Pyridinium 3-nitro­benzoate–3-nitro­benzoic acid (1/1)

The crystal structure of the product of the neutralization reaction between 3-nitro­benzoic acid and pyridine is reported. The entities that crystallized are a pyridinium cation, a 3-nitrobenzoate anion and a 3-nitrobenzoic acid molecule in a 1:1:1 molar ratio, C₅H₆N⁺·C₇H₄NO₄⁻·C₇H₅NO₄. Distinct sets of hydrogen bonds link the pyridinium and benzoate ions (N—H...O) and the acid and benzoate moieties (O—H...O). The hydrogen bonding along with π–π stacking between the acid and benzoate moieties accounts for the long-range ordering of the crystal.

Key indicators

• Single-crystal X-ray study
• T = 150 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.044
• wR factor = 0.107
• Data-to-parameter ratio = 16.0

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT111_ALERT_2_B ADDSYM Detects New (Pseudo) Centre of Symmetry .        100 %Fit

Author Response: The structure was solved and refined using the suggested space group P21/c. In this structure the pyridinium cation is 1:1 disordered across an inversion center, R1 and wR1 values are substantially increased (roughly tripled) as compared to the solution in Pc, indicating breaking of inversion symmetry by ordering of the pyridinium cation.

PLAT113_ALERT_2_B ADDSYM Suggests Possible Pseudo/New  Space Group      P21/c Check

Alert level C
PLAT340_ALERT_3_C Low Bond Precision on  C-C Bonds ...............    0.00467 Ang.

Alert level G
PLAT042_ALERT_1_G Calc. and Reported Moiety Formula Strings Differ     Please Check
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         13 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.         17 Info

   0 ALERT level A = Most likely a serious problem - resolve or explain
   2 ALERT level B = A potentially serious problem, consider carefully
   1 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   4 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
   2 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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Computing details

Data collection: APEX3 (Bruker, 2020); cell refinement: SAINT (Bruker, 2020); data reduction: SAINT (Bruker, 2020); program(s) used to solve structure: SHELXT2018/2 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); Mercury (Macrae et al., 2020); software used to prepare material for publication: publCIF (Westrip, 2010), CSD (Groom et al., 2016) and enCIFer (Allen et al., 2004).

(I)

Crystal data

C5H6N^+·C7H4NO4^−·C7H5NO4	F(000) = 428
Mr = 413.34	Dx = 1.495 Mg m^−3
Monoclinic, Pc	Mo Kα radiation, λ = 0.71073 Å
a = 6.2434 (3) Å	Cell parameters from 3891 reflections
b = 21.3584 (10) Å	θ = 3.0–28.3°
c = 6.8938 (3) Å	µ = 0.12 mm^−1
β = 93.118 (2)°	T = 150 K
V = 917.92 (7) Å^3	Plate, colourless
Z = 2	0.35 × 0.15 × 0.05 mm

Data collection

Bruker AXS D8 Quest diffractometer with PhotonII charge-integrating pixel array detector (CPAD)	4437 independent reflections
Radiation source: 1 kW fine focus sealed tube X-ray source	3733 reflections with I > 2σ(I)
Detector resolution: 7.4074 pixels mm^-1	Rint = 0.023
ω and φ scans	θmax = 28.4°, θmin = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2020)	h = −8→8
Tmin = 0.636, Tmax = 0.746	k = −28→28
7895 measured reflections	l = −9→9

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.044	Hydrogen site location: mixed
wR(F^2) = 0.107	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.044P)^2 + 0.2733P] where P = (Fo^2 + 2Fc^2)/3
4437 reflections	(Δ/σ)max < 0.001
277 parameters	Δρmax = 0.25 e Å^−3
2 restraints	Δρmin = −0.19 e Å^−3

Special details

Refinement. H atoms on the aromatic (sp²) carbons were included in calculated positions and treated as riding atoms: C—H = 0.95 Å with U_iso(H) = 1.2 × U_eq(carrier atom). H atoms H1 and H3A were located as residual electron density and allowed to refine freely with U_iso(H) = 1.5 × U_eq(O or N).

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

	x	y	z	Uiso*/Ueq
C1	0.3880 (5)	0.35185 (15)	0.2998 (4)	0.0229 (7)
C2	0.5147 (5)	0.40980 (15)	0.3404 (4)	0.0203 (7)
C3	0.4093 (5)	0.46720 (14)	0.3147 (4)	0.0190 (7)
H3	0.262180	0.468543	0.271691	0.023*
C4	0.5217 (5)	0.52186 (15)	0.3528 (4)	0.0198 (7)
C5	0.7352 (5)	0.52249 (16)	0.4169 (5)	0.0241 (7)
H5	0.809070	0.560736	0.442560	0.029*
C6	0.8384 (5)	0.46494 (16)	0.4425 (5)	0.0261 (7)
H6	0.985232	0.463902	0.486611	0.031*
C7	0.7308 (5)	0.40954 (16)	0.4048 (5)	0.0235 (7)
H7	0.804206	0.370838	0.422786	0.028*
N1	0.4075 (5)	0.58181 (13)	0.3261 (4)	0.0254 (6)
O1	0.5027 (4)	0.30049 (11)	0.3136 (4)	0.0325 (6)
H1	0.419 (7)	0.2717 (19)	0.283 (7)	0.049*
O2	0.1965 (4)	0.35353 (11)	0.2591 (4)	0.0346 (6)
O3	0.2159 (4)	0.58001 (12)	0.2787 (5)	0.0421 (7)
O4	0.5076 (5)	0.63004 (12)	0.3523 (4)	0.0410 (7)
C8	0.3862 (6)	0.15289 (15)	0.2486 (5)	0.0246 (7)
C9	0.2590 (5)	0.09406 (15)	0.1956 (4)	0.0213 (7)
C10	0.3561 (6)	0.03643 (14)	0.2200 (4)	0.0208 (7)
H10	0.501855	0.033298	0.266289	0.025*
C11	0.2370 (5)	−0.01667 (14)	0.1758 (4)	0.0213 (7)
C12	0.0235 (5)	−0.01458 (16)	0.1095 (4)	0.0239 (7)
H12	−0.055428	−0.051872	0.082220	0.029*
C13	−0.0699 (6)	0.04316 (16)	0.0848 (5)	0.0275 (8)
H13	−0.215401	0.046060	0.037739	0.033*
C14	0.0457 (6)	0.09765 (16)	0.1278 (5)	0.0266 (7)
H14	−0.021382	0.137334	0.110787	0.032*
N2	0.3439 (5)	−0.07747 (13)	0.2017 (4)	0.0278 (7)
O5	0.2900 (4)	0.20430 (11)	0.2221 (4)	0.0343 (6)
O6	0.5729 (4)	0.14586 (12)	0.3167 (4)	0.0366 (6)
O7	0.5346 (5)	−0.07837 (13)	0.2492 (5)	0.0448 (7)
O8	0.2350 (5)	−0.12516 (12)	0.1741 (4)	0.0376 (6)
C15	0.9530 (6)	0.23917 (17)	0.5534 (5)	0.0337 (8)
H15	1.002933	0.233689	0.426833	0.040*
C16	1.0720 (6)	0.27288 (17)	0.6888 (6)	0.0337 (8)
H16	1.204965	0.290825	0.657419	0.040*
C17	0.9967 (6)	0.28047 (15)	0.8709 (5)	0.0352 (8)
H17	1.078436	0.303379	0.967064	0.042*
C18	0.8023 (7)	0.25478 (17)	0.9138 (6)	0.0392 (9)
H18	0.747524	0.260163	1.038592	0.047*
C19	0.6901 (7)	0.22142 (16)	0.7730 (6)	0.0372 (8)
H19	0.555815	0.203374	0.799899	0.045*
N3	0.7677 (5)	0.21406 (13)	0.5984 (5)	0.0321 (7)
H3A	0.694 (7)	0.198 (2)	0.498 (6)	0.048*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0250 (17)	0.0217 (15)	0.0224 (15)	0.0023 (13)	0.0047 (13)	0.0001 (12)
C2	0.0209 (16)	0.0212 (15)	0.0189 (15)	0.0001 (12)	0.0026 (12)	0.0000 (11)
C3	0.0177 (17)	0.0205 (15)	0.0188 (15)	0.0009 (12)	0.0017 (12)	−0.0010 (11)
C4	0.0218 (17)	0.0199 (14)	0.0178 (14)	0.0021 (12)	0.0021 (12)	−0.0021 (11)
C5	0.0260 (19)	0.0249 (16)	0.0215 (16)	−0.0050 (13)	0.0023 (13)	−0.0017 (12)
C6	0.0149 (16)	0.0374 (19)	0.0259 (16)	0.0000 (13)	−0.0005 (12)	−0.0001 (13)
C7	0.0201 (17)	0.0264 (16)	0.0241 (16)	0.0062 (13)	0.0019 (13)	0.0034 (12)
N1	0.0302 (16)	0.0175 (13)	0.0286 (15)	0.0028 (12)	0.0018 (12)	−0.0019 (11)
O1	0.0352 (14)	0.0188 (11)	0.0432 (15)	0.0014 (10)	−0.0021 (11)	0.0014 (10)
O2	0.0270 (13)	0.0249 (12)	0.0516 (15)	−0.0031 (10)	0.0005 (11)	−0.0095 (11)
O3	0.0301 (14)	0.0248 (13)	0.0699 (19)	0.0093 (12)	−0.0115 (13)	−0.0070 (13)
O4	0.0391 (16)	0.0209 (12)	0.0625 (18)	−0.0042 (11)	−0.0030 (13)	−0.0034 (12)
C8	0.0320 (19)	0.0172 (15)	0.0247 (15)	−0.0062 (13)	0.0027 (13)	−0.0059 (12)
C9	0.0243 (17)	0.0204 (15)	0.0195 (15)	−0.0018 (12)	0.0035 (13)	−0.0024 (11)
C10	0.0202 (17)	0.0229 (16)	0.0192 (15)	−0.0023 (13)	0.0003 (12)	−0.0037 (11)
C11	0.0275 (18)	0.0193 (15)	0.0175 (14)	−0.0003 (13)	0.0041 (12)	−0.0008 (12)
C12	0.0230 (18)	0.0285 (17)	0.0204 (15)	−0.0072 (13)	0.0025 (13)	−0.0034 (13)
C13	0.0222 (18)	0.0349 (19)	0.0251 (17)	−0.0019 (13)	−0.0001 (13)	−0.0003 (13)
C14	0.0314 (19)	0.0235 (16)	0.0249 (16)	0.0013 (13)	−0.0001 (14)	0.0005 (13)
N2	0.0353 (18)	0.0204 (13)	0.0274 (15)	−0.0017 (13)	−0.0003 (13)	−0.0049 (11)
O5	0.0388 (14)	0.0184 (11)	0.0454 (15)	−0.0015 (10)	−0.0008 (12)	−0.0011 (10)
O6	0.0296 (14)	0.0266 (13)	0.0529 (16)	−0.0034 (11)	−0.0054 (12)	−0.0146 (11)
O7	0.0380 (16)	0.0282 (14)	0.066 (2)	0.0069 (13)	−0.0156 (14)	−0.0071 (13)
O8	0.0461 (16)	0.0173 (11)	0.0493 (15)	−0.0075 (11)	0.0033 (13)	−0.0027 (11)
C15	0.037 (2)	0.0301 (16)	0.0328 (18)	0.0057 (15)	−0.0043 (15)	0.0010 (14)
C16	0.0286 (18)	0.0296 (17)	0.042 (2)	−0.0019 (14)	−0.0051 (15)	0.0037 (14)
C17	0.041 (2)	0.0240 (16)	0.0384 (19)	0.0009 (15)	−0.0174 (16)	−0.0036 (14)
C18	0.051 (2)	0.0314 (18)	0.0358 (19)	0.0082 (17)	0.0066 (17)	0.0024 (15)
C19	0.0296 (18)	0.0252 (16)	0.057 (2)	−0.0014 (14)	0.0043 (16)	0.0026 (16)
N3	0.0319 (16)	0.0193 (12)	0.0431 (17)	0.0009 (11)	−0.0152 (13)	−0.0053 (11)

Geometric parameters (Å, º)

C1—C2	1.488 (4)	C10—C11	1.381 (4)
C1—O1	1.311 (4)	C11—C12	1.386 (5)
C1—O2	1.214 (4)	C11—N2	1.467 (4)
C2—C3	1.398 (4)	C12—H12	0.9500
C2—C7	1.397 (4)	C12—C13	1.371 (5)
C3—H3	0.9500	C13—H13	0.9500
C3—C4	1.380 (4)	C13—C14	1.393 (5)
C4—C5	1.382 (4)	C14—H14	0.9500
C4—N1	1.472 (4)	N2—O7	1.217 (4)
C5—H5	0.9500	N2—O8	1.234 (4)
C5—C6	1.395 (4)	C15—H15	0.9500
C6—H6	0.9500	C15—C16	1.366 (5)
C6—C7	1.378 (5)	C15—N3	1.327 (5)
C7—H7	0.9500	C16—H16	0.9500
N1—O3	1.223 (4)	C16—C17	1.374 (6)
N1—O4	1.213 (4)	C17—H17	0.9500
O1—H1	0.83 (4)	C17—C18	1.379 (6)
C8—C9	1.520 (4)	C18—H18	0.9500
C8—O5	1.260 (4)	C18—C19	1.366 (6)
C8—O6	1.242 (4)	C19—H19	0.9500
C9—C10	1.378 (4)	C19—N3	1.331 (5)
C9—C14	1.389 (5)	N3—H3A	0.88 (4)
C10—H10	0.9500
O1—C1—C2	113.5 (3)	C10—C11—C12	122.9 (3)
O2—C1—C2	121.8 (3)	C10—C11—N2	117.6 (3)
O2—C1—O1	124.7 (3)	C12—C11—N2	119.5 (3)
C3—C2—C1	117.6 (3)	C11—C12—H12	121.2
C7—C2—C1	123.4 (3)	C13—C12—C11	117.7 (3)
C7—C2—C3	118.9 (3)	C13—C12—H12	121.2
C2—C3—H3	120.4	C12—C13—H13	119.6
C4—C3—C2	119.1 (3)	C12—C13—C14	120.9 (3)
C4—C3—H3	120.4	C14—C13—H13	119.6
C3—C4—C5	122.7 (3)	C9—C14—C13	120.1 (3)
C3—C4—N1	118.3 (3)	C9—C14—H14	119.9
C5—C4—N1	118.9 (3)	C13—C14—H14	119.9
C4—C5—H5	121.2	O7—N2—C11	118.6 (3)
C4—C5—C6	117.6 (3)	O7—N2—O8	123.4 (3)
C6—C5—H5	121.2	O8—N2—C11	117.9 (3)
C5—C6—H6	119.5	C16—C15—H15	119.9
C7—C6—C5	121.0 (3)	N3—C15—H15	119.9
C7—C6—H6	119.5	N3—C15—C16	120.1 (4)
C2—C7—H7	119.7	C15—C16—H16	120.5
C6—C7—C2	120.6 (3)	C15—C16—C17	119.1 (4)
C6—C7—H7	119.7	C17—C16—H16	120.5
O3—N1—C4	117.8 (3)	C16—C17—H17	120.1
O4—N1—C4	118.5 (3)	C16—C17—C18	119.9 (3)
O4—N1—O3	123.7 (3)	C18—C17—H17	120.1
C1—O1—H1	105 (3)	C17—C18—H18	120.7
O5—C8—C9	116.6 (3)	C19—C18—C17	118.6 (4)
O6—C8—C9	117.3 (3)	C19—C18—H18	120.7
O6—C8—O5	126.2 (3)	C18—C19—H19	119.8
C10—C9—C8	119.2 (3)	N3—C19—C18	120.4 (4)
C10—C9—C14	119.8 (3)	N3—C19—H19	119.8
C14—C9—C8	120.9 (3)	C15—N3—C19	121.9 (3)
C9—C10—H10	120.7	C15—N3—H3A	113 (3)
C9—C10—C11	118.6 (3)	C19—N3—H3A	124 (3)
C11—C10—H10	120.7
C1—C2—C3—C4	179.4 (3)	C9—C10—C11—N2	179.6 (3)
C1—C2—C7—C6	−179.1 (3)	C10—C9—C14—C13	0.1 (5)
C2—C3—C4—C5	−0.4 (5)	C10—C11—C12—C13	1.1 (5)
C2—C3—C4—N1	−179.6 (3)	C10—C11—N2—O7	−4.4 (5)
C3—C2—C7—C6	0.0 (5)	C10—C11—N2—O8	175.5 (3)
C3—C4—C5—C6	0.2 (5)	C11—C12—C13—C14	−0.9 (5)
C3—C4—N1—O3	2.8 (4)	C12—C11—N2—O7	175.8 (3)
C3—C4—N1—O4	−177.3 (3)	C12—C11—N2—O8	−4.2 (4)
C4—C5—C6—C7	0.1 (5)	C12—C13—C14—C9	0.4 (5)
C5—C4—N1—O3	−176.4 (3)	C14—C9—C10—C11	0.0 (5)
C5—C4—N1—O4	3.5 (4)	N2—C11—C12—C13	−179.2 (3)
C5—C6—C7—C2	−0.2 (5)	O5—C8—C9—C10	179.5 (3)
C7—C2—C3—C4	0.3 (4)	O5—C8—C9—C14	−2.1 (5)
N1—C4—C5—C6	179.4 (3)	O6—C8—C9—C10	−1.7 (5)
O1—C1—C2—C3	175.3 (3)	O6—C8—C9—C14	176.7 (3)
O1—C1—C2—C7	−5.6 (4)	C15—C16—C17—C18	−0.7 (5)
O2—C1—C2—C3	−5.1 (5)	C16—C15—N3—C19	1.1 (5)
O2—C1—C2—C7	174.0 (3)	C16—C17—C18—C19	0.8 (5)
C8—C9—C10—C11	178.4 (3)	C17—C18—C19—N3	0.0 (5)
C8—C9—C14—C13	−178.3 (3)	C18—C19—N3—C15	−1.0 (5)
C9—C10—C11—C12	−0.6 (5)	N3—C15—C16—C17	−0.2 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O5	0.83 (4)	1.69 (4)	2.508 (3)	169 (5)
N3—H3A···O6	0.88 (4)	1.81 (4)	2.667 (4)	164 (4)