4-Amino-3,5-di­chloro­pyridinium 3-hy­droxy­pico­linate monohydrate

In the title hydrated salt, C₅H₅Cl₂N₂⁺·C₆H₄NO₃⁻·H₂O, the pyridine N atom of the cation is protonated and an intra­molecular O—H...O hydrogen bond is observed in the anion, which generates an S(6) ring. The crystal packing features N—H...N, O—H...O, N—H...O, C—H...Cl and C—H...O hydrogen bonds, which generate a three-dimensional network.

Key indicators

Structure: I

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.033
• wR factor = 0.091
• Data-to-parameter ratio = 17.8

checkCIF/PLATON results

No syntax errors found



Alert level C
ABSTY02_ALERT_1_C  An _exptl_absorpt_correction_type has been given without
            a literature citation. This should be contained in the
            _exptl_absorpt_process_details field.
            Absorption correction given as multi-scan
PLAT042_ALERT_1_C Calc. and Reported MoietyFormula Strings  Differ     Please Check
PLAT906_ALERT_3_C Large K Value in the Analysis of Variance ......      2.087 Check
PLAT977_ALERT_2_C Check Negative Difference Density on H1        .      -0.31 eA-3

Alert level G
PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms ..............          6 Report
PLAT066_ALERT_1_G Predicted and Reported Tmin&Tmax Range Identical          ? Check
PLAT432_ALERT_2_G Short Inter X...Y Contact  O1       ..C5       .       2.99 Ang.
                                                   -1+x,y,z  =      1_455 Check
PLAT480_ALERT_4_G Long H...A H-Bond Reported H5       ..CL2      .       2.97 Ang.
PLAT883_ALERT_1_G No Info/Value for _atom_sites_solution_primary .     Please Do !
PLAT899_ALERT_4_G SHELXL2018 is Deprecated and Succeeded by SHELXL     2019/3 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         40 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          0 Info

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

   4 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
   1 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: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis PRO (Agilent, 2012); program(s) used to solve structure: SHELXT2018/2 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: PLATON (Spek, 2020); software used to prepare material for publication: PLATON (Spek, 2020).

4-Amino-3,5-dichloropyridinium 3-hydroxypyridine-2-carboxylate monohydrate

Crystal data

C5H5Cl2N2^+·C6H4NO3^−·H2O	F(000) = 656
Mr = 320.13	Dx = 1.645 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 8.4267 (19) Å	Cell parameters from 3676 reflections
b = 14.084 (3) Å	θ = 2.5–28.8°
c = 10.900 (2) Å	µ = 0.52 mm^−1
β = 91.953 (8)°	T = 296 K
V = 1292.9 (5) Å^3	Plate, colourless
Z = 4	0.46 × 0.32 × 0.13 mm

Data collection

Agilent Xcalibur, Atlas, Gemini diffractometer	2853 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.038
ω scans	θmax = 28.7°, θmin = 2.4°
Absorption correction: multi-scan	h = −11→11
Tmin = 0.819, Tmax = 0.937	k = −18→18
45801 measured reflections	l = −14→14
3296 independent reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.033	H-atom parameters constrained
wR(F^2) = 0.091	w = 1/[σ^2(Fo^2) + (0.0465P)^2 + 0.3959P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max < 0.001
3296 reflections	Δρmax = 0.24 e Å^−3
185 parameters	Δρmin = −0.35 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. The water H atoms were located in a difference Fourier map and allowed to refine freely. The remaining H atoms were positioned geometrically (C—H = 0.93 and N—H = 0.86 Å) and were refined using a riding model, with U_iso(H) = 1.2 U_eq(C).

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

	x	y	z	Uiso*/Ueq
Cl1	0.85851 (4)	0.68420 (3)	0.15096 (4)	0.04683 (12)
Cl2	0.89478 (5)	0.30311 (2)	0.10521 (4)	0.04737 (12)
O1	0.42463 (12)	0.67099 (7)	0.27823 (11)	0.0439 (3)
O2	0.61861 (13)	0.71788 (7)	0.40818 (11)	0.0459 (3)
O3	0.82471 (14)	0.60173 (8)	0.48694 (13)	0.0535 (3)
H3	0.780642	0.653220	0.477230	0.080*
N3	0.50360 (13)	0.48436 (8)	0.31752 (10)	0.0321 (2)
N1	1.19792 (14)	0.49866 (8)	0.22147 (11)	0.0371 (3)
H1	1.294531	0.500301	0.249479	0.045*
N2	0.73770 (13)	0.49223 (8)	0.08094 (11)	0.0355 (3)
H2A	0.685153	0.544264	0.072057	0.043*
H2B	0.694906	0.439155	0.059109	0.043*
C10	0.59379 (14)	0.55395 (9)	0.36845 (11)	0.0288 (3)
C11	0.53872 (15)	0.65512 (9)	0.34965 (13)	0.0326 (3)
C3	0.88438 (14)	0.49383 (9)	0.12820 (11)	0.0291 (3)
C4	0.96128 (15)	0.57881 (9)	0.16585 (12)	0.0321 (3)
C6	0.73510 (16)	0.53325 (10)	0.43364 (13)	0.0353 (3)
C2	0.97853 (16)	0.41096 (9)	0.14404 (12)	0.0325 (3)
C5	1.11412 (16)	0.57934 (10)	0.21103 (13)	0.0362 (3)
H5	1.160941	0.636508	0.234961	0.043*
C1	1.13192 (17)	0.41529 (10)	0.18845 (13)	0.0373 (3)
H1A	1.191375	0.359836	0.195919	0.045*
C9	0.55198 (17)	0.39478 (10)	0.32671 (14)	0.0388 (3)
H9	0.488901	0.347163	0.291583	0.047*
C8	0.69351 (18)	0.37002 (10)	0.38699 (15)	0.0428 (3)
H8	0.725723	0.306886	0.390273	0.051*
C7	0.78549 (17)	0.43927 (11)	0.44166 (15)	0.0431 (3)
H7	0.880028	0.423758	0.483433	0.052*
O1W	0.48614 (13)	0.86692 (8)	0.53048 (11)	0.0441 (3)
H1W	0.518086	0.816660	0.495934	0.066*
H2W	0.462944	0.849278	0.602250	0.066*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0388 (2)	0.03527 (19)	0.0658 (3)	0.00513 (13)	−0.00686 (17)	−0.01076 (16)
Cl2	0.0497 (2)	0.03070 (18)	0.0608 (3)	−0.00776 (14)	−0.01108 (18)	0.00405 (15)
O1	0.0385 (5)	0.0339 (5)	0.0585 (7)	0.0032 (4)	−0.0120 (5)	0.0042 (5)
O2	0.0429 (6)	0.0320 (5)	0.0621 (7)	−0.0008 (4)	−0.0073 (5)	−0.0116 (5)
O3	0.0416 (6)	0.0449 (6)	0.0723 (8)	−0.0023 (5)	−0.0249 (6)	−0.0072 (6)
N3	0.0294 (5)	0.0297 (5)	0.0371 (6)	0.0000 (4)	−0.0023 (4)	−0.0008 (4)
N1	0.0295 (5)	0.0419 (6)	0.0393 (6)	−0.0021 (5)	−0.0075 (5)	0.0026 (5)
N2	0.0278 (5)	0.0345 (6)	0.0438 (6)	−0.0027 (4)	−0.0051 (5)	−0.0019 (5)
C10	0.0268 (6)	0.0282 (6)	0.0313 (6)	−0.0006 (5)	0.0004 (5)	−0.0009 (5)
C11	0.0294 (6)	0.0290 (6)	0.0397 (7)	0.0010 (5)	0.0023 (5)	−0.0010 (5)
C3	0.0273 (6)	0.0342 (6)	0.0258 (6)	−0.0031 (5)	0.0007 (5)	0.0009 (5)
C4	0.0299 (6)	0.0327 (6)	0.0335 (6)	−0.0009 (5)	−0.0010 (5)	−0.0027 (5)
C6	0.0290 (6)	0.0371 (7)	0.0396 (7)	−0.0004 (5)	−0.0039 (5)	0.0003 (6)
C2	0.0340 (6)	0.0304 (6)	0.0329 (6)	−0.0047 (5)	−0.0028 (5)	0.0039 (5)
C5	0.0323 (6)	0.0387 (7)	0.0374 (7)	−0.0054 (5)	−0.0035 (5)	−0.0036 (6)
C1	0.0357 (7)	0.0363 (7)	0.0396 (7)	0.0008 (5)	−0.0048 (6)	0.0065 (6)
C9	0.0387 (7)	0.0292 (6)	0.0483 (8)	−0.0009 (5)	−0.0021 (6)	−0.0018 (6)
C8	0.0413 (8)	0.0320 (7)	0.0549 (9)	0.0084 (6)	0.0016 (7)	0.0068 (6)
C7	0.0327 (7)	0.0436 (8)	0.0526 (9)	0.0074 (6)	−0.0066 (6)	0.0075 (7)
O1W	0.0418 (6)	0.0358 (5)	0.0542 (7)	0.0069 (4)	−0.0077 (5)	−0.0016 (5)

Geometric parameters (Å, º)

Cl1—C4	1.7233 (14)	C10—C11	1.5103 (18)
Cl2—C2	1.7217 (14)	C3—C4	1.4151 (17)
O1—C11	1.2366 (17)	C3—C2	1.4184 (18)
O2—C11	1.2697 (17)	C4—C5	1.3631 (18)
O3—C6	1.3446 (17)	C6—C7	1.392 (2)
O3—H3	0.8200	C2—C1	1.3661 (19)
N3—C9	1.3287 (18)	C5—H5	0.9300
N3—C10	1.3481 (16)	C1—H1A	0.9300
N1—C5	1.3406 (18)	C9—C8	1.386 (2)
N1—C1	1.3430 (18)	C9—H9	0.9300
N1—H1	0.8600	C8—C7	1.370 (2)
N2—C3	1.3229 (16)	C8—H8	0.9300
N2—H2A	0.8600	C7—H7	0.9300
N2—H2B	0.8600	O1W—H1W	0.8499
C10—C6	1.3965 (18)	O1W—H2W	0.8500
C6—O3—H3	109.5	O3—C6—C10	121.79 (13)
C9—N3—C10	119.47 (12)	C7—C6—C10	118.91 (13)
C5—N1—C1	120.41 (12)	C1—C2—C3	121.66 (12)
C5—N1—H1	119.8	C1—C2—Cl2	120.10 (11)
C1—N1—H1	119.8	C3—C2—Cl2	118.24 (10)
C3—N2—H2A	120.0	N1—C5—C4	120.96 (13)
C3—N2—H2B	120.0	N1—C5—H5	119.5
H2A—N2—H2B	120.0	C4—C5—H5	119.5
N3—C10—C6	121.12 (12)	N1—C1—C2	120.81 (13)
N3—C10—C11	117.62 (11)	N1—C1—H1A	119.6
C6—C10—C11	121.24 (11)	C2—C1—H1A	119.6
O1—C11—O2	125.31 (13)	N3—C9—C8	122.09 (13)
O1—C11—C10	118.99 (12)	N3—C9—H9	119.0
O2—C11—C10	115.68 (12)	C8—C9—H9	119.0
N2—C3—C4	122.67 (12)	C7—C8—C9	119.48 (13)
N2—C3—C2	123.00 (12)	C7—C8—H8	120.3
C4—C3—C2	114.33 (11)	C9—C8—H8	120.3
C5—C4—C3	121.81 (12)	C8—C7—C6	118.88 (13)
C5—C4—Cl1	119.66 (11)	C8—C7—H7	120.6
C3—C4—Cl1	118.52 (10)	C6—C7—H7	120.6
O3—C6—C7	119.29 (12)	H1W—O1W—H2W	104.5
C9—N3—C10—C6	−1.8 (2)	C4—C3—C2—C1	−1.97 (19)
C9—N3—C10—C11	176.65 (12)	N2—C3—C2—Cl2	−2.54 (18)
N3—C10—C11—O1	−7.84 (19)	C4—C3—C2—Cl2	178.22 (10)
C6—C10—C11—O1	170.60 (13)	C1—N1—C5—C4	−0.6 (2)
N3—C10—C11—O2	173.80 (12)	C3—C4—C5—N1	0.0 (2)
C6—C10—C11—O2	−7.76 (19)	Cl1—C4—C5—N1	−178.74 (11)
N2—C3—C4—C5	−178.05 (13)	C5—N1—C1—C2	−0.2 (2)
C2—C3—C4—C5	1.20 (19)	C3—C2—C1—N1	1.5 (2)
N2—C3—C4—Cl1	0.74 (18)	Cl2—C2—C1—N1	−178.65 (11)
C2—C3—C4—Cl1	179.99 (10)	C10—N3—C9—C8	−0.2 (2)
N3—C10—C6—O3	−178.70 (13)	N3—C9—C8—C7	1.6 (2)
C11—C10—C6—O3	2.9 (2)	C9—C8—C7—C6	−0.9 (2)
N3—C10—C6—C7	2.4 (2)	O3—C6—C7—C8	−179.94 (15)
C11—C10—C6—C7	−175.97 (13)	C10—C6—C7—C8	−1.0 (2)
N2—C3—C2—C1	177.27 (13)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O2	0.82	1.79	2.5155 (17)	147
N1—H1···N3^i	0.86	1.90	2.7546 (17)	171
N2—H2A···O1W^ii	0.86	2.13	2.9414 (17)	157
N2—H2B···O1W^iii	0.86	2.05	2.8269 (17)	149
O1W—H1W···O2	0.85	1.90	2.7442 (17)	170
O1W—H2W···O1^iv	0.85	1.98	2.8181 (18)	170
C5—H5···O1^i	0.93	2.31	2.9864 (18)	129
C5—H5···Cl2^v	0.93	2.97	3.7363 (16)	141
C7—H7···O3^vi	0.93	2.52	3.399 (2)	157

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