Crystal structure and Hirshfeld surface analysis of (E)-4-{[2-(4-hy­droxy­benzo­yl)hydrazin-1-yl­idene]meth­yl}pyridin-1-ium nitrate

The title aroyl hydrazone Schiff base salt, consists of one mol­ecular cation in the keto tautomeric form, adopting an E configuration with respect to the azomethine bond, and one nitrate anion.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.049
• wR factor = 0.149
• Data-to-parameter ratio = 16.6

checkCIF/PLATON results

No syntax errors found



Alert level C
DIFMX02_ALERT_1_C  The maximum difference density is > 0.1*ZMAX*0.75
            The relevant atom site should be identified.
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.96 Report
PLAT097_ALERT_2_C Large Reported Max.  (Positive) Residual Density       0.75 eA-3
PLAT244_ALERT_4_C Low    'Solvent' Ueq as Compared to Neighbors of         N4 Check
PLAT905_ALERT_3_C Negative K value in the Analysis of Variance ...     -2.409 Report

Alert level G
PLAT005_ALERT_5_G No Embedded Refinement Details Found  in the CIF     Please Do !
PLAT899_ALERT_4_G SHELXL97   is Deprecated and Succeeded by SHELXL       2017 Note
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min).          2 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         29 Note
PLAT913_ALERT_3_G Missing # of Very Strong Reflections in FCF ....          1 Note
PLAT960_ALERT_3_G Number of Intensities with I  <   - 2*sig(I) ...          3 Check
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.         10 Info

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   5 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   7 ALERT level G = General information/check it is not something unexpected

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   4 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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Computing details

Data collection: APEX2 (Bruker, 2012); cell refinement: SAINT (Bruker, 2012); data reduction: SAINT (Bruker, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2008); software used to prepare material for publication: WinGX (Farrugia, 2012) and PLATON (Spek, 2015).

(E)-4-{[2-(4-Hydroxybenzoyl)hydrazin-1-ylidene]methyl}pyridin-1-ium nitrate

Crystal data

C13H12N3O2^+·NO3^−	F(000) = 632
Mr = 304.27	Dx = 1.436 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 9700 reflections
a = 8.335 (3) Å	θ = 3.1–27.5°
b = 13.929 (5) Å	µ = 0.11 mm^−1
c = 12.184 (4) Å	T = 296 K
β = 95.902 (10)°	Block, colourless
V = 1407.1 (8) Å^3	0.15 × 0.14 × 0.12 mm
Z = 4

Data collection

Bruker APEXII CCD diffractometer	3499 independent reflections
Radiation source: fine-focus sealed tube	2508 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.052
φ and ω scans	θmax = 28.4°, θmin = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2012)	h = −11→10
Tmin = 0.945, Tmax = 0.976	k = −18→18
44410 measured reflections	l = −16→16

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.149	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0782P)^2 + 0.4149P] where P = (Fo^2 + 2Fc^2)/3
3499 reflections	(Δ/σ)max < 0.001
211 parameters	Δρmax = 0.75 e Å^−3
0 restraints	Δρmin = −0.25 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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 (Ų)

	x	y	z	Uiso*/Ueq
O1	1.15687 (19)	0.08055 (9)	0.24127 (12)	0.0576 (4)
H1A	1.207 (3)	0.1109 (18)	0.183 (2)	0.080 (8)*
O2	0.82328 (18)	0.32288 (9)	0.59284 (11)	0.0549 (4)
O3	0.3316 (2)	0.99298 (10)	0.57667 (11)	0.0619 (4)
O4	0.37385 (19)	0.95570 (10)	0.74819 (11)	0.0595 (4)
O5	0.22205 (19)	1.07556 (11)	0.69841 (15)	0.0730 (5)
N1	0.81569 (17)	0.43407 (10)	0.45738 (12)	0.0392 (3)
H1B	0.830 (3)	0.4512 (15)	0.3928 (19)	0.055 (6)*
N2	0.74051 (16)	0.49881 (10)	0.51883 (11)	0.0368 (3)
N3	0.50122 (17)	0.80177 (10)	0.64341 (12)	0.0408 (3)
H3A	0.456 (3)	0.8548 (17)	0.6811 (19)	0.069 (7)*
N4	0.30832 (18)	1.00915 (10)	0.67253 (13)	0.0438 (4)
C1	1.08209 (19)	0.24460 (12)	0.27240 (13)	0.0367 (4)
H1	1.1286	0.2655	0.2104	0.044*
C2	1.0865 (2)	0.14803 (12)	0.30031 (14)	0.0386 (4)
C3	1.0173 (2)	0.11743 (13)	0.39341 (15)	0.0452 (4)
H3	1.0208	0.0528	0.4129	0.054*
C4	0.9439 (2)	0.18265 (12)	0.45671 (14)	0.0410 (4)
H4	0.8980	0.1616	0.5189	0.049*
C5	0.93716 (18)	0.27990 (11)	0.42900 (13)	0.0334 (3)
C6	1.00883 (18)	0.30970 (12)	0.33645 (13)	0.0353 (4)
H6	1.0073	0.3744	0.3176	0.042*
C7	0.85500 (18)	0.34613 (11)	0.50025 (13)	0.0352 (3)
C8	0.7030 (2)	0.57893 (12)	0.47233 (14)	0.0417 (4)
H8	0.7236	0.5893	0.3997	0.050*
C9	0.62801 (18)	0.65447 (11)	0.53250 (13)	0.0347 (3)
C10	0.56331 (19)	0.63741 (12)	0.63168 (14)	0.0377 (4)
H10	0.5629	0.5758	0.6610	0.045*
C11	0.5004 (2)	0.71264 (12)	0.68521 (15)	0.0402 (4)
H11	0.4565	0.7019	0.7513	0.048*
C12	0.5620 (2)	0.82024 (12)	0.54903 (15)	0.0441 (4)
H12	0.5613	0.8827	0.5221	0.053*
C13	0.6257 (2)	0.74791 (12)	0.49147 (14)	0.0401 (4)
H13	0.6673	0.7610	0.4251	0.048*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0805 (10)	0.0412 (7)	0.0580 (9)	−0.0054 (6)	0.0395 (8)	−0.0132 (6)
O2	0.0797 (10)	0.0457 (7)	0.0451 (7)	0.0120 (6)	0.0345 (7)	0.0058 (6)
O3	0.0884 (11)	0.0562 (9)	0.0452 (8)	0.0093 (7)	0.0264 (7)	0.0067 (6)
O4	0.0837 (10)	0.0566 (8)	0.0401 (7)	0.0142 (7)	0.0156 (7)	−0.0006 (6)
O5	0.0723 (10)	0.0593 (9)	0.0875 (12)	0.0217 (8)	0.0090 (9)	−0.0260 (8)
N1	0.0496 (8)	0.0387 (8)	0.0316 (7)	0.0066 (6)	0.0145 (6)	−0.0011 (6)
N2	0.0385 (7)	0.0374 (7)	0.0360 (7)	0.0026 (5)	0.0107 (6)	−0.0047 (6)
N3	0.0446 (8)	0.0330 (7)	0.0466 (8)	0.0026 (6)	0.0132 (6)	−0.0013 (6)
N4	0.0502 (8)	0.0359 (7)	0.0473 (9)	−0.0017 (6)	0.0142 (7)	−0.0056 (6)
C1	0.0379 (8)	0.0441 (9)	0.0296 (8)	−0.0016 (7)	0.0103 (6)	−0.0001 (7)
C2	0.0416 (8)	0.0398 (9)	0.0364 (8)	−0.0050 (7)	0.0134 (7)	−0.0096 (7)
C3	0.0586 (11)	0.0329 (9)	0.0479 (10)	−0.0051 (7)	0.0236 (8)	−0.0023 (7)
C4	0.0500 (9)	0.0389 (9)	0.0373 (9)	−0.0059 (7)	0.0198 (7)	−0.0004 (7)
C5	0.0327 (7)	0.0369 (8)	0.0315 (8)	−0.0005 (6)	0.0080 (6)	−0.0027 (6)
C6	0.0355 (8)	0.0375 (8)	0.0340 (8)	0.0018 (6)	0.0085 (6)	0.0034 (6)
C7	0.0359 (8)	0.0368 (8)	0.0343 (8)	−0.0011 (6)	0.0104 (6)	−0.0018 (6)
C8	0.0496 (9)	0.0437 (9)	0.0333 (8)	0.0058 (8)	0.0110 (7)	−0.0005 (7)
C9	0.0346 (8)	0.0363 (8)	0.0334 (8)	0.0004 (6)	0.0046 (6)	−0.0009 (6)
C10	0.0421 (8)	0.0314 (8)	0.0412 (9)	−0.0028 (6)	0.0113 (7)	0.0022 (7)
C11	0.0434 (9)	0.0373 (9)	0.0422 (9)	−0.0030 (7)	0.0154 (7)	0.0006 (7)
C12	0.0522 (10)	0.0350 (9)	0.0464 (10)	0.0042 (7)	0.0106 (8)	0.0088 (7)
C13	0.0449 (9)	0.0425 (9)	0.0342 (8)	0.0030 (7)	0.0096 (7)	0.0070 (7)

Geometric parameters (Å, º)

O1—C2	1.354 (2)	C4—C3	1.376 (2)
O1—H1A	0.96 (3)	C4—H4	0.9300
O2—C7	1.228 (2)	C5—C4	1.396 (2)
O3—N4	1.224 (2)	C5—C6	1.393 (2)
O4—N4	1.264 (2)	C5—C7	1.482 (2)
N1—C7	1.359 (2)	C6—C1	1.379 (2)
N1—H1B	0.84 (2)	C6—H6	0.9300
N2—N1	1.3649 (19)	C8—H8	0.9300
N2—C8	1.276 (2)	C9—C8	1.459 (2)
N3—C11	1.342 (2)	C9—C10	1.393 (2)
N3—C12	1.329 (2)	C9—C13	1.394 (2)
N3—H3A	0.97 (2)	C10—C11	1.367 (2)
N4—O5	1.2325 (19)	C10—H10	0.9300
C1—H1	0.9300	C11—H11	0.9300
C2—C1	1.387 (2)	C12—H12	0.9300
C2—C3	1.391 (2)	C13—C12	1.366 (2)
C3—H3	0.9300	C13—H13	0.9300
O1···H10^i	2.48	C7···H1A^ii	2.72 (2)
O2···H1^ii	2.58	H1···H1A	2.28
O2···H1A^ii	1.79 (2)	H1B···O4^iii	2.25 (2)
O2···H4	2.52	H1B···O5^iii	2.47 (2)
O3···H3A	2.48 (2)	H1B···N4^iii	2.73 (2)
O3···H12	2.59	H6···O4^iii	2.71
O4···H3A	1.80 (2)	H6···O5^iii	2.75
N1···H6	2.59	H6···N4^iii	2.81
N2···H1A^ii	2.56 (2)	H6···H1B	2.11
N2···H10	2.62	H8···O4^iii	2.42
N4···H3A	2.47 (2)	H8···H1B	2.12
C6···H1B	2.61 (2)	H8···H13	2.46
C2—O1—H1A	109.6 (15)	C6—C5—C7	123.46 (15)
N2—N1—H1B	116.3 (15)	C1—C6—C5	120.92 (15)
C7—N1—N2	119.41 (14)	C1—C6—H6	119.5
C7—N1—H1B	124.2 (15)	C5—C6—H6	119.5
C8—N2—N1	116.08 (14)	O2—C7—N1	121.65 (15)
C11—N3—H3A	120.6 (14)	O2—C7—C5	122.00 (15)
C12—N3—C11	121.66 (15)	N1—C7—C5	116.35 (14)
C12—N3—H3A	117.7 (14)	N2—C8—C9	120.38 (15)
O3—N4—O4	119.23 (15)	N2—C8—H8	119.8
O3—N4—O5	122.40 (17)	C9—C8—H8	119.8
O5—N4—O4	118.37 (16)	C10—C9—C8	122.46 (15)
C2—C1—H1	120.0	C10—C9—C13	118.54 (14)
C6—C1—C2	120.06 (14)	C13—C9—C8	118.96 (15)
C6—C1—H1	120.0	C9—C10—H10	120.5
O1—C2—C1	123.03 (15)	C11—C10—C9	119.00 (15)
O1—C2—C3	117.33 (16)	C11—C10—H10	120.5
C1—C2—C3	119.64 (15)	N3—C11—C10	120.71 (16)
C2—C3—H3	120.0	N3—C11—H11	119.6
C4—C3—C2	120.02 (16)	C10—C11—H11	119.6
C4—C3—H3	120.0	N3—C12—C13	120.30 (16)
C3—C4—C5	120.96 (15)	N3—C12—H12	119.9
C3—C4—H4	119.5	C13—C12—H12	119.9
C5—C4—H4	119.5	C9—C13—H13	120.1
C4—C5—C7	118.16 (14)	C12—C13—C9	119.79 (15)
C6—C5—C4	118.38 (14)	C12—C13—H13	120.1
N2—N1—C7—O2	0.7 (2)	C7—C5—C6—C1	−179.26 (15)
N2—N1—C7—C5	−179.66 (13)	C4—C5—C7—O2	15.3 (2)
C8—N2—N1—C7	−178.09 (15)	C4—C5—C7—N1	−164.34 (15)
N1—N2—C8—C9	−177.58 (14)	C6—C5—C7—O2	−164.23 (16)
C12—N3—C11—C10	0.3 (3)	C6—C5—C7—N1	16.1 (2)
C11—N3—C12—C13	0.1 (3)	C5—C6—C1—C2	−0.6 (2)
O1—C2—C1—C6	−179.76 (15)	C10—C9—C8—N2	−13.9 (3)
C3—C2—C1—C6	−0.3 (3)	C13—C9—C8—N2	163.87 (16)
O1—C2—C3—C4	−179.94 (17)	C8—C9—C10—C11	177.61 (16)
C1—C2—C3—C4	0.6 (3)	C13—C9—C10—C11	−0.1 (2)
C5—C4—C3—C2	0.0 (3)	C8—C9—C13—C12	−177.27 (16)
C6—C5—C4—C3	−0.9 (3)	C10—C9—C13—C12	0.6 (2)
C7—C5—C4—C3	179.50 (16)	C9—C10—C11—N3	−0.3 (3)
C4—C5—C6—C1	1.2 (2)	C9—C13—C12—N3	−0.6 (3)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O2^i	0.96 (2)	1.79 (2)	2.742 (2)	170 (2)
N1—H1B···O4^iii	0.84 (2)	2.25 (2)	3.057 (2)	161 (2)
N1—H1B···O5^iii	0.84 (2)	2.47 (2)	3.174 (3)	141 (2)
N3—H3A···O4	0.97 (2)	1.80 (2)	2.763 (2)	178 (2)
C1—H1···O2^i	0.93	2.58	3.258 (2)	130
C8—H8···O4^iii	0.93	2.42	3.243 (2)	148
C10—H10···O1^ii	0.93	2.48	3.375 (2)	162
C11—H11···O5^iv	0.93	2.42	3.104 (3)	130
C12—H12···O3^v	0.93	2.34	3.191 (2)	152

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