Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807032461/wk2058sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807032461/wk2058Isup2.hkl |
CCDC reference: 657549
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.008 Å
- R factor = 0.058
- wR factor = 0.114
- Data-to-parameter ratio = 17.9
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.95 PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent ..... ? PLAT154_ALERT_1_C The su's on the Cell Angles are Equal (x 10000) 3000 Deg. PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 8 PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 54 N5 -MN1 -N1 -C5 168.50 0.80 2.666 1.555 1.555 1.555 PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 58 N5 -MN1 -N1 -C1 -10.80 1.20 2.666 1.555 1.555 1.555
Alert level G PLAT794_ALERT_5_G Check Predicted Bond Valency for Mn1 (2) 2.13
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 6 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 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 3 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
For related literature, see: Liang et al. (2002, 2004); Montalvo-Gonzalez & Arisa-Castolo (2003); O'Donnell (2004); Rajendran & Sreeletha (2002); Raman et al. (2001); Wang et al. (2003).
A 25 ml Teflon-lined stainless steel autoclave was charged with 0.215 g (1 mmol) MnBr2, 0.260 g (1 mmol) L and 15 ml CH3OH and heated at 80 °C for 24 h in oven, then cooled to room temperature. Red crystals were obtained in 60% yield based on the initial MnBr2.
All H atoms on sp2 C atoms were positioned geometrically and allowed to ride on their respective parent atoms, with C—H = 0.93 and Uiso(H) = 1.2 Ueq(C); All H atoms on sp3 C (Me groups) atoms were located and refined by using the hfix 137 command.
Great effort is currently being devoted to the design and syntheses of metal Schiff base complexes due to their potential applications as functional materials (O'Donnell, 2004). The Schiff bases of 4-aminoantipyrine and their complexes have been extensively investigated because of their biological, clinical and pharmacological applications (Rajendran & Sreeletha, 2002; Raman et al., 2001). However, only a few structurally characterized metal complexes with 4-aminoantipyrine Schiff base derived ligands have been reported, and its coordination chemistry remains largely unexplored (Liang et al., 2004; Liang et al., 2002; Wang et al., 2003). Herein we report the synthesis and crystal structure of a new dinuclear manganese(II) complex with a 4-aminoantipyrine derived Schiff base ligand: Mn2(L4)Br4 (L = (E)-1,5-dimethyl-2-phenyl-4-(pyridin-3-ylmethyleneamino)-1,2-dihydropyrazol-3-one) (I).
The ligand L was synthesized as reported previously by the base condensation of 4-aminoantipyrine with pyridine-3-carboxaldehyde (Montalvo-Gonzalez & Arisa-Castolo 2003). The title complex (I) was obtained under solvothermal conditions and characterized by X-ray crystallography. The molecular structure of (I) is shown in Fig. 1. Selected bond distances and bond angles are normal and listed in Table 1. (I) is a dinuclear MnII complex arranged around an inversion center. Each Mn atom is coordinated by two pyridine N atoms from two ligands, and one pyrazole O atom from another ligand, and two Br anions in a trigonal-bipyramidal geometry. There are two kinds of coordination modes of ligand L: one is monodentately linked to the Mn center through the N atom of the pyridine group, the other bidentately bridges two Mn centers by pyridine N atom and pyrazole O atom. The dimer Mn2L2 ring is formed with Mn···Mn separation of 8.878 (4) Å.
For related literature, see: Liang et al. (2002, 2004); Montalvo-Gonzalez & Arisa-Castolo (2003); O'Donnell (2004); Rajendran & Sreeletha (2002); Raman et al. (2001); Wang et al. (2003).
Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL.
Fig. 1. The molecular structure of (I), with displacement ellipsoids drawn at the 30% probability level. H atoms were omitted for clarity. (Symmetry codes: (A) -x + 1, -y + 1, -z + 1.) |
[Mn2Br4(C17H16N4O)4] | V = 1699.2 (6) Å3 |
Mr = 1598.87 | Z = 1 |
Triclinic, P1 | F(000) = 806 |
Hall symbol: -P 1 | Dx = 1.563 Mg m−3 |
a = 10.052 (2) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 12.372 (3) Å | θ = 3.1–27.5° |
c = 15.257 (3) Å | µ = 2.78 mm−1 |
α = 72.68 (3)° | T = 298 K |
β = 77.66 (3)° | Block, red |
γ = 71.09 (3)° | 0.24 × 0.20 × 0.18 mm |
Bruker SMART APEX II CCD diffractometer | 7658 independent reflections |
Radiation source: fine-focus sealed tube | 4058 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.073 |
Detector resolution: 8.40 pixels mm-1 | θmax = 27.5°, θmin = 3.1° |
ω scans | h = −13→12 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | k = −16→13 |
Tmin = 0.555, Tmax = 0.634 | l = −19→19 |
16756 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)] = 0.058 | Hydrogen site location: geom, Me from difmap |
wR(F2) = 0.114 | H-atom parameters constrained |
S = 0.99 | w = 1/[σ2(Fo2) + (0.0306P)2 + 1.9264P] where P = (Fo2 + 2Fc2)/3 |
7658 reflections | (Δ/σ)max = 0.001 |
428 parameters | Δρmax = 0.48 e Å−3 |
0 restraints | Δρmin = −0.53 e Å−3 |
[Mn2Br4(C17H16N4O)4] | γ = 71.09 (3)° |
Mr = 1598.87 | V = 1699.2 (6) Å3 |
Triclinic, P1 | Z = 1 |
a = 10.052 (2) Å | Mo Kα radiation |
b = 12.372 (3) Å | µ = 2.78 mm−1 |
c = 15.257 (3) Å | T = 298 K |
α = 72.68 (3)° | 0.24 × 0.20 × 0.18 mm |
β = 77.66 (3)° |
Bruker SMART APEX II CCD diffractometer | 7658 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 4058 reflections with I > 2σ(I) |
Tmin = 0.555, Tmax = 0.634 | Rint = 0.073 |
16756 measured reflections |
R[F2 > 2σ(F2)] = 0.058 | 0 restraints |
wR(F2) = 0.114 | H-atom parameters constrained |
S = 0.99 | Δρmax = 0.48 e Å−3 |
7658 reflections | Δρmin = −0.53 e Å−3 |
428 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 | ||
Br1 | 0.63805 (6) | 0.05458 (5) | 0.35815 (4) | 0.04788 (16) | |
Br2 | 0.63104 (6) | 0.44060 (5) | 0.23134 (4) | 0.05393 (18) | |
Mn1 | 0.51827 (8) | 0.27528 (6) | 0.31633 (5) | 0.03622 (19) | |
C1 | 0.4160 (5) | 0.1657 (5) | 0.1809 (4) | 0.0478 (14) | |
H1A | 0.4031 | 0.1123 | 0.2373 | 0.057* | |
C2 | 0.3812 (5) | 0.1489 (5) | 0.1036 (3) | 0.0441 (13) | |
C3 | 0.4052 (6) | 0.2288 (5) | 0.0195 (4) | 0.0579 (16) | |
H3A | 0.3857 | 0.2203 | −0.0346 | 0.069* | |
C4 | 0.4569 (6) | 0.3189 (5) | 0.0165 (4) | 0.0592 (16) | |
H4A | 0.4725 | 0.3725 | −0.0394 | 0.071* | |
C5 | 0.4861 (6) | 0.3296 (5) | 0.0976 (4) | 0.0511 (14) | |
H5A | 0.5204 | 0.3920 | 0.0951 | 0.061* | |
C6 | 0.3263 (5) | 0.0506 (5) | 0.1086 (4) | 0.0503 (14) | |
H6A | 0.3232 | −0.0083 | 0.1631 | 0.060* | |
C7 | 0.2306 (5) | −0.0400 (5) | 0.0312 (3) | 0.0444 (13) | |
C8 | 0.2039 (6) | −0.1426 (5) | 0.1000 (4) | 0.0532 (15) | |
C9 | 0.1419 (7) | −0.1849 (6) | −0.1123 (4) | 0.0653 (17) | |
H9A | 0.1759 | −0.1408 | −0.1713 | 0.098* | |
H9B | 0.0449 | −0.1813 | −0.1116 | 0.098* | |
H9C | 0.1985 | −0.2656 | −0.1019 | 0.098* | |
C10 | 0.1982 (6) | −0.0416 (5) | −0.0504 (3) | 0.0478 (14) | |
C11 | 0.2115 (7) | 0.0452 (5) | −0.1417 (4) | 0.0659 (17) | |
H11A | 0.2774 | 0.0057 | −0.1856 | 0.099* | |
H11B | 0.2450 | 0.1061 | −0.1346 | 0.099* | |
H11C | 0.1205 | 0.0795 | −0.1635 | 0.099* | |
C12 | 0.1099 (6) | −0.3036 (5) | 0.0855 (3) | 0.0456 (13) | |
C13 | 0.1934 (6) | −0.4053 (6) | 0.1355 (4) | 0.0611 (17) | |
H13A | 0.2790 | −0.4059 | 0.1498 | 0.073* | |
C14 | 0.1494 (7) | −0.5066 (6) | 0.1643 (4) | 0.0684 (19) | |
H14A | 0.2055 | −0.5752 | 0.1988 | 0.082* | |
C15 | 0.0245 (8) | −0.5076 (6) | 0.1429 (4) | 0.0716 (19) | |
H15A | −0.0033 | −0.5766 | 0.1614 | 0.086* | |
C16 | −0.0588 (7) | −0.4060 (5) | 0.0940 (4) | 0.0633 (17) | |
H16A | −0.1443 | −0.4059 | 0.0798 | 0.076* | |
C17 | −0.0176 (6) | −0.3035 (5) | 0.0656 (4) | 0.0537 (15) | |
H17A | −0.0757 | −0.2345 | 0.0331 | 0.064* | |
C18 | 0.5023 (5) | 0.7949 (4) | 0.4609 (4) | 0.0428 (13) | |
H18A | 0.5413 | 0.8495 | 0.4687 | 0.051* | |
C19 | 0.5012 (6) | 0.7883 (5) | 0.3727 (4) | 0.0475 (13) | |
H19A | 0.5408 | 0.8370 | 0.3221 | 0.057* | |
C20 | 0.4414 (5) | 0.7093 (4) | 0.3593 (4) | 0.0464 (13) | |
H20A | 0.4409 | 0.7036 | 0.2999 | 0.056* | |
C21 | 0.3823 (5) | 0.6389 (4) | 0.4360 (3) | 0.0379 (12) | |
C22 | 0.3906 (5) | 0.6490 (4) | 0.5229 (3) | 0.0388 (12) | |
H22A | 0.3535 | 0.6000 | 0.5746 | 0.047* | |
C23 | 0.3187 (5) | 0.5523 (4) | 0.4278 (4) | 0.0415 (12) | |
H23A | 0.3280 | 0.5357 | 0.3709 | 0.050* | |
C24 | 0.1985 (5) | 0.4090 (4) | 0.4968 (3) | 0.0350 (11) | |
C25 | 0.2266 (5) | 0.3429 (4) | 0.4310 (3) | 0.0342 (11) | |
C26 | 0.1086 (5) | 0.3641 (4) | 0.5703 (3) | 0.0405 (12) | |
C27 | 0.0579 (6) | 0.3964 (5) | 0.6601 (4) | 0.0620 (16) | |
H27A | −0.0420 | 0.4352 | 0.6639 | 0.093* | |
H27B | 0.1074 | 0.4485 | 0.6650 | 0.093* | |
H27C | 0.0755 | 0.3265 | 0.7098 | 0.093* | |
C28 | 0.0008 (6) | 0.1944 (5) | 0.6100 (4) | 0.0629 (17) | |
H28A | 0.0684 | 0.1202 | 0.6311 | 0.094* | |
H28B | −0.0619 | 0.1841 | 0.5757 | 0.094* | |
H28C | −0.0531 | 0.2236 | 0.6624 | 0.094* | |
C29 | 0.1161 (5) | 0.1969 (4) | 0.4157 (3) | 0.0371 (11) | |
C30 | 0.2016 (5) | 0.0863 (4) | 0.4116 (4) | 0.0475 (14) | |
H30A | 0.2800 | 0.0520 | 0.4437 | 0.057* | |
C31 | 0.1695 (6) | 0.0269 (5) | 0.3593 (4) | 0.0592 (16) | |
H31A | 0.2277 | −0.0476 | 0.3549 | 0.071* | |
C32 | 0.0524 (6) | 0.0767 (5) | 0.3135 (4) | 0.0578 (16) | |
H32A | 0.0318 | 0.0360 | 0.2781 | 0.069* | |
C33 | −0.0341 (6) | 0.1856 (5) | 0.3195 (4) | 0.0664 (18) | |
H33A | −0.1144 | 0.2184 | 0.2893 | 0.080* | |
C34 | −0.0025 (6) | 0.2472 (5) | 0.3706 (4) | 0.0548 (15) | |
H34A | −0.0606 | 0.3218 | 0.3745 | 0.066* | |
N1 | 0.4672 (4) | 0.2542 (4) | 0.1794 (3) | 0.0422 (10) | |
N2 | 0.2830 (4) | 0.0471 (4) | 0.0375 (3) | 0.0460 (11) | |
N3 | 0.1569 (5) | −0.2006 (4) | 0.0520 (3) | 0.0510 (12) | |
N4 | 0.1516 (5) | −0.1351 (4) | −0.0398 (3) | 0.0498 (12) | |
N5 | 0.4485 (4) | 0.7247 (3) | 0.5364 (3) | 0.0376 (10) | |
N6 | 0.2502 (4) | 0.4994 (3) | 0.4991 (3) | 0.0408 (10) | |
N7 | 0.1511 (4) | 0.2608 (3) | 0.4669 (3) | 0.0390 (10) | |
N8 | 0.0750 (4) | 0.2783 (4) | 0.5509 (3) | 0.0434 (10) | |
O1 | 0.2122 (5) | −0.1777 (4) | 0.1843 (3) | 0.0763 (13) | |
O2 | 0.3029 (3) | 0.3472 (3) | 0.3532 (2) | 0.0402 (8) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0660 (4) | 0.0392 (3) | 0.0413 (3) | −0.0147 (3) | −0.0104 (3) | −0.0116 (2) |
Br2 | 0.0723 (4) | 0.0535 (3) | 0.0454 (3) | −0.0370 (3) | −0.0010 (3) | −0.0092 (3) |
Mn1 | 0.0430 (4) | 0.0372 (4) | 0.0343 (4) | −0.0177 (4) | −0.0038 (3) | −0.0111 (3) |
C1 | 0.054 (3) | 0.048 (3) | 0.043 (3) | −0.015 (3) | −0.015 (3) | −0.008 (3) |
C2 | 0.046 (3) | 0.053 (3) | 0.039 (3) | −0.013 (3) | −0.009 (3) | −0.018 (3) |
C3 | 0.069 (4) | 0.073 (4) | 0.032 (3) | −0.022 (3) | −0.011 (3) | −0.009 (3) |
C4 | 0.071 (4) | 0.069 (4) | 0.036 (3) | −0.027 (3) | −0.009 (3) | −0.002 (3) |
C5 | 0.058 (4) | 0.052 (3) | 0.045 (3) | −0.021 (3) | −0.008 (3) | −0.006 (3) |
C6 | 0.056 (3) | 0.061 (4) | 0.040 (3) | −0.015 (3) | −0.015 (3) | −0.017 (3) |
C7 | 0.037 (3) | 0.063 (4) | 0.036 (3) | −0.011 (3) | −0.006 (2) | −0.020 (3) |
C8 | 0.057 (4) | 0.078 (4) | 0.035 (3) | −0.023 (3) | −0.006 (3) | −0.023 (3) |
C9 | 0.083 (4) | 0.086 (5) | 0.046 (4) | −0.039 (4) | −0.010 (3) | −0.027 (3) |
C10 | 0.051 (3) | 0.056 (3) | 0.037 (3) | −0.008 (3) | −0.007 (3) | −0.020 (3) |
C11 | 0.098 (5) | 0.063 (4) | 0.041 (3) | −0.023 (4) | −0.014 (3) | −0.016 (3) |
C12 | 0.051 (3) | 0.056 (3) | 0.033 (3) | −0.016 (3) | −0.005 (3) | −0.014 (3) |
C13 | 0.048 (3) | 0.086 (5) | 0.042 (3) | −0.002 (4) | −0.007 (3) | −0.022 (3) |
C14 | 0.074 (5) | 0.062 (4) | 0.049 (4) | 0.007 (4) | −0.009 (3) | −0.013 (3) |
C15 | 0.096 (5) | 0.054 (4) | 0.062 (4) | −0.025 (4) | 0.000 (4) | −0.014 (3) |
C16 | 0.067 (4) | 0.064 (4) | 0.069 (4) | −0.024 (3) | −0.013 (3) | −0.022 (3) |
C17 | 0.054 (3) | 0.056 (4) | 0.052 (3) | −0.010 (3) | −0.017 (3) | −0.012 (3) |
C18 | 0.052 (3) | 0.039 (3) | 0.047 (3) | −0.019 (3) | −0.013 (3) | −0.013 (2) |
C19 | 0.059 (3) | 0.049 (3) | 0.038 (3) | −0.022 (3) | −0.009 (3) | −0.006 (2) |
C20 | 0.057 (3) | 0.045 (3) | 0.039 (3) | −0.013 (3) | −0.011 (3) | −0.011 (2) |
C21 | 0.040 (3) | 0.039 (3) | 0.042 (3) | −0.013 (2) | −0.009 (2) | −0.015 (2) |
C22 | 0.043 (3) | 0.039 (3) | 0.040 (3) | −0.015 (2) | −0.010 (2) | −0.012 (2) |
C23 | 0.050 (3) | 0.040 (3) | 0.042 (3) | −0.015 (3) | −0.014 (3) | −0.014 (2) |
C24 | 0.036 (3) | 0.038 (3) | 0.035 (3) | −0.013 (2) | −0.008 (2) | −0.011 (2) |
C25 | 0.037 (3) | 0.038 (3) | 0.033 (3) | −0.014 (2) | −0.006 (2) | −0.011 (2) |
C26 | 0.040 (3) | 0.044 (3) | 0.039 (3) | −0.012 (2) | −0.002 (2) | −0.016 (2) |
C27 | 0.076 (4) | 0.067 (4) | 0.047 (3) | −0.021 (3) | 0.004 (3) | −0.026 (3) |
C28 | 0.059 (4) | 0.061 (4) | 0.062 (4) | −0.032 (3) | 0.010 (3) | −0.002 (3) |
C29 | 0.040 (3) | 0.038 (3) | 0.043 (3) | −0.020 (2) | −0.005 (2) | −0.013 (2) |
C30 | 0.048 (3) | 0.044 (3) | 0.060 (4) | −0.013 (3) | −0.019 (3) | −0.019 (3) |
C31 | 0.065 (4) | 0.041 (3) | 0.080 (4) | −0.016 (3) | −0.021 (4) | −0.017 (3) |
C32 | 0.079 (4) | 0.053 (4) | 0.057 (4) | −0.034 (3) | −0.020 (3) | −0.012 (3) |
C33 | 0.065 (4) | 0.056 (4) | 0.090 (5) | −0.019 (3) | −0.044 (4) | −0.010 (4) |
C34 | 0.051 (3) | 0.043 (3) | 0.074 (4) | −0.008 (3) | −0.028 (3) | −0.013 (3) |
N1 | 0.047 (3) | 0.047 (2) | 0.035 (2) | −0.013 (2) | −0.006 (2) | −0.014 (2) |
N2 | 0.045 (3) | 0.061 (3) | 0.041 (3) | −0.014 (2) | −0.005 (2) | −0.026 (2) |
N3 | 0.057 (3) | 0.074 (3) | 0.033 (2) | −0.028 (3) | −0.007 (2) | −0.017 (2) |
N4 | 0.062 (3) | 0.060 (3) | 0.033 (2) | −0.011 (2) | −0.013 (2) | −0.021 (2) |
N5 | 0.045 (2) | 0.032 (2) | 0.042 (2) | −0.0137 (19) | −0.012 (2) | −0.0093 (18) |
N6 | 0.044 (2) | 0.043 (2) | 0.044 (3) | −0.016 (2) | −0.009 (2) | −0.017 (2) |
N7 | 0.043 (2) | 0.043 (2) | 0.038 (2) | −0.017 (2) | −0.003 (2) | −0.0165 (19) |
N8 | 0.051 (3) | 0.050 (3) | 0.035 (2) | −0.025 (2) | 0.004 (2) | −0.012 (2) |
O1 | 0.114 (4) | 0.101 (3) | 0.035 (2) | −0.056 (3) | −0.019 (2) | −0.013 (2) |
O2 | 0.0418 (19) | 0.054 (2) | 0.0354 (19) | −0.0218 (17) | −0.0022 (16) | −0.0186 (16) |
Br1—Mn1 | 2.5441 (12) | C17—H17A | 0.9300 |
Br2—Mn1 | 2.5387 (12) | C18—N5 | 1.348 (6) |
Mn1—O2 | 2.080 (3) | C18—C19 | 1.374 (7) |
Mn1—N5i | 2.341 (4) | C18—H18A | 0.9300 |
Mn1—N1 | 2.360 (4) | C19—C20 | 1.384 (7) |
C1—N1 | 1.345 (6) | C19—H19A | 0.9300 |
C1—C2 | 1.386 (7) | C20—C21 | 1.383 (7) |
C1—H1A | 0.9300 | C20—H20A | 0.9300 |
C2—C3 | 1.395 (7) | C21—C22 | 1.389 (6) |
C2—C6 | 1.467 (7) | C21—C23 | 1.459 (6) |
C3—C4 | 1.360 (8) | C22—N5 | 1.334 (6) |
C3—H3A | 0.9300 | C22—H22A | 0.9300 |
C4—C5 | 1.384 (7) | C23—N6 | 1.279 (6) |
C4—H4A | 0.9300 | C23—H23A | 0.9300 |
C5—N1 | 1.336 (6) | C24—C26 | 1.380 (7) |
C5—H5A | 0.9300 | C24—N6 | 1.389 (6) |
C6—N2 | 1.270 (6) | C24—C25 | 1.405 (7) |
C6—H6A | 0.9300 | C25—O2 | 1.265 (5) |
C7—C10 | 1.361 (7) | C25—N7 | 1.378 (6) |
C7—N2 | 1.378 (7) | C26—N8 | 1.337 (6) |
C7—C8 | 1.446 (8) | C26—C27 | 1.482 (7) |
C8—O1 | 1.241 (6) | C27—H27A | 0.9600 |
C8—N3 | 1.399 (7) | C27—H27B | 0.9600 |
C9—N4 | 1.450 (7) | C27—H27C | 0.9600 |
C9—H9A | 0.9600 | C28—N8 | 1.450 (6) |
C9—H9B | 0.9600 | C28—H28A | 0.9600 |
C9—H9C | 0.9600 | C28—H28B | 0.9600 |
C10—N4 | 1.339 (7) | C28—H28C | 0.9600 |
C10—C11 | 1.494 (7) | C29—C30 | 1.371 (7) |
C11—H11A | 0.9600 | C29—C34 | 1.378 (6) |
C11—H11B | 0.9600 | C29—N7 | 1.423 (6) |
C11—H11C | 0.9600 | C30—C31 | 1.377 (7) |
C12—C13 | 1.374 (7) | C30—H30A | 0.9300 |
C12—C17 | 1.378 (7) | C31—C32 | 1.370 (7) |
C12—N3 | 1.418 (7) | C31—H31A | 0.9300 |
C13—C14 | 1.381 (9) | C32—C33 | 1.364 (8) |
C13—H13A | 0.9300 | C32—H32A | 0.9300 |
C14—C15 | 1.368 (9) | C33—C34 | 1.379 (8) |
C14—H14A | 0.9300 | C33—H33A | 0.9300 |
C15—C16 | 1.365 (8) | C34—H34A | 0.9300 |
C15—H15A | 0.9300 | N3—N4 | 1.395 (5) |
C16—C17 | 1.380 (8) | N5—Mn1i | 2.341 (4) |
C16—H16A | 0.9300 | N7—N8 | 1.383 (5) |
O2—Mn1—N5i | 87.27 (13) | C21—C20—C19 | 118.5 (5) |
O2—Mn1—N1 | 89.45 (14) | C21—C20—H20A | 120.7 |
N5i—Mn1—N1 | 171.60 (15) | C19—C20—H20A | 120.7 |
O2—Mn1—Br2 | 109.22 (10) | C20—C21—C22 | 117.9 (5) |
N5i—Mn1—Br2 | 94.75 (10) | C20—C21—C23 | 121.9 (5) |
N1—Mn1—Br2 | 93.63 (11) | C22—C21—C23 | 120.1 (5) |
O2—Mn1—Br1 | 122.63 (10) | N5—C22—C21 | 123.9 (5) |
N5i—Mn1—Br1 | 86.76 (10) | N5—C22—H22A | 118.1 |
N1—Mn1—Br1 | 88.51 (11) | C21—C22—H22A | 118.1 |
Br2—Mn1—Br1 | 128.13 (4) | N6—C23—C21 | 119.8 (5) |
N1—C1—C2 | 124.3 (5) | N6—C23—H23A | 120.1 |
N1—C1—H1A | 117.9 | C21—C23—H23A | 120.1 |
C2—C1—H1A | 117.9 | C26—C24—N6 | 121.0 (4) |
C1—C2—C3 | 116.5 (5) | C26—C24—C25 | 107.5 (4) |
C1—C2—C6 | 122.2 (5) | N6—C24—C25 | 131.4 (5) |
C3—C2—C6 | 121.3 (5) | O2—C25—N7 | 121.1 (4) |
C4—C3—C2 | 120.2 (5) | O2—C25—C24 | 132.7 (5) |
C4—C3—H3A | 119.9 | N7—C25—C24 | 106.2 (4) |
C2—C3—H3A | 119.9 | N8—C26—C24 | 109.2 (4) |
C3—C4—C5 | 119.1 (5) | N8—C26—C27 | 122.4 (5) |
C3—C4—H4A | 120.4 | C24—C26—C27 | 128.3 (5) |
C5—C4—H4A | 120.4 | C26—C27—H27A | 109.5 |
N1—C5—C4 | 122.7 (5) | C26—C27—H27B | 109.5 |
N1—C5—H5A | 118.6 | H27A—C27—H27B | 109.5 |
C4—C5—H5A | 118.6 | C26—C27—H27C | 109.5 |
N2—C6—C2 | 119.0 (5) | H27A—C27—H27C | 109.5 |
N2—C6—H6A | 120.5 | H27B—C27—H27C | 109.5 |
C2—C6—H6A | 120.5 | N8—C28—H28A | 109.5 |
C10—C7—N2 | 121.4 (5) | N8—C28—H28B | 109.5 |
C10—C7—C8 | 107.6 (5) | H28A—C28—H28B | 109.5 |
N2—C7—C8 | 131.0 (5) | N8—C28—H28C | 109.5 |
O1—C8—N3 | 123.0 (5) | H28A—C28—H28C | 109.5 |
O1—C8—C7 | 132.3 (5) | H28B—C28—H28C | 109.5 |
N3—C8—C7 | 104.7 (4) | C30—C29—C34 | 121.0 (5) |
N4—C9—H9A | 109.5 | C30—C29—N7 | 119.4 (4) |
N4—C9—H9B | 109.5 | C34—C29—N7 | 119.6 (5) |
H9A—C9—H9B | 109.5 | C29—C30—C31 | 118.9 (5) |
N4—C9—H9C | 109.5 | C29—C30—H30A | 120.5 |
H9A—C9—H9C | 109.5 | C31—C30—H30A | 120.5 |
H9B—C9—H9C | 109.5 | C32—C31—C30 | 120.4 (5) |
N4—C10—C7 | 110.6 (5) | C32—C31—H31A | 119.8 |
N4—C10—C11 | 122.3 (5) | C30—C31—H31A | 119.8 |
C7—C10—C11 | 127.2 (6) | C33—C32—C31 | 120.4 (5) |
C10—C11—H11A | 109.5 | C33—C32—H32A | 119.8 |
C10—C11—H11B | 109.5 | C31—C32—H32A | 119.8 |
H11A—C11—H11B | 109.5 | C32—C33—C34 | 120.0 (5) |
C10—C11—H11C | 109.5 | C32—C33—H33A | 120.0 |
H11A—C11—H11C | 109.5 | C34—C33—H33A | 120.0 |
H11B—C11—H11C | 109.5 | C29—C34—C33 | 119.2 (5) |
C13—C12—C17 | 119.6 (6) | C29—C34—H34A | 120.4 |
C13—C12—N3 | 120.1 (5) | C33—C34—H34A | 120.4 |
C17—C12—N3 | 120.2 (5) | C5—N1—C1 | 117.2 (4) |
C12—C13—C14 | 119.6 (6) | C5—N1—Mn1 | 121.8 (4) |
C12—C13—H13A | 120.2 | C1—N1—Mn1 | 121.0 (3) |
C14—C13—H13A | 120.2 | C6—N2—C7 | 125.6 (5) |
C15—C14—C13 | 120.9 (6) | N4—N3—C8 | 108.8 (4) |
C15—C14—H14A | 119.5 | N4—N3—C12 | 121.6 (4) |
C13—C14—H14A | 119.5 | C8—N3—C12 | 129.4 (4) |
C16—C15—C14 | 119.2 (6) | C10—N4—N3 | 108.2 (4) |
C16—C15—H15A | 120.4 | C10—N4—C9 | 127.0 (5) |
C14—C15—H15A | 120.4 | N3—N4—C9 | 122.0 (5) |
C15—C16—C17 | 120.7 (6) | C22—N5—C18 | 117.5 (4) |
C15—C16—H16A | 119.6 | C22—N5—Mn1i | 122.6 (3) |
C17—C16—H16A | 119.6 | C18—N5—Mn1i | 119.5 (3) |
C12—C17—C16 | 119.8 (5) | C23—N6—C24 | 122.0 (4) |
C12—C17—H17A | 120.1 | C25—N7—N8 | 108.7 (4) |
C16—C17—H17A | 120.1 | C25—N7—C29 | 125.7 (4) |
N5—C18—C19 | 122.1 (5) | N8—N7—C29 | 122.4 (4) |
N5—C18—H18A | 118.9 | C26—N8—N7 | 108.3 (4) |
C19—C18—H18A | 118.9 | C26—N8—C28 | 129.9 (5) |
C18—C19—C20 | 120.0 (5) | N7—N8—C28 | 120.4 (5) |
C18—C19—H19A | 120.0 | C25—O2—Mn1 | 132.0 (3) |
C20—C19—H19A | 120.0 | ||
N1—C1—C2—C3 | 1.6 (8) | Br2—Mn1—N1—C5 | −7.7 (4) |
N1—C1—C2—C6 | 179.7 (5) | Br1—Mn1—N1—C5 | −135.8 (4) |
C1—C2—C3—C4 | −1.5 (8) | O2—Mn1—N1—C1 | −77.7 (4) |
C6—C2—C3—C4 | −179.6 (5) | N5i—Mn1—N1—C1 | −10.8 (12) |
C2—C3—C4—C5 | 0.4 (9) | Br2—Mn1—N1—C1 | 173.1 (4) |
C3—C4—C5—N1 | 0.8 (9) | Br1—Mn1—N1—C1 | 44.9 (4) |
C1—C2—C6—N2 | 172.9 (5) | C2—C6—N2—C7 | 179.1 (5) |
C3—C2—C6—N2 | −9.1 (8) | C10—C7—N2—C6 | −174.2 (5) |
C10—C7—C8—O1 | −177.1 (6) | C8—C7—N2—C6 | 3.6 (9) |
N2—C7—C8—O1 | 4.8 (11) | O1—C8—N3—N4 | 176.4 (5) |
C10—C7—C8—N3 | 0.6 (6) | C7—C8—N3—N4 | −1.6 (6) |
N2—C7—C8—N3 | −177.5 (5) | O1—C8—N3—C12 | 0.9 (9) |
N2—C7—C10—N4 | 179.0 (4) | C7—C8—N3—C12 | −177.1 (5) |
C8—C7—C10—N4 | 0.7 (6) | C13—C12—N3—N4 | 131.6 (5) |
N2—C7—C10—C11 | −0.5 (9) | C17—C12—N3—N4 | −46.3 (7) |
C8—C7—C10—C11 | −178.8 (5) | C13—C12—N3—C8 | −53.4 (8) |
C17—C12—C13—C14 | 0.7 (8) | C17—C12—N3—C8 | 128.7 (6) |
N3—C12—C13—C14 | −177.2 (5) | C7—C10—N4—N3 | −1.8 (6) |
C12—C13—C14—C15 | 0.8 (9) | C11—C10—N4—N3 | 177.8 (5) |
C13—C14—C15—C16 | −1.4 (10) | C7—C10—N4—C9 | −162.7 (5) |
C14—C15—C16—C17 | 0.6 (10) | C11—C10—N4—C9 | 16.9 (8) |
C13—C12—C17—C16 | −1.5 (9) | C8—N3—N4—C10 | 2.1 (6) |
N3—C12—C17—C16 | 176.4 (5) | C12—N3—N4—C10 | 178.1 (5) |
C15—C16—C17—C12 | 0.9 (9) | C8—N3—N4—C9 | 164.2 (5) |
N5—C18—C19—C20 | 1.2 (8) | C12—N3—N4—C9 | −19.9 (7) |
C18—C19—C20—C21 | 0.6 (8) | C21—C22—N5—C18 | −0.2 (7) |
C19—C20—C21—C22 | −2.1 (7) | C21—C22—N5—Mn1i | −173.3 (4) |
C19—C20—C21—C23 | −179.2 (4) | C19—C18—N5—C22 | −1.4 (7) |
C20—C21—C22—N5 | 1.9 (7) | C19—C18—N5—Mn1i | 172.0 (4) |
C23—C21—C22—N5 | 179.2 (4) | C21—C23—N6—C24 | −174.2 (4) |
C20—C21—C23—N6 | −171.5 (5) | C26—C24—N6—C23 | −171.0 (4) |
C22—C21—C23—N6 | 11.4 (7) | C25—C24—N6—C23 | 13.1 (7) |
C26—C24—C25—O2 | −179.0 (5) | O2—C25—N7—N8 | −178.5 (4) |
N6—C24—C25—O2 | −2.6 (8) | C24—C25—N7—N8 | 1.9 (5) |
C26—C24—C25—N7 | 0.6 (5) | O2—C25—N7—C29 | −18.5 (7) |
N6—C24—C25—N7 | 176.9 (4) | C24—C25—N7—C29 | 161.9 (4) |
N6—C24—C26—N8 | −179.8 (4) | C30—C29—N7—C25 | 95.3 (6) |
C25—C24—C26—N8 | −3.0 (5) | C34—C29—N7—C25 | −84.4 (6) |
N6—C24—C26—C27 | −2.6 (8) | C30—C29—N7—N8 | −107.3 (5) |
C25—C24—C26—C27 | 174.2 (5) | C34—C29—N7—N8 | 72.9 (6) |
C34—C29—C30—C31 | 1.9 (8) | C24—C26—N8—N7 | 4.2 (5) |
N7—C29—C30—C31 | −177.8 (5) | C27—C26—N8—N7 | −173.2 (4) |
C29—C30—C31—C32 | −1.3 (9) | C24—C26—N8—C28 | 170.5 (5) |
C30—C31—C32—C33 | −0.3 (9) | C27—C26—N8—C28 | −6.9 (8) |
C31—C32—C33—C34 | 1.2 (10) | C25—N7—N8—C26 | −3.8 (5) |
C30—C29—C34—C33 | −1.0 (8) | C29—N7—N8—C26 | −164.6 (4) |
N7—C29—C34—C33 | 178.8 (5) | C25—N7—N8—C28 | −171.7 (4) |
C32—C33—C34—C29 | −0.6 (9) | C29—N7—N8—C28 | 27.6 (6) |
C4—C5—N1—C1 | −0.7 (8) | N7—C25—O2—Mn1 | −95.7 (5) |
C4—C5—N1—Mn1 | 180.0 (4) | C24—C25—O2—Mn1 | 83.8 (6) |
C2—C1—N1—C5 | −0.5 (8) | N5i—Mn1—O2—C25 | −24.9 (4) |
C2—C1—N1—Mn1 | 178.8 (4) | N1—Mn1—O2—C25 | 147.3 (4) |
O2—Mn1—N1—C5 | 101.5 (4) | Br2—Mn1—O2—C25 | −119.0 (4) |
N5i—Mn1—N1—C5 | 168.5 (8) | Br1—Mn1—O2—C25 | 59.4 (4) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Mn2Br4(C17H16N4O)4] |
Mr | 1598.87 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 298 |
a, b, c (Å) | 10.052 (2), 12.372 (3), 15.257 (3) |
α, β, γ (°) | 72.68 (3), 77.66 (3), 71.09 (3) |
V (Å3) | 1699.2 (6) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 2.78 |
Crystal size (mm) | 0.24 × 0.20 × 0.18 |
Data collection | |
Diffractometer | Bruker SMART APEX II CCD |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.555, 0.634 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 16756, 7658, 4058 |
Rint | 0.073 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.058, 0.114, 0.99 |
No. of reflections | 7658 |
No. of parameters | 428 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.48, −0.53 |
Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003), SAINT, SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b), SHELXTL.
Br1—Mn1 | 2.5441 (12) | Mn1—N5i | 2.341 (4) |
Br2—Mn1 | 2.5387 (12) | Mn1—N1 | 2.360 (4) |
Mn1—O2 | 2.080 (3) | ||
O2—Mn1—N5i | 87.27 (13) | N1—Mn1—Br2 | 93.63 (11) |
O2—Mn1—N1 | 89.45 (14) | O2—Mn1—Br1 | 122.63 (10) |
N5i—Mn1—N1 | 171.60 (15) | N5i—Mn1—Br1 | 86.76 (10) |
O2—Mn1—Br2 | 109.22 (10) | N1—Mn1—Br1 | 88.51 (11) |
N5i—Mn1—Br2 | 94.75 (10) | Br2—Mn1—Br1 | 128.13 (4) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
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Great effort is currently being devoted to the design and syntheses of metal Schiff base complexes due to their potential applications as functional materials (O'Donnell, 2004). The Schiff bases of 4-aminoantipyrine and their complexes have been extensively investigated because of their biological, clinical and pharmacological applications (Rajendran & Sreeletha, 2002; Raman et al., 2001). However, only a few structurally characterized metal complexes with 4-aminoantipyrine Schiff base derived ligands have been reported, and its coordination chemistry remains largely unexplored (Liang et al., 2004; Liang et al., 2002; Wang et al., 2003). Herein we report the synthesis and crystal structure of a new dinuclear manganese(II) complex with a 4-aminoantipyrine derived Schiff base ligand: Mn2(L4)Br4 (L = (E)-1,5-dimethyl-2-phenyl-4-(pyridin-3-ylmethyleneamino)-1,2-dihydropyrazol-3-one) (I).
The ligand L was synthesized as reported previously by the base condensation of 4-aminoantipyrine with pyridine-3-carboxaldehyde (Montalvo-Gonzalez & Arisa-Castolo 2003). The title complex (I) was obtained under solvothermal conditions and characterized by X-ray crystallography. The molecular structure of (I) is shown in Fig. 1. Selected bond distances and bond angles are normal and listed in Table 1. (I) is a dinuclear MnII complex arranged around an inversion center. Each Mn atom is coordinated by two pyridine N atoms from two ligands, and one pyrazole O atom from another ligand, and two Br anions in a trigonal-bipyramidal geometry. There are two kinds of coordination modes of ligand L: one is monodentately linked to the Mn center through the N atom of the pyridine group, the other bidentately bridges two Mn centers by pyridine N atom and pyrazole O atom. The dimer Mn2L2 ring is formed with Mn···Mn separation of 8.878 (4) Å.