research communications
Synthesis and H-benzo[d][1,2,3]triazole-κN2){2,2′-[N-(phenylphosphorylmethyl-κO)azanediyl]diacetato-κ3O,N,O′}cobalt(II)–1H-benzo[d][1,2,3]triazole (1/1)
of bis(1aSchool of Biochemical and Chemical Engineering, Nanyang Institute of Technology, Nanyang 473000, People's Republic of China
*Correspondence e-mail: hyperchem@126.com
In the title compound, [Co(C11H12NO6P)(C6H5N3)2]·C6H5N3, the 2,2′-[N-(phenylphosphorylmethyl-κO)azanediyl]diacetate dianion N,O,O′,O′′-chelates the CoII cation and two 1H-benzo[d][1,2,3]triazole molecules coordinate to the CoII cation to complete the slightly distorted octahedral coordination. In the crystal, classical O—H⋯O, N—H⋯O hydrogen bonds and weak C—H⋯N hydrogen bonds link the molecules into a three-dimensional supramolecular architecture. π–π stacking between the triazole and benzene rings and between the benzene rings is also observed in the crystal.
Keywords: crystal structure; CoII complex; aminophosphonate; organophosphorus materials; flame retardants.
CCDC reference: 1573300
1. Chemical context
Over the past few decades, many researchers have focused their attention on the preparation of organophosphorus materials because of their biological activities (Miller et al., 2008; Leonova et al., 2010; Sharma & Clearfield, 2000). In particular, aminophosphinic acid ligands as phosphorus analogues of natural amino acids have attracted significant attention because of their strong coordination ability with metals. It has been shown that aminophosphinic acid derivatives can be used as potent and selective inhibitors of many proteolytic enzymes, especially metalloproteases (Latajka et al., 2008; Cates & Li, 1985; Katoh et al., 1996). For the design and preparation of extraordinary enzyme inhibitors with considerable pharmacological activity and low toxicity, it is necessary to understand the metal-binding properties in order to obtain a profound insight into the mechanism of their biological activity.
In addition to their biological activities, aminophosphinic acids are also attracting interest in many areas such as the construction industry, aerospace and electronics for their excellent flame retardancy to polymeric materials (Lin, 2004; Lin et al., 2010; Lu & Hamerton, 2002). Aminophosphinic acid reactive flame retardants also have the advantage of low evolution of toxic gases and smoke in the event of fire, but cannot be used to make polyesters flame retardant because their decomposed temperatures do not match those of the polymers. In the early 80s, many metal salts of dialkylphosphinates were used by Pennwalt to increase the fire safety of polyesters (Sandler, 1979, 1980). Later, researchers from the Clariant company researched in detail the variety of dialkylphosphinates aluminum salts in glass-filled nylons (Kleiner et al., 1998, 1999; Weferling et al., 2001). They found that the aluminum diethylphosphinate can give a V-0 rating at 15 wt% in plain PBT and commercialized it as Exolit OP 930 (DEPAL), which is also used in thermoset resins (Horold et al., 2002; Campbell et al., 2005). Unfortunately, aluminum diethylphosphinate was prepared at high temperature and pressure. The coordination complexes of aminophosphinic acids and metals that are easily obtained at normal temperature have the elements phosphorus, nitrogen and the metal coexisting in the molecular structure, which may give a significant improvement of flame-retardant efficiency for polyesters. We therefore decided to explore new coordination complexes of aminophosphinic acids and metals as halogen-free flame retardants and as excellent candidates to replace the aluminum diethylphosphinate flame retardant. To the best of our knowledge, neither the title ligand 2,2′-({[(phenyl)phosphoryl]methyl}azanediyl)diacetic acid (synthesized by a typical Mannich reaction) nor any complexes based on this ligand have been reported anywhere. We therefore report herein the synthesis and of a cobalt(II) complex of this ligand, [Co(C11H12NO6P)(C6H5N3)2]·C6H5N3. Research of its potential applications (especially for use as a flame retardant) of this and analogous complexes is currently being undertaken.
2. Structural commentary
The molecular structure of the title complex is shown in Fig. 1. The CoII cation is N,O,O′,O"-chelated by a 2,2′-({[(phenyl)phosphoryl]methyl}azanediyl)diacetate dianion and coordinates two 1H-benzo[d][1,2,3]triazole molecules in a slightly distorted octahedral coordination (Table 1). The 2,2′-({[(phenyl)phosphoryl]methyl}azanediyl)diacetate dianion forms three five-membered chelate rings. The N atom comes from the imino group, the two O atoms from carboxyl groups and another O atom from the organophosphorus group.
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3. Supramolecular features
In the crystal, the complex molecules are linked by N—H⋯O hydrogen bonds involving the 1H-benzo[d][1,2,3]triazole molecules and O—H⋯O bonds involving the aminophosphonate groups into a three-dimensional supramolecular architecture (Fig. 2, Table 2). π–π stacking between organophosphorus aromatic rings is also observed, the centroid-to-centroid distances being 3.8622 (16), 3.7961 (16) 3.7331 (18) and 3.5001 (17) Å.
4. Database survey
Aminophosphonates acting as ligands have been widely used in coordination chemistry. Over the past two decades, many studies have been reported that use alkylamino-N,N-bis methylenephosphonates to coordinate with main group metals such as Ca, Ba (Vivani et al., 2006), transition metals such as Cd, Mn, Zn, and Pb (Taddei et al., 2011) and lanthanide metals (Mao et al., 2002) to obtain large numbers of zero-, one- two- and three-dimensional structures. However, the use of 2,2′-({[(phenyl)phosphoryl]methyl}azanediyl)diacetic acid as a ligand has not been reported elsewhere. The ligand has three functional groups, carboxyl, imino and organophosphate, and all of them are affected by pH values in solution. One of the key factors for the ligand used is to adjust the acidity of the reaction solution. Exploiting more analogous ligands and their complexes and developing their potential applications remains a big challenge.
5. Synthesis and crystallization
Phenylphosphinic acid (1.42 g, 0.01 mol) and iminodiacetic acid (41.33 g, 0.01 mol) were dissolved in hydrochloric acid (6 M, 50 ml) and refluxed for 1 h under a nitrogen atmosphere. 50 ml of formaldehyde in hydrochloric acid (37%) was added dropwise under vigorous stirring, and the temperature was maintained at 378–383 K for 4 h. This solution was then concentrated under reduced pressure and allowed to cool to room temperature. 100 ml of acetone was added, and the white precipitate of 2,2′-({[(phenyl)phosphoryl]methyl}azanediyl)diacetic acid was collected by filtration. Colourless crystals of the title compound were obtained as follows: 2.38 g CoCl2·6H2O (0.01 mol) and 3.57 g 1H-benzo[d][1,2,3]triazole (0.03 mol) were added to a stirred hydrochloric acid solution (4 M, 40 ml), then 3.24 g of 2,2′-({[(phenyl)phosphoryl]methyl}azanediyl)diacetic acid (0.01 mol) were added in one portion. The mixture was stirred for 1 h, then filtered and left undisturbed. Single crystals were obtained by slow evaporation of the reaction mixture after several days.
6. Refinement
Crystal data, data collection and structure . Water H atoms were located in difference-Fourier maps and O—H distances were restrained to 0.82 Å. Other H atoms (CH and CH2 groups) were positioned geometrically and refined using a riding model with Uiso(H) = 1.2Ueq(C). The carboxyl H atom was refined as rotating group with Uiso(H) = 1.5Ueq(O).
details are summarized in Table 3
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Supporting information
CCDC reference: 1573300
https://doi.org/10.1107/S2056989017015079/xu5906sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989017015079/xu5906Isup3.hkl
Data collection: CrysAlis PRO (Agilent, 2011); cell
CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).[Co(C11H12NO6P)(C6H5N3)2]·C6H5N3 | Z = 2 |
Mr = 701.50 | F(000) = 722 |
Triclinic, P1 | Dx = 1.511 Mg m−3 |
a = 7.5701 (3) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 14.1261 (4) Å | Cell parameters from 7159 reflections |
c = 14.9018 (5) Å | θ = 2.8–29.4° |
α = 97.351 (3)° | µ = 0.67 mm−1 |
β = 102.335 (3)° | T = 293 K |
γ = 91.206 (3)° | Block, colourless |
V = 1542.03 (9) Å3 | 0.30 × 0.25 × 0.20 mm |
Agilent Xcalibur Atlas Gemini ultra diffractometer | 6722 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 5440 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.032 |
Detector resolution: 10.4170 pixels mm-1 | θmax = 27.1°, θmin = 2.8° |
ω scans | h = −8→9 |
Absorption correction: multi-scan (CrysAlis Pro; Agilent, 2011) | k = −18→18 |
Tmin = 0.905, Tmax = 1.000 | l = −19→18 |
14339 measured reflections |
Refinement on F2 | Primary atom site location: dual |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.038 | H-atom parameters constrained |
wR(F2) = 0.097 | w = 1/[σ2(Fo2) + (0.042P)2 + 0.4782P] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max = 0.001 |
6722 reflections | Δρmax = 0.42 e Å−3 |
425 parameters | Δρmin = −0.26 e Å−3 |
121 restraints |
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. |
x | y | z | Uiso*/Ueq | ||
Co1 | −0.05582 (3) | 0.24613 (2) | 0.88580 (2) | 0.03100 (9) | |
P1 | 0.00092 (7) | 0.05593 (3) | 0.77757 (4) | 0.03346 (13) | |
O1 | −0.5457 (2) | 0.36152 (11) | 0.84311 (12) | 0.0487 (4) | |
O2 | −0.26323 (19) | 0.33099 (10) | 0.90211 (10) | 0.0390 (3) | |
O3 | −0.07905 (19) | 0.16185 (10) | 0.99428 (10) | 0.0385 (3) | |
O4 | −0.2239 (2) | 0.03247 (11) | 1.02198 (11) | 0.0482 (4) | |
H4 | −0.145757 | 0.039665 | 1.070122 | 0.072* | |
O5 | 0.0013 (2) | −0.03141 (10) | 0.82718 (11) | 0.0477 (4) | |
O6 | 0.09929 (18) | 0.14478 (9) | 0.83555 (10) | 0.0359 (3) | |
N1 | −0.0358 (2) | 0.31090 (12) | 0.75891 (12) | 0.0374 (4) | |
N2 | −0.1649 (2) | 0.30501 (13) | 0.68392 (13) | 0.0435 (4) | |
N3 | 0.1202 (2) | 0.34112 (12) | 0.74030 (13) | 0.0426 (4) | |
H3 | 0.222267 | 0.350335 | 0.779575 | 0.051* | |
N4 | 0.1601 (2) | 0.33299 (11) | 0.96562 (11) | 0.0344 (4) | |
N5 | 0.1596 (3) | 0.42687 (12) | 0.97157 (12) | 0.0421 (4) | |
N6 | 0.3092 (3) | 0.46220 (13) | 1.03207 (13) | 0.0481 (5) | |
H6 | 0.338370 | 0.522214 | 1.046881 | 0.058* | |
N10 | −0.2928 (2) | 0.14824 (11) | 0.81479 (11) | 0.0316 (4) | |
C1 | 0.1002 (3) | 0.02925 (15) | 0.67820 (15) | 0.0407 (5) | |
C2 | 0.1773 (4) | −0.0567 (2) | 0.6597 (2) | 0.0694 (8) | |
H2 | 0.168755 | −0.105273 | 0.695437 | 0.083* | |
C3 | 0.2682 (5) | −0.0708 (3) | 0.5871 (3) | 0.0953 (12) | |
H3A | 0.323420 | −0.127941 | 0.575531 | 0.114* | |
C4 | 0.2756 (4) | 0.0009 (3) | 0.5325 (2) | 0.0891 (11) | |
H4A | 0.333480 | −0.009027 | 0.483230 | 0.107* | |
C5 | 0.2002 (4) | 0.0844 (3) | 0.5499 (2) | 0.0775 (9) | |
H5 | 0.207219 | 0.132418 | 0.513342 | 0.093* | |
C6 | 0.1125 (4) | 0.09900 (19) | 0.62221 (17) | 0.0568 (6) | |
H6A | 0.060220 | 0.157067 | 0.633634 | 0.068* | |
C7 | −0.2342 (3) | 0.08818 (13) | 0.73759 (13) | 0.0342 (4) | |
H7A | −0.242846 | 0.123287 | 0.685100 | 0.041* | |
H7B | −0.312610 | 0.030742 | 0.717894 | 0.041* | |
C8 | −0.4400 (3) | 0.21247 (14) | 0.78471 (15) | 0.0364 (5) | |
H8A | −0.555535 | 0.181491 | 0.784763 | 0.044* | |
H8B | −0.441006 | 0.223997 | 0.721824 | 0.044* | |
C9 | −0.4163 (3) | 0.30816 (14) | 0.84836 (14) | 0.0352 (4) | |
C10 | −0.3395 (3) | 0.08937 (15) | 0.88264 (14) | 0.0398 (5) | |
H10A | −0.355049 | 0.022944 | 0.854848 | 0.048* | |
H10B | −0.454127 | 0.108574 | 0.896454 | 0.048* | |
C11 | −0.1990 (3) | 0.09783 (14) | 0.97153 (14) | 0.0359 (4) | |
C12 | −0.0903 (4) | 0.33164 (15) | 0.61468 (16) | 0.0479 (6) | |
C13 | −0.1688 (5) | 0.3351 (2) | 0.5210 (2) | 0.0781 (9) | |
H13 | −0.291141 | 0.319494 | 0.496573 | 0.094* | |
C14 | −0.0567 (8) | 0.3623 (3) | 0.4679 (2) | 0.1141 (15) | |
H14 | −0.103623 | 0.365014 | 0.405342 | 0.137* | |
C15 | 0.1263 (8) | 0.3864 (3) | 0.5043 (3) | 0.1173 (16) | |
H15 | 0.196461 | 0.405710 | 0.465057 | 0.141* | |
C16 | 0.2073 (5) | 0.3829 (2) | 0.5947 (3) | 0.0865 (10) | |
H16 | 0.330116 | 0.398091 | 0.618044 | 0.104* | |
C17 | 0.0921 (4) | 0.35481 (15) | 0.65044 (17) | 0.0486 (6) | |
C18 | 0.4099 (3) | 0.39200 (17) | 1.06754 (15) | 0.0439 (5) | |
C19 | 0.5708 (3) | 0.3909 (2) | 1.13410 (17) | 0.0602 (7) | |
H19 | 0.637276 | 0.446797 | 1.162961 | 0.072* | |
C20 | 0.6243 (3) | 0.3031 (2) | 1.15410 (19) | 0.0672 (8) | |
H20 | 0.729652 | 0.299478 | 1.198757 | 0.081* | |
C21 | 0.5271 (3) | 0.2173 (2) | 1.11010 (18) | 0.0575 (6) | |
H21 | 0.570254 | 0.159174 | 1.126133 | 0.069* | |
C22 | 0.3703 (3) | 0.21803 (17) | 1.04418 (16) | 0.0448 (5) | |
H22 | 0.305819 | 0.161858 | 1.014559 | 0.054* | |
C23 | 0.3128 (3) | 0.30737 (15) | 1.02394 (14) | 0.0360 (5) | |
N7 | 0.4354 (4) | 0.24725 (17) | 0.3610 (2) | 0.0865 (9) | |
N8 | 0.3398 (4) | 0.17053 (17) | 0.3187 (2) | 0.0874 (9) | |
N9 | 0.2049 (3) | 0.19459 (15) | 0.25306 (18) | 0.0672 (6) | |
H9 | 0.125578 | 0.154709 | 0.216782 | 0.081* | |
C24 | 0.1059 (4) | 0.3510 (2) | 0.1986 (2) | 0.0626 (7) | |
H24 | 0.006926 | 0.328408 | 0.151491 | 0.075* | |
C25 | 0.1578 (5) | 0.4475 (2) | 0.2201 (3) | 0.0749 (9) | |
H25 | 0.090204 | 0.491257 | 0.187424 | 0.090* | |
C26 | 0.3083 (5) | 0.4801 (2) | 0.2892 (3) | 0.0767 (9) | |
H26 | 0.339739 | 0.545220 | 0.300696 | 0.092* | |
C27 | 0.4112 (4) | 0.4206 (2) | 0.3407 (2) | 0.0727 (8) | |
H27 | 0.511455 | 0.443467 | 0.387029 | 0.087* | |
C28 | 0.3593 (4) | 0.32319 (18) | 0.3209 (2) | 0.0599 (7) | |
C29 | 0.2101 (3) | 0.29056 (17) | 0.25143 (19) | 0.0518 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co1 | 0.02873 (15) | 0.02622 (14) | 0.03550 (16) | −0.00256 (11) | 0.00329 (11) | 0.00159 (10) |
P1 | 0.0386 (3) | 0.0257 (2) | 0.0332 (3) | 0.0004 (2) | 0.0023 (2) | 0.0028 (2) |
O1 | 0.0327 (8) | 0.0417 (8) | 0.0708 (11) | 0.0047 (7) | 0.0110 (7) | 0.0048 (8) |
O2 | 0.0314 (7) | 0.0325 (7) | 0.0490 (9) | −0.0011 (6) | 0.0058 (6) | −0.0040 (6) |
O3 | 0.0383 (8) | 0.0373 (7) | 0.0375 (8) | −0.0059 (7) | 0.0032 (6) | 0.0065 (6) |
O4 | 0.0542 (10) | 0.0431 (8) | 0.0457 (9) | −0.0082 (8) | 0.0020 (7) | 0.0169 (7) |
O5 | 0.0572 (10) | 0.0328 (8) | 0.0483 (9) | −0.0044 (7) | −0.0027 (7) | 0.0121 (7) |
O6 | 0.0342 (7) | 0.0310 (7) | 0.0401 (8) | 0.0000 (6) | 0.0062 (6) | −0.0007 (6) |
N1 | 0.0343 (9) | 0.0331 (9) | 0.0456 (10) | 0.0023 (8) | 0.0066 (8) | 0.0112 (7) |
N2 | 0.0395 (10) | 0.0384 (9) | 0.0497 (11) | −0.0001 (8) | 0.0006 (8) | 0.0109 (8) |
N3 | 0.0363 (10) | 0.0382 (9) | 0.0521 (11) | −0.0049 (8) | 0.0073 (8) | 0.0066 (8) |
N4 | 0.0342 (9) | 0.0272 (8) | 0.0400 (9) | −0.0047 (7) | 0.0072 (7) | 0.0004 (7) |
N5 | 0.0500 (11) | 0.0310 (9) | 0.0429 (10) | −0.0093 (8) | 0.0095 (8) | −0.0011 (7) |
N6 | 0.0599 (12) | 0.0349 (10) | 0.0453 (11) | −0.0215 (9) | 0.0099 (9) | −0.0035 (8) |
N10 | 0.0315 (9) | 0.0291 (8) | 0.0316 (8) | −0.0023 (7) | 0.0024 (7) | 0.0031 (6) |
C1 | 0.0389 (12) | 0.0399 (11) | 0.0380 (12) | 0.0033 (10) | 0.0028 (9) | −0.0054 (9) |
C2 | 0.0746 (19) | 0.0618 (17) | 0.0636 (18) | 0.0280 (15) | 0.0042 (14) | −0.0077 (13) |
C3 | 0.078 (2) | 0.114 (3) | 0.082 (2) | 0.049 (2) | 0.0116 (18) | −0.030 (2) |
C4 | 0.0503 (17) | 0.149 (3) | 0.059 (2) | −0.001 (2) | 0.0168 (15) | −0.026 (2) |
C5 | 0.074 (2) | 0.104 (2) | 0.0548 (17) | −0.0217 (19) | 0.0271 (15) | −0.0042 (16) |
C6 | 0.0680 (17) | 0.0545 (14) | 0.0505 (14) | 0.0003 (13) | 0.0209 (12) | 0.0034 (11) |
C7 | 0.0377 (11) | 0.0277 (9) | 0.0337 (10) | −0.0039 (8) | 0.0027 (8) | 0.0006 (8) |
C8 | 0.0287 (10) | 0.0353 (10) | 0.0418 (11) | −0.0030 (9) | 0.0015 (8) | 0.0043 (9) |
C9 | 0.0327 (11) | 0.0338 (10) | 0.0409 (11) | −0.0028 (9) | 0.0109 (9) | 0.0073 (9) |
C10 | 0.0393 (12) | 0.0379 (11) | 0.0409 (12) | −0.0093 (9) | 0.0071 (9) | 0.0056 (9) |
C11 | 0.0397 (11) | 0.0310 (10) | 0.0380 (11) | 0.0020 (9) | 0.0102 (9) | 0.0052 (8) |
C12 | 0.0632 (15) | 0.0338 (11) | 0.0459 (13) | 0.0003 (11) | 0.0074 (11) | 0.0100 (10) |
C13 | 0.114 (3) | 0.0591 (17) | 0.0522 (16) | −0.0011 (18) | −0.0044 (16) | 0.0136 (13) |
C14 | 0.207 (5) | 0.086 (3) | 0.051 (2) | −0.012 (3) | 0.029 (2) | 0.0192 (18) |
C15 | 0.191 (5) | 0.097 (3) | 0.090 (3) | −0.013 (3) | 0.085 (3) | 0.024 (2) |
C16 | 0.107 (3) | 0.072 (2) | 0.096 (2) | −0.0171 (19) | 0.059 (2) | 0.0131 (18) |
C17 | 0.0624 (15) | 0.0345 (11) | 0.0542 (14) | −0.0015 (11) | 0.0227 (12) | 0.0093 (10) |
C18 | 0.0390 (12) | 0.0523 (13) | 0.0384 (12) | −0.0177 (11) | 0.0104 (9) | −0.0015 (10) |
C19 | 0.0446 (14) | 0.0790 (18) | 0.0490 (14) | −0.0255 (14) | 0.0005 (11) | 0.0001 (13) |
C20 | 0.0337 (13) | 0.108 (2) | 0.0543 (16) | −0.0042 (15) | −0.0009 (11) | 0.0083 (16) |
C21 | 0.0448 (14) | 0.0717 (17) | 0.0573 (16) | 0.0143 (13) | 0.0110 (12) | 0.0123 (13) |
C22 | 0.0384 (12) | 0.0482 (13) | 0.0468 (13) | 0.0023 (10) | 0.0093 (10) | 0.0027 (10) |
C23 | 0.0325 (10) | 0.0402 (11) | 0.0336 (11) | −0.0068 (9) | 0.0078 (8) | −0.0009 (8) |
N7 | 0.0813 (18) | 0.0538 (14) | 0.109 (2) | −0.0115 (13) | −0.0140 (15) | 0.0136 (14) |
N8 | 0.0901 (19) | 0.0463 (13) | 0.113 (2) | −0.0089 (13) | −0.0093 (16) | 0.0186 (13) |
N9 | 0.0651 (14) | 0.0432 (11) | 0.0872 (16) | −0.0120 (11) | 0.0050 (13) | 0.0087 (11) |
C24 | 0.0531 (15) | 0.0686 (17) | 0.0759 (18) | 0.0093 (13) | 0.0313 (13) | 0.0163 (14) |
C25 | 0.078 (2) | 0.0608 (16) | 0.107 (2) | 0.0278 (15) | 0.0513 (18) | 0.0305 (16) |
C26 | 0.081 (2) | 0.0429 (14) | 0.118 (2) | 0.0052 (15) | 0.0486 (19) | 0.0099 (15) |
C27 | 0.0689 (18) | 0.0461 (14) | 0.103 (2) | −0.0099 (14) | 0.0268 (16) | 0.0001 (14) |
C28 | 0.0584 (15) | 0.0408 (13) | 0.0812 (18) | −0.0044 (12) | 0.0181 (14) | 0.0063 (12) |
C29 | 0.0498 (14) | 0.0404 (12) | 0.0703 (16) | −0.0025 (11) | 0.0243 (12) | 0.0080 (11) |
Co1—N1 | 2.2350 (17) | C8—H8A | 0.9700 |
Co1—N4 | 2.0742 (15) | C8—H8B | 0.9700 |
Co1—N10 | 2.2274 (15) | C8—C9 | 1.532 (3) |
Co1—O2 | 2.0320 (15) | C10—H10A | 0.9700 |
Co1—O3 | 2.1602 (14) | C10—H10B | 0.9700 |
Co1—O6 | 2.0399 (14) | C10—C11 | 1.501 (3) |
P1—O5 | 1.5171 (15) | C12—C13 | 1.403 (4) |
P1—O6 | 1.5115 (13) | C12—C17 | 1.385 (3) |
P1—C1 | 1.801 (2) | C13—H13 | 0.9300 |
P1—C7 | 1.839 (2) | C13—C14 | 1.359 (6) |
O1—C9 | 1.244 (2) | C14—H14 | 0.9300 |
O2—C9 | 1.269 (2) | C14—C15 | 1.393 (6) |
O3—C11 | 1.230 (2) | C15—H15 | 0.9300 |
O4—H4 | 0.8200 | C15—C16 | 1.364 (6) |
O4—C11 | 1.298 (2) | C16—H16 | 0.9300 |
N1—N2 | 1.310 (2) | C16—C17 | 1.410 (4) |
N1—N3 | 1.343 (2) | C18—C19 | 1.399 (3) |
N2—C12 | 1.366 (3) | C18—C23 | 1.397 (3) |
N3—H3 | 0.8600 | C19—H19 | 0.9300 |
N3—C17 | 1.350 (3) | C19—C20 | 1.363 (4) |
N4—N5 | 1.318 (2) | C20—H20 | 0.9300 |
N4—C23 | 1.375 (3) | C20—C21 | 1.412 (4) |
N5—N6 | 1.330 (3) | C21—H21 | 0.9300 |
N6—H6 | 0.8600 | C21—C22 | 1.371 (3) |
N6—C18 | 1.356 (3) | C22—H22 | 0.9300 |
N10—C7 | 1.491 (3) | C22—C23 | 1.392 (3) |
N10—C8 | 1.483 (3) | N7—N8 | 1.301 (3) |
N10—C10 | 1.481 (2) | N7—C28 | 1.372 (4) |
C1—C2 | 1.381 (3) | N8—N9 | 1.337 (3) |
C1—C6 | 1.384 (3) | N9—H9 | 0.8600 |
C2—H2 | 0.9300 | N9—C29 | 1.359 (3) |
C2—C3 | 1.396 (5) | C24—H24 | 0.9300 |
C3—H3A | 0.9300 | C24—C25 | 1.388 (4) |
C3—C4 | 1.385 (5) | C24—C29 | 1.380 (4) |
C4—H4A | 0.9300 | C25—H25 | 0.9300 |
C4—C5 | 1.341 (5) | C25—C26 | 1.388 (5) |
C5—H5 | 0.9300 | C26—H26 | 0.9300 |
C5—C6 | 1.378 (4) | C26—C27 | 1.356 (4) |
C6—H6A | 0.9300 | C27—H27 | 0.9300 |
C7—H7A | 0.9700 | C27—C28 | 1.400 (4) |
C7—H7B | 0.9700 | C28—C29 | 1.384 (4) |
O2—Co1—O3 | 95.92 (6) | C9—C8—H8A | 109.3 |
O2—Co1—O6 | 163.36 (6) | C9—C8—H8B | 109.3 |
O2—Co1—N1 | 89.43 (6) | O1—C9—O2 | 122.73 (19) |
O2—Co1—N4 | 99.74 (6) | O1—C9—C8 | 118.80 (18) |
O2—Co1—N10 | 79.23 (6) | O2—C9—C8 | 118.43 (18) |
O3—Co1—N1 | 170.82 (6) | N10—C10—H10A | 108.9 |
O3—Co1—N10 | 79.15 (5) | N10—C10—H10B | 108.9 |
O6—Co1—O3 | 89.22 (6) | N10—C10—C11 | 113.31 (16) |
O6—Co1—N1 | 83.63 (6) | H10A—C10—H10B | 107.7 |
O6—Co1—N4 | 95.57 (6) | C11—C10—H10A | 108.9 |
O6—Co1—N10 | 86.25 (6) | C11—C10—H10B | 108.9 |
N4—Co1—O3 | 94.76 (6) | O3—C11—O4 | 124.72 (19) |
N4—Co1—N1 | 91.67 (6) | O3—C11—C10 | 123.09 (18) |
N4—Co1—N10 | 173.64 (6) | O4—C11—C10 | 112.14 (17) |
N10—Co1—N1 | 94.59 (6) | N2—C12—C13 | 130.2 (3) |
O5—P1—C1 | 109.77 (10) | N2—C12—C17 | 108.4 (2) |
O5—P1—C7 | 109.02 (9) | C17—C12—C13 | 121.4 (3) |
O6—P1—O5 | 115.55 (8) | C12—C13—H13 | 121.8 |
O6—P1—C1 | 107.76 (9) | C14—C13—C12 | 116.4 (4) |
O6—P1—C7 | 105.87 (8) | C14—C13—H13 | 121.8 |
C1—P1—C7 | 108.64 (10) | C13—C14—H14 | 119.0 |
C9—O2—Co1 | 117.27 (13) | C13—C14—C15 | 122.1 (3) |
C11—O3—Co1 | 114.42 (13) | C15—C14—H14 | 119.0 |
C11—O4—H4 | 109.5 | C14—C15—H15 | 118.5 |
P1—O6—Co1 | 116.94 (8) | C16—C15—C14 | 123.0 (3) |
N2—N1—Co1 | 124.52 (13) | C16—C15—H15 | 118.5 |
N2—N1—N3 | 109.50 (17) | C15—C16—H16 | 122.3 |
N3—N1—Co1 | 124.31 (13) | C15—C16—C17 | 115.4 (4) |
N1—N2—C12 | 107.56 (18) | C17—C16—H16 | 122.3 |
N1—N3—H3 | 125.3 | N3—C17—C12 | 105.1 (2) |
N1—N3—C17 | 109.50 (18) | N3—C17—C16 | 133.1 (3) |
C17—N3—H3 | 125.3 | C12—C17—C16 | 121.8 (3) |
N5—N4—Co1 | 121.69 (14) | N6—C18—C19 | 134.2 (2) |
N5—N4—C23 | 109.44 (16) | N6—C18—C23 | 104.45 (18) |
C23—N4—Co1 | 128.68 (13) | C23—C18—C19 | 121.3 (2) |
N4—N5—N6 | 107.51 (18) | C18—C19—H19 | 122.0 |
N5—N6—H6 | 124.2 | C20—C19—C18 | 116.0 (2) |
N5—N6—C18 | 111.69 (17) | C20—C19—H19 | 122.0 |
C18—N6—H6 | 124.2 | C19—C20—H20 | 118.5 |
C7—N10—Co1 | 106.01 (11) | C19—C20—C21 | 123.0 (2) |
C8—N10—Co1 | 104.74 (11) | C21—C20—H20 | 118.5 |
C8—N10—C7 | 114.68 (15) | C20—C21—H21 | 119.4 |
C10—N10—Co1 | 108.48 (11) | C22—C21—C20 | 121.2 (3) |
C10—N10—C7 | 111.46 (15) | C22—C21—H21 | 119.4 |
C10—N10—C8 | 110.95 (16) | C21—C22—H22 | 121.8 |
C2—C1—P1 | 121.9 (2) | C21—C22—C23 | 116.5 (2) |
C2—C1—C6 | 118.3 (3) | C23—C22—H22 | 121.8 |
C6—C1—P1 | 119.54 (18) | N4—C23—C18 | 106.90 (19) |
C1—C2—H2 | 120.0 | N4—C23—C22 | 130.98 (18) |
C1—C2—C3 | 119.9 (3) | C22—C23—C18 | 122.1 (2) |
C3—C2—H2 | 120.0 | N8—N7—C28 | 107.3 (2) |
C2—C3—H3A | 120.2 | N7—N8—N9 | 109.2 (2) |
C4—C3—C2 | 119.6 (3) | N8—N9—H9 | 124.6 |
C4—C3—H3A | 120.2 | N8—N9—C29 | 110.9 (2) |
C3—C4—H4A | 119.6 | C29—N9—H9 | 124.6 |
C5—C4—C3 | 120.8 (3) | C25—C24—H24 | 122.0 |
C5—C4—H4A | 119.6 | C29—C24—H24 | 122.0 |
C4—C5—H5 | 120.1 | C29—C24—C25 | 116.0 (3) |
C4—C5—C6 | 119.8 (3) | C24—C25—H25 | 119.3 |
C6—C5—H5 | 120.1 | C24—C25—C26 | 121.5 (3) |
C1—C6—H6A | 119.2 | C26—C25—H25 | 119.3 |
C5—C6—C1 | 121.6 (3) | C25—C26—H26 | 118.8 |
C5—C6—H6A | 119.2 | C27—C26—C25 | 122.5 (3) |
P1—C7—H7A | 109.8 | C27—C26—H26 | 118.8 |
P1—C7—H7B | 109.8 | C26—C27—H27 | 121.6 |
N10—C7—P1 | 109.28 (12) | C26—C27—C28 | 116.8 (3) |
N10—C7—H7A | 109.8 | C28—C27—H27 | 121.6 |
N10—C7—H7B | 109.8 | N7—C28—C27 | 129.9 (3) |
H7A—C7—H7B | 108.3 | N7—C28—C29 | 109.4 (2) |
N10—C8—H8A | 109.3 | C29—C28—C27 | 120.7 (3) |
N10—C8—H8B | 109.3 | N9—C29—C24 | 134.3 (3) |
N10—C8—C9 | 111.71 (16) | N9—C29—C28 | 103.2 (2) |
H8A—C8—H8B | 107.9 | C24—C29—C28 | 122.5 (2) |
Co1—O2—C9—O1 | −169.65 (15) | C3—C4—C5—C6 | −0.8 (5) |
Co1—O2—C9—C8 | 7.9 (2) | C4—C5—C6—C1 | 0.2 (4) |
Co1—O3—C11—O4 | 172.11 (17) | C6—C1—C2—C3 | 1.3 (4) |
Co1—O3—C11—C10 | −10.6 (3) | C7—P1—O6—Co1 | 19.78 (11) |
Co1—N1—N2—C12 | −165.41 (14) | C7—P1—C1—C2 | −124.5 (2) |
Co1—N1—N3—C17 | 165.45 (14) | C7—P1—C1—C6 | 60.4 (2) |
Co1—N4—N5—N6 | 175.84 (13) | C7—N10—C8—C9 | −143.90 (16) |
Co1—N4—C23—C18 | −175.15 (14) | C7—N10—C10—C11 | 105.60 (19) |
Co1—N4—C23—C22 | 2.4 (3) | C8—N10—C7—P1 | 154.75 (13) |
Co1—N10—C7—P1 | 39.72 (13) | C8—N10—C10—C11 | −125.29 (18) |
Co1—N10—C8—C9 | −28.13 (18) | C10—N10—C7—P1 | −78.13 (16) |
Co1—N10—C10—C11 | −10.8 (2) | C10—N10—C8—C9 | 88.72 (19) |
P1—C1—C2—C3 | −173.8 (2) | C12—C13—C14—C15 | −0.5 (6) |
P1—C1—C6—C5 | 174.7 (2) | C13—C12—C17—N3 | −178.4 (2) |
O5—P1—O6—Co1 | −100.98 (11) | C13—C12—C17—C16 | 0.0 (4) |
O5—P1—C1—C2 | −5.4 (2) | C13—C14—C15—C16 | 1.2 (7) |
O5—P1—C1—C6 | 179.53 (18) | C14—C15—C16—C17 | −1.2 (6) |
O5—P1—C7—N10 | 84.17 (14) | C15—C16—C17—N3 | 178.5 (3) |
O6—P1—C1—C2 | 121.2 (2) | C15—C16—C17—C12 | 0.6 (5) |
O6—P1—C1—C6 | −53.9 (2) | C17—C12—C13—C14 | −0.1 (4) |
O6—P1—C7—N10 | −40.74 (14) | C18—C19—C20—C21 | 1.0 (4) |
N1—N2—C12—C13 | 178.0 (3) | C19—C18—C23—N4 | 177.9 (2) |
N1—N2—C12—C17 | −0.2 (3) | C19—C18—C23—C22 | 0.0 (3) |
N1—N3—C17—C12 | 0.2 (2) | C19—C20—C21—C22 | −0.4 (4) |
N1—N3—C17—C16 | −177.9 (3) | C20—C21—C22—C23 | −0.4 (4) |
N2—N1—N3—C17 | −0.3 (2) | C21—C22—C23—N4 | −176.7 (2) |
N2—C12—C13—C14 | −178.1 (3) | C21—C22—C23—C18 | 0.6 (3) |
N2—C12—C17—N3 | 0.0 (3) | C23—N4—N5—N6 | 0.3 (2) |
N2—C12—C17—C16 | 178.4 (2) | C23—C18—C19—C20 | −0.8 (4) |
N3—N1—N2—C12 | 0.3 (2) | N7—N8—N9—C29 | −0.1 (4) |
N4—N5—N6—C18 | −0.5 (2) | N7—C28—C29—N9 | −0.4 (3) |
N5—N4—C23—C18 | 0.0 (2) | N7—C28—C29—C24 | −179.9 (3) |
N5—N4—C23—C22 | 177.6 (2) | N8—N7—C28—C27 | −179.7 (3) |
N5—N6—C18—C19 | −177.3 (3) | N8—N7—C28—C29 | 0.4 (4) |
N5—N6—C18—C23 | 0.5 (2) | N8—N9—C29—C24 | 179.7 (3) |
N6—C18—C19—C20 | 176.7 (3) | N8—N9—C29—C28 | 0.3 (3) |
N6—C18—C23—N4 | −0.3 (2) | C24—C25—C26—C27 | −1.2 (5) |
N6—C18—C23—C22 | −178.1 (2) | C25—C24—C29—N9 | 179.7 (3) |
N10—C8—C9—O1 | −166.14 (18) | C25—C24—C29—C28 | −1.0 (4) |
N10—C8—C9—O2 | 16.2 (3) | C25—C26—C27—C28 | 0.2 (5) |
N10—C10—C11—O3 | 15.2 (3) | C26—C27—C28—N7 | −179.7 (3) |
N10—C10—C11—O4 | −167.21 (18) | C26—C27—C28—C29 | 0.3 (5) |
C1—P1—O6—Co1 | 135.88 (10) | C27—C28—C29—N9 | 179.6 (3) |
C1—P1—C7—N10 | −156.24 (12) | C27—C28—C29—C24 | 0.1 (4) |
C1—C2—C3—C4 | −1.9 (5) | C28—N7—N8—N9 | −0.2 (4) |
C2—C1—C6—C5 | −0.5 (4) | C29—C24—C25—C26 | 1.5 (4) |
C2—C3—C4—C5 | 1.6 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H4···O5i | 0.82 | 1.70 | 2.507 (2) | 168 |
N3—H3···O1ii | 0.86 | 1.80 | 2.651 (2) | 169 |
N6—H6···O1iii | 0.86 | 2.44 | 3.173 (2) | 144 |
N6—H6···O2iii | 0.86 | 2.24 | 3.012 (2) | 149 |
N9—H9···O5iv | 0.86 | 1.94 | 2.743 (3) | 156 |
C3—H3A···N7v | 0.93 | 2.62 | 3.440 (5) | 147 |
C26—H26···N2vi | 0.93 | 2.53 | 3.251 (4) | 134 |
Symmetry codes: (i) −x, −y, −z+2; (ii) x+1, y, z; (iii) −x, −y+1, −z+2; (iv) −x, −y, −z+1; (v) −x+1, −y, −z+1; (vi) −x, −y+1, −z+1. |
Funding information
Funding for this research was provided by the key research projects of Henan Province Higher Education (No. 17A430027).
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