6-Hydrazinylnicotinic acid: a powder study.

The structure of the title compound, C(6)H(7)N(3)O(2), is of inter-est with respect to radiopharmacueticals. The crystal packing is characterized by N-H⋯O and O-H⋯N hydrogen bonds, which form a three-dimensional network. The molecule is planar except for one of the amine H atoms.

Related literature

For background on radiopharmacueticals, see: Callahan et al. (1996 ▶); Rennen et al. (2000 ▶). For general background, see: Abrams et al. (1990 ▶). For details of the synthesis, see: Schwartz et al. (1995 ▶). For geometric data, see: Allen et al. (1987 ▶). For descriptions of the powder diffraction profile, see: Thompson et al. (1987 ▶); Finger et al. (1994 ▶); Stephens (1999 ▶); Von Dreele (1997 ▶). For refinement by the LeBail method, see: Le Bail et al. (1988 ▶).

Experimental

Crystal data

C6H7N3O2

M = 153.15

Monoclinic,

a = 6.69930 (14) Å

b = 13.8834 (2) Å

c = 7.10677 (9) Å

β = 91.7805 (11)°

V = 660.67 (2) Å3

Z = 4

Cu Kα1 radiation

λ = 1.5406 Å

μ = 1.01 mm−1

T = 298 K

Flat sheet, 8 × 8 mm

Data collection

Stoe STADI P diffractometer

Specimen mounting: powder loaded between two Mylar foils

Data collection mode: transmission

Scan method: step

Absorption correction: for a cylinder mounted on the ϕ axis [flat-plate transmission absorption correction (GSAS absorption/surface roughness correction function number 4 with a non-refined term of μd = 0.1482)] T min = 0.732, T max = 0.795

2θmin = 9.969°, 2θmax = 84.949°, 2θstep = 0.02°

Refinement

R p = 0.023

R wp = 0.030

R exp = 0.021

R(F 2) = 0.01796

χ2 = 2.016

4250 data points

146 parameters

26 restraints

Only H-atom coordinates refined

Data collection: WinXPOW (Stoe & Cie, 1999 ▶); cell refinement: FULLPROF (Rodriguez-Carvajal, 2001 ▶) and GSAS (Larson & Von Dreele, 2004 ▶); data reduction: WinXPOW, DICVOL04 (Boultif & Louër, 2004 ▶), and CheckGroup interfaced by WinPLOTR (Roisnel & Rodriguez-Carvajal, 2001 ▶); program(s) used to solve structure: EXPO2009 (Altomare et al., 2009 ▶); program(s) used to refine structure: GSAS interfaced by EXPGUI (Toby, 2001 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S160053681200637X/fy2040sup1.cif

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C6H7N3O2	F(000) = 320
Mr = 153.15	Dx = 1.54 Mg m−3
Monoclinic, P21/c	Cu Kα1 radiation, λ = 1.5406 Å
Hall symbol: -P 2ybc	µ = 1.01 mm−1
a = 6.69930 (14) Å	T = 298 K
b = 13.8834 (2) Å	Particle morphology: Fine powder
c = 7.10677 (9) Å	pale brown
β = 91.7805 (11)°	flat sheet, 8 × 8 mm
V = 660.67 (2) Å3	Specimen preparation: Prepared at 298 K and 101.3 kPa
Z = 4

Stoe STADI P diffractometer	Scan method: step
Radiation source: sealed X-ray tube	Absorption correction: for a cylinder mounted on the φ axis [Flat-plate transmission absorption correction (GSAS absorption/surface roughness correction function number 4 with a non-refined term of µd = 0.1482)]
Curved Ge(111) monochromator	Tmin = 0.732, Tmax = 0.795
Specimen mounting: powder loaded between two Mylar foils	2θmin = 9.969°, 2θmax = 84.949°, 2θstep = 0.02°
Data collection mode: transmission

Least-squares matrix: full	146 parameters
Rp = 0.023	26 restraints
Rwp = 0.030	Primary atom site location: structure-invariant direct methods
Rexp = 0.021	Secondary atom site location: difference Fourier map
R(F2) = 0.01796	Hydrogen site location: difference Fourier map
χ2 = 2.016	Only H-atom coordinates refined
4250 data points	(Δ/σ)max = 0.03
Excluded region(s): The use of the excluded region from 85 to 95° (2θ) leads to better molecular geometry.	Background function: Shifted Chebyshev function of 1st kind (GSAS Background function number 1) with 15 terms 1: 1800.66 2: -1847.80 3: 941.880 4: -249.680 5: 12.6164 6: 58.5368 7: -22.4573 8: -39.9081 9: 32.2315 10: 0.665645 11: -20.8095 12: 16.0647 13: -6.68008 14: -5.95330 15: 5.95798
Profile function: GSAS CW profile function number 4 with 21 terms, i.e., pseudovoigt profile coefficients as parameterized in (Thompson et al., 1987), asymmetry correction of Finger et al. (1994) and microstrain broadening by Stephens (1999). #1(GU) = 0.000 #2(GV) = 0.000 #3(GW) = 8.378 #4(GP) = 0.000 #5(LX) = 1.698 #6(ptec) = 0.00 #7(trns) = 0.00 #8(shft) = 0.0000 #9(sfec) = 0.00 #10(S/L) = 0.0225 #11(H/L) = 0.0228 #12(eta) = 0.6000 #13(S400 ) = 2.2E-01 #14(S040 ) = 3.7E-03 #15(S004 ) = 4.3E-01 #16(S220 ) = 3.8E-02 #17(S202 ) = 2.3E-01 #18(S022 ) = 5.1E-01 #19(S301 ) = -2.6E-01 #20(S103 ) = 1.6E-01 #21(S121 ) = -1.9E-01. Peak tails are ignored where the intensity is below 0.0010 times the peak. Aniso. broadening axis 0.0 0.0 1.0	Preferred orientation correction: spherical hamonics function

Experimental. The sample was ground lightly in a mortar, loaded between two Mylar foils and fixed in the sample holder with a mask of 8.0 mm internal diameter.

	x	y	z	Uiso*/Ueq
C1	0.0949 (15)	0.0911 (6)	0.7824 (15)	0.025 (3)*
C2	0.3019 (11)	0.0838 (5)	0.8434 (12)	0.024 (3)*
C3	0.4127 (11)	0.1653 (6)	0.8763 (12)	0.035 (4)*
C4	0.3286 (12)	0.2568 (6)	0.8428 (14)	0.018 (3)*
C5	0.0146 (12)	0.1829 (7)	0.7521 (12)	0.039 (5)*
C6	−0.035 (2)	0.0069 (9)	0.7503 (17)	0.047 (4)*
N1	0.1331 (11)	0.2628 (5)	0.7828 (11)	0.026 (3)*
N2	0.4164 (12)	0.3424 (4)	0.8716 (12)	0.034 (3)*
N3	0.6139 (10)	0.3455 (6)	0.9453 (13)	0.050 (3)*
O1	−0.2097 (8)	0.0126 (4)	0.7110 (10)	0.032 (3)*
O2	0.0600 (8)	−0.0758 (5)	0.7824 (11)	0.043 (3)*
H2	0.362 (2)	0.0198 (11)	0.869 (3)	0.029 (4)*
H3	0.554 (3)	0.1597 (10)	0.917 (3)	0.042 (4)*
H5	−0.127 (3)	0.1905 (12)	0.707 (3)	0.047 (5)*
H1N2	0.364 (4)	0.3948 (12)	0.816 (6)	0.052 (4)*
H1N3	0.696 (2)	0.325 (5)	0.861 (5)	0.075 (5)*
H2N3	0.644 (4)	0.4040 (17)	0.977 (10)	0.075 (5)*
H1O2	−0.018 (3)	−0.1211 (10)	0.768 (4)	0.065 (4)*

C1—C2	1.444 (10)	C6—C1	1.471 (15)
C2—C3	1.369 (9)	C6—O1	1.198 (12)
C2—H2	0.990 (14)	C6—O2	1.328 (11)
C3—C4	1.407 (10)	N2—C4	1.339 (7)
C3—H3	0.981 (14)	N2—N3	1.409 (7)
C4—N1	1.367 (9)	N2—H1N2	0.89 (3)
N1—C5	1.378 (9)	N3—H1N3	0.87 (3)
C5—C1	1.397 (12)	N3—H2N3	0.87 (3)
C5—H5	0.997 (14)	O2—H1O2	0.824 (14)
C2—C1—C5	118.2 (7)	C1—C5—H5	120.3 (13)
C2—C1—C6	123.3 (9)	N1—C5—H5	120.2 (13)
C5—C1—C6	118.6 (9)	C1—C6—O1	123.5 (12)
C1—C2—C3	120.3 (6)	C1—C6—O2	112.5 (10)
C1—C2—H2	119.9 (6)	O1—C6—O2	123.8 (13)
C3—C2—H2	119.7 (6)	C4—N1—C5	122.8 (8)
C2—C3—C4	120.3 (7)	C4—N2—N3	119.2 (7)
C2—C3—H3	119.8 (6)	C4—N2—H1N2	119 (2)
C4—C3—H3	119.8 (6)	N3—N2—H1N2	119.4 (18)
C3—C4—N1	118.9 (7)	N2—N3—H1N3	110 (2)
C3—C4—N2	127.1 (8)	N2—N3—H2N3	110 (2)
N1—C4—N2	113.9 (8)	H1N3—N3—H2N3	110 (5)
C1—C5—N1	119.5 (6)	C6—O2—H1O2	109.9 (15)
C4—N1—C5—C1	−0.1 (13)	C5—C1—C2—C3	2.2 (14)
C5—N1—C4—N2	−177.5 (8)	C2—C1—C6—O2	−0.5 (15)
C5—N1—C4—C3	−0.5 (13)	C5—C1—C6—O1	−4.9 (17)
N3—N2—C4—N1	175.9 (8)	C2—C1—C6—O1	175.2 (10)
N3—N2—C4—C3	−0.8 (15)	C5—C1—C6—O2	179.4 (9)
C2—C1—C5—N1	−0.7 (13)	C1—C2—C3—C4	−2.9 (13)
C6—C1—C5—N1	179.5 (9)	C2—C3—C4—N2	178.6 (9)
C6—C1—C2—C3	−178.0 (10)	C2—C3—C4—N1	2.1 (13)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1N2···O1i	0.89 (3)	1.94 (2)	2.792 (8)	158 (4)
N3—H1N3···O2ii	0.87 (3)	2.39 (4)	2.967 (10)	124 (6)
N3—H2N3···O1iii	0.87 (3)	2.23 (6)	2.950 (11)	141 (5)
O2—H1O2···N1iv	0.822 (15)	1.818 (16)	2.622 (10)	165.2 (18)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1N2⋯O1i	0.89 (3)	1.94 (2)	2.792 (8)	158 (4)
N3—H1N3⋯O2ii	0.87 (3)	2.39 (4)	2.967 (10)	124 (6)
N3—H2N3⋯O1iii	0.87 (3)	2.23 (6)	2.950 (11)	141 (5)
O2—H1O2⋯N1iv	0.822 (15)	1.818 (16)	2.622 (10)	165.2 (18)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .