




Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S160053681003970X/rz2494sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S160053681003970X/rz2494Isup2.hkl |
CCDC reference: 799445
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean
(C-C) = 0.004 Å
- R factor = 0.040
- wR factor = 0.080
- Data-to-parameter ratio = 13.2
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.97 PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) ..... 1 PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L= 0.600 47 PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L= 0.600 16
Alert level G PLAT180_ALERT_4_G Check Cell Rounding: # of Values Ending with 0 = 3 PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature 293 K
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 4 ALERT level C = Check and explain 3 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 3 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
A mixture of Zn(NO3)2.6H2O (29.7 mg, 0.1 mmol), biphenyl-4,4'-dicarboxylic acid (H2BPDC) (24.2 mg, 0.1 mmol), 1,4-bis(1,2,4-triazol-1-yl)butane (BTB) (19.2 mg, 0.1 mmol), and KOH (11.2 mg, 0.2 mmol) in H2O (10 ml) was sealed in a 16 ml Teflon-lined stainless steel container and heated at 180°C for 72 h. After cooling to room temperature, white block crystals of the title compound were collected by filtration and washed with water and ethanol several times (yield 51.3%, based on H2BPDC). Elemental analysis for C22H28ZnN6O8 (Mr = 569.87): C 46.37, H 4.95, N 14.75%; found: 46.46, H 4.98, N 14.79%.
The water H atoms were located in a difference Fourier map and fixed in the refinement, with Uiso(H)=1.2Ueq(O). All C-bound H atoms were placed in calculated positions and refined using a riding model, with C—H = 0.93 (triazole, aromatic) or 0.97 Å(methylene) and Uiso(H) = 1.2Ueq(C).
Interest in crystal engineering and supramolecular chemistry is rapidly increasing not only because of their fascinating structures and topologies but also owing to their potential use in optical, electrical, catalytic and adsorptive applications (Kitagawa et al., 2004; Ferey et al., 2005; Roy et al., 2009; Zhang et al., 2009). The construction of such coordination polymers is highly influenced by several factors. However, the key factor in the manipulating coordination polymers is undoubtedly the selection of appropriate ligands. Comparing to rigid ligands, bifunctional flexible ligands can induce variability of the structure and may lead to the formation of supramolecular isomers because of their conformational flexibility. Recently, a series of transition metal coordination polymers based on the flexible ligand 1,4-bis(1,2,4-triazol-1-yl)butane have been reported (Liu et al., 2008; Gu et al., 2008; Wang et al., 2008; Zhu et al., 2009). In this paper, biphenyl-4,4'-dicarboxylic acid (H2BPDC) and 1,4-bis(1,2,4-triazol-1-yl)butane (BTB) have been selected as organic linkers, generating the title new zinc(II) coordination polymer, (I), the crystal structure of which is reported herein.
Compound (I) crystallizes in the triclinic space group P -1, and the asymmetric unit contains half a [Zn(C8H12N6)(H2O)4]2+ cation and half a uncoordinated BPDC anion. Each zinc(II) metal is located on an inversion centre and is six-coordinated in a octahedron geometry by two triazole nitrogen atoms from two different BTB ligand in the axial positions, and four oxygen atom from coordinated water molecules at the equatorial plane (Figure 1). The Zn–N bond length is 2.096 (2) Å, while the Zn–O bond lengths are 2.1234 (18) Å, 2.1693 (19)Å respectively. The BTB ligand adopts a trans–trans-trans conformation and acts as a N,N'-bidentate ligand linking centrosymmetrically-related zinc(II) cations into one-dimensional zig-zag cationic chains parallel to the c axis. The doubly deprotonated BPDC anion, which has crystallographically imposed centre of symmetry, does not coordinate to the zinc(II) centres and only acts as counter-ion. The anionic and cationic parts of (I) interact to form a three-dimensional network through intermolecular interactions such as conventional O—H···O hydrogen bonds, non-conventional C—H···O contacts and C—H···π interactions (Table 1). The C—H···π interaction is observed between the H3B atom and the centroid of the C6–C11 ring. As shown in Figure 2, interchain O1—H1C···O3, O1—H1D···O3, O2—H2D···O3 bonds between coordinated water molecules and the carboxylate anion are found to assemble the 1-D motifs into a 2-D layer parallel to the bc plane. These layers are further connected by interlayer O2—H2C···O4, C2—H2A···O4 hydrogen bonds, forming a 3-D supramolecular network (Figure 3).
For general background to the structures and applications of supramolecular compounds, see: Kitagawa et al. (2004); Ferey et al. (2005); Roy et al. (2009); Zhang et al. (2009). For related compounds based on 1,4-bis(1,2,4-triazol-1-yl)butane, see: Li et al. (2006); Liu et al. (2008); Gu et al. (2008); Wang et al. (2008); Zhu et al. (2009).
Data collection: SMART (Bruker 2000); cell refinement: SAINT (Bruker 2000); data reduction: SAINT (Bruker 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
[Zn(C8H12N6)(H2O)4](C14H8O4) | Z = 1 |
Mr = 569.89 | F(000) = 296 |
Triclinic, P1 | Dx = 1.611 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 6.4344 (15) Å | Cell parameters from 1152 reflections |
b = 7.1490 (18) Å | θ = 3.0–25.0° |
c = 13.539 (3) Å | µ = 1.11 mm−1 |
α = 89.250 (4)° | T = 293 K |
β = 81.348 (4)° | Block, white |
γ = 72.620 (3)° | 0.21 × 0.19 × 0.17 mm |
V = 587.3 (2) Å3 |
Bruker SMART APEX CCD diffractometer | 2299 independent reflections |
Radiation source: fine-focus sealed tube | 1788 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.032 |
phi and ω scans | θmax = 26.0°, θmin = 3.0° |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −6→7 |
Tmin = 0.792, Tmax = 0.828 | k = −6→8 |
3162 measured reflections | l = −16→16 |
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)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.080 | H-atom parameters constrained |
S = 0.92 | w = 1/[σ2(Fo2) + (0.0317P)2] where P = (Fo2 + 2Fc2)/3 |
2237 reflections | (Δ/σ)max < 0.001 |
169 parameters | Δρmax = 0.47 e Å−3 |
0 restraints | Δρmin = −0.31 e Å−3 |
[Zn(C8H12N6)(H2O)4](C14H8O4) | γ = 72.620 (3)° |
Mr = 569.89 | V = 587.3 (2) Å3 |
Triclinic, P1 | Z = 1 |
a = 6.4344 (15) Å | Mo Kα radiation |
b = 7.1490 (18) Å | µ = 1.11 mm−1 |
c = 13.539 (3) Å | T = 293 K |
α = 89.250 (4)° | 0.21 × 0.19 × 0.17 mm |
β = 81.348 (4)° |
Bruker SMART APEX CCD diffractometer | 2299 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | 1788 reflections with I > 2σ(I) |
Tmin = 0.792, Tmax = 0.828 | Rint = 0.032 |
3162 measured reflections |
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.080 | H-atom parameters constrained |
S = 0.92 | Δρmax = 0.47 e Å−3 |
2237 reflections | Δρmin = −0.31 e Å−3 |
169 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.1236 (5) | 0.0898 (4) | 0.1819 (2) | 0.0408 (7) | |
H1A | 0.0180 | 0.1181 | 0.1395 | 0.049* | |
C2 | 0.4301 (4) | −0.0006 (4) | 0.23078 (18) | 0.0323 (6) | |
H2A | 0.5802 | −0.0473 | 0.2337 | 0.039* | |
C3 | 0.2822 (4) | 0.0747 (4) | 0.41485 (17) | 0.0347 (7) | |
H3A | 0.1835 | 0.0101 | 0.4519 | 0.042* | |
H3B | 0.2282 | 0.2125 | 0.4350 | 0.042* | |
C4 | 0.5070 (4) | −0.0100 (4) | 0.44352 (17) | 0.0311 (6) | |
H4A | 0.6059 | 0.0584 | 0.4103 | 0.037* | |
H4B | 0.5653 | −0.1473 | 0.4224 | 0.037* | |
C5 | 0.1402 (5) | 0.5973 (4) | 0.18630 (19) | 0.0319 (6) | |
C6 | 0.2502 (4) | 0.5703 (4) | 0.27840 (17) | 0.0275 (6) | |
C7 | 0.1272 (4) | 0.6255 (4) | 0.37179 (19) | 0.0375 (7) | |
H7 | −0.0245 | 0.6825 | 0.3773 | 0.045* | |
C8 | 0.2241 (4) | 0.5981 (4) | 0.45708 (19) | 0.0367 (7) | |
H8 | 0.1358 | 0.6366 | 0.5187 | 0.044* | |
C9 | 0.4489 (4) | 0.5149 (3) | 0.45388 (17) | 0.0262 (6) | |
C10 | 0.5721 (4) | 0.4649 (4) | 0.35941 (19) | 0.0389 (7) | |
H10 | 0.7243 | 0.4120 | 0.3534 | 0.047* | |
C11 | 0.4747 (5) | 0.4915 (4) | 0.27460 (19) | 0.0393 (7) | |
H11 | 0.5629 | 0.4552 | 0.2128 | 0.047* | |
N1 | 0.3416 (3) | 0.0186 (3) | 0.14818 (15) | 0.0333 (6) | |
N2 | 0.0731 (4) | 0.1156 (3) | 0.27853 (16) | 0.0416 (6) | |
N3 | 0.2730 (4) | 0.0566 (3) | 0.30894 (15) | 0.0299 (5) | |
O1 | 0.6429 (3) | 0.2192 (3) | 0.04395 (12) | 0.0405 (5) | |
H1C | 0.5383 | 0.3192 | 0.0681 | 0.049* | |
H1D | 0.7103 | 0.2541 | −0.0085 | 0.049* | |
O2 | 0.2224 (3) | 0.2334 (3) | −0.02699 (13) | 0.0459 (5) | |
H2C | 0.2093 | 0.2385 | −0.0886 | 0.055* | |
H2D | 0.2284 | 0.3433 | −0.0065 | 0.055* | |
O3 | 0.2593 (3) | 0.5246 (3) | 0.10408 (13) | 0.0407 (5) | |
O4 | −0.0583 (3) | 0.6896 (3) | 0.19568 (13) | 0.0484 (6) | |
Zn1 | 0.5000 | 0.0000 | 0.0000 | 0.03341 (17) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0328 (18) | 0.0533 (19) | 0.0323 (16) | −0.0054 (14) | −0.0083 (13) | 0.0027 (13) |
C2 | 0.0283 (15) | 0.0366 (16) | 0.0266 (14) | −0.0028 (13) | −0.0014 (12) | 0.0002 (12) |
C3 | 0.0380 (17) | 0.0397 (16) | 0.0211 (14) | −0.0057 (13) | 0.0000 (12) | −0.0039 (12) |
C4 | 0.0349 (16) | 0.0298 (15) | 0.0243 (14) | −0.0051 (12) | −0.0007 (12) | −0.0001 (11) |
C5 | 0.0369 (18) | 0.0294 (15) | 0.0293 (15) | −0.0086 (13) | −0.0078 (13) | 0.0016 (11) |
C6 | 0.0302 (15) | 0.0275 (14) | 0.0246 (13) | −0.0069 (12) | −0.0072 (11) | 0.0009 (11) |
C7 | 0.0236 (15) | 0.0506 (18) | 0.0302 (15) | 0.0012 (13) | −0.0049 (12) | 0.0033 (13) |
C8 | 0.0284 (16) | 0.0504 (18) | 0.0238 (14) | −0.0026 (13) | 0.0000 (12) | 0.0025 (12) |
C9 | 0.0246 (15) | 0.0250 (14) | 0.0285 (14) | −0.0058 (11) | −0.0057 (11) | 0.0005 (11) |
C10 | 0.0222 (15) | 0.0561 (19) | 0.0311 (15) | −0.0005 (13) | −0.0045 (12) | −0.0085 (13) |
C11 | 0.0314 (17) | 0.0554 (19) | 0.0238 (14) | −0.0041 (14) | 0.0008 (12) | −0.0086 (12) |
N1 | 0.0317 (14) | 0.0398 (14) | 0.0238 (12) | −0.0028 (11) | −0.0058 (10) | 0.0009 (10) |
N2 | 0.0296 (14) | 0.0589 (16) | 0.0300 (13) | −0.0044 (12) | −0.0035 (11) | 0.0003 (11) |
N3 | 0.0286 (13) | 0.0324 (13) | 0.0247 (11) | −0.0038 (10) | −0.0027 (10) | −0.0013 (9) |
O1 | 0.0406 (12) | 0.0466 (12) | 0.0289 (10) | −0.0073 (10) | 0.0000 (9) | −0.0030 (9) |
O2 | 0.0524 (13) | 0.0422 (12) | 0.0344 (11) | 0.0043 (10) | −0.0178 (9) | −0.0028 (9) |
O3 | 0.0408 (12) | 0.0480 (12) | 0.0257 (10) | −0.0010 (10) | −0.0059 (9) | −0.0036 (9) |
O4 | 0.0322 (12) | 0.0707 (15) | 0.0306 (11) | 0.0062 (11) | −0.0125 (9) | −0.0015 (10) |
Zn1 | 0.0329 (3) | 0.0407 (3) | 0.0206 (2) | −0.0017 (2) | −0.00443 (19) | −0.00010 (19) |
C1—N2 | 1.301 (3) | C7—H7 | 0.9300 |
C1—N1 | 1.350 (3) | C8—C9 | 1.384 (4) |
C1—H1A | 0.9300 | C8—H8 | 0.9300 |
C2—N1 | 1.317 (3) | C9—C10 | 1.389 (3) |
C2—N3 | 1.323 (3) | C9—C9ii | 1.481 (5) |
C2—H2A | 0.9300 | C10—C11 | 1.374 (4) |
C3—N3 | 1.453 (3) | C10—H10 | 0.9300 |
C3—C4 | 1.500 (4) | C11—H11 | 0.9300 |
C3—H3A | 0.9700 | N1—Zn1 | 2.096 (2) |
C3—H3B | 0.9700 | N2—N3 | 1.354 (3) |
C4—C4i | 1.524 (5) | O1—Zn1 | 2.1693 (19) |
C4—H4A | 0.9700 | O1—H1C | 0.8500 |
C4—H4B | 0.9700 | O1—H1D | 0.8499 |
C5—O4 | 1.238 (3) | O2—Zn1 | 2.1234 (18) |
C5—O3 | 1.272 (3) | O2—H2C | 0.8500 |
C5—C6 | 1.507 (4) | O2—H2D | 0.8500 |
C6—C11 | 1.378 (4) | Zn1—N1iii | 2.096 (2) |
C6—C7 | 1.381 (3) | Zn1—O2iii | 2.1234 (18) |
C7—C8 | 1.378 (4) | Zn1—O1iii | 2.1693 (19) |
N2—C1—N1 | 114.6 (3) | C11—C10—H10 | 119.2 |
N2—C1—H1A | 122.7 | C9—C10—H10 | 119.2 |
N1—C1—H1A | 122.7 | C10—C11—C6 | 122.0 (2) |
N1—C2—N3 | 109.7 (2) | C10—C11—H11 | 119.0 |
N1—C2—H2A | 125.1 | C6—C11—H11 | 119.0 |
N3—C2—H2A | 125.1 | C2—N1—C1 | 103.1 (2) |
N3—C3—C4 | 114.8 (2) | C2—N1—Zn1 | 128.25 (18) |
N3—C3—H3A | 108.6 | C1—N1—Zn1 | 127.55 (18) |
C4—C3—H3A | 108.6 | C1—N2—N3 | 102.5 (2) |
N3—C3—H3B | 108.6 | C2—N3—N2 | 110.0 (2) |
C4—C3—H3B | 108.6 | C2—N3—C3 | 131.7 (2) |
H3A—C3—H3B | 107.5 | N2—N3—C3 | 118.2 (2) |
C3—C4—C4i | 109.7 (3) | Zn1—O1—H1C | 108.1 |
C3—C4—H4A | 109.7 | Zn1—O1—H1D | 107.9 |
C4i—C4—H4A | 109.7 | H1C—O1—H1D | 107.4 |
C3—C4—H4B | 109.7 | Zn1—O2—H2C | 111.6 |
C4i—C4—H4B | 109.7 | Zn1—O2—H2D | 111.7 |
H4A—C4—H4B | 108.2 | H2C—O2—H2D | 109.6 |
O4—C5—O3 | 124.7 (2) | N1iii—Zn1—N1 | 180.00 (5) |
O4—C5—C6 | 118.0 (2) | N1iii—Zn1—O2 | 93.74 (8) |
O3—C5—C6 | 117.3 (2) | N1—Zn1—O2 | 86.26 (8) |
C11—C6—C7 | 116.7 (2) | N1iii—Zn1—O2iii | 86.26 (8) |
C11—C6—C5 | 122.7 (2) | N1—Zn1—O2iii | 93.74 (8) |
C7—C6—C5 | 120.6 (2) | O2—Zn1—O2iii | 180.00 (9) |
C8—C7—C6 | 121.5 (2) | N1iii—Zn1—O1 | 93.19 (8) |
C8—C7—H7 | 119.3 | N1—Zn1—O1 | 86.81 (8) |
C6—C7—H7 | 119.3 | O2—Zn1—O1 | 87.85 (8) |
C7—C8—C9 | 122.0 (2) | O2iii—Zn1—O1 | 92.15 (8) |
C7—C8—H8 | 119.0 | N1iii—Zn1—O1iii | 86.81 (8) |
C9—C8—H8 | 119.0 | N1—Zn1—O1iii | 93.19 (8) |
C8—C9—C10 | 116.1 (2) | O2—Zn1—O1iii | 92.15 (8) |
C8—C9—C9ii | 121.5 (3) | O2iii—Zn1—O1iii | 87.85 (8) |
C10—C9—C9ii | 122.4 (3) | O1—Zn1—O1iii | 180.00 (10) |
C11—C10—C9 | 121.7 (2) | ||
N3—C3—C4—C4i | −177.5 (3) | N2—C1—N1—C2 | 0.1 (3) |
O4—C5—C6—C11 | −171.9 (3) | N2—C1—N1—Zn1 | −168.61 (19) |
O3—C5—C6—C11 | 7.6 (4) | N1—C1—N2—N3 | 0.0 (3) |
O4—C5—C6—C7 | 7.9 (4) | N1—C2—N3—N2 | 0.2 (3) |
O3—C5—C6—C7 | −172.7 (2) | N1—C2—N3—C3 | −176.2 (2) |
C11—C6—C7—C8 | −1.7 (4) | C1—N2—N3—C2 | −0.1 (3) |
C5—C6—C7—C8 | 178.6 (2) | C1—N2—N3—C3 | 176.9 (2) |
C6—C7—C8—C9 | 0.3 (4) | C4—C3—N3—C2 | −9.0 (4) |
C7—C8—C9—C10 | 1.5 (4) | C4—C3—N3—N2 | 174.8 (2) |
C7—C8—C9—C9ii | −179.6 (3) | C2—N1—Zn1—O2 | −141.6 (2) |
C8—C9—C10—C11 | −1.8 (4) | C1—N1—Zn1—O2 | 24.4 (2) |
C9ii—C9—C10—C11 | 179.3 (3) | C2—N1—Zn1—O2iii | 38.4 (2) |
C9—C10—C11—C6 | 0.4 (5) | C1—N1—Zn1—O2iii | −155.6 (2) |
C7—C6—C11—C10 | 1.3 (4) | C2—N1—Zn1—O1 | −53.5 (2) |
C5—C6—C11—C10 | −178.9 (3) | C1—N1—Zn1—O1 | 112.5 (2) |
N3—C2—N1—C1 | −0.2 (3) | C2—N1—Zn1—O1iii | 126.5 (2) |
N3—C2—N1—Zn1 | 168.47 (17) | C1—N1—Zn1—O1iii | −67.5 (2) |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+1, −y+1, −z+1; (iii) −x+1, −y, −z. |
Cg is the centroid of the C6–C11 benzene ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2A···O4iv | 0.93 | 2.50 | 3.342 (3) | 150 |
O1—H1D···O3v | 0.85 | 2.07 | 2.825 (3) | 148 |
O1—H1C···O3 | 0.85 | 1.95 | 2.783 (2) | 167 |
O2—H2C···O4vi | 0.85 | 1.85 | 2.642 (3) | 155 |
O2—H2D···O3 | 0.85 | 2.06 | 2.839 (3) | 151 |
C3—H3B···Cg | 0.97 | 2.82 | 3.552 (3) | 133 |
Symmetry codes: (iv) x+1, y−1, z; (v) −x+1, −y+1, −z; (vi) −x, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | [Zn(C8H12N6)(H2O)4](C14H8O4) |
Mr | 569.89 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 6.4344 (15), 7.1490 (18), 13.539 (3) |
α, β, γ (°) | 89.250 (4), 81.348 (4), 72.620 (3) |
V (Å3) | 587.3 (2) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 1.11 |
Crystal size (mm) | 0.21 × 0.19 × 0.17 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD |
Absorption correction | Multi-scan (SADABS; Bruker, 2000) |
Tmin, Tmax | 0.792, 0.828 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3162, 2299, 1788 |
Rint | 0.032 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.080, 0.92 |
No. of reflections | 2237 |
No. of parameters | 169 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.47, −0.31 |
Computer programs: SMART (Bruker 2000), SAINT (Bruker 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 1999), SHELXTL (Sheldrick, 2008).
Cg is the centroid of the C6–C11 benzene ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2A···O4i | 0.93 | 2.50 | 3.342 (3) | 150.2 |
O1—H1D···O3ii | 0.85 | 2.07 | 2.825 (3) | 148.3 |
O1—H1C···O3 | 0.85 | 1.95 | 2.783 (2) | 166.6 |
O2—H2C···O4iii | 0.85 | 1.85 | 2.642 (3) | 154.7 |
O2—H2D···O3 | 0.85 | 2.06 | 2.839 (3) | 151.4 |
C3—H3B···Cg | 0.97 | 2.82 | 3.552 (3) | 133.2 |
Symmetry codes: (i) x+1, y−1, z; (ii) −x+1, −y+1, −z; (iii) −x, −y+1, −z. |
Interest in crystal engineering and supramolecular chemistry is rapidly increasing not only because of their fascinating structures and topologies but also owing to their potential use in optical, electrical, catalytic and adsorptive applications (Kitagawa et al., 2004; Ferey et al., 2005; Roy et al., 2009; Zhang et al., 2009). The construction of such coordination polymers is highly influenced by several factors. However, the key factor in the manipulating coordination polymers is undoubtedly the selection of appropriate ligands. Comparing to rigid ligands, bifunctional flexible ligands can induce variability of the structure and may lead to the formation of supramolecular isomers because of their conformational flexibility. Recently, a series of transition metal coordination polymers based on the flexible ligand 1,4-bis(1,2,4-triazol-1-yl)butane have been reported (Liu et al., 2008; Gu et al., 2008; Wang et al., 2008; Zhu et al., 2009). In this paper, biphenyl-4,4'-dicarboxylic acid (H2BPDC) and 1,4-bis(1,2,4-triazol-1-yl)butane (BTB) have been selected as organic linkers, generating the title new zinc(II) coordination polymer, (I), the crystal structure of which is reported herein.
Compound (I) crystallizes in the triclinic space group P -1, and the asymmetric unit contains half a [Zn(C8H12N6)(H2O)4]2+ cation and half a uncoordinated BPDC anion. Each zinc(II) metal is located on an inversion centre and is six-coordinated in a octahedron geometry by two triazole nitrogen atoms from two different BTB ligand in the axial positions, and four oxygen atom from coordinated water molecules at the equatorial plane (Figure 1). The Zn–N bond length is 2.096 (2) Å, while the Zn–O bond lengths are 2.1234 (18) Å, 2.1693 (19)Å respectively. The BTB ligand adopts a trans–trans-trans conformation and acts as a N,N'-bidentate ligand linking centrosymmetrically-related zinc(II) cations into one-dimensional zig-zag cationic chains parallel to the c axis. The doubly deprotonated BPDC anion, which has crystallographically imposed centre of symmetry, does not coordinate to the zinc(II) centres and only acts as counter-ion. The anionic and cationic parts of (I) interact to form a three-dimensional network through intermolecular interactions such as conventional O—H···O hydrogen bonds, non-conventional C—H···O contacts and C—H···π interactions (Table 1). The C—H···π interaction is observed between the H3B atom and the centroid of the C6–C11 ring. As shown in Figure 2, interchain O1—H1C···O3, O1—H1D···O3, O2—H2D···O3 bonds between coordinated water molecules and the carboxylate anion are found to assemble the 1-D motifs into a 2-D layer parallel to the bc plane. These layers are further connected by interlayer O2—H2C···O4, C2—H2A···O4 hydrogen bonds, forming a 3-D supramolecular network (Figure 3).