Charge-transfer complexes of 4-(di­methyl­amino)­pyridine with 2,4-, 3,4- and 3,5-di­nitro­benzoic acid

In the three title crystal structures 4-(di­methyl­amino)­pyridinium 2,4-di­nitro­benzoate, (I), 4-(di­methyl­amino)­pyri­dinium 3,4-di­nitro­benzo­ate, (II), and 4-(di­methyl­amino)pyri­din­ium 3,5-di­nitro­benzo­ate, (III), all C₇H₁₁N₂⁺·C₇H₃N₂O₆^-, the ions are connected by an N-H...O hydrogen bond. Dihedral angles between the pyridine and phenyl rings are 69.9 (1), 26.7 (1) and 56.2 (1)° in (I), (II) and (III), respectively. Donor-acceptor [pi]-[pi] stacking is observed in (II) and (III), but not in (I).

S1. Comment

The efficiency for second harmonic generation (SHG) of (III) was 0.1 relative to an SHG signal of urea (Ito et al., 1998).

Dihedral angles between the pyridine and phenyl rings are 69.9 (1), 26.7 (1) and 56.2 (1)° in (I), (II) and (III), respectively.

S2. Experimental

For the preparation of (I), (II) and (III), equimolecular mixtures of 4-(dimethylamino)pyridine and 2,4-, 3,4- or 3,5-dinitrobenzoic acid were recrystallized from acetone.

S3. Refinement

No Friedel opposites were measured for (III); anomalous dispersion effects are negligible. All H atoms were located from difference syntheses and were refined isotropically. In compounds (I)-(III), N—H bond lengths are in the range 0.87 (3)–0.96 (2) Å, and the C—H lengths are in the range 0.87 (6)–1.06 (4) Å.

Computing details

For all compounds, data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1993); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: TEXSAN.

(I)

Crystal data

C7H11N2^+·C7H3N2O6^−	Z = 2
Mr = 334.29	Dx = 1.475 Mg m^−3
Triclinic, P1	Mo Kα radiation, λ = 0.71073 Å
a = 8.785 (1) Å	Cell parameters from 25 reflections
b = 12.276 (2) Å	θ = 12.0–14.9°
c = 7.696 (1) Å	µ = 0.12 mm^−1
α = 107.37 (1)°	T = 298 K
β = 105.86 (1)°	Prism, colourless
γ = 77.01 (1)°	0.2 × 0.2 × 0.1 mm
V = 752.7 (2) Å^3

Data collection

Rigaku AFC-7R diffractometer	θmax = 27.5°, θmin = 2.5°
θ–2θ scans	h = −11→11
3604 measured reflections	k = −16→0
3444 independent reflections	l = −10→10
1740 reflections with I > 2σ(I)	3 standard reflections every 150 reflections
Rint = 0.016	intensity decay: none

Refinement

Refinement on F^2	All H-atom parameters refined
R[F^2 > 2σ(F^2)] = 0.050	w = 1/[σ^2(Fo^2) + (0.0632P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.136	(Δ/σ)max = 0.001
S = 0.98	Δρmax = 0.19 e Å^−3
3444 reflections	Δρmin = −0.17 e Å^−3
273 parameters

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

	x	y	z	Uiso*/Ueq
O1	0.0524 (3)	0.1208 (2)	−0.3632 (3)	0.0716 (6)
O2	−0.1910 (3)	0.1966 (2)	−0.4609 (3)	0.0763 (7)
O3	−0.4670 (3)	−0.0921 (2)	−0.3359 (3)	0.0778 (7)
O4	−0.4026 (2)	−0.1117 (2)	−0.0545 (3)	0.0622 (5)
O5	0.1313 (2)	0.2701 (2)	0.2011 (2)	0.0583 (5)
O6	0.0156 (2)	0.3306 (2)	−0.0564 (3)	0.0667 (6)
N7	−0.0873 (3)	0.1508 (2)	−0.3524 (3)	0.0484 (5)
N8	−0.3914 (3)	−0.0689 (2)	−0.1744 (3)	0.0520 (6)
N9	0.6718 (3)	0.6106 (2)	0.2812 (3)	0.0502 (6)
N10	0.3542 (3)	0.3968 (2)	0.2347 (3)	0.0511 (6)
C11	0.0345 (3)	0.2670 (2)	0.0466 (4)	0.0429 (6)
C12	−0.0723 (3)	0.1736 (2)	−0.0163 (3)	0.0366 (5)
C13	−0.1366 (3)	0.1248 (2)	−0.2026 (3)	0.0361 (5)
C14	−0.2424 (3)	0.0467 (2)	−0.2590 (3)	0.0406 (6)
C15	−0.2814 (3)	0.0157 (2)	−0.1207 (3)	0.0392 (6)
C16	−0.2207 (3)	0.0597 (2)	0.0670 (3)	0.0419 (6)
C17	−0.1168 (3)	0.1392 (2)	0.1164 (3)	0.0410 (6)
C18	0.5685 (3)	0.5405 (2)	0.2642 (3)	0.0417 (6)
C19	0.4015 (3)	0.5706 (3)	0.2028 (4)	0.0472 (6)
C20	0.3002 (3)	0.4976 (3)	0.1888 (4)	0.0507 (7)
C21	0.5115 (3)	0.3651 (3)	0.2942 (4)	0.0512 (7)
C22	0.6197 (3)	0.4326 (2)	0.3086 (4)	0.0462 (6)
C23	0.6160 (6)	0.7248 (3)	0.2446 (6)	0.0734 (10)
C24	0.8446 (4)	0.5770 (4)	0.3415 (6)	0.0661 (9)
H10	0.281 (4)	0.348 (3)	0.229 (4)	0.0889 (1)*
H14	−0.284 (3)	0.012 (2)	−0.386 (3)	0.04494 (8)*
H16	−0.255 (3)	0.039 (2)	0.161 (3)	0.04981 (9)*
H17	−0.076 (3)	0.174 (2)	0.248 (4)	0.05210 (9)*
H19	0.360 (3)	0.640 (2)	0.173 (3)	0.04818 (9)*
H20	0.191 (3)	0.519 (2)	0.145 (4)	0.0620 (1)*
H21	0.542 (3)	0.291 (3)	0.324 (4)	0.0597 (1)*
H22	0.722 (3)	0.405 (2)	0.346 (3)	0.04577 (9)*
H23A	0.697 (6)	0.758 (4)	0.254 (6)	0.1416 (2)*
H23B	0.557 (5)	0.772 (4)	0.343 (6)	0.1366 (2)*
H23C	0.539 (5)	0.723 (4)	0.122 (6)	0.1184 (2)*
H24A	0.874 (4)	0.575 (3)	0.465 (5)	0.0829 (1)*
H24B	0.879 (5)	0.501 (5)	0.261 (6)	0.1448 (2)*
H24C	0.895 (5)	0.624 (4)	0.309 (6)	0.1240 (2)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.062 (1)	0.092 (2)	0.078 (1)	−0.017 (1)	0.033 (1)	0.026 (1)
O2	0.081 (1)	0.107 (2)	0.049 (1)	−0.015 (1)	0.004 (1)	0.040 (1)
O3	0.078 (1)	0.091 (2)	0.066 (1)	−0.055 (1)	−0.009 (1)	0.013 (1)
O4	0.068 (1)	0.052 (1)	0.079 (1)	−0.0207 (10)	0.027 (1)	0.017 (1)
O5	0.058 (1)	0.074 (1)	0.045 (1)	−0.038 (1)	−0.0002 (9)	0.0079 (9)
O6	0.075 (1)	0.054 (1)	0.076 (1)	−0.030 (1)	−0.003 (1)	0.027 (1)
N7	0.057 (1)	0.053 (1)	0.039 (1)	−0.021 (1)	0.010 (1)	0.008 (1)
N8	0.048 (1)	0.047 (1)	0.062 (2)	−0.018 (1)	0.010 (1)	0.009 (1)
N9	0.053 (1)	0.048 (1)	0.052 (1)	−0.018 (1)	0.012 (1)	0.008 (1)
N10	0.052 (1)	0.052 (1)	0.047 (1)	−0.023 (1)	0.004 (1)	0.005 (1)
C11	0.038 (1)	0.041 (1)	0.049 (1)	−0.014 (1)	0.011 (1)	0.004 (1)
C12	0.032 (1)	0.036 (1)	0.039 (1)	−0.007 (1)	0.0083 (10)	0.004 (1)
C13	0.034 (1)	0.038 (1)	0.036 (1)	−0.005 (1)	0.0083 (10)	0.009 (1)
C14	0.038 (1)	0.044 (1)	0.036 (1)	−0.015 (1)	0.001 (1)	0.006 (1)
C15	0.033 (1)	0.038 (1)	0.048 (1)	−0.012 (1)	0.007 (1)	0.010 (1)
C16	0.038 (1)	0.049 (2)	0.043 (1)	−0.013 (1)	0.010 (1)	0.013 (1)
C17	0.040 (1)	0.046 (1)	0.035 (1)	−0.010 (1)	0.008 (1)	0.004 (1)
C18	0.046 (1)	0.043 (1)	0.032 (1)	−0.013 (1)	0.008 (1)	0.002 (1)
C19	0.049 (2)	0.045 (2)	0.045 (1)	−0.010 (1)	0.007 (1)	0.008 (1)
C20	0.041 (2)	0.062 (2)	0.043 (1)	−0.013 (1)	0.004 (1)	0.007 (1)
C21	0.059 (2)	0.043 (2)	0.049 (2)	−0.017 (1)	0.003 (1)	0.010 (1)
C22	0.042 (2)	0.045 (2)	0.048 (1)	−0.012 (1)	0.005 (1)	0.009 (1)
C23	0.090 (3)	0.054 (2)	0.085 (3)	−0.027 (2)	0.021 (2)	0.018 (2)
C24	0.049 (2)	0.085 (3)	0.068 (2)	−0.028 (2)	0.007 (2)	0.017 (2)

Geometric parameters (Å, º)

O1—N7	1.218 (3)	C14—H14	0.95 (2)
O2—N7	1.215 (3)	C15—C16	1.380 (3)
O3—N8	1.220 (3)	C16—C17	1.386 (4)
O4—N8	1.225 (4)	C16—H16	0.97 (3)
O5—C11	1.254 (3)	C17—H17	0.97 (2)
O6—C11	1.227 (4)	C18—C19	1.412 (3)
N7—C13	1.475 (4)	C18—C22	1.411 (4)
N8—C15	1.470 (4)	C19—C20	1.361 (5)
N9—C18	1.342 (4)	C19—H19	0.92 (3)
N9—C23	1.461 (5)	C20—H20	0.93 (3)
N9—C24	1.462 (4)	C21—C22	1.358 (5)
N10—C20	1.338 (4)	C21—H21	0.96 (3)
N10—C21	1.337 (3)	C22—H22	0.89 (2)
N10—H10	0.95 (4)	C23—H23A	0.87 (6)
C11—C12	1.527 (4)	C23—H23B	1.00 (5)
C12—C13	1.390 (3)	C23—H23C	1.00 (4)
C12—C17	1.387 (4)	C24—H24A	0.92 (4)
C13—C14	1.379 (4)	C24—H24B	0.99 (5)
C14—C15	1.377 (4)	C24—H24C	0.92 (6)
O1—N7—O2	124.7 (3)	C12—C17—C16	121.9 (2)
O1—N7—C13	117.9 (2)	C12—C17—H17	119 (2)
O2—N7—C13	117.3 (2)	C16—C17—H17	119 (2)
O3—N8—O4	123.7 (3)	N9—C18—C19	122.1 (3)
O3—N8—C15	118.1 (3)	N9—C18—C22	122.1 (2)
O4—N8—C15	118.2 (2)	C19—C18—C22	115.7 (3)
C18—N9—C23	121.3 (3)	C18—C19—C20	120.5 (3)
C18—N9—C24	121.3 (3)	C18—C19—H19	120 (2)
C23—N9—C24	117.3 (3)	C20—C19—H19	119 (2)
C20—N10—C21	119.8 (3)	N10—C20—C19	121.6 (2)
C20—N10—H10	120 (2)	N10—C20—H20	120 (2)
C21—N10—H10	120 (2)	C19—C20—H20	118 (2)
O5—C11—O6	127.4 (3)	N10—C21—C22	121.8 (3)
O5—C11—C12	115.2 (3)	N10—C21—H21	115 (2)
O6—C11—C12	117.4 (2)	C22—C21—H21	123 (2)
C11—C12—C13	123.3 (3)	C18—C22—C21	120.5 (2)
C11—C12—C17	119.5 (2)	C18—C22—H22	123 (2)
C13—C12—C17	117.1 (2)	C21—C22—H22	117 (2)
N7—C13—C12	120.5 (2)	N9—C23—H23A	110 (3)
N7—C13—C14	116.2 (2)	N9—C23—H23B	107 (3)
C12—C13—C14	123.3 (3)	N9—C23—H23C	113 (2)
C13—C14—C15	116.9 (2)	H23A—C23—H23B	108 (4)
C13—C14—H14	123 (2)	H23A—C23—H23C	111 (4)
C15—C14—H14	120 (2)	H23B—C23—H23C	107 (3)
N8—C15—C14	118.8 (2)	N9—C24—H24A	112 (2)
N8—C15—C16	118.2 (3)	N9—C24—H24B	110 (2)
C14—C15—C16	123.0 (2)	N9—C24—H24C	108 (2)
C15—C16—C17	117.8 (3)	H24A—C24—H24B	110 (4)
C15—C16—H16	121 (1)	H24A—C24—H24C	115 (3)
C17—C16—H16	121 (1)	H24B—C24—H24C	101 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N10—H10···O5	0.95 (4)	1.73 (4)	2.677 (4)	173 (3)

(II)

Crystal data

C7H11N2^+·C7H3N2O6^−	Dx = 1.471 Mg m^−3
Mr = 334.29	Mo Kα radiation, λ = 0.71073 Å
Monoclinic, P21/n	Cell parameters from 25 reflections
a = 8.102 (2) Å	θ = 14.0–14.9°
b = 7.734 (1) Å	µ = 0.12 mm^−1
c = 24.218 (1) Å	T = 298 K
β = 95.77 (1)°	Prism, yellow
V = 1509.7 (4) Å^3	0.5 × 0.3 × 0.3 mm
Z = 4

Data collection

Rigaku AFC-7R diffractometer	θmax = 27.5°, θmin = 2.5°
ω scans	h = 0→11
3708 measured reflections	k = 0→10
3468 independent reflections	l = −31→31
2383 reflections with I > 2σ(I)	3 standard reflections every 150 reflections
Rint = 0.005	intensity decay: none

Refinement

Refinement on F^2	All H-atom parameters refined
R[F^2 > 2σ(F^2)] = 0.040	w = 1/[σ^2(Fo^2) + (0.0516P)^2 + 0.3113P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.112	(Δ/σ)max = 0.001
S = 1.01	Δρmax = 0.21 e Å^−3
3468 reflections	Δρmin = −0.15 e Å^−3
273 parameters

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

	x	y	z	Uiso*/Ueq
O1	0.4270 (2)	0.3060 (2)	0.74480 (6)	0.0745 (4)
O2	0.2005 (2)	0.4333 (2)	0.71349 (5)	0.0756 (4)
O3	0.0007 (2)	0.2318 (2)	0.77268 (6)	0.0705 (4)
O4	−0.1539 (2)	0.4358 (3)	0.79930 (6)	0.0846 (5)
O5	0.5180 (2)	0.7517 (2)	0.96496 (6)	0.0663 (4)
O6	0.6862 (2)	0.5795 (2)	0.92232 (6)	0.0652 (4)
N7	0.3038 (2)	0.3893 (2)	0.75095 (6)	0.0510 (4)
N8	−0.0206 (2)	0.3667 (2)	0.79672 (5)	0.0515 (4)
N9	1.2297 (2)	0.9530 (2)	1.12078 (6)	0.0505 (3)
N10	0.7928 (2)	0.8408 (2)	1.02556 (6)	0.0478 (3)
C11	0.5491 (2)	0.6399 (2)	0.92954 (7)	0.0479 (4)
C12	0.3987 (2)	0.5756 (2)	0.89255 (6)	0.0415 (3)
C13	0.4177 (2)	0.5077 (2)	0.84036 (6)	0.0417 (3)
C14	0.2807 (2)	0.4467 (2)	0.80775 (6)	0.0394 (3)
C15	0.1247 (2)	0.4498 (2)	0.82698 (6)	0.0398 (3)
C16	0.1039 (2)	0.5199 (2)	0.87796 (6)	0.0450 (4)
C17	0.2422 (2)	0.5826 (2)	0.91046 (7)	0.0472 (4)
C18	1.0872 (2)	0.9157 (2)	1.09029 (6)	0.0396 (3)
C19	1.0799 (2)	0.7940 (2)	1.04649 (7)	0.0467 (4)
C20	0.9341 (2)	0.7613 (2)	1.01595 (7)	0.0480 (4)
C21	0.7947 (2)	0.9561 (2)	1.06694 (7)	0.0519 (4)
C22	0.9356 (2)	0.9953 (2)	1.09970 (7)	0.0477 (4)
C23	1.3827 (3)	0.8654 (4)	1.1104 (1)	0.0799 (7)
C24	1.2381 (3)	1.0826 (4)	1.1645 (1)	0.0716 (6)
H10	0.690 (3)	0.810 (3)	1.0049 (9)	0.07353 (8)*
H13	0.522 (2)	0.508 (2)	0.8261 (7)	0.04431 (5)*
H16	−0.004 (2)	0.518 (2)	0.8910 (7)	0.04955 (6)*
H17	0.231 (2)	0.629 (2)	0.9474 (7)	0.05414 (6)*
H19	1.175 (2)	0.734 (2)	1.0386 (8)	0.06220 (7)*
H20	0.925 (2)	0.679 (3)	0.9874 (9)	0.06444 (7)*
H21	0.693 (3)	1.011 (3)	1.0705 (8)	0.06654 (7)*
H22	0.928 (2)	1.076 (3)	1.1277 (8)	0.06195 (7)*
H23A	1.462 (4)	0.895 (4)	1.138 (1)	0.1199 (1)*
H23B	1.365 (3)	0.738 (4)	1.108 (1)	0.0994 (1)*
H23C	1.415 (4)	0.891 (4)	1.070 (1)	0.1399 (2)*
H24A	1.351 (4)	1.108 (4)	1.175 (1)	0.1168 (1)*
H24B	1.177 (4)	1.053 (4)	1.193 (1)	0.1199 (1)*
H24C	1.192 (4)	1.199 (4)	1.150 (1)	0.1329 (1)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0672 (9)	0.087 (1)	0.0725 (9)	0.0020 (8)	0.0218 (7)	−0.0292 (8)
O2	0.0802 (9)	0.108 (1)	0.0368 (6)	−0.0057 (9)	−0.0032 (6)	−0.0025 (7)
O3	0.0772 (9)	0.0629 (8)	0.0689 (9)	−0.0188 (7)	−0.0053 (7)	−0.0147 (7)
O4	0.0412 (7)	0.138 (1)	0.0730 (9)	0.0027 (8)	−0.0019 (6)	−0.0252 (9)
O5	0.0507 (7)	0.0723 (9)	0.0723 (8)	0.0055 (6)	−0.0124 (6)	−0.0327 (7)
O6	0.0430 (6)	0.0797 (9)	0.0708 (8)	0.0038 (6)	−0.0044 (6)	−0.0226 (7)
N7	0.0538 (8)	0.0573 (9)	0.0434 (7)	−0.0119 (7)	0.0117 (6)	−0.0089 (7)
N8	0.0456 (8)	0.0684 (10)	0.0398 (7)	−0.0108 (7)	0.0003 (6)	0.0010 (7)
N9	0.0416 (7)	0.0612 (9)	0.0470 (7)	−0.0025 (7)	−0.0047 (6)	−0.0003 (7)
N10	0.0385 (7)	0.0536 (8)	0.0496 (8)	−0.0033 (6)	−0.0039 (6)	0.0019 (7)
C11	0.0449 (9)	0.0496 (9)	0.0474 (9)	−0.0015 (7)	−0.0045 (7)	−0.0056 (7)
C12	0.0413 (8)	0.0404 (8)	0.0417 (8)	0.0002 (7)	−0.0017 (6)	−0.0021 (7)
C13	0.0387 (8)	0.0428 (8)	0.0439 (8)	0.0003 (7)	0.0055 (6)	−0.0005 (7)
C14	0.0438 (8)	0.0401 (8)	0.0342 (7)	−0.0010 (7)	0.0036 (6)	−0.0006 (6)
C15	0.0402 (8)	0.0420 (8)	0.0361 (7)	−0.0036 (6)	−0.0016 (6)	0.0033 (6)
C16	0.0412 (8)	0.0532 (9)	0.0413 (8)	−0.0009 (7)	0.0066 (6)	−0.0012 (7)
C17	0.0481 (9)	0.0537 (10)	0.0398 (8)	−0.0006 (8)	0.0046 (7)	−0.0071 (7)
C18	0.0381 (7)	0.0458 (8)	0.0348 (7)	−0.0020 (6)	0.0026 (6)	0.0052 (6)
C19	0.0405 (8)	0.0528 (9)	0.0468 (9)	0.0061 (7)	0.0052 (7)	−0.0047 (7)
C20	0.0492 (9)	0.0520 (10)	0.0424 (8)	−0.0014 (8)	0.0026 (7)	−0.0044 (8)
C21	0.0356 (8)	0.059 (1)	0.062 (1)	0.0036 (8)	0.0067 (7)	−0.0030 (9)
C22	0.0440 (9)	0.0539 (10)	0.0461 (9)	0.0006 (7)	0.0085 (7)	−0.0090 (8)
C23	0.0387 (10)	0.088 (2)	0.108 (2)	0.008 (1)	−0.015 (1)	−0.008 (2)
C24	0.064 (1)	0.093 (2)	0.057 (1)	−0.022 (1)	−0.0029 (10)	−0.019 (1)

Geometric parameters (Å, º)

O1—N7	1.210 (2)	C14—C15	1.390 (2)
O2—N7	1.219 (2)	C15—C16	1.374 (2)
O3—N8	1.216 (2)	C16—C17	1.390 (2)
O4—N8	1.212 (2)	C16—H16	0.96 (2)
O5—C11	1.262 (2)	C17—H17	0.98 (2)
O6—C11	1.233 (2)	C18—C19	1.415 (2)
N7—C14	1.475 (2)	C18—C22	1.412 (2)
N8—C15	1.470 (2)	C19—C20	1.353 (2)
N9—C18	1.338 (2)	C19—H19	0.94 (2)
N9—C23	1.457 (3)	C20—H20	0.94 (2)
N9—C24	1.455 (3)	C21—C22	1.357 (2)
N10—C20	1.340 (2)	C21—H21	0.94 (2)
N10—C21	1.340 (2)	C22—H22	0.93 (2)
N10—H10	0.96 (2)	C23—H23A	0.91 (3)
C11—C12	1.522 (2)	C23—H23B	1.00 (3)
C12—C13	1.391 (2)	C23—H23C	1.06 (3)
C12—C17	1.382 (2)	C24—H24A	0.95 (3)
C13—C14	1.379 (2)	C24—H24B	0.92 (3)
C13—H13	0.94 (2)	C24—H24C	1.02 (3)
O1—N7—O2	124.8 (2)	C12—C17—C16	121.4 (2)
O1—N7—C14	117.3 (1)	C12—C17—H17	119 (1)
O2—N7—C14	117.9 (1)	C16—C17—H17	120 (1)
O3—N8—O4	124.9 (2)	N9—C18—C19	121.7 (1)
O3—N8—C15	117.9 (1)	N9—C18—C22	122.2 (1)
O4—N8—C15	117.1 (1)	C19—C18—C22	116.1 (1)
C18—N9—C23	120.4 (2)	C18—C19—C20	120.1 (2)
C18—N9—C24	121.7 (2)	C18—C19—H19	121 (1)
C23—N9—C24	117.9 (2)	C20—C19—H19	119 (1)
C20—N10—C21	119.3 (1)	N10—C20—C19	122.2 (2)
C20—N10—H10	120 (1)	N10—C20—H20	116 (1)
C21—N10—H10	120 (1)	C19—C20—H20	122 (1)
O5—C11—O6	126.9 (2)	N10—C21—C22	122.1 (2)
O5—C11—C12	114.9 (1)	N10—C21—H21	115 (1)
O6—C11—C12	118.2 (2)	C22—C21—H21	123 (1)
C11—C12—C13	120.2 (1)	C18—C22—C21	120.1 (2)
C11—C12—C17	120.6 (1)	C18—C22—H22	122 (1)
C13—C12—C17	119.3 (1)	C21—C22—H22	118 (1)
C12—C13—C14	119.5 (1)	N9—C23—H23A	108 (2)
C12—C13—H13	121 (1)	N9—C23—H23B	110 (1)
C14—C13—H13	119 (1)	N9—C23—H23C	112 (2)
N7—C14—C13	117.8 (1)	H23A—C23—H23B	112 (2)
N7—C14—C15	121.5 (1)	H23A—C23—H23C	114 (3)
C13—C14—C15	120.6 (1)	H23B—C23—H23C	101 (2)
N8—C15—C14	122.3 (1)	N9—C24—H24A	108 (2)
N8—C15—C16	117.1 (1)	N9—C24—H24B	113 (2)
C14—C15—C16	120.3 (1)	N9—C24—H24C	111 (2)
C15—C16—C17	118.8 (2)	H24A—C24—H24B	116 (2)
C15—C16—H16	119 (1)	H24A—C24—H24C	103 (2)
C17—C16—H16	122 (1)	H24B—C24—H24C	106 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N10—H10···O5	0.96 (2)	1.68 (2)	2.633 (2)	176 (2)

(III)

Crystal data

C7H11N2^+·C7H3N2O6^−	Dx = 1.471 Mg m^−3
Mr = 334.29	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 25 reflections
a = 13.774 (2) Å	θ = 11.6–13.5°
b = 18.615 (1) Å	µ = 0.12 mm^−1
c = 5.888 (2) Å	T = 298 K
V = 1509.7 (5) Å^3	Needle, yellow
Z = 4	0.8 × 0.15 × 0.1 mm

Data collection

Rigaku AFC-7R diffractometer	θmax = 27.5°, θmin = 2.5°
θ–2θ scans	h = −10→18
2409 measured reflections	k = 0→24
2020 independent reflections	l = −4→8
1452 reflections with I > 2σ(I)	3 standard reflections every 150 reflections
Rint = 0.006	intensity decay: none

Refinement

Refinement on F^2	All H-atom parameters refined
R[F^2 > 2σ(F^2)] = 0.035	w = 1/[σ^2(Fo^2) + (0.0524P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.093	(Δ/σ)max = 0.001
S = 1.04	Δρmax = 0.13 e Å^−3
2020 reflections	Δρmin = −0.15 e Å^−3
273 parameters

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

	x	y	z	Uiso*/Ueq
O1	0.6423 (2)	0.5368 (1)	0.0984 (4)	0.0690 (7)
O2	0.7276 (2)	0.4404 (1)	0.1010 (4)	0.0635 (6)
O3	0.7105 (2)	0.2870 (1)	0.7662 (5)	0.0907 (9)
O4	0.5958 (2)	0.3011 (1)	1.0091 (4)	0.0672 (7)
O5	0.3704 (1)	0.5017 (1)	0.9388 (4)	0.0547 (6)
O6	0.3729 (1)	0.5675 (1)	0.6237 (4)	0.0554 (5)
N7	0.6645 (2)	0.4795 (1)	0.1806 (4)	0.0471 (6)
N8	0.6383 (2)	0.3175 (1)	0.8343 (5)	0.0519 (6)
N9	0.0622 (2)	0.7795 (1)	1.1244 (4)	0.0472 (6)
N10	0.2373 (2)	0.6028 (1)	1.0220 (4)	0.0439 (5)
C11	0.4023 (2)	0.5188 (1)	0.7469 (5)	0.0379 (6)
C12	0.4881 (2)	0.4748 (1)	0.6607 (4)	0.0341 (5)
C13	0.5336 (2)	0.4943 (1)	0.4594 (5)	0.0349 (5)
C14	0.6138 (2)	0.4557 (1)	0.3869 (5)	0.0371 (6)
C15	0.6487 (2)	0.3966 (2)	0.5027 (5)	0.0400 (6)
C16	0.6015 (2)	0.3788 (1)	0.7005 (5)	0.0378 (6)
C17	0.5226 (2)	0.4167 (1)	0.7838 (5)	0.0354 (6)
C18	0.1207 (2)	0.7215 (1)	1.0897 (5)	0.0348 (5)
C19	0.1145 (2)	0.6805 (1)	0.8887 (5)	0.0379 (6)
C20	0.1739 (2)	0.6225 (1)	0.8599 (5)	0.0425 (6)
C21	0.2453 (2)	0.6402 (2)	1.2141 (5)	0.0444 (6)
C22	0.1890 (2)	0.6995 (2)	1.2521 (5)	0.0423 (6)
C23	−0.0084 (3)	0.8033 (2)	0.9601 (7)	0.0639 (10)
C24	0.0733 (3)	0.8251 (2)	1.3233 (7)	0.0674 (10)
H10	0.277 (3)	0.568 (2)	0.993 (6)	0.0723 (1)*
H13	0.511 (2)	0.533 (1)	0.370 (4)	0.03585 (8)*
H15	0.700 (2)	0.371 (1)	0.447 (4)	0.02979 (8)*
H17	0.493 (2)	0.404 (1)	0.936 (5)	0.03737 (9)*
H19	0.067 (2)	0.691 (2)	0.769 (6)	0.0624 (1)*
H20	0.169 (2)	0.594 (2)	0.727 (6)	0.0591 (1)*
H21	0.293 (2)	0.625 (2)	1.334 (5)	0.0581 (1)*
H22	0.196 (2)	0.723 (1)	1.403 (5)	0.04323 (9)*
H23A	−0.059 (3)	0.836 (2)	1.037 (8)	0.1219 (2)*
H23B	0.020 (3)	0.824 (2)	0.839 (7)	0.0947 (2)*
H23C	−0.045 (2)	0.759 (2)	0.885 (7)	0.0875 (1)*
H24A	0.016 (4)	0.860 (3)	1.344 (10)	0.1529 (2)*
H24B	0.083 (3)	0.802 (3)	1.461 (9)	0.1118 (2)*
H24C	0.140 (4)	0.846 (3)	1.35 (1)	0.1667 (3)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.065 (1)	0.078 (1)	0.064 (1)	−0.001 (1)	0.012 (1)	0.030 (1)
O2	0.054 (1)	0.081 (1)	0.055 (1)	−0.003 (1)	0.017 (1)	−0.007 (1)
O3	0.100 (2)	0.098 (2)	0.074 (2)	0.067 (2)	0.018 (2)	0.018 (2)
O4	0.075 (1)	0.067 (1)	0.059 (1)	0.016 (1)	0.010 (1)	0.025 (1)
O5	0.056 (1)	0.054 (1)	0.055 (1)	0.0172 (10)	0.019 (1)	0.007 (1)
O6	0.053 (1)	0.055 (1)	0.058 (1)	0.0193 (9)	0.004 (1)	0.012 (1)
N7	0.039 (1)	0.064 (2)	0.039 (1)	−0.009 (1)	0.003 (1)	−0.001 (1)
N8	0.058 (1)	0.049 (1)	0.048 (1)	0.019 (1)	−0.004 (1)	0.001 (1)
N9	0.053 (1)	0.038 (1)	0.050 (1)	0.012 (1)	−0.001 (1)	−0.007 (1)
N10	0.042 (1)	0.040 (1)	0.050 (1)	0.010 (1)	0.011 (1)	0.004 (1)
C11	0.033 (1)	0.037 (1)	0.044 (1)	0.002 (1)	−0.001 (1)	−0.003 (1)
C12	0.032 (1)	0.032 (1)	0.038 (1)	−0.0018 (10)	−0.004 (1)	−0.005 (1)
C13	0.036 (1)	0.034 (1)	0.036 (1)	−0.003 (1)	−0.004 (1)	0.000 (1)
C14	0.031 (1)	0.047 (1)	0.033 (1)	−0.008 (1)	0.001 (1)	−0.005 (1)
C15	0.033 (1)	0.049 (1)	0.038 (1)	0.005 (1)	0.001 (1)	−0.009 (1)
C16	0.039 (1)	0.035 (1)	0.040 (1)	0.004 (1)	−0.006 (1)	0.000 (1)
C17	0.034 (1)	0.037 (1)	0.035 (1)	−0.003 (1)	−0.001 (1)	−0.005 (1)
C18	0.035 (1)	0.033 (1)	0.037 (1)	−0.002 (1)	0.007 (1)	0.001 (1)
C19	0.038 (1)	0.038 (1)	0.038 (1)	0.000 (1)	0.003 (1)	0.000 (1)
C20	0.046 (1)	0.039 (1)	0.042 (2)	0.001 (1)	0.010 (1)	−0.003 (1)
C21	0.041 (1)	0.050 (2)	0.043 (2)	0.004 (1)	0.003 (1)	0.006 (1)
C22	0.042 (1)	0.046 (1)	0.039 (1)	0.001 (1)	−0.001 (1)	−0.002 (1)
C23	0.070 (2)	0.063 (2)	0.059 (2)	0.027 (2)	−0.010 (2)	−0.001 (2)
C24	0.082 (3)	0.058 (2)	0.063 (2)	0.018 (2)	−0.010 (2)	−0.022 (2)

Geometric parameters (Å, º)

O1—N7	1.209 (4)	C14—C15	1.381 (4)
O2—N7	1.227 (3)	C15—C16	1.375 (4)
O3—N8	1.214 (4)	C15—H15	0.91 (2)
O4—N8	1.223 (4)	C16—C17	1.386 (4)
O5—C11	1.253 (4)	C17—H17	1.01 (3)
O6—C11	1.230 (3)	C18—C19	1.412 (4)
N7—C14	1.469 (3)	C18—C22	1.403 (4)
N8—C16	1.475 (4)	C19—C20	1.365 (4)
N9—C18	1.362 (3)	C19—H19	0.98 (3)
N9—C23	1.441 (5)	C20—H20	0.95 (3)
N9—C24	1.454 (5)	C21—C22	1.368 (4)
N10—C20	1.345 (4)	C21—H21	1.00 (3)
N10—C21	1.332 (4)	C22—H22	1.00 (3)
N10—H10	0.87 (3)	C23—H23A	1.02 (5)
C11—C12	1.525 (3)	C23—H23B	0.90 (4)
C12—C13	1.388 (4)	C23—H23C	1.06 (4)
C12—C17	1.387 (3)	C24—H24A	1.03 (5)
C13—C14	1.386 (3)	C24—H24B	0.93 (5)
C13—H13	0.95 (2)	C24—H24C	1.01 (5)
O1—N7—O2	123.3 (2)	C12—C17—C16	118.7 (2)
O1—N7—C14	118.5 (2)	C12—C17—H17	120 (1)
O2—N7—C14	118.2 (2)	C16—C17—H17	121 (1)
O3—N8—O4	123.6 (3)	N9—C18—C19	121.3 (2)
O3—N8—C16	117.8 (3)	N9—C18—C22	121.7 (2)
O4—N8—C16	118.6 (2)	C19—C18—C22	117.0 (2)
C18—N9—C23	122.8 (3)	C18—C19—C20	119.8 (2)
C18—N9—C24	121.4 (3)	C18—C19—H19	122 (2)
C23—N9—C24	115.6 (3)	C20—C19—H19	118 (2)
C20—N10—C21	121.0 (2)	N10—C20—C19	121.1 (3)
C20—N10—H10	118 (2)	N10—C20—H20	119 (2)
C21—N10—H10	120 (2)	C19—C20—H20	120 (2)
O5—C11—O6	127.1 (2)	N10—C21—C22	120.9 (3)
O5—C11—C12	115.9 (2)	N10—C21—H21	120 (2)
O6—C11—C12	117.0 (2)	C22—C21—H21	119 (2)
C11—C12—C13	119.6 (2)	C18—C22—C21	120.3 (3)
C11—C12—C17	120.7 (2)	C18—C22—H22	123 (1)
C13—C12—C17	119.7 (2)	C21—C22—H22	117 (1)
C12—C13—C14	119.2 (2)	N9—C23—H23A	110 (3)
C12—C13—H13	121 (2)	N9—C23—H23B	112 (3)
C14—C13—H13	119 (2)	N9—C23—H23C	111 (2)
N7—C14—C13	118.5 (2)	H23A—C23—H23B	113 (4)
N7—C14—C15	118.9 (2)	H23A—C23—H23C	108 (3)
C13—C14—C15	122.6 (2)	H23B—C23—H23C	102 (3)
C14—C15—C16	116.5 (2)	N9—C24—H24A	113 (3)
C14—C15—H15	120 (2)	N9—C24—H24B	117 (3)
C16—C15—H15	123 (2)	N9—C24—H24C	117 (4)
N8—C16—C15	118.5 (2)	H24A—C24—H24B	107 (4)
N8—C16—C17	118.3 (2)	H24A—C24—H24C	116 (4)
C15—C16—C17	123.3 (2)	H24B—C24—H24C	83 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N10—H10···O5	0.87 (3)	1.81 (3)	2.673 (3)	174 (3)