PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2010 August 1; 66(Pt 8): o2042.
Published online 2010 July 17. doi:  10.1107/S1600536810027443
PMCID: PMC3007199

4-[(2′-Cyano­biphenyl-4-yl)methyl]­morpholin-4-ium nitrate

Abstract

The title ion pair, C18H19N2O+·NO3 , features an N—H(...)O hydrogen bond linking the cation to the anion. The morpholine portion adopts a chair conformation; the aromatic rings of the biphenyl­ene portion are twisted [torsion angles for the four atoms involving the ar­yl–aryl bond = 35.1 (2)–40.4 (2)°].

Related literature

For the synthesis, see: Li et al. (2008 [triangle]); Zhang et al. (2009 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o2042-scheme1.jpg

Experimental

Crystal data

  • C18H19N2O+·NO3
  • M r = 341.36
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o2042-efi1.jpg
  • a = 12.670 (6) Å
  • b = 13.120 (5) Å
  • c = 10.865 (5) Å
  • β = 110.927 (8)°
  • V = 1687.0 (12) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.10 mm−1
  • T = 293 K
  • 0.20 × 0.20 × 0.20 mm

Data collection

  • Rigaku SCXmini diffractometer
  • Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 [triangle]) T min = 0.981, T max = 0.981
  • 18242 measured reflections
  • 3852 independent reflections
  • 2848 reflections with I > 2σ(I)
  • R int = 0.052

Refinement

  • R[F 2 > 2σ(F 2)] = 0.062
  • wR(F 2) = 0.178
  • S = 1.17
  • 3852 reflections
  • 226 parameters
  • H-atom parameters constrained
  • Δρmax = 0.24 e Å−3
  • Δρmin = −0.24 e Å−3

Data collection: CrystalClear (Rigaku, 2005 [triangle]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810027443/ng2795sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810027443/ng2795Isup2.hkl

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

Acknowledgments

The author acknowledges the starter fund of Southeast University for the purchase of the X-ray diffractometer.

supplementary crystallographic information

Comment

As a continuation of our study of dielectric-ferroelectric materials, including organic ligands (Li et al., 2008), metal-organic coordination compounds (Zhang et al., 2009), organic-inorganic hybrids, we are interested in the dielectric properties (capacitance and dielectric loss measurements) of the title compound(I), unfortunately, there was no distinct anomaly observed from 93 K to 350 K. In thisarticle, the crystal structure of (I) has been presented.

The asymmetric unit of the title compound consists of one 4'-morpholinemethylbiphenyl-2-carbonitrile cation and one nitrate e-66-o2042-fig1). The intermolecular N—H···O, N—H···N hydrogen bonds link the cations and anions to chains along be-66-o2042-fig2), and make great contribution to the stability of the structure.The title compound crystallizes in the monoclinic system, space groupP21/c.

Experimental

4'-morpholinemethylbiphenyl-2-carbonitrile (10 mmol)was dissolved in 10 ml e thanol, to which nitrate acid(10 mmol) was added dropwise under stirring, the reaction solution was stirred for a few minutes.water was added untill all suspended substrates disappeared. Colorless crystals suitable for X-ray analysis were formed after several days by slow evaporation of the solvent at room temperature.

Refinement

Positional parameters of all the H atoms were calculated geometrically and were allowed to ride on the C, N atoms to which they are bonded, with C—H =0.93 to 0.97 Å, Uiso(H) = 1.2 Ueq(C), N—H = 0.91 Å, Uiso(H)= 1.5 Ueq(N).

Figures

Fig. 1.
The molecular structure of the title compound, with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
Fig. 2.
A view of the packing of the title compound, stacking along the b axis. Dashed lines indicate hydrogen bonds.

Crystal data

C18H19N2O+·NO3F(000) = 720
Mr = 341.36Dx = 1.344 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3727 reflections
a = 12.670 (6) Åθ = 2.3–27.5°
b = 13.120 (5) ŵ = 0.10 mm1
c = 10.865 (5) ÅT = 293 K
β = 110.927 (8)°Prism, colourless
V = 1687.0 (12) Å30.20 × 0.20 × 0.20 mm
Z = 4

Data collection

Rigaku SCXmini diffractometer3852 independent reflections
Radiation source: fine-focus sealed tube2848 reflections with I > 2σ(I)
graphiteRint = 0.052
Detector resolution: 13.6612 pixels mm-1θmax = 27.5°, θmin = 1.7°
ω scansh = −16→16
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)k = −17→17
Tmin = 0.981, Tmax = 0.981l = −14→14
18242 measured reflections

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.062Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.178H-atom parameters constrained
S = 1.17w = 1/[σ2(Fo2) + (0.0839P)2 + 0.0408P] where P = (Fo2 + 2Fc2)/3
3852 reflections(Δ/σ)max < 0.001
226 parametersΔρmax = 0.24 e Å3
0 restraintsΔρmin = −0.24 e Å3

Special details

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.

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

xyzUiso*/Ueq
N20.45201 (13)0.21560 (12)0.92144 (15)0.0332 (4)
H2A0.48620.27160.90320.040*
O10.63116 (14)0.06839 (12)0.98832 (15)0.0521 (5)
C50.12498 (16)0.35987 (15)0.5246 (2)0.0358 (5)
C60.12785 (18)0.25575 (16)0.5517 (2)0.0417 (5)
H6A0.08400.21100.48730.050*
C70.45639 (18)0.13253 (16)0.8303 (2)0.0392 (5)
H7A0.42170.15560.73990.047*
H7B0.41400.07420.84230.047*
C90.26229 (17)0.28322 (17)0.7722 (2)0.0393 (5)
C100.51627 (19)0.18427 (17)1.06051 (19)0.0430 (5)
H10A0.47670.12911.08490.052*
H10B0.52060.24121.11900.052*
C110.19283 (18)0.42418 (16)0.6230 (2)0.0419 (5)
H11A0.19300.49370.60650.050*
C120.26004 (18)0.38675 (17)0.7450 (2)0.0441 (5)
H12A0.30410.43140.80930.053*
C130.05740 (17)0.40207 (15)0.3931 (2)0.0371 (5)
C150.5770 (2)0.10142 (19)0.8560 (2)0.0485 (6)
H15A0.57820.04670.79640.058*
H15B0.61810.15880.83890.058*
C16−0.05099 (18)0.36520 (16)0.3153 (2)0.0416 (5)
C170.19541 (18)0.21840 (17)0.6737 (2)0.0447 (5)
H17A0.19610.14880.69010.054*
C180.33288 (18)0.24421 (19)0.9069 (2)0.0459 (6)
H18A0.29600.18490.92650.055*
H18B0.33590.29620.97160.055*
C190.1012 (2)0.47979 (17)0.3390 (2)0.0482 (6)
H19A0.17130.50720.38830.058*
C20−0.1077 (2)0.40316 (19)0.1893 (2)0.0533 (6)
H20A−0.17830.37740.13900.064*
C210.63421 (19)0.14995 (18)1.0763 (2)0.0494 (6)
H21A0.67580.20681.05880.059*
H21B0.67340.12781.16630.059*
C220.0438 (2)0.5178 (2)0.2140 (3)0.0586 (7)
H22A0.07550.57010.18070.070*
C23−0.11159 (19)0.29425 (19)0.3668 (2)0.0513 (6)
N1−0.1659 (2)0.2409 (2)0.4032 (3)0.0747 (7)
C25−0.0596 (2)0.4786 (2)0.1392 (3)0.0606 (7)
H25A−0.09720.50310.05450.073*
O20.54586 (15)0.38211 (13)0.83891 (15)0.0550 (5)
N30.60177 (17)0.43391 (14)0.93873 (18)0.0465 (5)
O40.60072 (17)0.40818 (14)1.04806 (16)0.0646 (5)
O30.65691 (17)0.50803 (15)0.92616 (18)0.0771 (6)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
N20.0332 (9)0.0350 (9)0.0292 (9)−0.0012 (7)0.0086 (7)0.0015 (7)
O10.0519 (10)0.0499 (10)0.0448 (9)0.0160 (7)0.0054 (8)0.0012 (7)
C50.0265 (9)0.0401 (11)0.0396 (11)0.0025 (8)0.0102 (8)−0.0027 (9)
C60.0344 (11)0.0383 (12)0.0457 (12)−0.0037 (9)0.0063 (9)−0.0019 (9)
C70.0430 (12)0.0375 (11)0.0322 (11)−0.0007 (9)0.0075 (9)−0.0028 (8)
C90.0290 (10)0.0500 (12)0.0385 (12)0.0021 (9)0.0115 (9)0.0009 (9)
C100.0486 (13)0.0479 (13)0.0275 (10)0.0041 (10)0.0073 (9)0.0029 (9)
C110.0402 (11)0.0350 (11)0.0454 (12)0.0045 (9)0.0089 (10)−0.0062 (9)
C120.0394 (11)0.0441 (12)0.0418 (12)0.0035 (9)0.0059 (10)−0.0089 (9)
C130.0327 (10)0.0347 (11)0.0406 (11)0.0066 (8)0.0092 (9)−0.0026 (9)
C150.0489 (13)0.0535 (14)0.0397 (12)0.0093 (11)0.0116 (11)−0.0016 (10)
C160.0348 (11)0.0423 (12)0.0436 (12)0.0057 (9)0.0089 (10)−0.0037 (9)
C170.0367 (11)0.0400 (12)0.0508 (13)−0.0032 (9)0.0077 (10)0.0064 (10)
C180.0361 (11)0.0621 (15)0.0405 (12)0.0040 (10)0.0149 (10)0.0049 (10)
C190.0422 (12)0.0469 (13)0.0503 (14)0.0010 (10)0.0102 (11)0.0017 (10)
C200.0441 (13)0.0616 (16)0.0428 (13)0.0069 (11)0.0015 (11)−0.0046 (11)
C210.0446 (13)0.0540 (14)0.0388 (12)0.0050 (10)0.0018 (10)−0.0002 (10)
C220.0632 (16)0.0534 (15)0.0562 (15)0.0029 (12)0.0178 (13)0.0099 (12)
C230.0306 (11)0.0584 (15)0.0557 (15)0.0016 (10)0.0043 (11)−0.0023 (12)
N10.0444 (13)0.0834 (18)0.0884 (18)−0.0072 (12)0.0139 (13)0.0157 (14)
C250.0644 (17)0.0659 (17)0.0423 (13)0.0150 (13)0.0075 (12)0.0088 (12)
O20.0617 (11)0.0570 (10)0.0381 (9)−0.0137 (8)0.0075 (8)−0.0069 (7)
N30.0480 (11)0.0412 (11)0.0392 (11)−0.0038 (8)0.0022 (9)0.0047 (8)
O40.0876 (14)0.0602 (11)0.0383 (9)−0.0121 (9)0.0129 (9)0.0019 (8)
O30.0796 (14)0.0641 (12)0.0676 (13)−0.0319 (10)0.0018 (11)0.0168 (10)

Geometric parameters (Å, °)

N2—C71.487 (3)C13—C191.388 (3)
N2—C101.495 (3)C13—C161.416 (3)
N2—C181.508 (3)C15—H15A0.9700
N2—H2A0.9100C15—H15B0.9700
O1—C151.422 (3)C16—C201.391 (3)
O1—C211.426 (3)C16—C231.441 (3)
C5—C111.392 (3)C17—H17A0.9300
C5—C61.395 (3)C18—H18A0.9700
C5—C131.485 (3)C18—H18B0.9700
C6—C171.386 (3)C19—C221.384 (3)
C6—H6A0.9300C19—H19A0.9300
C7—C151.508 (3)C20—C251.372 (4)
C7—H7A0.9700C20—H20A0.9300
C7—H7B0.9700C21—H21A0.9700
C9—C121.388 (3)C21—H21B0.9700
C9—C171.392 (3)C22—C251.372 (4)
C9—C181.506 (3)C22—H22A0.9300
C10—C211.511 (3)C23—N11.146 (3)
C10—H10A0.9700C25—H25A0.9300
C10—H10B0.9700O2—N31.261 (2)
C11—C121.384 (3)N3—O31.233 (2)
C11—H11A0.9300N3—O41.240 (2)
C12—H12A0.9300
C7—N2—C10109.59 (16)C7—C15—H15A109.4
C7—N2—C18112.76 (16)O1—C15—H15B109.4
C10—N2—C18109.72 (16)C7—C15—H15B109.4
C7—N2—H2A108.2H15A—C15—H15B108.0
C10—N2—H2A108.2C20—C16—C13121.0 (2)
C18—N2—H2A108.2C20—C16—C23117.0 (2)
C15—O1—C21109.68 (17)C13—C16—C23121.7 (2)
C11—C5—C6117.98 (19)C6—C17—C9121.2 (2)
C11—C5—C13119.90 (19)C6—C17—H17A119.4
C6—C5—C13122.03 (19)C9—C17—H17A119.4
C17—C6—C5120.6 (2)C9—C18—N2114.26 (17)
C17—C6—H6A119.7C9—C18—H18A108.7
C5—C6—H6A119.7N2—C18—H18A108.7
N2—C7—C15110.57 (17)C9—C18—H18B108.7
N2—C7—H7A109.5N2—C18—H18B108.7
C15—C7—H7A109.5H18A—C18—H18B107.6
N2—C7—H7B109.5C22—C19—C13122.1 (2)
C15—C7—H7B109.5C22—C19—H19A119.0
H7A—C7—H7B108.1C13—C19—H19A119.0
C12—C9—C17118.2 (2)C25—C20—C16120.1 (2)
C12—C9—C18120.0 (2)C25—C20—H20A119.9
C17—C9—C18121.8 (2)C16—C20—H20A119.9
N2—C10—C21110.85 (18)O1—C21—C10111.03 (18)
N2—C10—H10A109.5O1—C21—H21A109.4
C21—C10—H10A109.5C10—C21—H21A109.4
N2—C10—H10B109.5O1—C21—H21B109.4
C21—C10—H10B109.5C10—C21—H21B109.4
H10A—C10—H10B108.1H21A—C21—H21B108.0
C12—C11—C5121.4 (2)C25—C22—C19120.1 (3)
C12—C11—H11A119.3C25—C22—H22A120.0
C5—C11—H11A119.3C19—C22—H22A120.0
C11—C12—C9120.7 (2)N1—C23—C16175.7 (3)
C11—C12—H12A119.7C20—C25—C22120.1 (2)
C9—C12—H12A119.7C20—C25—H25A120.0
C19—C13—C16116.55 (19)C22—C25—H25A120.0
C19—C13—C5120.05 (19)O3—N3—O4121.4 (2)
C16—C13—C5123.37 (19)O3—N3—O2119.7 (2)
O1—C15—C7111.16 (18)O4—N3—O2118.84 (19)
O1—C15—H15A109.4
C11—C5—C6—C170.8 (3)C5—C13—C16—C239.9 (3)
C13—C5—C6—C17177.3 (2)C5—C6—C17—C9−0.2 (3)
C10—N2—C7—C15−53.1 (2)C12—C9—C17—C6−0.3 (3)
C18—N2—C7—C15−175.65 (17)C18—C9—C17—C6177.73 (19)
C7—N2—C10—C2152.7 (2)C12—C9—C18—N2−90.3 (3)
C18—N2—C10—C21177.06 (18)C17—C9—C18—N291.7 (3)
C6—C5—C11—C12−0.9 (3)C7—N2—C18—C9−61.1 (2)
C13—C5—C11—C12−177.56 (19)C10—N2—C18—C9176.48 (18)
C5—C11—C12—C90.5 (3)C16—C13—C19—C22−1.7 (3)
C17—C9—C12—C110.1 (3)C5—C13—C19—C22176.6 (2)
C18—C9—C12—C11−177.9 (2)C13—C16—C20—C25−1.0 (3)
C11—C5—C13—C1936.9 (3)C23—C16—C20—C25173.4 (2)
C6—C5—C13—C19−139.6 (2)C15—O1—C21—C1060.9 (2)
C11—C5—C13—C16−144.9 (2)N2—C10—C21—O1−57.1 (2)
C6—C5—C13—C1638.6 (3)C13—C19—C22—C25−0.1 (4)
C21—O1—C15—C7−61.6 (2)C20—C16—C23—N1−30 (4)
N2—C7—C15—O158.4 (2)C13—C16—C23—N1144 (4)
C19—C13—C16—C202.3 (3)C16—C20—C25—C22−1.0 (4)
C5—C13—C16—C20−176.0 (2)C19—C22—C25—C201.5 (4)
C19—C13—C16—C23−171.9 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N2—H2A···O20.911.882.784 (2)172
N2—H2A···O40.912.483.158 (3)131
N2—H2A···N30.912.533.404 (3)160

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: NG2795).

References

  • Li, X. Z., Qu, Z. R. & Xiong, R. G. (2008). Chin. J. Chem.11, 1959–1962.
  • Rigaku (2005). CrystalClear Rigaku Corporation, Tokyo, Japan.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Zhang, W., Chen, L. Z., Xiong, R. G., Nakamura, T. & Huang, S. D. (2009). J. Am. Chem. Soc.131, 12544–12545. [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography