Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270108025900/sf3085sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270108025900/sf3085Isup2.hkl |
CCDC reference: 684844
For related literature, see: Abrahams et al. (1999); Amo-Ochoa, Givaja, Miguel, Sanz, Castillo & Zamora (2007); Batten et al. (1998); Chun et al. (2004); Fang et al. (2007); Halasyamani et al. (1996); Horike et al. (2008); Kuhlman et al. (1999); Luo et al. (2005); MacGillivray et al. (1994); Nouar et al. (2008); O'Keeffe et al. (2000); Otieno et al. (1993); Vaqueiro (2008); Wells (1986); Zhang et al. (2008).
A mixture of Cu(OH)2 (19.5 mg, 0.2 mmol), NaH2SIP (26.8 mg, 0.1 mmol), pyrazine (12.1 mg, 0.15 mmol) and water (15 ml) was heated at 448 K for 5 d. Black block-shaped crystals of (I) were obtained when the sample was cooled to room temperature at a rate of 5 K h-1. The crystals were recovered by filtration, washed with distilled water and dried in air (yield 42.3% based on Cu). Analysis calculated for C16H15CuN4O8S: C 39.43, H 3.08, N 11.50%; found: C 40.02, H 3.56, N 11.71%. IR spectrum (KBr pellet, cm-1): 3440 (ms), 1713 (s), 1478 (s), 1417 (s), 1241 (w), 1187 (ms), 1157 (m), 1101 (m), 1037 (s), 1000 (ms), 847 (w), 800 (s), 755 (ms), 721 (ms), 680 (w), 669 (ms), 653 (w), 622 (s), 574 (w), 485 (ms), 466 (w), 449 (ms).
H atoms attached to C atoms were positioned geometrically and refined using a riding model, with C—H = 0.93Å and Uiso(H) = 1.2Ueq(C). The carboxyl H atoms were located in a difference Fourier map and were refined with O—H distance restraints of 0.86 (2)Å. Water H atoms were located in a difference map and refined with O—H and H···H distance restraints of 0.85 (2) and 1.39 (1)Å, respectively, and with Uiso(H) = 1.5Ueq(O).
Data collection: SMART (Siemens, 1994); cell refinement: SAINT (Siemens, 1994); data reduction: SAINT (Siemens, 1994); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
[Cu(C4H4N2)2](C8H5O7S)·H2O | F(000) = 992 |
Mr = 486.94 | Dx = 1.702 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 17722 reflections |
a = 11.124 (2) Å | θ = 3.2–27.4° |
b = 15.709 (3) Å | µ = 1.32 mm−1 |
c = 11.337 (2) Å | T = 293 K |
β = 106.48 (3)° | Block, yellow |
V = 1899.7 (6) Å3 | 0.33 × 0.24 × 0.16 mm |
Z = 4 |
Siemens SMART CCD area-detector diffractometer | 4323 independent reflections |
Radiation source: fine-focus sealed tube | 2960 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.059 |
ω scans | θmax = 27.4°, θmin = 3.2° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −12→14 |
Tmin = 0.692, Tmax = 0.810 | k = −20→20 |
17404 measured reflections | l = −14→14 |
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)] = 0.049 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.111 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | w = 1/[σ2(Fo2) + (0.043P)2 + 1.528P] where P = (Fo2 + 2Fc2)/3 |
4323 reflections | (Δ/σ)max < 0.001 |
277 parameters | Δρmax = 0.36 e Å−3 |
5 restraints | Δρmin = −0.30 e Å−3 |
[Cu(C4H4N2)2](C8H5O7S)·H2O | V = 1899.7 (6) Å3 |
Mr = 486.94 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 11.124 (2) Å | µ = 1.32 mm−1 |
b = 15.709 (3) Å | T = 293 K |
c = 11.337 (2) Å | 0.33 × 0.24 × 0.16 mm |
β = 106.48 (3)° |
Siemens SMART CCD area-detector diffractometer | 4323 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2960 reflections with I > 2σ(I) |
Tmin = 0.692, Tmax = 0.810 | Rint = 0.059 |
17404 measured reflections |
R[F2 > 2σ(F2)] = 0.049 | 5 restraints |
wR(F2) = 0.111 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | Δρmax = 0.36 e Å−3 |
4323 reflections | Δρmin = −0.30 e Å−3 |
277 parameters |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
Cu1 | 0.76105 (4) | 0.12696 (3) | 0.03342 (4) | 0.04321 (14) | |
S1 | 0.28990 (8) | 0.22243 (5) | 0.60633 (8) | 0.0418 (2) | |
O1 | 0.3362 (2) | 0.22587 (15) | 0.7400 (2) | 0.0562 (7) | |
O2 | 0.3744 (3) | 0.26158 (16) | 0.5475 (3) | 0.0668 (8) | |
O3 | 0.1622 (2) | 0.25185 (16) | 0.5607 (3) | 0.0612 (7) | |
O4 | −0.0240 (2) | −0.00017 (17) | 0.3174 (3) | 0.0675 (8) | |
O5 | 0.0789 (2) | −0.12285 (16) | 0.3329 (3) | 0.0677 (8) | |
H5 | 0.0136 | −0.1385 | 0.2832 | 0.102* | |
O6 | 0.5910 (3) | −0.04670 (18) | 0.7356 (3) | 0.0767 (9) | |
O7 | 0.4912 (2) | −0.15758 (16) | 0.6277 (3) | 0.0664 (8) | |
H7 | 0.5480 | −0.1847 | 0.6745 | 0.100* | |
N1 | 0.7597 (2) | 0.20714 (17) | −0.1100 (3) | 0.0407 (6) | |
N2 | 0.7654 (2) | 0.30509 (16) | −0.3145 (2) | 0.0391 (6) | |
N3 | 0.9030 (2) | 0.04938 (17) | 0.0204 (3) | 0.0405 (6) | |
N4 | 0.6042 (2) | 0.05176 (16) | 0.0094 (2) | 0.0366 (6) | |
C1 | 0.2862 (3) | 0.1122 (2) | 0.5684 (3) | 0.0372 (7) | |
C2 | 0.1839 (3) | 0.0779 (2) | 0.4828 (3) | 0.0415 (8) | |
H2 | 0.1152 | 0.1120 | 0.4460 | 0.050* | |
C3 | 0.1832 (3) | −0.0077 (2) | 0.4512 (3) | 0.0411 (8) | |
C4 | 0.2868 (3) | −0.0588 (2) | 0.5070 (3) | 0.0423 (8) | |
H4 | 0.2871 | −0.1160 | 0.4860 | 0.051* | |
C5 | 0.3892 (3) | −0.0240 (2) | 0.5938 (3) | 0.0387 (7) | |
C6 | 0.3876 (3) | 0.0613 (2) | 0.6237 (3) | 0.0416 (8) | |
H6 | 0.4560 | 0.0846 | 0.6821 | 0.050* | |
C7 | 0.0687 (3) | −0.0425 (2) | 0.3606 (3) | 0.0464 (8) | |
C8 | 0.5009 (3) | −0.0761 (2) | 0.6604 (3) | 0.0485 (9) | |
C9 | 0.8485 (3) | 0.2639 (2) | −0.1062 (3) | 0.0486 (9) | |
H9A | 0.9116 | 0.2713 | −0.0330 | 0.058* | |
C10 | 0.6742 (4) | 0.2008 (3) | −0.2189 (4) | 0.0688 (13) | |
H10 | 0.6096 | 0.1616 | −0.2274 | 0.083* | |
C11 | 0.8510 (4) | 0.3122 (2) | −0.2063 (3) | 0.0533 (9) | |
H11 | 0.9154 | 0.3516 | −0.1980 | 0.064* | |
C12 | 0.6765 (3) | 0.2488 (3) | −0.3185 (3) | 0.0567 (10) | |
H12 | 0.6132 | 0.2416 | −0.3916 | 0.068* | |
C13 | 1.0240 (3) | 0.0668 (2) | 0.0746 (3) | 0.0450 (8) | |
H13 | 1.0442 | 0.1132 | 0.1273 | 0.054* | |
C14 | 0.8811 (3) | −0.0184 (2) | −0.0549 (3) | 0.0461 (8) | |
H14 | 0.7986 | −0.0330 | −0.0951 | 0.055* | |
C15 | 0.6146 (3) | −0.0279 (2) | 0.0527 (3) | 0.0412 (8) | |
H15 | 0.6941 | −0.0495 | 0.0906 | 0.049* | |
C16 | 0.4877 (3) | 0.0788 (2) | −0.0430 (3) | 0.0385 (7) | |
H16 | 0.4755 | 0.1339 | −0.0740 | 0.046* | |
O1W | −0.1163 (3) | −0.1882 (3) | 0.1797 (4) | 0.1155 (16) | |
H1WA | −0.129 (5) | −0.205 (4) | 0.108 (3) | 0.139* | |
H1WB | −0.166 (5) | −0.208 (4) | 0.215 (4) | 0.139* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0416 (2) | 0.0453 (2) | 0.0441 (3) | −0.00452 (19) | 0.01438 (19) | −0.00297 (19) |
S1 | 0.0427 (5) | 0.0354 (4) | 0.0422 (5) | 0.0001 (4) | 0.0036 (4) | 0.0007 (4) |
O1 | 0.0679 (17) | 0.0471 (14) | 0.0416 (14) | 0.0000 (12) | −0.0040 (12) | −0.0041 (11) |
O2 | 0.0776 (19) | 0.0490 (15) | 0.082 (2) | −0.0124 (14) | 0.0358 (17) | 0.0062 (14) |
O3 | 0.0507 (15) | 0.0538 (15) | 0.0700 (19) | 0.0126 (12) | 0.0022 (13) | −0.0063 (14) |
O4 | 0.0486 (15) | 0.0601 (17) | 0.076 (2) | 0.0076 (13) | −0.0106 (14) | −0.0085 (15) |
O5 | 0.0510 (15) | 0.0558 (16) | 0.076 (2) | 0.0006 (13) | −0.0143 (14) | −0.0209 (14) |
O6 | 0.0555 (17) | 0.0609 (18) | 0.087 (2) | 0.0020 (14) | −0.0224 (16) | −0.0077 (16) |
O7 | 0.0582 (16) | 0.0465 (15) | 0.076 (2) | 0.0068 (13) | −0.0114 (15) | −0.0006 (14) |
N1 | 0.0388 (15) | 0.0439 (16) | 0.0368 (15) | −0.0069 (12) | 0.0063 (13) | −0.0009 (12) |
N2 | 0.0370 (15) | 0.0404 (15) | 0.0387 (16) | −0.0007 (12) | 0.0089 (13) | −0.0001 (12) |
N3 | 0.0369 (14) | 0.0428 (15) | 0.0433 (16) | −0.0023 (12) | 0.0137 (13) | −0.0022 (13) |
N4 | 0.0336 (14) | 0.0363 (14) | 0.0408 (15) | −0.0024 (11) | 0.0119 (12) | −0.0006 (12) |
C1 | 0.0362 (16) | 0.0380 (17) | 0.0341 (17) | −0.0005 (14) | 0.0046 (14) | 0.0011 (14) |
C2 | 0.0352 (17) | 0.0414 (19) | 0.0420 (19) | 0.0027 (14) | 0.0015 (15) | 0.0017 (15) |
C3 | 0.0367 (17) | 0.0420 (18) | 0.0411 (19) | −0.0038 (14) | 0.0055 (15) | −0.0031 (15) |
C4 | 0.0403 (18) | 0.0371 (17) | 0.045 (2) | 0.0016 (15) | 0.0049 (16) | −0.0010 (15) |
C5 | 0.0342 (16) | 0.0399 (17) | 0.0382 (18) | −0.0006 (14) | 0.0040 (14) | 0.0020 (14) |
C6 | 0.0348 (17) | 0.0427 (18) | 0.0403 (19) | −0.0057 (15) | −0.0007 (15) | −0.0039 (15) |
C7 | 0.0435 (19) | 0.047 (2) | 0.042 (2) | −0.0017 (17) | 0.0012 (16) | −0.0044 (16) |
C8 | 0.045 (2) | 0.043 (2) | 0.051 (2) | −0.0020 (16) | 0.0029 (18) | −0.0019 (17) |
C9 | 0.047 (2) | 0.052 (2) | 0.0375 (19) | −0.0166 (17) | −0.0024 (16) | 0.0018 (16) |
C10 | 0.058 (2) | 0.096 (3) | 0.045 (2) | −0.042 (2) | 0.0021 (19) | 0.010 (2) |
C11 | 0.053 (2) | 0.052 (2) | 0.047 (2) | −0.0211 (18) | 0.0014 (18) | 0.0046 (18) |
C12 | 0.045 (2) | 0.080 (3) | 0.038 (2) | −0.019 (2) | 0.0003 (17) | 0.0064 (19) |
C13 | 0.0386 (19) | 0.0452 (19) | 0.050 (2) | −0.0093 (15) | 0.0105 (16) | −0.0071 (16) |
C14 | 0.0318 (17) | 0.053 (2) | 0.052 (2) | −0.0054 (16) | 0.0092 (16) | −0.0041 (17) |
C15 | 0.0316 (16) | 0.0426 (18) | 0.049 (2) | 0.0060 (14) | 0.0109 (15) | 0.0048 (16) |
C16 | 0.0392 (18) | 0.0339 (16) | 0.0451 (19) | 0.0039 (14) | 0.0163 (15) | 0.0048 (14) |
O1W | 0.076 (2) | 0.204 (4) | 0.073 (2) | −0.068 (3) | 0.032 (2) | −0.072 (3) |
Cu1—N2i | 2.017 (3) | C2—C3 | 1.391 (4) |
Cu1—N3 | 2.033 (3) | C2—H2 | 0.9300 |
Cu1—N1 | 2.054 (3) | C3—C4 | 1.400 (4) |
Cu1—N4 | 2.061 (2) | C3—C7 | 1.494 (5) |
S1—O2 | 1.437 (3) | C4—C5 | 1.389 (4) |
S1—O3 | 1.443 (3) | C4—H4 | 0.9300 |
S1—O1 | 1.457 (3) | C5—C6 | 1.383 (4) |
S1—C1 | 1.781 (3) | C5—C8 | 1.500 (5) |
O4—C7 | 1.208 (4) | C6—H6 | 0.9300 |
O5—C7 | 1.313 (4) | C9—C11 | 1.372 (5) |
O5—H5 | 0.8200 | C9—H9A | 0.9300 |
O6—C8 | 1.208 (4) | C10—C12 | 1.364 (5) |
O7—C8 | 1.328 (4) | C10—H10 | 0.9300 |
O7—H7 | 0.8200 | C11—H11 | 0.9300 |
N1—C9 | 1.322 (4) | C12—H12 | 0.9300 |
N1—C10 | 1.331 (5) | C13—C14iii | 1.369 (5) |
N2—C12 | 1.318 (4) | C13—H13 | 0.9300 |
N2—C11 | 1.327 (4) | C14—C13iii | 1.369 (5) |
N2—Cu1ii | 2.017 (3) | C14—H14 | 0.9300 |
N3—C13 | 1.340 (4) | C15—C16iv | 1.370 (4) |
N3—C14 | 1.343 (4) | C15—H15 | 0.9300 |
N4—C16 | 1.332 (4) | C16—C15iv | 1.370 (4) |
N4—C15 | 1.337 (4) | C16—H16 | 0.9300 |
C1—C2 | 1.380 (4) | O1W—H1WA | 0.830 (19) |
C1—C6 | 1.380 (4) | O1W—H1WB | 0.829 (19) |
N2i—Cu1—N3 | 123.27 (11) | C6—C5—C4 | 119.3 (3) |
N2i—Cu1—N1 | 110.21 (11) | C6—C5—C8 | 118.1 (3) |
N3—Cu1—N1 | 98.14 (11) | C4—C5—C8 | 122.5 (3) |
N2i—Cu1—N4 | 103.33 (11) | C1—C6—C5 | 121.1 (3) |
N3—Cu1—N4 | 107.02 (11) | C1—C6—H6 | 119.5 |
N1—Cu1—N4 | 115.53 (11) | C5—C6—H6 | 119.5 |
O2—S1—O3 | 113.82 (18) | O4—C7—O5 | 123.6 (3) |
O2—S1—O1 | 112.49 (18) | O4—C7—C3 | 122.7 (3) |
O3—S1—O1 | 112.50 (17) | O5—C7—C3 | 113.7 (3) |
O2—S1—C1 | 106.08 (16) | O6—C8—O7 | 123.4 (3) |
O3—S1—C1 | 105.78 (15) | O6—C8—C5 | 123.3 (3) |
O1—S1—C1 | 105.33 (15) | O7—C8—C5 | 113.3 (3) |
C7—O5—H5 | 109.5 | N1—C9—C11 | 122.4 (3) |
C8—O7—H7 | 109.5 | N1—C9—H9A | 118.8 |
C9—N1—C10 | 114.3 (3) | C11—C9—H9A | 118.8 |
C9—N1—Cu1 | 123.4 (2) | N1—C10—C12 | 123.3 (3) |
C10—N1—Cu1 | 122.1 (2) | N1—C10—H10 | 118.3 |
C12—N2—C11 | 115.0 (3) | C12—C10—H10 | 118.3 |
C12—N2—Cu1ii | 119.3 (2) | N2—C11—C9 | 122.7 (3) |
C11—N2—Cu1ii | 125.6 (2) | N2—C11—H11 | 118.7 |
C13—N3—C14 | 115.5 (3) | C9—C11—H11 | 118.7 |
C13—N3—Cu1 | 123.0 (2) | N2—C12—C10 | 122.2 (3) |
C14—N3—Cu1 | 121.1 (2) | N2—C12—H12 | 118.9 |
C16—N4—C15 | 115.7 (3) | C10—C12—H12 | 118.9 |
C16—N4—Cu1 | 123.8 (2) | N3—C13—C14iii | 122.2 (3) |
C15—N4—Cu1 | 120.4 (2) | N3—C13—H13 | 118.9 |
C2—C1—C6 | 119.8 (3) | C14iii—C13—H13 | 118.9 |
C2—C1—S1 | 120.5 (2) | N3—C14—C13iii | 122.3 (3) |
C6—C1—S1 | 119.6 (2) | N3—C14—H14 | 118.8 |
C1—C2—C3 | 120.2 (3) | C13iii—C14—H14 | 118.8 |
C1—C2—H2 | 119.9 | N4—C15—C16iv | 122.2 (3) |
C3—C2—H2 | 119.9 | N4—C15—H15 | 118.9 |
C2—C3—C4 | 119.6 (3) | C16iv—C15—H15 | 118.9 |
C2—C3—C7 | 118.2 (3) | N4—C16—C15iv | 122.1 (3) |
C4—C3—C7 | 122.2 (3) | N4—C16—H16 | 119.0 |
C5—C4—C3 | 120.0 (3) | C15iv—C16—H16 | 119.0 |
C5—C4—H4 | 120.0 | H1WA—O1W—H1WB | 114 (3) |
C3—C4—H4 | 120.0 | ||
N2i—Cu1—N1—C9 | 58.4 (3) | C3—C4—C5—C8 | 177.6 (3) |
N3—Cu1—N1—C9 | −71.7 (3) | C2—C1—C6—C5 | 0.7 (5) |
N4—Cu1—N1—C9 | 175.0 (3) | S1—C1—C6—C5 | −178.2 (3) |
N2i—Cu1—N1—C10 | −127.7 (3) | C4—C5—C6—C1 | −0.3 (5) |
N3—Cu1—N1—C10 | 102.3 (3) | C8—C5—C6—C1 | −178.2 (3) |
N4—Cu1—N1—C10 | −11.1 (4) | C2—C3—C7—O4 | −2.6 (5) |
N2i—Cu1—N3—C13 | −34.8 (3) | C4—C3—C7—O4 | 175.5 (4) |
N1—Cu1—N3—C13 | 86.0 (3) | C2—C3—C7—O5 | 177.4 (3) |
N4—Cu1—N3—C13 | −154.1 (3) | C4—C3—C7—O5 | −4.5 (5) |
N2i—Cu1—N3—C14 | 152.6 (2) | C6—C5—C8—O6 | −2.7 (6) |
N1—Cu1—N3—C14 | −86.6 (3) | C4—C5—C8—O6 | 179.5 (4) |
N4—Cu1—N3—C14 | 33.3 (3) | C6—C5—C8—O7 | 177.9 (3) |
N2i—Cu1—N4—C16 | 80.6 (3) | C4—C5—C8—O7 | 0.1 (5) |
N3—Cu1—N4—C16 | −147.9 (2) | C10—N1—C9—C11 | 0.4 (6) |
N1—Cu1—N4—C16 | −39.8 (3) | Cu1—N1—C9—C11 | 174.8 (3) |
N2i—Cu1—N4—C15 | −95.9 (3) | C9—N1—C10—C12 | −0.4 (6) |
N3—Cu1—N4—C15 | 35.6 (3) | Cu1—N1—C10—C12 | −174.9 (4) |
N1—Cu1—N4—C15 | 143.7 (2) | C12—N2—C11—C9 | 0.9 (6) |
O2—S1—C1—C2 | −105.3 (3) | Cu1ii—N2—C11—C9 | 180.0 (3) |
O3—S1—C1—C2 | 15.9 (3) | N1—C9—C11—N2 | −0.7 (6) |
O1—S1—C1—C2 | 135.3 (3) | C11—N2—C12—C10 | −0.9 (6) |
O2—S1—C1—C6 | 73.6 (3) | Cu1ii—N2—C12—C10 | 179.9 (4) |
O3—S1—C1—C6 | −165.2 (3) | N1—C10—C12—N2 | 0.7 (7) |
O1—S1—C1—C6 | −45.8 (3) | C14—N3—C13—C14iii | −0.3 (6) |
C6—C1—C2—C3 | −0.7 (5) | Cu1—N3—C13—C14iii | −173.3 (3) |
S1—C1—C2—C3 | 178.2 (3) | C13—N3—C14—C13iii | 0.3 (6) |
C1—C2—C3—C4 | 0.1 (5) | Cu1—N3—C14—C13iii | 173.4 (3) |
C1—C2—C3—C7 | 178.3 (3) | C16—N4—C15—C16iv | 0.5 (5) |
C2—C3—C4—C5 | 0.3 (5) | Cu1—N4—C15—C16iv | 177.3 (2) |
C7—C3—C4—C5 | −177.8 (3) | C15—N4—C16—C15iv | −0.5 (5) |
C3—C4—C5—C6 | −0.3 (5) | Cu1—N4—C16—C15iv | −177.2 (2) |
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) x, −y+1/2, z−1/2; (iii) −x+2, −y, −z; (iv) −x+1, −y, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WA···O3v | 0.83 (2) | 1.96 (2) | 2.790 (4) | 178 (6) |
O1W—H1WB···O1vi | 0.83 (2) | 2.11 (3) | 2.903 (4) | 159 (6) |
O5—H5···O1W | 0.82 | 1.76 | 2.578 (4) | 171 |
O7—H7···O1vii | 0.82 | 1.97 | 2.766 (4) | 165 |
Symmetry codes: (v) −x, y−1/2, −z+1/2; (vi) −x, −y, −z+1; (vii) −x+1, y−1/2, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C4H4N2)2](C8H5O7S)·H2O |
Mr | 486.94 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 11.124 (2), 15.709 (3), 11.337 (2) |
β (°) | 106.48 (3) |
V (Å3) | 1899.7 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.32 |
Crystal size (mm) | 0.33 × 0.24 × 0.16 |
Data collection | |
Diffractometer | Siemens SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.692, 0.810 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 17404, 4323, 2960 |
Rint | 0.059 |
(sin θ/λ)max (Å−1) | 0.648 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.111, 1.01 |
No. of reflections | 4323 |
No. of parameters | 277 |
No. of restraints | 5 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.36, −0.30 |
Computer programs: SMART (Siemens, 1994), SAINT (Siemens, 1994), SHELXTL (Sheldrick, 2008).
Cu1—N2i | 2.017 (3) | Cu1—N1 | 2.054 (3) |
Cu1—N3 | 2.033 (3) | Cu1—N4 | 2.061 (2) |
N2i—Cu1—N3 | 123.27 (11) | N2i—Cu1—N4 | 103.33 (11) |
N2i—Cu1—N1 | 110.21 (11) | N3—Cu1—N4 | 107.02 (11) |
N3—Cu1—N1 | 98.14 (11) | N1—Cu1—N4 | 115.53 (11) |
Symmetry code: (i) x, −y+1/2, z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WA···O3ii | 0.830 (19) | 1.96 (2) | 2.790 (4) | 178 (6) |
O1W—H1WB···O1iii | 0.829 (19) | 2.11 (3) | 2.903 (4) | 159 (6) |
O5—H5···O1W | 0.82 | 1.76 | 2.578 (4) | 171.1 |
O7—H7···O1iv | 0.82 | 1.97 | 2.766 (4) | 165.3 |
Symmetry codes: (ii) −x, y−1/2, −z+1/2; (iii) −x, −y, −z+1; (iv) −x+1, y−1/2, −z+3/2. |
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The design and synthesis of porous coordination polymers is of great interest due to their intriguing topology architecture and significant potential applications in many fields, such as gas molecules, ion exchange, catalytic activity and polymer synthesis (Batten et al., 1998; Abrahams et al., 1999; Fang et al., 2007; Horike et al., 2008; Zhang et al., 2008; Vaqueiro, 2008; Nouar et al., 2008). Although these kinds of materials have promising applications, it would be a big challenge to achieve a major advance without understanding the structural aspects. Thereby, the synthesis of high-dimensional coordination polymers and analysis of the interesting topology become more important. The classification of structures by Wells (1986) and O'Keeffe (O'Keeffe et al., 2000) laid the foundation for our general understanding and the design of special inorganic compounds, as well as covalent organic frameworks. On the basis of the classification, a great number of such compounds are characterized by the prototype of mineral topologies, such as CdSO4, NbO, Pt3O4, pyrite, quartz, rutile, halite, and sodalite (Luo et al.,2005; Chun et al., 2004). Pyrazine, as a normal rigid linear ligand, has been utilized to synthesize a number of orangic–inorganic hydrids thus far (MacGillivray et al., 1994; Kuhlman et al., 1999; Halasyamani et al., 1996; Amo-Ochoa et al., 2007). In order to enrich the coordination chemistry of the three-dimensional open framework constructed from this ligand with one-dimensional channels, in this communcation, we describe the synthsis and crystal structure of a novel three-dimensional porous coordination polymer constructed from pyrazine (pyz) and CuI, namely {[CuI(pyz)2](H2SIP).H2O}n (H3SIP is 5-sulfoisophthalic acid), (I).
As shown in Fig. 1, the asymmetric unit of (I) consists of one CuI ion, one whole and two half pyrazine ligands, one H2SIP- anion and one lattice water molecule. The CuI centre is coordinated by four N atoms from pyrazine ligands to form a slightly distorted tetrahedral configuration, in which the four Cu—N bond lengths are 2.017 (3), 2.033 (3), 2.054 (3) and 2.061 (3)Å, and the N—Cu—N bond angles are in the range 98.21 (11)–123.27 (11)° (Table 1). The mean Cu—N bond length of 2.042Å is similar to that found in [Cu(2,5-Me2-pyz)2]PF6 (2,5-Me2-pyz is 2,5-dimethylpyrazine; Otieno et al., 1993).
The linear pyrazine ligands act as pillars along different directions and link CuI ions to form an extended three-dimensional porous coordination network (Fig. 2). As a consequence of this assembly, one-dimensional channels occupied by guest water and monodepronated H2SIP- anions are formed. As shown in Fig. 3, the one-dimensional porous channels in the three-dimensional open framework features a large hexagonal 26-membered ring with approximate dimensions 15.1 × 13.0Å2, which contains six Cu atoms and six pyrazine ligands. Although a good number of hexagonal-shaped metallacycles are known in coordination polymers, such nano-sized metallacycles constructed from CuI and simple linear ligands guested by H2SIP- anions and water molecules are still unprecedented.
A better insight into the nature of this intricate framework can be achieved by the application of a topological approach, i.e., reducing multidimensional structures to simple node and connection nets. As depicted in Fig. 4, each CuI site in (I) is coordinated by four pyrazine N atoms, while each pyrazine ligand serves as a two-connected node bridging two CuI atoms. Therefore, the CuI ion can be simplified to a four-connected node and, accordingly, each pyrazine ligand becomes a two-connected linker and the overall topology can thus be described as a diamondoid network.
Notably, the free water molecules and the H2SIP- anions are encapsulated in the channels and are further linked with each other through O—H···O hydrogen-bonding interactions into a three-dimensional supramolecular open framework, as shown in Fig. 5. There are three types of hydrogen bonds: (a) between the lattice water molecules and sulfonate O atoms [O1W···O3 = 2.790 (5)Å; O1W···O1 = 2.903 (4)Å]; (b) between a carboxyl O atom and lattice water [O5···O1W = 2.578 (5)Å]; (c) between a carboxyl O atom and a sulfonate O atom [O7···O1 = 2.767 (4)Å]. Thus, the guest molecules have a significant influence on the coordination geometry of the host metal ions. The guest–water hydrogen-bond network is also a diamondoid network, which interpenetrates the metal–pyrazine network.
Complex (I) is stable in air and insoluble in water and most organic solvents, so no additional measurements in solution could be performed. Interestingly, (I) shows strong photoluminescence in the solid state, with an emission maximum at 645 nm upon excitation at 385 nm at room temperature. According to the structural features of the compound, the emission band might be assigned to a combination of metal-to-ligand charge transfer (MLCT) and ligand-to-metal charge transfer (LMCT). The compound appears to be a good candidate as a novel hybrid inorganic–organic photoactive material.
In summary, a new three-dimensional porous metal–organic framework with open channels featuring an unusual (2,4)-connected topology has been synthesized and characterized. The structure of (I) provides another valuable prototype of (2,4)-connected nets which may be important for the design of PCPS [Please define.