organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890

Crystal structure of ammonium bis­­[(pyridin-2-yl)meth­yl]ammonium dichloride

CROSSMARK_Color_square_no_text.svg

aDepartment of Chemistry & Physics, Saint Marys College, Notre Dame, IN 46556, USA, and bDepartment of Chemistry and Biochemistry, Duquesne University, Pittsburgh, PA 15282, USA
*Correspondence e-mail: koshin@saintmarys.edu

Edited by A. J. Lough, University of Toronto, Canada (Received 9 August 2015; accepted 22 August 2015; online 29 August 2015)

In the title molecular salt, C12H14N3+·NH4+·2Cl, the central, secondary-amine, N atom is protonated. The bis­[(pyridin-2-yl)meth­yl]ammonium and ammonium cations both lie across a twofold rotation axis. The dihedral angles between the planes of the pyridine rings is 68.43 (8)°. In the crystal, N—H⋯N and N—H⋯Cl hydrogen bonds link the components of the structure, forming a two-dimensional network parallel to (010). In addition, weak C—H⋯Cl hydrogen bonds exist within the two-dimensional network.

1. Related literature

For background to atom-transfer radical addition reactions, see: Eckenhoff & Pintauer (2010[Eckenhoff, W. T. & Pintauer, T. (2010). Catal. Rev. 52, 1-59.]); Kharasch et al. (1945[Kharasch, M. S., Jensen, E. V. & Urry, W. H. (1945). Science, 102, 128-129.]); Iqbal et al. (1994[Iqbal, J., Bhatia, B. & Nayyar, N. K. (1994). Chem. Rev. 94, 519-564.]); Braunecker & Matyjaszewski (2007[Braunecker, W. A. & Matyjaszewski, K. (2007). Prog. Polym. Sci. 32, 93-146.]); Matyjaszewski et al. (2001[Matyjaszewski, K., Göbelt, B., Paik, H. & Horwitz, C. (2001). Macromolecules, 34, 430-440.]); Tang et al. (2008[Tang, W., Kwak, Y., Braunecker, W., Tsarevsky, N. V., Coote, M. L. & Matyjaszewski, K. (2008). J. Am. Chem. Soc. 130, 10702-10713.]). For the synthesis, see: Carvalho et al. (2006[Carvalho, N. M. F., Horn, A. Jr, Bortoluzzi, A. J., Drago, V. & Antunes, O. A. (2006). Inorg. Chim. Acta, 359, 90-98.]). For related structures, see: Junk et al. (2006[Junk, P. C., Kim, Y., Skelton, B. W. & White, A. H. (2006). Z. Anorg. Allg. Chem. 632, 1340-1350.]).

[Scheme 1]

2. Experimental

2.1. Crystal data

  • C12H14N3+·H4N+·2(Cl)

  • Mr = 289.20

  • Orthorhombic, P 21 21 2

  • a = 8.895 (1) Å

  • b = 17.676 (2) Å

  • c = 4.4360 (5) Å

  • V = 697.47 (14) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 0.45 mm−1

  • T = 100 K

  • 0.55 × 0.30 × 0.25 mm

2.2. Data collection

  • Bruker APEXII CCD diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2013[Bruker (2013). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.605, Tmax = 0.746

  • 4292 measured reflections

  • 2126 independent reflections

  • 2088 reflections with I > 2σ(I)

  • Rint = 0.016

2.3. Refinement

  • R[F2 > 2σ(F2)] = 0.025

  • wR(F2) = 0.066

  • S = 1.06

  • 2126 reflections

  • 89 parameters

  • 1 restraint

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.42 e Å−3

  • Δρmin = −0.17 e Å−3

  • Absolute structure: Flack x determined using 748 quotients [(I+)−(I)]/[(I+)+(I)] (Parsons et al., 2013[Parsons, S., Flack, H. D. & Wagner, T. (2013). Acta Cryst. B69, 249-259.])

  • Absolute structure parameter: 0.04 (2)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
C1—H1B⋯Cl1i 0.99 2.80 3.7145 (15) 154
C6—H6⋯Cl1ii 0.95 2.75 3.6410 (15) 157
N1—H1C⋯Cl1iii 0.91 2.23 3.1239 (9) 168
N1—H1D⋯Cl1iv 0.91 2.23 3.1239 (9) 168
N4—H4A⋯N2 0.90 (2) 2.09 (2) 2.9748 (15) 167 (2)
N4—H4B⋯Cl1 0.93 (2) 2.32 (2) 3.2362 (12) 170 (2)
Symmetry codes: (i) -x+2, -y+2, z; (ii) -x+1, -y+2, z-1; (iii) -x+2, -y+2, z-1; (iv) x, y, z-1.

Data collection: APEX2 (Bruker, 2013[Bruker (2013). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2013[Bruker (2013). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015[Sheldrick, G. M. (2015). Acta Cryst. A71, 3-8.]) and SHELXLE (Hübschle et al., 2011[Hübschle, C. B., Sheldrick, G. M. & Dittrich, B. (2011). J. Appl. Cryst. 44, 1281-1284.]); molecular graphics: OLEX2 (Dolomanov et al., 2009[Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339-341.]); software used to prepare material for publication: publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information


Chemical context top

Atom transfer Radical Addition (ATRA) reactions involve the formation of carbon-carbon bonds through the addition of saturated poly-halogenated hydro­carbons to alkenes (Eckenhoff & Pintauer, 2010). First reported by Kharasch in the 1940s (Kharasch et al., 1945), the reaction incorporates halogen group functionalities within products; which can then be used as starting reagents in further functionalization reactions (Iqbal et al., 1994). Subsequently, ATRA has emerged as some of the most atom economical methods for simultaneously forming C–C and C–X bonds; leading to the production of more attractive molecules with well-defined compositions, architectures, and functionalities (Braunecker & Matyjaszewski , 2007). Structural studies suggest that the type of ligand used in atom transfer radical reactions significantly influence the behavior of catalyst generated due to different steric and electronic inter­actions with the metal center (Matyjaszewski et al., 2001). Copper complexes made with tetra­dentate nitro­gen-based ligands such as 1,4,8,11-tetra­aza-1,4,8,11-tetra­methyl­cyclo­tetra­decane (Me6CYCLAM), tris(2-pyridyl­methyl)­amine (TPMA), tris(2-(di­methyl­amino)­ethyl)­amine (Me6TREN), and bis(2-pyridyl­methyl) amine (BPMA) are currently some of the most active multi-dentate structures used in atom transfer radical reactions (Tang et al., 2008). Given the significance of these ligands, we present the crystal structure of a protonated bis(2-pyridyl­methyl)­amine (BPMA) salt.

Structural commentary top

The molecular structure of the title compound is shown in Fig 1. The bis­[(pyridin-2-yl)methyl]­ammonium and ammonium cations both lie across a twofold rotation axis. The dihedral angles between the pyridine rings is 68.43 (8)°. This is in contrast to the values of the dihedral anlges in bis­(2-pyridyl­methyl)­ammonium bromide and bis­(2-pyridyl­methyl)­ammonium iodide (Junk et al., 2006) which are 38.47 (13) and 5.17 (9)°, respectively. In the crystal, N—H···N and N—H···Cl hydrogen bonds link the components of the structure forming a two-dimensional network parallel to (010) (Fig. 2). In addition, weak C—H···Cl hydrogen bonds exist within the two-dimensional network.

Synthesis and crystallization top

Bis(2-pyridyl­methyl)­amine salt (BPMA) was synthesized and purified following literature procedures (Carvalho et al., 2006) and the reaction scheme is shown in Fig. 3. A 500 mL round bottom flask was filled with 100 mL of methanol then 2-pyridine­carboxaldehyde (8.90 mL, 94.0 mmol) added. The flask was placed in an ice bath to cool with the solution mixing. After 15 minutes, 2-pyridyl­methyl­amine (9.70 mL, 94.0 mmol) was added to give a dull yellow colored solution. Flask was removed from ice bath and mixture allowed to react at room temperature for 1 hour to give a red colored solution. The flask was placed back in an ice bath and sodium borohydride (3.500 g, 94.0 mmol) was added in small amounts to prevent foaming. After this addition, the flask was removed from the ice bath and the mixture left to stir overnight. Concentrated hydro­chloric acid was added to the mixture drop-wise until a pH of 4 was attained producing an orange mixture. An extraction was performed on the mixture in a separatory funnel with di­chloro­methane until the organic phase became colorless. The aqueous phase was separated and its pH adjusted to 10 with Na2CO3. A second extraction was performed with di­chloro­methane on this mixture and the organic layer isolated and dried using MgSO4. Solvent was removed to produce the desired ligand as a dark-brown colored oil (14.910 g, 80%). 1H NMR (CDCl3, 400 MHz): δ3.48 (s, 1H), δ4.01 (s, 4H), δ7.14 (t, J = 7.6 Hz, 2H), δ 7.34 (d, J = 7.6 Hz, 2H), δ 7.63 (t, J = 7.6 Hz, 2H), δ 8.53 (d, J = 4.8 Hz, 2H). 13C NMR (CDCl3, 400 MHz): δ 156.67, 149.20, 136.74, 122.73, 122.48, 53.25. FT—IR (liquid) v (cm-1): 3283 (b), 3003 (m), 2818 (b), 1587 (s), 1566 (m), 1471 (s), 1429 (s), 1356 (b). Colorless single crystals suitable for X-Ray analysis were obtained from slow cooling of BPMA ligand in the refrigerator.

Refinement top

All H atoms, except for those of the ammonium cation, were placed in calculated positions and refined in a riding-model approximation, with C—H = 0.95 - 0.99 Å, N—H = 0.91 Å and Uiso(H) = 1.2Ueq(C,N). The two unique H atoms of the ammonium cation were refined indpendently with isotropic displacement parameters.

Related literature top

For background to atom-transfer radical addition reactions, see: Eckenhoff & Pintauer (2010); Kharasch et al. (1945); Iqbal et al. (1994); Braunecker & Matyjaszewski (2007); Matyjaszewski et al. (2001); Tang et al. (2008). For the synthesis, see: Carvalho et al. (2006). For related structures, see: Junk et al. (2006). .

Structure description top

Atom transfer Radical Addition (ATRA) reactions involve the formation of carbon-carbon bonds through the addition of saturated poly-halogenated hydro­carbons to alkenes (Eckenhoff & Pintauer, 2010). First reported by Kharasch in the 1940s (Kharasch et al., 1945), the reaction incorporates halogen group functionalities within products; which can then be used as starting reagents in further functionalization reactions (Iqbal et al., 1994). Subsequently, ATRA has emerged as some of the most atom economical methods for simultaneously forming C–C and C–X bonds; leading to the production of more attractive molecules with well-defined compositions, architectures, and functionalities (Braunecker & Matyjaszewski , 2007). Structural studies suggest that the type of ligand used in atom transfer radical reactions significantly influence the behavior of catalyst generated due to different steric and electronic inter­actions with the metal center (Matyjaszewski et al., 2001). Copper complexes made with tetra­dentate nitro­gen-based ligands such as 1,4,8,11-tetra­aza-1,4,8,11-tetra­methyl­cyclo­tetra­decane (Me6CYCLAM), tris(2-pyridyl­methyl)­amine (TPMA), tris(2-(di­methyl­amino)­ethyl)­amine (Me6TREN), and bis(2-pyridyl­methyl) amine (BPMA) are currently some of the most active multi-dentate structures used in atom transfer radical reactions (Tang et al., 2008). Given the significance of these ligands, we present the crystal structure of a protonated bis(2-pyridyl­methyl)­amine (BPMA) salt.

The molecular structure of the title compound is shown in Fig 1. The bis­[(pyridin-2-yl)methyl]­ammonium and ammonium cations both lie across a twofold rotation axis. The dihedral angles between the pyridine rings is 68.43 (8)°. This is in contrast to the values of the dihedral anlges in bis­(2-pyridyl­methyl)­ammonium bromide and bis­(2-pyridyl­methyl)­ammonium iodide (Junk et al., 2006) which are 38.47 (13) and 5.17 (9)°, respectively. In the crystal, N—H···N and N—H···Cl hydrogen bonds link the components of the structure forming a two-dimensional network parallel to (010) (Fig. 2). In addition, weak C—H···Cl hydrogen bonds exist within the two-dimensional network.

For background to atom-transfer radical addition reactions, see: Eckenhoff & Pintauer (2010); Kharasch et al. (1945); Iqbal et al. (1994); Braunecker & Matyjaszewski (2007); Matyjaszewski et al. (2001); Tang et al. (2008). For the synthesis, see: Carvalho et al. (2006). For related structures, see: Junk et al. (2006). .

Synthesis and crystallization top

Bis(2-pyridyl­methyl)­amine salt (BPMA) was synthesized and purified following literature procedures (Carvalho et al., 2006) and the reaction scheme is shown in Fig. 3. A 500 mL round bottom flask was filled with 100 mL of methanol then 2-pyridine­carboxaldehyde (8.90 mL, 94.0 mmol) added. The flask was placed in an ice bath to cool with the solution mixing. After 15 minutes, 2-pyridyl­methyl­amine (9.70 mL, 94.0 mmol) was added to give a dull yellow colored solution. Flask was removed from ice bath and mixture allowed to react at room temperature for 1 hour to give a red colored solution. The flask was placed back in an ice bath and sodium borohydride (3.500 g, 94.0 mmol) was added in small amounts to prevent foaming. After this addition, the flask was removed from the ice bath and the mixture left to stir overnight. Concentrated hydro­chloric acid was added to the mixture drop-wise until a pH of 4 was attained producing an orange mixture. An extraction was performed on the mixture in a separatory funnel with di­chloro­methane until the organic phase became colorless. The aqueous phase was separated and its pH adjusted to 10 with Na2CO3. A second extraction was performed with di­chloro­methane on this mixture and the organic layer isolated and dried using MgSO4. Solvent was removed to produce the desired ligand as a dark-brown colored oil (14.910 g, 80%). 1H NMR (CDCl3, 400 MHz): δ3.48 (s, 1H), δ4.01 (s, 4H), δ7.14 (t, J = 7.6 Hz, 2H), δ 7.34 (d, J = 7.6 Hz, 2H), δ 7.63 (t, J = 7.6 Hz, 2H), δ 8.53 (d, J = 4.8 Hz, 2H). 13C NMR (CDCl3, 400 MHz): δ 156.67, 149.20, 136.74, 122.73, 122.48, 53.25. FT—IR (liquid) v (cm-1): 3283 (b), 3003 (m), 2818 (b), 1587 (s), 1566 (m), 1471 (s), 1429 (s), 1356 (b). Colorless single crystals suitable for X-Ray analysis were obtained from slow cooling of BPMA ligand in the refrigerator.

Refinement details top

All H atoms, except for those of the ammonium cation, were placed in calculated positions and refined in a riding-model approximation, with C—H = 0.95 - 0.99 Å, N—H = 0.91 Å and Uiso(H) = 1.2Ueq(C,N). The two unique H atoms of the ammonium cation were refined indpendently with isotropic displacement parameters.

Computing details top

Data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015) and SHELXLE (Hübschle et al., 2011); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. The molecular structure, shown with 50% probability ellipsoids for non-H atoms and circles of arbitrary size for H atoms [symmetry code: (i) -x+2, -y+2, z].
[Figure 2] Fig. 2. Part of the crystal structure with hydrogen bonds shown as dashed lines.
Ammonium bis[(pyridin-2-yl)methyl]ammonium dichloride top
Crystal data top
C12H14N3+·H4N+·2(Cl)Dx = 1.377 Mg m3
Mr = 289.20Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P21212Cell parameters from 3559 reflections
a = 8.895 (1) Åθ = 2.3–31.8°
b = 17.676 (2) ŵ = 0.45 mm1
c = 4.4360 (5) ÅT = 100 K
V = 697.47 (14) Å3Rod, colourless
Z = 20.55 × 0.30 × 0.25 mm
F(000) = 304
Data collection top
Bruker APEXII CCD
diffractometer
2126 independent reflections
Radiation source: fine focus sealed tube2088 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.016
ω and φ scansθmax = 31.9°, θmin = 2.6°
Absorption correction: multi-scan
(SADABS; Bruker, 2013)
h = 1212
Tmin = 0.605, Tmax = 0.746k = 2520
4292 measured reflectionsl = 65
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.025H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.066 w = 1/[σ2(Fo2) + (0.0393P)2 + 0.1504P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max = 0.001
2126 reflectionsΔρmax = 0.42 e Å3
89 parametersΔρmin = 0.17 e Å3
1 restraintAbsolute structure: Flack x determined using 748 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.04 (2)
Crystal data top
C12H14N3+·H4N+·2(Cl)V = 697.47 (14) Å3
Mr = 289.20Z = 2
Orthorhombic, P21212Mo Kα radiation
a = 8.895 (1) ŵ = 0.45 mm1
b = 17.676 (2) ÅT = 100 K
c = 4.4360 (5) Å0.55 × 0.30 × 0.25 mm
Data collection top
Bruker APEXII CCD
diffractometer
2126 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2013)
2088 reflections with I > 2σ(I)
Tmin = 0.605, Tmax = 0.746Rint = 0.016
4292 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.025H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.066Δρmax = 0.42 e Å3
S = 1.06Δρmin = 0.17 e Å3
2126 reflectionsAbsolute structure: Flack x determined using 748 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
89 parametersAbsolute structure parameter: 0.04 (2)
1 restraint
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
C10.92866 (15)0.93964 (7)1.2090 (3)0.0121 (2)
H1A0.85290.96291.34360.015*
H1B1.00640.91561.33670.015*
C20.85420 (16)0.88021 (7)1.0170 (3)0.0110 (2)
C30.93696 (16)0.81886 (8)0.9096 (4)0.0149 (3)
H31.04120.81460.95250.018*
C40.86432 (17)0.76416 (8)0.7391 (4)0.0169 (3)
H40.91740.72100.66830.020*
C50.71328 (17)0.77338 (8)0.6736 (4)0.0164 (3)
H50.66150.73750.55260.020*
C60.63891 (16)0.83632 (8)0.7888 (4)0.0168 (3)
H60.53510.84240.74420.020*
N11.00001.00001.0188 (4)0.0103 (3)
H1C1.07110.97870.89820.012*0.5
H1D0.92891.02130.89820.012*0.5
N20.70678 (14)0.88881 (7)0.9597 (3)0.0134 (2)
Cl10.73444 (4)1.08251 (2)1.69586 (8)0.01425 (9)
N40.50001.00001.2452 (4)0.0142 (3)
H4A0.558 (2)0.9696 (11)1.131 (5)0.021*
H4B0.563 (2)1.0295 (11)1.363 (5)0.021*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0123 (5)0.0129 (5)0.0112 (5)0.0025 (4)0.0005 (5)0.0010 (5)
C20.0108 (6)0.0111 (5)0.0111 (5)0.0015 (4)0.0004 (5)0.0024 (5)
C30.0109 (6)0.0145 (6)0.0194 (6)0.0008 (5)0.0020 (5)0.0002 (5)
C40.0163 (6)0.0136 (5)0.0208 (7)0.0005 (5)0.0044 (6)0.0024 (5)
C50.0165 (6)0.0151 (5)0.0176 (6)0.0034 (5)0.0001 (6)0.0038 (5)
C60.0126 (6)0.0152 (6)0.0225 (7)0.0001 (5)0.0036 (6)0.0016 (6)
N10.0099 (7)0.0105 (6)0.0104 (7)0.0006 (6)0.0000.000
N20.0118 (5)0.0118 (4)0.0167 (6)0.0002 (4)0.0006 (4)0.0007 (4)
Cl10.01141 (14)0.01526 (14)0.01608 (15)0.00146 (10)0.00198 (11)0.00017 (11)
N40.0120 (7)0.0136 (7)0.0170 (9)0.0008 (6)0.0000.000
Geometric parameters (Å, º) top
C1—N11.5010 (16)C5—C61.392 (2)
C1—C21.5060 (19)C5—H50.9500
C1—H1A0.9900C6—N21.3418 (19)
C1—H1B0.9900C6—H60.9500
C2—N21.3442 (18)N1—C1i1.5010 (16)
C2—C31.3944 (19)N1—H1C0.9100
C3—C41.387 (2)N1—H1D0.9100
C3—H30.9500N4—H4A0.898 (18)
C4—C51.384 (2)N4—H4B0.926 (18)
C4—H40.9500
N1—C1—C2111.33 (12)C4—C5—C6118.59 (14)
N1—C1—H1A109.4C4—C5—H5120.7
C2—C1—H1A109.4C6—C5—H5120.7
N1—C1—H1B109.4N2—C6—C5123.12 (13)
C2—C1—H1B109.4N2—C6—H6118.4
H1A—C1—H1B108.0C5—C6—H6118.4
N2—C2—C3122.57 (13)C1i—N1—C1111.59 (15)
N2—C2—C1117.19 (12)C1i—N1—H1C109.3
C3—C2—C1120.23 (12)C1—N1—H1C109.3
C4—C3—C2118.84 (13)C1i—N1—H1D109.3
C4—C3—H3120.6C1—N1—H1D109.3
C2—C3—H3120.6H1C—N1—H1D108.0
C5—C4—C3118.98 (13)C6—N2—C2117.87 (12)
C5—C4—H4120.5H4A—N4—H4B108.0 (19)
C3—C4—H4120.5
N1—C1—C2—N294.13 (14)C4—C5—C6—N20.3 (2)
N1—C1—C2—C386.76 (15)C2—C1—N1—C1i178.68 (13)
N2—C2—C3—C40.5 (2)C5—C6—N2—C21.1 (2)
C1—C2—C3—C4178.53 (13)C3—C2—N2—C60.9 (2)
C2—C3—C4—C51.9 (2)C1—C2—N2—C6179.97 (13)
C3—C4—C5—C61.7 (2)
Symmetry code: (i) x+2, y+2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C1—H1B···Cl1i0.992.803.7145 (15)154
C6—H6···Cl1ii0.952.753.6410 (15)157
N1—H1C···Cl1iii0.912.233.1239 (9)168
N1—H1D···Cl1iv0.912.233.1239 (9)168
N4—H4A···N20.90 (2)2.09 (2)2.9748 (15)167 (2)
N4—H4B···Cl10.93 (2)2.32 (2)3.2362 (12)170 (2)
Symmetry codes: (i) x+2, y+2, z; (ii) x+1, y+2, z1; (iii) x+2, y+2, z1; (iv) x, y, z1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C1—H1B···Cl1i0.992.803.7145 (15)153.5
C6—H6···Cl1ii0.952.753.6410 (15)156.7
N1—H1C···Cl1iii0.912.233.1239 (9)167.7
N1—H1D···Cl1iv0.912.233.1239 (9)167.7
N4—H4A···N20.898 (18)2.092 (17)2.9748 (15)167 (2)
N4—H4B···Cl10.926 (18)2.322 (18)3.2362 (12)169.5 (18)
Symmetry codes: (i) x+2, y+2, z; (ii) x+1, y+2, z1; (iii) x+2, y+2, z1; (iv) x, y, z1.
 

Acknowledgements

KO would like to thank Dr. Matthias Zeller for crystallographic support and Youngstown State University for instrument support. The X-ray diffractometer was funded by NSF grant No. 1337296, and Project SEED student (AT) was funded by the American Chemical Society. Research funding from The Weber Foundation, Cambridge Isotope Laboratories Inc., and Thermo-Fisher Scientific are also gratefully acknowledged.

References

First citationBraunecker, W. A. & Matyjaszewski, K. (2007). Prog. Polym. Sci. 32, 93–146.  CrossRef CAS Google Scholar
First citationBruker (2013). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationCarvalho, N. M. F., Horn, A. Jr, Bortoluzzi, A. J., Drago, V. & Antunes, O. A. (2006). Inorg. Chim. Acta, 359, 90–98.  CSD CrossRef CAS Google Scholar
First citationDolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationEckenhoff, W. T. & Pintauer, T. (2010). Catal. Rev. 52, 1–59.  Web of Science CrossRef CAS Google Scholar
First citationHübschle, C. B., Sheldrick, G. M. & Dittrich, B. (2011). J. Appl. Cryst. 44, 1281–1284.  Web of Science CrossRef IUCr Journals Google Scholar
First citationIqbal, J., Bhatia, B. & Nayyar, N. K. (1994). Chem. Rev. 94, 519–564.  CrossRef CAS Web of Science Google Scholar
First citationJunk, P. C., Kim, Y., Skelton, B. W. & White, A. H. (2006). Z. Anorg. Allg. Chem. 632, 1340–1350.  Web of Science CSD CrossRef CAS Google Scholar
First citationKharasch, M. S., Jensen, E. V. & Urry, W. H. (1945). Science, 102, 128–129.  CrossRef PubMed CAS Web of Science Google Scholar
First citationMatyjaszewski, K., Göbelt, B., Paik, H. & Horwitz, C. (2001). Macromolecules, 34, 430–440.  Web of Science CrossRef CAS Google Scholar
First citationParsons, S., Flack, H. D. & Wagner, T. (2013). Acta Cryst. B69, 249–259.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSheldrick, G. M. (2015). Acta Cryst. A71, 3–8.  Web of Science CrossRef IUCr Journals Google Scholar
First citationTang, W., Kwak, Y., Braunecker, W., Tsarevsky, N. V., Coote, M. L. & Matyjaszewski, K. (2008). J. Am. Chem. Soc. 130, 10702–10713.  Web of Science CrossRef PubMed CAS Google Scholar
First citationWestrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.  Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds