Download citation
Download citation
link to html
Two ionic hydrogen-bonded organic frameworks (iHOFs) assembled from 4-cyano-N-(4-cyano­benz­yl)pyridinium, have been crystallized with Br and an­ti­­mony(III) penta­bromide, [SbBr5]2−, as counter-ions and characterized. These are 4-cyano-N-(4-cyano­benz­yl)pyridinium bromide, C14H10N3+·Br, and bis­[4-cyano-N-(4-cyano­benz­yl)pyridinium] anti­mony(III) penta­bromide, (C14H10N3)2[SbBr5]. The CH...NC inter­actions induced by templating anions con­struct disparate frameworks. Hirshfeld surface analysis indicated that these crystals exhibit two types of hydrogen-bonding inter­actions, specifically CH...NC and CH...Br. Consecutive reverse-parallel CH...NC hydrogen-bonding inter­actions in these crystals induced the formation of a large number of CH...NC bonds which exhibit both cis and trans configurations.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229624005850/jx3084sup1.cif
Contains datablocks iHOFI, iHOFII, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229624005850/jx3084iHOFIsup2.hkl
Contains datablock iHOFI

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229624005850/jx3084iHOFIIsup3.hkl
Contains datablock iHOFII

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229624005850/jx3084iHOFIsup4.cml
Supplementary material

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229624005850/jx3084iHOFIIsup5.cml
Supplementary material

pdf

Portable Document Format (PDF) file https://doi.org/10.1107/S2053229624005850/jx3084sup6.pdf
PXRD patterns

CCDC references: 2351706; 2351705

Computing details top

4-Cyano-N-(4-cyanobenzyl)pyridinium bromide (iHOFI) top
Crystal data top
C14H10N3+·BrDx = 1.630 Mg m3
Mr = 300.16Ga Kα radiation, λ = 1.34138 Å
Orthorhombic, PnmaCell parameters from 6776 reflections
a = 8.7734 (4) Åθ = 3.9–59.4°
b = 7.0554 (3) ŵ = 2.94 mm1
c = 19.7544 (10) ÅT = 150 K
V = 1222.79 (10) Å3Block, colourless
Z = 40.1 × 0.08 × 0.05 mm
F(000) = 600
Data collection top
Bruker D8 VENTURE PHOTON III
diffractometer
1245 reflections with I > 2σ(I)
Radiation source: MetalJetRint = 0.055
φ and ω scansθmax = 59.4°, θmin = 3.9°
Absorption correction: multi-scan
(SADABS; Bruker, 2016)
h = 1111
Tmin = 0.657, Tmax = 0.752k = 89
15238 measured reflectionsl = 2425
1461 independent reflections
Refinement top
Refinement on F2Primary atom site location: dual
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.028H-atom parameters constrained
wR(F2) = 0.069 w = 1/[σ2(Fo2) + (0.0252P)2 + 1.2992P]
where P = (Fo2 + 2Fc2)/3
S = 1.09(Δ/σ)max < 0.001
1461 reflectionsΔρmax = 0.83 e Å3
97 parametersΔρmin = 0.59 e Å3
0 restraints
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Br10.65349 (4)0.7500000.24449 (2)0.02461 (12)
N10.3682 (3)0.2500000.19981 (12)0.0191 (5)
N20.7171 (4)0.2500000.01965 (15)0.0355 (7)
N30.7791 (4)0.2500000.53003 (14)0.0349 (7)
C10.4120 (2)0.4177 (3)0.17268 (10)0.0231 (5)
H10.3790920.5330220.1927250.028*
C20.5038 (2)0.4218 (3)0.11626 (10)0.0232 (4)
H20.5354490.5388830.0971300.028*
C30.5492 (3)0.2500000.08783 (14)0.0208 (6)
C40.6446 (4)0.2500000.02813 (15)0.0264 (7)
C50.2776 (3)0.2500000.26353 (14)0.0212 (6)
H5A0.2115070.1363490.2649550.025*0.5
H5B0.2115070.3636510.2649550.025*0.5
C60.3826 (3)0.2500000.32356 (14)0.0199 (6)
C70.4332 (2)0.4210 (3)0.35092 (11)0.0248 (5)
H70.3979350.5375740.3325930.030*
C80.5343 (3)0.4217 (3)0.40457 (11)0.0264 (5)
H80.5689180.5383160.4230710.032*
C90.5850 (3)0.2500000.43138 (15)0.0233 (7)
C100.6925 (4)0.2500000.48684 (16)0.0276 (7)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.02063 (17)0.01648 (17)0.03671 (19)0.0000.00149 (13)0.000
N10.0165 (12)0.0193 (13)0.0216 (11)0.0000.0025 (9)0.000
N20.0462 (18)0.0288 (17)0.0315 (15)0.0000.0072 (13)0.000
N30.0394 (17)0.0338 (18)0.0317 (15)0.0000.0054 (13)0.000
C10.0240 (10)0.0182 (12)0.0272 (10)0.0016 (9)0.0015 (8)0.0000 (8)
C20.0266 (11)0.0175 (11)0.0256 (10)0.0016 (9)0.0027 (8)0.0008 (8)
C30.0195 (14)0.0231 (17)0.0197 (13)0.0000.0030 (11)0.000
C40.0323 (17)0.0207 (17)0.0261 (15)0.0000.0029 (14)0.000
C50.0170 (13)0.0191 (14)0.0276 (15)0.0000.0033 (11)0.000
C60.0180 (14)0.0190 (16)0.0228 (14)0.0000.0045 (10)0.000
C70.0264 (11)0.0170 (12)0.0310 (11)0.0007 (9)0.0024 (9)0.0015 (8)
C80.0301 (12)0.0209 (12)0.0283 (10)0.0029 (10)0.0011 (9)0.0027 (8)
C90.0210 (15)0.0258 (18)0.0232 (14)0.0000.0044 (11)0.000
C100.0312 (17)0.0240 (18)0.0275 (16)0.0000.0067 (13)0.000
Geometric parameters (Å, º) top
N1—C1i1.354 (3)C5—H5A0.9900
N1—C11.354 (3)C5—H5B0.9900
N1—C51.489 (4)C5—C61.502 (4)
N2—C41.138 (4)C6—C71.395 (3)
N3—C101.143 (4)C6—C7i1.395 (3)
C1—H10.9500C7—H70.9500
C1—C21.375 (3)C7—C81.382 (3)
C2—H20.9500C8—H80.9500
C2—C31.394 (3)C8—C91.395 (3)
C3—C41.446 (4)C9—C101.445 (5)
C1i—N1—C1121.7 (3)H5A—C5—H5B108.2
C1—N1—C5119.08 (13)C6—C5—H5A109.7
C1i—N1—C5119.07 (13)C6—C5—H5B109.7
N1—C1—H1119.8C7i—C6—C5120.07 (14)
N1—C1—C2120.3 (2)C7—C6—C5120.07 (14)
C2—C1—H1119.8C7—C6—C7i119.8 (3)
C1—C2—H2120.8C6—C7—H7119.9
C1—C2—C3118.4 (2)C8—C7—C6120.3 (2)
C3—C2—H2120.8C8—C7—H7119.9
C2i—C3—C2120.8 (3)C7—C8—H8120.2
C2—C3—C4119.60 (13)C7—C8—C9119.5 (2)
C2i—C3—C4119.60 (13)C9—C8—H8120.2
N2—C4—C3178.6 (4)C8i—C9—C8120.5 (3)
N1—C5—H5A109.7C8—C9—C10119.73 (14)
N1—C5—H5B109.7C8i—C9—C10119.73 (14)
N1—C5—C6109.9 (2)N3—C10—C9179.0 (3)
N1—C1—C2—C30.4 (3)C1—C2—C3—C4179.5 (2)
N1—C5—C6—C789.1 (2)C5—N1—C1—C2175.9 (2)
N1—C5—C6—C7i89.1 (2)C5—C6—C7—C8177.6 (2)
C1i—N1—C1—C20.3 (4)C6—C7—C8—C90.2 (4)
C1—N1—C5—C688.1 (2)C7i—C6—C7—C80.7 (4)
C1i—N1—C5—C688.1 (2)C7—C8—C9—C8i0.2 (4)
C1—C2—C3—C2i0.6 (4)C7—C8—C9—C10179.1 (2)
Symmetry code: (i) x, y+1/2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C1—H1···Br1ii0.952.793.649 (2)151
C2—H2···N3iii0.952.573.448 (3)153
C5—H5A···Br1iv0.992.783.6953 (9)154
C5—H5B···Br1ii0.992.783.6953 (9)154
C8—H8···N2v0.952.653.516 (3)151
Symmetry codes: (ii) x1/2, y+3/2, z+1/2; (iii) x+3/2, y+1, z1/2; (iv) x1/2, y+1/2, z+1/2; (v) x+3/2, y+1, z+1/2.
Bis[4-cyano-N-(4-cyanobenzyl)pyridinium] antimony(III) pentabromide (iHOFII) top
Crystal data top
(C14H10N3)2[SbBr5]Dx = 1.536 Mg m3
Mr = 959.80Ga Kα radiation, λ = 1.34138 Å
Tetragonal, I4/mCell parameters from 9796 reflections
a = 23.8054 (12) Åθ = 4.6–59.4°
c = 7.3222 (4) ŵ = 7.57 mm1
V = 4149.5 (5) Å3T = 150 K
Z = 4NEEDLE, brown
F(000) = 18200.08 × 0.03 × 0.02 mm
Data collection top
Bruker D8 VENTURE PHOTON III
diffractometer
2327 reflections with I > 2σ(I)
φ and ω scansRint = 0.056
Absorption correction: multi-scan
(SADABS; Bruker, 2016)
θmax = 59.3°, θmin = 4.6°
Tmin = 0.022, Tmax = 0.098h = 2730
32444 measured reflectionsk = 2630
2447 independent reflectionsl = 98
Refinement top
Refinement on F2Primary atom site location: dual
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.073H-atom parameters constrained
wR(F2) = 0.220 w = 1/[σ2(Fo2) + (0.132P)2 + 37.369P]
where P = (Fo2 + 2Fc2)/3
S = 1.10(Δ/σ)max < 0.001
2447 reflectionsΔρmax = 2.40 e Å3
150 parametersΔρmin = 1.75 e Å3
0 restraints
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
N10.4835 (2)0.3428 (3)0.50000.0304 (12)
N20.6685 (4)0.2200 (4)0.50000.058 (2)
N30.2405 (4)0.1467 (4)0.50000.061 (2)
C10.5073 (2)0.3297 (2)0.6587 (7)0.0358 (11)
H10.49030.34140.76960.043*
C20.5568 (2)0.2991 (3)0.6635 (8)0.0394 (12)
H20.57400.28930.77620.047*
C30.5802 (3)0.2833 (3)0.50000.0328 (15)
C40.6308 (3)0.2486 (4)0.50000.0414 (18)
C50.4262 (3)0.3677 (3)0.50000.0314 (14)
H5A0.42100.39150.39030.038*0.5
H5B0.42100.39150.60970.038*0.5
C60.3839 (3)0.3206 (3)0.50000.0309 (14)
C70.3658 (2)0.2980 (2)0.3359 (7)0.0362 (11)
H70.37820.31380.22370.043*
C80.3294 (2)0.2522 (2)0.3351 (8)0.0402 (12)
H80.31670.23660.22310.048*
C90.3120 (3)0.2298 (3)0.50000.0369 (16)
C100.2730 (4)0.1835 (4)0.50000.046 (2)
Sb10.47999 (9)0.11701 (9)0.2488 (3)0.0244 (5)0.125
Br10.46859 (15)0.18576 (12)0.50000.0377 (7)0.25
Br20.46397 (16)0.21197 (16)0.00000.0418 (8)0.25
Br30.4986 (2)0.03254 (14)0.50000.0523 (9)0.25
Br40.5934 (5)0.1320 (6)0.218 (2)0.068 (3)0.125
Br4A0.3678 (5)0.0819 (8)0.257 (3)0.113 (7)0.125
Sb20.50000.50000.05741 (14)0.0210 (3)0.5
Br50.41593 (3)0.41812 (3)0.00000.0347 (3)0.9
Br60.50000.50000.2922 (2)0.0239 (4)0.45
Br70.50000.50000.50000.0259 (6)0.45
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.025 (3)0.034 (3)0.032 (3)0.003 (2)0.0000.000
N20.053 (5)0.060 (5)0.060 (5)0.023 (4)0.0000.000
N30.069 (6)0.054 (5)0.061 (5)0.028 (4)0.0000.000
C10.032 (2)0.048 (3)0.028 (2)0.003 (2)0.002 (2)0.006 (2)
C20.035 (3)0.053 (3)0.030 (3)0.004 (2)0.004 (2)0.002 (2)
C30.029 (3)0.033 (3)0.037 (4)0.004 (3)0.0000.000
C40.037 (4)0.045 (4)0.042 (4)0.010 (3)0.0000.000
C50.025 (3)0.033 (3)0.035 (4)0.001 (3)0.0000.000
C60.026 (3)0.032 (3)0.035 (4)0.002 (3)0.0000.000
C70.038 (3)0.041 (3)0.029 (3)0.007 (2)0.003 (2)0.000 (2)
C80.041 (3)0.043 (3)0.036 (3)0.011 (2)0.000 (2)0.005 (2)
C90.039 (4)0.034 (4)0.038 (4)0.003 (3)0.0000.000
C100.053 (5)0.046 (5)0.037 (4)0.015 (4)0.0000.000
Sb10.0232 (10)0.0202 (10)0.0299 (12)0.0005 (8)0.0056 (9)0.0091 (8)
Br10.0503 (18)0.0232 (13)0.0396 (17)0.0016 (12)0.0000.000
Br20.0516 (19)0.0536 (19)0.0202 (13)0.0145 (15)0.0000.000
Br30.070 (3)0.0273 (17)0.060 (2)0.0023 (16)0.0000.000
Br40.034 (3)0.089 (8)0.080 (6)0.009 (3)0.016 (3)0.018 (5)
Br4A0.047 (6)0.112 (12)0.180 (17)0.026 (6)0.045 (8)0.012 (10)
Sb20.0235 (4)0.0235 (4)0.0159 (5)0.0000.0000.000
Br50.0232 (4)0.0253 (4)0.0555 (6)0.0053 (3)0.0000.000
Br60.0301 (6)0.0301 (6)0.0113 (9)0.0000.0000.000
Br70.0278 (9)0.0278 (9)0.0222 (14)0.0000.0000.000
Geometric parameters (Å, º) top
N1—C1i1.330 (6)Sb1—Br4ii2.736 (15)
N1—C11.330 (6)Sb1—Br42.733 (11)
N1—C51.488 (9)Sb1—Br4Aiii2.453 (19)
N2—C41.127 (11)Sb1—Br4A2.800 (14)
N3—C101.169 (12)Br1—Sb1i2.477 (3)
C1—H10.9500Br2—Sb1iv2.928 (4)
C1—C21.386 (8)Br3—Sb1i2.761 (3)
C2—H20.9500Br3—Br3v1.550 (7)
C2—C31.372 (7)Br4—Sb1iii2.736 (15)
C3—C2i1.372 (7)Br4—Br4Aiii0.33 (3)
C3—C41.461 (10)Br4A—Sb1ii2.454 (19)
C5—H5A0.9900Br4A—Br4ii0.33 (3)
C5—H5B0.9900Sb2—Sb2vi0.841 (2)
C5—C61.507 (10)Sb2—Br5vii2.8251 (8)
C6—C71.386 (6)Sb2—Br52.8251 (8)
C6—C7i1.386 (6)Sb2—Br5vi2.8251 (8)
C7—H70.9500Sb2—Br5viii2.8251 (8)
C7—C81.394 (7)Sb2—Br62.560 (2)
C8—H80.9500Sb2—Br6vi1.719 (2)
C8—C91.383 (7)Br5—Sb2vi2.8251 (8)
C9—C8i1.383 (7)Br6—Sb2vi1.719 (2)
C9—C101.442 (11)Br6—Br7ix1.5213 (18)
Sb1—Br12.477 (3)Br7—Br6vi1.5214 (18)
Sb1—Br22.928 (4)Br7—Br6x1.5214 (18)
Sb1—Br32.761 (3)
C1i—N1—C1121.7 (6)Br4ii—Sb1—Br4A6.8 (5)
C1i—N1—C5119.0 (3)Br4Aiii—Sb1—Br191.3 (4)
C1—N1—C5119.0 (3)Br4A—Sb1—Br296.8 (4)
N1—C1—H1119.7Br4Aiii—Sb1—Br290.3 (5)
N1—C1—C2120.5 (5)Br4Aiii—Sb1—Br387.7 (5)
C2—C1—H1119.7Br4Aiii—Sb1—Br4ii174.6 (7)
C1—C2—H2121.1Br4Aiii—Sb1—Br44.0 (7)
C3—C2—C1117.8 (5)Br4Aiii—Sb1—Br4A171.1 (5)
C3—C2—H2121.1Sb1i—Br1—Sb195.89 (15)
C2—C3—C2i121.5 (7)Sb1iv—Br2—Sb176.95 (12)
C2i—C3—C4119.3 (4)Sb1—Br3—Sb1i83.54 (13)
C2—C3—C4119.3 (4)Br3v—Br3—Sb1i137.27 (10)
N2—C4—C3177.3 (10)Br3v—Br3—Sb1137.27 (10)
N1—C5—H5A110.0Sb1—Br4—Sb1iii93.9 (4)
N1—C5—H5B110.0Br4Aiii—Br4—Sb131 (6)
N1—C5—C6108.3 (6)Br4Aiii—Br4—Sb1iii98 (5)
H5A—C5—H5B108.4Sb1ii—Br4A—Sb198.8 (5)
C6—C5—H5A110.0Br4ii—Br4A—Sb176 (5)
C6—C5—H5B110.0Br4ii—Br4A—Sb1ii145 (6)
C7i—C6—C5119.8 (3)Sb2vi—Sb2—Br5vii81.44 (2)
C7—C6—C5119.8 (3)Sb2vi—Sb2—Br5viii81.44 (2)
C7i—C6—C7120.3 (7)Sb2vi—Sb2—Br581.44 (2)
C6—C7—H7120.0Sb2vi—Sb2—Br5vi81.44 (2)
C6—C7—C8120.1 (5)Sb2vi—Sb2—Br6vi180.0
C8—C7—H7120.0Sb2vi—Sb2—Br60.000 (1)
C7—C8—H8120.5Br5vii—Sb2—Br588.731 (6)
C9—C8—C7119.0 (5)Br5vi—Sb2—Br5viii88.731 (6)
C9—C8—H8120.5Br5vi—Sb2—Br5vii88.731 (6)
C8i—C9—C8121.6 (7)Br5viii—Sb2—Br588.732 (6)
C8—C9—C10119.2 (4)Br5vi—Sb2—Br5162.89 (4)
C8i—C9—C10119.2 (4)Br5vii—Sb2—Br5viii162.89 (4)
N3—C10—C9178.7 (11)Br6—Sb2—Br5viii81.44 (2)
Br1—Sb1—Br286.42 (9)Br6vi—Sb2—Br598.56 (2)
Br1—Sb1—Br390.25 (10)Br6—Sb2—Br5vii81.44 (2)
Br1—Sb1—Br494.8 (3)Br6vi—Sb2—Br5viii98.56 (2)
Br1—Sb1—Br4ii87.8 (3)Br6—Sb2—Br581.44 (2)
Br1—Sb1—Br4A94.4 (4)Br6vi—Sb2—Br5vii98.56 (2)
Br3—Sb1—Br2176.05 (12)Br6—Sb2—Br5vi81.44 (2)
Br3—Sb1—Br4A85.5 (4)Br6vi—Sb2—Br5vi98.56 (2)
Br4—Sb1—Br288.6 (3)Br6vi—Sb2—Br6180.0
Br4ii—Sb1—Br295.0 (3)Sb2—Br5—Sb2vi17.11 (4)
Br4—Sb1—Br389.6 (3)Sb2vi—Br6—Sb20.0
Br4ii—Sb1—Br387.0 (3)Br7ix—Br6—Sb2180.0
Br4—Sb1—Br4ii175.6 (4)Br7ix—Br6—Sb2vi180.0
Br4—Sb1—Br4A169.5 (5)Br6vi—Br7—Br6x180.0
N1—C1—C2—C30.4 (9)C1—C2—C3—C4176.9 (7)
N1—C5—C6—C7i88.2 (6)C5—N1—C1—C2170.6 (6)
N1—C5—C6—C788.2 (6)C5—C6—C7—C8176.1 (6)
C1i—N1—C1—C23.4 (11)C6—C7—C8—C90.2 (10)
C1i—N1—C5—C687.1 (5)C7i—C6—C7—C80.2 (11)
C1—N1—C5—C687.1 (5)C7—C8—C9—C8i0.7 (12)
C1—C2—C3—C2i2.6 (12)C7—C8—C9—C10178.1 (7)
Symmetry codes: (i) x, y, z+1; (ii) y+1/2, x1/2, z+1/2; (iii) y+1/2, x+1/2, z+1/2; (iv) x, y, z; (v) x+1, y, z+1; (vi) x+1, y+1, z; (vii) y, x+1, z; (viii) y+1, x, z; (ix) x, y, z1; (x) x, y, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C1—H1···Br5x0.953.053.924 (4)153
C2—H2···N3xi0.952.493.397 (7)160
C5—H5A···Br50.992.933.8568 (19)157
C5—H5A···Br6xii0.993.273.910 (5)124
C5—H5B···Br50.992.933.8568 (19)157
C5—H5B···Br60.993.273.910 (5)124
C7—H7···Br50.953.113.960 (4)149
C8—H8···N2xiii0.952.463.371 (6)161
Symmetry codes: (x) x, y, z+1; (xi) y+1/2, x+1/2, z+1/2; (xii) x+1, y+1, z; (xiii) y+1/2, x1/2, z1/2.
 

Follow Acta Cryst. C
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds