4-(4,5-Dihydro-1H-benzo[g]indazol-3-yl)pyridinium chloride dihydrate.

In the cation of the title compound, C(16)H(14)N(3) (+)·Cl(-)·2H(2)O, the cyclo-hexa-1,3-diene ring displays a screw-boat conformation and the pyridine ring is slightly twisted with respect to the pyrazole ring with a dihedral angle of 4.56 (12)°. In the crystal, ions and water mol-ecules are linked into a three-dimensional network by classical N-H⋯O, N-H⋯Cl, O-H⋯Cl and O-H⋯O hydrogen bonds and by π-π stacking inter-actions, with centroid-centroid distances of 3.7580 (14) and 3.7794 (14) Å.

Related literature

For background to the pharmacological properties of indazole derivatives, see: Bistochi et al. (1981 ▶); Keppler & Hartmann (1994 ▶); Gomtsyan et al. (2008 ▶).

Experimental

Crystal data

C16H14N3 +·Cl−·2H2O

M = 319.78

Triclinic,

a = 6.7977 (5) Å

b = 9.4406 (7) Å

c = 12.2691 (9) Å

α = 93.846 (3)°

β = 96.883 (3)°

γ = 93.490 (3)°

V = 778.04 (10) Å3

Z = 2

Mo Kα radiation

μ = 0.26 mm−1

T = 293 K

0.22 × 0.19 × 0.18 mm

Data collection

Bruker SMART CCD area-detector diffractometer

8076 measured reflections

2710 independent reflections

2185 reflections with I > 2σ(I)

R int = 0.033

Refinement

R[F 2 > 2σ(F 2)] = 0.045

wR(F 2) = 0.119

S = 1.06

2710 reflections

199 parameters

H-atom parameters constrained

Δρmax = 0.40 e Å−3

Δρmin = −0.32 e Å−3

Data collection: SMART (Bruker, 2002 ▶); cell refinement: SAINT (Bruker, 2002 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S160053681203019X/rz2781sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681203019X/rz2781Isup2.hkl

Supplementary material file. DOI: 10.1107/S160053681203019X/rz2781Isup3.cml

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

C16H14N3+·Cl−·2H2O	Z = 2
Mr = 319.78	F(000) = 336
Triclinic, P1	Dx = 1.365 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.7977 (5) Å	Cell parameters from 2710 reflections
b = 9.4406 (7) Å	θ = 1.7–25.0°
c = 12.2691 (9) Å	µ = 0.26 mm−1
α = 93.846 (3)°	T = 293 K
β = 96.883 (3)°	Block, colourless
γ = 93.490 (3)°	0.22 × 0.19 × 0.18 mm
V = 778.04 (10) Å3

Bruker SMART CCD area-detector diffractometer	2185 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.033
Graphite monochromator	θmax = 25.0°, θmin = 1.7°
φ and ω scans	h = −8→7
8076 measured reflections	k = −10→11
2710 independent reflections	l = −14→14

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.119	H-atom parameters constrained
S = 1.06	w = 1/[σ2(Fo2) + (0.0498P)2 + 0.5403P] where P = (Fo2 + 2Fc2)/3
2710 reflections	(Δ/σ)max < 0.001
199 parameters	Δρmax = 0.40 e Å−3
0 restraints	Δρmin = −0.32 e Å−3

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
C1	0.3584 (4)	0.6698 (3)	0.8547 (2)	0.0387 (6)
H1	0.3680	0.6302	0.9224	0.046*
C2	0.3132 (4)	0.5827 (3)	0.75906 (19)	0.0339 (6)
H2	0.2903	0.4850	0.7622	0.041*
C3	0.3018 (3)	0.6421 (2)	0.65730 (17)	0.0247 (5)
C4	0.3295 (3)	0.7899 (2)	0.65869 (18)	0.0286 (5)
H4	0.3181	0.8331	0.5925	0.034*
C5	0.3731 (3)	0.8721 (3)	0.75539 (19)	0.0318 (5)
H5	0.3921	0.9705	0.7551	0.038*
C6	0.2672 (3)	0.5559 (2)	0.55224 (17)	0.0230 (5)
C7	0.2449 (3)	0.4070 (2)	0.52895 (17)	0.0240 (5)
C8	0.2336 (4)	0.2806 (2)	0.5973 (2)	0.0322 (6)
H8A	0.1014	0.2683	0.6190	0.039*
H8B	0.3274	0.2978	0.6636	0.039*
C9	0.2217 (3)	0.3888 (2)	0.41550 (18)	0.0240 (5)
C10	0.2804 (4)	0.1448 (3)	0.5328 (2)	0.0364 (6)
H10A	0.4234	0.1391	0.5418	0.044*
H10B	0.2237	0.0638	0.5659	0.044*
C11	0.2075 (3)	0.1303 (2)	0.4108 (2)	0.0312 (5)
C12	0.1880 (3)	0.2522 (2)	0.35072 (19)	0.0271 (5)
C13	0.1380 (3)	0.2384 (3)	0.2367 (2)	0.0315 (5)
H13	0.1258	0.3190	0.1975	0.038*
C14	0.1064 (4)	0.1042 (3)	0.1821 (2)	0.0403 (6)
H14	0.0743	0.0949	0.1060	0.048*
C15	0.1224 (4)	−0.0156 (3)	0.2399 (2)	0.0437 (7)
H15	0.0997	−0.1054	0.2028	0.052*
C16	0.1723 (4)	−0.0027 (3)	0.3532 (2)	0.0395 (6)
H16	0.1824	−0.0843	0.3914	0.047*
N1	0.3885 (3)	0.8098 (2)	0.85102 (16)	0.0349 (5)
H1N	0.4187	0.8619	0.9116	0.042*
N2	0.2606 (3)	0.62466 (19)	0.45875 (14)	0.0249 (4)
N3	0.2321 (3)	0.52067 (19)	0.37761 (14)	0.0248 (4)
H3	0.2214	0.5357	0.3089	0.030*
O1W	0.8185 (3)	0.6654 (3)	0.04112 (19)	0.0691 (7)
H1WA	0.9413	0.6435	0.0647	0.083*
H1WB	0.7964	0.5906	−0.0050	0.083*
O2W	0.5429 (3)	0.85870 (19)	0.07832 (14)	0.0399 (5)
H2WA	0.4837	0.7898	0.1118	0.048*
H2WB	0.6532	0.8085	0.0732	0.048*
Cl1	0.25495 (10)	0.60918 (7)	0.13519 (5)	0.0441 (2)

	U11	U22	U33	U12	U13	U23
C1	0.0428 (15)	0.0472 (17)	0.0268 (12)	0.0083 (12)	0.0023 (10)	0.0076 (11)
C2	0.0393 (14)	0.0321 (14)	0.0313 (12)	0.0048 (11)	0.0043 (10)	0.0078 (11)
C3	0.0193 (11)	0.0282 (13)	0.0277 (11)	0.0045 (9)	0.0045 (8)	0.0048 (9)
C4	0.0290 (12)	0.0281 (13)	0.0299 (12)	0.0040 (10)	0.0061 (9)	0.0043 (10)
C5	0.0298 (13)	0.0295 (13)	0.0362 (13)	0.0028 (10)	0.0062 (10)	−0.0008 (11)
C6	0.0206 (11)	0.0237 (12)	0.0259 (11)	0.0022 (9)	0.0043 (8)	0.0069 (9)
C7	0.0185 (11)	0.0239 (12)	0.0308 (11)	0.0033 (9)	0.0044 (9)	0.0057 (9)
C8	0.0338 (13)	0.0265 (13)	0.0383 (13)	0.0043 (10)	0.0067 (10)	0.0114 (11)
C9	0.0202 (11)	0.0216 (12)	0.0314 (12)	0.0028 (9)	0.0053 (9)	0.0062 (9)
C10	0.0356 (14)	0.0262 (14)	0.0503 (15)	0.0063 (10)	0.0094 (11)	0.0122 (12)
C11	0.0221 (12)	0.0234 (13)	0.0496 (14)	0.0024 (9)	0.0100 (10)	0.0042 (11)
C12	0.0200 (11)	0.0247 (13)	0.0372 (12)	0.0011 (9)	0.0080 (9)	0.0001 (10)
C13	0.0238 (12)	0.0305 (14)	0.0412 (13)	0.0021 (10)	0.0088 (10)	0.0005 (11)
C14	0.0342 (14)	0.0385 (16)	0.0463 (15)	−0.0001 (11)	0.0064 (11)	−0.0101 (13)
C15	0.0367 (15)	0.0264 (14)	0.0659 (18)	−0.0017 (11)	0.0103 (13)	−0.0144 (13)
C16	0.0321 (14)	0.0236 (13)	0.0637 (18)	0.0008 (10)	0.0104 (12)	0.0032 (12)
N1	0.0318 (11)	0.0424 (14)	0.0292 (10)	0.0034 (9)	0.0020 (8)	−0.0063 (9)
N2	0.0266 (10)	0.0214 (10)	0.0270 (9)	0.0023 (8)	0.0035 (7)	0.0033 (8)
N3	0.0286 (10)	0.0227 (10)	0.0232 (9)	0.0024 (8)	0.0030 (7)	0.0021 (8)
O1W	0.0588 (14)	0.0699 (16)	0.0761 (15)	0.0245 (12)	−0.0030 (11)	−0.0103 (12)
O2W	0.0382 (10)	0.0376 (11)	0.0409 (10)	0.0052 (8)	0.0003 (8)	−0.0142 (8)
Cl1	0.0570 (4)	0.0417 (4)	0.0343 (3)	0.0068 (3)	0.0048 (3)	0.0064 (3)

C1—N1	1.330 (3)	C10—C11	1.514 (4)
C1—C2	1.378 (3)	C10—H10A	0.9700
C1—H1	0.9300	C10—H10B	0.9700
C2—C3	1.398 (3)	C11—C16	1.392 (3)
C2—H2	0.9300	C11—C12	1.413 (3)
C3—C4	1.395 (3)	C12—C13	1.395 (3)
C3—C6	1.464 (3)	C13—C14	1.385 (3)
C4—C5	1.365 (3)	C13—H13	0.9300
C4—H4	0.9300	C14—C15	1.378 (4)
C5—N1	1.344 (3)	C14—H14	0.9300
C5—H5	0.9300	C15—C16	1.386 (4)
C6—N2	1.353 (3)	C15—H15	0.9300
C6—C7	1.411 (3)	C16—H16	0.9300
C7—C9	1.380 (3)	N1—H1N	0.8600
C7—C8	1.507 (3)	N2—N3	1.339 (2)
C8—C10	1.532 (3)	N3—H3	0.8600
C8—H8A	0.9700	O1W—H1WA	0.8917
C8—H8B	0.9700	O1W—H1WB	0.8693
C9—N3	1.359 (3)	O2W—H2WA	0.8928
C9—C12	1.459 (3)	O2W—H2WB	0.9171
N1—C1—C2	120.6 (2)	C8—C10—H10A	108.1
N1—C1—H1	119.7	C11—C10—H10B	108.1
C2—C1—H1	119.7	C8—C10—H10B	108.1
C1—C2—C3	119.6 (2)	H10A—C10—H10B	107.3
C1—C2—H2	120.2	C16—C11—C12	118.1 (2)
C3—C2—H2	120.2	C16—C11—C10	121.2 (2)
C4—C3—C2	117.2 (2)	C12—C11—C10	120.5 (2)
C4—C3—C6	120.0 (2)	C13—C12—C11	120.4 (2)
C2—C3—C6	122.8 (2)	C13—C12—C9	123.8 (2)
C5—C4—C3	121.2 (2)	C11—C12—C9	115.8 (2)
C5—C4—H4	119.4	C14—C13—C12	119.8 (2)
C3—C4—H4	119.4	C14—C13—H13	120.1
N1—C5—C4	119.4 (2)	C12—C13—H13	120.1
N1—C5—H5	120.3	C15—C14—C13	120.4 (3)
C4—C5—H5	120.3	C15—C14—H14	119.8
N2—C6—C7	111.32 (19)	C13—C14—H14	119.8
N2—C6—C3	117.73 (19)	C14—C15—C16	120.2 (2)
C7—C6—C3	130.9 (2)	C14—C15—H15	119.9
C9—C7—C6	104.38 (19)	C16—C15—H15	119.9
C9—C7—C8	120.7 (2)	C15—C16—C11	121.1 (2)
C6—C7—C8	134.9 (2)	C15—C16—H16	119.4
C7—C8—C10	111.05 (19)	C11—C16—H16	119.4
C7—C8—H8A	109.4	C1—N1—C5	121.9 (2)
C10—C8—H8A	109.4	C1—N1—H1N	119.0
C7—C8—H8B	109.4	C5—N1—H1N	119.0
C10—C8—H8B	109.4	N3—N2—C6	104.52 (17)
H8A—C8—H8B	108.0	N2—N3—C9	112.78 (17)
N3—C9—C7	106.99 (19)	N2—N3—H3	123.6
N3—C9—C12	127.6 (2)	C9—N3—H3	123.6
C7—C9—C12	125.4 (2)	H1WA—O1W—H1WB	93.0
C11—C10—C8	116.6 (2)	H2WA—O2W—H2WB	92.1
C11—C10—H10A	108.1
N1—C1—C2—C3	1.0 (4)	C16—C11—C12—C13	−1.0 (3)
C1—C2—C3—C4	−2.6 (3)	C10—C11—C12—C13	174.2 (2)
C1—C2—C3—C6	176.0 (2)	C16—C11—C12—C9	178.5 (2)
C2—C3—C4—C5	2.4 (3)	C10—C11—C12—C9	−6.2 (3)
C6—C3—C4—C5	−176.3 (2)	N3—C9—C12—C13	−7.7 (4)
C3—C4—C5—N1	−0.4 (3)	C7—C9—C12—C13	170.8 (2)
C4—C3—C6—N2	−0.9 (3)	N3—C9—C12—C11	172.8 (2)
C2—C3—C6—N2	−179.5 (2)	C7—C9—C12—C11	−8.8 (3)
C4—C3—C6—C7	176.5 (2)	C11—C12—C13—C14	0.3 (3)
C2—C3—C6—C7	−2.0 (4)	C9—C12—C13—C14	−179.2 (2)
N2—C6—C7—C9	−0.7 (2)	C12—C13—C14—C15	0.6 (4)
C3—C6—C7—C9	−178.3 (2)	C13—C14—C15—C16	−0.7 (4)
N2—C6—C7—C8	−177.6 (2)	C14—C15—C16—C11	−0.1 (4)
C3—C6—C7—C8	4.8 (4)	C12—C11—C16—C15	0.9 (3)
C9—C7—C8—C10	23.2 (3)	C10—C11—C16—C15	−174.3 (2)
C6—C7—C8—C10	−160.4 (2)	C2—C1—N1—C5	1.1 (4)
C6—C7—C9—N3	0.4 (2)	C4—C5—N1—C1	−1.4 (3)
C8—C7—C9—N3	177.81 (19)	C7—C6—N2—N3	0.7 (2)
C6—C7—C9—C12	−178.3 (2)	C3—C6—N2—N3	178.68 (17)
C8—C7—C9—C12	−0.9 (3)	C6—N2—N3—C9	−0.5 (2)
C7—C8—C10—C11	−36.3 (3)	C7—C9—N3—N2	0.0 (2)
C8—C10—C11—C16	−155.3 (2)	C12—C9—N3—N2	178.70 (19)
C8—C10—C11—C12	29.6 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O2Wi	0.86	2.12	2.856 (2)	143
N3—H3···Cl1	0.86	2.32	3.1618 (19)	167
O1W—H1WA···Cl1ii	0.89	2.25	3.142 (2)	174
O1W—H1WB···Cl1iii	0.87	2.37	3.237 (3)	178
O2W—H2WA···Cl1	0.89	2.29	3.139 (2)	158
O2W—H2WB···O1W	0.92	1.86	2.749 (3)	162

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O2W i	0.86	2.12	2.856 (2)	143
N3—H3⋯Cl1	0.86	2.32	3.1618 (19)	167
O1W—H1WA⋯Cl1ii	0.89	2.25	3.142 (2)	174
O1W—H1WB⋯Cl1iii	0.87	2.37	3.237 (3)	178
O2W—H2WA⋯Cl1	0.89	2.29	3.139 (2)	158
O2W—H2WB⋯O1W	0.92	1.86	2.749 (3)	162

Symmetry codes: (i) ; (ii) ; (iii) .