Synthesis and structural investigation of salts of 2-amino-3-methyl­pyridine with carb­oxy­lic acid derivatives: an experimental and theoretical study

The salts bis­(2-amino-3-methyl­pyridinium) fumarate dihydrate, 2C₆H₉N₂⁺·C₄H₂O₂²⁻·2H₂O (I), and 2-amino-3-methyl­pyridinium 5-chloro­salicylate, C₆H₉N₂⁺·C₇H₄ClO₃⁻ (II), were synthesized from 2-amino-3-methyl­pyridine with fumaric acid and 5-chloro­salicylic acid, respectively. The crystal structures of these salts were characterized by single-crystal X-ray diffraction, revealing protonation in I and II by the transfer of a H atom from the acid to the pyridine base. In the crystals of both I and II, N—H...O inter­actions form an R₂²(8) ring motif. Hirshfeld surface analysis distinguishes the inter­actions present in the crystal structures of I and II, and the two-dimensional (2D) fingerprint plot analysis shows the percentage contribution of each type of inter­action in the crystal packing. The volumes of the crystal voids of I (39.65 ų) and II (118.10 ų) have been calculated and reveal that the crystal of I is more mechanically stable than II. Frontier mol­ecular orbital (FMO) analysis predicts that the band gap energy of II (2.6577 eV) is lower compared to I (4.0035 eV). The Quantum Theory of Atoms In Mol­ecules (QTAIM) analysis shows that the pyridinium–carboxyl­ate N—H...O inter­action present in I is stronger than the other inter­actions, whereas in II, the hy­droxy–carboxyl­ate O—H...O inter­action is stronger than the pyridinium–carboxyl­ate N—H...O inter­action; the bond dissociation energies also confirm these results. The positive Laplacian [∇²ρ(r) > 0] of these inter­actions shows that the inter­actions are of the closed shell type. An in-silico ADME (Absorption, Distribution, Metabolism and Excretion) study predicts that both salts will exhibit good pharmacokinetic properties and druglikeness.

Computing details

Bis(2-amino-3-methylpyridin-1-ium) (2E)-but-2-enedioate dihydrate (I)

Crystal data

2C6H9N2^+·C4H2O4^2^−·2H2O	Z = 1
Mr = 368.39	F(000) = 196
Triclinic, P1	Dx = 1.324 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.8383 (2) Å	Cell parameters from 2285 reflections
b = 7.2272 (2) Å	θ = 3.1–28.3°
c = 9.7427 (2) Å	µ = 0.10 mm^−1
α = 82.921 (1)°	T = 293 K
β = 76.809 (1)°	Block, green
γ = 82.043 (1)°	0.64 × 0.50 × 0.28 mm
V = 462.18 (2) Å^3

Data collection

Bruker D8 QUEST ECO diffractometer	2118 reflections with I > 2σ(I)
ω and φ scans	Rint = 0.021
Absorption correction: numerical	θmax = 28.3°, θmin = 3.1°
Tmin = 0.985, Tmax = 0.993	h = −9→9
13678 measured reflections	k = −9→9
2285 independent reflections	l = −12→12

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: dual
R[F^2 > 2σ(F^2)] = 0.041	Hydrogen site location: difference Fourier map
wR(F^2) = 0.127	All H-atom parameters refined
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0831P)^2 + 0.0403P] where P = (Fo^2 + 2Fc^2)/3
2285 reflections	(Δ/σ)max < 0.001
166 parameters	Δρmax = 0.27 e Å^−3
0 restraints	Δρmin = −0.21 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.

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

	x	y	z	Uiso*/Ueq
O1	0.45370 (10)	0.59625 (12)	0.74961 (7)	0.0462 (2)
O2	0.78438 (11)	0.51702 (12)	0.72217 (7)	0.0484 (2)
O3	0.04724 (15)	0.74470 (16)	0.79679 (12)	0.0659 (3)
N2	0.47857 (12)	0.76067 (12)	0.48593 (8)	0.0376 (2)
N1	0.81571 (14)	0.65419 (14)	0.42588 (10)	0.0477 (3)
C1	0.65232 (14)	0.75031 (13)	0.38781 (9)	0.0351 (2)
C7	0.60883 (13)	0.53625 (13)	0.79683 (9)	0.0337 (2)
C8	0.58517 (13)	0.48544 (14)	0.95351 (9)	0.0380 (2)
C5	0.65334 (17)	0.84300 (14)	0.25000 (10)	0.0414 (2)
C2	0.30349 (16)	0.85702 (16)	0.46070 (12)	0.0460 (3)
C4	0.4763 (2)	0.94154 (15)	0.22736 (11)	0.0503 (3)
C3	0.29758 (19)	0.94987 (17)	0.33208 (13)	0.0532 (3)
C6	0.8443 (2)	0.8279 (2)	0.13837 (13)	0.0622 (3)
H2A	0.479 (2)	0.694 (2)	0.5790 (19)	0.062 (4)*
H2	0.192 (3)	0.855 (2)	0.538 (2)	0.076 (5)*
H1B	0.804 (2)	0.603 (2)	0.5182 (18)	0.060 (4)*
H4	0.475 (3)	1.009 (3)	0.133 (2)	0.078 (5)*
H1A	0.931 (3)	0.639 (2)	0.3676 (17)	0.063 (4)*
H6A	0.826 (3)	0.893 (3)	0.053 (3)	0.096 (6)*
H3	0.174 (3)	1.019 (2)	0.3195 (19)	0.070 (4)*
H6C	0.948 (4)	0.884 (3)	0.162 (2)	0.100 (7)*
H6B	0.887 (4)	0.694 (4)	0.116 (2)	0.108 (7)*
H8	0.710 (3)	0.427 (2)	0.9823 (17)	0.067 (4)*
H3A	0.172 (3)	0.686 (3)	0.797 (2)	0.082 (5)*
H3B	−0.022 (4)	0.653 (3)	0.777 (2)	0.096 (6)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0314 (4)	0.0726 (5)	0.0304 (4)	−0.0010 (3)	−0.0074 (3)	0.0071 (3)
O2	0.0309 (4)	0.0762 (5)	0.0308 (4)	0.0044 (3)	−0.0001 (3)	−0.0007 (3)
O3	0.0435 (5)	0.0768 (6)	0.0760 (6)	0.0055 (4)	−0.0130 (4)	−0.0160 (5)
N2	0.0350 (4)	0.0467 (4)	0.0284 (4)	0.0003 (3)	−0.0051 (3)	−0.0014 (3)
N1	0.0359 (5)	0.0675 (6)	0.0326 (4)	0.0078 (4)	−0.0028 (3)	−0.0011 (4)
C1	0.0364 (5)	0.0399 (4)	0.0276 (4)	−0.0020 (3)	−0.0050 (3)	−0.0040 (3)
C7	0.0298 (4)	0.0428 (4)	0.0264 (4)	−0.0024 (3)	−0.0039 (3)	−0.0009 (3)
C8	0.0303 (4)	0.0532 (5)	0.0277 (4)	0.0004 (4)	−0.0064 (3)	0.0010 (3)
C5	0.0504 (6)	0.0447 (5)	0.0280 (4)	−0.0071 (4)	−0.0060 (4)	−0.0014 (3)
C2	0.0359 (5)	0.0555 (6)	0.0441 (6)	0.0031 (4)	−0.0075 (4)	−0.0069 (4)
C4	0.0665 (7)	0.0492 (6)	0.0359 (5)	−0.0016 (5)	−0.0195 (5)	0.0031 (4)
C3	0.0503 (6)	0.0572 (6)	0.0525 (6)	0.0101 (5)	−0.0229 (5)	−0.0035 (5)
C6	0.0644 (8)	0.0813 (9)	0.0321 (5)	−0.0120 (7)	0.0054 (5)	0.0029 (5)

Geometric parameters (Å, º)

O1—C7	1.2535 (11)	C8—C8^i	1.3112 (18)
O2—C7	1.2529 (11)	C8—H8	0.981 (18)
O3—H3A	0.90 (2)	C5—C4	1.3662 (16)
O3—H3B	0.93 (2)	C5—C6	1.4971 (16)
N2—C1	1.3438 (12)	C2—C3	1.3530 (17)
N2—C2	1.3565 (13)	C2—H2	0.94 (2)
N2—H2A	0.974 (17)	C4—C3	1.4012 (19)
N1—C1	1.3339 (12)	C4—H4	0.984 (19)
N1—H1B	0.920 (17)	C3—H3	0.942 (19)
N1—H1A	0.863 (18)	C6—H6A	0.93 (2)
C1—C5	1.4236 (13)	C6—H6C	0.95 (2)
C7—C8	1.5022 (12)	C6—H6B	1.01 (2)
H3A—O3—H3B	103.8 (18)	C4—C5—C6	123.52 (10)
C1—N2—C2	123.19 (8)	C1—C5—C6	119.32 (10)
C1—N2—H2A	118.1 (10)	C3—C2—N2	120.28 (10)
C2—N2—H2A	118.7 (10)	C3—C2—H2	124.2 (11)
C1—N1—H1B	118.3 (10)	N2—C2—H2	115.5 (11)
C1—N1—H1A	122.6 (10)	C5—C4—C3	122.70 (10)
H1B—N1—H1A	119.0 (15)	C5—C4—H4	118.4 (11)
N1—C1—N2	117.74 (8)	C3—C4—H4	118.9 (11)
N1—C1—C5	123.53 (9)	C2—C3—C4	117.91 (10)
N2—C1—C5	118.73 (9)	C2—C3—H3	117.8 (11)
O2—C7—O1	124.41 (8)	C4—C3—H3	124.2 (11)
O2—C7—C8	117.18 (8)	C5—C6—H6A	111.3 (14)
O1—C7—C8	118.41 (8)	C5—C6—H6C	112.2 (14)
C8^i—C8—C7	124.23 (10)	H6A—C6—H6C	104.2 (18)
C8^i—C8—H8	121.5 (9)	C5—C6—H6B	111.1 (14)
C7—C8—H8	114.2 (9)	H6A—C6—H6B	104.8 (18)
C4—C5—C1	117.16 (10)	H6C—C6—H6B	112.8 (19)
C2—N2—C1—N1	178.78 (9)	N2—C1—C5—C6	−178.18 (10)
C2—N2—C1—C5	−0.67 (14)	C1—N2—C2—C3	−0.37 (16)
O2—C7—C8—C8^i	173.25 (13)	C1—C5—C4—C3	−1.54 (17)
O1—C7—C8—C8^i	−6.09 (18)	C6—C5—C4—C3	178.20 (12)
N1—C1—C5—C4	−177.84 (10)	N2—C2—C3—C4	0.45 (18)
N2—C1—C5—C4	1.58 (14)	C5—C4—C3—C2	0.54 (19)
N1—C1—C5—C6	2.41 (16)

Symmetry code: (i) −x+1, −y+1, −z+2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2^ii	0.86 (19)	2.16 (19)	2.96 (13)	154.5 (14)
N1—H1B···O2	0.92 (17)	1.98 (17)	2.90 (12)	174.3 (14)
N2—H2A···O1	0.97 (17)	1.70 (18)	2.67 (10)	173.2 (14)
O3—H3A···O1	0.90 (2)	1.92 (2)	2.79 (13)	165.0 (18)
O3—H3B···O2^iii	0.93 (2)	1.95 (3)	2.85 (14)	165 (2)
C2—H2···O3	0.94 (2)	2.55 (19)	3.40 (16)	149.1 (15)
C3—H3···O3^iv	0.95 (2)	2.46 (18)	3.35 (17)	156.1 (15)

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

2-Amino-3-methylpyridin-1-ium 5-chloro-2-hydroxybenzoate (II)

Crystal data

C6H9N2^+·C7H4ClO3^−	F(000) = 584
Mr = 280.7	Dx = 1.448 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3194 reflections
a = 11.7399 (2) Å	θ = 2.9–28.3°
b = 8.3731 (1) Å	µ = 0.30 mm^−1
c = 13.6779 (2) Å	T = 293 K
β = 106.782 (1)°	Plate, green
V = 1287.27 (3) Å^3	0.74 × 0.45 × 0.36 mm
Z = 4

Data collection

Bruker D8 QUEST ECO diffractometer	2907 reflections with I > 2σ(I)
ω and φ scans	Rint = 0.021
Absorption correction: numerical	θmax = 28.3°, θmin = 2.9°
Tmin = 0.606, Tmax = 0.647	h = −15→15
30652 measured reflections	k = −11→10
3194 independent reflections	l = −18→18

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: dual
R[F^2 > 2σ(F^2)] = 0.035	Hydrogen site location: difference Fourier map
wR(F^2) = 0.107	All H-atom parameters refined
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0598P)^2 + 0.2514P] where P = (Fo^2 + 2Fc^2)/3
3194 reflections	(Δ/σ)max = 0.002
224 parameters	Δρmax = 0.30 e Å^−3
0 restraints	Δρmin = −0.28 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.

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

	x	y	z	Uiso*/Ueq
Cl	1.05112 (3)	0.27065 (6)	0.57782 (3)	0.06891 (15)
O3	0.64726 (8)	0.60188 (11)	0.49608 (6)	0.0494 (2)
O1	0.70973 (9)	0.46216 (12)	0.79510 (7)	0.0506 (2)
O2	0.59619 (8)	0.61202 (12)	0.64034 (7)	0.0513 (2)
N2	0.46431 (9)	0.79911 (11)	0.40726 (7)	0.0359 (2)
N1	0.40130 (10)	0.81870 (13)	0.55084 (7)	0.0415 (2)
C8	0.38904 (9)	0.86283 (12)	0.45482 (7)	0.0329 (2)
C2	0.76984 (9)	0.46817 (12)	0.64153 (8)	0.0333 (2)
C7	0.66395 (10)	0.56791 (12)	0.58751 (8)	0.0366 (2)
C3	0.85209 (10)	0.42167 (14)	0.59101 (8)	0.0386 (2)
C9	0.30097 (10)	0.97273 (13)	0.40035 (8)	0.0372 (2)
C1	0.78668 (10)	0.41900 (14)	0.74288 (8)	0.0383 (2)
C12	0.46073 (11)	0.83664 (15)	0.31002 (9)	0.0423 (3)
C4	0.94755 (10)	0.32745 (16)	0.64037 (9)	0.0438 (3)
C11	0.37977 (12)	0.94218 (16)	0.25540 (9)	0.0472 (3)
C6	0.88328 (12)	0.32154 (17)	0.79078 (9)	0.0492 (3)
C10	0.29943 (12)	1.00941 (15)	0.30240 (9)	0.0457 (3)
C5	0.96310 (11)	0.27580 (17)	0.73958 (10)	0.0499 (3)
C13	0.21525 (12)	1.04167 (18)	0.45147 (11)	0.0499 (3)
H1A	0.3562 (15)	0.859 (2)	0.5827 (12)	0.059 (4)*
H12	0.5156 (15)	0.784 (2)	0.2873 (13)	0.056 (4)*
H3	0.8388 (13)	0.4560 (18)	0.5223 (12)	0.048 (4)*
H1B	0.4565 (15)	0.7444 (19)	0.5780 (12)	0.053 (4)*
H11	0.3748 (15)	0.969 (2)	0.1868 (12)	0.058 (4)*
H10	0.2410 (15)	1.085 (2)	0.2641 (12)	0.060 (4)*
H1	0.6558 (19)	0.517 (3)	0.7472 (16)	0.086 (6)*
H6	0.8933 (15)	0.283 (2)	0.8605 (14)	0.064 (5)*
H2	0.5216 (18)	0.725 (2)	0.4376 (15)	0.073 (5)*
H13A	0.1607 (19)	1.111 (3)	0.4046 (15)	0.088 (6)*
H13B	0.2567 (17)	1.100 (2)	0.5144 (15)	0.075 (5)*
H5	1.0313 (17)	0.199 (2)	0.7694 (15)	0.075 (5)*
H13C	0.1699 (19)	0.957 (3)	0.4738 (16)	0.086 (6)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl	0.0479 (2)	0.0929 (3)	0.0708 (3)	0.01654 (17)	0.02496 (18)	−0.0117 (2)
O3	0.0525 (5)	0.0564 (5)	0.0393 (4)	0.0140 (4)	0.0131 (4)	0.0070 (4)
O1	0.0533 (5)	0.0649 (6)	0.0398 (4)	0.0047 (4)	0.0233 (4)	0.0057 (4)
O2	0.0510 (5)	0.0582 (5)	0.0502 (5)	0.0176 (4)	0.0233 (4)	0.0074 (4)
N2	0.0385 (5)	0.0380 (4)	0.0336 (4)	0.0007 (4)	0.0139 (4)	−0.0013 (3)
N1	0.0468 (5)	0.0477 (5)	0.0332 (5)	0.0080 (4)	0.0165 (4)	0.0019 (4)
C8	0.0344 (5)	0.0327 (5)	0.0324 (5)	−0.0041 (4)	0.0107 (4)	−0.0038 (4)
C2	0.0325 (5)	0.0332 (5)	0.0337 (5)	−0.0038 (4)	0.0088 (4)	−0.0025 (4)
C7	0.0378 (5)	0.0336 (5)	0.0389 (5)	−0.0007 (4)	0.0117 (4)	−0.0006 (4)
C3	0.0366 (5)	0.0440 (6)	0.0355 (5)	−0.0020 (4)	0.0110 (4)	−0.0032 (4)
C9	0.0362 (5)	0.0379 (5)	0.0367 (5)	−0.0005 (4)	0.0091 (4)	−0.0024 (4)
C1	0.0376 (5)	0.0432 (5)	0.0345 (5)	−0.0044 (4)	0.0110 (4)	−0.0010 (4)
C12	0.0487 (6)	0.0461 (6)	0.0372 (5)	−0.0043 (5)	0.0205 (5)	−0.0043 (4)
C4	0.0333 (5)	0.0512 (6)	0.0465 (6)	0.0009 (5)	0.0111 (4)	−0.0087 (5)
C11	0.0584 (7)	0.0522 (7)	0.0325 (5)	−0.0043 (5)	0.0155 (5)	0.0023 (5)
C6	0.0466 (6)	0.0602 (7)	0.0364 (6)	0.0028 (5)	0.0050 (5)	0.0070 (5)
C10	0.0475 (6)	0.0470 (6)	0.0391 (6)	0.0031 (5)	0.0070 (5)	0.0045 (5)
C5	0.0377 (6)	0.0557 (7)	0.0493 (7)	0.0063 (5)	0.0016 (5)	0.0012 (5)
C13	0.0441 (6)	0.0554 (7)	0.0511 (7)	0.0116 (6)	0.0153 (5)	−0.0012 (6)

Geometric parameters (Å, º)

Cl—C4	1.7428 (12)	C3—H3	0.952 (15)
O3—C7	1.2417 (13)	C9—C10	1.3694 (17)
O1—C1	1.3525 (14)	C9—C13	1.4971 (16)
O1—H1	0.90 (2)	C1—C6	1.3972 (17)
O2—C7	1.2741 (13)	C12—C11	1.3538 (19)
N2—C8	1.3494 (13)	C12—H12	0.907 (17)
N2—C12	1.3554 (14)	C4—C5	1.3851 (19)
N2—H2	0.92 (2)	C11—C10	1.4036 (19)
N1—C8	1.3315 (14)	C11—H11	0.951 (16)
N1—H1A	0.849 (18)	C6—C5	1.376 (2)
N1—H1B	0.897 (17)	C6—H6	0.982 (18)
C8—C9	1.4233 (15)	C10—H10	0.967 (17)
C2—C3	1.3953 (15)	C5—H5	1.01 (2)
C2—C1	1.4043 (15)	C13—H13A	0.96 (2)
C2—C7	1.5028 (15)	C13—H13B	0.99 (2)
C3—C4	1.3774 (17)	C13—H13C	0.99 (2)
C1—O1—H1	101.0 (13)	C11—C12—N2	120.72 (11)
C8—N2—C12	122.84 (10)	C11—C12—H12	125.8 (11)
C8—N2—H2	122.9 (12)	N2—C12—H12	113.5 (11)
C12—N2—H2	114.2 (12)	C3—C4—C5	121.16 (11)
C8—N1—H1A	119.3 (11)	C3—C4—Cl	119.99 (10)
C8—N1—H1B	117.4 (10)	C5—C4—Cl	118.84 (10)
H1A—N1—H1B	123.3 (15)	C12—C11—C10	117.81 (11)
N1—C8—N2	117.81 (10)	C12—C11—H11	122.3 (10)
N1—C8—C9	123.44 (10)	C10—C11—H11	119.9 (10)
N2—C8—C9	118.76 (9)	C5—C6—C1	120.24 (11)
C3—C2—C1	119.13 (10)	C5—C6—H6	119.6 (10)
C3—C2—C7	120.27 (9)	C1—C6—H6	120.2 (10)
C1—C2—C7	120.59 (10)	C9—C10—C11	122.50 (11)
O3—C7—O2	124.20 (10)	C9—C10—H10	118.9 (10)
O3—C7—C2	119.34 (10)	C11—C10—H10	118.6 (10)
O2—C7—C2	116.46 (9)	C6—C5—C4	119.68 (11)
C4—C3—C2	119.90 (10)	C6—C5—H5	123.0 (11)
C4—C3—H3	122.4 (9)	C4—C5—H5	117.2 (11)
C2—C3—H3	117.7 (9)	C9—C13—H13A	109.3 (12)
C10—C9—C8	117.36 (10)	C9—C13—H13B	111.7 (11)
C10—C9—C13	123.34 (11)	H13A—C13—H13B	110.6 (16)
C8—C9—C13	119.30 (10)	C9—C13—H13C	111.3 (12)
O1—C1—C6	118.94 (10)	H13A—C13—H13C	109.0 (17)
O1—C1—C2	121.19 (10)	H13B—C13—H13C	104.9 (16)
C6—C1—C2	119.87 (11)
C12—N2—C8—N1	−179.32 (10)	C3—C2—C1—C6	−1.56 (17)
C12—N2—C8—C9	0.82 (16)	C7—C2—C1—C6	177.71 (10)
C3—C2—C7—O3	3.52 (16)	C8—N2—C12—C11	0.10 (18)
C1—C2—C7—O3	−175.75 (10)	C2—C3—C4—C5	0.77 (18)
C3—C2—C7—O2	−176.66 (10)	C2—C3—C4—Cl	−179.44 (8)
C1—C2—C7—O2	4.08 (15)	N2—C12—C11—C10	−0.70 (19)
C1—C2—C3—C4	0.64 (16)	O1—C1—C6—C5	−179.95 (12)
C7—C2—C3—C4	−178.64 (10)	C2—C1—C6—C5	1.10 (19)
N1—C8—C9—C10	179.07 (11)	C8—C9—C10—C11	0.50 (18)
N2—C8—C9—C10	−1.08 (15)	C13—C9—C10—C11	−179.30 (12)
N1—C8—C9—C13	−1.13 (17)	C12—C11—C10—C9	0.4 (2)
N2—C8—C9—C13	178.72 (10)	C1—C6—C5—C4	0.3 (2)
C3—C2—C1—O1	179.51 (10)	C3—C4—C5—C6	−1.2 (2)
C7—C2—C1—O1	−1.22 (16)	Cl—C4—C5—C6	178.96 (11)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2	0.90 (2)	1.63 (2)	2.49 (13)	159 (2)
N1—H1A···O1^i	0.85 (18)	2.20 (17)	3.02 (15)	162.2 (16)
N1—H1B···O2^ii	0.89 (17)	1.95 (17)	2.84 (15)	170.3 (16)
N2—H2···O3^ii	0.92 (19)	1.79 (2)	2.70 (14)	172.2)
C3—H3···O3	0.95 (16)	2.49 (16)	2.81 (15)	100.0 (11)

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