 (2) | C8—N2—C12—C11 | 0.2 (6) |
N1—Mn1—N3—C14 | −19.6 (5) | Mn1—N2—C12—C11 | −178.4 (3) |
N2—Mn1—N3—C14 | −175.0 (2) | C10—C11—C12—N2 | 0.4 (6) |
O1W—Mn1—N3—C14 | −101.8 (3) | C2—N4—C13—O2 | 2.3 (7) |
Cl1—Mn1—N3—C14 | 97.1 (2) | Mn1—N4—C13—O2 | −179.1 (4) |
N1—Mn1—N4—C13 | 175.0 (3) | C2—N4—C13—C14 | −178.9 (3) |
N2—Mn1—N4—C13 | 163.0 (3) | Mn1—N4—C13—C14 | −0.3 (4) |
N3—Mn1—N4—C13 | 0.9 (3) | C18—N3—C14—C15 | 0.4 (5) |
O1W—Mn1—N4—C13 | 79.4 (3) | Mn1—N3—C14—C15 | −179.3 (3) |
Cl1—Mn1—N4—C13 | −86.4 (3) | C18—N3—C14—C13 | −178.6 (3) |
N1—Mn1—N4—C2 | −6.4 (2) | Mn1—N3—C14—C13 | 1.7 (4) |
N2—Mn1—N4—C2 | −18.3 (5) | O2—C13—C14—N3 | 177.9 (4) |
N3—Mn1—N4—C2 | 179.6 (3) | N4—C13—C14—N3 | −1.0 (5) |
O1W—Mn1—N4—C2 | −101.9 (3) | O2—C13—C14—C15 | −1.0 (6) |
Cl1—Mn1—N4—C2 | 92.3 (2) | N4—C13—C14—C15 | −180.0 (3) |
C7—N1—C1—C6 | −2.1 (6) | N3—C14—C15—C16 | −0.4 (6) |
Mn1—N1—C1—C6 | 175.4 (3) | C13—C14—C15—C16 | 178.6 (3) |
C7—N1—C1—C2 | 179.3 (3) | C14—C15—C16—C17 | −0.1 (5) |
Mn1—N1—C1—C2 | −3.1 (4) | C14—C15—C16—C20 | −179.2 (3) |
C6—C1—C2—C3 | −2.9 (5) | C15—C16—C17—C18 | 0.6 (6) |
N1—C1—C2—C3 | 175.8 (3) | C20—C16—C17—C18 | 179.6 (4) |
C6—C1—C2—N4 | 179.3 (3) | C14—N3—C18—C17 | 0.1 (6) |
N1—C1—C2—N4 | −2.0 (4) | Mn1—N3—C18—C17 | 179.8 (3) |
C13—N4—C2—C3 | 7.4 (6) | C16—C17—C18—N3 | −0.6 (6) |
Mn1—N4—C2—C3 | −171.2 (3) | C22—N5—C21—O3 | −2.2 (10) |
C13—N4—C2—C1 | −175.0 (3) | C23—N5—C21—O3 | −177.5 (6) |
Mn1—N4—C2—C1 | 6.4 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WA···O1i | 0.86 | 1.90 | 2.728 (3) | 162.3 |
O1W—H1WB···O3 | 0.86 | 1.78 | 2.627 (5) | 170.2 |
Symmetry code: (i) −x, −y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Mn(C20H16N4O2)Cl(H2O)]·C3H7NO |
Mr | 525.87 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 294 |
a, b, c (Å) | 11.7182 (15), 15.503 (2), 14.0158 (19) |
β (°) | 99.892 (3) |
V (Å3) | 2508.4 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.67 |
Crystal size (mm) | 0.24 × 0.16 × 0.12 |
Data collection | |
Diffractometer | Bruker CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.856, 0.924 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 16639, 5805, 2687 |
Rint | 0.087 |
(sin θ/λ)max (Å−1) | 0.652 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.059, 0.178, 1.02 |
No. of reflections | 5805 |
No. of parameters | 310 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.57, −0.41 |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997).
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WA···O1i | 0.86 | 1.90 | 2.728 (3) | 162.3 |
O1W—H1WB···O3 | 0.86 | 1.78 | 2.627 (5) | 170.2 |
Symmetry code: (i) −x, −y, −z+1. |
Manganese complexes are involved in numerous biological redox reactions performed by metalloenzymes (Larson et al., 1992). The carboxamide [–C(O)NH–] group, ubiquitous throughout nature in the primary structure of proteins, is an important ligand for coordination chemists. On the other hand, pyridine carboxamides, a burgeoning class of multidentate ligands containing this linkage, are available from condensation reactions. Here we describe the coordination chemistry of manganese(III) with a tetradentate pyridine carboxamide ligand prepared from 4-methylpyridine carboxylic acid and 1,2-diaminobenzene.
The crystal structure of the title compound is represented in Figure 1. As shown in Fig. 1, the mononuclear MnIII ion is six-coordinated, forming a distorted octahedron with two pyridine and two deprotonated amide N atoms in the equatorial plane, while the two axial sites are occupied by Cl ion and O atom provided by a water molecule. The Mn—N(amide) distances of ca 1.92 Å are significantly shorter than the Mn—N(pyridine) distances of ca 2.07 Å, both of which are appreciably shorter than the Mn—N distances found in related Mn—N4 complexes such as cis-[MnII(mep)Cl2] and [MnIII(mpp)Cl(OH2)](ClO4) [mep = N,N'-dimethyl-N,N'- bis(2-pyridylmethyl)ethane-1,2-diamino, mpp = N,N'-dimethyl-N,N'-bis(2-pyridylmethyl)propane-1,2-diamino] (Hureau et al., 2005). The Mn—N(amide) and Mn—N(pyridine) distances are also comparable to those of [Mn(bpc)Cl(DMF)] [H2bpc =1,2- bis(2- pyridinecarboxamido)-4,5-dichlorobenzene] (Liang et al., 2007). The Mn—Cl distance at 2.463 Å is very similar to what is observed for [(mpp)MnCl(OH2)](ClO4)(Hureau et al., 2005). However, The Mn—O distance (ca 2.27 Å) in the title compound is longer than the corresponding Mn—O distances (ca 2.19 Å) in [(mpp)MnCl(OH2)](ClO4) (Hureau et al., 2005), due to the distinctive hydrogen-bond effect.