Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680702822X/fb2050sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680702822X/fb2050Isup2.hkl |
CCDC reference: 654957
Key indicators
- Single-crystal X-ray study
- T = 299 K
- Mean (C-C) = 0.004 Å
- R factor = 0.058
- wR factor = 0.137
- Data-to-parameter ratio = 15.2
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.80 PLAT369_ALERT_2_C Long C(sp2)-C(sp2) Bond C8 - C9 ... 1.54 Ang. PLAT731_ALERT_1_C Bond Calc 0.88(3), Rep 0.882(9) ...... 3.33 su-Ra N3 -H3 1.555 1.555 PLAT731_ALERT_1_C Bond Calc 0.89(3), Rep 0.891(9) ...... 3.33 su-Ra N4 -H4B 1.555 1.555 PLAT735_ALERT_1_C D-H Calc 0.89(3), Rep 0.891(9) ...... 3.33 su-Ra N4 -H4B 1.555 1.555 PLAT735_ALERT_1_C D-H Calc 0.88(3), Rep 0.882(9) ...... 3.33 su-Ra N3 -H3 1.555 1.555 PLAT735_ALERT_1_C D-H Calc 0.88(3), Rep 0.882(9) ...... 3.33 su-Ra N3 -H3 1.555 1.555 PLAT736_ALERT_1_C H...A Calc 2.12(3), Rep 2.120(10) ...... 3.00 su-Ra H4B -O1 1.555 1.565 PLAT736_ALERT_1_C H...A Calc 1.93(3), Rep 1.930(12) ...... 2.50 su-Ra H3 -O3 1.555 1.555
Alert level G PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 6
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 10 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 8 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 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 0 ALERT type 5 Informative message, check
For related literature, see: Banachiewicz & Banachiewicz (2004); Case (1965); Ejsmont (2007); Krishnakumar et al. (2002); Subha Nandhini et al. (2001); Etter et al. (1990).
The 2-pyridinecarboxamidrazone was prepared as described by Case (1965). A solution of oxalic acid dihydrate (0.126 g, 1 mmol) in ethanol (15 ml) was added to the solution of 2-pyridinecarboxamidrazone (0.136 g, 1 mmol) in ethanol (15 ml). The suspension was stirred for one hour at room temperature and filtrated, the light yellow solution was allowed to stand at room temperature, then light yellow well shaped crystals with typical dimensions about 0.5 x 1 x 1 mm were obtained after about one week.
All the H-atoms were discernible in the difference Fourier map. H atoms bound to C atoms were included in calculated positions and allowed to ride during refinement, with C—H = 0.93 Å, and Uiso(H) = 1.2Ueq(C). H atoms bound to O or N atoms were refined with restraints for O—H = 0.82 (1) Å, N(sp2-state)-H = 0.86 (1) Å, N(sp3-state)-H = 0.89 (1) Å, and Uiso(H) = 1.5Ueq(O, N).
Pyridinecarboxamidrazones are well studied, due to their high antituberculosis activities (Banachiewicz et al., 2004). As a part of our investigation of the reactions of 2-pyridinecarboxamidrazone with dicarboxylic acids, we report the crystal structure of the title compound, (I).
Unlike other similar semi-oxalate complexes (Krishnakumar et al., 2002; Subha Nandhini et al., 2001; Ejsmont, 2007) the hydrogenoxalate ion in (I) is not planar. The dihedral angle O1—C8—C9—O3 is 14.49 (16)°. In the cation, the dihedral angle N2—C1—C2—N1 is -151.1 (2)°.
For related literature, see: Banachiewicz & Banachiewicz (2004); Case (1965); Ejsmont (2007); Krishnakumar et al. (2002); Subha Nandhini et al. (2001); Etter et al. (1990).
Data collection: SMART (Bruker, 2000); cell refinement: SMART; data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
C6H9N4+·C2HO4− | F(000) = 944 |
Mr = 226.20 | Dx = 1.445 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 1565 reflections |
a = 26.634 (3) Å | θ = 3.0–22.8° |
b = 5.6454 (7) Å | µ = 0.12 mm−1 |
c = 18.337 (2) Å | T = 299 K |
β = 131.030 (2)° | Plate, light yellow |
V = 2079.9 (4) Å3 | 0.24 × 0.24 × 0.12 mm |
Z = 8 |
Bruker APEX CCD area-detector diffractometer | 2470 independent reflections |
Radiation source: fine-focus sealed tube | 1649 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.091 |
φ and ω scans | θmax = 28.0°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2001) | h = −34→34 |
Tmin = 0.972, Tmax = 0.986 | k = −7→7 |
9695 measured reflections | l = −24→21 |
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)] = 0.058 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.137 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.99 | w = 1/[σ2(Fo2) + (0.061P)2] where P = (Fo2 + 2Fc2)/3 |
2470 reflections | (Δ/σ)max < 0.001 |
163 parameters | Δρmax = 0.32 e Å−3 |
6 restraints | Δρmin = −0.33 e Å−3 |
22 constraints |
C6H9N4+·C2HO4− | V = 2079.9 (4) Å3 |
Mr = 226.20 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 26.634 (3) Å | µ = 0.12 mm−1 |
b = 5.6454 (7) Å | T = 299 K |
c = 18.337 (2) Å | 0.24 × 0.24 × 0.12 mm |
β = 131.030 (2)° |
Bruker APEX CCD area-detector diffractometer | 2470 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2001) | 1649 reflections with I > 2σ(I) |
Tmin = 0.972, Tmax = 0.986 | Rint = 0.091 |
9695 measured reflections |
R[F2 > 2σ(F2)] = 0.058 | 6 restraints |
wR(F2) = 0.137 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.99 | Δρmax = 0.32 e Å−3 |
2470 reflections | Δρmin = −0.33 e Å−3 |
163 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 | ||
N1 | 0.19244 (10) | 0.5643 (4) | 0.56883 (16) | 0.0487 (6) | |
N2 | 0.06855 (10) | 0.6941 (3) | 0.58191 (15) | 0.0361 (5) | |
H2A | 0.0365 (9) | 0.797 (3) | 0.5560 (16) | 0.043* | |
H2B | 0.0798 (11) | 0.609 (4) | 0.6303 (12) | 0.043* | |
N3 | 0.07582 (9) | 0.7962 (3) | 0.46892 (14) | 0.0299 (4) | |
H3 | 0.0878 (10) | 0.761 (4) | 0.4353 (14) | 0.036* | |
N4 | 0.02341 (9) | 0.9613 (3) | 0.42661 (13) | 0.0298 (4) | |
H4A | −0.0122 (8) | 0.887 (4) | 0.3731 (11) | 0.036* | |
H4B | 0.0319 (11) | 1.073 (3) | 0.4017 (15) | 0.036* | |
C1 | 0.09544 (10) | 0.6720 (3) | 0.54292 (15) | 0.0259 (5) | |
C2 | 0.15045 (10) | 0.5003 (4) | 0.58226 (15) | 0.0304 (5) | |
C4 | 0.15572 (11) | 0.2932 (4) | 0.62603 (16) | 0.0339 (5) | |
H4 | 0.1258 | 0.2573 | 0.6347 | 0.041* | |
C5 | 0.20684 (12) | 0.1395 (4) | 0.65693 (18) | 0.0446 (6) | |
H5 | 0.2114 | −0.0039 | 0.6857 | 0.054* | |
C6 | 0.25023 (13) | 0.2003 (5) | 0.6447 (2) | 0.0542 (8) | |
H6 | 0.2852 | 0.1002 | 0.6657 | 0.065* | |
C7 | 0.24161 (14) | 0.4136 (5) | 0.6005 (2) | 0.0624 (8) | |
H7 | 0.2716 | 0.4538 | 0.5925 | 0.075* | |
O1 | 0.06808 (8) | 0.3398 (2) | 0.36510 (12) | 0.0411 (4) | |
O2 | 0.09533 (8) | 0.1966 (2) | 0.28170 (12) | 0.0367 (4) | |
H2C | 0.0937 (12) | 0.061 (2) | 0.2986 (17) | 0.044* | |
O3 | 0.08940 (9) | 0.7835 (2) | 0.33181 (13) | 0.0412 (4) | |
O4 | 0.08870 (8) | 0.6301 (2) | 0.21993 (12) | 0.0379 (4) | |
C8 | 0.08279 (10) | 0.3658 (3) | 0.31594 (15) | 0.0247 (4) | |
C9 | 0.08774 (10) | 0.6146 (3) | 0.28618 (15) | 0.0253 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0439 (12) | 0.0554 (14) | 0.0590 (15) | 0.0103 (10) | 0.0391 (12) | 0.0110 (11) |
N2 | 0.0506 (12) | 0.0368 (11) | 0.0381 (12) | 0.0156 (9) | 0.0367 (11) | 0.0144 (9) |
N3 | 0.0409 (10) | 0.0308 (9) | 0.0322 (10) | 0.0089 (8) | 0.0301 (9) | 0.0058 (8) |
N4 | 0.0398 (10) | 0.0260 (9) | 0.0305 (11) | 0.0060 (8) | 0.0261 (9) | 0.0054 (8) |
C1 | 0.0311 (11) | 0.0245 (10) | 0.0250 (11) | −0.0007 (8) | 0.0196 (9) | −0.0023 (9) |
C2 | 0.0320 (11) | 0.0309 (11) | 0.0280 (12) | 0.0029 (9) | 0.0197 (10) | −0.0018 (9) |
C4 | 0.0371 (12) | 0.0324 (11) | 0.0340 (13) | 0.0007 (10) | 0.0242 (11) | −0.0020 (10) |
C5 | 0.0458 (14) | 0.0320 (12) | 0.0431 (15) | 0.0079 (11) | 0.0236 (13) | 0.0038 (11) |
C6 | 0.0442 (15) | 0.0547 (17) | 0.0614 (19) | 0.0198 (13) | 0.0337 (15) | 0.0057 (15) |
C7 | 0.0500 (16) | 0.074 (2) | 0.079 (2) | 0.0152 (15) | 0.0497 (17) | 0.0138 (17) |
O1 | 0.0732 (12) | 0.0269 (8) | 0.0515 (11) | −0.0049 (8) | 0.0533 (11) | −0.0008 (7) |
O2 | 0.0617 (11) | 0.0166 (7) | 0.0540 (11) | 0.0023 (7) | 0.0476 (10) | 0.0019 (7) |
O3 | 0.0825 (12) | 0.0186 (7) | 0.0527 (11) | 0.0015 (8) | 0.0575 (10) | −0.0015 (7) |
O4 | 0.0702 (11) | 0.0256 (8) | 0.0444 (10) | 0.0013 (7) | 0.0490 (10) | 0.0016 (7) |
C8 | 0.0320 (11) | 0.0209 (9) | 0.0259 (11) | −0.0005 (8) | 0.0211 (10) | −0.0009 (9) |
C9 | 0.0351 (11) | 0.0203 (10) | 0.0312 (12) | 0.0026 (8) | 0.0263 (10) | 0.0030 (9) |
N1—C7 | 1.333 (3) | C4—H4 | 0.9300 |
N1—C2 | 1.343 (3) | C5—C6 | 1.358 (4) |
N2—C1 | 1.308 (3) | C5—H5 | 0.9300 |
N2—H2A | 0.871 (10) | C6—C7 | 1.384 (4) |
N2—H2B | 0.870 (10) | C6—H6 | 0.9300 |
N3—C1 | 1.294 (3) | C7—H7 | 0.9300 |
N3—N4 | 1.413 (2) | O1—C8 | 1.205 (2) |
N3—H3 | 0.882 (9) | O2—C8 | 1.301 (2) |
N4—H4A | 0.904 (9) | O2—H2C | 0.837 (10) |
N4—H4B | 0.891 (9) | O3—C9 | 1.250 (2) |
C1—C2 | 1.489 (3) | O4—C9 | 1.235 (2) |
C2—C4 | 1.372 (3) | C8—C9 | 1.543 (3) |
C4—C5 | 1.384 (3) | ||
C7—N1—C2 | 116.5 (2) | C5—C4—H4 | 121.0 |
C1—N2—H2A | 117.2 (16) | C6—C5—C4 | 119.3 (2) |
C1—N2—H2B | 124.0 (16) | C6—C5—H5 | 120.4 |
H2A—N2—H2B | 119 (2) | C4—C5—H5 | 120.4 |
C1—N3—N4 | 120.41 (17) | C5—C6—C7 | 119.0 (2) |
C1—N3—H3 | 122.0 (15) | C5—C6—H6 | 120.5 |
N4—N3—H3 | 116.3 (15) | C7—C6—H6 | 120.5 |
N3—N4—H4A | 104.2 (14) | N1—C7—C6 | 123.3 (3) |
N3—N4—H4B | 105.0 (14) | N1—C7—H7 | 118.4 |
H4A—N4—H4B | 102 (2) | C6—C7—H7 | 118.4 |
N3—C1—N2 | 122.16 (19) | C8—O2—H2C | 113.5 (17) |
N3—C1—C2 | 116.87 (18) | O1—C8—O2 | 125.73 (18) |
N2—C1—C2 | 120.97 (19) | O1—C8—C9 | 121.40 (17) |
N1—C2—C4 | 124.0 (2) | O2—C8—C9 | 112.87 (17) |
N1—C2—C1 | 114.14 (19) | O4—C9—O3 | 126.15 (19) |
C4—C2—C1 | 121.87 (19) | O4—C9—C8 | 118.31 (17) |
C2—C4—C5 | 118.0 (2) | O3—C9—C8 | 115.53 (18) |
C2—C4—H4 | 121.0 | ||
N4—N3—C1—N2 | −0.5 (3) | C1—C2—C4—C5 | 177.4 (2) |
N4—N3—C1—C2 | 179.35 (18) | C2—C4—C5—C6 | 1.3 (4) |
C7—N1—C2—C4 | 0.2 (4) | C4—C5—C6—C7 | −0.8 (4) |
C7—N1—C2—C1 | −178.3 (2) | C2—N1—C7—C6 | 0.4 (5) |
N3—C1—C2—N1 | 29.1 (3) | C5—C6—C7—N1 | −0.1 (5) |
N2—C1—C2—N1 | −151.0 (2) | O1—C8—C9—O4 | −164.6 (2) |
N3—C1—C2—C4 | −149.4 (2) | O2—C8—C9—O4 | 14.7 (3) |
N2—C1—C2—C4 | 30.5 (3) | O1—C8—C9—O3 | 14.3 (3) |
N1—C2—C4—C5 | −1.0 (4) | O2—C8—C9—O3 | −166.32 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···N4i | 0.87 (1) | 2.28 (2) | 3.051 (3) | 148 (2) |
N2—H2B···O4ii | 0.87 (1) | 2.02 (1) | 2.874 (2) | 168 (2) |
N4—H4A···O4iii | 0.90 (1) | 2.15 (1) | 3.016 (2) | 162 (2) |
N4—H4B···O1iv | 0.89 (1) | 2.12 (1) | 3.002 (2) | 171 (2) |
O2—H2C···O3v | 0.84 (1) | 1.71 (1) | 2.550 (2) | 179 (4) |
N3—H3···O3 | 0.88 (1) | 1.93 (1) | 2.766 (2) | 158 (2) |
N3—H3···O1 | 0.88 (1) | 2.59 (2) | 3.129 (2) | 120 (2) |
C4—H4···O4ii | 0.93 | 2.42 | 3.221 (4) | 144 |
Symmetry codes: (i) −x, −y+2, −z+1; (ii) x, −y+1, z+1/2; (iii) −x, y, −z+1/2; (iv) x, y+1, z; (v) x, y−1, z. |
Experimental details
Crystal data | |
Chemical formula | C6H9N4+·C2HO4− |
Mr | 226.20 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 299 |
a, b, c (Å) | 26.634 (3), 5.6454 (7), 18.337 (2) |
β (°) | 131.030 (2) |
V (Å3) | 2079.9 (4) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.12 |
Crystal size (mm) | 0.24 × 0.24 × 0.12 |
Data collection | |
Diffractometer | Bruker APEX CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2001) |
Tmin, Tmax | 0.972, 0.986 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9695, 2470, 1649 |
Rint | 0.091 |
(sin θ/λ)max (Å−1) | 0.661 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.058, 0.137, 0.99 |
No. of reflections | 2470 |
No. of parameters | 163 |
No. of restraints | 6 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.32, −0.33 |
Computer programs: SMART (Bruker, 2000), SMART, SAINT (Bruker, 2000), SHELXTL (Bruker, 2000), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···N4i | 0.871 (10) | 2.277 (15) | 3.051 (3) | 148 (2) |
N2—H2B···O4ii | 0.870 (10) | 2.018 (11) | 2.874 (2) | 168 (2) |
N4—H4A···O4iii | 0.904 (9) | 2.145 (12) | 3.016 (2) | 162 (2) |
N4—H4B···O1iv | 0.891 (9) | 2.120 (10) | 3.002 (2) | 171 (2) |
O2—H2C···O3v | 0.837 (10) | 1.713 (10) | 2.550 (2) | 179 (4) |
N3—H3···O3 | 0.882 (9) | 1.930 (12) | 2.766 (2) | 158 (2) |
N3—H3···O1 | 0.882 (9) | 2.59 (2) | 3.129 (2) | 120.3 (17) |
C4—H4···O4ii | 0.93 | 2.42 | 3.221 (4) | 144 |
Symmetry codes: (i) −x, −y+2, −z+1; (ii) x, −y+1, z+1/2; (iii) −x, y, −z+1/2; (iv) x, y+1, z; (v) x, y−1, z. |
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Pyridinecarboxamidrazones are well studied, due to their high antituberculosis activities (Banachiewicz et al., 2004). As a part of our investigation of the reactions of 2-pyridinecarboxamidrazone with dicarboxylic acids, we report the crystal structure of the title compound, (I).
Unlike other similar semi-oxalate complexes (Krishnakumar et al., 2002; Subha Nandhini et al., 2001; Ejsmont, 2007) the hydrogenoxalate ion in (I) is not planar. The dihedral angle O1—C8—C9—O3 is 14.49 (16)°. In the cation, the dihedral angle N2—C1—C2—N1 is -151.1 (2)°.