New organophosphorus proligands and amide precursors: Crystal and molecular structures of Ph2P(X)NH(C6H3Pr i2-2,6) (X = O, S) and (OPPh2)(O 2SMe)N(C6H3Pri2-2,6)

Article abstract of DOI:10.1080/10426500903029464

The new organophosphorus proligand (OPPh₂)(O₂SMe)NR (R = C₆H₃Prⁱ₂-2,6)(3) was prepared as a white crystalline solid by reacting the lithiated compound Li[Ph ₂P(O)NR] with MeSO2Cl in a 1:1 molar ratio. The precursor Ph ₂P(O)NHR (1), as well as its thio analogue Ph₂P(S)NHR (2), were obtained in the reaction between the lithiated amine RNHLi and the corresponding organophosphorus chloride. All compounds were characterized by multinuclear (1H, 13C, and 31P) NMR spectroscopy. The molecular structures of 1-3 were established by single-crystal X-ray diffraction. A zigzag polymeric chain is formed in the crystals of 1 and 2 by hydrogen N-HX (X = O, S) bonding, while the crystal of 3 contains discrete monomeric units with a syn-syn conformation of the O=P(C)2-N-S(C)(=O)2 skeleton. Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.

Full text of DOI:10.1080/10426500903029464

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New Organophosphorus Proligands and
Amide Precursors: Crystal and Molecular
Structures of Ph2P(X)NH(C6H3Pri -2,6)
2
(X = O, S) and (OPPh2)(O2SMe)N(C6H3Pri
2-2,6)
Alpar Pöllnitz a , Sevil Irisli b , Cristian Silvestru a & Anca Silvestru a
a Faculty of Chemistry & Chemical Engineering , “Babes-Bolyai”
University , Cluj-Napoca, Romania
b Chemistry Department, Faculty of Science , Ege University ,
Bomova-Izmir, Turkey
Published online: 23 Mar 2010.
To cite this article: Alpar Pöllnitz , Sevil Irisli , Cristian Silvestru & Anca Silvestru (2010)
New Organophosphorus Proligands and Amide Precursors: Crystal and Molecular Structures of
Ph2P(X)NH(C6H3Pri -2,6) (X = O, S) and (OPPh2)(O2SMe)N(C6H3Pri -2,6), Phosphorus, Sulfur, and Silicon
2
2
and the Related Elements, 185:4, 910-919, DOI: 10.1080/10426500903029464
To link to this article: http://dx.doi.org/10.1080/10426500903029464
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Phosphorus, Sulfur, and Silicon, 185:910–919, 2010
Copyright ꢀC Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500903029464
NEW ORGANOPHOSPHORUS PROLIGANDS AND AMIDE
PRECURSORS: CRYSTAL AND MOLECULAR
STRUCTURES OF Ph2P(X)NH(C6H3Pri2-2,6) (X = O, S)
AND (OPPh2)(O2SMe)N(C6H3Pri2-2,6)
Alpar Po¨llnitz,1 Sevil Irisli,2 Cristian Silvestru,1
and Anca Silvestru1
1Faculty of Chemistry & Chemical Engineering, “Babes-Bolyai” University,
Cluj-Napoca, Romania
2Chemistry Department, Faculty of Science, Ege University, Bomova-Izmir, Turkey
The new organophosphorus proligand (OPPh2)(O2SMe)NR (R = C6H3Pri2–2,6) (3) was
prepared as a white crystalline solid by reacting the lithiated compound Li[Ph2P(O)NR]
with MeSO2Cl in a 1:1 molar ratio. The precursor Ph2P(O)NHR (1), as well as its thio ana-
logue Ph2P(S)NHR (2), were obtained in the reaction between the lithiated amine RNHLi
and the corresponding organophosphorus chloride. All compounds were characterized by
multinuclear (1H, 13C, and 31P) NMR spectroscopy. The molecular structures of 1–3 were
established by single-crystal X-ray diffraction. A zigzag polymeric chain is formed in the
crystals of 1 and 2 by hydrogen N–H···X (X = O, S) bonding, while the crystal of 3 con-
tains discrete monomeric units with a syn–syn conformation of the O P(C)2–N–S(C)( O)2
skeleton.
Supplemental materials are available for this article. Go to the publisher’s online edition of
Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.
Keywords Molecular structure; NMR spectroscopy; organophosphorus ligands
INTRODUCTION
Tetraorganodichalcogenoimidodiphosphinic acids, (XPR2)(YPRꢁ2)NH (X, Y = O,
S, Se; R, R’ = alkyl, aryl, OR) (A), have been investigated for a long time as versatile
ligands for main group or transition metals.1–3 In the deprotonated form they act usually as
bidentate ligands, exhibiting a high tendency to generate six-membered, carbon-free met-
allacycles. Due to the high flexibility of the XPNPY skeleton, other coordination patterns
have also been observed in metal complexes.1 At the same time, bis(organosulfonyl)imides
(O2SR)(O2SR’)NH (B) have attracted interest as ligands and they act in either a mon-
odentate or bidentate manner.4–19 Recently we have reported on the new organophoshorus
Received 18 February 2009; accepted 8 May 2009.
This work was supported by the National University Research Council of Romania (CNCSIS grant: A-
1456/2008). S.I. is grateful for financial support in the form of a Scientific and Technical Research Council of
Turkey (TUBITAK)–NATO B2 fellowship.
Address correspondence to Anca Silvestru, Faculty of Chemistry & Chemical Engineering, “Babes-Bolyai”
University RO-400028, Cluj-Napoca, Romania. E-mail: ancas@chem.ubbcluj.ro
910

ORGANOPHOSPHORUS PROLIGANDS AND AMIDE PRECURSORS
911
ligands (SPPh2)(O2SR)NH (C), which combine the properties of the above mentioned
species.20,21 We have extended our research to neutral ligands of type (XPPh2)(O2SR)NR’
(X = O, S) (D) (Scheme 1) in order to investigate the influence of a bulky organic group
attached to nitrogen upon the structure and the properties of these new species.
Scheme 1
We report in this article on the synthesis of a new proligand, namely
(OPPh2)(O2SMe)NR (3), as well as the precursor Ph2P(O)NHR (1) and its thio
analogue Ph2P(S)NHR (2) (R = C6H3Pri2-2,6). The compounds were characterized
by multinuclear NMR spectroscopy, and their crystal and molecular structures were
established by single-crystal X-ray diffraction.
RESULTS AND DISCUSSION
Preparation and Solution NMR Characterization
Compound Ph2P(O)NH(C6H3Pri2–2,6) (1) and its thio analogue 2 were prepared
according to Scheme 2, by lithiation of 2,6-isopropylaniline, followed by the reaction be-
tween the lithiated compound and diphenylphosphinyl or diphenylthiophosphinyl chloride,
respectively, in a 1:1 molar ratio.
Scheme 2

¨
912
A. POLLNITZ ET AL.
The proligand (OPPh2)(O2SMe)N(C6H3Pri2-2,6) (3) was obtained by deprotona-
tion of compound 1 with BunLi, followed by addition of MeSO2Cl in a 1:1 molar ratio
(Scheme 3).
Scheme 3
The NMR spectra of all three new derivatives display the expected resonances for
the organic groups attached to phosphorus, nitrogen, and sulfur. The multiplicity of the
1H and 13C NMR resonances is determined by proton–proton, phosphorus–proton, and
phosphorus–carbon couplings, respectively. The NH protons in the amides 1 and 2 were
observed at δ 4.42 and 4.28 ppm as doublet resonances due to phosphorus–proton couplings.
1
In contrast to the amides 1 and 2, the H and 13C NMR spectra of 3 show two different
resonances for the diastereotopic methyls of the Pri substituents. The 31P NMR spectra
of all compounds display singlet resonances (i.e., 21.6 ppm for 1, 57.9 ppm for 2, and
26.7 ppm for 3, respectively), low-field shifted for the neutral proligand 3 in comparison
with the amide precursor 1.
Crystal and Molecular Structures of Ph2P(O)NH(C6H3Pri2–2,6) (1),
Ph2P(S)NH(C6H3Pri2–2,6) (2), and (OPPh2)(O2SMe)N(C6H3Pri2–2,6) (3)
ORTEP representations of compounds 1 and 2 with the corresponding atom number-
ing schemes are depicted in Figures 1 and 2, respectively, while important bond lengths
and angles are given in Tables S1 and S2 (available online in the Supplemental Materials).
Derivatives 1 and 2 have similar structures in the solid state, except that in
the case of the thio derivative 2, three independent molecules are present in the
unit cell. The coordination geometry around phosphorus is distorted tetrahedral. The
phosphorus–chalcogen bond lengths [P(1)–O(1) 1.478(2) Å in 1; averaged P S 1.943 Å
in 2] are consistent with a double-bond character [cf. Ph2P( O)OH:22 P O 1.486(6) Å,
P–O 1.526(6) Å; Ph2P( S)–N PPh2( SMe):23 P S 1.954(1) Å, P–S 2.071(1) Å]. The
phosphorus–nitrogen bond distances [P(1)–N(1) 1.643(3) Å in 1 and 1.652(3) Å (av. value)
in 2] suggest a single P N bond [cf. Ph2P( S) N PPh2( SMe):23 P N 1.562(2) Å,
P–N 1.610(2) Å], although the nitrogen atoms are essentially sp2 [ꢀ(Nangles) 359.73◦ in 1
and 357.37◦ (av. value) in 2].
In the crystal of 1, the molecules are associated into polymeric chains built through
strong intermolecular Hamide···O hydrogen bonding [H(1)···O(1a) 2.10(2) Å] (Figure S1,
Supplemental Materials), similar to those observed in the crystal of (SPPh2)(O2SMe)NH.20
Additional weak intermolecular Hphenyl···O contacts [H(6)···O(1a) 2.481(2) Å; c.f. ꢀrvdW
(H,O) ca. 2.60 Å]24 are also present. There are no interchain contacts that involve heavier
atoms.

ORGANOPHOSPHORUS PROLIGANDS AND AMIDE PRECURSORS
913
Figure 1 ORTEP plot of Ph2P(O)NH(C6H3Pri2–2,6) (1). The atoms are drawn with 30% probability ellipsoids.
Hydrogen atoms, except that one attached to nitrogen, are omitted for clarity.
Similar polymeric chains with repeating 2a–2b–2c sequence of molecules are formed
in the crystal of the thio derivative through strong intermolecular Hamide···S hydrogen
bonding (Table S2, Supplemental Materials). Within a chain, there are also weak in-
termolecular Hphenyl···S contacts [H(36)···S(1) 2.940(1) Å, H(8)···S(3a) 2.972(1) Å; c.f.
ꢀrvdW (H,S) ca. 3.05 Å].24
The crystal of 3 contains discrete molecules and an ORTEP diagram with the atom
numbering scheme is depicted in Figure 3. Important bond lengths and angles are listed in
Table S1.
The coordination geometries around phosphorus and sulfur, respectively, are distorted
tetrahedral, while the nitrogen atom has again an sp2 hybridization [ꢀ(Nangles) 359.93◦].
The P–N–S system is angular [S(1)–N(1)–P(1) 120.58(12)◦], but bent at a smaller angle
than in the related (SPPh2)(O2SR)NH derivatives, i.e., 126.02(17) ◦ (R = Ph);21 126.4(1)◦
(R = Me), 126.95(8)◦ (R = C6H4Me–4)].20 The phosphorus–oxygen distance [1.4736(19)
Å] is consistent with a P O double bond, while the phosphorus–nitrogen distance is again
consistent with a P–N single bond [P(1)–N(1) 1.721(2) Å], considerably longer than that
found in the precursor 1 [P(1)–N(1) 1.642(3) Å] or in related (SPPh2)(O2SR)NH [1.708(2)
Å (R = Me), 1.703(1) Å (R = C6H4Me–4);20 1.702(3) Å (R = Ph)21]. The sulfur–oxygen
[S(1)–O(2) 1.422(2) Å; S(1)–O(3) 1.418(2) Å] and sulfur–nitrogen distances [S(1)–N(1)
1.677(2) Å] are consistent with double S O and single S–N bonds, respectively, of same
magnitudes as found for the (SPPh2)(O2SR)NH [S O / S O / S–N: 1.4267(1) / 1.428(1)/

¨
A. POLLNITZ ET AL.
914
Figure 2 ORTEP plot of Ph2P(S)NH(C6H3Pri2–2,6) (molecule 2a). The atoms are drawn with 30% probability
ellipsoids. Hydrogen atoms, except that one attached to nitrogen, are omitted for clarity.
Figure 3 ORTEP plot of (OPPh2)(O2SMe)N(C6H3Pri2–2,6) (3). The atoms are drawn with 30% probability
ellipsoids. Hydrogen atoms are omitted for clarity.

ORGANOPHOSPHORUS PROLIGANDS AND AMIDE PRECURSORS
915
1.634(1) Å (R = Me), 1.429(1) / 1.446(1) / 1.641(1) Å (R = C6H4Me–4);20 1.422(2) /
1.429(2) / 1.634(3) Å (R = Ph)21] or bis(organosulfonyl)imides (O2SR)2NH [S–N 1.647(2) /
1.656(1) Å, S–O 1.428(2)-1.435(1) Å (R = Me);25 S–N 1.645(2) / 1.666(2) Å, S–O
1.420(1)−1.431(1) Å (R = C6H4Me–4)26].
The O = P–N–S(C)( O)2 skeleton in 3 is similar to those described for the deriva-
tives (SPPh2)(O2SR)NH,20,21 as reflected by the torsion angles [O(2)S(1)N(1)P(1) 174.5(1),
O(3)S(1)N(1)P(1) 45.6(2), O(1)P(1)N(1)S(1) 28.6(2), C(25)S(1)N(1)P(1) –69.4(2)◦]. Tak-
ing into account the magnitude of the OPNS and CSNP torsion angles, the extreme con-
formations of the O P(C)2–N–S(C)( O)2 skeleton can be described as either syn–syn (E)
or syn–anti (F) (Scheme 4), by assigning the terms syn and anti for angles of 0 and 180◦,
respectively.1
Scheme 4
Thus, for compound 3, a syn–syn conformation can be considered, the deviations
of the O(1) and C(25) atoms from the P(1)N(1)S(1) plane being –0.668 and –1.572 Å,
respectively. Similar syn–syn conformations were assigned for the previously described
derivatives (SPPh2)(O2SR)NH [R = Me, C6H4Me–4,20 Ph21].
EXPERIMENTAL
Materials and Methods
All reactions were carried out under inert argon atmosphere using standard Schlenk
techniques. The solvents were dried (CH2Cl2 on P2O5, hexane and diethyl ether on Na,
tetrahydrofurane and toluene on K) and distilled prior to use. Ph2P(O)Cl and Ph2P(S)Cl
were prepared according to methods in the literature.27 Other reagents, e.g., BunLi (1.6 M
solution in hexane), 2,6-diisopropylaniline, and MeSO2Cl, were commercially available
and used without further purification. Elemental analyses were performed on a VarioEL
analyzer. The NMR spectra were recorded in dry CDCl3, at room temperature, on Bruker
Avance DRX 400 (for 1 and 2) and Bruker Avance 300 (for 3) instruments. The chemical
shifts are reported in δ units (ppm) relative to the residual peak of the deuterated solvent
(ref. CHCl3: 1H 7.26, 13C 77.0 ppm) and H3PO4 85%, respectively. 1H and 13C resonances
were assigned using 2D NMR experiments.

¨
A. POLLNITZ ET AL.
916
Synthesis of LiNH(C6H3Pri2–2,6)
A solution of BunLi in hexane (27.5 mL, 1.6 M, 44 mmol) was slowly added to a
stirred solution of 2,6–iPr2C6H3NH2 (7.80 g, 8.45 mL, 44 mmol) in anhydrous hexane
(80 mL) under an argon atmosphere. The reaction mixture was stirred overnight. The
lithiated compound was separated by filtration, washed several times with hexane, and
dried under vacuum. Yield: 7.58 g (94%).
Synthesis of Ph2P(O)NH(C6H3Pri2–2,6) (1)
Ph2P(O)Cl (9.06 g, 38.3 mmol) was added dropwise to a THF (100 mL) solution of
LiNH(C6H3Pri2–2,6) (7.01 g, 38.3 mmol), and the reaction mixture was stirred at room
temperature overnight. The solvent was removed under vacuum, and the remaining solid
was treated with dichloromethane. LiCl was filtered off, and the solvent was removed in
vacuum. The colorless solid product was washed several times with anhydrous hexane and
recrystallized from dichloromethane (70 mL). Yield: 9.1 g (63%), Mp 149–150◦C. Anal.
Calcd. for C24H28NOP (MW 377.47): C, 76.37; H, 7.48; N, 3.71. Found: C, 76.42; H,
1
3
7.41; N, 3.75. H NMR (400 MHz): 1.04 (d, 12H, CH3, JHH = 6.9 Hz), 3.58 (hept, 2H,
CH, 3JHH = 6.8 Hz), 4.44 (d, 1H, NH, 2JPH = 4.7 Hz), 7.05 (d, 2H, H-3,5, C6H3, 3JHH
=
7.7 Hz), 7.16 (t, 1H, H-4, C6H3, 3JHH = 7.6 Hz), 7.40 (m, 4H, C6H5-meta), 7.49 (m, 2H,
C6H5-para), 7.73 (ddd, 4H, C6H5-ortho, JPH = 12.0, JHH = 8.3, JHH = 1.4 Hz). 13C
NMR (100.6 MHz): 23.65 (s, CH3), 28.39 (s, CH), 123.51 (d, C-3,5, C6H3, 4JPC = 1.5 Hz),
127.21 (d, C-4, C6H3, 5JPC = 1.7 Hz), 128.30 (d, C6H5-meta, 3JPC = 12.7 Hz), 131.79 (d,
C6H5-para, 4JPC = 2.8 Hz), 131.88 (d, C6H5-ortho, 2JPC = 9.5 Hz), 131.95 (d, C6H5-ipso,
1JPC = 129.2 Hz), 147.45 (d, C-2,6, C6H3, 3JPC = 3.1 Hz); the resonance for C-1 atom of
C6H3 is overlapped by the resonance of the C6H5-ortho carbons. 31P NMR (121.4 MHz):
21.6 (1JPC = 127.2 Hz).
3
3
4
i
The thio analog Ph2P(S)NH(C6H3 Pr2–2,6) (2) was similarly prepared, from
Ph2P(S)Cl (5.9 g, 23.4 mmol) and LiNH(C6H3Pri2–2,6) (4.3 g, 23.4 mmol), in CH2Cl2.
After removing the solvent under vacuum, the title compound was extracted with diethyl
ether. Yield: 3.42 g (27%), Mp 127◦C. Anal. Calcd. for C24H28NPS (MW 393.53): C,
1
73.25; H, 7.17; N, 3.56, S, 8.15. Found: C, 73.31; H, 7.41; N, 3.75, S, 7.98. H NMR
(400 MHz): 0.99 (d, 12H, CH3, 3JHH = 6.8 Hz), 3.16 (hept, 2H, CH, 3JHH = 6.8 Hz), 4.28
(d, 1H, NH, 2JPH = 3.8 Hz), 7.07 (d, 2H, H-3,5, C6H3, 3JHH = 7.7 Hz), 7.18 (t, 1H, H-4,
C6H3, 3JHH = 7.7 Hz), 7.47 (m, 6H, C6H5-meta+para), 7.90 (ddd, 4H, C6H5-ortho, 3JPH
=
13.3, 3JHH = 8.4, 4JHH = 1.5 Hz). 13C NMR (100.6 MHz): 23.45 (s, CH3), 28.84 (s, CH),
4
5
123.35 (d, C-3,5, C6H3, JPC = 1.7 Hz), 126.90 (d, C-4, C6H3, JPC = 2.2 Hz), 128.23
3
2
(d, C6H5-meta, JPC = 12.9 Hz), 131.17 (d, C6H5-ortho, JPC = 10.8 Hz), 131.38 (d,
C6H5-para, 4JPC = 2.9 Hz), 133.02 (d, C-1, C6H3, 2JPC = 5.8 Hz), 135.40 (d, C6H5-ipso,
1JPC = 101.0 Hz), 147.19 (d, C-2,6, C6H3, 3JPC = 3.3 Hz). 31P NMR (121.4 MHz): 57.9.
Synthesis of (OPPh2)(O2SMe)N(C6H3Pri2–2,6) (3)
A solution of BunLi in hexane (1.66 mL, 1.6 M, 2.64 mmol) was added dropwise,
under an argon atmosphere, to a stirred solution of 1 (1 g, 2.64 mmol) in anhydrous THF
(30 mL). The reaction mixture was left overnight for completion. MeSO2Cl (0.302 g,
2.64 mmol) was added to the solution of Ph2P(O)N(C6H3Pri2–2,6)Li, and the reaction
mixture was stirred for 4 h at room temperature. The solvent was evaporated under vacuum,

ORGANOPHOSPHORUS PROLIGANDS AND AMIDE PRECURSORS
917
and the remaining solid was treated with diethyl ether. LiCl was filtered off, and the solvent
was removed in vacuum. The remaining solid was a mixture of the title compound and
unreacted 1. The desired compound 3 was separated by column chromatography on silica
gel, using Et2O as eluent. Recrystallization from a mixture of CH2Cl2 and hexane (1/4, v/v)
gave 3 as a white solid. Yield: 0.46 g (38%), Mp 148–149◦C. Anal. Calcd. for C25H30NO3PS
(MW 455.55): C, 65.91; H, 6.64; N, 3.07, S, 7.04. Found: C, 65.82; H, 6.51; N, 3.14, S,
6.98. 1H NMR (300 MHz): 0.55 (d, 6H, CH3, 3JHH = 6.7 Hz), 1.14 (d, 6H, CH3, 3JHH
=
3
6.7 Hz), 3.08 (hept, 2H, CH, JHH = 6.7 Hz), 3.35 (s, 3H, S-CH3), 7.08 (d, 2H, H-3,5,
C6H3, 3JHH = 7.7 Hz), 7.32 (t, 1H, H-4, C6H3, 3JHH = 7.7 Hz), 7.40 (m, 4H, C6H5-meta),
3
3
7.52 (m, 2H, C6H5-para), 7.84 (dd, 4H, C6H5-ortho, JPH = 12.5, JHH = 8.1 Hz). 13C
NMR (75.5 MHz): 22.72 (s, CH3), 25.26 (s, CH3), 29.24 (s, CH), 43.58 (s, S-CH3), 124.83
3
1
(s, C-3,5, C6H3), 128.10 (d, C6H5-meta, JPC = 13.4 Hz), 129.45 (d, C6H5-ipso, JPC
=
=
4
124.2 Hz), 129.89 (s, C-4, C6H3), 130.60 (s, C-1, C6H3), 132.51 (d, C6H5-para, JPC
2.9 Hz), 133.27 (d, C6H5-ortho, 2JPC = 10.1 Hz), 150.03 (d, C-2,6, C6H3, 3JPC = 1.6 Hz).
31P NMR (121.5 MHz): 26.7 (1JPC = 124.2 Hz).
Table I Crystal data and structure refinement for 1–3
1
2
3
Empirical formula
Formula weight
Temperature, K
Wavelength, Å
Crystal system
Space group
C24H28NOP
377.44
297(2)
0.71073
monoclinic
P2(1)/c
C24H28NPS
393.51
297(2)
0.71073
monoclinic
P2(1)/n
C25H30NO3PS
455.53
297(2)
0.71073
monoclinic
P2(1)/c
a (Å)
b (Å)
10.5240(10)
19.1679(19)
10.6394(10)
90
90.401(2)
90
2146.2(4)
4
1.168
10.4302(13)
35.373(4)
19.143(2)
90
104.949(2)
90
6823.8(14)
12
1.149
11.9823(12)
13.3682(14)
15.2962(16)
90
92.529(2)
90
2447.8(4)
4
1.236
c (Å)
α (◦)
β (◦)
γ (◦)
Volume, Å3
Z
Density (calculated), g/cm3
Absorption coefficient, mm−1
F(000)
0.141
808
0.221
2520
0.223
968
Crystal size, mm
θ range for data collections (◦)
Reflections collected
Independent reflections
Max. and min. transmissions
0.21 × 0.20 × 0.17
1.94 to 26.37
17135
0.34 × 0.29 × 0.25
1.59 to 25.00
49318
0.38 × 0.26 × 0.20
2.02 to 25.00
17382
4393 [R(int) = 0.0958] 12004 [R(int) = 0.0633] 4311 [R(int) = 0.0490]
0.9785 and 0.9700
0.9469 and 0.9287
0.9607 and 0.9200
Refinement method
Data/restraints/parameters
Goodness-of-fit on F2
Full-matrix least-squares on F2
12004/0/754
4393/1/253
1.144
4311/0/285
1.258
1.148
Final R indicies [I > 2sigma(I)]
R1 = 0.0927,
wR2 = 0.1664
R1 = 0.1442,
wR2 = 0.1863
R1 = 0.0958,
R1 = 0.0598,
wR2 = 0.1284
R1 = 0.0727,
wR2 = 0.1346
0.345 and –0.289
wR2 = 0.1843
R1 = 0.1208,
R indices (all data)
wR2 = 0.1951
0.443 and –0.285
Largest diff. peak and hole, eÅ−3 0.415 and –0.343

¨
918
A. POLLNITZ ET AL.
Crystal Structure Determination of Compounds 1–3
X-ray quality crystals were grown from a mixture of solvents (1/5, v/v), i.e.,
dichloromethane/hexaneforPh2P(O)NH(C6H3Pri2–2,6) (1)andPh2P(S)NH(C6H3Pri2–2,6)
(2), and toluene/hexane for (OPPh2)(O2SMe)N(C6H3Pri2–2,6) (3), respectively. Colorless,
block crystals of 1–3 were attached with Paratone N oil on cryoloops. Data collection
and processing was carried out on a Bruker SMART APEX instrument (Babes-Bolyai
University, Cluj-Napoca) using graphite monochromated Mo-Kα radiation (λ = 0.71073
Å). Details of the crystal structure determination and refinement for compounds 1–3 are
given in Table I.
The structures were solved by direct methods and refined using SHELX–97.28 All
of the non-hydrogen atoms were treated anisotropically. The hydrogen atoms attached to
nitrogen in 1 and 2 were located from the difference map. The other hydrogen atoms were
included in idealized positions with isotropic thermal parameters set at 1.2 times that of
the carbon atom to which they were attached, except the methyl protons for which the
isotropic thermal parameters were set at 1.5. The drawings were created with the Diamond
program.29
Supplementary Material
Crystallographic data for the structural analysis of compounds 1–3 have been de-
posited with the Cambridge Crystallographic Data Centre CCDC, Nos. 663515 (1), 714095
(2), and 663516 (3). Copies of the information may be obtained free of charge from The Di-
rector, CCDC, 12 Union Road, Cambridge CB2 1EZ, UK (fax: +44-1223-336033; e-mail:
deposit@ccdc.cam.ac.uk or www: http://www.ccdc.cam.ac.uk).
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