A one-dimensional copper(II) phenyl-ene-diphospho-nate: catena-poly[[(1,10-phenanthroline-κN,N')copper(II)]-μ(3)-[m-phenyl-enediphospho-nato-κO:O':O'']].

The title compound, [Cu(1,3-HO(3)PC(6)H(4)PO(3)H)(C(12)H(8)N(2))](n), is a coordination polymer of the metal-diphospho-nate family. The chain structure is constructed from '4+1' square-py-rami-dally coordinated copper(II) atoms bonded to chelating phenanthroline (phen) ligands and linked through 1,3-phenyldihydrogendiphospho-nate ligands. The basal plane of the Cu(II) site is defined by the phen nitro-gen donors and phospho-nate oxygen atoms from two diphospho-nate ligands, while the apical position is occupied by an oxygen donor from a third diphospho-nate 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 inter-actions 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 = 479.79

Triclinic,

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[F 2 > 2σ(F 2)] = 0.033

wR(F 2) = 0.087

S = 1.09

4190 reflections

262 parameters

H-atom parameters constrained

Δρmax = 0.71 e Å−3

Δρmin = −0.67 e Å−3

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 ▶).

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

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

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

[Cu(C12H8N2)(C6H6O6P2)]	Z = 2
Mr = 479.79	F(000) = 486
Triclinic, P1	Dx = 1.823 Mg m−3Dm = 1.81 (2) Mg m−3Dm 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

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

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(Fo2) + (0.0425P)2 + 1.0147P] where P = (Fo2 + 2Fc2)/3
4190 reflections	(Δ/σ)max = 0.001
262 parameters	Δρmax = 0.71 e Å−3
0 restraints	Δρmin = −0.67 e Å−3

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
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*

	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)

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)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O3iv	0.84	1.81	2.489 (2)	136
O5—H5···O1iii	0.84	1.74	2.574 (2)	173

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) ; (ii) .