Three new [XC(O)NH]P(O)[N(CH2-C6H5) 2]2 phosphoric triamides (X = CClF2, 3-F-C 6H4 and 3,5-F2-C6H3): A database analysis of tertiary N-atom geometry in compounds with a C(O)NHP(O)[N] 2 core

organic compounds

Acta Crystallographica Section C

Crystal Structure

Communications

have not been reported to date. In the crystal structures of all

three title compounds, adjacent molecules are linked via pairs

of P Oꢂ ꢂ ꢂH—N hydrogen bonds, forming dimers with C_i

symmetry.

ISSN 0108-2701

Comment

Three new [XC(O)NH]P(O)[N(CH₂-

C₆H₅)₂]₂phosphoric triamides (X =

CClF₂, 3-F-C₆H₄and 3,5-F₂-C₆H₃):

a database analysis of tertiary

N-atom geometry in compounds

with a C(O)NHP(O)[N]₂core

The N—P O group is the basic skeleton of a large family of

compounds called phosphoramides. The environment of the N

atom bonded to the P atom in these compounds tends toward

planarity (Pourayoubi et al., 2011), similar to N atoms bonded

¨

to C atoms in organic amides (Doring et al., 2012), unless the N

atom is in an environment with an inherent distortion

(Rebrova et al., 1992).

Mehrdad Pourayoubi,^a* Jerry P. Jasinski,^bSamad

Shoghpour Bayraq,^aHossein Eshghi,^aAmanda C. Keeley,^b

Giuseppe Bruno^cand Hadi Amiri Rudbari^c,d

^aDepartment of Chemistry, Ferdowsi University of Mashhad, Mashhad, Iran,

^bDepartment of Chemistry, Keene State College, 229 Main Street, Keene,

NH 03435-2001, USA, ^cDipartimento di Chimica Inorganica, Vill. S. Agata, Salita

Sperone 31, Universita di Messina, 98166 Messina, Italy, and ^dDepartment of

`

Chemistry, University of Isfahan, Isfahan 81746-73441, Iran

Correspondence e-mail: pourayoubi@um.ac.ir

Received 18 June 2012

Accepted 20 August 2012

Online 12 September 2012

In the phosphoric triamides N,N,N⁰,N⁰-tetrabenzyl-N⁰⁰-(2-

chloro-2,2-diﬂuoroacetyl)phosphoric triamide, C₃₀H₂₉ClF₂N₃-

O₂P, (I), N,N,N⁰,N⁰-tetrabenzyl-N⁰⁰-(3-ﬂuorobenzoyl)phos-

phoric triamide, C₃₅H₃₃FN₃O₂P, (II), and N,N,N⁰,N⁰-tetra-

benzyl-N⁰⁰-(3,5-diﬂuorobenzoyl)phosphoric triamide, C₃₅H₃₂-

F₂N₃O₂P, (III), the tertiary N atoms of the dibenzylamido

groups have sp²character with minimal deviation from

planarity. The sums of the three bond angles about the N

atoms in (I)–(III) deviate by less than 8^ꢀfrom the planar value

of 360^ꢀ. The geometries of the tertiary N atoms in all

phosphoric triamides with C(O)NHP(O)[N]₂skeletons depos-

ited in the Cambridge Structural Database [CSD; Allen

(2002). Acta Cryst. B58, 380–388] have been examined and the

bond-angle sums at the two tertiary N atoms (SUM1 and

SUM2) and the parameter ÁSUM (= SUM1 ꢁ SUM2)

considered. It was found that in compounds with a consider-

able ÁSUM value, the more pyramidal N atoms are usually

oriented so that the corresponding lone electron pair is anti

with respect to the P O group. In (I), (II) and (III), the

phosphoryl and carbonyl groups, separated by an N atom, are

anti with respect to each other. In the C(O)NHP(O) fragment

of (I)–(III), the P—N bond is longer and the O—P—N angle is

contracted compared with the other two P—N bonds and the

O—P—N angles in the molecules. These effects are also seen

in analogous compounds deposited in the CSD. Compounds

with [C(O)NH]P(O)[N]X (X ¼ N), such as compounds with a

[C(O)NH]P(O)[N][O] skeleton, have not been considered

here. Also, compounds with a [C(O)NH]₂P(O)[N] fragment

We present here three new phosphoric triamides with a

C(O)NHP(O)[N]₂skeleton, where ‘[N]₂’ denotes two tertiary

N atoms belonging to an amide group; these compounds are

N,N,N⁰,N⁰-tetrabenzyl-N⁰⁰-(2-chloro-2,2-diﬂuoroacetyl)phos-

phoric triamide, (I), N,N,N⁰,N⁰-tetrabenzyl-N⁰⁰-(3-ﬂuoroben-

zoyl)phosphoric triamide, (II), and N,N,N⁰,N⁰-tetrabenzyl-N⁰⁰-

(3,5-diﬂuorobenzoyl)phosphoric triamide, (III). The geome-

tries of the tertiary N atoms in these compounds are analyzed

and compared with those of analogous structures deposited in

the Cambridge Structural Database (CSD, Version 5.32, May

2011 update; Allen, 2002; for each example, the CSD refcode

is given in capitals followed by the primary reference). All

three N atoms in the C(O)NHP(O)[N]₂core are amide N

atoms. For clarity, the N atom in the C(O)NHP(O) fragment is

designated as N_C(O)NHP(O), whereas the other two N atoms are

designated as N_amideatoms.

In (I), (II) and (III), the asymmetric unit contains one

molecule with the C(O)NHP(O)[N]₂skeleton (Figs. 1, 2 and 3).

The P atom exhibits a distorted tetrahedral environment,

which is reﬂected in the bond lengths and angles in the

[N]P(O)[N]₂fragment (Tables 1, 3 and 5), similar to that

observed for related phosphoramide derivatives (Pourayoubi

Acta Cryst. (2012). C68, o399–o404

doi:10.1107/S0108270112036396

# 2012 International Union of Crystallography o399

organic compounds

Figure 1

Displacement ellipsoid plot (50% probability) and atom-numbering

scheme for (I). H atoms are drawn as circles of arbitrary radii.

Figure 3

Displacement ellipsoid plot (50% probability) and atom-numbering

scheme for (III). H atoms are drawn as circles of arbitrary radii.

et al., 2011). The P O and P—N bond lengths, as well as the

bond angles at the P atom, are comparable to those in similar

compounds (Pourayoubi et al., 2011). In (I)–(III), the widest

angle about the P atom is observed in one of the two O—P—

lengths in all phosphoric triamides with C(O)NHP(O)[N]₂and

C(O)NHP(O)[NH]₂fragments found in the CSD. In the range

N_amideangles, whereas the narrowest angle for (I) and (III) is

O—P—N_C(O)NHP(O)and for (II) is an N_amide—P—N_C(O)NHP(O)

angle.

˚

1.60–1.66 A, only P—N_amidebonds are found, and in the range

˚

1.70–1.74 A, only P—N_C(O)NHP(O)bonds are found, while in

In the C(O)NHP(O) fragment of (I), (II) and (III), the

P—N bond is longer and the O—P—N angle is contracted

compared with the other two P—N bonds and the other two

O—P—N angles in each molecule. The bond distance trend is

shown in a histogram of P—N_amideand P—N_C(O)NHP(O)

distances (Fig. 4). This histogram covers the P—N bond

˚

the range 1.66–1.70 A, both types of P—N bonds are observed.

The number of P—N_amidebond entries is twice the number of

Figure 4

Histogram of P—N_amide(ﬁrst entry, blue in the electronic version of the

paper) and P—N_C(O)NHP(O)(second entry, brown) bond distances in

phosphoric triamides with C(O)NHP(O)[N]₂and C(O)NHP(O)[NH]₂

fragments. The numbers of data found in each region are given above the

column. Seven CSD refcodes with unusual values for P—N_amideor P—

N_C(O)NHP(O)and/or with strong disorder have not been considered.

Figure 2

Displacement ellipsoid plot (50% probability) and atom-numbering

scheme for (II). H atoms are drawn as circles of arbitrary radii.

ꢃ

o400 Pourayoubi et al. C₃₀H₂₉ClF₂N₃O₂P, C₃₅H₃₃FN₃O₂P and C₃₅H₃₂F₂N₃O₂P

Acta Cryst. (2012). C68, o399–o404

organic compounds

The bond-angle sums for phosphoric triamides with

C(O)NHP(O)[N]₂skeletons found in the CSD were also

examined (‘[N]’ denotes a tertiary N atom). Compounds with

three-membered cyclic amide substituents were excluded from

consideration, as ring strain affects the sum of the surrounding

bond angles at the tertiary N atoms, which can deviate

signiﬁcantly from 360^ꢀ(in the range 292.3–311.8^ꢀ). Com-

pounds with disorder in the N or surrounding atoms were also

excluded. Moreover, one structure with unusual bond angles

was excluded.

Fig. 6 shows the sum of the bond angles around the two

tertiary N atoms (as different colors) in 58 compounds with

C(O)NHP(O)[N]₂fragments; the bond-angle sum varies in the

range 339.1–360^ꢀ. The entries are arranged from smallest

difference (leftmost) to largest (rightmost). The greatest

difference is found for C₆H₅C(O)NHP(O)[NC₃H₆]₂(LAY-

MII; Gholivand et al., 2005), with values of 357.96 and 340.49^ꢀ,

respectively. In this example, similar to compounds (I), (II)

and (III), the LEP of the more pyramidal N atom adopts an

anti orientation relative to the P O group (entry 58; Fig. 6).

This situation is also observed for entries 57 (LARTII01;

Marsh, 2009), 56 (WIYTUT; Gubina et al., 2000), 55

(VEHTAE; Gholivand, Alizadehgan et al., 2006), 54

(VEFLUO; Gholivand, Mojahed et al., 2006), 53 (LIVWAP;

Dehghanpour et al., 2008), 52 (KEBPUD; Gholivand, Shar-

iatinia & Pourayoubi, 2006), 51 (BUVJOS; Dehghanpour et

al., 2010), 50 and 49 (SIRXIB and SIRXEX; Gholivand et al.,

2007), 48 (BUVJIM; Dehghanpour et al., 2010) and 47

(VEHTAE; Gholivand, Alizadehgan et al., 2006), with ÁSUM

(= SUM1 ꢁ SUM2) ranging from 14.3 to 5.9^ꢀ, where the LEP

of the more pyramidal N atom is anti relative to P O.

Of the three angles at the tertiary N atoms, the C—N—C

angles in most of the studied structures have a signiﬁcantly

lower value than those of the two P—N—C angles.

Figure 5

The anti orientation of the N3 lone electron pair (LEP) relative to P

in compound (I). For the benzyl groups, only the ipso C atoms are shown

for clarity. (In the electronic version of the paper, colour key: Cl green, F

yellow–green and C dark grey.)

O

P—N_C(O)NHP(O)bonds found in the CSD for phosphoric tri-

amides with C(O)NHP(O) fragments. Compounds with

[C(O)NH]P(O)[N]X (X ¼ N), such as compounds with a

[C(O)NH]P(O)[N][O] skeleton, have not been considered

here. Also, compounds with a [C(O)NH]₂P(O)[N] fragment

have not been reported to date.

The two tertiary N atoms in each of (I), (II) and (III) show

sp²character with a slight deviation from planarity, wherein

one of the two dibenzylamido N atoms shows a slightly greater

deviation than the other. The sums of the surrounding bond

angles (2 ꢄ P—N—C + C—N—C) at N2 and N3 in (I) are

359.6 (2) and 355.2 (2)^ꢀ, respectively. In (II) and (III), the

higher values are 359.71 (15) and 357.45 (15)^ꢀ, respectively,

while the lower values are 352.39 (15) and 355.14 (14)^ꢀ,

respectively. Thus, the differences in these bond-angle sums

are small. The more pyramidal of the tertiary N atoms in these

molecules [i.e. N3 in (I) and (III), and N2 in (II)] are oriented

so that the lone electron pair (LEP) is anti with respect to the

P

O group.

Fig. 5 shows the slight pyramidality of one of the N atoms in

compound (I) with the LEP anti relative to P O.

Figure 6

Figure 7

Part of the crystal structure of compound (III). H atoms not involved in

hydrogen bonding have been omitted.

Sum of the surrounding bond angles (2 ꢄ P—N—C + C—N—C) at two

tertiary N atoms (as different colors) from 58 database entries.

ꢃ

Acta Cryst. (2012). C68, o399–o404

Pourayoubi et al.

C₃₀H₂₉ClF₂N₃O₂P, C₃₅H₃₃FN₃O₂P and C₃₅H₃₂F₂N₃O₂P o401

organic compounds

Table 2

Hydrogen-bond geometry (A, ) for (I).

For each of (I), (II) and (III), the phosphoryl and carbonyl

groups, which are separated by an N atom, have a relative anti

disposition. The O—P—N—C torsion angles in (I), (II) and

(III) are 169.65 (12), ꢁ177.83 (10) and ꢁ174.13 (10)^ꢀ, res-

pectively. Similar relative orientations have been observed for

a majority of compounds with C(O)NHP(O)[N]₂skeletons

(Toghraee et al., 2011).

ꢀ

˚

D—Hꢂ ꢂ ꢂA

D—H

Hꢂ ꢂ ꢂA

Dꢂ ꢂ ꢂA

D—Hꢂ ꢂ ꢂA

N1—H1Nꢂ ꢂ ꢂO2ⁱ

0.80 (2)

1.98 (2)

2.7788 (17)

172 (2)

Symmetry code: (i) ꢁx; ꢁy þ 2; ꢁz þ 2.

In (I), (II) and (III), adjacent molecules are linked via pairs

of P Oꢂ ꢂ ꢂH—N hydrogen bonds, forming dimers with C_i

symmetry (Tables 2, 4 and 6). For structures (II) and (III),

phosphoryl atom O2 receives a second hydrogen bond (C—

Hꢂ ꢂ ꢂO) from the inversion-related molecule. A view of the

packing in the crystal structure of compound (III) is shown in

Fig. 7. Another C—Hꢂ ꢂ ꢂO interaction is also observed in

structure (II) (Table 4) involving carbonyl atom O1 as

acceptor.

In summary, three new [XC(O)NH]P(O)[N(CH₂C₆H₅)₂]₂

phosphoric triamides (X = CClF₂, 3-F-C₆H₄and 3,5-F₂-C₆H₃)

were studied by X-ray crystallography and compared with

analogous compounds deposited in the CSD. In the

C(O)NHP(O) fragment of these compounds, the P—N bond is

longer and the O—P—N angle is contracted compared with

the two remaining P—N bonds and O—P—N angles. For

For the preparation of (I), a solution of dibenzylamine (4 mmol) in

dry CHCl₃(5 ml) was added to a solution of CClF₂C(O)NHP(O)Cl₂

(1 mmol) in the same solvent (10 ml) at 273 K. After stirring for 5 h,

the solvent was removed and the product was washed with distilled

water. Single crystals were obtained from a solution of (I) in CH₃OH–

CHCl₃(3:1 v/v) by slow evaporation at room temperature.

For the preparation of (II), a solution of dibenzylamine (4 mmol)

in dry CHCl₃(5 ml) was added to a solution of 3-F-C₆H₄C(O)NH-

P(O)Cl₂(1 mmol) in the same solvent (20 ml) and the mixture stirred

at 273 K for 4 h. The solvent was evaporated in vacuo and the product

washed with distilled water. Colorless single crystals were obtained

from a CH₃CN solution by slow evaporation at room temperature.

For the preparation of (III), a solution of dibenzylamine (4 mmol)

in dry CHCl₃was added to a solution of 3,5-F₂-C₆H₃C(O)NHP(O)Cl₂

(1 mmol) in the same solvent (20 ml). After stirring at 273 K for 4 h,

the solvent was evaporated in vacuo and the product was washed with

distilled water. Colorless single crystals were obtained from a CH₃CN

solution by slow evaporation at room temperature.

compounds having

a C(O)NHP(O)[N]₂fragment, the

geometry of the tertiary N atoms was also examined. Among

the three angles around these atoms, the C—N—C angles in

most of the reported structures have signiﬁcantly lower values

than do the two P—N—C angles. The sums of the bond angles

at the tertiary N atoms have been used to evaluate their

pyramidality. An anti orientation of the lone electron pair of

the more pyramidal N atom relative to P O is observed for

compounds with considerable ÁSUM (= SUM1 ꢁ SUM2).

Compound (I)

Crystal data

3

˚

C₃₀H₂₉ClF₂N₃O₂P

M_r= 567.98

V = 2863.56 (15) A

Z = 4

Mo Kꢁ radiation

ꢂ = 0.23 mm^ꢁ1

T = 296 K

Monoclinic, P2₁=n

˚

a = 10.8298 (3) A

˚

b = 9.9164 (3) A

˚

c = 26.6740 (8) A

0.56 ꢄ 0.51 ꢄ 0.48 mm

ꢀ = 91.539 (1)^ꢀ

Experimental

Data collection

Three starting materials with the general formula XC(O)NHP(O)Cl₂

(X = CClF₂, 3-F-C₆H₄and 3,5-F₂-C₆H₃) were synthesized from the

reaction between phosphorus pentachloride (16.7 mmol) and the

corresponding XC(O)NH₂amide (16.7 mmol) in dry CCl₄at 358 K

(about 3 h) followed by treatment with formic acid (16.7 mmol) at

ice-bath temperature.

Bruker APEXII CCD

diffractometer

Absorption correction: multi-scan

(SADABS; Bruker, 2008)

T_min= 0.694, T_max= 0.746

31854 measured reﬂections

6905 independent reﬂections

5873 reﬂections with I > 2ꢃ(I)

R_int= 0.019

Reﬁnement

R[F²> 2ꢃ(F²)] = 0.046

wR(F²) = 0.134

S = 1.05

6905 reﬂections

356 parameters

H atoms treated by a mixture of

independent and constrained

reﬁnement

Table 1

Selected geometric parameters (A, ) for (I).

ꢀ

˚

ꢁ3

˚

Áꢄ_max= 0.78 e A

ꢁ3

˚

P1—N1

P1—N2

P1—N3

P1—O2

Cl1—C30

O1—C29

F2—C30

1.7011 (13)

1.6331 (14)

1.6373 (13)

1.4739 (11)

1.748 (2)

F3—C30

N2—C1

N2—C8

N3—C22

N3—C15

N1—C29

1.322 (2)

1.465 (2)

1.480 (2)

1.477 (2)

1.4788 (19)

1.348 (2)

Áꢄ_min= ꢁ0.68 e A

Compound (II)

1.208 (2)

1.338 (2)

Crystal data

O2—P1—N1

O2—P1—N2

O2—P1—N3

N1—P1—N2

N1—P1—N3

N2—P1—N3

C1—N2—C8

C1—N2—P1

104.82 (7)

111.59 (7)

118.57 (7)

110.25 (7)

105.08 (7)

106.23 (7)

114.75 (14)

124.74 (11)

C8—N2—P1

C22—N3—C15

C15—N3—P1

C22—N3—P1

C29—N1—P1

O1—C29—N1

F3—C30—F2

F3—C30—Cl1

120.13 (11)

114.69 (13)

120.57 (11)

119.96 (10)

126.83 (11)

126.99 (15)

107.49 (17)

109.36 (15)

C₃₅H₃₃FN₃O₂P

M_r= 577.61

Triclinic, P1

ꢅ = 91.135 (7)^ꢀ

V = 1519.0 (2) A

Z = 2

Mo Kꢁ radiation

ꢂ = 0.13 mm^ꢁ1

T = 173 K

3

˚

a = 10.0173 (10) A

˚

b = 11.2362 (8) A

˚

c = 14.5992 (12) A

ꢁ = 99.351 (6)^ꢀ

ꢀ = 109.960 (8)^ꢀ

0.48 ꢄ 0.40 ꢄ 0.36 mm

ꢃ

o402 Pourayoubi et al. C₃₀H₂₉ClF₂N₃O₂P, C₃₅H₃₃FN₃O₂P and C₃₅H₃₂F₂N₃O₂P

Acta Cryst. (2012). C68, o399–o404

organic compounds

Table 3

Selected geometric parameters (A, ) for (II).

Table 5

Selected geometric parameters (A, ) for (III).

ꢀ

˚

P1—N1

P1—N2

P1—N3

P1—O2

F1—C3

O1—C7

1.6922 (10)

1.6484 (11)

1.6400 (11)

1.4786 (9)

1.3500 (19)

1.2200 (15)

N1—C7

N2—C22

N2—C29

N3—C8

N3—C15

1.3716 (15)

1.4768 (15)

1.4868 (16)

1.4672 (15)

1.4844 (16)

P1—N1

P1—N2

P1—N3

P1—O2

F1—C5

F2—C3

1.6880 (10)

1.6488 (11)

1.6443 (11)

1.4798 (9)

1.3537 (15)

1.3538 (14)

O1—C7

N1—C7

N2—C22

N2—C29

N3—C8

N3—C15

1.2236 (14)

1.3664 (14)

1.4748 (14)

1.4756 (15)

1.4687 (15)

1.4829 (14)

N1—P1—N2

N1—P1—N3

N2—P1—N3

O2—P1—N1

O2—P1—N2

O2—P1—N3

C7—N1—P1

103.81 (5)

112.50 (5)

106.54 (5)

105.60 (5)

118.92 (5)

109.48 (5)

127.16 (8)

C22—N2—C29

C22—N2—P1

C29—N2—P1

C8—N3—C15

C8—N3—P1

C15—N3—P1

O1—C7—N1

113.09 (10)

117.96 (8)

121.34 (8)

114.81 (10)

124.58 (8)

120.32 (8)

122.00 (11)

N1—P1—N2

N1—P1—N3

N2—P1—N3

O2—P1—N1

O2—P1—N2

O2—P1—N3

C7—N1—P1

113.07 (5)

105.18 (5)

105.51 (5)

105.15 (5)

109.06 (5)

119.05 (5)

125.60 (8)

C22—N2—C29

C22—N2—P1

C29—N2—P1

C8—N3—C15

C8—N3—P1

C15—N3—P1

O1—C7—N1

115.46 (10)

125.00 (8)

116.99 (8)

113.59 (9)

125.14 (8)

116.41 (8)

121.81 (10)

Table 4

Hydrogen-bond geometry (A, ) for (II).

ꢀ

˚

Table 6

Hydrogen-bond geometry (A, ) for (III).

ꢀ

˚

D—Hꢂ ꢂ ꢂA

D—H

Hꢂ ꢂ ꢂA

Dꢂ ꢂ ꢂA

D—Hꢂ ꢂ ꢂA

D—H

Hꢂ ꢂ ꢂA

Dꢂ ꢂ ꢂA

D—Hꢂ ꢂ ꢂA

C2—H2ꢂ ꢂ ꢂO2ⁱ

0.93

0.837 (18)

2.45

2.017 (18)

3.1124 (16)

3.2342 (17)

2.8497 (13)

128

142

173.7 (17)

C25—H25ꢂ ꢂ ꢂO1ⁱⁱ

N1—H1Nꢂ ꢂ ꢂO2ⁱ

C6—H6ꢂ ꢂ ꢂO2ⁱ

0.93

0.847 (19)

2.22

2.024 (19)

3.1123 (14)

2.8659 (13)

162

172.8 (17)

N1—H1Nꢂ ꢂ ꢂO2ⁱ

Symmetry codes: (i) ꢁx þ 1; ꢁy þ 1; ꢁz; (ii) ꢁx þ 1; ꢁy þ 1; ꢁz þ 1.

Symmetry code: (i) ꢁx þ 1; ꢁy; ꢁz þ 1.

Data collection

For compounds (I), (II) and (III), atom H1N was located in a

difference map and reﬁned isotropically. All of the remaining H

atoms were placed at calculated positions and reﬁned using a riding

Oxford Diffraction Xcalibur (Eos,

Gemini) diffractometer

Absorption correction: multi-scan

(CrysAlis PRO; Oxford Diffrac-

tion, 2010)

17423 measured reﬂections

9840 independent reﬂections

8118 reﬂections with I > 2ꢃ(I)

R_int= 0.021

˚

model, with C—H bond lengths of 0.93 (CH) or 0.97 A (CH₂). The

isotropic displacement parameters for these H atoms were set at 1.2

times U_eqof their respective parent atoms. The largest difference

T_min= 0.943, T_max= 1.000

˚

peak and hole for (II) were 1.117 (3.01 A from H15A) and

ꢁ3

3

˚

Reﬁnement

ꢁ0.322 e A , with the positive peak in a small void of 57 A . This

and a second difference peak in the void appeared to represent

occupation by a diffuse source of electron density. The SQUEEZE

routine in PLATON (Spek, 2009) estimated a total of 4 electrons per

cell in the void, and no further action was taken. The results reported

for this structure have not had SQUEEZE applied.

R[F²> 2ꢃ(F²)] = 0.048

wR(F²) = 0.143

S = 1.04

9840 reﬂections

383 parameters

H atoms treated by a mixture of

independent and constrained

reﬁnement

ꢁ3

˚

Áꢄ_max= 1.12 e A

ꢁ3

˚

Áꢄ_min= ꢁ0.32 e A

Data collection: APEX2 (Bruker, 2007) for (I); CrysAlis PRO

(Oxford Diffraction, 2010) for (II) and (III). Cell reﬁnement: SAINT

(Bruker, 2007) for (I); CrysAlis PRO for (II) and (III). Data reduc-

tion: SAINT for (I); CrysAlis RED (Oxford Diffraction, 2010) for (II)

and (III). For all compounds, program(s) used to solve structure:

SHELXS97 (Sheldrick, 2008); program(s) used to reﬁne structure:

SHELXL97 (Sheldrick, 2008). Molecular graphics: XPW (Siemens,

1996) for (I), (II) and (III), Mercury (Macrae et al., 2008) for (I) and

SHELXTL (Sheldrick, 2008) for (III). For all compounds, software

used to prepare material for publication: SHELXTL and enCIFer

(Allen et al., 2004).

Compound (III)

Crystal data

C₃₅H₃₂F₂N₃O₂P

M_r= 595.61

Triclinic, P1

ꢅ = 118.262 (9)^ꢀ

3

˚

V = 1474.5 (2) A

Z = 2

˚

a = 11.9526 (11) A

Mo Kꢁ radiation

ꢂ = 0.14 mm^ꢁ1

T = 173 K

0.32 ꢄ 0.28 ꢄ 0.16 mm

b = 12.2897 (10) A

˚

c = 12.7463 (12) A

ꢁ = 102.074 (7)^ꢀ

ꢀ = 104.462 (8)^ꢀ

Data collection

Support of this investigation by Ferdowsi University of

Mashhad is gratefully acknowledged. JPJ acknowledges the

NSF–MRI (grant No. CHE1039027) for funds to purchase the

X-ray diffractometer.

Oxford Diffraction Xcalibur (Eos,

Gemini) diffractometer

Absorption correction: multi-scan

(CrysAlis PRO; Oxford Diffrac-

tion, 2010)

17265 measured reﬂections

9523 independent reﬂections

7763 reﬂections with I > 2ꢃ(I)

R_int= 0.019

T_min= 0.992, T_max= 1.000

Supplementary data for this paper are available from the IUCr electronic

archives (Reference: FA3282). Services for accessing these data are

described at the back of the journal.

Reﬁnement

R[F²> 2ꢃ(F²)] = 0.042

wR(F²) = 0.116

S = 1.05

9523 reﬂections

392 parameters

H atoms treated by a mixture of

independent and constrained

reﬁnement

References

ꢁ3

˚

Áꢄ_max= 0.41 e A

ꢁ3

˚

Áꢄ_min= ꢁ0.37 e A

Allen, F . H . (2002). Acta Cryst. B 58 , 380–388.

ꢃ

Acta Cryst. (2012). C68, o399–o404

Pourayoubi et al.

C₃₀H₂₉ClF₂N₃O₂P, C₃₅H₃₃FN₃O₂P and C₃₅H₃₂F₂N₃O₂P o403

organic compounds

Allen, F . H ., Johnson, O., Shields, G. P ., Smith, B. R. & Towler, M. (2004).

J. Appl. Cryst. 37 , 335–338.

Bruker (2007). APEX2 and SAINT . Bruker AXS Inc., Madison, Wisconsin,

USA.

Bruker (2008). SADABS . Bruker AXS Inc., Madison, Wisconsin, USA.

Dehghanpour, S., Welter, R., Barry, A. H. & Tabasi, F. (2008). Acta Cryst. E 64 , o633.

Dehghanpour, S., Welter, R., Barry, A. H. & Tabasi, F . (2010). Spectrochim.

Acta Part A , 75 , 1236–1243.

Gubina, K. E., Ovchynnikov, V . A ., Amirkhanov, V . M ., Skopenko, V . V. &

Shishkin, O. V . (2000). Z. Naturforsch. Teil B , 55 , 495–498.

Macrae, C. F ., Bruno, I. J., Chisholm, J. A., Edgington, P . R ., McCabe, P .,

Pidcock, E., Rodriguez-Monge, L., T a ylor, R., van de Streek, J. & Wood, P .

A. (2008). J. Appl. Cryst. 41 , 466–470.

Marsh, R. E. (2009). Acta Cryst. B 65 , 782–783.

Oxford Diffraction (2010). CrysAlis PRO and CrysAlis RED . Oxford

Diffraction Ltd, Yarnton, Oxfordshire, England.

¨

Doring, C., T a ouss, C. & Jones, P . G. (2012). Acta Cryst. C 68 , o108–o110.

Pourayoubi, M., Tarahhomi, A., Saneei, A., Rheingold, A. L. & Golen, J. A.

(2011). Acta Cryst. C 67 , o265–o272.

Rebrova, O. N., Biyushkin, V . N ., Malinovsk y , T. I., Ovrutsky, V . M ., Protsenko,

L. D., Dneprova, T. N. & Mazus, M. D. (1992). Proc. Nat. Acad. Sci. USSR ,

324 , 103–106.

Gholivand, K., Alizadehgan, A. M., Arshadi, S. & Firooz, A. A. (2006). J. Mol.

Struct. 791 , 193–200.

Gholivand, K., Hosseini, Z., Pourayoubi, M. & Shariatinia, Z. (2005). Z.

Anorg. Allg. Chem. 631 , 3074–3079.

Gholivand, K., Mojahed, F . & A lizadehgan, A. M. (2007). Pol. J. Chem. 81 ,

393–402.

Sheldrick, G. M. (2008). Acta Cryst. A 64 , 112–122.

Spek, A. L. (2009). Acta Cryst. D 65 , 148–155.

Gholivand, K., Mojahed, F ., Salehi, M. & Alizadehgan, A. M. (2006). Anal. Sci.

X-Ray Struct. Anal. Online , 22 , x13–x14.

Siemens (1996). XPW . Siemens Analytical X-ray Instruments Inc., Madison,

Wisconsin, USA.

Gholivand, K., Shariatinia, Z. & Pourayoubi, M. (2006). Z. Anorg. Allg. Chem.

632 , 160–166.

T o ghraee, M., Pourayoubi, M. & Divjakovic, V . (2011). Polyhedron , 30 , 1680–

1690.

ꢃ

o404 Pourayoubi et al. C₃₀H₂₉ClF₂N₃O₂P, C₃₅H₃₃FN₃O₂P and C₃₅H₃₂F₂N₃O₂P

Acta Cryst. (2012). C68, o399–o404

supplementary materials

Acta Cryst. (2012). C68, o399–o404 [doi:10.1107/S0108270112036396]

Three new [XC(O)NH]P(O)[N(CH₂C₆H₅)₂]₂phosphoric triamides (X = CClF₂, 3-

F-C₆H₄and 3,5-F₂-C₆H₃): a database analysis of tertiary N-atom geometry in

compounds with a C(O)NHP(O)[N]₂core

Mehrdad Pourayoubi, Jerry P. Jasinski, Samad Shoghpour Bayraq, Hossein Eshghi, Amanda C.

Keeley, Giuseppe Bruno and Hadi Amiri Rudbari

(I) N,N,N′,N′-Tetrabenzyl-N′′-(2-chloro- 2,2-difluoroacetyl)phosphoric triamide

Crystal data

C₃₀H₂₉ClF₂N₃O₂P

M_r= 567.98

F(000) = 1184

D_x= 1.317 Mg m⁻³

Mo Kα radiation, λ = 0.71073 Å

Cell parameters from 9995 reflections

θ = 2.6–29.0°

Monoclinic, P2₁/n

Hall symbol: -P 2yn

a = 10.8298 (3) Å

b = 9.9164 (3) Å

c = 26.6740 (8) Å

β = 91.539 (1)°

V = 2863.56 (15) Å³

Z = 4

µ = 0.23 mm⁻¹

T = 296 K

Irregular, colorless

0.56 × 0.51 × 0.48 mm

Data collection

Bruker APEXII CCD

diffractometer

Radiation source: fine-focus sealed tube

Graphite monochromator

φ and ω scans

31854 measured reflections

6905 independent reflections

5873 reflections with I > 2σ(I)

R_int= 0.019

θ

_max= 28.0°, θ_min= 2.0°

Absorption correction: multi-scan

(SADABS; Bruker, 2008)

h = −14→14

k = −13→13

l = −35→22

T

_min= 0.694, T_max= 0.746

Refinement

Refinement on F²

Least-squares matrix: full

R[F²> 2σ(F²)] = 0.046

wR(F²) = 0.134

Secondary atom site location: difference Fourier

map

Hydrogen site location: inferred from

neighbouring sites

S = 1.05

6905 reflections

356 parameters

0 restraints

H atoms treated by a mixture of independent

and constrained refinement

w = 1/[σ²(F_o²) + (0.0663P)²+ 1.1866P]

where P = (F_o²+ 2F_c²)/3

Primary atom site location: structure-invariant

direct methods

(Δ/σ)_max= 0.001

Δρ_max= 0.78 e Å⁻³

Δρ_min= −0.68 e Å⁻³

Acta Cryst. (2012). C68, o399–o404

sup-1

supplementary materials

Special details

Experimental. IR (KBr, ν, cm^-1): 3064, 3036, 2901, 2868, 2758, 1736, 1602, 1586, 1494, 1454, 1372, 1360, 1347, 1301,

1285, 1213, 1185, 1173, 1137, 1124, 1103, 1068, 1026, 977, 954, 944, 921, 905, 858, 833, 820, 808, 747, 725, 699, 671,

622, 609, 599, 581, 543, 520, 486, 465, 437, 416.

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance

matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles;

correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate

(isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes.

Refinement. Refinement of F²against 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> 2σ(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 F²are 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 (Å²)

x

y

z

U_iso*/U_eq

Cl1

P1

0.34696 (6)

−0.01521 (3)

0.25772 (12)

0.33710 (12)

−0.10455 (10)

0.45045 (11)

0.21381 (19)

0.1984

0.83086 (7)

0.88010 (4)

0.85020 (15)

1.06452 (13)

0.92420 (13)

0.9261 (2)

0.5602 (2)

0.6344

1.01897 (2)

0.925175 (13)

0.89093 (5)

0.98342 (5)

0.96253 (4)

0.94339 (6)

0.94220 (7)

0.9624

0.0761 (2)

0.03216 (11)

0.0507 (3)

0.0678 (3)

0.0423 (3)

0.0911 (5)

0.0526 (4)

0.063*

O1

F2

O2

F3

C3

H3

N2

−0.01394 (12)

−0.02763 (13)

0.3281 (2)

0.3909

0.71619 (14)

0.94120 (13)

0.3594 (3)

0.2994

0.91926 (5)

0.86824 (5)

0.92671 (13)

0.9357

0.0366 (3)

0.0359 (3)

0.0817 (8)

0.098*

N3

C5

H5

C4

0.3070 (2)

0.3550

0.4708 (3)

0.4861

0.95599 (10)

0.9849

0.0676 (6)

0.081*

H4

C2

0.14316 (17)

0.04933 (16)

0.0907

0.54042 (17)

0.64269 (17)

0.7074

0.89859 (7)

0.87983 (6)

0.8588

0.0435 (4)

0.0406 (3)

0.049*

C1

H1A

H1B

C15

H15A

H15B

C16

C17

H17

C18

H18

C19

H19

C12

H12

C11

H11

C10

H10

−0.0122

0.5966

0.8590

0.049*

−0.11343 (17)

−0.1387

0.87955 (18)

0.7921

0.83075 (6)

0.8432

0.0431 (4)

0.052*

−0.0690

0.8644

0.8002

0.052*

−0.22776 (18)

−0.3107 (2)

−0.2945

0.96065 (18)

0.9971 (2)

0.9747

0.81805 (6)

0.85393 (9)

0.8873

0.0464 (4)

0.0591 (5)

0.071*

−0.4180 (2)

−0.4734

1.0668 (3)

1.0899

0.84101 (13)

0.8656

0.0811 (8)

0.097*

−0.4422 (3)

−0.5138

1.1013 (3)

1.1486

0.79216 (17)

0.7835

0.0992 (11)

0.119*

−0.4023 (3)

−0.4691

0.4794 (4)

0.4473

0.86672 (11)

0.8476

0.0975 (11)

0.117*

−0.2996 (3)

−0.2968

0.4016 (3)

0.3163

0.87355 (12)

0.8591

0.0941 (10)

0.113*

−0.1990 (2)

−0.1299

0.4484 (2)

0.3939

0.90186 (10)

0.9068

0.0679 (6)

0.081*

Acta Cryst. (2012). C68, o399–o404

sup-2

supplementary materials

C9

−0.20186 (17)

−0.3073 (2)

−0.3108

0.57579 (19)

0.6534 (3)

0.7391

0.92262 (7)

0.91567 (9)

0.9298

0.0464 (4)

0.0618 (5)

0.074*

C14

H14

C13

H13

C8

−0.4071 (2)

−0.4778

0.6045 (4)

0.6570

0.88796 (11)

0.8837

0.0859 (9)

0.103*

−0.09195 (17)

−0.1202

0.63158 (19)

0.6851

0.95136 (6)

0.9792

0.0450 (4)

0.054*

H8A

H8B

C22

H22A

H22B

C23

C24

H24

C25

H25

C26

H26

C27

H27

C28

H28

C20

H20

C21

H21

N1

−0.0429

0.5576

0.9650

0.054*

0.00184 (18)

0.0603

1.08433 (17)

1.1155

0.85889 (6)

0.8845

0.0428 (4)

0.051*

−0.0728

1.1376

0.8615

0.051*

0.05588 (17)

0.0088 (2)

−0.0581

1.10691 (18)

1.2072 (2)

1.2583

0.80788 (6)

0.77678 (8)

0.7869

0.0450 (4)

0.0567 (5)

0.068*

0.0605 (3)

0.0287

1.2321 (3)

1.3004

0.73065 (9)

0.7102

0.0738 (7)

0.089*

0.1577 (3)

0.1921

1.1569 (3)

1.1736

0.71521 (9)

0.6842

0.0805 (8)

0.097*

0.2046 (3)

0.2705

1.0564 (3)

1.0045

0.74549 (9)

0.7349

0.0818 (8)

0.098*

0.1544 (2)

0.1875

1.0320 (3)

0.9644

0.79184 (8)

0.8123

0.0635 (6)

0.076*

−0.3615 (4)

−0.3786

1.0664 (3)

1.0897

0.75625 (13)

0.7230

0.1020 (12)

0.122*

−0.2532 (3)

−0.1985

0.9960 (3)

0.9729

0.76855 (8)

0.7437

0.0723 (7)

0.087*

0.12407 (12)

0.23604 (15)

0.34493 (16)

0.2570 (3)

0.2709

0.93551 (15)

0.90400 (17)

0.9375 (2)

0.3369 (2)

0.2607

0.94785 (5)

0.93035 (6)

0.96680 (7)

0.88443 (13)

0.8650

0.0365 (3)

0.0388 (3)

0.0486 (4)

0.0815 (8)

0.098*

C29

C30

C6

H6

C7

0.1647 (2)

0.1165

0.4263 (2)

0.4096

0.87036 (9)

0.8416

0.0608 (5)

0.073*

H7

H1N

0.1250 (19)

0.973 (2)

0.9743 (8)

0.045 (5)*

Atomic displacement parameters (Å²)

U¹¹

U²²

U³³

U¹²

U¹³

U²³

Cl1

P1

0.0827 (4)

0.03187 (19)

0.0456 (7)

0.0607 (7)

0.0358 (6)

0.0335 (6)

0.0542 (11)

0.0418 (7)

0.0429 (7)

0.0554 (13)

0.0511 (12)

0.0454 (9)

0.0806 (4)

0.0408 (2)

0.0691 (9)

0.0626 (8)

0.0590 (7)

0.1605 (16)

0.0543 (11)

0.0402 (7)

0.0371 (7)

0.0619 (14)

0.0753 (15)

0.0393 (8)

0.0631 (3)

0.02364 (17)

0.0377 (6)

0.0790 (8)

0.0321 (5)

0.0793 (9)

0.0492 (10)

0.0278 (6)

0.0271 (6)

0.129 (2)

−0.0111 (3)

−0.00448 (15)

0.0010 (6)

−0.0368 (3)

−0.00330 (13)

0.0033 (5)

0.0119 (3)

−0.00506 (14)

−0.0091 (6)

−0.0090 (6)

−0.0121 (5)

−0.0236 (10)

0.0084 (8)

O1

F2

−0.0172 (6)

−0.0039 (5)

−0.0125 (8)

−0.0010 (8)

−0.0057 (5)

−0.0051 (5)

0.0098 (11)

−0.0016 (10)

−0.0060 (7)

−0.0199 (6)

0.0005 (4)

O2

F3

0.0032 (6)

C3

N2

N3

C5

C4

C2

−0.0022 (8)

0.0005 (5)

−0.0005 (5)

−0.0019 (5)

0.0348 (16)

0.0312 (12)

0.0017 (7)

−0.0071 (5)

0.0169 (15)

−0.0018 (10)

0.0042 (7)

0.0761 (15)

0.0459 (9)

Acta Cryst. (2012). C68, o399–o404

sup-3

supplementary materials

C1

0.0495 (9)

0.0546 (10)

0.0542 (10)

0.0599 (12)

0.0569 (13)

0.0776 (19)

0.0754 (19)

0.102 (2)

0.0419 (8)

0.0459 (9)

0.0432 (9)

0.0556 (11)

0.0632 (14)

0.0694 (17)

0.140 (3)

0.0302 (7)

0.0282 (7)

0.0406 (8)

0.0613 (12)

0.122 (2)

−0.0039 (7)

−0.0052 (7)

−0.0112 (8)

−0.0002 (9)

0.0019 (11)

−0.0003 (14)

−0.058 (2)

−0.0020 (6)

−0.0117 (6)

−0.0184 (7)

−0.0104 (9)

−0.0191 (14)

−0.059 (2)

−0.0049 (6)

0.0063 (7)

C15

C16

C17

C18

C19

C12

C11

C10

C9

0.0066 (9)

0.0033 (15)

0.0147 (19)

−0.0003 (18)

−0.0222 (16)

−0.0052 (11)

0.0089 (7)

0.147 (3)

0.0764 (17)

0.094 (2)

−0.0095 (14)

0.0100 (17)

0.0070 (11)

0.0015 (7)

0.087 (2)

−0.0529 (18)

−0.0201 (10)

−0.0145 (8)

−0.0083 (10)

−0.0183 (15)

−0.0097 (8)

−0.0042 (7)

−0.0095 (7)

−0.0031 (9)

−0.0141 (13)

−0.0216 (16)

0.0108 (15)

0.0117 (11)

−0.0125 (19)

−0.0152 (13)

−0.0058 (5)

−0.0056 (6)

−0.0062 (8)

0.0051 (11)

−0.0061 (9)

0.0686 (14)

0.0500 (10)

0.0556 (12)

0.0547 (13)

0.0509 (9)

0.0543 (10)

0.0512 (10)

0.0730 (13)

0.103 (2)

0.0563 (12)

0.0484 (9)

0.0673 (13)

0.121 (3)

0.0788 (15)

0.0408 (8)

0.0624 (12)

0.0815 (18)

0.0345 (8)

0.0380 (8)

0.0384 (8)

0.0506 (10)

0.0536 (12)

0.0501 (12)

0.0577 (13)

0.0467 (10)

0.089 (2)

C14

C13

C8

−0.0022 (9)

−0.0113 (12)

−0.0010 (7)

−0.0024 (7)

−0.0054 (7)

−0.0087 (9)

−0.0128 (12)

0.0092 (12)

0.0155 (11)

0.0044 (9)

0.0120 (10)

0.0195 (17)

0.0089 (7)

0.0496 (10)

0.0360 (8)

0.0451 (9)

0.0460 (10)

0.0638 (14)

0.104 (2)

C22

C23

C24

C25

C26

C27

C28

C20

C21

N1

−0.0016 (6)

0.0040 (7)

0.0065 (8)

0.0232 (11)

0.0218 (13)

0.0137 (14)

0.0156 (10)

0.0334 (17)

0.0169 (10)

−0.0085 (5)

0.0012 (6)

0.0878 (18)

0.0684 (15)

0.0617 (12)

0.120 (3)

0.120 (2)

0.0823 (15)

0.094 (2)

−0.066 (2)

0.0889 (16)

0.0337 (6)

0.0350 (8)

0.0346 (8)

0.0720 (16)

0.0618 (12)

0.0790 (15)

0.0485 (8)

0.0483 (9)

0.0640 (12)

0.0443 (11)

0.0457 (10)

0.0471 (11)

0.0271 (6)

0.0330 (7)

0.0470 (9)

0.129 (2)

−0.0307 (11)

−0.0035 (5)

−0.0024 (6)

−0.0048 (7)

0.0243 (17)

0.0092 (10)

C29

C30

C6

−0.0033 (8)

−0.0049 (14)

−0.0103 (10)

C7

0.0753 (14)

Geometric parameters (Å, º)

P1—N1

P1—N2

P1—N3

P1—O2

Cl1—C30

O1—C29

F2—C30

F3—C30

C3—C4

C3—C2

C3—H3

N2—C1

N2—C8

N3—C22

N3—C15

C5—C6

C5—C4

C5—H5

C4—H4

C2—C7

1.7011 (13)

C12—H12

C11—C10

C11—H11

C10—C9

0.9300

1.6331 (14)

1.6373 (13)

1.4739 (11)

1.748 (2)

1.208 (2)

1.338 (2)

1.322 (2)

1.385 (3)

1.389 (3)

0.9300

1.388 (4)

0.9300

1.380 (3)

0.9300

C10—H10

C9—C14

1.385 (3)

1.504 (2)

1.381 (3)

0.9300

C9—C8

C14—C13

C14—H14

C13—H13

C8—H8A

C8—H8B

C22—C23

C22—H22A

C22—H22B

C23—C28

C23—C24

C24—C25

C24—H24

C25—C26

0.9300

0.9700

1.465 (2)

1.480 (2)

1.477 (2)

1.4788 (19)

1.367 (4)

1.375 (4)

0.9300

0.9700

1.512 (2)

0.9700

1.378 (3)

1.383 (3)

1.388 (3)

0.9300

1.383 (3)

1.363 (4)

Acta Cryst. (2012). C68, o399–o404

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supplementary materials

C2—C1

1.511 (2)

0.9700

C25—H25

C26—C27

C26—H26

C27—C28

C27—H27

C28—H28

C20—C21

C20—H20

C21—H21

N1—C29

N1—H1N

C29—C30

C6—C7

0.9300

C1—H1A

C1—H1B

C15—C16

C15—H15A

C15—H15B

C16—C17

C16—C21

C17—C18

C17—H17

C18—C19

C18—H18

C19—C20

C19—H19

C12—C11

C12—C13

1.372 (4)

0.9300

0.9700

1.507 (3)

0.9700

1.385 (3)

0.9300

0.9700

0.9300

1.378 (3)

1.387 (2)

1.387 (3)

0.9300

1.396 (4)

0.9300

1.348 (2)

0.80 (2)

1.544 (2)

1.381 (4)

0.9300

1.366 (5)

0.9300

1.359 (5)

0.9300

C6—H6

1.362 (5)

1.366 (5)

C7—H7

0.9300

O2—P1—N1

O2—P1—N2

O2—P1—N3

N1—P1—N2

N1—P1—N3

N2—P1—N3

C4—C3—C2

C4—C3—H3

C2—C3—H3

C1—N2—C8

C1—N2—P1

C8—N2—P1

C22—N3—C15

C15—N3—P1

C22—N3—P1

C6—C5—C4

C6—C5—H5

C4—C5—H5

C5—C4—C3

C5—C4—H4

C3—C4—H4

C7—C2—C3

C7—C2—C1

C3—C2—C1

N2—C1—C2

N2—C1—H1A

C2—C1—H1A

N2—C1—H1B

C2—C1—H1B

H1A—C1—H1B

N3—C15—C16

N3—C15—H15A

104.82 (7)

111.59 (7)

118.57 (7)

110.25 (7)

105.08 (7)

106.23 (7)

120.9 (2)

119.6

C13—C14—C9

C13—C14—H14

C9—C14—H14

C12—C13—C14

C12—C13—H13

C14—C13—H13

N2—C8—C9

120.5 (3)

119.8

120.2 (3)

119.9

111.72 (13)

109.3

N2—C8—H8A

C9—C8—H8A

N2—C8—H8B

C9—C8—H8B

H8A—C8—H8B

N3—C22—C23

N3—C22—H22A

C23—C22—H22A

N3—C22—H22B

C23—C22—H22B

119.6

109.3

114.75 (14)

124.74 (11)

120.13 (11)

114.69 (13)

120.57 (11)

119.96 (10)

120.1 (2)

120.0

109.3

107.9

112.63 (14)

109.1

120.0

H22A—C22—H22B

C28—C23—C24

C28—C23—C22

C24—C23—C22

C23—C24—C25

C23—C24—H24

C25—C24—H24

C26—C25—C24

C26—C25—H25

C24—C25—H25

C25—C26—C27

C25—C26—H26

C27—C26—H26

C26—C27—C28

C26—C27—H27

107.8

119.6 (2)

120.2

118.53 (18)

121.41 (17)

120.04 (18)

120.6 (2)

119.7

120.2

118.32 (19)

119.39 (17)

122.20 (16)

114.80 (13)

108.6

119.7

120.3 (2)

119.9

108.6

119.9

108.6

119.8 (2)

120.1

108.6

107.5

120.1

115.39 (14)

108.4

120.3 (3)

119.9

Acta Cryst. (2012). C68, o399–o404

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supplementary materials

C16—C15—H15A

N3—C15—H15B

C16—C15—H15B

H15A—C15—H15B

C17—C16—C21

C17—C16—C15

C21—C16—C15

C16—C17—C18

C16—C17—H17

C18—C17—H17

C19—C18—C17

C19—C18—H18

C17—C18—H18

C20—C19—C18

C20—C19—H19

C18—C19—H19

C11—C12—C13

C11—C12—H12

C13—C12—H12

C12—C11—C10

C12—C11—H11

C10—C11—H11

C9—C10—C11

C9—C10—H10

C11—C10—H10

C10—C9—C14

C10—C9—C8

108.4

C28—C27—H27

C23—C28—C27

C23—C28—H28

C27—C28—H28

C19—C20—C21

C19—C20—H20

C21—C20—H20

C16—C21—C20

C16—C21—H21

C20—C21—H21

C29—N1—P1

C29—N1—H1N

P1—N1—H1N

O1—C29—N1

O1—C29—C30

N1—C29—C30

F3—C30—F2

119.9

108.4

120.6 (2)

119.7

108.4

107.5

119.7

118.6 (2)

122.06 (16)

119.3 (2)

121.0 (2)

119.5

120.9 (3)

119.5

119.6 (3)

120.2

119.5

120.2

120.0 (3)

120.0

126.83 (11)

115.1 (15)

117.1 (15)

126.99 (15)

118.70 (15)

114.27 (14)

107.49 (17)

109.84 (15)

110.93 (16)

109.36 (15)

107.76 (13)

111.35 (13)

120.5 (2)

119.8

120.0

119.8 (3)

120.1

120.0 (3)

120.0

F3—C30—C29

F2—C30—C29

F3—C30—Cl1

F2—C30—Cl1

C29—C30—Cl1

C5—C6—C7

120.0

120.6 (3)

119.7

119.9 (3)

120.0

C5—C6—H6

120.0

C7—C6—H6

119.8

118.8 (2)

121.0 (2)

120.13 (19)

C6—C7—C2

120.6 (2)

119.7

C6—C7—H7

C14—C9—C8

C2—C7—H7

119.7

O2—P1—N2—C1

N3—P1—N2—C1

N1—P1—N2—C1

O2—P1—N2—C8

N3—P1—N2—C8

N1—P1—N2—C8

O2—P1—N3—C22

N2—P1—N3—C22

N1—P1—N3—C22

O2—P1—N3—C15

N2—P1—N3—C15

N1—P1—N3—C15

C6—C5—C4—C3

C2—C3—C4—C5

C4—C3—C2—C7

C4—C3—C2—C1

C8—N2—C1—C2

P1—N2—C1—C2

C7—C2—C1—N2

C3—C2—C1—N2

169.65 (12)

39.05 (15)

−74.29 (14)

−2.96 (14)

−133.56 (12)

113.09 (12)

69.94 (15)

−163.55 (13)

−46.70 (14)

−84.28 (14)

42.23 (14)

159.09 (13)

−0.4 (4)

C1—N2—C8—C9

P1—N2—C8—C9

−67.4 (2)

105.97 (16)

C10—C9—C8—N2

95.6 (2)

C14—C9—C8—N2

−83.1 (2)

−57.0 (2)

147.32 (13)

−51.2 (2)

130.71 (18)

−0.5 (3)

177.64 (19)

0.7 (4)

C15—N3—C22—C23

P1—N3—C22—C23

N3—C22—C23—C28

N3—C22—C23—C24

C28—C23—C24—C25

C22—C23—C24—C25

C23—C24—C25—C26

C24—C25—C26—C27

C25—C26—C27—C28

C24—C23—C28—C27

C22—C23—C28—C27

C26—C27—C28—C23

C18—C19—C20—C21

C17—C16—C21—C20

C15—C16—C21—C20

C19—C20—C21—C16

−0.2 (4)

−0.6 (5)

−0.3 (4)

−178.4 (2)

0.8 (4)

−1.4 (3)

2.7 (3)

−173.96 (18)

−64.23 (18)

122.80 (14)

149.48 (17)

−33.9 (2)

−0.4 (5)

−0.3 (3)

177.4 (2)

0.3 (4)

Acta Cryst. (2012). C68, o399–o404

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supplementary materials

C22—N3—C15—C16

P1—N3—C15—C16

N3—C15—C16—C17

N3—C15—C16—C21

C21—C16—C17—C18

C15—C16—C17—C18

C16—C17—C18—C19

C17—C18—C19—C20

C13—C12—C11—C10

C12—C11—C10—C9

C11—C10—C9—C14

C11—C10—C9—C8

C10—C9—C14—C13

C8—C9—C14—C13

C11—C12—C13—C14

C9—C14—C13—C12

−48.0 (2)

107.54 (15)

−58.8 (2)

123.49 (19)

0.5 (3)

O2—P1—N1—C29

170.32 (14)

50.10 (16)

−63.97 (16)

13.5 (3)

N2—P1—N1—C29

N3—P1—N1—C29

P1—N1—C29—O1

P1—N1—C29—C30

O1—C29—C30—F3

N1—C29—C30—F3

O1—C29—C30—F2

N1—C29—C30—F2

O1—C29—C30—Cl1

N1—C29—C30—Cl1

C4—C5—C6—C7

C5—C6—C7—C2

C3—C2—C7—C6

C1—C2—C7—C6

−164.11 (13)

13.3 (3)

−177.19 (19)

−0.6 (4)

0.5 (4)

−168.88 (17)

131.99 (18)

−50.2 (2)

−108.00 (17)

69.82 (19)

0.9 (4)

−0.2 (5)

−1.2 (4)

1.6 (3)

−177.0 (2)

−0.7 (3)

177.9 (2)

1.1 (4)

0.4 (4)

−2.2 (3)

174.6 (2)

−0.6 (4)

Hydrogen-bond geometry (Å, º)

D—H···A

N1—H1N···O2ⁱ

D—H

0.80 (2)

H···A

D···A

D—H···A

172 (2)

1.98 (2)

2.7788 (17)

Symmetry code: (i) −x, −y+2, −z+2.

(II) N,N,N′,N′-Tetrabenzyl-N′′-(3- fluorobenzoyl)phosphoric triamide

Crystal data

C₃₅H₃₃FN₃O₂P

Z = 2

M_r= 577.61

Triclinic, P1

F(000) = 608

D_x= 1.263 Mg m⁻³

Hall symbol: -P 1

a = 10.0173 (10) Å

b = 11.2362 (8) Å

c = 14.5992 (12) Å

α = 99.351 (6)°

β = 109.960 (8)°

γ = 91.135 (7)°

V = 1519.0 (2) Å³

Mo Kα radiation, λ = 0.71073 Å

Cell parameters from 6536 reflections

θ = 3.3–32.3°

µ = 0.13 mm⁻¹

T = 173 K

Chunk, colorless

0.48 × 0.40 × 0.36 mm

Data collection

Xcalibur, Eos, Gemini

diffractometer

Radiation source: Enhance (Mo) X-ray Source

Graphite monochromator

Detector resolution: 16.1500 pixels mm^-1

ω scans

17423 measured reflections

9840 independent reflections

8118 reflections with I > 2σ(I)

R_int= 0.021

θ_max= 32.3°, θ_min= 3.3°

h = −14→14

k = −15→16

l = −21→21

Absorption correction: multi-scan

CrysAlis PRO, Oxford Diffraction, 2010.

T

_min= 0.943, T_max= 1.000

Acta Cryst. (2012). C68, o399–o404

sup-7

supplementary materials

Refinement

Refinement on F²

Least-squares matrix: full

R[F²> 2σ(F²)] = 0.048

wR(F²) = 0.143

Secondary atom site location: difference Fourier

map

Hydrogen site location: inferred from

neighbouring sites

S = 1.04

9840 reflections

383 parameters

0 restraints

Primary atom site location: structure-invariant

direct methods

H atoms treated by a mixture of independent

and constrained refinement

w = 1/[σ²(F_o²) + (0.0785P)²+ 0.4137P]

where P = (F_o²+ 2F_c²)/3

(Δ/σ)_max= 0.001

Δρ_max= 1.12 e Å⁻³

Δρ_min= −0.32 e Å⁻³

Special details

Experimental. IR (KBr, ν, cm^-1): 3080, 3064, 3031, 2888, 2864, 1681, 1588, 1495, 1455, 1365, 1356, 1316, 1285, 1279,

1209, 1190, 1099, 1064, 1029, 1004, 951, 936, 916, 902, 887, 884, 802, 748, 700, 675, 604, 596, 585, 557, 527, 485, 462,

432.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full

covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and

torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry.

An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F²against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F²,

conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F²> σ(F²) is used

only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F²

are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²)

x

y

z

U_iso*/U_eq

P1

0.61224 (3)

0.09542 (14)

0.43362 (11)

0.64579 (9)

0.46767 (11)

0.4313 (18)

0.56350 (11)

0.75016 (11)

0.26260 (13)

0.24014 (15)

0.3069

0.52499 (3)

0.11276 (10)

0.37517 (10)

0.56565 (8)

0.42457 (9)

0.4221 (15)

0.62438 (9)

0.46451 (10)

0.28721 (11)

0.23735 (12)

0.2517

0.17147 (2)

−0.14885 (8)

0.25151 (7)

0.08984 (6)

0.11608 (7)

0.0549 (13)

0.24783 (7)

0.24019 (7)

0.09631 (9)

−0.00175 (10)

−0.0308

0.01907 (8)

0.0595 (3)

0.0341 (2)

0.02406 (18)

0.02139 (19)

0.029 (4)*

0.02175 (19)

0.02328 (19)

0.0248 (2)

0.0301 (3)

0.036*

F1

O1

O2

N1

H1N

N2

N3

C1

C2

H2

C3

C4

H4

C5

H5

C6

H6

C7

C8

H8A

H8B

0.11489 (18)

0.01102 (18)

−0.0735

0.16555 (13)

0.14373 (15)

0.0977

−0.05481 (11)

−0.01578 (15)

−0.0545

0.0378 (3)

0.0471 (4)

0.057*

0.03640 (18)

−0.0311

0.19228 (17)

0.1777

0.08265 (16)

0.1111

0.0509 (4)

0.061*

0.16203 (16)

0.1794

0.26254 (14)

0.2933

0.13908 (13)

0.2056

0.0380 (3)

0.046*

0.39457 (13)

0.76361 (13)

0.6737

0.36511 (11)

0.43097 (12)

0.4397

0.16160 (9)

0.33578 (8)

0.3466

0.0233 (2)

0.0248 (2)

0.030*

0.8355

0.4861

0.3883

0.030*

Acta Cryst. (2012). C68, o399–o404

sup-8

supplementary materials

C9

0.80392 (14)

0.71824 (16)

0.6336

0.30247 (12)

0.20475 (13)

0.2185

0.34142 (9)

0.27461 (11)

0.2269

0.0265 (2)

0.0347 (3)

0.042*

C10

H10

C11

H11

C12

H12

C13

H13

C14

H14

C15

H15A

H15B

C16

C17

H17

C18

H18

C19

H19

C20

H20

C21

H21

C22

H22A

H22B

C23

C24

H24

C25

H25

C26

H26

C27

H27

C28

H28

C29

H29A

H29B

C30

C31

H31

C32

H32

C33

H33

0.75667 (19)

0.6990

0.08760 (15)

0.0235

0.27790 (14)

0.2319

0.0442 (4)

0.053*

0.8805 (2)

0.9072

0.06598 (16)

−0.0126

0.34936 (16)

0.3513

0.0492 (4)

0.059*

0.96441 (19)

1.0469

0.16098 (18)

0.1462

0.41774 (15)

0.4670

0.0514 (4)

0.062*

0.92681 (16)

0.9847

0.27899 (15)

0.3427

0.41383 (12)

0.4602

0.0392 (3)

0.047*

0.87940 (14)

0.8555

0.45173 (13)

0.4606

0.21260 (9)

0.1440

0.0277 (2)

0.033*

0.9101

0.3711

0.2182

0.033*

1.00150 (13)

1.11964 (15)

1.1249

0.54409 (12)

0.51077 (14)

0.4305

0.27702 (10)

0.34877 (11)

0.3572

0.0272 (2)

0.0326 (3)

0.039*

1.23005 (16)

1.3085

0.59669 (16)

0.5734

0.40806 (12)

0.4557

0.0391 (3)

0.047*

1.22389 (17)

1.2972

0.71609 (16)

0.7735

0.39659 (13)

0.4369

0.0402 (3)

0.048*

1.10789 (17)

1.1036

0.74988 (15)

0.8301

0.32468 (14)

0.3161

0.0415 (3)

0.050*

0.99754 (16)

0.9201

0.66420 (14)

0.6877

0.26510 (12)

0.2167

0.0365 (3)

0.044*

0.67207 (13)

0.6710

0.71875 (11)

0.7887

0.31683 (8)

0.2855

0.0241 (2)

0.029*

0.7655

0.6883

0.3304

0.029*

0.64753 (13)

0.61737 (16)

0.6060

0.75728 (11)

0.67221 (13)

0.5905

0.41343 (8)

0.46430 (10)

0.4365

0.0241 (2)

0.0312 (3)

0.037*

0.60394 (18)

0.5848

0.70759 (16)

0.6497

0.55601 (10)

0.5897

0.0375 (3)

0.045*

0.61904 (19)

0.6110

0.82884 (18)

0.8527

0.59725 (11)

0.6591

0.0450 (4)

0.054*

0.6460 (2)

0.6547

0.91451 (16)

0.9963

0.54692 (13)

0.5743

0.0471 (4)

0.057*

0.66030 (16)

0.6786

0.87901 (13)

0.9373

0.45523 (11)

0.4216

0.0342 (3)

0.041*

0.41673 (13)

0.3962

0.66476 (12)

0.6948

0.21893 (9)

0.2785

0.0250 (2)

0.030*

0.3496

0.5956

0.1823

0.030*

0.39415 (13)

0.39678 (17)

0.4097

0.76240 (12)

0.88282 (13)

0.9041

0.15641 (9)

0.19750 (11)

0.2644

0.0253 (2)

0.0367 (3)

0.044*

0.38032 (19)

0.3821

0.97234 (15)

1.0530

0.13996 (15)

0.1683

0.0476 (4)

0.057*

0.36147 (18)

0.3524

0.94131 (17)

1.0011

0.04103 (16)

0.0026

0.0482 (4)

0.058*

Acta Cryst. (2012). C68, o399–o404

sup-9

supplementary materials

C34

H34

C35

H35

0.3560 (2)

0.3417

0.82113 (18)

0.8001

−0.00112 (13)

−0.0683

0.0480 (4)

0.058*

0.37159 (18)

0.3670

0.73209 (15)

0.6514

0.05590 (10)

0.0268

0.0369 (3)

0.044*

Atomic displacement parameters (Å²)

U¹¹

U²²

U³³

U¹²

U¹³

U²³

P1

0.02207 (14)

0.0821 (8)

0.0346 (5)

0.0274 (4)

0.0246 (5)

0.0239 (5)

0.0242 (5)

0.0259 (5)

0.0378 (7)

0.0462 (8)

0.0340 (8)

0.0346 (8)

0.0339 (7)

0.0242 (5)

0.0289 (6)

0.0274 (6)

0.0352 (7)

0.0485 (9)

0.0491 (9)

0.0391 (9)

0.0321 (7)

0.0275 (6)

0.0243 (5)

0.0283 (6)

0.0280 (7)

0.0329 (7)

0.0355 (7)

0.0288 (6)

0.0294 (6)

0.0261 (5)

0.0441 (7)

0.0466 (8)

0.0524 (9)

0.0596 (10)

0.0404 (7)

0.0266 (5)

0.0268 (5)

0.0397 (7)

0.0430 (9)

0.0367 (8)

0.0572 (10)

0.0504 (8)

0.02263 (14)

0.0427 (6)

0.0483 (6)

0.0299 (4)

0.0254 (5)

0.0245 (5)

0.0304 (5)

0.0213 (5)

0.0233 (6)

0.0236 (6)

0.0339 (8)

0.0483 (10)

0.0377 (7)

0.0261 (5)

0.0293 (6)

0.0309 (6)

0.0324 (7)

0.0311 (7)

0.0391 (8)

0.0531 (10)

0.0436 (8)

0.0338 (6)

0.0377 (7)

0.0510 (9)

0.0449 (8)

0.0357 (7)

0.0397 (8)

0.0246 (5)

0.0273 (6)

0.0310 (6)

0.0493 (9)

0.0598 (10)

0.0396 (8)

0.0289 (6)

0.0276 (6)

0.0306 (7)

0.0289 (7)

0.0540 (10)

0.0644 (11)

0.0398 (8)

0.01297 (12)

0.0359 (5)

0.0208 (4)

0.0163 (3)

0.0139 (4)

0.0159 (4)

0.0169 (4)

0.0276 (6)

0.0279 (6)

0.0334 (7)

0.0615 (11)

0.0705 (12)

0.0447 (8)

0.0215 (5)

0.0155 (5)

0.0227 (5)

0.0322 (7)

0.0523 (9)

0.0676 (12)

0.0589 (11)

0.0351 (7)

0.0238 (5)

0.0269 (6)

0.0337 (7)

0.0367 (7)

0.0420 (8)

0.0568 (10)

0.0433 (8)

0.0181 (5)

0.0164 (5)

0.0218 (5)

0.0214 (6)

0.0223 (6)

0.0371 (8)

0.0313 (6)

0.0212 (5)

0.0228 (5)

0.0321 (7)

0.0616 (11)

0.0666 (11)

0.0406 (8)

0.0252 (6)

0.00043 (10)

−0.0171 (5)

−0.0061 (4)

−0.0020 (3)

−0.0018 (3)

0.0023 (3)

0.0048 (4)

0.0018 (4)

−0.0022 (5)

−0.0032 (5)

−0.0078 (6)

−0.0095 (7)

−0.0047 (6)

0.0016 (4)

0.0047 (4)

0.0060 (4)

0.0044 (5)

0.0040 (6)

0.0176 (7)

0.0186 (7)

0.0076 (6)

0.0064 (5)

0.0053 (4)

0.0060 (5)

0.0013 (6)

−0.0046 (6)

0.0021 (6)

0.0055 (5)

−0.0011 (4)

0.0039 (4)

0.0070 (5)

0.0119 (6)

0.0142 (8)

0.0067 (7)

0.0033 (5)

0.0053 (4)

0.0075 (4)

0.0088 (5)

0.0060 (6)

0.0153 (7)

0.0331 (9)

0.0202 (6)

0.00599 (10)

0.0037 (5)

0.0085 (4)

0.0084 (3)

0.0059 (3)

0.0056 (3)

0.0079 (4)

0.0084 (4)

0.0086 (5)

0.0017 (6)

0.0049 (7)

0.0257 (8)

0.0204 (6)

0.0083 (4)

0.0056 (4)

0.0080 (4)

0.0052 (5)

0.0159 (7)

0.0238 (9)

0.0051 (8)

0.0003 (6)

0.0114 (5)

0.0121 (5)

0.0103 (5)

0.0064 (6)

0.0134 (6)

0.0177 (7)

0.0109 (6)

0.0083 (4)

0.0050 (4)

0.0143 (5)

0.0151 (6)

0.0154 (6)

0.0179 (7)

0.0123 (6)

0.0091 (4)

0.0089 (4)

0.0038 (6)

0.0039 (8)

0.0202 (8)

0.0283 (8)

0.0156 (6)

0.00493 (10)

−0.0028 (4)

0.0136 (4)

0.0070 (3)

0.0054 (3)

0.0038 (3)

0.0072 (4)

0.0076 (4)

0.0075 (5)

0.0045 (5)

0.0027 (7)

−0.0017 (9)

−0.0002 (6)

0.0084 (4)

0.0064 (4)

0.0101 (5)

0.0084 (5)

0.0089 (7)

0.0229 (8)

0.0264 (9)

0.0127 (6)

0.0053 (5)

0.0080 (5)

0.0121 (6)

0.0144 (7)

0.0062 (7)

0.0145 (7)

0.0176 (6)

0.0034 (4)

0.0025 (4)

0.0069 (5)

0.0117 (6)

−0.0007 (6)

−0.0096 (6)

0.0004 (5)

0.0072 (4)

0.0071 (4)

0.0025 (5)

0.0132 (7)

0.0404 (9)

0.0321 (8)

0.0120 (5)

F1

O1

O2

N1

N2

N3

C1

C2

C3

C4

C5

C6

C7

C8

C9

C10

C11

C12

C13

C14

C15

C16

C17

C18

C19

C20

C21

C22

C23

C24

C25

C26

C27

C28

C29

C30

C31

C32

C33

C34

C35

Acta Cryst. (2012). C68, o399–o404

sup-10

supplementary materials

Geometric parameters (Å, º)

P1—N1

1.6922 (10)

1.6484 (11)

1.6400 (11)

1.4786 (9)

1.3500 (19)

1.2200 (15)

1.3716 (15)

0.837 (18)

1.4768 (15)

1.4868 (16)

1.4672 (15)

1.4844 (16)

1.3886 (18)

1.3987 (19)

1.4984 (17)

1.3851 (19)

0.9300

C16—C21

C16—C17

C17—C18

C17—H17

C18—C19

C18—H18

C19—C20

C19—H19

C20—C21

C20—H20

C21—H21

C22—C23

C22—H22A

C22—H22B

C23—C28

C23—C24

C24—C25

C24—H24

C25—C26

C25—H25

C26—C27

C26—H26

C27—C28

C27—H27

C28—H28

C29—C30

C29—H29A

C29—H29B

C30—C31

C30—C35

C31—C32

C31—H31

C32—C33

C32—H32

C33—C34

C33—H33

C34—C35

C34—H34

C35—H35

1.388 (2)

1.3916 (18)

1.392 (2)

0.9300

P1—N2

P1—N3

P1—O2

F1—C3

1.379 (2)

0.9300

O1—C7

N1—C7

1.382 (2)

0.9300

N1—H1N

N2—C22

N2—C29

N3—C8

1.391 (2)

0.9300

N3—C15

C1—C2

1.5096 (17)

0.9700

C1—C6

0.9700

C1—C7

1.3886 (19)

1.3888 (18)

1.3860 (19)

0.9300

C2—C3

C2—H2

C3—C4

1.381 (3)

1.385 (3)

0.9300

C4—C5

1.380 (2)

0.9300

C4—H4

C5—C6

1.388 (2)

0.9300

1.376 (3)

0.9300

C5—H5

C6—H6

0.9300

1.390 (2)

0.9300

C8—C9

1.5144 (18)

0.9700

C8—H8A

C8—H8B

C9—C14

C9—C10

C10—C11

C10—H10

C11—C12

C11—H11

C12—C13

C12—H12

C13—C14

C13—H13

C14—H14

C15—C16

C15—H15A

C15—H15B

0.9300

0.9700

1.5107 (17)

0.9700

1.3847 (18)

1.3917 (19)

1.382 (2)

0.9300

0.9700

1.3839 (19)

1.3887 (18)

1.390 (2)

0.9300

1.377 (3)

0.9300

1.374 (3)

0.9300

1.375 (3)

0.9300

1.390 (2)

0.9300

1.382 (3)

0.9300

1.381 (2)

0.9300

1.5181 (19)

0.9700

0.9300

0.9700

N1—P1—N2

N1—P1—N3

N2—P1—N3

O2—P1—N1

O2—P1—N2

O2—P1—N3

C7—N1—P1

103.81 (5)

112.50 (5)

106.54 (5)

105.60 (5)

118.92 (5)

109.48 (5)

127.16 (8)

C21—C16—C17

C21—C16—C15

C17—C16—C15

C16—C17—C18

C16—C17—H17

C18—C17—H17

C19—C18—C17

118.52 (13)

120.36 (12)

121.13 (12)

120.50 (14)

119.8

120.46 (14)

Acta Cryst. (2012). C68, o399–o404

sup-11

supplementary materials

C7—N1—H1N

P1—N1—H1N

C22—N2—C29

C22—N2—P1

C29—N2—P1

C8—N3—C15

C8—N3—P1

118.5 (12)

113.4 (12)

113.09 (10)

117.96 (8)

121.34 (8)

114.81 (10)

124.58 (8)

120.32 (8)

120.18 (13)

122.70 (12)

117.09 (12)

117.73 (14)

121.1

C19—C18—H18

C17—C18—H18

C18—C19—C20

C18—C19—H19

C20—C19—H19

C19—C20—C21

C19—C20—H20

C21—C20—H20

C16—C21—C20

C16—C21—H21

C20—C21—H21

N2—C22—C23

N2—C22—H22A

C23—C22—H22A

N2—C22—H22B

C23—C22—H22B

119.8

119.51 (15)

120.2

120.18 (15)

119.9

C15—N3—P1

C2—C1—C6

C2—C1—C7

C6—C1—C7

119.9

120.82 (14)

119.6

C3—C2—C1

C3—C2—H2

C1—C2—H2

F1—C3—C4

112.56 (10)

109.1

121.1

109.1

118.74 (14)

117.89 (15)

123.36 (15)

118.09 (14)

121.0

109.1

F1—C3—C2

109.1

C4—C3—C2

C3—C4—C5

C3—C4—H4

C5—C4—H4

C4—C5—C6

C4—C5—H5

C6—C5—H5

C5—C6—C1

C5—C6—H6

C1—C6—H6

O1—C7—N1

O1—C7—C1

N1—C7—C1

N3—C8—C9

N3—C8—H8A

C9—C8—H8A

N3—C8—H8B

C9—C8—H8B

H8A—C8—H8B

C14—C9—C10

C14—C9—C8

C10—C9—C8

C11—C10—C9

C11—C10—H10

C9—C10—H10

C12—C11—C10

C12—C11—H11

C10—C11—H11

C13—C12—C11

C13—C12—H12

C11—C12—H12

C12—C13—C14

C12—C13—H13

H22A—C22—H22B

C28—C23—C24

C28—C23—C22

C24—C23—C22

C25—C24—C23

C25—C24—H24

C23—C24—H24

C26—C25—C24

C26—C25—H25

C24—C25—H25

C27—C26—C25

C27—C26—H26

C25—C26—H26

C26—C27—C28

C26—C27—H27

C28—C27—H27

C23—C28—C27

C23—C28—H28

C27—C28—H28

N2—C29—C30

N2—C29—H29A

C30—C29—H29A

N2—C29—H29B

C30—C29—H29B

H29A—C29—H29B

C31—C30—C35

C31—C30—C29

C35—C30—C29

C30—C31—C32

C30—C31—H31

C32—C31—H31

C33—C32—C31

C33—C32—H32

107.8

118.56 (12)

120.38 (12)

121.01 (11)

120.85 (14)

119.6

121.0

120.33 (16)

119.8

119.6

120.23 (15)

119.9

119.88 (15)

120.1

119.9

120.1

122.00 (11)

120.72 (11)

117.28 (10)

112.68 (10)

109.1

120.03 (14)

120.0

120.08 (15)

120.0

109.1

120.0

109.1

120.58 (15)

119.7

109.1

107.8

119.7

118.16 (13)

120.79 (12)

121.05 (11)

121.19 (14)

119.4

113.65 (10)

108.8

119.4

107.7

119.90 (16)

120.1

118.79 (13)

121.26 (12)

119.95 (12)

120.80 (15)

119.6

120.1

119.76 (16)

120.1

119.6

120.42 (15)

119.8

119.79 (16)

120.1

Acta Cryst. (2012). C68, o399–o404

sup-12

supplementary materials

C14—C13—H13

C9—C14—C13

119.8

C31—C32—H32

C32—C33—C34

C32—C33—H33

C34—C33—H33

C35—C34—C33

C35—C34—H34

C33—C34—H34

C34—C35—C30

C34—C35—H35

C30—C35—H35

120.1

120.55 (16)

119.7

119.86 (15)

120.1

C9—C14—H14

C13—C14—H14

N3—C15—C16

119.7

120.1

112.84 (10)

109.0

120.36 (16)

119.8

N3—C15—H15A

C16—C15—H15A

N3—C15—H15B

C16—C15—H15B

H15A—C15—H15B

109.0

119.8

109.0

120.37 (15)

119.8

109.0

107.8

119.8

O2—P1—N1—C7

N3—P1—N1—C7

N2—P1—N1—C7

O2—P1—N2—C22

N3—P1—N2—C22

N1—P1—N2—C22

O2—P1—N2—C29

N3—P1—N2—C29

N1—P1—N2—C29

O2—P1—N3—C8

N2—P1—N3—C8

N1—P1—N3—C8

O2—P1—N3—C15

N2—P1—N3—C15

N1—P1—N3—C15

C6—C1—C2—C3

C7—C1—C2—C3

C1—C2—C3—F1

C1—C2—C3—C4

F1—C3—C4—C5

C2—C3—C4—C5

C3—C4—C5—C6

C4—C5—C6—C1

C2—C1—C6—C5

C7—C1—C6—C5

P1—N1—C7—O1

P1—N1—C7—C1

C2—C1—C7—O1

C6—C1—C7—O1

C2—C1—C7—N1

C6—C1—C7—N1

C15—N3—C8—C9

P1—N3—C8—C9

N3—C8—C9—C14

N3—C8—C9—C10

C14—C9—C10—C11

C8—C9—C10—C11

C9—C10—C11—C12

−177.83 (10)

62.80 (12)

−51.98 (12)

−69.72 (10)

54.45 (9)

C10—C9—C14—C13

C8—C9—C14—C13

C12—C13—C14—C9

C8—N3—C15—C16

P1—N3—C15—C16

N3—C15—C16—C21

N3—C15—C16—C17

C21—C16—C17—C18

C15—C16—C17—C18

C16—C17—C18—C19

C17—C18—C19—C20

C18—C19—C20—C21

C17—C16—C21—C20

C15—C16—C21—C20

C19—C20—C21—C16

C29—N2—C22—C23

P1—N2—C22—C23

N2—C22—C23—C28

N2—C22—C23—C24

C28—C23—C24—C25

C22—C23—C24—C25

C23—C24—C25—C26

C24—C25—C26—C27

C25—C26—C27—C28

C24—C23—C28—C27

C22—C23—C28—C27

C26—C27—C28—C23

C22—N2—C29—C30

P1—N2—C29—C30

N2—C29—C30—C31

N2—C29—C30—C35

C35—C30—C31—C32

C29—C30—C31—C32

C30—C31—C32—C33

C31—C32—C33—C34

C32—C33—C34—C35

C33—C34—C35—C30

C31—C30—C35—C34

1.4 (2)

−179.03 (15)

0.4 (3)

−69.52 (14)

104.64 (11)

−73.76 (16)

106.47 (14)

1.0 (2)

173.40 (8)

77.75 (10)

−158.08 (9)

−39.13 (10)

170.38 (10)

40.57 (11)

−72.54 (11)

−3.18 (11)

−132.99 (10)

113.90 (10)

1.3 (2)

−179.27 (13)

0.1 (2)

−0.9 (2)

0.7 (3)

−1.1 (2)

179.08 (14)

0.3 (2)

61.38 (13)

−148.57 (9)

−135.97 (12)

46.59 (16)

−1.7 (2)

179.24 (12)

−177.25 (13)

1.5 (2)

176.03 (16)

−2.7 (3)

175.83 (13)

0.7 (2)

1.2 (3)

1.5 (3)

0.6 (3)

−2.7 (2)

−1.0 (3)

179.17 (15)

−3.97 (19)

175.47 (9)

−156.09 (13)

21.96 (19)

24.46 (18)

−157.50 (13)

−57.00 (14)

129.12 (10)

121.40 (14)

−59.07 (17)

−2.2 (2)

1.3 (2)

−176.22 (14)

0.0 (3)

67.33 (13)

−81.59 (12)

−100.23 (15)

79.14 (15)

−1.4 (2)

177.98 (14)

−0.1 (3)

1.4 (3)

−1.0 (3)

178.24 (15)

1.2 (3)

−0.5 (3)

1.7 (2)

Acta Cryst. (2012). C68, o399–o404

sup-13

supplementary materials

C10—C11—C12—C13

C11—C12—C13—C14

0.7 (3)

C29—C30—C35—C34

−177.66 (14)

−1.5 (3)

Hydrogen-bond geometry (Å, º)

D—H···A

D—H

H···A

D···A

D—H···A

C2—H2···O2ⁱ

C25—H25···O1ⁱⁱ

N1—H1N···O2ⁱ

0.93

2.45

3.1124 (16)

3.2342 (17)

2.8497 (13)

128

0.93

2.45

142

0.837 (18)

2.017 (18)

173.7 (17)

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

(III) N,N,N′,N′-Tetrabenzyl-N′′-(3,5- difluorobenzoyl)phosphoric triamide

Crystal data

C₃₅H₃₂F₂N₃O₂P

Z = 2

M_r= 595.61

Triclinic, P1

F(000) = 624

D_x= 1.341 Mg m⁻³

Hall symbol: -P 1

a = 11.9526 (11) Å

b = 12.2897 (10) Å

c = 12.7463 (12) Å

α = 102.074 (7)°

β = 104.462 (8)°

γ = 118.262 (9)°

V = 1474.5 (2) Å³

Mo Kα radiation, λ = 0.71073 Å

Cell parameters from 6783 reflections

θ = 3.2–32.3°

µ = 0.14 mm⁻¹

T = 173 K

Chunk, colorless

0.32 × 0.28 × 0.16 mm

Data collection

Oxford Diffraction Xcalibur (Eos, Gemini)

diffractometer

Radiation source: Enhance (Mo) X-ray Source

Graphite monochromator

Detector resolution: 16.1500 pixels mm^-1

ω scans

17265 measured reflections

9523 independent reflections

7763 reflections with I > 2σ(I)

R_int= 0.019

θ_max= 32.4°, θ_min= 3.2°

h = −17→17

k = −17→18

l = −18→18

Absorption correction: multi-scan

(CrysAlis PRO; Oxford Diffraction, 2010)

T

_min= 0.992, T_max= 1.000

Refinement

Refinement on F²

Least-squares matrix: full

R[F²> 2σ(F²)] = 0.042

wR(F²) = 0.116

Secondary atom site location: difference Fourier

map

Hydrogen site location: inferred from

neighbouring sites

S = 1.05

9523 reflections

392 parameters

0 restraints

H atoms treated by a mixture of independent

and constrained refinement

w = 1/[σ²(F_o²) + (0.0513P)²+ 0.4759P]

where P = (F_o²+ 2F_c²)/3

Primary atom site location: structure-invariant

direct methods

(Δ/σ)_max< 0.001

Δρ_max= 0.41 e Å⁻³

Δρ_min= −0.37 e Å⁻³

Special details

Experimental. IR (KBr, ν, cm^-1): 3089, 3076, 3032, 2921, 2860, 1675, 1623, 1599, 1494, 1447, 1355, 1321, 1224, 1190,

1124, 1101, 1068, 1057, 1030, 987, 949, 913, 902, 871, 807, 796, 773, 749, 743, 697, 665, 614, 600, 571, 542, 523, 516,

476, 465, 410.

Acta Cryst. (2012). C68, o399–o404

sup-14