Extensive analysis of N—H...O hydrogen bonding in four classes of phosphorus compounds: a combined experimental and database study

The N—H...O hydrogen bond is the characteristic inter­action in the crystal structures of N-benzyl-P-phenyl-N′-(p-tol­yl)phospho­nic di­amide, C₂₀H₂₁N₂OP or (C₆H₅)P(O)(NHCH₂C₆H₅)(NHC₆H₄-p-CH₃), (I), di­phenyl­phosphinic 1-methyl­propyl­amide, C₁₆H₂₀NOP or (C₆H₅)₂P(O)[NHCH(CH₃)(C₂H₅)], (II), (S)-1-phenyl­ethyl­ammonium N-[(S)-1-phenyl­eth­yl]phenyl­phospho­namidate, C₈H₁₂N⁺·C₁₄H₁₅NO₂P⁻ or [S-(C₆H₅)CH(CH₃)NH₃][(C₆H₅)P(O){S-NHCH(CH₃)(C₆H₅)}(O)], (III), and (4-methyl­benz­yl)ammonium di­phenyl­phosphinate, C₈H₁₂N⁺·C₁₂H₁₀O₂P⁻ or [4-CH₃-C₆H₄CH₂NH₃][(C₆H₅)₂P(O)(O)], (IV). This article focuses on the N—H...O hydrogen bonds by considering the structures of (I), (II), (III) and (IV), and reviewing their analogous compounds, including 43 (C)P(O)(N)₂, 102 (C)₂P(O)(N), 31 (C)P(O)(N)(O) and 96 (C)₂P(O)(O) structures, deposited in the Cambridge Structural Database (CSD). For the structures with a (C)P(O)(N)₂ segment, only neutral hydrogen bonds were found in the CSD. The other three classes of compounds included both neutral and `charge-assisted' hydrogen bonds, and the (C)₂P(O)(O) structures were particularly noticeable for a high number of cation–anion compounds. The overall tendencies of N...O distances in neutral and cation–anion compounds were compared. The N—H...O hydrogen-bond angles were also analyzed for the four classes of phospho­rus compounds.

Computing details

Data collection: CrystalClear-SM Expert (Rigaku, 2011) for (I), (II), (III); APEX3 (Bruker, 2016) for fh24. Cell refinement: CrysAlis PRO (Agilent, 2014) for (I); CrysAlis PRO (Rigaku OD, 2015) for (II), (III); APEX3 (Bruker, 2016) for fh24. Data reduction: CrysAlis PRO (Agilent, 2014) for (I); CrysAlis PRO (Rigaku OD, 2015) for (II), (III); SAINT (Bruker, 2015) for fh24. For all compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008). Molecular graphics: Mercury (Macrae et al., 2008) for (I), (II), (III); OLEX2 (Macrae et al., 2008) for fh24. Software used to prepare material for publication: enCIFer (Allen et al., 2004) for (I); enCIFer (Allen et al., 2004 for (II), (III); OLEX2 (Dolomanov et al., 2009) for fh24.

(I) N-Benzyl-P-phenyl-N'-(p-tolyl)phosphonic diamide

Crystal data

C20H21N2OP	Dx = 1.273 Mg m^−3
Mr = 336.36	Melting point: 402 K
Orthorhombic, Pna21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 11918 reflections
a = 17.4366 (4) Å	θ = 2.1–29.2°
b = 22.7127 (5) Å	µ = 0.17 mm^−1
c = 8.8598 (2) Å	T = 120 K
V = 3508.77 (14) Å^3	Block, colourless
Z = 8	0.20 × 0.20 × 0.10 mm
F(000) = 1424

Data collection

Rigaku Saturn724+ (2x2 bin mode) diffractometer	6363 independent reflections
Radiation source: Rotating Anode	5746 reflections with I > 2σ(I)
Multilayer monochromator	Rint = 0.047
Detector resolution: 28.5714 pixels mm^-1	θmax = 25.4°, θmin = 2.9°
profile data from ω–scans	h = −21→20
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	k = −27→26
Tmin = 0.885, Tmax = 1.000	l = −10→10
21879 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.036	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.089	w = 1/[σ^2(Fo^2) + (0.0489P)^2 + 0.3795P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.001
6363 reflections	Δρmax = 0.29 e Å^−3
447 parameters	Δρmin = −0.25 e Å^−3
5 restraints	Absolute structure: Flack (1983), 2931 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.02 (7)

Special details

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 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 > 2sigma(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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
P1	0.20191 (3)	0.72514 (2)	0.71389 (7)	0.01958 (12)
O1	0.17778 (9)	0.74673 (7)	0.56429 (17)	0.0264 (4)
N1	0.16342 (10)	0.66156 (8)	0.7592 (2)	0.0228 (4)
H1N	0.1895 (12)	0.6443 (10)	0.832 (2)	0.027*
N2	0.17917 (10)	0.77043 (8)	0.8523 (2)	0.0226 (4)
H2N	0.1497 (11)	0.7566 (11)	0.923 (2)	0.027*
C1	0.30324 (10)	0.71086 (8)	0.7218 (3)	0.0206 (4)
C2	0.33453 (12)	0.67063 (9)	0.6187 (2)	0.0229 (5)
H2B	0.3023	0.6525	0.5459	0.028*
C3	0.41163 (12)	0.65715 (10)	0.6220 (3)	0.0258 (5)
H3A	0.4323	0.6294	0.5529	0.031*
C4	0.45872 (12)	0.68430 (9)	0.7268 (3)	0.0280 (5)
H4A	0.5119	0.6751	0.7292	0.034*
C5	0.42888 (12)	0.72474 (10)	0.8281 (3)	0.0273 (5)
H5A	0.4617	0.7435	0.8989	0.033*
C6	0.35139 (12)	0.73787 (10)	0.8266 (3)	0.0239 (5)
H6A	0.3310	0.7653	0.8969	0.029*
C7	0.08007 (12)	0.65341 (10)	0.7576 (3)	0.0288 (5)
H7A	0.0554	0.6916	0.7339	0.035*
H7B	0.0631	0.6415	0.8597	0.035*
C8	0.05302 (12)	0.60801 (10)	0.6452 (3)	0.0256 (5)
C9	−0.02137 (13)	0.61103 (11)	0.5917 (3)	0.0336 (6)
H9A	−0.0544	0.6410	0.6285	0.040*
C10	−0.04878 (16)	0.57169 (12)	0.4865 (4)	0.0445 (7)
H10A	−0.0996	0.5754	0.4491	0.053*
C11	−0.00172 (17)	0.52668 (12)	0.4354 (3)	0.0452 (7)
H11A	−0.0203	0.4991	0.3636	0.054*
C12	0.07225 (16)	0.52230 (11)	0.4897 (3)	0.0383 (6)
H12A	0.1045	0.4913	0.4558	0.046*
C13	0.09978 (13)	0.56291 (10)	0.5936 (3)	0.0299 (5)
H13A	0.1510	0.5598	0.6295	0.036*
C14	0.18656 (12)	0.83229 (9)	0.8579 (2)	0.0216 (5)
C15	0.23128 (12)	0.86432 (9)	0.7569 (3)	0.0258 (5)
H15A	0.2576	0.8447	0.6776	0.031*
C16	0.23724 (13)	0.92527 (10)	0.7726 (3)	0.0288 (5)
H16A	0.2676	0.9469	0.7028	0.035*
C17	0.19980 (12)	0.95509 (10)	0.8878 (3)	0.0261 (5)
C18	0.15560 (13)	0.92253 (10)	0.9869 (3)	0.0272 (5)
H18A	0.1298	0.9421	1.0669	0.033*
C19	0.14812 (12)	0.86219 (9)	0.9722 (3)	0.0233 (5)
H19A	0.1165	0.8410	1.0406	0.028*
C20	0.20544 (15)	1.02143 (10)	0.9034 (3)	0.0369 (6)
H20A	0.2565	1.0345	0.8717	0.055*
H20B	0.1969	1.0326	1.0089	0.055*
H20C	0.1665	1.0401	0.8396	0.055*
P2	0.04486 (3)	0.71518 (2)	0.21889 (7)	0.01941 (12)
O2	0.06608 (8)	0.73328 (7)	0.06447 (16)	0.0245 (3)
N3	0.09188 (10)	0.65682 (8)	0.2761 (2)	0.0238 (4)
H3N	0.0676 (12)	0.6382 (10)	0.348 (2)	0.029*
N4	0.06232 (10)	0.76608 (8)	0.3473 (2)	0.0228 (4)
H4N	0.0926 (11)	0.7567 (11)	0.4229 (19)	0.027*
C21	−0.05454 (11)	0.69441 (9)	0.2327 (3)	0.0220 (4)
C22	−0.08405 (13)	0.65408 (10)	0.1285 (3)	0.0270 (5)
H22A	−0.0516	0.6381	0.0526	0.032*
C23	−0.16043 (13)	0.63729 (11)	0.1354 (3)	0.0319 (5)
H23A	−0.1802	0.6095	0.0655	0.038*
C24	−0.20782 (12)	0.66129 (10)	0.2449 (3)	0.0311 (5)
H24A	−0.2602	0.6500	0.2495	0.037*
C25	−0.17947 (13)	0.70143 (11)	0.3471 (3)	0.0298 (5)
H25A	−0.2124	0.7179	0.4214	0.036*
C26	−0.10295 (12)	0.71777 (10)	0.3418 (3)	0.0251 (5)
H26A	−0.0835	0.7451	0.4132	0.030*
C27	0.17596 (12)	0.65569 (10)	0.2688 (3)	0.0285 (5)
H27A	0.1959	0.6398	0.3652	0.034*
H27B	0.1948	0.6966	0.2592	0.034*
C28	0.20848 (12)	0.61993 (10)	0.1415 (3)	0.0260 (5)
C29	0.28105 (12)	0.63336 (10)	0.0882 (3)	0.0273 (5)
H29A	0.3078	0.6662	0.1289	0.033*
C30	0.31560 (13)	0.59950 (11)	−0.0245 (3)	0.0314 (5)
H30A	0.3654	0.6094	−0.0601	0.038*
C31	0.27733 (14)	0.55181 (11)	−0.0838 (3)	0.0333 (6)
H31A	0.3007	0.5282	−0.1595	0.040*
C32	0.20375 (14)	0.53850 (11)	−0.0314 (3)	0.0336 (6)
H32A	0.1768	0.5059	−0.0728	0.040*
C33	0.16999 (14)	0.57194 (10)	0.0791 (3)	0.0295 (5)
H33A	0.1199	0.5623	0.1135	0.035*
C34	0.04819 (11)	0.82734 (9)	0.3348 (2)	0.0213 (4)
C35	−0.00629 (11)	0.85024 (9)	0.2371 (3)	0.0237 (5)
H35A	−0.0353	0.8247	0.1743	0.028*
C36	−0.01838 (11)	0.91083 (9)	0.2310 (3)	0.0246 (5)
H36A	−0.0558	0.9260	0.1634	0.029*
C37	0.02266 (12)	0.94973 (9)	0.3209 (3)	0.0246 (5)
C38	0.07609 (12)	0.92604 (10)	0.4203 (3)	0.0253 (5)
H38A	0.1042	0.9517	0.4845	0.030*
C39	0.08933 (12)	0.86593 (10)	0.4279 (2)	0.0226 (5)
H39A	0.1264	0.8509	0.4964	0.027*
C40	0.01109 (14)	1.01544 (10)	0.3069 (3)	0.0336 (6)
H40A	−0.0393	1.0233	0.2622	0.050*
H40B	0.0512	1.0321	0.2423	0.050*
H40C	0.0138	1.0335	0.4072	0.050*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P1	0.0210 (2)	0.0161 (3)	0.0216 (3)	−0.00005 (19)	−0.0007 (2)	−0.0001 (3)
O1	0.0279 (8)	0.0257 (9)	0.0255 (8)	0.0023 (7)	−0.0016 (7)	0.0031 (7)
N1	0.0225 (9)	0.0186 (9)	0.0272 (10)	−0.0020 (7)	−0.0041 (8)	0.0012 (8)
N2	0.0259 (9)	0.0191 (10)	0.0228 (10)	−0.0015 (7)	0.0042 (8)	0.0009 (8)
C1	0.0217 (9)	0.0176 (10)	0.0226 (10)	−0.0019 (8)	0.0010 (10)	0.0028 (10)
C2	0.0256 (10)	0.0214 (12)	0.0219 (11)	−0.0016 (9)	−0.0020 (9)	0.0015 (9)
C3	0.0283 (12)	0.0215 (12)	0.0276 (12)	0.0026 (9)	0.0034 (10)	0.0047 (10)
C4	0.0224 (9)	0.0276 (12)	0.0341 (12)	0.0019 (9)	−0.0004 (10)	0.0072 (12)
C5	0.0248 (11)	0.0279 (13)	0.0293 (12)	−0.0054 (9)	−0.0073 (10)	0.0036 (10)
C6	0.0285 (11)	0.0196 (11)	0.0235 (11)	−0.0010 (9)	−0.0016 (10)	−0.0009 (9)
C7	0.0254 (11)	0.0283 (13)	0.0329 (13)	−0.0039 (9)	0.0005 (10)	−0.0036 (10)
C8	0.0298 (12)	0.0200 (13)	0.0268 (11)	−0.0078 (9)	0.0012 (10)	0.0049 (9)
C9	0.0299 (12)	0.0274 (13)	0.0437 (15)	−0.0074 (10)	−0.0046 (12)	0.0052 (12)
C10	0.0379 (14)	0.0381 (17)	0.0576 (18)	−0.0134 (12)	−0.0161 (14)	0.0065 (14)
C11	0.0618 (18)	0.0311 (15)	0.0428 (15)	−0.0177 (13)	−0.0105 (14)	−0.0020 (12)
C12	0.0515 (16)	0.0245 (14)	0.0389 (14)	−0.0057 (11)	0.0000 (13)	−0.0002 (12)
C13	0.0330 (12)	0.0252 (12)	0.0316 (12)	−0.0041 (10)	−0.0010 (11)	0.0030 (11)
C14	0.0246 (10)	0.0150 (11)	0.0251 (11)	0.0005 (8)	−0.0032 (9)	0.0012 (9)
C15	0.0301 (11)	0.0204 (11)	0.0271 (12)	−0.0015 (9)	0.0039 (10)	0.0007 (9)
C16	0.0332 (12)	0.0228 (12)	0.0303 (12)	−0.0034 (9)	0.0026 (10)	0.0062 (10)
C17	0.0267 (11)	0.0180 (11)	0.0335 (12)	0.0002 (9)	−0.0044 (10)	0.0025 (10)
C18	0.0293 (12)	0.0210 (12)	0.0311 (12)	0.0028 (9)	0.0031 (10)	−0.0034 (10)
C19	0.0246 (11)	0.0182 (11)	0.0270 (11)	−0.0001 (8)	0.0022 (9)	0.0023 (9)
C20	0.0451 (14)	0.0174 (13)	0.0482 (16)	0.0001 (11)	0.0015 (13)	0.0006 (11)
P2	0.0204 (2)	0.0162 (2)	0.0216 (2)	−0.00022 (19)	−0.0005 (2)	0.0002 (3)
O2	0.0253 (7)	0.0233 (9)	0.0248 (8)	−0.0011 (6)	−0.0005 (7)	0.0019 (7)
N3	0.0236 (9)	0.0191 (10)	0.0287 (10)	0.0017 (7)	0.0035 (8)	0.0037 (8)
N4	0.0253 (9)	0.0203 (10)	0.0227 (10)	0.0014 (8)	−0.0044 (8)	−0.0005 (8)
C21	0.0246 (10)	0.0183 (10)	0.0230 (11)	−0.0002 (8)	−0.0029 (10)	0.0032 (10)
C22	0.0283 (12)	0.0251 (13)	0.0276 (12)	−0.0003 (9)	0.0003 (10)	−0.0028 (10)
C23	0.0300 (12)	0.0325 (14)	0.0332 (13)	−0.0084 (10)	−0.0019 (11)	−0.0066 (11)
C24	0.0229 (10)	0.0356 (13)	0.0349 (14)	−0.0046 (9)	0.0018 (10)	0.0015 (11)
C25	0.0280 (12)	0.0323 (13)	0.0292 (12)	0.0024 (10)	0.0043 (11)	−0.0004 (10)
C26	0.0288 (11)	0.0225 (12)	0.0238 (11)	−0.0008 (9)	0.0026 (10)	−0.0005 (9)
C27	0.0271 (11)	0.0253 (12)	0.0330 (12)	0.0038 (9)	−0.0051 (10)	0.0003 (10)
C28	0.0269 (11)	0.0210 (12)	0.0300 (12)	0.0046 (9)	−0.0048 (10)	0.0069 (10)
C29	0.0279 (11)	0.0213 (12)	0.0327 (12)	−0.0008 (9)	−0.0032 (10)	0.0040 (10)
C30	0.0264 (11)	0.0324 (14)	0.0354 (13)	0.0053 (10)	0.0014 (11)	0.0098 (11)
C31	0.0423 (14)	0.0266 (13)	0.0311 (13)	0.0112 (11)	0.0007 (11)	0.0013 (11)
C32	0.0394 (14)	0.0214 (13)	0.0401 (15)	0.0003 (10)	−0.0018 (12)	0.0020 (11)
C33	0.0319 (12)	0.0233 (12)	0.0334 (13)	−0.0025 (9)	−0.0053 (11)	0.0054 (11)
C34	0.0224 (10)	0.0173 (11)	0.0243 (11)	0.0012 (8)	0.0036 (9)	0.0012 (9)
C35	0.0238 (10)	0.0211 (11)	0.0262 (12)	−0.0006 (8)	−0.0008 (10)	−0.0031 (10)
C36	0.0240 (10)	0.0236 (11)	0.0261 (12)	0.0035 (8)	−0.0015 (10)	0.0039 (10)
C37	0.0254 (11)	0.0209 (11)	0.0274 (11)	0.0003 (9)	0.0051 (10)	0.0013 (10)
C38	0.0258 (11)	0.0212 (12)	0.0289 (11)	−0.0031 (9)	0.0025 (10)	−0.0023 (10)
C39	0.0228 (11)	0.0227 (12)	0.0223 (10)	0.0010 (9)	−0.0016 (9)	0.0009 (9)
C40	0.0381 (13)	0.0203 (12)	0.0425 (14)	0.0022 (10)	−0.0036 (12)	−0.0027 (11)

Geometric parameters (Å, º)

P1—O1	1.4746 (16)	P2—O2	1.4757 (15)
P1—N1	1.6422 (18)	P2—N3	1.6391 (19)
P1—N2	1.6489 (19)	P2—N4	1.6502 (19)
P1—C1	1.7978 (19)	P2—C21	1.800 (2)
N1—C7	1.465 (3)	N3—C27	1.468 (3)
N1—H1N	0.878 (10)	N3—H3N	0.874 (10)
N2—C14	1.412 (3)	N4—C34	1.417 (3)
N2—H2N	0.868 (10)	N4—H4N	0.879 (10)
C1—C6	1.394 (3)	C21—C26	1.389 (3)
C1—C2	1.402 (3)	C21—C22	1.399 (3)
C2—C3	1.379 (3)	C22—C23	1.387 (3)
C2—H2B	0.9500	C22—H22A	0.9500
C3—C4	1.384 (3)	C23—C24	1.386 (3)
C3—H3A	0.9500	C23—H23A	0.9500
C4—C5	1.386 (3)	C24—C25	1.377 (3)
C4—H4A	0.9500	C24—H24A	0.9500
C5—C6	1.384 (3)	C25—C26	1.386 (3)
C5—H5A	0.9500	C25—H25A	0.9500
C6—H6A	0.9500	C26—H26A	0.9500
C7—C8	1.509 (3)	C27—C28	1.501 (3)
C7—H7A	0.9900	C27—H27A	0.9900
C7—H7B	0.9900	C27—H27B	0.9900
C8—C9	1.383 (3)	C28—C29	1.385 (3)
C8—C13	1.387 (3)	C28—C33	1.394 (3)
C9—C10	1.377 (4)	C29—C30	1.397 (3)
C9—H9A	0.9500	C29—H29A	0.9500
C10—C11	1.387 (4)	C30—C31	1.376 (4)
C10—H10A	0.9500	C30—H30A	0.9500
C11—C12	1.380 (4)	C31—C32	1.397 (3)
C11—H11A	0.9500	C31—H31A	0.9500
C12—C13	1.389 (3)	C32—C33	1.372 (3)
C12—H12A	0.9500	C32—H32A	0.9500
C13—H13A	0.9500	C33—H33A	0.9500
C14—C19	1.391 (3)	C34—C35	1.387 (3)
C14—C15	1.392 (3)	C34—C39	1.401 (3)
C15—C16	1.395 (3)	C35—C36	1.393 (3)
C15—H15A	0.9500	C35—H35A	0.9500
C16—C17	1.388 (3)	C36—C37	1.388 (3)
C16—H16A	0.9500	C36—H36A	0.9500
C17—C18	1.383 (3)	C37—C38	1.390 (3)
C17—C20	1.516 (3)	C37—C40	1.511 (3)
C18—C19	1.383 (3)	C38—C39	1.386 (3)
C18—H18A	0.9500	C38—H38A	0.9500
C19—H19A	0.9500	C39—H39A	0.9500
C20—H20A	0.9800	C40—H40A	0.9800
C20—H20B	0.9800	C40—H40B	0.9800
C20—H20C	0.9800	C40—H40C	0.9800
O1—P1—N1	113.30 (10)	O2—P2—N3	112.76 (10)
O1—P1—N2	113.11 (10)	O2—P2—N4	113.43 (10)
N1—P1—N2	105.57 (9)	N3—P2—N4	105.12 (10)
O1—P1—C1	112.06 (10)	O2—P2—C21	112.16 (10)
N1—P1—C1	103.50 (9)	N3—P2—C21	104.40 (9)
N2—P1—C1	108.66 (10)	N4—P2—C21	108.33 (10)
C7—N1—P1	120.93 (15)	C27—N3—P2	120.01 (15)
C7—N1—H1N	117.6 (16)	C27—N3—H3N	120.4 (16)
P1—N1—H1N	111.1 (16)	P2—N3—H3N	112.1 (16)
C14—N2—P1	128.68 (16)	C34—N4—P2	127.02 (16)
C14—N2—H2N	112.9 (17)	C34—N4—H4N	113.6 (17)
P1—N2—H2N	116.8 (17)	P2—N4—H4N	117.8 (17)
C6—C1—C2	119.09 (18)	C26—C21—C22	119.09 (19)
C6—C1—P1	122.57 (17)	C26—C21—P2	122.16 (16)
C2—C1—P1	118.33 (16)	C22—C21—P2	118.75 (16)
C3—C2—C1	120.7 (2)	C23—C22—C21	120.3 (2)
C3—C2—H2B	119.7	C23—C22—H22A	119.9
C1—C2—H2B	119.7	C21—C22—H22A	119.9
C2—C3—C4	119.6 (2)	C24—C23—C22	119.7 (2)
C2—C3—H3A	120.2	C24—C23—H23A	120.1
C4—C3—H3A	120.2	C22—C23—H23A	120.1
C3—C4—C5	120.47 (19)	C25—C24—C23	120.4 (2)
C3—C4—H4A	119.8	C25—C24—H24A	119.8
C5—C4—H4A	119.8	C23—C24—H24A	119.8
C6—C5—C4	120.2 (2)	C24—C25—C26	120.0 (2)
C6—C5—H5A	119.9	C24—C25—H25A	120.0
C4—C5—H5A	119.9	C26—C25—H25A	120.0
C5—C6—C1	120.0 (2)	C25—C26—C21	120.4 (2)
C5—C6—H6A	120.0	C25—C26—H26A	119.8
C1—C6—H6A	120.0	C21—C26—H26A	119.8
N1—C7—C8	113.75 (18)	N3—C27—C28	114.82 (19)
N1—C7—H7A	108.8	N3—C27—H27A	108.6
C8—C7—H7A	108.8	C28—C27—H27A	108.6
N1—C7—H7B	108.8	N3—C27—H27B	108.6
C8—C7—H7B	108.8	C28—C27—H27B	108.6
H7A—C7—H7B	107.7	H27A—C27—H27B	107.5
C9—C8—C13	118.4 (2)	C29—C28—C33	118.5 (2)
C9—C8—C7	119.0 (2)	C29—C28—C27	118.8 (2)
C13—C8—C7	122.6 (2)	C33—C28—C27	122.6 (2)
C10—C9—C8	121.7 (3)	C28—C29—C30	121.1 (2)
C10—C9—H9A	119.1	C28—C29—H29A	119.4
C8—C9—H9A	119.1	C30—C29—H29A	119.4
C9—C10—C11	119.6 (3)	C31—C30—C29	119.8 (2)
C9—C10—H10A	120.2	C31—C30—H30A	120.1
C11—C10—H10A	120.2	C29—C30—H30A	120.1
C12—C11—C10	119.5 (3)	C30—C31—C32	119.3 (2)
C12—C11—H11A	120.3	C30—C31—H31A	120.4
C10—C11—H11A	120.3	C32—C31—H31A	120.4
C11—C12—C13	120.4 (3)	C33—C32—C31	120.7 (2)
C11—C12—H12A	119.8	C33—C32—H32A	119.6
C13—C12—H12A	119.8	C31—C32—H32A	119.6
C8—C13—C12	120.4 (2)	C32—C33—C28	120.6 (2)
C8—C13—H13A	119.8	C32—C33—H33A	119.7
C12—C13—H13A	119.8	C28—C33—H33A	119.7
C19—C14—C15	118.9 (2)	C35—C34—C39	118.92 (19)
C19—C14—N2	117.9 (2)	C35—C34—N4	122.40 (19)
C15—C14—N2	123.3 (2)	C39—C34—N4	118.65 (19)
C14—C15—C16	119.8 (2)	C34—C35—C36	119.9 (2)
C14—C15—H15A	120.1	C34—C35—H35A	120.1
C16—C15—H15A	120.1	C36—C35—H35A	120.1
C17—C16—C15	121.5 (2)	C37—C36—C35	121.9 (2)
C17—C16—H16A	119.3	C37—C36—H36A	119.0
C15—C16—H16A	119.3	C35—C36—H36A	119.0
C18—C17—C16	117.9 (2)	C36—C37—C38	117.5 (2)
C18—C17—C20	120.6 (2)	C36—C37—C40	120.9 (2)
C16—C17—C20	121.4 (2)	C38—C37—C40	121.6 (2)
C17—C18—C19	121.5 (2)	C39—C38—C37	121.6 (2)
C17—C18—H18A	119.2	C39—C38—H38A	119.2
C19—C18—H18A	119.2	C37—C38—H38A	119.2
C18—C19—C14	120.5 (2)	C38—C39—C34	120.1 (2)
C18—C19—H19A	119.8	C38—C39—H39A	119.9
C14—C19—H19A	119.8	C34—C39—H39A	119.9
C17—C20—H20A	109.5	C37—C40—H40A	109.5
C17—C20—H20B	109.5	C37—C40—H40B	109.5
H20A—C20—H20B	109.5	H40A—C40—H40B	109.5
C17—C20—H20C	109.5	C37—C40—H40C	109.5
H20A—C20—H20C	109.5	H40A—C40—H40C	109.5
H20B—C20—H20C	109.5	H40B—C40—H40C	109.5

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···O2^i	0.87 (1)	2.00 (1)	2.852 (2)	169 (2)
N4—H4N···O1	0.88 (1)	1.96 (1)	2.818 (2)	167 (2)

Symmetry code: (i) x, y, z+1.

(II) Diphenylphosphinic 1-methylpropylamide

Crystal data

C16H20NOP	Dx = 1.205 Mg m^−3
Mr = 273.30	Melting point: 381 K
Tetragonal, P421c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P -4 2n	Cell parameters from 9050 reflections
a = 18.7952 (3) Å	θ = 1.5–29.7°
c = 8.5279 (3) Å	µ = 0.18 mm^−1
V = 3012.56 (13) Å^3	T = 120 K
Z = 8	Block, colourless
F(000) = 1168	0.25 × 0.20 × 0.20 mm

Data collection

Rigaku Saturn724+ (2x2 bin mode) diffractometer	2762 independent reflections
Radiation source: Rotating Anode	2550 reflections with I > 2σ(I)
Multilayer monochromator	Rint = 0.064
Detector resolution: 28.5714 pixels mm^-1	θmax = 25.3°, θmin = 3.1°
profile data from ω–scans	h = −20→22
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2015)	k = −22→22
Tmin = 0.008, Tmax = 1.000	l = −10→9
15254 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.054	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.146	w = 1/[σ^2(Fo^2) + (0.0737P)^2 + 2.3114P] where P = (Fo^2 + 2Fc^2)/3
S = 1.09	(Δ/σ)max < 0.001
2762 reflections	Δρmax = 0.55 e Å^−3
177 parameters	Δρmin = −0.34 e Å^−3
1 restraint	Absolute structure: Flack (1983), 1192 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.37 (17)

Special details

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 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 > 2sigma(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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
P1	0.67735 (4)	0.27034 (4)	−0.00139 (10)	0.0257 (2)
O1	0.71589 (13)	0.21220 (12)	0.0818 (3)	0.0339 (5)
N1	0.62736 (15)	0.25104 (15)	−0.1523 (3)	0.0294 (6)
H1N	0.6507 (16)	0.249 (2)	−0.241 (2)	0.035*
C1	0.73865 (16)	0.33488 (16)	−0.0780 (4)	0.0272 (7)
C2	0.80764 (17)	0.33419 (18)	−0.0194 (4)	0.0374 (8)
H2	0.8214	0.2988	0.0543	0.045*
C3	0.8563 (2)	0.3846 (2)	−0.0677 (5)	0.0450 (9)
H3	0.9034	0.3840	−0.0273	0.054*
C4	0.8364 (2)	0.43563 (19)	−0.1747 (5)	0.0425 (9)
H4	0.8699	0.4703	−0.2080	0.051*
C5	0.76852 (19)	0.43680 (17)	−0.2335 (4)	0.0370 (8)
H5	0.7552	0.4724	−0.3069	0.044*
C6	0.71975 (18)	0.38665 (16)	−0.1867 (4)	0.0309 (7)
H6	0.6729	0.3874	−0.2287	0.037*
C7	0.62012 (16)	0.31622 (16)	0.1345 (4)	0.0266 (7)
C8	0.63071 (17)	0.30557 (18)	0.2952 (4)	0.0326 (7)
H8	0.6658	0.2729	0.3302	0.039*
C9	0.59024 (18)	0.3425 (2)	0.4028 (4)	0.0390 (9)
H9	0.5977	0.3349	0.5117	0.047*
C10	0.53954 (19)	0.3899 (2)	0.3550 (5)	0.0413 (9)
H10	0.5123	0.4151	0.4305	0.050*
C11	0.52773 (18)	0.40119 (18)	0.1941 (5)	0.0378 (9)
H11	0.4924	0.4338	0.1599	0.045*
C12	0.56827 (18)	0.36420 (17)	0.0866 (4)	0.0316 (7)
H12	0.5606	0.3717	−0.0223	0.038*
C13	0.5687 (2)	0.2003 (2)	−0.1361 (4)	0.0426 (9)
H13	0.5448	0.2090	−0.0331	0.051*
C14	0.5959 (2)	0.1212 (2)	−0.1387 (5)	0.0525 (11)
H14A	0.6153	0.1103	−0.2426	0.079*
H14B	0.5563	0.0890	−0.1157	0.079*
H14C	0.6332	0.1152	−0.0595	0.079*
C15	0.5155 (2)	0.2120 (3)	−0.2631 (6)	0.0559 (11)
H15A	0.5399	0.2072	−0.3654	0.067*
H15B	0.4792	0.1741	−0.2568	0.067*
C16	0.4807 (2)	0.2787 (3)	−0.2590 (6)	0.0681 (13)
H16A	0.4563	0.2843	−0.1583	0.102*
H16B	0.4459	0.2811	−0.3444	0.102*
H16C	0.5158	0.3168	−0.2717	0.102*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P1	0.0312 (4)	0.0257 (4)	0.0203 (4)	0.0035 (3)	0.0007 (4)	0.0007 (4)
O1	0.0430 (13)	0.0319 (12)	0.0268 (12)	0.0103 (10)	0.0011 (11)	0.0022 (10)
N1	0.0346 (15)	0.0327 (14)	0.0209 (13)	−0.0056 (12)	0.0039 (12)	−0.0014 (11)
C1	0.0280 (15)	0.0277 (16)	0.0258 (15)	0.0014 (13)	0.0042 (13)	−0.0057 (13)
C2	0.0318 (16)	0.0403 (18)	0.0401 (19)	0.0073 (14)	−0.0048 (15)	−0.0003 (16)
C3	0.0312 (18)	0.049 (2)	0.055 (2)	−0.0010 (17)	−0.0005 (17)	−0.0075 (19)
C4	0.040 (2)	0.0347 (18)	0.052 (2)	−0.0065 (16)	0.0083 (18)	−0.0070 (17)
C5	0.043 (2)	0.0233 (15)	0.045 (2)	0.0058 (15)	0.0054 (17)	0.0000 (15)
C6	0.0340 (17)	0.0272 (16)	0.0316 (17)	0.0034 (13)	0.0010 (15)	−0.0010 (14)
C7	0.0279 (15)	0.0246 (15)	0.0273 (16)	−0.0023 (13)	0.0010 (13)	−0.0021 (13)
C8	0.0292 (16)	0.0422 (19)	0.0264 (16)	0.0032 (15)	0.0011 (14)	−0.0045 (14)
C9	0.0378 (18)	0.050 (2)	0.0289 (18)	−0.0042 (17)	0.0016 (15)	−0.0130 (16)
C10	0.0329 (18)	0.044 (2)	0.047 (2)	−0.0021 (16)	0.0078 (16)	−0.0220 (18)
C11	0.0259 (16)	0.0318 (17)	0.056 (2)	−0.0006 (14)	0.0014 (17)	−0.0078 (17)
C12	0.0340 (17)	0.0288 (16)	0.0321 (17)	−0.0022 (14)	0.0007 (15)	−0.0022 (14)
C13	0.046 (2)	0.051 (2)	0.0307 (18)	−0.0153 (18)	0.0085 (17)	−0.0068 (16)
C14	0.058 (2)	0.050 (2)	0.049 (2)	−0.003 (2)	−0.001 (2)	−0.014 (2)
C15	0.041 (2)	0.068 (3)	0.059 (3)	−0.009 (2)	−0.0042 (19)	0.000 (2)
C16	0.053 (3)	0.091 (4)	0.060 (3)	0.002 (3)	0.000 (2)	−0.010 (3)

Geometric parameters (Å, º)

P1—O1	1.491 (2)	C8—H8	0.9500
P1—N1	1.634 (3)	C9—C10	1.366 (5)
P1—C1	1.796 (3)	C9—H9	0.9500
P1—C7	1.801 (3)	C10—C11	1.407 (6)
N1—C13	1.465 (4)	C10—H10	0.9500
N1—H1N	0.874 (10)	C11—C12	1.380 (5)
C1—C2	1.390 (4)	C11—H11	0.9500
C1—C6	1.390 (4)	C12—H12	0.9500
C2—C3	1.380 (5)	C13—C15	1.489 (6)
C2—H2	0.9500	C13—C14	1.572 (6)
C3—C4	1.375 (5)	C13—H13	1.0000
C3—H3	0.9500	C14—H14A	0.9800
C4—C5	1.371 (5)	C14—H14B	0.9800
C4—H4	0.9500	C14—H14C	0.9800
C5—C6	1.374 (5)	C15—C16	1.414 (7)
C5—H5	0.9500	C15—H15A	0.9900
C6—H6	0.9500	C15—H15B	0.9900
C7—C12	1.389 (5)	C16—H16A	0.9800
C7—C8	1.399 (4)	C16—H16B	0.9800
C8—C9	1.380 (5)	C16—H16C	0.9800
O1—P1—N1	119.42 (14)	C8—C9—H9	119.5
O1—P1—C1	110.88 (14)	C9—C10—C11	120.0 (3)
N1—P1—C1	103.43 (14)	C9—C10—H10	120.0
O1—P1—C7	109.58 (14)	C11—C10—H10	120.0
N1—P1—C7	105.65 (14)	C12—C11—C10	119.0 (3)
C1—P1—C7	107.09 (14)	C12—C11—H11	120.5
C13—N1—P1	120.2 (2)	C10—C11—H11	120.5
C13—N1—H1N	116 (2)	C11—C12—C7	121.3 (3)
P1—N1—H1N	114 (2)	C11—C12—H12	119.4
C2—C1—C6	119.0 (3)	C7—C12—H12	119.4
C2—C1—P1	117.5 (3)	N1—C13—C15	109.9 (3)
C6—C1—P1	123.5 (3)	N1—C13—C14	111.6 (3)
C3—C2—C1	120.3 (3)	C15—C13—C14	110.4 (3)
C3—C2—H2	119.8	N1—C13—H13	108.3
C1—C2—H2	119.8	C15—C13—H13	108.3
C4—C3—C2	119.8 (3)	C14—C13—H13	108.3
C4—C3—H3	120.1	C13—C14—H14A	109.5
C2—C3—H3	120.1	C13—C14—H14B	109.5
C5—C4—C3	120.5 (3)	H14A—C14—H14B	109.5
C5—C4—H4	119.8	C13—C14—H14C	109.5
C3—C4—H4	119.8	H14A—C14—H14C	109.5
C4—C5—C6	120.2 (3)	H14B—C14—H14C	109.5
C4—C5—H5	119.9	C16—C15—C13	115.1 (4)
C6—C5—H5	119.9	C16—C15—H15A	108.5
C5—C6—C1	120.2 (3)	C13—C15—H15A	108.5
C5—C6—H6	119.9	C16—C15—H15B	108.5
C1—C6—H6	119.9	C13—C15—H15B	108.5
C12—C7—C8	118.7 (3)	H15A—C15—H15B	107.5
C12—C7—P1	122.7 (3)	C15—C16—H16A	109.5
C8—C7—P1	118.5 (2)	C15—C16—H16B	109.5
C9—C8—C7	120.1 (3)	H16A—C16—H16B	109.5
C9—C8—H8	120.0	C15—C16—H16C	109.5
C7—C8—H8	120.0	H16A—C16—H16C	109.5
C10—C9—C8	120.9 (3)	H16B—C16—H16C	109.5
C10—C9—H9	119.5

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1^i	0.87 (1)	2.01 (2)	2.850 (3)	162 (3)

Symmetry code: (i) y+1/2, x−1/2, z−1/2.

(III) (S)-1-Phenylethylammonium N-[(S)-1-phenylethyl]phenylphosphonamidate

Crystal data

C8H12N^+·C14H15NO2P^−	Dx = 1.238 Mg m^−3
Mr = 382.43	Melting point: 436 K
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 7210 reflections
a = 5.3629 (1) Å	θ = 2.1–29.5°
b = 13.7260 (3) Å	µ = 0.15 mm^−1
c = 27.8653 (6) Å	T = 120 K
V = 2051.20 (7) Å^3	Needle, colourless
Z = 4	0.20 × 0.10 × 0.05 mm
F(000) = 816

Data collection

Rigaku Saturn724+ (2x2 bin mode) diffractometer	3764 independent reflections
Radiation source: Rotating Anode	3557 reflections with I > 2σ(I)
Multilayer monochromator	Rint = 0.031
Detector resolution: 28.5714 pixels mm^-1	θmax = 25.4°, θmin = 2.9°
profile data from ω–scans	h = −6→6
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2015)	k = −16→16
Tmin = 0.752, Tmax = 1.000	l = −33→33
11806 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.031	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.076	w = 1/[σ^2(Fo^2) + (0.0396P)^2 + 0.4266P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.001
3764 reflections	Δρmax = 0.28 e Å^−3
249 parameters	Δρmin = −0.23 e Å^−3
1 restraint	Absolute structure: Flack (1983), 1551 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.06 (8)

Special details

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 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 > 2sigma(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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
P1	0.53649 (8)	0.70582 (3)	0.102705 (14)	0.01661 (11)
O1	0.4176 (2)	0.70034 (8)	0.05362 (4)	0.0203 (3)
O2	0.7760 (2)	0.76070 (8)	0.10844 (4)	0.0231 (3)
N1	0.3244 (3)	0.75517 (11)	0.13835 (5)	0.0176 (3)
H1N	0.169 (2)	0.7447 (14)	0.1329 (7)	0.021*
N2	0.0745 (3)	0.84111 (9)	0.03747 (5)	0.0172 (3)
H2A	−0.0506	0.8368	0.0594	0.021*
H2B	0.1809	0.7901	0.0413	0.021*
H2C	0.0089	0.8396	0.0074	0.021*
C1	0.5869 (3)	0.58138 (12)	0.12223 (6)	0.0216 (4)
C2	0.4168 (4)	0.50824 (12)	0.10923 (6)	0.0266 (4)
H2D	0.2779	0.5240	0.0896	0.032*
C3	0.4497 (4)	0.41288 (13)	0.12488 (7)	0.0328 (4)
H3A	0.3332	0.3640	0.1160	0.039*
C4	0.6523 (4)	0.38909 (14)	0.15346 (7)	0.0320 (5)
H4A	0.6760	0.3238	0.1639	0.038*
C5	0.8196 (4)	0.46083 (14)	0.16670 (7)	0.0319 (5)
H5A	0.9582	0.4447	0.1864	0.038*
C6	0.7865 (4)	0.55663 (13)	0.15131 (7)	0.0266 (4)
H6A	0.9020	0.6054	0.1609	0.032*
C7	0.3941 (4)	0.89561 (14)	0.19150 (7)	0.0349 (5)
H7A	0.5263	0.9213	0.1708	0.052*
H7B	0.4274	0.9142	0.2248	0.052*
H7C	0.2331	0.9225	0.1814	0.052*
C8	0.3873 (3)	0.78453 (12)	0.18750 (6)	0.0207 (4)
H8A	0.5601	0.7606	0.1940	0.025*
C9	0.2165 (3)	0.73636 (12)	0.22426 (6)	0.0189 (4)
C10	0.2671 (4)	0.64161 (13)	0.23949 (6)	0.0256 (4)
H10A	0.4066	0.6078	0.2267	0.031*
C11	0.1164 (4)	0.59637 (14)	0.27301 (7)	0.0311 (5)
H11A	0.1535	0.5319	0.2832	0.037*
C12	−0.0881 (4)	0.64447 (14)	0.29186 (7)	0.0299 (4)
H12A	−0.1909	0.6133	0.3150	0.036*
C13	−0.1419 (4)	0.73817 (14)	0.27678 (7)	0.0279 (4)
H13A	−0.2823	0.7716	0.2895	0.034*
C14	0.0096 (3)	0.78320 (12)	0.24312 (6)	0.0234 (4)
H14A	−0.0291	0.8474	0.2328	0.028*
C15	0.3990 (3)	0.94562 (13)	0.00361 (6)	0.0239 (4)
H15A	0.5082	0.8884	0.0026	0.036*
H15B	0.4997	1.0043	0.0087	0.036*
H15C	0.3087	0.9512	−0.0268	0.036*
C16	0.2133 (3)	0.93465 (12)	0.04454 (6)	0.0188 (4)
H16A	0.3110	0.9286	0.0750	0.023*
C17	0.0305 (3)	1.01829 (11)	0.05097 (6)	0.0198 (4)
C18	−0.1226 (4)	1.01897 (14)	0.09136 (6)	0.0286 (4)
H18A	−0.1114	0.9673	0.1139	0.034*
C19	−0.2905 (4)	1.09362 (15)	0.09915 (7)	0.0358 (5)
H19A	−0.3944	1.0928	0.1267	0.043*
C20	−0.3070 (4)	1.16981 (14)	0.06657 (8)	0.0364 (5)
H20A	−0.4204	1.2218	0.0720	0.044*
C21	−0.1583 (4)	1.16967 (14)	0.02640 (8)	0.0377 (5)
H21A	−0.1708	1.2214	0.0039	0.045*
C22	0.0107 (4)	1.09435 (13)	0.01841 (7)	0.0294 (4)
H22A	0.1127	1.0951	−0.0094	0.035*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P1	0.0155 (2)	0.01943 (19)	0.0150 (2)	0.00198 (18)	0.00143 (17)	0.00226 (15)
O1	0.0222 (6)	0.0244 (6)	0.0145 (5)	0.0052 (6)	0.0002 (5)	0.0005 (5)
O2	0.0164 (6)	0.0275 (6)	0.0253 (6)	−0.0016 (5)	0.0018 (5)	0.0058 (5)
N1	0.0130 (7)	0.0249 (7)	0.0148 (7)	−0.0001 (6)	−0.0011 (5)	−0.0020 (6)
N2	0.0163 (7)	0.0187 (6)	0.0165 (6)	0.0020 (6)	−0.0012 (6)	−0.0005 (5)
C1	0.0231 (10)	0.0260 (9)	0.0159 (8)	0.0072 (8)	0.0024 (7)	0.0015 (7)
C2	0.0271 (10)	0.0243 (8)	0.0283 (9)	0.0019 (8)	0.0002 (8)	0.0011 (8)
C3	0.0337 (11)	0.0260 (9)	0.0386 (11)	−0.0027 (9)	0.0031 (10)	−0.0013 (8)
C4	0.0333 (11)	0.0266 (9)	0.0360 (11)	0.0088 (9)	0.0069 (9)	0.0079 (8)
C5	0.0298 (11)	0.0304 (10)	0.0355 (11)	0.0044 (9)	−0.0019 (9)	0.0090 (8)
C6	0.0233 (10)	0.0273 (9)	0.0293 (10)	−0.0011 (8)	−0.0017 (8)	0.0033 (8)
C7	0.0476 (13)	0.0284 (9)	0.0287 (10)	−0.0149 (10)	0.0104 (10)	−0.0051 (8)
C8	0.0199 (8)	0.0263 (9)	0.0159 (8)	−0.0043 (8)	−0.0012 (7)	−0.0010 (7)
C9	0.0189 (9)	0.0248 (9)	0.0131 (7)	−0.0046 (7)	−0.0020 (7)	−0.0019 (6)
C10	0.0245 (10)	0.0280 (9)	0.0242 (9)	0.0023 (8)	0.0018 (8)	−0.0003 (7)
C11	0.0370 (12)	0.0273 (9)	0.0289 (10)	0.0013 (9)	−0.0004 (9)	0.0077 (8)
C12	0.0292 (11)	0.0374 (10)	0.0230 (9)	−0.0087 (9)	0.0037 (8)	0.0053 (8)
C13	0.0208 (9)	0.0373 (10)	0.0257 (9)	−0.0008 (8)	0.0052 (8)	−0.0059 (8)
C14	0.0230 (9)	0.0242 (8)	0.0228 (8)	0.0005 (8)	−0.0020 (8)	0.0000 (7)
C15	0.0179 (9)	0.0257 (9)	0.0282 (9)	−0.0034 (8)	0.0025 (8)	−0.0001 (7)
C16	0.0161 (8)	0.0218 (8)	0.0184 (8)	−0.0026 (7)	−0.0038 (7)	−0.0012 (6)
C17	0.0186 (9)	0.0189 (8)	0.0220 (8)	−0.0012 (8)	−0.0041 (7)	−0.0027 (6)
C18	0.0332 (11)	0.0301 (9)	0.0224 (9)	0.0080 (9)	−0.0014 (8)	−0.0009 (7)
C19	0.0382 (12)	0.0411 (11)	0.0282 (10)	0.0139 (10)	0.0013 (10)	−0.0074 (9)
C20	0.0372 (12)	0.0255 (10)	0.0464 (12)	0.0105 (9)	−0.0036 (10)	−0.0083 (9)
C21	0.0358 (12)	0.0213 (9)	0.0559 (14)	0.0029 (9)	0.0015 (11)	0.0108 (9)
C22	0.0247 (10)	0.0251 (9)	0.0383 (10)	−0.0019 (8)	0.0045 (9)	0.0063 (8)

Geometric parameters (Å, º)

P1—O2	1.4979 (13)	C9—C10	1.395 (2)
P1—O1	1.5111 (11)	C10—C11	1.382 (3)
P1—N1	1.6551 (14)	C10—H10A	0.9500
P1—C1	1.8129 (17)	C11—C12	1.383 (3)
N1—C8	1.467 (2)	C11—H11A	0.9500
N1—H1N	0.861 (9)	C12—C13	1.384 (3)
N2—C16	1.497 (2)	C12—H12A	0.9500
N2—H2A	0.9100	C13—C14	1.386 (3)
N2—H2B	0.9100	C13—H13A	0.9500
N2—H2C	0.9100	C14—H14A	0.9500
C1—C6	1.385 (3)	C15—C16	1.522 (2)
C1—C2	1.404 (3)	C15—H15A	0.9800
C2—C3	1.391 (3)	C15—H15B	0.9800
C2—H2D	0.9500	C15—H15C	0.9800
C3—C4	1.386 (3)	C16—C17	1.520 (2)
C3—H3A	0.9500	C16—H16A	1.0000
C4—C5	1.382 (3)	C17—C22	1.387 (2)
C4—H4A	0.9500	C17—C18	1.393 (3)
C5—C6	1.394 (3)	C18—C19	1.381 (3)
C5—H5A	0.9500	C18—H18A	0.9500
C6—H6A	0.9500	C19—C20	1.388 (3)
C7—C8	1.529 (2)	C19—H19A	0.9500
C7—H7A	0.9800	C20—C21	1.374 (3)
C7—H7B	0.9800	C20—H20A	0.9500
C7—H7C	0.9800	C21—C22	1.393 (3)
C8—C9	1.525 (2)	C21—H21A	0.9500
C8—H8A	1.0000	C22—H22A	0.9500
C9—C14	1.386 (3)
O2—P1—O1	118.92 (7)	C10—C9—C8	119.47 (16)
O2—P1—N1	108.63 (7)	C11—C10—C9	120.71 (18)
O1—P1—N1	105.88 (7)	C11—C10—H10A	119.6
O2—P1—C1	108.29 (8)	C9—C10—H10A	119.6
O1—P1—C1	106.72 (7)	C10—C11—C12	120.36 (17)
N1—P1—C1	107.94 (8)	C10—C11—H11A	119.8
C8—N1—P1	120.99 (12)	C12—C11—H11A	119.8
C8—N1—H1N	115.6 (13)	C11—C12—C13	119.58 (18)
P1—N1—H1N	119.6 (13)	C11—C12—H12A	120.2
C16—N2—H2A	109.5	C13—C12—H12A	120.2
C16—N2—H2B	109.5	C12—C13—C14	119.84 (18)
H2A—N2—H2B	109.5	C12—C13—H13A	120.1
C16—N2—H2C	109.5	C14—C13—H13A	120.1
H2A—N2—H2C	109.5	C9—C14—C13	121.26 (16)
H2B—N2—H2C	109.5	C9—C14—H14A	119.4
C6—C1—C2	118.55 (16)	C13—C14—H14A	119.4
C6—C1—P1	121.47 (14)	C16—C15—H15A	109.5
C2—C1—P1	119.95 (13)	C16—C15—H15B	109.5
C3—C2—C1	120.62 (18)	H15A—C15—H15B	109.5
C3—C2—H2D	119.7	C16—C15—H15C	109.5
C1—C2—H2D	119.7	H15A—C15—H15C	109.5
C4—C3—C2	120.10 (19)	H15B—C15—H15C	109.5
C4—C3—H3A	120.0	N2—C16—C17	110.04 (14)
C2—C3—H3A	120.0	N2—C16—C15	108.16 (13)
C5—C4—C3	119.62 (18)	C17—C16—C15	115.83 (14)
C5—C4—H4A	120.2	N2—C16—H16A	107.5
C3—C4—H4A	120.2	C17—C16—H16A	107.5
C4—C5—C6	120.46 (19)	C15—C16—H16A	107.5
C4—C5—H5A	119.8	C22—C17—C18	118.56 (16)
C6—C5—H5A	119.8	C22—C17—C16	122.74 (16)
C1—C6—C5	120.64 (18)	C18—C17—C16	118.71 (15)
C1—C6—H6A	119.7	C19—C18—C17	121.06 (18)
C5—C6—H6A	119.7	C19—C18—H18A	119.5
C8—C7—H7A	109.5	C17—C18—H18A	119.5
C8—C7—H7B	109.5	C18—C19—C20	119.9 (2)
H7A—C7—H7B	109.5	C18—C19—H19A	120.1
C8—C7—H7C	109.5	C20—C19—H19A	120.1
H7A—C7—H7C	109.5	C21—C20—C19	119.66 (19)
H7B—C7—H7C	109.5	C21—C20—H20A	120.2
N1—C8—C9	111.72 (14)	C19—C20—H20A	120.2
N1—C8—C7	110.33 (14)	C20—C21—C22	120.56 (18)
C9—C8—C7	113.45 (15)	C20—C21—H21A	119.7
N1—C8—H8A	107.0	C22—C21—H21A	119.7
C9—C8—H8A	107.0	C17—C22—C21	120.28 (18)
C7—C8—H8A	107.0	C17—C22—H22A	119.9
C14—C9—C10	118.23 (16)	C21—C22—H22A	119.9
C14—C9—C8	122.30 (15)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O2^i	0.86 (1)	2.22 (1)	3.0576 (19)	163 (2)
N2—H2A···O2^i	0.91	1.95	2.7733 (18)	149
N2—H2B···O1	0.91	1.80	2.7058 (18)	172
N2—H2C···O1^ii	0.91	1.85	2.7340 (17)	163

Symmetry codes: (i) x−1, y, z; (ii) x−1/2, −y+3/2, −z.

(fh24) (4-Methylbenzyl)ammonium diphenylphosphinate

Crystal data

C8H12N^+·C12H10O2P^−	F(000) = 720
Mr = 339.35	Dx = 1.291 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 6.0483 (1) Å	Cell parameters from 8313 reflections
b = 18.8540 (5) Å	θ = 2.5–27.5°
c = 15.4364 (5) Å	µ = 0.17 mm^−1
β = 97.231 (1)°	T = 100 K
V = 1746.28 (8) Å^3	Block, clear colourless
Z = 4	0.12 × 0.1 × 0.1 mm

Data collection

Bruker D8 Venture diffractometer	3565 independent reflections
Radiation source: high brilliance microfocus sealed tube	2819 reflections with I > 2σ(I)
Multilayer monochromator	Rint = 0.044
φ and ω scans	θmax = 26.4°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2016)	h = −7→7
Tmin = 0.662, Tmax = 0.746	k = −23→20
11792 measured reflections	l = −17→19

Refinement

Refinement on F^2	3 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.041	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.101	w = 1/[σ^2(Fo^2) + (0.0362P)^2 + 0.9756P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max = 0.001
3565 reflections	Δρmax = 0.38 e Å^−3
227 parameters	Δρmin = −0.44 e Å^−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.1896 (3)	0.55594 (9)	0.24611 (11)	0.0133 (4)
O1	0.2613 (2)	0.55658 (7)	0.42213 (8)	0.0157 (3)
P1	0.11183 (8)	0.59115 (2)	0.34817 (3)	0.01203 (13)
C2	0.0448 (3)	0.50911 (10)	0.19710 (12)	0.0186 (4)
H2	−0.0935	0.4974	0.2165	0.022*
O2	−0.1347 (2)	0.58177 (7)	0.34598 (8)	0.0166 (3)
C3	0.1004 (3)	0.47955 (11)	0.12041 (13)	0.0233 (5)
H3	0.0000	0.4480	0.0875	0.028*
C4	0.3027 (3)	0.49613 (11)	0.09177 (13)	0.0218 (4)
H4	0.3414	0.4758	0.0394	0.026*
C5	0.4478 (3)	0.54239 (10)	0.13975 (13)	0.0196 (4)
H5	0.5860	0.5539	0.1200	0.023*
C6	0.3925 (3)	0.57220 (10)	0.21681 (12)	0.0153 (4)
H6	0.4934	0.6037	0.2495	0.018*
C7	0.1784 (3)	0.68466 (10)	0.34784 (11)	0.0128 (4)
C8	0.3891 (3)	0.70912 (10)	0.38182 (12)	0.0163 (4)
H8	0.4998	0.6765	0.4060	0.020*
C9	0.4377 (3)	0.78129 (10)	0.38046 (13)	0.0190 (4)
H9	0.5817	0.7978	0.4032	0.023*
C10	0.2758 (3)	0.82892 (10)	0.34591 (12)	0.0185 (4)
H10	0.3087	0.8782	0.3456	0.022*
C11	0.0660 (3)	0.80514 (10)	0.31172 (12)	0.0191 (4)
H11	−0.0440	0.8380	0.2875	0.023*
C12	0.0170 (3)	0.73318 (10)	0.31290 (12)	0.0165 (4)
H12	−0.1271	0.7169	0.2898	0.020*
N1	0.3728 (3)	0.52482 (8)	0.59635 (10)	0.0140 (3)
H1A	0.316 (3)	0.5395 (11)	0.5425 (11)	0.017*
H1B	0.275 (3)	0.4924 (10)	0.6153 (13)	0.017*
H1C	0.497 (3)	0.4996 (10)	0.5901 (13)	0.017*
C13	0.4157 (3)	0.58479 (10)	0.65881 (12)	0.0156 (4)
H13A	0.4882	0.5662	0.7154	0.019*
H13B	0.2716	0.6061	0.6689	0.019*
C14	0.5616 (3)	0.64174 (10)	0.62711 (11)	0.0143 (4)
C15	0.5115 (3)	0.71268 (10)	0.64020 (12)	0.0175 (4)
H15	0.3828	0.7246	0.6666	0.021*
C16	0.6477 (3)	0.76609 (10)	0.61505 (12)	0.0192 (4)
H16	0.6109	0.8142	0.6249	0.023*
C17	0.8367 (3)	0.75089 (10)	0.57578 (12)	0.0170 (4)
C18	0.9852 (3)	0.80966 (10)	0.55062 (13)	0.0230 (5)
H18A	1.0674	0.8303	0.6034	0.035*
H18B	0.8939	0.8464	0.5187	0.035*
H18C	1.0908	0.7905	0.5134	0.035*
C19	0.8846 (3)	0.67987 (10)	0.56126 (12)	0.0164 (4)
H19	1.0111	0.6681	0.5334	0.020*
C20	0.7502 (3)	0.62596 (10)	0.58698 (12)	0.0168 (4)
H20	0.7870	0.5779	0.5772	0.020*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0151 (9)	0.0122 (9)	0.0120 (9)	0.0007 (7)	−0.0007 (7)	0.0041 (7)
O1	0.0191 (7)	0.0138 (6)	0.0143 (7)	0.0014 (5)	0.0026 (5)	0.0023 (5)
P1	0.0122 (2)	0.0110 (2)	0.0130 (2)	−0.00091 (18)	0.00157 (17)	0.00126 (18)
C2	0.0188 (10)	0.0176 (10)	0.0201 (10)	−0.0034 (8)	0.0051 (8)	0.0004 (8)
O2	0.0136 (7)	0.0166 (7)	0.0201 (7)	−0.0033 (5)	0.0038 (5)	0.0004 (5)
C3	0.0290 (11)	0.0212 (10)	0.0198 (10)	−0.0084 (9)	0.0038 (9)	−0.0042 (8)
C4	0.0299 (11)	0.0198 (10)	0.0174 (10)	−0.0011 (9)	0.0093 (8)	−0.0015 (8)
C5	0.0186 (10)	0.0184 (10)	0.0229 (11)	0.0010 (8)	0.0078 (8)	0.0031 (8)
C6	0.0139 (9)	0.0157 (9)	0.0158 (9)	0.0004 (7)	0.0001 (7)	0.0020 (7)
C7	0.0141 (9)	0.0138 (9)	0.0109 (9)	−0.0007 (7)	0.0030 (7)	0.0006 (7)
C8	0.0161 (9)	0.0168 (9)	0.0158 (9)	0.0007 (8)	0.0014 (7)	0.0029 (8)
C9	0.0173 (10)	0.0202 (10)	0.0195 (10)	−0.0071 (8)	0.0025 (8)	−0.0011 (8)
C10	0.0287 (11)	0.0126 (9)	0.0154 (10)	−0.0031 (8)	0.0075 (8)	−0.0001 (7)
C11	0.0245 (11)	0.0157 (10)	0.0174 (10)	0.0048 (8)	0.0029 (8)	0.0026 (8)
C12	0.0162 (9)	0.0184 (9)	0.0146 (9)	0.0013 (8)	0.0015 (7)	0.0001 (8)
N1	0.0146 (8)	0.0131 (8)	0.0144 (8)	0.0003 (6)	0.0028 (6)	0.0022 (6)
C13	0.0182 (10)	0.0150 (9)	0.0139 (9)	−0.0009 (8)	0.0034 (7)	−0.0007 (7)
C14	0.0170 (9)	0.0165 (9)	0.0089 (9)	0.0006 (8)	0.0002 (7)	0.0003 (7)
C15	0.0188 (10)	0.0195 (10)	0.0144 (10)	0.0017 (8)	0.0035 (8)	−0.0002 (8)
C16	0.0261 (11)	0.0127 (9)	0.0185 (10)	0.0030 (8)	0.0020 (8)	−0.0015 (8)
C17	0.0206 (10)	0.0181 (10)	0.0114 (9)	−0.0030 (8)	−0.0020 (7)	−0.0004 (7)
C18	0.0267 (11)	0.0194 (10)	0.0228 (11)	−0.0068 (9)	0.0025 (9)	0.0015 (8)
C19	0.0148 (9)	0.0195 (10)	0.0150 (9)	−0.0010 (8)	0.0028 (7)	−0.0008 (8)
C20	0.0192 (10)	0.0137 (9)	0.0171 (10)	0.0018 (8)	0.0010 (8)	−0.0004 (7)

Geometric parameters (Å, º)

C1—P1	1.8248 (18)	C11—C12	1.389 (3)
C1—C2	1.397 (3)	C12—H12	0.9500
C1—C6	1.394 (3)	N1—H1A	0.902 (15)
O1—P1	1.5118 (13)	N1—H1B	0.922 (15)
P1—O2	1.4979 (13)	N1—H1C	0.905 (15)
P1—C7	1.8088 (18)	N1—C13	1.487 (2)
C2—H2	0.9500	C13—H13A	0.9900
C2—C3	1.387 (3)	C13—H13B	0.9900
C3—H3	0.9500	C13—C14	1.510 (3)
C3—C4	1.388 (3)	C14—C15	1.392 (3)
C4—H4	0.9500	C14—C20	1.397 (3)
C4—C5	1.384 (3)	C15—H15	0.9500
C5—H5	0.9500	C15—C16	1.387 (3)
C5—C6	1.394 (3)	C16—H16	0.9500
C6—H6	0.9500	C16—C17	1.390 (3)
C7—C8	1.394 (3)	C17—C18	1.508 (3)
C7—C12	1.396 (3)	C17—C19	1.394 (3)
C8—H8	0.9500	C18—H18A	0.9800
C8—C9	1.393 (3)	C18—H18B	0.9800
C9—H9	0.9500	C18—H18C	0.9800
C9—C10	1.385 (3)	C19—H19	0.9500
C10—H10	0.9500	C19—C20	1.390 (3)
C10—C11	1.386 (3)	C20—H20	0.9500
C11—H11	0.9500
C2—C1—P1	119.04 (14)	C7—C12—H12	119.8
C6—C1—P1	122.21 (14)	C11—C12—C7	120.32 (18)
C6—C1—C2	118.71 (17)	C11—C12—H12	119.8
O1—P1—C1	107.49 (8)	H1A—N1—H1B	108.2 (18)
O1—P1—C7	108.06 (8)	H1A—N1—H1C	106.7 (18)
O2—P1—C1	107.55 (8)	H1B—N1—H1C	105.0 (18)
O2—P1—O1	117.71 (7)	C13—N1—H1A	112.2 (13)
O2—P1—C7	109.66 (8)	C13—N1—H1B	111.3 (13)
C7—P1—C1	105.69 (8)	C13—N1—H1C	112.9 (13)
C1—C2—H2	119.6	N1—C13—H13A	109.0
C3—C2—C1	120.90 (18)	N1—C13—H13B	109.0
C3—C2—H2	119.6	N1—C13—C14	113.08 (15)
C2—C3—H3	120.0	H13A—C13—H13B	107.8
C2—C3—C4	119.94 (18)	C14—C13—H13A	109.0
C4—C3—H3	120.0	C14—C13—H13B	109.0
C3—C4—H4	120.1	C15—C14—C13	119.31 (16)
C5—C4—C3	119.77 (18)	C15—C14—C20	118.30 (17)
C5—C4—H4	120.1	C20—C14—C13	122.37 (16)
C4—C5—H5	119.8	C14—C15—H15	119.7
C4—C5—C6	120.43 (18)	C16—C15—C14	120.61 (17)
C6—C5—H5	119.8	C16—C15—H15	119.7
C1—C6—H6	119.9	C15—C16—H16	119.2
C5—C6—C1	120.24 (17)	C15—C16—C17	121.50 (18)
C5—C6—H6	119.9	C17—C16—H16	119.2
C8—C7—P1	120.99 (14)	C16—C17—C18	120.67 (17)
C8—C7—C12	119.37 (17)	C16—C17—C19	117.86 (17)
C12—C7—P1	119.64 (14)	C19—C17—C18	121.46 (17)
C7—C8—H8	119.9	C17—C18—H18A	109.5
C9—C8—C7	120.13 (18)	C17—C18—H18B	109.5
C9—C8—H8	119.9	C17—C18—H18C	109.5
C8—C9—H9	120.0	H18A—C18—H18B	109.5
C10—C9—C8	119.94 (18)	H18A—C18—H18C	109.5
C10—C9—H9	120.0	H18B—C18—H18C	109.5
C9—C10—H10	119.8	C17—C19—H19	119.5
C9—C10—C11	120.39 (18)	C20—C19—C17	121.03 (17)
C11—C10—H10	119.8	C20—C19—H19	119.5
C10—C11—H11	120.1	C14—C20—H20	119.7
C10—C11—C12	119.84 (18)	C19—C20—C14	120.69 (17)
C12—C11—H11	120.1	C19—C20—H20	119.7

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1	0.90 (2)	1.87 (2)	2.755 (2)	165 (2)
N1—H1B···O2^i	0.92 (2)	1.78 (2)	2.688 (2)	168 (2)
N1—H1C···O1^ii	0.91 (2)	1.83 (2)	2.738 (2)	177 (2)

Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1, −y+1, −z+1.