Preparation and single-crystal characterization of manganese(II) complexes of dichalcogenoimidodiphosphinato ligands. Monomeric versus dimeric Mn[(OPPh2)(XPPh2)N]2 (X = S, O)

Article abstract of DOI:10.1016/S0020-1693(99)00507-1

Manganese(II) compounds of the type Mn[(XPR₂)(YPR'₂)N]₂ (X, Y = O, S; R, R' = Me, Ph), were prepared by metathesis reactions between MnCl₂·4H₂O and the alkaline salt of the corresponding ligand. IR data are consistent with the coordination of the phosphorus ligand in a deprotonated form. The ESR spectra exhibit resolved hyperfine structure only for the Mn[(OPMe₂)(SPPh₂)N]₂ derivative. The crystal and molecular structures of Mn[(OPPh₂)(YPPh₂)N]₂ (Y = O, S) were determined by X-ray diffractometry. The crystal of the tetraphenylthioimidodiphosphinato derivative contains monomeric, spiro-bicyclic Mn[(OPPh₂)(SPPh₂)N]₂ units, with a distorted tetrahedral MnO₂S₂ core, as a result of monometallic biconnective phosphorus ligands. By contrast, in the crystal of the tetraphenylimidodiphosphinato analogue distinct [Mn{(OPPh₂)₂N}₂]₂ dimers are present, in which the MnO₅ core has a trigonal bipyramidal geometry. The coordination pattern of the four imidodiphosphinato ligands differs. Two of them act as monometallic biconnective (chelating) units, leading to six-membered MnO₂P₂N rings. The other two ligands act as bimetallic triconnective units, which results in a fused tricyclic Mn₂O₄P₄N₂ system. The central four-membered Mn₂O₂ ring is slightly bent [Mn(1)O(5)O(8)/Mn(2)O(5)O(8) dihedral angle 23.9°]. The overall conformation of the [Mn{(OPPh₂)₂N}₂]₂ dimer might be described as cis, i.e. with six-membered MnO₂P₂N rings formed by ligands of the same type placed on the same side of the four-membered Mn₂O₂ ring. (C) 2000 Elsevier Science S.A.

Full text of DOI:10.1016/S0020-1693(99)00507-1

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Inorganica Chimica Acta 299 (2000) 247–252
Preparation and single-crystal characterization of manganese(II)
complexes of dichalcogenoimidodiphosphinato ligands. Monomeric
versus dimeric Mn[(OPPh2)(XPPh2)N]2 (X=S, O)
Ildiko Szekely a, Cristian Silvestru a,*1, John E. Drake b,*2, Gabor Balazs a,
Sorin I. Farcas c, Ionel Haiduc a
a Facultatea de Chimie, Uni6ersitatea ‘Babes-Bolyai’, RO-3400 Cluj-Napoca, Romania
b Department of Chemistry and Biochemistry, Uni6ersity of Windsor Windsor, Ont., Canada N9B 3P4
c Institute for Isotopic and Molecular Technology, PO Box 700, RO-3400, Cluj-Napoca 5, Romania
Received 14 May 1999; accepted 19 October 1999
Abstract
Manganese(II) compounds of the type Mn[(XPR2)(YPR%2)N]2 (X, Y=O, S; R, R%=Me, Ph), were prepared by metathesis
reactions between MnCl2·4H2O and the alkaline salt of the corresponding ligand. IR data are consistent with the coordination of
the phosphorus ligand in a deprotonated form. The ESR spectra exhibit resolved hyperfine structure only for the
Mn[(OPMe2)(SPPh2)N]2 derivative. The crystal and molecular structures of Mn[(OPPh2)(YPPh2)N]2 (Y=O, S) were determined
by X-ray diffractometry. The crystal of the tetraphenylthioimidodiphosphinato derivative contains monomeric, spiro-bicyclic
Mn[(OPPh2)(SPPh2)N]2 units, with a distorted tetrahedral MnO2S2 core, as a result of monometallic biconnective phosphorus
ligands. By contrast, in the crystal of the tetraphenylimidodiphosphinato analogue distinct [Mn{(OPPh2)2N}2]2 dimers are present,
in which the MnO5 core has a trigonal bipyramidal geometry. The coordination pattern of the four imidodiphosphinato ligands
differs. Two of them act as monometallic biconnective (chelating) units, leading to six-membered MnO2P2N rings. The other two
ligands act as bimetallic triconnective units, which results in a fused tricyclic Mn2O4P4N2 system. The central four-membered
Mn2O2 ring is slightly bent [Mn(1)O(5)O(8)/Mn(2)O(5)O(8) dihedral angle 23.9°]. The overall conformation of the
[Mn{(OPPh2)2N}2]2 dimer might be described as cis, i.e. with six-membered MnO2P2N rings formed by ligands of the same type
placed on the same side of the four-membered Mn2O2 ring. © 2000 Elsevier Science S.A. All rights reserved.
Keywords: Crystal structures; Manganese complexes; Chalcogenoimidodiphosphinic complexes
ing symmetric ligands (R=R%=Me [7], Ph [8,9]), ex-
hibit a tetrahedral NiS4 core, while the complex of
1. Introduction
the related asymmetric ligand, Ni[(SPMe2)(SPPh2)N]2,
shows a square-planar NiS4 core [8]. On the other hand,
differences were also noted between the structures of
Over the past several years ligands of the type
(XPR2)(YPR%)NH (R, R%=Me, Pri, Ph; X, Y=O, S,
2
Se), which can be considered to be inorganic analogues
of b-diketonates, enjoyed renewed interest in the coor-
dination chemistry of both main group and transition
metals [1–6]. In some cases significant structural differ-
ences were noted depending on the nature of the or-
ganic groups and chalcogens attached to phosphorus
[(XPR2)(YPR%)N] metal complexes and the related b-
2
diketonato derivatives, e.g. Co[(SPMe2)(SPR2)N]2 (R=
Me [10], Ph [11]) and Co[(SCMe)2CH]2 [12], which
exhibit tetrahedral and square-planar CoS4 cores, re-
spectively. Conformational differences of the inorganic
MXYP2N rings have also been reported [13,14].
atoms. Thus, Ni[(SPR2)(SPR%)N]2 complexes contain-
2
So far, only the molecular structure of the
monomeric Mn[(SPPh2)2N]2 [15] and Mn[(OPPh2)2N]3
[16], which exhibit tetrahedral MnS4 and octahedral
MnO6, respectively, have been reported. By contrast,
1 *Corresponding author. Fax: +40-64-190 818; cristi@
chem.ubbcluj.ro
2 *Corresponding author.
0020-1693/00/$ - see front matter © 2000 Elsevier Science S.A. All rights reserved.
PII: S0020-1693(99)00507-1

248
I. Szekely et al. / Inorganica Chimica Acta 299 (2000) 247–252
the Mn(II) acetylacetonate derivative is a trimer, all
manganese atoms exhibiting octahedral MnO6 cores as
a result of the bimetallic triconnective coordination of
the ligands [17]. Here we report the synthesis of
Found: C, 49.9; H, 4.5; N, 3.9. C28H32N2O2P4S2Mn
requires: C, 50.1; H, 4.8; N, 4.2%. IR (cm−1): was(P2N)
1200vs; w(PO) 1135vs; w(PS) 565vs, 550vs. ESR (X
band): g 1.93290.001.
Mn[(XPR2)(YPR%)N]2 (X, Y=O, S; R, R%=Me, Ph)
Mn[(OPMe2)(SPPh2)N]2 (4) from Na[(OPMe2)-
(SPPh2)N] (0.79 g, 2.38 mmol) and MnCl2·4H2O (0.23
g, 1.16 mmol); colourless crystals obtained from chloro-
form. Yield: 0.65 g (83%), m.p. 156–158°C (dec.). Anal.
Found: C, 49.8; H, 4.6; N, 3.8. C28H32N2O2P4S2Mn
requires: C, 50.1; H, 4.8; N, 4.2%. IR (cm−1): was(P2N)
1200vs; w(PO) 1140vs; w(PS) 600vs. ESR (X band): g
1.9890.02, A 78 Gs.
2
complexes and the X-ray structures of monomeric
Mn[(OPPh2)(SPPh2)N]2 and dimeric [Mn{(OPPh2)2-
N}2]2 [18]3.
2. Experimental
Sodium or potassium dichalcogenoimidodiphosphi-
nates were prepared according to published methods:
Na[(OPPh2)2N] [19], K[(SPPh2)2N] [20], K[(OPPh2)-
(SPPh2)N] [21], K[(SPMe2)(OPPh2)N], Na[(OPMe2)-
(SPPh2)N] [22]. The IR spectra were recorded using
KBr pellets on a Specord 75 IR C. Zeiss–Jena (DDR)
instrument, in the range 4000–400 cm−1. ESR mea-
surements were performed on powder compounds at
room temperature (r.t.) on a Radiopan SE/X-2543
9GHz ESR spectrometer, using a 100 kHz field modu-
lation.
2.2. Crystallographic structure determination
Details of the data collections and refinements are
summarized in Table 1. Several attempts failed to pro-
duce high quality crystals. The results are those from
the best collections that could be obtained from crystals
that proved to be of relatively poor X-ray quality.
Table 1
Crystallographic data for Mn[(OPPh2)(SPPh2)N]2 (1) and Mn2-
[(OPPh2)2N]4 (2)
1
2
2.1. Synthesis of Mn[(XPR2)(YPR%)N]2 (1–4)
2
Molecular formula
M
Crystal system
Space group
Radiation
C48H40N2O2P4S2Mn C96H80N4O8P8Mn2
K[(OPPh2)(SPPh2)N] (0.97 g, 2.05 mmol) was added
to a solution of MnCl2·4H2O (0.20 g, 1.01 mmol) in
methanol (50 ml), and the mixture was stirred for 24 h
at r.t. The solvent was then completely removed in
vacuo, and the remaining solid product was extracted
with chloroform (30 ml). The filtrate was evaporated to
dryness leading to a white solid. Then colourless crys-
tals of Mn[(OPPh2)(SPPh2)N]2 (1) were obtained from
chloroform. Yield: 0.91 g (98%), m.p. 183–184°C. Anal.
Found: C, 62.3; H, 4.1; N, 2.8. C48H40N2O2P4S2Mn
requires: C, 62.7; H, 4.4; N, 3.0%. IR (cm−1): was(P2N)
1250vs; w(PO) 1130vs; w(PS) 570vs. ESR (X band): g
1.93290.001.
919.81
1775.38
monoclinic
P21/c
Mo Ka
12.6851(2)
18.2333(1)
19.4760(3)
triclinic
(
P1
Mo Ka
14.335(3)
22.712(6)
14.308(3)
96.60(2)
105.21(2)
81.78(2)
4434(1)
2
,
a (A)
,
b (A)
,
c (A)
h (°)
i (°)
k (°)
100.611(1)
3
,
V (A )
4427.6(1)
4
Z
Crystal size (mm)
0.40×0.38×0.36
1.38
0.44×0.40×0.40
1.33
Dc (g cm−3
)
F000
1900.00
50
1836.00
50
2q Range (°)
Similarly were obtained:
v(Mo Ka) (cm−1
)
5.78
4.88
Mn[(OPPh2)2N]2 (2) from Na[(OPPh2)2N] (0.99 g,
2.25 mmol) and MnCl2·4H2O (0.24 g, 1.21 mmol);
colourless crystals obtained from chloroform. Yield:
0.83 g (77%), m.p. 302–304°C. Anal. Found: C, 64.4;
H, 4.2; N, 3.1. C48H40N2O4P4Mn requires: C, 64.9; H,
4.5; N, 3.2%. IR (cm−1): was(P2N) 1240vs; w(PO)
1150vs; 1110vs. ESR (X band): g 1.93290.001.
Mn[(SPMe2)(OPPh2)N]2 (3) from K[(SPMe2)-
(OPPh2)N] (0.79 g, 2.27 mmol) and MnCl2·4H2O (0.22
g, 1.13 mmol); colourless crystals obtained from chloro-
form. Yield: 0.72 g (95%), m.p. 192–194°C. Anal.
Max./min. transmission 1.00–0.45
factors
Temperature (°C)
Reflections measured
Reflections observed
[Fo3]3|Fo)], No
Parameters refined, Np 292
Largest shift/e.s.d. in
final cycle
1.00–0.77
23
23
10875
2814
15591
4589
583
0.001
0.001
Max./min. residual
0.53, −0.41
0.42, −0.45
−3
,
density peaks (e A
)
a
R
0.0614
0.0778
1.37
0.0693
0.0603
2.04
R% b
Goodness of fit, c
S
3 A preliminary communication on the structure of [Mn-
{(OPPh2)2N}2]2 was previously presented at The VIII International
Symposium on Inorganic Ring Systems, Loughborough, UK, August
1997, Ref. [18].
a R=ꢀꢁFoꢁ−ꢁFcꢁ/ꢀꢁFoꢁ.
b R%=[ꢀw(ꢁFoꢁ−ꢁFcꢁ)2/ꢀwFo2)]1/2, where w=1/|2(Fo).
c S=[ꢀ(ꢁFoꢁ−ꢁFcꢁ)/s]/(No−Np).

I. Szekely et al. / Inorganica Chimica Acta 299 (2000) 247–252
249
Table 2
Colourless block crystals of Mn[(OPPh2)(SPPh2)N]2 (1)
and Mn2[(OPPh2)2N]4 (2) were mounted on glass fibres
and sealed with epoxy glue. Data were collected on a
Siemens SMART/CCD system (for 1) and on a Rigaku
AFC6S diffractometer (for 2) both with graphite-
monochromated Mo Ka radiation, operating at 50 kV
and 35 mA, the processed data for 1 being supplied by
the X-ray services at the University of Windsor under
the control of Dr D.W. Stephan. The data were cor-
rected for Lorentz and polarization effects. Based on
statistical analyses of intensity distributions and the
successful solution and refinement of the structure, the
space groups were determined to be P21/c (no. 14) and
,
Important bond lengths (A) and angles (°) for Mn[(OPPh2)-
(SPPh2)N]2 (1)
Bond lengths
Mn(1)ꢀO(1)
Mn(1)ꢀS(1)
P(1)ꢀO(1)
P(1)ꢀN(1)
P(2)ꢀN(1)
P(2)ꢀS(1)
2.041(6)
2.448(4)
1.559(7)
1.582(9)
1.577(9)
2.012(4)
3.595(8)
Mn(1)ꢀO(2)
Mn(1)ꢀS(2)
P(3)ꢀO(2)
P(3)ꢀN(2)
P(4)ꢀN(2)
P(4)ꢀS(2)
2.030(7)
2.446(3)
1.535(7)
1.588(8)
1.578(8)
2.016(4)
3.547(7)
O(1)···S(1) a
O(2)···S(2) a
Bond angles
O(1)ꢀMn(1)ꢀS(1)
O(1)ꢀMn(1)ꢀS(2)
O(1)ꢀMn(1)ꢀO(2)
Mn(1)ꢀO(1)ꢀP(1)
O(1)ꢀP(1)ꢀN(1)
P(1)ꢀN(1)ꢀP(2)
S(1)ꢀP(2)ꢀN(1)
Mn(1)ꢀS(1)ꢀP(2)
106.0(2)
114.6(2)
108.9(3)
125.7(4)
118.5(4)
134.2(6)
118.5(4)
98.5(2)
O(2)ꢀMn(1)ꢀS(2)
O(2)ꢀMn(1)ꢀS(1)
S(1)ꢀMn(1)ꢀS(2)
Mn(1)ꢀO(2)ꢀP(3)
O(2)ꢀP(3)ꢀN(2)
P(3)ꢀN(2)ꢀP(4)
S(2)ꢀP(4)ꢀN(2)
Mn(1)ꢀS(2)ꢀP(4)
104.5(2)
113.2(2)
109.9(1)
125.6(4)
117.6(4)
136.1(5)
118.2(3)
95.7(1)
(
P1 (no. 2). The structures were solved by direct meth-
ods [23]. All of the non-hydrogen atoms except carbon
were refined anisotropically. The positions of the hy-
drogens were idealized, with thermal parameters set at
1.2 times that of the carbon atom to which they were
attached. Refinements were by full-matrix least-squares
based on F using the TEXSAN [24] crystallographic
package of Molecular Structure Corporation. Neutral-
atom scattering factors were taken from Cromer and
Waber [25]. Anomalous dispersion effects were included
in Fc [26]; the values for Df % and Df ¦ were those of
Creagh and McAuley [27].
a Non-bonding distances.
The crystal and molecular structure of Mn-
[(OPPh2)(SPPh2)N]2 and Mn[(OPPh2)2N]2 were estab-
lished by single-crystal X-ray diffractometry, revealing
interesting differences on both the coordination pat-
terns of the phosphorus ligands and the coordination
geometry at the metal atom.
3.1. Molecular structure of Mn[(OPPh2)(SPPh2)N]2 (1)
3. Results and discussion
Selected bond distances and angles in Mn[(OPPh2)-
(SPPh2)N]2 are listed in Table 2 and Fig. 1 shows the
ORTEP plot of the molecular structure with the atom
numbering scheme.
Reaction of MnCl2·4H2O with tetraorganodi-
chalcogenoimidodiphosphinate salts gave compounds
1–4 in very good yields. All compounds gave satisfac-
tory elemental analyses and were characterized by IR
spectroscopy. The strong IR absorptions observed for
the Mn(II) complexes in the regions 1250–1200, 1150–
1110 and 600–550 cm−1 were assigned to was(P2N),
w(PO), and w(PS) stretching vibrations, respectively, by
comparison with the spectra of the proligands and their
alkaline salts. This behaviour is consistent with the
coordination of the ligands in the deprotonated form
through both chalcogens to the manganese atom.
All compounds exhibited a wide ESR spectrum (ca.
5000 Gs) of five fine structure lines as expected for
Mn(II) ions. The line width was around 500 Gs and the
distance between two fine structure lines is about 1000
Gs. The magnitude of these values is consistent with a
strong crystal field around the paramagnetic ion. Only
for the Mn[(OPMe2)(SPPh2)N]2 (4) derivative was a
hyperfine structure of 78 Gs observed on a line (413 Gs
width), at a g factor of 1.9890.02. This spectrum is
superimposed on the wide, low intensity, fine structure
spectrum, similar to those observed for the other man-
ganese(II) compounds. This particular behaviour might
suggest the presence of some paramagnetic ion clusters
in this sample.
Fig. 1. An ORTEP plot of the monomeric Mn[(OPPh2)(SPPh2)N]2 (1).
The atoms are drawn with 30% probability ellipsoids (hydrogen
atoms are omitted for clarity).

250
I. Szekely et al. / Inorganica Chimica Acta 299 (2000) 247–252
Table 3
The crystal contains discrete monomeric molecules of
,
Selected bond lengths (A) and angles (°) for Mn2[(OPPh2)2N]4 (2)
1 exhibiting a distorted tetrahedral MnO2S2 core in a
spiro-bicyclic NP2OSMnSOP2N system, as a result of
the monometallic biconnective coordination pattern of
the ligand. The bond angles at Mn are in the range
104.5(2)–114.6(2)°, with both endocyclic angles
O(1)ꢀMn(1)ꢀS(1) [106.0(2)°] and O(2)ꢀMn(1)ꢀS(2)
[104.5(2)°] less than the tetrahedral value (Table 2). The
dihedral angle between the O(1)Mn(1)S(1) and
Bond lengths
Mn(1)ꢀO(1)
Mn(1)ꢀO(2)
Mn(1)ꢀO(7)
2.057(8) Mn(2)ꢀO(3)
2.056(8) Mn(2)ꢀO(4)
2.063(8) Mn(2)ꢀO(6)
2.097(8)
2.065(8)
2.026(8)
Mn(1)ꢀO(8) (bridging) 2.267(7) Mn(2)ꢀO(5) (bridging) 2.382(7)
Mn(1)ꢀO(5) (bridging) 2.109(7) Mn(2)ꢀO(8) (bridging) 2.107(7)
P(1)ꢀO(1)
P(1)ꢀN(1)
P(2)ꢀN(1)
P(2)ꢀO(2)
P(5)ꢀO(5)
P(5)ꢀN(3)
P(6)ꢀN(3)
P(6)ꢀO(6)
O(1)···O(2) a
O(5)···O(6) a
1.508(8) P(3)ꢀO(3)
1.58(1) P(3)ꢀN(2)
1.60(1) P(4)ꢀN(2)
1.498(8) P(4)ꢀO(4)
1.526(7) P(7)ꢀO(7)
1.57(1) P(7)ꢀN(4)
1.60(1) P(8)ꢀN(4)
1.508(8) P(8)ꢀO(8)
2.91(1) O(3)···O(4) a
3.07(1) O(7)···O(8) a
1.516(8)
1.59(1)
O(2)Mn(1)S(2) planes is 86.7°. The MnꢀS bond lengths
1.594(9)
1.513(8)
1.524(8)
1.584(9)
1.571(9)
1.535(7)
3.00(1)
4
,
[av. 2.447(1) A] [28] are of the same magnitude as
observed for the dithio derivative Mn{(SPPh2)2N}2 [av.
,
2.443(12) A] [15], while the MnꢀO bond lengths [av.
,
2.036(8) A] are significantly shorter than those observed
in the monomeric, octahedral complexes Mn[(OCMe)2-
3.10(1)
,
CH]2(1,10-Phen) [2.116(5), 2.152(5) A] [29] or trans-
,
Mn[(OCPh)2CH]2(THF)2 [2.088(1), 2.136(1) A] [30].
Bond angles
O(1)ꢀMn(1)ꢀO(2)
O(1)ꢀMn(1)ꢀO(7)
O(1)ꢀMn(1)ꢀO(5)
O(2)ꢀMn(1)ꢀO(8)
O(7)ꢀMn(1)ꢀO(8)
O(5)ꢀMn(1)ꢀO(8)
O(1)ꢀMn(1)ꢀO(8)
O(2)ꢀMn(1)ꢀO(5)
O(2)ꢀMn(1)ꢀO(7)
O(5)ꢀMn(1)ꢀO(7)
Mn(1)ꢀO(5)ꢀMn(2)
Mn(1)ꢀO(1)ꢀP(1)
O(1)ꢀP(1)ꢀN(1)
P(1)ꢀN(1)ꢀP(2)
O(2)ꢀP(2)ꢀN(1)
Mn(1)ꢀO(2)ꢀP(2)
Mn(1)ꢀO(7)ꢀP(7)
O(7)ꢀP(7)ꢀN(4)
P(7)ꢀN(4)ꢀP(8)
O(8)ꢀP(8)ꢀN(4)
Mn(1)ꢀO(8)ꢀP(8)
Mn(1)ꢀO(5)ꢀP(5)
90.1(3) O(3)ꢀMn(2)ꢀO(4)
97.1(3) O(3)ꢀMn(2)ꢀO(6)
95.9(3) O(3)ꢀMn(2)ꢀO(8)
87.1(3) O(4)ꢀMn(2)ꢀO(5)
91.2(3) O(5)ꢀMn(2)ꢀO(6)
79.2(3) O(5)ꢀMn(2)ꢀO(8)
171.5(3) O(3)ꢀMn(2)ꢀO(5)
124.7(3) O(4)ꢀMn(2)ꢀO(8)
119.9(4) O(6)ꢀMn(2)ꢀO(8)
113.8(3) O(4)ꢀMn(2)ꢀO(6)
97.4(3) Mn(1)ꢀO(8)ꢀMn(2)
133.8(5) Mn(2)ꢀO(3)ꢀP(3)
117.2(5) O(3)ꢀP(3)ꢀN(2)
126.8(6) P(3)ꢀN(2)ꢀP(4)
118.0(5) O(4)ꢀP(4)ꢀN(2)
133.3(5) Mn(2)ꢀO(4)ꢀP(4)
126.3(5) Mn(2)ꢀO(5)ꢀP(5)
116.9(5) O(5)ꢀP(5)ꢀN(3)
133.8(6) P(5)ꢀN(3)ꢀP(6)
116.2(5) O(6)ꢀP(6)ꢀN(3)
121.1(4) Mn(2)ꢀO(6)ꢀP(6)
141.6(5) Mn(2)ꢀO(8)ꢀP(8)
92.3(3)
97.3(3)
95.4(3)
91.4(3)
87.8(3)
The PꢀNꢀP angles are slightly increased [av.
135.2(1.5)°] compared with those observed in the
(OPPh2)(SPPh2)NH [av. 132.2(1.1)°] [31]. The phospho-
,
rusꢀsulfur [av. 2.014(1) A] and phosphorusꢀoxygen [av.
,
1.547(17) A] bond lengths in 1 are longer than those of
76.6(3)
171.9(3)
126.0(3)
118.2(3)
113.6(3)
101.1(3)
129.9(5)
118.4(5)
123.5(6)
118.5(5)
127.5(5)
120.8(4)
116.6(5)
129.6(6)
117.9(5)
134.1(5)
137.1(4)
,
the proligand [av. PꢀO 1.503(16) A; av. PꢀS 1.925(14)
,
A] [31]. The phosphorusꢀnitrogen bonds are equivalent
regardless of the nature of the chalcogen atom attached
,
to phosphorus, and their magnitude [av. 1.581(5) A] is
clearly consistent with a considerable degree of double
bond character [cf. (OPPh2)(SPPh2)NH [31]: av. PꢀN
1.680(12) A; [(Me3Si)2NꢀP(=NBut)S]2 [32]: PꢁN
,
,
,
1.529(2) A, PꢀN 1.662(2) A]. The two six-membered
MnSOP2N chelate rings are not planar, but display
conformations, i.e. twisted boat and twisted chair with
P(1)/S(1) and P(3)/S(2) atoms, respectively, in the
apices.
3.2. Molecular structure of Mn2[(OPPh2)2N]4 (2)
a Non-bonding distances.
Selected bond distances and angles for the imi-
dodiphosphinato analogue 2 are listed in Table 3 and
Fig. 2 shows the ORTEP plot of the molecular structure
(only the ipso carbons are shown) with the atom num-
bering scheme.
(type B), resulting in a fused tricyclic Mn2O4P4N2
system. The MnꢀO(bridging) distances differ and are
longer than those involving the non-bridging oxygen
atom (Table 3). For a given OPNPO fragment the
PꢀO and PꢀN bond lengths are equivalent regardless of
the coordination pattern of the oxygen atoms, i.e.
In contrast to the monomeric Mn[(OPPh2)-
(SPPh2)N]2, the crystal of 2 contains distinct [Mn-
{(OPPh2)2N}2]2 dimers, which are separated by normal
van der Waals distances. All four imidodiphosphinato
ligands coordinate through both oxygen atoms to man-
ganese, but in a different mode. Two of them act as
monometallic biconnective ligands (type A) [av. MnꢀO
,
av. PꢀO 1.511(9), PꢀN 1.593(10) A for the A-type
ligands and av. PꢀO 1.531(5), PꢀN 1.571(10) A for the
,
B-type ligands, respectively. The four six-membered
MnO2P2N inorganic rings display different conforma-
tions. For the monometallic biconnective A-type lig-
ands the rings are quasi-planar [deviations from the
Mn(1)O2P2N plane are: Mn(1) −0.009, O(1) 0.039,
O(2) −0.005, P(1) −0.051, P(2) −0.006, N(1) 0.033
,
2.069(19) A], leading to six-membered MnO2P2N rings.
The other two act as bimetallic triconnective ligands
4 E.s.d.s for average bond lengths are calculated from the equation
|=[ꢀii==Nl (xi−x)2/(N−1)]1/2, where xi is ith bond length and x is the
mean of the N equivalent bond lengths. An analogous formula is used
for the calculation of e.s.d.s for average bond angles.
,
A] and twisted chair [with Mn(2)/N(2) atoms in the
apices]. The MnO2P2N rings formed by the bimetallic
triconnective B-type ligands are slightly distorted from

I. Szekely et al. / Inorganica Chimica Acta 299 (2000) 247–252
251
,
O(4) 0.046, O(6) 0.043, O(8) 0.048 A, respectively], with
the manganese atoms slightly out-of-plane towards
the axial non-bridging oxygen atom. The sum of
OeqꢀMnꢀOeq is close to 360° [ꢀ(OeqꢀMnꢀOeq)e=358.4°
for Mn(1), and 357.8° for Mn(2)].
The central four-membered Mn2O2 ring is slightly
folded [Mn(1)O(5)O(8)/Mn(2)O(5)O(8) dihedral angle
23.9°], with a non-bonding Mn(1)···Mn(2) distance
,
of 3.378(3) A. The overall conformation of the
[Mn{(OPPh2)2N}2]2 dimer might be described as cis, i.e.
with six-membered MnO2P2N rings formed by ligands
of the same type placed on the same side of the
four-membered Mn2O2 ring, resulting in a ‘butterfly’-
like structure (Fig. 3(a)). This contrasts with the overall
trans conformation observed for the ladder structure of
the [Mn(S2PEt2)2]2 dimer [33] (Fig. 3(b)), which also
contains five-coordinate metal atoms. The dimeric
structure of [Mn{(OPPh2)2N}2]2 also contrasts with that
of the Mn(II) acetylacetonate, which is associated into
trimeric units in the solid state [17] (Fig. 3(c)). The
decrease in the degree of association and the coordina-
tion number at the metal atom is probably due to the
bulky imidodiphosphinato ligand. It should be noted
here that dimeric, i.e. [Mn{(OCMe)2CH}2(NH2CH2-
CHꢁCH2)]2 [34], and monomeric structures, i.e. trans-
Mn[(OCR)2CH]2(L)2 (R=Ph, L=THF [30]; R=CF3,
L=H2O [35]), have also been reported and in all these
cases the manganese atom is exhibiting an octahedral
core.
Fig. 2. An ORTEP plot of the dimeric [Mn{(OPPh2)2N}2]2 (2). The
atoms are drawn with 30% probability ellipsoids (for clarity, only the
ipso carbons are shown).
planarity towards a boat conformation, with O(5)/P(6)
and Mn(1)/N(4) atoms, respectively, in the apices.
The coordination geometry of central manganese
atom is distorted trigonal bipyramidal as reflected by
the bond angles: OaxꢀMnꢀOax (av.) 171.7(1)°, Oeqꢀ
MnꢀOeq (range) 113.6(3)–126.0(3)°, OaxꢀMnꢀOeq
(range) 76.6(3)–97.3(3)°. The equatorial MnO3 systems
are quasi-planar [deviations from Mn(1)O(2)O(5)O(7)
and Mn(2)O(4)O(6)O(8) are Mn(1) −0.119, O(2)
,
0.042, O(5) 0.39, O(7) 0.038 A, and Mn(2) −0.137,
Fig. 3. View of (a) Mn2[(O2P2N]4 core in the dimeric [Mn{(OPPh2)2N}2]2; (b) dimeric [Mn(S2PEt2)2]2 structure; (c) Mn3[(O2C3]6 core in the
trimeric [Mn{(OCMe)2CH}2]3.

252
I. Szekely et al. / Inorganica Chimica Acta 299 (2000) 247–252
[11] C. Silvestru, R. Ro¨sler, J.E. Drake, J. Yang, G. Espinosa-Perez,
4. Supplementary material
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622.
[13] N. Zuniga-Villareal, C. Silvestru, M. Reyes Lezama, S. Hernan-
dez-Ortega, C. Alvarez Toledano, J. Organomet. Chem. 496
(1995) 169.
The complete listing of the crystal data is provided in
the Supporting Information which contains tables giv-
ing final fractional coordinates and Beq for non-hydro-
gen atoms, anisotropic thermal parameters for
non-hydrogen atoms, atomic coordinates and Beq for
hydrogen atoms, all bond lengths and angles and OR-
[14] J.R. Phillips, A.M.Z. Slawin, A.J.P. White, D.J. Williams, J.D.
Woollins, J. Chem. Soc., Dalton Trans. (1995) 2467.
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1185.
TEP
drawings for Mn[(OPPh2)(SPPh2)N]2 and
Mn[(OPPh2)2N]2 (19 pages). Structure factor tables are
available from the authors (J.E.D.).
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Chem. Ber. 124 (1991) 2443.
Acknowledgements
This work was supported by the Romanian Academy
and the Romanian National Council for Universitary
Scientific Research (CNCSU) and by the Natural Sci-
ences and Engineering Research Council of Canada.
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