Lamotriginium crotonate and lamotriginium salicylate ethanol monosolvate: the role of solvent mol­ecules in the packing organization

Two lamotriginium salts, namely lamotriginium crotonate [systematic name: 3,5-di­amino-6-(2,3-di­chloro­phen­yl)-1,2,4-triazin-2-ium but-2-enoate, C₉H₈Cl₂N₅⁺·C₄H₅O₂⁻, (III)] and lamotriginium salicylate [systematic name: 3,5-di­amino-6-(2,3-di­chloro­phen­yl)-1,2,4-triazin-2-ium 2-hy­droxy­benzoate ethanol monosolvate, C₉H₈Cl₂N₅⁺·C₇H₅O₃⁻·C₂H₅OH, (IV)] present extremely similar centrosymmetric hydrogen-bonded A...L...L...A packing building blocks (L is lamotriginium and A is the anion). The fact that salicylate salt (IV) is (ethanol) solvated, while crotonate salt (III) is not, has a profound effect on the way these elemental units aggregate to generate the final crystal structure. Possible reasons for this behaviour are analyzed and the hypothesis raised checked against similar structures in the literature.

Computing details

For both compounds, data collection: CrysAlis PRO (Rigaku OD, 2015); cell refinement: CrysAlis PRO (Rigaku OD, 2015); data reduction: CrysAlis PRO (Rigaku OD, 2015); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008). Program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015) for (III); SHELXL2014 (Sheldrick, 2015) for (IV). For both compounds, molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015) and PLATON (Spek, 2009).

(III) 3,5-Diamino-6-(2,3-dichlorophenyl)-1,2,4-triazin-2-ium but-2-enoate

Crystal data

C9H8Cl2N5^+·C4H5O2^−	Dx = 1.356 Mg m^−3
Mr = 342.18	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I41/a	Cell parameters from 2042 reflections
a = 19.513 (3) Å	θ = 3.7–26.8°
c = 17.613 (4) Å	µ = 0.40 mm^−1
V = 6706 (2) Å^3	T = 294 K
Z = 16	Fragment, pale_yellow
F(000) = 2816	0.35 × 0.22 × 0.16 mm

Data collection

Rigaku OD Xcalibur Eos Gemini diffractometer	3726 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source	2148 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.028
Detector resolution: 16.0604 pixels mm^-1	θmax = 28.7°, θmin = 3.3°
ω scans	h = −25→13
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2015)	k = −14→25
Tmin = 0.88, Tmax = 0.94	l = −17→23
8373 measured reflections

Refinement

Refinement on F^2	7 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.057	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.185	w = 1/[σ^2(Fo^2) + (0.0918P)^2 + 4.2506P] where P = (Fo^2 + 2Fc^2)/3
S = 0.97	(Δ/σ)max = 0.003
3726 reflections	Δρmax = 0.25 e Å^−3
240 parameters	Δρmin = −0.29 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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cl1	0.73692 (7)	0.34332 (6)	0.00171 (5)	0.0996 (5)	0.949 (3)
Cl2	0.77488 (6)	0.28325 (8)	−0.15600 (5)	0.1222 (6)	0.949 (3)
N1	0.57311 (12)	0.29306 (12)	0.10267 (12)	0.0557 (6)
N2	0.55588 (12)	0.31338 (12)	0.17307 (12)	0.0538 (6)
H2	0.5087 (16)	0.3303 (15)	0.1793 (16)	0.070 (9)*
N3	0.57590 (14)	0.32645 (14)	0.29991 (14)	0.0607 (7)
H3A	0.5373 (17)	0.3496 (16)	0.3028 (18)	0.073*
H3B	0.6011 (17)	0.3250 (16)	0.3366 (19)	0.073*
N4	0.66117 (10)	0.28023 (11)	0.22563 (11)	0.0484 (5)
N5	0.74067 (12)	0.23232 (14)	0.14769 (15)	0.0596 (7)
H5A	0.7687 (16)	0.2274 (16)	0.188 (2)	0.072*
H5B	0.7544 (16)	0.2227 (16)	0.103 (2)	0.072*
C1	0.59818 (13)	0.30640 (13)	0.23302 (14)	0.0476 (6)
C2	0.67972 (13)	0.25935 (13)	0.15677 (14)	0.0479 (6)
C3	0.63275 (14)	0.26608 (14)	0.09340 (14)	0.0518 (6)
C4	0.65009 (15)	0.23897 (16)	0.01699 (16)	0.0616 (7)
C5	0.69774 (16)	0.27052 (16)	−0.02847 (16)	0.0636 (8)
C6	0.71503 (19)	0.2437 (2)	−0.09959 (18)	0.0848 (11)
C7	0.6839 (3)	0.1856 (3)	−0.1233 (3)	0.1299 (18)
H7	0.6943	0.1677	−0.1709	0.156*
C8	0.6375 (3)	0.1529 (3)	−0.0785 (3)	0.156 (3)
H8	0.6185	0.1119	−0.0953	0.188*
C9	0.6176 (3)	0.1789 (2)	−0.0080 (2)	0.1163 (17)
H9	0.5843	0.1573	0.0212	0.140*
O11	0.42895 (10)	0.35815 (11)	0.18802 (11)	0.0673 (6)
O21	0.45000 (12)	0.39226 (13)	0.30578 (10)	0.0552 (5)	0.794 (5)
C11	0.41111 (13)	0.38516 (16)	0.24903 (12)	0.0473 (7)	0.794 (5)
C21	0.34109 (18)	0.4106 (2)	0.25422 (17)	0.0696 (13)	0.794 (5)
H21	0.3136	0.4061	0.2114	0.083*	0.794 (5)
C31	0.31388 (13)	0.4390 (2)	0.31349 (18)	0.0833 (15)	0.794 (5)
H31	0.3420	0.4453	0.3555	0.100*	0.794 (5)
C41	0.24060 (16)	0.4627 (3)	0.3204 (4)	0.138 (3)	0.794 (5)
H41A	0.2397	0.5100	0.3353	0.208*	0.794 (5)
H41B	0.2174	0.4355	0.3578	0.208*	0.794 (5)
H41C	0.2180	0.4576	0.2723	0.208*	0.794 (5)
O21'	0.4500 (3)	0.4020 (3)	0.30177 (15)	0.0552 (5)	0.206 (5)
C11'	0.4156 (2)	0.3981 (2)	0.24123 (15)	0.0473 (7)	0.206 (5)
C21'	0.3521 (5)	0.4431 (3)	0.2369 (3)	0.0696 (13)	0.206 (5)
H21'	0.3258	0.4414	0.1929	0.083*	0.206 (5)
C31'	0.33264 (19)	0.4836 (2)	0.2910 (3)	0.0833 (15)	0.206 (5)
H31'	0.3614	0.4880	0.3328	0.100*	0.206 (5)
C41'	0.2669 (2)	0.5242 (3)	0.2913 (17)	0.138 (3)	0.206 (5)
H41D	0.2410	0.5132	0.3360	0.208*	0.206 (5)
H41E	0.2405	0.5129	0.2470	0.208*	0.206 (5)
H41F	0.2773	0.5723	0.2910	0.208*	0.206 (5)
Cl1'	0.70186 (18)	0.3605 (3)	−0.00746 (18)	0.0996 (5)	0.051 (3)
Cl2'	0.74014 (19)	0.3010 (3)	−0.16535 (18)	0.1222 (6)	0.051 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.1377 (11)	0.0848 (7)	0.0763 (7)	−0.0353 (7)	0.0082 (6)	0.0146 (5)
Cl2	0.1006 (9)	0.2122 (15)	0.0539 (6)	0.0130 (9)	0.0176 (5)	0.0313 (7)
N1	0.0577 (14)	0.0688 (14)	0.0408 (13)	0.0039 (12)	−0.0053 (10)	−0.0046 (10)
N2	0.0496 (13)	0.0694 (15)	0.0424 (13)	0.0119 (11)	−0.0039 (10)	−0.0045 (11)
N3	0.0577 (14)	0.0851 (18)	0.0393 (13)	0.0208 (13)	0.0006 (11)	−0.0078 (12)
N4	0.0471 (11)	0.0621 (13)	0.0360 (11)	0.0073 (10)	0.0010 (9)	−0.0036 (9)
N5	0.0533 (13)	0.0900 (18)	0.0355 (12)	0.0171 (13)	0.0033 (10)	−0.0055 (12)
C1	0.0502 (14)	0.0522 (14)	0.0402 (14)	0.0042 (12)	−0.0012 (11)	−0.0009 (11)
C2	0.0494 (14)	0.0558 (15)	0.0384 (14)	0.0011 (12)	0.0002 (11)	−0.0012 (11)
C3	0.0532 (15)	0.0614 (16)	0.0408 (14)	0.0014 (13)	−0.0009 (11)	−0.0043 (12)
C4	0.0625 (17)	0.0777 (19)	0.0446 (16)	−0.0025 (16)	−0.0029 (13)	−0.0095 (14)
C5	0.0686 (18)	0.0792 (19)	0.0429 (16)	0.0057 (16)	−0.0042 (13)	0.0071 (14)
C6	0.087 (2)	0.125 (3)	0.0424 (18)	0.012 (2)	0.0002 (16)	−0.0035 (19)
C7	0.146 (4)	0.181 (5)	0.063 (3)	−0.016 (4)	0.013 (3)	−0.048 (3)
C8	0.191 (6)	0.177 (5)	0.101 (4)	−0.080 (5)	0.020 (4)	−0.074 (4)
C9	0.138 (4)	0.139 (4)	0.072 (3)	−0.059 (3)	0.014 (2)	−0.052 (2)
O11	0.0606 (12)	0.0911 (14)	0.0501 (12)	0.0128 (11)	−0.0086 (9)	−0.0218 (10)
O21	0.0535 (10)	0.0658 (13)	0.0462 (11)	0.0080 (10)	−0.0063 (8)	−0.0088 (9)
C11	0.0472 (14)	0.0504 (17)	0.0444 (15)	−0.0009 (13)	−0.0014 (12)	−0.0014 (13)
C21	0.057 (2)	0.087 (3)	0.064 (2)	0.020 (2)	−0.0159 (17)	−0.015 (2)
C31	0.058 (2)	0.111 (4)	0.081 (3)	0.035 (2)	−0.007 (2)	−0.014 (3)
C41	0.082 (4)	0.195 (7)	0.139 (6)	0.070 (4)	0.003 (3)	−0.016 (5)
O21'	0.0535 (10)	0.0658 (13)	0.0462 (11)	0.0080 (10)	−0.0063 (8)	−0.0088 (9)
C11'	0.0472 (14)	0.0504 (17)	0.0444 (15)	−0.0009 (13)	−0.0014 (12)	−0.0014 (13)
C21'	0.057 (2)	0.087 (3)	0.064 (2)	0.020 (2)	−0.0159 (17)	−0.015 (2)
C31'	0.058 (2)	0.111 (4)	0.081 (3)	0.035 (2)	−0.007 (2)	−0.014 (3)
C41'	0.082 (4)	0.195 (7)	0.139 (6)	0.070 (4)	0.003 (3)	−0.016 (5)
Cl1'	0.1377 (11)	0.0848 (7)	0.0763 (7)	−0.0353 (7)	0.0082 (6)	0.0146 (5)
Cl2'	0.1006 (9)	0.2122 (15)	0.0539 (6)	0.0130 (9)	0.0176 (5)	0.0313 (7)

Geometric parameters (Å, º)

Cl1—C5	1.698 (3)	C8—H8	0.9300
Cl2—C6	1.717 (4)	C9—H9	0.9300
N1—C3	1.288 (3)	O11—C11	1.247 (3)
N1—N2	1.345 (3)	O11—C11'	1.247 (3)
N2—C1	1.347 (3)	O21—C11	1.263 (2)
N2—H2	0.98 (3)	C11—C21	1.456 (4)
N3—C1	1.315 (3)	C21—C31	1.296 (4)
N3—H3A	0.88 (3)	C21—H21	0.9300
N3—H3B	0.81 (3)	C31—C41	1.508 (4)
N4—C2	1.330 (3)	C31—H31	0.9300
N4—C1	1.337 (3)	C41—H41A	0.9600
N5—C2	1.311 (3)	C41—H41B	0.9600
N5—H5A	0.90 (3)	C41—H41C	0.9600
N5—H5B	0.85 (3)	O21'—C11'	1.263 (2)
C2—C3	1.450 (4)	C11'—C21'	1.521 (9)
C3—C4	1.485 (4)	C21'—C31'	1.296 (4)
C4—C5	1.373 (4)	C21'—H21'	0.9300
C4—C9	1.403 (5)	C31'—C41'	1.508 (4)
C5—C6	1.399 (4)	C31'—H31'	0.9300
C6—C7	1.352 (6)	C41'—H41D	0.9600
C7—C8	1.359 (7)	C41'—H41E	0.9600
C7—H7	0.9300	C41'—H41F	0.9600
C8—C9	1.397 (6)
C3—N1—N2	117.6 (2)	C9—C8—H8	119.0
N1—N2—C1	122.7 (2)	C8—C9—C4	117.2 (4)
N1—N2—H2	115.8 (17)	C8—C9—H9	121.4
C1—N2—H2	121.3 (17)	C4—C9—H9	121.4
C1—N3—H3A	119 (2)	O11—C11—O21	124.1 (2)
C1—N3—H3B	120 (2)	O11—C11—C21	117.4 (2)
H3A—N3—H3B	119 (3)	O21—C11—C21	118.5 (2)
C2—N4—C1	117.1 (2)	C31—C21—C11	125.5 (3)
C2—N5—H5A	120 (2)	C31—C21—H21	117.2
C2—N5—H5B	119 (2)	C11—C21—H21	117.2
H5A—N5—H5B	121 (3)	C21—C31—C41	125.8 (4)
N3—C1—N4	120.3 (2)	C21—C31—H31	117.1
N3—C1—N2	118.0 (2)	C41—C31—H31	117.1
N4—C1—N2	121.7 (2)	C31—C41—H41A	109.5
N5—C2—N4	118.8 (2)	C31—C41—H41B	109.5
N5—C2—C3	121.1 (2)	H41A—C41—H41B	109.5
N4—C2—C3	120.2 (2)	C31—C41—H41C	109.5
N1—C3—C2	120.7 (2)	H41A—C41—H41C	109.5
N1—C3—C4	117.8 (2)	H41B—C41—H41C	109.5
C2—C3—C4	121.4 (2)	O11—C11'—O21'	124.1 (2)
C5—C4—C9	119.8 (3)	O11—C11'—C21'	119.5 (3)
C5—C4—C3	121.5 (3)	O21'—C11'—C21'	116.2 (3)
C9—C4—C3	118.6 (3)	C31'—C21'—C11'	123.6 (6)
C4—C5—C6	121.2 (3)	C31'—C21'—H21'	118.2
C4—C5—Cl1	119.8 (2)	C11'—C21'—H21'	118.2
C6—C5—Cl1	119.0 (3)	C21'—C31'—C41'	124.9 (12)
C7—C6—C5	118.8 (4)	C21'—C31'—H31'	117.5
C7—C6—Cl2	120.3 (3)	C41'—C31'—H31'	117.5
C5—C6—Cl2	120.9 (3)	C31'—C41'—H41D	109.5
C6—C7—C8	120.9 (4)	C31'—C41'—H41E	109.5
C6—C7—H7	119.6	H41D—C41'—H41E	109.5
C8—C7—H7	119.6	C31'—C41'—H41F	109.5
C7—C8—C9	122.0 (5)	H41D—C41'—H41F	109.5
C7—C8—H8	119.0	H41E—C41'—H41F	109.5

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5A···N4^i	0.90 (3)	2.06 (3)	2.951 (3)	176 (3)
N2—H2···O11	0.98 (3)	1.66 (3)	2.639 (3)	179 (3)
N3—H3A···O21	0.88 (3)	1.90 (3)	2.774 (4)	175 (3)
N3—H3B···O21^ii	0.81 (3)	2.12 (3)	2.899 (3)	162 (3)
N5—H5B···O21^iii	0.85 (3)	2.23 (3)	2.870 (3)	132 (3)

Symmetry codes: (i) −x+3/2, −y+1/2, −z+1/2; (ii) y+1/4, −x+3/4, −z+3/4; (iii) −y+5/4, x−1/4, z−1/4.

(IV) 3,5-Diamino-6-(2,3-dichlorophenyl)-1,2,4-triazin-2-ium 2-hydroxybenzoate ethanol monosolvate

Crystal data

C9H8Cl2N5^+·C7H5O3^−·C2H6O	Z = 2
Mr = 440.28	F(000) = 456
Triclinic, P1	Dx = 1.449 Mg m^−3
a = 7.9389 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.2938 (9) Å	Cell parameters from 1967 reflections
c = 12.3282 (8) Å	θ = 3.2–25.9°
α = 61.781 (7)°	µ = 0.36 mm^−1
β = 79.379 (5)°	T = 294 K
γ = 72.313 (5)°	Fragment, pale_yellow
V = 1008.92 (12) Å^3	0.42 × 0.28 × 0.18 mm

Data collection

Rigaku OD Xcalibur Eos Gemini diffractometer	4360 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source	2863 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
Detector resolution: 16.0604 pixels mm^-1	θmax = 28.8°, θmin = 2.9°
ω scans	h = −10→9
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2015)	k = −16→15
Tmin = 0.86, Tmax = 0.96	l = −15→16
8324 measured reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.056	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.168	w = 1/[σ^2(Fo^2) + (0.0776P)^2 + 0.1003P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max < 0.001
4360 reflections	Δρmax = 0.34 e Å^−3
284 parameters	Δρmin = −0.37 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.

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

	x	y	z	Uiso*/Ueq
Cl1	0.55710 (10)	0.81807 (7)	0.59053 (7)	0.0550 (2)
Cl2	0.53000 (11)	0.96585 (8)	0.74551 (9)	0.0641 (3)
N1	0.5333 (3)	0.4790 (2)	0.7616 (2)	0.0425 (5)
N2	0.5259 (3)	0.4109 (2)	0.7047 (2)	0.0428 (6)
H2	0.442 (4)	0.375 (3)	0.727 (3)	0.051*
N3	0.6164 (3)	0.3362 (2)	0.5606 (2)	0.0433 (6)
H3A	0.528 (4)	0.303 (3)	0.584 (3)	0.052*
H3B	0.694 (4)	0.321 (3)	0.510 (3)	0.052*
N4	0.7847 (3)	0.4482 (2)	0.58172 (19)	0.0368 (5)
N5	0.9385 (3)	0.5594 (3)	0.6148 (3)	0.0481 (6)
H5A	1.012 (4)	0.553 (3)	0.561 (3)	0.058*
H5B	0.941 (4)	0.607 (3)	0.644 (3)	0.058*
C1	0.6440 (3)	0.3985 (2)	0.6155 (2)	0.0358 (6)
C2	0.7992 (3)	0.5132 (3)	0.6391 (2)	0.0372 (6)
C3	0.6650 (3)	0.5315 (3)	0.7307 (2)	0.0375 (6)
C4	0.6723 (3)	0.6047 (3)	0.7962 (2)	0.0391 (6)
C5	0.6182 (3)	0.7363 (3)	0.7423 (2)	0.0383 (6)
C6	0.6126 (3)	0.8027 (3)	0.8083 (3)	0.0444 (7)
C7	0.6668 (4)	0.7374 (3)	0.9282 (3)	0.0513 (7)
H7	0.6637	0.7818	0.9724	0.062*
C8	0.7248 (4)	0.6073 (4)	0.9816 (3)	0.0573 (8)
H8	0.7635	0.5638	1.0615	0.069*
C9	0.7267 (4)	0.5395 (3)	0.9176 (3)	0.0497 (7)
H9	0.7640	0.4510	0.9552	0.060*
O21	0.3024 (2)	0.2441 (2)	0.65319 (18)	0.0503 (5)
O11	0.2676 (3)	0.3002 (2)	0.8044 (2)	0.0639 (6)
O31	0.0951 (3)	0.1304 (2)	0.6420 (2)	0.0583 (6)
H31A	0.177 (5)	0.169 (4)	0.629 (4)	0.087*
C11	0.0087 (4)	0.1393 (3)	0.7446 (3)	0.0430 (6)
C21	−0.1392 (4)	0.0895 (3)	0.7930 (3)	0.0555 (8)
H21	−0.1753	0.0500	0.7562	0.067*
C31	−0.2308 (4)	0.0989 (3)	0.8947 (3)	0.0615 (9)
H31	−0.3299	0.0661	0.9262	0.074*
C41	−0.1794 (4)	0.1563 (4)	0.9516 (3)	0.0640 (9)
H41	−0.2430	0.1625	1.0206	0.077*
C51	−0.0317 (4)	0.2041 (3)	0.9041 (3)	0.0501 (7)
H51	0.0045	0.2422	0.9424	0.060*
C61	0.0640 (3)	0.1968 (2)	0.8008 (2)	0.0377 (6)
C71	0.2219 (3)	0.2512 (3)	0.7493 (2)	0.0408 (6)
O12	0.9291 (3)	0.2327 (2)	0.4205 (2)	0.0604 (6)
H12	0.980 (5)	0.188 (4)	0.490 (4)	0.091*
C12	0.9330 (4)	0.1557 (3)	0.3627 (3)	0.0583 (8)
H12A	0.8547	0.0997	0.4082	0.070*
H12B	1.0520	0.1035	0.3613	0.070*
C22	0.8745 (5)	0.2409 (4)	0.2342 (3)	0.0775 (11)
H22A	0.9516	0.2968	0.1901	0.116*
H22B	0.7555	0.2906	0.2364	0.116*
H22C	0.8787	0.1901	0.1934	0.116*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0618 (5)	0.0581 (5)	0.0480 (5)	−0.0133 (4)	−0.0083 (3)	−0.0249 (4)
Cl2	0.0603 (5)	0.0586 (5)	0.0901 (7)	−0.0127 (4)	−0.0084 (4)	−0.0462 (5)
N1	0.0420 (13)	0.0527 (14)	0.0425 (13)	−0.0199 (11)	0.0068 (10)	−0.0271 (11)
N2	0.0391 (13)	0.0544 (15)	0.0491 (14)	−0.0246 (11)	0.0106 (10)	−0.0311 (12)
N3	0.0384 (13)	0.0546 (15)	0.0509 (15)	−0.0192 (11)	0.0063 (10)	−0.0331 (13)
N4	0.0319 (11)	0.0431 (13)	0.0436 (13)	−0.0131 (9)	0.0038 (9)	−0.0255 (11)
N5	0.0393 (13)	0.0700 (18)	0.0581 (17)	−0.0273 (12)	0.0139 (11)	−0.0445 (15)
C1	0.0348 (13)	0.0373 (14)	0.0374 (14)	−0.0094 (11)	−0.0033 (10)	−0.0174 (11)
C2	0.0346 (13)	0.0409 (15)	0.0412 (15)	−0.0125 (11)	0.0024 (11)	−0.0221 (12)
C3	0.0363 (14)	0.0439 (15)	0.0385 (15)	−0.0134 (12)	0.0029 (11)	−0.0229 (12)
C4	0.0353 (13)	0.0508 (17)	0.0406 (15)	−0.0178 (12)	0.0088 (11)	−0.0274 (13)
C5	0.0305 (13)	0.0543 (17)	0.0392 (15)	−0.0158 (12)	0.0045 (10)	−0.0271 (13)
C6	0.0331 (14)	0.0574 (18)	0.0586 (18)	−0.0161 (12)	0.0044 (12)	−0.0380 (15)
C7	0.0442 (16)	0.074 (2)	0.0556 (19)	−0.0199 (15)	0.0052 (13)	−0.0444 (17)
C8	0.0582 (19)	0.081 (2)	0.0447 (18)	−0.0200 (17)	0.0010 (14)	−0.0370 (17)
C9	0.0562 (18)	0.0559 (19)	0.0383 (16)	−0.0172 (15)	0.0038 (13)	−0.0223 (14)
O21	0.0509 (12)	0.0732 (14)	0.0454 (12)	−0.0327 (10)	0.0094 (9)	−0.0350 (11)
O11	0.0658 (14)	0.1030 (18)	0.0624 (14)	−0.0541 (13)	0.0188 (10)	−0.0563 (14)
O31	0.0568 (13)	0.0817 (16)	0.0625 (14)	−0.0342 (12)	0.0009 (10)	−0.0442 (13)
C11	0.0410 (15)	0.0474 (16)	0.0470 (17)	−0.0148 (13)	−0.0062 (12)	−0.0227 (13)
C21	0.0468 (17)	0.061 (2)	0.070 (2)	−0.0233 (15)	−0.0104 (15)	−0.0294 (17)
C31	0.0394 (16)	0.071 (2)	0.074 (2)	−0.0293 (15)	0.0032 (15)	−0.0255 (18)
C41	0.0451 (17)	0.090 (3)	0.062 (2)	−0.0265 (17)	0.0131 (14)	−0.0377 (19)
C51	0.0438 (16)	0.066 (2)	0.0485 (18)	−0.0190 (14)	−0.0002 (13)	−0.0293 (16)
C61	0.0336 (13)	0.0422 (15)	0.0405 (15)	−0.0113 (11)	−0.0044 (11)	−0.0189 (12)
C71	0.0427 (15)	0.0464 (16)	0.0401 (16)	−0.0177 (12)	−0.0044 (11)	−0.0201 (13)
O12	0.0626 (14)	0.0663 (15)	0.0688 (16)	−0.0174 (12)	−0.0092 (11)	−0.0401 (13)
C12	0.0554 (19)	0.068 (2)	0.068 (2)	−0.0180 (16)	−0.0043 (15)	−0.0407 (18)
C22	0.072 (2)	0.101 (3)	0.066 (2)	−0.020 (2)	−0.0096 (19)	−0.042 (2)

Geometric parameters (Å, º)

Cl1—C5	1.734 (3)	C9—H9	0.9300
Cl2—C6	1.724 (3)	O21—C71	1.267 (3)
N1—C3	1.298 (3)	O11—C71	1.251 (3)
N1—N2	1.342 (3)	O31—C11	1.360 (3)
N2—C1	1.343 (3)	O31—H31A	0.87 (4)
N2—H2	0.84 (3)	C11—C61	1.391 (3)
N3—C1	1.319 (3)	C11—C21	1.394 (4)
N3—H3A	0.85 (3)	C21—C31	1.365 (5)
N3—H3B	0.84 (3)	C21—H21	0.9300
N4—C2	1.331 (3)	C31—C41	1.380 (4)
N4—C1	1.341 (3)	C31—H31	0.9300
N5—C2	1.317 (3)	C41—C51	1.380 (4)
N5—H5A	0.82 (3)	C41—H41	0.9300
N5—H5B	0.82 (3)	C51—C61	1.385 (4)
C2—C3	1.453 (3)	C51—H51	0.9300
C3—C4	1.483 (3)	C61—C71	1.495 (4)
C4—C5	1.382 (4)	O12—C12	1.420 (3)
C4—C9	1.400 (4)	O12—H12	0.86 (4)
C5—C6	1.386 (3)	C12—C22	1.492 (5)
C6—C7	1.385 (4)	C12—H12A	0.9700
C7—C8	1.368 (5)	C12—H12B	0.9700
C7—H7	0.9300	C22—H22A	0.9600
C8—C9	1.388 (4)	C22—H22B	0.9600
C8—H8	0.9300	C22—H22C	0.9600
C3—N1—N2	117.6 (2)	C4—C9—H9	120.1
N1—N2—C1	123.1 (2)	C11—O31—H31A	101 (3)
N1—N2—H2	117 (2)	O31—C11—C61	121.6 (2)
C1—N2—H2	120 (2)	O31—C11—C21	118.3 (2)
C1—N3—H3A	120 (2)	C61—C11—C21	120.1 (3)
C1—N3—H3B	119 (2)	C31—C21—C11	119.7 (3)
H3A—N3—H3B	121 (3)	C31—C21—H21	120.1
C2—N4—C1	116.6 (2)	C11—C21—H21	120.1
C2—N5—H5A	120 (2)	C21—C31—C41	121.4 (3)
C2—N5—H5B	120 (2)	C21—C31—H31	119.3
H5A—N5—H5B	119 (3)	C41—C31—H31	119.3
N3—C1—N4	120.5 (2)	C51—C41—C31	118.7 (3)
N3—C1—N2	117.7 (2)	C51—C41—H41	120.7
N4—C1—N2	121.8 (2)	C31—C41—H41	120.7
N5—C2—N4	119.8 (2)	C41—C51—C61	121.6 (3)
N5—C2—C3	119.3 (2)	C41—C51—H51	119.2
N4—C2—C3	120.9 (2)	C61—C51—H51	119.2
N1—C3—C2	119.9 (2)	C51—C61—C11	118.6 (2)
N1—C3—C4	116.7 (2)	C51—C61—C71	120.8 (2)
C2—C3—C4	123.4 (2)	C11—C61—C71	120.6 (2)
C5—C4—C9	118.8 (2)	O11—C71—O21	123.8 (2)
C5—C4—C3	121.4 (2)	O11—C71—C61	118.0 (2)
C9—C4—C3	119.6 (2)	O21—C71—C61	118.2 (2)
C4—C5—C6	120.7 (2)	C12—O12—H12	111 (3)
C4—C5—Cl1	119.16 (19)	O12—C12—C22	108.6 (3)
C6—C5—Cl1	120.1 (2)	O12—C12—H12A	110.0
C7—C6—C5	120.0 (3)	C22—C12—H12A	110.0
C7—C6—Cl2	119.0 (2)	O12—C12—H12B	110.0
C5—C6—Cl2	120.9 (2)	C22—C12—H12B	110.0
C8—C7—C6	119.9 (3)	H12A—C12—H12B	108.4
C8—C7—H7	120.1	C12—C22—H22A	109.5
C6—C7—H7	120.1	C12—C22—H22B	109.5
C7—C8—C9	120.7 (3)	H22A—C22—H22B	109.5
C7—C8—H8	119.7	C12—C22—H22C	109.5
C9—C8—H8	119.7	H22A—C22—H22C	109.5
C8—C9—C4	119.9 (3)	H22B—C22—H22C	109.5
C8—C9—H9	120.1

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5A···N4^i	0.82 (3)	2.16 (3)	2.972 (3)	174 (3)
N2—H2···O11	0.84 (3)	1.77 (3)	2.599 (3)	168 (3)
N3—H3A···O21	0.85 (3)	2.03 (3)	2.872 (3)	171 (3)
N3—H3B···O12	0.84 (3)	2.24 (3)	3.057 (3)	164 (3)
N5—H5B···O12^i	0.82 (3)	2.24 (3)	2.870 (3)	134 (3)
O12—H12···O31^ii	0.86 (4)	1.96 (4)	2.801 (3)	165 (4)
O31—H31A···O21	0.87 (4)	1.69 (4)	2.518 (3)	159 (4)

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