Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807035209/pk2035sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807035209/pk2035Isup2.hkl |
CCDC reference: 657622
Key indicators
- Single-crystal X-ray study
- T = 173 K
- Mean (C-C) = 0.001 Å
- R factor = 0.024
- wR factor = 0.073
- Data-to-parameter ratio = 48.8
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT049_ALERT_1_B Calculated Density less than 1.0 gcm-3 ......... 0.94
Alert level C PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.98 PLAT602_ALERT_4_C VERY LARGE Solvent Accessible VOID(S) in Structure !
Alert level G PLAT794_ALERT_5_G Check Predicted Bond Valency for Zn1 (2) 1.91 PLAT804_ALERT_5_G ARU-Pack Problem in PLATON Analysis ............ 3 Times
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 2 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 1 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 1 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 2 ALERT type 5 Informative message, check
The title compound was synthesized by a hydrothermal reaction of Zn(NO3)2.6H2O, fumaric acid and trans-di-4-pyridylethylene (1:1:1 mole ratio) in DMF at 100 °C. Small, colorless crystals of the title compound formed and were collected in 38% yield.
Porous metal-organic frameworks (MOFs) self-assembled by the coordination of suitable metal ions/clusters with organic building blocks are of great interest for their potential applications in gas storage, separation, molecular recognition, magnetism and catalysis (Eddaoudi et al., 2001; Kitagawa et al., 2004; Yaghi et al., 2003; Janiak, 2003). Recently we have been interested in the construction of porous MOFs by making use of mixed organic linkers (Rather & Zaworotko, 2003; Chun et al., 2005; Ma et al., 2005; Chen et al., 2006). The title compound is one such MOF constructed from ZnII and the organic linkers fumarato and trans-di-4-pyridylethylene.
A small portion of the extended framework of (I) is shown in Fig. 1. Atom Zn1 is in a distorted tetrahedral geometry. These ZnII ions are bridged by fumarato and trans-di-4-pyridylethylene to form a porous triply-interpenetrated metal-organic framework with a diamond-like structure (Fig. 2).
For related literature, see: Chen et al. (2006); Chun et al. (2005); Eddaoudi et al. (2001); Janiak (2003); Kitagawa et al. (2004); Ma et al. (2005); Rather & Zaworotko (2003); Yaghi et al. (2003).
For related literature, see: Sluis & Spek (1990).
Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT-Plus (Bruker 2004); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL.
[Zn(C4H2O4)(C12H10N2)] | F(000) = 736 |
Mr = 361.67 | Dx = 0.941 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 8809 reflections |
a = 8.8488 (8) Å | θ = 2.4–32.0° |
b = 21.5285 (19) Å | µ = 0.98 mm−1 |
c = 13.5042 (11) Å | T = 173 K |
β = 97.144 (4)° | Block, colourless |
V = 2552.6 (4) Å3 | 0.30 × 0.15 × 0.10 mm |
Z = 4 |
Bruker X8 APEX II diffractometer | 5175 independent reflections |
Radiation source: fine-focus sealed tube | 4435 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.031 |
Detector resolution: 18 pixels mm-1 | θmax = 34.2°, θmin = 1.9° |
φ and ω scans | h = −13→13 |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | k = −33→33 |
Tmin = 0.759, Tmax = 0.909 | l = −18→21 |
25652 measured reflections |
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)] = 0.024 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.073 | H-atom parameters constrained |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0404P)2 + 0.1113P] where P = (Fo2 + 2Fc2)/3 |
5175 reflections | (Δ/σ)max < 0.001 |
106 parameters | Δρmax = 0.31 e Å−3 |
0 restraints | Δρmin = −0.53 e Å−3 |
[Zn(C4H2O4)(C12H10N2)] | V = 2552.6 (4) Å3 |
Mr = 361.67 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 8.8488 (8) Å | µ = 0.98 mm−1 |
b = 21.5285 (19) Å | T = 173 K |
c = 13.5042 (11) Å | 0.30 × 0.15 × 0.10 mm |
β = 97.144 (4)° |
Bruker X8 APEX II diffractometer | 5175 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | 4435 reflections with I > 2σ(I) |
Tmin = 0.759, Tmax = 0.909 | Rint = 0.031 |
25652 measured reflections |
R[F2 > 2σ(F2)] = 0.024 | 0 restraints |
wR(F2) = 0.073 | H-atom parameters constrained |
S = 1.09 | Δρmax = 0.31 e Å−3 |
5175 reflections | Δρmin = −0.53 e Å−3 |
106 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 > 2σ(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. Due to a complete solvent area disorder data were treated with the SQUEEZE routine of the PLATON software package (van der Sluis & Spek, 1990). The calculated density is for the MOF only and does not include the solvent. |
x | y | z | Uiso*/Ueq | ||
Zn1 | 0.0000 | 0.147618 (6) | 0.2500 | 0.01800 (5) | |
O1 | −0.10470 (8) | 0.20659 (3) | 0.15521 (5) | 0.02760 (14) | |
O2 | −0.21011 (10) | 0.12225 (4) | 0.07903 (6) | 0.03675 (18) | |
N1 | 0.14390 (8) | 0.09472 (4) | 0.18136 (6) | 0.02206 (14) | |
C1 | 0.28693 (11) | 0.11406 (5) | 0.17539 (8) | 0.02768 (19) | |
H1A | 0.3217 | 0.1509 | 0.2096 | 0.033* | |
C2 | 0.38538 (11) | 0.08249 (5) | 0.12157 (8) | 0.0313 (2) | |
H2A | 0.4852 | 0.0980 | 0.1184 | 0.038* | |
C3 | 0.33737 (10) | 0.02748 (5) | 0.07150 (7) | 0.02544 (18) | |
C4 | 0.19073 (11) | 0.00652 (5) | 0.08083 (8) | 0.0301 (2) | |
H4A | 0.1550 | −0.0314 | 0.0504 | 0.036* | |
C5 | 0.09708 (11) | 0.04145 (5) | 0.13489 (8) | 0.02801 (19) | |
H5A | −0.0035 | 0.0272 | 0.1392 | 0.034* | |
C6 | 0.43108 (11) | −0.00836 (5) | 0.00942 (8) | 0.0300 (2) | |
H6A | 0.3902 | −0.0460 | −0.0191 | 0.036* | |
C7 | −0.18907 (11) | 0.17920 (4) | 0.08416 (7) | 0.02391 (17) | |
C8 | −0.26287 (11) | 0.22001 (5) | 0.00310 (7) | 0.02724 (18) | |
H8A | −0.3330 | 0.2015 | −0.0474 | 0.033* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.01940 (7) | 0.01775 (7) | 0.01692 (7) | 0.000 | 0.00252 (5) | 0.000 |
O1 | 0.0334 (3) | 0.0235 (3) | 0.0233 (3) | 0.0000 (3) | −0.0070 (3) | 0.0022 (2) |
O2 | 0.0468 (5) | 0.0218 (4) | 0.0378 (4) | −0.0040 (3) | −0.0099 (3) | 0.0017 (3) |
N1 | 0.0205 (3) | 0.0232 (4) | 0.0229 (3) | −0.0019 (3) | 0.0045 (3) | −0.0043 (3) |
C1 | 0.0230 (4) | 0.0275 (5) | 0.0334 (5) | −0.0056 (3) | 0.0071 (3) | −0.0111 (4) |
C2 | 0.0229 (4) | 0.0340 (5) | 0.0383 (5) | −0.0071 (4) | 0.0094 (4) | −0.0129 (4) |
C3 | 0.0214 (4) | 0.0253 (4) | 0.0304 (4) | −0.0030 (3) | 0.0064 (3) | −0.0071 (3) |
C4 | 0.0263 (4) | 0.0266 (5) | 0.0391 (5) | −0.0059 (4) | 0.0112 (4) | −0.0122 (4) |
C5 | 0.0225 (4) | 0.0271 (5) | 0.0357 (5) | −0.0049 (3) | 0.0089 (4) | −0.0085 (4) |
C6 | 0.0255 (4) | 0.0291 (5) | 0.0365 (5) | −0.0036 (4) | 0.0079 (4) | −0.0130 (4) |
C7 | 0.0260 (4) | 0.0232 (4) | 0.0215 (4) | 0.0001 (3) | −0.0009 (3) | 0.0022 (3) |
C8 | 0.0302 (4) | 0.0272 (5) | 0.0218 (4) | −0.0003 (4) | −0.0068 (3) | 0.0002 (3) |
Zn1—O1i | 1.9529 (7) | C2—H2A | 0.9500 |
Zn1—O1 | 1.9529 (7) | C3—C4 | 1.3941 (13) |
Zn1—N1i | 2.0177 (8) | C3—C6 | 1.4693 (13) |
Zn1—N1 | 2.0177 (8) | C4—C5 | 1.3913 (13) |
O1—C7 | 1.2837 (11) | C4—H4A | 0.9500 |
O2—C7 | 1.2406 (13) | C5—H5A | 0.9500 |
N1—C1 | 1.3444 (11) | C6—C6ii | 1.3264 (19) |
N1—C5 | 1.3475 (12) | C6—H6A | 0.9500 |
C1—C2 | 1.3808 (13) | C7—C8 | 1.4895 (13) |
C1—H1A | 0.9500 | C8—C8iii | 1.316 (2) |
C2—C3 | 1.4031 (14) | C8—H8A | 0.9500 |
O1i—Zn1—O1 | 98.89 (4) | C4—C3—C6 | 118.63 (8) |
O1i—Zn1—N1i | 109.93 (3) | C2—C3—C6 | 124.04 (8) |
O1—Zn1—N1i | 113.14 (3) | C5—C4—C3 | 119.62 (9) |
O1i—Zn1—N1 | 113.14 (3) | C5—C4—H4A | 120.2 |
O1—Zn1—N1 | 109.93 (3) | C3—C4—H4A | 120.2 |
N1i—Zn1—N1 | 111.27 (5) | N1—C5—C4 | 122.39 (8) |
C7—O1—Zn1 | 112.06 (6) | N1—C5—H5A | 118.8 |
C1—N1—C5 | 118.22 (8) | C4—C5—H5A | 118.8 |
C1—N1—Zn1 | 120.35 (6) | C6ii—C6—C3 | 124.37 (12) |
C5—N1—Zn1 | 121.28 (6) | C6ii—C6—H6A | 117.8 |
N1—C1—C2 | 122.64 (9) | C3—C6—H6A | 117.8 |
N1—C1—H1A | 118.7 | O2—C7—O1 | 124.40 (8) |
C2—C1—H1A | 118.7 | O2—C7—C8 | 119.53 (8) |
C1—C2—C3 | 119.74 (9) | O1—C7—C8 | 116.06 (8) |
C1—C2—H2A | 120.1 | C8iii—C8—C7 | 124.20 (11) |
C3—C2—H2A | 120.1 | C8iii—C8—H8A | 117.9 |
C4—C3—C2 | 117.33 (8) | C7—C8—H8A | 117.9 |
Symmetry codes: (i) −x, y, −z+1/2; (ii) −x+1, −y, −z; (iii) −x−1/2, −y+1/2, −z. |
Experimental details
Crystal data | |
Chemical formula | [Zn(C4H2O4)(C12H10N2)] |
Mr | 361.67 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 173 |
a, b, c (Å) | 8.8488 (8), 21.5285 (19), 13.5042 (11) |
β (°) | 97.144 (4) |
V (Å3) | 2552.6 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.98 |
Crystal size (mm) | 0.30 × 0.15 × 0.10 |
Data collection | |
Diffractometer | Bruker X8 APEX II |
Absorption correction | Multi-scan (SADABS; Bruker, 2004) |
Tmin, Tmax | 0.759, 0.909 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 25652, 5175, 4435 |
Rint | 0.031 |
(sin θ/λ)max (Å−1) | 0.791 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.024, 0.073, 1.09 |
No. of reflections | 5175 |
No. of parameters | 106 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.31, −0.53 |
Computer programs: APEX2 (Bruker, 2004), SAINT-Plus (Bruker 2004), SAINT-Plus, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2000), SHELXTL.
Porous metal-organic frameworks (MOFs) self-assembled by the coordination of suitable metal ions/clusters with organic building blocks are of great interest for their potential applications in gas storage, separation, molecular recognition, magnetism and catalysis (Eddaoudi et al., 2001; Kitagawa et al., 2004; Yaghi et al., 2003; Janiak, 2003). Recently we have been interested in the construction of porous MOFs by making use of mixed organic linkers (Rather & Zaworotko, 2003; Chun et al., 2005; Ma et al., 2005; Chen et al., 2006). The title compound is one such MOF constructed from ZnII and the organic linkers fumarato and trans-di-4-pyridylethylene.
A small portion of the extended framework of (I) is shown in Fig. 1. Atom Zn1 is in a distorted tetrahedral geometry. These ZnII ions are bridged by fumarato and trans-di-4-pyridylethylene to form a porous triply-interpenetrated metal-organic framework with a diamond-like structure (Fig. 2).