Two pseudo-polymorphic copper-benzene-1,2,4,5-tetra­carboxyl­ate complexes

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 Cu^II centres are different. In (I), the Cu^II 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 Cu^II 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.

S1. Comment

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 Cu^II cation, one water molecule and two btc^4- ligands on inversion centres. The Cu^II cation has a square-pyramidal environment, completed by one aqua O atom in the axial position and four carboxyl O atoms from four btc^4- ligands in the basal plane of the square pyramid (Fig. 1). As expected, the Cu—O_aqua bond length is noticeably longer than the Cu—O_carboxyl bonds. Both of the btc^4- ligands adopt a µ₄-η¹:η¹:η¹:η¹ bridging mode to connect four Cu^II cations, resulting in a two-dimensional [Cu(btc)(H₂O)]_n^2n- 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 btc^4- ligands are tilted by different amounts with respect to the [CuO₄(H₂O)]_n^2n- 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 Cu^II 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 Cu^II atom sitting on a twofold axis, one H₂en cation on an inversion centre, one btc^4- 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 Cu^II centre has a square-planar coordination with four carboxyl O atoms from four btc^4- ligands (Fig. 3). The coordination mode of the btc^4- ligand and the topological structure of the anionic layer are essentially the same as in (I), producing the [Cu(btc)]_n^2n- anionic layer parallel to the ab plane. The phenyl groups of the btc^4- ligands are tilted with respect to the [CuO₄]_n^2n- 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)]_n^2n-.

Related literature

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).

S2. Experimental

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.

S3. Refinement

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 U_iso(H) = 1.2U_eq(O). [U_iso(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 U_iso(H) = 1.2U_eq(C). H atoms bonded to N were refined as riding, with N—H = 0.89 Å and U_iso(H) = 1.5U_eq(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

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

	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.]
	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.
	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.]
	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]

Crystal data

(C2H10N2)[Cu(C10H2O8)(H2O)]·2H2O	Z = 2
Mr = 429.83	F(000) = 442
Triclinic, P1	Dx = 1.761 Mg m^−3
a = 9.2104 (18) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.4058 (19) Å	Cell parameters from 3737 reflections
c = 10.225 (2) Å	θ = 3.4–27.5°
α = 75.00 (3)°	µ = 1.41 mm^−1
β = 75.50 (3)°	T = 293 K
γ = 75.15 (3)°	Block, blue
V = 810.8 (3) Å^3	0.30 × 0.28 × 0.28 mm

Data collection

Rigaku R-AXIS RAPID diffractometer	3467 reflections with I > 2σ(I)
Radiation source: rotating anode	Rint = 0.033
Graphite monochromator	θmax = 27.5°, θmin = 2.1°
oscillation scans	h = −11→11
3715 measured reflections	k = −12→0
3715 independent reflections	l = −13→12

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.026	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.072	w = 1/[σ^2(Fo^2) + (0.0401P)^2 + 0.5809P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.001
3715 reflections	Δρmax = 0.57 e Å^−3
308 parameters	Δρmin = −0.40 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0150 (15)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Cu1	0.99060 (2)	0.28496 (2)	0.760656 (19)	0.01342 (8)
O1	0.82828 (14)	0.39380 (14)	0.65881 (13)	0.0196 (2)
O2	0.87040 (17)	0.23022 (17)	0.52356 (18)	0.0352 (4)
O3	0.86216 (15)	0.62072 (16)	0.38431 (15)	0.0284 (3)
O4	0.6880 (2)	0.81088 (18)	0.4609 (2)	0.0434 (4)
O5	0.82726 (14)	0.19069 (13)	0.89632 (13)	0.0192 (2)
O6	0.89454 (15)	−0.02207 (15)	0.81841 (15)	0.0272 (3)
O7	0.85090 (14)	−0.16153 (13)	1.13541 (13)	0.0188 (2)
O8	0.76112 (9)	−0.35098 (8)	1.10985 (9)	0.0304 (3)
OW1	0.94149 (9)	0.47204 (8)	0.87716 (9)	0.0254 (3)
HW1A	1.0286	0.4582	0.8906	0.048 (8)*
HW1B	0.9194	0.5575	0.8319	0.052 (9)*
OW2	0.61525 (9)	0.58506 (8)	0.81357 (9)	0.0432 (4)
HW2A	0.6615	0.5221	0.7671	0.052 (9)*
HW2B	0.6552	0.6587	0.7856	0.112 (17)*
OW3	0.84307 (9)	−0.24462 (8)	0.71957 (9)	0.0532 (5)
HW3A	0.8398	−0.1712	0.7502	0.106 (15)*
HW3B	0.8508	−0.2220	0.6355	0.117 (17)*
N1	0.8196 (2)	1.05301 (19)	0.35928 (19)	0.0261 (3)
N2	0.6913 (2)	1.3824 (2)	0.08747 (19)	0.0266 (3)
H1	0.558 (2)	0.240 (2)	0.577 (2)	0.017 (5)*
H2	0.533 (3)	0.228 (3)	0.849 (3)	0.030 (6)*
H3	0.710 (3)	1.340 (3)	0.019 (3)	0.045 (8)*
H4	0.783 (3)	0.977 (3)	0.401 (3)	0.039 (7)*
H5	0.616 (3)	1.172 (3)	0.317 (3)	0.034 (6)*
H6	0.711 (3)	1.098 (3)	0.201 (3)	0.038 (7)*
H7	0.909 (3)	1.030 (3)	0.315 (3)	0.034 (7)*
H8	0.834 (3)	1.100 (3)	0.415 (3)	0.036 (7)*
H9	0.582 (4)	1.399 (3)	0.120 (3)	0.046 (8)*
H10	0.876 (3)	1.268 (3)	0.152 (3)	0.040 (7)*
H12	0.776 (3)	1.354 (3)	0.257 (3)	0.034 (6)*
H13	0.713 (3)	1.468 (3)	0.052 (3)	0.038 (7)*
C1	0.64694 (18)	0.42790 (18)	0.52429 (16)	0.0153 (3)
C2	0.61244 (18)	0.58413 (18)	0.47858 (16)	0.0153 (3)
C3	0.53356 (19)	0.34628 (18)	0.54472 (17)	0.0167 (3)
C4	0.79612 (19)	0.34382 (18)	0.56803 (18)	0.0175 (3)
C5	0.7308 (2)	0.6809 (2)	0.44002 (18)	0.0207 (3)
C6	0.64671 (18)	0.03331 (17)	0.95351 (16)	0.0147 (3)
C7	0.62665 (18)	−0.10337 (18)	1.04381 (17)	0.0151 (3)
C8	0.51940 (19)	0.13567 (18)	0.91228 (17)	0.0164 (3)
C9	0.80334 (18)	0.06731 (18)	0.88627 (16)	0.0152 (3)
C10	0.75727 (18)	−0.21590 (18)	1.09961 (17)	0.0161 (3)
C11	0.7189 (2)	1.1511 (2)	0.2652 (2)	0.0270 (4)
C12	0.7802 (2)	1.2927 (2)	0.1939 (2)	0.0272 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.00958 (11)	0.01335 (11)	0.01713 (12)	−0.00358 (7)	−0.00378 (7)	−0.00046 (7)
O1	0.0140 (6)	0.0245 (6)	0.0204 (6)	−0.0008 (5)	−0.0074 (5)	−0.0041 (5)
O2	0.0261 (7)	0.0305 (7)	0.0564 (10)	0.0067 (6)	−0.0190 (7)	−0.0233 (7)
O3	0.0139 (6)	0.0304 (7)	0.0324 (7)	−0.0079 (5)	−0.0029 (5)	0.0100 (6)
O4	0.0402 (9)	0.0309 (8)	0.0609 (11)	−0.0238 (7)	0.0117 (8)	−0.0169 (7)
O5	0.0153 (6)	0.0171 (6)	0.0251 (6)	−0.0079 (4)	−0.0002 (5)	−0.0036 (5)
O6	0.0196 (6)	0.0257 (7)	0.0360 (8)	−0.0078 (5)	0.0053 (6)	−0.0132 (6)
O7	0.0160 (5)	0.0149 (5)	0.0269 (6)	−0.0039 (4)	−0.0109 (5)	0.0004 (5)
O8	0.0274 (7)	0.0137 (6)	0.0555 (9)	−0.0015 (5)	−0.0227 (7)	−0.0055 (6)
OW1	0.0216 (7)	0.0225 (7)	0.0340 (7)	−0.0029 (5)	−0.0079 (6)	−0.0083 (5)
OW2	0.0243 (8)	0.0516 (10)	0.0558 (11)	−0.0009 (7)	−0.0024 (7)	−0.0270 (9)
OW3	0.0827 (15)	0.0347 (9)	0.0534 (12)	−0.0221 (9)	−0.0247 (10)	−0.0075 (8)
N1	0.0258 (9)	0.0187 (7)	0.0320 (9)	−0.0085 (6)	0.0008 (7)	−0.0049 (7)
N2	0.0256 (8)	0.0242 (8)	0.0299 (9)	−0.0067 (6)	−0.0034 (7)	−0.0058 (7)
C1	0.0118 (7)	0.0188 (7)	0.0156 (7)	−0.0031 (6)	−0.0043 (6)	−0.0026 (6)
C2	0.0133 (7)	0.0189 (8)	0.0146 (7)	−0.0071 (6)	−0.0021 (6)	−0.0020 (6)
C3	0.0163 (8)	0.0159 (7)	0.0175 (7)	−0.0048 (6)	−0.0040 (6)	−0.0009 (6)
C4	0.0133 (7)	0.0175 (7)	0.0212 (8)	−0.0049 (6)	−0.0045 (6)	−0.0003 (6)
C5	0.0186 (8)	0.0233 (8)	0.0214 (8)	−0.0117 (7)	−0.0053 (7)	0.0020 (6)
C6	0.0125 (7)	0.0144 (7)	0.0174 (7)	−0.0046 (6)	−0.0035 (6)	−0.0013 (6)
C7	0.0130 (7)	0.0136 (7)	0.0182 (7)	−0.0031 (6)	−0.0050 (6)	−0.0004 (6)
C8	0.0152 (8)	0.0138 (7)	0.0193 (7)	−0.0051 (6)	−0.0051 (6)	0.0021 (6)
C9	0.0123 (7)	0.0156 (7)	0.0170 (7)	−0.0043 (6)	−0.0044 (6)	0.0011 (6)
C10	0.0126 (7)	0.0150 (7)	0.0191 (8)	−0.0028 (6)	−0.0038 (6)	−0.0001 (6)
C11	0.0290 (10)	0.0233 (9)	0.0312 (10)	−0.0110 (7)	−0.0039 (8)	−0.0063 (7)
C12	0.0297 (10)	0.0229 (9)	0.0309 (10)	−0.0102 (8)	−0.0065 (8)	−0.0035 (7)

Geometric parameters (Å, º)

Cu1—O3^i	1.9372 (15)	N1—H8	0.86 (3)
Cu1—O1	1.9522 (14)	N2—C12	1.478 (3)
Cu1—O7^ii	1.9693 (14)	N2—H3	0.86 (3)
Cu1—O5	1.9940 (14)	N2—H9	0.96 (3)
Cu1—OW1	2.2644	N2—H13	0.85 (3)
O1—C4	1.267 (2)	C1—C3	1.394 (2)
O2—C4	1.240 (2)	C1—C2	1.399 (2)
O3—C5	1.257 (2)	C1—C4	1.510 (2)
O3—Cu1^i	1.9372 (15)	C2—C3^iii	1.386 (2)
O4—C5	1.242 (2)	C2—C5	1.510 (2)
O5—C9	1.269 (2)	C3—C2^iii	1.386 (2)
O6—C9	1.242 (2)	C3—H1	0.95 (2)
O7—C10	1.273 (2)	C6—C8	1.392 (2)
O7—Cu1^ii	1.9693 (14)	C6—C7	1.400 (2)
O8—C10	1.2395 (18)	C6—C9	1.511 (2)
OW1—HW1A	0.8200	C7—C8^iv	1.393 (2)
OW1—HW1B	0.8200	C7—C10	1.507 (2)
OW2—HW2A	0.8200	C8—C7^iv	1.393 (2)
OW2—HW2B	0.8200	C8—H2	0.96 (2)
OW3—HW3A	0.8200	C11—C12	1.517 (3)
OW3—HW3B	0.8199	C11—H5	0.96 (3)
N1—C11	1.478 (3)	C11—H6	0.95 (3)
N1—H4	0.84 (3)	C12—H10	0.88 (3)
N1—H7	0.84 (3)	C12—H12	0.96 (3)
O3^i—Cu1—O1	89.85 (6)	C2^iii—C3—C1	121.73 (15)
O3^i—Cu1—O7^ii	92.83 (6)	C2^iii—C3—H1	119.8 (13)
O1—Cu1—O7^ii	175.78 (5)	C1—C3—H1	118.4 (13)
O3^i—Cu1—O5	174.56 (5)	O2—C4—O1	125.27 (16)
O1—Cu1—O5	85.27 (6)	O2—C4—C1	120.71 (15)
O7^ii—Cu1—O5	91.91 (6)	O1—C4—C1	113.82 (14)
O3^i—Cu1—OW1	91.81 (6)	O4—C5—O3	127.27 (17)
O1—Cu1—OW1	90.55 (5)	O4—C5—C2	117.69 (16)
O7^ii—Cu1—OW1	92.61 (5)	O3—C5—C2	114.97 (16)
O5—Cu1—OW1	90.64 (5)	C8—C6—C7	119.19 (15)
C4—O1—Cu1	122.69 (11)	C8—C6—C9	118.10 (14)
C5—O3—Cu1^i	128.19 (12)	C7—C6—C9	122.36 (15)
C9—O5—Cu1	120.51 (11)	C8^iv—C7—C6	119.40 (15)
C10—O7—Cu1^ii	123.48 (11)	C8^iv—C7—C10	118.27 (14)
Cu1—OW1—HW1A	96.0	C6—C7—C10	122.30 (15)
Cu1—OW1—HW1B	115.5	C6—C8—C7^iv	121.39 (15)
HW1A—OW1—HW1B	108.7	C6—C8—H2	119.6 (15)
HW2A—OW2—HW2B	108.5	C7^iv—C8—H2	119.0 (15)
HW3A—OW3—HW3B	110.7	O6—C9—O5	125.15 (16)
C11—N1—H4	109.1 (19)	O6—C9—C6	117.80 (14)
C11—N1—H7	110.0 (18)	O5—C9—C6	116.88 (14)
H4—N1—H7	112 (3)	O8—C10—O7	126.46 (15)
C11—N1—H8	112.1 (18)	O8—C10—C7	117.63 (14)
H4—N1—H8	113 (2)	O7—C10—C7	115.88 (14)
H7—N1—H8	101 (2)	N1—C11—C12	109.55 (16)
C12—N2—H3	111 (2)	N1—C11—H5	109.0 (15)
C12—N2—H9	114.2 (17)	C12—C11—H5	112.6 (15)
H3—N2—H9	106 (3)	N1—C11—H6	110.0 (16)
C12—N2—H13	113.5 (19)	C12—C11—H6	111.9 (16)
H3—N2—H13	104 (3)	H5—C11—H6	104 (2)
H9—N2—H13	106 (3)	N2—C12—C11	109.77 (17)
C3—C1—C2	119.04 (15)	N2—C12—H10	107.5 (18)
C3—C1—C4	117.44 (15)	C11—C12—H10	109.3 (18)
C2—C1—C4	123.18 (14)	N2—C12—H12	109.0 (15)
C3^iii—C2—C1	119.23 (15)	C11—C12—H12	112.5 (15)
C3^iii—C2—C5	117.37 (15)	H10—C12—H12	109 (2)
C1—C2—C5	123.14 (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)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H3···O5^v	0.86 (3)	2.04 (3)	2.843 (2)	156 (3)
N1—H4···O4	0.84 (3)	1.87 (3)	2.701 (2)	169 (3)
N1—H7···O6^i	0.84 (3)	1.97 (3)	2.794 (2)	167 (3)
N1—H8···O2^vi	0.86 (3)	1.99 (3)	2.839 (2)	173 (3)
N2—H9···OW2^vii	0.96 (3)	1.75 (3)	2.716 (2)	175 (3)
OW1—HW1A···O8^ii	0.82	1.94	2.7059 (17)	155
N2—H13···O8^viii	0.85 (3)	2.12 (3)	2.820 (2)	140 (2)
OW2—HW2A···O1	0.82	1.98	2.7749 (18)	162
OW1—HW1B···OW3^vi	0.82	1.98	2.791	173
OW3—HW3A···O6	0.82	1.94	2.7334 (16)	164
OW2—HW2B···OW3^vi	0.82	2.04	2.794	152

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

(II) poly[ethylenediammonium [copper(II)-µ₄-benzene-1,2,4,5-tetracarboxylato] 2.5-hydrate]

Crystal data

(C2H10N2)[Cu(C10H2O8)]·2.5H2O	F(000) = 864
Mr = 420.83	Dx = 1.770 Mg m^−3
Monoclinic, C2/m	Mo Kα radiation, λ = 0.71073 Å
a = 11.432 (2) Å	Cell parameters from 5094 reflections
b = 18.484 (4) Å	θ = 2.1–27.5°
c = 7.4981 (15) Å	µ = 1.45 mm^−1
β = 94.80 (3)°	T = 293 K
V = 1578.8 (5) Å^3	Needle, blue
Z = 4	0.36 × 0.28 × 0.28 mm

Data collection

Rigaku R-AXIS RAPID diffractometer	1406 reflections with I > 2σ(I)
Radiation source: rotating anode	Rint = 0.044
Graphite monochromator	θmax = 27.5°, θmin = 2.1°
oscillation scans	h = 0→14
1871 measured reflections	k = 0→24
1871 independent reflections	l = −9→9

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.033	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.079	w = 1/[σ^2(Fo^2) + (0.038P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.98	(Δ/σ)max = 0.001
1870 reflections	Δρmax = 0.44 e Å^−3
130 parameters	Δρmin = −0.41 e Å^−3
4 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0008 (3)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cu1	0.5000	0.24370 (2)	0.0000	0.01459 (15)
O1	0.38012 (15)	0.31920 (9)	−0.0158 (3)	0.0202 (4)
O2	0.43585 (16)	0.35615 (10)	0.2638 (3)	0.0257 (5)
O3	0.11508 (17)	0.34645 (11)	−0.2347 (3)	0.0278 (5)
O4	0.11590 (15)	0.33154 (9)	0.0613 (3)	0.0191 (4)
C1	0.3188 (2)	0.43453 (13)	0.0677 (4)	0.0143 (5)
C2	0.3706 (3)	0.5000	0.1202 (5)	0.0163 (8)
H2	0.4412	0.5000	0.1916	0.020*
C3	0.2109 (2)	0.43458 (13)	−0.0378 (4)	0.0147 (5)
C4	0.1581 (3)	0.5000	−0.0900 (5)	0.0169 (8)
H4	0.0871	0.5000	−0.1602	0.020*
C5	0.3825 (2)	0.36478 (13)	0.1125 (4)	0.0162 (5)
C6	0.1439 (2)	0.36512 (13)	−0.0789 (4)	0.0170 (6)
N1	0.3215 (2)	0.33719 (13)	0.5812 (3)	0.0271 (6)
H1A	0.3800	0.3461	0.6641	0.041*
H1B	0.2568	0.3595	0.6104	0.041*
H1C	0.3405	0.3534	0.4756	0.041*
C7	0.3000 (2)	0.25815 (15)	0.5702 (4)	0.0273 (6)
H7A	0.2805	0.2403	0.6856	0.033*
H7B	0.3706	0.2337	0.5394	0.033*
OW1	0.1146 (3)	0.42380 (15)	0.3957 (4)	0.0538 (7)
HW1A	0.079 (3)	0.408 (2)	0.307 (3)	0.065*
HW1B	0.0952 (17)	0.3992 (18)	0.479 (3)	0.065*
OW2	0.3683 (10)	0.5000	0.5648 (15)	0.108 (4)	0.50
HW2A	0.3276	0.4640	0.5763	0.130*	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0118 (2)	0.0079 (2)	0.0239 (3)	0.000	0.00096 (16)	0.000
O1	0.0144 (9)	0.0132 (9)	0.0328 (11)	0.0023 (7)	0.0002 (8)	−0.0031 (8)
O2	0.0268 (10)	0.0265 (11)	0.0237 (10)	0.0078 (8)	0.0015 (8)	0.0058 (9)
O3	0.0339 (11)	0.0260 (11)	0.0236 (11)	−0.0079 (9)	0.0039 (9)	−0.0092 (9)
O4	0.0168 (9)	0.0132 (9)	0.0275 (11)	−0.0038 (7)	0.0020 (8)	0.0028 (8)
C1	0.0136 (12)	0.0107 (12)	0.0189 (14)	0.0003 (9)	0.0043 (10)	0.0014 (10)
C2	0.0106 (17)	0.0142 (17)	0.024 (2)	0.000	0.0006 (15)	0.000
C3	0.0128 (11)	0.0108 (12)	0.0212 (14)	−0.0003 (9)	0.0049 (10)	−0.0020 (10)
C4	0.0146 (17)	0.0152 (17)	0.021 (2)	0.000	0.0006 (15)	0.000
C5	0.0117 (11)	0.0103 (11)	0.0275 (15)	−0.0019 (9)	0.0071 (11)	0.0024 (11)
C6	0.0118 (12)	0.0116 (11)	0.0279 (15)	0.0019 (9)	0.0035 (11)	−0.0022 (11)
N1	0.0274 (13)	0.0308 (13)	0.0227 (13)	−0.0045 (11)	−0.0003 (10)	−0.0017 (11)
C7	0.0315 (14)	0.0261 (15)	0.0237 (14)	−0.0019 (13)	−0.0023 (12)	0.0005 (13)
OW1	0.077 (2)	0.0463 (16)	0.0372 (15)	0.0016 (14)	0.0007 (14)	0.0047 (12)
OW2	0.146 (10)	0.054 (6)	0.114 (9)	0.000	−0.046 (8)	0.000

Geometric parameters (Å, º)

Cu1—O4^i	1.9491 (18)	C3—C4	1.393 (3)
Cu1—O4^ii	1.9491 (18)	C3—C6	1.513 (3)
Cu1—O1^iii	1.9525 (17)	C4—C3^iv	1.393 (3)
Cu1—O1	1.9525 (17)	C4—H4	0.9300
O1—C5	1.277 (3)	N1—C7	1.483 (3)
O2—C5	1.253 (3)	N1—H1A	0.8900
O3—C6	1.237 (3)	N1—H1B	0.8900
O4—C6	1.284 (3)	N1—H1C	0.8900
O4—Cu1^i	1.9491 (18)	C7—C7^v	1.517 (5)
C1—C2	1.390 (3)	C7—H7A	0.9700
C1—C3	1.409 (3)	C7—H7B	0.9700
C1—C5	1.505 (3)	OW1—HW1A	0.808 (10)
C2—C1^iv	1.390 (3)	OW1—HW1B	0.816 (10)
C2—H2	0.9300	OW2—HW2A	0.8200
O4^i—Cu1—O4^ii	88.95 (11)	O2—C5—O1	125.2 (2)
O4^i—Cu1—O1^iii	169.77 (8)	O2—C5—C1	120.1 (2)
O4^ii—Cu1—O1^iii	92.05 (7)	O1—C5—C1	114.7 (2)
O4^i—Cu1—O1	92.05 (7)	O3—C6—O4	125.0 (2)
O4^ii—Cu1—O1	169.77 (8)	O3—C6—C3	121.3 (2)
O1^iii—Cu1—O1	88.77 (10)	O4—C6—C3	113.6 (2)
C5—O1—Cu1	117.08 (16)	C7—N1—H1A	109.5
C6—O4—Cu1^i	111.29 (16)	C7—N1—H1B	109.5
C2—C1—C3	119.4 (2)	H1A—N1—H1B	109.5
C2—C1—C5	119.7 (2)	C7—N1—H1C	109.5
C3—C1—C5	120.7 (2)	H1A—N1—H1C	109.5
C1—C2—C1^iv	121.1 (3)	H1B—N1—H1C	109.5
C1—C2—H2	119.5	N1—C7—C7^v	110.3 (3)
C1^iv—C2—H2	119.5	N1—C7—H7A	109.6
C4—C3—C1	119.8 (2)	C7^v—C7—H7A	109.6
C4—C3—C6	118.7 (2)	N1—C7—H7B	109.6
C1—C3—C6	121.2 (2)	C7^v—C7—H7B	109.6
C3^iv—C4—C3	120.5 (3)	H7A—C7—H7B	108.1
C3^iv—C4—H4	119.7	HW1A—OW1—HW1B	106 (2)
C3—C4—H4	119.7

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)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2^vi	0.89	2.14	2.938 (3)	149
N1—H1B···O3^vii	0.89	2.09	2.837 (3)	142
N1—H1C···O2	0.89	2.00	2.831 (3)	155

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