3 Phenyl­pyrazolium nitrate

organic papers

o876

Structure Reports

Online

ISSN 1600-5368

3-Phenylpyrazolium nitrate

Alireza Haghiri, Hans-Wolfram Lerner, Matthias Wagner and Michael Bolte*

Institut fuÈr Anorganische Chemie, J. W. Goethe-UniversitaÈt Frankfurt, Marie-Curie-Straûe 11, 60439 Frankfurt/Main, Germany

Correspondence e-mail: [email protected]

Key indicators

Single-crystal X-ray study T= 100 K

Mean(C±C) = 0.002 AÊ Rfactor = 0.037 wRfactor = 0.082

Data-to-parameter ratio = 14.6

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

#2004 International Union of Crystallography Printed in Great Britain ± all rights reserved

The title compound, C9H9N2+NO3ÿ, is composed of discrete

3-phenylpyrazolium cations and nitrate anions. The crystal

packing is stabilized by NÐH O and CÐH O hydrogen

bonds.

Comment

Recently, we have reported the X-ray crystal structure analysis of 3-phenylpyrazole, (2) (Haghiri et al., 2002; Haghiri et al.

1993). We describe here the X-ray crystal structure analysis of 3-phenylpyrazolium nitrate, (I). Tris(1-pyrazolyl)borates (`scorpinates'), (1), were invented by Tro®menko more than 30 years ago and are today well established as ligands in coordination chemistry (Tro®menko, 2003), but only a limited number of transition metal complexes with 3-phenylpyrazole, (2), as ligand have been structurally characterized.

Therefore, we are interested in the synthesis of FeIII

complexes with (2) as ligand. Surprisingly, only protonation of (2) takes place in the reaction of Fe(NO3)3 with (2). FeIII

reacts as an acid in solution.

Received 14 April 2004 Accepted 21 April 2004 Online 30 April 2004

Figure 1

The crystal structure of (I) is composed of discrete 3-phenylpyrazolium cations and nitrate anions (Fig. 1). Geometric parameters are as expected. The dihedral angle between the phenyl ring and the pyrazole ring is 15.50 (7)_.

Anions and cations are connected by bifurcated NÐH O

hydrogen bonds. In addition, the crystal packing is stabilized

by CÐH O hydrogen bonds (Fig. 2).

Experimental

X-ray quality crystals of (I) were obtained from a solution of 0.04 g (0.10 mmol) Fe(NO3)39H2O and 0.04 g (0.28 mmol) 3-phenyl-pyrazole in 5 ml CH3OH at ambient temperature.

Crystal data C9H9N2+NO3ÿ

Mr= 207.19

Monoclinic,C2=c a= 16.8447 (16) AÊ

b= 13.392 (2) AÊ

c= 8.3779 (8) AÊ = 95.211 (8)

V= 1882.2 (4) AÊ3

Z= 8

Dx= 1.462 Mg mÿ3

MoKradiation Cell parameters from 5297

re¯ections = 3.7±27.2 = 0.11 mmÿ1

T= 100 (2) K Plate, colourless 0.220.160.12 mm Data collection

Stoe IPDS-II two-circle diffractometer !scans

Absorption correction: none 8471 measured re¯ections 2106 independent re¯ections

1502 re¯ections withI> 2(I)

Rint= 0.058 max= 27.3

h=ÿ21!21

k=ÿ14!17

l=ÿ10!10 Re®nement

Re®nement onF2

R[F2_{> 2(F}2_{)] = 0.037}

wR(F2_{) = 0.082}

S= 0.90 2106 re¯ections 144 parameters

H atoms treated by a mixture of independent and constrained re®nement

w= 1/[2_(F

o2) + (0.0427P)2]

whereP= (Fo2+ 2Fc2)/3

(/)max< 0.001 max= 0.18 e AÊÿ3 min=ÿ0.27 e AÊÿ3

Table 1

Hydrogen-bonding geometry (AÊ,_).

DÐH A DÐH H A D A DÐH A

N4ÐH4 O1 0.90 (2) 2.40 (2) 2.9019 (17) 115.0 (16) N4ÐH4 O1i _{0.90 (2) 1.83 (2) 2.7233 (16) 169 (2)} N5ÐH5 O2 0.91 (2) 1.90 (2) 2.8060 (17) 177.0 (17) N5ÐH5 O1 0.91 (2) 2.297 (18) 2.8802 (16) 121.7 (14)

C16ÐH16 O2 0.95 2.51 3.3643 (17) 149

Symmetry code: (i)ÿx;1ÿy;ÿz.

H atoms bonded to C atoms were re®ned with ®xed individual displacement parameters [Uiso(H) = 1.2Ueq(C)], using a riding model, with CÐH = 0.95 AÊ. The H atoms bonded to N atoms were re®ned isotropically.

Data collection: X-AREA (Stoe & Cie, 2001); cell re®nement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to re®ne structure:SHELXL97 (Sheldrick, 1997); molecular graphics:XPin SHELXTL-Plus(Sheldrick, 1991); software used to prepare material for publication:SHELXL97 andPLATON(Spek, 2003).

References

Haghiri, A., Lerner, H.-W. & Bolte, M. (2003).Acta Cryst.E59, o873±o874. Haghiri, A., Lerner, H.-W., Wagner, M. & Bats, J. W. (2002).Acta Cryst.E58,

o1378±o1380.

Sheldrick, G. M. (1990).Acta Cryst.A46, 467±473.

Sheldrick, G. M. (1991). SHELXTL-Plus.Release 4.1. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.

Sheldrick, G. M. (1997).SHELXL97. University of GoÈttingen, Germany. Spek, A. L. (2003).J. Appl. Cryst.36, 7±13.

Stoe & Cie (2001).X-AREA. Stoe & Cie, Darmstadt, Germany. Tro®menko, S. (1993).Chem. Rev.93, 943±980.

Figure 2

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sup-1 Acta Cryst. (2004). E60, o876–o877

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Acta Cryst. (2004). E60, o876–o877 [https://doi.org/10.1107/S160053680400964X]

3-Phenylpyrazolium nitrate

Alireza Haghiri, Hans-Wolfram Lerner, Matthias Wagner and Michael Bolte

3-Phenylpyrazolium nitrate

Crystal data

C9H9N2+·NO3− Mr = 207.19 Monoclinic, C2/c Hall symbol: -C 2yc a = 16.8447 (16) Å b = 13.392 (2) Å c = 8.3779 (8) Å β = 95.211 (8)° V = 1882.2 (4) Å3 Z = 8

F(000) = 864 Dx = 1.462 Mg m−3

Mo Kα radiation, λ = 0.71073 Å Cell parameters from 5297 reflections θ = 3.7–27.2°

µ = 0.11 mm−1 T = 100 K Plate, colourless 0.22 × 0.16 × 0.12 mm

Data collection

Stoe IPDS-II two-circle diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

ω scans

8471 measured reflections 2106 independent reflections

1502 reflections with I > 2σ(I) Rint = 0.058

θmax = 27.3°, θmin = 3.9° h = −21→21

k = −14→17 l = −10→10

Refinement

Refinement on F2

Least-squares matrix: full R[F2 _{> 2σ(F}2_{)] = 0.037} wR(F2_{) = 0.082} S = 0.90 2106 reflections 144 parameters 0 restraints

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

H atoms treated by a mixture of independent and constrained refinement

w = 1/[σ2_(F

o2) + (0.0427P)2]

where P = (Fo2 + 2Fc2)/3

(Δ/σ)max < 0.001

Δρmax = 0.18 e Å−3

Δρmin = −0.27 e Å−3

Special details Experimental. ;

Refinement. Refinement of F2 _{against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F}2_,

conventional R-factors R are based on F, with F set to zero for negative F2_{. The threshold expression of F}2 _{> σ(F}2_{) 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2₎

x y z Uiso*/Ueq

N1 0.05985 (7) 0.33038 (9) 0.09262 (15) 0.0215 (3) O1 0.03373 (6) 0.41499 (8) 0.04439 (15) 0.0307 (3) O2 0.12049 (6) 0.32889 (8) 0.19301 (13) 0.0279 (3) O3 0.02765 (6) 0.25275 (8) 0.04050 (15) 0.0296 (3) C1 0.20509 (8) 0.58032 (11) 0.33199 (17) 0.0195 (3) C2 0.19243 (8) 0.68312 (11) 0.31445 (18) 0.0218 (3) H2 0.2252 0.7351 0.3612 0.026* C3 0.12284 (8) 0.69398 (11) 0.21563 (18) 0.0225 (3) H3 0.0987 0.7556 0.1824 0.027* N4 0.09514 (7) 0.60337 (10) 0.17463 (16) 0.0226 (3) H4 0.0523 (12) 0.5891 (16) 0.106 (2) 0.040 (5)* N5 0.14466 (6) 0.53404 (9) 0.24530 (14) 0.0201 (3) H5 0.1356 (10) 0.4681 (15) 0.225 (2) 0.028 (4)* C11 0.26969 (8) 0.52521 (11) 0.42300 (16) 0.0194 (3) C12 0.33958 (8) 0.57661 (11) 0.47614 (18) 0.0233 (3) H12 0.3446 0.6456 0.4529 0.028* C13 0.40151 (8) 0.52643 (13) 0.56284 (19) 0.0267 (3) H13 0.4487 0.5615 0.5993 0.032* C14 0.39499 (8) 0.42575 (12) 0.59653 (19) 0.0269 (3) H14 0.4376 0.3919 0.6558 0.032* C15 0.32599 (9) 0.37452 (12) 0.54338 (19) 0.0249 (3) H15 0.3215 0.3054 0.5663 0.030* C16 0.26333 (8) 0.42382 (11) 0.45666 (17) 0.0222 (3) H16 0.2163 0.3883 0.4205 0.027*

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

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sup-3 Acta Cryst. (2004). E60, o876–o877

C14 0.0255 (7) 0.0309 (9) 0.0237 (8) 0.0082 (6) −0.0005 (6) 0.0007 (6) C15 0.0311 (7) 0.0198 (7) 0.0240 (7) 0.0050 (6) 0.0037 (6) 0.0022 (6) C16 0.0227 (6) 0.0227 (8) 0.0211 (8) −0.0007 (5) 0.0018 (5) −0.0010 (6)

Geometric parameters (Å, º)

N1—O3 1.2340 (16) N5—H5 0.91 (2) N1—O2 1.2630 (16) C11—C16 1.393 (2) N1—O1 1.2683 (16) C11—C12 1.4010 (19) C1—N5 1.3466 (18) C12—C13 1.389 (2) C1—C2 1.399 (2) C12—H12 0.9500 C1—C11 1.4696 (19) C13—C14 1.384 (2) C2—C3 1.380 (2) C13—H13 0.9500 C2—H2 0.9500 C14—C15 1.388 (2) C3—N4 1.334 (2) C14—H14 0.9500 C3—H3 0.9500 C15—C16 1.392 (2) N4—N5 1.3486 (16) C15—H15 0.9500 N4—H4 0.90 (2) C16—H16 0.9500

O3—N1—O2 121.69 (12) C16—C11—C12 119.51 (13) O3—N1—O1 120.75 (12) C16—C11—C1 121.84 (12) O2—N1—O1 117.54 (12) C12—C11—C1 118.64 (13) N5—C1—C2 107.21 (12) C13—C12—C11 119.86 (14) N5—C1—C11 122.44 (13) C13—C12—H12 120.1 C2—C1—C11 130.35 (13) C11—C12—H12 120.1 C3—C2—C1 106.25 (13) C14—C13—C12 120.54 (14) C3—C2—H2 126.9 C14—C13—H13 119.7 C1—C2—H2 126.9 C12—C13—H13 119.7 N4—C3—C2 108.47 (13) C13—C14—C15 119.73 (14) N4—C3—H3 125.8 C13—C14—H14 120.1 C2—C3—H3 125.8 C15—C14—H14 120.1 C3—N4—N5 108.99 (12) C14—C15—C16 120.40 (14) C3—N4—H4 126.7 (14) C14—C15—H15 119.8 N5—N4—H4 124.2 (14) C16—C15—H15 119.8 C1—N5—N4 109.08 (12) C15—C16—C11 119.95 (13) C1—N5—H5 130.7 (11) C15—C16—H16 120.0 N4—N5—H5 120.1 (11) C11—C16—H16 120.0

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

N4—H4···O1 0.90 (2) 2.40 (2) 2.9019 (17) 115.0 (16) N4—H4···O1i _{0.90 (2) 1.83 (2) 2.7233 (16) 169 (2)}

N5—H5···O2 0.91 (2) 1.90 (2) 2.8060 (17) 177.0 (17) N5—H5···O1 0.91 (2) 2.297 (18) 2.8802 (16) 121.7 (14) C16—H16···O2 0.95 2.51 3.3643 (17) 149