N,N',N''-Tris(p-methoxy­phenyl)­phospho­ric triamide

The title compound, C₂₁H₂₄N₃O₄P, is a self-complementary hydrogen-bond (HB) building unit, with (P=)O as the primary HB acceptor and N-H as the HB donor. Each of the four crystallographically distinct and nearly parallel mol­ecules of the unit cell has a net dipole moment along the P=O bond direction and all of the dipoles are directed in the same general crystallographic direction. Head-to-tail N-H...O=P double-HB strands stack adjacent mol­ecules into one-dimensional infinite polar columns. Each polar column is a 2₁ helix and all columns are essentially parallel, resulting in polar order throughout the entire crystal.

S1. Comment

Realising polar order in organic systems has long been a goal in organic and material chemistry, due to applications that utilize non-linear optics, or piezo-, ferro- and pyroelectricity (Glaser & Kaszynski, 2001). Approaches to polar organic materials include the self-assembly of host–guest molecules (Hulliger et al., 1997), electric field poling of polymer films (Burland et al., 1994), Langmuir–Blodgett film multilayers (Ashwell, 1999) and grafted polymer brushes (Jaworek et al., 1998). However, spontaneous polar self-assembly potentially provides a pathway to the creation of polar order in thin organic films with a minimum number of processing steps (Stupp et al., 1997). By embracing supramolecular synthons as the critical design element for generating new organic materials (Desiraju, 1995), our efforts (Dyer et al., 2003) and those of others (Bushey et al., 2004; Facchetti et al., 2004) utilize hydrogen bond (HB) forces to direct spontaneous polar self-assembly, which requires the design of non-centrosymmetric building blocks with HB donors and acceptors incorporated in a single molecule. Such designed intermolecular HB interactions should favour head-to-tail molecular stacking and generate sheets, columns and three-dimensional polar domains. Nevertheless, nature's propensity for centrosymmetric aggregation of molecular dipole moments looms as a challenge for the design of polar order in organic materials (Hollingsworth, 2002). This communication details the crystal structure of N,N',N''-tris(p-methoxyphenyl)phosphoric triamide, (I), which represents one of our attempts at polar order through HB-directed spontaneous polar assembly. N,N',N''-tris(p-methyphenyl)phosphoric triamide has long been known (Audrieth & Toy, 1942). However, structural elucidation has been hindered by solvent inclusion (Cameron et al., 1976). Thus, our work represents the first crystal structure elucidation of an N,N',N''-triarylphosphoric triamide.

The molecule of (I) is composed of three aryloxy units bonded to the P atom via amide linkages, as shown in Fig. 1. Importantly, the amide H atoms should be capable of hydrogen bonding with neighbouring P═O bonds in order to bias the orientation and induce polar order. Geometric parameters of interest are listed in Table 1. The P1—O1 bond length in (I) is slightly longer than those in triphenylphosphine oxide [(C₆H₅)₃P═O 1.487 Å; Thomas & Hamor, 1993] and tris(tert-butyl)phosphoric triamide [(^tBu)NH]₃P═O 1.474 Å, hereinafter abbreviated as TBPA; Chivers et al., 2003]. This elongation reflects the generation of a more polar P⁺—O⁻ bond. The N3—P1—N1 angle in (I) is in good agreement with the N—P—N' angle (99.5°) in the crystal structure of tris(anilino)phosphine, (C₆H₅NH)₃P, which consists of a trigonal arrangement of aniline groups around a central P atom in a C₃ molecular symmetry (Tarassoli et al., 1982). It is noteworthy that both N1—H1 and N3—H3 point away from the P1—O1 bond vector, while N2—H2 is nearly parallel to it, in contrast with the three N—H bonds all directed below the N1—N2—N3 plane in (C₆H₅NH)₃P (Tarassoli et al., 1982). This upward twisting of N2—H2 probably minimizes the molecule dipole moment, a feature also observed in the structure of (C₆H₅NH)₃P═Se, a homologue of (I) without HB interactions (Chivers et al., 2003).

Since each molecule of (I) contains both HB donors and acceptors it is not surprising that significant HB interactions occur. Fig. 2 shows that each molecule acts as both donor and acceptor, atoms N1 and N3 acting as H-atom donors to the same atom O1 of an adjacent molecule at (−x, 1 − y, 1/2 + z), and atom N2 twisting to donate its H atom to atom O21 of a second adjacent molecule at (x, y, z − 1). Simultaneously, atom O1 acts as an H-atom acceptor from atoms N1 and N3 of a third molecule at (−x, 1 − y, z − 1/2), and atom O21 accepts an HB from atom N2 of a fourth adjacent molecule at (x, y, 1 + z). Thus, each molecule is hydrogen-bonded to four surrounding molecules. Details of the HB geometry are given in Table 2.

The resultant molecular chain is stacked in a head-to-tail manner and forms a one-dimensional columnar suprastructure parallel to the c axis. Within the column, double-HB strands exist as a result of the N1/N3—O(═P) interactions. There is a slight zigzag character to the column, due to the fact that the P═O bond is at an angle of 5.23 (5)° to the c axis, and the column is symmetrically disposed about a twofold screw axis. It is important to note that all P═O bonds are oriented in the same general direction; thus, the column is polar. Each polar column can be described as a 2₁ helix. Space-group symmetry generates additional parallel columns (Fig. 3) which are all oriented identically with respect to their polar axes, resulting in polar order and a net dipole moment along the c axis.

When compared with TBPA, the double-HB D···A distances in (I) are much shorter and the HB angles are significantly straighter. This indicates appreciably stronger HB interactions in (I) than in TBPA, the tripodal HB geometry of which is controlled by large steric factors (Chivers et al., 2003).

The N2—H2···O21 interaction seems fairly weak; however, the D—H···A bond is quite linear. A consequence of the upward twisting is that the N2—H2···O21 interaction reinforces the hydrogen-bonded molecular stacking inside a single column, and the upward-twisted phenyl ring encapsulates the double-HB strands inside the columnar core to avoid the formation of interpenetrating HBs. Concurrently, the encapsulation should also decrease the inter-columnar dipole interactions, therefore favouring the formation of polar order. Calculations indicate no intra- or intermolecular π–π or C—H···π(arene) interactions. The polar structure could be a consequence of the helical character of the columnar suprastructure.

S2. Experimental

Compound (I) was synthesized according to the literature procedure of Audrieth & Toy (1942). Rod-like single crystals of (I) were obtained by slow room-temperature evaporation of a dilute EtOH solution (m.p. 454.8 K). Spectroscopic analysis: R_F = 0.30 (95:5, CH₂Cl₂/CH₃OH); ¹H NMR (300 MHz, CDCl₃, δ, p.p.m.): 7.50 (d, J = 9.6 Hz, 1H), 7.10 (d, J = 8.7 Hz, 2H), 6.76 (d, J = 9.0 Hz, 2H), 3.67 (s, 3H); ¹³C NMR (75 MHz, CDCl₃, δ, p.p.m.): 154.00, 136.02, 119.41, 114.75, 55.90.

S3. Refinement

The three N-bound H atoms were refined isotropically. All other H atoms were treated as riding, with C—H distances ranging from 0.95 to 0.98 Å and with U_iso(H) values equal to 1.5 (methyl H atoms) or 1.2 (phenyl H atoms) times U_eq of the parent atom. The rotational orientations of the methyl H atoms were refined by the circular Fourier method available in SHELXTL (Bruker, 2005). Refinement of the N2 H atom improved the geometry of the N2—H2···O21 hydrogen bond significantly. The correct orientation of the structure with respect to the polar axis (Jones, 1986) in (I) was established from the value of 0.03 (7) for the Flack (1983) parameter.

Computing details

Data collection: APEX II (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT and SHELXTL (Bruker, 2005); program(s) used to solve structure: SHELXTL; program(s) used to refine structure: SHELXTL; molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXTL and PLATON.

Figures

	Fig. 1. The molecular structure and atom-numbering scheme for (I), with displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. The hydrogen bonding in (I) (dashed lines). The three crystallographically distinct hydrogen bonds generate one-dimensional molecular chains parallel to the c axis. [Symmetry codes: (i) −x, 1 − y, 1/2 + z; (ii) x, y, z − 1; (iii) −x, 1 − y, z − 1/2; (iv) x, y, 1 + z.]
	Fig. 3. The molecular packing in (I), viewed down [001], providing an end-on view of the one-dimensional molecular chains symmetrically disposed about twofold screw axes. Dashed lines represent hydrogen bonds.

N,N',N''-Tris(p-methoxyphenyl)phosphoric triamide

Crystal data

C21H24N3O4P	Dx = 1.359 Mg m^−3
Mr = 413.40	Melting point: 454.8 K
Orthorhombic, Pna21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 7209 reflections
a = 11.930 (2) Å	θ = 2.5–34.0°
b = 21.790 (4) Å	µ = 0.17 mm^−1
c = 7.7700 (16) Å	T = 100 K
V = 2019.9 (7) Å^3	Tabular, colourless
Z = 4	0.26 × 0.24 × 0.16 mm
F(000) = 872

Data collection

Bruker Kappa APEX-II CCD area-detector diffractometer	6527 independent reflections
Radiation source: sealed tube	5686 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.035
ω and ϕ scans	θmax = 34.1°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −18→17
Tmin = 0.755, Tmax = 0.973	k = −30→34
13717 measured reflections	l = −10→11

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)] = 0.040	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.100	w = 1/[σ^2(Fo^2) + (0.058P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max = 0.001
6527 reflections	Δρmax = 0.39 e Å^−3
277 parameters	Δρmin = −0.28 e Å^−3
1 restraint	Absolute structure: Flack (1983), with 2277 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.03 (7)

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

	x	y	z	Uiso*/Ueq
P1	0.12543 (3)	0.514029 (15)	0.00493 (5)	0.01419 (7)
O1	0.11435 (9)	0.51263 (5)	−0.18586 (16)	0.0199 (2)
O11	0.13401 (9)	0.82316 (5)	0.09961 (17)	0.0218 (2)
O21	0.42870 (9)	0.56760 (5)	0.70904 (16)	0.0211 (2)
O31	0.18503 (9)	0.20612 (5)	0.09595 (18)	0.0232 (2)
N1	0.05799 (10)	0.56947 (6)	0.10632 (19)	0.0166 (2)
N2	0.26083 (10)	0.51937 (5)	0.04899 (16)	0.0152 (2)
N3	0.07141 (10)	0.45476 (5)	0.10466 (19)	0.0166 (2)
C11	0.08164 (11)	0.63337 (6)	0.0984 (2)	0.0153 (2)
C12	0.01519 (11)	0.67334 (7)	0.1961 (2)	0.0171 (3)
H12	−0.0430	0.6572	0.2662	0.021*
C13	0.03343 (12)	0.73622 (7)	0.1916 (2)	0.0190 (3)
H13	−0.0132	0.7629	0.2567	0.023*
C14	0.12030 (11)	0.76033 (7)	0.0915 (2)	0.0170 (3)
C15	0.18676 (11)	0.72126 (6)	−0.0053 (2)	0.0182 (3)
H15	0.2459	0.7375	−0.0735	0.022*
C16	0.16701 (11)	0.65786 (6)	−0.0031 (2)	0.0171 (2)
H16	0.2121	0.6314	−0.0712	0.020*
C17	0.23094 (12)	0.84731 (7)	0.0144 (3)	0.0250 (3)
H17A	0.2981	0.8263	0.0567	0.038*
H17B	0.2371	0.8914	0.0380	0.038*
H17C	0.2239	0.8408	−0.1100	0.038*
C21	0.30652 (11)	0.53129 (6)	0.21555 (19)	0.0142 (2)
C22	0.40443 (12)	0.56568 (7)	0.2328 (2)	0.0187 (3)
H22	0.4407	0.5810	0.1328	0.022*
C23	0.45001 (11)	0.57789 (7)	0.3954 (2)	0.0194 (3)
H23	0.5172	0.6010	0.4054	0.023*
C24	0.39666 (11)	0.55605 (7)	0.5422 (2)	0.0164 (3)
C25	0.29977 (11)	0.52077 (6)	0.5250 (2)	0.0173 (3)
H25	0.2638	0.5050	0.6247	0.021*
C26	0.25561 (11)	0.50858 (7)	0.3643 (2)	0.0168 (3)
H26	0.1896	0.4844	0.3549	0.020*
C27	0.52381 (13)	0.60662 (8)	0.7312 (2)	0.0240 (3)
H27A	0.5901	0.5871	0.6806	0.036*
H27B	0.5366	0.6136	0.8543	0.036*
H27C	0.5101	0.6460	0.6740	0.036*
C31	0.10658 (11)	0.39279 (6)	0.0951 (2)	0.0151 (2)
C32	0.19732 (10)	0.37240 (6)	−0.0031 (2)	0.0157 (2)
H32	0.2397	0.4010	−0.0685	0.019*
C33	0.22639 (10)	0.31010 (6)	−0.0060 (2)	0.0168 (2)
H33	0.2882	0.2967	−0.0733	0.020*
C34	0.16482 (12)	0.26785 (6)	0.0895 (2)	0.0178 (3)
C35	0.07420 (13)	0.28830 (7)	0.1888 (2)	0.0212 (3)
H35	0.0319	0.2598	0.2547	0.025*
C36	0.04608 (11)	0.34993 (7)	0.1913 (2)	0.0184 (3)
H36	−0.0154	0.3633	0.2594	0.022*
C37	0.27586 (12)	0.18361 (7)	−0.0063 (3)	0.0245 (3)
H37A	0.2608	0.1920	−0.1281	0.037*
H37B	0.2836	0.1393	0.0109	0.037*
H37C	0.3454	0.2041	0.0281	0.037*
H1	0.0078 (18)	0.5599 (9)	0.166 (3)	0.023 (5)*
H2	0.3054 (16)	0.5274 (9)	−0.045 (3)	0.019 (5)*
H3	0.0167 (19)	0.4615 (10)	0.157 (3)	0.028 (6)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P1	0.01283 (12)	0.01857 (16)	0.01118 (16)	−0.00032 (11)	−0.00012 (13)	0.00007 (14)
O1	0.0161 (4)	0.0318 (6)	0.0119 (5)	0.0007 (4)	−0.0013 (4)	−0.0007 (4)
O11	0.0240 (5)	0.0161 (5)	0.0254 (6)	−0.0007 (4)	0.0006 (5)	0.0037 (4)
O21	0.0218 (5)	0.0284 (6)	0.0132 (5)	−0.0050 (4)	−0.0037 (4)	−0.0018 (4)
O31	0.0254 (5)	0.0164 (5)	0.0278 (7)	−0.0012 (4)	0.0090 (5)	−0.0017 (5)
N1	0.0157 (5)	0.0168 (6)	0.0174 (6)	−0.0003 (4)	0.0046 (4)	−0.0001 (5)
N2	0.0143 (5)	0.0211 (6)	0.0102 (6)	−0.0016 (4)	−0.0001 (4)	0.0006 (4)
N3	0.0143 (5)	0.0182 (6)	0.0174 (6)	−0.0015 (4)	0.0042 (4)	−0.0007 (5)
C11	0.0147 (5)	0.0187 (6)	0.0125 (6)	−0.0011 (4)	−0.0008 (5)	0.0006 (5)
C12	0.0141 (5)	0.0207 (6)	0.0167 (7)	0.0004 (5)	0.0011 (5)	0.0017 (5)
C13	0.0179 (6)	0.0198 (7)	0.0192 (8)	0.0035 (5)	0.0004 (5)	0.0014 (5)
C14	0.0180 (6)	0.0175 (6)	0.0155 (7)	−0.0005 (4)	−0.0031 (5)	0.0014 (5)
C15	0.0174 (5)	0.0203 (6)	0.0168 (7)	−0.0019 (4)	0.0003 (6)	0.0025 (5)
C16	0.0169 (5)	0.0191 (6)	0.0152 (6)	−0.0012 (4)	0.0021 (5)	0.0009 (5)
C17	0.0226 (6)	0.0207 (7)	0.0318 (9)	−0.0026 (5)	−0.0023 (7)	0.0054 (7)
C21	0.0150 (5)	0.0150 (6)	0.0126 (7)	0.0006 (4)	0.0000 (4)	0.0004 (5)
C22	0.0164 (6)	0.0240 (7)	0.0156 (7)	−0.0044 (5)	0.0003 (5)	0.0028 (5)
C23	0.0168 (5)	0.0223 (7)	0.0192 (8)	−0.0041 (5)	−0.0009 (5)	−0.0006 (6)
C24	0.0171 (5)	0.0170 (6)	0.0152 (7)	0.0013 (5)	−0.0025 (4)	−0.0019 (5)
C25	0.0193 (5)	0.0197 (6)	0.0130 (7)	−0.0026 (4)	−0.0001 (5)	0.0007 (5)
C26	0.0179 (5)	0.0177 (6)	0.0147 (7)	−0.0033 (4)	−0.0002 (5)	0.0002 (5)
C27	0.0218 (6)	0.0305 (8)	0.0198 (8)	−0.0028 (6)	−0.0053 (6)	−0.0060 (6)
C31	0.0141 (5)	0.0179 (6)	0.0133 (7)	−0.0021 (4)	−0.0006 (4)	−0.0024 (5)
C32	0.0148 (5)	0.0194 (6)	0.0129 (6)	−0.0022 (4)	0.0017 (5)	−0.0002 (5)
C33	0.0142 (5)	0.0207 (6)	0.0155 (7)	−0.0004 (4)	0.0003 (5)	−0.0016 (5)
C34	0.0189 (6)	0.0168 (6)	0.0176 (7)	−0.0027 (5)	0.0021 (5)	−0.0014 (5)
C35	0.0219 (6)	0.0208 (7)	0.0208 (8)	−0.0046 (5)	0.0066 (6)	−0.0015 (6)
C36	0.0175 (5)	0.0200 (7)	0.0177 (7)	−0.0023 (5)	0.0056 (5)	−0.0017 (5)
C37	0.0219 (6)	0.0193 (6)	0.0324 (9)	0.0005 (5)	0.0074 (7)	−0.0021 (7)

Geometric parameters (Å, º)

P1—O1	1.4886 (13)	C17—H17C	0.9800
P1—N1	1.6514 (13)	C21—C22	1.3942 (19)
P1—N3	1.6381 (13)	C21—C26	1.396 (2)
P1—N2	1.6552 (12)	C22—C23	1.401 (2)
O11—C14	1.3802 (18)	C22—H22	0.9500
O11—C17	1.4328 (19)	C23—C24	1.390 (2)
O21—C24	1.3748 (18)	C23—H23	0.9500
O21—C27	1.4284 (19)	C24—C25	1.3947 (19)
O31—C34	1.3674 (18)	C25—C26	1.381 (2)
O31—C37	1.4305 (19)	C25—H25	0.9500
N1—C11	1.4221 (19)	C26—H26	0.9500
N1—H1	0.78 (2)	C27—H27A	0.9800
N2—C21	1.4281 (19)	C27—H27B	0.9800
N2—H2	0.92 (2)	C27—H27C	0.9800
N3—C31	1.4161 (19)	C31—C36	1.397 (2)
N3—H3	0.78 (2)	C31—C32	1.3970 (19)
C11—C16	1.394 (2)	C32—C33	1.4012 (19)
C11—C12	1.401 (2)	C32—H32	0.9500
C12—C13	1.388 (2)	C33—C34	1.392 (2)
C12—H12	0.9500	C33—H33	0.9500
C13—C14	1.398 (2)	C34—C35	1.401 (2)
C13—H13	0.9500	C35—C36	1.384 (2)
C14—C15	1.386 (2)	C35—H35	0.9500
C15—C16	1.4016 (19)	C36—H36	0.9500
C15—H15	0.9500	C37—H37A	0.9800
C16—H16	0.9500	C37—H37B	0.9800
C17—H17A	0.9800	C37—H37C	0.9800
C17—H17B	0.9800
O1—P1—N3	114.83 (7)	C21—C22—C23	120.91 (14)
O1—P1—N2	107.10 (6)	C21—C22—H22	119.5
N3—P1—N2	109.97 (7)	C23—C22—H22	119.5
O1—P1—N1	116.54 (7)	C24—C23—C22	119.82 (13)
N3—P1—N1	99.17 (7)	C24—C23—H23	120.1
N1—P1—N2	108.98 (6)	C22—C23—H23	120.1
C14—O11—C17	116.03 (12)	O21—C24—C23	125.72 (13)
C24—O21—C27	116.33 (13)	O21—C24—C25	114.95 (14)
C34—O31—C37	116.78 (12)	C23—C24—C25	119.30 (14)
C11—N1—P1	126.80 (10)	C26—C25—C24	120.61 (15)
C11—N1—H1	115.9 (15)	C26—C25—H25	119.7
P1—N1—H1	117.3 (15)	C24—C25—H25	119.7
C21—N2—P1	124.94 (10)	C25—C26—C21	120.95 (13)
C21—N2—H2	117.6 (13)	C25—C26—H26	119.5
P1—N2—H2	114.5 (13)	C21—C26—H26	119.5
C31—N3—P1	127.62 (11)	O21—C27—H27A	109.5
C31—N3—H3	117.0 (16)	O21—C27—H27B	109.5
P1—N3—H3	115.2 (16)	H27A—C27—H27B	109.5
C16—C11—C12	118.81 (13)	O21—C27—H27C	109.5
C16—C11—N1	122.96 (13)	H27A—C27—H27C	109.5
C12—C11—N1	118.23 (12)	H27B—C27—H27C	109.5
C13—C12—C11	120.76 (13)	C36—C31—C32	118.68 (13)
C13—C12—H12	119.6	C36—C31—N3	117.16 (13)
C11—C12—H12	119.6	C32—C31—N3	124.16 (13)
C12—C13—C14	120.08 (14)	C31—C32—C33	120.58 (13)
C12—C13—H13	120.0	C31—C32—H32	119.7
C14—C13—H13	120.0	C33—C32—H32	119.7
O11—C14—C15	124.50 (13)	C34—C33—C32	120.10 (13)
O11—C14—C13	115.80 (13)	C34—C33—H33	120.0
C15—C14—C13	119.69 (13)	C32—C33—H33	120.0
C14—C15—C16	120.18 (13)	O31—C34—C33	125.23 (13)
C14—C15—H15	119.9	O31—C34—C35	115.40 (13)
C16—C15—H15	119.9	C33—C34—C35	119.37 (13)
C11—C16—C15	120.46 (13)	C36—C35—C34	120.20 (13)
C11—C16—H16	119.8	C36—C35—H35	119.9
C15—C16—H16	119.8	C34—C35—H35	119.9
O11—C17—H17A	109.5	C35—C36—C31	121.07 (13)
O11—C17—H17B	109.5	C35—C36—H36	119.5
H17A—C17—H17B	109.5	C31—C36—H36	119.5
O11—C17—H17C	109.5	O31—C37—H37A	109.5
H17A—C17—H17C	109.5	O31—C37—H37B	109.5
H17B—C17—H17C	109.5	H37A—C37—H37B	109.5
C22—C21—C26	118.39 (14)	O31—C37—H37C	109.5
C22—C21—N2	120.29 (13)	H37A—C37—H37C	109.5
C26—C21—N2	121.31 (12)	H37B—C37—H37C	109.5
O1—P1—N1—C11	−67.61 (14)	N2—C21—C22—C23	179.80 (13)
N3—P1—N1—C11	168.60 (13)	C21—C22—C23—C24	−0.6 (2)
N2—P1—N1—C11	53.68 (15)	C27—O21—C24—C23	1.5 (2)
O1—P1—N2—C21	170.02 (11)	C27—O21—C24—C25	−176.43 (13)
N3—P1—N2—C21	−64.57 (13)	C22—C23—C24—O21	−176.10 (14)
N1—P1—N2—C21	43.14 (13)	C22—C23—C24—C25	1.7 (2)
O1—P1—N3—C31	65.18 (15)	O21—C24—C25—C26	176.70 (13)
N1—P1—N3—C31	−169.84 (13)	C23—C24—C25—C26	−1.3 (2)
N2—P1—N3—C31	−55.68 (15)	C24—C25—C26—C21	−0.1 (2)
P1—N1—C11—C16	1.4 (2)	C22—C21—C26—C25	1.2 (2)
P1—N1—C11—C12	−179.26 (12)	N2—C21—C26—C25	−179.42 (13)
C16—C11—C12—C13	0.3 (2)	P1—N3—C31—C36	−179.29 (12)
N1—C11—C12—C13	−179.12 (14)	P1—N3—C31—C32	1.0 (2)
C11—C12—C13—C14	−1.3 (2)	C36—C31—C32—C33	0.5 (2)
C17—O11—C14—C15	−6.4 (2)	N3—C31—C32—C33	−179.75 (14)
C17—O11—C14—C13	172.67 (14)	C31—C32—C33—C34	−0.1 (2)
C12—C13—C14—O11	−178.06 (14)	C37—O31—C34—C33	−1.0 (2)
C12—C13—C14—C15	1.1 (2)	C37—O31—C34—C35	178.99 (15)
O11—C14—C15—C16	179.10 (14)	C32—C33—C34—O31	179.69 (15)
C13—C14—C15—C16	0.0 (2)	C32—C33—C34—C35	−0.3 (2)
C12—C11—C16—C15	0.9 (2)	O31—C34—C35—C36	−179.78 (15)
N1—C11—C16—C15	−179.78 (14)	C33—C34—C35—C36	0.2 (2)
C14—C15—C16—C11	−1.0 (2)	C34—C35—C36—C31	0.2 (2)
P1—N2—C21—C22	−145.93 (12)	C32—C31—C36—C35	−0.6 (2)
P1—N2—C21—C26	34.70 (18)	N3—C31—C36—C35	179.64 (15)
C26—C21—C22—C23	−0.8 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1^i	0.79 (2)	2.44 (2)	3.1678 (18)	155.0 (19)
N3—H3···O1^i	0.78 (2)	2.06 (2)	2.8400 (18)	172 (2)
N2—H2···O21^ii	0.92 (2)	2.57 (2)	3.4774 (18)	170.9 (17)

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