Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807046545/rk2036sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807046545/rk2036Isup2.hkl |
CCDC reference: 663651
Key indicators
- Single-crystal X-ray study
- T = 296 K
- Mean (C-C) = 0.006 Å
- R factor = 0.033
- wR factor = 0.068
- Data-to-parameter ratio = 16.9
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.97 PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety C1
Alert level G REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 27.70 From the CIF: _reflns_number_total 1994 Count of symmetry unique reflns 1200 Completeness (_total/calc) 166.17% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 794 Fraction of Friedel pairs measured 0.662 Are heavy atom types Z>Si present yes PLAT033_ALERT_2_G Flack Parameter Value Deviates 2 * su from zero. 0.05 PLAT794_ALERT_5_G Check Predicted Bond Valency for Zn1 (2) 2.02
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 3 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 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 2 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
A mixture of ZnCl2 (1 mmol), ion liquid 1-methyl-3-carboxymethylimidazole hydroxide (1 mmol) and water (20 ml) was sealed in a 25 ml Teflon-lined stainless steel reactor and heated at 393 K for 48 h. A colourless solution was obtained after cooling the reaction to room temperature, colourless single crystals were obtained after three weeks.
The H atoms bonded to C atoms were positioned geometrically (aromatic C–H = 0.93Å and aliphatic C–H = 0.97 Å, Uiso(H) = 1.2Ueq(C)). In the X-ray diffraction experiment 794 Friedel pairs were measured.
It is known that the research of coordination polymers receives great interest nowadays, because they may afford new materials with useful properties, such as catalytic activity, microporosity and so on (Shi et al., 2004). Recently, we have synthesized and reported cadmium polymer with 1-methyl-3-carboxymethylimidazole (Shi et al., 2007). As an extension of our work in this field, we synthesized the title compound and solved its crystal structure (I).
The asymmetric unit of (I) contains one Zn atom, one 1-methyl-3-carboxymethylimidazole molecule, and two chlorine atoms (Fig. 1). The structure of (I) is a one-dimensional coordination chain in which the adjacent (ZnCl2) groups are bridged by 1-methyl-3-carboxymethylimidazole through its two O atoms with the distance of 4.8362 (4)Å (a-translation) between two adjacent Zn atoms. There exists π-π interaction between the adjacent imidazole-ring planes (π-π distance = 3.618 Å), which strengthens the formation of the chain.
For related literature, see: Shi et al. (2004, 2007).
For related literature, see: Sheldrick (1997).
Data collection: SMART (Bruker, 2004); cell refinement: SMART (Bruker, 2004) and SAINT (Bruker, 2004); data reduction: XPREP (Bruker 2002); program(s) used to solve structure: SHELXTL (Bruker 2002); program(s) used to refine structure: SHELXTL (Bruker 2002); molecular graphics: SHELXTL (Bruker 2002); software used to prepare material for publication: SHELXTL (Bruker 2002).
[ZnCl2(C6H8N2O2)] | F(000) = 276 |
Mr = 276.43 | Dx = 1.814 Mg m−3 |
Monoclinic, Pc | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P -2yc | Cell parameters from 1309 reflections |
a = 4.8362 (4) Å | θ = 2.8–27.7° |
b = 10.5820 (9) Å | µ = 2.92 mm−1 |
c = 10.1164 (7) Å | T = 296 K |
β = 102.183 (5)° | Prism, colourless |
V = 506.06 (7) Å3 | 0.35 × 0.11 × 0.05 mm |
Z = 2 |
Bruker P4 diffractometer | 1994 independent reflections |
Radiation source: fine-focus sealed tube | 1691 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.020 |
ω scans | θmax = 27.7°, θmin = 2.8° |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | h = −6→6 |
Tmin = 0.687, Tmax = 0.864 | k = −13→13 |
3003 measured reflections | l = −12→12 |
Refinement on F2 | Secondary atom site location: Difmap |
Least-squares matrix: Full | Hydrogen site location: Geom |
R[F2 > 2σ(F2)] = 0.033 | H-atom parameters constrained |
wR(F2) = 0.068 | w = 1/[σ2(Fo2) + (0.025P)2], where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max < 0.001 |
1994 reflections | Δρmax = 0.45 e Å−3 |
118 parameters | Δρmin = −0.59 e Å−3 |
0 restraints | Absolute structure: Flack (1983) |
Primary atom site location: Direct | Absolute structure parameter: 0.055 (15) |
[ZnCl2(C6H8N2O2)] | V = 506.06 (7) Å3 |
Mr = 276.43 | Z = 2 |
Monoclinic, Pc | Mo Kα radiation |
a = 4.8362 (4) Å | µ = 2.92 mm−1 |
b = 10.5820 (9) Å | T = 296 K |
c = 10.1164 (7) Å | 0.35 × 0.11 × 0.05 mm |
β = 102.183 (5)° |
Bruker P4 diffractometer | 1994 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 1691 reflections with I > 2σ(I) |
Tmin = 0.687, Tmax = 0.864 | Rint = 0.020 |
3003 measured reflections |
R[F2 > 2σ(F2)] = 0.033 | H-atom parameters constrained |
wR(F2) = 0.068 | Δρmax = 0.45 e Å−3 |
S = 1.01 | Δρmin = −0.59 e Å−3 |
1994 reflections | Absolute structure: Flack (1983) |
118 parameters | Absolute structure parameter: 0.055 (15) |
0 restraints |
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. |
x | y | z | Uiso*/Ueq | ||
Zn1 | 0.03320 (7) | 0.76339 (4) | −0.06177 (5) | 0.03457 (14) | |
Cl1 | 0.0646 (3) | 0.96102 (10) | −0.13316 (14) | 0.0511 (3) | |
Cl2 | −0.0059 (2) | 0.61405 (10) | −0.21919 (13) | 0.0468 (3) | |
C1 | 0.3986 (10) | 0.8408 (5) | 0.6340 (4) | 0.0485 (12) | |
H1A | 0.4590 | 0.9268 | 0.6288 | 0.073* | |
H1B | 0.4907 | 0.8052 | 0.7192 | 0.073* | |
H1C | 0.1974 | 0.8386 | 0.6263 | 0.073* | |
C2 | 0.4180 (10) | 0.6411 (4) | 0.5010 (5) | 0.0415 (11) | |
H2A | 0.3230 | 0.5893 | 0.5510 | 0.050* | |
C3 | 0.5240 (9) | 0.6061 (4) | 0.3952 (4) | 0.0395 (11) | |
H3A | 0.5146 | 0.5260 | 0.3566 | 0.047* | |
C4 | 0.6128 (8) | 0.8075 (4) | 0.4347 (5) | 0.0339 (10) | |
H4A | 0.6756 | 0.8899 | 0.4289 | 0.041* | |
C5 | 0.7844 (8) | 0.7217 (4) | 0.2374 (4) | 0.0352 (9) | |
H5A | 0.8972 | 0.6465 | 0.2335 | 0.042* | |
H5B | 0.9111 | 0.7938 | 0.2495 | 0.042* | |
C6 | 0.5754 (8) | 0.7356 (4) | 0.1059 (4) | 0.0317 (9) | |
N1 | 0.4738 (8) | 0.7668 (3) | 0.5229 (4) | 0.0355 (9) | |
N2 | 0.6513 (7) | 0.7124 (4) | 0.3538 (4) | 0.0305 (8) | |
O1 | 0.6675 (6) | 0.7498 (3) | 0.0018 (3) | 0.0518 (9) | |
O2 | 0.3161 (5) | 0.7312 (3) | 0.1078 (3) | 0.0481 (9) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.02622 (18) | 0.0510 (3) | 0.0276 (2) | 0.0024 (3) | 0.00809 (14) | 0.0035 (3) |
Cl1 | 0.0555 (6) | 0.0378 (6) | 0.0633 (8) | 0.0024 (5) | 0.0199 (6) | −0.0084 (6) |
Cl2 | 0.0494 (6) | 0.0366 (6) | 0.0562 (7) | 0.0000 (5) | 0.0149 (5) | −0.0038 (5) |
C1 | 0.060 (3) | 0.056 (3) | 0.032 (3) | 0.006 (2) | 0.014 (2) | −0.005 (2) |
C2 | 0.045 (2) | 0.045 (3) | 0.038 (3) | −0.006 (2) | 0.014 (2) | 0.005 (2) |
C3 | 0.046 (2) | 0.035 (3) | 0.039 (3) | −0.002 (2) | 0.012 (2) | −0.0028 (19) |
C4 | 0.031 (2) | 0.041 (2) | 0.030 (2) | −0.0055 (16) | 0.007 (2) | 0.002 (2) |
C5 | 0.0240 (17) | 0.051 (3) | 0.032 (2) | 0.0018 (18) | 0.0103 (16) | 0.003 (2) |
C6 | 0.0272 (18) | 0.041 (2) | 0.029 (2) | 0.0004 (17) | 0.0096 (16) | 0.0044 (18) |
N1 | 0.035 (2) | 0.045 (2) | 0.027 (2) | 0.0004 (16) | 0.0067 (17) | 0.0027 (17) |
N2 | 0.0275 (17) | 0.042 (2) | 0.024 (2) | −0.0023 (16) | 0.0103 (15) | 0.0028 (17) |
O1 | 0.0256 (13) | 0.105 (3) | 0.0262 (18) | 0.0044 (15) | 0.0089 (12) | 0.0114 (16) |
O2 | 0.0210 (13) | 0.091 (3) | 0.0336 (17) | 0.0011 (14) | 0.0078 (12) | 0.0107 (17) |
Zn1—O2 | 1.985 (3) | C3—H3A | 0.9300 |
Zn1—O1i | 2.011 (3) | C4—N1 | 1.298 (6) |
Zn1—Cl2 | 2.2231 (13) | C4—N2 | 1.335 (6) |
Zn1—Cl1 | 2.2281 (12) | C4—H4A | 0.9300 |
C1—N1 | 1.477 (6) | C5—N2 | 1.460 (6) |
C1—H1A | 0.9600 | C5—C6 | 1.499 (6) |
C1—H1B | 0.9600 | C5—H5A | 0.9700 |
C1—H1C | 0.9600 | C5—H5B | 0.9700 |
C2—C3 | 1.334 (6) | C6—O1 | 1.235 (5) |
C2—N1 | 1.366 (5) | C6—O2 | 1.259 (5) |
C2—H2A | 0.9300 | O1—Zn1ii | 2.011 (3) |
C3—N2 | 1.388 (6) | ||
O2—Zn1—O1i | 101.74 (11) | N1—C4—H4A | 125.3 |
O2—Zn1—Cl2 | 115.85 (11) | N2—C4—H4A | 125.3 |
O1i—Zn1—Cl2 | 103.34 (11) | N2—C5—C6 | 113.2 (3) |
O2—Zn1—Cl1 | 111.06 (11) | N2—C5—H5A | 108.9 |
O1i—Zn1—Cl1 | 107.20 (11) | C6—C5—H5A | 108.9 |
Cl2—Zn1—Cl1 | 115.87 (5) | N2—C5—H5B | 108.9 |
N1—C1—H1A | 109.5 | C6—C5—H5B | 108.9 |
N1—C1—H1B | 109.5 | H5A—C5—H5B | 107.8 |
H1A—C1—H1B | 109.5 | O1—C6—O2 | 123.9 (4) |
N1—C1—H1C | 109.5 | O1—C6—C5 | 118.1 (3) |
H1A—C1—H1C | 109.5 | O2—C6—C5 | 118.0 (3) |
H1B—C1—H1C | 109.5 | C4—N1—C2 | 108.9 (4) |
C3—C2—N1 | 107.7 (4) | C4—N1—C1 | 126.4 (4) |
C3—C2—H2A | 126.1 | C2—N1—C1 | 124.6 (4) |
N1—C2—H2A | 126.1 | C4—N2—C3 | 107.3 (4) |
C2—C3—N2 | 106.7 (4) | C4—N2—C5 | 125.9 (4) |
C2—C3—H3A | 126.7 | C3—N2—C5 | 126.6 (4) |
N2—C3—H3A | 126.7 | C6—O1—Zn1ii | 141.3 (3) |
N1—C4—N2 | 109.4 (4) | C6—O2—Zn1 | 119.1 (3) |
N1—C2—C3—N2 | 1.1 (5) | C2—C3—N2—C5 | −176.8 (4) |
N2—C5—C6—O1 | 176.9 (4) | C6—C5—N2—C4 | −96.5 (5) |
N2—C5—C6—O2 | −3.7 (5) | C6—C5—N2—C3 | 78.6 (5) |
N2—C4—N1—C2 | 0.2 (5) | O2—C6—O1—Zn1ii | −180.0 (4) |
N2—C4—N1—C1 | 177.2 (4) | C5—C6—O1—Zn1ii | −0.6 (7) |
C3—C2—N1—C4 | −0.8 (5) | O1—C6—O2—Zn1 | −5.6 (6) |
C3—C2—N1—C1 | −178.0 (4) | C5—C6—O2—Zn1 | 175.0 (3) |
N1—C4—N2—C3 | 0.5 (5) | O1i—Zn1—O2—C6 | −178.3 (3) |
N1—C4—N2—C5 | 176.4 (4) | Cl2—Zn1—O2—C6 | 70.5 (3) |
C2—C3—N2—C4 | −1.0 (5) | Cl1—Zn1—O2—C6 | −64.5 (3) |
Symmetry codes: (i) x−1, y, z; (ii) x+1, y, z. |
Experimental details
Crystal data | |
Chemical formula | [ZnCl2(C6H8N2O2)] |
Mr | 276.43 |
Crystal system, space group | Monoclinic, Pc |
Temperature (K) | 296 |
a, b, c (Å) | 4.8362 (4), 10.5820 (9), 10.1164 (7) |
β (°) | 102.183 (5) |
V (Å3) | 506.06 (7) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 2.92 |
Crystal size (mm) | 0.35 × 0.11 × 0.05 |
Data collection | |
Diffractometer | Bruker P4 |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.687, 0.864 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3003, 1994, 1691 |
Rint | 0.020 |
(sin θ/λ)max (Å−1) | 0.654 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.033, 0.068, 1.01 |
No. of reflections | 1994 |
No. of parameters | 118 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.45, −0.59 |
Absolute structure | Flack (1983) |
Absolute structure parameter | 0.055 (15) |
Computer programs: SMART (Bruker, 2004) and SAINT (Bruker, 2004), XPREP (Bruker 2002), SHELXTL (Bruker 2002).
It is known that the research of coordination polymers receives great interest nowadays, because they may afford new materials with useful properties, such as catalytic activity, microporosity and so on (Shi et al., 2004). Recently, we have synthesized and reported cadmium polymer with 1-methyl-3-carboxymethylimidazole (Shi et al., 2007). As an extension of our work in this field, we synthesized the title compound and solved its crystal structure (I).
The asymmetric unit of (I) contains one Zn atom, one 1-methyl-3-carboxymethylimidazole molecule, and two chlorine atoms (Fig. 1). The structure of (I) is a one-dimensional coordination chain in which the adjacent (ZnCl2) groups are bridged by 1-methyl-3-carboxymethylimidazole through its two O atoms with the distance of 4.8362 (4)Å (a-translation) between two adjacent Zn atoms. There exists π-π interaction between the adjacent imidazole-ring planes (π-π distance = 3.618 Å), which strengthens the formation of the chain.