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Two pseudo-polymorphic polymers, poly[ethylenediammonium [[aquacopper(II)]-
4-benzene-1,2,4,5-tetracarboxylato] dihydrate], {(C
2H
10N
2)[Cu(C
10H
2O
8)(H
2O)]·2H
2O}
n, (I), and poly[ethylenediammonium [copper(II)-
4-benzene-1,2,4,5-tetracarboxylato] 2.5-hydrate], {(C
2H
10N
2)[Cu(C
10H
2O
8)]·2.5H
2O}
n, (II), contain two-dimensional anionic layers, ethylenediammonium (H
2en) 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 H
2en cation is on an inversion centre and the btc ligand is split by a mirror plane. Extensive hydrogen-bonding interactions between the complexes, H
2en cations and water molecules lead to the formation of three-dimensional supramolecular structures.
Supporting information
CCDC references: 652499; 652500
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.
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.
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).
(I) poly[ethylenediammonium
[[aquacopper(II)]-µ
4-benzene-1,2,4,5-tetracarboxylato] dihydrate]
top
Crystal data top
(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) Å3 | 0.30 × 0.28 × 0.28 mm |
Data collection top
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 top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.026 | H 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 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+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0150 (15) |
Crystal data top
(C2H10N2)[Cu(C10H2O8)(H2O)]·2H2O | γ = 75.15 (3)° |
Mr = 429.83 | V = 810.8 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.2104 (18) Å | Mo Kα radiation |
b = 9.4058 (19) Å | µ = 1.41 mm−1 |
c = 10.225 (2) Å | T = 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 reflections | Rint = 0.033 |
3715 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.026 | 0 restraints |
wR(F2) = 0.072 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.57 e Å−3 |
3715 reflections | Δρmin = −0.40 e Å−3 |
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 | 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 (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
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) top
Cu1—O3i | 1.9372 (15) | N1—H8 | 0.86 (3) |
Cu1—O1 | 1.9522 (14) | N2—C12 | 1.478 (3) |
Cu1—O7ii | 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—Cu1i | 1.9372 (15) | C2—C3iii | 1.386 (2) |
O4—C5 | 1.242 (2) | C2—C5 | 1.510 (2) |
O5—C9 | 1.269 (2) | C3—C2iii | 1.386 (2) |
O6—C9 | 1.242 (2) | C3—H1 | 0.95 (2) |
O7—C10 | 1.273 (2) | C6—C8 | 1.392 (2) |
O7—Cu1ii | 1.9693 (14) | C6—C7 | 1.400 (2) |
O8—C10 | 1.2395 (18) | C6—C9 | 1.511 (2) |
OW1—HW1A | 0.8200 | C7—C8iv | 1.393 (2) |
OW1—HW1B | 0.8200 | C7—C10 | 1.507 (2) |
OW2—HW2A | 0.8200 | C8—C7iv | 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) |
| | | |
O3i—Cu1—O1 | 89.85 (6) | C2iii—C3—C1 | 121.73 (15) |
O3i—Cu1—O7ii | 92.83 (6) | C2iii—C3—H1 | 119.8 (13) |
O1—Cu1—O7ii | 175.78 (5) | C1—C3—H1 | 118.4 (13) |
O3i—Cu1—O5 | 174.56 (5) | O2—C4—O1 | 125.27 (16) |
O1—Cu1—O5 | 85.27 (6) | O2—C4—C1 | 120.71 (15) |
O7ii—Cu1—O5 | 91.91 (6) | O1—C4—C1 | 113.82 (14) |
O3i—Cu1—OW1 | 91.81 (6) | O4—C5—O3 | 127.27 (17) |
O1—Cu1—OW1 | 90.55 (5) | O4—C5—C2 | 117.69 (16) |
O7ii—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—Cu1i | 128.19 (12) | C7—C6—C9 | 122.36 (15) |
C9—O5—Cu1 | 120.51 (11) | C8iv—C7—C6 | 119.40 (15) |
C10—O7—Cu1ii | 123.48 (11) | C8iv—C7—C10 | 118.27 (14) |
Cu1—OW1—HW1A | 96.0 | C6—C7—C10 | 122.30 (15) |
Cu1—OW1—HW1B | 115.5 | C6—C8—C7iv | 121.39 (15) |
HW1A—OW1—HW1B | 108.7 | C6—C8—H2 | 119.6 (15) |
HW2A—OW2—HW2B | 108.5 | C7iv—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) |
C3iii—C2—C1 | 119.23 (15) | C11—C12—H12 | 112.5 (15) |
C3iii—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) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H3···O5v | 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···O6i | 0.84 (3) | 1.97 (3) | 2.794 (2) | 167 (3) |
N1—H8···O2vi | 0.86 (3) | 1.99 (3) | 2.839 (2) | 173 (3) |
N2—H9···OW2vii | 0.96 (3) | 1.75 (3) | 2.716 (2) | 175 (3) |
OW1—HW1A···O8ii | 0.82 | 1.94 | 2.7059 (17) | 155 |
N2—H13···O8viii | 0.85 (3) | 2.12 (3) | 2.820 (2) | 140 (2) |
OW2—HW2A···O1 | 0.82 | 1.98 | 2.7749 (18) | 162 |
OW1—HW1B···OW3vi | 0.82 | 1.98 | 2.791 | 173 |
OW3—HW3A···O6 | 0.82 | 1.94 | 2.7334 (16) | 164 |
OW2—HW2B···OW3vi | 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)-µ
4-benzene-1,2,4,5-tetracarboxylato]
2.5-hydrate]
top
Crystal data top
(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) Å3 | Needle, blue |
Z = 4 | 0.36 × 0.28 × 0.28 mm |
Data collection top
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 top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.033 | H 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 reflections | Δρmax = 0.44 e Å−3 |
130 parameters | Δρmin = −0.41 e Å−3 |
4 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0008 (3) |
Crystal data top
(C2H10N2)[Cu(C10H2O8)]·2.5H2O | V = 1578.8 (5) Å3 |
Mr = 420.83 | Z = 4 |
Monoclinic, C2/m | Mo Kα radiation |
a = 11.432 (2) Å | µ = 1.45 mm−1 |
b = 18.484 (4) Å | T = 293 K |
c = 7.4981 (15) Å | 0.36 × 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 reflections | Rint = 0.044 |
1871 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.033 | 4 restraints |
wR(F2) = 0.079 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.98 | Δρmax = 0.44 e Å−3 |
1870 reflections | Δρmin = −0.41 e Å−3 |
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 | 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 (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
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) top
Cu1—O4i | 1.9491 (18) | C3—C4 | 1.393 (3) |
Cu1—O4ii | 1.9491 (18) | C3—C6 | 1.513 (3) |
Cu1—O1iii | 1.9525 (17) | C4—C3iv | 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—Cu1i | 1.9491 (18) | C7—C7v | 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—C1iv | 1.390 (3) | OW1—HW1B | 0.816 (10) |
C2—H2 | 0.9300 | OW2—HW2A | 0.8200 |
| | | |
O4i—Cu1—O4ii | 88.95 (11) | O2—C5—O1 | 125.2 (2) |
O4i—Cu1—O1iii | 169.77 (8) | O2—C5—C1 | 120.1 (2) |
O4ii—Cu1—O1iii | 92.05 (7) | O1—C5—C1 | 114.7 (2) |
O4i—Cu1—O1 | 92.05 (7) | O3—C6—O4 | 125.0 (2) |
O4ii—Cu1—O1 | 169.77 (8) | O3—C6—C3 | 121.3 (2) |
O1iii—Cu1—O1 | 88.77 (10) | O4—C6—C3 | 113.6 (2) |
C5—O1—Cu1 | 117.08 (16) | C7—N1—H1A | 109.5 |
C6—O4—Cu1i | 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—C1iv | 121.1 (3) | H1B—N1—H1C | 109.5 |
C1—C2—H2 | 119.5 | N1—C7—C7v | 110.3 (3) |
C1iv—C2—H2 | 119.5 | N1—C7—H7A | 109.6 |
C4—C3—C1 | 119.8 (2) | C7v—C7—H7A | 109.6 |
C4—C3—C6 | 118.7 (2) | N1—C7—H7B | 109.6 |
C1—C3—C6 | 121.2 (2) | C7v—C7—H7B | 109.6 |
C3iv—C4—C3 | 120.5 (3) | H7A—C7—H7B | 108.1 |
C3iv—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) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O2vi | 0.89 | 2.14 | 2.938 (3) | 149 |
N1—H1B···O3vii | 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. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | (C2H10N2)[Cu(C10H2O8)(H2O)]·2H2O | (C2H10N2)[Cu(C10H2O8)]·2.5H2O |
Mr | 429.83 | 420.83 |
Crystal system, space group | Triclinic, P1 | Monoclinic, C2/m |
Temperature (K) | 293 | 293 |
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 |
V (Å3) | 810.8 (3) | 1578.8 (5) |
Z | 2 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 1.41 | 1.45 |
Crystal size (mm) | 0.30 × 0.28 × 0.28 | 0.36 × 0.28 × 0.28 |
|
Data collection |
Diffractometer | Rigaku 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 |
Rint | 0.033 | 0.044 |
(sin θ/λ)max (Å−1) | 0.649 | 0.649 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.026, 0.072, 1.05 | 0.033, 0.079, 0.98 |
No. of reflections | 3715 | 1870 |
No. of parameters | 308 | 130 |
No. of restraints | 0 | 4 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.57, −0.40 | 0.44, −0.41 |
Selected geometric parameters (Å, º) for (I) topCu1—O3i | 1.9372 (15) | Cu1—O5 | 1.9940 (14) |
Cu1—O1 | 1.9522 (14) | Cu1—OW1 | 2.2644 |
Cu1—O7ii | 1.9693 (14) | | |
| | | |
O3i—Cu1—O1 | 89.85 (6) | O3i—Cu1—OW1 | 91.81 (6) |
O3i—Cu1—O7ii | 92.83 (6) | O1—Cu1—OW1 | 90.55 (5) |
O1—Cu1—O7ii | 175.78 (5) | O7ii—Cu1—OW1 | 92.61 (5) |
O1—Cu1—O5 | 85.27 (6) | O5—Cu1—OW1 | 90.64 (5) |
O7ii—Cu1—O5 | 91.91 (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···A | D—H | H···A | D···A | D—H···A |
N2—H3···O5iii | 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···O6i | 0.84 (3) | 1.97 (3) | 2.794 (2) | 167 (3) |
N1—H8···O2iv | 0.86 (3) | 1.99 (3) | 2.839 (2) | 173 (3) |
N2—H9···OW2v | 0.96 (3) | 1.75 (3) | 2.716 (2) | 175 (3) |
OW1—HW1A···O8ii | 0.82 | 1.94 | 2.7059 (17) | 155.1 |
N2—H13···O8vi | 0.85 (3) | 2.12 (3) | 2.820 (2) | 140 (2) |
OW2—HW2A···O1 | 0.82 | 1.98 | 2.7749 (18) | 162.1 |
OW1—HW1B···OW3iv | 0.82 | 1.98 | 2.791 | 172.6 |
OW3—HW3A···O6 | 0.82 | 1.94 | 2.7334 (16) | 163.5 |
OW2—HW2B···OW3iv | 0.82 | 2.04 | 2.794 | 151.8 |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+2, −y, −z+2; (iii) x, y+1, z−1; (iv) x, y+1, z; (v) −x+1, −y+2, −z+1; (vi) x, y+2, z−1. |
Selected geometric parameters (Å, º) for (II) topCu1—O4i | 1.9491 (18) | Cu1—O1 | 1.9525 (17) |
| | | |
O4i—Cu1—O4ii | 88.95 (11) | O1iii—Cu1—O1 | 88.77 (10) |
O4i—Cu1—O1 | 92.05 (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···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O2iv | 0.89 | 2.14 | 2.938 (3) | 149.3 |
N1—H1B···O3v | 0.89 | 2.09 | 2.837 (3) | 141.6 |
N1—H1C···O2 | 0.89 | 2.00 | 2.831 (3) | 154.8 |
Symmetry codes: (iv) −x+1, y, −z+1; (v) x, y, z+1. |
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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-.