Poly[diaqua­bis­[μ-1-hy­droxy-2-(imidazol-3-ium-1-yl)ethane-1,1-diyldiphospho­nato]tricopper(II)]

Li, Y.; Sun, D.; Zang, H.; Han, L.; Su, G.

doi:10.1107/S1600536810046398

Poly[diaquabis[μ-1-hydroxy-2-(imidazol-3-ium-1-yl)ethane-1,1-diyldiphosphonato]tricopper(II)]

Y. Li, D. Sun, H. Zang, L. Han and G. Su

In the title coordination polymer, [Cu₃(C₅H₇N₂O₇P₂)₂(H₂O)₂]_n, one Cu^II atom is five-coordinated by five O atoms from three 1-hydroxy-2-(imidazol-3-ium-1-yl)ethane-1,1-diyldiphosphonate (L) ligands in a distorted square-pyramidal geometry. The other Cu^II atom, lying on an inversion center, is six-coordinated in a distorted octahedral geometry by four O atoms from two L ligands and two O atoms from two water molecules. The five-coordinated Cu^II atoms are linked by phosphonate O atoms of the L ligands, forming a polymeric chain. These chains are further linked by the six-coordinated Cu atoms into a layer parallel to ( $\overline{1}$ 01). N—H

O and O—H

O hydrogen bonds connect the layers into a three-dimensional supramolecular structure.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536810046398/hy2377sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536810046398/hy2377Isup2.hkl Contains datablock I

CCDC reference: 802993

checkCIF report

Key indicators

Single-crystal X-ray study
T = 293 K
Mean (C-C) = 0.005 Å
R factor = 0.027
wR factor = 0.073
Data-to-parameter ratio = 11.3

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT411_ALERT_2_C Short Inter H...H Contact  H2     ..  H2      ..       2.04 Ang.
PLAT414_ALERT_2_C Short Intra D-H..H-X       H2     ..  H7      ..       1.96 Ang.
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600         16
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600         20

Alert level G
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          2
PLAT154_ALERT_1_G The su's on the Cell Angles are Equal  (x 10000)        200 Deg.
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported   _diffrn_ambient_temperature        293 K
PLAT793_ALERT_4_G The Model has Chirality at P1      (Verify) ....          S
PLAT793_ALERT_4_G The Model has Chirality at P2      (Verify) ....          S
PLAT793_ALERT_4_G The Model has Chirality at C5      (Verify) ....          S
PLAT794_ALERT_5_G Note: Tentative Bond Valency for Cu1     .......       1.99
PLAT794_ALERT_5_G Note: Tentative Bond Valency for Cu2     .......       2.08

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   4 ALERT level C = Check and explain
   9 ALERT level G = General alerts; check

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   4 ALERT type 4 Improvement, methodology, query or suggestion
   2 ALERT type 5 Informative message, check

Comment top

During the last two decades great research efforts have been devoted to the synthesis and design of metal phosphonates due to their potential applications in electrooptics, ion exchange, catalysis, and stent in intestinal or biliary (Katz et al., 1994). Herein, we present a new copper(II)–phosphonate complex.

The structure analysis reveals that the title compound has a two-dimensional polymeric structure. As shown in Fig. 1, there exist two kinds of crystallographically unique Cu^II ions. Atom Cu1 is five-coordinated by four phosphonate O atoms and one hydroxy O atom from three 2-(imidazol-3-ium-1-yl)-1-hydroxy-1,1-ethylidenediphosphonate (L) ligands. Atom Cu2 is six-coordinated by four O atoms from two L ligands and two O atoms from two water molecules. The Cu1 atoms are linked by the phosphonate O atoms, resulting in a one-dimensional polymeric chain. These chains are further linked by the Cu2 atoms into a layer (Fig. 2). N—H···O and O—H···O hydrogen bonds involving the coordinated water molecules and L ligands (Table 1) lead to the formation of a three-dimensional supramolecular network.

Related literature top

For general background to the applications of metal phosphonates, see: Katz et al. (1994).

Experimental top

The synthesis was performed under hydrothermal conditions. A mixture of CuCl₂.2H₂O (0.034 g, 0.2 mmol), L ligand (0.070 g, 0.2 mmol) and H₂O (15 ml) in a 25 ml stainless steel reactor with a Teflon liner was heated from 293 to 423 K in 2 h and maintained at 423 K for 72 h. After the mixture was cooled to 298 K, green crystals of the title compound were obtained (yield: 56%).

Structure description top

For general background to the applications of metal phosphonates, see: Katz et al. (1994).

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level. H atoms have been omitted for clarity. [Symmetry codes: (i) -x, -y - 1, -z; (ii) x - 1, y - 1, z - 1; (iii) -x, -y - 2, -z; (iv) x + 1, y + 1, z + 1; (v) -x + 1, -y, -z + 1; (vi) x, y + 1, z; (vii) -x - 1, -y - 2, -z - 1.]
	Fig. 2. Two-dimensional layer structure in the title compound.

Poly[diaquabis[µ-1-hydroxy-2-(imidazol-3-ium-1-yl)ethane-1,1- diyldiphosphonato]tricopper(II)] top

Crystal data top

[Cu₃(C₅H₇N₂O₇P₂)₂(H₂O)₂]	Z = 1
M_r = 764.81	F(000) = 381
Triclinic, P1	D_x = 2.510 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.4167 (9) Å	Cell parameters from 1973 reflections
b = 8.1502 (10) Å	θ = 1.9–28.3°
c = 9.5228 (12) Å	µ = 3.54 mm⁻¹
α = 104.747 (2)°	T = 293 K
β = 107.658 (2)°	Block, blue
γ = 101.484 (2)°	0.30 × 0.28 × 0.21 mm
V = 506.03 (11) Å³

Data collection top

Bruker APEX CCD diffractometer	1973 independent reflections
Radiation source: fine-focus sealed tube	1729 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.012
φ and ω scans	θ_max = 26.1°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→8
T_min = 0.58, T_max = 0.75	k = −10→6
2771 measured reflections	l = −11→11

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)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.073	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.039P)² + 0.8352P] where P = (F_o² + 2F_c²)/3
1973 reflections	(Δ/σ)_max = 0.001
175 parameters	Δρ_max = 0.55 e Å⁻³
2 restraints	Δρ_min = −0.68 e Å⁻³

Crystal data top

[Cu₃(C₅H₇N₂O₇P₂)₂(H₂O)₂]	γ = 101.484 (2)°
M_r = 764.81	V = 506.03 (11) Å³
Triclinic, P1	Z = 1
a = 7.4167 (9) Å	Mo Kα radiation
b = 8.1502 (10) Å	µ = 3.54 mm⁻¹
c = 9.5228 (12) Å	T = 293 K
α = 104.747 (2)°	0.30 × 0.28 × 0.21 mm
β = 107.658 (2)°

Data collection top

Bruker APEX CCD diffractometer	1973 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1729 reflections with I > 2σ(I)
T_min = 0.58, T_max = 0.75	R_int = 0.012
2771 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.027	2 restraints
wR(F²) = 0.073	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.55 e Å⁻³
1973 reflections	Δρ_min = −0.68 e Å⁻³
175 parameters

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

	x	y	z	U_iso*/U_eq
C1	0.2068 (5)	−0.5648 (4)	−0.4517 (4)	0.0140 (7)
H1	0.1047	−0.6119	−0.5497	0.017*
C2	0.3998 (5)	−0.5281 (5)	−0.2131 (4)	0.0173 (7)
H2	0.4524	−0.5475	−0.1190	0.021*
C3	0.4782 (5)	−0.3932 (5)	−0.2542 (4)	0.0186 (7)
H3	0.5935	−0.2995	−0.1928	0.022*
C4	0.0950 (5)	−0.7988 (4)	−0.3483 (4)	0.0122 (7)
H4A	0.1673	−0.8856	−0.3460	0.015*
H4B	−0.0147	−0.8435	−0.4487	0.015*
C5	0.0110 (5)	−0.7833 (4)	−0.2191 (4)	0.0090 (6)
N1	0.2266 (4)	−0.6324 (4)	−0.3368 (3)	0.0110 (6)
N2	0.3567 (4)	−0.4195 (4)	−0.4031 (3)	0.0159 (6)
H2A	0.3750	−0.3518	−0.4568	0.019*
O1	−0.2890 (3)	−1.0888 (3)	−0.3981 (2)	0.0104 (5)
O2	−0.2018 (3)	−0.9799 (3)	−0.1041 (2)	0.0098 (5)
O3	0.0217 (3)	−1.1193 (3)	−0.2195 (2)	0.0099 (5)
O4	0.2060 (3)	−0.3636 (3)	0.0771 (2)	0.0100 (5)
O5	0.0648 (3)	−0.5288 (3)	0.2312 (2)	0.0105 (5)
O6	0.3438 (3)	−0.2484 (3)	0.3787 (3)	0.0115 (5)
O7	0.1644 (3)	−0.7118 (3)	−0.0644 (2)	0.0105 (5)
H7	0.2315	−0.6121	−0.0511	0.016*
P1	−0.12407 (12)	−1.01022 (10)	−0.23716 (9)	0.00780 (18)
P2	0.16460 (12)	−0.34839 (10)	0.22756 (9)	0.00806 (18)
Cu1	−0.07744 (6)	−0.75596 (5)	0.06756 (4)	0.00871 (12)
Cu2	0.5000	0.0000	0.5000	0.01057 (15)
O1W	0.3909 (4)	−0.0271 (4)	0.7275 (3)	0.0282 (6)
H1A	0.302 (6)	−0.054 (7)	0.768 (5)	0.042*
H1B	0.491 (5)	−0.001 (6)	0.815 (4)	0.042*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0184 (18)	0.0150 (17)	0.0093 (15)	0.0056 (14)	0.0050 (13)	0.0048 (13)
C2	0.0147 (17)	0.0198 (18)	0.0129 (16)	0.0011 (14)	0.0017 (14)	0.0058 (14)
C3	0.0171 (18)	0.0175 (18)	0.0163 (17)	−0.0001 (14)	0.0032 (14)	0.0056 (14)
C4	0.0152 (17)	0.0084 (15)	0.0117 (16)	0.0021 (13)	0.0061 (13)	0.0011 (13)
C5	0.0099 (15)	0.0080 (15)	0.0064 (14)	−0.0002 (12)	0.0010 (12)	0.0026 (12)
N1	0.0119 (13)	0.0090 (13)	0.0128 (13)	0.0032 (11)	0.0050 (11)	0.0040 (11)
N2	0.0209 (16)	0.0133 (15)	0.0156 (14)	0.0029 (12)	0.0077 (12)	0.0089 (12)
O1	0.0133 (12)	0.0068 (11)	0.0075 (11)	0.0025 (9)	0.0004 (9)	0.0009 (9)
O2	0.0126 (11)	0.0060 (11)	0.0093 (10)	0.0004 (9)	0.0045 (9)	0.0019 (9)
O3	0.0137 (11)	0.0072 (11)	0.0089 (11)	0.0032 (9)	0.0036 (9)	0.0032 (9)
O4	0.0134 (11)	0.0080 (11)	0.0091 (11)	0.0042 (9)	0.0044 (9)	0.0029 (9)
O5	0.0149 (12)	0.0075 (11)	0.0072 (11)	0.0021 (9)	0.0028 (9)	0.0020 (9)
O6	0.0127 (11)	0.0082 (11)	0.0086 (11)	0.0016 (9)	−0.0003 (9)	0.0013 (9)
O7	0.0107 (11)	0.0075 (11)	0.0077 (11)	−0.0004 (9)	−0.0008 (9)	0.0008 (9)
P1	0.0101 (4)	0.0055 (4)	0.0064 (4)	0.0017 (3)	0.0022 (3)	0.0014 (3)
P2	0.0104 (4)	0.0049 (4)	0.0062 (4)	0.0012 (3)	0.0014 (3)	0.0006 (3)
Cu1	0.0123 (2)	0.0056 (2)	0.0063 (2)	0.00188 (15)	0.00214 (15)	0.00108 (15)
Cu2	0.0109 (3)	0.0053 (3)	0.0098 (3)	0.0012 (2)	−0.0012 (2)	0.0005 (2)
O1W	0.0233 (15)	0.0366 (17)	0.0267 (15)	0.0095 (13)	0.0093 (12)	0.0132 (13)

Geometric parameters (Å, º) top

C1—N2	1.318 (4)	O2—Cu1	1.936 (2)
C1—N1	1.329 (4)	O3—P1	1.529 (2)
C1—H1	0.9300	O3—Cu1ⁱⁱⁱ	1.962 (2)
C2—C3	1.343 (5)	O4—P2	1.534 (2)
C2—N1	1.377 (4)	O4—Cu1ⁱ	2.003 (2)
C2—H2	0.9300	O5—P2	1.523 (2)
C3—N2	1.364 (4)	O5—Cu1	1.930 (2)
C3—H3	0.9300	O6—P2	1.521 (2)
C4—N1	1.462 (4)	O6—Cu2	1.959 (2)
C4—C5	1.528 (4)	O7—H7	0.8200
C4—H4A	0.9700	P2—C5ⁱ	1.842 (3)
C4—H4B	0.9700	Cu1—O3ⁱⁱⁱ	1.962 (2)
C5—O7	1.444 (4)	Cu1—O4ⁱ	2.003 (2)
C5—P2ⁱ	1.842 (3)	Cu2—O1ⁱ	1.950 (2)
C5—P1	1.857 (3)	Cu2—O1^iv	1.950 (2)
N2—H2A	0.8600	Cu2—O6^v	1.959 (2)
O1—P1	1.519 (2)	O1W—H1A	0.88 (5)
O1—Cu2ⁱⁱ	1.950 (2)	O1W—H1B	0.87 (2)
O2—P1	1.530 (2)

N2—C1—N1	108.3 (3)	P2—O4—Cu1ⁱ	119.28 (13)
N2—C1—H1	125.8	P2—O5—Cu1	131.88 (14)
N1—C1—H1	125.8	P2—O6—Cu2	136.89 (14)
C3—C2—N1	107.0 (3)	C5—O7—H7	109.5
C3—C2—H2	126.5	O1—P1—O3	111.33 (12)
N1—C2—H2	126.5	O1—P1—O2	112.88 (13)
C2—C3—N2	107.0 (3)	O3—P1—O2	112.51 (12)
C2—C3—H3	126.5	O1—P1—C5	106.82 (13)
N2—C3—H3	126.5	O3—P1—C5	108.50 (14)
N1—C4—C5	114.6 (3)	O2—P1—C5	104.30 (13)
N1—C4—H4A	108.6	O6—P2—O5	109.75 (13)
C5—C4—H4A	108.6	O6—P2—O4	114.99 (13)
N1—C4—H4B	108.6	O5—P2—O4	112.22 (12)
C5—C4—H4B	108.6	O6—P2—C5ⁱ	107.03 (13)
H4A—C4—H4B	107.6	O5—P2—C5ⁱ	108.36 (14)
O7—C5—C4	112.5 (3)	O4—P2—C5ⁱ	104.02 (13)
O7—C5—P2ⁱ	108.6 (2)	O5—Cu1—O2	174.89 (9)
C4—C5—P2ⁱ	114.1 (2)	O5—Cu1—O3ⁱⁱⁱ	91.03 (9)
O7—C5—P1	105.3 (2)	O2—Cu1—O3ⁱⁱⁱ	91.03 (9)
C4—C5—P1	108.5 (2)	O5—Cu1—O4ⁱ	90.70 (9)
P2ⁱ—C5—P1	107.27 (16)	O2—Cu1—O4ⁱ	88.63 (9)
C1—N1—C2	108.3 (3)	O3ⁱⁱⁱ—Cu1—O4ⁱ	163.80 (9)
C1—N1—C4	124.8 (3)	O1ⁱ—Cu2—O1^iv	180.00 (13)
C2—N1—C4	126.7 (3)	O1ⁱ—Cu2—O6	92.58 (9)
C1—N2—C3	109.3 (3)	O1^iv—Cu2—O6	87.42 (9)
C1—N2—H2A	125.3	O1ⁱ—Cu2—O6^v	87.42 (9)
C3—N2—H2A	125.3	O1^iv—Cu2—O6^v	92.58 (9)
P1—O1—Cu2ⁱⁱ	131.22 (13)	O6—Cu2—O6^v	180.00 (19)
P1—O2—Cu1	118.08 (13)	H1A—O1W—H1B	93 (4)
P1—O3—Cu1ⁱⁱⁱ	125.96 (13)

N1—C2—C3—N2	−2.0 (4)	P2ⁱ—C5—P1—O1	63.64 (18)
N1—C4—C5—O7	−56.4 (4)	O7—C5—P1—O3	−60.7 (2)
N1—C4—C5—P2ⁱ	67.9 (3)	C4—C5—P1—O3	60.0 (2)
N1—C4—C5—P1	−172.6 (2)	P2ⁱ—C5—P1—O3	−176.24 (13)
N2—C1—N1—C2	−2.1 (4)	O7—C5—P1—O2	59.4 (2)
N2—C1—N1—C4	−176.7 (3)	C4—C5—P1—O2	−179.9 (2)
C3—C2—N1—C1	2.5 (4)	P2ⁱ—C5—P1—O2	−56.12 (17)
C3—C2—N1—C4	177.0 (3)	Cu2—O6—P2—O5	−156.45 (19)
C5—C4—N1—C1	−127.4 (3)	Cu2—O6—P2—O4	75.9 (2)
C5—C4—N1—C2	58.9 (4)	Cu2—O6—P2—C5ⁱ	−39.1 (2)
N1—C1—N2—C3	0.9 (4)	Cu1—O5—P2—O6	−147.75 (17)
C2—C3—N2—C1	0.7 (4)	Cu1—O5—P2—O4	−18.6 (2)
Cu2ⁱⁱ—O1—P1—O3	−172.39 (16)	Cu1—O5—P2—C5ⁱ	95.7 (2)
Cu2ⁱⁱ—O1—P1—O2	60.0 (2)	Cu1ⁱ—O4—P2—O6	−115.31 (15)
Cu2ⁱⁱ—O1—P1—C5	−54.1 (2)	Cu1ⁱ—O4—P2—O5	118.31 (14)
Cu1ⁱⁱⁱ—O3—P1—O1	−118.20 (16)	Cu1ⁱ—O4—P2—C5ⁱ	1.40 (18)
Cu1ⁱⁱⁱ—O3—P1—O2	9.7 (2)	P2—O5—Cu1—O3ⁱⁱⁱ	156.80 (19)
Cu1ⁱⁱⁱ—O3—P1—C5	124.53 (16)	P2—O5—Cu1—O4ⁱ	−39.31 (19)
Cu1—O2—P1—O1	−134.92 (14)	P1—O2—Cu1—O3ⁱⁱⁱ	−124.84 (14)
Cu1—O2—P1—O3	98.05 (15)	P1—O2—Cu1—O4ⁱ	71.36 (15)
Cu1—O2—P1—C5	−19.34 (18)	P2—O6—Cu2—O1ⁱ	19.3 (2)
O7—C5—P1—O1	179.20 (18)	P2—O6—Cu2—O1^iv	−160.7 (2)
C4—C5—P1—O1	−60.1 (2)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O6^vi	0.86	1.94	2.771 (4)	163
O7—H7···O4	0.82	2.16	2.724 (3)	126
O1W—H1A···O3^vii	0.88 (5)	2.09 (3)	2.921 (4)	157 (5)
O1W—H1B···O2^iv	0.87 (2)	2.13 (4)	2.851 (4)	140 (4)

Symmetry codes: (iv) x+1, y+1, z+1; (vi) x, y, z−1; (vii) x, y+1, z+1.

Experimental details

Crystal data
Chemical formula	[Cu₃(C₅H₇N₂O₇P₂)₂(H₂O)₂]
M_r	764.81
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	7.4167 (9), 8.1502 (10), 9.5228 (12)
α, β, γ (°)	104.747 (2), 107.658 (2), 101.484 (2)
V (Å³)	506.03 (11)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	3.54
Crystal size (mm)	0.30 × 0.28 × 0.21

Data collection
Diffractometer	Bruker APEX CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.58, 0.75
No. of measured, independent and observed [I > 2σ(I)] reflections	2771, 1973, 1729
R_int	0.012
(sin θ/λ)_max (Å⁻¹)	0.619

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.073, 1.05
No. of reflections	1973
No. of parameters	175
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.55, −0.68

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999), SHELXTL (Sheldrick, 2008).