Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807054876/hk2357sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807054876/hk2357Isup2.hkl |
CCDC reference: 1250492
Crystals of the title compound were synthesized using hydrothermal method in a 23 ml Teflon-lined Parr bomb. Copper dinitrate hexahydrate (147.8 mg, 0.5 mmol), 3-nitro-4-[N-(4-carbonylhydrazinopyridyl)-carbonyl]pyridine (278.4 mg, 1 mmol) and distilled water (6 g) were placed into the bomb and sealed. The bomb was then heated under autogenous pressure up to 453 K over the course of 7 d and allowed to cool at room temperature for 24 h. Upon opening the bomb, a clear colorless solution was decanted from small colorless crystals. These crystals were washed with distilled water followed by ethanol, and allowed to air-dry at room temperature.
H atoms were positioned geometrically, with N—H = 0.86 Å (for NH) and C—H = 0.93 Å for aromatic H, and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C,N).
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Siemens, 1996); software used to prepare material for publication: SHELXTL (Siemens, 1996).
Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. |
C12H9N5O4 | F(000) = 592 |
Mr = 287.24 | Dx = 1.393 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -p 2yn | Cell parameters from 2003 reflections |
a = 8.2027 (12) Å | θ = 2.4–20.9° |
b = 12.8813 (17) Å | µ = 0.11 mm−1 |
c = 12.970 (2) Å | T = 273 K |
β = 92.491 (7)° | Prism, colorless |
V = 1369.1 (3) Å3 | 0.27 × 0.17 × 0.16 mm |
Z = 4 |
Bruker SMART CCD area-detector diffractometer | 2718 independent reflections |
Radiation source: fine-focus sealed tube | 1360 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.043 |
ϕ and ω scans | θmax = 26.5°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −10→10 |
Tmin = 0.971, Tmax = 0.983 | k = −16→16 |
8849 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)] = 0.050 | H-atom parameters constrained |
wR(F2) = 0.144 | w = 1/[σ2(Fo2) + (0.0601P)2 + 0.155P] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max < 0.001 |
2718 reflections | Δρmax = 0.40 e Å−3 |
191 parameters | Δρmin = −0.26 e Å−3 |
0 restraints | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0065 (15) |
C12H9N5O4 | V = 1369.1 (3) Å3 |
Mr = 287.24 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 8.2027 (12) Å | µ = 0.11 mm−1 |
b = 12.8813 (17) Å | T = 273 K |
c = 12.970 (2) Å | 0.27 × 0.17 × 0.16 mm |
β = 92.491 (7)° |
Bruker SMART CCD area-detector diffractometer | 2718 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1360 reflections with I > 2σ(I) |
Tmin = 0.971, Tmax = 0.983 | Rint = 0.043 |
8849 measured reflections |
R[F2 > 2σ(F2)] = 0.050 | 0 restraints |
wR(F2) = 0.144 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.40 e Å−3 |
2718 reflections | Δρmin = −0.26 e Å−3 |
191 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 | ||
O1 | 0.9294 (2) | −0.01082 (13) | 0.62609 (13) | 0.0612 (5) | |
O2 | 0.5681 (2) | 0.15846 (13) | 0.51252 (15) | 0.0660 (5) | |
O3 | 0.7545 (4) | −0.37731 (18) | 0.5472 (2) | 0.1294 (10) | |
O4 | 0.8681 (3) | −0.23389 (16) | 0.51340 (15) | 0.0835 (7) | |
N1 | 0.7077 (3) | −0.02937 (16) | 0.51883 (17) | 0.0614 (6) | |
H1A | 0.6179 | −0.0622 | 0.5058 | 0.074* | |
N2 | 0.7559 (3) | 0.04917 (15) | 0.45297 (16) | 0.0611 (6) | |
H2A | 0.8306 | 0.0381 | 0.4098 | 0.073* | |
N3 | 0.8478 (5) | 0.3838 (3) | 0.2666 (4) | 0.1365 (15) | |
N4 | 0.5791 (3) | −0.2646 (2) | 0.8124 (2) | 0.0876 (8) | |
N5 | 0.7828 (3) | −0.28597 (18) | 0.56574 (19) | 0.0696 (7) | |
C1 | 0.7452 (3) | 0.22485 (19) | 0.38874 (19) | 0.0549 (7) | |
C2 | 0.7185 (4) | 0.3276 (2) | 0.4150 (2) | 0.0773 (9) | |
H2 | 0.6631 | 0.3429 | 0.4741 | 0.093* | |
C3 | 0.7725 (5) | 0.4065 (3) | 0.3550 (3) | 0.1009 (12) | |
H3 | 0.7577 | 0.4752 | 0.3745 | 0.121* | |
C4 | 0.8753 (4) | 0.2817 (3) | 0.2375 (3) | 0.0889 (10) | |
H4 | 0.9278 | 0.2668 | 0.1771 | 0.107* | |
C5 | 0.8225 (3) | 0.2021 (2) | 0.3006 (2) | 0.0683 (8) | |
H5 | 0.8399 | 0.1333 | 0.2825 | 0.082* | |
C6 | 0.6826 (3) | 0.14377 (19) | 0.45812 (19) | 0.0521 (6) | |
C7 | 0.8009 (3) | −0.05374 (18) | 0.6022 (2) | 0.0502 (6) | |
C8 | 0.7259 (3) | −0.13277 (17) | 0.67218 (18) | 0.0484 (6) | |
C9 | 0.7149 (3) | −0.23985 (17) | 0.65642 (18) | 0.0505 (6) | |
C10 | 0.6410 (3) | −0.30405 (19) | 0.7257 (2) | 0.0590 (7) | |
H10 | 0.6338 | −0.3749 | 0.7127 | 0.071* | |
C11 | 0.5878 (3) | −0.1582 (2) | 0.8306 (2) | 0.0645 (8) | |
H11 | 0.5439 | −0.1305 | 0.8896 | 0.077* | |
C12 | 0.6613 (3) | −0.0937 (2) | 0.7616 (2) | 0.0600 (7) | |
H12 | 0.6677 | −0.0229 | 0.7751 | 0.072* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0632 (12) | 0.0470 (10) | 0.0741 (12) | −0.0084 (9) | 0.0107 (9) | −0.0013 (8) |
O2 | 0.0679 (13) | 0.0583 (12) | 0.0729 (12) | −0.0038 (10) | 0.0167 (10) | 0.0012 (9) |
O3 | 0.207 (3) | 0.0549 (14) | 0.132 (2) | −0.0219 (16) | 0.0728 (18) | −0.0345 (14) |
O4 | 0.1065 (17) | 0.0721 (14) | 0.0751 (14) | 0.0053 (12) | 0.0420 (12) | −0.0020 (11) |
N1 | 0.0625 (14) | 0.0513 (13) | 0.0708 (15) | −0.0114 (11) | 0.0078 (12) | 0.0203 (11) |
N2 | 0.0683 (15) | 0.0504 (13) | 0.0664 (14) | −0.0034 (11) | 0.0216 (11) | 0.0176 (11) |
N3 | 0.144 (3) | 0.117 (3) | 0.144 (3) | −0.050 (3) | −0.038 (3) | 0.066 (3) |
N4 | 0.099 (2) | 0.0762 (19) | 0.088 (2) | 0.0024 (15) | 0.0108 (15) | 0.0131 (15) |
N5 | 0.0926 (19) | 0.0477 (15) | 0.0704 (16) | 0.0033 (13) | 0.0237 (14) | −0.0032 (12) |
C1 | 0.0558 (17) | 0.0486 (16) | 0.0599 (17) | −0.0075 (12) | −0.0019 (13) | 0.0120 (12) |
C2 | 0.091 (2) | 0.0503 (18) | 0.089 (2) | −0.0082 (16) | −0.0111 (17) | 0.0083 (15) |
C3 | 0.146 (4) | 0.0531 (19) | 0.101 (3) | −0.024 (2) | −0.018 (3) | 0.020 (2) |
C4 | 0.088 (2) | 0.096 (3) | 0.083 (2) | −0.017 (2) | 0.0013 (17) | 0.037 (2) |
C5 | 0.0700 (19) | 0.0669 (18) | 0.0683 (19) | −0.0063 (15) | 0.0055 (15) | 0.0214 (15) |
C6 | 0.0555 (17) | 0.0466 (16) | 0.0540 (16) | −0.0052 (13) | 0.0017 (13) | 0.0015 (12) |
C7 | 0.0579 (17) | 0.0346 (13) | 0.0592 (17) | 0.0020 (13) | 0.0157 (13) | 0.0002 (12) |
C8 | 0.0540 (15) | 0.0379 (13) | 0.0540 (15) | 0.0010 (12) | 0.0094 (12) | 0.0037 (11) |
C9 | 0.0586 (16) | 0.0396 (14) | 0.0539 (15) | 0.0043 (12) | 0.0096 (12) | 0.0012 (11) |
C10 | 0.0768 (19) | 0.0381 (14) | 0.0630 (17) | 0.0033 (13) | 0.0134 (14) | 0.0045 (12) |
C11 | 0.084 (2) | 0.0541 (17) | 0.0574 (16) | 0.0052 (15) | 0.0219 (14) | 0.0011 (13) |
C12 | 0.0736 (19) | 0.0454 (15) | 0.0624 (17) | −0.0006 (13) | 0.0194 (14) | −0.0014 (13) |
O1—C7 | 1.218 (3) | C1—C6 | 1.485 (3) |
O2—C6 | 1.213 (3) | C2—C3 | 1.365 (4) |
O3—N5 | 1.221 (3) | C2—H2 | 0.9300 |
O4—N5 | 1.201 (3) | C3—H3 | 0.9300 |
N1—C7 | 1.334 (3) | C4—C5 | 1.392 (4) |
N1—N2 | 1.392 (3) | C4—H4 | 0.9300 |
N1—H1A | 0.8600 | C5—H5 | 0.9300 |
N2—C6 | 1.362 (3) | C7—C8 | 1.512 (3) |
N2—H2A | 0.8600 | C8—C12 | 1.391 (3) |
N3—C3 | 1.357 (6) | C8—C9 | 1.397 (3) |
N3—C4 | 1.390 (6) | C9—C10 | 1.380 (3) |
N4—C10 | 1.353 (4) | C10—H10 | 0.9300 |
N4—C11 | 1.392 (3) | C11—C12 | 1.379 (3) |
N5—C9 | 1.450 (3) | C11—H11 | 0.9300 |
C1—C5 | 1.363 (4) | C12—H12 | 0.9300 |
C1—C2 | 1.386 (4) | ||
C7—N1—N2 | 120.0 (2) | C1—C5—H5 | 119.9 |
C7—N1—H1A | 120.0 | C4—C5—H5 | 119.9 |
N2—N1—H1A | 120.0 | O2—C6—N2 | 121.5 (2) |
C6—N2—N1 | 118.9 (2) | O2—C6—C1 | 122.7 (2) |
C6—N2—H2A | 120.6 | N2—C6—C1 | 115.8 (2) |
N1—N2—H2A | 120.6 | O1—C7—N1 | 123.9 (2) |
C3—N3—C4 | 121.2 (3) | O1—C7—C8 | 121.5 (2) |
C10—N4—C11 | 119.5 (2) | N1—C7—C8 | 114.3 (2) |
O4—N5—O3 | 122.5 (2) | C12—C8—C9 | 117.0 (2) |
O4—N5—C9 | 118.9 (2) | C12—C8—C7 | 115.9 (2) |
O3—N5—C9 | 118.6 (2) | C9—C8—C7 | 127.0 (2) |
C5—C1—C2 | 119.7 (2) | C10—C9—C8 | 121.6 (2) |
C5—C1—C6 | 122.9 (2) | C10—C9—N5 | 118.5 (2) |
C2—C1—C6 | 117.4 (3) | C8—C9—N5 | 119.9 (2) |
C3—C2—C1 | 120.8 (3) | N4—C10—C9 | 120.5 (2) |
C3—C2—H2 | 119.6 | N4—C10—H10 | 119.8 |
C1—C2—H2 | 119.6 | C9—C10—H10 | 119.8 |
N3—C3—C2 | 119.5 (3) | C12—C11—N4 | 120.2 (2) |
N3—C3—H3 | 120.3 | C12—C11—H11 | 119.9 |
C2—C3—H3 | 120.3 | N4—C11—H11 | 119.9 |
N3—C4—C5 | 118.6 (3) | C11—C12—C8 | 121.1 (2) |
N3—C4—H4 | 120.7 | C11—C12—H12 | 119.4 |
C5—C4—H4 | 120.7 | C8—C12—H12 | 119.4 |
C1—C5—C4 | 120.2 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O2i | 0.86 | 1.97 | 2.823 (3) | 170 |
N2—H2A···O1ii | 0.86 | 2.07 | 2.862 (3) | 152 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+2, −y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C12H9N5O4 |
Mr | 287.24 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 273 |
a, b, c (Å) | 8.2027 (12), 12.8813 (17), 12.970 (2) |
β (°) | 92.491 (7) |
V (Å3) | 1369.1 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.11 |
Crystal size (mm) | 0.27 × 0.17 × 0.16 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.971, 0.983 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8849, 2718, 1360 |
Rint | 0.043 |
(sin θ/λ)max (Å−1) | 0.628 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.050, 0.144, 1.02 |
No. of reflections | 2718 |
No. of parameters | 191 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.40, −0.26 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Siemens, 1996).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O2i | 0.86 | 1.97 | 2.823 (3) | 170 |
N2—H2A···O1ii | 0.86 | 2.07 | 2.862 (3) | 152 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+2, −y, −z+1. |
In the synthesis of crystal structures by design, the assembly of molecular units in predefined arrangements is a key goal (Desiraju, 1995, 1997; Braga et al., 1998). Due to pyridine groups are one of the most important classes of biological ligands, the coordination of metal-pyridine groups complexes are of critical importance in biological systems, organic materials and coordination chemistry. Recently, pyridine groups with variable coordination modes have been used to construct metal-organic supramolecular structures (Wu et al., 2003; Pan & Xu, 2004; Liu et al., 2004; Li et al., 2005). We originally attempted to synthesize complexes featuring Cu metal chains by the reaction of copper(II) ion with 3-nitro-4-[N-(4-carbonylhydrazinopyridyl)- carbonyl]pyridine ligand. Unfortunately, we obtained only the title compound, (I), and we report herein its crystal structure.
In the molecule of (I) (Fig. 1), the ligand bond lengths and angles are within normal ranges (Allen et al., 1987). The rings A (N3/C1—C5) and B (N4/C8—C12) are, of course, planar and they are oriented at a dihedral angle of 8.00 (2)°.
In the crystal structure, intermolecular N—H···O hydrogen bonds (Table 1) result in the formation of a supramolecular network structure.