Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S010827011302341X/lg3117sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827011302341X/lg3117Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827011302341X/lg3117IIsup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827011302341X/lg3117IIIsup4.hkl |
CCDC references: 969469; 969470; 969471
Recently, the syntheses and diffraction experiments were described for some racemic mixed-amide phosphinates having an (N1)P(═O)(O)(N2) skeleton, where two different amide groups are bonded to the P atom (Pourayoubi, Karimi Ahmadabad et al., 2011; Pourayoubi, Rheingold et al., 2011; Sabbaghi et al., 2011). The systematic study of such molecules may be useful for: (i) gaining insight into the reason why a particular amide group makes a stronger or weaker P—N bond; (ii) the preparation of racemic compounds (Pourayoubi et al., 2007); (iii) finding new synthesis and purification procedures (Pourayoubi, Rheingold et al., 2011); and (iv) comparison between the hydrogen-bond patterns for finding empirical rules to predict hydrogen-bond patterns based on molecular structure (Toghraee et al., 2011; Pourayoubi et al., 2012).
The strategy for the synthesis of racemic compounds with an (N1)P(═ O)(O)(N2) molecular skeleton and containing a heterocyclic segment including an X—P—N (X = NR' and O) fragment can be based on the reaction of a Cl2P(O)(OR) initial compound with a diamine of the type NHR–Y–NHR' (Gholivand et al., 2007), or the reaction of [R1R2N]P(O)Cl2 with an amino alcohol of the type NHR–Z–OH (Holmes et al., 1984) [Y and Z are the hydrocarbon fragments between two functional groups in NHR–Y–NHR' and NHR–Z–OH compounds, respectively].
In the case of acyclic compounds, Ghadimi et al. (2009) used a step-by-step nucleophilic substitution, using Cl2P(O)(OR) as a starting compound and its reaction with an NHR1R2 amine in the presence of an HCl scavenger (such as C5H5N, or an excess of an NHR1R2 amine as two moles of amine per one mole of P—Cl bond) in a suitable solvent to yield ClP(O)(OR)(NR1R2) compounds. For such a reaction, usually, a suitable solvent has low solubility of the C5H5NHCl (or [R1R2NH2]Cl alkyl/aryl ammonium chloride) by-product, while the solubility of ClP(O)(OR)(NR1R2) is good in this solvent. In such a case, the by-product is simply removed by filtering.
The well-known purification method in the preparation of (R1R2N)2P(O)(OR) amidophosphinates is the dissolution of the above-mentioned by-product(s) in H2O (Sabbaghi et al., 2010). This strategy is not suitable for the purification of a ClP(O)(OR)(NR1R2) compound, as the P—Cl bond is sensitive to moisture.
After purification, ClP(O)(OR)(NR1R2) reacts with an NHR3R4 amine (1:2 molar ratio) to yield the racemic (R3R4N)P(O)(OR)(NR1R2) mixed-amido phosphinate; the by-product of this step, [R3R4NH2]Cl, is removed by dissolving in H2O.
As examples where this or similar procedures have been used, we can mention [(CH3)2N][p-CH3—C6H4O]P(O)X, where X = NHC(CH3)3, p-CH3—C6H4NH (Ghadimi et al., 2009) and NHCH(CH3)2 (Pourayoubi et al., 2007). Another example is the compound [(ClC2H4)2N][C6H5O]P(O)[NHC6H5], which was studied by X-ray crystallography (Orji et al., 1994). When using [(CH3)2N][p-CH3—C6H4—O]P(O)Cl as a starting material, some new compounds were obtained, for example with the (N)P(O)(O)(C) skeleton, such as [(CH3)2N][p-CH3—C6H4O]P(O)CN (Ghadimi et al., 2007), also characterized by X-ray crystallography.
As was noted in the literature (Pourayoubi, Karimi Ahmadabad et al., 2011; Pourayoubi, Rheingold et al., 2011; Sabbaghi et al., 2011), the p-toluidine hydrochloride salt is relatively insoluble in CH3CN and also in CHCl3 (although the degree of solubility can be affected by the other starting materials used in the preparation method). The reaction of C6H5OP(O)Cl2 and p-CH3—C6H4NH2 (1:2 molar ratio) was performed in CH3CN (at ice-bath temperature), the [p-CH3—C6H4NH3]Cl by-product was simply filtered off and the racemic ClP(O)[OC6H5][NHC6H4-p-CH3] product was obtained from the solution.
Up to now, this starting racemate compound has been used for the preparation of rac-LP(O)(OC6H5)(NHC6H4-p-CH3) [L = NHC6H11 (Sabbaghi et al., 2011), NHC(CH3)3 (Pourayoubi, Rheingold et al., 2011) and NHCH2C6H5 (Pourayoubi, Karimi Ahmadabad et al., 2011). Here, we used the above-mentioned starting racemic compound to study the syntheses and crystal structures of rac-phenyl (N-methylcyclohexylamido)(p-tolylamido)phosphinate, (I) (Fig. 1), and rac-phenyl (allylamido)(p-tolylamido)phosphinate, (II) (Fig. 2).
Moreover, as the cyclohexylamine hydrochloride salt is also relatively insoluble in CH3CN (and in CHCl3), we used cyclohexylamine to obtain the starting phosphorus–chlorine compound ClP(O)(OC6H5)(NH-cyclo-C6H11) for the first time. This starting compound was used for the synthesis of rac-phenyl (benzylamido)(cyclohexylamido)phosphinate, (III) (Fig. 3). All three compounds crystallize in centrosymmetric space groups and the racemic character is reflected by the symmetry.
For the synthesis of (Cl)P(O)(OC6H5)(NHC6H4-p-CH3). a solution of 4-CH3–C6H4NH2 (20.0 mmol) in dry chloroform (Volume?) was added to a solution of (C6H5O)P(O)Cl2 (10.0 mmol) in the same solvent (Volume?) at 273 K. After stirring for 5 h, the solid which formed was filtered off. The product was obtained from the filtrate after removing the solvent in vacuo.
For the synthesis of (I), a solution of N-methyl-cyclohexylamine (4.6 mmol) in dry chloroform (Volume?) was added to a solution of (Cl)P(O)(OC6H5)(NHC6H4-p-CH3) (2.3 mmol) in the same solvent (Volume?) at 273 K. After stirring for 5 h, the solvent was removed in vacuo and the solid obtained was washed with distilled water. Single crystals of (I) were obtained from a solution of the product in CHCl3–CH3OH (Solvent ratio?) after slow evaporation at room temperature. [In the CIF, the crystal shape for this compound is missing (_exptl_crystal_description ''). Please supply details]
For the synthesis of (II), a solution of allylamine (6.0 mmol) in dry chloroform (Volume?) was added to a solution of (Cl)P(O)(OC6H5)(NHC6H4-p-CH3) (3.0 mmol) in the same solvent (Volume?) at 273 K. After stirring for 5 h, the solvent was removed in vacuo and the solid obtained was washed with distilled water. Single crystals of (II) were obtained from a solution of the product in CH3CN–CHCl3 (Solvent ratio?) after slow evaporation at room temperature.
For the synthesis of (Cl)P(O)(OC6H5)(NHC6H11), a solution of C6H11NH2 (20.0 mmol) in dry chloroform (Volume?) was added to a solution of (C6H5O)P(O)Cl2 (10.0 mmol) in same solvent (Volume?) at 273 K. After stirring for 5 h, the solid was filtered off. The product was obtained from the filtrate after removing the solvent in vacuo.
For the synthesis of (III), a solution of benzylamine (4.6 mmol) in dry chloroform (Volume?) was added to a solution of (Cl)P(O)(OC6H5)(NHC6H11) (2.3 mmol) in the same solvent (Volume?) at 273 K. After stirring for 5 h, the solvent was removed in vacuo and the solid obtained was washed with distilled water. Single crystals of (III) were obtained from a solution of the product in CH3CN–CHCl3 (Solvent ratio?) after slow evaporation at room temperature.
Crystal data, data collection and structure refinement details are summarized in Table 1. All H atoms were discernible in difference Fourier maps and could be refined to a reasonable geometry. H atoms bonded to C atoms were kept in ideal positions, with C—H = 0.96 Å, while the positions of H atoms bonded to N atoms were refined freely. In both cases, Uiso(H) = 1.2Ueq(C,N) and, for (I) and (II), 1.5Ueq(C) for methyl H atoms. All non-H atoms were refined using harmonic refinement. In (II), the H-atom positions of the disordered methyl group were found in a difference Fourier map, their geometry was fixed to tetrahedral and the occupancy was refined with a final ratio of 0.58 (2):0.42 (2).
In compounds (I), (II) and (III), the P atom exhibits a distorted tetrahedral environment, as has been noted for the other amidophosphoesters (Pourayoubi, Karimi Ahmadabad et al., 2011; Pourayoubi, Rheingold et al., 2011). In (I), the bond angles at the P atom are in the range 94.80 (7)–116.36 (7)°.
As can be seen in Table 2, the p-tolylamide part in (I) and (II) makes a longer P1—N1 bond relative to the P1—N17 bonds received from the N-methylcyclohexylamide and allylamide parts. This may be attributed to the electron-withdrawing effect of the phenyl group of the p-tolylamide substituent, which causes P—N bond weakening. Moreover, the hybridization of the C atom attached to the N atom in the p-tolylamide group is different from those of the N-methylcyclohexylamide and allylamide groups (sp2 and sp3). This is in accordance with the previously reported compounds rac-LP(O)(OC6H5)(NHC6H4-p-CH3) [L = NHC6H11 (Sabbaghi et al., 2011), NHC(CH3)3 (Pourayoubi, Rheingold et al., 2011) and NHCH2C6H5 (Pourayoubi, Karimi Ahmadabad et al., 2011)]. The P—N (p-tolylamido) bond is also longer than the related P—N (L) bond. In (III), though, the difference between the P—N bond lengths related to the cyclohexylamide and benzylamide fragments is not significant (see Table 2). Such a comparison may be useful for a study of the strengths of different P—N bonds in a given molecule in order to obtain an insight into the electronic effect produced by different amide fragments. For example, a comparison between the P—N bond lengths related to the dimethylamide fragment and the other amide fragments indicates that, in compounds of the general formula [(CH3)2N][p-CH3—C6H4O]P(O)X, the P—N(dimethylamide) bond is longer than the P—N(X) bond [(X) = NHC(CH3)3 (Ghadimi et al., 2009) and NHCH(CH3)2 (Pourayoubi et al., 2007)] and shorter than the P—N(NHC6H4-p-CH3) bond (Ghadimi et al., 2009).
In all three structures, the phosphoryl O atom takes part with the N—H unit in hydrogen-bonding interactions, viz. an N—H···OP hydrogen bond for (I) (Table 3) and (N—H)(N—H)···O═P hydrogen bonds for (II) (Table 4) and (III) (Table 5), building linear arrangements along [001] for (I) and [010] for (III), and a ladder arrangement (Fig. 4) along [100] for (II). The phenoxy O atom and the N atoms bonded to the P atom do not take part in hydrogen bonding as acceptors in (I), (II) and (III).
For related literature, see: Ghadimi et al. (2007, 2009); Gholivand et al. (2007); Holmes et al. (1984); Orji et al. (1994); Pourayoubi et al. (2007, 2012); Pourayoubi, Karimi Ahmadabad & Nečas (2011); Pourayoubi, Rheingold, Chen, Karimi Ahmadabad & Tarahhomi (2011); Sabbaghi et al. (2010, 2011); Toghraee et al. (2011).
For all compounds, data collection: CrysAlis PRO (Agilent, 2013); cell refinement: CrysAlis PRO (Agilent, 2013); data reduction: CrysAlis PRO (Agilent, 2013). Program(s) used to solve structure: Superflip (Palatinus & Chapuis, 2007) for (I), (II); SUPERFLIP (Palatinus & Chapuis, 2007) for (III). For all compounds, program(s) used to refine structure: JANA2006 (Petříček et al., 2006). Molecular graphics: DIAMOND (Brandenburg & Putz, 2005) for (I), (III); DIAMOND (Brandenburg & Putz, 2005) and Mercury (Macrae et al., 2008) for (II). For all compounds, software used to prepare material for publication: JANA2006 (Petříček et al., 2006).
C20H27N2O2P | F(000) = 768 |
Mr = 358.4 | Dx = 1.238 Mg m−3 |
Monoclinic, P21/c | Cu Kα radiation, λ = 1.5418 Å |
Hall symbol: -P 2ycb | Cell parameters from 6300 reflections |
a = 12.9137 (6) Å | θ = 4.6–66.8° |
b = 14.6324 (4) Å | µ = 1.39 mm−1 |
c = 10.3114 (4) Å | T = 120 K |
β = 99.484 (4)° | Prism, colourless |
V = 1921.79 (13) Å3 | 0.44 × 0.22 × 0.12 mm |
Z = 4 |
Agilent Xcalibur Gemini Ultra diffractometer with Atlas detector | 3420 independent reflections |
Radiation source: Enhance Ultra (Cu) X-ray Source | 2928 reflections with I > 3σ(I) |
Mirror monochromator | Rint = 0.031 |
Detector resolution: 10.3784 pixels mm-1 | θmax = 67°, θmin = 3.5° |
ω scans | h = −14→15 |
Absorption correction: analytical [CrysAlis PRO (Agilent, 2013); using a multifaceted crystal model based on expressions derived by Clark & Reid (1995)] | k = −17→16 |
Tmin = 0.706, Tmax = 0.877 | l = −12→11 |
11561 measured reflections |
Refinement on F2 | 105 constraints |
R[F2 > 2σ(F2)] = 0.040 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.111 | Weighting scheme based on measured s.u.'s w = 1/(σ2(I) + 0.0016I2) |
S = 1.75 | (Δ/σ)max = 0.013 |
3420 reflections | Δρmax = 0.55 e Å−3 |
229 parameters | Δρmin = −0.37 e Å−3 |
0 restraints |
C20H27N2O2P | V = 1921.79 (13) Å3 |
Mr = 358.4 | Z = 4 |
Monoclinic, P21/c | Cu Kα radiation |
a = 12.9137 (6) Å | µ = 1.39 mm−1 |
b = 14.6324 (4) Å | T = 120 K |
c = 10.3114 (4) Å | 0.44 × 0.22 × 0.12 mm |
β = 99.484 (4)° |
Agilent Xcalibur Gemini Ultra diffractometer with Atlas detector | 3420 independent reflections |
Absorption correction: analytical [CrysAlis PRO (Agilent, 2013); using a multifaceted crystal model based on expressions derived by Clark & Reid (1995)] | 2928 reflections with I > 3σ(I) |
Tmin = 0.706, Tmax = 0.877 | Rint = 0.031 |
11561 measured reflections |
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.111 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.75 | Δρmax = 0.55 e Å−3 |
3420 reflections | Δρmin = −0.37 e Å−3 |
229 parameters |
Experimental. CrysAlis PRO (Agilent Technologies, 2013) Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET) (compiled Feb 1 2013,16:14:44) Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by Clark & Reid (1995). |
x | y | z | Uiso*/Ueq | ||
P1 | 0.92505 (3) | 0.22177 (3) | 0.12180 (4) | 0.02155 (14) | |
N1 | 1.01936 (11) | 0.22570 (10) | 0.03315 (15) | 0.0251 (4) | |
C2 | 1.12027 (13) | 0.19066 (11) | 0.06727 (16) | 0.0233 (5) | |
C3 | 1.18909 (13) | 0.19806 (11) | −0.02420 (17) | 0.0258 (5) | |
C4 | 1.29106 (13) | 0.16683 (12) | 0.00592 (18) | 0.0294 (5) | |
C5 | 1.32966 (14) | 0.12681 (13) | 0.1265 (2) | 0.0323 (5) | |
C6 | 1.26075 (14) | 0.11880 (13) | 0.21662 (18) | 0.0319 (6) | |
C7 | 1.15761 (13) | 0.14976 (12) | 0.18874 (17) | 0.0281 (5) | |
C8 | 1.44047 (16) | 0.09078 (16) | 0.1563 (2) | 0.0454 (7) | |
O9 | 0.84656 (9) | 0.28686 (8) | 0.02516 (12) | 0.0288 (4) | |
C10 | 0.74259 (13) | 0.29973 (12) | 0.03959 (17) | 0.0279 (5) | |
C11 | 0.66557 (16) | 0.26084 (13) | −0.0524 (2) | 0.0364 (6) | |
C12 | 0.56139 (17) | 0.27827 (15) | −0.0460 (3) | 0.0486 (8) | |
C13 | 0.53456 (18) | 0.33402 (18) | 0.0503 (3) | 0.0544 (8) | |
C14 | 0.6125 (2) | 0.37254 (18) | 0.1414 (2) | 0.0540 (8) | |
C15 | 0.71737 (17) | 0.35658 (15) | 0.1363 (2) | 0.0402 (6) | |
O16 | 0.95110 (10) | 0.25560 (8) | 0.25732 (12) | 0.0283 (4) | |
N17 | 0.87575 (11) | 0.11905 (9) | 0.11646 (14) | 0.0253 (4) | |
C18 | 0.83979 (12) | 0.07626 (11) | 0.23119 (16) | 0.0234 (5) | |
C19 | 0.91248 (13) | −0.00213 (12) | 0.28778 (18) | 0.0290 (5) | |
C20 | 0.87503 (14) | −0.04334 (13) | 0.40807 (19) | 0.0321 (5) | |
C21 | 0.76305 (14) | −0.07870 (12) | 0.37201 (18) | 0.0301 (5) | |
C22 | 0.68872 (13) | −0.00268 (12) | 0.31399 (19) | 0.0302 (5) | |
C23 | 0.72622 (13) | 0.04343 (12) | 0.19689 (18) | 0.0275 (5) | |
C24 | 0.86069 (16) | 0.06812 (13) | −0.00773 (18) | 0.0331 (6) | |
H1C3 | 1.165023 | 0.225126 | −0.108593 | 0.031* | |
H1C4 | 1.336682 | 0.172925 | −0.058271 | 0.0353* | |
H1C6 | 1.285182 | 0.0911 | 0.300471 | 0.0383* | |
H1C7 | 1.112005 | 0.143072 | 0.252838 | 0.0337* | |
H1C8 | 1.458208 | 0.078111 | 0.248684 | 0.0681* | |
H2C8 | 1.445749 | 0.035652 | 0.10738 | 0.0681* | |
H3C8 | 1.487992 | 0.135657 | 0.13198 | 0.0681* | |
H1C11 | 0.68413 | 0.222092 | −0.120092 | 0.0437* | |
H1C12 | 0.507325 | 0.251167 | −0.109353 | 0.0583* | |
H1C13 | 0.462061 | 0.346108 | 0.05414 | 0.0653* | |
H1C14 | 0.593701 | 0.410961 | 0.209344 | 0.0648* | |
H1C15 | 0.771418 | 0.384522 | 0.198816 | 0.0483* | |
H1C18 | 0.842586 | 0.122356 | 0.297929 | 0.028* | |
H1C19 | 0.912802 | −0.04852 | 0.222015 | 0.0348* | |
H2C19 | 0.982692 | 0.020613 | 0.312445 | 0.0348* | |
H1C20 | 0.920598 | −0.092723 | 0.441723 | 0.0385* | |
H2C20 | 0.877759 | 0.002341 | 0.475379 | 0.0385* | |
H1C21 | 0.740111 | −0.102893 | 0.449046 | 0.0361* | |
H2C21 | 0.761251 | −0.127409 | 0.309316 | 0.0361* | |
H1C22 | 0.683221 | 0.042115 | 0.380535 | 0.0363* | |
H2C22 | 0.619749 | −0.027462 | 0.286591 | 0.0363* | |
H1C23 | 0.720209 | 0.001297 | 0.124666 | 0.033* | |
H2C23 | 0.68146 | 0.094393 | 0.16815 | 0.033* | |
H1C24 | 0.901843 | 0.095599 | −0.066782 | 0.0496* | |
H2C24 | 0.882516 | 0.005905 | 0.008876 | 0.0496* | |
H3C24 | 0.78784 | 0.069513 | −0.046572 | 0.0496* | |
H1N1 | 1.0030 (17) | 0.2382 (15) | −0.050 (3) | 0.0301* |
U11 | U22 | U33 | U12 | U13 | U23 | |
P1 | 0.0277 (2) | 0.0199 (2) | 0.0169 (2) | −0.00163 (14) | 0.00304 (16) | −0.00052 (15) |
N1 | 0.0290 (7) | 0.0292 (8) | 0.0172 (7) | −0.0022 (5) | 0.0043 (6) | 0.0014 (6) |
C2 | 0.0295 (8) | 0.0187 (8) | 0.0213 (8) | −0.0053 (6) | 0.0034 (6) | −0.0037 (7) |
C3 | 0.0301 (8) | 0.0217 (8) | 0.0257 (8) | −0.0036 (6) | 0.0043 (6) | −0.0009 (7) |
C4 | 0.0300 (8) | 0.0249 (8) | 0.0332 (9) | −0.0046 (6) | 0.0052 (7) | −0.0038 (7) |
C5 | 0.0278 (8) | 0.0279 (9) | 0.0390 (10) | 0.0001 (7) | −0.0011 (7) | −0.0063 (8) |
C6 | 0.0357 (9) | 0.0301 (10) | 0.0273 (9) | 0.0017 (7) | −0.0024 (7) | −0.0014 (8) |
C7 | 0.0327 (9) | 0.0271 (9) | 0.0243 (8) | −0.0028 (7) | 0.0040 (7) | −0.0040 (7) |
C8 | 0.0333 (10) | 0.0488 (12) | 0.0529 (13) | 0.0081 (9) | 0.0035 (9) | 0.0033 (11) |
O9 | 0.0332 (6) | 0.0290 (6) | 0.0250 (6) | 0.0053 (5) | 0.0075 (5) | 0.0062 (5) |
C10 | 0.0331 (9) | 0.0254 (8) | 0.0262 (9) | 0.0064 (7) | 0.0083 (7) | 0.0082 (7) |
C11 | 0.0443 (10) | 0.0258 (9) | 0.0378 (11) | −0.0005 (7) | 0.0032 (8) | 0.0012 (8) |
C12 | 0.0363 (10) | 0.0438 (12) | 0.0633 (15) | −0.0010 (8) | 0.0011 (10) | 0.0136 (11) |
C13 | 0.0422 (12) | 0.0622 (15) | 0.0616 (15) | 0.0167 (10) | 0.0167 (11) | 0.0245 (13) |
C14 | 0.0635 (15) | 0.0612 (15) | 0.0428 (12) | 0.0317 (12) | 0.0253 (11) | 0.0101 (11) |
C15 | 0.0543 (12) | 0.0389 (11) | 0.0276 (10) | 0.0125 (9) | 0.0071 (9) | 0.0007 (8) |
O16 | 0.0400 (7) | 0.0257 (6) | 0.0194 (6) | −0.0066 (5) | 0.0052 (5) | −0.0023 (5) |
N17 | 0.0354 (7) | 0.0216 (7) | 0.0188 (7) | −0.0048 (5) | 0.0040 (5) | −0.0025 (6) |
C18 | 0.0304 (8) | 0.0189 (8) | 0.0205 (8) | −0.0018 (6) | 0.0034 (6) | −0.0011 (7) |
C19 | 0.0278 (8) | 0.0279 (9) | 0.0300 (9) | 0.0003 (6) | 0.0011 (7) | 0.0045 (7) |
C20 | 0.0364 (9) | 0.0280 (9) | 0.0298 (9) | 0.0004 (7) | −0.0004 (7) | 0.0067 (8) |
C21 | 0.0387 (9) | 0.0223 (8) | 0.0298 (9) | −0.0019 (7) | 0.0071 (7) | 0.0043 (7) |
C22 | 0.0305 (9) | 0.0259 (9) | 0.0348 (10) | −0.0011 (7) | 0.0071 (7) | 0.0006 (8) |
C23 | 0.0289 (8) | 0.0235 (8) | 0.0287 (9) | 0.0023 (6) | 0.0004 (7) | 0.0024 (7) |
C24 | 0.0501 (11) | 0.0268 (9) | 0.0226 (9) | −0.0066 (7) | 0.0070 (7) | −0.0068 (7) |
P1—N1 | 1.6398 (16) | C13—C14 | 1.379 (3) |
P1—O9 | 1.6106 (13) | C13—H1C13 | 0.96 |
P1—O16 | 1.4683 (12) | C14—C15 | 1.384 (3) |
P1—N17 | 1.6297 (14) | C14—H1C14 | 0.96 |
N1—C2 | 1.391 (2) | C15—H1C15 | 0.96 |
N1—H1N1 | 0.87 (3) | N17—C18 | 1.479 (2) |
C2—C3 | 1.403 (3) | N17—C24 | 1.467 (2) |
C2—C7 | 1.400 (2) | C18—C19 | 1.535 (2) |
C3—C4 | 1.380 (2) | C18—C23 | 1.528 (2) |
C3—H1C3 | 0.96 | C18—H1C18 | 0.96 |
C4—C5 | 1.390 (3) | C19—C20 | 1.528 (3) |
C4—H1C4 | 0.96 | C19—H1C19 | 0.96 |
C5—C6 | 1.394 (3) | C19—H2C19 | 0.96 |
C5—C8 | 1.508 (3) | C20—C21 | 1.523 (2) |
C6—C7 | 1.391 (2) | C20—H1C20 | 0.96 |
C6—H1C6 | 0.96 | C20—H2C20 | 0.96 |
C7—H1C7 | 0.96 | C21—C22 | 1.526 (2) |
C8—H1C8 | 0.96 | C21—H1C21 | 0.96 |
C8—H2C8 | 0.96 | C21—H2C21 | 0.96 |
C8—H3C8 | 0.96 | C22—C23 | 1.530 (3) |
O9—C10 | 1.388 (2) | C22—H1C22 | 0.96 |
C10—C11 | 1.379 (3) | C22—H2C22 | 0.96 |
C10—C15 | 1.378 (3) | C23—H1C23 | 0.96 |
C11—C12 | 1.381 (3) | C23—H2C23 | 0.96 |
C11—H1C11 | 0.96 | C24—H1C24 | 0.96 |
C12—C13 | 1.373 (4) | C24—H2C24 | 0.96 |
C12—H1C12 | 0.96 | C24—H3C24 | 0.96 |
N1—P1—O9 | 94.80 (7) | C10—C15—C14 | 118.61 (19) |
N1—P1—O16 | 116.36 (7) | C10—C15—H1C15 | 120.7 |
N1—P1—N17 | 109.59 (8) | C14—C15—H1C15 | 120.7 |
O9—P1—O16 | 114.31 (7) | P1—N17—C18 | 122.39 (11) |
O9—P1—N17 | 108.78 (7) | P1—N17—C24 | 119.54 (12) |
O16—P1—N17 | 111.71 (7) | C18—N17—C24 | 117.99 (13) |
P1—N1—C2 | 126.67 (12) | N17—C18—C19 | 111.55 (14) |
P1—N1—H1N1 | 118.5 (15) | N17—C18—C23 | 111.32 (13) |
C2—N1—H1N1 | 113.1 (15) | N17—C18—H1C18 | 107.23 |
N1—C2—C3 | 118.21 (14) | C19—C18—C23 | 110.88 (13) |
N1—C2—C7 | 123.65 (16) | C19—C18—H1C18 | 107.7 |
C3—C2—C7 | 118.13 (15) | C23—C18—H1C18 | 107.95 |
C2—C3—C4 | 120.66 (16) | C18—C19—C20 | 110.36 (15) |
C2—C3—H1C3 | 119.67 | C18—C19—H1C19 | 109.47 |
C4—C3—H1C3 | 119.67 | C18—C19—H2C19 | 109.47 |
C3—C4—C5 | 121.94 (18) | C20—C19—H1C19 | 109.47 |
C3—C4—H1C4 | 119.03 | C20—C19—H2C19 | 109.47 |
C5—C4—H1C4 | 119.03 | H1C19—C19—H2C19 | 108.57 |
C4—C5—C6 | 117.23 (16) | C19—C20—C21 | 110.53 (14) |
C4—C5—C8 | 121.21 (19) | C19—C20—H1C20 | 109.47 |
C6—C5—C8 | 121.53 (18) | C19—C20—H2C20 | 109.47 |
C5—C6—C7 | 121.97 (17) | C21—C20—H1C20 | 109.47 |
C5—C6—H1C6 | 119.01 | C21—C20—H2C20 | 109.47 |
C7—C6—H1C6 | 119.01 | H1C20—C20—H2C20 | 108.39 |
C2—C7—C6 | 120.06 (17) | C20—C21—C22 | 111.03 (15) |
C2—C7—H1C7 | 119.97 | C20—C21—H1C21 | 109.47 |
C6—C7—H1C7 | 119.97 | C20—C21—H2C21 | 109.47 |
C5—C8—H1C8 | 109.47 | C22—C21—H1C21 | 109.47 |
C5—C8—H2C8 | 109.47 | C22—C21—H2C21 | 109.47 |
C5—C8—H3C8 | 109.47 | H1C21—C21—H2C21 | 107.87 |
H1C8—C8—H2C8 | 109.47 | C21—C22—C23 | 111.75 (15) |
H1C8—C8—H3C8 | 109.47 | C21—C22—H1C22 | 109.47 |
H2C8—C8—H3C8 | 109.47 | C21—C22—H2C22 | 109.47 |
O9—C10—C11 | 118.11 (17) | C23—C22—H1C22 | 109.47 |
O9—C10—C15 | 120.51 (16) | C23—C22—H2C22 | 109.47 |
C11—C10—C15 | 121.13 (18) | H1C22—C22—H2C22 | 107.1 |
C10—C11—C12 | 119.2 (2) | C18—C23—C22 | 111.87 (14) |
C10—C11—H1C11 | 120.38 | C18—C23—H1C23 | 109.47 |
C12—C11—H1C11 | 120.38 | C18—C23—H2C23 | 109.47 |
C11—C12—C13 | 120.5 (2) | C22—C23—H1C23 | 109.47 |
C11—C12—H1C12 | 119.73 | C22—C23—H2C23 | 109.47 |
C13—C12—H1C12 | 119.73 | H1C23—C23—H2C23 | 106.96 |
C12—C13—C14 | 119.5 (2) | N17—C24—H1C24 | 109.47 |
C12—C13—H1C13 | 120.24 | N17—C24—H2C24 | 109.47 |
C14—C13—H1C13 | 120.24 | N17—C24—H3C24 | 109.47 |
C13—C14—C15 | 120.9 (2) | H1C24—C24—H2C24 | 109.47 |
C13—C14—H1C14 | 119.53 | H1C24—C24—H3C24 | 109.47 |
C15—C14—H1C14 | 119.54 | H2C24—C24—H3C24 | 109.47 |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N1···O16i | 0.87 (3) | 1.99 (3) | 2.8487 (19) | 169 (2) |
Symmetry code: (i) x, −y+1/2, z−1/2. |
C16H19N2O2P | F(000) = 640 |
Mr = 302.3 | Dx = 1.291 Mg m−3 |
Monoclinic, P21/c | Cu Kα radiation, λ = 1.5418 Å |
Hall symbol: -P 2ycb | Cell parameters from 5797 reflections |
a = 5.4168 (2) Å | θ = 3.1–67.0° |
b = 20.3357 (9) Å | µ = 1.62 mm−1 |
c = 14.2398 (6) Å | T = 120 K |
β = 97.489 (3)° | Prism, colourless |
V = 1555.20 (11) Å3 | 0.65 × 0.10 × 0.07 mm |
Z = 4 |
Agilent Xcalibur Gemini Ultra diffractometer with Atlas detector | 2745 independent reflections |
Radiation source: Enhance Ultra (Cu) X-ray Source | 2333 reflections with I > 3σ(I) |
Mirror monochromator | Rint = 0.026 |
Detector resolution: 10.3784 pixels mm-1 | θmax = 67.2°, θmin = 3.8° |
ω scans | h = −6→6 |
Absorption correction: analytical [CrysAlis PRO (Agilent, 2013); using a multifaceted crystal model based on expressions derived by Clark & Reid (1995)] | k = −24→24 |
Tmin = 0.613, Tmax = 0.904 | l = −16→16 |
10454 measured reflections |
Refinement on F2 | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.028 | Weighting scheme based on measured s.u.'s w = 1/(σ2(I) + 0.0004I2) |
wR(F2) = 0.070 | (Δ/σ)max = 0.019 |
S = 1.81 | Δρmax = 0.16 e Å−3 |
2745 reflections | Δρmin = −0.26 e Å−3 |
198 parameters | Extinction correction: B-C type 1 Gaussian isotropic (Becker & Coppens, 1974) |
0 restraints | Extinction coefficient: 1070 (170) |
87 constraints |
C16H19N2O2P | V = 1555.20 (11) Å3 |
Mr = 302.3 | Z = 4 |
Monoclinic, P21/c | Cu Kα radiation |
a = 5.4168 (2) Å | µ = 1.62 mm−1 |
b = 20.3357 (9) Å | T = 120 K |
c = 14.2398 (6) Å | 0.65 × 0.10 × 0.07 mm |
β = 97.489 (3)° |
Agilent Xcalibur Gemini Ultra diffractometer with Atlas detector | 2745 independent reflections |
Absorption correction: analytical [CrysAlis PRO (Agilent, 2013); using a multifaceted crystal model based on expressions derived by Clark & Reid (1995)] | 2333 reflections with I > 3σ(I) |
Tmin = 0.613, Tmax = 0.904 | Rint = 0.026 |
10454 measured reflections |
R[F2 > 2σ(F2)] = 0.028 | 0 restraints |
wR(F2) = 0.070 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.81 | Δρmax = 0.16 e Å−3 |
2745 reflections | Δρmin = −0.26 e Å−3 |
198 parameters |
Experimental. CrysAlis PRO (Agilent Technologies, 2013) Version 1.171.35.21 (release 20-01-2012 CrysAlis171 .NET) (compiled Jan 23 2012,18:06:46) Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by Clark & Reid (1995). |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
P1 | 0.18488 (6) | 0.050592 (16) | 0.12760 (2) | 0.01772 (11) | |
N1 | 0.4263 (2) | 0.00759 (6) | 0.17371 (9) | 0.0211 (3) | |
C2 | 0.4578 (2) | −0.02454 (6) | 0.26308 (10) | 0.0209 (4) | |
C3 | 0.2879 (3) | −0.01881 (7) | 0.32763 (11) | 0.0267 (4) | |
C4 | 0.3286 (3) | −0.05143 (8) | 0.41368 (11) | 0.0302 (5) | |
C5 | 0.5360 (3) | −0.09073 (7) | 0.43834 (11) | 0.0301 (5) | |
C6 | 0.7029 (3) | −0.09599 (7) | 0.37260 (12) | 0.0324 (5) | |
C7 | 0.6668 (3) | −0.06367 (7) | 0.28651 (11) | 0.0276 (4) | |
C8 | 0.5764 (4) | −0.12675 (9) | 0.53139 (13) | 0.0445 (6) | |
O9 | 0.19758 (16) | 0.11180 (4) | 0.19856 (7) | 0.0205 (3) | |
C10 | 0.0084 (2) | 0.15911 (6) | 0.19621 (10) | 0.0203 (4) | |
C11 | −0.1630 (2) | 0.15344 (7) | 0.25954 (10) | 0.0234 (4) | |
C12 | −0.3391 (3) | 0.20295 (7) | 0.26244 (11) | 0.0271 (4) | |
C13 | −0.3425 (3) | 0.25665 (7) | 0.20307 (11) | 0.0293 (5) | |
C14 | −0.1713 (3) | 0.26086 (7) | 0.13908 (12) | 0.0287 (5) | |
C15 | 0.0069 (3) | 0.21214 (7) | 0.13540 (11) | 0.0248 (4) | |
O16 | −0.05512 (17) | 0.01539 (4) | 0.12077 (7) | 0.0212 (3) | |
N17 | 0.2421 (2) | 0.07885 (6) | 0.02639 (9) | 0.0213 (3) | |
C18 | 0.4585 (3) | 0.11949 (7) | 0.01298 (10) | 0.0231 (4) | |
C19 | 0.4016 (2) | 0.17120 (7) | −0.06164 (10) | 0.0276 (4) | |
C20 | 0.1826 (2) | 0.18363 (8) | −0.10972 (12) | 0.0349 (5) | |
H1C3 | 0.141812 | 0.007832 | 0.312621 | 0.0321* | |
H1C4 | 0.209455 | −0.046676 | 0.457565 | 0.0362* | |
H1C6 | 0.848234 | −0.122956 | 0.387411 | 0.0389* | |
H1C7 | 0.786537 | −0.068285 | 0.242815 | 0.0331* | |
H1C8 | 0.48946 | −0.104452 | 0.576643 | 0.0667* | 0.58 (2) |
H2C8 | 0.514335 | −0.170849 | 0.52273 | 0.0667* | 0.58 (2) |
H3C8 | 0.751119 | −0.127927 | 0.554159 | 0.0667* | 0.58 (2) |
H1C8' | 0.420119 | −0.143386 | 0.546166 | 0.0667* | 0.42 (2) |
H2C8' | 0.689223 | −0.162681 | 0.526954 | 0.0667* | 0.42 (2) |
H3C8' | 0.645572 | −0.097161 | 0.580413 | 0.0667* | 0.42 (2) |
H1C11 | −0.160725 | 0.116033 | 0.300773 | 0.0281* | |
H1C12 | −0.459333 | 0.199726 | 0.306159 | 0.0325* | |
H1C13 | −0.463015 | 0.29094 | 0.206089 | 0.0352* | |
H1C14 | −0.175758 | 0.297786 | 0.096892 | 0.0345* | |
H1C15 | 0.126701 | 0.215237 | 0.091492 | 0.0297* | |
H1N17 | 0.181 (3) | 0.0547 (8) | −0.0218 (13) | 0.0255* | |
H1C18 | 0.590475 | 0.091843 | −0.003039 | 0.0277* | |
H2C18 | 0.522375 | 0.139952 | 0.071923 | 0.0277* | |
H1C19 | 0.538375 | 0.197845 | −0.075719 | 0.0332* | |
H1C20 | 0.165555 | 0.217769 | −0.156689 | 0.0419* | |
H2C20 | 0.03963 | 0.158574 | −0.097868 | 0.0419* | |
H1N1 | 0.555 (3) | 0.0116 (8) | 0.1526 (12) | 0.0253* |
U11 | U22 | U33 | U12 | U13 | U23 | |
P1 | 0.01564 (18) | 0.01839 (18) | 0.01964 (19) | −0.00093 (13) | 0.00424 (13) | −0.00026 (13) |
N1 | 0.0157 (6) | 0.0238 (6) | 0.0252 (6) | 0.0002 (5) | 0.0077 (5) | 0.0025 (5) |
C2 | 0.0205 (7) | 0.0179 (6) | 0.0239 (7) | −0.0025 (5) | 0.0014 (5) | −0.0002 (5) |
C3 | 0.0236 (7) | 0.0291 (7) | 0.0279 (8) | 0.0026 (6) | 0.0052 (6) | 0.0023 (6) |
C4 | 0.0332 (8) | 0.0332 (8) | 0.0246 (8) | −0.0038 (7) | 0.0060 (6) | 0.0011 (6) |
C5 | 0.0380 (8) | 0.0225 (7) | 0.0277 (8) | −0.0068 (7) | −0.0042 (6) | 0.0025 (6) |
C6 | 0.0297 (8) | 0.0244 (7) | 0.0409 (9) | 0.0043 (6) | −0.0040 (7) | 0.0040 (7) |
C7 | 0.0240 (7) | 0.0243 (7) | 0.0349 (8) | 0.0020 (6) | 0.0057 (6) | 0.0013 (6) |
C8 | 0.0609 (12) | 0.0354 (9) | 0.0334 (10) | −0.0058 (8) | −0.0076 (8) | 0.0087 (8) |
O9 | 0.0168 (5) | 0.0212 (5) | 0.0235 (5) | 0.0017 (4) | 0.0024 (4) | −0.0024 (4) |
C10 | 0.0169 (6) | 0.0199 (6) | 0.0233 (7) | 0.0001 (5) | −0.0003 (5) | −0.0046 (5) |
C11 | 0.0226 (7) | 0.0248 (7) | 0.0231 (7) | 0.0004 (6) | 0.0035 (6) | −0.0006 (6) |
C12 | 0.0223 (7) | 0.0310 (7) | 0.0284 (8) | 0.0020 (6) | 0.0055 (6) | −0.0057 (6) |
C13 | 0.0216 (7) | 0.0250 (7) | 0.0402 (9) | 0.0028 (6) | −0.0002 (6) | −0.0070 (6) |
C14 | 0.0247 (7) | 0.0219 (7) | 0.0386 (9) | −0.0022 (6) | 0.0005 (6) | 0.0040 (6) |
C15 | 0.0204 (7) | 0.0245 (7) | 0.0295 (8) | −0.0034 (6) | 0.0035 (6) | 0.0011 (6) |
O16 | 0.0182 (5) | 0.0227 (5) | 0.0232 (5) | −0.0025 (4) | 0.0055 (4) | −0.0006 (4) |
N17 | 0.0213 (6) | 0.0231 (6) | 0.0196 (6) | −0.0065 (5) | 0.0039 (5) | −0.0012 (5) |
C18 | 0.0186 (7) | 0.0251 (7) | 0.0261 (8) | −0.0043 (6) | 0.0054 (6) | 0.0011 (6) |
C19 | 0.0294 (8) | 0.0269 (7) | 0.0278 (8) | −0.0056 (6) | 0.0081 (6) | 0.0034 (6) |
C20 | 0.0366 (9) | 0.0359 (8) | 0.0320 (9) | −0.0007 (7) | 0.0037 (7) | 0.0105 (7) |
P1—N1 | 1.6375 (12) | C10—C15 | 1.382 (2) |
P1—O9 | 1.5991 (10) | C11—C12 | 1.391 (2) |
P1—O16 | 1.4762 (10) | C11—H1C11 | 0.96 |
P1—N17 | 1.6184 (13) | C12—C13 | 1.380 (2) |
N1—C2 | 1.4208 (18) | C12—H1C12 | 0.96 |
N1—H1N1 | 0.798 (19) | C13—C14 | 1.385 (2) |
C2—C3 | 1.388 (2) | C13—H1C13 | 0.96 |
C2—C7 | 1.3886 (19) | C14—C15 | 1.389 (2) |
C3—C4 | 1.386 (2) | C14—H1C14 | 0.96 |
C3—H1C3 | 0.96 | C15—H1C15 | 0.96 |
C4—C5 | 1.386 (2) | N17—C18 | 1.4672 (18) |
C4—H1C4 | 0.96 | N17—H1N17 | 0.873 (17) |
C5—C6 | 1.388 (2) | C18—C19 | 1.498 (2) |
C5—C8 | 1.505 (2) | C18—H1C18 | 0.96 |
C6—C7 | 1.382 (2) | C18—H2C18 | 0.96 |
C6—H1C6 | 0.96 | C19—C20 | 1.3148 (18) |
C7—H1C7 | 0.96 | C19—H1C19 | 0.96 |
C8—H1C8 | 0.96 | C20—H1C20 | 0.96 |
C8—H2C8 | 0.96 | C20—H2C20 | 0.96 |
C8—H3C8 | 0.96 | H1C8—H1C8' | 0.9559 |
C8—H1C8' | 0.96 | H1C8—H3C8' | 0.8533 |
C8—H2C8' | 0.96 | H2C8—H1C8' | 0.8533 |
C8—H3C8' | 0.96 | H2C8—H2C8' | 0.9559 |
O9—C10 | 1.4027 (16) | H3C8—H2C8' | 0.8533 |
C10—C11 | 1.381 (2) | H3C8—H3C8' | 0.9559 |
N1—P1—O9 | 101.30 (5) | H2C8—C8—H3C8 | 109.47 |
N1—P1—O16 | 114.69 (6) | H1C8'—C8—H2C8' | 109.47 |
N1—P1—N17 | 108.13 (6) | H1C8'—C8—H3C8' | 109.47 |
O9—P1—O16 | 112.59 (5) | H2C8'—C8—H3C8' | 109.47 |
O9—P1—N17 | 106.79 (6) | P1—O9—C10 | 123.21 (8) |
O16—P1—N17 | 112.50 (6) | O9—C10—C11 | 118.57 (12) |
P1—N1—C2 | 126.96 (10) | O9—C10—C15 | 119.65 (12) |
P1—N1—H1N1 | 119.1 (12) | C11—C10—C15 | 121.65 (13) |
C2—N1—H1N1 | 112.0 (12) | C10—C11—C12 | 118.74 (13) |
N1—C2—C3 | 122.82 (12) | C10—C11—H1C11 | 120.63 |
N1—C2—C7 | 118.54 (13) | C12—C11—H1C11 | 120.63 |
C3—C2—C7 | 118.64 (13) | C11—C12—C13 | 120.60 (14) |
C2—C3—C4 | 120.19 (13) | C11—C12—H1C12 | 119.7 |
C2—C3—H1C3 | 119.9 | C13—C12—H1C12 | 119.7 |
C4—C3—H1C3 | 119.9 | C12—C13—C14 | 119.70 (14) |
C3—C4—C5 | 122.03 (15) | C12—C13—H1C13 | 120.15 |
C3—C4—H1C4 | 118.99 | C14—C13—H1C13 | 120.15 |
C5—C4—H1C4 | 118.99 | C13—C14—C15 | 120.60 (14) |
C4—C5—C6 | 116.83 (14) | C13—C14—H1C14 | 119.7 |
C4—C5—C8 | 121.59 (15) | C15—C14—H1C14 | 119.7 |
C6—C5—C8 | 121.57 (14) | C10—C15—C14 | 118.70 (14) |
C5—C6—C7 | 122.16 (14) | C10—C15—H1C15 | 120.65 |
C5—C6—H1C6 | 118.92 | C14—C15—H1C15 | 120.65 |
C7—C6—H1C6 | 118.92 | P1—N17—C18 | 124.40 (9) |
C2—C7—C6 | 120.14 (15) | P1—N17—H1N17 | 113.8 (12) |
C2—C7—H1C7 | 119.93 | C18—N17—H1N17 | 116.2 (12) |
C6—C7—H1C7 | 119.93 | N17—C18—C19 | 113.18 (11) |
C5—C8—H1C8 | 109.47 | N17—C18—H1C18 | 109.47 |
C5—C8—H2C8 | 109.47 | N17—C18—H2C18 | 109.47 |
C5—C8—H3C8 | 109.47 | C19—C18—H1C18 | 109.47 |
C5—C8—H1C8' | 109.47 | C19—C18—H2C18 | 109.47 |
C5—C8—H2C8' | 109.47 | H1C18—C18—H2C18 | 105.48 |
C5—C8—H3C8' | 109.47 | C18—C19—C20 | 126.35 (13) |
H1C8—C8—H2C8 | 109.47 | C18—C19—H1C19 | 116.82 |
H1C8—C8—H3C8 | 109.47 | C20—C19—H1C19 | 116.83 |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N1···O16i | 0.798 (19) | 2.219 (19) | 3.0063 (16) | 169.0 (16) |
N17—H1N17···O16ii | 0.873 (17) | 2.057 (17) | 2.9216 (15) | 170.3 (16) |
Symmetry codes: (i) x+1, y, z; (ii) −x, −y, −z. |
C19H25N2O2P | F(000) = 736 |
Mr = 344.4 | Dx = 1.291 Mg m−3 |
Monoclinic, P21/n | Cu Kα radiation, λ = 1.5418 Å |
Hall symbol: -P 2yabc | Cell parameters from 8367 reflections |
a = 13.3675 (5) Å | θ = 3.5–67.1° |
b = 8.0189 (2) Å | µ = 1.48 mm−1 |
c = 17.4416 (6) Å | T = 120 K |
β = 108.707 (3)° | Prism, colourless |
V = 1770.84 (11) Å3 | 0.17 × 0.12 × 0.10 mm |
Z = 4 |
Agilent Xcalibur Gemini Ultra diffractometer with Atlas detector | 3146 independent reflections |
Radiation source: Enhance Ultra (Cu) X-ray Source | 2774 reflections with I > 3σ(I) |
Mirror monochromator | Rint = 0.024 |
Detector resolution: 10.3784 pixels mm-1 | θmax = 67.1°, θmin = 3.7° |
ω scans | h = −15→15 |
Absorption correction: analytical [CrysAlis PRO (Agilent, 2013); analytical numerical absorption correction based on crystal shape] | k = −9→9 |
Tmin = 0.88, Tmax = 0.917 | l = −20→20 |
12735 measured reflections |
Refinement on F2 | 94 constraints |
R[F2 > 2σ(F2)] = 0.029 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.087 | Weighting scheme based on measured s.u.'s w = 1/(σ2(I) + 0.0016I2) |
S = 1.53 | (Δ/σ)max = 0.002 |
3146 reflections | Δρmax = 0.16 e Å−3 |
223 parameters | Δρmin = −0.23 e Å−3 |
0 restraints |
C19H25N2O2P | V = 1770.84 (11) Å3 |
Mr = 344.4 | Z = 4 |
Monoclinic, P21/n | Cu Kα radiation |
a = 13.3675 (5) Å | µ = 1.48 mm−1 |
b = 8.0189 (2) Å | T = 120 K |
c = 17.4416 (6) Å | 0.17 × 0.12 × 0.10 mm |
β = 108.707 (3)° |
Agilent Xcalibur Gemini Ultra diffractometer with Atlas detector | 3146 independent reflections |
Absorption correction: analytical [CrysAlis PRO (Agilent, 2013); analytical numerical absorption correction based on crystal shape] | 2774 reflections with I > 3σ(I) |
Tmin = 0.88, Tmax = 0.917 | Rint = 0.024 |
12735 measured reflections |
R[F2 > 2σ(F2)] = 0.029 | 0 restraints |
wR(F2) = 0.087 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.53 | Δρmax = 0.16 e Å−3 |
3146 reflections | Δρmin = −0.23 e Å−3 |
223 parameters |
x | y | z | Uiso*/Ueq | ||
P1 | 0.71355 (2) | 0.11093 (4) | 0.189090 (18) | 0.01674 (12) | |
N1 | 0.66090 (8) | 0.28539 (13) | 0.14825 (6) | 0.0194 (3) | |
C2 | 0.58563 (10) | 0.29715 (16) | 0.06605 (7) | 0.0218 (4) | |
C3 | 0.47414 (10) | 0.34243 (16) | 0.06186 (7) | 0.0202 (4) | |
C4 | 0.38903 (11) | 0.27421 (16) | 0.00134 (8) | 0.0255 (4) | |
C5 | 0.28614 (11) | 0.31666 (17) | −0.00480 (9) | 0.0309 (5) | |
C6 | 0.26684 (11) | 0.42688 (17) | 0.05023 (9) | 0.0291 (5) | |
C7 | 0.35120 (11) | 0.49612 (16) | 0.11023 (8) | 0.0250 (4) | |
C8 | 0.45453 (10) | 0.45565 (16) | 0.11581 (8) | 0.0220 (4) | |
O9 | 0.75651 (7) | 0.01290 (10) | 0.12532 (5) | 0.0209 (3) | |
C10 | 0.84955 (10) | 0.05993 (16) | 0.11136 (8) | 0.0197 (4) | |
C11 | 0.84434 (11) | 0.16886 (17) | 0.04868 (8) | 0.0255 (4) | |
C12 | 0.93691 (12) | 0.20763 (18) | 0.03224 (9) | 0.0313 (5) | |
C13 | 1.03197 (12) | 0.13873 (18) | 0.07779 (9) | 0.0321 (5) | |
C14 | 1.03541 (11) | 0.03000 (18) | 0.14028 (9) | 0.0312 (5) | |
C15 | 0.94397 (11) | −0.01049 (17) | 0.15729 (8) | 0.0252 (4) | |
O16 | 0.79798 (7) | 0.13961 (11) | 0.26706 (5) | 0.0220 (3) | |
N17 | 0.61720 (8) | −0.01643 (13) | 0.18485 (7) | 0.0204 (4) | |
C18 | 0.52451 (10) | 0.03001 (15) | 0.20812 (8) | 0.0201 (4) | |
C19 | 0.42742 (10) | −0.05824 (18) | 0.15236 (8) | 0.0252 (4) | |
C20 | 0.32791 (11) | −0.01393 (19) | 0.17285 (9) | 0.0319 (5) | |
C21 | 0.34172 (11) | −0.0506 (2) | 0.26121 (9) | 0.0341 (5) | |
C22 | 0.43866 (12) | 0.03763 (19) | 0.31688 (9) | 0.0320 (5) | |
C23 | 0.53794 (11) | −0.00843 (17) | 0.29628 (9) | 0.0266 (5) | |
H1C2 | 0.584902 | 0.193837 | 0.038069 | 0.0261* | |
H2C2 | 0.611017 | 0.376324 | 0.035348 | 0.0261* | |
H1C4 | 0.401669 | 0.196911 | −0.036564 | 0.0306* | |
H1C5 | 0.228154 | 0.269723 | −0.047199 | 0.0371* | |
H1C6 | 0.195679 | 0.454834 | 0.04672 | 0.0349* | |
H1C7 | 0.338278 | 0.572705 | 0.148303 | 0.0301* | |
H1C8 | 0.51245 | 0.505976 | 0.156993 | 0.0263* | |
H1C11 | 0.778131 | 0.216807 | 0.017123 | 0.0306* | |
H1C12 | 0.93459 | 0.282867 | −0.01111 | 0.0376* | |
H1C13 | 1.095558 | 0.166089 | 0.066206 | 0.0386* | |
H1C14 | 1.101613 | −0.017658 | 0.172033 | 0.0375* | |
H1C15 | 0.946258 | −0.086406 | 0.200379 | 0.0303* | |
H1C18 | 0.516071 | 0.148726 | 0.202415 | 0.0241* | |
H1C19 | 0.418091 | −0.028201 | 0.097216 | 0.0302* | |
H2C19 | 0.438263 | −0.176671 | 0.156645 | 0.0302* | |
H1C20 | 0.269303 | −0.076851 | 0.138885 | 0.0382* | |
H2C20 | 0.312149 | 0.102214 | 0.162088 | 0.0382* | |
H1C21 | 0.280087 | −0.014415 | 0.273467 | 0.0409* | |
H2C21 | 0.348851 | −0.168686 | 0.270407 | 0.0409* | |
H1C22 | 0.447909 | 0.007838 | 0.372041 | 0.0384* | |
H2C22 | 0.428115 | 0.156088 | 0.312102 | 0.0384* | |
H1C23 | 0.55251 | −0.125067 | 0.306332 | 0.0319* | |
H2C23 | 0.597085 | 0.052864 | 0.330611 | 0.0319* | |
H1N1 | 0.6846 (13) | 0.376 (2) | 0.1713 (10) | 0.0233* | |
H1N17 | 0.6347 (13) | −0.121 (2) | 0.1925 (9) | 0.0244* |
U11 | U22 | U33 | U12 | U13 | U23 | |
P1 | 0.01671 (18) | 0.01421 (18) | 0.01837 (19) | 0.00020 (11) | 0.00431 (13) | 0.00039 (11) |
N1 | 0.0202 (5) | 0.0145 (5) | 0.0205 (5) | −0.0008 (4) | 0.0024 (4) | −0.0003 (4) |
C2 | 0.0231 (6) | 0.0223 (6) | 0.0187 (6) | 0.0038 (5) | 0.0051 (5) | 0.0026 (5) |
C3 | 0.0224 (6) | 0.0166 (6) | 0.0201 (6) | 0.0019 (5) | 0.0049 (5) | 0.0046 (5) |
C4 | 0.0279 (7) | 0.0195 (6) | 0.0252 (7) | 0.0017 (5) | 0.0031 (5) | −0.0027 (5) |
C5 | 0.0239 (7) | 0.0240 (7) | 0.0375 (8) | −0.0019 (6) | −0.0002 (6) | −0.0020 (6) |
C6 | 0.0215 (7) | 0.0220 (7) | 0.0440 (9) | 0.0011 (5) | 0.0106 (6) | 0.0048 (6) |
C7 | 0.0295 (7) | 0.0187 (6) | 0.0304 (7) | 0.0010 (5) | 0.0145 (6) | 0.0019 (5) |
C8 | 0.0246 (7) | 0.0183 (6) | 0.0218 (6) | −0.0009 (5) | 0.0059 (5) | 0.0016 (5) |
O9 | 0.0195 (5) | 0.0186 (4) | 0.0260 (5) | −0.0017 (3) | 0.0092 (4) | −0.0033 (3) |
C10 | 0.0200 (6) | 0.0175 (6) | 0.0228 (6) | −0.0015 (5) | 0.0085 (5) | −0.0049 (5) |
C11 | 0.0285 (7) | 0.0237 (7) | 0.0255 (7) | 0.0031 (6) | 0.0102 (5) | 0.0014 (5) |
C12 | 0.0398 (8) | 0.0275 (7) | 0.0330 (8) | −0.0022 (6) | 0.0206 (6) | 0.0009 (6) |
C13 | 0.0295 (7) | 0.0297 (7) | 0.0438 (9) | −0.0057 (6) | 0.0210 (6) | −0.0085 (6) |
C14 | 0.0212 (7) | 0.0314 (8) | 0.0402 (8) | 0.0021 (6) | 0.0086 (6) | −0.0056 (6) |
C15 | 0.0252 (7) | 0.0233 (7) | 0.0266 (7) | 0.0010 (5) | 0.0075 (5) | −0.0005 (5) |
O16 | 0.0223 (5) | 0.0193 (4) | 0.0219 (5) | 0.0007 (3) | 0.0036 (4) | 0.0004 (3) |
N17 | 0.0204 (5) | 0.0141 (5) | 0.0280 (6) | 0.0011 (4) | 0.0098 (4) | 0.0010 (4) |
C18 | 0.0205 (6) | 0.0154 (6) | 0.0256 (7) | 0.0007 (5) | 0.0092 (5) | 0.0000 (5) |
C19 | 0.0224 (7) | 0.0272 (7) | 0.0264 (7) | −0.0019 (5) | 0.0083 (5) | −0.0006 (5) |
C20 | 0.0202 (7) | 0.0391 (8) | 0.0360 (8) | 0.0011 (6) | 0.0086 (6) | 0.0019 (6) |
C21 | 0.0273 (7) | 0.0384 (8) | 0.0429 (9) | 0.0026 (6) | 0.0199 (6) | 0.0049 (7) |
C22 | 0.0387 (8) | 0.0324 (8) | 0.0297 (8) | 0.0037 (6) | 0.0177 (6) | 0.0005 (6) |
C23 | 0.0270 (7) | 0.0272 (7) | 0.0257 (7) | −0.0010 (5) | 0.0087 (5) | −0.0002 (5) |
P1—N1 | 1.6243 (11) | C12—H1C12 | 0.96 |
P1—O9 | 1.6108 (9) | C13—C14 | 1.385 (2) |
P1—O16 | 1.4804 (8) | C13—H1C13 | 0.96 |
P1—N17 | 1.6267 (12) | C14—C15 | 1.386 (2) |
N1—C2 | 1.4667 (14) | C14—H1C14 | 0.96 |
N1—H1N1 | 0.839 (17) | C15—H1C15 | 0.96 |
C2—C3 | 1.5128 (19) | N17—C18 | 1.4702 (19) |
C2—H1C2 | 0.96 | N17—H1N17 | 0.871 (17) |
C2—H2C2 | 0.96 | C18—C19 | 1.5236 (16) |
C3—C4 | 1.3919 (16) | C18—C23 | 1.521 (2) |
C3—C8 | 1.3917 (19) | C18—H1C18 | 0.96 |
C4—C5 | 1.387 (2) | C19—C20 | 1.526 (2) |
C4—H1C4 | 0.96 | C19—H1C19 | 0.96 |
C5—C6 | 1.388 (2) | C19—H2C19 | 0.96 |
C5—H1C5 | 0.96 | C20—C21 | 1.521 (2) |
C6—C7 | 1.3849 (18) | C20—H1C20 | 0.96 |
C6—H1C6 | 0.96 | C20—H2C20 | 0.96 |
C7—C8 | 1.392 (2) | C21—C22 | 1.5218 (19) |
C7—H1C7 | 0.96 | C21—H1C21 | 0.96 |
C8—H1C8 | 0.96 | C21—H2C21 | 0.96 |
O9—C10 | 1.3937 (17) | C22—C23 | 1.527 (2) |
C10—C11 | 1.3835 (19) | C22—H1C22 | 0.96 |
C10—C15 | 1.3803 (17) | C22—H2C22 | 0.96 |
C11—C12 | 1.392 (2) | C23—H1C23 | 0.96 |
C11—H1C11 | 0.96 | C23—H2C23 | 0.96 |
C12—C13 | 1.380 (2) | ||
N1—P1—O9 | 108.53 (5) | C13—C14—C15 | 120.47 (13) |
N1—P1—O16 | 111.38 (5) | C13—C14—H1C14 | 119.76 |
N1—P1—N17 | 107.19 (5) | C15—C14—H1C14 | 119.76 |
O9—P1—O16 | 112.00 (5) | C10—C15—C14 | 119.02 (13) |
O9—P1—N17 | 96.58 (5) | C10—C15—H1C15 | 120.49 |
O16—P1—N17 | 119.90 (6) | C14—C15—H1C15 | 120.49 |
P1—N1—C2 | 123.30 (9) | P1—N17—C18 | 123.61 (9) |
P1—N1—H1N1 | 119.3 (10) | P1—N17—H1N17 | 115.4 (11) |
C2—N1—H1N1 | 116.6 (11) | C18—N17—H1N17 | 114.3 (13) |
N1—C2—C3 | 114.78 (11) | N17—C18—C19 | 109.08 (11) |
N1—C2—H1C2 | 109.47 | N17—C18—C23 | 113.02 (10) |
N1—C2—H2C2 | 109.47 | N17—C18—H1C18 | 107.7 |
C3—C2—H1C2 | 109.47 | C19—C18—C23 | 110.57 (12) |
C3—C2—H2C2 | 109.47 | C19—C18—H1C18 | 110.29 |
H1C2—C2—H2C2 | 103.58 | C23—C18—H1C18 | 106.12 |
C2—C3—C4 | 119.69 (12) | C18—C19—C20 | 111.74 (12) |
C2—C3—C8 | 121.34 (10) | C18—C19—H1C19 | 109.47 |
C4—C3—C8 | 118.93 (12) | C18—C19—H2C19 | 109.47 |
C3—C4—C5 | 120.74 (13) | C20—C19—H1C19 | 109.47 |
C3—C4—H1C4 | 119.63 | C20—C19—H2C19 | 109.47 |
C5—C4—H1C4 | 119.63 | H1C19—C19—H2C19 | 107.1 |
C4—C5—C6 | 120.14 (12) | C19—C20—C21 | 111.15 (11) |
C4—C5—H1C5 | 119.93 | C19—C20—H1C20 | 109.47 |
C6—C5—H1C5 | 119.93 | C19—C20—H2C20 | 109.47 |
C5—C6—C7 | 119.39 (14) | C21—C20—H1C20 | 109.47 |
C5—C6—H1C6 | 120.3 | C21—C20—H2C20 | 109.47 |
C7—C6—H1C6 | 120.3 | H1C20—C20—H2C20 | 107.74 |
C6—C7—C8 | 120.58 (14) | C20—C21—C22 | 111.00 (14) |
C6—C7—H1C7 | 119.71 | C20—C21—H1C21 | 109.47 |
C8—C7—H1C7 | 119.71 | C20—C21—H2C21 | 109.47 |
C3—C8—C7 | 120.19 (11) | C22—C21—H1C21 | 109.47 |
C3—C8—H1C8 | 119.9 | C22—C21—H2C21 | 109.47 |
C7—C8—H1C8 | 119.91 | H1C21—C21—H2C21 | 107.9 |
O9—C10—C11 | 119.16 (11) | C21—C22—C23 | 111.33 (13) |
O9—C10—C15 | 119.28 (12) | C21—C22—H1C22 | 109.47 |
C11—C10—C15 | 121.45 (14) | C21—C22—H2C22 | 109.47 |
C10—C11—C12 | 118.75 (12) | C23—C22—H1C22 | 109.47 |
C10—C11—H1C11 | 120.62 | C23—C22—H2C22 | 109.47 |
C12—C11—H1C11 | 120.63 | H1C22—C22—H2C22 | 107.54 |
C11—C12—C13 | 120.49 (14) | C18—C23—C22 | 111.04 (11) |
C11—C12—H1C12 | 119.76 | C18—C23—H1C23 | 109.47 |
C13—C12—H1C12 | 119.76 | C18—C23—H2C23 | 109.47 |
C12—C13—C14 | 119.82 (16) | C22—C23—H1C23 | 109.47 |
C12—C13—H1C13 | 120.09 | C22—C23—H2C23 | 109.47 |
C14—C13—H1C13 | 120.09 | H1C23—C23—H2C23 | 107.85 |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N1···O16i | 0.839 (17) | 2.351 (17) | 3.1673 (14) | 164.2 (16) |
N17—H1N17···O16ii | 0.871 (17) | 2.140 (17) | 2.9977 (14) | 168.2 (13) |
Symmetry codes: (i) −x+3/2, y+1/2, −z+1/2; (ii) −x+3/2, y−1/2, −z+1/2. |
Experimental details
(I) | (II) | (III) | |
Crystal data | |||
Chemical formula | C20H27N2O2P | C16H19N2O2P | C19H25N2O2P |
Mr | 358.4 | 302.3 | 344.4 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, P21/c | Monoclinic, P21/n |
Temperature (K) | 120 | 120 | 120 |
a, b, c (Å) | 12.9137 (6), 14.6324 (4), 10.3114 (4) | 5.4168 (2), 20.3357 (9), 14.2398 (6) | 13.3675 (5), 8.0189 (2), 17.4416 (6) |
β (°) | 99.484 (4) | 97.489 (3) | 108.707 (3) |
V (Å3) | 1921.79 (13) | 1555.20 (11) | 1770.84 (11) |
Z | 4 | 4 | 4 |
Radiation type | Cu Kα | Cu Kα | Cu Kα |
µ (mm−1) | 1.39 | 1.62 | 1.48 |
Crystal size (mm) | 0.44 × 0.22 × 0.12 | 0.65 × 0.10 × 0.07 | 0.17 × 0.12 × 0.10 |
Data collection | |||
Diffractometer | Agilent Xcalibur Gemini Ultra diffractometer with Atlas detector | Agilent Xcalibur Gemini Ultra diffractometer with Atlas detector | Agilent Xcalibur Gemini Ultra diffractometer with Atlas detector |
Absorption correction | Analytical [CrysAlis PRO (Agilent, 2013); using a multifaceted crystal model based on expressions derived by Clark & Reid (1995)] | Analytical [CrysAlis PRO (Agilent, 2013); using a multifaceted crystal model based on expressions derived by Clark & Reid (1995)] | Analytical [CrysAlis PRO (Agilent, 2013); analytical numerical absorption correction based on crystal shape] |
Tmin, Tmax | 0.706, 0.877 | 0.613, 0.904 | 0.88, 0.917 |
No. of measured, independent and observed [I > 3σ(I)] reflections | 11561, 3420, 2928 | 10454, 2745, 2333 | 12735, 3146, 2774 |
Rint | 0.031 | 0.026 | 0.024 |
(sin θ/λ)max (Å−1) | 0.597 | 0.598 | 0.597 |
Refinement | |||
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.111, 1.75 | 0.028, 0.070, 1.81 | 0.029, 0.087, 1.53 |
No. of reflections | 3420 | 2745 | 3146 |
No. of parameters | 229 | 198 | 223 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.55, −0.37 | 0.16, −0.26 | 0.16, −0.23 |
Computer programs: CrysAlis PRO (Agilent, 2013), Superflip (Palatinus & Chapuis, 2007), SUPERFLIP (Palatinus & Chapuis, 2007), JANA2006 (Petříček et al., 2006), DIAMOND (Brandenburg & Putz, 2005) and Mercury (Macrae et al., 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N1···O16i | 0.87 (3) | 1.99 (3) | 2.8487 (19) | 169 (2) |
Symmetry code: (i) x, −y+1/2, z−1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N1···O16i | 0.798 (19) | 2.219 (19) | 3.0063 (16) | 169.0 (16) |
N17—H1N17···O16ii | 0.873 (17) | 2.057 (17) | 2.9216 (15) | 170.3 (16) |
Symmetry codes: (i) x+1, y, z; (ii) −x, −y, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N1···O16i | 0.839 (17) | 2.351 (17) | 3.1673 (14) | 164.2 (16) |
N17—H1N17···O16ii | 0.871 (17) | 2.140 (17) | 2.9977 (14) | 168.2 (13) |
Symmetry codes: (i) −x+3/2, y+1/2, −z+1/2; (ii) −x+3/2, y−1/2, −z+1/2. |
Parameter | (I) | (II) | (III) |
P1—N1 | 1.6398 (16) | 1.6375 (12) | 1.6243 (11) |
P1—O9 | 1.6106 (13) | 1.5991 (10) | 1.6108 (9) |
P1—O16 | 1.4683 (12) | 1.4762 (10) | 1.4804 (8) |
P1—N17 | 1.6297 (14) | 1.6184 (13) | 1.6267 (12) |
N1—C2 | 1.391 (2) | 1.4208 (18) | 1.4667 (14) |
O9—C10 | 1.388 (2) | 1.4027 (16) | 1.3937 (17) |
N17—C18 | 1.479 (2) | 1.4672 (18) | 1.4702 (19) |
N1—P1—O9 | 94.80 (7) | 101.30 (5) | 108.53 (5) |
N1—P1—O16 | 116.36 (7) | 114.69 (6) | 111.38 (5) |
N1—P1—N17 | 109.59 (8) | 108.13 (6) | 107.19 (5) |
O9—P1—O16 | 114.31 (7) | 112.59 (5) | 112.00 (5) |
O9—P1—N17 | 108.78 (7) | 106.79 (6) | 96.58 (5) |
O16—P1—N17 | 111.71 (7) | 112.50 (6) | 119.90 (6) |
P1—N1—C2 | 126.67 (12) | 126.96 (10) | 123.30 (9) |
O9—C10—C11 | 118.11 (17) | 118.57 (12) | 119.16 (11) |
P1—N17—C18 | 122.39 (11) | 124.40 (9) | 123.61 (9) |
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