Supra­molecular inter­actions in carboxyl­ate and sulfonate salts of 2,6-di­amino-4-chloro­pyrimidinium

Two new salts, namely 2,6-di­amino-4-chloro­pyrimidinium 2-carb­oxy-3-nitro­benzoate, C₄H₆ClN₄⁺·C₈H₄NO₆⁻, (I), and 2,6-di­amino-4-chloro­pyrimidinium p-toluene­sulfonate monohydrate, C₄H₆ClN₄⁺·C₇H₇O₃S⁻·H₂O, (II), have been synthesized and characterized by single-crystal X-ray diffraction. In both crystal structures, the N atom in the 1-position of the pyrimidine ring is protonated. In salt (I), the protonated N atom and the amino group of the pyrimidinium cation inter­act with the carboxyl­ate group of the anion through N—H...O hydrogen bonds to form a heterosynthon with an R₂²(8) ring motif. In hydrated salt (II), the presence of the water mol­ecule prevents the formation of the familiar R₂²(8) ring motif. Instead, an expanded ring [i.e. R₃²(8)] is formed involving the sulfonate group, the pyrimidinium cation and the water mol­ecule. Both salts form a supra­molecular homosynthon [R₂²(8) ring motif] through N—H...N hydrogen bonds. The mol­ecular structures are further stabilized by π–π stacking, and C=O...π, C—H...O and C—H...Cl inter­actions.

Computing details

For both compounds, data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis PRO (Agilent, 2012); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015b); molecular graphics: PLATON (Spek, 2009), Mercury (Macrae et al., 2008) and POVRay (Cason, 2004); software used to prepare material for publication: PLATON (Spek, 2009) and publCIF (Westrip, 2010).

(I) 2,6-Diamino-4-chloropyrimidinium 2-carboxy-3-nitrobenzoate

Crystal data

C4H6ClN4^+·C8H4NO6^−	Z = 2
Mr = 355.70	F(000) = 364
Triclinic, P1	Dx = 1.710 Mg m^−3
a = 7.1403 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.6745 (6) Å	Cell parameters from 8897 reflections
c = 11.5730 (7) Å	θ = 2.9–41.1°
α = 93.721 (5)°	µ = 0.32 mm^−1
β = 93.714 (4)°	T = 120 K
γ = 104.230 (5)°	Prism, colorless
V = 690.94 (8) Å^3	0.51 × 0.18 × 0.15 mm

Data collection

SuperNova CCD diffractometer	8897 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	6381 reflections with I > 2σ(I)
Detector resolution: 10.6501 pixels mm^-1	Rint = 0.035
ω scans	θmax = 41.2°, θmin = 2.9°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	h = −12→13
Tmin = 0.853, Tmax = 0.953	k = −15→15
17128 measured reflections	l = −21→19

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.046	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.128	w = 1/[σ^2(Fo^2) + (0.0479P)^2 + 0.0574P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max = 0.001
8897 reflections	Δρmax = 0.65 e Å^−3
237 parameters	Δρmin = −0.47 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	0.63993 (4)	1.04519 (3)	0.25190 (2)	0.01979 (6)
N1	0.55013 (12)	0.74600 (11)	0.54072 (7)	0.01316 (14)
H1	0.538045	0.687385	0.600379	0.016*
C2	0.72602 (13)	0.84096 (12)	0.52499 (8)	0.01331 (15)
N3	0.75477 (12)	0.93419 (11)	0.43716 (7)	0.01410 (14)
N2	0.87159 (13)	0.84139 (13)	0.60229 (8)	0.01999 (18)
N4	0.22454 (13)	0.64581 (13)	0.49137 (8)	0.01789 (17)
C4	0.59860 (14)	0.92422 (12)	0.36472 (8)	0.01331 (15)
C5	0.41551 (15)	0.83130 (13)	0.37218 (8)	0.01498 (16)
H5	0.311152	0.829800	0.316505	0.018*
C6	0.39221 (14)	0.73863 (12)	0.46726 (8)	0.01292 (15)
O1	0.75260 (10)	0.56282 (10)	0.74864 (6)	0.01537 (13)
O2	0.45818 (10)	0.60234 (10)	0.72180 (7)	0.01692 (14)
O3	0.10958 (11)	0.36711 (11)	0.67139 (6)	0.01820 (15)
O4	0.06161 (10)	0.49596 (9)	0.83689 (6)	0.01432 (13)
O5	−0.08265 (11)	0.14856 (11)	0.85169 (8)	0.02178 (17)
O6	−0.03231 (11)	0.15588 (11)	1.03837 (7)	0.01980 (15)
N5	0.02342 (12)	0.17979 (11)	0.94195 (8)	0.01452 (14)
C7	0.49496 (12)	0.40920 (11)	0.84769 (8)	0.01049 (14)
C8	0.29398 (13)	0.35047 (11)	0.85034 (8)	0.01082 (14)
C9	0.23120 (13)	0.24587 (12)	0.93408 (8)	0.01163 (14)
C10	0.35520 (13)	0.19628 (12)	1.01241 (8)	0.01305 (15)
H10	0.305859	0.125158	1.068602	0.016*
C11	0.55244 (13)	0.25326 (13)	1.00635 (8)	0.01357 (16)
H11	0.641024	0.220092	1.057965	0.016*
C12	0.62066 (13)	0.35864 (12)	0.92504 (8)	0.01193 (15)
H12	0.756591	0.397529	0.921848	0.014*
C13	0.57611 (13)	0.53260 (12)	0.76673 (8)	0.01135 (14)
C14	0.14689 (13)	0.40599 (12)	0.77419 (8)	0.01242 (15)
H2A	0.852 (3)	0.773 (2)	0.6594 (15)	0.035 (5)*
H2B	0.991 (3)	0.907 (2)	0.5925 (14)	0.034 (5)*
H4A	0.123 (2)	0.631 (2)	0.4418 (14)	0.030 (4)*
H4B	0.217 (3)	0.594 (2)	0.5501 (15)	0.036 (5)*
H4	−0.045 (3)	0.512 (3)	0.7962 (16)	0.045 (5)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.02833 (13)	0.01828 (12)	0.01351 (10)	0.00545 (9)	0.00237 (8)	0.00795 (8)
N1	0.0119 (3)	0.0150 (4)	0.0121 (3)	0.0017 (3)	−0.0001 (2)	0.0061 (3)
C2	0.0119 (3)	0.0140 (4)	0.0142 (4)	0.0024 (3)	0.0015 (3)	0.0055 (3)
N3	0.0149 (3)	0.0145 (4)	0.0134 (3)	0.0036 (3)	0.0018 (3)	0.0052 (3)
N2	0.0124 (3)	0.0259 (5)	0.0204 (4)	0.0004 (3)	−0.0020 (3)	0.0132 (4)
N4	0.0126 (3)	0.0224 (5)	0.0159 (4)	−0.0012 (3)	−0.0026 (3)	0.0066 (3)
C4	0.0185 (4)	0.0125 (4)	0.0102 (3)	0.0055 (3)	0.0019 (3)	0.0033 (3)
C5	0.0176 (4)	0.0163 (4)	0.0107 (3)	0.0039 (3)	−0.0012 (3)	0.0027 (3)
C6	0.0136 (4)	0.0133 (4)	0.0114 (3)	0.0027 (3)	−0.0005 (3)	0.0019 (3)
O1	0.0104 (3)	0.0189 (4)	0.0185 (3)	0.0046 (2)	0.0027 (2)	0.0091 (3)
O2	0.0128 (3)	0.0221 (4)	0.0198 (3)	0.0085 (3)	0.0039 (2)	0.0130 (3)
O3	0.0175 (3)	0.0246 (4)	0.0130 (3)	0.0075 (3)	−0.0037 (2)	0.0011 (3)
O4	0.0114 (3)	0.0176 (3)	0.0159 (3)	0.0071 (2)	0.0003 (2)	0.0032 (2)
O5	0.0140 (3)	0.0219 (4)	0.0266 (4)	−0.0001 (3)	−0.0061 (3)	0.0071 (3)
O6	0.0154 (3)	0.0221 (4)	0.0237 (4)	0.0052 (3)	0.0076 (3)	0.0080 (3)
N5	0.0108 (3)	0.0119 (3)	0.0213 (4)	0.0024 (3)	0.0013 (3)	0.0059 (3)
C7	0.0103 (3)	0.0113 (4)	0.0105 (3)	0.0036 (3)	0.0003 (2)	0.0023 (3)
C8	0.0105 (3)	0.0110 (4)	0.0114 (3)	0.0034 (3)	0.0000 (2)	0.0026 (3)
C9	0.0096 (3)	0.0117 (4)	0.0137 (3)	0.0024 (3)	0.0006 (3)	0.0034 (3)
C10	0.0122 (3)	0.0139 (4)	0.0138 (4)	0.0036 (3)	0.0009 (3)	0.0052 (3)
C11	0.0120 (3)	0.0162 (4)	0.0137 (4)	0.0048 (3)	0.0002 (3)	0.0059 (3)
C12	0.0099 (3)	0.0146 (4)	0.0123 (3)	0.0041 (3)	0.0007 (3)	0.0043 (3)
C13	0.0110 (3)	0.0128 (4)	0.0110 (3)	0.0038 (3)	0.0010 (2)	0.0034 (3)
C14	0.0100 (3)	0.0133 (4)	0.0139 (4)	0.0026 (3)	−0.0008 (3)	0.0037 (3)

Geometric parameters (Å, º)

Cl1—C4	1.7230 (10)	O4—C14	1.3130 (12)
N1—C2	1.3525 (13)	O5—N5	1.2240 (12)
N1—C6	1.3534 (12)	O6—N5	1.2220 (12)
C2—N2	1.3258 (13)	N5—C9	1.4643 (12)
C2—N3	1.3348 (12)	C7—C12	1.3928 (12)
N3—C4	1.3326 (13)	C7—C8	1.4029 (13)
N4—C6	1.3259 (13)	C7—C13	1.5017 (13)
C4—C5	1.3681 (15)	C8—C9	1.3906 (13)
C5—C6	1.3991 (13)	C8—C14	1.5151 (12)
O1—C13	1.2568 (11)	C9—C10	1.3873 (13)
O2—C13	1.2569 (11)	C10—C11	1.3812 (13)
O3—C14	1.2095 (12)	C11—C12	1.3822 (13)
C2—N1—C6	121.83 (8)	C8—C7—C13	120.74 (8)
N2—C2—N3	120.19 (9)	C9—C8—C7	116.94 (8)
N2—C2—N1	117.42 (9)	C9—C8—C14	119.68 (8)
N3—C2—N1	122.38 (8)	C7—C8—C14	123.18 (8)
C4—N3—C2	115.13 (9)	C10—C9—C8	123.80 (8)
N3—C4—C5	127.05 (9)	C10—C9—N5	116.25 (8)
N3—C4—Cl1	114.17 (8)	C8—C9—N5	119.95 (8)
C5—C4—Cl1	118.78 (7)	C11—C10—C9	118.09 (9)
C4—C5—C6	115.54 (9)	C10—C11—C12	119.86 (8)
N4—C6—N1	117.68 (9)	C11—C12—C7	121.60 (8)
N4—C6—C5	124.26 (9)	O1—C13—O2	123.80 (9)
N1—C6—C5	118.05 (9)	O1—C13—C7	120.33 (8)
O6—N5—O5	124.15 (9)	O2—C13—C7	115.86 (8)
O6—N5—C9	117.69 (8)	O3—C14—O4	125.49 (9)
O5—N5—C9	118.14 (8)	O3—C14—C8	124.28 (9)
C12—C7—C8	119.68 (8)	O4—C14—C8	110.17 (8)
C12—C7—C13	119.50 (8)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	0.88	1.70	2.5477 (12)	162
N2—H2A···O1	0.911 (17)	2.144 (17)	3.0229 (13)	161.7 (16)
N2—H2B···N3^i	0.92 (2)	2.06 (2)	2.9725 (14)	175.0 (17)
O4—H4···O1^ii	0.91 (2)	1.68 (2)	2.5811 (11)	167.5 (19)
N4—H4A···O3^iii	0.873 (15)	2.052 (15)	2.9174 (12)	171.3 (16)
N4—H4B···O2	0.836 (17)	2.529 (19)	3.1465 (12)	131.5 (17)
N4—H4B···O3	0.836 (17)	2.488 (17)	3.2800 (13)	158.5 (17)
C5—H5···O5^iii	0.95	2.50	3.4434 (14)	170
C11—H11···Cl1^iv	0.95	2.79	3.5656 (10)	140
C11—H11···O6^v	0.95	2.55	3.2820 (13)	134
C12—H12···O4^v	0.95	2.43	3.3321 (12)	158

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

(II) 2,6-Diamino-4-chloropyrimidinium p-toluenesulfonate

Crystal data

C4H6ClN4^+·C7H7O3S^−·H2O	Z = 2
Mr = 334.78	F(000) = 348
Triclinic, P1	Dx = 1.562 Mg m^−3
a = 6.5400 (3) Å	Cu Kα radiation, λ = 1.54184 Å
b = 7.2557 (4) Å	Cell parameters from 2852 reflections
c = 15.7696 (9) Å	θ = 5.7–76.0°
α = 81.617 (5)°	µ = 3.97 mm^−1
β = 89.511 (4)°	T = 120 K
γ = 74.154 (5)°	Chunk, colorless
V = 711.79 (7) Å^3	0.53 × 0.27 × 0.15 mm

Data collection

SuperNova CCD diffractometer	2769 reflections with I > 2σ(I)
Detector resolution: 10.6501 pixels mm^-1	Rint = 0.023
ω scans	θmax = 76.0°, θmin = 5.7°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	h = −5→8
Tmin = 0.235, Tmax = 1.000	k = −9→9
5135 measured reflections	l = −19→18
2852 independent reflections

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.036	w = 1/[σ^2(Fo^2) + (0.0658P)^2 + 0.3251P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.100	(Δ/σ)max = 0.001
S = 1.09	Δρmax = 0.58 e Å^−3
2852 reflections	Δρmin = −0.51 e Å^−3
248 parameters	Extinction correction: SHELXL2016 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
6 restraints	Extinction coefficient: 0.0161 (19)

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)
S1	0.59305 (6)	0.47417 (5)	0.76110 (2)	0.00975 (15)
O1	0.4314 (7)	0.6351 (8)	0.7866 (2)	0.0166 (12)	0.434 (10)
O2A	0.7301 (7)	0.5395 (9)	0.6934 (2)	0.0164 (11)	0.434 (10)
O3	0.5103 (10)	0.3239 (5)	0.7378 (4)	0.0183 (11)	0.434 (10)
O1A	0.3780 (5)	0.5517 (7)	0.79333 (15)	0.0202 (10)	0.566 (10)
O2	0.6713 (6)	0.6232 (6)	0.7130 (2)	0.0156 (9)	0.566 (10)
O3A	0.6002 (8)	0.3136 (4)	0.7135 (2)	0.0169 (8)	0.566 (10)
C7	0.7635 (3)	0.3777 (2)	0.85250 (10)	0.0102 (3)
C8	0.6786 (3)	0.3586 (2)	0.93336 (11)	0.0145 (3)
H8	0.528911	0.394213	0.939629	0.017*
C9	0.8147 (3)	0.2870 (2)	1.00494 (11)	0.0175 (4)
H9	0.757134	0.274354	1.060306	0.021*
C10	1.0352 (3)	0.2332 (2)	0.99665 (11)	0.0163 (3)
C11	1.1164 (3)	0.2505 (2)	0.91506 (11)	0.0173 (3)
H11	1.265880	0.211412	0.908523	0.021*
C12	0.9826 (3)	0.3239 (2)	0.84284 (11)	0.0147 (3)
H12	1.040115	0.337184	0.787483	0.018*
C13	1.1814 (3)	0.1600 (3)	1.07498 (12)	0.0242 (4)
H13C	1.329168	0.121782	1.057226	0.036*
H13A	1.146670	0.047751	1.107934	0.036*
H13B	1.163505	0.262751	1.110675	0.036*
Cl1	−0.42219 (6)	1.26513 (5)	0.45624 (2)	0.01512 (15)
N1	0.0890 (2)	1.07905 (19)	0.65249 (9)	0.0121 (3)
C2	0.0553 (2)	1.2488 (2)	0.59743 (10)	0.0113 (3)
N3	−0.1003 (2)	1.30425 (19)	0.53725 (8)	0.0121 (3)
N2	0.1819 (2)	1.3607 (2)	0.60413 (10)	0.0174 (3)
N4	0.0070 (3)	0.7941 (2)	0.70361 (10)	0.0182 (3)
C4	−0.2252 (2)	1.1868 (2)	0.53614 (10)	0.0114 (3)
C5	−0.2073 (3)	1.0159 (2)	0.58918 (10)	0.0145 (3)
H5	−0.304024	0.940563	0.585270	0.017*
C6	−0.0371 (2)	0.9584 (2)	0.64984 (10)	0.0124 (3)
O1W	0.4194 (2)	0.9971 (2)	0.76361 (10)	0.0296 (3)
H1	0.201 (5)	1.049 (4)	0.6892 (19)	0.042 (7)*
H2B	0.161 (4)	1.466 (4)	0.5629 (18)	0.034 (7)*
H2A	0.289 (4)	1.329 (4)	0.6385 (17)	0.027 (6)*
H4B	−0.074 (4)	0.723 (4)	0.7013 (16)	0.029 (6)*
H4A	0.120 (4)	0.759 (4)	0.7309 (17)	0.027 (6)*
H2W	0.501 (4)	1.066 (3)	0.7608 (18)	0.035 (7)*
H1W	0.493 (5)	0.889 (3)	0.762 (3)	0.088 (14)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0113 (2)	0.0090 (2)	0.0093 (2)	−0.00425 (15)	−0.00184 (14)	0.00029 (14)
O1	0.0165 (17)	0.015 (2)	0.0151 (14)	0.0011 (15)	−0.0039 (11)	−0.0012 (12)
O2A	0.0157 (17)	0.024 (2)	0.0095 (15)	−0.0074 (17)	0.0006 (12)	0.0006 (15)
O3	0.023 (2)	0.0132 (15)	0.021 (2)	−0.0113 (15)	−0.0084 (18)	0.0013 (13)
O1A	0.0167 (13)	0.0231 (19)	0.0165 (11)	−0.0006 (12)	−0.0004 (9)	0.0016 (10)
O2	0.0169 (14)	0.0158 (17)	0.0145 (13)	−0.0093 (13)	−0.0022 (11)	0.0056 (12)
O3A	0.0252 (19)	0.0127 (11)	0.0141 (13)	−0.0055 (11)	−0.0036 (13)	−0.0052 (9)
C7	0.0135 (7)	0.0075 (7)	0.0097 (7)	−0.0032 (6)	−0.0022 (6)	−0.0001 (5)
C8	0.0147 (8)	0.0152 (8)	0.0132 (8)	−0.0034 (6)	0.0019 (6)	−0.0025 (6)
C9	0.0250 (9)	0.0170 (8)	0.0095 (8)	−0.0045 (7)	0.0012 (6)	−0.0013 (6)
C10	0.0246 (9)	0.0103 (7)	0.0140 (8)	−0.0042 (6)	−0.0070 (7)	−0.0017 (6)
C11	0.0129 (8)	0.0185 (8)	0.0196 (8)	−0.0029 (6)	−0.0033 (6)	−0.0021 (6)
C12	0.0149 (8)	0.0175 (8)	0.0117 (7)	−0.0046 (6)	0.0001 (6)	−0.0017 (6)
C13	0.0330 (10)	0.0197 (9)	0.0186 (9)	−0.0057 (8)	−0.0127 (8)	−0.0006 (7)
Cl1	0.0134 (2)	0.0179 (2)	0.0140 (2)	−0.00576 (15)	−0.00413 (15)	0.00123 (14)
N1	0.0127 (7)	0.0126 (6)	0.0100 (6)	−0.0024 (5)	−0.0004 (5)	0.0001 (5)
C2	0.0121 (7)	0.0122 (7)	0.0091 (7)	−0.0020 (6)	0.0007 (6)	−0.0028 (5)
N3	0.0144 (7)	0.0119 (6)	0.0094 (6)	−0.0031 (5)	−0.0011 (5)	−0.0005 (5)
N2	0.0211 (8)	0.0157 (7)	0.0161 (7)	−0.0084 (6)	−0.0078 (6)	0.0027 (6)
N4	0.0161 (8)	0.0174 (7)	0.0192 (7)	−0.0063 (6)	−0.0025 (6)	0.0071 (6)
C4	0.0092 (7)	0.0143 (7)	0.0098 (7)	−0.0013 (6)	0.0015 (6)	−0.0027 (6)
C5	0.0131 (8)	0.0166 (8)	0.0143 (8)	−0.0065 (6)	0.0013 (6)	0.0004 (6)
C6	0.0098 (7)	0.0144 (7)	0.0119 (7)	−0.0021 (6)	0.0047 (6)	−0.0009 (6)
O1W	0.0191 (7)	0.0351 (8)	0.0295 (8)	−0.0038 (6)	−0.0107 (6)	0.0048 (6)

Geometric parameters (Å, º)

S1—O3	1.435 (3)	C13—H13A	0.9800
S1—O2	1.436 (2)	C13—H13B	0.9800
S1—O1	1.448 (3)	Cl1—C4	1.7290 (16)
S1—O3A	1.466 (3)	N1—C6	1.361 (2)
S1—O1A	1.481 (3)	N1—C2	1.365 (2)
S1—O2A	1.495 (3)	N1—H1	0.90 (3)
S1—C7	1.7655 (16)	C2—N2	1.323 (2)
C7—C8	1.390 (2)	C2—N3	1.334 (2)
C7—C12	1.392 (2)	N3—C4	1.334 (2)
C8—C9	1.389 (2)	N2—H2B	0.91 (3)
C8—H8	0.9500	N2—H2A	0.85 (3)
C9—C10	1.397 (3)	N4—C6	1.321 (2)
C9—H9	0.9500	N4—H4B	0.84 (3)
C10—C11	1.389 (3)	N4—H4A	0.82 (3)
C10—C13	1.508 (2)	C4—C5	1.368 (2)
C11—C12	1.390 (2)	C5—C6	1.406 (2)
C11—H11	0.9500	C5—H5	0.9500
C12—H12	0.9500	O1W—H2W	0.824 (17)
C13—H13C	0.9800	O1W—H1W	0.805 (18)
O3—S1—O1	113.6 (2)	C10—C13—H13C	109.5
O2—S1—O3A	112.60 (17)	C10—C13—H13A	109.5
O2—S1—O1A	112.23 (17)	H13C—C13—H13A	109.5
O3A—S1—O1A	111.26 (18)	C10—C13—H13B	109.5
O3—S1—O2A	111.9 (2)	H13C—C13—H13B	109.5
O1—S1—O2A	112.1 (2)	H13A—C13—H13B	109.5
O3—S1—C7	108.41 (15)	C6—N1—C2	121.66 (14)
O2—S1—C7	107.07 (10)	C6—N1—H1	121.5 (18)
O1—S1—C7	105.04 (13)	C2—N1—H1	116.8 (19)
O3A—S1—C7	106.90 (12)	N2—C2—N3	119.34 (15)
O1A—S1—C7	106.34 (11)	N2—C2—N1	118.64 (15)
O2A—S1—C7	105.12 (13)	N3—C2—N1	122.02 (15)
C8—C7—C12	120.57 (15)	C4—N3—C2	115.85 (14)
C8—C7—S1	119.97 (12)	C2—N2—H2B	115.3 (17)
C12—C7—S1	119.45 (12)	C2—N2—H2A	123.4 (17)
C9—C8—C7	119.36 (15)	H2B—N2—H2A	121 (2)
C9—C8—H8	120.3	C6—N4—H4B	117.0 (18)
C7—C8—H8	120.3	C6—N4—H4A	118.8 (18)
C8—C9—C10	120.94 (15)	H4B—N4—H4A	123 (2)
C8—C9—H9	119.5	N3—C4—C5	126.65 (15)
C10—C9—H9	119.5	N3—C4—Cl1	113.71 (12)
C11—C10—C9	118.68 (16)	C5—C4—Cl1	119.62 (13)
C11—C10—C13	120.88 (17)	C4—C5—C6	116.00 (15)
C9—C10—C13	120.44 (16)	C4—C5—H5	122.0
C10—C11—C12	121.15 (16)	C6—C5—H5	122.0
C10—C11—H11	119.4	N4—C6—N1	118.68 (15)
C12—C11—H11	119.4	N4—C6—C5	123.55 (16)
C11—C12—C7	119.29 (15)	N1—C6—C5	117.77 (14)
C11—C12—H12	120.4	H2W—O1W—H1W	106 (2)
C7—C12—H12	120.4
O3—S1—C7—C8	−80.1 (4)	C9—C10—C11—C12	1.5 (3)
O2—S1—C7—C8	130.1 (3)	C13—C10—C11—C12	−177.86 (15)
O1—S1—C7—C8	41.7 (3)	C10—C11—C12—C7	−1.2 (3)
O3A—S1—C7—C8	−109.0 (3)	C8—C7—C12—C11	0.0 (2)
O1A—S1—C7—C8	10.0 (3)	S1—C7—C12—C11	179.12 (12)
O2A—S1—C7—C8	160.1 (3)	C6—N1—C2—N2	179.12 (14)
O3—S1—C7—C12	100.9 (4)	C6—N1—C2—N3	−1.1 (2)
O2—S1—C7—C12	−48.9 (3)	N2—C2—N3—C4	−178.06 (14)
O1—S1—C7—C12	−137.4 (3)	N1—C2—N3—C4	2.2 (2)
O3A—S1—C7—C12	72.0 (3)	C2—N3—C4—C5	−1.1 (2)
O1A—S1—C7—C12	−169.1 (3)	C2—N3—C4—Cl1	−179.46 (11)
O2A—S1—C7—C12	−18.9 (3)	N3—C4—C5—C6	−1.1 (2)
C12—C7—C8—C9	0.7 (2)	Cl1—C4—C5—C6	177.21 (12)
S1—C7—C8—C9	−178.40 (12)	C2—N1—C6—N4	178.46 (15)
C7—C8—C9—C10	−0.3 (2)	C2—N1—C6—C5	−1.2 (2)
C8—C9—C10—C11	−0.8 (3)	C4—C5—C6—N4	−177.45 (15)
C8—C9—C10—C13	178.60 (15)	C4—C5—C6—N1	2.1 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1W	0.90 (3)	1.78 (3)	2.674 (2)	178 (3)
O1W—H1W···O2	0.80 (2)	2.21 (3)	2.980 (4)	162 (4)
N2—H2A···O3A^i	0.85 (3)	2.33 (3)	3.158 (5)	165 (2)
N2—H2B···N3^ii	0.91 (3)	2.08 (3)	2.983 (2)	175 (3)
O1W—H2W···O3A^i	0.82 (3)	2.11 (2)	2.870 (4)	154 (3)
N4—H4A···O1A	0.82 (3)	2.07 (3)	2.826 (4)	154 (3)
N4—H4B···O2^iii	0.84 (3)	1.99 (3)	2.794 (5)	161 (3)
C5—H5···Cl1^iv	0.95	2.76	3.7008 (19)	170

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