Chloro-thia-zide-pyridine (1/3).

In the title compound, C(7)H(6)ClN(3)O(4)S(2)·3C(5)H(5)N, (systematic name: 6-chloro-2H-1,2,4-benzothia-diazine-7-sulfonamide 1,1-dioxide pyridine tris-olvate), chloro-thia-zide forms a 1:3 solvate with pyridine. The crystal structure is stabilized by strong inter-molecular N-H⋯N hydrogen bonds.

Related literature

For details on experimental methods used to obtain this form, see: Florence et al. (2003 ▶, 2006 ▶). For previous studies on the non-solvated form of chloro­thaizide, see: Dupont & Dideberg (1970 ▶); Shankland et al. (1997 ▶). For solvated forms see: Johnston et al. (2007a ▶,b ▶); Johnston, Florence & Kennedy (2007 ▶); Fernandes, Florence et al. (2006 ▶); Fernandes, Shankland et al. (2007 ▶). For studies of inter­molecular inter­actions in the related thia­zide diuretic, hydro­chloro­thia­zide, see: Johnston, Florence, Shankland et al. (2007 ▶). For additional literature on related thia­zide compounds, see: Fabbiani et al. (2007 ▶); Fernandes, Johnston et al. (2007 ▶); Fernandes, Leech et al. (2007 ▶).

Experimental

Crystal data

C7H6ClN3O4S2·3C5H5N

M = 533.02

Triclinic,

a = 9.0697 (15) Å

b = 11.863 (2) Å

c = 11.875 (2) Å

α = 100.691 (7)°

β = 98.667 (8)°

γ = 98.134 (7)°

V = 1222.1 (4) Å3

Z = 2

Mo Kα radiation

μ = 0.37 mm−1

T = 123 (2) K

0.18 × 0.10 × 0.05 mm

Data collection

Nonius KappaCCD diffractometer

Absorption correction: none

14598 measured reflections

4219 independent reflections

2998 reflections with I > 2σ(I)

R int = 0.085

Refinement

R[F 2 > 2σ(F 2)] = 0.059

wR(F 2) = 0.103

S = 1.04

4219 reflections

328 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.34 e Å−3

Δρmin = −0.49 e Å−3

Data collection: DENZO (Otwinowski & Minor, 1997 ▶) and COLLECT (Hooft, 1998 ▶); cell refinement: DENZO and COLLECT; data reduction: DENZO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: PLATON (Spek, 2003 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808014360/bx2144sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808014360/bx2144Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C7H6ClN3O4S2·3C5H5N	Z = 2
Mr = 533.02	F000 = 552
Triclinic, P1	Dx = 1.448 Mg m−3
Hall symbol: P -1	Mo Kα radiation λ = 0.71073 Å
a = 9.0697 (15) Å	Cell parameters from 3968 reflections
b = 11.863 (2) Å	θ = 1.0–27.1º
c = 11.875 (2) Å	µ = 0.37 mm−1
α = 100.691 (7)º	T = 123 (2) K
β = 98.667 (8)º	Cut fragment, colourless
γ = 98.134 (7)º	0.18 × 0.10 × 0.05 mm
V = 1222.1 (4) Å3

Nonius KappaCCD diffractometer	2998 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.085
Monochromator: graphite	θmax = 25.3º
T = 123(2) K	θmin = 1.8º
φ and ω scans	h = −10→0
Absorption correction: none	k = −13→14
14598 measured reflections	l = −13→14
4219 independent reflections

Refinement on F2	H atoms treated by a mixture of independent and constrained refinement
Least-squares matrix: full	w = 1/[σ2(Fo2) + (0.0253P)2 + 1.8286P] where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.059	(Δ/σ)max < 0.001
wR(F2) = 0.103	Δρmax = 0.34 e Å−3
S = 1.04	Δρmin = −0.49 e Å−3
4219 reflections	Extinction correction: none
328 parameters

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. 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 > σ(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.

	x	y	z	Uiso*/Ueq
Cl1	−0.11042 (9)	0.34675 (7)	0.54702 (7)	0.0161 (2)
S1	0.24543 (9)	−0.02698 (7)	0.33227 (7)	0.0127 (2)
S2	−0.16390 (10)	0.25714 (7)	0.26176 (7)	0.0134 (2)
O3	0.3649 (3)	0.0349 (2)	0.2890 (2)	0.0213 (6)
O1	0.1454 (3)	−0.1213 (2)	0.2501 (2)	0.0230 (6)
O2	−0.1320 (3)	0.20934 (19)	0.14895 (19)	0.0185 (6)
O4	−0.3120 (2)	0.2257 (2)	0.28715 (19)	0.0197 (6)
N3	0.3205 (3)	−0.0768 (2)	0.4406 (2)	0.0145 (7)
N2	0.2459 (3)	0.0587 (2)	0.5857 (3)	0.0121 (7)
N1	−0.1235 (4)	0.3939 (3)	0.2847 (3)	0.0178 (7)
C3	0.3177 (4)	−0.0285 (3)	0.5481 (3)	0.0137 (8)
H3	0.3730	−0.0587	0.6068	0.016*
C2	0.1548 (3)	0.1084 (3)	0.5117 (3)	0.0093 (7)
C7	0.1389 (3)	0.0736 (3)	0.3908 (3)	0.0098 (7)
C1	0.0429 (3)	0.1218 (3)	0.3176 (3)	0.0101 (7)
H1	0.0320	0.0968	0.2356	0.012*
C5	−0.0367 (3)	0.2054 (3)	0.3622 (3)	0.0098 (7)
C6	−0.0171 (4)	0.2406 (3)	0.4846 (3)	0.0108 (8)
C4	0.0752 (4)	0.1928 (3)	0.5575 (3)	0.0103 (7)
H4	0.0851	0.2173	0.6396	0.012*
N1S	0.7057 (3)	0.5432 (2)	0.4150 (3)	0.0195 (7)
C1S	0.6985 (4)	0.5848 (3)	0.5263 (3)	0.0202 (9)
H1S	0.7624	0.5608	0.5850	0.024*
C2S	0.6037 (4)	0.6605 (3)	0.5610 (3)	0.0242 (9)
H2S	0.6020	0.6870	0.6413	0.029*
C3S	0.5120 (4)	0.6967 (3)	0.4769 (4)	0.0291 (10)
H3S	0.4469	0.7500	0.4981	0.035*
C4S	0.5158 (4)	0.6547 (3)	0.3615 (4)	0.0308 (10)
H4S	0.4520	0.6769	0.3014	0.037*
C5S	0.6150 (4)	0.5793 (3)	0.3352 (3)	0.0255 (9)
H5S	0.6186	0.5516	0.2555	0.031*
N2S	0.2984 (3)	0.1270 (2)	0.8267 (2)	0.0200 (7)
C6S	0.2000 (4)	0.1232 (3)	0.9002 (3)	0.0237 (9)
H6S	0.0953	0.1160	0.8698	0.028*
C7S	0.2439 (5)	0.1292 (3)	1.0180 (3)	0.0335 (11)
H7S	0.1705	0.1246	1.0669	0.040*
C8S	0.3955 (5)	0.1419 (3)	1.0634 (3)	0.0319 (11)
H8S	0.4288	0.1467	1.1441	0.038*
C9S	0.4979 (4)	0.1475 (3)	0.9891 (3)	0.0263 (10)
H9S	0.6035	0.1570	1.0177	0.032*
C10S	0.4444 (4)	0.1391 (3)	0.8729 (3)	0.0237 (9)
H10S	0.5159	0.1420	0.8223	0.028*
N3S	0.1270 (3)	0.4933 (3)	0.1813 (3)	0.0245 (8)
C11S	0.2125 (4)	0.4257 (3)	0.1287 (3)	0.0302 (10)
H11S	0.2221	0.3542	0.1517	0.036*
C12S	0.2882 (4)	0.4540 (4)	0.0421 (3)	0.0336 (10)
H12S	0.3486	0.4034	0.0071	0.040*
C13S	0.2739 (4)	0.5576 (4)	0.0079 (3)	0.0313 (10)
H13S	0.3233	0.5792	−0.0520	0.038*
C14S	0.1872 (4)	0.6288 (3)	0.0617 (3)	0.0261 (9)
H14S	0.1760	0.7008	0.0403	0.031*
C15S	0.1165 (4)	0.5939 (3)	0.1478 (3)	0.0222 (9)
H15S	0.0573	0.6440	0.1851	0.027*
H2	0.261 (4)	0.083 (3)	0.665 (3)	0.034 (12)*
H5	−0.166 (4)	0.433 (3)	0.334 (3)	0.036 (13)*
H6	−0.046 (4)	0.420 (3)	0.262 (3)	0.014 (10)*

	U11	U22	U33	U12	U13	U23
Cl1	0.0195 (5)	0.0159 (5)	0.0153 (5)	0.0021 (4)	0.0067 (4)	0.0090 (4)
S1	0.0133 (5)	0.0150 (5)	0.0108 (5)	0.0021 (4)	0.0024 (4)	0.0065 (4)
S2	0.0141 (5)	0.0152 (5)	0.0120 (5)	0.0059 (4)	−0.0002 (4)	0.0045 (4)
O3	0.0187 (14)	0.0303 (15)	0.0237 (15)	0.0147 (12)	0.0141 (12)	0.0108 (11)
O1	0.0245 (15)	0.0209 (14)	0.0180 (14)	−0.0067 (11)	−0.0053 (11)	0.0089 (11)
O2	0.0274 (14)	0.0209 (14)	0.0083 (13)	0.0029 (10)	0.0014 (11)	0.0101 (11)
O4	0.0137 (13)	0.0261 (14)	0.0191 (14)	0.0106 (11)	−0.0027 (11)	0.0014 (11)
N3	0.0125 (16)	0.0176 (16)	0.0158 (18)	0.0070 (13)	0.0019 (13)	0.0067 (13)
N2	0.0136 (16)	0.0164 (16)	0.0066 (18)	0.0049 (13)	−0.0016 (13)	0.0037 (13)
N1	0.0214 (19)	0.0163 (17)	0.022 (2)	0.0100 (14)	0.0121 (16)	0.0064 (15)
C3	0.0083 (18)	0.0125 (18)	0.020 (2)	0.0083 (16)	0.0000 (16)	−0.0016 (15)
C2	0.0046 (17)	0.0105 (17)	0.012 (2)	0.0037 (14)	0.0000 (15)	−0.0015 (14)
C7	0.0072 (18)	0.0103 (17)	0.011 (2)	0.0013 (14)	0.0008 (15)	−0.0012 (14)
C1	0.0107 (18)	0.0127 (17)	0.0054 (19)	0.0002 (14)	0.0006 (15)	−0.0001 (14)
C5	0.0070 (18)	0.0113 (18)	0.010 (2)	0.0038 (14)	−0.0009 (15)	−0.0006 (14)
C6	0.0084 (18)	0.0083 (17)	0.016 (2)	0.0009 (14)	0.0062 (15)	0.0008 (14)
C4	0.0108 (18)	0.0115 (17)	0.0081 (19)	0.0037 (14)	0.0016 (15)	−0.0013 (14)
N1S	0.0182 (17)	0.0141 (16)	0.026 (2)	0.0021 (14)	0.0053 (15)	0.0029 (13)
C1S	0.020 (2)	0.016 (2)	0.024 (2)	0.0078 (17)	−0.0011 (17)	−0.0004 (16)
C2S	0.022 (2)	0.018 (2)	0.032 (2)	0.0007 (17)	0.0116 (19)	−0.0018 (17)
C3S	0.015 (2)	0.012 (2)	0.060 (3)	0.004 (2)	0.009 (2)	0.0043 (17)
C4S	0.019 (2)	0.026 (2)	0.044 (3)	0.017 (2)	−0.011 (2)	−0.0025 (18)
C5S	0.028 (2)	0.023 (2)	0.023 (2)	0.0068 (18)	0.0018 (19)	−0.0024 (18)
N2S	0.0232 (19)	0.0243 (18)	0.0105 (17)	0.0013 (13)	−0.0039 (15)	0.0077 (14)
C6S	0.018 (2)	0.021 (2)	0.026 (3)	−0.0027 (17)	0.0002 (18)	−0.0032 (17)
C7S	0.042 (3)	0.034 (2)	0.021 (3)	0.0019 (18)	0.017 (2)	−0.011 (2)
C8S	0.053 (3)	0.025 (2)	0.012 (2)	0.0080 (17)	−0.002 (2)	−0.006 (2)
C9S	0.027 (2)	0.022 (2)	0.025 (3)	0.0052 (17)	−0.011 (2)	0.0027 (18)
C10S	0.024 (2)	0.029 (2)	0.019 (2)	0.0038 (17)	0.0054 (19)	0.0084 (18)
N3S	0.031 (2)	0.0234 (18)	0.0208 (19)	0.0043 (14)	0.0106 (15)	0.0060 (15)
C11S	0.038 (3)	0.024 (2)	0.031 (3)	0.0078 (18)	0.008 (2)	0.0084 (19)
C12S	0.036 (3)	0.041 (3)	0.029 (3)	0.007 (2)	0.016 (2)	0.012 (2)
C13S	0.033 (2)	0.043 (3)	0.019 (2)	0.009 (2)	0.011 (2)	−0.001 (2)
C14S	0.033 (2)	0.024 (2)	0.021 (2)	0.0096 (17)	0.0016 (19)	0.0002 (19)
C15S	0.026 (2)	0.020 (2)	0.019 (2)	0.0021 (17)	0.0019 (18)	0.0035 (17)

Cl1—C6	1.730 (3)	C2S—H2S	0.9500
S1—O3	1.435 (2)	C3S—C4S	1.376 (6)
S1—O1	1.439 (2)	C3S—H3S	0.9500
S1—N3	1.613 (3)	C4S—C5S	1.384 (5)
S1—C7	1.749 (3)	C4S—H4S	0.9500
S2—O4	1.434 (2)	C5S—H5S	0.9500
S2—O2	1.443 (2)	N2S—C10S	1.332 (4)
S2—N1	1.575 (3)	N2S—C6S	1.340 (4)
S2—C5	1.785 (3)	C6S—C7S	1.381 (5)
N3—C3	1.304 (4)	C6S—H6S	0.9500
N2—C3	1.342 (4)	C7S—C8S	1.376 (5)
N2—C2	1.383 (4)	C7S—H7S	0.9500
N2—H2	0.91 (4)	C8S—C9S	1.377 (5)
N1—H5	0.85 (4)	C8S—H8S	0.9500
N1—H6	0.83 (3)	C9S—C10S	1.372 (5)
C3—H3	0.9500	C9S—H9S	0.9500
C2—C4	1.393 (4)	C10S—H10S	0.9500
C2—C7	1.398 (4)	N3S—C11S	1.330 (5)
C7—C1	1.392 (4)	N3S—C15S	1.338 (4)
C1—C5	1.381 (4)	C11S—C12S	1.384 (5)
C1—H1	0.9500	C11S—H11S	0.9500
C5—C6	1.413 (4)	C12S—C13S	1.381 (5)
C6—C4	1.368 (4)	C12S—H12S	0.9500
C4—H4	0.9500	C13S—C14S	1.371 (5)
N1S—C5S	1.331 (5)	C13S—H13S	0.9500
N1S—C1S	1.337 (4)	C14S—C15S	1.381 (5)
C1S—C2S	1.380 (5)	C14S—H14S	0.9500
C1S—H1S	0.9500	C15S—H15S	0.9500
C2S—C3S	1.372 (5)
?···?	?
O3—S1—O1	116.53 (15)	C3S—C2S—C1S	118.5 (4)
O3—S1—N3	108.29 (14)	C3S—C2S—H2S	120.8
O1—S1—N3	108.71 (14)	C1S—C2S—H2S	120.8
O3—S1—C7	108.12 (14)	C2S—C3S—C4S	119.0 (4)
O1—S1—C7	109.09 (14)	C2S—C3S—H3S	120.5
N3—S1—C7	105.55 (15)	C4S—C3S—H3S	120.5
O4—S2—O2	119.51 (14)	C3S—C4S—C5S	118.3 (4)
O4—S2—N1	108.62 (17)	C3S—C4S—H4S	120.8
O2—S2—N1	108.54 (16)	C5S—C4S—H4S	120.8
O4—S2—C5	106.13 (14)	N1S—C5S—C4S	124.0 (4)
O2—S2—C5	104.48 (14)	N1S—C5S—H5S	118.0
N1—S2—C5	109.16 (16)	C4S—C5S—H5S	118.0
C3—N3—S1	121.8 (2)	C10S—N2S—C6S	116.7 (3)
C3—N2—C2	123.4 (3)	N2S—C6S—C7S	123.0 (4)
C3—N2—H2	115 (2)	N2S—C6S—H6S	118.5
C2—N2—H2	122 (2)	C7S—C6S—H6S	118.5
S2—N1—H5	118 (3)	C8S—C7S—C6S	119.0 (4)
S2—N1—H6	115 (2)	C8S—C7S—H7S	120.5
H5—N1—H6	125 (3)	C6S—C7S—H7S	120.5
N3—C3—N2	127.6 (3)	C7S—C8S—C9S	118.5 (4)
N3—C3—H3	116.2	C7S—C8S—H8S	120.7
N2—C3—H3	116.2	C9S—C8S—H8S	120.7
N2—C2—C4	120.0 (3)	C10S—C9S—C8S	118.6 (4)
N2—C2—C7	120.9 (3)	C10S—C9S—H9S	120.7
C4—C2—C7	119.1 (3)	C8S—C9S—H9S	120.7
C1—C7—C2	120.1 (3)	N2S—C10S—C9S	124.1 (3)
C1—C7—S1	120.3 (2)	N2S—C10S—H10S	118.0
C2—C7—S1	119.6 (2)	C9S—C10S—H10S	118.0
C5—C1—C7	121.2 (3)	C11S—N3S—C15S	116.9 (3)
C5—C1—H1	119.4	N3S—C11S—C12S	123.5 (4)
C7—C1—H1	119.4	N3S—C11S—H11S	118.2
C1—C5—C6	117.7 (3)	C12S—C11S—H11S	118.2
C1—C5—S2	118.0 (2)	C13S—C12S—C11S	118.4 (4)
C6—C5—S2	124.2 (2)	C13S—C12S—H12S	120.8
C4—C6—C5	121.7 (3)	C11S—C12S—H12S	120.8
C4—C6—Cl1	117.8 (2)	C14S—C13S—C12S	118.9 (3)
C5—C6—Cl1	120.5 (2)	C14S—C13S—H13S	120.6
C6—C4—C2	120.1 (3)	C12S—C13S—H13S	120.6
C6—C4—H4	119.9	C13S—C14S—C15S	118.7 (3)
C2—C4—H4	119.9	C13S—C14S—H14S	120.6
C5S—N1S—C1S	116.3 (3)	C15S—C14S—H14S	120.6
N1S—C1S—C2S	124.0 (3)	N3S—C15S—C14S	123.4 (3)
N1S—C1S—H1S	118.0	N3S—C15S—H15S	118.3
C2S—C1S—H1S	118.0	C14S—C15S—H15S	118.3
O3—S1—N3—C3	104.1 (3)	C1—C5—C6—C4	−1.1 (4)
O1—S1—N3—C3	−128.4 (3)	S2—C5—C6—C4	176.0 (2)
C7—S1—N3—C3	−11.5 (3)	C1—C5—C6—Cl1	178.9 (2)
S1—N3—C3—N2	5.9 (5)	S2—C5—C6—Cl1	−4.1 (4)
C2—N2—C3—N3	3.1 (5)	C5—C6—C4—C2	0.9 (5)
C3—N2—C2—C4	175.3 (3)	Cl1—C6—C4—C2	−179.0 (2)
C3—N2—C2—C7	−3.5 (5)	N2—C2—C4—C6	−178.8 (3)
N2—C2—C7—C1	177.9 (3)	C7—C2—C4—C6	0.0 (4)
C4—C2—C7—C1	−0.9 (4)	C5S—N1S—C1S—C2S	0.4 (5)
N2—C2—C7—S1	−4.4 (4)	N1S—C1S—C2S—C3S	−0.7 (5)
C4—C2—C7—S1	176.8 (2)	C1S—C2S—C3S—C4S	1.2 (5)
O3—S1—C7—C1	72.7 (3)	C2S—C3S—C4S—C5S	−1.4 (5)
O1—S1—C7—C1	−54.9 (3)	C1S—N1S—C5S—C4S	−0.6 (5)
N3—S1—C7—C1	−171.6 (2)	C3S—C4S—C5S—N1S	1.1 (5)
O3—S1—C7—C2	−105.0 (3)	C10S—N2S—C6S—C7S	−1.1 (5)
O1—S1—C7—C2	127.4 (3)	N2S—C6S—C7S—C8S	1.3 (6)
N3—S1—C7—C2	10.7 (3)	C6S—C7S—C8S—C9S	−0.4 (6)
C2—C7—C1—C5	0.8 (4)	C7S—C8S—C9S—C10S	−0.6 (5)
S1—C7—C1—C5	−176.9 (2)	C6S—N2S—C10S—C9S	0.0 (5)
C7—C1—C5—C6	0.2 (4)	C8S—C9S—C10S—N2S	0.8 (6)
C7—C1—C5—S2	−177.0 (2)	C15S—N3S—C11S—C12S	−0.5 (6)
O4—S2—C5—C1	117.4 (2)	N3S—C11S—C12S—C13S	−0.4 (6)
O2—S2—C5—C1	−9.8 (3)	C11S—C12S—C13S—C14S	0.8 (6)
N1—S2—C5—C1	−125.7 (3)	C12S—C13S—C14S—C15S	−0.4 (6)
O4—S2—C5—C6	−59.7 (3)	C11S—N3S—C15S—C14S	0.9 (5)
O2—S2—C5—C6	173.2 (3)	C13S—C14S—C15S—N3S	−0.5 (6)
N1—S2—C5—C6	57.2 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···N2S	0.91 (4)	1.86 (4)	2.774 (4)	177 (4)
N1—H5···N1Si	0.85 (4)	2.07 (4)	2.900 (4)	165 (4)
N1—H6···N3S	0.83 (3)	2.13 (4)	2.946 (4)	170 (3)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯N2S	0.91 (4)	1.86 (4)	2.774 (4)	177 (4)
N1—H5⋯N1Si	0.85 (4)	2.07 (4)	2.900 (4)	165 (4)
N1—H6⋯N3S	0.83 (3)	2.13 (4)	2.946 (4)	170 (3)

Symmetry code: (i) .