Structural differences/similarities of diastereotopic groups in three new chiral phos­pho­ramides

The crystal structures of two single-enanti­omer amido­phos­pho­esters with an (O)₂P(O)(N) skeleton and one single-enanti­omer phos­pho­ric tri­amide with an (N)₂P(O)(N) skeleton were studied. The com­pounds are diphenyl [(R)-(+)-α-4-di­methyl­benzyl­amido]­phosphate, (I), and diphenyl [(S)-(−)-α-4-di­methyl­benzyl­amido]­phosphate, (II), both C₂₁H₂₂NO₃P, and N-(2,6-di­fluoro­benzo­yl)-N′,N′′-bis­[(R)-(+)-α-ethyl­benz­yl]phos­pho­ric tri­amide, C₂₅H₂₈F₂N₃O₂P, (III). The asymmetric units contain two amido­phos­pho­ester mol­ecules for (I) and (II), and one phos­pho­ric tri­amide mol­ecule for (III). In the crystal structures of (I) and (II), mol­ecules are assembled in a similar one-dimensional chiral ribbon architecture, but with almost a mirror-image relationship with respect to each other through N—H...O(P) and C—H...O(P) hydro­gen bonds along [010]. In the crystal structure of (III), the chiral tape architecture along [100] is mediated by N—H...O(P) and N—H...O(C) hydro­gen bonds, and the tapes are connected into slabs by C—H...O inter­actions (along the ab plane). The differences/similarities of the two diastereotopic phen­oxy groups in (I)/(II) and the two chiral amine fragments in (III) were studied on the grounds of geometry, conformation and contribution to the crystal packing, as well as ¹H and ¹³C signals in a solution NMR study.

Computing details

For all structures, data collection: GEMINI (Oxford Diffraction, 2006); cell refinement: CrysAlis PRO (Rigaku OD, 2017); data reduction: CrysAlis PRO (Rigaku OD, 2017). Program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007) for (I); SIR92 (Altomare et al., 1994) for (II), (III). For all structures, program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003); molecular graphics: CAMERON (Watkin et al., 1996); software used to prepare material for publication: CRYSTALS (Betteridge et al., 2003).

Diphenyl [(S)-(-)-α-4-dimethylbenzylamido]phosphate (I)

Crystal data

C21H22NO3P	F(000) = 776
Mr = 367.38	Dx = 1.296 Mg m^−3
Monoclinic, P21	Cu Kα radiation, λ = 1.54184 Å
a = 11.6763 (1) Å	Cell parameters from 27082 reflections
b = 7.2768 (1) Å	θ = 4–68°
c = 22.3075 (1) Å	µ = 1.46 mm^−1
β = 96.6429 (6)°	T = 120 K
V = 1882.66 (3) Å^3	Block, colourless
Z = 4	0.77 × 0.50 × 0.23 mm

Data collection

Oxford Diffraction Gemini diffractometer	6658 reflections with I > 2.0σ(I)
Graphite monochromator	Rint = 0.040
φ & ω scans	θmax = 67.7°, θmin = 3.8°
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2017)	h = −13→13
Tmin = 0.55, Tmax = 0.71	k = −8→8
37170 measured reflections	l = −26→26
6767 independent reflections

Refinement

Refinement on F^2	H atoms treated by a mixture of independent and constrained refinement
Least-squares matrix: full	Method = Modified Sheldrick w = 1/[σ^2(F^2) + ( 0.07P)^2 + 0.62P] , where P = (max(Fo^2,0) + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.037	(Δ/σ)max = 0.001
wR(F^2) = 0.094	Δρmax = 0.16 e Å^−3
S = 0.99	Δρmin = −0.24 e Å^−3
6767 reflections	Extinction correction: Larson (1970), Equation 22
479 parameters	Extinction coefficient: 4.7 (5)
9 restraints	Absolute structure: Parsons et al. (2013), 3063 Friedel Pairs
Primary atom site location: other	Absolute structure parameter: 0.005 (5)
Hydrogen site location: difference Fourier map

Special details

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems open-flow nitrogen cryostat (Cosier & Glazer, 1986) with a nominal stability of 0.1K.

Cosier, J. & Glazer, A.M., 1986. J. Appl. Cryst. 105-107.

Refinement. The X-ray diffraction measurements were carried out at 120 K on a Xcalibur, Gemini ultra diffractometer using the Cu Kα radiation (λ = 1.54184 Å) from a fine-focus sealed X-ray tube with a graphite monochromator and CCD detector Atlas S2. The data were corrected for absorption using the CrysAlis PRO software. The structures were solved by the charge-flipping method by program Superflip (Palatinus & Chapuis, 2007) and refined by full matrix least squares on F² with Crystals program (Betteridge et al., 2003).

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

	x	y	z	Uiso*/Ueq
P1	0.35645 (4)	0.36800 (8)	0.263727 (19)	0.0182
O1	0.23522 (11)	0.3562 (2)	0.23778 (6)	0.0240
O2	0.38873 (12)	0.26149 (19)	0.32613 (6)	0.0242
C1	0.36181 (17)	0.3214 (3)	0.38201 (9)	0.0235
C2	0.27620 (19)	0.4478 (3)	0.38935 (9)	0.0282
C3	0.2574 (2)	0.4979 (3)	0.44756 (10)	0.0348
C4	0.3230 (2)	0.4211 (3)	0.49727 (9)	0.0371
C5	0.4062 (2)	0.2922 (4)	0.48892 (10)	0.0363
C6	0.42627 (18)	0.2408 (3)	0.43115 (9)	0.0292
O3	0.44647 (11)	0.2549 (2)	0.23033 (6)	0.0227
C7	0.44610 (16)	0.2508 (3)	0.16727 (8)	0.0202
C8	0.35976 (17)	0.1576 (3)	0.13176 (9)	0.0248
C9	0.36807 (18)	0.1426 (3)	0.07036 (9)	0.0290
C10	0.46005 (19)	0.2196 (3)	0.04525 (9)	0.0298
C11	0.54447 (19)	0.3136 (3)	0.08172 (9)	0.0289
C12	0.53840 (17)	0.3289 (3)	0.14345 (9)	0.0258
N1	0.39639 (13)	0.5782 (2)	0.27308 (7)	0.0203
C13	0.51295 (16)	0.6428 (3)	0.29524 (8)	0.0209
C14	0.50335 (19)	0.8054 (3)	0.33747 (9)	0.0304
C15	0.58089 (16)	0.6928 (3)	0.24337 (9)	0.0199
C16	0.52780 (16)	0.7826 (3)	0.19243 (9)	0.0229
C17	0.58858 (18)	0.8192 (3)	0.14405 (9)	0.0258
C18	0.70361 (17)	0.7682 (3)	0.14501 (9)	0.0252
C19	0.75803 (16)	0.6860 (3)	0.19736 (9)	0.0235
C20	0.69675 (16)	0.6482 (3)	0.24568 (9)	0.0226
C21	0.76752 (19)	0.8001 (4)	0.09124 (10)	0.0382
P2	0.11485 (4)	0.87341 (8)	0.225528 (19)	0.0179
O4	0.24107 (11)	0.8664 (2)	0.23428 (6)	0.0232
O6	0.05091 (12)	0.7741 (2)	0.27593 (6)	0.0240
C28	0.05292 (17)	0.8443 (3)	0.33446 (8)	0.0221
C29	−0.04660 (17)	0.8187 (3)	0.36153 (9)	0.0266
C30	−0.05006 (18)	0.8808 (4)	0.42002 (9)	0.0316
C31	0.0439 (2)	0.9702 (3)	0.45047 (9)	0.0316
C32	0.14252 (19)	0.9949 (3)	0.42253 (9)	0.0313
C33	0.14817 (18)	0.9307 (3)	0.36428 (9)	0.0271
O5	0.05543 (11)	0.75067 (19)	0.17150 (6)	0.0222
C22	0.10223 (16)	0.7485 (3)	0.11609 (8)	0.0216
C23	0.1819 (2)	0.6154 (3)	0.10656 (10)	0.0310
C24	0.2232 (2)	0.6080 (4)	0.05062 (10)	0.0371
C25	0.1827 (2)	0.7300 (3)	0.00529 (9)	0.0334
C26	0.10249 (18)	0.8615 (4)	0.01565 (8)	0.0297
C27	0.06197 (16)	0.8733 (3)	0.07171 (8)	0.0251
N2	0.06771 (13)	1.0800 (2)	0.21615 (8)	0.0212
C34	−0.05409 (16)	1.1347 (3)	0.20458 (9)	0.0227
C35	−0.06374 (19)	1.2933 (3)	0.15932 (9)	0.0306
C36	−0.10619 (17)	1.1896 (3)	0.26143 (9)	0.0211
C37	−0.22077 (16)	1.1487 (3)	0.26727 (9)	0.0234
C38	−0.27116 (17)	1.2065 (3)	0.31741 (9)	0.0248
C39	−0.20789 (17)	1.3066 (3)	0.36353 (9)	0.0243
C40	−0.09269 (17)	1.3444 (3)	0.35766 (8)	0.0250
C41	−0.04268 (17)	1.2883 (3)	0.30748 (9)	0.0245
C42	−0.26229 (18)	1.3750 (4)	0.41733 (9)	0.0337
H1c2	0.2329	0.4986	0.3548	0.0338*
H1c3	0.1980	0.5832	0.4527	0.0412*
H1c4	0.3113	0.4572	0.5367	0.0433*
H1c5	0.4491	0.2374	0.5226	0.0430*
H1c6	0.4817	0.1518	0.4249	0.0347*
H1c8	0.2980	0.1032	0.1496	0.0290*
H1c9	0.3104	0.0751	0.0460	0.0354*
H1c10	0.4673	0.2064	0.0039	0.0367*
H1c11	0.6073	0.3656	0.0646	0.0352*
H1c12	0.5959	0.3938	0.1685	0.0303*
H1c13	0.5520	0.5391	0.3179	0.0245*
H1c14	0.5810	0.8463	0.3539	0.0456*
H2c14	0.4602	0.7679	0.3706	0.0459*
H3c14	0.4650	0.9104	0.3165	0.0459*
H1c16	0.4498	0.8167	0.1909	0.0268*
H1c17	0.5518	0.8813	0.1103	0.0306*
H1c19	0.8373	0.6548	0.2001	0.0285*
H1c20	0.7347	0.5864	0.2800	0.0259*
H1c21	0.8365	0.7266	0.0943	0.0578*
H2c21	0.7889	0.9273	0.0889	0.0582*
H3c21	0.7209	0.7707	0.0549	0.0582*
H1c29	−0.1095	0.7565	0.3406	0.0325*
H1c30	−0.1183	0.8633	0.4388	0.0381*
H1c31	0.0400	1.0157	0.4897	0.0371*
H1c32	0.2079	1.0592	0.4434	0.0374*
H1c33	0.2142	0.9454	0.3455	0.0329*
H1c23	0.2079	0.5319	0.1366	0.0377*
H1c24	0.2789	0.5205	0.0436	0.0450*
H1c25	0.2081	0.7210	−0.0333	0.0403*
H1c26	0.0769	0.9459	−0.0143	0.0353*
H1c27	0.0082	0.9643	0.0795	0.0287*
H1c34	−0.0965	1.0273	0.1868	0.0267*
H1c35	−0.1455	1.3272	0.1503	0.0459*
H3c35	−0.0207	1.3986	0.1767	0.0455*
H2c35	−0.0339	1.2550	0.1220	0.0455*
H1c37	−0.2653	1.0795	0.2364	0.0279*
H1c38	−0.3496	1.1792	0.3209	0.0300*
H1c40	−0.0486	1.4110	0.3885	0.0298*
H1c41	0.0355	1.3159	0.3041	0.0285*
H2c42	−0.2506	1.5066	0.4235	0.0502*
H3c42	−0.3447	1.3520	0.4121	0.0504*
H1c42	−0.2295	1.3101	0.4534	0.0507*
H1n1	0.3449 (14)	0.659 (2)	0.2629 (10)	0.0249 (19)*
H1n2	0.1201 (14)	1.167 (2)	0.2217 (10)	0.0263 (19)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P1	0.0194 (2)	0.0186 (2)	0.0164 (2)	−0.0007 (2)	0.00149 (16)	0.0001 (2)
O1	0.0205 (6)	0.0230 (7)	0.0282 (7)	−0.0034 (6)	0.0019 (5)	−0.0009 (6)
O2	0.0343 (8)	0.0216 (7)	0.0172 (6)	0.0031 (6)	0.0047 (5)	0.0030 (5)
C1	0.0275 (10)	0.0246 (11)	0.0187 (9)	−0.0058 (8)	0.0039 (7)	0.0000 (7)
C2	0.0338 (11)	0.0282 (11)	0.0234 (10)	−0.0020 (9)	0.0075 (8)	0.0017 (8)
C3	0.0379 (12)	0.0368 (12)	0.0321 (12)	−0.0055 (10)	0.0147 (10)	−0.0059 (10)
C4	0.0438 (13)	0.0487 (15)	0.0197 (10)	−0.0147 (11)	0.0071 (9)	−0.0079 (9)
C5	0.0342 (11)	0.0536 (15)	0.0201 (10)	−0.0115 (11)	−0.0014 (8)	0.0021 (10)
C6	0.0278 (11)	0.0363 (12)	0.0230 (10)	−0.0049 (9)	0.0011 (8)	0.0027 (9)
O3	0.0249 (7)	0.0266 (7)	0.0164 (6)	0.0041 (6)	0.0017 (5)	−0.0008 (6)
C7	0.0239 (9)	0.0201 (9)	0.0164 (9)	0.0042 (8)	0.0016 (7)	0.0005 (7)
C8	0.0223 (9)	0.0277 (10)	0.0243 (10)	−0.0006 (8)	0.0021 (8)	−0.0003 (8)
C9	0.0288 (10)	0.0345 (12)	0.0220 (10)	0.0013 (9)	−0.0038 (8)	−0.0036 (9)
C10	0.0360 (12)	0.0349 (12)	0.0186 (9)	0.0067 (9)	0.0040 (8)	−0.0002 (9)
C11	0.0294 (10)	0.0301 (11)	0.0290 (10)	0.0001 (8)	0.0111 (8)	0.0021 (8)
C12	0.0249 (10)	0.0250 (11)	0.0278 (10)	−0.0021 (8)	0.0043 (8)	−0.0045 (8)
N1	0.0183 (8)	0.0202 (8)	0.0212 (8)	0.0004 (7)	−0.0022 (6)	0.0021 (7)
C13	0.0203 (9)	0.0227 (10)	0.0184 (9)	−0.0033 (8)	−0.0036 (7)	0.0027 (8)
C14	0.0348 (11)	0.0339 (12)	0.0222 (10)	−0.0064 (9)	0.0018 (8)	−0.0060 (9)
C15	0.0226 (9)	0.0151 (9)	0.0211 (9)	−0.0027 (7)	−0.0010 (7)	−0.0003 (7)
C16	0.0206 (9)	0.0241 (10)	0.0238 (10)	0.0034 (8)	0.0015 (7)	0.0022 (8)
C17	0.0274 (10)	0.0276 (11)	0.0214 (9)	−0.0005 (8)	−0.0006 (8)	0.0040 (8)
C18	0.0245 (10)	0.0255 (11)	0.0258 (10)	−0.0058 (9)	0.0038 (8)	−0.0052 (8)
C19	0.0184 (9)	0.0203 (10)	0.0313 (11)	−0.0013 (8)	0.0005 (8)	−0.0043 (8)
C20	0.0209 (9)	0.0195 (10)	0.0258 (10)	−0.0020 (8)	−0.0047 (8)	0.0002 (8)
C21	0.0298 (11)	0.0565 (16)	0.0292 (11)	−0.0088 (11)	0.0073 (9)	−0.0041 (10)
P2	0.0183 (2)	0.0189 (2)	0.0165 (2)	−0.0005 (2)	0.00160 (15)	−0.0002 (2)
O4	0.0209 (6)	0.0240 (7)	0.0241 (6)	0.0019 (6)	0.0001 (5)	0.0001 (6)
O6	0.0290 (7)	0.0245 (7)	0.0189 (7)	−0.0046 (6)	0.0042 (5)	−0.0014 (6)
C28	0.0272 (9)	0.0223 (10)	0.0164 (8)	0.0012 (8)	0.0010 (7)	0.0018 (8)
C29	0.0239 (9)	0.0312 (12)	0.0245 (10)	−0.0039 (8)	0.0017 (8)	0.0009 (8)
C30	0.0301 (10)	0.0391 (12)	0.0269 (10)	0.0012 (10)	0.0084 (8)	0.0002 (11)
C31	0.0401 (12)	0.0366 (12)	0.0178 (9)	0.0004 (10)	0.0028 (9)	−0.0011 (9)
C32	0.0336 (12)	0.0382 (12)	0.0203 (10)	−0.0064 (10)	−0.0045 (8)	−0.0006 (9)
C33	0.0257 (10)	0.0349 (12)	0.0208 (9)	−0.0027 (9)	0.0030 (8)	0.0044 (8)
O5	0.0248 (7)	0.0230 (7)	0.0189 (6)	−0.0035 (6)	0.0029 (5)	−0.0036 (6)
C22	0.0221 (9)	0.0249 (10)	0.0179 (9)	−0.0032 (8)	0.0025 (7)	−0.0041 (8)
C23	0.0368 (12)	0.0315 (11)	0.0241 (10)	0.0088 (10)	0.0011 (9)	−0.0013 (9)
C24	0.0408 (13)	0.0410 (14)	0.0308 (11)	0.0128 (11)	0.0091 (10)	−0.0065 (10)
C25	0.0387 (12)	0.0411 (13)	0.0213 (10)	−0.0040 (10)	0.0074 (9)	−0.0062 (9)
C26	0.0337 (10)	0.0324 (11)	0.0223 (9)	−0.0067 (11)	0.0006 (8)	0.0020 (9)
C27	0.0246 (9)	0.0249 (9)	0.0256 (9)	0.0002 (9)	0.0020 (7)	−0.0020 (9)
N2	0.0172 (8)	0.0192 (8)	0.0263 (8)	−0.0021 (7)	−0.0013 (6)	−0.0021 (7)
C34	0.0202 (9)	0.0221 (10)	0.0246 (10)	0.0015 (8)	−0.0032 (7)	−0.0042 (8)
C35	0.0367 (12)	0.0310 (11)	0.0234 (10)	0.0102 (10)	0.0004 (9)	0.0002 (9)
C36	0.0229 (9)	0.0161 (9)	0.0233 (9)	0.0022 (7)	−0.0014 (7)	0.0006 (8)
C37	0.0212 (9)	0.0187 (9)	0.0286 (10)	−0.0006 (8)	−0.0036 (8)	−0.0001 (8)
C38	0.0212 (10)	0.0229 (10)	0.0300 (10)	−0.0018 (8)	0.0014 (8)	0.0049 (8)
C39	0.0279 (10)	0.0237 (10)	0.0208 (9)	0.0016 (8)	0.0008 (8)	0.0053 (8)
C40	0.0264 (10)	0.0249 (11)	0.0222 (9)	−0.0010 (8)	−0.0036 (7)	−0.0003 (8)
C41	0.0203 (9)	0.0254 (10)	0.0271 (10)	−0.0009 (8)	−0.0009 (8)	−0.0015 (8)
C42	0.0341 (11)	0.0436 (12)	0.0238 (9)	−0.0007 (11)	0.0049 (8)	0.0021 (11)

Geometric parameters (Å, º)

P1—O1	1.4685 (13)	P2—O4	1.4650 (13)
P1—O2	1.5997 (13)	P2—O6	1.5930 (14)
P1—O3	1.5870 (14)	P2—O5	1.5932 (13)
P1—N1	1.6056 (17)	P2—N2	1.6063 (17)
O2—C1	1.390 (2)	O6—C28	1.400 (2)
C1—C2	1.382 (3)	C28—C29	1.383 (3)
C1—C6	1.386 (3)	C28—C33	1.380 (3)
C2—C3	1.390 (3)	C29—C30	1.386 (3)
C2—H1c2	0.947	C29—H1c29	0.940
C3—C4	1.390 (3)	C30—C31	1.384 (3)
C3—H1c3	0.948	C30—H1c30	0.951
C4—C5	1.378 (4)	C31—C32	1.383 (3)
C4—H1c4	0.943	C31—H1c31	0.942
C5—C6	1.388 (3)	C32—C33	1.389 (3)
C5—H1c5	0.941	C32—H1c32	0.968
C6—H1c6	0.937	C33—H1c33	0.926
O3—C7	1.406 (2)	O5—C22	1.408 (2)
C7—C8	1.385 (3)	C22—C23	1.377 (3)
C7—C12	1.378 (3)	C22—C27	1.385 (3)
C8—C9	1.389 (3)	C23—C24	1.390 (3)
C8—H1c8	0.949	C23—H1c23	0.928
C9—C10	1.386 (3)	C24—C25	1.387 (3)
C9—H1c9	0.952	C24—H1c24	0.936
C10—C11	1.384 (3)	C25—C26	1.377 (3)
C10—H1c10	0.941	C25—H1c25	0.944
C11—C12	1.391 (3)	C26—C27	1.390 (3)
C11—H1c11	0.945	C26—H1c26	0.931
C12—H1c12	0.948	C27—H1c27	0.943
N1—C13	1.470 (2)	N2—C34	1.471 (2)
N1—H1n1	0.852 (16)	N2—H1n2	0.878 (16)
C13—C14	1.525 (3)	C34—C35	1.529 (3)
C13—C15	1.521 (3)	C34—C36	1.522 (3)
C13—H1c13	0.990	C34—H1c34	0.984
C14—H1c14	0.984	C35—H1c35	0.984
C14—H2c14	0.980	C35—H3c35	0.972
C14—H3c14	0.977	C35—H2c35	0.979
C15—C16	1.393 (3)	C36—C37	1.391 (3)
C15—C20	1.386 (3)	C36—C41	1.395 (3)
C16—C17	1.384 (3)	C37—C38	1.388 (3)
C16—H1c16	0.941	C37—H1c37	0.957
C17—C18	1.391 (3)	C38—C39	1.400 (3)
C17—H1c17	0.939	C38—H1c38	0.949
C18—C19	1.398 (3)	C39—C40	1.394 (3)
C18—C21	1.502 (3)	C39—C42	1.506 (3)
C19—C20	1.388 (3)	C40—C41	1.383 (3)
C19—H1c19	0.948	C40—H1c40	0.944
C20—H1c20	0.951	C41—H1c41	0.946
C21—H1c21	0.963	C42—H2c42	0.975
C21—H2c21	0.962	C42—H3c42	0.970
C21—H3c21	0.948	C42—H1c42	0.972
O1—P1—O2	115.72 (8)	O4—P2—O6	115.88 (8)
O1—P1—O3	116.43 (8)	O4—P2—O5	115.13 (8)
O2—P1—O3	93.15 (7)	O6—P2—O5	94.65 (7)
O1—P1—N1	111.06 (8)	O4—P2—N2	111.98 (9)
O2—P1—N1	108.23 (8)	O6—P2—N2	109.56 (8)
O3—P1—N1	110.91 (8)	O5—P2—N2	108.27 (8)
P1—O2—C1	124.99 (13)	P2—O6—C28	122.30 (13)
O2—C1—C2	123.81 (18)	O6—C28—C29	115.71 (17)
O2—C1—C6	114.72 (18)	O6—C28—C33	122.79 (17)
C2—C1—C6	121.46 (19)	C29—C28—C33	121.49 (18)
C1—C2—C3	118.7 (2)	C28—C29—C30	118.98 (19)
C1—C2—H1c2	119.2	C28—C29—H1c29	119.8
C3—C2—H1c2	122.1	C30—C29—H1c29	121.2
C2—C3—C4	120.5 (2)	C29—C30—C31	120.50 (19)
C2—C3—H1c3	118.8	C29—C30—H1c30	119.3
C4—C3—H1c3	120.6	C31—C30—H1c30	120.2
C3—C4—C5	119.8 (2)	C30—C31—C32	119.60 (19)
C3—C4—H1c4	120.4	C30—C31—H1c31	120.0
C5—C4—H1c4	119.7	C32—C31—H1c31	120.3
C4—C5—C6	120.4 (2)	C31—C32—C33	120.7 (2)
C4—C5—H1c5	119.9	C31—C32—H1c32	119.9
C6—C5—H1c5	119.6	C33—C32—H1c32	119.4
C5—C6—C1	119.1 (2)	C32—C33—C28	118.76 (19)
C5—C6—H1c6	121.2	C32—C33—H1c33	121.1
C1—C6—H1c6	119.8	C28—C33—H1c33	120.1
P1—O3—C7	123.70 (12)	P2—O5—C22	119.41 (11)
O3—C7—C8	120.00 (17)	O5—C22—C23	118.76 (18)
O3—C7—C12	117.70 (17)	O5—C22—C27	119.08 (17)
C8—C7—C12	122.09 (18)	C23—C22—C27	122.05 (18)
C7—C8—C9	118.24 (18)	C22—C23—C24	118.5 (2)
C7—C8—H1c8	120.2	C22—C23—H1c23	121.3
C9—C8—H1c8	121.5	C24—C23—H1c23	120.2
C8—C9—C10	120.86 (19)	C23—C24—C25	120.4 (2)
C8—C9—H1c9	118.6	C23—C24—H1c24	119.8
C10—C9—H1c9	120.5	C25—C24—H1c24	119.8
C9—C10—C11	119.65 (19)	C24—C25—C26	120.23 (19)
C9—C10—H1c10	121.1	C24—C25—H1c25	120.3
C11—C10—H1c10	119.2	C26—C25—H1c25	119.5
C10—C11—C12	120.45 (19)	C25—C26—C27	120.2 (2)
C10—C11—H1c11	119.6	C25—C26—H1c26	120.4
C12—C11—H1c11	119.9	C27—C26—H1c26	119.4
C11—C12—C7	118.70 (18)	C26—C27—C22	118.7 (2)
C11—C12—H1c12	120.6	C26—C27—H1c27	120.9
C7—C12—H1c12	120.7	C22—C27—H1c27	120.5
P1—N1—C13	126.30 (13)	P2—N2—C34	125.86 (14)
P1—N1—H1n1	115.9 (11)	P2—N2—H1n2	115.6 (11)
C13—N1—H1n1	117.8 (11)	C34—N2—H1n2	118.3 (11)
N1—C13—C14	108.94 (16)	N2—C34—C35	108.42 (16)
N1—C13—C15	111.39 (15)	N2—C34—C36	113.36 (15)
C14—C13—C15	111.50 (16)	C35—C34—C36	110.23 (16)
N1—C13—H1c13	106.3	N2—C34—H1c34	106.7
C14—C13—H1c13	109.8	C35—C34—H1c34	109.8
C15—C13—H1c13	108.8	C36—C34—H1c34	108.2
C13—C14—H1c14	109.5	C34—C35—H1c35	108.7
C13—C14—H2c14	109.3	C34—C35—H3c35	109.6
H1c14—C14—H2c14	109.6	H1c35—C35—H3c35	109.2
C13—C14—H3c14	112.0	C34—C35—H2c35	109.8
H1c14—C14—H3c14	107.1	H1c35—C35—H2c35	109.2
H2c14—C14—H3c14	109.3	H3c35—C35—H2c35	110.2
C13—C15—C16	120.72 (17)	C34—C36—C37	120.23 (17)
C13—C15—C20	120.55 (17)	C34—C36—C41	121.28 (18)
C16—C15—C20	118.72 (18)	C37—C36—C41	118.43 (18)
C15—C16—C17	120.43 (18)	C36—C37—C38	120.85 (18)
C15—C16—H1c16	119.4	C36—C37—H1c37	119.5
C17—C16—H1c16	120.2	C38—C37—H1c37	119.6
C16—C17—C18	121.17 (18)	C37—C38—C39	120.87 (18)
C16—C17—H1c17	119.4	C37—C38—H1c38	120.4
C18—C17—H1c17	119.4	C39—C38—H1c38	118.7
C17—C18—C19	118.15 (18)	C38—C39—C40	117.83 (18)
C17—C18—C21	120.94 (19)	C38—C39—C42	121.49 (19)
C19—C18—C21	120.90 (19)	C40—C39—C42	120.67 (18)
C18—C19—C20	120.53 (18)	C39—C40—C41	121.34 (18)
C18—C19—H1c19	120.1	C39—C40—H1c40	119.0
C20—C19—H1c19	119.4	C41—C40—H1c40	119.7
C19—C20—C15	120.87 (18)	C36—C41—C40	120.67 (18)
C19—C20—H1c20	118.9	C36—C41—H1c41	119.1
C15—C20—H1c20	120.1	C40—C41—H1c41	120.2
C18—C21—H1c21	110.3	C39—C42—H2c42	111.9
C18—C21—H2c21	110.3	C39—C42—H3c42	110.6
H1c21—C21—H2c21	108.6	H2c42—C42—H3c42	107.9
C28—C21—H3c21	111.1	C39—C42—H1c42	109.7
H1c21—C21—H3c21	109.1	H2c42—C42—H1c42	108.9
H2c21—C21—H3c21	107.4	H3c42—C42—H1c42	107.7

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C23—H1c23···O1	0.93	2.58	3.477 (3)	162 (1)
N1—H1n1···O4	0.85	1.99	2.841 (2)	172 (2)
N2—H1n2···O1^i	0.88	1.93	2.807 (3)	177 (2)

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

Diphenyl [(S)-(-)-α-4-dimethylbenzylamido]phosphate (II)

Crystal data

C21H22NO3P	Dx = 1.296 Mg m^−3
Mr = 367.38	Melting point: not measured K
Monoclinic, P21	Cu Kα radiation, λ = 1.54184 Å
a = 11.6739 (1) Å	Cell parameters from 15780 reflections
b = 7.2783 (1) Å	θ = 4–68°
c = 22.3071 (2) Å	µ = 1.46 mm^−1
β = 96.6380 (9)°	T = 120 K
V = 1882.64 (4) Å^3	Needle, colourless
Z = 4	1.00 × 0.21 × 0.14 mm
F(000) = 776

Data collection

Oxford Diffraction Gemini diffractometer	6508 reflections with I > 2.0σ(I)
Graphite monochromator	Rint = 0.035
ω scans	θmax = 67.6°, θmin = 3.8°
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2017)	h = −13→13
Tmin = 0.55, Tmax = 0.81	k = −8→8
21509 measured reflections	l = −25→26
6650 independent reflections

Refinement

Refinement on F^2	H atoms treated by a mixture of independent and constrained refinement
Least-squares matrix: full	Method = Modified Sheldrick w = 1/[σ^2(F^2) + ( 0.16P)^2 + 1.04P] , where P = (max(Fo^2,0) + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.072	(Δ/σ)max = 0.0002
wR(F^2) = 0.182	Δρmax = 0.32 e Å^−3
S = 0.98	Δρmin = −0.30 e Å^−3
6650 reflections	Extinction correction: Larson (1970), Equation 22
479 parameters	Extinction coefficient: 3.6 (10)
9 restraints	Absolute structure: Parsons et al. (2013), 2934 Friedel Pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.021 (7)
Hydrogen site location: difference Fourier map

Special details

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems open-flow nitrogen cryostat (Cosier & Glazer, 1986) with a nominal stability of 0.1K.

Cosier, J. & Glazer, A.M., 1986. J. Appl. Cryst. 105-107.

Refinement. The X-ray diffraction measurements were carried out at 120 K on a Xcalibur, Gemini ultra diffractometer using the Cu Kα radiation (λ = 1.54184 Å) from a fine-focus sealed X-ray tube with a graphite monochromator and CCD detector Atlas S2. The data were corrected for absorption using the CrysAlis PRO software. The structures were solved by the charge-flipping method by program Superflip (Palatinus & Chapuis, 2007) and refined by full matrix least squares on F² with Crystals program (Betteridge et al., 2003).

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

	x	y	z	Uiso*/Ueq
N1	0.3964 (2)	0.0468 (4)	0.27317 (12)	0.0203
C13	0.5128 (3)	−0.0186 (5)	0.29517 (14)	0.0216
C14	0.5033 (3)	−0.1810 (5)	0.33730 (16)	0.0306
C15	0.5806 (3)	−0.0682 (4)	0.24347 (15)	0.0197
C20	0.6967 (3)	−0.0240 (5)	0.24571 (15)	0.0226
C19	0.7582 (3)	−0.0619 (5)	0.19730 (16)	0.0235
C18	0.7037 (3)	−0.1442 (5)	0.14503 (16)	0.0250
C17	0.5886 (3)	−0.1948 (5)	0.14403 (15)	0.0251
C16	0.5279 (3)	−0.1580 (5)	0.19244 (15)	0.0229
C21	0.7675 (3)	−0.1761 (7)	0.09098 (17)	0.0382
O3	0.4465 (2)	0.3693 (4)	0.23027 (10)	0.0225
C7	0.4461 (3)	0.3733 (5)	0.16733 (14)	0.0199
C12	0.5384 (3)	0.2951 (5)	0.14355 (16)	0.0255
C11	0.5444 (3)	0.3109 (5)	0.08152 (16)	0.0290
C10	0.4602 (3)	0.4048 (6)	0.04515 (15)	0.0295
C9	0.3679 (3)	0.4816 (6)	0.07042 (15)	0.0287
C8	0.3597 (3)	0.4664 (5)	0.13181 (15)	0.0246
P1	0.35637 (6)	0.25602 (14)	0.26374 (3)	0.0180
O1	0.23506 (19)	0.2679 (4)	0.23769 (10)	0.0246
O2	0.3884 (2)	0.3628 (3)	0.32602 (10)	0.0240
C1	0.3617 (3)	0.3026 (5)	0.38214 (14)	0.0230
C6	0.4262 (3)	0.3833 (6)	0.43106 (16)	0.0289
C5	0.4064 (4)	0.3313 (7)	0.48892 (16)	0.0360
C3	0.2571 (4)	0.1258 (6)	0.44756 (17)	0.0346
C2	0.2760 (3)	0.1766 (5)	0.38936 (16)	0.0285
N2	0.0676 (2)	0.5445 (4)	0.21613 (13)	0.0214
C34	−0.0539 (3)	0.4896 (5)	0.20444 (15)	0.0221
C35	−0.0638 (3)	0.3308 (5)	0.15931 (16)	0.0304
C36	−0.1062 (3)	0.4345 (5)	0.26153 (15)	0.0210
C41	−0.0429 (3)	0.3362 (5)	0.30732 (16)	0.0244
C40	−0.0927 (3)	0.2797 (5)	0.35766 (15)	0.0255
C39	−0.2081 (3)	0.3178 (5)	0.36352 (15)	0.0240
C38	−0.2716 (3)	0.4177 (5)	0.31749 (16)	0.0250
C37	−0.2206 (3)	0.4754 (5)	0.26736 (15)	0.0227
C42	−0.2625 (3)	0.2482 (7)	0.41730 (15)	0.0334
P2	0.11485 (6)	0.75073 (14)	0.22552 (3)	0.0179
O4	0.24126 (19)	0.7572 (4)	0.23436 (10)	0.0233
O5	0.05540 (19)	0.8733 (3)	0.17161 (10)	0.0228
C22	0.1020 (3)	0.8753 (5)	0.11603 (14)	0.0214
C27	0.0619 (3)	0.7503 (6)	0.07185 (14)	0.0256
C26	0.1025 (3)	0.7618 (6)	0.01574 (14)	0.0296
C25	0.1825 (3)	0.8947 (6)	0.00518 (16)	0.0327
C24	0.2234 (4)	1.0158 (6)	0.05033 (17)	0.0373
C23	0.1819 (3)	1.0082 (6)	0.10664 (16)	0.0312
O6	0.0508 (2)	0.8505 (3)	0.27597 (10)	0.0235
C28	0.0530 (3)	0.7800 (5)	0.33446 (14)	0.0219
C33	0.1483 (3)	0.6930 (5)	0.36425 (15)	0.0269
C32	0.1421 (3)	0.6282 (6)	0.42248 (16)	0.0314
C31	0.0438 (4)	0.6539 (6)	0.45056 (16)	0.0318
C30	−0.0500 (3)	0.7430 (6)	0.42011 (15)	0.0317
C29	−0.0470 (3)	0.8056 (5)	0.36153 (16)	0.0258
C4	0.3228 (4)	0.2033 (6)	0.49735 (16)	0.0366
H1c13	0.5527	0.0826	0.3182	0.0225*
H1c14	0.5777	−0.2249	0.3532	0.0440*
H3c14	0.4618	−0.2810	0.3157	0.0439*
H2c14	0.4607	−0.1448	0.3699	0.0440*
H1c20	0.7348	0.0356	0.2797	0.0238*
H1c19	0.8365	−0.0309	0.1999	0.0250*
H1c17	0.5516	−0.2587	0.1106	0.0279*
H1c16	0.4508	−0.1934	0.1909	0.0249*
H3c21	0.7171	−0.1636	0.0544	0.0543*
H2c21	0.7996	−0.2992	0.0926	0.0543*
H1c21	0.8295	−0.0875	0.0911	0.0542*
H1c12	0.5956	0.2303	0.1681	0.0279*
H1c11	0.6054	0.2560	0.0646	0.0331*
H1c10	0.4662	0.4194	0.0043	0.0332*
H1c9	0.3114	0.5468	0.0458	0.0320*
H1c8	0.2980	0.5197	0.1486	0.0269*
H1c6	0.4818	0.4733	0.4253	0.0318*
H1c5	0.4495	0.3864	0.5220	0.0422*
H1c3	0.1998	0.0424	0.4533	0.0379*
H1c2	0.2316	0.1255	0.3559	0.0309*
H1c34	−0.0971	0.5952	0.1858	0.0236*
H1c35	−0.1434	0.2952	0.1503	0.0420*
H2c35	−0.0342	0.3691	0.1228	0.0423*
H3c35	−0.0197	0.2258	0.1763	0.0418*
H1c41	0.0346	0.3082	0.3044	0.0260*
H1c40	−0.0483	0.2114	0.3877	0.0289*
H1c38	−0.3486	0.4461	0.3206	0.0278*
H1c37	−0.2649	0.5433	0.2370	0.0249*
H3c42	−0.3453	0.2549	0.4100	0.0461*
H2c42	−0.2415	0.1195	0.4246	0.0460*
H1c42	−0.2369	0.3187	0.4525	0.0462*
H1c27	0.0087	0.6591	0.0796	0.0269*
H1c26	0.0764	0.6759	−0.0144	0.0331*
H1c25	0.2078	0.9067	−0.0327	0.0371*
H1c24	0.2785	1.1018	0.0432	0.0418*
H1c23	0.2075	1.0922	0.1366	0.0339*
H1c33	0.2155	0.6763	0.3462	0.0300*
H1c32	0.2051	0.5666	0.4430	0.0340*
H1c31	0.0406	0.6095	0.4896	0.0350*
H1c30	−0.1165	0.7585	0.4388	0.0351*
H1c29	−0.1100	0.8667	0.3409	0.0290*
H1c4	0.3119	0.1633	0.5361	0.0401*
H1n2	0.1182 (17)	0.457 (3)	0.2231 (18)	0.026 (2)*
H1n1	0.3456 (19)	−0.035 (3)	0.2610 (17)	0.024 (2)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0168 (13)	0.0203 (14)	0.0234 (14)	−0.0001 (11)	0.0004 (10)	−0.0020 (11)
C13	0.0206 (15)	0.0238 (17)	0.0192 (15)	0.0027 (13)	−0.0030 (12)	−0.0027 (13)
C14	0.0330 (18)	0.036 (2)	0.0226 (16)	0.0074 (15)	0.0025 (14)	0.0060 (15)
C15	0.0212 (16)	0.0154 (15)	0.0218 (15)	0.0019 (12)	0.0003 (12)	0.0008 (12)
C20	0.0203 (16)	0.0191 (16)	0.0269 (16)	0.0021 (13)	−0.0039 (13)	0.0002 (14)
C19	0.0168 (14)	0.0211 (17)	0.0324 (18)	0.0009 (13)	0.0020 (13)	0.0042 (14)
C18	0.0231 (16)	0.0264 (18)	0.0258 (17)	0.0065 (14)	0.0044 (13)	0.0059 (14)
C17	0.0262 (17)	0.0273 (19)	0.0211 (15)	−0.0007 (13)	0.0006 (13)	−0.0029 (13)
C16	0.0199 (15)	0.0247 (17)	0.0238 (16)	−0.0030 (14)	0.0020 (12)	−0.0032 (13)
C21	0.0284 (18)	0.058 (3)	0.0293 (18)	0.0075 (18)	0.0081 (15)	0.0037 (18)
O3	0.0239 (11)	0.0273 (13)	0.0163 (11)	−0.0048 (10)	0.0021 (8)	0.0006 (9)
C7	0.0228 (16)	0.0211 (16)	0.0162 (14)	−0.0035 (13)	0.0035 (12)	0.0001 (12)
C12	0.0242 (16)	0.0257 (19)	0.0272 (16)	0.0022 (13)	0.0047 (13)	0.0049 (13)
C11	0.0303 (17)	0.031 (2)	0.0284 (17)	−0.0002 (14)	0.0129 (14)	−0.0012 (14)
C10	0.0340 (19)	0.036 (2)	0.0193 (16)	−0.0060 (15)	0.0051 (13)	0.0006 (14)
C9	0.0291 (17)	0.034 (2)	0.0221 (16)	−0.0007 (15)	−0.0021 (13)	0.0031 (15)
C8	0.0206 (15)	0.0288 (18)	0.0244 (16)	0.0003 (14)	0.0029 (12)	0.0003 (14)
P1	0.0180 (4)	0.0188 (4)	0.0172 (4)	0.0008 (3)	0.0024 (3)	0.0003 (3)
O1	0.0197 (11)	0.0248 (12)	0.0290 (11)	0.0040 (10)	0.0018 (8)	0.0016 (10)
O2	0.0330 (13)	0.0220 (12)	0.0177 (11)	−0.0023 (10)	0.0061 (9)	−0.0024 (9)
C1	0.0256 (16)	0.0256 (18)	0.0183 (14)	0.0058 (13)	0.0045 (12)	0.0005 (12)
C6	0.0254 (18)	0.036 (2)	0.0255 (17)	0.0044 (15)	0.0017 (13)	−0.0028 (15)
C5	0.0332 (18)	0.054 (3)	0.0201 (16)	0.0091 (19)	−0.0005 (14)	−0.0031 (17)
C3	0.036 (2)	0.038 (2)	0.0334 (19)	0.0041 (17)	0.0164 (16)	0.0062 (17)
C2	0.0320 (19)	0.0301 (19)	0.0243 (17)	0.0024 (15)	0.0074 (14)	−0.0009 (14)
N2	0.0174 (13)	0.0186 (14)	0.0275 (14)	0.0024 (11)	0.0006 (10)	0.0016 (11)
C34	0.0186 (15)	0.0227 (17)	0.0241 (16)	−0.0020 (13)	−0.0017 (12)	0.0055 (13)
C35	0.0344 (19)	0.0318 (19)	0.0241 (17)	−0.0096 (16)	0.0002 (14)	−0.0002 (15)
C36	0.0216 (16)	0.0182 (16)	0.0226 (15)	−0.0040 (13)	0.0003 (12)	−0.0005 (13)
C41	0.0197 (15)	0.0243 (17)	0.0287 (17)	0.0010 (13)	0.0007 (13)	0.0017 (14)
C40	0.0251 (16)	0.0276 (19)	0.0226 (15)	0.0021 (14)	−0.0020 (12)	0.0006 (14)
C39	0.0282 (17)	0.0234 (17)	0.0201 (15)	−0.0023 (13)	0.0018 (13)	−0.0051 (13)
C38	0.0184 (16)	0.0248 (18)	0.0316 (18)	0.0008 (13)	0.0020 (13)	−0.0051 (14)
C37	0.0189 (15)	0.0193 (16)	0.0286 (17)	0.0001 (13)	−0.0025 (13)	−0.0017 (14)
C42	0.0316 (18)	0.045 (2)	0.0245 (16)	0.0009 (18)	0.0062 (13)	−0.0012 (18)
P2	0.0171 (4)	0.0189 (4)	0.0177 (4)	0.0002 (3)	0.0024 (3)	0.0002 (3)
O4	0.0203 (11)	0.0251 (12)	0.0243 (10)	−0.0022 (11)	0.0013 (8)	−0.0008 (10)
O5	0.0247 (11)	0.0243 (13)	0.0201 (11)	0.0035 (10)	0.0057 (9)	0.0040 (9)
C22	0.0213 (15)	0.0257 (18)	0.0174 (15)	0.0038 (14)	0.0024 (12)	0.0024 (13)
C27	0.0260 (15)	0.0247 (16)	0.0261 (15)	−0.0004 (15)	0.0034 (12)	0.0020 (15)
C26	0.0324 (17)	0.034 (2)	0.0221 (15)	0.0060 (18)	0.0026 (13)	−0.0029 (16)
C25	0.037 (2)	0.040 (2)	0.0217 (16)	0.0045 (16)	0.0084 (14)	0.0066 (15)
C24	0.041 (2)	0.042 (2)	0.0304 (19)	−0.0128 (18)	0.0093 (16)	0.0057 (16)
C23	0.037 (2)	0.033 (2)	0.0239 (17)	−0.0098 (16)	0.0026 (14)	0.0006 (15)
O6	0.0278 (12)	0.0244 (13)	0.0188 (11)	0.0049 (10)	0.0047 (9)	0.0010 (9)
C28	0.0255 (16)	0.0229 (17)	0.0174 (14)	−0.0010 (13)	0.0023 (12)	−0.0016 (13)
C33	0.0251 (17)	0.033 (2)	0.0223 (16)	0.0028 (14)	0.0034 (13)	−0.0040 (13)
C32	0.0327 (19)	0.039 (2)	0.0205 (16)	0.0075 (16)	−0.0038 (14)	0.0001 (15)
C31	0.041 (2)	0.036 (2)	0.0184 (16)	−0.0018 (17)	0.0043 (14)	−0.0003 (15)
C30	0.0292 (17)	0.040 (2)	0.0275 (16)	−0.0004 (17)	0.0095 (13)	0.0007 (17)
C29	0.0229 (16)	0.0291 (19)	0.0251 (16)	0.0037 (13)	0.0018 (13)	−0.0011 (14)
C4	0.041 (2)	0.050 (3)	0.0200 (16)	0.0150 (18)	0.0082 (14)	0.0072 (16)

Geometric parameters (Å, º)

N1—C13	1.469 (4)	N2—P2	1.604 (3)
N1—P1	1.600 (3)	N2—H1n2	0.873 (18)
N1—H1n1	0.863 (18)	C34—C35	1.528 (5)
C13—C14	1.522 (5)	C34—C36	1.528 (5)
C13—C15	1.516 (4)	C34—H1c34	0.984
C13—H1c13	0.984	C35—H1c35	0.963
C14—H1c14	0.955	C35—H2c35	0.961
C14—H3c14	0.971	C35—H3c35	0.974
C14—H2c14	0.965	C36—C41	1.388 (5)
C15—C20	1.388 (5)	C36—C37	1.389 (5)
C15—C16	1.393 (5)	C41—C40	1.385 (5)
C20—C19	1.392 (5)	C41—H1c41	0.937
C20—H1c20	0.940	C40—C39	1.396 (5)
C19—C18	1.397 (5)	C40—H1c40	0.940
C19—H1c19	0.936	C39—C38	1.399 (5)
C18—C17	1.390 (5)	C39—C42	1.509 (5)
C18—C21	1.507 (5)	C38—C37	1.391 (5)
C17—C16	1.384 (5)	C38—H1c38	0.933
C17—H1c17	0.941	C37—H1c37	0.943
C16—H1c16	0.934	C42—H3c42	0.962
C21—H3c21	0.954	C42—H2c42	0.977
C21—H2c21	0.971	C42—H1c42	0.958
C21—H1c21	0.969	P2—O4	1.467 (2)
O3—C7	1.404 (4)	P2—O5	1.591 (2)
O3—P1	1.589 (2)	P2—O6	1.596 (2)
C7—C12	1.378 (5)	O5—C22	1.411 (4)
C7—C8	1.386 (5)	C22—C27	1.382 (5)
C12—C11	1.398 (5)	C22—C23	1.376 (5)
C12—H1c12	0.939	C27—C26	1.391 (5)
C11—C10	1.381 (5)	C27—H1c27	0.939
C11—H1c11	0.933	C26—C25	1.383 (6)
C10—C9	1.389 (5)	C26—H1c26	0.942
C10—H1c10	0.927	C25—C24	1.381 (6)
C9—C8	1.388 (5)	C25—H1c25	0.930
C9—H1c9	0.937	C24—C23	1.399 (5)
C8—H1c8	0.934	C24—H1c24	0.925
P1—O1	1.470 (2)	C23—H1c23	0.930
P1—O2	1.598 (2)	O6—C28	1.399 (4)
O2—C1	1.395 (4)	C28—C33	1.382 (5)
C1—C6	1.383 (5)	C28—C29	1.387 (5)
C1—C2	1.380 (5)	C33—C32	1.392 (5)
C6—C5	1.390 (5)	C33—H1c33	0.930
C6—H1c6	0.942	C32—C31	1.383 (6)
C5—C4	1.377 (6)	C32—H1c32	0.934
C5—H1c5	0.934	C31—C30	1.381 (6)
C3—C2	1.392 (5)	C31—H1c31	0.933
C3—C4	1.394 (6)	C30—C29	1.388 (5)
C3—H1c3	0.923	C30—H1c30	0.930
C2—H1c2	0.936	C29—H1c29	0.934
N2—C34	1.468 (4)	C4—H1c4	0.934
C13—N1—P1	126.7 (2)	N2—C34—C35	108.7 (3)
C13—N1—H1n1	117.1 (13)	N2—C34—C36	113.2 (3)
P1—N1—H1n1	116.0 (13)	C35—C34—C36	110.1 (3)
N1—C13—C14	109.1 (3)	N2—C34—H1c34	107.4
N1—C13—C15	111.5 (3)	C35—C34—H1c34	108.5
C14—C13—C15	111.5 (3)	C36—C34—H1c34	108.8
N1—C13—H1c13	107.2	C34—C35—H1c35	109.8
C14—C13—H1c13	108.9	C34—C35—H2c35	109.3
C15—C13—H1c13	108.5	H1c35—C35—H2c35	109.5
C13—C14—H1c14	111.2	C34—C35—H3c35	109.9
C13—C14—H3c14	110.1	H1c35—C35—H3c35	108.9
H1c14—C14—H3c14	108.3	H2c35—C35—H3c35	109.4
C13—C14—H2c14	109.6	C34—C36—C41	121.2 (3)
H1c14—C14—H2c14	109.7	C34—C36—C37	120.2 (3)
H3c14—C14—H2c14	108.0	C41—C36—C37	118.5 (3)
C13—C15—C20	120.7 (3)	C36—C41—C40	120.8 (3)
C13—C15—C16	120.9 (3)	C36—C41—H1c41	119.8
C20—C15—C16	118.4 (3)	C40—C41—H1c41	119.4
C15—C20—C19	121.0 (3)	C41—C40—C39	121.1 (3)
C15—C20—H1c20	120.3	C41—C40—H1c40	119.1
C19—C20—H1c20	118.7	C39—C40—H1c40	119.8
C20—C19—C18	120.4 (3)	C40—C39—C38	118.0 (3)
C20—C19—H1c19	119.5	C40—C39—C42	120.5 (3)
C18—C19—H1c19	120.1	C38—C39—C42	121.4 (3)
C19—C18—C17	118.2 (3)	C39—C38—C37	120.5 (3)
C19—C18—C21	120.9 (3)	C39—C38—H1c38	119.6
C17—C18—C21	120.8 (3)	C37—C38—H1c38	120.0
C18—C17—C16	121.1 (3)	C38—C37—C36	121.0 (3)
C18—C17—H1c17	119.8	C38—C37—H1c37	119.0
C16—C17—H1c17	119.0	C36—C37—H1c37	119.9
C15—C16—C17	120.7 (3)	C39—C42—H3c42	110.8
C15—C16—H1c16	119.5	C39—C42—H2c42	109.5
C17—C16—H1c16	119.8	H3c42—C42—H2c42	107.8
C18—C21—H3c21	110.9	C39—C42—H1c42	110.6
C18—C21—H2c21	109.7	H3c42—C42—H1c42	108.9
H3c21—C21—H2c21	108.5	H2c42—C42—H1c42	109.1
C18—C21—H1c21	109.5	N2—P2—O4	111.88 (15)
H3c21—C21—H1c21	109.0	N2—P2—O5	108.22 (14)
H2c21—C21—H1c21	109.2	O4—P2—O5	115.33 (13)
C7—O3—P1	123.7 (2)	N2—P2—O6	109.62 (14)
O3—C7—C12	117.7 (3)	O4—P2—O6	115.90 (13)
O3—C7—C8	120.0 (3)	O5—P2—O6	94.52 (12)
C12—C7—C8	122.1 (3)	P2—O5—C22	119.4 (2)
C7—C12—C11	118.5 (3)	O5—C22—C27	119.1 (3)
C7—C12—H1c12	121.1	O5—C22—C23	118.5 (3)
C11—C12—H1c12	120.3	C27—C22—C23	122.2 (3)
C12—C11—C10	120.6 (3)	C22—C27—C26	118.6 (3)
C12—C11—H1c11	119.4	C22—C27—H1c27	120.7
C10—C11—H1c11	120.0	C26—C27—H1c27	120.6
C11—C10—C9	119.6 (3)	C27—C26—C25	120.2 (4)
C11—C10—H1c10	120.3	C27—C26—H1c26	119.1
C9—C10—H1c10	120.2	C25—C26—H1c26	120.8
C10—C9—C8	120.9 (3)	C26—C25—C24	120.3 (3)
C10—C9—H1c9	119.5	C26—C25—H1c25	120.8
C8—C9—H1c9	119.5	C24—C25—H1c25	118.9
C9—C8—C7	118.3 (3)	C25—C24—C23	120.3 (4)
C9—C8—H1c8	120.4	C25—C24—H1c24	119.7
C7—C8—H1c8	121.3	C23—C24—H1c24	120.0
N1—P1—O3	110.88 (14)	C24—C23—C22	118.4 (4)
N1—P1—O1	111.20 (14)	C24—C23—H1c23	120.3
O3—P1—O1	116.33 (13)	C22—C23—H1c23	121.3
N1—P1—O2	108.25 (14)	P2—O6—C28	122.1 (2)
O3—P1—O2	93.14 (13)	O6—C28—C33	122.9 (3)
O1—P1—O2	115.68 (13)	O6—C28—C29	115.5 (3)
P1—O2—C1	125.0 (2)	C33—C28—C29	121.6 (3)
O2—C1—C6	114.6 (3)	C28—C33—C32	118.5 (3)
O2—C1—C2	123.6 (3)	C28—C33—H1c33	121.5
C6—C1—C2	121.7 (3)	C32—C33—H1c33	119.9
C1—C6—C5	118.9 (4)	C33—C32—C31	120.9 (3)
C1—C6—H1c6	120.6	C33—C32—H1c32	119.8
C5—C6—H1c6	120.5	C31—C32—H1c32	119.4
C6—C5—C4	120.5 (4)	C32—C31—C30	119.5 (3)
C6—C5—H1c5	118.9	C32—C31—H1c31	120.0
C4—C5—H1c5	120.5	C30—C31—H1c31	120.5
C2—C3—C4	120.3 (4)	C31—C30—C29	120.8 (3)
C2—C3—H1c3	119.9	C31—C30—H1c30	119.5
C4—C3—H1c3	119.8	C29—C30—H1c30	119.7
C3—C2—C1	118.7 (4)	C30—C29—C28	118.7 (3)
C3—C2—H1c2	120.4	C30—C29—H1c29	121.0
C1—C2—H1c2	120.9	C28—C29—H1c29	120.3
C34—N2—P2	126.0 (2)	C3—C4—C5	119.9 (3)
C34—N2—H1n2	116.9 (13)	C3—C4—H1c4	119.3
P2—N2—H1n2	116.6 (13)	C5—C4—H1c4	120.8

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C23—H1c23···O1^i	0.93	2.58	3.476 (5)	162 (1)
N2—H1n2···O1	0.87	1.94	2.809 (4)	178 (2)
N1—H1n1···O4^ii	0.86	1.99	2.848 (4)	174 (2)

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

N-(2,6-Difluorobenzoyl)-N',N''-bis[(R)-(+)-α-ethylbenzyl]phosphoric triamide (III)

Crystal data

C25H28F2N3O2P	Dx = 1.373 Mg m^−3
Mr = 471.49	Cu Kα radiation, λ = 1.54184 Å
Orthorhombic, P212121	Cell parameters from 24203 reflections
a = 4.9712 (1) Å	θ = 4–68°
b = 20.1758 (2) Å	µ = 1.45 mm^−1
c = 22.7451 (3) Å	T = 120 K
V = 2281.29 (6) Å^3	Blade, clear colourless
Z = 4	0.59 × 0.13 × 0.07 mm
F(000) = 992

Data collection

Oxford Diffraction Gemini diffractometer	3979 reflections with I > 2.0σ(I)
Graphite monochromator	Rint = 0.057
ω scans	θmax = 67.7°, θmin = 2.9°
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2017)	h = −5→5
Tmin = 0.50, Tmax = 0.90	k = −24→24
46145 measured reflections	l = −27→27
4088 independent reflections

Refinement

Refinement on F^2	Hydrogen site location: difference Fourier map
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.030	Method = Modified Sheldrick w = 1/[σ^2(F^2) + ( 0.04P)^2 + 1.67P] , where P = (max(Fo^2,0) + 2Fc^2)/3
wR(F^2) = 0.078	(Δ/σ)max = 0.005
S = 0.92	Δρmax = 0.19 e Å^−3
4088 reflections	Δρmin = −0.32 e Å^−3
311 parameters	Absolute structure: Parsons et al. (2013), 1653 Friedel Pairs
12 restraints	Absolute structure parameter: 0.007 (8)
Primary atom site location: structure-invariant direct methods

Special details

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems open-flow nitrogen cryostat (Cosier & Glazer, 1986) with a nominal stability of 0.1K.

Cosier, J. & Glazer, A.M., 1986. J. Appl. Cryst. 105-107.

Refinement. The X-ray diffraction measurements were carried out at 120 K on a Xcalibur, Gemini ultra diffractometer using the Cu Kα radiation (λ = 1.54184 Å) from a fine-focus sealed X-ray tube with a graphite monochromator and CCD detector Atlas S2. The data were corrected for absorption using the CrysAlis PRO software. The structures were solved by the charge-flipping method by program Superflip (Palatinus & Chapuis, 2007) and refined by full matrix least squares on F² with Crystals program (Betteridge et al., 2003).

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

	x	y	z	Uiso*/Ueq
P1	0.07561 (10)	0.66910 (2)	0.73635 (2)	0.0154
O2	−0.1943 (3)	0.64055 (6)	0.74758 (6)	0.0193
N3	0.0035 (3)	0.74731 (8)	0.71194 (8)	0.0184
C4	0.1933 (4)	0.79514 (9)	0.70452 (8)	0.0176
O5	0.4344 (3)	0.78367 (7)	0.70908 (6)	0.0223
C6	0.0926 (4)	0.86420 (9)	0.69282 (8)	0.0189
C7	−0.1059 (4)	0.87973 (10)	0.65208 (9)	0.0226
C8	−0.1952 (5)	0.94327 (11)	0.64216 (10)	0.0291
C9	−0.0815 (5)	0.99459 (10)	0.67407 (10)	0.0310
C10	0.1194 (5)	0.98211 (10)	0.71476 (10)	0.0300
C11	0.2004 (5)	0.91766 (10)	0.72311 (9)	0.0245
F12	0.3887 (3)	0.90571 (6)	0.76440 (6)	0.0369
F13	−0.2090 (3)	0.83004 (6)	0.61943 (5)	0.0283
N14	0.2733 (3)	0.67199 (8)	0.79303 (7)	0.0184
C15	0.1893 (4)	0.69598 (10)	0.85128 (8)	0.0191
C16	0.3211 (4)	0.65541 (10)	0.90037 (9)	0.0211
C17	0.5328 (4)	0.61208 (10)	0.89036 (9)	0.0228
C18	0.6495 (5)	0.57716 (11)	0.93681 (10)	0.0297
C19	0.5563 (6)	0.58553 (12)	0.99347 (9)	0.0338
C20	0.3440 (6)	0.62834 (13)	1.00383 (10)	0.0372
C21	0.2288 (5)	0.66332 (11)	0.95787 (9)	0.0299
C22	0.2386 (4)	0.77051 (10)	0.85989 (9)	0.0234
C23	0.5339 (5)	0.78974 (10)	0.85830 (10)	0.0280
N24	0.2604 (3)	0.63258 (8)	0.68762 (7)	0.0178
C25	0.1588 (4)	0.61409 (10)	0.62893 (8)	0.0194
C26	0.3720 (4)	0.62699 (10)	0.58186 (8)	0.0206
C27	0.5128 (4)	0.68640 (10)	0.58219 (9)	0.0230
C28	0.6998 (5)	0.70132 (11)	0.53869 (9)	0.0265
C29	0.7507 (5)	0.65638 (11)	0.49428 (9)	0.0274
C30	0.6115 (5)	0.59720 (11)	0.49313 (9)	0.0306
C31	0.4222 (5)	0.58281 (10)	0.53591 (9)	0.0266
C32	0.0389 (4)	0.54377 (10)	0.62948 (9)	0.0248
C33	0.2337 (5)	0.48950 (10)	0.64869 (10)	0.0327
H81	−0.3287	0.9503	0.6140	0.0359*
H91	−0.1395	1.0394	0.6668	0.0376*
H101	0.1991	1.0169	0.7367	0.0367*
H151	−0.0057	0.6873	0.8547	0.0227*
H171	0.5954	0.6063	0.8518	0.0273*
H181	0.7955	0.5491	0.9300	0.0370*
H191	0.6370	0.5615	1.0247	0.0407*
H201	0.2794	0.6344	1.0419	0.0438*
H211	0.0858	0.6934	0.9662	0.0375*
H222	0.1610	0.7842	0.8978	0.0284*
H221	0.1473	0.7943	0.8294	0.0278*
H233	0.5494	0.8373	0.8629	0.0422*
H232	0.6311	0.7676	0.8893	0.0428*
H231	0.6152	0.7772	0.8207	0.0417*
H251	0.0063	0.6449	0.6219	0.0236*
H271	0.4795	0.7170	0.6122	0.0283*
H281	0.7928	0.7419	0.5402	0.0326*
H291	0.8843	0.6664	0.4649	0.0346*
H301	0.6427	0.5663	0.4631	0.0370*
H311	0.3221	0.5426	0.5339	0.0318*
H321	−0.1156	0.5460	0.6567	0.0292*
H322	−0.0366	0.5322	0.5913	0.0302*
H332	0.1515	0.4464	0.6501	0.0491*
H331	0.2988	0.5003	0.6875	0.0479*
H333	0.3906	0.4866	0.6221	0.0488*
H31	−0.163 (3)	0.7587 (8)	0.7110 (10)	0.0220 (19)*
H141	0.439 (3)	0.6737 (11)	0.7864 (7)	0.0229 (19)*
H241	0.428 (3)	0.6274 (11)	0.6939 (7)	0.0225 (19)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P1	0.0122 (2)	0.0150 (2)	0.0190 (2)	0.00001 (19)	0.00033 (19)	−0.00053 (18)
O2	0.0125 (6)	0.0190 (6)	0.0264 (7)	−0.0011 (5)	0.0004 (5)	0.0010 (5)
N3	0.0103 (8)	0.0174 (8)	0.0277 (8)	0.0007 (6)	−0.0002 (6)	0.0010 (7)
C4	0.0169 (10)	0.0186 (9)	0.0174 (9)	−0.0008 (8)	0.0009 (8)	−0.0013 (7)
O5	0.0121 (7)	0.0217 (7)	0.0332 (7)	0.0005 (6)	0.0006 (6)	0.0012 (6)
C6	0.0166 (9)	0.0190 (9)	0.0212 (9)	0.0013 (8)	0.0027 (8)	0.0006 (7)
C7	0.0199 (10)	0.0231 (10)	0.0247 (10)	−0.0015 (8)	0.0022 (8)	0.0020 (8)
C8	0.0245 (11)	0.0312 (11)	0.0316 (11)	0.0049 (9)	−0.0004 (10)	0.0096 (9)
C9	0.0353 (13)	0.0191 (10)	0.0385 (12)	0.0085 (10)	0.0094 (11)	0.0051 (9)
C10	0.0387 (14)	0.0188 (10)	0.0324 (11)	−0.0016 (9)	0.0043 (10)	−0.0020 (8)
C11	0.0266 (11)	0.0222 (10)	0.0247 (10)	−0.0013 (9)	−0.0003 (9)	0.0019 (8)
F12	0.0419 (8)	0.0255 (6)	0.0432 (7)	−0.0050 (6)	−0.0210 (7)	−0.0020 (5)
F13	0.0285 (6)	0.0281 (6)	0.0284 (6)	−0.0046 (6)	−0.0083 (5)	0.0023 (5)
N14	0.0115 (8)	0.0231 (8)	0.0205 (8)	−0.0001 (7)	0.0010 (6)	−0.0029 (7)
C15	0.0125 (9)	0.0255 (10)	0.0194 (9)	0.0005 (8)	0.0010 (8)	−0.0044 (8)
C16	0.0208 (10)	0.0213 (10)	0.0211 (10)	−0.0061 (8)	−0.0003 (8)	−0.0011 (7)
C17	0.0230 (11)	0.0250 (10)	0.0205 (10)	−0.0022 (8)	0.0021 (8)	0.0007 (8)
C18	0.0307 (13)	0.0265 (11)	0.0318 (11)	−0.0008 (9)	−0.0013 (9)	0.0058 (9)
C19	0.0424 (15)	0.0338 (12)	0.0252 (11)	−0.0056 (11)	−0.0056 (11)	0.0073 (9)
C20	0.0481 (17)	0.0428 (14)	0.0209 (11)	−0.0061 (12)	0.0047 (10)	0.0016 (9)
C21	0.0306 (12)	0.0345 (11)	0.0245 (10)	0.0011 (10)	0.0046 (9)	−0.0042 (9)
C22	0.0216 (11)	0.0231 (10)	0.0255 (10)	0.0016 (9)	−0.0010 (9)	−0.0047 (8)
C23	0.0264 (12)	0.0230 (10)	0.0345 (11)	−0.0030 (9)	−0.0062 (10)	−0.0028 (9)
N24	0.0110 (8)	0.0228 (8)	0.0196 (8)	0.0011 (7)	−0.0008 (6)	−0.0019 (6)
C25	0.0158 (10)	0.0225 (10)	0.0200 (9)	0.0028 (8)	−0.0039 (8)	−0.0022 (7)
C26	0.0201 (11)	0.0234 (10)	0.0183 (9)	0.0040 (8)	−0.0035 (8)	0.0018 (7)
C27	0.0227 (11)	0.0251 (10)	0.0211 (10)	0.0020 (8)	0.0007 (8)	−0.0005 (8)
C28	0.0245 (11)	0.0306 (11)	0.0245 (10)	−0.0009 (9)	−0.0009 (9)	0.0034 (8)
C29	0.0251 (12)	0.0353 (12)	0.0217 (10)	0.0049 (9)	0.0019 (9)	0.0046 (8)
C30	0.0386 (14)	0.0326 (12)	0.0208 (10)	0.0085 (10)	0.0034 (10)	−0.0032 (8)
C31	0.0315 (12)	0.0241 (10)	0.0242 (10)	0.0013 (10)	−0.0008 (10)	−0.0023 (8)
C32	0.0240 (11)	0.0255 (11)	0.0249 (10)	−0.0023 (9)	−0.0023 (9)	−0.0036 (8)
C33	0.0412 (14)	0.0227 (11)	0.0342 (12)	0.0002 (10)	0.0036 (11)	0.0013 (9)

Geometric parameters (Å, º)

P1—O2	1.4823 (14)	C20—C21	1.385 (3)
P1—N3	1.7107 (16)	C20—H201	0.932
P1—N14	1.6221 (16)	C21—H211	0.954
P1—N24	1.6173 (16)	C22—C23	1.519 (3)
N3—C4	1.360 (3)	C22—H222	0.984
N3—H31	0.861 (16)	C22—H221	0.958
C4—O5	1.225 (3)	C23—H233	0.969
C4—C6	1.504 (3)	C23—H232	0.965
C6—C7	1.389 (3)	C23—H231	0.979
C6—C11	1.387 (3)	N24—C25	1.475 (2)
C7—C8	1.375 (3)	N24—H241	0.849 (16)
C7—F13	1.349 (2)	C25—C26	1.529 (3)
C8—C9	1.385 (3)	C25—C32	1.539 (3)
C8—H81	0.933	C25—H251	0.993
C9—C10	1.385 (3)	C26—C27	1.388 (3)
C9—H91	0.962	C26—C31	1.396 (3)
C10—C11	1.375 (3)	C27—C28	1.390 (3)
C10—H101	0.948	C27—H271	0.936
C11—F12	1.348 (3)	C28—C29	1.381 (3)
N14—C15	1.471 (2)	C28—H281	0.940
N14—H141	0.836 (16)	C29—C30	1.380 (3)
C15—C16	1.532 (3)	C29—H291	0.963
C15—C22	1.536 (3)	C30—C31	1.384 (3)
C15—H151	0.988	C30—H301	0.936
C16—C17	1.387 (3)	C31—H311	0.953
C16—C21	1.395 (3)	C32—C33	1.526 (3)
C17—C18	1.396 (3)	C32—H321	0.988
C17—H171	0.938	C32—H322	0.974
C18—C19	1.380 (3)	C33—H332	0.962
C18—H181	0.933	C33—H331	0.965
C19—C20	1.384 (4)	C33—H333	0.989
C19—H191	0.948
O2—P1—N3	102.99 (8)	C16—C21—C20	120.9 (2)
O2—P1—N14	115.18 (8)	C16—C21—H211	120.3
N3—P1—N14	110.60 (9)	C20—C21—H211	118.8
O2—P1—N24	117.08 (8)	C15—C22—C23	113.66 (17)
N3—P1—N24	108.47 (8)	C15—C22—H222	108.9
N14—P1—N24	102.52 (8)	C23—C22—H222	109.2
P1—N3—C4	123.32 (14)	C15—C22—H221	108.8
P1—N3—H31	117.1 (11)	C23—C22—H221	108.2
C4—N3—H31	118.4 (11)	H222—C22—H221	108.0
N3—C4—O5	122.30 (18)	C22—C23—H233	109.1
N3—C4—C6	116.62 (17)	C22—C23—H232	110.4
O5—C4—C6	121.04 (17)	H233—C23—H232	109.8
C4—C6—C7	124.28 (17)	C22—C23—H231	110.7
C4—C6—C11	120.24 (18)	H233—C23—H231	108.6
C7—C6—C11	115.48 (18)	H232—C23—H231	108.2
C6—C7—C8	123.28 (19)	P1—N24—C25	122.74 (13)
C6—C7—F13	118.01 (17)	P1—N24—H241	119.9 (11)
C8—C7—F13	118.67 (19)	C25—N24—H241	117.0 (11)
C7—C8—C9	118.6 (2)	N24—C25—C26	110.68 (15)
C7—C8—H81	119.0	N24—C25—C32	111.00 (16)
C9—C8—H81	122.4	C26—C25—C32	115.55 (16)
C8—C9—C10	120.58 (19)	N24—C25—H251	104.4
C8—C9—H91	119.3	C26—C25—H251	108.1
C10—C9—H91	120.1	C32—C25—H251	106.4
C9—C10—C11	118.4 (2)	C25—C26—C27	119.53 (17)
C9—C10—H101	121.2	C25—C26—C31	122.65 (18)
C11—C10—H101	120.4	C27—C26—C31	117.72 (19)
C6—C11—C10	123.6 (2)	C26—C27—C28	121.35 (19)
C6—C11—F12	118.37 (18)	C26—C27—H271	119.0
C10—C11—F12	117.96 (19)	C28—C27—H271	119.7
P1—N14—C15	123.74 (13)	C27—C28—C29	120.1 (2)
P1—N14—H141	117.0 (11)	C27—C28—H281	119.4
C15—N14—H141	115.3 (11)	C29—C28—H281	120.5
N14—C15—C16	111.04 (16)	C28—C29—C30	119.3 (2)
N14—C15—C22	113.06 (16)	C28—C29—H291	119.7
C16—C15—C22	111.22 (16)	C30—C29—H291	120.9
N14—C15—H151	107.0	C29—C30—C31	120.6 (2)
C16—C15—H151	105.5	C29—C30—H301	120.4
C22—C15—H151	108.6	C31—C30—H301	119.0
C15—C16—C17	122.81 (17)	C26—C31—C30	120.9 (2)
C15—C16—C21	118.77 (19)	C26—C31—H311	119.0
C17—C16—C21	118.40 (19)	C30—C31—H311	120.0
C16—C17—C18	120.60 (19)	C25—C32—C33	114.71 (18)
C16—C17—H171	119.0	C25—C32—H321	105.3
C18—C17—H171	120.4	C33—C32—H321	110.3
C17—C18—C19	120.4 (2)	C25—C32—H322	111.3
C17—C18—H181	120.3	C33—C32—H322	109.1
C19—C18—H181	119.3	H321—C32—H322	105.7
C18—C19—C20	119.4 (2)	C32—C33—H332	112.9
C18—C19—H191	119.6	C32—C33—H331	108.2
C20—C19—H191	120.9	H332—C33—H331	108.4
C19—C20—C21	120.3 (2)	C32—C33—H333	111.6
C19—C20—H201	120.2	H332—C33—H333	107.5
C21—C20—H201	119.4	H331—C33—H333	108.0

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C10—H101···O2^i	0.95	2.52	3.330 (3)	144
C27—H271···O5	0.94	2.59	3.512 (3)	168
N3—H31···O5^ii	0.86	2.06	2.923 (3)	179 (2)
N14—H141···O2^iii	0.84	2.13	2.911 (3)	154 (2)
N24—H241···O2^iii	0.85	2.26	3.039 (3)	153 (1)
C28—H281···F13^iii	0.94	2.53	3.213 (2)	130 (1)
C17—H171···O2^iii	0.94	2.68	3.566 (2)	158 (1)

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