Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807048192/lh2515sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807048192/lh2515Isup2.hkl |
CCDC reference: 667120
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.005 Å
- R factor = 0.038
- wR factor = 0.081
- Data-to-parameter ratio = 13.7
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density .... 2.65 PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent ..... ? PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) . 1.13 Ratio
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 25.98 From the CIF: _reflns_number_total 1072 Count of symmetry unique reflns 601 Completeness (_total/calc) 178.37% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 471 Fraction of Friedel pairs measured 0.784 Are heavy atom types Z>Si present yes PLAT794_ALERT_5_G Check Predicted Bond Valency for Zn1 (2) 1.83
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 4 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 2 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 0 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
For background information see: Kuang et al. (2006). For related structures, see: Shi et al. (2006a,b,c); Zhang et al. (2007).
Zn(NO3)2·6H2O (0.0354 g, 0.119 mmol) in H2O (10 ml) was added to 6,6'-diamino-2,2'-bipyridine (0.0110 g, 0.059 mmol) in acetonitrile (5 ml), and the solution was stirred for a few minutes. Colorless crystals were obtained after allowing the solution to stand at room temperature for one week. The infrared stretching vibrations of pyridine ring and amino groups appeared at 1638 cm-1, 1465 cm-1 and 1384 cm-1.
The H atoms were placed in calculated positions and refined as riding, with C—H = 0.93 Å, Uiso(H) = 1.2eq(C); N—H = 0.86 Å, Uiso(H) = 1.2eq(N) for amino group.
2,2'-Bipyridine and its derivatives play a pivotal role in the area of modern coordination chemistry. For example, some dye-sensitized solar cells deal with complexes of derivatives of 2,2'-bispyridine as a ligand (Kuang et al., 2006). We have an interest in complexes containing 3,3'-diamino-2,2'-bipyridine and have synthesized the complexes containing NiII, CdII, MnII and CuII ions (Shi et al., 2006a,b; Min et al., 2006; Zhang et al., 2007). Here we report the structure of the title complex (Fig. 1).
The ZnII atom, located on the intersection of a threefold axis and a twofold axis, assumes a slightly distorted octahedral ZnN6 coordination geometry. The nitrate anion lies on a threefold axis. In the 3,3'-diamino-2,2'-bipyridine ligand, each pyridine ring is essentially planar with a maximum deviation of -0.029 (4) Å for atom C1; the dihedral angle between the two pyridine rings is 34.77 (18), which is larger than that in the Ni(II) complex, but smaller than that in Cd(II) and Mn(II) complexes. Just as with the Ni(II), Mn(II) and Cd(II) complexes the deviation from planarity in the title compound is expected in terms of steric relief. The hydrogen bonds (Table 1) that arise from nitrate anions and amino group result in the connection of the cations and the nitrate anions and contribute to the formation of a supermolecular two-dimensional sheet parallel ab plane, as shown in Fig. 2.
For background information see: Kuang et al. (2006). For related structures, see: Shi et al. (2006a,b,c); Zhang et al. (2007).
Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXTL (Bruker, 2001); program(s) used to refine structure: SHELXTL (Bruker, 2001); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL (Bruker, 2001).
[Zn(C10H10N4)3](NO3)2 | Dx = 1.527 Mg m−3 |
Mr = 748.05 | Mo Kα radiation, λ = 0.71073 Å |
Trigonal, R32 | Cell parameters from 918 reflections |
Hall symbol: R 3 2" | θ = 2.2–19.0° |
a = 14.6116 (19) Å | µ = 0.82 mm−1 |
c = 13.199 (4) Å | T = 298 K |
V = 2440.4 (8) Å3 | Prism, colourless |
Z = 3 | 0.20 × 0.14 × 0.10 mm |
F(000) = 1158 |
Bruker SMART APEX CCD diffractometer | 1072 independent reflections |
Radiation source: fine-focus sealed tube | 1005 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.051 |
φ and ω scans | θmax = 26.0°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −18→10 |
Tmin = 0.853, Tmax = 0.922 | k = −15→18 |
4419 measured reflections | l = −16→15 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.038 | H-atom parameters constrained |
wR(F2) = 0.081 | w = 1/[σ2(Fo2) + (0.0391P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max < 0.001 |
1072 reflections | Δρmax = 0.49 e Å−3 |
78 parameters | Δρmin = −0.18 e Å−3 |
0 restraints | Absolute structure: Flack (1983), with 469 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.03 (2) |
[Zn(C10H10N4)3](NO3)2 | Z = 3 |
Mr = 748.05 | Mo Kα radiation |
Trigonal, R32 | µ = 0.82 mm−1 |
a = 14.6116 (19) Å | T = 298 K |
c = 13.199 (4) Å | 0.20 × 0.14 × 0.10 mm |
V = 2440.4 (8) Å3 |
Bruker SMART APEX CCD diffractometer | 1072 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1005 reflections with I > 2σ(I) |
Tmin = 0.853, Tmax = 0.922 | Rint = 0.051 |
4419 measured reflections |
R[F2 > 2σ(F2)] = 0.038 | H-atom parameters constrained |
wR(F2) = 0.081 | Δρmax = 0.49 e Å−3 |
S = 1.05 | Δρmin = −0.18 e Å−3 |
1072 reflections | Absolute structure: Flack (1983), with 469 Friedel pairs |
78 parameters | Absolute structure parameter: 0.03 (2) |
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 > 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 | 1.0000 | 0.0000 | 0.0332 (2) | |
N2 | 0.0862 (2) | 0.9399 (2) | 0.08301 (16) | 0.0354 (6) | |
C5 | 0.1754 (2) | 0.9566 (2) | 0.0369 (2) | 0.0363 (7) | |
C3 | 0.1693 (4) | 0.8141 (4) | 0.1330 (2) | 0.0585 (9) | |
H3 | 0.1969 | 0.7711 | 0.1505 | 0.070* | |
C1 | 0.0411 (3) | 0.8668 (3) | 0.1543 (3) | 0.0487 (8) | |
H1 | −0.0206 | 0.8564 | 0.1851 | 0.058* | |
C2 | 0.0846 (3) | 0.8054 (3) | 0.1838 (3) | 0.0593 (10) | |
H2 | 0.0559 | 0.7588 | 0.2380 | 0.071* | |
C4 | 0.2154 (3) | 0.8876 (2) | 0.0541 (3) | 0.0478 (8) | |
N1 | 0.3333 | 0.6667 | 0.0452 (2) | 0.0415 (8) | |
O1 | 0.3647 (2) | 0.6020 (2) | 0.04535 (17) | 0.0631 (7) | |
N3 | 0.2931 (3) | 0.8874 (3) | −0.0037 (3) | 0.0721 (10) | |
H3A | 0.3133 | 0.8425 | 0.0085 | 0.087* | |
H3B | 0.3217 | 0.9323 | −0.0522 | 0.087* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.0295 (3) | 0.0295 (3) | 0.0407 (4) | 0.01473 (14) | 0.000 | 0.000 |
N2 | 0.0331 (16) | 0.0286 (15) | 0.0419 (12) | 0.0135 (13) | 0.0018 (12) | 0.0051 (12) |
C5 | 0.0318 (15) | 0.0314 (16) | 0.0463 (18) | 0.0163 (13) | −0.0014 (13) | −0.0018 (13) |
C3 | 0.065 (3) | 0.044 (2) | 0.077 (2) | 0.0356 (19) | −0.006 (3) | 0.011 (2) |
C1 | 0.051 (2) | 0.047 (2) | 0.0494 (19) | 0.0249 (16) | 0.0071 (15) | 0.0095 (15) |
C2 | 0.073 (3) | 0.048 (2) | 0.059 (2) | 0.031 (2) | −0.0009 (19) | 0.0202 (17) |
C4 | 0.0407 (19) | 0.0358 (17) | 0.069 (2) | 0.0204 (15) | −0.0072 (16) | −0.0034 (16) |
N1 | 0.0402 (13) | 0.0402 (13) | 0.044 (2) | 0.0201 (7) | 0.000 | 0.000 |
O1 | 0.0538 (17) | 0.0466 (17) | 0.0985 (16) | 0.0322 (15) | 0.0023 (13) | 0.0010 (13) |
N3 | 0.062 (2) | 0.059 (2) | 0.116 (3) | 0.0456 (18) | 0.022 (2) | 0.0168 (19) |
Zn1—N2i | 2.159 (2) | C3—C4 | 1.404 (5) |
Zn1—N2ii | 2.159 (2) | C3—H3 | 0.9300 |
Zn1—N2iii | 2.159 (2) | C1—C2 | 1.390 (5) |
Zn1—N2iv | 2.159 (2) | C1—H1 | 0.9300 |
Zn1—N2 | 2.159 (2) | C2—H2 | 0.9300 |
Zn1—N2v | 2.159 (2) | C4—N3 | 1.368 (4) |
N2—C1 | 1.325 (4) | N1—O1vi | 1.239 (2) |
N2—C5 | 1.345 (4) | N1—O1vii | 1.239 (2) |
C5—C4 | 1.414 (4) | N1—O1 | 1.239 (2) |
C5—C5iii | 1.467 (6) | N3—H3A | 0.8600 |
C3—C2 | 1.357 (5) | N3—H3B | 0.8600 |
N2i—Zn1—N2ii | 169.86 (16) | C4—C5—C5iii | 124.6 (2) |
N2i—Zn1—N2iii | 96.53 (8) | C2—C3—C4 | 120.3 (3) |
N2ii—Zn1—N2iii | 91.45 (14) | C2—C3—H3 | 119.8 |
N2i—Zn1—N2iv | 96.53 (8) | C4—C3—H3 | 119.8 |
N2ii—Zn1—N2iv | 76.28 (14) | N2—C1—C2 | 121.1 (3) |
N2iii—Zn1—N2iv | 96.53 (8) | N2—C1—H1 | 119.5 |
N2i—Zn1—N2 | 91.45 (14) | C2—C1—H1 | 119.5 |
N2ii—Zn1—N2 | 96.53 (8) | C3—C2—C1 | 119.4 (3) |
N2iii—Zn1—N2 | 76.28 (14) | C3—C2—H2 | 120.3 |
N2iv—Zn1—N2 | 169.86 (16) | C1—C2—H2 | 120.3 |
N2i—Zn1—N2v | 76.28 (14) | N3—C4—C3 | 119.5 (3) |
N2ii—Zn1—N2v | 96.53 (8) | N3—C4—C5 | 123.5 (3) |
N2iii—Zn1—N2v | 169.86 (16) | C3—C4—C5 | 117.0 (3) |
N2iv—Zn1—N2v | 91.45 (14) | O1vi—N1—O1vii | 120.000 (2) |
N2—Zn1—N2v | 96.53 (8) | O1vi—N1—O1 | 120.000 (2) |
C1—N2—C5 | 120.9 (3) | O1vii—N1—O1 | 120.000 (3) |
C1—N2—Zn1 | 122.1 (2) | C4—N3—H3A | 120.0 |
C5—N2—Zn1 | 113.92 (18) | C4—N3—H3B | 120.0 |
N2—C5—C4 | 120.4 (3) | H3A—N3—H3B | 120.0 |
N2—C5—C5iii | 114.69 (17) | ||
N2ii—Zn1—N2—C1 | 101.6 (2) | C5—N2—C1—C2 | 0.2 (5) |
N2iii—Zn1—N2—C1 | −168.5 (3) | Zn1—N2—C1—C2 | 159.3 (3) |
N2v—Zn1—N2—C1 | 4.2 (3) | C4—C3—C2—C1 | 2.7 (6) |
N2ii—Zn1—N2—C5 | −98.0 (3) | N2—C1—C2—C3 | −5.7 (6) |
N2iii—Zn1—N2—C5 | −8.12 (15) | C2—C3—C4—N3 | −172.8 (4) |
N2v—Zn1—N2—C5 | 164.6 (2) | C2—C3—C4—C5 | 5.2 (6) |
C1—N2—C5—C4 | 8.2 (4) | N2—C5—C4—N3 | 167.3 (3) |
Zn1—N2—C5—C4 | −152.5 (2) | C5iii—C5—C4—N3 | −6.8 (5) |
C1—N2—C5—C5iii | −177.2 (3) | N2—C5—C4—C3 | −10.7 (5) |
Zn1—N2—C5—C5iii | 22.1 (4) | C5iii—C5—C4—C3 | 175.2 (4) |
Symmetry codes: (i) −x, −x+y, −z; (ii) −y+1, x−y+2, z; (iii) x−y+1, −y+2, −z; (iv) y−1, x+1, −z; (v) −x+y−1, −x+1, z; (vi) −x+y, −x+1, z; (vii) −y+1, x−y+1, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3A···O1vii | 0.86 | 2.14 | 2.980 (4) | 167 |
N3—H3B···N3iii | 0.86 | 2.40 | 2.851 (6) | 113 |
Symmetry codes: (iii) x−y+1, −y+2, −z; (vii) −y+1, x−y+1, z. |
Experimental details
Crystal data | |
Chemical formula | [Zn(C10H10N4)3](NO3)2 |
Mr | 748.05 |
Crystal system, space group | Trigonal, R32 |
Temperature (K) | 298 |
a, c (Å) | 14.6116 (19), 13.199 (4) |
V (Å3) | 2440.4 (8) |
Z | 3 |
Radiation type | Mo Kα |
µ (mm−1) | 0.82 |
Crystal size (mm) | 0.20 × 0.14 × 0.10 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.853, 0.922 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4419, 1072, 1005 |
Rint | 0.051 |
(sin θ/λ)max (Å−1) | 0.616 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.081, 1.05 |
No. of reflections | 1072 |
No. of parameters | 78 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.49, −0.18 |
Absolute structure | Flack (1983), with 469 Friedel pairs |
Absolute structure parameter | 0.03 (2) |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXTL (Bruker, 2001).
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3A···O1i | 0.86 | 2.14 | 2.980 (4) | 166.8 |
N3—H3B···N3ii | 0.86 | 2.40 | 2.851 (6) | 113.3 |
Symmetry codes: (i) −y+1, x−y+1, z; (ii) x−y+1, −y+2, −z. |
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2,2'-Bipyridine and its derivatives play a pivotal role in the area of modern coordination chemistry. For example, some dye-sensitized solar cells deal with complexes of derivatives of 2,2'-bispyridine as a ligand (Kuang et al., 2006). We have an interest in complexes containing 3,3'-diamino-2,2'-bipyridine and have synthesized the complexes containing NiII, CdII, MnII and CuII ions (Shi et al., 2006a,b; Min et al., 2006; Zhang et al., 2007). Here we report the structure of the title complex (Fig. 1).
The ZnII atom, located on the intersection of a threefold axis and a twofold axis, assumes a slightly distorted octahedral ZnN6 coordination geometry. The nitrate anion lies on a threefold axis. In the 3,3'-diamino-2,2'-bipyridine ligand, each pyridine ring is essentially planar with a maximum deviation of -0.029 (4) Å for atom C1; the dihedral angle between the two pyridine rings is 34.77 (18), which is larger than that in the Ni(II) complex, but smaller than that in Cd(II) and Mn(II) complexes. Just as with the Ni(II), Mn(II) and Cd(II) complexes the deviation from planarity in the title compound is expected in terms of steric relief. The hydrogen bonds (Table 1) that arise from nitrate anions and amino group result in the connection of the cations and the nitrate anions and contribute to the formation of a supermolecular two-dimensional sheet parallel ab plane, as shown in Fig. 2.