research communications
Synthesis and crystal structures of manganese(I) carbonyl complexes bearing ester-substituted α-diimine ligands
aGraduate School of Science and Engineering, Fukushima University, 1 Kanayagawa, Fukushima 960-1296, Japan, and bDepartment of Natural Sciences and Informatics, Fukushima University, 1, Kanayagawa, Fukushima 960-1296, Japan
*Correspondence e-mail: daio@sss.fukushima-u.ac.jp
The crystal structures of two manganese(I) complexes with ester-substituted bipyridine or biquinoline supporting ligands are reported, namely, fac-bromidotricarbonyl(diethyl 2,2′-bipyridine-4,4′-dicarboxylate-κ2N,N′)manganese(I), [MnBr(C16H16N2O4)(CO)3], I, and fac-bromidotricarbonyl(diethyl 2,2′-biquinoline-4,4′-dicarboxylate-κ2N,N′)manganese(I), [MnBr(C24H20N2O4)(CO)3], II. In both complexes, the manganese(I) atom adopts a distorted octahedral coordination sphere defined by three carbonyl C atoms, a Br− anion and two N atoms from the chelating α-diimine ligand. Both complexes show fac configurations of the carbonyl ligands. In I, the complex molecules are linked by C—H⋯Br hydrogen bonds and aromatic π–π contacts. In II, intramolecular C—H⋯O hydrogen bonds are present as well as intermolecular C—H⋯O and C—H⋯Br hydrogen bonds and π–π interactions.
1. Chemical context
Similar to carbonyl complexes of precious metals, such as ruthenium and rhenium, those with less expensive manganese are attracting attention for their application in CO2 reduction catalysts (Bourrez et al., 2011) and as CO-releasing molecules (CORMs) under external stimuli (Chakraborty et al., 2014a). For example, CORMs using manganese(I) carbonyl complexes controllably release CO by photoirradiation (Motterlini et al., 2002). Considering their application in vivo, photo-CORMs are expected to utilize light at lower energy. In general, extended π-conjugation systems in organic ligands lead to redshifts of charge-transfer (CT) transition bands of manganese(I) carbonyl complexes (Chakraborty et al., 2014b). Therefore, it is essential to investigate the relationship between molecular structures including π-conjugation systems and photophysical properties.
Thus, we focused on the comparison of bipyridines, which are prototypes of the α-diimine ligand, and biquinolines with a more extended π-conjugation system. In addition, the introduction of ester groups into these ligands allows with various metal oxides (Ardo & Meyer, 2009; Zhang et al., 2006). In this study, we synthesized manganese(I) tricarbonyl complexes bearing two types of α-diimine compounds, which contain both an ester substituent and different π-conjugation systems, viz. diethyl 2,2′-bipyridine-4,4′-dicarboxylate (debpy) and diethyl 2,2′-biquinoline-4,4′-didicarboxylate (debqn): fac-[MnBr(CO)3(debpy)] (I) and fac-[MnBr(CO)3(debqn)] (II). We successfully compared their crystal structures and photophysical properties. As expected, a CT band shift in the visible region was confirmed, depending on the size of the π-conjugation system in α-diimine ligands. This finding will provide information in the future design of suitable complexes for a variety of photoreactions (Chakraborty et al., 2014b).
2. Structural commentary
The molecular structures of compounds I and II are shown in Figs. 1 and 2, respectively. In both complexes, the manganese(I) atoms exhibit distorted octahedral coordination geometries and display primary coordination spheres that are similar to those reported for other structurally related complexes (Chakraborty et al., 2014a; Walsh et al., 2015). The metal–ligand bond lengths are similar to those previously reported for compounds of this type; in I, the Mn—N bond lengths are 2.046 (3) and 2.047 (2) Å, while in II, the Mn—N bond lengths are 2.063 (2) and 2.068 (2) Å. In I and II, the fac configuration of three CO ligands around the central manganese(I) atom is in agreement with their IR data. On the basis of their bond parameters, all CO ligands have typical triple-bond characters.
The torsion angles between the equatorial plane and the debpy pyridyl ring in I (C3—Mn1—N1—C8 and C2—Mn1—N2—C9) are −169.17 (15) and 168.81 (14)°, respectively; the corresponding torsion angles in II (C3—Mn1—N1—C12 and C2—Mn1—N2—C13) are −147.52 (16) and 147.08 (17)°, respectively (Fig. 3). The large differences in torsion angles between I and II are mainly due to between H atoms (H1 and H10) in debqn, and the equatorial CO ligands (C3≡O3 and C2≡O2). On the basis of similar comparable torsion angles [150.4 (15) and −150.7 (5)°] have been also observed in the related ReI complex (Hallett et al., 2011).
Despite similar molecular skeletons, only II exhibits intramolecular hydrogen bonds between the ester group and the quinolyl ring (Table 2). The C—C bond lengths of the coordinated pyridyl rings in I [C6—C7 = 1.395 (3) Å and C10—C11 = 1.392 (3) Å] are considerably longer than the corresponding one in II [C10—C11 = 1.364 (4) Å and C14—C15 = 1.368 (4) Å]. This difference in structural parameters may eventually affect the intramolecular hydrogen-bond formation.
3. Supramolecular features
In the I, complex molecules are linked by pairs of weak C—H⋯Br hydrogen bonds (Table 1) and π–π interactions [Cg1⋯Cg2iii = 3.683 (1) Å; Cg1 and Cg2 are the centroids of the N1/C4–C8 and N2/C9–C13 rings, respectively; symmetry code: (iii) 1 − x, −y, 1 − z], forming a three-dimensional supramolecular structure (Fig. 4).
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In the II, there are weak C—H⋯O and C—H⋯Br hydrogen-bonding interactions (Table 2) as well as the above-mentioned intramolecular hydrogen bonds. Additional π–π contacts are observed [Cg3⋯Cg4iv = 3.732 (2) Å and Cg5⋯Cg6iv = 4.002 (2) Å; Cg3, Cg4, Cg5 and Cg6 are the centroids of the C4–C9, C16–C21, N1/C8–C12 and N2/C13–C17 rings, respectively; symmetry code: (iv) 1 − x, 1 − y, −z]. These interactions lead to the formation of a three-dimensional network structure (Fig. 5).
of4. Database survey
With respect to manganese(I) complexes with a bidentate bipyridine derivative ligand (N-N) of the form fac-[MnBr(CO)3(N-N)], some structures have been reported (CSD refcode POKGAZ; Chakraborty et al., 2014a, FUMKOQ and FUMKUW; Henke et al., 2020, NIBSOJ; Lense et al., 2018, XUVMUY and XUVNAF; Walsh et al., 2015). However, no structures of bidentate biquinoline derivative–coordinated manganese(I) complexes have been reported; two structures of the corresponding rhenium(I) complexes have been determined by Hallett et al., 2011 (EBANEC) and Kurz et al., 2006 (XELXOC).
5. Synthesis and crystallization
The ligands, debpy and debqn, were prepared as described by Chandrasekharam et al. (2011) and Hoertz et al. (2006). The ligands were confirmed to be spectroscopically pure (by IR and 1H NMR analyses).
Synthesis of I and II: Compounds I and II were handled and stored in the dark to minimize exposure to light. For the synthesis of I, [MnBr(CO)5] (31 mg, 0.11 mmol) and debpy (33 mg, 0.11 mmol) were dissolved in CHCl3 (10 ml). The reaction mixture was stirred at 313 K for 14 h under N2. After the solvent was evaporated under reduced pressure, an excess of Et2O (30 ml) was added to the solution; then, the solution was allowed to stand at 253 K overnight. The resultant precipitate was collected by filtration, washed with Et2O, and then dried under vacuum (37 mg yield, 64%). Red crystals, suitable for the X-ray diffraction experiment, were grown by diffusion of n-hexane into an acetone solution of I for one week. FTIR (KBr pellet): νCO /cm−1 = 2028, 1918 (br) (C≡O), 1730 (C=O). UV–vis (CHCl3): λ /nm (∊ /M−1 cm−1) = 483 (3700), 367 (4100), 318 (21000), 247 (24000).
A similar reaction between [MnBr(CO)5] (8 mg, 0.029 mmol) and debqn (10 mg, 0.026 mmol) for 20 h afforded II (11 mg yield, 66%). Purple crystals, suitable for the X-ray diffraction experiment, were grown by diffusion of n-hexane into an acetone solution of II for one week. FTIR (KBr pellet): νCO /cm−1 = 2016, 1942, 1926 (C≡O), 1725 (C=O). UV–vis (CHCl3): λ /nm (∊ /M−1 cm−1) = 548 (3200), 383 (19000), 276 (37000).
6. Refinement
Crystal data, data collection and structure . All hydrogen atoms were placed at calculated positions (C—H = 0.95—0.99 Å) and refined using a riding model with Uiso(H) = 1.2Ueq(C).
details are summarized in Table 3Supporting information
https://doi.org/10.1107/S2056989020010750/dj2012sup1.cif
contains datablocks global, I, II. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989020010750/dj2012Isup2.hkl
Structure factors: contains datablock II. DOI: https://doi.org/10.1107/S2056989020010750/dj2012IIsup3.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2056989020010750/dj2012Isup4.mol
Supporting information file. DOI: https://doi.org/10.1107/S2056989020010750/dj2012IIsup5.mol
Data collection: CrystalClear (Rigaku, 2015) for (I); PROCESS-AUTO (Rigaku, 1998) for (II). Cell
CrystalClear (Rigaku, 2015) for (I); PROCESS-AUTO (Rigaku, 1998) for (II). Data reduction: CrystalClear (Rigaku, 2015) for (I); PROCESS-AUTO (Rigaku, 1998) for (II). Program(s) used to solve structure: SIR97 (Altomare et al., 1999) for (I); SHELXT2018/3 (Sheldrick, 2015a) for (II). For both structures, program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: Mercury (Macrae et al., 2020), ORTEP-3 for Windows (Farrugia, 2012). Software used to prepare material for publication: CrystalStructure (Rigaku, 2019), PLATON (Spek, 2020), publCIF (Westrip, 2010) for (I); CrystalStructure Rigaku, 2019), PLATON (Spek, 2020), publCIF (Westrip, 2010) for (II).[MnBr(C16H16N2O4)(CO)3] | F(000) = 1040.00 |
Mr = 519.19 | Dx = 1.694 Mg m−3 |
Monoclinic, P21/a | Mo Kα radiation, λ = 0.71075 Å |
a = 11.7054 (7) Å | Cell parameters from 5049 reflections |
b = 13.9151 (7) Å | θ = 3.2–27.5° |
c = 13.3273 (8) Å | µ = 2.66 mm−1 |
β = 110.347 (2)° | T = 93 K |
V = 2035.3 (2) Å3 | Block, red |
Z = 4 | 0.25 × 0.20 × 0.05 mm |
Rigaku Saturn724 diffractometer | 4050 reflections with F2 > 2.0σ(F2) |
Detector resolution: 28.626 pixels mm-1 | Rint = 0.029 |
ω scans | θmax = 27.5°, θmin = 3.2° |
Absorption correction: multi-scan (REQAB; Rigaku, 1998) | h = −15→15 |
Tmin = 0.730, Tmax = 0.875 | k = −18→18 |
20542 measured reflections | l = −16→17 |
4653 independent reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.098 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.055P)2 + 1.4779P] where P = (Fo2 + 2Fc2)/3 |
4653 reflections | (Δ/σ)max = 0.001 |
273 parameters | Δρmax = 1.05 e Å−3 |
0 restraints | Δρmin = −0.56 e Å−3 |
Primary atom site location: structure-invariant direct methods |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
Refinement. Refinement was performed using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F2. R-factor (gt) are based on F. The threshold expression of F2 > 2.0 sigma(F2) is used only for calculating R-factor (gt). |
x | y | z | Uiso*/Ueq | ||
Br1 | 0.61566 (2) | 0.30862 (2) | 0.74453 (2) | 0.02885 (10) | |
Mn1 | 0.59428 (3) | 0.13106 (3) | 0.76285 (3) | 0.02227 (11) | |
O1 | 0.56476 (18) | −0.07302 (16) | 0.80205 (17) | 0.0373 (5) | |
O2 | 0.4659 (2) | 0.17993 (16) | 0.91224 (17) | 0.0383 (5) | |
O3 | 0.82383 (19) | 0.14080 (17) | 0.94807 (17) | 0.0445 (6) | |
O4 | 0.9317 (2) | 0.0758 (2) | 0.4214 (2) | 0.0611 (8) | |
O5 | 0.74278 (19) | 0.0819 (2) | 0.30486 (17) | 0.0491 (6) | |
O6 | 0.06293 (17) | 0.21138 (15) | 0.31716 (16) | 0.0348 (5) | |
O7 | 0.18898 (17) | 0.15004 (15) | 0.23897 (15) | 0.0337 (5) | |
N1 | 0.67488 (18) | 0.10977 (15) | 0.65084 (17) | 0.0225 (4) | |
N2 | 0.44701 (18) | 0.13714 (14) | 0.62383 (16) | 0.0204 (4) | |
C1 | 0.57649 (19) | −0.00038 (19) | 0.78541 (18) | 0.0184 (5) | |
C2 | 0.5130 (2) | 0.1609 (2) | 0.8528 (2) | 0.0281 (6) | |
C3 | 0.7357 (2) | 0.1367 (2) | 0.8760 (2) | 0.0300 (6) | |
C4 | 0.7938 (2) | 0.09076 (19) | 0.6709 (2) | 0.0277 (6) | |
H1 | 0.846290 | 0.085051 | 0.743314 | 0.033* | |
C5 | 0.8427 (2) | 0.07926 (19) | 0.5918 (2) | 0.0286 (6) | |
H2 | 0.926942 | 0.065380 | 0.609537 | 0.034* | |
C6 | 0.7678 (2) | 0.08816 (17) | 0.4859 (2) | 0.0248 (5) | |
C7 | 0.6442 (2) | 0.10676 (17) | 0.4631 (2) | 0.0227 (5) | |
H3 | 0.590464 | 0.112142 | 0.391116 | 0.027* | |
C8 | 0.6010 (2) | 0.11726 (17) | 0.5469 (2) | 0.0212 (5) | |
C9 | 0.4718 (2) | 0.13526 (16) | 0.53200 (19) | 0.0195 (5) | |
C10 | 0.3818 (2) | 0.14873 (17) | 0.4324 (2) | 0.0218 (5) | |
H4 | 0.401900 | 0.149195 | 0.369186 | 0.026* | |
C11 | 0.2618 (2) | 0.16152 (17) | 0.42677 (19) | 0.0218 (5) | |
C12 | 0.2358 (2) | 0.16067 (18) | 0.5208 (2) | 0.0228 (5) | |
H5 | 0.154399 | 0.167911 | 0.518946 | 0.027* | |
C13 | 0.3306 (2) | 0.14909 (17) | 0.6174 (2) | 0.0219 (5) | |
H6 | 0.312656 | 0.149609 | 0.681603 | 0.026* | |
C14 | 0.8236 (2) | 0.08021 (19) | 0.4011 (2) | 0.0300 (6) | |
C15 | 0.7888 (3) | 0.0781 (3) | 0.2161 (3) | 0.0509 (9) | |
H7 | 0.812429 | 0.143292 | 0.200741 | 0.061* | |
H8 | 0.861458 | 0.036113 | 0.234873 | 0.061* | |
C16 | 0.6927 (3) | 0.0403 (3) | 0.1227 (3) | 0.0487 (8) | |
H9 | 0.720196 | 0.040532 | 0.061186 | 0.058* | |
H10 | 0.619799 | 0.080493 | 0.106964 | 0.058* | |
H11 | 0.673358 | −0.025646 | 0.137198 | 0.058* | |
C17 | 0.1594 (2) | 0.17805 (19) | 0.3228 (2) | 0.0256 (5) | |
C18 | 0.0934 (3) | 0.1635 (3) | 0.1343 (2) | 0.0437 (8) | |
H12 | 0.067516 | 0.231576 | 0.124367 | 0.052* | |
H13 | 0.021624 | 0.123338 | 0.128791 | 0.052* | |
C19 | 0.1454 (4) | 0.1343 (3) | 0.0510 (2) | 0.0577 (11) | |
H14 | 0.170249 | 0.066677 | 0.061456 | 0.069* | |
H15 | 0.216324 | 0.174389 | 0.057323 | 0.069* | |
H16 | 0.083590 | 0.142579 | −0.020197 | 0.069* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.02690 (15) | 0.02926 (15) | 0.03069 (16) | −0.00070 (10) | 0.01041 (11) | −0.00024 (10) |
Mn1 | 0.01673 (19) | 0.0283 (2) | 0.01915 (19) | 0.00051 (14) | 0.00286 (14) | −0.00025 (14) |
O1 | 0.0297 (11) | 0.0444 (13) | 0.0364 (11) | 0.0040 (9) | 0.0096 (9) | 0.0013 (9) |
O2 | 0.0380 (12) | 0.0490 (13) | 0.0330 (11) | −0.0006 (9) | 0.0187 (10) | −0.0064 (9) |
O3 | 0.0273 (11) | 0.0608 (15) | 0.0333 (11) | −0.0066 (10) | −0.0047 (9) | 0.0106 (10) |
O4 | 0.0359 (13) | 0.099 (2) | 0.0583 (16) | 0.0226 (13) | 0.0288 (12) | 0.0239 (15) |
O5 | 0.0283 (11) | 0.0907 (19) | 0.0335 (11) | −0.0039 (11) | 0.0173 (9) | −0.0114 (12) |
O6 | 0.0197 (9) | 0.0471 (12) | 0.0318 (11) | 0.0090 (8) | 0.0015 (8) | −0.0025 (9) |
O7 | 0.0248 (10) | 0.0503 (12) | 0.0200 (9) | 0.0118 (8) | 0.0003 (7) | 0.0020 (8) |
N1 | 0.0160 (9) | 0.0241 (10) | 0.0241 (10) | 0.0007 (8) | 0.0027 (8) | −0.0001 (8) |
N2 | 0.0164 (9) | 0.0221 (10) | 0.0215 (10) | −0.0004 (7) | 0.0052 (8) | −0.0011 (8) |
C1 | 0.0063 (9) | 0.0344 (14) | 0.0133 (10) | 0.0023 (9) | 0.0021 (8) | −0.0008 (9) |
C2 | 0.0232 (13) | 0.0321 (13) | 0.0237 (13) | −0.0027 (10) | 0.0015 (11) | 0.0001 (10) |
C3 | 0.0273 (13) | 0.0344 (14) | 0.0278 (13) | −0.0011 (11) | 0.0089 (11) | 0.0042 (11) |
C4 | 0.0167 (11) | 0.0316 (13) | 0.0308 (13) | 0.0030 (10) | 0.0033 (10) | −0.0014 (11) |
C5 | 0.0164 (11) | 0.0268 (13) | 0.0410 (15) | 0.0020 (9) | 0.0080 (11) | −0.0020 (11) |
C6 | 0.0214 (12) | 0.0197 (12) | 0.0361 (14) | −0.0015 (9) | 0.0136 (11) | −0.0030 (10) |
C7 | 0.0192 (11) | 0.0231 (12) | 0.0258 (12) | −0.0022 (9) | 0.0076 (10) | −0.0033 (9) |
C8 | 0.0153 (11) | 0.0210 (11) | 0.0257 (12) | −0.0008 (9) | 0.0051 (9) | −0.0019 (9) |
C9 | 0.0160 (11) | 0.0198 (11) | 0.0223 (11) | −0.0012 (8) | 0.0060 (9) | −0.0014 (9) |
C10 | 0.0195 (11) | 0.0227 (12) | 0.0232 (12) | 0.0013 (9) | 0.0074 (10) | −0.0013 (9) |
C11 | 0.0185 (11) | 0.0217 (11) | 0.0217 (12) | 0.0006 (9) | 0.0026 (9) | −0.0008 (9) |
C12 | 0.0151 (11) | 0.0246 (12) | 0.0275 (13) | −0.0004 (9) | 0.0058 (10) | −0.0018 (10) |
C13 | 0.0177 (11) | 0.0245 (12) | 0.0238 (12) | 0.0000 (9) | 0.0078 (9) | −0.0011 (9) |
C14 | 0.0264 (14) | 0.0261 (13) | 0.0433 (16) | 0.0003 (10) | 0.0194 (12) | 0.0022 (11) |
C15 | 0.0442 (19) | 0.076 (3) | 0.0455 (19) | −0.0077 (17) | 0.0318 (16) | −0.0074 (17) |
C16 | 0.054 (2) | 0.065 (2) | 0.0344 (17) | −0.0040 (17) | 0.0246 (15) | 0.0039 (16) |
C17 | 0.0202 (12) | 0.0275 (13) | 0.0252 (13) | 0.0000 (10) | 0.0028 (10) | −0.0001 (10) |
C18 | 0.0335 (16) | 0.066 (2) | 0.0220 (14) | 0.0164 (15) | −0.0026 (12) | 0.0040 (14) |
C19 | 0.056 (2) | 0.084 (3) | 0.0250 (15) | 0.034 (2) | 0.0043 (15) | 0.0070 (16) |
Br1—Mn1 | 2.5038 (5) | C6—C14 | 1.493 (4) |
Mn1—C3 | 1.812 (3) | C7—C8 | 1.385 (4) |
Mn1—C2 | 1.819 (3) | C7—H3 | 0.9500 |
Mn1—C1 | 1.877 (3) | C8—C9 | 1.477 (3) |
Mn1—N1 | 2.046 (2) | C9—C10 | 1.391 (3) |
Mn1—N2 | 2.047 (2) | C10—C11 | 1.392 (3) |
O1—C1 | 1.054 (3) | C10—H4 | 0.9500 |
O2—C2 | 1.142 (3) | C11—C12 | 1.389 (4) |
O3—C3 | 1.141 (3) | C11—C17 | 1.502 (3) |
O4—C14 | 1.200 (3) | C12—C13 | 1.386 (3) |
O5—C14 | 1.303 (4) | C12—H5 | 0.9500 |
O5—C15 | 1.461 (4) | C13—H6 | 0.9500 |
O6—C17 | 1.199 (3) | C15—C16 | 1.455 (5) |
O7—C17 | 1.337 (3) | C15—H7 | 0.9900 |
O7—C18 | 1.466 (3) | C15—H8 | 0.9900 |
N1—C4 | 1.350 (3) | C16—H9 | 0.9800 |
N1—C8 | 1.358 (3) | C16—H10 | 0.9800 |
N2—C13 | 1.345 (3) | C16—H11 | 0.9800 |
N2—C9 | 1.353 (3) | C18—C19 | 1.495 (5) |
C4—C5 | 1.373 (4) | C18—H12 | 0.9900 |
C4—H1 | 0.9500 | C18—H13 | 0.9900 |
C5—C6 | 1.384 (4) | C19—H14 | 0.9800 |
C5—H2 | 0.9500 | C19—H15 | 0.9800 |
C6—C7 | 1.395 (3) | C19—H16 | 0.9800 |
C3—Mn1—C2 | 88.72 (12) | C10—C9—C8 | 123.5 (2) |
C3—Mn1—C1 | 91.66 (11) | C9—C10—C11 | 118.9 (2) |
C2—Mn1—C1 | 90.24 (11) | C9—C10—H4 | 120.5 |
C3—Mn1—N1 | 95.38 (11) | C11—C10—H4 | 120.5 |
C2—Mn1—N1 | 173.53 (10) | C12—C11—C10 | 119.0 (2) |
C1—Mn1—N1 | 94.63 (9) | C12—C11—C17 | 118.6 (2) |
C3—Mn1—N2 | 171.65 (11) | C10—C11—C17 | 122.4 (2) |
C2—Mn1—N2 | 96.79 (10) | C13—C12—C11 | 118.9 (2) |
C1—Mn1—N2 | 94.58 (9) | C13—C12—H5 | 120.6 |
N1—Mn1—N2 | 78.60 (8) | C11—C12—H5 | 120.6 |
C3—Mn1—Br1 | 86.86 (9) | N2—C13—C12 | 122.7 (2) |
C2—Mn1—Br1 | 86.10 (9) | N2—C13—H6 | 118.7 |
C1—Mn1—Br1 | 176.08 (7) | C12—C13—H6 | 118.7 |
N1—Mn1—Br1 | 89.12 (6) | O4—C14—O5 | 124.8 (3) |
N2—Mn1—Br1 | 87.26 (6) | O4—C14—C6 | 122.6 (3) |
C14—O5—C15 | 116.8 (2) | O5—C14—C6 | 112.6 (2) |
C17—O7—C18 | 115.1 (2) | C16—C15—O5 | 108.2 (3) |
C4—N1—C8 | 117.7 (2) | C16—C15—H7 | 110.1 |
C4—N1—Mn1 | 126.13 (17) | O5—C15—H7 | 110.1 |
C8—N1—Mn1 | 116.18 (16) | C16—C15—H8 | 110.1 |
C13—N2—C9 | 118.4 (2) | O5—C15—H8 | 110.1 |
C13—N2—Mn1 | 125.35 (17) | H7—C15—H8 | 108.4 |
C9—N2—Mn1 | 116.12 (15) | C15—C16—H9 | 109.5 |
O1—C1—Mn1 | 176.5 (2) | C15—C16—H10 | 109.5 |
O2—C2—Mn1 | 177.5 (2) | H9—C16—H10 | 109.5 |
O3—C3—Mn1 | 179.0 (3) | C15—C16—H11 | 109.5 |
N1—C4—C5 | 123.2 (2) | H9—C16—H11 | 109.5 |
N1—C4—H1 | 118.4 | H10—C16—H11 | 109.5 |
C5—C4—H1 | 118.4 | O6—C17—O7 | 124.9 (2) |
C4—C5—C6 | 119.1 (2) | O6—C17—C11 | 123.3 (3) |
C4—C5—H2 | 120.4 | O7—C17—C11 | 111.7 (2) |
C6—C5—H2 | 120.4 | O7—C18—C19 | 107.4 (2) |
C5—C6—C7 | 118.7 (2) | O7—C18—H12 | 110.2 |
C5—C6—C14 | 118.4 (2) | C19—C18—H12 | 110.2 |
C7—C6—C14 | 122.9 (2) | O7—C18—H13 | 110.2 |
C8—C7—C6 | 119.1 (2) | C19—C18—H13 | 110.2 |
C8—C7—H3 | 120.5 | H12—C18—H13 | 108.5 |
C6—C7—H3 | 120.5 | C18—C19—H14 | 109.5 |
N1—C8—C7 | 122.2 (2) | C18—C19—H15 | 109.5 |
N1—C8—C9 | 114.2 (2) | H14—C19—H15 | 109.5 |
C7—C8—C9 | 123.6 (2) | C18—C19—H16 | 109.5 |
N2—C9—C10 | 122.1 (2) | H14—C19—H16 | 109.5 |
N2—C9—C8 | 114.4 (2) | H15—C19—H16 | 109.5 |
C8—N1—C4—C5 | 0.3 (4) | C8—C9—C10—C11 | 177.5 (2) |
Mn1—N1—C4—C5 | −178.5 (2) | C9—C10—C11—C12 | 0.2 (4) |
N1—C4—C5—C6 | 0.5 (4) | C9—C10—C11—C17 | 179.0 (2) |
C4—C5—C6—C7 | −1.2 (4) | C10—C11—C12—C13 | 1.3 (4) |
C4—C5—C6—C14 | 177.1 (2) | C17—C11—C12—C13 | −177.6 (2) |
C5—C6—C7—C8 | 1.1 (4) | C9—N2—C13—C12 | −0.8 (4) |
C14—C6—C7—C8 | −177.1 (2) | Mn1—N2—C13—C12 | 174.46 (18) |
C4—N1—C8—C7 | −0.5 (4) | C11—C12—C13—N2 | −1.0 (4) |
Mn1—N1—C8—C7 | 178.47 (18) | C15—O5—C14—O4 | 0.0 (5) |
C4—N1—C8—C9 | 178.3 (2) | C15—O5—C14—C6 | 177.8 (3) |
Mn1—N1—C8—C9 | −2.8 (3) | C5—C6—C14—O4 | −7.4 (4) |
C6—C7—C8—N1 | −0.2 (4) | C7—C6—C14—O4 | 170.8 (3) |
C6—C7—C8—C9 | −178.8 (2) | C5—C6—C14—O5 | 174.7 (2) |
C13—N2—C9—C10 | 2.4 (3) | C7—C6—C14—O5 | −7.1 (4) |
Mn1—N2—C9—C10 | −173.32 (18) | C14—O5—C15—C16 | 156.1 (3) |
C13—N2—C9—C8 | −177.2 (2) | C18—O7—C17—O6 | 0.5 (4) |
Mn1—N2—C9—C8 | 7.0 (3) | C18—O7—C17—C11 | 179.7 (2) |
N1—C8—C9—N2 | −2.8 (3) | C12—C11—C17—O6 | 17.2 (4) |
C7—C8—C9—N2 | 175.9 (2) | C10—C11—C17—O6 | −161.6 (3) |
N1—C8—C9—C10 | 177.6 (2) | C12—C11—C17—O7 | −162.0 (2) |
C7—C8—C9—C10 | −3.7 (4) | C10—C11—C17—O7 | 19.2 (3) |
N2—C9—C10—C11 | −2.1 (4) | C17—O7—C18—C19 | 176.5 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H2···Br1i | 0.95 | 2.90 | 3.502 (3) | 122 |
C13—H6···Br1ii | 0.95 | 2.78 | 3.537 (3) | 138 |
Symmetry codes: (i) x+1/2, −y+1/2, z; (ii) x−1/2, −y+1/2, z. |
[MnBr(C24H20N2O4)(CO)3] | F(000) = 1248.00 |
Mr = 619.31 | Dx = 1.627 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71075 Å |
a = 8.8953 (9) Å | Cell parameters from 9084 reflections |
b = 12.0086 (13) Å | θ = 3.0–27.7° |
c = 23.790 (3) Å | µ = 2.16 mm−1 |
β = 95.794 (2)° | T = 93 K |
V = 2528.3 (5) Å3 | Block, purple |
Z = 4 | 0.20 × 0.08 × 0.05 mm |
Rigaku Saturn70 diffractometer | 4100 reflections with F2 > 2.0σ(F2) |
Detector resolution: 7.143 pixels mm-1 | Rint = 0.080 |
ω scans | θmax = 27.5°, θmin = 3.0° |
Absorption correction: multi-scan (REQAB; Rigaku, 1998) | h = −11→11 |
Tmin = 0.461, Tmax = 0.898 | k = −15→15 |
25401 measured reflections | l = −30→30 |
5757 independent reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.134 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.062P)2 + 0.6421P] where P = (Fo2 + 2Fc2)/3 |
5757 reflections | (Δ/σ)max = 0.001 |
345 parameters | Δρmax = 0.79 e Å−3 |
0 restraints | Δρmin = −1.07 e Å−3 |
Primary atom site location: structure-invariant direct methods |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
Refinement. Refinement was performed using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F2. R-factor (gt) are based on F. The threshold expression of F2 > 2.0 sigma(F2) is used only for calculating R-factor (gt). |
x | y | z | Uiso*/Ueq | ||
Br1 | 0.09534 (4) | 0.75013 (2) | 0.04399 (2) | 0.03365 (12) | |
Mn1 | 0.37395 (6) | 0.74975 (3) | 0.03376 (2) | 0.02720 (14) | |
O1 | 0.6977 (3) | 0.77263 (19) | 0.02409 (12) | 0.0455 (6) | |
O2 | 0.4042 (4) | 0.8863 (2) | 0.13644 (11) | 0.0659 (8) | |
O3 | 0.3198 (3) | 0.96864 (19) | −0.02110 (11) | 0.0478 (6) | |
O4 | −0.0202 (3) | 0.4693 (2) | −0.19464 (10) | 0.0522 (7) | |
O5 | 0.1200 (2) | 0.33393 (18) | −0.15029 (8) | 0.0358 (5) | |
O6 | 0.2414 (4) | 0.2443 (2) | 0.17911 (12) | 0.0616 (9) | |
O7 | 0.0767 (3) | 0.25994 (16) | 0.10327 (10) | 0.0372 (5) | |
N1 | 0.3222 (3) | 0.64858 (19) | −0.03560 (9) | 0.0255 (5) | |
N2 | 0.3736 (3) | 0.59349 (19) | 0.07024 (9) | 0.0265 (5) | |
C1 | 0.5744 (4) | 0.7601 (2) | 0.02755 (14) | 0.0331 (7) | |
C2 | 0.3926 (4) | 0.8304 (3) | 0.09774 (14) | 0.0400 (8) | |
C3 | 0.3401 (4) | 0.8825 (3) | −0.00119 (13) | 0.0342 (7) | |
C4 | 0.3949 (4) | 0.7704 (3) | −0.10815 (15) | 0.0380 (8) | |
H1 | 0.459451 | 0.809647 | −0.080705 | 0.046* | |
C5 | 0.3815 (4) | 0.8050 (3) | −0.16335 (15) | 0.0468 (9) | |
H2 | 0.437453 | 0.867719 | −0.173866 | 0.056* | |
C6 | 0.2868 (5) | 0.7494 (3) | −0.20404 (16) | 0.0489 (10) | |
H3 | 0.273651 | 0.777152 | −0.241603 | 0.059* | |
C7 | 0.2124 (4) | 0.6553 (3) | −0.19061 (13) | 0.0417 (8) | |
H4 | 0.151309 | 0.616168 | −0.219148 | 0.050* | |
C8 | 0.2262 (3) | 0.6154 (3) | −0.13391 (12) | 0.0308 (7) | |
C9 | 0.3148 (3) | 0.6779 (3) | −0.09197 (12) | 0.0301 (6) | |
C10 | 0.1627 (3) | 0.5137 (2) | −0.11728 (11) | 0.0283 (6) | |
C11 | 0.1841 (3) | 0.4822 (2) | −0.06195 (11) | 0.0273 (6) | |
H5 | 0.146315 | 0.412652 | −0.050550 | 0.033* | |
C12 | 0.2616 (3) | 0.5524 (2) | −0.02203 (12) | 0.0251 (6) | |
C13 | 0.2867 (3) | 0.5228 (2) | 0.03829 (11) | 0.0253 (6) | |
C14 | 0.2265 (3) | 0.4258 (2) | 0.06018 (12) | 0.0284 (6) | |
H6 | 0.161956 | 0.379064 | 0.036264 | 0.034* | |
C15 | 0.2605 (3) | 0.3983 (2) | 0.11581 (12) | 0.0276 (6) | |
C16 | 0.3641 (3) | 0.4668 (2) | 0.15020 (12) | 0.0290 (6) | |
C17 | 0.4186 (3) | 0.5636 (2) | 0.12506 (11) | 0.0271 (6) | |
C18 | 0.4134 (4) | 0.4435 (3) | 0.20761 (12) | 0.0348 (7) | |
H7 | 0.373534 | 0.381128 | 0.225729 | 0.042* | |
C19 | 0.5173 (4) | 0.5101 (3) | 0.23671 (13) | 0.0392 (8) | |
H8 | 0.550979 | 0.492906 | 0.274893 | 0.047* | |
C20 | 0.5755 (4) | 0.6038 (3) | 0.21124 (13) | 0.0369 (8) | |
H9 | 0.648519 | 0.649313 | 0.232167 | 0.044* | |
C21 | 0.5280 (3) | 0.6298 (3) | 0.15676 (12) | 0.0322 (7) | |
H10 | 0.568787 | 0.693090 | 0.139770 | 0.039* | |
C22 | 0.0748 (3) | 0.4380 (3) | −0.15902 (12) | 0.0342 (7) | |
C23 | 0.0446 (5) | 0.2485 (3) | −0.18631 (15) | 0.0476 (10) | |
H11 | 0.043775 | 0.269435 | −0.226591 | 0.057* | |
H12 | −0.061144 | 0.238971 | −0.177556 | 0.057* | |
C24 | 0.1315 (5) | 0.1432 (3) | −0.17463 (17) | 0.0592 (11) | |
H13 | 0.081839 | 0.082438 | −0.196838 | 0.071* | |
H14 | 0.135231 | 0.125364 | −0.134315 | 0.071* | |
H15 | 0.234523 | 0.152836 | −0.185052 | 0.071* | |
C25 | 0.1941 (4) | 0.2929 (3) | 0.13743 (13) | 0.0324 (7) | |
C26 | 0.0195 (4) | 0.1492 (3) | 0.11252 (15) | 0.0412 (8) | |
H16 | −0.088192 | 0.144696 | 0.097417 | 0.049* | |
H17 | 0.026769 | 0.133367 | 0.153545 | 0.049* | |
C27 | 0.1078 (5) | 0.0658 (3) | 0.0841 (2) | 0.0663 (12) | |
H18 | 0.059641 | −0.007362 | 0.085839 | 0.080* | |
H19 | 0.210688 | 0.062260 | 0.103066 | 0.080* | |
H20 | 0.111507 | 0.087199 | 0.044501 | 0.080* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0304 (2) | 0.03101 (19) | 0.0392 (2) | 0.00088 (13) | 0.00171 (14) | −0.00383 (12) |
Mn1 | 0.0290 (3) | 0.0223 (2) | 0.0293 (2) | −0.00015 (18) | −0.0018 (2) | −0.00277 (17) |
O1 | 0.0346 (15) | 0.0311 (13) | 0.0702 (17) | 0.0026 (10) | 0.0027 (13) | 0.0027 (11) |
O2 | 0.085 (2) | 0.0514 (16) | 0.0556 (16) | 0.0189 (15) | −0.0224 (15) | −0.0289 (13) |
O3 | 0.0572 (16) | 0.0252 (12) | 0.0606 (15) | 0.0045 (11) | 0.0037 (13) | 0.0056 (11) |
O4 | 0.0465 (15) | 0.0670 (18) | 0.0383 (12) | 0.0050 (13) | −0.0198 (11) | −0.0010 (12) |
O5 | 0.0377 (12) | 0.0377 (12) | 0.0302 (11) | −0.0082 (10) | −0.0056 (9) | −0.0087 (9) |
O6 | 0.070 (2) | 0.0594 (18) | 0.0497 (16) | −0.0249 (14) | −0.0218 (15) | 0.0294 (12) |
O7 | 0.0397 (14) | 0.0282 (12) | 0.0418 (13) | −0.0056 (10) | −0.0056 (11) | 0.0058 (9) |
N1 | 0.0261 (13) | 0.0241 (12) | 0.0259 (12) | 0.0008 (10) | −0.0002 (10) | −0.0010 (9) |
N2 | 0.0270 (13) | 0.0259 (12) | 0.0257 (12) | 0.0024 (10) | −0.0014 (10) | −0.0011 (10) |
C1 | 0.045 (2) | 0.0181 (14) | 0.0350 (16) | −0.0033 (13) | −0.0036 (15) | 0.0017 (12) |
C2 | 0.0393 (19) | 0.0360 (18) | 0.0423 (18) | 0.0075 (15) | −0.0079 (15) | −0.0064 (15) |
C3 | 0.0329 (17) | 0.0296 (16) | 0.0394 (17) | −0.0005 (14) | 0.0002 (14) | −0.0057 (13) |
C4 | 0.042 (2) | 0.0348 (18) | 0.0369 (17) | 0.0002 (14) | 0.0045 (15) | 0.0036 (13) |
C5 | 0.055 (2) | 0.043 (2) | 0.044 (2) | −0.0002 (18) | 0.0138 (18) | 0.0119 (16) |
C6 | 0.061 (3) | 0.051 (2) | 0.0350 (18) | 0.0026 (19) | 0.0100 (18) | 0.0139 (16) |
C7 | 0.047 (2) | 0.050 (2) | 0.0285 (16) | 0.0056 (17) | 0.0015 (15) | 0.0047 (14) |
C8 | 0.0326 (17) | 0.0323 (16) | 0.0268 (14) | 0.0072 (13) | 0.0000 (13) | 0.0004 (12) |
C9 | 0.0298 (16) | 0.0298 (15) | 0.0301 (15) | 0.0060 (13) | 0.0009 (12) | 0.0057 (12) |
C10 | 0.0251 (15) | 0.0330 (16) | 0.0260 (14) | 0.0062 (13) | −0.0011 (12) | 0.0001 (12) |
C11 | 0.0275 (15) | 0.0263 (14) | 0.0272 (14) | 0.0022 (12) | −0.0022 (12) | 0.0001 (12) |
C12 | 0.0259 (15) | 0.0248 (14) | 0.0240 (13) | 0.0029 (12) | −0.0002 (11) | 0.0022 (11) |
C13 | 0.0272 (15) | 0.0216 (14) | 0.0260 (13) | 0.0005 (12) | −0.0022 (11) | −0.0018 (11) |
C14 | 0.0311 (16) | 0.0259 (14) | 0.0267 (14) | 0.0003 (13) | −0.0037 (12) | −0.0010 (11) |
C15 | 0.0271 (16) | 0.0260 (14) | 0.0291 (14) | 0.0018 (12) | 0.0002 (12) | 0.0007 (11) |
C16 | 0.0298 (16) | 0.0322 (16) | 0.0239 (13) | 0.0048 (13) | −0.0027 (12) | −0.0008 (12) |
C17 | 0.0296 (16) | 0.0289 (15) | 0.0218 (13) | 0.0018 (13) | −0.0021 (12) | −0.0022 (11) |
C18 | 0.0425 (19) | 0.0378 (17) | 0.0236 (14) | 0.0040 (15) | 0.0002 (13) | 0.0015 (12) |
C19 | 0.046 (2) | 0.045 (2) | 0.0246 (14) | 0.0085 (17) | −0.0044 (14) | −0.0025 (14) |
C20 | 0.0384 (18) | 0.0401 (18) | 0.0300 (16) | 0.0040 (15) | −0.0079 (14) | −0.0103 (13) |
C21 | 0.0315 (17) | 0.0310 (16) | 0.0327 (15) | 0.0005 (13) | −0.0025 (13) | −0.0033 (13) |
C22 | 0.0305 (17) | 0.0468 (19) | 0.0246 (14) | 0.0010 (15) | −0.0010 (13) | −0.0032 (13) |
C23 | 0.051 (2) | 0.057 (2) | 0.0325 (17) | −0.0223 (18) | −0.0034 (17) | −0.0177 (15) |
C24 | 0.075 (3) | 0.045 (2) | 0.056 (2) | −0.016 (2) | 0.000 (2) | −0.0206 (18) |
C25 | 0.0337 (18) | 0.0309 (15) | 0.0318 (16) | −0.0003 (14) | −0.0003 (13) | 0.0052 (13) |
C26 | 0.045 (2) | 0.0267 (16) | 0.051 (2) | −0.0054 (15) | 0.0005 (16) | 0.0047 (14) |
C27 | 0.080 (3) | 0.0310 (19) | 0.091 (3) | 0.003 (2) | 0.023 (3) | −0.001 (2) |
Br1—Mn1 | 2.5146 (6) | C10—C22 | 1.506 (4) |
Mn1—C2 | 1.798 (3) | C11—C12 | 1.398 (4) |
Mn1—C1 | 1.809 (4) | C11—H5 | 0.9500 |
Mn1—C3 | 1.809 (3) | C12—C13 | 1.473 (4) |
Mn1—N1 | 2.063 (2) | C13—C14 | 1.404 (4) |
Mn1—N2 | 2.068 (2) | C14—C15 | 1.368 (4) |
O1—C1 | 1.118 (4) | C14—H6 | 0.9500 |
O2—C2 | 1.135 (4) | C15—C16 | 1.429 (4) |
O3—C3 | 1.144 (4) | C15—C25 | 1.508 (4) |
O4—C22 | 1.195 (4) | C16—C17 | 1.416 (4) |
O5—C22 | 1.323 (4) | C16—C18 | 1.419 (4) |
O5—C23 | 1.457 (4) | C17—C21 | 1.414 (4) |
O6—C25 | 1.190 (4) | C18—C19 | 1.358 (4) |
O7—C25 | 1.318 (4) | C18—H7 | 0.9500 |
O7—C26 | 1.449 (4) | C19—C20 | 1.402 (5) |
N1—C12 | 1.328 (4) | C19—H8 | 0.9500 |
N1—C9 | 1.382 (4) | C20—C21 | 1.358 (4) |
N2—C13 | 1.333 (3) | C20—H9 | 0.9500 |
N2—C17 | 1.373 (3) | C21—H10 | 0.9500 |
C4—C5 | 1.371 (5) | C23—C24 | 1.493 (5) |
C4—C9 | 1.394 (4) | C23—H11 | 0.9900 |
C4—H1 | 0.9500 | C23—H12 | 0.9900 |
C5—C6 | 1.389 (6) | C24—H13 | 0.9800 |
C5—H2 | 0.9500 | C24—H14 | 0.9800 |
C6—C7 | 1.363 (5) | C24—H15 | 0.9800 |
C6—H3 | 0.9500 | C26—C27 | 1.478 (5) |
C7—C8 | 1.425 (4) | C26—H16 | 0.9900 |
C7—H4 | 0.9500 | C26—H17 | 0.9900 |
C8—C10 | 1.418 (4) | C27—H18 | 0.9800 |
C8—C9 | 1.422 (4) | C27—H19 | 0.9800 |
C10—C11 | 1.364 (4) | C27—H20 | 0.9800 |
C2—Mn1—C1 | 91.40 (15) | C14—C13—C12 | 122.4 (2) |
C2—Mn1—C3 | 84.91 (15) | C15—C14—C13 | 120.3 (3) |
C1—Mn1—C3 | 91.23 (14) | C15—C14—H6 | 119.9 |
C2—Mn1—N1 | 171.30 (13) | C13—C14—H6 | 119.9 |
C1—Mn1—N1 | 96.74 (12) | C14—C15—C16 | 118.8 (3) |
C3—Mn1—N1 | 97.94 (11) | C14—C15—C25 | 118.5 (3) |
C2—Mn1—N2 | 97.89 (12) | C16—C15—C25 | 122.6 (3) |
C1—Mn1—N2 | 98.04 (11) | C17—C16—C18 | 118.9 (3) |
C3—Mn1—N2 | 170.22 (12) | C17—C16—C15 | 117.3 (2) |
N1—Mn1—N2 | 77.97 (9) | C18—C16—C15 | 123.8 (3) |
C2—Mn1—Br1 | 85.68 (11) | N2—C17—C21 | 118.6 (3) |
C1—Mn1—Br1 | 175.86 (9) | N2—C17—C16 | 122.5 (3) |
C3—Mn1—Br1 | 85.59 (10) | C21—C17—C16 | 118.9 (3) |
N1—Mn1—Br1 | 86.34 (7) | C19—C18—C16 | 120.2 (3) |
N2—Mn1—Br1 | 85.29 (7) | C19—C18—H7 | 119.9 |
C22—O5—C23 | 117.3 (3) | C16—C18—H7 | 119.9 |
C25—O7—C26 | 116.8 (2) | C18—C19—C20 | 121.0 (3) |
C12—N1—C9 | 118.5 (2) | C18—C19—H8 | 119.5 |
C12—N1—Mn1 | 112.39 (18) | C20—C19—H8 | 119.5 |
C9—N1—Mn1 | 127.65 (19) | C21—C20—C19 | 120.2 (3) |
C13—N2—C17 | 118.1 (2) | C21—C20—H9 | 119.9 |
C13—N2—Mn1 | 111.33 (18) | C19—C20—H9 | 119.9 |
C17—N2—Mn1 | 128.58 (19) | C20—C21—C17 | 120.7 (3) |
O1—C1—Mn1 | 176.2 (3) | C20—C21—H10 | 119.6 |
O2—C2—Mn1 | 176.4 (3) | C17—C21—H10 | 119.6 |
O3—C3—Mn1 | 177.1 (3) | O4—C22—O5 | 126.2 (3) |
C5—C4—C9 | 120.6 (3) | O4—C22—C10 | 124.1 (3) |
C5—C4—H1 | 119.7 | O5—C22—C10 | 109.7 (2) |
C9—C4—H1 | 119.7 | O5—C23—C24 | 106.7 (3) |
C4—C5—C6 | 120.6 (3) | O5—C23—H11 | 110.4 |
C4—C5—H2 | 119.7 | C24—C23—H11 | 110.4 |
C6—C5—H2 | 119.7 | O5—C23—H12 | 110.4 |
C7—C6—C5 | 120.7 (3) | C24—C23—H12 | 110.4 |
C7—C6—H3 | 119.7 | H11—C23—H12 | 108.6 |
C5—C6—H3 | 119.7 | C23—C24—H13 | 109.5 |
C6—C7—C8 | 120.2 (3) | C23—C24—H14 | 109.5 |
C6—C7—H4 | 119.9 | H13—C24—H14 | 109.5 |
C8—C7—H4 | 119.9 | C23—C24—H15 | 109.5 |
C10—C8—C9 | 117.9 (3) | H13—C24—H15 | 109.5 |
C10—C8—C7 | 123.7 (3) | H14—C24—H15 | 109.5 |
C9—C8—C7 | 118.4 (3) | O6—C25—O7 | 123.9 (3) |
N1—C9—C4 | 119.7 (3) | O6—C25—C15 | 125.3 (3) |
N1—C9—C8 | 121.0 (3) | O7—C25—C15 | 110.8 (2) |
C4—C9—C8 | 119.3 (3) | O7—C26—C27 | 110.0 (3) |
C11—C10—C8 | 119.2 (3) | O7—C26—H16 | 109.7 |
C11—C10—C22 | 118.8 (3) | C27—C26—H16 | 109.7 |
C8—C10—C22 | 122.1 (3) | O7—C26—H17 | 109.7 |
C10—C11—C12 | 119.9 (3) | C27—C26—H17 | 109.7 |
C10—C11—H5 | 120.0 | H16—C26—H17 | 108.2 |
C12—C11—H5 | 120.0 | C26—C27—H18 | 109.5 |
N1—C12—C11 | 122.9 (3) | C26—C27—H19 | 109.5 |
N1—C12—C13 | 114.9 (2) | H18—C27—H19 | 109.5 |
C11—C12—C13 | 122.1 (3) | C26—C27—H20 | 109.5 |
N2—C13—C14 | 122.5 (3) | H18—C27—H20 | 109.5 |
N2—C13—C12 | 115.1 (2) | H19—C27—H20 | 109.5 |
C9—C4—C5—C6 | 0.6 (6) | C12—C13—C14—C15 | 176.0 (3) |
C4—C5—C6—C7 | −4.0 (6) | C13—C14—C15—C16 | −3.2 (4) |
C5—C6—C7—C8 | 2.6 (6) | C13—C14—C15—C25 | −179.7 (3) |
C6—C7—C8—C10 | −174.7 (3) | C14—C15—C16—C17 | 3.7 (4) |
C6—C7—C8—C9 | 2.0 (5) | C25—C15—C16—C17 | 180.0 (3) |
C12—N1—C9—C4 | −171.2 (3) | C14—C15—C16—C18 | −176.8 (3) |
Mn1—N1—C9—C4 | 23.8 (4) | C25—C15—C16—C18 | −0.5 (5) |
C12—N1—C9—C8 | 8.9 (4) | C13—N2—C17—C21 | 170.9 (3) |
Mn1—N1—C9—C8 | −156.1 (2) | Mn1—N2—C17—C21 | −26.4 (4) |
C5—C4—C9—N1 | −175.8 (3) | C13—N2—C17—C16 | −6.5 (4) |
C5—C4—C9—C8 | 4.1 (5) | Mn1—N2—C17—C16 | 156.1 (2) |
C10—C8—C9—N1 | −8.5 (4) | C18—C16—C17—N2 | −178.4 (3) |
C7—C8—C9—N1 | 174.6 (3) | C15—C16—C17—N2 | 1.1 (4) |
C10—C8—C9—C4 | 171.6 (3) | C18—C16—C17—C21 | 4.2 (4) |
C7—C8—C9—C4 | −5.3 (4) | C15—C16—C17—C21 | −176.3 (3) |
C9—C8—C10—C11 | 2.4 (4) | C17—C16—C18—C19 | −3.5 (4) |
C7—C8—C10—C11 | 179.1 (3) | C15—C16—C18—C19 | 177.0 (3) |
C9—C8—C10—C22 | −176.4 (3) | C16—C18—C19—C20 | 1.2 (5) |
C7—C8—C10—C22 | 0.3 (5) | C18—C19—C20—C21 | 0.3 (5) |
C8—C10—C11—C12 | 3.0 (4) | C19—C20—C21—C17 | 0.5 (5) |
C22—C10—C11—C12 | −178.2 (3) | N2—C17—C21—C20 | 179.7 (3) |
C9—N1—C12—C11 | −3.3 (4) | C16—C17—C21—C20 | −2.8 (4) |
Mn1—N1—C12—C11 | 163.9 (2) | C23—O5—C22—O4 | −1.8 (5) |
C9—N1—C12—C13 | 174.6 (2) | C23—O5—C22—C10 | 178.8 (3) |
Mn1—N1—C12—C13 | −18.2 (3) | C11—C10—C22—O4 | 135.9 (3) |
C10—C11—C12—N1 | −2.7 (4) | C8—C10—C22—O4 | −45.3 (5) |
C10—C11—C12—C13 | 179.5 (3) | C11—C10—C22—O5 | −44.7 (4) |
C17—N2—C13—C14 | 7.2 (4) | C8—C10—C22—O5 | 134.1 (3) |
Mn1—N2—C13—C14 | −158.3 (2) | C22—O5—C23—C24 | 171.0 (3) |
C17—N2—C13—C12 | −171.3 (2) | C26—O7—C25—O6 | −10.5 (5) |
Mn1—N2—C13—C12 | 23.2 (3) | C26—O7—C25—C15 | 168.4 (3) |
N1—C12—C13—N2 | −3.5 (4) | C14—C15—C25—O6 | 159.9 (4) |
C11—C12—C13—N2 | 174.4 (3) | C16—C15—C25—O6 | −16.4 (5) |
N1—C12—C13—C14 | 178.0 (3) | C14—C15—C25—O7 | −18.9 (4) |
C11—C12—C13—C14 | −4.1 (4) | C16—C15—C25—O7 | 164.7 (3) |
N2—C13—C14—C15 | −2.4 (4) | C25—O7—C26—C27 | −83.7 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
C7—H4···O4 | 0.95 | 2.44 | 3.040 (4) | 121 |
C11—H5···Br1i | 0.95 | 2.92 | 3.789 (3) | 153 |
C14—H6···O7 | 0.95 | 2.33 | 2.659 (3) | 100 |
C18—H7···O6 | 0.95 | 2.25 | 2.883 (5) | 124 |
C19—H8···O2ii | 0.95 | 2.47 | 3.373 (4) | 160 |
C20—H9···O6iii | 0.95 | 2.51 | 3.383 (4) | 153 |
Symmetry codes: (i) −x, −y+1, −z; (ii) −x+1, y−1/2, −z+1/2; (iii) −x+1, y+1/2, −z+1/2. |
Funding information
Funding for this research was provided by: Japan Society for the Promotion of Science (grant No. JP17K05799).
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