Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807033016/hk2280sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807033016/hk2280Isup2.hkl |
CCDC reference: 639266
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.005 Å
- R factor = 0.037
- wR factor = 0.093
- Data-to-parameter ratio = 16.0
checkCIF/PLATON results
No syntax errors found
Alert level C ABSTM02_ALERT_3_C The ratio of expected to reported Tmax/Tmin(RR) is > 1.10 Tmin and Tmax reported: 0.123 0.205 Tmin and Tmax expected: 0.092 0.205 RR = 1.331 Please check that your absorption correction is appropriate. PLAT060_ALERT_3_C Ratio Tmax/Tmin (Exp-to-Rep) (too) Large ....... 1.28 PLAT153_ALERT_1_C The su's on the Cell Axes are Equal (x 100000) 300 Ang. PLAT222_ALERT_3_C Large Non-Solvent H Ueq(max)/Ueq(min) ... 3.12 Ratio PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.31
Alert level G PLAT794_ALERT_5_G Check Predicted Bond Valency for Zn1 (2) 1.80 PLAT794_ALERT_5_G Check Predicted Bond Valency for Zn2 (2) 1.99 PLAT794_ALERT_5_G Check Predicted Bond Valency for Zn3 (2) 2.05
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 5 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 3 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 3 ALERT type 5 Informative message, check
For a related structure, see: Lu & Babb (2001). For bond-length data, see: Allen et al. (1987). Scheme should show polymeric nature and complete repeat unit.
For the preparation of the title compound, (I), ZnBr2 (1 mmol) and HIN (1.5 mmol) were dissolved in water (10 ml). The solution was heated in a 25 ml Teflon lined reaction vessel at 433 K for ca 3 d, and then cooled to room temperature. Colorless crystals of (I) were obtained (yield; 72%).
H4A (for NH) was located in a difference syntheses, and only its thermal parameter was refined [N—H = 0.8622 Å and Uiso(H) = 0.10 (2) Å2]. The remaining H atoms were positioned geometrically, with C—H = 0.93 Å, for aromatic H atoms, and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C).
In recent years, isonicotinic acid (HIN) have been extensively studied, because of its ability of acting either as monodentate, bidentate, tridentate bridging or as chelating ligand. Novel complexes such as [Cu2(IN)4(H2O)3][Cu2(IN)4(H2O)2].3H2O (Lu & Babb, 2001) have been reported. The title compound, (I), was synthesized by hydrothermal synthesis at about 443 K. It was air stable and insoluble in most solvents. We report herein its crystal structure.
In the molecule of (I) (Fig. 1), the ligand bond lengths and angles are generally within normal ranges (Allen et al., 1987). Zn1 is located on an inversion centre and has ZnO4N2 octahedral geometry, which is completed by IN and 1H-IN oxygen atoms (where IN is isonicotinate), as well as IN nitrogen atoms, while Zn2 and Zn3 adopt the four-coordinated ZnO2NBr pyramidal geometry, which is completed by IN oxygen and nitrogen atoms, as well as bromine ions.
The Zn—O/N bonds for Zn2 and Zn3 are in the range of 1.933 (3)–2.075 (3) Å, which are shorter than that observed for Zn1 within 2.118 (3)–2.191 (3) Å. The Zn—Br bonds are 2.3369 (9) Å for Zn3, and 2.3798 (10) Å for Zn2 (Table 1).
Furthermore, these metal centers are in turn connected by intermolecular N—H···O hydrogen bonds (Table 2), IN and 1H-IN to construct the two-dimensional bilayer structure (Fig. 2), where the 1H-IN ligands contribute to bidentate coordinated mode, while IN ligands to bidentate and tridentate coordinated modes. In addition, the closest Zn—Zn distance is ca 4.031 Å, and the edges of the present two-dimensional bilayer stucture is ca 8.8 x 8.5 Å.
For a related structure, see: Lu & Babb (2001). For bond-length data, see: Allen et al. (1987). Scheme should show polymeric nature and complete repeat unit.
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL.
[Zn5Br4(C6H4NO2)6(C6H5NO2)2] | F(000) = 1592 |
Mr = 1625.32 | Dx = 2.092 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 19365 reflections |
a = 14.096 (3) Å | θ = 3.0–27.5° |
b = 13.614 (3) Å | µ = 5.47 mm−1 |
c = 14.781 (3) Å | T = 298 K |
β = 114.53 (3)° | Block, colorless |
V = 2580.5 (11) Å3 | 0.47 × 0.42 × 0.29 mm |
Z = 2 |
Bruker SMART CCD area-detector diffractometer | 5899 independent reflections |
Radiation source: fine-focus sealed tube | 4756 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.059 |
φ and ω scans | θmax = 27.5°, θmin = 3.0° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −18→18 |
Tmin = 0.123, Tmax = 0.205 | k = −17→16 |
24795 measured reflections | l = −19→19 |
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)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.093 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0355P)2 + 3.1559P] where P = (Fo2 + 2Fc2)/3 |
5899 reflections | (Δ/σ)max = 0.001 |
368 parameters | Δρmax = 1.01 e Å−3 |
0 restraints | Δρmin = −1.05 e Å−3 |
[Zn5Br4(C6H4NO2)6(C6H5NO2)2] | V = 2580.5 (11) Å3 |
Mr = 1625.32 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 14.096 (3) Å | µ = 5.47 mm−1 |
b = 13.614 (3) Å | T = 298 K |
c = 14.781 (3) Å | 0.47 × 0.42 × 0.29 mm |
β = 114.53 (3)° |
Bruker SMART CCD area-detector diffractometer | 5899 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 4756 reflections with I > 2σ(I) |
Tmin = 0.123, Tmax = 0.205 | Rint = 0.059 |
24795 measured reflections |
R[F2 > 2σ(F2)] = 0.037 | 0 restraints |
wR(F2) = 0.093 | H-atom parameters constrained |
S = 1.06 | Δρmax = 1.01 e Å−3 |
5899 reflections | Δρmin = −1.05 e Å−3 |
368 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 | ||
Zn1 | 0.0000 | 0.5000 | 0.5000 | 0.02606 (14) | |
Zn2 | −0.42512 (3) | −0.01650 (3) | 0.32550 (4) | 0.02699 (11) | |
Zn3 | 0.05811 (3) | 0.60169 (3) | 0.27190 (3) | 0.02547 (11) | |
Br1 | −0.50694 (3) | 0.03530 (3) | 0.15671 (4) | 0.04128 (12) | |
Br2 | −0.02848 (3) | 0.54039 (3) | 0.11049 (3) | 0.04207 (12) | |
O1 | −0.03829 (18) | −0.31624 (18) | 0.3020 (2) | 0.0328 (6) | |
O2 | −0.10618 (19) | −0.43045 (18) | 0.3646 (2) | 0.0340 (6) | |
O3 | −0.4360 (2) | 0.1908 (2) | 0.3990 (3) | 0.0490 (9) | |
O4 | −0.32061 (18) | 0.07798 (18) | 0.4031 (2) | 0.0383 (7) | |
O5 | 0.48779 (19) | 0.90252 (19) | 0.3679 (2) | 0.0380 (7) | |
O6 | 0.3734 (2) | 1.0190 (2) | 0.3589 (3) | 0.0557 (10) | |
O7 | 0.07644 (19) | 0.40797 (18) | 0.4283 (2) | 0.0351 (6) | |
O8 | 0.15352 (19) | 0.49998 (18) | 0.3529 (2) | 0.0343 (6) | |
N1 | −0.3216 (2) | −0.1282 (2) | 0.3338 (2) | 0.0248 (6) | |
N2 | −0.1145 (2) | 0.3882 (2) | 0.4622 (2) | 0.0265 (6) | |
N3 | 0.1677 (2) | 0.7084 (2) | 0.2982 (2) | 0.0266 (6) | |
N4 | 0.3694 (2) | 0.2063 (2) | 0.4284 (3) | 0.0362 (8) | |
H4A | 0.4172 | 0.1632 | 0.4369 | 0.10 (2)* | |
C1 | −0.3497 (3) | −0.2229 (2) | 0.3181 (3) | 0.0278 (8) | |
H1 | −0.4179 | −0.2398 | 0.3060 | 0.033* | |
C2 | −0.2817 (3) | −0.2966 (2) | 0.3190 (3) | 0.0268 (8) | |
H2 | −0.3031 | −0.3619 | 0.3099 | 0.032* | |
C3 | −0.1811 (2) | −0.2712 (2) | 0.3338 (3) | 0.0217 (7) | |
C4 | −0.1525 (3) | −0.1733 (3) | 0.3487 (3) | 0.0274 (8) | |
H4 | −0.0858 | −0.1542 | 0.3580 | 0.033* | |
C5 | −0.2234 (3) | −0.1045 (2) | 0.3498 (3) | 0.0283 (8) | |
H5 | −0.2026 | −0.0392 | 0.3620 | 0.034* | |
C6 | −0.1033 (2) | −0.3465 (2) | 0.3341 (3) | 0.0235 (7) | |
C7 | −0.2650 (2) | 0.2425 (2) | 0.4292 (3) | 0.0241 (7) | |
C8 | −0.1620 (3) | 0.2180 (2) | 0.4520 (3) | 0.0266 (8) | |
H8 | −0.1416 | 0.1525 | 0.4569 | 0.032* | |
C9 | −0.0904 (3) | 0.2923 (2) | 0.4674 (3) | 0.0270 (8) | |
H9 | −0.0217 | 0.2751 | 0.4821 | 0.032* | |
C10 | −0.2148 (3) | 0.4110 (2) | 0.4362 (3) | 0.0279 (8) | |
H10 | −0.2339 | 0.4769 | 0.4283 | 0.033* | |
C11 | −0.2909 (3) | 0.3415 (3) | 0.4205 (3) | 0.0282 (8) | |
H11 | −0.3593 | 0.3608 | 0.4041 | 0.034* | |
C12 | −0.3486 (3) | 0.1654 (3) | 0.4097 (3) | 0.0297 (8) | |
C13 | 0.2260 (2) | 0.3467 (2) | 0.4124 (3) | 0.0204 (7) | |
C14 | 0.2064 (3) | 0.2487 (2) | 0.4237 (3) | 0.0275 (8) | |
H14 | 0.1442 | 0.2303 | 0.4267 | 0.033* | |
C15 | 0.2793 (3) | 0.1791 (3) | 0.4305 (3) | 0.0358 (9) | |
H15 | 0.2660 | 0.1131 | 0.4366 | 0.043* | |
C16 | 0.3927 (3) | 0.3009 (3) | 0.4220 (3) | 0.0361 (9) | |
H16 | 0.4573 | 0.3177 | 0.4236 | 0.043* | |
C17 | 0.3216 (3) | 0.3721 (3) | 0.4132 (3) | 0.0297 (8) | |
H17 | 0.3372 | 0.4376 | 0.4078 | 0.036* | |
C18 | 0.1439 (2) | 0.4238 (2) | 0.3974 (3) | 0.0244 (7) | |
C19 | 0.2674 (3) | 0.6857 (3) | 0.3206 (3) | 0.0320 (9) | |
H19 | 0.2856 | 0.6199 | 0.3220 | 0.038* | |
C20 | 0.3436 (3) | 0.7555 (3) | 0.3415 (3) | 0.0335 (9) | |
H20 | 0.4121 | 0.7370 | 0.3568 | 0.040* | |
C21 | 0.3179 (3) | 0.8534 (2) | 0.3394 (3) | 0.0263 (8) | |
C22 | 0.2149 (3) | 0.8774 (3) | 0.3152 (3) | 0.0364 (10) | |
H22 | 0.1946 | 0.9428 | 0.3125 | 0.044* | |
C23 | 0.1431 (3) | 0.8032 (3) | 0.2953 (3) | 0.0366 (10) | |
H23 | 0.0739 | 0.8199 | 0.2790 | 0.044* | |
C24 | 0.3993 (3) | 0.9333 (3) | 0.3577 (3) | 0.0320 (9) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.0207 (3) | 0.0190 (3) | 0.0406 (4) | −0.0014 (2) | 0.0148 (2) | 0.0005 (2) |
Zn2 | 0.01712 (19) | 0.01695 (19) | 0.0482 (3) | −0.00093 (15) | 0.01486 (18) | −0.00226 (18) |
Zn3 | 0.01996 (19) | 0.01928 (19) | 0.0404 (3) | 0.00171 (15) | 0.01574 (17) | −0.00049 (17) |
Br1 | 0.0345 (2) | 0.0343 (2) | 0.0505 (3) | −0.00131 (17) | 0.01318 (19) | 0.00503 (18) |
Br2 | 0.0394 (2) | 0.0388 (2) | 0.0445 (3) | 0.00509 (18) | 0.01385 (19) | −0.00973 (19) |
O1 | 0.0283 (12) | 0.0258 (13) | 0.0546 (18) | 0.0055 (11) | 0.0274 (13) | 0.0006 (12) |
O2 | 0.0282 (13) | 0.0210 (12) | 0.0506 (18) | 0.0057 (11) | 0.0142 (12) | 0.0068 (12) |
O3 | 0.0237 (13) | 0.0311 (15) | 0.097 (3) | −0.0053 (12) | 0.0304 (15) | −0.0130 (16) |
O4 | 0.0205 (12) | 0.0209 (12) | 0.068 (2) | −0.0041 (10) | 0.0136 (13) | −0.0096 (13) |
O5 | 0.0247 (13) | 0.0273 (13) | 0.068 (2) | 0.0002 (11) | 0.0255 (13) | 0.0047 (13) |
O6 | 0.0386 (16) | 0.0200 (14) | 0.118 (3) | −0.0047 (12) | 0.0417 (19) | −0.0116 (16) |
O7 | 0.0267 (13) | 0.0267 (13) | 0.062 (2) | −0.0002 (11) | 0.0280 (13) | −0.0013 (13) |
O8 | 0.0281 (13) | 0.0245 (12) | 0.0543 (18) | 0.0080 (11) | 0.0210 (13) | 0.0118 (13) |
N1 | 0.0190 (13) | 0.0192 (13) | 0.0377 (18) | 0.0021 (11) | 0.0133 (12) | −0.0018 (13) |
N2 | 0.0210 (13) | 0.0222 (14) | 0.0391 (18) | −0.0010 (12) | 0.0151 (13) | 0.0020 (13) |
N3 | 0.0206 (13) | 0.0221 (14) | 0.0396 (18) | −0.0010 (12) | 0.0151 (13) | 0.0000 (13) |
N4 | 0.0336 (17) | 0.0340 (17) | 0.039 (2) | 0.0187 (15) | 0.0134 (15) | 0.0022 (15) |
C1 | 0.0176 (15) | 0.0231 (17) | 0.043 (2) | −0.0011 (13) | 0.0127 (15) | −0.0023 (16) |
C2 | 0.0247 (16) | 0.0180 (16) | 0.039 (2) | 0.0000 (13) | 0.0142 (15) | −0.0009 (15) |
C3 | 0.0187 (14) | 0.0217 (16) | 0.0258 (18) | 0.0036 (13) | 0.0105 (13) | 0.0016 (14) |
C4 | 0.0192 (15) | 0.0222 (16) | 0.043 (2) | −0.0006 (14) | 0.0148 (15) | 0.0008 (16) |
C5 | 0.0252 (17) | 0.0184 (16) | 0.046 (2) | −0.0024 (14) | 0.0193 (16) | −0.0020 (16) |
C6 | 0.0194 (15) | 0.0221 (16) | 0.0283 (19) | −0.0011 (13) | 0.0093 (14) | −0.0037 (14) |
C7 | 0.0184 (15) | 0.0213 (16) | 0.033 (2) | −0.0042 (13) | 0.0116 (14) | −0.0048 (14) |
C8 | 0.0221 (16) | 0.0196 (16) | 0.039 (2) | 0.0022 (13) | 0.0134 (15) | −0.0014 (15) |
C9 | 0.0189 (15) | 0.0240 (17) | 0.039 (2) | −0.0007 (13) | 0.0132 (15) | −0.0013 (16) |
C10 | 0.0239 (16) | 0.0184 (16) | 0.044 (2) | 0.0002 (14) | 0.0169 (16) | 0.0001 (15) |
C11 | 0.0175 (15) | 0.0258 (17) | 0.042 (2) | 0.0006 (14) | 0.0129 (15) | −0.0036 (16) |
C12 | 0.0224 (17) | 0.0250 (17) | 0.043 (2) | −0.0026 (14) | 0.0146 (16) | −0.0048 (16) |
C13 | 0.0192 (15) | 0.0185 (15) | 0.0235 (17) | 0.0023 (13) | 0.0089 (13) | −0.0006 (13) |
C14 | 0.0288 (17) | 0.0223 (17) | 0.035 (2) | −0.0006 (14) | 0.0167 (16) | −0.0015 (15) |
C15 | 0.047 (2) | 0.0225 (18) | 0.041 (2) | 0.0056 (17) | 0.0215 (19) | 0.0015 (17) |
C16 | 0.0232 (17) | 0.038 (2) | 0.049 (3) | 0.0034 (16) | 0.0174 (17) | −0.0029 (19) |
C17 | 0.0244 (17) | 0.0262 (18) | 0.040 (2) | 0.0016 (14) | 0.0148 (16) | 0.0001 (16) |
C18 | 0.0201 (15) | 0.0224 (16) | 0.0304 (19) | 0.0000 (14) | 0.0101 (14) | −0.0037 (15) |
C19 | 0.0267 (17) | 0.0185 (16) | 0.056 (3) | 0.0038 (14) | 0.0218 (17) | 0.0021 (17) |
C20 | 0.0243 (17) | 0.0233 (17) | 0.059 (3) | 0.0026 (15) | 0.0238 (18) | 0.0021 (18) |
C21 | 0.0218 (16) | 0.0212 (16) | 0.041 (2) | −0.0017 (14) | 0.0179 (15) | 0.0003 (15) |
C22 | 0.0267 (18) | 0.0181 (17) | 0.069 (3) | 0.0051 (14) | 0.0242 (19) | 0.0054 (18) |
C23 | 0.0218 (17) | 0.0271 (19) | 0.063 (3) | 0.0036 (15) | 0.0203 (18) | 0.0042 (19) |
C24 | 0.0282 (18) | 0.0242 (17) | 0.051 (3) | −0.0011 (15) | 0.0239 (17) | −0.0011 (17) |
Zn1—N2i | 2.118 (3) | C2—C1 | 1.384 (5) |
Zn1—O2ii | 2.158 (3) | C2—H2 | 0.9300 |
Zn1—O2iii | 2.158 (3) | C3—C4 | 1.383 (5) |
Zn1—O7i | 2.191 (3) | C3—C2 | 1.386 (4) |
Zn2—O4 | 1.933 (3) | C4—H4 | 0.9300 |
Zn2—O5iv | 1.938 (3) | C5—C4 | 1.374 (5) |
Zn2—N1 | 2.075 (3) | C5—H5 | 0.9300 |
Zn2—Br1 | 2.3798 (10) | C6—C3 | 1.500 (4) |
Zn3—O1ii | 1.948 (2) | C7—C11 | 1.389 (5) |
Zn3—O8 | 1.955 (3) | C7—C12 | 1.513 (5) |
Zn3—N3 | 2.037 (3) | C8—C9 | 1.380 (5) |
Zn3—Br2 | 2.3369 (9) | C8—C7 | 1.388 (4) |
O1—C6 | 1.263 (4) | C8—H8 | 0.9300 |
O1—Zn3v | 1.948 (2) | C9—H9 | 0.9300 |
O2—C6 | 1.236 (4) | C10—C11 | 1.376 (5) |
O2—Zn1v | 2.158 (3) | C10—H10 | 0.9300 |
O3—C12 | 1.225 (4) | C11—H11 | 0.9300 |
O4—C12 | 1.270 (4) | C13—C17 | 1.387 (4) |
O5—C24 | 1.265 (4) | C13—C14 | 1.387 (5) |
O5—Zn2vi | 1.938 (3) | C13—C18 | 1.508 (4) |
O6—C24 | 1.224 (4) | C14—C15 | 1.371 (5) |
O7—C18 | 1.233 (4) | C14—H14 | 0.9300 |
O7—Zn1 | 2.191 (3) | C15—H15 | 0.9300 |
O8—C18 | 1.266 (4) | C16—H16 | 0.9300 |
N1—C1 | 1.341 (4) | C17—C16 | 1.360 (5) |
N1—C5 | 1.344 (4) | C17—H17 | 0.9300 |
N2—C10 | 1.338 (4) | C19—H19 | 0.9300 |
N2—C9 | 1.343 (4) | C20—C19 | 1.371 (5) |
N2—Zn1 | 2.118 (3) | C20—H20 | 0.9300 |
N3—C23 | 1.334 (5) | C21—C20 | 1.378 (5) |
N3—C19 | 1.338 (4) | C21—C22 | 1.383 (5) |
N4—C15 | 1.336 (5) | C21—C24 | 1.521 (5) |
N4—C16 | 1.342 (5) | C22—C23 | 1.373 (5) |
N4—H4A | 0.8622 | C22—H22 | 0.9300 |
C1—H1 | 0.9300 | C23—H23 | 0.9300 |
N2—Zn1—N2i | 180.0 | C4—C5—H5 | 118.8 |
N2—Zn1—O2ii | 84.93 (11) | O2—C6—O1 | 125.3 (3) |
N2i—Zn1—O2ii | 95.07 (11) | O2—C6—C3 | 119.9 (3) |
N2—Zn1—O2iii | 95.07 (11) | O1—C6—C3 | 114.8 (3) |
N2i—Zn1—O2iii | 84.93 (11) | C8—C7—C11 | 117.6 (3) |
O2ii—Zn1—O2iii | 180.000 (1) | C8—C7—C12 | 122.2 (3) |
N2—Zn1—O7 | 86.31 (10) | C11—C7—C12 | 120.1 (3) |
N2i—Zn1—O7 | 93.69 (10) | C9—C8—C7 | 118.9 (3) |
O2ii—Zn1—O7 | 95.36 (11) | C9—C8—H8 | 120.5 |
O2iii—Zn1—O7 | 84.64 (11) | C7—C8—H8 | 120.5 |
N2—Zn1—O7i | 93.69 (10) | N2—C9—C8 | 123.6 (3) |
N2i—Zn1—O7i | 86.31 (10) | N2—C9—H9 | 118.2 |
O2ii—Zn1—O7i | 84.64 (11) | C8—C9—H9 | 118.2 |
O2iii—Zn1—O7i | 95.36 (11) | N2—C10—C11 | 123.1 (3) |
O7—Zn1—O7i | 180.00 (13) | N2—C10—H10 | 118.5 |
O4—Zn2—O5iv | 127.98 (14) | C11—C10—H10 | 118.5 |
O4—Zn2—N1 | 96.22 (11) | C10—C11—C7 | 119.7 (3) |
O5iv—Zn2—N1 | 95.07 (11) | C10—C11—H11 | 120.1 |
O4—Zn2—Br1 | 110.08 (10) | C7—C11—H11 | 120.1 |
O5iv—Zn2—Br1 | 114.30 (9) | O3—C12—O4 | 125.6 (3) |
N1—Zn2—Br1 | 107.59 (9) | O3—C12—C7 | 119.4 (3) |
O1ii—Zn3—O8 | 129.35 (12) | O4—C12—C7 | 115.0 (3) |
O1ii—Zn3—N3 | 95.37 (11) | C17—C13—C14 | 118.7 (3) |
O8—Zn3—N3 | 96.52 (11) | C17—C13—C18 | 120.8 (3) |
O1ii—Zn3—Br2 | 108.65 (9) | C14—C13—C18 | 120.5 (3) |
O8—Zn3—Br2 | 107.89 (9) | C15—C14—C13 | 119.6 (3) |
N3—Zn3—Br2 | 118.85 (10) | C15—C14—H14 | 120.2 |
C6—O1—Zn3v | 125.6 (2) | C13—C14—H14 | 120.2 |
C6—O2—Zn1v | 129.0 (2) | N4—C15—C14 | 119.9 (3) |
C12—O4—Zn2 | 119.0 (2) | N4—C15—H15 | 120.1 |
C24—O5—Zn2vi | 120.0 (2) | C14—C15—H15 | 120.1 |
C18—O7—Zn1 | 133.6 (2) | N4—C16—C17 | 119.9 (3) |
C18—O8—Zn3 | 134.8 (2) | N4—C16—H16 | 120.0 |
C1—N1—C5 | 118.0 (3) | C17—C16—H16 | 120.0 |
C1—N1—Zn2 | 123.0 (2) | C16—C17—C13 | 119.9 (3) |
C5—N1—Zn2 | 118.9 (2) | C16—C17—H17 | 120.1 |
C10—N2—C9 | 117.0 (3) | C13—C17—H17 | 120.1 |
C10—N2—Zn1 | 120.5 (2) | O7—C18—O8 | 126.9 (3) |
C9—N2—Zn1 | 122.4 (2) | O7—C18—C13 | 119.1 (3) |
C23—N3—C19 | 117.7 (3) | O8—C18—C13 | 113.9 (3) |
C23—N3—Zn3 | 121.1 (2) | N3—C19—C20 | 122.7 (3) |
C19—N3—Zn3 | 121.2 (2) | N3—C19—H19 | 118.7 |
C15—N4—C16 | 122.0 (3) | C20—C19—H19 | 118.7 |
C15—N4—H4A | 120.1 | C19—C20—C21 | 119.4 (3) |
C16—N4—H4A | 117.7 | C19—C20—H20 | 120.3 |
N1—C1—C2 | 122.8 (3) | C21—C20—H20 | 120.3 |
N1—C1—H1 | 118.6 | C20—C21—C22 | 118.2 (3) |
C2—C1—H1 | 118.6 | C20—C21—C24 | 121.0 (3) |
C1—C2—C3 | 118.7 (3) | C22—C21—C24 | 120.7 (3) |
C1—C2—H2 | 120.7 | C23—C22—C21 | 118.9 (3) |
C3—C2—H2 | 120.7 | C23—C22—H22 | 120.6 |
C4—C3—C2 | 118.5 (3) | C21—C22—H22 | 120.6 |
C4—C3—C6 | 119.6 (3) | N3—C23—C22 | 123.1 (3) |
C2—C3—C6 | 122.0 (3) | N3—C23—H23 | 118.4 |
C5—C4—C3 | 119.6 (3) | C22—C23—H23 | 118.4 |
C5—C4—H4 | 120.2 | O6—C24—O5 | 126.8 (3) |
C3—C4—H4 | 120.2 | O6—C24—C21 | 118.5 (3) |
N1—C5—C4 | 122.4 (3) | O5—C24—C21 | 114.7 (3) |
N1—C5—H5 | 118.8 | ||
O4—Zn2—N1—C1 | 159.6 (3) | C9—N2—C10—C11 | 3.7 (6) |
O5iv—Zn2—N1—C1 | 30.5 (3) | Zn1—N2—C10—C11 | −173.4 (3) |
Br1—Zn2—N1—C1 | −87.0 (3) | C23—N3—C19—C20 | 0.8 (6) |
O4—Zn2—N1—C5 | −24.6 (3) | Zn3—N3—C19—C20 | −178.1 (3) |
O5iv—Zn2—N1—C5 | −153.7 (3) | C19—N3—C23—C22 | −0.8 (7) |
Br1—Zn2—N1—C5 | 88.8 (3) | Zn3—N3—C23—C22 | 178.1 (4) |
O5iv—Zn2—O4—C12 | −86.0 (3) | C16—N4—C15—C14 | 1.6 (6) |
N1—Zn2—O4—C12 | 172.6 (3) | C15—N4—C16—C17 | −2.8 (6) |
Br1—Zn2—O4—C12 | 61.3 (3) | C3—C2—C1—N1 | −2.1 (6) |
O1ii—Zn3—O8—C18 | 53.0 (4) | C4—C3—C2—C1 | 1.1 (6) |
N3—Zn3—O8—C18 | 155.5 (4) | C6—C3—C2—C1 | −179.0 (3) |
Br2—Zn3—O8—C18 | −81.4 (4) | C2—C3—C4—C5 | 0.8 (6) |
O1ii—Zn3—N3—C23 | −21.3 (3) | C6—C3—C4—C5 | −179.1 (4) |
O8—Zn3—N3—C23 | −152.0 (3) | N1—C5—C4—C3 | −2.0 (6) |
Br2—Zn3—N3—C23 | 93.5 (3) | O2—C6—C3—C4 | 147.9 (4) |
O1ii—Zn3—N3—C19 | 157.5 (3) | O1—C6—C3—C4 | −32.0 (5) |
O8—Zn3—N3—C19 | 26.9 (3) | O2—C6—C3—C2 | −32.0 (5) |
Br2—Zn3—N3—C19 | −87.7 (3) | O1—C6—C3—C2 | 148.2 (4) |
Zn3v—O1—C6—O2 | 10.7 (5) | C8—C7—C11—C10 | −1.1 (6) |
Zn3v—O1—C6—C3 | −169.4 (2) | C12—C7—C11—C10 | −178.5 (4) |
Zn1v—O2—C6—O1 | 71.3 (5) | C8—C7—C12—O3 | 173.2 (4) |
Zn1v—O2—C6—C3 | −108.6 (3) | C11—C7—C12—O3 | −9.5 (6) |
Zn2—O4—C12—O3 | 24.3 (6) | C8—C7—C12—O4 | −8.6 (6) |
Zn2—O4—C12—C7 | −153.7 (3) | C11—C7—C12—O4 | 168.7 (4) |
Zn2vi—O5—C24—O6 | −29.5 (6) | C9—C8—C7—C11 | 1.6 (6) |
Zn2vi—O5—C24—C21 | 148.7 (3) | C9—C8—C7—C12 | 179.0 (4) |
C18—O7—Zn1—N2 | 163.4 (4) | C7—C8—C9—N2 | 0.5 (6) |
C18—O7—Zn1—N2i | −16.6 (4) | N2—C10—C11—C7 | −1.7 (6) |
C18—O7—Zn1—O2ii | 78.8 (4) | C17—C13—C14—C15 | −3.2 (6) |
C18—O7—Zn1—O2iii | −101.2 (4) | C18—C13—C14—C15 | 175.6 (4) |
Zn1—O7—C18—O8 | −38.8 (6) | C14—C13—C17—C16 | 2.0 (6) |
Zn1—O7—C18—C13 | 141.1 (3) | C18—C13—C17—C16 | −176.8 (4) |
Zn3—O8—C18—O7 | −25.3 (6) | C17—C13—C18—O7 | −156.4 (4) |
Zn3—O8—C18—C13 | 154.9 (3) | C14—C13—C18—O7 | 24.9 (5) |
C5—N1—C1—C2 | 1.0 (6) | C17—C13—C18—O8 | 23.5 (5) |
Zn2—N1—C1—C2 | 176.8 (3) | C14—C13—C18—O8 | −155.3 (3) |
C1—N1—C5—C4 | 1.1 (6) | C13—C14—C15—N4 | 1.5 (6) |
Zn2—N1—C5—C4 | −174.9 (3) | C13—C17—C16—N4 | 1.0 (6) |
C10—N2—Zn1—O2ii | −48.6 (3) | C21—C20—C19—N3 | −0.1 (7) |
C9—N2—Zn1—O2ii | 134.4 (3) | C20—C21—C24—O6 | −177.2 (4) |
C10—N2—Zn1—O2iii | 131.4 (3) | C22—C21—C24—O6 | 6.1 (6) |
C9—N2—Zn1—O2iii | −45.6 (3) | C20—C21—C24—O5 | 4.4 (6) |
C10—N2—Zn1—O7 | −144.4 (3) | C22—C21—C24—O5 | −172.2 (4) |
C9—N2—Zn1—O7 | 38.7 (3) | C22—C21—C20—C19 | −0.6 (6) |
C10—N2—Zn1—O7i | 35.6 (3) | C24—C21—C20—C19 | −177.3 (4) |
C9—N2—Zn1—O7i | −141.3 (3) | C20—C21—C22—C23 | 0.6 (7) |
C10—N2—C9—C8 | −3.2 (6) | C24—C21—C22—C23 | 177.3 (4) |
Zn1—N2—C9—C8 | 173.9 (3) | C21—C22—C23—N3 | 0.1 (7) |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) x, y+1, z; (iii) −x, −y, −z+1; (iv) x−1, y−1, z; (v) x, y−1, z; (vi) x+1, y+1, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4A···O6v | 0.86 | 2.23 | 2.758 (4) | 119 |
N4—H4A···O3vii | 0.86 | 2.39 | 2.957 (4) | 124 |
Symmetry codes: (v) x, y−1, z; (vii) x+1, y, z. |
Experimental details
Crystal data | |
Chemical formula | [Zn5Br4(C6H4NO2)6(C6H5NO2)2] |
Mr | 1625.32 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 298 |
a, b, c (Å) | 14.096 (3), 13.614 (3), 14.781 (3) |
β (°) | 114.53 (3) |
V (Å3) | 2580.5 (11) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 5.47 |
Crystal size (mm) | 0.47 × 0.42 × 0.29 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.123, 0.205 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 24795, 5899, 4756 |
Rint | 0.059 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.093, 1.06 |
No. of reflections | 5899 |
No. of parameters | 368 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.01, −1.05 |
Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1998), SHELXTL.
Zn1—N2i | 2.118 (3) | Zn2—Br1 | 2.3798 (10) |
Zn1—O2ii | 2.158 (3) | Zn3—O1ii | 1.948 (2) |
Zn1—O7i | 2.191 (3) | Zn3—O8 | 1.955 (3) |
Zn2—O4 | 1.933 (3) | Zn3—N3 | 2.037 (3) |
Zn2—O5iii | 1.938 (3) | Zn3—Br2 | 2.3369 (9) |
Zn2—N1 | 2.075 (3) | ||
N2—Zn1—O2ii | 84.93 (11) | O4—Zn2—Br1 | 110.08 (10) |
N2i—Zn1—O2ii | 95.07 (11) | O5iii—Zn2—Br1 | 114.30 (9) |
N2—Zn1—O7 | 86.31 (10) | N1—Zn2—Br1 | 107.59 (9) |
N2i—Zn1—O7 | 93.69 (10) | O1ii—Zn3—O8 | 129.35 (12) |
O2ii—Zn1—O7 | 95.36 (11) | O1ii—Zn3—N3 | 95.37 (11) |
O2iv—Zn1—O7 | 84.64 (11) | O8—Zn3—N3 | 96.52 (11) |
O4—Zn2—O5iii | 127.98 (14) | O1ii—Zn3—Br2 | 108.65 (9) |
O4—Zn2—N1 | 96.22 (11) | O8—Zn3—Br2 | 107.89 (9) |
O5iii—Zn2—N1 | 95.07 (11) | N3—Zn3—Br2 | 118.85 (10) |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) x, y+1, z; (iii) x−1, y−1, z; (iv) −x, −y, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4A···O6v | 0.86 | 2.23 | 2.758 (4) | 119 |
N4—H4A···O3vi | 0.86 | 2.39 | 2.957 (4) | 124 |
Symmetry codes: (v) x, y−1, z; (vi) x+1, y, z. |
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In recent years, isonicotinic acid (HIN) have been extensively studied, because of its ability of acting either as monodentate, bidentate, tridentate bridging or as chelating ligand. Novel complexes such as [Cu2(IN)4(H2O)3][Cu2(IN)4(H2O)2].3H2O (Lu & Babb, 2001) have been reported. The title compound, (I), was synthesized by hydrothermal synthesis at about 443 K. It was air stable and insoluble in most solvents. We report herein its crystal structure.
In the molecule of (I) (Fig. 1), the ligand bond lengths and angles are generally within normal ranges (Allen et al., 1987). Zn1 is located on an inversion centre and has ZnO4N2 octahedral geometry, which is completed by IN and 1H-IN oxygen atoms (where IN is isonicotinate), as well as IN nitrogen atoms, while Zn2 and Zn3 adopt the four-coordinated ZnO2NBr pyramidal geometry, which is completed by IN oxygen and nitrogen atoms, as well as bromine ions.
The Zn—O/N bonds for Zn2 and Zn3 are in the range of 1.933 (3)–2.075 (3) Å, which are shorter than that observed for Zn1 within 2.118 (3)–2.191 (3) Å. The Zn—Br bonds are 2.3369 (9) Å for Zn3, and 2.3798 (10) Å for Zn2 (Table 1).
Furthermore, these metal centers are in turn connected by intermolecular N—H···O hydrogen bonds (Table 2), IN and 1H-IN to construct the two-dimensional bilayer structure (Fig. 2), where the 1H-IN ligands contribute to bidentate coordinated mode, while IN ligands to bidentate and tridentate coordinated modes. In addition, the closest Zn—Zn distance is ca 4.031 Å, and the edges of the present two-dimensional bilayer stucture is ca 8.8 x 8.5 Å.