Literature DB >> 23424479

P,P-Bis[4-(dimethyl-amino)-phen-yl]-N,N-bis-(propan-2-yl)phosphinic amide.

Stephen J Evans1, C Alicia Renison, D Bradley G Williams, Alfred Muller.   

Abstract

The mol-ecular structure of the title compound, C(22)H(34)N(3)OP, adopts a distorted tetra-hedral geometry at the P atom, with the most noticeable distortion being for the O-P-N angle [117.53 (10)°]. An effective cone angle of 187° was calculated for the compound. In the crystal, weak C-H⋯O inter-actions create infinite chains along [100], whereas C-H⋯π inter-actions propagating in [001] generate a herringbone motif.

Entities:  

Year:  2013        PMID： 23424479      PMCID： PMC3569256          DOI： 10.1107/S1600536812050398

Source DB:  PubMed          Journal:  Acta Crystallogr Sect E Struct Rep Online        ISSN： 1600-5368


Related literature

For the synthesis of ligands derived from phosphinic amides, see: Williams et al. (2009 ▶). For background to DoM technology, see: Snieckus (1990 ▶). For cone angles, see: Tolman (1977 ▶); Otto (2001 ▶).

Experimental

Crystal data

C22H34N3OP M = 387.49 Orthorhombic, a = 6.2960 (4) Å b = 16.6389 (8) Å c = 19.9475 (11) Å V = 2089.7 (2) Å3 Z = 4 Mo Kα radiation μ = 0.15 mm−1 T = 100 K 0.13 × 0.11 × 0.1 mm

Data collection

Bruker X8 APEXII 4K KappaCCD diffractometer Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T min = 0.981, T max = 0.985 18896 measured reflections 5212 independent reflections 3840 reflections with I > 2σ(I) R int = 0.074

Refinement

R[F 2 > 2σ(F 2)] = 0.050 wR(F 2) = 0.110 S = 1.04 5212 reflections 252 parameters H-atom parameters constrained Δρmax = 0.30 e Å−3 Δρmin = −0.35 e Å−3 Absolute structure: Flack (1983 ▶), 2224 Friedel pairs Flack parameter: 0.11 (10) Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT-Plus (Bruker, 2004 ▶); data reduction: SAINT-Plus and XPREP (Bruker, 2004 ▶); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg & Putz, 2005 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶) and WinGX (Farrugia, 2012 ▶). Click here for additional data file. Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812050398/bt6869sup1.cif Click here for additional data file. Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812050398/bt6869Isup2.hkl Click here for additional data file. Supplementary material file. DOI: 10.1107/S1600536812050398/bt6869Isup3.cml Additional supplementary materials: crystallographic information; 3D view; checkCIF report
C22H34N3OPF(000) = 840
Mr = 387.49Dx = 1.232 Mg m−3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 3113 reflections
a = 6.2960 (4) Åθ = 2.4–25.9°
b = 16.6389 (8) ŵ = 0.15 mm−1
c = 19.9475 (11) ÅT = 100 K
V = 2089.7 (2) Å3Prism, colourless
Z = 40.13 × 0.11 × 0.1 mm
Bruker X8 APEXII 4K KappaCCD diffractometer3840 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.074
φ and ω scansθmax = 28.3°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2004)h = −4→8
Tmin = 0.981, Tmax = 0.985k = −19→22
18896 measured reflectionsl = −26→26
5212 independent reflections
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.050H-atom parameters constrained
wR(F2) = 0.110w = 1/[σ2(Fo2) + (0.0467P)2] where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max = 0.002
5212 reflectionsΔρmax = 0.30 e Å−3
252 parametersΔρmin = −0.35 e Å−3
0 restraintsAbsolute structure: Flack (1983), 2224 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.11 (10)
Experimental. The intensity data was collected on a Bruker X8 APEXII 4 K KappaCCD diffractometer using an exposure time of 20 s/frame. A total of 1010 frames were collected with a frame width of 0.5° covering up to θ = 28.33° with 99.9% completeness accomplished.
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.
xyzUiso*/Ueq
C110.7556 (4)−0.08285 (14)0.92323 (10)0.0145 (5)
C120.9663 (4)−0.10305 (14)0.91217 (10)0.0161 (5)
H121.0688−0.06150.90790.019*
C131.0314 (4)−0.18282 (14)0.90711 (11)0.0161 (5)
H131.1769−0.19480.89940.019*
C140.8830 (4)−0.24597 (13)0.91337 (10)0.0162 (5)
C150.6722 (4)−0.22578 (13)0.92635 (11)0.0166 (5)
H150.5697−0.26710.93220.02*
C160.6103 (4)−0.14573 (14)0.93076 (11)0.0164 (5)
H160.4654−0.13340.93910.02*
C170.7881 (4)−0.38862 (14)0.91197 (13)0.0247 (6)
H17A0.6801−0.3820.8770.037*
H17B0.7206−0.3860.95620.037*
H17C0.858−0.44090.90650.037*
C181.1650 (5)−0.34575 (14)0.89615 (11)0.0208 (6)
H18A1.2488−0.3280.93480.031*
H18B1.218−0.31950.85550.031*
H18C1.1775−0.40420.89130.031*
C210.7295 (4)0.05075 (13)1.01511 (11)0.0145 (5)
C220.9324 (4)0.04153 (13)1.04203 (11)0.0152 (5)
H221.04110.01791.01550.018*
C230.9787 (4)0.06615 (14)1.10679 (10)0.0177 (5)
H231.11830.0591.12390.021*
C240.8226 (4)0.10145 (13)1.14755 (11)0.0171 (5)
C250.6184 (4)0.10968 (14)1.12077 (11)0.0181 (6)
H250.50910.13281.14740.022*
C260.5730 (4)0.08471 (13)1.05623 (11)0.0166 (5)
H260.43280.09071.03940.02*
C270.7173 (5)0.17979 (17)1.24584 (12)0.0276 (7)
H27A0.58150.15191.25170.041*
H27B0.69550.22821.21870.041*
H27C0.77390.19491.28980.041*
C281.0833 (4)0.12767 (16)1.23701 (12)0.0253 (6)
H28A1.1630.17081.21490.038*
H28B1.15080.07591.22730.038*
H28C1.08260.13681.28550.038*
C310.8422 (4)0.15896 (13)0.88452 (11)0.0178 (5)
H310.87430.17840.83820.021*
C320.6577 (5)0.21017 (14)0.90928 (13)0.0262 (6)
H32A0.61890.19360.95480.039*
H32B0.53550.2030.87940.039*
H32C0.69990.26690.90950.039*
C331.0435 (5)0.17255 (15)0.92493 (13)0.0276 (6)
H33A1.1510.1330.91170.041*
H33B1.01210.16650.97280.041*
H33C1.09730.22690.91640.041*
C340.7688 (4)0.04290 (14)0.80697 (11)0.0187 (6)
H340.7268−0.0150.80930.022*
C350.5943 (4)0.08600 (16)0.76836 (12)0.0248 (6)
H35A0.63170.14280.76330.037*
H35B0.460.08150.79290.037*
H35C0.57860.06140.7240.037*
C360.9802 (4)0.04601 (15)0.77057 (12)0.0244 (6)
H36A1.08820.01810.79720.037*
H36B1.02250.10220.76420.037*
H36C0.96630.01980.72680.037*
N10.9457 (4)−0.32461 (12)0.90623 (10)0.0226 (5)
N20.8668 (4)0.12702 (12)1.21223 (9)0.0207 (5)
N30.7898 (3)0.07164 (11)0.87759 (9)0.0155 (5)
O10.4187 (3)0.01727 (9)0.92616 (7)0.0194 (4)
P10.65325 (10)0.01773 (4)0.93260 (3)0.01474 (14)
U11U22U33U12U13U23
C110.0215 (13)0.0097 (11)0.0122 (11)−0.0013 (9)0.0018 (10)−0.0008 (9)
C120.0240 (14)0.0117 (12)0.0127 (10)−0.0043 (11)−0.0032 (10)−0.0016 (9)
C130.0190 (14)0.0140 (12)0.0154 (10)0.0026 (10)−0.0004 (10)−0.0007 (9)
C140.0266 (16)0.0102 (11)0.0116 (9)−0.0017 (10)−0.0041 (10)0.0009 (8)
C150.0230 (14)0.0112 (11)0.0155 (11)−0.0054 (11)−0.0008 (11)0.0017 (9)
C160.0186 (14)0.0163 (12)0.0142 (10)−0.0017 (10)0.0001 (11)−0.0004 (9)
C170.0333 (17)0.0087 (12)0.0322 (14)−0.0014 (11)−0.0030 (12)−0.0009 (11)
C180.0296 (16)0.0118 (12)0.0209 (12)0.0017 (12)−0.0001 (12)−0.0014 (9)
C210.0254 (15)0.0054 (12)0.0126 (10)−0.0044 (10)0.0026 (10)0.0009 (8)
C220.0206 (14)0.0071 (11)0.0179 (11)0.0009 (10)0.0039 (10)−0.0003 (8)
C230.0223 (15)0.0129 (12)0.0179 (11)0.0005 (11)−0.0009 (10)0.0030 (9)
C240.0287 (16)0.0089 (11)0.0136 (10)−0.0022 (11)0.0018 (10)0.0017 (8)
C250.0249 (16)0.0132 (12)0.0163 (11)0.0000 (11)0.0057 (11)0.0028 (9)
C260.0208 (14)0.0109 (12)0.0180 (11)0.0002 (10)0.0003 (10)0.0043 (9)
C270.0339 (19)0.0338 (16)0.0152 (12)0.0073 (13)−0.0013 (11)−0.0078 (11)
C280.0310 (18)0.0296 (16)0.0153 (11)0.0006 (12)−0.0012 (11)−0.0011 (10)
C310.0291 (15)0.0079 (11)0.0165 (10)−0.0023 (11)0.0022 (11)0.0011 (8)
C320.0367 (17)0.0144 (13)0.0275 (12)0.0034 (13)0.0108 (13)0.0031 (10)
C330.0352 (17)0.0160 (13)0.0317 (14)−0.0079 (12)−0.0089 (14)0.0037 (11)
C340.0268 (15)0.0137 (13)0.0157 (11)−0.0002 (11)−0.0012 (11)−0.0018 (9)
C350.0324 (17)0.0232 (15)0.0187 (12)−0.0005 (12)−0.0038 (11)0.0011 (10)
C360.0325 (17)0.0218 (14)0.0189 (12)−0.0001 (12)0.0047 (12)−0.0028 (10)
N10.0260 (13)0.0086 (10)0.0331 (11)−0.0005 (9)−0.0009 (10)−0.0024 (9)
N20.0266 (13)0.0231 (12)0.0124 (9)0.0042 (10)0.0003 (9)−0.0037 (8)
N30.0267 (13)0.0081 (10)0.0118 (9)−0.0036 (9)0.0004 (8)−0.0021 (8)
O10.0211 (10)0.0136 (8)0.0235 (8)0.0005 (7)−0.0008 (7)−0.0014 (7)
P10.0209 (3)0.0094 (3)0.0140 (3)0.0000 (3)−0.0002 (3)−0.0005 (2)
C11—C121.386 (3)C26—H260.95
C11—C161.398 (3)C27—N21.451 (3)
C11—P11.803 (2)C27—H27A0.98
C12—C131.393 (3)C27—H27B0.98
C12—H120.95C27—H27C0.98
C13—C141.412 (3)C28—N21.450 (3)
C13—H130.95C28—H28A0.98
C14—N11.374 (3)C28—H28B0.98
C14—C151.393 (3)C28—H28C0.98
C15—C161.391 (3)C31—N31.496 (3)
C15—H150.95C31—C331.519 (4)
C16—H160.95C31—C321.523 (4)
C17—N11.460 (3)C31—H311
C17—H17A0.98C32—H32A0.98
C17—H17B0.98C32—H32B0.98
C17—H17C0.98C32—H32C0.98
C18—N11.439 (3)C33—H33A0.98
C18—H18A0.98C33—H33B0.98
C18—H18B0.98C33—H33C0.98
C18—H18C0.98C34—N31.493 (3)
C21—C221.395 (3)C34—C361.517 (4)
C21—C261.401 (3)C34—C351.521 (3)
C21—P11.800 (2)C34—H341
C22—C231.386 (3)C35—H35A0.98
C22—H220.95C35—H35B0.98
C23—C241.404 (3)C35—H35C0.98
C23—H230.95C36—H36A0.98
C24—N21.387 (3)C36—H36B0.98
C24—C251.399 (3)C36—H36C0.98
C25—C261.383 (3)N3—P11.658 (2)
C25—H250.95O1—P11.4825 (17)
C12—C11—C16117.5 (2)H28A—C28—H28B109.5
C12—C11—P1125.71 (18)N2—C28—H28C109.5
C16—C11—P1116.71 (19)H28A—C28—H28C109.5
C11—C12—C13121.6 (2)H28B—C28—H28C109.5
C11—C12—H12119.2N3—C31—C33112.16 (19)
C13—C12—H12119.2N3—C31—C32113.9 (2)
C12—C13—C14120.5 (2)C33—C31—C32112.4 (2)
C12—C13—H13119.7N3—C31—H31105.9
C14—C13—H13119.7C33—C31—H31105.9
N1—C14—C15121.5 (2)C32—C31—H31105.9
N1—C14—C13120.6 (2)C31—C32—H32A109.5
C15—C14—C13117.9 (2)C31—C32—H32B109.5
C16—C15—C14120.6 (2)H32A—C32—H32B109.5
C16—C15—H15119.7C31—C32—H32C109.5
C14—C15—H15119.7H32A—C32—H32C109.5
C15—C16—C11121.8 (2)H32B—C32—H32C109.5
C15—C16—H16119.1C31—C33—H33A109.5
C11—C16—H16119.1C31—C33—H33B109.5
N1—C17—H17A109.5H33A—C33—H33B109.5
N1—C17—H17B109.5C31—C33—H33C109.5
H17A—C17—H17B109.5H33A—C33—H33C109.5
N1—C17—H17C109.5H33B—C33—H33C109.5
H17A—C17—H17C109.5N3—C34—C36111.3 (2)
H17B—C17—H17C109.5N3—C34—C35113.0 (2)
N1—C18—H18A109.5C36—C34—C35112.0 (2)
N1—C18—H18B109.5N3—C34—H34106.7
H18A—C18—H18B109.5C36—C34—H34106.7
N1—C18—H18C109.5C35—C34—H34106.7
H18A—C18—H18C109.5C34—C35—H35A109.5
H18B—C18—H18C109.5C34—C35—H35B109.5
C22—C21—C26117.6 (2)H35A—C35—H35B109.5
C22—C21—P1124.24 (18)C34—C35—H35C109.5
C26—C21—P1118.10 (19)H35A—C35—H35C109.5
C23—C22—C21121.2 (2)H35B—C35—H35C109.5
C23—C22—H22119.4C34—C36—H36A109.5
C21—C22—H22119.4C34—C36—H36B109.5
C22—C23—C24121.1 (2)H36A—C36—H36B109.5
C22—C23—H23119.5C34—C36—H36C109.5
C24—C23—H23119.5H36A—C36—H36C109.5
N2—C24—C25120.6 (2)H36B—C36—H36C109.5
N2—C24—C23121.8 (2)C14—N1—C18121.5 (2)
C25—C24—C23117.6 (2)C14—N1—C17119.4 (2)
C26—C25—C24121.0 (2)C18—N1—C17119.0 (2)
C26—C25—H25119.5C24—N2—C28120.5 (2)
C24—C25—H25119.5C24—N2—C27119.1 (2)
C25—C26—C21121.4 (2)C28—N2—C27116.6 (2)
C25—C26—H26119.3C34—N3—C31114.68 (17)
C21—C26—H26119.3C34—N3—P1113.89 (16)
N2—C27—H27A109.5C31—N3—P1125.34 (15)
N2—C27—H27B109.5O1—P1—N3117.53 (10)
H27A—C27—H27B109.5O1—P1—C21110.27 (11)
N2—C27—H27C109.5N3—P1—C21107.57 (11)
H27A—C27—H27C109.5O1—P1—C11110.03 (11)
H27B—C27—H27C109.5N3—P1—C11104.36 (11)
N2—C28—H28A109.5C21—P1—C11106.42 (11)
N2—C28—H28B109.5
C16—C11—C12—C131.5 (3)C23—C24—N2—C27165.3 (2)
P1—C11—C12—C13178.49 (16)C36—C34—N3—C3166.8 (3)
C11—C12—C13—C14−0.2 (3)C35—C34—N3—C31−60.2 (3)
C12—C13—C14—N1177.9 (2)C36—C34—N3—P1−139.05 (18)
C12—C13—C14—C15−1.6 (3)C35—C34—N3—P193.9 (2)
N1—C14—C15—C16−177.4 (2)C33—C31—N3—C34−123.5 (2)
C13—C14—C15—C162.0 (3)C32—C31—N3—C34107.4 (2)
C14—C15—C16—C11−0.8 (3)C33—C31—N3—P185.7 (3)
C12—C11—C16—C15−1.0 (3)C32—C31—N3—P1−43.4 (3)
P1—C11—C16—C15−178.30 (17)C34—N3—P1—O1−63.71 (19)
C26—C21—C22—C23−0.9 (3)C31—N3—P1—O187.2 (2)
P1—C21—C22—C23−177.98 (17)C34—N3—P1—C21171.21 (16)
C21—C22—C23—C24−0.2 (3)C31—N3—P1—C21−37.9 (2)
C22—C23—C24—N2−179.4 (2)C34—N3—P1—C1158.44 (18)
C22—C23—C24—C251.0 (3)C31—N3—P1—C11−150.6 (2)
N2—C24—C25—C26179.7 (2)C22—C21—P1—O1165.50 (18)
C23—C24—C25—C26−0.7 (3)C26—C21—P1—O1−11.5 (2)
C24—C25—C26—C21−0.4 (3)C22—C21—P1—N3−65.2 (2)
C22—C21—C26—C251.2 (3)C26—C21—P1—N3117.78 (18)
P1—C21—C26—C25178.44 (17)C22—C21—P1—C1146.2 (2)
C15—C14—N1—C18−176.9 (2)C26—C21—P1—C11−130.84 (18)
C13—C14—N1—C183.7 (3)C12—C11—P1—O1165.47 (17)
C15—C14—N1—C170.3 (3)C16—C11—P1—O1−17.5 (2)
C13—C14—N1—C17−179.1 (2)C12—C11—P1—N338.5 (2)
C25—C24—N2—C28−172.3 (2)C16—C11—P1—N3−144.44 (17)
C23—C24—N2—C288.1 (3)C12—C11—P1—C21−75.1 (2)
C25—C24—N2—C27−15.2 (3)C16—C11—P1—C21101.96 (19)
D—H···AD—HH···AD···AD—H···A
C12—H12···O1i0.952.593.493 (3)159
C33—H33A···O1i0.982.583.501 (3)158
C18—H18A···Cg1ii0.982.963.821 (2)148
C18—H18C···Cg2ii0.982.973.915 (3)162
C27—H27C···Cg1iii0.982.693.468 (3)137
Table 1

Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids of the C11—C16 and C21—C26 rings, respectively.

D—H⋯A D—HH⋯A D⋯A D—H⋯A
C12—H12⋯O1i 0.952.593.493 (3)159
C33—H33A⋯O1i 0.982.583.501 (3)158
C18—H18A⋯Cg1ii 0.982.963.821 (2)148
C18—H18C⋯Cg2ii 0.982.973.915 (3)162
C27—H27C⋯Cg1iii 0.982.693.468 (3)137

Symmetry codes: (i) ; (ii) ; (iii) .

  2 in total

1.  trans-Chloro(methyl)bis(tricyclohexylphosphine)platinum(II).

Authors:  S Otto
Journal:  Acta Crystallogr C       Date:  2001-07-09       Impact factor: 1.172

2.  A short history of SHELX.

Authors:  George M Sheldrick
Journal:  Acta Crystallogr A       Date:  2007-12-21       Impact factor: 2.290
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