A one-dimensional copper(II) phenyl­ene­diphospho­nate: catena-poly[[(1,10-phenanthroline-κ2N,N′)copper(II)]-μ3-[m-phenyl­enediphospho­nato-κ3O:O′:O′′]]

DeBurgomaster, P.; Zubieta, J.

doi:10.1107/S1600536810037359

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 10| October 2010| Pages m1304-m1305

doi:10.1107/S1600536810037359

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A one-dimensional copper(II) phenylenediphosphonate: catena-poly[[(1,10-phenanthroline-κ²N,N′)copper(II)]-μ₃-[m-phenylenediphosphonato-κ³O:O′:O′′]]

Paul DeBurgomaster ^a and Jon Zubieta ^a ^*

^aDepartment of Chemistry, Syracuse University, Syracuse, New York 13244, USA
^*Correspondence e-mail: jazubiet@syr.edu

(Received 4 August 2010; accepted 17 September 2010; online 30 September 2010)

The title compound, [Cu(1,3-HO₃PC₆H₄PO₃H)(C₁₂H₈N₂)]_n, is a coordination polymer of the metal–diphosphonate family. The chain structure is constructed from `4+1' square-pyramidally coordinated copper(II) atoms bonded to chelating phenanthroline (phen) ligands and linked through 1,3-phenyldihydrogendiphosphonate ligands. The basal plane of the Cu(II) site is defined by the phen nitrogen donors and phosphonate oxygen atoms from two diphosphonate ligands, while the apical position is occupied by an oxygen donor from a third diphosphonate ligand. The chains propagate along the a-axis direction. Inversion-related phen groups engage in π-π stacking with a mean distance of 3.376 (2) Å between the ring planes. O—H⋯O hydrogen-bonding interactions between the protonated {P—OH} groups of one chain and the {P=O} groups of adjacent chains stabilize the crystal packing.

Related literature

For general background to metal-organophosphonates, see: Clearfield (1998 ); Finn et al. (2003 ); Vermeulen (1997 ). For copper-organophosphonates, see: DeBurgomaster et al. (2010 ) and references therein; Arnold et al. (2002 ) and references therein. For our recent studies of metal-organophosphonates, see: Armatas et al. (2009 ); Ouellette et al. (2009 ). For the catalytic, ion exchange, sensor and non-linear optical properties of transition metal compounds of organophosphonic ligands, see: Bakmutova et al. (2008 ); Konar et al. (2007 ); Vermeulen (1997); Turner et al. (2003 ).

Experimental

Crystal data

[Cu(C₆H₆O₆P₂)(C₁₂H₈N₂)]
M_r = 479.79
Triclinic, $[P \overline 1]$
a = 8.6142 (10) Å
b = 9.0554 (10) Å
c = 12.1094 (13) Å
α = 99.688 (2)°
β = 106.542 (2)°
γ = 98.184 (2)°
V = 874.30 (17) Å³
Z = 2
Mo Kα radiation
μ = 1.48 mm⁻¹
T = 98 K
0.35 × 0.30 × 0.21 mm

Data collection

Bruker APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1998 ) T_min = 0.626, T_max = 0.747
8704 measured reflections
4190 independent reflections
4042 reflections with I > 2σ(I)
R_int = 0.018

Refinement

R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.087
S = 1.09
4190 reflections
262 parameters
H-atom parameters constrained
Δρ_max = 0.71 e Å⁻³
Δρ_min = −0.67 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O3ⁱ	0.84	1.81	2.489 (2)	136
O5—H5⋯O1ⁱⁱ	0.84	1.74	2.574 (2)	173
Symmetry codes: (i) -x+1, -y+2, -z+2; (ii) x-1, y, z.

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: CrystalMaker (Palmer, 2006 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810037359/pk2259sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810037359/pk2259Isup2.hkl

checkCIF report

Comment top

Metal organophosphonate materials are prototypical organic-inorganic hybrid composites, often exhibiting layered or pillared-layer structures (Clearfield, 1998; Finn et al., (2003)). A variety of transition metal compounds of organophosphonic ligands have been investigated for their catalytic, ion exchange, sensor and non-linear optical properties (Bakmutova et al. (2008); Konar et al.,(2007); Vermeulen, (1997); Turner et al. (2003)). In the specific case of copper-organophosphonate materials, layered structures are the most common, adopting the prototypical 'pillared' layer motif (Arnold, et al. (2002)). In the course of our extensive studies of metal-organophosphonate chemistry (Armatas et al. (2009); Ouellette et al. (2009); DeBurgomaster, et al. (2010)), we have noted the structural influences of coligands and/or secondary metal-organic moieties. For the title compound, [Cu(phen)(1,3-HO₃PC₆H₄PO₃H)] (Fig.), the bidentate phenanthroline ligand by occupying three coordination sites about the Cu(II) centers constrains structural extension to one-dimension. The material exhibits a chain motif running parallel to the [100] direction (Fig. 2). The five coordinate {CuO₃N₂} geometry at the Cu(II) site is defined by the nitrogen donors of the chelating phenanthroline ligand and oxygen donors from two distinct 1,3-phenyldiphosphonate ligands in the basal and an oxygen donor from a third diphosphosphonate ligand in the apical position. The '4 + 1' axially distorted Jahn-Teller geometry exhibits an elongated Cu—O bond length of 2.292 (2) Å, compared to Cu—O bond distances of 1.934 (2)Å and 1.937 (2)Å for the oxygen donors in the basal plane. Each phenyldiphosphonate ligand bridges three copper sites in the chain. The resultant connectivity pattern generates two repeating heterocyclic rings; the first consists of two copper sites bridged by two diphosphonate ligands to give the sixteen-membered {–Cu—O—P—C—C—C—P—O–}₂ ring while the second is the common {M2(µ₂-phosphonate-O,O')₂} motif or in this case the eight-membered {–Cu—O—P—O–}₂ ring. The alternating ring structure is similar to that observed for the previously reported [Cu(2,2'-bipyridine)(1,3,5-(HO₃P)₂C₆H₃PO₃H₂)] (DeBurgomaster, et al. (2010)). Charge-balance requirements dictate that the diphosphonate ligand must be doubly protonated, that is (HO₃PC₆H₄PO₃H)^2-. The P2—O5 bond distance of 1.574 (2) Å, compared to distances of 1.509 (2)Å and 1.517 (2)Å for P2—O4 and P2—O6, establishes O5 as one protonation site, an observation confirmed by the appearance of a peak consistent with the O5 proton on the difference Fourier map. The location of the second proton is less clear with O2 and O3 as possibilities. Based on the appearance of a peak consistent with an O2 proton in the difference Fourier, oxygen atom O2 was deemed the site of protonation. The pendant {P = O} and {P—OH} groups of adjacent chains engage in hydrogen-bonding to link the chains into a three-dimensional framework (Fig. 3).

Related literature top

For general background to metal-organophosphonates, see: Clearfield (1998); Finn et al. (2003); Vermeulen (1997). For copper-organophosphonates, see: DeBurgomaster et al. (2010) and references therein; Arnold et al. (2002) and references therein. For our recent studies of metal-organophosphonates, see Armatas et al. (2009); Ouellette et al. (2009). For the catalytic, ion exchange, sensor and non-linear optical properties of transition metal compounds of organophosphonic ligands, see: Bakmutova et al. (2008); Konar et al. (2007); Vermeulen (1997); Turner et al. (2003).

Experimental top

A mixture of copper acetate monohydrate (0.096 g, 0.48 mmol), 1,10-phenanthroline (0.117 g, 0.50 mmol), 1,3-phenyldiphosphonic acid (0.118 g, 0.50 mmol), and H₂O (10.00 ml, 554.94 mmol) in the mole ratio 1.00:1.04:1.04:1156 was heated to 170°C for 4 days. Initial and final pH values of 3.0 and 3.0, respectively, were recorded. Blue rods suitable for X-ray diffraction were isolated in 70% yield. Anal. Calcd. for C₁₈H₁₄CuN₂O₆P₂: C, 45.0; H, 2.92; N, 5.84. Found: C, 44.8; H, 2.86; N, 5.95.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: CrystalMaker (Palmer, 2006); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The asymmetric unit of the title compound, showing the atom-labeling scheme and displacement ellipsoids at the 50% probability level. Color scheme: copper, blue; phosphorus, yellow; nitrogen, light blue; oxygen, red; carbon, black; hydrogen, pink.
	Fig. 2. A view of the chain structure of [Cu(phen)(1,3-HO₃PC₆H₄PO₃H)]_n which propagates along the a-axis direction. The π-π stacking of phen groups is also shown. Color scheme as for Fig. 1.
	Fig. 3. The packing diagram of the compound viewed down the a axis. Hydrogen bonds are shown as dashed lines. Color scheme as for Fig. 1.

catena-poly[[(1,10-phenanthroline-κ²N,N')copper(II)]- µ₃-[m-phenylenediphosphonato-κ³O:O':O'']] top

Crystal data top

[Cu(C₁₂H₈N₂)(C₆H₆O₆P₂)]	Z = 2
M_r = 479.79	F(000) = 486
Triclinic, P1	D_x = 1.823 Mg m⁻³ D_m = 1.81 (2) Mg m⁻³ D_m measured by not measured
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.6142 (10) Å	Cell parameters from 5367 reflections
b = 9.0554 (10) Å	θ = 2.3–28.4°
c = 12.1094 (13) Å	µ = 1.48 mm⁻¹
α = 99.688 (2)°	T = 98 K
β = 106.542 (2)°	Block, blue
γ = 98.184 (2)°	0.35 × 0.30 × 0.21 mm
V = 874.30 (17) Å³

Data collection top

Bruker APEX CCD area-detector diffractometer	4190 independent reflections
Radiation source: fine-focus sealed tube	4042 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.018
ϕ and ω scans	θ_max = 28.1°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −11→11
T_min = 0.626, T_max = 0.747	k = −11→11
8704 measured reflections	l = −15→15

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.087	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0425P)² + 1.0147P] where P = (F_o² + 2F_c²)/3
4190 reflections	(Δ/σ)_max = 0.001
262 parameters	Δρ_max = 0.71 e Å⁻³
0 restraints	Δρ_min = −0.67 e Å⁻³

Crystal data top

[Cu(C₁₂H₈N₂)(C₆H₆O₆P₂)]	γ = 98.184 (2)°
M_r = 479.79	V = 874.30 (17) Å³
Triclinic, P1	Z = 2
a = 8.6142 (10) Å	Mo Kα radiation
b = 9.0554 (10) Å	µ = 1.48 mm⁻¹
c = 12.1094 (13) Å	T = 98 K
α = 99.688 (2)°	0.35 × 0.30 × 0.21 mm
β = 106.542 (2)°

Data collection top

Bruker APEX CCD area-detector diffractometer	4190 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1998)	4042 reflections with I > 2σ(I)
T_min = 0.626, T_max = 0.747	R_int = 0.018
8704 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	0 restraints
wR(F²) = 0.087	H-atom parameters constrained
S = 1.09	Δρ_max = 0.71 e Å⁻³
4190 reflections	Δρ_min = −0.67 e Å⁻³
262 parameters

Special details top

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.

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

	x	y	z	U_iso*/U_eq
Cu1	0.32660 (3)	0.82971 (3)	0.58802 (2)	0.01190 (8)
P1	0.32369 (6)	1.03977 (6)	0.85348 (4)	0.01186 (11)
P2	−0.33649 (6)	1.05190 (6)	0.64714 (4)	0.01144 (11)
O1	0.31787 (17)	1.03279 (17)	0.72590 (12)	0.0148 (3)
O2	0.33003 (18)	0.88390 (17)	0.88644 (13)	0.0163 (3)
H2	0.3720	0.8969	0.9599	0.025*
O3	0.46333 (18)	1.16671 (18)	0.94061 (13)	0.0162 (3)
O4	−0.43602 (17)	0.89210 (17)	0.62759 (13)	0.0138 (3)
O5	−0.44080 (17)	1.17467 (17)	0.67394 (13)	0.0151 (3)
H5	−0.5181	1.1348	0.6956	0.023*
O6	−0.26911 (17)	1.08135 (18)	0.54895 (13)	0.0151 (3)
N1	0.0864 (2)	0.7410 (2)	0.55889 (15)	0.0134 (3)
N2	0.3570 (2)	0.6720 (2)	0.68729 (15)	0.0138 (3)
C1	0.1322 (2)	1.0872 (2)	0.86658 (17)	0.0124 (4)
C2	−0.0105 (2)	1.0504 (2)	0.76856 (17)	0.0130 (4)
H2A	−0.0062	1.0002	0.6943	0.016*
C3	−0.1596 (2)	1.0864 (2)	0.77792 (17)	0.0122 (4)
C4	−0.1667 (2)	1.1571 (2)	0.88791 (18)	0.0145 (4)
H4	−0.2678	1.1808	0.8953	0.017*
C5	−0.0249 (3)	1.1930 (2)	0.98692 (18)	0.0160 (4)
H5A	−0.0298	1.2404	1.0617	0.019*
C6	0.1235 (2)	1.1592 (2)	0.97584 (18)	0.0143 (4)
H6	0.2198	1.1853	1.0431	0.017*
C7	−0.0474 (3)	0.7773 (2)	0.49048 (18)	0.0153 (4)
H7	−0.0340	0.8447	0.4401	0.018*
C8	−0.2076 (3)	0.7190 (3)	0.49042 (19)	0.0184 (4)
H8	−0.3007	0.7471	0.4408	0.022*
C9	−0.2286 (3)	0.6210 (3)	0.56286 (19)	0.0179 (4)
H9	−0.3364	0.5812	0.5636	0.021*
C10	−0.0895 (3)	0.5798 (2)	0.63595 (18)	0.0154 (4)
C11	0.0661 (2)	0.6437 (2)	0.62948 (18)	0.0134 (4)
C12	−0.0956 (3)	0.4795 (3)	0.7153 (2)	0.0187 (4)
H12	−0.1994	0.4363	0.7209	0.022*
C13	0.0445 (3)	0.4451 (3)	0.78248 (19)	0.0192 (4)
H13	0.0370	0.3798	0.8353	0.023*
C14	0.2038 (3)	0.5059 (2)	0.77509 (18)	0.0165 (4)
C15	0.2133 (3)	0.6059 (2)	0.69964 (18)	0.0138 (4)
C16	0.3533 (3)	0.4700 (3)	0.83802 (19)	0.0194 (4)
H16	0.3534	0.4010	0.8891	0.023*
C17	0.4990 (3)	0.5359 (3)	0.82459 (19)	0.0192 (4)
H17	0.6005	0.5120	0.8659	0.023*
C18	0.4971 (3)	0.6387 (2)	0.74959 (18)	0.0166 (4)
H18	0.5988	0.6860	0.7430	0.020*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.00830 (12)	0.01613 (14)	0.01135 (13)	0.00099 (9)	0.00196 (9)	0.00652 (9)
P1	0.0083 (2)	0.0170 (3)	0.0100 (2)	0.00289 (18)	0.00145 (18)	0.00446 (19)
P2	0.0076 (2)	0.0163 (3)	0.0108 (2)	0.00190 (18)	0.00179 (18)	0.00644 (18)
O1	0.0121 (6)	0.0218 (8)	0.0115 (7)	0.0033 (6)	0.0042 (5)	0.0056 (6)
O2	0.0172 (7)	0.0183 (7)	0.0130 (7)	0.0043 (6)	0.0024 (6)	0.0053 (6)
O3	0.0107 (6)	0.0199 (8)	0.0160 (7)	0.0019 (6)	0.0014 (5)	0.0044 (6)
O4	0.0090 (6)	0.0176 (7)	0.0145 (7)	0.0013 (5)	0.0026 (5)	0.0058 (6)
O5	0.0109 (6)	0.0186 (7)	0.0172 (7)	0.0041 (6)	0.0038 (5)	0.0080 (6)
O6	0.0106 (6)	0.0240 (8)	0.0123 (7)	0.0029 (6)	0.0033 (5)	0.0089 (6)
N1	0.0130 (8)	0.0138 (8)	0.0129 (8)	0.0012 (6)	0.0035 (6)	0.0039 (6)
N2	0.0122 (8)	0.0165 (8)	0.0128 (8)	0.0031 (6)	0.0032 (6)	0.0043 (6)
C1	0.0102 (8)	0.0153 (9)	0.0126 (9)	0.0028 (7)	0.0028 (7)	0.0063 (7)
C2	0.0119 (9)	0.0163 (10)	0.0112 (9)	0.0027 (7)	0.0035 (7)	0.0044 (7)
C3	0.0094 (8)	0.0153 (9)	0.0113 (9)	0.0006 (7)	0.0020 (7)	0.0053 (7)
C4	0.0125 (9)	0.0181 (10)	0.0151 (10)	0.0034 (7)	0.0057 (7)	0.0069 (8)
C5	0.0161 (9)	0.0202 (10)	0.0122 (9)	0.0036 (8)	0.0051 (8)	0.0041 (8)
C6	0.0117 (9)	0.0176 (10)	0.0116 (9)	0.0009 (7)	0.0007 (7)	0.0046 (7)
C7	0.0138 (9)	0.0169 (10)	0.0142 (9)	0.0024 (8)	0.0029 (7)	0.0043 (8)
C8	0.0130 (9)	0.0224 (11)	0.0181 (10)	0.0042 (8)	0.0026 (8)	0.0029 (8)
C9	0.0125 (9)	0.0200 (10)	0.0196 (10)	−0.0002 (8)	0.0063 (8)	0.0007 (8)
C10	0.0149 (9)	0.0156 (10)	0.0148 (10)	−0.0004 (8)	0.0062 (8)	0.0010 (8)
C11	0.0136 (9)	0.0132 (9)	0.0132 (9)	0.0009 (7)	0.0049 (7)	0.0023 (7)
C12	0.0192 (10)	0.0183 (10)	0.0195 (10)	−0.0012 (8)	0.0101 (8)	0.0041 (8)
C13	0.0248 (11)	0.0171 (10)	0.0166 (10)	−0.0012 (8)	0.0092 (8)	0.0060 (8)
C14	0.0207 (10)	0.0139 (10)	0.0143 (10)	0.0014 (8)	0.0055 (8)	0.0035 (8)
C15	0.0152 (9)	0.0139 (9)	0.0119 (9)	0.0018 (7)	0.0040 (7)	0.0030 (7)
C16	0.0257 (11)	0.0178 (10)	0.0148 (10)	0.0056 (9)	0.0041 (8)	0.0073 (8)
C17	0.0201 (10)	0.0207 (11)	0.0158 (10)	0.0069 (8)	0.0018 (8)	0.0061 (8)
C18	0.0148 (9)	0.0186 (10)	0.0153 (10)	0.0034 (8)	0.0034 (8)	0.0033 (8)

Geometric parameters (Å, º) top

Cu1—O6ⁱ	1.9339 (15)	C4—C5	1.399 (3)
Cu1—O4ⁱⁱ	1.9371 (14)	C4—H4	0.9500
Cu1—N2	2.0142 (18)	C5—C6	1.393 (3)
Cu1—N1	2.0166 (17)	C5—H5A	0.9500
Cu1—O1	2.2918 (15)	C6—H6	0.9500
P1—O1	1.5215 (15)	C7—C8	1.406 (3)
P1—O2	1.5341 (16)	C7—H7	0.9500
P1—O3	1.5352 (16)	C8—C9	1.377 (3)
P1—C1	1.805 (2)	C8—H8	0.9500
P2—O6	1.5092 (15)	C9—C10	1.411 (3)
P2—O4	1.5169 (15)	C9—H9	0.9500
P2—O5	1.5741 (15)	C10—C11	1.411 (3)
P2—C3	1.803 (2)	C10—C12	1.435 (3)
O2—H2	0.8400	C11—C15	1.433 (3)
O4—Cu1ⁱⁱⁱ	1.9371 (14)	C12—C13	1.360 (3)
O5—H5	0.8400	C12—H12	0.9500
O6—Cu1ⁱ	1.9340 (15)	C13—C14	1.437 (3)
N1—C7	1.333 (3)	C13—H13	0.9500
N1—C11	1.354 (3)	C14—C15	1.400 (3)
N2—C18	1.333 (3)	C14—C16	1.410 (3)
N2—C15	1.356 (3)	C16—C17	1.376 (3)
C1—C2	1.396 (3)	C16—H16	0.9500
C1—C6	1.401 (3)	C17—C18	1.404 (3)
C2—C3	1.400 (3)	C17—H17	0.9500
C2—H2A	0.9500	C18—H18	0.9500
C3—C4	1.399 (3)

O6ⁱ—Cu1—O4ⁱⁱ	96.46 (6)	C3—C4—H4	120.0
O6ⁱ—Cu1—N2	160.52 (7)	C6—C5—C4	120.02 (19)
O4ⁱⁱ—Cu1—N2	90.51 (7)	C6—C5—H5A	120.0
O6ⁱ—Cu1—N1	90.87 (7)	C4—C5—H5A	120.0
O4ⁱⁱ—Cu1—N1	171.94 (7)	C5—C6—C1	120.71 (19)
N2—Cu1—N1	81.49 (7)	C5—C6—H6	119.6
O6ⁱ—Cu1—O1	98.12 (6)	C1—C6—H6	119.6
O4ⁱⁱ—Cu1—O1	91.46 (6)	N1—C7—C8	122.1 (2)
N2—Cu1—O1	99.88 (6)	N1—C7—H7	118.9
N1—Cu1—O1	90.82 (6)	C8—C7—H7	118.9
O1—P1—O2	111.95 (9)	C9—C8—C7	119.4 (2)
O1—P1—O3	112.39 (9)	C9—C8—H8	120.3
O2—P1—O3	112.01 (9)	C7—C8—H8	120.3
O1—P1—C1	107.19 (9)	C8—C9—C10	119.79 (19)
O2—P1—C1	106.22 (9)	C8—C9—H9	120.1
O3—P1—C1	106.62 (9)	C10—C9—H9	120.1
O6—P2—O4	115.35 (9)	C11—C10—C9	116.6 (2)
O6—P2—O5	110.16 (8)	C11—C10—C12	118.5 (2)
O4—P2—O5	110.15 (8)	C9—C10—C12	124.91 (19)
O6—P2—C3	106.07 (9)	N1—C11—C10	123.45 (19)
O4—P2—C3	109.09 (9)	N1—C11—C15	116.48 (18)
O5—P2—C3	105.48 (9)	C10—C11—C15	120.06 (19)
P1—O1—Cu1	128.96 (9)	C13—C12—C10	121.23 (19)
P1—O2—H2	109.5	C13—C12—H12	119.4
P2—O4—Cu1ⁱⁱⁱ	127.78 (9)	C10—C12—H12	119.4
P2—O5—H5	109.5	C12—C13—C14	121.2 (2)
P2—O6—Cu1ⁱ	138.73 (9)	C12—C13—H13	119.4
C7—N1—C11	118.57 (18)	C14—C13—H13	119.4
C7—N1—Cu1	128.72 (15)	C15—C14—C16	117.0 (2)
C11—N1—Cu1	112.34 (13)	C15—C14—C13	118.7 (2)
C18—N2—C15	118.12 (18)	C16—C14—C13	124.3 (2)
C18—N2—Cu1	128.83 (15)	N2—C15—C14	123.71 (19)
C15—N2—Cu1	112.63 (13)	N2—C15—C11	115.95 (18)
C2—C1—C6	118.83 (18)	C14—C15—C11	120.34 (19)
C2—C1—P1	120.67 (15)	C17—C16—C14	119.2 (2)
C6—C1—P1	120.50 (15)	C17—C16—H16	120.4
C1—C2—C3	121.07 (18)	C14—C16—H16	120.4
C1—C2—H2A	119.5	C16—C17—C18	119.7 (2)
C3—C2—H2A	119.5	C16—C17—H17	120.1
C4—C3—C2	119.43 (18)	C18—C17—H17	120.1
C4—C3—P2	120.71 (15)	N2—C18—C17	122.1 (2)
C2—C3—P2	119.75 (15)	N2—C18—H18	118.9
C5—C4—C3	119.92 (18)	C17—C18—H18	118.9
C5—C4—H4	120.0

O2—P1—O1—Cu1	−2.35 (13)	C2—C3—C4—C5	0.9 (3)
O3—P1—O1—Cu1	124.73 (10)	P2—C3—C4—C5	−175.41 (16)
C1—P1—O1—Cu1	−118.45 (11)	C3—C4—C5—C6	0.4 (3)
O6ⁱ—Cu1—O1—P1	169.38 (10)	C4—C5—C6—C1	−1.0 (3)
O4ⁱⁱ—Cu1—O1—P1	−93.88 (11)	C2—C1—C6—C5	0.4 (3)
N2—Cu1—O1—P1	−3.11 (12)	P1—C1—C6—C5	−178.59 (16)
N1—Cu1—O1—P1	78.39 (11)	C11—N1—C7—C8	0.7 (3)
O6—P2—O4—Cu1ⁱⁱⁱ	−106.17 (11)	Cu1—N1—C7—C8	−171.75 (16)
O5—P2—O4—Cu1ⁱⁱⁱ	19.28 (13)	N1—C7—C8—C9	−0.1 (3)
C3—P2—O4—Cu1ⁱⁱⁱ	134.62 (11)	C7—C8—C9—C10	−0.2 (3)
O4—P2—O6—Cu1ⁱ	97.16 (15)	C8—C9—C10—C11	−0.1 (3)
O5—P2—O6—Cu1ⁱ	−28.29 (17)	C8—C9—C10—C12	179.7 (2)
C3—P2—O6—Cu1ⁱ	−141.97 (14)	C7—N1—C11—C10	−1.0 (3)
O6ⁱ—Cu1—N1—C7	−16.18 (18)	Cu1—N1—C11—C10	172.65 (16)
N2—Cu1—N1—C7	−178.19 (19)	C7—N1—C11—C15	178.83 (18)
O1—Cu1—N1—C7	81.95 (18)	Cu1—N1—C11—C15	−7.6 (2)
O6ⁱ—Cu1—N1—C11	171.00 (14)	C9—C10—C11—N1	0.7 (3)
N2—Cu1—N1—C11	9.00 (14)	C12—C10—C11—N1	−179.16 (19)
O1—Cu1—N1—C11	−90.87 (14)	C9—C10—C11—C15	−179.11 (18)
O6ⁱ—Cu1—N2—C18	110.8 (2)	C12—C10—C11—C15	1.0 (3)
O4ⁱⁱ—Cu1—N2—C18	−0.45 (18)	C11—C10—C12—C13	−0.4 (3)
N1—Cu1—N2—C18	178.63 (19)	C9—C10—C12—C13	179.7 (2)
O1—Cu1—N2—C18	−92.02 (18)	C10—C12—C13—C14	−1.1 (3)
O6ⁱ—Cu1—N2—C15	−76.9 (2)	C12—C13—C14—C15	2.0 (3)
O4ⁱⁱ—Cu1—N2—C15	171.83 (14)	C12—C13—C14—C16	−177.0 (2)
N1—Cu1—N2—C15	−9.08 (14)	C18—N2—C15—C14	0.7 (3)
O1—Cu1—N2—C15	80.27 (14)	Cu1—N2—C15—C14	−172.44 (16)
O1—P1—C1—C2	26.20 (19)	C18—N2—C15—C11	−179.11 (18)
O2—P1—C1—C2	−93.64 (17)	Cu1—N2—C15—C11	7.7 (2)
O3—P1—C1—C2	146.75 (16)	C16—C14—C15—N2	−2.1 (3)
O1—P1—C1—C6	−154.87 (16)	C13—C14—C15—N2	178.79 (19)
O2—P1—C1—C6	85.30 (18)	C16—C14—C15—C11	177.76 (19)
O3—P1—C1—C6	−34.31 (19)	C13—C14—C15—C11	−1.4 (3)
C6—C1—C2—C3	0.9 (3)	N1—C11—C15—N2	−0.1 (3)
P1—C1—C2—C3	179.87 (16)	C10—C11—C15—N2	179.72 (18)
C1—C2—C3—C4	−1.5 (3)	N1—C11—C15—C14	−179.95 (18)
C1—C2—C3—P2	174.77 (16)	C10—C11—C15—C14	−0.1 (3)
O6—P2—C3—C4	141.91 (17)	C15—C14—C16—C17	1.3 (3)
O4—P2—C3—C4	−93.26 (18)	C13—C14—C16—C17	−179.6 (2)
O5—P2—C3—C4	25.05 (19)	C14—C16—C17—C18	0.6 (3)
O6—P2—C3—C2	−34.34 (19)	C15—N2—C18—C17	1.3 (3)
O4—P2—C3—C2	90.49 (17)	Cu1—N2—C18—C17	173.27 (16)
O5—P2—C3—C2	−151.21 (16)	C16—C17—C18—N2	−2.0 (3)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O3^iv	0.84	1.81	2.489 (2)	136
O5—H5···O1ⁱⁱⁱ	0.84	1.74	2.574 (2)	173

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

Experimental details

Crystal data
Chemical formula	[Cu(C₁₂H₈N₂)(C₆H₆O₆P₂)]
M_r	479.79
Crystal system, space group	Triclinic, P1
Temperature (K)	98
a, b, c (Å)	8.6142 (10), 9.0554 (10), 12.1094 (13)
α, β, γ (°)	99.688 (2), 106.542 (2), 98.184 (2)
V (Å³)	874.30 (17)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.48
Crystal size (mm)	0.35 × 0.30 × 0.21

Data collection
Diffractometer	Bruker APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1998)
T_min, T_max	0.626, 0.747
No. of measured, independent and observed [I > 2σ(I)] reflections	8704, 4190, 4042
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.662

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.087, 1.09
No. of reflections	4190
No. of parameters	262
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.71, −0.67

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), CrystalMaker (Palmer, 2006), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O3ⁱ	0.84	1.81	2.489 (2)	136.4
O5—H5···O1ⁱⁱ	0.84	1.74	2.574 (2)	172.8

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

Acknowledgements

This work was supported by a grant from the National Science Foundation, CHE-0907787.

References

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