New organotin(IV)-phosphoramidate complexes: Breaking of the PO?HN hydrogen bonds and its influence on the molecular packing

Article abstract of DOI:10.1016/j.molstruc.2012.01.024

Phosphoryl donor (PO) ligands (^tBuNH)₃PO (1), (C ₆H₅CH₂NH)₃PO (2) and (4-NO ₂-C₆H₄C(O)NH)(OC₄H ₈N)₂PO (3) were used for the

Full text of DOI:10.1016/j.molstruc.2012.01.024

Journal of Molecular Structure 1014 (2012) 38–46
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Journal of Molecular Structure
journal homepage: www.elsevier.com/locate/molstruc
New organotin(IV)-phosphoramidate complexes: Breaking of the P@Oꢀ ꢀ ꢀHAN
hydrogen bonds and its influence on the molecular packing
Alejandro J. Metta-Magaña a, Mehrdad Pourayoubi b, , Keith H. Pannell a,1, Mahnaz Rostami Chaijan b,
⇑
Hossein Eshtiagh-Hosseini b
a Chemistry Department, University of Texas at El Paso, El Paso, TX 79968, USA
b Department of Chemistry, Ferdowsi University of Mashhad, Mashhad 91779, Iran
a r t i c l e i n f o
a b s t r a c t
Phosphoryl donor (PO) ligands (tBuNH)3PO (1), (C6H5CH2NH)3PO (2) and (4-NO2–C6H4C(O)N-
H)(OC4H8N)2PO (3) were used for the preparation of new organotin(IV) complexes Cl2Me2Sn(PO)2 (4–
6). The environment at the nitrogen atom in the phosphoramide ligand is almost planar and it does
not take part in hydrogen bonding as an acceptor in complexes 4–6, reflecting its low Lewis base char-
acter, and the Sn atom is located at the inversion center, making half of the molecule related by symme-
try. The Sn coordination geometry is octahedral with the pair of similar ligands in a trans orientation. The
crystal structure of 6 demonstrates that the phosphoryl group, and not the carbonyl group, coordinates to
the tin center. A blue shift in the NAH stretching frequencies of 4 and 6, in comparison to the free ligands
1 and 3, is attributed to vanish of the NAHꢀ ꢀ ꢀO hydrogen bonds, but the P@O stretching frequencies of the
complexes exhibit no significant changes with respect to the related ligands because of minor differences
caused by forming the P@Oꢀ ꢀ ꢀSn instead of the P@Oꢀ ꢀ ꢀHAN. The NMR experiments indicate an increasing
in 2J(P,H) coupling constants in 4 and 6 and 3J(P,C) in 5 compared to the related ligands. The hydrogen
bond pattern of the ligands and the complexes were compared.
Article history:
Received 21 October 2011
Received in revised form 11 January 2012
Accepted 18 January 2012
Available online 31 January 2012
Keywords:
Organotin(IV)
Tris(alkylamido)orthophosphate
Phosphoric triamide
NMR experiment
X-ray crystallography
Ó 2012 Elsevier B.V. All rights reserved.
1. Introduction
sub-class, those having three tertiary nitrogen atoms, such as
[(CH3)2N]3PO, are more studied [13–16].
The chemistry of organotin(IV)–organophosphorus(V) com-
plexes has attracted attention owing to the importance of both
phosphoryl [1,2] and organotin [3–5] components in the biological
sciences. In addition to the organophosphorus compounds, which
The example containing a [RNH]3PO phosphoric triamide ligand
is limited to one recently published structure, Cl2Me2Sn([C6H11
NH]3PO)2 [10] where the remaining of the P@Oꢀ ꢀ ꢀHAN hydrogen
bond between the two phosphoramide molecules in the complex
enforces a cis-position of phosphoramide ligands around Sn center.
Here we report the use of tris(alkylamido)orthophosphates of
the type [RNH]3PO (R = tBu and Bz) in the synthesis of new organo-
tin(IV)-phosphoric triamide compounds. Additionally, the (4-NO2–
C6H4C(O)NH)(OC4H8N)2PO ligand [17], with a gauche orientation of
P(O) versus C(O), was selected for the preparation of a new organo-
tin(IV)-N-carbacylamidophosphate complex (Scheme 1).
contain the phosphorusAcarbon bond(s), the ligands with
a
NAP(O) skeleton (phosphoramides, especially phosphoric triam-
ides) with the better oxygen-donicity, are the other interesting
choices of phosphoryl donor ligands [6–10].
It is found that, through a search on the Cambridge Structural
Database (CSD version 5.32 (May 2011) [11]), two sub-classes of
phosphoric triamide compounds namely N-carbacylamidophos-
phates, (RC(O)NH)(R00R0N)2P(O), and tris(alkylamido)orthophos-
phates, [R0R00N]3PO, were used to synthesize a few organotin(IV)
complexes, up to now. Some ligands of the former type, with a more
common anti position of C(O) relative to P(O) [12], were reported
for preparation of some organotin(IV) complexes. For the latter
Then, the change of hydrogen-bond pattern in the free ligands’
packing relative to the complexes was studied. Finally, the spectro-
scopic features of the ligands and complexes were compared.
2. Materials and methods
2.1. Single crystal X-ray diffraction
⇑
Corresponding author. Tel.: +98 511 8795457; fax: +98 511 8796416.
E-mail addresses: mehrdad_pourayoubi@yahoo.com (M. Pourayoubi), kpannel-
A single crystal of each compound was mounted on a cryoloop
using paratone oil. X-ray data were collected on a Bruker APEX
CCD diffractometer with monochromatized Mo Ka radiation
l@utep.edu (K.H. Pannell).
1
Tel.: +1 915 747 5796; fax: +1 915 747 5748.
0022-2860/$ - see front matter Ó 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.molstruc.2012.01.024

A.J. Metta-Magaña et al. / Journal of Molecular Structure 1014 (2012) 38–46
39
NHR
RHN
NHR
P
O
R = C(CH3)3 (4),
Cl
CH3
Cl
CH2C6H5 (5)
Sn
O
P
H3C
NO2
RHN
RHN
O
NHR
O
Cl
N
CH3
HN
N
O
P
O
Sn
O
P
O
N
NH
Cl
H3C
N
O
Compound 6
O
O2N
Scheme 1. Chemical structures of complexes 4–6.
(k = 0.71073 Å) using SMART [18]. Cell refinement and data reduc-
tion were carried out with SAINT, and SADABS was employed to
make incident beam and decay corrections in the SAINT-PLUS suite
[18]. The structures were solved by direct methods with SHELXS
and refined by full-matrix least-squares techniques with SHELXL in
the SHELXTL suite [18].
(3) [17] ligands were synthesized according to the literature meth-
ods using of dry CHCl3 instead of dry n-hexane as solvent for 2.
2.4. Syntheses
2.4.1. [(tBuNH)3PO]2Cl2Me2Sn (4)
To a solution of (tBuNH)3PO (0.401 g, 1.52 mmol) in methanol
(15 ml),
a methanolic solution (5 ml) of Me2Cl2Sn (0.167 g,
2.2. Spectroscopic measurements
0.76 mmol) was added dropwise. The clear solution was stirred un-
der reflux for 24 h. Colorless single crystals, suitable for X-ray anal-
ysis, were obtained upon cooling in a refrigerator after a few days.
Yield: 88%. M.p. 121–124 °C. Anal. Calc. for C26H66Cl2N6O2P2Sn
(746.38): C, 41.80; H, 8.84; N, 11.25. Found: C, 41.83; H, 8.90; N,
11.26. 31P{1H} NMR (CD3CN): 6.34. 1H NMR (CD3CN): 1.23 (s, 6H,
2CH3), 1.30 (s, 54H, 6tBu), 3.04 (d, 2J(P,H) = 8.1 Hz, 6H, 6NH). 13C
NMR (CD3CN): 20.03 (s, 2C, Sn–CH3), 31.91 (d, 3J(P,C) = 4.6 Hz,
18C, CH3), 51.74 (s, 6C, Ctert). 119Sn{1H} NMR (CD3CN): ꢁ270.01
(t, 2J(Sn,P) = 2667.2 Hz). IR (KBr, cmꢁ1): 3409, 3248, 2955, 1461,
1218, 1126, 1046, 868, 792, 732. Raman (cmꢁ1): 2927, 2852,
1442, 1261, 1188, 1051, 1030, 796, 505 (SnAC).
1H, 13C{1H}, 31P{1H} and 119Sn{1H} NMR spectra were recorded
on a FT-NMR Bruker Avance DRS 500 spectrometer. 1H and 13C
chemical shifts were determined relative to TMS, 31P chemical
shifts relative to 85% H3PO4 and 119Sn chemical shifts relative to
Sn(CH3)4 as external standards. Infrared (IR) spectra were recorded
on a Buck 500 scientific spectrometer using KBr disks. Elemental
analyses (C, H, and N) were performed on a Thermo Finnigan Flash
1112EA elemental analyzer. Melting points were determined using
an Electrothermal IA-9100 apparatus and are uncorrected.
2.3. Materials
2.4.2. [(C6H5CH2NH)3PO]2Cl2Me2Sn (5)
Dimethyltin dichloride, tert-butyl amine, morpholine, benzyl-
amine, phosphorus pentachloride, phosphorus pentoxide, phos-
phoryl chloride and formic acid were purchased from Merck and
para-nitrobenzamide from Aldrich. Chloroform was dried with
P2O5 and distilled prior to use. Preparation of (tBuNH)3PO (1) was
performed as a literature procedure [19,20] with some minor mod-
ifications (POCl3 to tert-butyl amine mole ratio was 1:6, solvent
was dry CHCl3, and removal of the tert-butyl ammonium chloride
by-product was carried out with distilled H2O). The
(C6H5CH2NH)3PO (2) [21] and (4-NO2–C6H4C(O)NH)(OC4H8N)2PO
To a solution of (C6H5CH2NH)3PO (0.798 g, 2.18 mmol) in etha-
nol (15 ml), an ethanolic solution (5 ml) of Me2Cl2Sn (0.240 g,
1.09 mmol) was added dropwise. The clear solution was stirred
under reflux for 24 h. Colorless crystals were obtained after a few
days of refrigeration. Yield: 86%. M.p. 99–101 °C. Anal. Calc. for
C44H54Cl2N6O2P2Sn (950.46): C, 55.59; H, 5.68; N, 8.84. Found: C,
55.59; H, 5.72; N, 8.84. 31P{1H} NMR (CD3CN): 15.85. 1H NMR
(CD3CN): 1.16 (s, 6H, 2CH3, 2J(119Sn,H) = 100.2 Hz [satellites]
and 2J(117Sn,H) = 103.9 Hz [satellites]), 3.83 (m, 6H, NH),
4.03 (dd, 3J(P,H) = 10.3 Hz, 3J(H,H) = 7.2 Hz, 12H, 6CH2), 7.23

40
A.J. Metta-Magaña et al. / Journal of Molecular Structure 1014 (2012) 38–46
9.70 (d, 2J(P,H) = 6.1 Hz, 2H, NH). 13C NMR (DMSO-d6): 22.49 (s, 2C,
SnACH3), 44.37 (s, 8C), 66.37 (d, 3J(P,C) = 5.3 Hz, 8C), 123.33 (s),
129.68 (s), 139.23 (s), 149.44 (s), 167.13 (s, 2C, C@O). IR (KBr,
cmꢁ1): 3236, 2988, 2906, 2857, 1693, 1602, 1529, 1446, 1349,
1257, 1155, 1101, 1022, 975, 916, 838, 795 and 717.
Table 1
Selected NMR data (d, ppm and J, Hz) of compounds 1–6.
Compound
d(31P) 2J(P,H) 2J(P,C) 3J(P,C) Solvent
(tBuNH)3PO (1)
(tBuNH)3PO (1)
[1]2Cl2Me2Sn
(C6H5CH2NH)3PO (2)
(C6H5CH2NH)3PO (2)
[2]2Cl2Me2Sn
(4-NO2–C6H4C(O)NH)(OC4H8N)2PO (3) 11.73 4.3
(4-NO2–C6H4C(O)NH)(OC4H8N)2PO (3) 8.76
[3]2Cl2Me2Sn 8.75 6.1
5.5
6
–
–
CDCl3
a
a
7.74 0.0
6.34 8.1
0.0
0
0
0
0
1.5
0
0
4.5
4.6
6.3
6.1
6.6
5.0
5.3
5.3
CD3CN
CD3CN
DMSO-d6
CD3CN
CD3CN
CDCl3
DMSO-d6
DMSO-d6
7.11
m
16.07 m
15.85 m
3. Results and discussion
3.1. NMR and IR studies
0
As the chemical shifts are affected by the deuterated solvent
used, the NMR data were obtained for the previously reported li-
gands 1–3 [17,20,21] in the same solvent used for the respective
complexes (e.g. d31P of 7.11 ppm for 2 in DMSO-d6 [21] changes
to 16.07 ppm in CD3CN (present work)). The 31P signals for the
a
Has not been reported in Ref. [20]; in Ref. [20], the values of chemical shift and
2J(PH) were reported as one integer after point and one integer, respectively.
(m, 6H, ArAH), 7.23–7.28 (m, 24H, ArAH). 13C NMR (CD3CN): 19.39
(s, 2C, SnACH3), 45.50 (s, 6C, CH2), 127.88 (s), 128.33 (s), 129.35 (s),
141.60 (d, 3J(P,C) = 6.6 Hz, 6C, Cipso). IR (KBr, cmꢁ1): 3289, 3032,
2925, 1442, 1242, 1208, 1094, 916, 868, 795 and 736. Raman
(cmꢁ1): 3304, 3060, 2989, 2924, 1608, 1585, 1444, 1205, 1194,
1159, 1030, 1001, 820, 800, 621 and 511 (SnAC).
new tin(IV) complexes 4,
5 and 6 are at 6.34, 15.85 and
8.75 ppm, respectively. These values exhibit a small difference to
the free ligands with values of 7.74, 16.07 and 8.76 ppm for 1–3.
Selected NMR data of 1–6 are given in Table 1. The 2J(P,H) coupling
constants are 8.1 Hz for 4 [ligand 1: 0.0 Hz] and 6.1 Hz for 6 [ligand
3: 0.0 Hz]. In complex 5 (similar to free ligand 2), the NH signal ap-
pears as a multiplet due to the further coupling with the benzyl’
CH2 protons, Fig. 1. The methyl protons in the (CH3)2Sn moiety in
each of 4–6 appear as a singlet with at least two observable pairs
of satellites which may be used to evaluate 2J(119SnA1H) and
2J(117SnA1H) coupling constants: 100.2 and 103.9 Hz for 5 and
109.4 and 113.2 Hz for 6. The satellites of such CH3 protons in 4
intermix with the satellites caused to the natural abundance of
the 13C nuclei in C(CH3)3 moiety. The 3J(P,C) coupling constants
for 4 and 6 are 4.6 and 5.3 Hz, whereas the PAC couplings with
two bonds separation were not observed. This is in agreement
with the reported values for (4-NO2–C6H4NH)(NC4H8O)2PO with
2J(P,C) = 0.0, 3J(P,C) = 5.7 Hz [22] and (CCl3C(O)NH)(tBuNH)2PO
with 2J(P,C) = 0.0, 3J(P,C) = 4.9 Hz [23]. In compound 5, the 3J(P,C)
2.4.3. [(4-NO2–C6H4C(O)NH)(OC4H8N)2PO]2Cl2Me2Sn (6)
A solution of Me2Cl2Sn (0.052 g, 0.24 mmol) in dichloromethane
(5 ml) was added dropwise to a solution of (4-NO2–C6H4C(O)N-
H)(OC4H8N)2PO (0.182 g, 0.43 mmol) in dichloromethane (15 ml).
The clear solution was stirred under reflux for 24 h. Colorless crys-
tals were obtained after a few days of refrigeration. Yield: 80%. M.p.
193–195 °C. Anal. Calc. for C32H48Cl2N8O12P2Sn (988.31): C, 38.89;
H, 4.90; N, 11.33. Found: C, 38.87; H, 4.89; N, 11.34. 31P{1H} NMR
(DMSO-d6): 8.75. 1H NMR (DMSO-d6): 1.02 (s, 6H, CH3,
2J(119Sn,H) = 109.4 Hz [satellites] and 2J(117Sn,H) = 113.2 Hz [satel-
lites]), 3.10 (m, 16H, CH), 3.54 (t, 3J(H,H) = 4.6 Hz, 16H, CH), 8.11
(d, 3J(H,H) = 8.7 Hz, 4H, ArAH), 8.29 (d, 3J(H,H) = 8.8 Hz, 4H, ArAH),
Fig. 1. 1H NMR spectrum of 5.

A.J. Metta-Magaña et al. / Journal of Molecular Structure 1014 (2012) 38–46
41
absorption bands at 3381, 3232 and 3120 cmꢁ1, whereas in the re-
lated complex (5) only one band appears at 3289 cmꢁ1. The PAO
stretching frequencies of ligands and related complexes show no
remarkable changes, e.g. 1215 cmꢁ1 for 2 and 1208 cmꢁ1 for 5, sig-
nifying only minor differences as has been observed before for
monodentate PAO interactions with organotins [1b].
Table 2
Selected crystal parameters.
4
5
6
Formula
C26H66Cl2N6O2P2Sn C44H54Cl2N6O2P2Sn C32H48Cl2N8O12P2Sn
746.38
Triclinic
P1
9.2975(6)
13.4725(8)
15.8864(10)
91.7290(10)
91.4110(10)
103.0180(10)
1936.9(2)
2
Formula weight
Crystal system
Space group
a (Å)
b (Å)
c (Å)
950.46
Triclinic
P1
988.31
Monoclinic
P21/c
15.9281(10)
8.3865(5)
15.9242(10)
90
103.9340(10)
90
ꢀ
ꢀ
8.1893(14)
11.919(2)
13.240(2)
115.303(3)
93.906(3)
95.826(3)
1153.4(3)
1
3.2. X-ray crystallography investigation
a
(°)
b (°)
The crystal data for 4, 5 and 6 are presented in Table 2. The data
for 4 and 6 were obtained at low temperature to reduce thermal
vibrations, but even at low temperature (100 K) the disorder is still
present. For 5 no disorder was found at room temperature. The dis-
order in 4 is at one of the asymmetric molecules with an average
occupancy level of 57%. In the case of 6, disorder was solved for
the NO2 moiety and the ether sections of the morpholine moieties
with an average occupancy level of 70%. All the nitrogen bonded H
atoms were found in the difference Fourier map and their bond dis-
tance was restrained to 0.87 Å with exception to the ones disor-
dered in 4. In all the structures, the environment of the N atom
bonded to P in the phosphoramide is almost planar and, as ex-
pected, it does not participate in any hydrogen bonding. This is
in agreement with that found for the phosphoramidate molecules
[17,24].
c
(°)
V (Å3)
Z
2064.6(2)
2
100(2)
T (K)
100(2)
298(2)
1.368
Calculated density 1.280
1.590
(g/cm3)
Total data
Unique data
(Rint
Data (I > 2
Parameters/
restraints
2h (°),
completeness
(%)
29,358
756 (0.0372)
12,205
4508 (0.0243)
31,873
4949 (0.0336)
)
r
(I))
7009
542/178
4289
292/3
4741
396/109
52, 99.3
52, 99.7
56, 99.5
R1 (I > 2
wR2 (I > 2
GOF
r
(I))
0.0314
0.0693
1.078
0.0301
0.0743
1.072
0.0226
0.0598
1.048
r(I))
In each tin complex, 4, 5 and 6, the coordination geometry at
the tin atom is octahedral with the two pairs of equivalent ligands
trans to each other, Figs. 2–4. This is common for such complexes,
and SnAO, SnACl and SnAC bond distances are within the ex-
pected ranges (Table 3) [11]: [(Me2N)3PO]2X2Me2Sn, X = Br (ref-
code: BDMSAP) [25], Cl (CDMSAP01) [26], [(Me2N)3PO]2X2Et2Sn,
X = I (DUCJAM) [27], Br (FILCIM and FILCIM01) [28], [(C5H10N)2
(p-F-PhC(O)NH)PO]2Cl2Me2Sn (LEHWIF) [8], [(R)2(PhC(O)NH)-
value of 6.6 Hz for the ipso carbon atom of phenyl ring is slightly
more than that of the related ligand (6.1 Hz). The signal of CH3ASn
in 13C NMR spectrum should exhibit the satellites by 119SnA13C
and 117SnA13C couplings, but due to the low intensity of signal,
the 1J values are not measurable. The NAH stretching frequencies
for 4 of 3248 and 3409 cmꢁ1 and for 6 of 3236 cmꢁ1 show a blue
shift relative to the free ligands (1: 3192 and 3307 cmꢁ1 and 3:
3115 cmꢁ1). These significant shifts are due to the loss of NAHꢀ ꢀ ꢀO
hydrogen bonds in the solid state upon SnAO bond formation. As
noted later, these NAHꢀ ꢀ ꢀO HBs are replaced by weaker NAHꢀ ꢀ ꢀCl
interactions in the tin complexes. Compound 2 shows three NAH
PO]2Cl2Me2Sn [7], R = tBuNH (YERGEI), C4H8N (YERGIM), C5H10
(YERGOS), and (Me)(Cy)N (YERGUY).
N
In the unique published [(RNH)3PO]2SnMe2Cl2 complex, where
R = cyclohexyl group [10], the geometry is different, containing
cis-dichlorido, trans-dimethyl and cis phosphoric triamide ligands.
The cis position of the two N,N0,N00-tricyclohexylphosphoric tria-
mide molecules had been attributed to the existence of
a
POꢀ ꢀ ꢀHAN hydrogen bond between the two ligands which had
Fig. 2. The molecular structure of one of the conformers of 4 is shown at 50% of probability level. The hydrogens and the disordered part have been omitted for clarity.

42
A.J. Metta-Magaña et al. / Journal of Molecular Structure 1014 (2012) 38–46
Fig. 3. ORTEP view at 35% probability level of 5.
not been broken in the coordination process to the tin(IV) center
[10].
The crystal packing of a ligand of the type [NHR]3PO contains
the P(O)ꢀ ꢀ ꢀHAN hydrogen bond(s); so, it is expected that the reac-
tion of such ligands with metal cations be more difficult than the
phosphoric triamide [NRR’]3PO (R and R0 – H).
(NAH)3ꢀ ꢀ ꢀOP hydrogen bond (Scheme 2) and for 2 with forming
R23(10) loops (Scheme 3, for graph-set notation, see: Ref. [29]). In
the process of coordination of such compounds to a metal center,
the P@Oꢀ ꢀ ꢀHAN hydrogen bond is replaced with a P@OASn bond
and as a result in complex 4, one of the NAH units is involved in
the NAHꢀ ꢀ ꢀClASn hydrogen bond.
In the crystal packing of ligands 1 and 2, molecules are aggre-
gated in a linear arrangement, for 1 through a four-centered
The structure of 4 exhibits some weak intramolecular interac-
tions in the non-disordered molecule, namely two CAHꢀ ꢀ ꢀO (avg.
Fig. 4. ORTEP view at 50% probability level of 6, the disordered part and hydrogens have been omitted for clarity. Both rings are in a chair conformation.

A.J. Metta-Magaña et al. / Journal of Molecular Structure 1014 (2012) 38–46
43
Table 3
Selected bond lengths and angles for compounds 4, 5 and 6.
4a
5
6
SnACl
2.6179(6)/2.5861(13),
2.6031(14)
2.5965(8)
2.5723(4)
SnAC
SnAO
PAO
PAN1
PAN2
PAN3
2.109(2)/2.116(5), 2.104(5)
2.2149(5)/2.2097(17)
1.4976(17)/1.4622(18)
1.625(2)/1.625(2)
1.634(2)/1.534(5), 1.729(4)
1.632(2)/1.589(3), 1.763(5)
2.100(2)
2.1173(14)
2.2090(10)
1.4947(10)
1.6852(13)
1.6286(12)
1.6196(12)
2.2315(14)
1.5022(14)
1.623(2)
1.620(2)
1.630(2)
SnAOAP 143.16(9)/147.48(12)
145.73(9)
146.25(6)
a
The values separated by slashes correspond to conformers A and B; for B two
values are included when disorder is present.
N
H
O
N
P
H
N
N
O
H
H
P
N
N
H
Fig. 5. 2-D layer generated by Sn–Clꢀ ꢀ ꢀH interactions on the plane bc. The
H
conformer on green is the not-disordered one.
O
Scheme 2. A four-centered (NAH)3ꢀ ꢀ ꢀOP hydrogen bond in the crystal packing of
ligand 1 [20].
chlorine atoms (avg. 2.85 Å), which generate layers on the bc plane.
The molecular axis PAOASnAOAP lies on this plane (Fig. 5).
In the structure of
5 there is again the intramolecular
N3AHꢀ ꢀ ꢀCl (2.60 Å); but because the replacement of the tBu groups
for Bz the intramolecular CAHꢀ ꢀ ꢀO interaction was not found, but it
H
N
N
is replaced by N1AHꢀ ꢀ ꢀO (2.41 Å). An intramolecular CAHꢀ ꢀ ꢀ
p
(3.01 Å) HB is observed together with N2AHꢀ ꢀ ꢀCl (2.46 Å) that form
an extended chain motif in the a direction (Fig. 6); due to these
interactions the benzyl groups are not equally distributed over
H
P
O
O
O
N
N
H
t
P
the space as the Bu groups in 4 but confined to a ‘‘hemisphere’’.
H
H
N
The structure expands through CAHꢀ ꢀ ꢀCl (2.98 Å) and
pꢀ ꢀ ꢀp
N
H
(3.64 Å) interactions generating a 2-D structure. The crystal struc-
ture shows the known gear-like arrangement (Fig. 7), the interpla-
nar distances between symmetrically equivalent Ph rings are 3.64,
3.72 and 3.83 Å for R9, R16, and R2 respectively. These distances
suggest that the arrangement is obtained via dipolar interactions,
the benzyl hydrogens are at a distance close enough to be interact-
ing with the Ph ring in a g2 interaction type for H8Bꢀ ꢀ ꢀR9 (2.87 Å)
and H15Bꢀ ꢀ ꢀR16 (2.80 Å). Interestingly in the case of complex 5, de-
spite the P@OASn linkage, there is an interaction with one NAH
unit to form a P@O(ASn)(ꢀ ꢀ ꢀHAN) grouping (Scheme 4). A pair of
such hydrogen bonds form an R22ð8Þ ring motif. Moreover, similar
to complex 4, the NAHꢀ ꢀ ꢀCl cooperates in hydrogen bonding inter-
action forming R22ð8Þ, where the chlorine and oxygen atoms act as
the acceptors.
P
H
N
N
N
H
H
Scheme 3. The R23ð10Þ loops in the crystal packing of ligand 2 [21], the oxygen atom
acts as a double-H acceptor (for a definition of double-H atom acceptor, see: Refs.
[30,31]).
2.60 Å), and one NAHꢀ ꢀ ꢀCl (2.50 Å) that have their symmetry re-
lated counterparts (Table 4). For the disordered molecule in the
unit cell of 4 a similar scheme is observable; however, it cannot
be well-characterized due to the disorder. The 2-D crystal structure
is achieved by intermolecular hydrogen bonds through the
In 5 all the NH groups form HB’s, Table 5, so that the last NAH
unit (N3AH3 N) involves in an intramolecular hydrogen bond
forming an S6 ring containing six different elements: Cl, Sn, O, P,
N and H. This HB network explains the lack of disorder for this
structure even at room temperature.
Table 4
Ligand 3 has the potential to act as both a monodentate ligand,
via either of the P@O or C@O Lewis bases, or bidentate ligand uti-
lizing both. In this sense it is similar to the widely used
carbamoylmethylphosphine oxide (e.g. Ar2P(O)CH2C(O)NR2,
CMPO) actinide extraction ligands. In the case of these latter li-
gands complexes with organotins have been shown to act as both
mono- and bidentate, dependent upon the nature of organotin
[1b]. Thus, for example, with Me2SnCl2 CMPO forms a monoden-
tate 5-coordinate Sn complex via the P@O group. As has been pre-
Hydrogen bonds’ geometrical parameters for 4.
r(DAH)
(Å)
r(Hꢀ ꢀ ꢀA)
r(Dꢀ ꢀ ꢀA)
\(DAHꢀ ꢀ ꢀA)
(°)
DAHꢀ ꢀ ꢀA
(Å)
(Å)
0.98
0.98
0.80(3)
0.98
0.98
2.56
2.64
2.50(3)
2.90
2.75
3.242(3)
3.287(3)
3.292(2)
3.784(3)
3.650(4)
126.6
124.0
172(3)
150.6
152.7
C6AH6Cꢀ ꢀ ꢀO1
C7AH7Aꢀ ꢀ ꢀO1
N1AH1 Nꢀ ꢀ ꢀCl1
C2AH2Cꢀ ꢀ ꢀCl2
C11AH11Cꢀ ꢀ ꢀCl2
C23AH23Aꢀ ꢀ ꢀCl1[x,
1 + y, z]
0.98
2.90
3.786(11) 151.3
viously noted for the structure of ligand 3, with
a gauche

44
A.J. Metta-Magaña et al. / Journal of Molecular Structure 1014 (2012) 38–46
Fig. 6. Chain motif formed by 5. View through crystallographic c axis.
Table 5
Hydrogen bonds’ geometrical parameters for 5.
r(DAH) r(Dꢀ ꢀ ꢀA) \(DAHꢀ ꢀ ꢀA)
r(HꢀꢀꢀA)
DAHꢀ ꢀ ꢀA
(Å) (Å) (Å) (°)
0.838(17) 2.590(18) 3.390(2)
0.813(17) 2.410(18) 3.186(2)
160(2)
160(2)
N3AH3 Nꢀ ꢀ ꢀCl1
N1AH1 Nꢀ ꢀ ꢀO1[1 ꢁ x,
1 ꢁ y, 1 ꢁ z]
0.847(17) 2.462(17) 3.307(2)
175(2)
130.6
N2AH2 Nꢀ ꢀ ꢀCl1[1 + x, y, z]
C18AH18ꢀ ꢀ ꢀCl1[ꢁx, ꢁy,
ꢁz]
0.93
2.98
3.650(3)
Table 6
Hydrogen bonds’ geometrical parameters for 6.
r(DAH)
(Å)
r(Hꢀ ꢀ ꢀA)
r(Dꢀ ꢀ ꢀA)
\(DAHꢀ ꢀ ꢀA)
(°)
DAHꢀ ꢀ ꢀA
(Å)
(Å)
0.79(2)
0.94(2)
0.93(2)
0.89(2)
2.60(2)
2.71(2)
2.37(2)
2.68(2)
3.3495(14) 157.6(16)
3.6070(15) 158.5(17)
3.0586(19) 130.5(16)
N1AH1 Nꢀ ꢀ ꢀCl1
C7AH7ꢀ ꢀ ꢀCl1
C12AH12Bꢀ ꢀ ꢀO2
C16AH16Bꢀ ꢀ ꢀO6[1 ꢁ x,
ꢁ1/2 + y, 3/2 ꢁ z]
C4AH4ꢀ ꢀ ꢀO2[2 ꢁ x, 1/
2 + y, 3/2 ꢁ z]
3.510(8)
3.3987(19) 157.7(16)
3.140(8) 125.4(16)
156.0(18)
0.95(2)
1.00(2)
0.98(2)
2.50(2)
2.46(2)
2.84(2)
C13AH13Aꢀ ꢀ ꢀO3[2 ꢁ x,
ꢁ1/2 + y, 3/2 ꢁ z]
C12AH12Aꢀ ꢀ ꢀCl1[x, 3/
2 ꢁ y, 1/2 + z]
3.7876(16) 160.8(15)
3.5076(17) 139.2(15)
Fig. 7. Gear-like organization in the crystal packing of 5.
0.946(19) 2.74(2)
C11AH11Aꢀ ꢀ ꢀCl1[x, 3/
2 ꢁ y, 1/2 + z]
H
N
N
H3C
Cl
H
P
O
O
Sn
Cl
Cl
N
O
H3C
O
O
H
H
O
N
CH3
Sn
O
O
N
P
H
CH3
Cl
N
P
N
O
O
N
N
N
N
X
H
O
P
H
C
N
Scheme 4. A view of two different R22ð8Þ H-bonded ring motifs in the crystal
packing of 5.
C
O
X
orientation of P@O versus C@O in the C(O)NHP(O) skeleton [17],
the P@Oꢀ ꢀ ꢀHAN hydrogen bond is responsible to the linear
Scheme 5. A view of the linear arrangement in the crystal packing of ligand 3 [17],
X is 4-NO2–C6H4 moiety.

A.J. Metta-Magaña et al. / Journal of Molecular Structure 1014 (2012) 38–46
45
Fig. 8. The HB network in 6 formed by the CAHꢀ ꢀ ꢀCl interactions, the atoms involved in the rings that are formed are depicted as balls; all others are drawn as wireframe for
clarity. The hanging contacts were left in the figure.
arrangement of molecules in the crystal packing (Scheme 5). This
hydrogen bond is completely broken in complex 6. The environ-
ment of each N atom in the morpholine moieties is almost planar;
so, such atom does not participate in hydrogen bonding interac-
tion. The N-benzoyl group is rigid and planar and its N atom also
forms no H-bonding interaction as an acceptor. The crystal packing
adopted permits the benzoyl substituent to be in a position where
it has the less steric effect and it is parallel stacked with a separa-
example, the two CAHꢀ ꢀ ꢀCl HBs (2.74 and 2.84 Å) form a tetramer
R48ð40Þ which is shown in Fig. 8 in a lateral view, and the layer
formed can be observed. The HB through the Me and oxygen O6
in the morpholine moiety is also cooperating in the formation of
this layer (Fig. 9). The expansion then happens due to a binary
interaction that links the Sn-complex through the N-benzoyl group
via CAHꢀ ꢀ ꢀO HB’s. The interactions which form the binary graph set
R22ð13Þ {NAO3ꢀ ꢀ ꢀH13A [2.46(2) Å] and H4ꢀ ꢀ ꢀO2 [2.50(2) Å]}. The
interaction is between two different molecules, the atoms in the
left side of the interaction in each case correspond to one and
the atoms in the right side belong to the other one, the second mol-
ecule is generated by the symmetry operator 2 ꢁ x, 1/2 + y, 3/2 ꢁ z.
tion of 3.69 Å. This is a long interaction suggesting any
pꢀ ꢀ ꢀp inter-
action is very weak. The HB network is complicated, because the
HB listed on Table 6 cooperate to form different patterns generat-
ing a 3-D crystal structure; all of them of cyclic nature. For
Fig. 9. The HB’s formed through the N-benzoyl and morpholine moieties in 6 are shown.

46
A.J. Metta-Magaña et al. / Journal of Molecular Structure 1014 (2012) 38–46
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The coordination of phosphoryl ligands containing the
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Acknowledgement
Support of this investigation by Ferdowsi University of Mash-
had is gratefully acknowledged.
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