Pyridine-2-carboxamidrazonium hydrogenoxalate

Wang, M.; Hu, B.; Wang, X.-Y.; Wang, C.-G.; Cao, M.-N.

doi:10.1107/S160053680702822X

Pyridine-2-carboxamidrazonium hydrogenoxalate

M. Wang, B. Hu, X.-Y. Wang, C.-G. Wang and M.-N. Cao

In the title structure, C₆H₉N₄⁺·C₂HO₄⁻, there are O—H

O, N—H

N and N—H

O hydrogen bonds that form a three-dimensional network. The hydrogenoxalate anions are bonded by O—H

O hydrogen bonds to form chains parallel to the b axis. The pyridine-2-carboxamidrazonium cations are linked by the N—H

N bonds into dimeric centrosymmetric entities with an R₂²(10) motif. These dimers are connected to hydrogenoxalates via N—H

O hydrogen bonds. In addition, there is a weak C—H

O hydrogen bond, as well as a C—H

π interaction with the 2-pyridyl ring [C—H

Cg: C—H = 0.93 Å, H

Cg = 2.90 Å, C

Cg = 3.581 (3) Å and C—H

Cg = 131°; Cg is the centroid of the 2-pyridyl ring at ( ${1\over 2}$ − x, − ${1\over 2}$ + y, ${3\over 2}$ − z)]. It is interesting to note that the two NH₂ groups in the structure occur both in planar and pyramidal arrangements.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680702822X/fb2050sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S160053680702822X/fb2050Isup2.hkl Contains datablock I

CCDC reference: 654957

checkCIF report

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

Comment top

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)°.

Related literature top

For related literature, see: Banachiewicz & Banachiewicz (2004); Case (1965); Ejsmont (2007); Krishnakumar et al. (2002); Subha Nandhini et al. (2001); Etter et al. (1990).

Experimental top

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.

Structure description top

For related literature, see: Banachiewicz & Banachiewicz (2004); Case (1965); Ejsmont (2007); Krishnakumar et al. (2002); Subha Nandhini et al. (2001); Etter et al. (1990).

Computing details top

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.

Figures top

	Fig. 1. The title molecules of the asymmetric unit with displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. Packing diagram of the title molecule viewed down the b axis, showing the formation of columns.

Pyridine-2-carboxamidrazonium hydrogenoxalate top

Crystal data top

C₆H₉N₄⁺·C₂HO₄⁻	F(000) = 944
M_r = 226.20	D_x = 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

Data collection top

Bruker APEX CCD area-detector diffractometer	2470 independent reflections
Radiation source: fine-focus sealed tube	1649 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.091
φ and ω scans	θ_max = 28.0°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	h = −34→34
T_min = 0.972, T_max = 0.986	k = −7→7
9695 measured reflections	l = −24→21

Refinement top

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(F_o²) + (0.061P)²] where P = (F_o² + 2F_c²)/3
2470 reflections	(Δ/σ)_max < 0.001
163 parameters	Δρ_max = 0.32 e Å⁻³
6 restraints	Δρ_min = −0.33 e Å⁻³
22 constraints

Crystal data top

C₆H₉N₄⁺·C₂HO₄⁻	V = 2079.9 (4) Å³
M_r = 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)°

Data collection top

Bruker APEX CCD area-detector diffractometer	2470 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	1649 reflections with I > 2σ(I)
T_min = 0.972, T_max = 0.986	R_int = 0.091
9695 measured reflections

Refinement top

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	Δρ_max = 0.32 e Å⁻³
2470 reflections	Δρ_min = −0.33 e Å⁻³
163 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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)

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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···O1^iv	0.89 (1)	2.12 (1)	3.002 (2)	171 (2)
O2—H2C···O3^v	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⁻
M_r	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)
T_min, T_max	0.972, 0.986
No. of measured, independent and observed [I > 2σ(I)] reflections	9695, 2470, 1649
R_int	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
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.33

Computer programs: SMART (Bruker, 2000), SMART, SAINT (Bruker, 2000), SHELXTL (Bruker, 2000), SHELXTL.

Hydrogen-bond geometry (Å, º) top

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···O1^iv	0.891 (9)	2.120 (10)	3.002 (2)	171 (2)
O2—H2C···O3^v	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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