Three-dimensional hydrogen-bonded supra-molecular assembly in tetrakis-(1,3,5-triaza-7-phosphaadamantane)copper(I) chloride hexa-hydrate.

Abstract

The structure of the title compound, [Cu(PTA)(4)]Cl·6H(2)O (PTA is 1,3,5-triaza-7-phosphaadamantane, C(6)H(12)N(3)P), is composed of discrete monomeric [Cu(PTA)(4)](+) cations, chloride anions and uncoordinated water mol-ecules. The Cu(I) atom exhibits tetra-hedral coordination geometry, involving four symmetry-equivalent P-bound PTA ligands. The structure is extended to a regular three-dimensional supra-molecular framework via numerous equivalent O-H⋯N hydrogen bonds between all solvent water mol-ecules (six per cation) and all PTA N atoms, thus simultaneously bridging each [Cu(PTA)(4)](+) cation with 12 neighbouring units in multiple directions. The study also shows that PTA can be a convenient ligand in crystal engineering for the construction of supra-molecular architectures.

Full text

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Three-dimensional hydrogen-bonded
supramolecular assembly in tetrakis-
(1,3,5-triaza-7-phosphaadamantane)-
copper(I) chloride hexahydrate
Alexander M. Kirillov,aPiotr Smolen ´ski,aM. Fa ´tima C.
Guedes da Silva,a,b* Maximilian N. Kopylovichaand
Armando J. L. Pombeiroa
aCentro de Quı ´mica Estrutural, Complexo Interdisciplinar, Instituto Superior Te ´cnico,
TU Lisbon, Av. Rovisco Pais, 1049-001 Lisbon, Portugal, andbUniversidade
Luso ´fona de Humanidades e Tecnologias, ULHT Lisbon, Av. do Campo Grande 376,
1749-024 Lisbon, Portugal
Correspondence e-mail: fatima.guedes@ist.utl.pt
Received 22 March 2008; accepted 26 March 2008
Key indicators: single-crystal X-ray study; T = 150 K; mean ?(N–C) = 0.003 A ˚;
R factor = 0.034; wR factor = 0.093; data-to-parameter ratio = 16.0.
The structure of the title compound, [Cu(PTA)4]Cl?6H2O
(PTA is 1,3,5-triaza-7-phosphaadamantane, C6H12N3P), is
composed of discrete monomeric [Cu(PTA)4]+
chloride anions and uncoordinated water molecules. The CuI
atom exhibits tetrahedral coordination geometry, involving
four symmetry-equivalent P–bound PTA ligands. The struc-
ture is extended to a regular three-dimensional supra-
molecular framework via numerous equivalent O—H???N
hydrogen bonds between all solvent water molecules (six per
cation) and all PTA N atoms, thus simultaneously bridging
each [Cu(PTA)4]+cation with 12 neighbouring units in
multiple directions. The study also shows that PTA can be a
convenient ligand in crystal engineering for the construction
of supramolecular architectures.
cations,
Related literature
For general background, see: Kirillov et al. (2007, 2008);
Karabach et al. (2006); Di Nicola et al. (2007). For a compre-
hensive review of PTA chemistry, see: Phillips et al. (2004). For
PTA-derived polymeric networks, see: Lidrissi et al. (2005);
Frost et al. (2006); Mohr et al. (2006). For related compounds,
see: Forward et al. (1996); Darensbourg et al. (1997, 1999).
Experimental
Crystal data
[Cu(C6H12N3P)4]Cl?6H2O
Mr= 835.71
Cubic, Fd3m
a = 19.795 (4) A˚
V = 7757 (3) A˚3
Z = 8
Mo K? radiation
? = 0.85 mm?1
T = 150 (2) K
0.20 ? 0.17 ? 0.12 mm
Data collection
Bruker APEXII CCD area-detector
diffractometer
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
Tmin= 0.848, Tmax= 0.905
3022 measured reflections
447 independent reflections
361 reflections with I > 2?(I)
Rint= 0.049
Refinement
R[F2> 2?(F2)] = 0.034
wR(F2) = 0.092
S = 1.08
447 reflections
28 parameters
H-atom parameters constrained
??max= 0.75 e A˚?3
??min= ?0.32 e A˚?3
Table 1
Hydrogen-bond geometry (A˚,?).
D—H???A
O10—H10???N1
D—HH???AD???AD—H???A
0.812.042.843 (3)174
Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT
(Bruker, 2004); data reduction: SAINT; program(s) used to solve
structure: SIR97 (Altomare et al., 1999); program(s) used to refine
structure:SHELXL97(Sheldrick,
ORTEPIII (Burnett & Johnson, 1996), PLATON (Spek, 2003) and
Mercury (Macrae et al., 2006); software used to prepare material for
publication: SHELXL97.
2008);moleculargraphics:
This work has been supported by the FCT, Portugal, and its
POCI 2010 programme (FEDER funded).
Supplementary data and figures for this paper are available from the
IUCr electronic archives (Reference: DN2329).
metal-organic compounds
Acta Cryst. (2008). E64, m603–m604doi:10.1107/S1600536808008179 Kirillov et al.
m603
Acta Crystallographica Section E
Structure Reports
Online
ISSN 1600-5368

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(2007). Eur. J. Inorg. Chem. pp. 2686–2692.
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3154.
Phillips, A. D., Gonsalvi, L., Romerosa, A., Vizza, F. & Peruzzini, M. (2004).
Coord. Chem. Rev. 248, 955–993.
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metal-organic compounds
m604
Kirillov et al.
? [Cu(C6H12N3P)4]Cl?6H2O
Acta Cryst. (2008). E64, m603–m604

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Acta Cryst. (2008). E64, m603-m604 [ doi:10.1107/S1600536808008179 ]
Three-dimensional hydrogen-bonded supramolecular assembly in tetrakis(1,3,5-triaza-7-
phosphaadamantane)copper(I) chloride hexahydrate
A. M. Kirillov, P. Smolenski, M. F. C. Guedes da Silva, M. N. Kopylovich and A. J. L. Pombeiro
Comment
1,3,5-triaza-7-phosphaadamantane (PTA) is a water soluble aminophosphine that has sparked recent interest in coordination
chemistry in view of the significance of transition metal PTA complexes in aqueous phase catalysis, photochemistry and
medicinal chemistry (Phillips et al., 2004). Besides, PTA and its derivatives can also be convenient building blocks for the
construction of polymeric networks (Lidrissi et al., 2005; Frost et al., 2006; Mohr et al., 2006) due to several potentially
available coordination sites, protonation ability of N atoms, and strong affinity towards hydrogen bonds. Nevertheless, the
use of PTA ligands in crystal design and engineering has remained little explored. Hence, in pursuit of our recent studies
directed towards the synthesis of new copper compounds including PTA complexes (Kirillov et al., 2007) and various
coordination polymers, supramolecular frameworks and host–guest systems with other ligands (Karabach et al., 2006; Di
Nicola et al., 2007; Kirillov et al., 2008), we have prepared compound (I) whose crystal structure and supramolecular
features are reported herein.
The moiety formula of (I) consists of the [Cu(PTA)4]+ cation (Fig. 1), one chloride anion and six symmetry equivalent
crystallization water molecules. The [Cu(PTA)4]+ unit possesses a very high symmetry, being generated from only five
symmetry nonequivalent atoms (Cu1, P1, N1, C1 and C2). The CuI atom lies on -43m site symmetry and its coordination
environment is filled by four equivalent P–bound PTA ligands, arranged in a perfect tetrahedral coordination geometry with
the corresponding P—Cu—P angles of 109.47 (2)°. The Cu—P bond distances of 2.2598 (6) Å as well as other bonding
parameters within the cage-like PTA cores are comparable to those reported for tetrahedral PTA complexes of Cu (Kirillov
et al., 2007), Au (Forward et al., 1996), Pt (Darensbourg et al., 1999) and Ni (Darensbourg et al., 1997).
An interesting feature of (I) consists in the extensive intermolecular hydrogen bonding that arises from only one type
of O-H···N H-bond (Table 1). Hence, each crystallization water molecule (O10) repeatedly acts as a double H-bond donor
bridging to two N1 atoms of two different [Cu(PTA)4]+ units. This results in the extensive interlinkage in multiple direc-
tions of every monomeric copper unit with twelve neighbouring ones (Fig. 2), thus leading to the formation of a regular
three-dimensional supramolecular framework (Fig. 3). That framework has the shortest Cu···Cu separation of 13.977 (1) Å
and possesses the repeating channels (ca 4.8 Å diameter) filled by water molecules.
Experimental
To the ethanolic solution (5 ml) of CuCl2 (27 mg, 0.20 mmol) was added solid PTA (126 mg, 0.80 mmol). The obtained
mixture was refluxed for 3 h resulting in a white suspension. This was filtered off and the colourless filtrate was left to
evaporate in a beaker in air and at ambient temperature. A small crop of the colourless X-ray quality crystals of (I) was
formed in several days. 1H NMR data are similar to those reported for [Cu(PTA)4]NO3 (Kirillov et al., 2007). FT–IR (KBr
pellet), cm-1: 3430 m, br and 3195 w [ν(H2O)], 2940 m and 2901 m [νas(C—H)], 2863 m and 2808 w [νs(C—H)], 1645 w

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br [δ(H2O)], 1437 m, 1413 m, 1365 m, 1296 s, 1242 s, 1180 m, 1105 m, 1037 w, 1015 s, 971 s, 906 w, 890 m, 808 s, 797 s,
744 m, 694 m, 670 w, 582 s, 551 w, 451 s, 406 m [PTA bands]. FAB-MS+ (m-nitrobenzylalcohol), m/z: 691 [Cu(PTA)4]+.
Refinement
All H atoms attached to C atoms were fixed geometrically and treated as riding with C—H = 0.97 Å and Uiso(H) = 1.2Ueq(C).
H atom of the water molecule were located in difference Fourier maps and included in the subsequent refinement using
restraint (O-H= 0.82 (1)Å) with Uiso(H) = 1.5Ueq(O). In the last stage of refinement,it was treated as riding on the O atom.
Figures
Fig. 1. Molecular view of the cation with the atom-labelling scheme. Displacement ellipsoids
are drawn at the 50% probability level. Hydrogen atoms are omitted for clarity. [Symmetry
codes: (i) z, x, y; (ii) y, z, x; (iii) -x+1/4, y, -z+1/4; (iv) -x+1/4, -y+1/4, z; (v) x, -y+1/4, -z+1/
4]
Fig. 2. Fragment of the crystal packing diagram of (I) showing the simultaneous multidimen-
sional interlinkage of the central monomeric [Cu(PTA)4]+ unit (black coloured) with twelve
neighbouring ones (each represented by different colour) via repeating O10—H10···N1 hy-
drogen bonding interactions (black dashed lines) between crystallization water molecules O10
(coloured balls) and PTA N1 atoms. H and Cl atoms are omitted for clarity.
Fig. 3. Fragment of the crystal packing diagram of (I) (view along the a axis) showing the ex-
tensive hydrogen bonding interactions (pale blue dashed lines) resulting in the formation of a
regular three-dimensional H-bonded supramolecular assembly. H atoms are omitted for clar-
ity. Cu, green; P, orange; N, blue; C, grey; O, red (balls); Cl, yellow (balls).
tetrakis(1,3,5-triaza-7-phosphaadamantane)copper(I) chloride hexahydrate
Crystal data
[Cu(C6H12N3P)4]Cl·6H2O
Mr = 835.71
Z = 8
F000 = 3536
Dx = 1.431 Mg m−3
Mo Kα radiation
λ = 0.71069 Å
Cell parameters from 743 reflections
θ = 2.9–27.0º
Cubic, Fd3m
Hall symbol: -F 4vw 2vw 3
a = 19.795 (4) Å
b = 19.795 (4) Å

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c = 19.795 (4) Å
µ = 0.85 mm−1
T = 150 (2) K
Prism, colourless
0.20 × 0.17 × 0.12 mm
α = 90º
β = 90º
γ = 90º
V = 7757 (3) Å3
Data collection
Bruker APEXII CCD area-detector
diffractometer
Radiation source: fine-focus sealed tube
Monochromator: graphite
T = 150(2) K
φ and ω scans
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
Tmin = 0.848, Tmax = 0.905
3022 measured reflections
447 independent reflections
361 reflections with I > 2σ(I)
Rint = 0.049
θmax = 27.0º
θmin = 2.9º
h = −24→23
k = −16→11
l = −6→25
Refinement
Refinement on F2
Secondary atom site location: difference Fourier map
Least-squares matrix: full
Hydrogen site location: inferred from neighbouring
sites
R[F2 > 2σ(F2)] = 0.034
H-atom parameters constrained
wR(F2) = 0.092
w = 1/[σ2(Fo2) + (0.0463P)2 + 19.2954P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max < 0.001
Δρmax = 0.75 e Å−3
Δρmin = −0.32 e Å−3
S = 1.08
447 reflections
28 parameters
Primary atom site location: structure-invariant direct
methods
Extinction correction: none
Special details
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The
cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds
in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used
for estimating esds involving l.s. planes.
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, convention-
al R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-
factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large
as those based on F, and R- factors based on ALL data will be even larger.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
xyz
Uiso*/Ueq
Occ. (<1)

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C1
H1A
H1B
C2
H2A
H2B
N1
Cu1
P1
Cl1
O10
H10
0.25075 (10)
0.2258
0.2818
0.33080 (15)
0.3607
0.3587
0.29002 (8)
0.1250
0.19090 (4)
0.3750
0.3750
0.3521
0.15137 (15)
0.1228
0.1228
0.24509 (11)
0.2726
0.2166
0.20160 (12)
0.1250
0.19090 (4)
0.3750
0.12300 (14)
0.1480
0.25075 (10)
0.2818
0.2258
0.24509 (11)
0.2726
0.2166
0.29002 (8)
0.1250
0.19090 (4)
0.3750
0.3750
0.3521
0.0199 (6)
0.024*
0.024*
0.0239 (7)
0.029*
0.029*
0.0212 (6)
0.0134 (3)
0.0156 (3)
0.0165 (5)
0.0240 (7)
0.036*
0.50
0.50
Atomic displacement parameters (Å2)
U11
0.0193 (8)
0.0193 (15)
0.0218 (8)
0.0134 (3)
0.0156 (3)
0.0165 (5)
0.0255 (10)
U22
0.0212 (14)
0.0262 (10)
0.0202 (13)
0.0134 (3)
0.0156 (3)
0.0165 (5)
0.0210 (16)
U33
0.0193 (8)
0.0262 (10)
0.0218 (8)
0.0134 (3)
0.0156 (3)
0.0165 (5)
0.0255 (10)
U12
−0.0005 (7)
−0.0036 (8)
−0.0019 (7)
0.000
−0.0009 (3)
0.000
0.000
U13
−0.0053 (11)
−0.0036 (8)
−0.0056 (10)
0.000
−0.0009 (3)
0.000
−0.0083 (12)
U23
−0.0005 (7)
−0.0027 (12)
−0.0019 (7)
0.000
−0.0009 (3)
0.000
0.000
C1
C2
N1
Cu1
P1
Cl1
O10
Geometric parameters (Å, °)
C1—N1
C1—P1
C1—H1A
1.482 (3)
1.849 (3)
0.9700
C2—H2A
C2—H2B
Cu1—P1
P1—C1i
0.9700
0.9700
2.2596 (13)
C1—H1B0.9700 1.849 (3)
C2—N1i
C2—N1
1.478 (2) O10—H10 0.8104
1.478 (2)
N1—C1—P1 112.8 (2)
P1—Cu1—P1iv
P1iii—Cu1—P1iv
P1—Cu1—P1v
P1iii—Cu1—P1v
P1iv—Cu1—P1v
C1ii—P1—C1i
C1ii—P1—C1
C1i—P1—C1
C1ii—P1—Cu1
C1i—P1—Cu1
C1—P1—Cu1
109.5
N1—C1—H1A 109.0109.5
P1—C1—H1B 109.0 109.5
H1A—C1—H1B 107.8109.5
N1i—C2—N1
113.7 (3) 109.5
N1—C2—H2A108.8 97.57 (12)
N1—C2—H2B108.8 97.57 (12)
H2A—C2—H2B107.797.57 (12)
C2ii—N1—C2
C2ii—N1—C1
C2—N1—C1
P1—Cu1—P1iii
Symmetry codes: (i) z, x, y; (ii) y, z, x; (iii) −x+1/4, y, −z+1/4; (iv) −x+1/4, −y+1/4, z; (v) x, −y+1/4, −z+1/4.
108.5 (3) 119.70 (9)
111.21 (16)119.70 (9)
111.21 (16)119.70 (9)
109.5

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Hydrogen-bond geometry (Å, °)
D—H···A
O10—H10···N1
D—H
0.81
H···A
2.04
D···A
2.843 (3)
D—H···A
174

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Fig. 1

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Fig. 2

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Fig. 3