Insights on structure and inter­actions of 2-amino-4-meth­oxy-6-methyl­pyrimidinium salts with 4-amino­salicylate and 5-chloro­salicylate: a combined experimental and theoretical charge–density analysis

The proton-transfer com­plexes 2-amino-4-meth­oxy-6-methyl­pyrimidinium (2A4M6MP) 4-amino­salicylate (4AMSA), C₆H₁₀N₃O⁺·C₇H₆NO₃⁻, I, and 5-chloro­salicylate (5ClSA), C₆H₁₀N₃O⁺·C₇H₄ClO₃⁻, II, were synthesized by slow evaporation and crystallized. The crystal structures of both I and II were determined by single-crystal X-ray structure analysis. The crystal structures of both salts exhibit O—H...O, N—H...O, N—H...N and C—H...O inter­actions in their crystals. The 4AMSA and 5ClSA anions in combination with the 2A4M6MP cations form distinct synthons, which are represented by the graph-set notations R₂²(8), R₄²(8) and R₂²(8). Furthermore, the ΔpK_a values were calculated and clearly demonstrate that 2A4M6MP is a good salt former when combined with carb­oxy­lic acids. Hirshfeld surface analysis was used to qu­antify the weak and strong inter­actions in the solid state, and energy framework calculations showed the stability of the hydrogen-bonding inter­actions. QTAIM (quantum theory of atoms in mol­ecules) analysis revealed the nature of the chemical bonding in I and II, and the charge–density distribution in the inter­molecular inter­actions in the crystal structures.

Computing details

For both structures, data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006). Program(s) used to solve structure: SHELXS (Sheldrick, 2008) for (I); SHELXT2014 (Sheldrick, 2015a) for (II). For both structures, program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b). Molecular graphics: OLEX2 (Dolomanov et al., 2009), PLATON (Spek, 2020) and Mercury (Macrae et al., 2020) and ORTEP-3 for Windows (Farrugia, 2012) for (I); OLEX2 (Dolomanov et al., 2009), PLATON (Spek, 2020) and Mercury (Macrae et al., 2020) for (II). Software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015b) and WinGX (Farrugia, 2012) for (I); SHELXL2014 (Sheldrick, 2015b) for (II).

2-Amino-4-methoxy-6-methylpyrimidinium 4-amino-2-hydroxybenzoate (I)

Crystal data

C6H10N3O^+·C7H6NO3^−	F(000) = 616
Mr = 292.3	Dx = 1.392 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 21/n	Cell parameters from 6906 reflections
a = 8.8829 (2) Å	θ = 2.7–28.2°
b = 15.1248 (3) Å	µ = 0.11 mm^−1
c = 10.4933 (3) Å	T = 293 K
β = 98.392 (1)°	Block, brown
V = 1394.70 (6) Å^3	0.28 × 0.23 × 0.18 mm
Z = 4

Data collection

Bruker D8 QUEST ECO diffractometer	2573 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.019
phi scans	θmax = 25.9°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2006)	h = −8→10
Tmin = 0.710, Tmax = 0.746	k = −18→17
8088 measured reflections	l = −12→12
2690 independent reflections

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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.126	H atoms treated by a mixture of independent and constrained refinement
S = 1.17	w = 1/[σ^2(Fo^2) + (0.0578P)^2 + 0.2501P] where P = (Fo^2 + 2Fc^2)/3
2690 reflections	(Δ/σ)max < 0.001
228 parameters	Δρmax = 0.19 e Å^−3
0 restraints	Δρmin = −0.14 e Å^−3
0 constraints

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.

Single crystal X-ray diffraction intensity data for the crystals of I and II were collected on Bruker D8 QUEST ECO diffractometer (Bruker, 2006) equipped with APEX III photon detector and Molybdenum monochromator (Mo Kα radiation, λ = 0.71073 Å). The unit cell refinement and data reduction were carried out using Bruker SAINT (Bruker, 2006) and the necessary absorption corrections were performed by multiscan method using SADABS (Bruker, 2006). The structure of both crystals I and II were solved by direct methods using SHELXS incorporated to WinGX-2014 program suite and refined by full-matrix least-squares techniques using SHELXL (Sheldrick, 2008, 2015). The unit cell, X-ray intensity data collection and crystal structure refinement details of salt (I) and (II) are presented in Table 1. Diagrams and publication material were generated using Olex2 (Dolomanov et al., 2009), PLATON (Spek, 2020) and Mercury softwares (Macrae et al., 2020).

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

	x	y	z	Uiso*/Ueq
H8	0.557 (2)	0.2155 (14)	0.9816 (19)	0.062 (6)*
H11	0.119 (2)	0.3848 (12)	0.8608 (16)	0.043 (4)*
H4	0.509 (3)	0.307 (2)	0.678 (3)	0.111 (9)*
H3	0.473 (2)	0.5151 (13)	0.8772 (19)	0.058 (6)*
H3A	0.882 (2)	0.5480 (14)	0.540 (2)	0.059 (6)*
H13	0.646 (2)	0.5910 (14)	0.566 (2)	0.067 (6)*
H4B	0.463 (3)	0.1857 (16)	1.177 (2)	0.066 (7)*
H3B	0.984 (3)	0.4953 (15)	0.651 (2)	0.065 (6)*
H4A	0.314 (2)	0.2248 (13)	1.206 (2)	0.054 (6)*
O2	0.16222 (13)	0.41781 (8)	0.63413 (11)	0.0499 (3)
N1	0.80749 (15)	0.47671 (9)	0.80428 (12)	0.0423 (3)
C12	0.31316 (17)	0.33716 (10)	0.79760 (14)	0.0357 (4)
O1	0.70149 (14)	0.43536 (9)	0.98058 (11)	0.0527 (4)
O3	0.37952 (14)	0.36188 (9)	0.59087 (11)	0.0529 (4)
N2	0.65577 (15)	0.56046 (9)	0.64433 (13)	0.0420 (3)
C13	0.28234 (18)	0.37514 (11)	0.66724 (15)	0.0387 (4)
O4	0.54959 (14)	0.27302 (10)	0.75865 (13)	0.0610 (4)
C11	0.21193 (18)	0.35023 (11)	0.88628 (15)	0.0378 (4)
C4	0.69030 (19)	0.47687 (11)	0.86762 (15)	0.0405 (4)
C9	0.36391 (18)	0.26076 (11)	1.04421 (15)	0.0418 (4)
N3	0.90016 (19)	0.52269 (12)	0.62232 (16)	0.0593 (5)
N4	0.3878 (2)	0.22401 (13)	1.16520 (16)	0.0608 (5)
C10	0.23558 (18)	0.31375 (11)	1.00685 (15)	0.0410 (4)
H10	0.1667	0.3241	1.0639	0.049*
C2	0.53537 (18)	0.56017 (11)	0.71129 (16)	0.0403 (4)
C3	0.55101 (19)	0.51842 (12)	0.82589 (16)	0.0445 (4)
C7	0.44378 (18)	0.28625 (11)	0.83790 (16)	0.0411 (4)
C1	0.78794 (19)	0.51967 (11)	0.69082 (15)	0.0419 (4)
C8	0.4677 (2)	0.24902 (12)	0.95922 (17)	0.0470 (4)
C6	0.8393 (3)	0.38770 (16)	1.0263 (2)	0.0688 (6)
H6A	0.8568	0.3438	0.9639	0.103*
H6B	0.8294	0.3594	1.1065	0.103*
H6C	0.9234	0.4281	1.0388	0.103*
C5	0.3953 (2)	0.60699 (14)	0.65024 (19)	0.0548 (5)
H5A	0.3104	0.5889	0.6911	0.082*
H5B	0.3758	0.5925	0.5603	0.082*
H5C	0.4096	0.6697	0.6601	0.082*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O2	0.0450 (7)	0.0616 (8)	0.0434 (7)	0.0130 (6)	0.0079 (5)	0.0123 (6)
N1	0.0459 (8)	0.0471 (8)	0.0362 (7)	0.0073 (6)	0.0133 (6)	0.0057 (6)
C12	0.0357 (8)	0.0357 (8)	0.0355 (8)	−0.0021 (6)	0.0047 (6)	0.0008 (6)
O1	0.0562 (7)	0.0644 (8)	0.0409 (7)	0.0102 (6)	0.0184 (6)	0.0144 (6)
O3	0.0505 (7)	0.0701 (9)	0.0411 (7)	0.0132 (6)	0.0166 (5)	0.0125 (6)
N2	0.0437 (8)	0.0464 (8)	0.0376 (7)	0.0072 (6)	0.0119 (6)	0.0054 (6)
C13	0.0390 (8)	0.0387 (8)	0.0384 (8)	−0.0009 (7)	0.0056 (6)	0.0015 (7)
O4	0.0494 (7)	0.0853 (10)	0.0517 (8)	0.0247 (7)	0.0187 (6)	0.0140 (7)
C11	0.0359 (8)	0.0394 (9)	0.0381 (8)	−0.0009 (7)	0.0048 (6)	−0.0005 (6)
C4	0.0468 (9)	0.0417 (9)	0.0351 (8)	−0.0007 (7)	0.0128 (7)	0.0006 (7)
C9	0.0456 (9)	0.0424 (9)	0.0363 (8)	−0.0064 (7)	0.0018 (7)	0.0030 (7)
N3	0.0516 (9)	0.0817 (13)	0.0494 (9)	0.0243 (9)	0.0236 (7)	0.0279 (9)
N4	0.0611 (11)	0.0755 (12)	0.0458 (9)	0.0092 (9)	0.0084 (8)	0.0211 (8)
C10	0.0415 (9)	0.0460 (9)	0.0366 (8)	−0.0029 (7)	0.0094 (7)	−0.0011 (7)
C2	0.0408 (8)	0.0390 (8)	0.0422 (9)	0.0008 (7)	0.0094 (7)	−0.0042 (7)
C3	0.0425 (9)	0.0509 (10)	0.0431 (9)	0.0009 (7)	0.0160 (7)	−0.0001 (7)
C7	0.0383 (8)	0.0445 (9)	0.0412 (9)	0.0032 (7)	0.0086 (7)	0.0020 (7)
C1	0.0448 (9)	0.0445 (9)	0.0384 (8)	0.0068 (7)	0.0130 (7)	0.0040 (7)
C8	0.0430 (9)	0.0499 (10)	0.0469 (10)	0.0080 (8)	0.0025 (7)	0.0068 (8)
C6	0.0699 (13)	0.0839 (15)	0.0553 (12)	0.0228 (11)	0.0178 (10)	0.0276 (11)
C5	0.0458 (10)	0.0592 (12)	0.0596 (11)	0.0089 (8)	0.0081 (8)	0.0032 (9)

Geometric parameters (Å, º)

O2—C13	1.2521 (19)	C9—C10	1.402 (2)
N1—C4	1.314 (2)	N3—C1	1.312 (2)
N1—C1	1.345 (2)	N3—H3A	0.94 (2)
C12—C11	1.399 (2)	N3—H3B	0.87 (2)
C12—C7	1.405 (2)	N4—H4B	0.88 (2)
C12—C13	1.472 (2)	N4—H4A	0.83 (2)
O1—C4	1.3322 (19)	C10—H10	0.93
O1—C6	1.441 (2)	C2—C3	1.347 (2)
O3—C13	1.2765 (19)	C2—C5	1.493 (2)
N2—C1	1.353 (2)	C3—H3	0.94 (2)
N2—C2	1.363 (2)	C7—C8	1.380 (2)
N2—H13	0.94 (2)	C8—H8	0.94 (2)
O4—C7	1.3577 (19)	C6—H6A	0.96
O4—H4	1.01 (3)	C6—H6B	0.96
C11—C10	1.368 (2)	C6—H6C	0.96
C11—H11	0.981 (18)	C5—H5A	0.96
C4—C3	1.400 (2)	C5—H5B	0.96
C9—N4	1.374 (2)	C5—H5C	0.96
C9—C8	1.385 (2)
C4—N1—C1	115.93 (14)	C9—C10—H10	120.1
C11—C12—C7	117.38 (14)	C3—C2—N2	118.38 (15)
C11—C12—C13	120.83 (14)	C3—C2—C5	125.20 (15)
C7—C12—C13	121.79 (14)	N2—C2—C5	116.42 (15)
C4—O1—C6	118.77 (14)	C2—C3—C4	117.45 (15)
C1—N2—C2	121.18 (14)	C2—C3—H3	123.3 (12)
C1—N2—H13	120.2 (13)	C4—C3—H3	119.2 (12)
C2—N2—H13	118.6 (13)	O4—C7—C8	118.53 (15)
O2—C13—O3	122.26 (14)	O4—C7—C12	120.76 (14)
O2—C13—C12	119.63 (14)	C8—C7—C12	120.71 (15)
O3—C13—C12	118.10 (14)	N3—C1—N1	119.43 (15)
C7—O4—H4	104.1 (16)	N3—C1—N2	118.38 (15)
C10—C11—C12	122.08 (15)	N1—C1—N2	122.19 (14)
C10—C11—H11	118.5 (10)	C7—C8—C9	120.94 (16)
C12—C11—H11	119.4 (10)	C7—C8—H8	117.5 (12)
N1—C4—O1	119.17 (15)	C9—C8—H8	121.6 (12)
N1—C4—C3	124.88 (15)	O1—C6—H6A	109.5
O1—C4—C3	115.96 (14)	O1—C6—H6B	109.5
N4—C9—C8	121.03 (17)	H6A—C6—H6B	109.5
N4—C9—C10	119.97 (17)	O1—C6—H6C	109.5
C8—C9—C10	118.95 (15)	H6A—C6—H6C	109.5
C1—N3—H3A	118.4 (12)	H6B—C6—H6C	109.5
C1—N3—H3B	118.2 (14)	C2—C5—H5A	109.5
H3A—N3—H3B	122.9 (19)	C2—C5—H5B	109.5
C9—N4—H4B	114.4 (14)	H5A—C5—H5B	109.5
C9—N4—H4A	116.3 (14)	C2—C5—H5C	109.5
H4B—N4—H4A	125 (2)	H5A—C5—H5C	109.5
C11—C10—C9	119.88 (15)	H5B—C5—H5C	109.5
C11—C10—H10	120.1
C11—C12—C13—O2	−1.8 (2)	C5—C2—C3—C4	179.16 (16)
C7—C12—C13—O2	177.82 (15)	N1—C4—C3—C2	1.1 (3)
C11—C12—C13—O3	179.25 (15)	O1—C4—C3—C2	−179.28 (15)
C7—C12—C13—O3	−1.1 (2)	C11—C12—C7—O4	−177.92 (15)
C7—C12—C11—C10	−1.4 (2)	C13—C12—C7—O4	2.4 (2)
C13—C12—C11—C10	178.20 (15)	C11—C12—C7—C8	1.7 (2)
C1—N1—C4—O1	179.81 (14)	C13—C12—C7—C8	−177.93 (15)
C1—N1—C4—C3	−0.5 (3)	C4—N1—C1—N3	179.71 (17)
C6—O1—C4—N1	−3.2 (3)	C4—N1—C1—N2	−0.1 (2)
C6—O1—C4—C3	177.10 (17)	C2—N2—C1—N3	−179.58 (17)
C12—C11—C10—C9	−0.6 (2)	C2—N2—C1—N1	0.3 (3)
N4—C9—C10—C11	−179.95 (16)	O4—C7—C8—C9	179.68 (16)
C8—C9—C10—C11	2.3 (2)	C12—C7—C8—C9	0.0 (3)
C1—N2—C2—C3	0.3 (2)	N4—C9—C8—C7	−179.76 (17)
C1—N2—C2—C5	−179.75 (16)	C10—C9—C8—C7	−2.1 (3)
N2—C2—C3—C4	−0.9 (2)

2-Amino-4-methoxy-6-methylpyrimidinium 5-chloro-2-hydroxybenzoate (II)

Crystal data

C6H10N3O^+·C7H4ClO3^−	Z = 2
Mr = 311.72	F(000) = 324
Triclinic, P1	Dx = 1.483 Mg m^−3 Dm = 1.483 Mg m^−3 Dm measured by ?
a = 8.329 (6) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.962 (8) Å	Cell parameters from 3294 reflections
c = 9.998 (7) Å	θ = 3.1–28.3°
α = 111.66 (2)°	µ = 0.29 mm^−1
β = 111.263 (13)°	T = 293 K
γ = 94.052 (18)°	Block, colourless
V = 698.1 (9) Å^3	0.33 × 0.16 × 0.10 mm

Data collection

Bruker D8 QUEST ECO diffractometer	2483 reflections with I > 2σ(I)
phi scans	Rint = 0.030
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	θmax = 28.3°, θmin = 2.5°
Tmin = 0.594, Tmax = 0.746	h = −11→11
9507 measured reflections	k = −13→13
3433 independent reflections	l = −13→13

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.064	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.162	w = 1/[σ^2(Fo^2) + (0.0741P)^2 + 0.2462P] where P = (Fo^2 + 2Fc^2)/3
S = 1.09	(Δ/σ)max < 0.001
3433 reflections	Δρmax = 0.42 e Å^−3
216 parameters	Δρmin = −0.27 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. Single crystal X-ray diffraction intensity data for the crystals of I and II were collected on Bruker D8 QUEST ECO diffractometer (Bruker, 2006) equipped with APEXIII photon detector and Molybdenum monochromator (Mo Kα radiation, λ = 0.71073 Å). The unit cell refinement and data reduction were carried out using Bruker SAINT (Bruker, 2006) and the necessary absorption corrections were performed by multiscan method using SADABS (Bruker, 2006). The structure of both crystals I and II were solved by direct methods using SHELXS incorporated to WinGX-2014 program suite and refined by full-matrix least-squares techniques using SHELXL (Sheldrick, 2008, 2015). The unit cell, X-ray intensity data collection and crystal structure refinement details of salt (I) and (II) are presented in Table 1. Diagrams and publication material were generated using Olex2 (Dolomanov et al., 2009), PLATON (Spek, 2020) and Mercury softwares (Macrae et al., 2020).

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

	x	y	z	Uiso*/Ueq
H9	0.526 (4)	0.902 (3)	0.910 (3)	0.059 (8)*
H11	0.697 (4)	0.677 (3)	0.590 (3)	0.049 (8)*
H3	1.176 (3)	0.438 (3)	0.092 (3)	0.044 (7)*
H8	0.750 (4)	1.120 (3)	1.005 (3)	0.048 (7)*
H13	1.074 (4)	0.724 (3)	0.438 (4)	0.059 (8)*
H4	1.033 (5)	1.111 (4)	0.832 (4)	0.077 (11)*
Cl1	0.42523 (9)	0.62173 (8)	0.68319 (10)	0.0615 (3)
N1	1.1392 (2)	0.7017 (2)	0.3749 (2)	0.0354 (5)
N2	1.3851 (2)	0.7841 (2)	0.3361 (2)	0.0341 (4)
C4	1.3439 (3)	0.6505 (3)	0.2202 (3)	0.0380 (5)
C12	0.8394 (3)	0.8872 (3)	0.7207 (3)	0.0360 (5)
O3	1.0850 (2)	0.9862 (2)	0.6925 (2)	0.0553 (5)
O2	0.9380 (3)	0.7520 (2)	0.5297 (2)	0.0568 (5)
O1	1.4390 (2)	0.61839 (19)	0.1345 (2)	0.0483 (5)
N3	1.3071 (3)	0.9393 (2)	0.5279 (2)	0.0424 (5)
H3A	1.3943	1.0097	0.5548	0.051*
H3B	1.2388	0.9544	0.5764	0.051*
C3	1.2024 (3)	0.5346 (3)	0.1761 (3)	0.0450 (6)
C2	1.1004 (3)	0.5644 (3)	0.2587 (3)	0.0386 (5)
O4	0.9775 (3)	1.1457 (2)	0.8921 (3)	0.0530 (5)
C13	0.9628 (3)	0.8736 (3)	0.6413 (3)	0.0406 (6)
C1	1.2784 (3)	0.8089 (2)	0.4130 (3)	0.0321 (5)
C11	0.7070 (3)	0.7642 (3)	0.6725 (3)	0.0391 (6)
C10	0.5941 (3)	0.7747 (3)	0.7457 (3)	0.0408 (6)
C7	0.8553 (3)	1.0214 (3)	0.8433 (3)	0.0401 (6)
C8	0.7394 (4)	1.0286 (3)	0.9164 (4)	0.0520 (7)
C5	0.9474 (4)	0.4539 (3)	0.2308 (4)	0.0554 (7)
H5A	0.9724	0.4364	0.3238	0.083*
H5B	0.9286	0.3623	0.1425	0.083*
H5C	0.8427	0.4919	0.2083	0.083*
C9	0.6111 (4)	0.9056 (3)	0.8679 (4)	0.0529 (7)
C6	1.5901 (4)	0.7267 (3)	0.1751 (4)	0.0539 (7)
H6A	1.5546	0.8150	0.1701	0.081*
H6B	1.6425	0.6880	0.1020	0.081*
H6C	1.6750	0.7502	0.2807	0.081*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0509 (4)	0.0591 (5)	0.0830 (6)	0.0011 (3)	0.0410 (4)	0.0283 (4)
N1	0.0358 (10)	0.0348 (10)	0.0385 (11)	0.0022 (8)	0.0238 (9)	0.0117 (9)
N2	0.0324 (9)	0.0351 (10)	0.0371 (11)	0.0058 (7)	0.0210 (8)	0.0118 (9)
C4	0.0383 (12)	0.0388 (12)	0.0415 (13)	0.0087 (9)	0.0238 (11)	0.0148 (11)
C12	0.0364 (12)	0.0413 (13)	0.0388 (13)	0.0106 (9)	0.0225 (10)	0.0188 (11)
O3	0.0514 (11)	0.0548 (12)	0.0598 (12)	−0.0031 (8)	0.0364 (10)	0.0145 (10)
O2	0.0606 (11)	0.0522 (11)	0.0616 (12)	0.0024 (9)	0.0472 (10)	0.0092 (10)
O1	0.0524 (10)	0.0436 (10)	0.0495 (11)	0.0061 (8)	0.0370 (9)	0.0061 (8)
N3	0.0412 (11)	0.0359 (10)	0.0466 (12)	−0.0031 (8)	0.0304 (10)	0.0043 (9)
C3	0.0505 (14)	0.0340 (13)	0.0473 (15)	0.0026 (10)	0.0282 (12)	0.0076 (12)
C2	0.0395 (12)	0.0335 (12)	0.0412 (13)	0.0023 (9)	0.0195 (11)	0.0129 (11)
O4	0.0582 (12)	0.0372 (10)	0.0613 (13)	0.0039 (8)	0.0333 (10)	0.0116 (9)
C13	0.0399 (13)	0.0461 (14)	0.0413 (14)	0.0065 (10)	0.0248 (11)	0.0171 (12)
C1	0.0322 (11)	0.0336 (11)	0.0338 (12)	0.0055 (8)	0.0180 (9)	0.0143 (10)
C11	0.0427 (13)	0.0369 (13)	0.0417 (14)	0.0078 (10)	0.0265 (11)	0.0126 (11)
C10	0.0387 (12)	0.0428 (13)	0.0506 (15)	0.0084 (10)	0.0266 (11)	0.0224 (12)
C7	0.0427 (13)	0.0388 (13)	0.0428 (14)	0.0099 (10)	0.0220 (11)	0.0175 (11)
C8	0.0658 (18)	0.0435 (15)	0.0551 (17)	0.0177 (13)	0.0427 (15)	0.0116 (13)
C5	0.0552 (16)	0.0378 (14)	0.0685 (19)	−0.0056 (11)	0.0352 (14)	0.0115 (13)
C9	0.0592 (16)	0.0543 (16)	0.0637 (18)	0.0174 (13)	0.0463 (15)	0.0234 (14)
C6	0.0512 (15)	0.0532 (16)	0.0588 (17)	0.0066 (12)	0.0394 (14)	0.0104 (14)

Geometric parameters (Å, º)

Cl1—C10	1.746 (3)	C3—H3	0.96 (3)
N1—C2	1.348 (3)	C2—C5	1.494 (3)
N1—C1	1.354 (3)	O4—C7	1.350 (3)
N1—H13	0.95 (3)	O4—H4	0.87 (4)
N2—C4	1.319 (3)	C11—C10	1.374 (3)
N2—C1	1.353 (3)	C11—H11	0.92 (3)
C4—O1	1.338 (3)	C10—C9	1.373 (4)
C4—C3	1.404 (3)	C7—C8	1.398 (4)
C12—C11	1.392 (3)	C8—C9	1.371 (4)
C12—C7	1.399 (4)	C8—H8	0.98 (3)
C12—C13	1.496 (3)	C5—H5A	0.9600
O3—C13	1.262 (3)	C5—H5B	0.9600
O2—C13	1.247 (3)	C5—H5C	0.9600
O1—C6	1.423 (3)	C9—H9	0.95 (3)
N3—C1	1.311 (3)	C6—H6A	0.9600
N3—H3A	0.8600	C6—H6B	0.9600
N3—H3B	0.8600	C6—H6C	0.9600
C3—C2	1.362 (3)
C2—N1—C1	121.7 (2)	C10—C11—C12	120.2 (2)
C2—N1—H13	120.7 (19)	C10—C11—H11	121.7 (17)
C1—N1—H13	117.5 (19)	C12—C11—H11	118.1 (17)
C4—N2—C1	116.17 (19)	C9—C10—C11	120.7 (2)
N2—C4—O1	120.0 (2)	C9—C10—Cl1	118.95 (19)
N2—C4—C3	124.6 (2)	C11—C10—Cl1	120.3 (2)
O1—C4—C3	115.4 (2)	O4—C7—C8	118.7 (2)
C11—C12—C7	119.3 (2)	O4—C7—C12	122.1 (2)
C11—C12—C13	119.6 (2)	C8—C7—C12	119.2 (2)
C7—C12—C13	121.1 (2)	C9—C8—C7	120.4 (3)
C4—O1—C6	119.38 (19)	C9—C8—H8	118.6 (17)
C1—N3—H3A	120.0	C7—C8—H8	121.0 (17)
C1—N3—H3B	120.0	C2—C5—H5A	109.5
H3A—N3—H3B	120.0	C2—C5—H5B	109.5
C2—C3—C4	116.9 (2)	H5A—C5—H5B	109.5
C2—C3—H3	120.2 (16)	C2—C5—H5C	109.5
C4—C3—H3	122.8 (16)	H5A—C5—H5C	109.5
N1—C2—C3	118.8 (2)	H5B—C5—H5C	109.5
N1—C2—C5	116.9 (2)	C8—C9—C10	120.2 (2)
C3—C2—C5	124.4 (2)	C8—C9—H9	125.2 (18)
C7—O4—H4	100 (2)	C10—C9—H9	114.6 (18)
O2—C13—O3	124.7 (2)	O1—C6—H6A	109.5
O2—C13—C12	117.8 (2)	O1—C6—H6B	109.5
O3—C13—C12	117.5 (2)	H6A—C6—H6B	109.5
N3—C1—N2	120.42 (19)	O1—C6—H6C	109.5
N3—C1—N1	117.8 (2)	H6A—C6—H6C	109.5
N2—C1—N1	121.8 (2)	H6B—C6—H6C	109.5
C1—N2—C4—O1	177.7 (2)	C2—N1—C1—N3	−179.8 (2)
C1—N2—C4—C3	−1.8 (4)	C2—N1—C1—N2	0.4 (4)
N2—C4—O1—C6	3.4 (4)	C7—C12—C11—C10	−0.5 (4)
C3—C4—O1—C6	−177.1 (2)	C13—C12—C11—C10	179.3 (2)
N2—C4—C3—C2	0.9 (4)	C12—C11—C10—C9	−0.7 (4)
O1—C4—C3—C2	−178.7 (2)	C12—C11—C10—Cl1	178.82 (19)
C1—N1—C2—C3	−1.4 (4)	C11—C12—C7—O4	−177.9 (2)
C1—N1—C2—C5	178.0 (2)	C13—C12—C7—O4	2.3 (4)
C4—C3—C2—N1	0.8 (4)	C11—C12—C7—C8	0.9 (4)
C4—C3—C2—C5	−178.5 (3)	C13—C12—C7—C8	−178.8 (3)
C11—C12—C13—O2	2.4 (4)	O4—C7—C8—C9	178.6 (3)
C7—C12—C13—O2	−177.9 (2)	C12—C7—C8—C9	−0.3 (4)
C11—C12—C13—O3	−177.5 (2)	C7—C8—C9—C10	−0.8 (5)
C7—C12—C13—O3	2.2 (4)	C11—C10—C9—C8	1.3 (5)
C4—N2—C1—N3	−178.7 (2)	Cl1—C10—C9—C8	−178.2 (2)
C4—N2—C1—N1	1.2 (3)