[Hydrogen N-(phosphono­meth­yl)imino­diacetato](1,10-phen­an­throline)copper(II) trihydrate: a low-temperature redetermination

Almeida Paz, F.A.; Shi, F.-N.; Trindade, T.; Klinowski, J.; Rocha, J.

doi:10.1107/S1600536805031806

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 61| Part 11| November 2005| Pages m2247-m2250

https://doi.org/10.1107/S1600536805031806

[Hydrogen N-(phosphonomethyl)iminodiacetato](1,10-phenanthroline)copper(II) trihydrate: a low-temperature redetermination

Filipe A. Almeida Paz,^a ^* Fa-Nian Shi,^a Tito Trindade,^a Jacek Klinowski ^b and João Rocha ^a

^aDepartment of Chemistry, University of Aveiro, CICECO, 3810-193 Aveiro, Portugal, and ^bDepartment of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, England
^*Correspondence e-mail: fpaz@dq.ua.pt

(Received 4 July 2005; accepted 5 October 2005; online 12 October 2005)

The room-temperature crystal structure of the title compound, [Cu(H₂pmida)(phen)]·3H₂O [where H₂pmida²⁻ is hydrogen N-(phosphonomethyl)iminodiacetate, C₅H₁₀NO₇P²⁻, and phen is 1,10-phenanthroline, C₁₂H₈N₂], was recently determined by Pei Lu, Ke, Li, Qin, Zhou, Wu & Du [Struct. Chem. (2004), 15, 207–210]. We report here a redetermination, at 180 (2) K, with greatly improved precision. Hydrogen bonds lead to the formation of one-dimensional tapes which run along the [100] direction of the unit cell. Adjacent tapes are interconnected via π–π offset stacking (between the 1,10-phenanthroline ligands) and by hydrogen bonds involving the water molecules of crystallization.

Comment

During the course of our research on novel crystalline organic–inorganic hybrid materials (Almeida Paz, Khimyak et al., 2002 ; Almeida Paz et al., 2005 ; Almeida Paz & Klinowski, 2004a ,b ), containing organic ligands with chelating and highly flexible `arms', such as diethylenetriaminepentaacetic acid (Almeida Paz, Bond et al., 2002 ), nitrilotriacetic acid (Almeida Paz & Klinowski, 2003 ) and N-(phosphonomethyl)iminodiacetic acid (H₄pmida) (Mafra et al., 2005 ; Shi et al., 2005 ; Almeida Paz et al., 2004 ), we recently isolated, in quantitative yield, large single crystals of the title compound, (I), which is composed of discrete complexes of Cu²⁺ with 1,10-phenanthroline (phen) and H₂pmida²⁻ ligands, co-crystallizing with three solvent molecules in space group P $[\overline{1}]$ .

Although the crystal structure of this compound has recently been reported (Pei et al., 2004 ), we redetermined it at 180 (2) K, with a final R value of 0.0376, to gain more precise data for our studies of the magnetic properties of such crystalline hybrid materials. The low-temperature redetermination allowed the direct location of all H atoms associated with the protonated carboxylic and phosphonic acid groups, and with the three water molecules of crystallization, thus giving a much better insight into the hydrogen-bond network present in the crystal structure of (I).

The unit-cell volume decreased by ca 13 Å³, consistent with determination at a lower temperature. The asymmetric unit composed of a complete [Cu(H₂pmida)(phen)] complex (Fig. 1) plus three water molecules of crystallization (O1W, O2W and O3W). The crystallographically unique Cu²⁺ atom is coordinated by one phen residue via the two N-donor atoms, leading to a bite angle of 82.18 (9)°, which is in good agreement with that reported by Pei et al. [82.06 (16)°], and also with those typically found in related compounds as revealed by a search in the Cambridge Structural Database (CSD, Version 5.26; Allen, 2002 ; Allen & Motherwell, 2002 ). The remaining four positions of the Cu²⁺ coordination are occupied by the N- and O-donor atoms from the H₂pmida²⁻ anionic ligand, leading to a typical Jahn–Teller distorted octahedral coordination geometry, {CuN₃O₃}. In general, the Cu—N and Cu—O bond lengths and angles (Table 1) are not significantly different from those obtained from the room-temperature determination (Pei et al., 2004). Each [Cu(H₂pmida)(phen)] complex is connected to adjacent molecules via a series of hydrogen bonds between the protonated carboxylic and phosphonic acid groups (donors), and the coordinated carboxylate groups (acceptors) of a neighbouring complex (Fig. 2 and Table 2). Such a regular arrangement of hydrogen bonds between adjacent complexes leads to the formation of two graph-set motifs, viz. R₂²(16) and R₄⁴(24) (Fig. 2), which are recursively repeated along the [100] direction of the unit cell, creating a one-dimensional hydrogen-bonded tape. The intermetallic Cu1⋯Cu1ⁱ distance across the O7⋯O1 hydrogen-bond bridge is 7.571 (2) Å, while across the O2⋯O5 bridge, Cu1⋯Cu1ⁱⁱ is 9.162 (2) Å [symmetry codes: (i) −1 + x, y, z; (ii) 1 − x, 1 − y, −z]. The one-dimensional tape is formed in such a way that the coordinated phen molecules are external to the hydrogen-bonded core (Fig. 2). Therefore, the aromatic residues are engaged in offset π–π stacking along the [100] direction of the unit cell, thus linking neighbouring hydrogen-bonded tapes (Fig. 3). Further connections between tapes are made by hydrogen bonds involving the water molecules of crystallization (Fig. 4 and Table 2), thus leading, along with the above-mentioned π–π interactions, to a three-dimensional supramolecular arrangement of [Cu(H₂pmida)(phen)] complexes.

Figure 1
A view of the [Cu(H₂pmida)(phen)] complex molecule present in the crystal structure of the title compound, showing the labelling scheme for all non-H atoms and for the two H atoms belonging to the carboxylic and phosphonic acid groups. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres.

Figure 2
Hydrogen bonding in (I)

represented as green-filled dashed bonds giving a one-dimensional tape running along the [100] direction of the unit cell with a schematic diagram showing the two graph-set motifs, viz. R₂²(16) and R₄⁴(24). [Symmetry codes: (i) 1 − x, 1 − y, −z; (ii) 1 + x, y, z; (iii) −1 + x, y, z; (iv) −x, 1 − y, −z; (v) 2 − x, 1 − y, −z.]

Figure 3
π-π offset interactions, running along the [100] direction of the unit cell between 1,10-phenanthroline residues belonging to adjacent one-dimensional hydrogen-bonded tapes (see Fig. 2

). Hydrogen bonds are represented as green-filled dashed bonds.

Figure 4
Perspective view of the crystal packing of the title compound viewed along the [100] direction of the unit cell. Hydrogen bonds are represented as green-filled dashed bonds. For hydrogen-bonding geometry, see Table 2

Experimental

Chemicals were readily available from commercial sources and were used as received without further purification, i.e. N-(phosphonomethyl)iminodiacetic acid hydrate (H₄pmida, 97% Fluka), 1,10-phenanthroline monohydrate (phen, >99.0% Fluka) and copper(II) hydroxide [CuCO₃·Cu(OH)₂, 55% in Cu, Panreac]. The title compound was synthesized from a mixture containing 0.19 g of CuCO₃·Cu(OH)₂, 0.38 g of H₄pmida and 0.23 g of phen in ca 6.7 g of distilled water. The mixture was stirred at ambient temperature for 30 min, yielding a homogeneous suspension with a molar composition of ca 1.0:1.9:1.4:433, which was transferred to PTFE-lined stainless steel reaction vessels (ca 40 ml). Reactions took place over a period of 3 d, under autogeneous pressure and static conditions, in a preheated oven at 373 K. The vessels were left to cool to ambient temperature before opening. The mother liquor was filtered off and allowed to stand in the open air for approximately 2 d, yielding a large amount of a dark-green single-crystalline phase. Individual single crystals were washed with copious amounts of distilled water (3 × ca 50 ml), and then air-dried at ambient temperature to give the title compound.

Crystal data

[Cu(C₅H₁₀NO₇P)(C₁₂H₈N₂)]·3H₂O
M_r = 522.89
Triclinic, $[P \overline 1]$
a = 7.5714 (15) Å
b = 10.696 (2) Å
c = 13.047 (3) Å
α = 81.98 (3)°
β = 85.04 (3)°
γ = 78.40 (3)°
V = 1023.1 (4) Å³
Z = 2
D_x = 1.697 Mg m⁻³
Mo Kα radiation
Cell parameters from 6202 reflections
θ = 1.0–27.5°
μ = 1.21 mm⁻¹
T = 180 (2) K
Block, green
0.10 × 0.10 × 0.07 mm

Data collection

Nonius KappaCCD diffractometer
Thin–slice ω and φ scans
Absorption correction: multi-scan(SORTAV; Blessing, 1995 )T_min = 0.843, T_max = 0.922
11202 measured reflections
4641 independent reflections
3999 reflections with I > 2σ(I)
R_int = 0.038
θ_max = 27.4°
h = −9 → 9
k = −13 → 13
l = −14 → 16

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.089
S = 1.06
4641 reflections
313 parameters
H atoms treated by a mixture of independent and constrained refinement
w = 1/[σ²(F_o²) + (0.0207P)² + 1.6723P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.81 e Å⁻³
Δρ_min = −0.51 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Cu1—O1	2.474 (2)
Cu1—O4	1.9412 (18)
Cu1—N2	2.005 (2)
Cu1—N3	2.032 (2)
Cu1—N1	2.118 (2)
Cu1—O6	2.3489 (18)

O4—Cu1—N2	90.72 (8)
O4—Cu1—N3	166.90 (8)
N2—Cu1—N3	82.18 (9)
O4—Cu1—N1	84.52 (8)
N2—Cu1—N1	167.49 (8)
N3—Cu1—N1	104.59 (8)
O4—Cu1—O6	102.28 (7)
N2—Cu1—O6	94.96 (8)
N3—Cu1—O6	89.34 (8)
N1—Cu1—O6	74.86 (7)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2C⋯O5ⁱ	0.90 (1)	1.67 (1)	2.564 (3)	175 (3)
O7—H7A⋯O1ⁱⁱ	0.89 (3)	1.66 (3)	2.540 (3)	168 (3)
O1W—H1C⋯O3ⁱⁱⁱ	0.95 (1)	1.77 (1)	2.717 (3)	178 (3)
O1W—H1D⋯O1^iv	0.95 (1)	1.94 (2)	2.853 (3)	162 (3)
O2W—H2D⋯O1W	0.95 (1)	1.76 (1)	2.704 (4)	166 (3)
O2W—H2E⋯O2ⁱⁱⁱ	0.96 (3)	2.17 (2)	3.087 (3)	160 (3)
O3W—H3A⋯O2W^v	0.97 (3)	1.85 (4)	2.805 (4)	166 (3)
O3W—H3B⋯O4	0.95 (3)	2.06 (3)	2.999 (3)	172 (3)
Symmetry codes: (i) -x+1, -y+1, -z; (ii) x+1, y, z; (iii) x+1, y, z+1; (iv) -x+1, -y+2, -z+1; (v) -x+1, -y+1, -z+1.

H atoms associated with the three water molecules of crystallization, and with the protonated carboxylic and phosphonic acid groups (H2C and H7A), were clearly visible in difference Fourier maps, and were included in subsequent least-squares refinements. For the water molecules, the O—H and H⋯H distances were restrained to 0.95 (1) and 1.55 (1) Å, respectively, to ensure a chemically reasonable geometry for these groups. For the hydroxyl groups, the O—H distances were restrained to 0.90 (1) Å. These H atoms were further refined with an isotropic displacement parameter fixed at 1.5U_eq of the parent O atoms. H atoms bound to carbon were placed in idealized positions and allowed to ride on their parent atoms with relative isotropic displacement parameters (U_iso) fixed at 1.2U_eq of the parent C atom and C—H = 0.95 Å.

Data collection: COLLECT (Nonius 1998 ); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ); data reduction: SCALEPACK and DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994 ); program(s) used to refine structure: SHELXTL (Bruker 2001 ); molecular graphics: DIAMOND (Brandenburg, 2001 ); software used to prepare material for publication: SHELXTL (Bruker 2001).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536805031806/rn6059sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536805031806/rn6059Isup2.hkl

Computing details top

Data collection: COLLECT (Nonius 1998); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: SCALEPACK and DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al.,1994); program(s) used to refine structure: SHELXTL (Bruker 2001); molecular graphics: DIAMOND (Brandenburg, 2001); software used to prepare material for publication: SHELXTL (Bruker 2001).

[hydrogen N-(phosphonomethyl)iminodiacetato](1,10-phenanthroline)copper(II) trihydrate top

Crystal data top

[Cu(C₅H₁₀NO₇P)(C₁₂H₈N₂)]·3H₂O	Z = 2
M_r = 522.89	F(000) = 538
Triclinic, P1	D_x = 1.697 Mg m⁻³ D_m = no Mg m⁻³ D_m measured by not measured
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.5714 (15) Å	Cell parameters from 6202 reflections
b = 10.696 (2) Å	θ = 1.0–27.5°
c = 13.047 (3) Å	µ = 1.21 mm⁻¹
α = 81.98 (3)°	T = 180 K
β = 85.04 (3)°	Block, green
γ = 78.40 (3)°	0.10 × 0.10 × 0.07 mm
V = 1023.1 (4) Å³

Data collection top

Nonius KappaCCD diffractometer	3999 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.038
Thin–slice ω and φ scans	θ_max = 27.4°, θ_min = 3.6°
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	h = −9→9
T_min = 0.843, T_max = 0.922	k = −13→13
11202 measured reflections	l = −14→16
4641 independent reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.038	Hydrogen site location: mixed
wR(F²) = 0.089	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0207P)² + 1.6723P] where P = (F_o² + 2F_c²)/3
4641 reflections	(Δ/σ)_max < 0.001
313 parameters	Δρ_max = 0.81 e Å⁻³
11 restraints	Δρ_min = −0.51 e Å⁻³

Special details top

Experimental. (Please see the Experimental Section in the main paper)

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cu1	0.46760 (4)	0.73527 (3)	0.27104 (2)	0.01480 (9)
P1	0.32199 (8)	0.80933 (6)	0.03658 (5)	0.01451 (14)
N1	0.6456 (3)	0.72640 (18)	0.13668 (16)	0.0141 (4)
O1	0.2374 (2)	0.82883 (17)	0.14408 (14)	0.0192 (4)
O2	0.2983 (2)	0.67179 (17)	0.01640 (15)	0.0213 (4)
H2C	0.356 (4)	0.647 (3)	−0.0425 (15)	0.032*
O3	0.2619 (2)	0.91124 (17)	−0.05012 (14)	0.0209 (4)
O4	0.4395 (2)	0.56551 (16)	0.24691 (14)	0.0206 (4)
O5	0.5322 (3)	0.41073 (17)	0.14714 (15)	0.0279 (4)
O6	0.7588 (2)	0.69422 (17)	0.33266 (14)	0.0196 (4)
O7	1.0177 (2)	0.75556 (19)	0.28737 (14)	0.0236 (4)
H7A	1.086 (4)	0.778 (3)	0.2311 (17)	0.035*
C1	0.5623 (3)	0.8038 (2)	0.04237 (19)	0.0156 (5)
H1A	0.6259	0.7679	−0.0197	0.019*
H1B	0.5825	0.8930	0.0390	0.019*
C2	0.6869 (3)	0.5863 (2)	0.1248 (2)	0.0184 (5)
H2A	0.8023	0.5464	0.1565	0.022*
H2B	0.7028	0.5765	0.0501	0.022*
C3	0.5413 (3)	0.5159 (2)	0.1743 (2)	0.0189 (5)
C4	0.8155 (3)	0.7684 (2)	0.15323 (19)	0.0166 (5)
H4A	0.8006	0.8627	0.1344	0.020*
H4B	0.9151	0.7267	0.1078	0.020*
C5	0.8630 (3)	0.7334 (2)	0.26503 (19)	0.0165 (5)
N2	0.3410 (3)	0.71320 (19)	0.41193 (16)	0.0168 (4)
N3	0.4347 (3)	0.91999 (19)	0.30146 (16)	0.0163 (4)
C6	0.4759 (3)	1.0235 (2)	0.2436 (2)	0.0204 (5)
H6	0.5387	1.0135	0.1781	0.024*
C7	0.4316 (4)	1.1467 (3)	0.2743 (2)	0.0264 (6)
H7	0.4618	1.2185	0.2297	0.032*
C8	0.3441 (4)	1.1628 (3)	0.3694 (2)	0.0270 (6)
H8	0.3136	1.2458	0.3915	0.032*
C9	0.2998 (3)	1.0555 (3)	0.4337 (2)	0.0213 (5)
C10	0.3469 (3)	0.9361 (2)	0.39543 (19)	0.0162 (5)
C11	0.2990 (3)	0.8240 (2)	0.45614 (19)	0.0166 (5)
C12	0.2099 (3)	0.8325 (3)	0.5542 (2)	0.0226 (5)
C13	0.1672 (4)	0.9556 (3)	0.5930 (2)	0.0268 (6)
H13	0.1089	0.9622	0.6600	0.032*
C14	0.2093 (4)	1.0615 (3)	0.5348 (2)	0.0262 (6)
H14	0.1784	1.1418	0.5615	0.031*
C15	0.1632 (4)	0.7192 (3)	0.6078 (2)	0.0296 (6)
H15	0.1035	0.7198	0.6749	0.035*
C16	0.2042 (4)	0.6079 (3)	0.5627 (2)	0.0306 (6)
H16	0.1724	0.5309	0.5979	0.037*
C17	0.2934 (3)	0.6086 (3)	0.4641 (2)	0.0235 (6)
H17	0.3208	0.5309	0.4335	0.028*
O1W	0.9747 (3)	0.9223 (2)	0.83545 (17)	0.0360 (5)
H1C	1.073 (3)	0.920 (3)	0.876 (2)	0.054*
H1D	0.885 (3)	0.995 (2)	0.846 (3)	0.054*
O2W	0.9472 (3)	0.6777 (2)	0.9103 (2)	0.0462 (6)
H2D	0.939 (5)	0.7657 (16)	0.880 (3)	0.069*
H2E	1.053 (4)	0.654 (3)	0.949 (3)	0.069*
O3W	0.0897 (3)	0.4767 (2)	0.2406 (2)	0.0468 (6)
H3A	0.098 (5)	0.418 (3)	0.189 (3)	0.070*
H3B	0.203 (3)	0.503 (4)	0.236 (3)	0.070*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.01678 (16)	0.01334 (15)	0.01508 (16)	−0.00573 (11)	0.00260 (11)	−0.00256 (11)
P1	0.0135 (3)	0.0157 (3)	0.0150 (3)	−0.0049 (2)	−0.0002 (2)	−0.0017 (2)
N1	0.0136 (9)	0.0130 (10)	0.0170 (10)	−0.0049 (7)	−0.0011 (8)	−0.0023 (8)
O1	0.0160 (8)	0.0241 (9)	0.0182 (9)	−0.0056 (7)	0.0027 (7)	−0.0049 (7)
O2	0.0235 (9)	0.0192 (9)	0.0240 (10)	−0.0101 (7)	0.0012 (7)	−0.0049 (7)
O3	0.0201 (9)	0.0219 (9)	0.0196 (9)	−0.0044 (7)	−0.0037 (7)	0.0030 (7)
O4	0.0250 (9)	0.0176 (9)	0.0211 (9)	−0.0090 (7)	0.0041 (7)	−0.0053 (7)
O5	0.0405 (11)	0.0160 (9)	0.0301 (11)	−0.0130 (8)	0.0083 (9)	−0.0080 (8)
O6	0.0175 (9)	0.0227 (9)	0.0187 (9)	−0.0065 (7)	0.0004 (7)	−0.0009 (7)
O7	0.0176 (9)	0.0367 (11)	0.0188 (10)	−0.0121 (8)	−0.0014 (7)	−0.0012 (8)
C1	0.0141 (11)	0.0184 (12)	0.0148 (12)	−0.0048 (9)	−0.0012 (9)	−0.0007 (9)
C2	0.0179 (12)	0.0135 (11)	0.0247 (14)	−0.0036 (9)	0.0003 (10)	−0.0056 (10)
C3	0.0212 (12)	0.0150 (12)	0.0207 (13)	−0.0050 (9)	−0.0007 (10)	−0.0006 (10)
C4	0.0151 (11)	0.0187 (12)	0.0177 (12)	−0.0074 (9)	−0.0004 (9)	−0.0019 (9)
C5	0.0150 (11)	0.0148 (11)	0.0205 (13)	−0.0034 (9)	−0.0011 (9)	−0.0045 (10)
N2	0.0164 (10)	0.0177 (10)	0.0164 (10)	−0.0042 (8)	−0.0005 (8)	−0.0014 (8)
N3	0.0172 (10)	0.0173 (10)	0.0157 (10)	−0.0062 (8)	−0.0001 (8)	−0.0027 (8)
C6	0.0259 (13)	0.0182 (12)	0.0177 (13)	−0.0072 (10)	−0.0008 (10)	−0.0006 (10)
C7	0.0316 (15)	0.0183 (13)	0.0306 (16)	−0.0109 (11)	−0.0014 (12)	0.0008 (11)
C8	0.0301 (15)	0.0184 (13)	0.0343 (16)	−0.0042 (11)	−0.0033 (12)	−0.0096 (12)
C9	0.0202 (12)	0.0222 (13)	0.0225 (14)	−0.0033 (10)	−0.0026 (10)	−0.0064 (10)
C10	0.0131 (11)	0.0184 (12)	0.0174 (12)	−0.0030 (9)	−0.0024 (9)	−0.0026 (9)
C11	0.0121 (11)	0.0226 (13)	0.0156 (12)	−0.0032 (9)	−0.0016 (9)	−0.0034 (10)
C12	0.0189 (13)	0.0284 (14)	0.0191 (13)	−0.0026 (10)	0.0001 (10)	−0.0020 (11)
C13	0.0251 (14)	0.0369 (16)	0.0179 (13)	−0.0018 (12)	0.0026 (10)	−0.0101 (12)
C14	0.0251 (14)	0.0310 (15)	0.0239 (15)	−0.0013 (11)	−0.0018 (11)	−0.0138 (12)
C15	0.0290 (15)	0.0381 (17)	0.0179 (14)	−0.0056 (12)	0.0064 (11)	0.0032 (12)
C16	0.0328 (15)	0.0284 (15)	0.0276 (16)	−0.0090 (12)	0.0024 (12)	0.0091 (12)
C17	0.0230 (13)	0.0204 (13)	0.0260 (14)	−0.0054 (10)	0.0013 (11)	0.0014 (11)
O1W	0.0303 (11)	0.0443 (13)	0.0325 (12)	0.0029 (9)	−0.0091 (9)	−0.0116 (10)
O2W	0.0379 (13)	0.0457 (14)	0.0583 (17)	−0.0115 (11)	0.0007 (11)	−0.0157 (12)
O3W	0.0364 (13)	0.0486 (15)	0.0603 (17)	−0.0151 (11)	0.0086 (11)	−0.0214 (13)

Geometric parameters (Å, º) top

Cu1—O1	2.474 (2)	N3—C6	1.326 (3)
Cu1—O4	1.9412 (18)	N3—C10	1.359 (3)
Cu1—N2	2.005 (2)	C6—C7	1.399 (4)
Cu1—N3	2.032 (2)	C6—H6	0.9500
Cu1—N1	2.118 (2)	C7—C8	1.371 (4)
Cu1—O6	2.3489 (18)	C7—H7	0.9500
P1—O3	1.4902 (19)	C8—C9	1.404 (4)
P1—O1	1.5145 (18)	C8—H8	0.9500
P1—O2	1.5775 (19)	C9—C10	1.405 (3)
P1—C1	1.816 (2)	C9—C14	1.436 (4)
N1—C4	1.486 (3)	C10—C11	1.435 (3)
N1—C2	1.495 (3)	C11—C12	1.399 (3)
N1—C1	1.496 (3)	C12—C15	1.406 (4)
O2—H2C	0.897 (10)	C12—C13	1.443 (4)
O4—C3	1.274 (3)	C13—C14	1.351 (4)
O5—C3	1.242 (3)	C13—H13	0.9500
O6—C5	1.219 (3)	C14—H14	0.9500
O7—C5	1.306 (3)	C15—C16	1.370 (4)
O7—H7A	0.89 (3)	C15—H15	0.9500
C1—H1A	0.9900	C16—C17	1.399 (4)
C1—H1B	0.9900	C16—H16	0.9500
C2—C3	1.508 (3)	C17—H17	0.9500
C2—H2A	0.9900	O1W—H1C	0.947 (10)
C2—H2B	0.9900	O1W—H1D	0.946 (10)
C4—C5	1.510 (3)	O2W—H2D	0.961 (10)
C4—H4A	0.9900	O2W—H2E	0.96 (3)
C4—H4B	0.9900	O3W—H3A	0.97 (3)
N2—C17	1.324 (3)	O3W—H3B	0.95 (3)
N2—C11	1.358 (3)

O4—Cu1—N2	90.72 (8)	O6—C5—C4	122.4 (2)
O4—Cu1—N3	166.90 (8)	O7—C5—C4	116.4 (2)
N2—Cu1—N3	82.18 (9)	C17—N2—C11	118.1 (2)
O4—Cu1—N1	84.52 (8)	C17—N2—Cu1	129.03 (18)
N2—Cu1—N1	167.49 (8)	C11—N2—Cu1	112.88 (16)
N3—Cu1—N1	104.59 (8)	C6—N3—C10	117.5 (2)
O4—Cu1—O6	102.28 (7)	C6—N3—Cu1	130.76 (17)
N2—Cu1—O6	94.96 (8)	C10—N3—Cu1	111.66 (16)
N3—Cu1—O6	89.34 (8)	N3—C6—C7	123.2 (2)
N1—Cu1—O6	74.86 (7)	N3—C6—H6	118.4
O3—P1—O1	117.43 (11)	C7—C6—H6	118.4
O3—P1—O2	112.75 (11)	C8—C7—C6	119.3 (3)
O1—P1—O2	106.59 (10)	C8—C7—H7	120.4
O3—P1—C1	105.72 (11)	C6—C7—H7	120.4
O1—P1—C1	106.49 (11)	C7—C8—C9	119.5 (2)
O2—P1—C1	107.30 (11)	C7—C8—H8	120.3
C4—N1—C2	109.19 (18)	C9—C8—H8	120.3
C4—N1—C1	109.67 (18)	C8—C9—C10	117.2 (2)
C2—N1—C1	110.71 (19)	C8—C9—C14	124.0 (2)
C4—N1—Cu1	110.98 (15)	C10—C9—C14	118.9 (2)
C2—N1—Cu1	103.24 (14)	N3—C10—C9	123.4 (2)
C1—N1—Cu1	112.86 (14)	N3—C10—C11	116.9 (2)
P1—O2—H2C	113 (2)	C9—C10—C11	119.6 (2)
C3—O4—Cu1	116.37 (16)	N2—C11—C12	123.3 (2)
C5—O6—Cu1	109.37 (16)	N2—C11—C10	116.3 (2)
C5—O7—H7A	113 (2)	C12—C11—C10	120.3 (2)
N1—C1—P1	115.22 (16)	C11—C12—C15	117.0 (2)
N1—C1—H1A	108.5	C11—C12—C13	119.0 (2)
P1—C1—H1A	108.5	C15—C12—C13	124.0 (2)
N1—C1—H1B	108.5	C14—C13—C12	120.6 (2)
P1—C1—H1B	108.5	C14—C13—H13	119.7
H1A—C1—H1B	107.5	C12—C13—H13	119.7
N1—C2—C3	113.06 (19)	C13—C14—C9	121.6 (2)
N1—C2—H2A	109.0	C13—C14—H14	119.2
C3—C2—H2A	109.0	C9—C14—H14	119.2
N1—C2—H2B	109.0	C16—C15—C12	119.5 (3)
C3—C2—H2B	109.0	C16—C15—H15	120.2
H2A—C2—H2B	107.8	C12—C15—H15	120.2
O5—C3—O4	123.3 (2)	C15—C16—C17	119.4 (3)
O5—C3—C2	119.5 (2)	C15—C16—H16	120.3
O4—C3—C2	117.1 (2)	C17—C16—H16	120.3
N1—C4—C5	110.69 (19)	N2—C17—C16	122.6 (3)
N1—C4—H4A	109.5	N2—C17—H17	118.7
C5—C4—H4A	109.5	C16—C17—H17	118.7
N1—C4—H4B	109.5	H1C—O1W—H1D	109.3 (15)
C5—C4—H4B	109.5	H2D—O2W—H2E	107.8 (15)
H4A—C4—H4B	108.1	H3A—O3W—H3B	106 (3)
O6—C5—O7	121.1 (2)

O4—Cu1—N1—C4	−133.86 (16)	O6—Cu1—N2—C11	88.28 (17)
N2—Cu1—N1—C4	−65.9 (4)	O4—Cu1—N3—C6	−119.3 (4)
N3—Cu1—N1—C4	55.73 (16)	N2—Cu1—N3—C6	−176.9 (2)
O6—Cu1—N1—C4	−29.53 (14)	N1—Cu1—N3—C6	13.8 (2)
O4—Cu1—N1—C2	−16.99 (14)	O6—Cu1—N3—C6	88.0 (2)
N2—Cu1—N1—C2	51.0 (4)	O4—Cu1—N3—C10	57.0 (4)
N3—Cu1—N1—C2	172.59 (14)	N2—Cu1—N3—C10	−0.72 (16)
O6—Cu1—N1—C2	87.33 (14)	N1—Cu1—N3—C10	−169.99 (16)
O4—Cu1—N1—C1	102.58 (16)	O6—Cu1—N3—C10	−95.82 (16)
N2—Cu1—N1—C1	170.6 (3)	C10—N3—C6—C7	−0.8 (4)
N3—Cu1—N1—C1	−67.84 (16)	Cu1—N3—C6—C7	175.2 (2)
O6—Cu1—N1—C1	−153.10 (16)	N3—C6—C7—C8	1.2 (4)
N2—Cu1—O4—C3	−162.28 (19)	C6—C7—C8—C9	−0.4 (4)
N3—Cu1—O4—C3	140.9 (3)	C7—C8—C9—C10	−0.8 (4)
N1—Cu1—O4—C3	6.14 (18)	C7—C8—C9—C14	179.6 (3)
O6—Cu1—O4—C3	−67.04 (19)	C6—N3—C10—C9	−0.4 (4)
O4—Cu1—O6—C5	105.68 (17)	Cu1—N3—C10—C9	−177.19 (19)
N2—Cu1—O6—C5	−162.50 (16)	C6—N3—C10—C11	178.5 (2)
N3—Cu1—O6—C5	−80.40 (17)	Cu1—N3—C10—C11	1.7 (3)
N1—Cu1—O6—C5	24.90 (16)	C8—C9—C10—N3	1.2 (4)
C4—N1—C1—P1	−158.30 (16)	C14—C9—C10—N3	−179.1 (2)
C2—N1—C1—P1	81.2 (2)	C8—C9—C10—C11	−177.6 (2)
Cu1—N1—C1—P1	−34.0 (2)	C14—C9—C10—C11	2.0 (4)
O3—P1—C1—N1	168.57 (16)	C17—N2—C11—C12	0.7 (4)
O1—P1—C1—N1	42.95 (19)	Cu1—N2—C11—C12	179.84 (19)
O2—P1—C1—N1	−70.88 (19)	C17—N2—C11—C10	−177.8 (2)
C4—N1—C2—C3	142.9 (2)	Cu1—N2—C11—C10	1.4 (3)
C1—N1—C2—C3	−96.3 (2)	N3—C10—C11—N2	−2.1 (3)
Cu1—N1—C2—C3	24.8 (2)	C9—C10—C11—N2	176.8 (2)
Cu1—O4—C3—O5	−176.5 (2)	N3—C10—C11—C12	179.4 (2)
Cu1—O4—C3—C2	7.5 (3)	C9—C10—C11—C12	−1.7 (4)
N1—C2—C3—O5	160.4 (2)	N2—C11—C12—C15	0.0 (4)
N1—C2—C3—O4	−23.5 (3)	C10—C11—C12—C15	178.4 (2)
C2—N1—C4—C5	−80.9 (2)	N2—C11—C12—C13	−178.3 (2)
C1—N1—C4—C5	157.64 (19)	C10—C11—C12—C13	0.1 (4)
Cu1—N1—C4—C5	32.3 (2)	C11—C12—C13—C14	1.2 (4)
Cu1—O6—C5—O7	160.49 (19)	C15—C12—C13—C14	−177.0 (3)
Cu1—O6—C5—C4	−14.7 (3)	C12—C13—C14—C9	−0.9 (4)
N1—C4—C5—O6	−10.2 (3)	C8—C9—C14—C13	178.9 (3)
N1—C4—C5—O7	174.4 (2)	C10—C9—C14—C13	−0.7 (4)
O4—Cu1—N2—C17	9.7 (2)	C11—C12—C15—C16	−0.6 (4)
N3—Cu1—N2—C17	178.7 (2)	C13—C12—C15—C16	177.6 (3)
N1—Cu1—N2—C17	−57.7 (5)	C12—C15—C16—C17	0.5 (4)
O6—Cu1—N2—C17	−92.7 (2)	C11—N2—C17—C16	−0.8 (4)
O4—Cu1—N2—C11	−169.33 (17)	Cu1—N2—C17—C16	−179.8 (2)
N3—Cu1—N2—C11	−0.38 (16)	C15—C16—C17—N2	0.2 (4)
N1—Cu1—N2—C11	123.3 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2C···O5ⁱ	0.90 (1)	1.67 (1)	2.564 (3)	175 (3)
O7—H7A···O1ⁱⁱ	0.89 (3)	1.66 (3)	2.540 (3)	168 (3)
O1W—H1C···O3ⁱⁱⁱ	0.95 (1)	1.77 (1)	2.717 (3)	178 (3)
O1W—H1D···O1^iv	0.95 (1)	1.94 (2)	2.853 (3)	162 (3)
O2W—H2D···O1W	0.95 (1)	1.76 (1)	2.704 (4)	166 (3)
O2W—H2E···O2ⁱⁱⁱ	0.96 (3)	2.17 (2)	3.087 (3)	160 (3)
O3W—H3A···O2W^v	0.97 (3)	1.85 (4)	2.805 (4)	166 (3)
O3W—H3B···O4	0.95 (3)	2.06 (3)	2.999 (3)	172 (3)

Symmetry codes: (i) −x+1, −y+1, −z; (ii) x+1, y, z; (iii) x+1, y, z+1; (iv) −x+1, −y+2, −z+1; (v) −x+1, −y+1, −z+1.

Acknowledgements

The authors are grateful to the Fundação para a Ciência e Tecnologia (FCT, Portugal) for their general financial support under the POCTI programme (supported by FEDER), and also for the postdoctoral research grant No. SFRH/BPD/9309/2002 (to FNS).

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