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In the solid state, crystals of both 1-(7-chloro-1,4-di­hydro­quinolin-4-yl­idene)thio­semicarbazide-methanol-water (2/1/1), 2C10H9ClN4S·CH3OH·H2O, (I), and its hydro­chloride salt {systematic name: [(7-chloro-1,4-di­hydro­quinolin-4-yl­idene)aza­niumyl]thio­urea chloride}, C10H10ClN4S+·Cl-, (II), assume the imine tautomeric form, contrary to other 4-amino-7-chloro­quinolines. Of particular inter­est are the N-C bond lengths, which have appreciable double-bond character, and the C-N-C aromatic ring bond angle. Both of these parameters have been studied extensively in 4-amino-substituted quinolines. The crystal structures of (I) and (II) in this study provide inter­esting examples of the amino-imino tautomerism which exists in this class of compound and is, to the best of our knowledge, hitherto unreported.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229615010311/fn3197sup1.cif
Contains datablocks global, I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229615010311/fn3197Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229615010311/fn3197IIsup3.hkl
Contains datablock II

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229615010311/fn3197Isup4.cml
Supplementary material

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229615010311/fn3197IIsup5.cml
Supplementary material

pdf

Portable Document Format (PDF) file https://doi.org/10.1107/S2053229615010311/fn3197sup6.pdf
NMR data and spectra for (I) and (II)

CCDC references: 1403757; 1403756

Computing details top

For both compounds, data collection: CrysAlis PRO (Agilent, 2014); cell refinement: CrysAlis PRO (Agilent, 2014); data reduction: CrysAlis PRO (Agilent, 2014); program(s) used to solve structure: SHELXS2013 (Sheldrick, 2015); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015); molecular graphics: Mercury (Macrae et al., 2008) and ORTEP-3 for Windows (Farrugia, 2012). Software used to prepare material for publication: WinGX (Farrugia, 2012) for (I); WinGX (Farrugia, 2012) and PLATON (Spek, 2009) for (II).

(I) 1-(7-Chloroquinolin-4-yl)thiosemicarbazide–methanol–water (2/1/1) top
Crystal data top
2C10H9ClN4S·CH4O·H2OZ = 2
Mr = 555.50F(000) = 576
Triclinic, P1Dx = 1.528 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.7107 Å
a = 7.1462 (2) ÅCell parameters from 6106 reflections
b = 13.1927 (5) Åθ = 3.0–29.6°
c = 13.6379 (5) ŵ = 0.48 mm1
α = 94.905 (3)°T = 298 K
β = 104.416 (3)°Prismatic, yellow
γ = 101.579 (3)°0.38 × 0.04 × 0.03 mm
V = 1207.43 (8) Å3
Data collection top
Agilent Xcalibur Gemini Ultra
diffractometer with Atlas detector
5778 independent reflections
Radiation source: Enhance (Mo) X-ray Source4091 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.021
Detector resolution: 10.4186 pixels mm-1θmax = 29.6°, θmin = 3.0°
ω scansh = 99
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2014)
k = 1817
Tmin = 0.855, Tmax = 1.000l = 1818
12034 measured reflections
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullH atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.034 W = 1/[Σ2(FO2) + (0.0498P)2]
where P = (FO2 + 2FC2)/3
wR(F2) = 0.089(Δ/σ)max = 0.001
S = 0.97Δρmax = 0.31 e Å3
5778 reflectionsΔρmin = 0.30 e Å3
353 parameters
Special details top

Experimental. #__ type_ start__ end____ width___ exp.time_ 1 omega 57.00 103.00 1.0000 25.0000 omega____ theta____ kappa____ phi______ frames - 12.8811 179.0000 - 150.0000 46

#__ type_ start__ end____ width___ exp.time_ 2 omega -50.00 39.00 1.0000 25.0000 omega____ theta____ kappa____ phi______ frames - 12.8811 - 38.0000 0.0000 89

#__ type_ start__ end____ width___ exp.time_ 3 omega -42.00 0.00 1.0000 25.0000 omega____ theta____ kappa____ phi______ frames - 12.8811 121.0000 - 88.0000 42

#__ type_ start__ end____ width___ exp.time_ 4 omega -43.00 43.00 1.0000 25.0000 omega____ theta____ kappa____ phi______ frames - 12.8811 - 77.0000 - 180.0000 86

#__ type_ start__ end____ width___ exp.time_ 5 omega -63.00 39.00 1.0000 25.0000 omega____ theta____ kappa____ phi______ frames - 12.8811 - 38.0000 - 90.0000 102

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Reflections were merged by SHELXL according to the crystal class for the calculation of statistics and refinement.

Item _reflns_Friedel_fraction is defined as the number of unique Friedel pairs measured divided by the number that would be possible theoretically, ignoring centric projections and systematic absences.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S10.10461 (7)0.34104 (3)0.93447 (3)0.03228 (11)
S1A0.33413 (7)0.11031 (4)0.50264 (3)0.03807 (13)
Cl10.22944 (8)0.45169 (5)0.19129 (3)0.05632 (16)
Cl1A0.92970 (8)0.06098 (5)1.28161 (3)0.05420 (15)
NQ0.2430 (2)0.65246 (11)0.52842 (10)0.0310 (3)
H1Q0.24410.70710.49820.037*
NQA0.6796 (2)0.17090 (11)0.93755 (10)0.0335 (3)
H2Q0.68960.22300.97080.040*
N10.22697 (19)0.38947 (10)0.67242 (9)0.0263 (3)
N1A0.6305 (2)0.07906 (10)0.77966 (9)0.0291 (3)
N20.2206 (2)0.40149 (11)0.77549 (10)0.0280 (3)
H2N0.293 (3)0.4520 (15)0.8177 (14)0.038 (5)*
N2A0.5422 (2)0.06029 (11)0.67346 (10)0.0293 (3)
HN2A0.554 (3)0.0128 (15)0.6385 (13)0.034 (5)*
N40.0080 (2)0.24564 (12)0.74333 (11)0.0351 (3)
H4NA0.012 (2)0.2403 (14)0.6748 (14)0.032 (4)*
H4NB0.089 (3)0.1977 (17)0.7648 (16)0.054 (6)*
N4A0.4436 (3)0.21142 (13)0.69268 (12)0.0397 (4)
H4NC0.497 (3)0.2146 (15)0.7568 (16)0.043 (5)*
H4ND0.383 (3)0.2549 (18)0.6700 (16)0.057 (7)*
O10.1142 (3)0.84669 (12)0.47815 (11)0.0472 (4)
H1A0.192 (4)0.909 (3)0.485 (2)0.102 (11)*
H1B0.008 (4)0.8553 (19)0.4845 (18)0.066 (8)*
O20.4410 (2)0.58402 (11)0.92904 (10)0.0421 (3)
H2O0.555 (4)0.583 (2)0.9660 (19)0.076 (8)*
C20.2371 (2)0.65886 (13)0.62650 (12)0.0311 (4)
H20.23070.72240.65910.037*
C2A0.6117 (3)0.18817 (13)0.83499 (12)0.0336 (4)
H2A0.57910.25650.80190.040*
C30.1068 (2)0.32828 (12)0.80947 (11)0.0241 (3)
C3A0.4475 (2)0.12911 (13)0.63094 (11)0.0277 (3)
C3B0.2399 (2)0.57738 (13)0.67963 (12)0.0285 (4)
H30.24180.58700.74830.034*
C3D0.5890 (2)0.11091 (13)0.77818 (12)0.0309 (4)
H3A0.53700.12720.70760.037*
C40.2398 (2)0.47610 (12)0.63220 (11)0.0228 (3)
C4A0.6437 (2)0.00374 (12)0.82459 (11)0.0232 (3)
C50.2505 (2)0.37740 (13)0.46936 (11)0.0289 (4)
H50.25350.31810.50150.035*
C5A0.7782 (2)0.11399 (13)0.99288 (12)0.0315 (4)
H5A0.77270.17170.95850.038*
C60.2480 (2)0.37101 (14)0.36745 (12)0.0326 (4)
H60.24840.30830.33080.039*
C6A0.8430 (3)0.12866 (14)1.09808 (12)0.0362 (4)
H6A0.88090.19571.13460.043*
C70.2448 (2)0.46072 (15)0.32086 (12)0.0334 (4)
C7A0.8510 (2)0.04256 (15)1.14878 (12)0.0334 (4)
C80.2462 (2)0.55421 (14)0.37251 (12)0.0312 (4)
H80.24630.61330.33990.037*
C8A0.7984 (2)0.05678 (14)1.09764 (12)0.0325 (4)
H8A0.80550.11371.13300.039*
C90.2473 (2)0.55939 (13)0.47591 (11)0.0257 (3)
C9A0.7334 (2)0.07104 (13)0.99022 (11)0.0256 (3)
C100.2485 (2)0.47090 (12)0.52545 (11)0.0228 (3)
C10A0.7205 (2)0.01376 (12)0.93684 (11)0.0235 (3)
C110.3299 (3)0.62297 (16)0.98945 (16)0.0495 (5)
H11A0.21810.64190.94600.074*
H11B0.41210.68341.03580.074*
H11C0.28390.57011.02770.074*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0422 (3)0.0336 (2)0.0237 (2)0.0070 (2)0.01350 (18)0.00931 (17)
S1A0.0536 (3)0.0383 (3)0.0235 (2)0.0225 (2)0.00280 (19)0.00596 (18)
Cl10.0739 (4)0.0830 (4)0.0250 (2)0.0318 (3)0.0222 (2)0.0185 (2)
Cl1A0.0616 (3)0.0741 (4)0.0207 (2)0.0099 (3)0.0053 (2)0.0045 (2)
NQ0.0382 (8)0.0218 (7)0.0323 (7)0.0047 (6)0.0076 (6)0.0121 (6)
NQA0.0477 (9)0.0225 (7)0.0298 (7)0.0093 (7)0.0061 (6)0.0110 (6)
N10.0358 (7)0.0262 (7)0.0183 (6)0.0065 (6)0.0096 (5)0.0066 (5)
N1A0.0404 (8)0.0249 (7)0.0208 (6)0.0094 (6)0.0039 (6)0.0060 (5)
N20.0370 (8)0.0253 (7)0.0196 (6)0.0013 (7)0.0084 (6)0.0043 (6)
N2A0.0424 (8)0.0255 (8)0.0203 (6)0.0130 (7)0.0048 (6)0.0035 (6)
N40.0425 (9)0.0327 (9)0.0253 (7)0.0017 (7)0.0085 (7)0.0051 (7)
N4A0.0571 (11)0.0371 (9)0.0272 (8)0.0252 (9)0.0044 (7)0.0035 (7)
O10.0583 (10)0.0368 (9)0.0476 (8)0.0118 (8)0.0160 (7)0.0052 (6)
O20.0424 (8)0.0463 (8)0.0358 (7)0.0088 (7)0.0108 (6)0.0015 (6)
C20.0321 (9)0.0242 (8)0.0328 (8)0.0055 (7)0.0030 (7)0.0007 (7)
C2A0.0452 (10)0.0209 (8)0.0318 (8)0.0050 (8)0.0076 (8)0.0025 (7)
C30.0281 (8)0.0235 (8)0.0228 (7)0.0096 (7)0.0065 (6)0.0074 (6)
C3A0.0315 (9)0.0264 (8)0.0272 (8)0.0076 (7)0.0094 (7)0.0081 (7)
C3B0.0326 (9)0.0281 (9)0.0235 (7)0.0059 (7)0.0064 (7)0.0030 (7)
C3D0.0404 (10)0.0253 (9)0.0240 (8)0.0053 (8)0.0052 (7)0.0031 (7)
C40.0192 (7)0.0253 (8)0.0232 (7)0.0033 (6)0.0045 (6)0.0070 (6)
C4A0.0228 (8)0.0245 (8)0.0229 (7)0.0058 (7)0.0063 (6)0.0048 (6)
C50.0336 (9)0.0301 (9)0.0267 (8)0.0115 (7)0.0100 (7)0.0088 (7)
C5A0.0397 (9)0.0257 (9)0.0286 (8)0.0064 (8)0.0086 (7)0.0051 (7)
C60.0368 (9)0.0392 (10)0.0255 (8)0.0134 (8)0.0117 (7)0.0052 (7)
C6A0.0436 (10)0.0321 (10)0.0287 (8)0.0048 (8)0.0073 (8)0.0013 (7)
C70.0284 (9)0.0522 (12)0.0245 (8)0.0124 (8)0.0117 (7)0.0117 (8)
C7A0.0305 (9)0.0473 (11)0.0217 (7)0.0089 (8)0.0058 (7)0.0048 (7)
C80.0287 (9)0.0399 (10)0.0293 (8)0.0084 (8)0.0104 (7)0.0192 (8)
C8A0.0353 (9)0.0391 (10)0.0262 (8)0.0119 (8)0.0079 (7)0.0143 (7)
C90.0210 (8)0.0297 (9)0.0273 (8)0.0057 (7)0.0060 (6)0.0100 (7)
C9A0.0264 (8)0.0262 (8)0.0262 (7)0.0070 (7)0.0087 (6)0.0082 (6)
C100.0202 (7)0.0271 (8)0.0224 (7)0.0060 (6)0.0063 (6)0.0078 (6)
C10A0.0245 (8)0.0248 (8)0.0228 (7)0.0071 (7)0.0070 (6)0.0064 (6)
C110.0613 (13)0.0407 (12)0.0571 (12)0.0197 (11)0.0290 (11)0.0080 (10)
Geometric parameters (Å, º) top
S1—C31.7029 (14)C2A—C3D1.343 (2)
Cl1—C71.7350 (16)C2A—H2A0.9300
N1—C41.3060 (19)C3B—C41.434 (2)
N1—N21.4140 (17)C3B—H30.9300
N2—C31.326 (2)C3D—C4A1.433 (2)
N4—C31.334 (2)C3D—H3A0.9300
S1A—C3A1.7084 (16)C4—C101.469 (2)
Cl1A—C7A1.7376 (16)C4A—C10A1.473 (2)
N1A—C4A1.3057 (19)C5—C61.381 (2)
N1A—N2A1.4065 (18)C5—C101.399 (2)
N2A—C3A1.3266 (19)C5—H50.9300
N4A—C3A1.325 (2)C5A—C6A1.377 (2)
NQ—C21.345 (2)C5A—C10A1.398 (2)
NQ—C91.377 (2)C5A—H5A0.9300
NQ—H1Q0.8600C6—C71.392 (2)
NQA—C2A1.344 (2)C6—H60.9300
NQA—C9A1.377 (2)C6A—C7A1.383 (2)
NQA—H2Q0.8600C6A—H6A0.9300
N2—H2N0.83 (2)C7—C81.364 (2)
N2A—HN2A0.787 (18)C7A—C8A1.364 (2)
N4—H4NA0.924 (18)C8—C91.404 (2)
N4—H4NB0.89 (2)C8—H80.9300
N4A—H4NC0.86 (2)C8A—C9A1.406 (2)
N4A—H4ND0.82 (2)C8A—H8A0.9300
O1—H1A0.88 (3)C9—C101.398 (2)
O1—H1B0.81 (3)C9A—C10A1.392 (2)
O2—C111.411 (2)C11—H11A0.9600
O2—H2O0.85 (3)C11—H11B0.9600
C2—C3B1.347 (2)C11—H11C0.9600
C2—H20.9300
Cl1···S1i3.4988 (6)O1···N4vi3.007 (2)
Cl1···O2ii3.2709 (16)O1···NQ2.969 (2)
Cl1A···S1Aiii3.5262 (7)O2···O2v3.169 (2)
S1···NQAiv3.3440 (15)O2···N22.939 (2)
S1···O2v3.2207 (15)N1···N42.683 (2)
S1A···O1vi3.432 (2)N1···N4A3.058 (2)
S1A···O1vii3.4675 (17)N1A···N4A2.597 (2)
S1A···N2Aviii3.5420 (15)N1A···N4ix3.208 (2)
C2—NQ—C9120.71 (14)N1—C4—C3B127.21 (13)
C2—NQ—H1Q119.6N1—C4—C10117.77 (13)
C9—NQ—H1Q119.6C3B—C4—C10114.99 (14)
C2A—NQA—C9A120.99 (14)N1A—C4A—C3D127.94 (14)
C2A—NQA—H2Q119.5N1A—C4A—C10A116.72 (13)
C9A—NQA—H2Q119.5C3D—C4A—C10A115.33 (14)
C4—N1—N2114.12 (12)C6—C5—C10121.59 (15)
C4A—N1A—N2A115.90 (12)C6—C5—H5119.2
C3—N2—N1120.51 (13)C10—C5—H5119.2
N2—C3—S1120.49 (12)C6A—C5A—C10A121.09 (16)
N4—C3—S1120.94 (13)C6A—C5A—H5A119.5
C6—C7—Cl1118.57 (13)C10A—C5A—H5A119.5
C8—C7—Cl1119.02 (13)C5—C6—C7118.37 (15)
C3A—N2A—N1A118.44 (13)C5—C6—H6120.8
N2A—C3A—S1A120.89 (11)C7—C6—H6120.8
N4A—C3A—S1A122.21 (12)C5A—C6A—C7A119.23 (16)
C6A—C7A—Cl1A119.22 (13)C5A—C6A—H6A120.4
C8A—C7A—Cl1A118.81 (14)C7A—C6A—H6A120.4
C3—N2—H2N117.7 (13)C8—C7—C6122.37 (14)
N1—N2—H2N121.7 (13)C8A—C7A—C6A121.96 (15)
C3A—N2A—HN2A119.5 (13)C7—C8—C9118.64 (15)
N1A—N2A—HN2A121.9 (13)C7—C8—H8120.7
C3—N4—H4NA121.0 (12)C9—C8—H8120.7
C3—N4—H4NB119.2 (13)C7A—C8A—C9A118.45 (15)
H4NA—N4—H4NB119.6 (18)C7A—C8A—H8A120.8
C3A—N4A—H4NC117.8 (13)C9A—C8A—H8A120.8
C3A—N4A—H4ND120.2 (15)NQ—C9—C10119.73 (13)
H4NC—N4A—H4ND121.8 (19)NQ—C9—C8119.39 (15)
H1A—O1—H1B107 (2)C10—C9—C8120.87 (14)
C11—O2—H2O110.2 (16)NQA—C9A—C10A119.82 (13)
NQ—C2—C3B123.00 (15)NQA—C9A—C8A119.09 (14)
NQ—C2—H2118.5C10A—C9A—C8A121.08 (14)
C3B—C2—H2118.5C9—C10—C5118.15 (13)
C3D—C2A—NQA122.82 (15)C9—C10—C4120.32 (13)
C3D—C2A—H2A118.6C5—C10—C4121.49 (14)
NQA—C2A—H2A118.6C9A—C10A—C5A118.17 (13)
N2—C3—N4118.56 (14)C9A—C10A—C4A119.94 (13)
N4A—C3A—N2A116.90 (14)C5A—C10A—C4A121.88 (14)
C2—C3B—C4121.16 (14)O2—C11—H11A109.5
C2—C3B—H3119.4O2—C11—H11B109.5
C4—C3B—H3119.4H11A—C11—H11B109.5
C2A—C3D—C4A121.05 (14)O2—C11—H11C109.5
C2A—C3D—H3A119.5H11A—C11—H11C109.5
C4A—C3D—H3A119.5H11B—C11—H11C109.5
C4—N1—N2—C3142.58 (15)C6—C7—C8—C91.2 (2)
N2—N1—C4—C3B2.7 (2)Cl1—C7—C8—C9176.44 (12)
N2—N1—C4—C10179.62 (13)C7—C8—C9—C100.5 (2)
C9—NQ—C2—C3B1.7 (2)C7—C8—C9—NQ178.16 (15)
C2—NQ—C9—C8177.72 (15)NQ—C9—C10—C41.6 (2)
C2—NQ—C9—C101.0 (2)C8—C9—C10—C4177.00 (14)
N1—N2—C3—S1178.10 (11)C8—C9—C10—C50.6 (2)
N1—N2—C3—N43.0 (2)NQ—C9—C10—C5179.25 (14)
N2A—N1A—C4A—C10A175.11 (13)NQA—C2A—C3D—C4A2.3 (3)
C4A—N1A—N2A—C3A151.25 (15)C2A—C3D—C4A—N1A179.94 (18)
N2A—N1A—C4A—C3D3.7 (2)C2A—C3D—C4A—C10A1.3 (2)
C9A—NQA—C2A—C3D1.1 (3)N1A—C4A—C10A—C5A0.5 (2)
C2A—NQA—C9A—C8A178.24 (17)N1A—C4A—C10A—C9A178.17 (15)
C2A—NQA—C9A—C10A1.0 (2)C3D—C4A—C10A—C5A179.44 (14)
N1A—N2A—C3A—S1A179.14 (12)C3D—C4A—C10A—C9A0.8 (2)
N1A—N2A—C3A—N4A0.1 (2)C10A—C5A—C6A—C7A0.1 (3)
NQ—C2—C3B—C43.1 (2)C6A—C5A—C10A—C4A177.65 (16)
C2—C3B—C4—N1174.30 (16)C6A—C5A—C10A—C9A1.1 (2)
C2—C3B—C4—C103.5 (2)C5A—C6A—C7A—Cl1A179.17 (14)
N1—C4—C10—C52.3 (2)C5A—C6A—C7A—C8A0.7 (3)
N1—C4—C10—C9175.19 (14)Cl1A—C7A—C8A—C9A179.50 (12)
C3B—C4—C10—C5179.66 (14)C6A—C7A—C8A—C9A0.3 (2)
C3B—C4—C10—C92.8 (2)C7A—C8A—C9A—NQA179.93 (15)
C10—C5—C6—C70.5 (2)C7A—C8A—C9A—C10A0.7 (2)
C6—C5—C10—C4176.50 (14)NQA—C9A—C10A—C4A1.9 (2)
C6—C5—C10—C91.1 (2)NQA—C9A—C10A—C5A179.40 (14)
C5—C6—C7—Cl1176.91 (12)C8A—C9A—C10A—C4A177.34 (14)
C5—C6—C7—C80.7 (2)C8A—C9A—C10A—C5A1.4 (2)
Symmetry codes: (i) x, y, z1; (ii) x+1, y+1, z+1; (iii) x+1, y, z+1; (iv) x+1, y, z+2; (v) x+1, y+1, z+2; (vi) x, y+1, z+1; (vii) x, y1, z; (viii) x+1, y, z+1; (ix) x+1, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2N···O20.83 (2)2.113 (19)2.939 (2)172 (2)
N2A—HN2A···S1Aviii0.786 (19)2.781 (19)3.5420 (15)163.7 (19)
N4—H4NA···N10.924 (18)2.341 (17)2.683 (2)101.5 (13)
N4—H4NA···O1vi0.924 (18)2.167 (18)3.007 (2)150.6 (15)
N4—H4NB···N1Ax0.89 (2)2.35 (2)3.208 (2)163.4 (19)
N4A—H4NC···N1A0.86 (2)2.20 (2)2.597 (2)108.1 (16)
N4A—H4ND···N10.82 (2)2.28 (2)3.058 (2)158 (2)
NQ—H1Q···O10.862.232.969 (2)144
NQA—H2Q···S1iv0.862.563.3440 (15)151
O1—H1A···S1Axi0.88 (4)2.61 (4)3.4675 (17)165 (3)
O1—H1B···S1Avi0.81 (3)2.62 (3)3.432 (2)177 (2)
O2—H2O···S1v0.85 (3)2.43 (3)3.2207 (15)155 (2)
C3B—H3···O20.932.533.333 (2)145
Symmetry codes: (iv) x+1, y, z+2; (v) x+1, y+1, z+2; (vi) x, y+1, z+1; (viii) x+1, y, z+1; (x) x1, y, z; (xi) x, y+1, z.
(II) [(7-Chloro-1,4-dihydroquinolin-4-ylidene)azaniumyl]thiourea chloride top
Crystal data top
C10H10ClN4S+·ClF(000) = 592
Mr = 289.18Dx = 1.578 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.7107 Å
Hall symbol: -P 2ybcCell parameters from 2277 reflections
a = 9.4517 (6) Åθ = 2.2–29.4°
b = 7.8839 (5) ŵ = 0.69 mm1
c = 16.5172 (10) ÅT = 293 K
β = 98.477 (5)°Prismatic, colourless
V = 1217.36 (14) Å30.22 × 0.17 × 0.12 mm
Z = 4
Data collection top
Agilent Xcalibur Gemini Ultra
diffractometer with Atlas detector
2973 independent reflections
Radiation source: Enhance (Mo) X-ray Source1904 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.050
Detector resolution: 10.4186 pixels mm-1θmax = 29.5°, θmin = 2.2°
ω scansh = 1111
Absorption correction: multi-scan
(CrysAlisPro; Agilent, 2014)
k = 710
Tmin = 0.944, Tmax = 1.000l = 2021
8726 measured reflections
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullH atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.048 w = 1/[σ2(Fo2) + (0.0319P)2 + 0.0815P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.103(Δ/σ)max = 0.001
S = 1.05Δρmax = 0.36 e Å3
2973 reflectionsΔρmin = 0.35 e Å3
170 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Reflections were merged by SHELXL according to the crystal class for the calculation of statistics and refinement.

Item _reflns_Friedel_fraction is defined as the number of unique Friedel pairs measured divided by the number that would be possible theoretically, ignoring centric projections and systematic absences.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cl110.06195 (7)0.44805 (9)0.23521 (4)0.0364 (2)
Cl10.35755 (8)0.66636 (11)0.55457 (5)0.0552 (3)
S10.54665 (8)0.86733 (9)0.25829 (4)0.0422 (2)
N10.2161 (2)0.7087 (3)0.35553 (12)0.0282 (5)
N20.3499 (2)0.7240 (3)0.33059 (12)0.0308 (5)
C3A0.3840 (3)0.8615 (3)0.28812 (13)0.0280 (6)
C30.3053 (3)0.8407 (3)0.48349 (15)0.0353 (6)
H30.39460.85710.46760.042*
NQ0.1543 (2)0.8739 (3)0.58381 (12)0.0390 (6)
HNQ0.14230.91150.63120.047*
C60.1821 (3)0.6324 (3)0.44035 (15)0.0347 (6)
H60.25850.57830.40880.042*
N40.2910 (3)0.9868 (3)0.27668 (15)0.0410 (6)
C90.0426 (3)0.7936 (3)0.53616 (14)0.0312 (6)
C70.1961 (3)0.6932 (3)0.51826 (15)0.0347 (6)
C100.0610 (3)0.7345 (3)0.45785 (13)0.0259 (6)
C40.1966 (3)0.7605 (3)0.43074 (13)0.0265 (6)
C50.0563 (3)0.6527 (3)0.41095 (14)0.0308 (6)
H50.04740.61200.35910.037*
C80.0864 (3)0.7721 (3)0.56650 (15)0.0348 (6)
H80.09720.81080.61840.042*
C20.2798 (3)0.8949 (4)0.55868 (16)0.0428 (7)
H20.35300.94810.59330.051*
H2N0.397 (3)0.629 (4)0.3240 (16)0.047 (9)*
H4B0.325 (4)1.088 (4)0.255 (2)0.075 (11)*
H4A0.208 (3)0.978 (4)0.2832 (16)0.049 (10)*
H1N0.147 (3)0.645 (4)0.3213 (18)0.062 (10)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl110.0404 (4)0.0407 (4)0.0296 (3)0.0076 (3)0.0102 (3)0.0041 (3)
Cl10.0404 (5)0.0683 (6)0.0637 (5)0.0075 (4)0.0306 (4)0.0161 (4)
S10.0382 (4)0.0337 (4)0.0610 (5)0.0023 (3)0.0286 (3)0.0005 (3)
N10.0260 (12)0.0336 (13)0.0272 (11)0.0045 (10)0.0108 (9)0.0026 (10)
N20.0290 (13)0.0282 (13)0.0389 (12)0.0036 (11)0.0173 (9)0.0035 (10)
C3A0.0322 (15)0.0299 (15)0.0235 (12)0.0035 (12)0.0089 (10)0.0073 (11)
C30.0278 (15)0.0426 (17)0.0359 (15)0.0005 (12)0.0058 (11)0.0047 (12)
NQ0.0438 (15)0.0462 (15)0.0274 (11)0.0046 (12)0.0063 (10)0.0098 (10)
C60.0311 (15)0.0403 (17)0.0336 (14)0.0037 (13)0.0077 (11)0.0032 (12)
N40.0322 (16)0.0369 (16)0.0578 (16)0.0028 (13)0.0193 (12)0.0078 (12)
C90.0363 (16)0.0313 (15)0.0266 (13)0.0059 (12)0.0070 (11)0.0017 (11)
C70.0329 (16)0.0358 (16)0.0390 (15)0.0096 (13)0.0176 (12)0.0148 (12)
C100.0289 (14)0.0253 (14)0.0248 (12)0.0043 (11)0.0086 (10)0.0045 (10)
C40.0288 (15)0.0231 (14)0.0284 (13)0.0050 (11)0.0070 (10)0.0028 (11)
C50.0337 (15)0.0349 (16)0.0252 (13)0.0012 (12)0.0088 (11)0.0021 (11)
C80.0424 (18)0.0354 (16)0.0297 (13)0.0096 (13)0.0153 (12)0.0028 (12)
C20.0366 (17)0.0517 (19)0.0385 (16)0.0007 (15)0.0004 (12)0.0073 (14)
Geometric parameters (Å, º) top
Cl1—C71.733 (3)C6—C51.358 (3)
S1—C3A1.683 (2)C6—C71.398 (3)
N1—C41.346 (3)C6—H60.9300
N1—N21.392 (3)N4—H4B0.95 (3)
N1—H1N0.94 (3)N4—H4A0.81 (3)
N2—C3A1.356 (3)C9—C81.395 (3)
N2—H2N0.88 (3)C9—C101.409 (3)
C3A—N41.317 (3)C7—C81.362 (4)
C3—C21.368 (4)C10—C51.411 (3)
C3—C41.396 (3)C10—C41.434 (3)
C3—H30.9300C5—H50.9300
NQ—C21.324 (3)C8—H80.9300
NQ—C91.375 (3)C2—H20.9300
NQ—HNQ0.8600
Cl1···C3i3.510 (3)Cl11···HNQ2.2700
Cl1···S1ii3.6210 (11)Cl11···H8ix3.1400
Cl11···S1iii3.7398 (10)Cl11···H5x2.7500
Cl1···N1iv3.486 (2)S1···N2xi3.383 (2)
Cl11···NQv3.103 (2)S1···N4iii3.457 (3)
Cl11···N4vi3.327 (3)S1···Cl11xi3.7398 (10)
Cl11···N13.073 (2)S1···H4Biii2.54 (3)
Cl11···N1vi3.399 (2)S1···H2Nxi2.57 (3)
Cl1···H3vii2.9700S1···H2xii2.8900
Cl1···H2Niv3.13 (3)N1···N42.698 (3)
Cl11···H1N2.18 (3)N4···C43.335 (3)
Cl11···H4Avi2.54 (3)N1···H4A2.43 (3)
Cl11···H82.9600N1···H52.6100
Cl11···H5viii3.0700N2···H32.4700
C4—N1—N2120.0 (2)NQ—C9—C8119.2 (2)
C4—N1—H1N122.3 (18)NQ—C9—C10119.3 (2)
N2—N1—H1N116.9 (18)C8—C9—C10121.5 (2)
C3A—N2—N1121.2 (2)C8—C7—C6121.9 (2)
C3A—N2—H2N116.7 (18)C8—C7—Cl1119.1 (2)
N1—N2—H2N117.3 (18)C6—C7—Cl1119.0 (2)
N4—C3A—N2118.0 (2)C9—C10—C5117.5 (2)
N4—C3A—S1123.8 (2)C9—C10—C4118.4 (2)
N2—C3A—S1118.1 (2)C5—C10—C4124.1 (2)
C2—C3—C4119.8 (3)N1—C4—C3121.7 (2)
C2—C3—H3120.1N1—C4—C10119.7 (2)
C4—C3—H3120.1C3—C4—C10118.6 (2)
C2—NQ—C9121.7 (2)C6—C5—C10121.0 (2)
C2—NQ—HNQ119.1C6—C5—H5119.5
C9—NQ—HNQ119.1C10—C5—H5119.5
C5—C6—C7119.7 (2)C7—C8—C9118.4 (2)
C5—C6—H6120.1C7—C8—H8120.8
C7—C6—H6120.1C9—C8—H8120.8
C3A—N4—H4B115 (2)NQ—C2—C3122.1 (3)
C3A—N4—H4A124 (2)NQ—C2—H2118.9
H4B—N4—H4A121 (3)C3—C2—H2118.9
C4—N1—N2—C3A93.9 (3)C3—C4—C10—C91.0 (3)
N2—N1—C4—C34.4 (4)C10—C5—C6—C70.0 (4)
N2—N1—C4—C10176.1 (2)C6—C5—C10—C4179.9 (2)
C9—NQ—C2—C31.1 (4)C6—C5—C10—C90.2 (3)
C2—NQ—C9—C8178.7 (3)C5—C6—C7—Cl1179.89 (19)
C2—NQ—C9—C101.1 (4)C5—C6—C7—C80.4 (4)
N1—N2—C3A—S1178.46 (17)Cl1—C7—C8—C9179.62 (19)
N1—N2—C3A—N45.3 (3)C6—C7—C8—C90.7 (4)
NQ—C2—C3—C40.1 (4)C7—C8—C9—NQ179.6 (2)
C2—C3—C4—N1178.5 (2)C7—C8—C9—C100.5 (4)
C2—C3—C4—C101.1 (4)NQ—C9—C10—C40.1 (3)
N1—C4—C10—C51.6 (4)NQ—C9—C10—C5180.0 (2)
N1—C4—C10—C9178.5 (2)C8—C9—C10—C4179.8 (2)
C3—C4—C10—C5178.9 (2)C8—C9—C10—C50.1 (4)
Symmetry codes: (i) x1, y, z; (ii) x1, y+3/2, z+1/2; (iii) x+1, y1/2, z+1/2; (iv) x, y+1, z+1; (v) x, y+3/2, z1/2; (vi) x, y1/2, z+1/2; (vii) x+1, y, z; (viii) x, y+1, z; (ix) x, y+1/2, z1/2; (x) x, y1/2, z3/2; (xi) x+1, y+1/2, z+1/2; (xii) x1, y+1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
NQ—HNQ···Cl11xiii0.862.273.103 (2)164
N1—H1N···Cl110.94 (3)2.18 (3)3.073 (2)158 (3)
N2—H2N···S1iii0.89 (3)2.57 (3)3.383 (2)153 (2)
N4—H4A···N10.81 (3)2.43 (3)2.698 (3)100 (2)
N4—H4A···Cl11xiv0.81 (3)2.54 (3)3.327 (3)166 (2)
N4—H4B···S1xi0.95 (3)2.54 (3)3.457 (3)163 (3)
C5—H5···Cl110.932.753.638 (3)161
Symmetry codes: (iii) x+1, y1/2, z+1/2; (xi) x+1, y+1/2, z+1/2; (xiii) x, y+3/2, z+1/2; (xiv) x, y+1/2, z+1/2.
 

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