Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807037750/bg2083sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807037750/bg2083Isup2.hkl |
CCDC reference: 660094
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.005 Å
- R factor = 0.041
- wR factor = 0.093
- Data-to-parameter ratio = 12.8
checkCIF/PLATON results
No syntax errors found
Alert level G PLAT794_ALERT_5_G Check Predicted Bond Valency for Zn1 (2) 2.18 PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 3
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 0 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 0 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 0 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
A diluted sodium hydroxide H2O solution was added dropwise into 30 ml of a, aqueous solution containing Zn(ClO4)2.6H2O (0.1862 g, 0.500 mmol) and 2-hydroxyl-3-carboxylpyridine (0.1232 g, 1.00 mmol) until the pH value reached 4, and the solution was stirred for another a few minutes. Colorless single crystals were obtained after the mixed solutions were allowed to stand at room temperature for one week.
H atoms of water molecule and N—H bond were located in a difference Fourier map and refined as riding in their as-found positions, with O—H = 0.842–0.844 Å, Uiso(H) = 1.5 Ueq(O), N—H = 0.86 Å, Uiso(H) = 1.2 Ueq(N). other H atoms were placed in calculated positions, and refined as riding, with C—H = 0.93 Å, Uiso(H) = 1.2eq(C).
Metal complexes containing N-heterocyclic ligands play a pivotal role in the area of modern coordination chemistry, and it has been reported that complexes containing 3-hydroxypicolinamide ligand display strong fluorescent emission (Sakai et al. 2006). The interest in this area prompted us to synthesize the title complex, (I), which crystal structure we report herein.
Fig. 1 shows the asymmetric unit and symmetry-related fragment of (I). The ZnII atom lies at an inversion centre and adopts a slightly distored octahedral geometry (Table 1). Between neighboring complexes there is a weak π-π stacking interaction, which links adjacent pyridyl rings; the relevant distances are Cg1···Cg1i = 3.840 (2) Å and Cg1···Cg1iperp = 3.582 Å [symmetry codes: (i) X, 1/2-Y, -1/2+Z; Cg1 is the centroid of pyridyl ring; Cg1···Cg1perp is the perpendicular distance from ring Cg1 to ring Cg1i]. Table 2 and Fig. 2 show the information of O—H···O and N—H···O hydrogen bonds, which consolidate the crystal structure.
For a related crystal structure, see: Sakai et al. (2006).
Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
[Zn(C6H4NO3)2(H2O)2] | F(000) = 384 |
Mr = 377.61 | Dx = 1.814 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 899 reflections |
a = 7.491 (3) Å | θ = 2.8–23.7° |
b = 12.316 (4) Å | µ = 1.82 mm−1 |
c = 7.621 (3) Å | T = 298 K |
β = 100.437 (5)° | Block, colourless |
V = 691.5 (4) Å3 | 0.24 × 0.18 × 0.10 mm |
Z = 2 |
Bruker SMART APEX CCD diffractometer | 1352 independent reflections |
Radiation source: fine-focus sealed tube | 1069 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.048 |
φ and ω scans | θmax = 26.0°, θmin = 2.8° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −9→7 |
Tmin = 0.669, Tmax = 0.839 | k = −15→15 |
3479 measured reflections | l = −9→6 |
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)] = 0.042 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.093 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0397P)2 + 0.1015P] where P = (Fo2 + 2Fc2)/3 |
1352 reflections | (Δ/σ)max < 0.001 |
106 parameters | Δρmax = 0.57 e Å−3 |
3 restraints | Δρmin = −0.40 e Å−3 |
[Zn(C6H4NO3)2(H2O)2] | V = 691.5 (4) Å3 |
Mr = 377.61 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.491 (3) Å | µ = 1.82 mm−1 |
b = 12.316 (4) Å | T = 298 K |
c = 7.621 (3) Å | 0.24 × 0.18 × 0.10 mm |
β = 100.437 (5)° |
Bruker SMART APEX CCD diffractometer | 1352 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1069 reflections with I > 2σ(I) |
Tmin = 0.669, Tmax = 0.839 | Rint = 0.048 |
3479 measured reflections |
R[F2 > 2σ(F2)] = 0.042 | 3 restraints |
wR(F2) = 0.093 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.57 e Å−3 |
1352 reflections | Δρmin = −0.40 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 > 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 | 0.5000 | 0.5000 | 0.0000 | 0.02360 (19) | |
O3 | 0.7719 (3) | 0.45670 (17) | −0.0125 (3) | 0.0286 (6) | |
O2 | 0.4399 (3) | 0.34197 (17) | −0.0143 (3) | 0.0292 (6) | |
N1 | 1.0205 (4) | 0.3608 (2) | 0.1060 (4) | 0.0311 (7) | |
H4 | 1.0815 | 0.4196 | 0.1018 | 0.037* | |
O1 | 0.4702 (3) | 0.16478 (17) | −0.0133 (3) | 0.0311 (6) | |
O4 | 0.5772 (4) | 0.49450 (16) | 0.2831 (3) | 0.0380 (7) | |
H6 | 0.5680 | 0.5530 | 0.3379 | 0.057* | |
H5 | 0.5382 | 0.4413 | 0.3350 | 0.057* | |
C5 | 0.5381 (4) | 0.2586 (3) | 0.0077 (4) | 0.0228 (8) | |
C4 | 0.7405 (5) | 0.2668 (2) | 0.0606 (4) | 0.0223 (7) | |
C3 | 0.8381 (5) | 0.1755 (3) | 0.1208 (5) | 0.0314 (8) | |
H1 | 0.7760 | 0.1103 | 0.1241 | 0.038* | |
C6 | 0.8375 (4) | 0.3666 (2) | 0.0498 (4) | 0.0227 (7) | |
C1 | 1.1143 (5) | 0.2713 (3) | 0.1673 (5) | 0.0364 (9) | |
H3 | 1.2396 | 0.2746 | 0.2030 | 0.044* | |
C2 | 1.0253 (5) | 0.1758 (3) | 0.1770 (5) | 0.0394 (10) | |
H2 | 1.0874 | 0.1130 | 0.2197 | 0.047* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.0219 (3) | 0.0139 (3) | 0.0354 (4) | −0.0001 (2) | 0.0063 (2) | 0.0005 (2) |
O3 | 0.0201 (12) | 0.0185 (12) | 0.0485 (16) | 0.0002 (10) | 0.0099 (11) | 0.0047 (11) |
O2 | 0.0235 (13) | 0.0132 (12) | 0.0500 (17) | −0.0005 (9) | 0.0040 (11) | −0.0004 (10) |
N1 | 0.0239 (17) | 0.0284 (16) | 0.041 (2) | −0.0038 (12) | 0.0047 (13) | 0.0047 (13) |
O1 | 0.0294 (15) | 0.0143 (12) | 0.0481 (17) | −0.0043 (9) | 0.0030 (12) | −0.0012 (10) |
O4 | 0.0605 (19) | 0.0224 (13) | 0.0321 (15) | −0.0024 (12) | 0.0107 (13) | −0.0018 (11) |
C5 | 0.025 (2) | 0.0215 (18) | 0.0217 (18) | 0.0005 (13) | 0.0047 (15) | 0.0018 (13) |
C4 | 0.0251 (18) | 0.0194 (16) | 0.0229 (18) | 0.0008 (14) | 0.0057 (14) | 0.0011 (13) |
C3 | 0.034 (2) | 0.0257 (19) | 0.035 (2) | 0.0005 (15) | 0.0062 (16) | 0.0052 (15) |
C6 | 0.0184 (17) | 0.0271 (18) | 0.0235 (18) | 0.0024 (13) | 0.0059 (14) | −0.0004 (14) |
C1 | 0.0199 (19) | 0.047 (2) | 0.042 (2) | 0.0052 (16) | 0.0042 (16) | 0.0102 (18) |
C2 | 0.032 (2) | 0.036 (2) | 0.049 (3) | 0.0134 (17) | 0.0055 (18) | 0.0166 (17) |
Zn1—O2 | 1.996 (2) | O1—C5 | 1.261 (4) |
Zn1—O2i | 1.996 (2) | O4—H6 | 0.8415 |
Zn1—O3i | 2.124 (2) | O4—H5 | 0.8440 |
Zn1—O3 | 2.124 (2) | C5—C4 | 1.500 (4) |
Zn1—O4 | 2.131 (3) | C4—C3 | 1.374 (4) |
Zn1—O4i | 2.131 (3) | C4—C6 | 1.438 (4) |
O3—C6 | 1.270 (4) | C3—C2 | 1.390 (5) |
O2—C5 | 1.256 (4) | C3—H1 | 0.9300 |
N1—C1 | 1.345 (4) | C1—C2 | 1.361 (5) |
N1—C6 | 1.362 (4) | C1—H3 | 0.9300 |
N1—H4 | 0.8600 | C2—H2 | 0.9300 |
O2—Zn1—O2i | 180.0 | Zn1—O4—H5 | 116.4 |
O2—Zn1—O3i | 92.22 (9) | H6—O4—H5 | 111.5 |
O2i—Zn1—O3i | 87.78 (9) | O2—C5—O1 | 121.3 (3) |
O2—Zn1—O3 | 87.78 (9) | O2—C5—C4 | 121.3 (3) |
O2i—Zn1—O3 | 92.22 (9) | O1—C5—C4 | 117.4 (3) |
O3i—Zn1—O3 | 180.00 (13) | C3—C4—C6 | 118.4 (3) |
O2—Zn1—O4 | 92.38 (8) | C3—C4—C5 | 119.1 (3) |
O2i—Zn1—O4 | 87.62 (8) | C6—C4—C5 | 122.6 (3) |
O3i—Zn1—O4 | 92.82 (9) | C4—C3—C2 | 123.1 (3) |
O3—Zn1—O4 | 87.18 (9) | C4—C3—H1 | 118.4 |
O2—Zn1—O4i | 87.62 (8) | C2—C3—H1 | 118.4 |
O2i—Zn1—O4i | 92.38 (8) | O3—C6—N1 | 117.6 (3) |
O3i—Zn1—O4i | 87.18 (9) | O3—C6—C4 | 127.1 (3) |
O3—Zn1—O4i | 92.82 (9) | N1—C6—C4 | 115.3 (3) |
O4—Zn1—O4i | 180.0 | N1—C1—C2 | 119.8 (3) |
C6—O3—Zn1 | 120.79 (19) | N1—C1—H3 | 120.1 |
C5—O2—Zn1 | 132.0 (2) | C2—C1—H3 | 120.1 |
C1—N1—C6 | 125.8 (3) | C1—C2—C3 | 117.6 (3) |
C1—N1—H4 | 117.1 | C1—C2—H2 | 121.2 |
C6—N1—H4 | 117.1 | C3—C2—H2 | 121.2 |
Zn1—O4—H6 | 116.3 | ||
O2—Zn1—O3—C6 | −30.0 (2) | C6—C4—C3—C2 | 2.1 (5) |
O2i—Zn1—O3—C6 | 150.0 (2) | C5—C4—C3—C2 | −178.3 (3) |
O4—Zn1—O3—C6 | 62.5 (2) | Zn1—O3—C6—N1 | −153.4 (2) |
O4i—Zn1—O3—C6 | −117.5 (2) | Zn1—O3—C6—C4 | 29.8 (4) |
O3i—Zn1—O2—C5 | −164.5 (3) | C1—N1—C6—O3 | −176.6 (3) |
O3—Zn1—O2—C5 | 15.5 (3) | C1—N1—C6—C4 | 0.6 (5) |
O4—Zn1—O2—C5 | −71.6 (3) | C3—C4—C6—O3 | 175.3 (3) |
O4i—Zn1—O2—C5 | 108.4 (3) | C5—C4—C6—O3 | −4.3 (5) |
Zn1—O2—C5—O1 | −177.9 (2) | C3—C4—C6—N1 | −1.6 (4) |
Zn1—O2—C5—C4 | 2.3 (4) | C5—C4—C6—N1 | 178.8 (3) |
O2—C5—C4—C3 | 165.9 (3) | C6—N1—C1—C2 | 0.0 (6) |
O1—C5—C4—C3 | −13.9 (4) | N1—C1—C2—C3 | 0.4 (6) |
O2—C5—C4—C6 | −14.5 (5) | C4—C3—C2—C1 | −1.5 (6) |
O1—C5—C4—C6 | 165.6 (3) |
Symmetry code: (i) −x+1, −y+1, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H4···O3ii | 0.86 | 2.06 | 2.895 (4) | 162 |
O4—H5···O1iii | 0.84 | 1.88 | 2.711 (3) | 170 |
O4—H6···O1iv | 0.84 | 1.98 | 2.798 (3) | 165 |
Symmetry codes: (ii) −x+2, −y+1, −z; (iii) x, −y+1/2, z+1/2; (iv) −x+1, y+1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Zn(C6H4NO3)2(H2O)2] |
Mr | 377.61 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 298 |
a, b, c (Å) | 7.491 (3), 12.316 (4), 7.621 (3) |
β (°) | 100.437 (5) |
V (Å3) | 691.5 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.82 |
Crystal size (mm) | 0.24 × 0.18 × 0.10 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.669, 0.839 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3479, 1352, 1069 |
Rint | 0.048 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.093, 1.04 |
No. of reflections | 1352 |
No. of parameters | 106 |
No. of restraints | 3 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.57, −0.40 |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SAINT, SHELXTL (Bruker, 2001), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H4···O3i | 0.86 | 2.06 | 2.895 (4) | 162.2 |
O4—H5···O1ii | 0.84 | 1.88 | 2.711 (3) | 170.1 |
O4—H6···O1iii | 0.84 | 1.98 | 2.798 (3) | 165.2 |
Symmetry codes: (i) −x+2, −y+1, −z; (ii) x, −y+1/2, z+1/2; (iii) −x+1, y+1/2, −z+1/2. |
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Metal complexes containing N-heterocyclic ligands play a pivotal role in the area of modern coordination chemistry, and it has been reported that complexes containing 3-hydroxypicolinamide ligand display strong fluorescent emission (Sakai et al. 2006). The interest in this area prompted us to synthesize the title complex, (I), which crystal structure we report herein.
Fig. 1 shows the asymmetric unit and symmetry-related fragment of (I). The ZnII atom lies at an inversion centre and adopts a slightly distored octahedral geometry (Table 1). Between neighboring complexes there is a weak π-π stacking interaction, which links adjacent pyridyl rings; the relevant distances are Cg1···Cg1i = 3.840 (2) Å and Cg1···Cg1iperp = 3.582 Å [symmetry codes: (i) X, 1/2-Y, -1/2+Z; Cg1 is the centroid of pyridyl ring; Cg1···Cg1perp is the perpendicular distance from ring Cg1 to ring Cg1i]. Table 2 and Fig. 2 show the information of O—H···O and N—H···O hydrogen bonds, which consolidate the crystal structure.