Bis(4-hydroxybenzoato-O)(1,4,8,11-tetraazacyclotetradecane-κ 4N)-nickel(II): A three-dimensional framework built from O - H. . .O and N - H. . .O hydrogen bonds

Full text of DOI:10.1107/S0108270199014249

metal-organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
III conformation of the macrocyclic ligand is retained (Ito et
al., 1984; Mochizuki & Kondo, 1995; Choi et al., 1999) or
mutually cis when the macrocycle is necessarily heavily folded
(Whimp et al., 1970; Curtis et al., 1973; Bare®eld, Bianchi et al.,
1986). Entirely similar properties are exhibited by the tetra-C-
methyl derivative of cyclam (Hay et al., 1982; Bare®eld,
Freeman & Van Derveer, 1986; Hambley, 1986) con®rming
that the behaviour of the macrocycle is independent of the
degree of C-methyl substitution.
In view of both the con®gurational versatility of a cation
such as [Ni(cyclam)]2+ and the great structural diversity of the
metal-free macrocycles in supramolecular chemistry
(Ferguson et al., 1998, 1999; Gregson et al., 2000; Lough et al.,
2000), it is of interest to investigate the behaviour of [Ni(cy-
clam)]2+ with oxygen-containing hydrogen-bond donors which
themselves contain suf®cient additional hydrogen-bonding
capacity to generate supramolecular aggregates. Anionic
ligands L could, in principle, be attached to the [Ni(cyclam)]2+
cation either via NiÐL coordinate bonds, via NÐHÁ Á ÁL
hydrogen bonds or by some combination of the two, thus
affording the possibility of either square-planar or octahedral
NiII. We report here the structural characterization of one
such adduct, [Ni(C10H24N4)]2+Á2[(HOC6H4COO) ], (I),
formed with 4-hydroxybenzoic acid.
ISSN 0108-2701
Bis(4-hydroxybenzoato-O)(1,4,8,11-
tetraazacyclotetradecane-j4N)-
nickel(II): a three-dimensional frame-
work built from OÐHÁ Á ÁO and
NÐHÁ Á ÁO hydrogen bonds
Christopher Glidewell,a* George Ferguson,b Richard M.
Gregsona and Alan J. Loughc
aSchool of Chemistry, University of St Andrews, St Andrews, Fife KY16 9ST,
Scotland, bDepartment of Chemistry and Biochemistry, University of Guelph,
Guelph, Ontario, Canada N1G 2W1, and cLash Miller Chemical Laboratories,
University of Toronto, Toronto, Ontario, Canada M5S 3H6
Correspondence e-mail: cg@st-andrews.ac.uk
Received 22 October 1999
Accepted 4 November 1999
The title compound, [Ni(C7H5O3)2(C10H24N4)], contains
octahedral NiII in a centrosymmetric trans con®guration with
Ê
NiÐN distances of 2.0637 (17) and 2.0699 (16) A and an NiÐ
Ê
O distance of 2.1100 (14) A. The molecules are linked by a
Ê
single type of OÐHÁ Á ÁO hydrogen bond [OÁ Á ÁO 2.618 (2) A
and OÐHÁ Á ÁO 161ꢁ] into two-dimensional sheets; a single
Ê
type of NÐHÁ Á ÁO hydrogen bond [NÁ Á ÁO 2.991 (2) A and
NÐHÁ Á ÁO 139ꢁ] links these sheets into a three-dimensional
framework.
In compound (I), the Ni atom adopts a trans-octahedral
con®guration (Fig. 1) with 4-hydroxybenzoate anions acting as
the axial ligands. The molecules lie across centres of inversion
in P21/n giving a pseudo-I arrangement of Ni atoms. The axial
4-hydroxybenzoate ligands bind to the metal in only a
monodentate fashion, although they are also connected to the
cyclam ligand by means of NÐHÁ Á ÁO hydrogen bonds (Fig. 1
and Table 2), so generating a novel S(6) synthon (Bernstein et
Comment
The tetraaza macrocycles 1,4,8,11-tetraazacyclotetradecane
(cyclam, C10H24N4) and its hexa-C-methyl analogue
5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane
[tet-a (meso form) and tet-b (racemic), C16H36N4] form
adducts with oxygen-containing hydrogen-bond donors which
exhibit
a wide range of supramolecular architectures
(Ferguson et al., 1998, 1999; Gregson et al., 2000; Lough et al.,
2000). However, despite the great structural variety exhibited
by these adducts, a common feature is the formation by double
proton capture of the dications (C10H26N4)2+ and
(C16H38N4)2+ in which two protons are held within the N4
cavity by means of NÐHÁ Á ÁN hydrogen bonds. Associated
with this intramolecular constraint is the adoption by the
macrocycles of the fairly rigid and nearly planar trans-III
conformation (Bare®eld, Bianchi et al., 1986).
Both of these macrocycles form nickel(II) complexes in
which the coordination of the metal may be either square
planar (Prasad & McAuley, 1983; Bare®eld, Bianchi et al.,
1986; Adam et al., 1991) or, in the presence of two additional
ligands, octahedral; in the octahedral complexes, the two
additional ligand sites may be mutually trans when the trans-
Figure 1
A view of (I) showing the atom-labelling scheme. Displacement ellipsoids
are drawn at the 30% probability level.
ꢀ
174 Christopher Glidewell et al. [Ni(C7H5O3)2(C10H24N4)]
Acta Cryst. (2000). C56, 174±176

metal-organic compounds
are four axial NÐH bonds which are almost normal to the
mean plane of the macrocycle, two on each face. One
symmetry-related pair of these bonds is engaged in forming
intramolecular NÐHÁ Á ÁO hydrogen bonds; the other pair
forms intermolecular NÐHÁ Á ÁO hydrogen bonds. In the
anion, the carboxylate group is twisted out of the plane of the
aryl ring by 8.2 (2)ꢁ.
A combination of OÐHÁ Á ÁO and NÐHÁ Á ÁO hydrogen
bonds (Table 2) links the neutral molecules (Fig. 1) into a
continuous three-dimensional framework. It simpli®es
considerably the structural description if the effects of the OÐ
HÁ Á ÁO and NÐHÁ Á ÁO hydrogen bonds are treated separately.
A single type of intermolecular OÐHÁ Á ÁO hydrogen bond
serves to link the molecules into two-dimensional nets lying
ꢀ
parallel to the (101) plane (Fig. 2) and built from a single type
Figure 2
Part of the crystal structure of (I) showing the formation of a (101) sheet
of centrosymmetric R44(40) ring. The hydroxyl O14 at (x, y, z)
acts as donor to the carboxylate O12 at (12 + x, 23 y, 21 + z), so
producing a C(8) chain parallel to the [101] direction and
generated by the glide plane; the action of the centres of
inversion upon these chains generates the two-dimensional
ꢀ
built from R44(40) rings.
al., 1995; Desiraju, 1995). By contrast, in the salt formed
between the trans-[Ni(cyclam)(H2O)2]2+ cation and the tri-
anion of benzene-1,3,5-tricarboxylic acid, the cations and
anions are linked solely by OÐHÁ Á ÁO hydrogen bonds in
which water ligands act as hydrogen-bond donors (Choi et al.,
1999). It is noteworthy that in both the cations [Ni(tet-
b)OCOCH3]+ (Whimp et al., 1970) and [Ni(tet-a)(acac)]+
(Curtis et al., 1973) [(acac) = (CH3COCHCOCH3) ] the
oxygen ligands are each bound to Ni in a bidentate fashion so
that the two O sites are mutually cis and the macrocycle is
folded; indeed the [Ni(tet-a)(acac)]+ cations lie on twofold
rotation axes. On the other hand, when H2O molecules act as
the additional ligands, both cis (folded) and trans (planar)
con®gurations of the cation [Ni(cyclam)(H2O)2]2+ can be
observed (Bare®eld, Bianchi et al., 1986; Mochizuki & Kondo,
1995; Choi et al., 1999).
The NiÐN distances in (I) (Table 1) are typical of those
observed in octahedral NiII complexes of cyclam and its C-
methyl derivatives (Whimp et al., 1970; Curtis et al., 1973; Hay
et al., 1982; Ito et al., 1984; Bare®eld, Bianchi et al., 1986;
Bare®eld, Freeman & Van Derveer, 1986; Hambley, 1986;
Mochizuki & Kondo, 1995; Choi et al., 1999), but signi®cantly
shorter than those observed in the square-planar systems
(Prasad & McAuley, 1983; Bare®eld, Bianchi et al., 1986;
Adam et al., 1991). The unique NiÐO distance in (I) is a little
shorter than those observed in [Ni(cyclam)(H2O)2]2+ cations.
In the chloride salt of the cis isomer, the values are 2.130 (2)
net. The molecule centred at (12, , ) is a donor of OÐHÁ Á ÁO
1
1
2
2
hydrogen bonds to the pair of molecules centred at (0,0,0) and
(1,1,1), and an acceptor of OÐHÁ Á ÁO hydrogen bonds from
the molecules centred at (0,1,0) and (1,0,1). Just one net of this
type is suf®cient to account for all the unit-cell contents.
The continuous stack of parallel nets is linked into a three-
dimensional framework by chains running parallel to the [100]
direction; N4 at (x, y, z) acts as donor to the hydroxylic O14 at
( 1 + x, y, z) and propagation of this interaction by the space
group generates a C(10)[R22(20)] chain-of-rings (Bernstein et
1 1
2 2
al., 1995), where the rings are centred at (n, , ) (n = zero or
integer) (Fig. 3). Thus, just two types of intermolecular
hydrogen bond serve to link all the molecules into a single
supramolecular aggregate. Although the aryl ring planes of
the 4-hydroxybenzoate ligands in neighbouring molecules are
Ê
separated by only ca 3.59 A, the centroid offset effectively
precludes the occurrence of any aromatic ꢀÁ Á Áꢀ stacking
interactions between these rings.
The orange±brown colour of (I) is that commonly asso-
ciated with diamagnetic square-planar NiII, although in (I) the
coordination of the Ni is metrically octahedral. The Angular
Overlap Model (Burdett, 1980) readily shows that spin-pairing
in metrically octahedral d8 complexes of type trans-MX4Y2 is
possible, provided only that the ligand-®eld characteristics of
Ê
and 2.140 (1) A (Bare®eld, Bianchi et al., 1986) and for the
centrosymmetric trans isomer the unique NiÐO distance is
Ê
2.176 (2) A in the chloride salt (Mochizuki & Kondo, 1995)
Ê
and 2.160 (3) A in the benzene-1,3,5-tricarboxylate salt (Choi
et al., 1999). The shorter bond in (I) possibly arises from the
anionic nature of the axial ligand; this is supported by the NiÐ
O distances in the acetato complex [Ni(tet-b)OCOCH3]+
Ê
[2.103 (9) and 2.116 (9) A; Whimp et al., 1970].
Within the macrocyclic ligand, the torsional angles (Table 1)
indicate almost perfect staggering about all the CÐC and CÐ
N bonds, as expected for the trans-III conformation (Bare-
®eld, Bianchi et al., 1986); as usual in this conformation, there
Figure 3
Part of the crystal structure showing the C(10)[R22(20)] chain-of-rings
parallel to the [100] direction.
ꢀ
Acta Cryst. (2000). C56, 174±176
Christopher Glidewell et al. [Ni(C7H5O3)2(C10H24N4)] 175

metal-organic compounds
Table 2
Hydrogen-bonding geometry (A, ).
the equatorial and axial ligands X and Y are suf®ciently
different.
ꢁ
Ê
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
Experimental
N1ÐH1Á Á ÁO12
N4ÐH4Á Á ÁO14i
O14ÐH14Á Á ÁO12ii
0.93
0.93
0.84
2.06
2.23
1.81
2.909 (2)
2.991 (2)
2.618 (2)
152
139
161
Stoichiometric quantities of [Ni(cyclam)](ClO4)2 and the sodium salt
of 4-hydroxybenzoic acid were separately dissolved in water. The
solutions were mixed and set aside to crystallize, producing orange±
brown crystals of compound (I). Analysis: found C 54.0, H 6.2, N
10.4%; C24H34N4NiO6 requires C 54.0, H 6.4, N 10.5%. Crystals
suitable for single-crystal X-ray diffraction were selected directly
from the analytical sample.
Symmetry codes: (i) x 1; y; z; (ii) ‡ x; 32 y; 21 ‡ z.
1
2
All H atoms were clearly resolved in difference maps and were
treated as riding atoms in the re®nement with CÐH 0.95 and 0.99,
Ê
NÐH 0.93 and OÐH 0.84 A.
Data collection: KappaCCD Server Software (Nonius, 1997); cell
re®nement: DENZO-SMN (Otwinowski & Minor, 1997); data
reduction: DENZO-SMN; program(s) used to solve structure:
Patterson heavy-atom method and SHELXL97 (Sheldrick, 1997);
program(s) used to re®ne structure: SHELXL97; molecular graphics:
ORTEPII (Johnson, 1976) and PLATON (Spek, 1999); software used
to prepare material for publication: SHELXL97 and WordPerfect
macro PRPKAPPA (Ferguson, 1999).
Crystal data
3
[Ni(C7H5O3)2(C10H24N4)]
Mr = 533.26
Dx = 1.488 Mg m
Mo Kꢂ radiation
Cell parameters from 2696
re¯ections
Monoclinic, P21=n
Ê
a = 10.8397 (6) A
ꢃ = 2.76±27.56ꢁ
ꢄ = 0.864 mm
T = 100 (1) K
Ê
b = 8.7317 (6) A
1
Ê
c = 12.8670 (9) A
ꢁ = 102.160 (4)ꢁ
V = 1190.52 (13) A
Z = 2
3
Ê
Plate, orange±brown
0.40 Â 0.35 Â 0.10 mm
X-ray data were collected at the University of Toronto using
a Nonius KappaCCD diffractometer purchased with funds
from NSERC Canada. RMG thanks EPSRC (UK) for ®nan-
cial support.
Data collection
KappaCCD diffractometer
' and ! scans with ꢅ offset scans
Absorption correction: multi-scan
(DENZO-SMN; Otwinowski &
Minor, 1997)
Tmin = 0.724, Tmax = 0.919
19 420 measured re¯ections
2696 independent re¯ections
2124 re¯ections with I > 2ꢆ(I)
Rint = 0.040
ꢃ
max = 27.56ꢁ
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: SK1344). Services for accessing these data are
described at the back of the journal.
h = 0 ! 14
k = 0 ! 11
l = 16 ! 16
Intensity decay: negligible
References
Re®nement
Adam, K. R., Antolovich, M., Brigden, L. G., Leong, A. J., Lindoy, L. F.,
Baillie, P. J., Uppal, D. K., McPartlin, M., Shah, B., Proserpio, D., Fabbrizzi,
L. & Tasker, P. A. (1991). J. Chem. Soc. Dalton Trans. pp. 2493±2501.
Bare®eld, E. K., Bianchi, A., Billo, E. J., Connolly, P. J., Paoletti, P., Summers,
J. S. & Van Derveer, D. G. (1986). Inorg. Chem. 25, 4197±4202.
Bare®eld, E. K., Freeman, G. M. & Van Derveer, D. G. (1986). Inorg. Chem.
25, 552±558.
Re®nement on F2
R[F2 > 2ꢆ(F2)] = 0.039
wR(F2) = 0.089
S = 1.027
2696 re¯ections
w = 1/[ꢆ2(Fo2) + (0.0304P)2
+ 0.7434P]
where P = (Fo2 + 2Fc2)/3
(Á/ꢆ)max < 0.001
3
Ê
Áꢇmax = 0.411 e A
3
Ê
0.405 e A
161 parameters
H-atom parameters constrained
Áꢇmin
=
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem.
Int. Ed. Engl. 34, 1555±1573.
Burdett, J. K. (1980). In Molecular Shapes. New York: Wiley.
Choi, H. J., Lee, T. S. & Suh, M. P. (1999). Angew. Chem. Int. Ed. Engl. 38,
1405±1408.
Table 1
Selected geometric parameters (A, ).
Curtis, N. F., Swann, D. A. & Waters, T. N. (1973). J. Chem. Soc. Dalton Trans.
pp. 1408±1413.
ꢁ
Ê
Desiraju, G. R. (1995). Angew. Chem. Int. Ed. Engl. 34, 2311±2327.
Ferguson, G. (1999). PRPKAPPA. University of Guelph, Canada.
Ferguson, G., Glidewell, C., Gregson, R. M. & Meehan, P. R. (1998). Acta
Cryst. B54, 139±150.
Ferguson, G., Gregson, R. M. & Glidewell, C. (1999). Acta Cryst. C55, 815±817.
Gregson, R. M., Glidewell, C., Ferguson, G. & Lough, A. J. (2000). Acta Cryst.
B56. In the press.
Hambley, T. W. (1986). J. Chem. Soc. Dalton Trans. pp. 565±569.
Hay, R. W., Jeragh, B., Ferguson, G., Kaitner, B. & Ruhl, B. L. (1982). J. Chem.
Soc. Dalton Trans. pp. 1531±1539.
Ni1ÐN1
Ni1ÐN4
2.0699 (16)
2.0637 (17)
2.1100 (14)
1.263 (2)
1.265 (2)
1.373 (2)
1.503 (3)
N1ÐC2
C2ÐC3
C3ÐN4
N4ÐC5
C5ÐC6
C6ÐC7
C7ÐN1i
1.474 (3)
1.525 (3)
1.474 (3)
1.478 (3)
1.524 (3)
1.520 (3)
1.478 (3)
Ni1ÐO11
O11ÐC17
O12ÐC17
O14ÐC14
C11ÐC17
Ito, T., Kato, M. & Ito, H. (1984). Bull. Chem. Soc. Jpn, 57, 2641±2649.
Johnson, C. K. (1976). ORTEPII. Report ORNL-5138. Oak Ridge National
Laboratory, Tennessee, USA.
Lough, A. J., Gregson, R. M., Ferguson, G. & Glidewell, C. (2000). Acta Cryst.
B56. In the press.
Mochizuki, K. & Kondo, T. (1995). Inorg. Chem. 34, 6241±6243.
Nonius (1997). KappaCCD Server Software. Windows 3.11. Nonius BV, Delft,
The Netherlands.
N1ÐNi1ÐN4
85.29 (7)
86.29 (6)
92.07 (6)
121.63 (19)
118.23 (19)
124.62 (18)
116.78 (18)
118.54 (18)
C7iÐN1ÐC2
N1ÐC2ÐC3
C2ÐC3ÐN4
C3ÐN4ÐC5
N4ÐC5ÐC6
C5ÐC6ÐC7
C6ÐC7ÐN1i
113.82 (16)
108.76 (17)
108.61 (17)
113.27 (16)
111.15 (17)
115.98 (18)
112.03 (17)
N1ÐNi1ÐO11i
N4ÐNi1ÐO11
O14ÐC14ÐC13
O14ÐC14ÐC15
O11ÐC17ÐO12
O11ÐC17ÐC11
O12ÐC17ÐC11
Otwinowski, Z. & Minor, W. (1997). Methods Enzymol. 276, 307±326.
Prasad, L. & McAuley, A. (1983). Acta Cryst. C39, 1175±1177.
È
Sheldrick, G. M. (1997). SHELXL97. University of Gottingen, Germany.
Spek, A. L. (1999). PLATON. Version of October 1999. University of Utrecht,
The Netherlands.
Whimp, P. O., Bailey, M. F. & Curtis, N. F. (1970). J. Chem. Soc. A, pp. 1956±
1963.
C7iÐN1ÐC2ÐC3
N1ÐC2ÐC3ÐN4
C2ÐC3ÐN4ÐC5
C3ÐN4ÐC5ÐC6
169.9 (2)
56.4 (2)
169.7 (2)
179.9 (2)
N4ÐC5ÐC6ÐC7
C5ÐC6ÐC7ÐN1i
C6ÐC7ÐN1iÐC2i
71.6 (2)
71.4 (2)
178.5 (2)
Symmetry code: (i) 1 x; 1 y; 1 z.
ꢀ
176 Christopher Glidewell et al. [Ni(C7H5O3)2(C10H24N4)]
Acta Cryst. (2000). C56, 174±176