1H-Nicotinamidium 3,5-di­nitro­salicyl­ate

The crystal and molecular structure of the title compound, C₆H₇N₂O⁺·C₇H₃N₂O₇^-, has been studied by single-crystal X-ray diffraction at 293 (2) K. The structure consists of pairs of 1H-nicotinamidium cations and 3,5-di­nitro­salicyl­ato anions which are held together by ionic interactions and by additional hydrogen-bond interactions. The ions are also held together by weaker hydrogen bonds and by van der Waals interactions.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.040
• wR factor = 0.110
• Data-to-parameter ratio = 9.6

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level A:



PLAT_305  Alert A Isolated Hydrogen Atom (Outside Bond Range ??)      <H(3')


 Alert Level B:



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           65.10
         From the CIF: _reflns_number_total               2212
         TEST2: Reflns within _diffrn_reflns_theta_max
         Count of symmetry unique reflns         2466
         Completeness (_total/calc)             89.70%
          Alert B: < 90% complete (theta max?)

PLAT_420  Alert B D-H Without Acceptor       O(2)   -  >H(3)              ?


 Alert Level C:



REFNR_01  Alert C Ratio of reflections to parameters is < 10 for a
          centrosymmetric structure
          sine(theta)/lambda                0.5883
          Proportion of unique data used    1.0000
          Ratio reflections to parameters   9.5758

THETM_01  Alert C The value of sine(theta_max)/wavelength is less than 0.590
          Calculated sin(theta_max)/wavelength =    0.5883

General Notes



ABSTM_02  When printed, the submitted absorption T values will be replaced
          by the scaled T values. Since the ratio of scaled T's is
          identical to the ratio of reported T values, the scaling does
          not imply a change to the absorption corrections used in the
          study.
          Ratio of Tmax expected/reported      1.127
          Tmax scaled      0.835 Tmin scaled      0.613


 1 Alert Level A = Potentially serious problem

 2 Alert Level B = Potential problem

 2 Alert Level C = Please check

---

S1. Comment

As part of our study of new copper(II) complexes with 3,5-dinitrosalicylate anions and nicotinamide, the title compound, (I), was prepared. Later, the same compound were also prepared by reaction of nicotinamide with 3,5-dinitrosalicylic acid in water solution. To our knowledge, salt formation is typical for 3,5-dinitrosalicylic acid, e.g. with 3-amino-1,2,4-triazole (Smith et al., 1996) or even with different aminobenzoic acids (Smith et al., 1995).

Neighbouring protonated molecules of nicotinamide and 3,5-dinitrosalicylate anions form dimers via hydrogen bonds N4—H41···O1^iv (see Table 2). Additional hydrogen bonds are formed by the amide H atoms of the nicotinamide cation and by the O atom of the nitro groups of the salicylate anion (Table 2). Atom H3 forms an intramolecular hydrogen bond with atoms O2 and O3. Atom O3 is statistically distributed between two positions.

S2. Experimental

Crystals of the title compound suitable for X-ray crystal structure analysis were obtained by slow crystallization of the yellow–green reaction mixture containing copper(II) sulfate (0.0926 g CuSO₄·5H₂O, 0.37 mmol), 3,5-dinitrosalicylic acid (0.2811 g, 0.74 mmol) and nicotinamide (0.186 g, 1.52 mmol) in water solution (50 ml) in an Erlenmayer flask at room temperature for three months.

S3. Refinement

The O atom of the hydroxide group is disordered, occupying two statistic positions represented by O3 and O3' with occupancy factors of 0.758 (5) and 0.242 (5), respectively. Atom O3 was refined anisotropically and O3' isotropically. The crystal structure of the title compound was also recalculated by two other ways. For atom O3 (anisotropic refinement) in a single position, R1 = 0.0707 for 1631 reflections and Δρ_max = 1.58 e Å⁻³. For statistically distributed atom O3 (isotropically refined), R1 and Δρ_max were 0.0444 and 0.43 e Å⁻³, respectively. The H atoms were placed in calculated positions, except for H3, which was located from a difference Fourier map.

Computing details

Data collection: Syntax P2₁ Software (Syntex, 1974); cell refinement: Syntax P2₁ Software; data reduction: XP21 (Pavelčík, 1993); program(s) used to solve structure: SHELXS86 (Sheldrick, 1985); program(s) used to refine structure: SHELXL93 (Sheldrick, 1994); molecular graphics: ORTEP (Johnson, 1965); software used to prepare material for publication: SHELXL93.

Figures

Fig. 1. The anion and cation in the crystal structure of the title compound. Displacement ellipsoids are drawn at the 35% probability level and H atoms are shown as spheres of arbitary radii. The statistical atoms O3' and H3' have been omited for clarity.

1H-nicotinamidium 3,5-dinitrosalicylate

Crystal data

C6H7N2O^+·C7H3N2O7^−	Dx = 1.617 Mg m^−3
Mr = 350.25	Melting point: 458 K
Monoclinic, P21/n	Cu Kα radiation, λ = 1.54180 Å
a = 4.740 (1) Å	Cell parameters from 25 reflections
b = 21.968 (4) Å	θ = 4.5–11.8°
c = 13.858 (3) Å	µ = 1.20 mm^−1
β = 94.62 (3)°	T = 293 K
V = 1438.3 (5) Å^3	Needle, yellow
Z = 4	0.40 × 0.20 × 0.15 mm
F(000) = 720

Data collection

Syntex P21 diffractometer	1631 reflections with I > 2˘I)
Radiation source: fine-focus sealed tube	Rint = 0.031
Graphite monochromator	θmax = 65.1°, θmin = 3.8°
θ–2θ scans	h = −5→2
Absorption correction: ψ scan (North et al., 1968)	k = 0→25
Tmin = 0.544, Tmax = 0.741	l = −16→16
3511 measured reflections	2 standard reflections every 100 reflections
2212 independent reflections	intensity decay: 15%

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.110	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0618P)^2 + 0.1656P] where P = (Fo^2 + 2Fc^2)/3
2212 reflections	(Δ/σ)max < 0.001
231 parameters	Δρmax = 0.15 e Å^−3
0 restraints	Δρmin = −0.18 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1	0.1009 (3)	0.61448 (7)	0.90611 (10)	0.0531 (4)
O2	0.0081 (4)	0.67232 (7)	0.77654 (11)	0.0593 (5)
O3	0.2416 (5)	0.65338 (10)	0.62978 (14)	0.0598 (8)	0.756 (5)
O3'	0.4525 (12)	0.5346 (3)	0.9078 (4)	0.049 (2)*	0.244 (5)
O4	0.4483 (6)	0.61849 (12)	0.47593 (14)	0.0961 (8)
O5	0.7735 (6)	0.55335 (13)	0.48105 (16)	0.1091 (9)
O6	1.0494 (4)	0.44392 (8)	0.76707 (17)	0.0766 (6)
O7	0.8103 (5)	0.44969 (9)	0.89099 (14)	0.0822 (6)
O8	−0.4078 (3)	0.80338 (7)	0.72734 (10)	0.0483 (4)
N1	0.5982 (5)	0.58166 (9)	0.51934 (13)	0.0545 (5)
N2	0.8625 (4)	0.46639 (8)	0.81108 (15)	0.0527 (5)
N3	0.0148 (4)	0.84673 (9)	0.76834 (12)	0.0486 (5)
N4	0.2075 (4)	0.82145 (8)	0.48136 (11)	0.0417 (4)
C1	0.3446 (4)	0.59331 (8)	0.76774 (13)	0.0374 (4)
C2	0.3772 (4)	0.60750 (8)	0.67004 (13)	0.0401 (4)
C3	0.5656 (5)	0.57173 (9)	0.62151 (14)	0.0421 (5)
C4	0.7235 (5)	0.52589 (9)	0.66740 (15)	0.0440 (5)
C5	0.6888 (4)	0.51422 (8)	0.76299 (15)	0.0409 (5)
C6	0.4990 (4)	0.54693 (8)	0.81421 (13)	0.0396 (4)
C7	0.1375 (5)	0.62926 (9)	0.82058 (14)	0.0429 (5)
C8	−0.0685 (4)	0.80166 (8)	0.61132 (13)	0.0349 (4)
C9	0.1295 (4)	0.83650 (8)	0.56883 (13)	0.0378 (4)
C10	0.1022 (5)	0.77346 (10)	0.43197 (14)	0.0487 (5)
C11	−0.0966 (5)	0.73825 (10)	0.47096 (16)	0.0551 (6)
C12	−0.1842 (5)	0.75225 (9)	0.56066 (15)	0.0445 (5)
C13	−0.1675 (4)	0.81733 (9)	0.70847 (13)	0.0372 (4)
H3	0.1131	0.6712	0.7090	0.050*	0.76
H3'	0.2913	0.5630	0.9303	0.050*	0.24
H4	0.8527	0.5034	0.6347	0.050*
H6	0.4753	0.5377	0.8786	0.050*
H9	0.2072	0.8702	0.6011	0.050*
H10	0.1642	0.7639	0.3716	0.050*
H11	−0.1711	0.7047	0.4365	0.050*
H12	−0.3232	0.7291	0.5869	0.050*
H31	−0.0332	0.8576	0.8245	0.050*
H32	0.1790	0.8558	0.7509	0.050*
H41	0.3310	0.8441	0.4561	0.050*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0586 (10)	0.0660 (9)	0.0370 (8)	0.0080 (7)	0.0174 (7)	0.0003 (6)
O2	0.0709 (11)	0.0599 (10)	0.0490 (9)	0.0242 (8)	0.0169 (8)	0.0055 (7)
O3	0.0790 (17)	0.0604 (13)	0.0404 (12)	0.0208 (11)	0.0076 (10)	0.0139 (9)
O4	0.130 (2)	0.1174 (17)	0.0435 (10)	0.0287 (15)	0.0240 (11)	0.0298 (11)
O5	0.141 (2)	0.136 (2)	0.0572 (11)	0.0480 (17)	0.0518 (13)	0.0005 (12)
O6	0.0665 (12)	0.0561 (10)	0.1099 (16)	0.0213 (8)	0.0242 (11)	0.0127 (10)
O7	0.1089 (17)	0.0757 (12)	0.0615 (11)	0.0250 (11)	0.0040 (10)	0.0258 (10)
O8	0.0393 (8)	0.0639 (9)	0.0435 (8)	−0.0026 (7)	0.0150 (6)	0.0048 (7)
N1	0.0757 (14)	0.0542 (10)	0.0358 (9)	−0.0080 (10)	0.0176 (9)	−0.0021 (8)
N2	0.0538 (12)	0.0398 (9)	0.0637 (12)	0.0015 (8)	0.0007 (9)	0.0045 (8)
N3	0.0428 (11)	0.0746 (12)	0.0295 (8)	−0.0067 (8)	0.0102 (7)	−0.0069 (8)
N4	0.0417 (10)	0.0534 (9)	0.0311 (8)	0.0005 (7)	0.0096 (7)	0.0053 (7)
C1	0.0409 (11)	0.0397 (9)	0.0321 (9)	−0.0041 (8)	0.0064 (8)	−0.0003 (8)
C2	0.0496 (12)	0.0386 (10)	0.0324 (9)	−0.0002 (8)	0.0049 (8)	0.0023 (8)
C3	0.0543 (13)	0.0419 (10)	0.0314 (9)	−0.0057 (9)	0.0105 (8)	−0.0014 (8)
C4	0.0484 (12)	0.0377 (10)	0.0478 (11)	−0.0021 (9)	0.0157 (9)	−0.0046 (9)
C5	0.0440 (12)	0.0337 (9)	0.0450 (10)	−0.0011 (8)	0.0033 (8)	0.0027 (8)
C6	0.0462 (12)	0.0409 (10)	0.0317 (9)	−0.0060 (8)	0.0039 (8)	0.0037 (7)
C7	0.0485 (12)	0.0455 (10)	0.0358 (10)	−0.0021 (9)	0.0114 (9)	−0.0042 (8)
C8	0.0333 (10)	0.0410 (10)	0.0306 (8)	0.0020 (8)	0.0043 (7)	0.0033 (7)
C9	0.0394 (12)	0.0433 (10)	0.0309 (9)	−0.0001 (8)	0.0039 (8)	−0.0004 (7)
C10	0.0579 (14)	0.0574 (13)	0.0316 (9)	0.0061 (10)	0.0079 (9)	−0.0058 (9)
C11	0.0684 (16)	0.0495 (11)	0.0470 (12)	−0.0050 (11)	0.0031 (11)	−0.0125 (9)
C12	0.0484 (12)	0.0419 (10)	0.0436 (11)	−0.0073 (9)	0.0050 (9)	0.0001 (9)
C13	0.0392 (12)	0.0419 (10)	0.0310 (9)	0.0049 (8)	0.0069 (8)	0.0059 (7)

Geometric parameters (Å, º)

O1—C7	1.254 (2)	C1—C2	1.410 (3)
O2—C7	1.258 (3)	C1—C7	1.497 (3)
O3—C2	1.297 (3)	C2—C3	1.402 (3)
O4—N1	1.205 (3)	C3—C4	1.379 (3)
O5—N1	1.196 (3)	C4—C5	1.372 (3)
O6—N2	1.220 (3)	C4—H4	0.9317
O7—N2	1.211 (3)	C5—C6	1.390 (3)
O8—C13	1.228 (2)	C6—H6	0.9302
N1—C3	1.453 (3)	C8—C9	1.379 (3)
N2—C5	1.462 (3)	C8—C12	1.382 (3)
N3—C13	1.318 (3)	C8—C13	1.501 (2)
N3—H31	0.8622	C9—H9	0.9256
N3—H32	0.8565	C10—C11	1.364 (3)
N4—C9	1.337 (3)	C10—H10	0.9324
N4—C10	1.332 (3)	C11—C12	1.377 (3)
N4—H41	0.8637	C11—H11	0.9317
C1—C6	1.383 (3)	C12—H12	0.9299
C7—O1—H3'	106.6	C4—C5—C6	121.96 (19)
C7—O2—H3	99.2	C4—C5—N2	117.87 (18)
C2—O3—H3	96.6	C6—C5—N2	120.16 (18)
C6—O3'—H3'	109.9	O3'—C6—C1	118.1 (3)
C6—O3'—H6	5.5	O3'—C6—C5	123.0 (3)
H3'—O3'—H6	115.0	C1—C6—C5	118.88 (17)
O5—N1—O4	122.0 (2)	O3'—C6—H6	2.6
O5—N1—C3	119.1 (2)	C1—C6—H6	120.5
O4—N1—C3	118.8 (2)	C5—C6—H6	120.7
O7—N2—O6	123.0 (2)	O1—C7—O2	123.63 (18)
O7—N2—C5	119.1 (2)	O1—C7—C1	118.15 (19)
O6—N2—C5	117.9 (2)	O2—C7—C1	118.22 (17)
C13—N3—H31	119.8	C9—C8—C12	118.35 (17)
C13—N3—H32	120.1	C9—C8—C13	121.89 (17)
H31—N3—H32	120.1	C12—C8—C13	119.73 (17)
C9—N4—C10	122.82 (17)	N4—C9—C8	119.81 (18)
C9—N4—H41	118.1	N4—C9—H9	120.5
C10—N4—H41	119.1	C8—C9—H9	119.7
C6—C1—C2	121.02 (18)	N4—C10—C11	119.19 (18)
C6—C1—C7	120.29 (17)	N4—C10—H10	120.5
C2—C1—C7	118.68 (18)	C11—C10—H10	120.3
O3—C2—C3	122.82 (18)	C10—C11—C12	119.95 (19)
O3—C2—C1	119.74 (19)	C10—C11—H11	119.4
C3—C2—C1	117.40 (18)	C12—C11—H11	120.7
C4—C3—C2	122.08 (17)	C8—C12—C11	119.87 (19)
C4—C3—N1	117.56 (19)	C8—C12—H12	119.7
C2—C3—N1	120.35 (19)	C11—C12—H12	120.4
C5—C4—C3	118.61 (18)	O8—C13—N3	124.10 (18)
C5—C4—H4	120.3	O8—C13—C8	119.74 (18)
C3—C4—H4	121.0	N3—C13—C8	116.15 (17)
C6—C1—C2—O3	−176.2 (2)	C2—C1—C6—C5	0.1 (3)
C7—C1—C2—O3	4.2 (3)	C7—C1—C6—C5	179.73 (18)
C6—C1—C2—C3	1.7 (3)	C4—C5—C6—O3'	177.2 (3)
C7—C1—C2—C3	−177.91 (18)	N2—C5—C6—O3'	−3.8 (4)
O3—C2—C3—C4	175.2 (2)	C4—C5—C6—C1	−1.2 (3)
C1—C2—C3—C4	−2.6 (3)	N2—C5—C6—C1	177.80 (18)
O3—C2—C3—N1	−5.5 (3)	C6—C1—C7—O1	−2.8 (3)
C1—C2—C3—N1	176.67 (18)	C2—C1—C7—O1	176.84 (19)
O5—N1—C3—C4	−5.6 (3)	C6—C1—C7—O2	177.76 (19)
O4—N1—C3—C4	174.8 (2)	C2—C1—C7—O2	−2.6 (3)
O5—N1—C3—C2	175.1 (2)	C10—N4—C9—C8	−0.1 (3)
O4—N1—C3—C2	−4.5 (3)	C12—C8—C9—N4	−1.0 (3)
C2—C3—C4—C5	1.6 (3)	C13—C8—C9—N4	−178.76 (17)
N1—C3—C4—C5	−177.70 (18)	C9—N4—C10—C11	0.9 (3)
C3—C4—C5—C6	0.4 (3)	N4—C10—C11—C12	−0.5 (3)
C3—C4—C5—N2	−178.65 (17)	C9—C8—C12—C11	1.3 (3)
O7—N2—C5—C4	−170.3 (2)	C13—C8—C12—C11	179.13 (19)
O6—N2—C5—C4	7.7 (3)	C10—C11—C12—C8	−0.6 (3)
O7—N2—C5—C6	10.7 (3)	C9—C8—C13—O8	150.58 (19)
O6—N2—C5—C6	−171.4 (2)	C12—C8—C13—O8	−27.2 (3)
C2—C1—C6—O3'	−178.4 (3)	C9—C8—C13—N3	−28.4 (3)
C7—C1—C6—O3'	1.2 (4)	C12—C8—C13—N3	153.80 (19)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H31···O4^i	0.86	2.17	3.018 (2)	167
N3—H32···O8^ii	0.86	2.32	2.995 (2)	136
N3—H32···O6^iii	0.86	2.35	3.038 (3)	138
N4—H41···O1^iv	0.86	1.76	2.619 (2)	176

Symmetry codes: (i) x−1/2, −y+3/2, z+1/2; (ii) x+1, y, z; (iii) −x+3/2, y+1/2, −z+3/2; (iv) x+1/2, −y+3/2, z−1/2.