Six-membered metalla-coronands. Synthesis and crystal packing: Columns, compartments, and 3D-networks

Article abstract of DOI:10.1021/ic049799w

Reaction of various N-substituted diethanolamines H₂L ³ (4) with calcium hydride and iron(III) chloride leads to the self-assembly of six-membered ferric wheels [Fe₆X₆(L ³)₆] (5). Principal

Full text of DOI:10.1021/ic049799w

Inorg. Chem. 2004, 43, 4372−4382
Six-Membered Metalla-coronands. Synthesis and Crystal Packing:
Columns, Compartments, and 3D-Networks†,‡
,§
Rolf W. Saalfrank,* Christian Deutscher,§ Stefan Sperner,§ Takayuki Nakajima,§ Ayuk M. Ako,§
Eveline Uller,§ Frank Hampel,§ and Frank W. Heinemann|
Institut fu¨r Organische Chemie der UniVersita¨t Erlangen-Nu¨rnberg, Henkestrasse 42,
91054 Erlangen, Germany, and Institut fu¨r Anorganische Chemie der UniVersita¨t
Erlangen-Nu¨rnberg, Egerlandstrasse 1, 91058 Erlangen, Germany
Received February 16, 2004
Reaction of various N-substituted diethanolamines H L3 (4) with calcium hydride and iron(III) chloride leads to the
2
self-assembly of six-membered ferric wheels [Fe6X (L3)6] (5). Principally, all the iron coronands are isostructural;
6
however, they differ fundamentally with respect to their crystal packing. Exemplarily, this is discussed for selected
members of the space groups R3h, P3h, P21/c, P21/n, C2/c, and P1h. Depending on the nature of their sidearms, the
ferric wheels create various substructures. For instance, the ferric wheels 5a−i of space group R3h or P3h are piled
in parallel in cylindrical columns, which are surrounded by six parallel columns alternately dislocated by 1/3c and
2/3c against the central one. Pronounced van der Waals interactions give rise to compartmentation and incarceration
of guest molecules as seen for 5e,g. However, in 5h strong π−π interactions create a three-dimensional scaffold.
The most significant difference of the ferric wheels 5j−p of space groups P21/c, P21/n, and C2/c is that these ferric
wheels are arranged in parallel in two orientations. They differ mainly only by the included angle of the two groups
of parallel wheels. In the case of 5l, molecular chains are formed in the crystal due to π−π interactions. The ferric
wheels 5q−y of space group P1h are packed in the crystal most simply, with all the ferric wheels piled in parallel.
Introduction
bonds.2 A particular symmetric class are the so-called ferric
wheels with 6, 8, 10, 12, and even 18 iron(III) ions.3 The
magnetization of the ferric wheels exhibits steplike field
dependencies at low temperatures and can be regarded as
ideal model systems for so-called single molecule magnets
(SMMs), the finite-size version of the linear Heisenberg
chain.4 Since SMMs are promising new materials, this class
of molecules becomes more and more important.
Polyoxometalates have become the focus of intense
research activities, because these compounds exhibit an
enormous variety of structures as well as magnetic proper-
ties.1 Over the past several years, considerable progress has
been made toward the predictability of ordered supramo-
lecular assemblies on the basis of coordinative metal/ligand
We reported on the template-mediated self-assembly of
six- and eight-membered iron-coronates {Na⊂[Fe6(L1)6]}+
(1) and {Cs⊂[Fe8(L1)8]}+ (2).5 They were prepared from
triethanolamine H3L1 with iron(III) chloride, sodium hydride,
or cesium carbonate (Scheme 1). For instance, ferric wheel
1 allowed us to demonstrate the exciting effect of cooling
by adiabatic magnetization.6
A common feature of complexes 1 and 2 is that the oxygen
donors of one kind of ethanolate arm solely function as
ligands for the coordinative saturation of the iron centers
and for charge compensation, whereas the ethanolato µ2-O
donors are structure determining. They are linkers, necessary
for the ring formation. Consequently, reaction of N-methyldi-
* To whom correspondence should be addressed. E-mail: saalfrank@
chemie.uni-erlangen.de. Fax: (+49)9131-852-1165.
† Dedicated to Professor Fritz Vo¨gtle on the occasion of his 65th birthday.
‡ Chelate complexes (metalla-coronands). 27. Part 26: see ref 9.
§ Institut fu¨r Organische Chemie der Universita¨t Erlangen-Nu¨rnberg.
| Institut fu¨r Anorganische Chemie der Universita¨t Erlangen-Nu¨rnberg.
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4372 Inorganic Chemistry, Vol. 43, No. 14, 2004
10.1021/ic049799w CCC: $27.50 © 2004 American Chemical Society
Published on Web 06/05/2004

Crystal Packing of Metalla-coronands
Scheme 1. Schematic Representation of the Metalla-Coronates 1 and
2 and Metalla-Coronand 3
ligands (Scheme 1). Consequently, this new synthesis for
six-membered ferric wheels was applied for the convergent
synthesis of metallo-dendrimers.8 Variable temperature NMR
spectroscopy, exemplarily carried out on a diamagnetic
indium analogue, revealed that these species are not rigid
and undergo nondissociative topomerization processes.9
A precondition for a crystal to behave like a ferromagnetic
particle is the alignment of all magnetic moments and a
minimum of intermolecular interactions. Therefore, it is
decisive to control the crystal packing.10
An additional interesting feature of oligonuclear assemblies
is their readiness to frame compartments and three-
dimensional networks with discrete channels and pores.10-12
ethanolamine H2L2 with calcium hydride and iron(III)
chloride yielded the unoccupied neutral iron-coronand
[Fe6Cl6(L2)6] (3).7 Like in 1 and 2, the µ2-O donors of the
N-methyldiethanolamine ligands in 3 are structure determin-
ing. Completion of the octahedral coordination sphere at iron
and charge compensation is achieved by the chloride co-
Results and Discussion
Herein we report on the crystal packing of several six-
membered ferric wheels [Fe6X6(L3)6] (5), generated from
various N-substituted diethanolamines H2L3 (4), calcium
hydride, and iron(III) chloride (Scheme 2).
The focal point of the present manuscript is to gain insights
to which extent the crystal packing of basically similar
molecules can be controlled by variation of their periphery
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Inorganic Chemistry, Vol. 43, No. 14, 2004 4373

Saalfrank et al.
Scheme 2. Synthesis of [Fe6X6(L3)6] (5)
Figure 1. Top: stereo presentation of the crystal packing of 5a-h.
Bottom: stereoview of the crystal packing of the ferric wheel 5a. View
along the c-axis. Solvent molecules omitted for clarity.
cipally, all the six-membered ferric wheels [Fe6X6(L3)6] (5)
are isostructural with iron-coronand [Fe6Cl6(L2)6] (3); how-
ever, there are fundamental differences concerning their
crystal packing. Exemplarily, this will be discussed for
selected members of the space groups R3h, P3h, P21/c, P21/n,
C2/c, and P1h.
Crystal Packing of Ferric Wheels 5a-i of Space Group
R3h or P3h. The ferric wheels [Fe6X6(L3)6] (5a-i) have
idealized S6 molecular symmetry and crystallize in the space
group R3h (5a-f,h,i) or P3h (5g) (Table 1). The crystal packing
of the ferric wheels 5a-h is pretty much the same. For
example, all the disklike clusters of 5a are arranged in parallel
and are piled in cylindrical columns, with all the iron centers
superimposed. Each column is surrounded by six parallel
1
2
columns which are alternately dislocated by /3c and /3c
against the central one (Figure 1).
The most significant difference between 5b and 5c is the
arrangement of the ferric wheels to one another. For instance,
in 5b the mean intra- and intercolumnar midpoint distances
amount to 12.6 and 21.9 Å, and for 5c to 23.6 and 15.1 Å,
respectively. It is clearly seen that, for 5b and 5c, the relative
arrangement of the ferric wheels is reciprocally proportional.
That is to say, large intercolumnar distances correspond with
small intracolumnar distances and vice versa (Figure 2).
An additional interesting feature of some ferric wheels is
their readiness to create various substructures, depending on
the nature of their sidearms. For instance, van der Waals
interactions cause the sidearms of 5e and 5g15 to interlock
(14) CCDC-231538 (5a), CCDC-230001 (5b), CCDC-231544 (5c), CCDC-
231539 (5d), CCDC-231548 (5e), CCDC-231540 (5f), CCDC-231553
(5g), CCDC-211208 (5h), CCDC-230004 (5i), CCDC-231547 (5j),
CCDC-231536 (5k), CCDC-231554 (5l), CCDC-231545 (5m), CCDC-
231555 (5n), CCDC-231552 (5o), CCDC-231549 (5p), CCDC-230002
(5q), CCDC-230003 (5r), CCDC-231550 (5s), CCDC-231551 (5t),
CCDC-231546 (5u), CCDC-231542 (5v), CCDC-231537 (5w), CCDC-
231543 (5x), and CCDC-231541 (5y) contain the supplementary
crystallographic data for this paper. These data can be obtained free
of charge via www.ccdc.cam.ac.uk/const/retrieving.html (or from the
Cambridge Crystallographic Data Centre, 12, Union Road, Cambridge
CB21EZ, U.K.; fax (+44)1223-336-033; or deposit@ccdc.cam.ac.uk).
(15) Compound 5g belongs to space group P3h but is best discussed here.
by means of different substituents. In order to classify the
numerous structures, space groups were applied.
For an unambiguous characterization, we carried out X-ray
crystallographic structure analyses of 5 (Table 1).13,14 Prin-
(13) Sheldrick, G. M.; Kru¨ger, C.; Goddard, P. Crystallographic Computing
3; Oxford University Press: Oxford, 1985; p 175. Sheldrick, G. M.
SHELXL-97, program for crystal structure refinement; University of
Go¨ttingen: Go¨ttingen, Germany, 1997. Sheldrick, G. M. SHELXTL
NT 5.10; Bruker AXS, Inc.: Madison WI, 1998.
4374 Inorganic Chemistry, Vol. 43, No. 14, 2004

Crystal Packing of Metalla-coronands
Table 1. X-ray Crystallographic Data and Structure Refinements for Compounds 5a-y
5aa
5bb
5cc
5da
5ea
empirical formula
C66H138Cl6Fe6-
N6O30‚CHCl3
2162.99
C48H102Cl6Fe6-
N6O12‚0.75CHCl3
1592.68
C36H78Cl6Fe6-
N6O12‚2CHCl3
1573.58
C102H150Fe6-
C72H150Cl6Fe6-
N6O30‚CHCl3
2247.15
N
12O30S6
Mr [g mol-1
]
2551.80
cryst size [mm3]
cryst syst
space group
T [K]
0.35 × 0.35 × 0.30
rhombohedral
R3h
0.45 × 0.40 × 0.28
rhombohedral
R3h
0.35 × 0.30 × 0.30
rhombohedral
R3h
0.35 × 0.30 × 0.20
rhombohedral
R3h
0.40 × 0.30 × 0.20
rhombohedral
R3h
173(2)
200(2)
275(2)
173(2)
173(2)
a [Å]
26.161(4)
21.919(2)
15.095(2)
25.0845(6)
26.731(4)
b [Å]
c [Å]
12.283(3)
12.603(2)
23.647(3)
16.0454(7)
12.236(2)
R [deg]
â [deg]
γ [deg]
V [Å3]
7280(2)
3
1.480
1.89-27.49
11425
5243.8(11)
3
1.513
1.86-27.99
3396
4666.5(9)
3
1.680
2.58-26.25
2352
8743.6(5)
3
1.454
2.71-27.49
9523
7572(2)
3
1.478
6.90-26.37
16083
Z
F
calcd [Mg m-3
]
θ range [deg]
reflns collected
unique reflns
3635
2741
2110
4168
3374
[Rint
]
0.0437
3005
184
0.0692
1924
182
0.0608
1137
113
0.0368
3316
235
0.0270
3060
200
reflns obsd [I > 2σ(I)]
params
abs corr method
final R1 [I > 2σ(I)]
wR2 (all data)
empirical (Scalepack)
0.0435
0.1255
ψ-scans
0.0558
0.1461
0.523/-0.581
ψ-scans
0.0716
0.2315
1.395/-1.092
empirical (Scalepack)
0.0389
0.1138
empirical (Scalepack)
0.0348
0.0940
largest residuals [e Å-3
]
0.624/-0.632
0.615/-0.442
0.716/-0.469
5fa
5ga
5ha
5ia
5jc
empirical formula
C78H102Fe6N12O18
S6‚CHCl3‚6CH2Cl2
2652.10
-
C90H102Cl6Fe6N6-
O12‚13CHCl3
3559.47
C90H102Cl6Fe6N6-
O12‚H2O
C120H132Cl6Fe6-
C60H126Cl6Fe6-
N6O24
1859.44
0.30 × 0.20 × 0.20
monoclinic
P21/c
N
12O12‚6CHCl3
Mr [g mol-1
]
2020.68
3198.38
cryst size [mm3]
cryst syst
space group
T [K]
0.35 × 0.20 × 0.20
rhombohedral
R3h
0.30 × 0.20 × 0.20
hexagonal
P3h
0.40 × 0.30 × 0.30
rhombohedral
R3h
0.39 × 0.23 × 0.21
rhombohedral
R3h
173(2)
173(2)
173(2)
100(2)
173(2)
a [Å]
b [Å]
c [Å]
29.0350(7)
32.4052(2)
30.060(3)
41.114(2)
17.101(3)
16.264(3)
15.114(3)
11.8571(5)
11.8909(2)
12.127(2)
21.987(1)
R [deg]
â [deg]
γ [deg]
V [Å3]
96.74(3)
8656.7(5)
3
1.526
1.90-27.46
8460
3932
0.0402
3121
221
10813.7(3)
3
1.639
1.26-27.49
24880
15649
0.0348
9064
836
9490(2)
3
1.105
3.71-25.02
4585
1937
0.0712
32187(3)
9
1.485
3.32-27.51
120889
16363
0.0657
11050
4174.4(14)
2
1.479
1.20-27.49
9558
Z
F
calcd [Mg m-3
]
θ range [deg]
reflns collected
unique reflns
9558
[Rint
]
0.0000d
8276
reflns obsd [I > 2σ(I)]
params
1426
190
775
468
abs corr method
final R1 [I > 2σ(I)]
wR2 (all data)
empirical (Scalepack)
0.0817
0.2556
empirical (Scalepack)
0.0743
0.2232
empirical (Scalepack)
0.1001
0.2760
none
ψ-scans
0.0406
0.1589
0.868/-1.268
0.0576
0.1849
1.655/-2.632
largest residuals [e Å-3
]
1.641/-1.130
1.725/-0.861
0.851/-0.380
5ka
5la
5mc
5na
5oa
empirical formula
C90H126Fe6N12
-
C66H90Cl6Fe6N6-
O12‚2H2O‚4CHCl3
2220.74
0.20 × 0.20 × 0.20
monoclinic
P21/c
C42H78Cl6Fe6N6-
O12‚2CHCl3
1645.68
0.60 × 0.30 × 0.20
monoclinic
P21/n
C96H138Fe6N12
-
C66H114Fe6N12-
O
24S6‚4CH2Cl2
O
12S6‚4CHCl3
O24S6‚8CHCl3
Mr [g mol-1
]
2627.19
2657.12
2942.10
cryst size [mm3]
cryst syst
space group
T [K]
0.35 × 0.30 × 0.30
monoclinic
P21/c
0.20 × 0.20 × 0.10
monoclinic
P21/n
0.20 × 0.20 × 0.20
monoclinic
P21/n
173(2)
173(2)
173(2)
173(2)
173(2)
a [Å]
b [Å]
c [Å]
17.30930(10)
20.8732(2)
16.27560(10)
16.833(3)
16.866(3)
16.068(3)
13.074(3)
11.660(2)
22.592(5)
13.2578(4)
19.2200(3)
24.8933(8)
13.5427(2)
21.8038(3)
20.6024(4)
R [deg]
â [deg]
γ [deg]
V [Å3]
91.0410(10)
106.81(3)
105.51(3)
96.6350(11)
97.3160(10)
5879.41(8)
2
1.484
1.96-27.47
24701
4367.2(15)
2
1.689
2.40-27.51
18049
3318.6(11)
2
1.647
2.38-24.98
6092
6300.7(3)
2
1.401
2.70-25.04
21194
6034.00(17)
2
1.619
1.99-27.49
25527
Z
F
calcd [Mg m-3
]
θ range [deg]
reflns collected
unique reflns
13455
9951
5822
11015
13732
[Rint
]
0.0196
10554
695
0.0255
7731
514
0.0366
4249
403
0.0442
8204
668
0.0329
9807
658
reflns obsd [I > 2σ(I)]
params
abs corr method
final R1 [I > 2σ(I)]
wR2 (all data)
empirical (Scalepack)
0.0363
0.1039
empirical (Scalepack)
0.0712
0.2344
ψ-scans
0.0434
0.1193
0.974/-0.591
empirical (Scalepack)
0.0781
0.2334
empirical (Scalepack)
0.0593
0.1804
largest residuals [e Å-3
]
0.718/-0.669
2.009/-1.622
1.057/-0.850
2.477/-1.407
Inorganic Chemistry, Vol. 43, No. 14, 2004 4375

Saalfrank et al.
Table 1 (Continued)
5pc
5qb
5rb
5sa
C84H174Cl6-
Fe6N6O12
2008.09
5ta
empirical formula
C60H114Cl6Fe6-
N6O12
1659.37
0.30 × 0.30 × 0.30
monoclinic
C2/c
C60H126Cl6Fe6N6-
O12‚2CHCl3
1910.20
0.65 × 0.45 × 0.22
triclinic
P1h
C72H150Cl6Fe6-
N6O12
1839.78
0.38 × 0.26 × 0.20
triclinic
P1h
C90H174Fe6-
N12O12S6
2143.87
0.35 × 0.30 × 0.30
triclinic
Mr [g mol-1
]
cryst size [mm3]
cryst syst
space group
T [K]
0.35 × 0.35 × 0.30
triclinic
P1h
173(2)
P1h
173(2)
173(2)
200(2)
200(2)
a [Å]
b [Å]
c [Å]
R [deg]
â [deg]
γ [deg]
V [Å3]
21.1158(4)
16.4674(4)
22.4019(5)
11.306(2)
13.128(1)
15.502(1)
110.07(1)
97.16(1)
91.21(1)
2139.3(4)
1
12.056(1)
13.106(1)
15.006(2)
76.53(1)
78.46(1)
84.73(1)
2256.7(4)
1
13.0050(2)
13.8403(2)
16.4992(2)
65.7690(10)
69.8380(10)
80.8020(10)
2541.57(6)
1
14.254(3)
15.202(3)
15.362(3)
115.01(3)
92.71(3)
111.09(3)
2735.0(10)
1
97.2888(13)
7726.7(3)
4
1.426
1.57-27.47
16854
Z
F
calcd [Mg m-3
]
1.483
1.76-27.00
10530
1.354
1.89-27.00
11249
1.312
1.42-27.50
21970
1.302
1.51-27.51
23824
θ range [deg]
reflns collected
unique reflns
8821
9118
9816
11633
12547
[Rint
]
0.0388
6065
410
0.0233
7352
635
0.0449
6063
460
0.0199
9189
514
0.0199
9807
568
reflns obsd [I > 2σ(I)]
params
abs corr method
final R1 [I > 2σ(I)]
wR2 (all data)
ψ-scans
0.0385
0.1014
0.613/-0.489
ψ-scans
ψ-scans
empirical (Scalepack)
0.0361
0.1130
empirical (Scalepack)
0.0439
0.1423
0.0386
0.0618
0.1024
0.611/-0.474
0.1481
1.374/-0.746
largest residuals [e Å-3
]
1.008/-0.730
1.345/-0.616
5uc
5va
5wa
5xa
5ya
empirical formula
C48H102Cl6Fe6-
N6O18‚2CHCl3
1833.89
0.30 × 0.30 × 0.30
triclinic
P1h
173(2)
C96H150Cl6-
Fe6N6O30
2416.02
C108H138Cl6-
Fe6N6O24
2452.04
C132H150Cl6Fe6N6O24
2C5H12‚2CH2Cl2
3066.52
‚
C102H138Cl6Fe6-
N6O24‚Et2O
2454.10
Mr [g mol-1
]
cryst size [mm3]
cryst syst
space group
T [K]
0.20 × 0.20 × 0.15
0.40 × 0.30 × 0.25
0.20 × 0.20 × 0.20
0.20 × 0.20 × 0.10
triclinic
triclinic
triclinic
triclinic
P1h
173(2)
P1h
173(2)
P1h
173(2)
P1h
173(2)
a [Å]
b [Å]
c [Å]
R [deg]
â [deg]
γ [deg]
V [Å3]
12.420(3)
16.726(3)
18.384(4)
89.95(3)
82.56(3)
89.73(3)
3786.8(13)
2
11.9911(2)
15.0678(4)
15.7072(4)
87.4551(1)
80.3979(14)
75.6373(13)
2710.74(11)
1
12.63210(10)
15.0623(2)
16.9855(2)
110.0940(10)
100.3340(10)
105.6920(10)
2786.29(5)
1
15.3262(5)
15.7033(4)
16.1823(5)
79.255(2)
76.0670(10)
76.438(2)
3639.61(19)
1
12.9941(2)
14.8203(3)
16.3250(3)
74.1320(10)
77.8580(10)
80.4040(10)
2936.37(9)
1
Z
F
calcd [Mg m-3
]
1.608
2.43-24.97
13984
1.480
2.20-27.51
23421
1.461
2.37-27.54
24235
1.399
1.71-25.14
24741
1.388
2.03-27.53
25519
θ range [deg]
reflns collected
unique reflns
13312
12433
12789
12930
13425
[Rint
]
0.0682
5197
857
0.0272
9362
949
0.0232
9858
676
0.0229
10112
832
0.0485
8283
677
reflns obsd [I > 2σ(I)]
params
abs corr method
final R1 [I > 2σ(I)]
wR2 (all data)
ψ-scans
empirical (Scalepack)
0.0332
0.0837
empirical (Scalepack)
0.0350
0.1023
empirical (Scalepack)
0.0800
0.2549
empirical (Scalepack)
0.0512
0.1456
0.0482
0.1803
0.890/-1.243
largest residuals [e Å-3
]
0.700/-0.369
0.405/-0.432
1.656/-1.079
0.696/-0.697
a Nonius KappaCCD. b Siemens-P4. c Nonius MACH3. d The data have been collected on a four-circle diffractometer equipped with a scintillation counter.
Only a set of symmetrically independent reflections has been collected.
and give rise to the formation of compartments occupied by
chloroform. In contrast, the sidearms of 5d give rise to a
self-contained ball-shaped capsule, lacking further intermo-
lecular interactions (Figure 3).
5i, the interpenetrating sidearms create large loose-fitting
voids (Figure 5).
Crystal Packing of Ferric Wheels 5j-l of Space Group
P21/c. The ferric wheels [Fe6X6(L3)6] (5j-l) have idealized
S2 (5j,k) and S6 (5l) molecular symmetry and crystallize in
the space group P21/c (Table 1). The crystal packing of the
ferric wheels 5j-l is almost identical and differs only by
the included angle of the two groups of parallel wheels
(Figure 6, top). For example, all the disklike clusters of 5j
are arranged in parallel in two orientations (Figure 6, center)
and are piled in cylindrical columns, with all the iron centers
superimposed. Whereas the interpenetrating sidearms of the
ferric wheels 5j,k are subject to van der Waals interactions,
An especially interesting example of crystal packing
leading to porous frameworks is caused by three-dimensional
π-π stacking of the naphthyl groups of the sidearms of ferric
wheels 5h (Figure 4). This leads to two different kinds of
voids. Of the voids formed outside and between discrete
wheels, only the outside voids host water molecules. Self-
assembly by hydrogen bonding, van der Waals interaction,
and π-π stacking are widespread binding modes in su-
pramolecular hybrid organic-inorganic 3D-networks.9,10
Unlike 5a-h, the ferric wheels of 5i are not arranged in
parallel but are rather three-dimensionally perpendicular, a
well-known construction for 3D coordination polymers.16 In
(16) Saalfrank, R. W.; Maid, H.; Hampel, F.; Peters, K. Eur. J. Inorg. Chem.
1999, 1859-1876.
4376 Inorganic Chemistry, Vol. 43, No. 14, 2004

Crystal Packing of Metalla-coronands
Figure 5. Left: crystal packing of 5i. Right: graphical presentation,
highlighting the three-dimensional perpendicular arrangement of the ferric
wheels.
Figure 2. Presentation of the arrangement of the ferric wheels in 5b (top)
and 5c (bottom). Left: view along the c-axis. Right: view along the b-axis.
Figure 3. Top, left: presentation of the columnar crystal packing of 5e,
highlighting the compartments with encapsulated chloroform. Top, right:
space-filling model, demonstrating the tight incarceration of chloroform by
two interlocking entities of 5g. Bottom: stereoview presentation of space-
filling model of ball shaped 5d.
Figure 6. Top: schematic stereo presentation of the crystal packing of
5j-l. Center: presentation of the two orientations of 5j. Bottom: stereoview
highlighting the one-dimensional π-π interactions between parallel com-
plexes of 5l.
Crystal Packing of Ferric Wheels 5m-o of Space
Group P21/n and 5p of Space Group C2/c. Whereas the
unit cells of 5j-l of space group P21/c are most simply
depicted with five wheels (Figure 6, top), the crystal packings
of 5m-o of space group P21/n and 5p of space group C2/c
are more complex. The unit cells of 5m-o are basically
represented by six wheels (Figure 7, top), and that for 5p is
represented by 15 wheels (Figure 7, bottom).
Figure 4. Stereoview of the crystal packing of 5h, highlighting the π-π
interactions together with encapsulated water (black spheres) in the outside
voids.
Crystal Packing of Ferric Wheels 5q-y of Space Group
P1h. The ferric wheels [Fe6X6(L3)6] (5q-y) have idealized
the packing of the ferric wheels of 5l is governed by π-π
interactions (Figure 6, bottom).
Inorganic Chemistry, Vol. 43, No. 14, 2004 4377

Saalfrank et al.
General Method for H2L3 (4a-y). A suspension of the
corresponding chloride, bromide, or toluenesulfonate (30 mmol),
diethanolamine (1.1 equiv), and Na2CO3 (1.2 equivalents) in MeCN
(125 mL) was heated at reflux for 48 h. The reaction mixture was
then cooled, filtered to remove any residual salts, and concentrated
under vacuum. The residue was taken up in CHCl3 (100 mL) and
washed with water (50 mL). The organic phase was dried over
Na2SO4 and concentrated under vacuum to give the product.17
4g-i,l-s. The corresponding halides were commercially avail-
able.
4a,e,j,u. The corresponding halides were prepared according to
a literature procedure.18
4d,f,k,w,x. The corresponding toluenesulfonate compounds were
prepared according to a literature procedure.19
4y. 3,5-Bis(allyloxy)benzyl bromide was prepared according to
a literature procedure.20
Figure 7. Schematic stereo presentation of the crystal packing of 5m-o
(top) and 5p (bottom, for reasons of clarity only nine complexes are shown).
H2L3 (4a). Yield: 6.11 g (81%) pale yellow oil. IR (neat): ν˜ )
3417, 2878, 1655, 1089 cm-1. 1H NMR (400 MHz, CDCl3): δ )
3.65-3.50 (m, 14H, 5 CH2-O, 2 CH2-OH), 3.34 (s, 3H, CH3),
2.71 (t, 2H, J ) 5.0 Hz, CH2-N), 2.66 (t, 4H, J ) 5.0 Hz, 2
N-CH2) ppm. 13C NMR (100.5 MHz, CDCl3): δ ) 71.84, 70.38
(two superimposed peaks), 70.17, 69.55 (5 CH2-O), 59.71 (2 CH2-
OH), 58.92 (CH3-O), 57.27 (2 N-CH2), 54.02 (CH2-N) ppm.
FAB-MS (3-NBA): m/z (%) ) 252 (100) [M]+, 220 (40) [M -
CH2OH]+. Anal. Calcd (%) for C11H25NO5 (251.32): C 52.57, H
10.03, N 5.57. Found: C 49.73, H 10.17, N 4.54.
H2L3 (4b,c). Commercially available.
H2L3 (4d). Yield: 8.74 g (93%) pale yellow oil. IR (neat): ν˜ )
1
3373, 2874, 1059, 757, 693 cm-1. H NMR (400 MHz, CDCl3):
δ ) 7.25-7.21 (m, 2H, 2 Ar-H), 6.92-6.88 (m, 3H, 3 Ar-H),
4.11 (t, 2H, J ) 4.9 Hz, CH2-O), 3.81 (t, 2H, J ) 4.9 Hz, CH2-
O), 3.70-3.61 (m, 4H, 2 CH2-O), 3.74-3.50 (m, 6H, CH2-O, 2
CH2-OH), 2.71 (t, 2H, J ) 5.2 Hz, CH2-N), 2.66 (t, 4H, J ) 5.1
Hz, 2 N-CH2) ppm. 13C NMR (100.5 MHz, CDCl3): δ ) 158.47
(Ar-C), 129.21, 120.64, 114.47 (5 Ar-CH), 70.62, 70.16, 69.66,
69.63, 67.18 (5 CH2-O), 59.71 (2 CH2-OH), 57.09 (2 N-CH2),
53.82 (CH2-N) ppm. FAB-MS (3-NBA): m/z (%) ) 314 (100)
[M]+, 282 (45) [M - CH2OH]+. Anal. Calcd (%) for C16H27NO5
(313.39): C 61.32, H 8.68, N 4.47. Found: C 57.98, H 7.94, N
4.14.
Figure 8. Schematic stereo presentation of the crystal packing of 5q-y.
S2 molecular symmetry and are packed in the crystal most
simply, with all the ferric wheels piled in parallel (Figure
8).
Conclusion
Earlier, we described an efficient, simple route for the
template-mediated self-assembly of iron(III) ions and tri-
ethanolamine to give six-membered iron coronates. Careful
analysis of the construction plan of these systems was the
basis for the rational design of six-membered iron coronands,
starting from N-substituted diethanolamines and iron(III)
chloride. Although the structures of the iron coronands are
almost identical and have idealized S6 or S2 molecular
symmetry, their variable sidearms give rise to a whole variety
of different crystal packing modes. Most interestingly, the
iron coronands readily frame compartments and three-
dimensional networks with discrete channels and pores,
suitable for the encapsulation of guest molecules. Aiming
at the use of oligonuclear clusters as single-molecule magnets
(SMMs), efforts toward crystal engineering are indispensable.
H2L3 (4e). Yield: 3.34 g (42%) colorless oil. IR (neat): ν˜ )
3385, 2950, 2873, 1452, 1112 cm-1. 1H NMR (400 MHz, CDCl3):
δ ) 3.61-3.42 (m, 16H, 2 CH2-OH, 6 CH2-O), 3.42 (br s, 2H,
2 OH), 2.76 (t, 2H, J ) 5.1 Hz, CH2-N), 2.72 (t, 4H, J ) 5.1 Hz,
2 N-CH2), 1.21 (t, 3H, J ) 7.1 Hz, CH3) ppm. 13C NMR (100.5
MHz, CDCl3): δ ) 70.65, 70.49, 70.27, 69.81, 69.65, 66.63 (6
CH2-O), 59.78 (2 CH2-OH), 57.28 (2 N-CH2), 54.04 (CH2-
N), 15.15 (CH3) ppm. MS (EI, 70 eV): m/z (%) ) 265 (5) [M]+,
234 (100) [M - CH2OH]+. Anal. Calcd (%) for C12H27NO2
(265.35): C 54.32, H 10.26, N 5.28. Found: C 52.50, H 10.02, N
4.72.
H2L3 (4f). Yield: 6.42 g (95%) pale yellow oil. IR (neat): ν˜ )
3359, 2949, 2879, 1037, 756, 693 cm-1 1H NMR (400 MHz,
.
(17) Meadows, E. S.; De Wall, S. L.; Barbour, L. J.; Fronczek, F. R.; Kim,
M.-S.; Gokel, G. W. J. Am. Chem. Soc. 2000, 122, 3325-3335.
Schultz, R. N.; White, B. D.; Dishong, D. M.; Arnold, K. A.; Gokel,
G. W. J. Am. Chem. Soc. 1985, 107, 6659-6668.
Experimental Section
(18) Brockmann, T. W.; Tour, J. M. J. Am. Chem. Soc. 1995, 117, 4437-
General Techniques. All reactions were carried out under an
atmosphere of dry nitrogen. All solvents used were purified and
dried according to standard procedures. NMR spectra were recorded
on JEOL EX 400 and JEOL GX 400 spectrometers. Solvent signals
were employed as internal standards: CDCl3 (1H, 7.24 ppm; 13C,
77.0 ppm); D3CCOCD3 (1H, 2.04 ppm; 13C, 29.30, 206.30 ppm).
4447.
(19) Ashton, P. R.; Ballardini, R.; Balzani, V.; Constable, E. C.; Credi,
A.; Kocian, O.; Langford, S. J.; Preece, J. A.; Prodi, L.; Schofield, E.
R.; Spencer, N.; Stoddart, J. F.; Wenger, S. Chem. Eur. J. 1998, 4,
2413-2422.
(20) Yamakawa, Y.; Ueda, M.; Nagahata, R.; Takeuchi, K.; Asai, M. J.
Chem. Soc., Perkin Trans 1 1998, 4135-4139.
4378 Inorganic Chemistry, Vol. 43, No. 14, 2004

Crystal Packing of Metalla-coronands
CDCl3): δ ) 7.30-7.23 (m, 2H, 2 Ar-H), 6.95-6.87 (m, 3H, 3
Ar-H), 4.02 (t, 2H, J ) 5.1 Hz, CH2-O), 3.60 (t, 4H, J ) 5.2 Hz,
2 CH2-OH), 2.94 (t, 2H, J ) 5.1 Hz, CH2-N), 2.74 (t, 4H, J )
5.2 Hz, 2 N-CH2) ppm. 13C NMR (100.5 MHz, CDCl3): δ )
158.34 (Ar-C), 129.50, 121.08, 114.46 (5 Ar-CH), 66.22 (O-
CH2), 59.68 (2 N-CH2), 56.87 (2 CH2-OH), 53.48 (CH2-N) ppm.
FAB-MS (3-NBA): m/z (%) ) 226 (100) [M]+, 194 (50) [M -
CH2OH]+. Anal. Calcd (%) for C12H19NO3 (225.28): C 63.98, H
8.50, N 6.22. Found: C 60.96, H 8.68, N 5.81.
CDCl3): δ ) 7.27-7.23 (m, 2H, Ar-H), 6.94-6.89 (m, 3H, Ar-
H), 4.09 (t, 2H, J ) 4.7 Hz, CH2-O), 3.79 (t, 2H, J ) 4.7 Hz,
CH2-O), 3.59 (t, 2H, J ) 5.3 Hz, CH2-O), 3.56 (t, 4H, J ) 5.2
Hz, 2 CH2-OH), 3.30 (br s, 2H, 2 OH), 2.75 (t, 2H, J ) 5.3 Hz,
CH2-N), 2.68 (t, 4H, J ) 5.2 Hz, 2 N-CH2) ppm. 13C NMR (100.5
MHz, CDCl3): δ ) 158.47 (Ar-C), 129.41, 120.97, 114.52 (5 Ar-
CH), 69.76, 69.43, 66.96 (3 CH2-O), 59.68 (2 CH2-OH), 56.96
(2 N-CH2), 53.72 (CH2-N) ppm. FAB-MS (3-NBA): m/z (%) )
270 (100) [M]+, 238 (50) [M - CH2OH]+. Anal. Calcd (%) for
C14H23NO4 (269.34): C 62.43, H 8.61, N 5.20. Found: C 59.73,
H 8.53, N 4.63.
H2L3 (4g). Yield: 5.08 g (69%) thick pale yellow oil. IR (neat):
1
ν˜ ) 3355, 3054, 1690, 1406, 1037 cm-1. H NMR (400 MHz,
CDCl3): δ ) 7.79-7.69 (m, 4H, 4 Naph-H), 7.47-7.45 (m, 1H,
1 Naph-H), 7.44-7.42 (m, 1H, 1 Naph-H), 7.24 (br s, 1H, 1 Naph-
H), 3.79 (s, 2H, CH2-N), 3.58 (t, 4H, J ) 5.4 Hz, 2 CH2-OH),
3.57 (br s, 2H, 2 OH), 2.68 (t, 4H, J ) 5.4 Hz, 2 N-CH2) ppm.
13C NMR (100.5 MHz, CDCl3): δ ) 136.36, 133.27, 132.27,
129.09, 128.45, 127.89, 127.37, 127.09, 126.05, 125.68 (3 Naph-
C, 7 Naph-CH), 59.61 (2 CH2-OH), 59.43 (CH2-N), 55.98 (2
N-CH2) ppm. MS (EI, 70 eV): m/z (%) ) 245 (10) [M]+, 214
(20) [M - CH2OH]+, 141 (100) [M - N(CH2CH2OH)2]+. Anal.
Calcd (%) for C15H19NO2 (245.33): C 73.44, H 7.81, N 5.71.
Found: C 73.59, H 7.93, N 5.67.
H2L3 (4h). Yield: 5.12 g (74%) pale yellow oil. IR (neat): ν˜ )
3396, 2946, 2881, 1406, 1064 cm-1. 1H NMR (400 MHz, CDCl3):
δ ) 8.13-7.96 (m, 4H, 4 Naph-H), 7.81-7.79 (m, 1H, 1 Naph-
H), 7.48-7.37 (m, 1H, 1 Naph-H), 7.18 (br s, 1H, 1 Naph-H), 4.09
(s, 2H, CH2-N), 3.53 (t, 4H, J ) 5.3 Hz, 2 CH2-OH), 3.14 (br s,
2H, 2 OH), 2.65 (t, 4H, J ) 5.3 Hz, 2 N-CH2) ppm. 13C NMR
(100.5 MHz, CDCl3): δ ) 134.44, 133.87, 133.27, 132.75, 132.21,
128.67, 127.64, 127.04, 125.16, 123.90 (3 Naph-C, 7 Naph-CH),
59.74 (2 CH2-OH), 58.34 (CH2-N), 56.12 (2 N-CH2) ppm. MS
(EI, 70 eV): m/z (%) ) 245 (10) [M]+, 214 (20) [M - CH2OH]+,
142 (100) [M - N(CH2CH2OH)2]+. Anal. Calcd (%) for C15H19-
NO2 (245.33): C 73.44, H 7.81, N 5.71. Found: C 73.51, H 7.79,
N 5.68.
H2L3 (4l). Yield: 5.27 g (90%) pale yellow oil. IR (neat): ν˜ )
3353, 2947, 2880, 2826, 1039, 734, 700 cm-1. 1H NMR (400 MHz,
CDCl3): δ ) 7.24-7.16 (m, 5H, 5 Ar-H), 3.61 (s, 2H, CH2-N),
3.52 (t, 4H, J ) 5.3 Hz, 2 CH2-OH), 3.19 (br s, 2H, 2 OH), 2.61
(t, 4H, J ) 5.3 Hz, 2 N-CH2) ppm. 13C NMR (100.5 MHz,
CDCl3): δ ) 139.07 (Ar-C), 129.39, 128.84, 127.90 (5 Ar-CH),
59.97 (2 CH2-OH), 59.59 (CH2-N), 56.14 (2 N-CH2) ppm. FAB-
MS (3-NBA): m/z (%) ) 196 (100) [M]+, 164 (70) [M - CH2-
OH]+. Anal. Calcd (%) for C11H17NO2 (195.26): C 67.66, H 8.78,
N 7.17. Found: C 65.65, H 8.95, N 6.88.
H2L3 (4m). Yield: 2.61 g (60%) yellow oil. IR (neat): ν˜ ) 3347,
1
3077, 2955, 2882, 2823, 1643, 1077, 921 cm-1. H NMR (400
MHz, CD3COCD3): δ ) 5.87 (m, 1H, CH2dCH), 5.14 (m, 2H,
CH2dCH), 3.62 (br s, 2H, 2 OH), 3.55 (t, 4H, J ) 5.6 Hz, 2 CH2-
OH), 3.20 (d, 2H, J ) 6.4 Hz, CH2-N), 2.63 (t, 4H, J ) 5.6 Hz,
2 N-CH2). 13C NMR (100.5 MHz, CD3COCD3): δ ) 137.04
(CH2dCH), 117.26 (CH2dCH), 60.27 (2 CH2-OH), 58.59 (CH2-
N), 57.06 (2 N-CH2) ppm. MS (EI, 70 eV): m/z (%) ) 145 (4)
[M]+, 114 (100) [M - CH2OH]+. Anal. Calcd (%) for C7H15NO2
(145.20): C 57.90, H 10.41, N 9.65. Found: C 54.41, H 9.11, N
9.83.
H2L3 (4n). Yield: 7.16 g (95%) colorless oil. IR (neat): ν˜ )
3356, 2961, 2875, 1364, 1038 cm-1. 1H NMR (400 MHz, CDCl3):
δ ) 7.32 (d, 2H, J ) 8.3 Hz, 2 Ar-H), 7.21 (d, 2H, J ) 8.8 Hz,
2 Ar-H), 3.65 (s, 2H, CH2-N), 3.60 (t, 4H, J ) 5.5 Hz, 2 CH2-
OH), 2.78 (br s, 2H, 2 OH), 2.69 (t, 4H, J ) 5.5 Hz, 2 N-CH2),
1.29 (s, 9H, 3 CH3) ppm. 13C NMR (100.5 MHz, CDCl3): δ )
150.15, 135.49 (2 Ar-C), 128.56, 125.32 (4 Ar-CH), 59.56 (2
CH2-OH), 58.78 (CH2-N), 55.64 (2 N-CH2), 34.42 (tBu-Cq),
31.33 ppm (3 CH3). FAB-MS (3-NBA): m/z (%) ) 252 (75) [M]+,
220 (45) [M - CH2OH]+, 147 (100) [M - N(CH2CH2OH)2]+.
Anal. Calcd (%) for C15H25NO2 (251.37): C 71.67, H 10.03, N
5.57. Found: C 70.28, H 10.15, N 5.20.
H2L3 (4i). Yield: 7.10 g (66%) colorless oil that solidifies on
standing. IR (neat): ν˜ ) 3377, 3060, 2953, 2250, 1598, 1448, 1033
1
cm-1. H NMR (400 MHz, CDCl3): δ ) 7.41-7.26 (m, 10H, 10
Ar-H), 3.64 (t, 4H, J ) 5.4 Hz, 2 CH2-OH), 3.30 (t, 4H, J ) 5.3
Hz, 2 N-CH2), 3.22 (br s, 2H, 2 OH), 2.90 (t, J ) 5.4 Hz, 2H,
Cq-CH2), 2.64 (t, 2H, J ) 5.4 Hz, CH2-N), 2.55 (t, 2H, J ) 5.4
Hz, 2 N-CH2) ppm. 13C NMR (100.5 MHz, CDCl3): δ ) 129.11,
128.92, 128.31, 128.28, 127.98, 127,76, 127.56, 126.95, 126.64,
126.54, 126.21, 126.04 (2 Ar-C, 10 Ar-CH), 119.16 (CN), 59.37
(2 CH2-OH), 56.11 (2 N-CH2), 53.10 (CH2-N), 26.51 (Cq), 26.48
(Cq-CH2) ppm. FAB-MS (3-NBA): m/z (%) ) 325 (100) [M]+,
293 (20) [M - CH2OH]+. Anal. Calcd (%) for C20H24N2O2
(324.43): C 74.04, H 7.46, N 8.64. Found: C 74.17, H 7.39, N
8.66.
H2L3 (4o). Yield: 5.70 g (81%) thick pink oil. IR (neat): ν˜ )
3422, 2964, 2797, 1610, 1045 cm-1. 1H NMR (400 MHz, CDCl3):
δ ) 4.62 (t, 1H, J ) 5.4 Hz, CH-O), 3.98 (m, 2H, CH2-CH-O),
3.46 (t, 4H, J ) 5.4 Hz, 2 CH2-O), 3.30 (t, 4H, J ) 5.4 Hz, 2
CH2-OH), 3.22 (br s, 2H, 2 OH), 2.61 (t, 2H, J ) 5.4 Hz, CH2-
N), 2.58 (t, 4H, J ) 5.4 Hz, 2 N-CH2), 1.59 (m, 2H, CH2-CH2-
O) ppm. 13C NMR (100.5 MHz, CDCl3): δ ) 101.35 (CH-O),
67.21 (2 CH2-O), 60.48 (2 CH2-OH), 55.84 (2 N-CH2), 48.44
(CH2-N), 32.32 (CH2-CH-O), 25.44 (CH2-CH2-O) ppm. MS
(EI, 70 eV): m/z (%) ) 219 (5) [M]+, 188 (10) [M - CH2OH]+,
130 (10) [M - NCH2CH2OH]+, 83 (100) [M - CH2 - N(CH2-
CH2OH)2]+. Anal. Calcd (%) for C10H21NO4 (219.29): C 54.77,
H 9.65, N 6.39. Found: C 53.96, H 9.41, N 6.28.
H2L3 (4j). Yield: 3.05 g (46%) colorless oil. IR (neat): ν˜ )
3390, 2950, 2870, 1451, 1108 cm-1. 1H NMR (400 MHz, CDCl3):
δ ) 3.63 (t, 4H, J ) 4.2 Hz, 2 CH2-OH), 3.56 (m, 8H, 4 CH2-
O), 3.38 (br s, 2H, 2 OH), 2.76 (t, 2H, J ) 5.1 Hz, CH2-N), 2.72
(t, 4H, J ) 4.6 Hz, 2 N-CH2), 1.22 (t, 3H, J ) 7.1 Hz, CH3) ppm.
13C NMR (100.5 MHz, CDCl3): δ ) 70.23, 69.61, 69.50, 66.78
(4 CH2-O), 59.74 (2 CH2-OH), 57.28 (2 N-CH2), 53.82 (CH2-
N), 14.98 (CH3) ppm. MS (EI, 70 eV): m/z (%) ) 221 (1) [M]+,
190 (60) [M - CH2OH]+, 146 (19) [M - CH2OH, - OC2H5]+,
118 (100) [M - CH2OH, - C2H4OC2H5]+. Anal. Calcd (%) for
C10H23NO2 (221.30): C 54.28, H 10.48, N 6.33. Found: C 53.67,
H 10.70, N 5.92.
H2L3 (4p). Yield: 3.20 g (57%) yellow oil. IR (neat): ν˜ ) 3354,
1
3079, 2946, 2881, 2827, 1639, 1047, 910 cm-1. H NMR (400
MHz, CDCl3): δ ) 5.80 (m, 1H, CH2dCH), 5.10 (m, 2H, CH2d
CH), 3.61 (t, 4H, J ) 5.6 Hz, 2 CH2-OH), 3.25 (br s, 2H, 2 OH),
2.65 (t, 4H, J ) 5.6 Hz, 2 N-CH2), 2.64 (t, 2H, J ) 7.1 Hz, CH2-
N), 2.30 (m, 6H, 3 CH2) ppm. 13C NMR (100.5 MHz, CDCl3):
H2L3 (4k). Yield: 7.43 g (92%) pale yellow oil. IR (neat): ν˜ )
3371, 2945, 2875, 1043, 756, 693 cm-1 1H NMR (400 MHz,
.
Inorganic Chemistry, Vol. 43, No. 14, 2004 4379

Saalfrank et al.
δ ) 136.40 (CH2dCH), 116.12 (CH2dCH), 69.42 (2 CH2-OH),
55.85 (CH2-N), 53.65 (2 N-CH2), 32.12, 31.68, 31.44 (3 CH2)
ppm. MS (EI, 70 eV): m/z (%) ) 187 (8) [M]+, 156 (100) [M -
CH2OH]+. Anal. Calcd (%) for C10H21NO2 (187.28): C 64.13, H
11.30, N 7.48. Found: C 63.74, H 11.28, N 7.32.
H2L3 (4q). Yield: 2.73 g (48%) colorless oil. IR (neat): ν˜ )
3346, 2929, 2858, 1466, 1047 cm-1. 1H NMR (400 MHz, CDCl3):
δ ) 3.61 (t, 4H, J ) 5.4 Hz, 2 CH2-OH), 3.18 (br s, 2H, 2 OH),
2.65 (t, 4H, J ) 5.4 Hz, 2 N-CH2), 2.52 (t, 2H, J ) 7.6 Hz, CH2-
N), 1.44 (m, 2H, CH2-CH3), 1.28 (m, 6H, 3 CH2) 0.89 (t, 3H,
J ) 7.1 Hz, CH3) ppm. 13C NMR (100.5 MHz, CDCl3): δ ) 59.63
(2 CH2-OH), 56.06 (CH2-N), 54.80 (2 N-CH2), 31.71, 27.00,
26.96, 22.59 (4 CH2), 13.99 (CH3) ppm. MS (EI, 70 eV): m/z (%)
) 189 (6) [M]+, 158 (100) [M - CH2OH]+. Anal. Calcd (%) for
C10H23NO2 (189.31): C 63.45, H 12.25, N 7.40. Found: C 60.77,
H 11.99, N 6.91.
H2L3 (4r). Yield: 2.93 g (45%) colorless oil. IR (neat): ν˜ )
3355, 2925, 2855, 1465, 1043 cm-1. 1H NMR (400 MHz, CDCl3):
δ ) 3.61 (t, 4H, J ) 5.4 Hz, 2 CH2-OH), 3.15 (br s, 2H, 2 OH),
2.65 (t, 4H, J ) 5.4 Hz, 2 N-CH2), 2.53 (t, 2H, J ) 7.6 Hz, CH2-
N), 1.46 (m, 2H, CH2-CH3), 1.27 (m, 10H, 5 CH2), 0.88 (t, 3H,
J ) 6.6 Hz, CH3) ppm. 13C NMR (100.5 MHz, CDCl3): δ ) 59.63
(2 CH2-OH), 56.13 (CH2-N), 54.86 (2 N-CH2), 31.86, 29.54,
29.31, 27.42, 26.97, 22.66 (6 CH2), 14.10 (CH3) ppm. MS (EI, 70
eV): m/z (%) ) 217 (4) [M]+, 186 (100) [M - CH2OH]+. Anal.
Calcd (%) for C12H27NO2 (217.35): C 66.31, H 12.52, N 6.44.
Found: C 65.95, H 12.74, N 6.41.
[M - CH2OH]+. Anal. Calcd (%) for C18H25NO4 (319.40): C
67.69, H 7.89, N 4.39. Found: C 64.67, H 7.72, N 4.08.
H2L3 (4x). Yield: 9.20 g (83%) pale red oil. IR (neat): ν˜ )
3386, 2942, 2875, 1047, 757, 692 cm-1 1H NMR (400 MHz,
.
CDCl3): δ ) 7.52-7.46 (m, 3H, 3 Ar-H), 7.34-7.25 (m, 4H, 4
Ar-H), 6.95-6.89 (m, 2H, 2 Ar-H), 4.21 (t, 2H, J ) 4.7 Hz,
CH2-O), 3.90 (t, 2H, J ) 4.7 Hz, CH2-O), 3.72 (t, 2H, J ) 5.2
Hz, CH2-O), 3.52 (t, 4H, J ) 5.2 Hz, 2 CH2-OH), 2.72 (t, 2H,
J ) 5.2 Hz, CH2-N), 2.65 (t, 4H, J ) 5.2 Hz, 2 N-CH2) ppm.
13C NMR (100.5 MHz, CDCl3): δ ) 159.23 (Ar-C), 133.42,
131.48, 129.74, 128.28, 128.10 (5 Ar-CH), 123.66 (Ar-C), 121.01
(Ar-CH), 113.09 (Ar-C), 112.60 (Ar-CH), 93.35, 85.91 (2 Ct),
70.43, 69.52, 68.85 (3 CH2-O), 59.77 (2 CH2-OH), 56.85 (2
N-CH2), 53.94 (CH2-N) ppm. FAB-MS (3-NBA): m/z (%) )
370 (100) [M]+, 338 (40) [M - CH2OH]+. Anal. Calcd (%) for
C22H27NO4 (369.45): C 71.52, H 7.37, N 3.79. Found: C 69.40,
H 7.30, N 3.32.
H2L3 (4y). Yield: 7.38 g (80%) pale yellow oil. IR (neat): ν˜ )
1
3371, 2946, 2874, 1053, 995 cm-1. H NMR (400 MHz, CDCl3):
δ ) 6.48-6.47 (m, 2H, 2 Ar-H), 6.37-6.36 (m, 1H, 1 Ar-H),
6.05-5.96 (m, 2H, 2 CHdCH2), 5.37 (dd, 2H, J ) 17.0 Hz, 1.6
Hz; 2 CHdCH2 cis), 5.25 (d, 2H, J ) 9.9 Hz, 2 CHdCH2 trans),
4.47 (d, 4H, J ) 5.5 Hz, 2 O-CH2), 3.59 (s, 2H, CH2-N), 3.58 (t,
4H, J ) 5.2 Hz, 2 CH2-OH), 2.67 (t, 4H, J ) 5.2 Hz, 2 N-CH2)
ppm. 13C NMR (100.5 MHz, CDCl3): δ )159.71 (2 Ar-C), 141.27
(Ar-C), 133.13 (2 CHdCH2), 117.70 (2 CHdCH2), 107.62 (2 Ar-
CH), 100.42 (Ar-CH), 68.77 (O-CH2), 59.59 (2 CH2-OH), 59.36
(CH2-N), 55.87 (2 N-CH2) ppm. FAB-MS (3-NBA): m/z (%) )
308 (100) [M]+, 276 (80) [M - CH2OH]+. Anal. Calcd (%) for
C17H25NO4 (307.38): C 66.43, H 8.20, N 4.56. Found: C 63.44,
H 8.17, N 4.20.
General Method for [Fe6Cl6(L3)6] (5a-c,e,g-j,l,m,p-s,u-y).
To a suspension of calcium hydride (189 mg, 4.5 mmol) in
anhydrous THF (75 mL) was added H2L3 (4a-y) (3.0 mmol). After
the suspension was stirred for 1 h at 20 °C, a solution of iron(III)
chloride (487 mg, 3.0 mmol) in anhydrous THF (25 mL) was added.
The reaction mixture was stirred at 20 °C for 72 h, and then, the
solvent was removed under vacuum. The precipitate was dissolved
in CH2Cl2 (50 mL), and the remaining residue was filtered off.
After evaporation of the solvent, a yellow powder was obtained.
General Method for [Fe6(SCN)6(L3)6] (5d,f,k,n,o,t). In order
to prepare the rhodanide complexes, 3.0 mmol of the corresponding
chloride complexes [Fe6Cl6(L3)6], vide supra, were dissolved in
CHCl3 (50 mL), and a solution of KSCN (1.46 g, 15 mmol) in
anhydrous MeOH (50 mL) was added. The reaction mixture was
refluxed for 1 h (in the case of 5n, the suspension was stirred at 20
°C for 24 h), and then, the solvent was removed under vacuum.
The precipitate was dissolved in CH2Cl2 (50 mL), and the remaining
residue was filtered off. After evaporation of the solvent, a red
powder was obtained.
H2L3 (4s). Yield: 3.90 g (73%) yellow oil. IR (neat): ν˜ ) 3370,
1
2980, 2881, 1466, 1068, 766 cm-1. H NMR (400 MHz, CDCl3):
δ ) 3.62 (t, 4H, J ) 5.4 Hz, 2 CH2-OH), 3.21 (br s, 2H, 2 OH),
2.72 (t, 4H, J ) 5.4 Hz, 2 N-CH2), 1.64 (m, 18H, 9 CH2), 0.96 (t,
3H, CH3) ppm. 13C NMR (100.5 MHz, CDCl3): δ ) 61.42 (2
CH2-OH), 55.95 (2 N-CH2), 55.85 (CH2-N), 33.24, 32.19, 31.89,
28.74, 28.15, 27.36, 26.93, 26.17, 22.66 (9 CH2), 19.33 (CH3) ppm.
MS (EI, 70 eV): m/z (%) ) 245 (10) [M]+, 214 (100) [M - CH2-
OH]+. Anal. Calcd (%) for C14H31NO2 (245.41): C 68.52, H 12.73,
N 5.71. Found: C 67.16, H 12.96, N 5.49.
H2L3 (4t). Same as 4s.
H2L3 (4u). Yield: 2.55 g (48%) colorless oil. IR (neat): ν˜ )
3373, 2949, 2869, 1447, 1114 cm-1. 1H NMR (400 MHz, CDCl3):
δ ) 3.57 (br s, 2H, 2 OH), 3.52 (t, 4H, J ) 5.4 Hz, 2 CH2-OH),
3.47 (m, 4H, 2 CH2-O), 2.75 (t, 2H, J ) 5.9 Hz, CH2-N), 2.69
(t, 4H, J ) 5.4 Hz, 2 N-CH2), 1.13 (t, 3H, J ) 7.0 Hz, CH3) ppm.
13C NMR (100.5 MHz, CDCl3): δ ) 69.88, 66.65 (2 CH2-O),
60.48 (2 CH2-OH), 58.06 (2 N-CH2), 53.82 (CH2-N), 15.68
(CH3) ppm. MS (EI, 70 eV): m/z (%) ) 177 (6) [M]+, 146 (61)
[M - CH2OH]+, 118 (100) [M - CH2OH, - CH2OC2H5]+. Anal.
Calcd (%) for C8H19NO2 (177.24): C 54.21, H 10.81, N 7.90.
Found: C 53.27, H 10.96, N 7.96.
H2L3 (4v). Same as 4d.
[Fe6Cl6(L3)6] (5a). Educt: 4a (754 mg). Yield: 296 mg (29%)
yellow rhombic crystals from chloroform/n-pentane. Mp 99 °C.21
IR (KBr): ν˜ ) 2869, 1460, 1089 cm-1. FAB-MS (3-NBA): m/z
(%) ) 2043 (1) [Fe6Cl6(L3)6]+, 2007 (10) [Fe6Cl5(L3)6]+, 1325 (20)
[Fe4Cl3(L3)4]+, 701 (80) [Fe3Cl(L3)2]+, 645 (100) [Fe2Cl(L3)2]+.
Anal. Calcd (%) for C66H138Cl6Fe6N6O30 (2043.61): C 38.79, H
6.82, N 3.68. Found: C 37.38, H 7.24, N 3.68.
[Fe6Cl6(L3)6] (5b). Educt: 4b (484 mg). Yield: 188 mg (25%)
yellow rhombic crystals from chloroform/n-pentane. Mp >220 °C
(dec). IR (KBr): ν˜ ) 2958, 2929, 2865, 1457, 1089 cm-1. FAB-
H2L3 (4w). Yield: 8.62 g (90%) pale red oil. IR (neat): ν˜ )
3371, 2942, 2875, 1047, 757, 692 cm-1 1H NMR (400 MHz,
.
CDCl3): δ ) 8.28-8.26 (m, 1H, Naph-H), 7.78-7.76 (m, 1H,
Naph-H), 7.47-7.32 (m, 4H, 4 Naph-H), 6.81-6.79 (m, 1H, Naph-
H), 4.28 (t, 2H, J ) 4.8 Hz, CH2-O), 3.95 (t, 2H, J ) 4.8 Hz,
CH2-O), 3.67 (t, 2H, J ) 5.2 Hz, CH2-O), 3.56 (t, 4H, J ) 5.2
Hz, 2 CH2-OH), 2.79 (t, 2H, J ) 5.2 Hz, CH2-N), 2.70 (t, 4H,
J ) 5.2 Hz, 2 N-CH2) ppm. 13C NMR (100.5 MHz, CDCl3): δ )
154.41, 134.49, 127.39, 126.38, 125.75, 125.64, 125.20, 122.01,
120.58, 104.99 (3 Naph-C, 7 Naph-CH), 70.10, 69.61, 67.67 (3
CH2-O), 59.78 (2 CH2-OH), 56.95 (2 N-CH2), 53.92 (CH2-N)
ppm. FAB-MS (3-NBA): m/z (%) ) 320 (100) [M]+, 288 (80)
(21) The low melting points of 5a,k,v,x (99, 117, 118, 100 °C) are
noteworthy.
4380 Inorganic Chemistry, Vol. 43, No. 14, 2004

Crystal Packing of Metalla-coronands
MS (3-NBA): m/z (%) ) 1502 (52) [Fe6Cl6(L3)6]+, 1469 (100)
[Fe6Cl5(L3)6]+, 1399 (88) [Fe6Cl3(L3)6]+. Anal. Calcd (%) for
C48H102Cl6Fe6N6O12 (1503.17): C 38.35, H 6.84, N 5.59. Found:
C 34.88, H 6.10, N 4.65.
MS (3-NBA): m/z (%) ) 1467 (20) [Fe4(SCN)3(L3)4]+, 1408 (35)
[Fe4(SCN)2(L3)4]+, 1027 (100) [Fe4(SCN)(L3)3]+; elemental analysis
calcd (%) for C90H126Fe6N12O24S6 (2287.50): C 47.25, H 5.56, N
7.35; found: C 47.23, H 5.74, N 6.91.
[Fe6Cl6(L3)6] (5c). Educt: 4c (400 mg). Yield: 167 mg (25%)
yellow rhombic crystals from chloroform/n-pentane. Mp >220 °C
(dec). IR (KBr): ν˜ ) 2970, 2934, 2903, 2858, 1473, 1447, 1077
cm-1. FAB-MS (3-NBA): m/z (%) ) 1334 (11) [Fe6Cl6(L3)6]+,
1299 (15) [Fe6Cl5(L3)6]+, 759 (100) [Fe4Cl4(L3)3]+. Anal. Calcd
(%) for C36H78Cl6Fe6N6O12 (1334.36): C 32.39, H 5.89, N 6.30.
Found: C 29.47, H 5.36, N 5.30.
[Fe6Cl6(L3)6] (5l). Educt: 4l (586 mg). Yield: 324 mg (38%)
yellow rhombic crystals from chloroform/n-pentane. Mp >220 °C
(dec). IR (KBr): ν˜ ) 3062, 3030, 2909, 2865, 1496 cm-1. FAB-
MS (3-NBA): m/z (%) ) 1707 (10) [Fe6Cl6(L3)6]+, 1671 (25) [Fe6-
Cl5(L3)6]+, 1513 (15) [Fe6Cl6(L3)5]+, 1229 (15) [Fe5Cl5(L3)4]+, 1101
(100) [Fe4Cl3(L3)4]+, 1066 (40) [Fe4Cl2(L3)4]+, 945 (70) [Fe4Cl4-
(L3)3]+, 873 (35) [Fe4Cl2(L3)3]+, 838 (25) [Fe4Cl(L3)3]+, 817 (95)
[Fe3Cl2(L3)3]+, 782 (100) [Fe3Cl(L3)3]+, 749 (75) [Fe3(L3)3]+. Anal.
Calcd (%) for C66H90Cl6Fe6N6O12 (1707.24): C 46.43, H 5.31, N
4.92. Found: C 46.11, H 5.25, N 4.70.
[Fe6Cl6(L3)6] (5m). Educt: 4m (436 mg). Yield: 197 mg (28%)
yellow rhombic crystals from chloroform/n-pentane. Mp >220 °C
(dec). IR (KBr): ν˜ ) 3074, 3000, 2907, 2865, 1638, 1085, 929
cm-1. FAB-MS (3-NBA): m/z (%) ) 1406 (100) [Fe6Cl6(L3)6]+.
Anal. Calcd (%) for C42H78Cl6Fe6N6O12 (1406.92): C 35.86, H 5.59,
N 5.97. Found: C 32.45, H 4.93, N 4.81.
[Fe6(SCN)6(L3)6] (5n). Educt: 4n (754 mg). Yield: 606 mg
(55%) red rhombic crystals from chloroform/n-pentane. Mp >220
°C (dec). IR (KBr): ν˜ ) 2963, 2928, 2869, 2032, 1460, 1264, 1081
cm-1. FAB-MS (3-NBA): m/z (%) ) 2179 (1) [Fe6(SCN)6(L3)6]+,
2121 (4) [Fe6(SCN)5(L3)6]+, 1336 (35) [Fe4(SCN)2(L3)4]+, 1087 (30)
[Fe4(SCN)2(L3)3]+, 973 (52) [Fe3(SCN)(L3)3]+, 724 (100) [Fe3-
(SCN)(L3)2]+. Anal. Calcd (%) for C96H138Fe6N12O24S6 (2179.73):
C 52.90, H 6.38, N 7.71. Found: C 52.59, H 6.21, N 7.56.
[Fe6(SCN)6(L3)6] (5o). Educt: 4o (658 mg). Yield: 210 mg
(35%) pink crystals from chloroform/n-pentane. Mp >240 °C (dec).
IR (KBr): ν˜ ) 3490, 2864, 2250, 2190, 1250, 1088 cm-1. FAB-
MS (3-NBA): m/z (%) ) 1987 (10) [Fe6(SCN)6(L3)6]+, 1928 (100)
[Fe6(SCN)5(L3)6]+, 1266 (100) [Fe4(SCN)3(L3)4]+. Anal. Calcd (%)
for C66H114Fe6N12O24S6 (1987.22): C 39.89, H 5.78, N 8.46.
Found: C 39.58, H 5.82, N 7.58.
[Fe6(SCN)6(L3)6] (5d). Educt: 4d (940 mg). Yield: 434 mg
(34%) brown rhombic crystals from dichlorometane/n-pentane. Mp
>165 °C (dec). IR (KBr): ν˜ ) 2915, 2876, 2050, 1249, 1080 cm-1
.
FAB-MS (3-NBA): m/z (%) ) 2492 (5) [Fe6(SCN)5(L3)6]+, 1642
(10) [Fe4(SCN)3(L3)4]+, 1159 (15) [Fe3(SCN)(L3)3]+, 849 (50) [Fe5-
(SCN)(L3)3]+, 792 (50) [Fe4(SCN)(L3)3]+, 734 (100) [Fe2(L3)2]+.
Anal. Calcd (%) for C102H150Fe6N12O30S6 (2551.80): C 48.00, H
5.93, N 6.59. Found: C 47.24, H 5.73, N 6.45.
[Fe6Cl6(L3)6] (5e). Educt: 4e (796 mg). Yield: 223 mg (21%)
light yellow crystals from chloroform/n-pentane. Mp >220 °C (dec).
IR (KBr): ν˜ ) 2974, 2904, 2868, 1458, 1441, 1142, 1089 cm-1
.
FAB-MS (3-NBA): m/z (%) ) 2127 (15) [Fe6Cl6(L3)6]+, 2091
(100) [Fe6Cl5(L3)6]+, 1863 (45) [Fe6Cl6(L3)5]+. Anal. Calcd (%)
for C72H150Cl6Fe6N6O30 (2127.80): C 40.64, H 7.11, N 3.95.
Found: C 39.22, H 7.20, N 3.51.
[Fe6(SCN)6(L3)6] (5f). Educt: 4f (676 mg). Yield: 233 mg (23%)
brown rhombic crystals from dichloromethane/n-pentane. Mp >220
°C (dec). IR (KBr): ν˜ ) 2922, 2871, 2040, 1240, 1081 cm-1. FAB-
MS (3-NBA): m/z (%) ) 1045 (100) [Fe5Cl3(L3)3]+. Anal. Calcd
(%) for C78H102Fe6N12O18S6 (2023.18): C 46.31, H 5.08, N 8.31.
Found: C 45.19, H 5.22, N 8.37.
[Fe6Cl6(L3)6] (5g). Educt: 4g (736 mg). Yield: 412 g (41%)
yellow hexagonal crystals from chloroform/diethyl ether. Mp >220
°C (dec). IR (KBr): ν˜ ) 3024, 2866, 2250, 1081, 756 cm-1. FAB-
MS (3-NBA): m/z (%) ) 2007 (55) [Fe6Cl6(L3)6]+, 1972 (90) [Fe6-
[Fe6Cl6(L3)6] (5p). Educt: 4p (562 mg). Yield: 66 mg (8%)
light green rhombic crystals from chloroform/n-pentane. Mp >220
°C (dec). IR (KBr): ν˜ ) 3098, 3072, 2909, 2870, 1638, 1081, 925
cm-1. FAB-MS (3-NBA): m/z (%) ) 1659 (100) [Fe6Cl6(L3)6]+.
Anal. calcd (%) for C60H114Cl6Fe6N6O12 (1659.40): C 43.43, H
6.92, N 5.06. Found: C 42.34, H 7.05, N 4.87.
Cl5(L3)6]+, 1303 (25) [Fe4Cl3(L3)4]+. Anal. Calcd (%) for C90H102
-
Cl6Fe6N6O12 (2007.67): C 53.84, H 5.12, N 4.19. Found: C 53.63,
H 5.19, N 4.26.
[Fe6Cl6(L3)6] (5h). Educt: 4h (736 mg). Yield: 446 mg (39%)
yellow crystals from chloroform/diethyl ether. Mp >240 °C (dec).
IR (KBr): ν˜ ) 3021, 2863, 2256, 1083, 758 cm-1. FAB-MS (3-
NBA): m/z (%) ) 2008 (25) [Fe6Cl6(L3)6]+, 1971 (40) [Fe6Cl5-
[Fe6Cl6(L3)6] (5q). Educt: 4q (568 mg). Yield: 176 mg (21%)
yellow rhombic crystals from chloroform/n-pentane. Mp >220 °C
(dec). IR (KBr): ν˜ ) 2956, 2927, 2859, 1458, 1089 cm-1. FAB-
MS (3-NBA): m/z (%) ) 1671 (29) [Fe6Cl6(L3)6]+, 1636 (94) [Fe6-
(L3)6]+, 1303 (100) [Fe4Cl3(L3)4]+. Anal. Calcd (%) for C90H102
-
Cl6Fe6N6O12 (2007.67): C 53.84, H 5.12, N 4.19. Found: C 53.45,
H 5.09, N 4.19.
Cl5(L3)6]+, 1483 (100) [Fe6Cl6(L3)5]+. Anal. Calcd (%) for C60H126
-
[Fe6Cl6(L3)6] (5i). Educt: 4i (973 mg). Yield: 760 mg (41%)
yellow rhombic crystals from chloroform/n-pentane. Mp >200 °C
Cl6Fe6N6O12 (1671.50): C 43.12, H 7.60, N 5.03. Found: C 43.46,
H 7.66, N 5.06.
(dec). IR (KBr): ν˜ ) 3443, 2906, 2865, 1493, 1086, 754, 698 cm-1
.
[Fe6Cl6(L3)6] (5r). Educt: 4r (652 mg). Yield: 166 mg (18%)
yellow rhombic crystals from chloroform/n-pentane. Mp >220
FAB-MS (3-NBA): m/z (%) ) 2483 (15) [Fe6Cl6(L3)6]+, 2444 (20)
[Fe6Cl5(L3)6]+, 2160 (100) [Fe6Cl6(L3)5]+, 1619 (40) [Fe4Cl3(L3)4]+.
Anal. Calcd (%) for C120H132Cl6Fe6N6O12 (2482.30): C 58.06, H
5.36, N 6.77. Found: C 58.33, H 5.28, N 6.89.
°C (dec). IR (KBr): ν˜ ) 3005, 2924, 2855, 1468, 1089 cm-1
.
FAB-MS (3-NBA): m/z (%) ) 1837 (64) [Fe6Cl6(L3)6]+, 1802
(100) [Fe6Cl5(L3)6]+. Anal. Calcd (%) for C72H150Cl6Fe6N6O12
(1839.82): C 47.00, H 8.22, N 4.57. Found: C 45.71, H 8.12, N
4.37.
[Fe6Cl6(L3)6] (5j). Educt: 4j (664 mg). Yield: 205 mg (22%)
yellow rhombic crystals from chloroform/n-pentane. Mp >220 °C
(dec). IR (KBr): ν˜ ) 2974, 2905, 2867, 1458, 1440, 1143, 1088
cm-1. FAB-MS (3-NBA): m/z (%) ) 1863 (12) [Fe6Cl6(L3)6]+,
1827 (100) [Fe6Cl5(L3)6]+, 1792 (6) [Fe6Cl4(L3)6]+. Anal. Calcd
(%) for C60H138Cl6Fe6N6O24 (1863.49): C 38.67, H 6.49, N 5.24.
Found: C 46.20, H 8.42, N 5.24.
[Fe6(SCN)6(L3)6] (5k). Educt: 4k (808 mg). Yield: 332 mg
(29%) brown rhombic crystals from dichloromethane/n-pentane. Mp
117 °C.21 IR (KBr): ν˜ ) 2930, 2870, 2046, 1248, 1082 cm-1; FAB-
[Fe6Cl6(L3)6] (5s). Educt: 4s (736 mg). Yield: 440 mg (36%)
yellow crystals from dichloromethane/n-pentane. Mp >240 °C
(dec). IR (KBr): ν˜ ) 3354, 2926, 2854, 1469, 1082 cm-1. FAB-
MS (3-NBA): m/z (%) ) 2091 (50) [Fe6Cl6(L3)6]+, 2055 (85) [Fe6-
Cl5(L3)6]+, 1833 (80) [Fe6Cl6(L3)5]+, 1485 (100) [Fe3Cl3(L3)4]+.
Anal. Calcd (%) for C84H174Cl6Fe6N6O12 (2008.18): C 50.24, H
8.73, N 4.19. Found: C 51.59, H 8.88, N 4.16.
Inorganic Chemistry, Vol. 43, No. 14, 2004 4381

Saalfrank et al.
[Fe6(SCN)6(L3)6] (5t). Educt: 4t (736 mg). Yield: 160 mg (30%)
pink crystals from dichloromethane/n-pentane. Mp >240 °C (dec).
IR (KBr): ν˜ ) 3440, 2925, 2855, 2247, 1084, 609 cm-1. FAB-
MS (3-NBA): m/z (%) ) 2141 (10) [Fe6(SCN)6(L3)6]+, 2085 (55)
[Fe6(SCN)5(L3)6]+, 1427 (80) [Fe4(SCN)4(L3)4]+, 1370 (65) [Fe4-
(SCN)3(L3)4]+, 1312 (70) [Fe4(SCN)2(L3)4]+. Anal. Calcd (%) for
C90H174Fe6N12O12S6 (2143.60): C 50.43, H 8.18, N 7.84, S 8.96.
Found: C 50.68, H 8.19, N 7.93, S 9.04.
[Fe6Cl6(L3)6] (5y). Educt: 4y (922 mg). Yield 619 mg (52%)
yellow rhombic crystals from dichloromethane/n-pentane. Mp
>255 °C (dec). IR (KBr): ν˜ ) 2910, 2865, 1596, 1167, 1086 cm-1
.
FAB-MS (3-NBA): m/z (%) ) 2380 (3) [Fe6Cl6(L3)6]+, 2343 (3)
[Fe6Cl5(L3)6]+, 2073 (3) [Fe6Cl6(L3)5]+, 1551 (35) [Fe4Cl3(L3)4]+,
1281 (30) [Fe4Cl4(L3)3]+, 1154 (55) [Fe3Cl2(L3)3]+, 1118 (55) [Fe3-
Cl(L3)3]+, 848 (60) [Fe3Cl2(L3)3]+, 813 (90) [Fe3Cl(L3)3]+, 757 (100)
[Fe2Cl(L3)2]+, 722 (60) [Fe2(L3)2]+. Anal. Calcd (%) for C102H138
-
[Fe6Cl6(L3)6] (5u). Educt: 4u (532 mg). Yield: 144 mg (18%)
yellow rhombic crystals from chloroform/n-pentane. Mp >220 °C
(dec). IR (KBr): ν˜ ) 2971, 2928, 2904, 2865, 1485, 1442, 1104,
1087 cm-1. FAB-MS (3-NBA): m/z (%) ) 1599 (26) [Fe6Cl6-
(L3)6]+, 1563 (100) [Fe6Cl5(L3)6]+, 1422 (24) [Fe6Cl6(L3)5]+. Anal.
Calcd (%) for C48H102Cl6Fe6N6O12 (1599.55): C 36.04, H 7.18, N
5.25. Found: C 32.60, H 5.86, N 4.42.
Cl6Fe6N6O24 (2380.00): C 51.47, H 5.84, N 3.53. Found: C 49.75,
H 5.67, N 3.33.
Single-Crystal X-ray Structure Analyses. Final crystallographic
data and R1 and wR2 values are listed in Table 1. X-ray data for
all complexes were collected at low temperatures with a Nonius
KappaCCD area detector, a Siemens-P4 diffractometer, or a Nonius
MACH3 diffractometer using graphite monochromated Mo KR
radiation (λ ) 0.71073 Å). The structures were solved by direct
methods using SHELXS-86 or SHELXS-97, and the structure
refinements were carried out using full-matrix least-squares
(SHELXL-93, SHELXL-97, or SHELXTL NT 5.1013,14). All non-
hydrogen atoms were refined anisotropically.
[Fe6Cl6(L3)6] (5v). Educt: 4v (940 mg). Yield: 519 mg (43%)
yellow rhombic crystals from chloroform/diethyl ether. Mp 118
°C.21 IR (KBr): ν˜ ) 2910, 2870, 1598, 1493, 1248, 1087 cm-1
.
FAB-MS (3-NBA): m/z (%) ) 2416 (1) [Fe6Cl6(L3)6]+, 2379 (5)
[Fe6Cl5(L3)6]+, 1575 (10) [Fe4Cl3(L3)4]+, 825 (45) [Fe3Cl(L3)2]+,
769 (100) [Fe2Cl(L3)2]+. Anal. Calcd (%) for C96H150Cl6Fe6N6O30
(2416.02): C 47.72, H 6.62, N 3.48. Found: C 47.34, H 6.49, N
3.48.
Acknowledgment. This work was supported by the
Deutsche Forschungsgemeinschaft (Sa 276/25-1, SFB 583,
GK 312, SPP 1137), the Bayerisches Langzeitprogrammm
Neue Werkstoffe, and the Fonds der Chemischen Industrie.
T.N. thanks the Alexander von Humboldt-Stiftung for a
postdoctoral fellowship. The generous allocation of X-ray
facilities by Professor D. Sellmann, Institut fu¨r Anorganische
Chemie, Universita¨t Erlangen-Nu¨rnberg, is also gratefully
acknowledged.
[Fe6Cl6(L3)6] (5w). Educt: 4w (958 mg). Yield: 1.02 g (80%)
yellow rhombic crystals from chloroform/n-pentane. Mp >195 °C
(dec). IR (KBr): ν˜ ) 2932, 2863, 1102, 1088 cm-1. FAB-MS (3-
NBA): m/z (%) ) 1266 (100) [Fe3Cl3(L3)3]+. Anal. Calcd (%) for
C108H138Cl6Fe6N6O24 (2452.04): C 52.90, H 5.67, N 3.43. Found:
C 51.72, H 5.20, N 3.18.
[Fe6Cl6(L3)6] (5x). Educt: 4x (1.11 g). Yield: 317 mg (23%)
yellow rhombic crystals from dichloromethane/diethyl ether. Mp
100 °C.21 IR (KBr): ν˜ ) 2914, 2867, 1088 cm-1. FAB-MS (3-
NBA): m/z (%) ) 2717 (2) [Fe6Cl5(L3)6]+, 1800 (5) [Fe4Cl3(L3)4]+,
1467 (5) [Fe4Cl4(L3)3]+, 1339 (5) [Fe3Cl2(L3)3]+, 972 (15) [Fe3Cl-
(L3)2]+, 937 (40) [Fe3(L3)2]+, 881 (100) [Fe2(L3)2]+. Anal. Calcd
(%) for C132H150Cl6Fe6N6O24 (2752.42): C 57.60, H 5.49, N 3.05.
Found: C 57.21, H 5.51, N 3.05.
Supporting Information Available: X-ray crystallographic data
in CIF format. This material is available free of charge via the
Internet at http://pubs.acs.org.
IC049799W
4382 Inorganic Chemistry, Vol. 43, No. 14, 2004