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Two pseudo-polymorphic polymers, poly[ethyl­ene­diammo­nium [[aqua­copper(II)]-[mu]4-benzene-1,2,4,5-tetra­carboxyl­ato] dihydrate], {(C2H10N2)[Cu(C10H2O8)(H2O)]·2H2O}n, (I), and poly[ethyl­ene­diammonium [copper(II)-[mu]4-benzene-1,2,4,5-tetra­carboxyl­ato] 2.5-hydrate], {(C2H10N2)[Cu(C10H2O8)]·2.5H2O}n, (II), contain two-dimensional anionic layers, ethyl­enediammonium (H2en) cations acting as counter-ions and free water mol­ecules. Although the topological structures of the two anionic layers are homologous, the coordination environments of the CuII centres are different. In (I), the CuII centre, sitting on a general position, has a square-pyramidal environment. The two independent benzene-1,2,4,5-tetra­carboxyl­ate (btc) anions rest on centres of inversion. The CuII cation in (II) is located on a twofold axis in a square-planar coordination. The H2en cation is on an inversion centre and the btc ligand is split by a mirror plane. Extensive hydrogen-bonding inter­actions between the complexes, H2en cations and water mol­ecules lead to the formation of three-dimensional supra­molecular structures.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107019853/sq3073sup1.cif
Contains datablocks global, I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270107019853/sq3073Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270107019853/sq3073IIsup3.hkl
Contains datablock II

CCDC references: 652499; 652500

Comment top

Research on metal–organic coordination polymers (MOCPs) has received continuous interest, due to their novel topologies and potential application as functional materials (Yaghi et al., 1998). A key strategy in the design of MOCPs is to select suitable bi- or multidentate bridging ligands. Recently, MOCPs using polycarboxylic acids as bridging ligands have become the most fruitful family in this field (Eddaoudi et al., 2001; Shi et al., 2001). A prime example of such a ligand is 1,2,4,5-benzenetetracarboxylic acid (H4btc), which has very versatile coordination behaviour to generate many unexpected and interesting MOCPs (Barthelet et al., 2003; Kumagai et al., 2002). However, polycarboxylic acid-based MOCPs with protonated organic amines as counter-ions remain rare (Cheng et al., 2002), which might be due to the propensity of amines to coordinate metal cations (Ganesan & Natarajan, 2004). We report here the synthesis and structure of two pseudo-polymorphic coordination polymers, (I) and (II). Both complexes exhibit two-dimensional structures and contain protonated ethylenediamine molecules (H2en) as counter-ions.

The asymmetric part of the anionic layer of (I) contains one CuII cation, one water molecule and two btc4- ligands on inversion centres. The CuII cation has a square-pyramidal environment, completed by one aqua O atom in the axial position and four carboxyl O atoms from four btc4- ligands in the basal plane of the square pyramid (Fig. 1). As expected, the Cu—Oaqua bond length is noticeably longer than the Cu—Ocarboxyl bonds. Both of the btc4- ligands adopt a µ4-η1:η1:η1:η1 bridging mode to connect four CuII cations, resulting in a two-dimensional [Cu(btc)(H2O)]n2n- anionic layer with a (4,4) topological network running parallel to the (011) plane (Fig. 2).

A notable feature of complex (I) is that the two btc ligands form distinctly different arrays. The phenyl groups of two btc4- ligands are tilted by different amounts with respect to the [CuO4(H2O)]n2n- anionic layer: 25.48 (8)° for the C7/C6/C8/C7i/C6i/C8i plane and 42.37 (7)° for the C2/C1/C3/C2ii/C1ii/C3ii plane [symmetry codes: (i) 1 - x, -y, 2 - z; (ii) 1 - x, 1 - y, 1 - z].

Within the anionic layer, the water molecules coordinated to the CuII cations are alternately directed up and down (Fig. 2). These anionic layers are separated by the H2en cations and two free water molecules. Extensive N—H···O and O—H···O hydrogen-bonding interactions, with N···O or O···O distances within the 3 Å range, connect the two-dimensional networks, H2en cations and free water molecules, resulting in a three-dimensional supramolecular structure.

In (II), the asymmetric unit contains one CuII atom sitting on a twofold axis, one H2en cation on an inversion centre, one btc4- ligand straddling a mirror plane, and free water molecules in general positions. The water molecule of crystallization (OW2) is disordered across a mirror plane and the occupancy was fixed at 0.5. The CuII centre has a square-planar coordination with four carboxyl O atoms from four btc4- ligands (Fig. 3). The coordination mode of the btc4- ligand and the topological structure of the anionic layer are essentially the same as in (I), producing the [Cu(btc)]n2n- anionic layer parallel to the ab plane. The phenyl groups of the btc4- ligands are tilted with respect to the [CuO4]n2n- anionic layer by 34.32 (7)° for the C1/C3/C4/C3i/C1i/C2 plane [symmetry code: (i) x, 1 - y, z] (Fig. 4). As in (I), there are also many hydrogen-bonding interactions with N···O or O···O distances within the 3 Å range, which lead to a three-dimensional supramolecular structure for (II).

Comparison of complexes (I) and (II) with a zinc pyromellitate previously reported by Ganesan et al. (2004) shows that, in both cases, there are anionic layers with the same topological network and a similar connection mode between the metal centres and the btc ligands. However, the tetrahedral coordination environment of the Zn centre is significantly different from the Cu coordination in (I) and (II), resulting in a corrugated anionic layer in [Zn(btc)]n2n-.

Related literature top

For related literature, see: Barthelet et al. (2003); Cheng et al. (2002); Eddaoudi et al. (2001); Ganesan & Natarajan (2004); Ganesan, Lightfoot & Natarajan (2004); Kumagai et al. (2002); Shi et al. (2001); Yaghi et al. (1998).

Experimental top

For the preparation of (I), CuCl2·2H2O (85 mg, 0.5 mmol), 1,2,4,5-benzenetetracarboxylate anhydride (109 mg, 0.5 mmol) and 2 M 1,2-ethylenediamine solution (0.25 ml) were dissolved in water (18 ml). The mixture was stirred and then a small quantity of 2 M HCl solution was added to adjust the pH to 3.0. The resulting solution was filtered and left to stand at room temperature. After approximately one week, blue block-shaped crystals of (I) suitable for X-ray crystallographic study were obtained.

For the preparation of (II), 2 M 1,2-ethylenediamine solution (0.25 ml), CuCl2·2H2O (170 mg, 1 mmol) and 1,2,4,5-benzenetetracarboxylate anhydride (164 mg, 0.75 mmol) were dissolved in water (15 ml), the mixture was heated to 333 K for 20 min, and a small quantity of 2 M NaOH solution was added to adjust the pH to 4.0. The resulting solution was left to stand at room temperature for about 3 d, after which blue needle-shaped crystals of (II) were collected for X-ray analysis.

Refinement top

In (I), all H atoms bonded to C and N atoms were located in difference Fourier maps and refined isotropically. H atoms bonded to water O atoms were located in difference maps and treated as riding atoms, with O—H = 0.82 Å and Uiso(H) = 1.2Ueq(O). [Uiso(H) in CIF have s.u.s - Please clarify] In (II), H atoms bonded to water O atoms were treated as for (I). [Positions for two of them have s.u.s in CIF, and the third has O—H = 0.85 Å - Please clarify] H atoms bonded to C were refined in idealized positions in the riding-model approximation, with C—H = 0.93 and 0.97 Å, and with Uiso(H) = 1.2Ueq(C). H atoms bonded to N were refined as riding, with N—H = 0.89 Å and Uiso(H) = 1.5Ueq(N). The occupancy factor of the water atom OW2 was initially calculated by linking it to a free variable; it was then fixed at 0.5 according to the value found after ten least-squares cycles.

Computing details top

For both compounds, data collection: RAPID AUTO (Rigaku, 1998); cell refinement: RAPID AUTO; data reduction: RAPID AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL/PC (Sheldrick, 1993); software used to prepare material for publication: SHELXL97/2 (Sheldrick,1997).

Figures top
[Figure 1] Fig. 1. The structure of (I), showing the atom-labelling scheme and with 50% probability displacement ellipsoids. [Symmetry codes: (a) 2 - x, -y, 2 - z; (b) 2 - x, 1 - y, 1 - z.]
[Figure 2] Fig. 2. A packing diagram for (I), viewed down the a axis. Anionic layers run parallel to the (011) plane. Hydrogen bonds are shown as open dashed lines.
[Figure 3] Fig. 3. The structure of (II), showing the atom-labelling scheme and with 50% probability displacement ellipsoids. [Symmetry codes: (a) 1 - x, y, -z; (b) 1/2 + x, 1/2 - y, z; (c) 1/2 - x, 1/2 - y, -z.]
[Figure 4] Fig. 4. A packing diagram for (II), viewed along the b axis. Anionic layers run parallel to the ab plane. Hydrogen bonds are shown as dashed lines.
(I) poly[ethylenediammonium [[aquacopper(II)]-µ4-benzene-1,2,4,5-tetracarboxylato] dihydrate] top
Crystal data top
(C2H10N2)[Cu(C10H2O8)(H2O)]·2H2OZ = 2
Mr = 429.83F(000) = 442
Triclinic, P1Dx = 1.761 Mg m3
a = 9.2104 (18) ÅMo Kα radiation, λ = 0.71073 Å
b = 9.4058 (19) ÅCell parameters from 3737 reflections
c = 10.225 (2) Åθ = 3.4–27.5°
α = 75.00 (3)°µ = 1.41 mm1
β = 75.50 (3)°T = 293 K
γ = 75.15 (3)°Block, blue
V = 810.8 (3) Å30.30 × 0.28 × 0.28 mm
Data collection top
Rigaku R-AXIS RAPID
diffractometer
3467 reflections with I > 2σ(I)
Radiation source: rotating anodeRint = 0.033
Graphite monochromatorθmax = 27.5°, θmin = 2.1°
oscillation scansh = 1111
3715 measured reflectionsk = 120
3715 independent reflectionsl = 1312
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.026H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.072 w = 1/[σ2(Fo2) + (0.0401P)2 + 0.5809P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max = 0.001
3715 reflectionsΔρmax = 0.57 e Å3
308 parametersΔρmin = 0.40 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0150 (15)
Crystal data top
(C2H10N2)[Cu(C10H2O8)(H2O)]·2H2Oγ = 75.15 (3)°
Mr = 429.83V = 810.8 (3) Å3
Triclinic, P1Z = 2
a = 9.2104 (18) ÅMo Kα radiation
b = 9.4058 (19) ŵ = 1.41 mm1
c = 10.225 (2) ÅT = 293 K
α = 75.00 (3)°0.30 × 0.28 × 0.28 mm
β = 75.50 (3)°
Data collection top
Rigaku R-AXIS RAPID
diffractometer
3467 reflections with I > 2σ(I)
3715 measured reflectionsRint = 0.033
3715 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0260 restraints
wR(F2) = 0.072H atoms treated by a mixture of independent and constrained refinement
S = 1.05Δρmax = 0.57 e Å3
3715 reflectionsΔρmin = 0.40 e Å3
308 parameters
Special details top

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
xyzUiso*/Ueq
Cu10.99060 (2)0.28496 (2)0.760656 (19)0.01342 (8)
O10.82828 (14)0.39380 (14)0.65881 (13)0.0196 (2)
O20.87040 (17)0.23022 (17)0.52356 (18)0.0352 (4)
O30.86216 (15)0.62072 (16)0.38431 (15)0.0284 (3)
O40.6880 (2)0.81088 (18)0.4609 (2)0.0434 (4)
O50.82726 (14)0.19069 (13)0.89632 (13)0.0192 (2)
O60.89454 (15)0.02207 (15)0.81841 (15)0.0272 (3)
O70.85090 (14)0.16153 (13)1.13541 (13)0.0188 (2)
O80.76112 (9)0.35098 (8)1.10985 (9)0.0304 (3)
OW10.94149 (9)0.47204 (8)0.87716 (9)0.0254 (3)
HW1A1.02860.45820.89060.048 (8)*
HW1B0.91940.55750.83190.052 (9)*
OW20.61525 (9)0.58506 (8)0.81357 (9)0.0432 (4)
HW2A0.66150.52210.76710.052 (9)*
HW2B0.65520.65870.78560.112 (17)*
OW30.84307 (9)0.24462 (8)0.71957 (9)0.0532 (5)
HW3A0.83980.17120.75020.106 (15)*
HW3B0.85080.22200.63550.117 (17)*
N10.8196 (2)1.05301 (19)0.35928 (19)0.0261 (3)
N20.6913 (2)1.3824 (2)0.08747 (19)0.0266 (3)
H10.558 (2)0.240 (2)0.577 (2)0.017 (5)*
H20.533 (3)0.228 (3)0.849 (3)0.030 (6)*
H30.710 (3)1.340 (3)0.019 (3)0.045 (8)*
H40.783 (3)0.977 (3)0.401 (3)0.039 (7)*
H50.616 (3)1.172 (3)0.317 (3)0.034 (6)*
H60.711 (3)1.098 (3)0.201 (3)0.038 (7)*
H70.909 (3)1.030 (3)0.315 (3)0.034 (7)*
H80.834 (3)1.100 (3)0.415 (3)0.036 (7)*
H90.582 (4)1.399 (3)0.120 (3)0.046 (8)*
H100.876 (3)1.268 (3)0.152 (3)0.040 (7)*
H120.776 (3)1.354 (3)0.257 (3)0.034 (6)*
H130.713 (3)1.468 (3)0.052 (3)0.038 (7)*
C10.64694 (18)0.42790 (18)0.52429 (16)0.0153 (3)
C20.61244 (18)0.58413 (18)0.47858 (16)0.0153 (3)
C30.53356 (19)0.34628 (18)0.54472 (17)0.0167 (3)
C40.79612 (19)0.34382 (18)0.56803 (18)0.0175 (3)
C50.7308 (2)0.6809 (2)0.44002 (18)0.0207 (3)
C60.64671 (18)0.03331 (17)0.95351 (16)0.0147 (3)
C70.62665 (18)0.10337 (18)1.04381 (17)0.0151 (3)
C80.51940 (19)0.13567 (18)0.91228 (17)0.0164 (3)
C90.80334 (18)0.06731 (18)0.88627 (16)0.0152 (3)
C100.75727 (18)0.21590 (18)1.09961 (17)0.0161 (3)
C110.7189 (2)1.1511 (2)0.2652 (2)0.0270 (4)
C120.7802 (2)1.2927 (2)0.1939 (2)0.0272 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.00958 (11)0.01335 (11)0.01713 (12)0.00358 (7)0.00378 (7)0.00046 (7)
O10.0140 (6)0.0245 (6)0.0204 (6)0.0008 (5)0.0074 (5)0.0041 (5)
O20.0261 (7)0.0305 (7)0.0564 (10)0.0067 (6)0.0190 (7)0.0233 (7)
O30.0139 (6)0.0304 (7)0.0324 (7)0.0079 (5)0.0029 (5)0.0100 (6)
O40.0402 (9)0.0309 (8)0.0609 (11)0.0238 (7)0.0117 (8)0.0169 (7)
O50.0153 (6)0.0171 (6)0.0251 (6)0.0079 (4)0.0002 (5)0.0036 (5)
O60.0196 (6)0.0257 (7)0.0360 (8)0.0078 (5)0.0053 (6)0.0132 (6)
O70.0160 (5)0.0149 (5)0.0269 (6)0.0039 (4)0.0109 (5)0.0004 (5)
O80.0274 (7)0.0137 (6)0.0555 (9)0.0015 (5)0.0227 (7)0.0055 (6)
OW10.0216 (7)0.0225 (7)0.0340 (7)0.0029 (5)0.0079 (6)0.0083 (5)
OW20.0243 (8)0.0516 (10)0.0558 (11)0.0009 (7)0.0024 (7)0.0270 (9)
OW30.0827 (15)0.0347 (9)0.0534 (12)0.0221 (9)0.0247 (10)0.0075 (8)
N10.0258 (9)0.0187 (7)0.0320 (9)0.0085 (6)0.0008 (7)0.0049 (7)
N20.0256 (8)0.0242 (8)0.0299 (9)0.0067 (6)0.0034 (7)0.0058 (7)
C10.0118 (7)0.0188 (7)0.0156 (7)0.0031 (6)0.0043 (6)0.0026 (6)
C20.0133 (7)0.0189 (8)0.0146 (7)0.0071 (6)0.0021 (6)0.0020 (6)
C30.0163 (8)0.0159 (7)0.0175 (7)0.0048 (6)0.0040 (6)0.0009 (6)
C40.0133 (7)0.0175 (7)0.0212 (8)0.0049 (6)0.0045 (6)0.0003 (6)
C50.0186 (8)0.0233 (8)0.0214 (8)0.0117 (7)0.0053 (7)0.0020 (6)
C60.0125 (7)0.0144 (7)0.0174 (7)0.0046 (6)0.0035 (6)0.0013 (6)
C70.0130 (7)0.0136 (7)0.0182 (7)0.0031 (6)0.0050 (6)0.0004 (6)
C80.0152 (8)0.0138 (7)0.0193 (7)0.0051 (6)0.0051 (6)0.0021 (6)
C90.0123 (7)0.0156 (7)0.0170 (7)0.0043 (6)0.0044 (6)0.0011 (6)
C100.0126 (7)0.0150 (7)0.0191 (8)0.0028 (6)0.0038 (6)0.0001 (6)
C110.0290 (10)0.0233 (9)0.0312 (10)0.0110 (7)0.0039 (8)0.0063 (7)
C120.0297 (10)0.0229 (9)0.0309 (10)0.0102 (8)0.0065 (8)0.0035 (7)
Geometric parameters (Å, º) top
Cu1—O3i1.9372 (15)N1—H80.86 (3)
Cu1—O11.9522 (14)N2—C121.478 (3)
Cu1—O7ii1.9693 (14)N2—H30.86 (3)
Cu1—O51.9940 (14)N2—H90.96 (3)
Cu1—OW12.2644N2—H130.85 (3)
O1—C41.267 (2)C1—C31.394 (2)
O2—C41.240 (2)C1—C21.399 (2)
O3—C51.257 (2)C1—C41.510 (2)
O3—Cu1i1.9372 (15)C2—C3iii1.386 (2)
O4—C51.242 (2)C2—C51.510 (2)
O5—C91.269 (2)C3—C2iii1.386 (2)
O6—C91.242 (2)C3—H10.95 (2)
O7—C101.273 (2)C6—C81.392 (2)
O7—Cu1ii1.9693 (14)C6—C71.400 (2)
O8—C101.2395 (18)C6—C91.511 (2)
OW1—HW1A0.8200C7—C8iv1.393 (2)
OW1—HW1B0.8200C7—C101.507 (2)
OW2—HW2A0.8200C8—C7iv1.393 (2)
OW2—HW2B0.8200C8—H20.96 (2)
OW3—HW3A0.8200C11—C121.517 (3)
OW3—HW3B0.8199C11—H50.96 (3)
N1—C111.478 (3)C11—H60.95 (3)
N1—H40.84 (3)C12—H100.88 (3)
N1—H70.84 (3)C12—H120.96 (3)
O3i—Cu1—O189.85 (6)C2iii—C3—C1121.73 (15)
O3i—Cu1—O7ii92.83 (6)C2iii—C3—H1119.8 (13)
O1—Cu1—O7ii175.78 (5)C1—C3—H1118.4 (13)
O3i—Cu1—O5174.56 (5)O2—C4—O1125.27 (16)
O1—Cu1—O585.27 (6)O2—C4—C1120.71 (15)
O7ii—Cu1—O591.91 (6)O1—C4—C1113.82 (14)
O3i—Cu1—OW191.81 (6)O4—C5—O3127.27 (17)
O1—Cu1—OW190.55 (5)O4—C5—C2117.69 (16)
O7ii—Cu1—OW192.61 (5)O3—C5—C2114.97 (16)
O5—Cu1—OW190.64 (5)C8—C6—C7119.19 (15)
C4—O1—Cu1122.69 (11)C8—C6—C9118.10 (14)
C5—O3—Cu1i128.19 (12)C7—C6—C9122.36 (15)
C9—O5—Cu1120.51 (11)C8iv—C7—C6119.40 (15)
C10—O7—Cu1ii123.48 (11)C8iv—C7—C10118.27 (14)
Cu1—OW1—HW1A96.0C6—C7—C10122.30 (15)
Cu1—OW1—HW1B115.5C6—C8—C7iv121.39 (15)
HW1A—OW1—HW1B108.7C6—C8—H2119.6 (15)
HW2A—OW2—HW2B108.5C7iv—C8—H2119.0 (15)
HW3A—OW3—HW3B110.7O6—C9—O5125.15 (16)
C11—N1—H4109.1 (19)O6—C9—C6117.80 (14)
C11—N1—H7110.0 (18)O5—C9—C6116.88 (14)
H4—N1—H7112 (3)O8—C10—O7126.46 (15)
C11—N1—H8112.1 (18)O8—C10—C7117.63 (14)
H4—N1—H8113 (2)O7—C10—C7115.88 (14)
H7—N1—H8101 (2)N1—C11—C12109.55 (16)
C12—N2—H3111 (2)N1—C11—H5109.0 (15)
C12—N2—H9114.2 (17)C12—C11—H5112.6 (15)
H3—N2—H9106 (3)N1—C11—H6110.0 (16)
C12—N2—H13113.5 (19)C12—C11—H6111.9 (16)
H3—N2—H13104 (3)H5—C11—H6104 (2)
H9—N2—H13106 (3)N2—C12—C11109.77 (17)
C3—C1—C2119.04 (15)N2—C12—H10107.5 (18)
C3—C1—C4117.44 (15)C11—C12—H10109.3 (18)
C2—C1—C4123.18 (14)N2—C12—H12109.0 (15)
C3iii—C2—C1119.23 (15)C11—C12—H12112.5 (15)
C3iii—C2—C5117.37 (15)H10—C12—H12109 (2)
C1—C2—C5123.14 (15)
Symmetry codes: (i) x+2, y+1, z+1; (ii) x+2, y, z+2; (iii) x+1, y+1, z+1; (iv) x+1, y, z+2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H3···O5v0.86 (3)2.04 (3)2.843 (2)156 (3)
N1—H4···O40.84 (3)1.87 (3)2.701 (2)169 (3)
N1—H7···O6i0.84 (3)1.97 (3)2.794 (2)167 (3)
N1—H8···O2vi0.86 (3)1.99 (3)2.839 (2)173 (3)
N2—H9···OW2vii0.96 (3)1.75 (3)2.716 (2)175 (3)
OW1—HW1A···O8ii0.821.942.7059 (17)155
N2—H13···O8viii0.85 (3)2.12 (3)2.820 (2)140 (2)
OW2—HW2A···O10.821.982.7749 (18)162
OW1—HW1B···OW3vi0.821.982.791173
OW3—HW3A···O60.821.942.7334 (16)164
OW2—HW2B···OW3vi0.822.042.794152
Symmetry codes: (i) x+2, y+1, z+1; (ii) x+2, y, z+2; (v) x, y+1, z1; (vi) x, y+1, z; (vii) x+1, y+2, z+1; (viii) x, y+2, z1.
(II) poly[ethylenediammonium [copper(II)-µ4-benzene-1,2,4,5-tetracarboxylato] 2.5-hydrate] top
Crystal data top
(C2H10N2)[Cu(C10H2O8)]·2.5H2OF(000) = 864
Mr = 420.83Dx = 1.770 Mg m3
Monoclinic, C2/mMo Kα radiation, λ = 0.71073 Å
a = 11.432 (2) ÅCell parameters from 5094 reflections
b = 18.484 (4) Åθ = 2.1–27.5°
c = 7.4981 (15) ŵ = 1.45 mm1
β = 94.80 (3)°T = 293 K
V = 1578.8 (5) Å3Needle, blue
Z = 40.36 × 0.28 × 0.28 mm
Data collection top
Rigaku R-AXIS RAPID
diffractometer
1406 reflections with I > 2σ(I)
Radiation source: rotating anodeRint = 0.044
Graphite monochromatorθmax = 27.5°, θmin = 2.1°
oscillation scansh = 014
1871 measured reflectionsk = 024
1871 independent reflectionsl = 99
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.033H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.079 w = 1/[σ2(Fo2) + (0.038P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.98(Δ/σ)max = 0.001
1870 reflectionsΔρmax = 0.44 e Å3
130 parametersΔρmin = 0.41 e Å3
4 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0008 (3)
Crystal data top
(C2H10N2)[Cu(C10H2O8)]·2.5H2OV = 1578.8 (5) Å3
Mr = 420.83Z = 4
Monoclinic, C2/mMo Kα radiation
a = 11.432 (2) ŵ = 1.45 mm1
b = 18.484 (4) ÅT = 293 K
c = 7.4981 (15) Å0.36 × 0.28 × 0.28 mm
β = 94.80 (3)°
Data collection top
Rigaku R-AXIS RAPID
diffractometer
1406 reflections with I > 2σ(I)
1871 measured reflectionsRint = 0.044
1871 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0334 restraints
wR(F2) = 0.079H atoms treated by a mixture of independent and constrained refinement
S = 0.98Δρmax = 0.44 e Å3
1870 reflectionsΔρmin = 0.41 e Å3
130 parameters
Special details top

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
xyzUiso*/UeqOcc. (<1)
Cu10.50000.24370 (2)0.00000.01459 (15)
O10.38012 (15)0.31920 (9)0.0158 (3)0.0202 (4)
O20.43585 (16)0.35615 (10)0.2638 (3)0.0257 (5)
O30.11508 (17)0.34645 (11)0.2347 (3)0.0278 (5)
O40.11590 (15)0.33154 (9)0.0613 (3)0.0191 (4)
C10.3188 (2)0.43453 (13)0.0677 (4)0.0143 (5)
C20.3706 (3)0.50000.1202 (5)0.0163 (8)
H20.44120.50000.19160.020*
C30.2109 (2)0.43458 (13)0.0378 (4)0.0147 (5)
C40.1581 (3)0.50000.0900 (5)0.0169 (8)
H40.08710.50000.16020.020*
C50.3825 (2)0.36478 (13)0.1125 (4)0.0162 (5)
C60.1439 (2)0.36512 (13)0.0789 (4)0.0170 (6)
N10.3215 (2)0.33719 (13)0.5812 (3)0.0271 (6)
H1A0.38000.34610.66410.041*
H1B0.25680.35950.61040.041*
H1C0.34050.35340.47560.041*
C70.3000 (2)0.25815 (15)0.5702 (4)0.0273 (6)
H7A0.28050.24030.68560.033*
H7B0.37060.23370.53940.033*
OW10.1146 (3)0.42380 (15)0.3957 (4)0.0538 (7)
HW1A0.079 (3)0.408 (2)0.307 (3)0.065*
HW1B0.0952 (17)0.3992 (18)0.479 (3)0.065*
OW20.3683 (10)0.50000.5648 (15)0.108 (4)0.50
HW2A0.32760.46400.57630.130*0.50
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0118 (2)0.0079 (2)0.0239 (3)0.0000.00096 (16)0.000
O10.0144 (9)0.0132 (9)0.0328 (11)0.0023 (7)0.0002 (8)0.0031 (8)
O20.0268 (10)0.0265 (11)0.0237 (10)0.0078 (8)0.0015 (8)0.0058 (9)
O30.0339 (11)0.0260 (11)0.0236 (11)0.0079 (9)0.0039 (9)0.0092 (9)
O40.0168 (9)0.0132 (9)0.0275 (11)0.0038 (7)0.0020 (8)0.0028 (8)
C10.0136 (12)0.0107 (12)0.0189 (14)0.0003 (9)0.0043 (10)0.0014 (10)
C20.0106 (17)0.0142 (17)0.024 (2)0.0000.0006 (15)0.000
C30.0128 (11)0.0108 (12)0.0212 (14)0.0003 (9)0.0049 (10)0.0020 (10)
C40.0146 (17)0.0152 (17)0.021 (2)0.0000.0006 (15)0.000
C50.0117 (11)0.0103 (11)0.0275 (15)0.0019 (9)0.0071 (11)0.0024 (11)
C60.0118 (12)0.0116 (11)0.0279 (15)0.0019 (9)0.0035 (11)0.0022 (11)
N10.0274 (13)0.0308 (13)0.0227 (13)0.0045 (11)0.0003 (10)0.0017 (11)
C70.0315 (14)0.0261 (15)0.0237 (14)0.0019 (13)0.0023 (12)0.0005 (13)
OW10.077 (2)0.0463 (16)0.0372 (15)0.0016 (14)0.0007 (14)0.0047 (12)
OW20.146 (10)0.054 (6)0.114 (9)0.0000.046 (8)0.000
Geometric parameters (Å, º) top
Cu1—O4i1.9491 (18)C3—C41.393 (3)
Cu1—O4ii1.9491 (18)C3—C61.513 (3)
Cu1—O1iii1.9525 (17)C4—C3iv1.393 (3)
Cu1—O11.9525 (17)C4—H40.9300
O1—C51.277 (3)N1—C71.483 (3)
O2—C51.253 (3)N1—H1A0.8900
O3—C61.237 (3)N1—H1B0.8900
O4—C61.284 (3)N1—H1C0.8900
O4—Cu1i1.9491 (18)C7—C7v1.517 (5)
C1—C21.390 (3)C7—H7A0.9700
C1—C31.409 (3)C7—H7B0.9700
C1—C51.505 (3)OW1—HW1A0.808 (10)
C2—C1iv1.390 (3)OW1—HW1B0.816 (10)
C2—H20.9300OW2—HW2A0.8200
O4i—Cu1—O4ii88.95 (11)O2—C5—O1125.2 (2)
O4i—Cu1—O1iii169.77 (8)O2—C5—C1120.1 (2)
O4ii—Cu1—O1iii92.05 (7)O1—C5—C1114.7 (2)
O4i—Cu1—O192.05 (7)O3—C6—O4125.0 (2)
O4ii—Cu1—O1169.77 (8)O3—C6—C3121.3 (2)
O1iii—Cu1—O188.77 (10)O4—C6—C3113.6 (2)
C5—O1—Cu1117.08 (16)C7—N1—H1A109.5
C6—O4—Cu1i111.29 (16)C7—N1—H1B109.5
C2—C1—C3119.4 (2)H1A—N1—H1B109.5
C2—C1—C5119.7 (2)C7—N1—H1C109.5
C3—C1—C5120.7 (2)H1A—N1—H1C109.5
C1—C2—C1iv121.1 (3)H1B—N1—H1C109.5
C1—C2—H2119.5N1—C7—C7v110.3 (3)
C1iv—C2—H2119.5N1—C7—H7A109.6
C4—C3—C1119.8 (2)C7v—C7—H7A109.6
C4—C3—C6118.7 (2)N1—C7—H7B109.6
C1—C3—C6121.2 (2)C7v—C7—H7B109.6
C3iv—C4—C3120.5 (3)H7A—C7—H7B108.1
C3iv—C4—H4119.7HW1A—OW1—HW1B106 (2)
C3—C4—H4119.7
Symmetry codes: (i) x+1/2, y+1/2, z; (ii) x+1/2, y+1/2, z; (iii) x+1, y, z; (iv) x, y+1, z; (v) x+1/2, y+1/2, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O2vi0.892.142.938 (3)149
N1—H1B···O3vii0.892.092.837 (3)142
N1—H1C···O20.892.002.831 (3)155
Symmetry codes: (vi) x+1, y, z+1; (vii) x, y, z+1.

Experimental details

(I)(II)
Crystal data
Chemical formula(C2H10N2)[Cu(C10H2O8)(H2O)]·2H2O(C2H10N2)[Cu(C10H2O8)]·2.5H2O
Mr429.83420.83
Crystal system, space groupTriclinic, P1Monoclinic, C2/m
Temperature (K)293293
a, b, c (Å)9.2104 (18), 9.4058 (19), 10.225 (2)11.432 (2), 18.484 (4), 7.4981 (15)
α, β, γ (°)75.00 (3), 75.50 (3), 75.15 (3)90, 94.80 (3), 90
V3)810.8 (3)1578.8 (5)
Z24
Radiation typeMo KαMo Kα
µ (mm1)1.411.45
Crystal size (mm)0.30 × 0.28 × 0.280.36 × 0.28 × 0.28
Data collection
DiffractometerRigaku R-AXIS RAPID
diffractometer
Rigaku R-AXIS RAPID
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
3715, 3715, 3467 1871, 1871, 1406
Rint0.0330.044
(sin θ/λ)max1)0.6490.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.026, 0.072, 1.05 0.033, 0.079, 0.98
No. of reflections37151870
No. of parameters308130
No. of restraints04
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.57, 0.400.44, 0.41

Computer programs: RAPID AUTO (Rigaku, 1998), RAPID AUTO, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL/PC (Sheldrick, 1993), SHELXL97/2 (Sheldrick,1997).

Selected geometric parameters (Å, º) for (I) top
Cu1—O3i1.9372 (15)Cu1—O51.9940 (14)
Cu1—O11.9522 (14)Cu1—OW12.2644
Cu1—O7ii1.9693 (14)
O3i—Cu1—O189.85 (6)O3i—Cu1—OW191.81 (6)
O3i—Cu1—O7ii92.83 (6)O1—Cu1—OW190.55 (5)
O1—Cu1—O7ii175.78 (5)O7ii—Cu1—OW192.61 (5)
O1—Cu1—O585.27 (6)O5—Cu1—OW190.64 (5)
O7ii—Cu1—O591.91 (6)
Symmetry codes: (i) x+2, y+1, z+1; (ii) x+2, y, z+2.
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
N2—H3···O5iii0.86 (3)2.04 (3)2.843 (2)156 (3)
N1—H4···O40.84 (3)1.87 (3)2.701 (2)169 (3)
N1—H7···O6i0.84 (3)1.97 (3)2.794 (2)167 (3)
N1—H8···O2iv0.86 (3)1.99 (3)2.839 (2)173 (3)
N2—H9···OW2v0.96 (3)1.75 (3)2.716 (2)175 (3)
OW1—HW1A···O8ii0.821.942.7059 (17)155.1
N2—H13···O8vi0.85 (3)2.12 (3)2.820 (2)140 (2)
OW2—HW2A···O10.821.982.7749 (18)162.1
OW1—HW1B···OW3iv0.821.982.791172.6
OW3—HW3A···O60.821.942.7334 (16)163.5
OW2—HW2B···OW3iv0.822.042.794151.8
Symmetry codes: (i) x+2, y+1, z+1; (ii) x+2, y, z+2; (iii) x, y+1, z1; (iv) x, y+1, z; (v) x+1, y+2, z+1; (vi) x, y+2, z1.
Selected geometric parameters (Å, º) for (II) top
Cu1—O4i1.9491 (18)Cu1—O11.9525 (17)
O4i—Cu1—O4ii88.95 (11)O1iii—Cu1—O188.77 (10)
O4i—Cu1—O192.05 (7)
Symmetry codes: (i) x+1/2, y+1/2, z; (ii) x+1/2, y+1/2, z; (iii) x+1, y, z.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O2iv0.892.142.938 (3)149.3
N1—H1B···O3v0.892.092.837 (3)141.6
N1—H1C···O20.892.002.831 (3)154.8
Symmetry codes: (iv) x+1, y, z+1; (v) x, y, z+1.
 

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