4,5,6,7,8,9-Hexahydro-2H-cyclo-octa[c]pyrazol-1-ium-3-olate.

The title compound, C(9)H(14)N(2)O, exists in the zwitterionic form in the crystal. The cyclo-octane ring adopts a twisted boat-chair conformation. In the crystal, inter-molecular N-H⋯O hydrogen bonds link the mol-ecules into sheets lying parallel to bc. The structure is also stabilized by π-π inter-actions, with a centroid-to-centroid distance of 3.5684 (8) Å.

Related literature

For pyrazole derivatives and their microbial activities, see: Ragavan et al. (2009 ▶, 2010 ▶). For a related structure, see: Xiong et al. (2007 ▶). For the stability of the temperature controller used for data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C9H14N2O

M = 166.22

Monoclinic,

a = 12.8078 (2) Å

b = 6.7758 (1) Å

c = 10.7096 (2) Å

β = 111.620 (1)°

V = 864.03 (2) Å3

Z = 4

Mo Kα radiation

μ = 0.09 mm−1

T = 100 K

0.54 × 0.24 × 0.11 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.956, T max = 0.991

6990 measured reflections

1680 independent reflections

1474 reflections with I > 2σ(I)

R int = 0.026

Refinement

R[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.095

S = 1.05

1680 reflections

117 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.25 e Å−3

Δρmin = −0.25 e Å−3

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810043904/fj2356sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810043904/fj2356Isup2.hkl

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

C9H14N2O	F(000) = 360
Mr = 166.22	Dx = 1.278 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3802 reflections
a = 12.8078 (2) Å	θ = 3.5–30.1°
b = 6.7758 (1) Å	µ = 0.09 mm−1
c = 10.7096 (2) Å	T = 100 K
β = 111.620 (1)°	Plate, colourless
V = 864.03 (2) Å3	0.54 × 0.24 × 0.11 mm
Z = 4

Bruker SMART APEXII CCD area-detector diffractometer	1680 independent reflections
Radiation source: fine-focus sealed tube	1474 reflections with I > 2σ(I)
graphite	Rint = 0.026
φ and ω scans	θmax = 26.0°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −15→15
Tmin = 0.956, Tmax = 0.991	k = −8→8
6990 measured reflections	l = −13→12

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.095	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.047P)2 + 0.3516P] where P = (Fo2 + 2Fc2)/3
1680 reflections	(Δ/σ)max < 0.001
117 parameters	Δρmax = 0.25 e Å−3
0 restraints	Δρmin = −0.25 e Å−3

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

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
O1	0.41579 (8)	0.06094 (13)	0.31883 (8)	0.0190 (2)
N1	0.44456 (9)	0.21181 (16)	0.52370 (10)	0.0160 (3)
N2	0.41423 (9)	0.38447 (16)	0.56789 (11)	0.0154 (3)
C1	0.34257 (10)	0.48051 (18)	0.46046 (12)	0.0149 (3)
C2	0.28502 (11)	0.66563 (19)	0.47482 (13)	0.0177 (3)
H2A	0.2711	0.7476	0.3961	0.021*
H2B	0.3335	0.7384	0.5525	0.021*
C3	0.17257 (11)	0.6209 (2)	0.49123 (12)	0.0189 (3)
H3A	0.1883	0.5734	0.5818	0.023*
H3B	0.1306	0.7430	0.4807	0.023*
C4	0.09909 (11)	0.4691 (2)	0.39200 (12)	0.0185 (3)
H4A	0.0295	0.4555	0.4075	0.022*
H4B	0.1371	0.3426	0.4113	0.022*
C5	0.07002 (11)	0.5164 (2)	0.24164 (12)	0.0191 (3)
H5A	−0.0105	0.5025	0.1954	0.023*
H5B	0.0888	0.6534	0.2339	0.023*
C6	0.12881 (11)	0.38840 (19)	0.16907 (12)	0.0189 (3)
H6A	0.0905	0.4065	0.0731	0.023*
H6B	0.1202	0.2510	0.1889	0.023*
C7	0.25452 (11)	0.42986 (19)	0.20469 (12)	0.0177 (3)
H7A	0.2795	0.3581	0.1424	0.021*
H7B	0.2640	0.5695	0.1918	0.021*
C8	0.32877 (10)	0.37496 (19)	0.34518 (12)	0.0153 (3)
C9	0.39626 (10)	0.20329 (18)	0.38724 (12)	0.0150 (3)
H1N1	0.4969 (14)	0.125 (3)	0.5823 (17)	0.030 (4)*
H1N2	0.4229 (14)	0.397 (3)	0.6572 (19)	0.037 (5)*

	U11	U22	U33	U12	U13	U23
O1	0.0272 (5)	0.0181 (5)	0.0123 (4)	0.0062 (4)	0.0082 (4)	0.0006 (3)
N1	0.0201 (6)	0.0158 (5)	0.0122 (5)	0.0031 (4)	0.0061 (4)	0.0007 (4)
N2	0.0181 (6)	0.0167 (5)	0.0122 (5)	0.0012 (4)	0.0065 (4)	−0.0012 (4)
C1	0.0149 (6)	0.0163 (6)	0.0150 (6)	−0.0015 (5)	0.0072 (5)	0.0013 (5)
C2	0.0214 (7)	0.0155 (6)	0.0166 (6)	−0.0001 (5)	0.0076 (5)	−0.0017 (5)
C3	0.0204 (7)	0.0207 (7)	0.0165 (6)	0.0025 (5)	0.0078 (5)	−0.0021 (5)
C4	0.0179 (7)	0.0212 (7)	0.0182 (6)	0.0003 (5)	0.0090 (5)	−0.0014 (5)
C5	0.0179 (7)	0.0217 (7)	0.0163 (7)	0.0025 (5)	0.0045 (5)	−0.0006 (5)
C6	0.0223 (7)	0.0203 (7)	0.0130 (6)	0.0034 (5)	0.0051 (5)	0.0004 (5)
C7	0.0227 (7)	0.0192 (6)	0.0126 (6)	0.0053 (5)	0.0082 (5)	0.0035 (5)
C8	0.0165 (6)	0.0168 (6)	0.0144 (6)	0.0001 (5)	0.0078 (5)	0.0012 (5)
C9	0.0168 (6)	0.0172 (6)	0.0118 (6)	−0.0001 (5)	0.0061 (5)	0.0011 (5)

O1—C9	1.2902 (15)	C4—C5	1.5467 (17)
N1—C9	1.3622 (16)	C4—H4A	0.9700
N1—N2	1.3708 (15)	C4—H4B	0.9700
N1—H1N1	0.939 (18)	C5—C6	1.5343 (17)
N2—C1	1.3459 (16)	C5—H5A	0.9700
N2—H1N2	0.925 (19)	C5—H5B	0.9700
C1—C8	1.3807 (17)	C6—C7	1.5377 (18)
C1—C2	1.4912 (17)	C6—H6A	0.9700
C2—C3	1.5438 (17)	C6—H6B	0.9700
C2—H2A	0.9700	C7—C8	1.5007 (17)
C2—H2B	0.9700	C7—H7A	0.9700
C3—C4	1.5283 (18)	C7—H7B	0.9700
C3—H3A	0.9700	C8—C9	1.4199 (17)
C3—H3B	0.9700
C9—N1—N2	109.39 (10)	H4A—C4—H4B	107.4
C9—N1—H1N1	128.4 (10)	C6—C5—C4	115.83 (11)
N2—N1—H1N1	121.9 (10)	C6—C5—H5A	108.3
C1—N2—N1	107.96 (10)	C4—C5—H5A	108.3
C1—N2—H1N2	128.7 (11)	C6—C5—H5B	108.3
N1—N2—H1N2	119.5 (11)	C4—C5—H5B	108.3
N2—C1—C8	109.65 (11)	H5A—C5—H5B	107.4
N2—C1—C2	121.73 (11)	C5—C6—C7	115.82 (11)
C8—C1—C2	128.51 (11)	C5—C6—H6A	108.3
C1—C2—C3	111.34 (10)	C7—C6—H6A	108.3
C1—C2—H2A	109.4	C5—C6—H6B	108.3
C3—C2—H2A	109.4	C7—C6—H6B	108.3
C1—C2—H2B	109.4	H6A—C6—H6B	107.4
C3—C2—H2B	109.4	C8—C7—C6	114.98 (10)
H2A—C2—H2B	108.0	C8—C7—H7A	108.5
C4—C3—C2	114.47 (10)	C6—C7—H7A	108.5
C4—C3—H3A	108.6	C8—C7—H7B	108.5
C2—C3—H3A	108.6	C6—C7—H7B	108.5
C4—C3—H3B	108.6	H7A—C7—H7B	107.5
C2—C3—H3B	108.6	C1—C8—C9	106.16 (11)
H3A—C3—H3B	107.6	C1—C8—C7	126.38 (11)
C3—C4—C5	115.79 (11)	C9—C8—C7	127.44 (11)
C3—C4—H4A	108.3	O1—C9—N1	122.31 (11)
C5—C4—H4A	108.3	O1—C9—C8	130.92 (11)
C3—C4—H4B	108.3	N1—C9—C8	106.76 (11)
C5—C4—H4B	108.3
C9—N1—N2—C1	2.98 (13)	C2—C1—C8—C9	−175.54 (12)
N1—N2—C1—C8	−2.13 (13)	N2—C1—C8—C7	178.99 (11)
N1—N2—C1—C2	174.25 (11)	C2—C1—C8—C7	2.9 (2)
N2—C1—C2—C3	−89.09 (14)	C6—C7—C8—C1	−77.60 (16)
C8—C1—C2—C3	86.55 (15)	C6—C7—C8—C9	100.55 (14)
C1—C2—C3—C4	−46.15 (14)	N2—N1—C9—O1	176.18 (11)
C2—C3—C4—C5	−55.64 (15)	N2—N1—C9—C8	−2.61 (13)
C3—C4—C5—C6	108.08 (13)	C1—C8—C9—O1	−177.37 (13)
C4—C5—C6—C7	−72.87 (15)	C7—C8—C9—O1	4.2 (2)
C5—C6—C7—C8	68.15 (15)	C1—C8—C9—N1	1.29 (13)
N2—C1—C8—C9	0.52 (14)	C7—C8—C9—N1	−177.16 (11)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O1i	0.938 (19)	1.757 (19)	2.6900 (14)	173.0 (19)
N2—H1N2···O1ii	0.925 (19)	1.789 (19)	2.7056 (14)	170.1 (18)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯O1i	0.938 (19)	1.757 (19)	2.6900 (14)	173.0 (19)
N2—H1N2⋯O1ii	0.925 (19)	1.789 (19)	2.7056 (14)	170.1 (18)

Symmetry codes: (i) ; (ii) .