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

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.

Related literature

For general background, see: Kirillov et al. (2007 ▶, 2008 ▶); Karabach et al. (2006 ▶); Di Nicola et al. (2007 ▶). For a comprehensive review of PTA chemistry, see: Phillips et al. (2004 ▶). For n class="Chemical">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(C6n class="Species">H12N3P)4]Cl·6H2O

M = 835.71

Cubic,

a = 19.795 (4) Å

V = 7757 (3) Å3

Z = 8

Mo Kα radiation

μ = 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 ▶) T min = 0.848, T max = 0.905

3022 measured reflections

447 independent reflections

361 reflections with I > 2σ(I)

R int = 0.049

Refinement

R[F 2 > 2σ(F 2)] = 0.034

wR(F 2) = 0.092

S = 1.08

447 reflections

28 parameters

H-atom parameters constrained

Δρmax = 0.75 e Å−3

Δρmin = −0.32 e Å−3

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, 2008 ▶); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ▶), PLATON (Spek, 2003 ▶) and Mern class="Chemical">cury (Macrae et al., 2006 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks I. DOI: 10.1107/S1600536808008179/dn2329sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808008179/dn2329Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Cu(C6H12N3P)4]Cl·6H2O	Z = 8
Mr = 835.71	F000 = 3536
Cubic, Fd3m	Dx = 1.431 Mg m−3
Hall symbol: -F 4vw 2vw 3	Mo Kα radiation λ = 0.71069 Å
a = 19.795 (4) Å	Cell parameters from 743 reflections
b = 19.795 (4) Å	θ = 2.9–27.0º
c = 19.795 (4) Å	µ = 0.85 mm−1
α = 90º	T = 150 (2) K
β = 90º	Prism, colourless
γ = 90º	0.20 × 0.17 × 0.12 mm
V = 7757 (3) Å3

Bruker APEXII CCD area-detector diffractometer	447 independent reflections
Radiation source: fine-focus sealed tube	361 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.049
T = 150(2) K	θmax = 27.0º
φ and ω scans	θmin = 2.9º
Absorption correction: multi-scan(SADABS; Sheldrick, 2003)	h = −24→23
Tmin = 0.848, Tmax = 0.905	k = −16→11
3022 measured reflections	l = −6→25

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
S = 1.08	(Δ/σ)max < 0.001
447 reflections	Δρmax = 0.75 e Å−3
28 parameters	Δρmin = −0.32 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

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, conventional 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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
C1	0.25075 (10)	0.15137 (15)	0.25075 (10)	0.0199 (6)
H1A	0.2258	0.1228	0.2818	0.024*	0.50
H1B	0.2818	0.1228	0.2258	0.024*	0.50
C2	0.33080 (15)	0.24509 (11)	0.24509 (11)	0.0239 (7)
H2A	0.3607	0.2726	0.2726	0.029*
H2B	0.3587	0.2166	0.2166	0.029*
N1	0.29002 (8)	0.20160 (12)	0.29002 (8)	0.0212 (6)
Cu1	0.1250	0.1250	0.1250	0.0134 (3)
P1	0.19090 (4)	0.19090 (4)	0.19090 (4)	0.0156 (3)
Cl1	0.3750	0.3750	0.3750	0.0165 (5)
O10	0.3750	0.12300 (14)	0.3750	0.0240 (7)
H10	0.3521	0.1480	0.3521	0.036*

	U11	U22	U33	U12	U13	U23
C1	0.0193 (8)	0.0212 (14)	0.0193 (8)	−0.0005 (7)	−0.0053 (11)	−0.0005 (7)
C2	0.0193 (15)	0.0262 (10)	0.0262 (10)	−0.0036 (8)	−0.0036 (8)	−0.0027 (12)
N1	0.0218 (8)	0.0202 (13)	0.0218 (8)	−0.0019 (7)	−0.0056 (10)	−0.0019 (7)
Cu1	0.0134 (3)	0.0134 (3)	0.0134 (3)	0.000	0.000	0.000
P1	0.0156 (3)	0.0156 (3)	0.0156 (3)	−0.0009 (3)	−0.0009 (3)	−0.0009 (3)
Cl1	0.0165 (5)	0.0165 (5)	0.0165 (5)	0.000	0.000	0.000
O10	0.0255 (10)	0.0210 (16)	0.0255 (10)	0.000	−0.0083 (12)	0.000

C1—N1	1.482 (3)	C2—H2A	0.9700
C1—P1	1.849 (3)	C2—H2B	0.9700
C1—H1A	0.9700	Cu1—P1	2.2596 (13)
C1—H1B	0.9700	P1—C1i	1.849 (3)
C2—N1i	1.478 (2)	O10—H10	0.8104
C2—N1	1.478 (2)
N1—C1—P1	112.8 (2)	P1—Cu1—P1iv	109.5
N1—C1—H1A	109.0	P1iii—Cu1—P1iv	109.5
P1—C1—H1B	109.0	P1—Cu1—P1v	109.5
H1A—C1—H1B	107.8	P1iii—Cu1—P1v	109.5
N1i—C2—N1	113.7 (3)	P1iv—Cu1—P1v	109.5
N1—C2—H2A	108.8	C1ii—P1—C1i	97.57 (12)
N1—C2—H2B	108.8	C1ii—P1—C1	97.57 (12)
H2A—C2—H2B	107.7	C1i—P1—C1	97.57 (12)
C2ii—N1—C2	108.5 (3)	C1ii—P1—Cu1	119.70 (9)
C2ii—N1—C1	111.21 (16)	C1i—P1—Cu1	119.70 (9)
C2—N1—C1	111.21 (16)	C1—P1—Cu1	119.70 (9)
P1—Cu1—P1iii	109.5

D—H···A	D—H	H···A	D···A	D—H···A
O10—H10···N1	0.81	2.04	2.843 (3)	174

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O10—H10⋯N1	0.81	2.04	2.843 (3)	174