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ISSN: 2056-9890

Crystal structure of tris­­(3-methyl-1H-pyrazol-1-yl)methane

aChemistry Department, D'Youville College, 320 Porter Avenue, Buffalo, NY 14201, USA, and bChemistry Department, SUNY Buffalo State, 1300 Elmwood Ave, Buffalo, NY 14222, USA
*Correspondence e-mail: nazareay@buffalostate.edu

Edited by M. Zeller, Youngstown State University, USA (Received 12 September 2015; accepted 15 September 2015; online 3 October 2015)

The title mol­ecule, C13H16N6, crystallizes from hexane as a mol­ecular crystal with no strong inter­molecular inter­actions (the shortest C—H⋯N contact is longer than 3.38 Å). A relatively short intra­molecular contact (3.09 Å) has a C—H⋯N angle of 118° which is quite small to be still considered a hydrogen bond. The three pyrazole rings form a propeller-like motif, with one methylpyrazole unit almost perpendicular to the mean plane of the three rings [82.20 (6)°]. The other two methylpyrazole units, with nitrogen donor atoms oriented in opposite directions, are oriented at 67.26 (6) and 72.53 (6)° to the mean plane.

1. Related literature

For syntheses and reactions of tris­pyrazolyl­methanes and their complexes with transition metals, see: Goodman et al. (2012[Goodman, M. A., Nazarenko, A. Y., Casavant, B. J., Li, Z., Brennessel, W. W., DeMarco, M. J., Long, G. & Goodman, M. S. (2012). Inorg. Chem. 51, 1084-1093.]); Jameson & Castellano (1998[Jameson, D. L. & Castellano, R. K. (1998). Inorg. Synth. 32, 51-63.]); Reger et al. (2000[Reger, D. L., Grattan, T. C., Brown, K. J., Little, C. A., Lamba, J. J. S., Rheingold, A. L. & Sommer, R. D. (2000). J. Organomet. Chem. 607, 120-128.]).

[Scheme 1]

2. Experimental

2.1. Crystal data

  • C13H16N6

  • Mr = 256.32

  • Monoclinic, P 21 /c

  • a = 12.0881 (8) Å

  • b = 13.4178 (10) Å

  • c = 9.0985 (6) Å

  • β = 111.630 (2)°

  • V = 1371.82 (16) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.08 mm−1

  • T = 173 K

  • 0.60 × 0.48 × 0.29 mm

2.2. Data collection

  • Bruker Photon-100 CMOS diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2014[Bruker (2014). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.706, Tmax = 0.747

  • 22036 measured reflections

  • 2612 independent reflections

  • 2171 reflections with I > 2σ(I)

  • Rint = 0.029

2.3. Refinement

  • R[F2 > 2σ(F2)] = 0.037

  • wR(F2) = 0.099

  • S = 1.05

  • 2612 reflections

  • 225 parameters

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

  • Δρmax = 0.28 e Å−3

  • Δρmin = −0.19 e Å−3

Data collection: APEX2 (Bruker, 2013[Bruker (2013). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2013[Bruker (2013). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXT (Sheldrick, 2015a[Sheldrick, G. M. (2015a). Acta Cryst. A71, 3-8.]); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b[Sheldrick, G. M. (2015b). Acta Cryst. C71, 3-8.]); 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: OLEX2.

Supporting information


Chemical context top

This report is part of our continious effort to study substituted tris­pyrazolyl­methanes and their complexes with various metal ions. Because all synthetic procedures yield a complex mixture of isomers, positive identification of the ligand molecule by X-ray diffractometry is essential for future research.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1.

All hydrogen atoms were located in electron difference density Fourier maps and were refined in an isotropic approximation. One methyl group (C5) was treated as disordered (SHELXL instruction AFIX 124). Isotropic parameters of atoms H1 and of disordered methyl group hydrogen atoms were constrained as UH = 1.2 UC.

Reflections 1 0 0 and 1 1 0 were too close to the beamstop to be measured reliably and were excluded from refinement.

Synthesis and crystallization top

Following the general method of Reger et al. (2000), 3-methyl­pyrazole (6.0 mL, 75.0 mmol), tetra­butyl­ammonium bromide (1.21 g, 3.75 mmol), and sodium carbonate (47.0 g, 0.45 mol) were heated together in a biphasic mixture of deionized water (75 mL) and chloro­form (40 mL). The reaction mixture was allowed to gently reflux for approximately 72 hours under argon. After cooling and filtering, the organic layer was separated from the aqueous layer. The aqueous layer was extracted three times with di­ethyl ether (100 mL), and the combined organic portions were washed twice with 100 mL portions of H2O. The organic mixture was dried (Na2SO4) and the solvents were removed under vacuum to give a dark, brown oil. 1H NMR analysis showed this to be mainly a mixture of all four regioisomers of the tris­(pyrazolyl)methanes derived from 3-methyl­pyrazole.

The crude mixture of tris­(pyrazolyl)methane regioisomers was first isomerized according to the method of Jameson & Castellano (1998). The crude brown oil (1.0 g) was combined with a catalytic amount of p-toluene­sulfonic acid (0.060 g) and a small amount (50 µL) of 3-methyl­pyrazole and heated at reflux in dry toluene (15 mL) for 24 hours under argon. After cooling, the mixture was washed twice with 100 mL portions of saturated NaHCO3 (aq). The aqueous extracts were then extracted once with CH2Cl2 (100 mL). The organic layers were combined, dried with Na2SO4, and evaporated under reduced pressure to give a dark yellow oil. NMR analysis of this oil showed that it contained a 2:1 mixture of the desired tris­(pyrazolyl)methane and another regioisomer.

For purification, the material was dissolved in a minimum amount of hot hexane and allowed to crystallize at room temperature for 24 hours. The resulting yellow/brown crystals were separated under a microscope. The larger, clear, and darker-colored lozenges were separated from the smaller, opaque, and lighter plates. These smaller crystals tend to form in masses, often growing on the larger crystals and the bottom of the flask. The larger crystals were scraped clean of as much of the other material as possible under the microscope. The large crystals separated in this fashion were typically at least 85% of target compound. This material was then carefully crystallized from hot hexanes after decolorization with carbon in the same solvent.

A suitable crystal was carefully cut from a larger block. A bigger crystal demonstrated the same structure in a preliminary X-ray experiment.

Related literature top

For syntheses and reactions of trispyrazolylmethanes and their complexes with transition metals, see: Goodman et al. (2012); Jameson & Castellano (1998); Reger et al. (2000).

Structure description top

This report is part of our continious effort to study substituted tris­pyrazolyl­methanes and their complexes with various metal ions. Because all synthetic procedures yield a complex mixture of isomers, positive identification of the ligand molecule by X-ray diffractometry is essential for future research.

For syntheses and reactions of trispyrazolylmethanes and their complexes with transition metals, see: Goodman et al. (2012); Jameson & Castellano (1998); Reger et al. (2000).

Synthesis and crystallization top

Following the general method of Reger et al. (2000), 3-methyl­pyrazole (6.0 mL, 75.0 mmol), tetra­butyl­ammonium bromide (1.21 g, 3.75 mmol), and sodium carbonate (47.0 g, 0.45 mol) were heated together in a biphasic mixture of deionized water (75 mL) and chloro­form (40 mL). The reaction mixture was allowed to gently reflux for approximately 72 hours under argon. After cooling and filtering, the organic layer was separated from the aqueous layer. The aqueous layer was extracted three times with di­ethyl ether (100 mL), and the combined organic portions were washed twice with 100 mL portions of H2O. The organic mixture was dried (Na2SO4) and the solvents were removed under vacuum to give a dark, brown oil. 1H NMR analysis showed this to be mainly a mixture of all four regioisomers of the tris­(pyrazolyl)methanes derived from 3-methyl­pyrazole.

The crude mixture of tris­(pyrazolyl)methane regioisomers was first isomerized according to the method of Jameson & Castellano (1998). The crude brown oil (1.0 g) was combined with a catalytic amount of p-toluene­sulfonic acid (0.060 g) and a small amount (50 µL) of 3-methyl­pyrazole and heated at reflux in dry toluene (15 mL) for 24 hours under argon. After cooling, the mixture was washed twice with 100 mL portions of saturated NaHCO3 (aq). The aqueous extracts were then extracted once with CH2Cl2 (100 mL). The organic layers were combined, dried with Na2SO4, and evaporated under reduced pressure to give a dark yellow oil. NMR analysis of this oil showed that it contained a 2:1 mixture of the desired tris­(pyrazolyl)methane and another regioisomer.

For purification, the material was dissolved in a minimum amount of hot hexane and allowed to crystallize at room temperature for 24 hours. The resulting yellow/brown crystals were separated under a microscope. The larger, clear, and darker-colored lozenges were separated from the smaller, opaque, and lighter plates. These smaller crystals tend to form in masses, often growing on the larger crystals and the bottom of the flask. The larger crystals were scraped clean of as much of the other material as possible under the microscope. The large crystals separated in this fashion were typically at least 85% of target compound. This material was then carefully crystallized from hot hexanes after decolorization with carbon in the same solvent.

A suitable crystal was carefully cut from a larger block. A bigger crystal demonstrated the same structure in a preliminary X-ray experiment.

Refinement details top

Crystal data, data collection and structure refinement details are summarized in Table 1.

All hydrogen atoms were located in electron difference density Fourier maps and were refined in an isotropic approximation. One methyl group (C5) was treated as disordered (SHELXL instruction AFIX 124). Isotropic parameters of atoms H1 and of disordered methyl group hydrogen atoms were constrained as UH = 1.2 UC.

Reflections 1 0 0 and 1 1 0 were too close to the beamstop to be measured reliably and were excluded from refinement.

Computing details top

Data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound. Displacement elipsoids are drawn at the 50% probability level. Disorder of H atoms bonded to C5 are omitted for clarity.
[Figure 2] Fig. 2. Packing diagram of the title molecule. View along the c axis.
1,1',1''-Methanetriyltris(3-methyl-1H-pyrazole) top
Crystal data top
C13H16N6F(000) = 544
Mr = 256.32Dx = 1.241 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 12.0881 (8) ÅCell parameters from 9433 reflections
b = 13.4178 (10) Åθ = 2.9–25.7°
c = 9.0985 (6) ŵ = 0.08 mm1
β = 111.630 (2)°T = 173 K
V = 1371.82 (16) Å3Block, colourless
Z = 40.60 × 0.48 × 0.29 mm
Data collection top
Bruker Photon-100 CMOS
diffractometer
2171 reflections with I > 2σ(I)
Radiation source: sealedtubeRint = 0.029
φ and ω scansθmax = 25.7°, θmin = 2.9°
Absorption correction: multi-scan
(SADABS; Bruker, 2014)
h = 1414
Tmin = 0.706, Tmax = 0.747k = 1616
22036 measured reflectionsl = 1011
2612 independent reflections
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.037H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.099 w = 1/[σ2(Fo2) + (0.0457P)2 + 0.5131P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max < 0.001
2612 reflectionsΔρmax = 0.28 e Å3
225 parametersΔρmin = 0.19 e Å3
Crystal data top
C13H16N6V = 1371.82 (16) Å3
Mr = 256.32Z = 4
Monoclinic, P21/cMo Kα radiation
a = 12.0881 (8) ŵ = 0.08 mm1
b = 13.4178 (10) ÅT = 173 K
c = 9.0985 (6) Å0.60 × 0.48 × 0.29 mm
β = 111.630 (2)°
Data collection top
Bruker Photon-100 CMOS
diffractometer
2612 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2014)
2171 reflections with I > 2σ(I)
Tmin = 0.706, Tmax = 0.747Rint = 0.029
22036 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0370 restraints
wR(F2) = 0.099H atoms treated by a mixture of independent and constrained refinement
S = 1.05Δρmax = 0.28 e Å3
2612 reflectionsΔρmin = 0.19 e Å3
225 parameters
Special details top

Experimental. SADABS-2014/5 (Bruker,2014/5) was used for absorption correction. wR2(int) was 0.0499 before and 0.0468 after correction. The ratio of minimum to maximum transmission is 0.9453. The λ/2 correction factor is 0.00150.

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.

Refinement. 1. Fixed Uiso At 1.2 times of: All C(H) groups, All C(H,H,H,H,H,H) groups 2. Others Sof(H5D)=Sof(H5E)=Sof(H5F)=1-FVAR(1) Sof(H5A)=Sof(H5B)=Sof(H5C)=FVAR(1) 3.a Disordered Me refined with riding coordinates and stretchable bonds: C5(H5A,H5B,H5C,H5D,H5E,H5F)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
N10.75721 (10)0.58635 (9)0.89470 (13)0.0257 (3)
C10.81554 (12)0.51681 (10)0.82664 (15)0.0231 (3)
H10.8972 (14)0.5366 (11)0.8603 (18)0.028*
N20.64449 (11)0.57102 (10)0.88717 (14)0.0322 (3)
C20.80352 (15)0.67251 (12)0.96750 (19)0.0379 (4)
H20.8860 (18)0.6925 (14)0.984 (2)0.051 (5)*
N30.76487 (10)0.52045 (9)0.65612 (13)0.0247 (3)
C30.71772 (17)0.71542 (14)1.0092 (2)0.0469 (4)
H30.7246 (19)0.7797 (18)1.066 (3)0.074 (7)*
N40.83993 (11)0.50592 (9)0.57737 (14)0.0288 (3)
C40.62038 (14)0.65090 (12)0.95767 (18)0.0358 (4)
N50.81296 (9)0.41679 (8)0.88404 (12)0.0224 (3)
C50.50296 (17)0.66100 (16)0.9753 (2)0.0547 (5)
H5A0.50076 (17)0.7279 (9)1.0330 (8)0.066*0.544 (19)
H5B0.4350 (9)0.66087 (16)0.8637 (14)0.066*0.544 (19)
H5C0.4909 (2)0.6013 (8)1.0416 (9)0.066*0.544 (19)
H5D0.4504 (7)0.5989 (8)0.9259 (7)0.066*0.456 (19)
H5E0.5161 (2)0.66585 (18)1.0952 (15)0.066*0.456 (19)
H5F0.4602 (6)0.7254 (8)0.9172 (8)0.066*0.456 (19)
N60.90717 (10)0.38708 (9)1.01297 (12)0.0249 (3)
C60.64987 (13)0.52449 (12)0.55706 (17)0.0310 (3)
H60.5895 (15)0.5348 (12)0.5961 (19)0.031 (4)*
C70.64953 (14)0.51349 (12)0.40812 (17)0.0332 (4)
H70.5830 (16)0.5140 (13)0.313 (2)0.043 (5)*
C80.76915 (13)0.50248 (11)0.42596 (16)0.0299 (3)
C90.82000 (19)0.48816 (18)0.3011 (2)0.0473 (5)
H9A0.905 (2)0.4833 (17)0.347 (3)0.072 (7)*
H9B0.784 (2)0.433 (2)0.236 (3)0.084 (8)*
H9C0.805 (2)0.548 (2)0.234 (3)0.088 (8)*
C100.72423 (13)0.34908 (11)0.84262 (18)0.0311 (3)
H100.6507 (15)0.3624 (12)0.755 (2)0.036 (4)*
C110.76199 (14)0.27160 (12)0.94568 (19)0.0332 (4)
H110.7205 (15)0.2122 (13)0.945 (2)0.039 (5)*
C120.87610 (13)0.29819 (11)1.04977 (16)0.0285 (3)
C130.95886 (18)0.24190 (16)1.1873 (2)0.0454 (4)
H13A1.032 (2)0.2793 (19)1.244 (3)0.086 (8)*
H13B0.921 (2)0.2225 (19)1.253 (3)0.088 (8)*
H13C0.982 (2)0.183 (2)1.150 (3)0.094 (9)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0252 (6)0.0268 (6)0.0242 (6)0.0002 (5)0.0081 (5)0.0029 (5)
C10.0219 (7)0.0251 (7)0.0210 (7)0.0020 (5)0.0063 (5)0.0013 (5)
N20.0272 (7)0.0379 (7)0.0315 (7)0.0033 (5)0.0108 (5)0.0050 (5)
C20.0404 (10)0.0334 (9)0.0411 (9)0.0069 (7)0.0163 (7)0.0108 (7)
N30.0224 (6)0.0305 (7)0.0209 (6)0.0011 (5)0.0077 (5)0.0003 (5)
C30.0528 (11)0.0350 (10)0.0560 (11)0.0016 (8)0.0237 (9)0.0134 (8)
N40.0281 (7)0.0350 (7)0.0261 (6)0.0001 (5)0.0134 (5)0.0006 (5)
C40.0351 (9)0.0406 (9)0.0316 (8)0.0104 (7)0.0122 (7)0.0000 (7)
N50.0199 (6)0.0241 (6)0.0221 (6)0.0007 (4)0.0064 (4)0.0015 (5)
C50.0450 (11)0.0647 (13)0.0602 (12)0.0151 (9)0.0260 (9)0.0059 (10)
N60.0231 (6)0.0310 (7)0.0207 (6)0.0004 (5)0.0081 (5)0.0023 (5)
C60.0236 (7)0.0424 (9)0.0252 (7)0.0006 (6)0.0070 (6)0.0003 (6)
C70.0317 (8)0.0409 (9)0.0224 (7)0.0006 (7)0.0048 (6)0.0004 (6)
C80.0347 (8)0.0309 (8)0.0245 (7)0.0015 (6)0.0115 (6)0.0007 (6)
C90.0467 (11)0.0697 (14)0.0302 (9)0.0003 (10)0.0195 (8)0.0020 (9)
C100.0236 (8)0.0287 (8)0.0374 (8)0.0033 (6)0.0069 (7)0.0032 (6)
C110.0314 (8)0.0262 (8)0.0455 (9)0.0045 (6)0.0182 (7)0.0001 (7)
C120.0302 (8)0.0309 (8)0.0295 (7)0.0018 (6)0.0169 (6)0.0040 (6)
C130.0448 (11)0.0479 (11)0.0436 (10)0.0026 (9)0.0163 (9)0.0205 (9)
Geometric parameters (Å, º) top
N1—C11.4398 (18)C5—H5D1.045 (13)
N1—N21.3546 (17)C5—H5E1.045 (13)
N1—C21.347 (2)C5—H5F1.045 (13)
C1—H10.956 (16)N6—C121.3298 (19)
C1—N31.4436 (17)C6—H60.932 (17)
C1—N51.4446 (17)C6—C71.362 (2)
N2—C41.3353 (19)C7—H70.939 (18)
C2—H20.99 (2)C7—C81.402 (2)
C2—C31.357 (2)C8—C91.490 (2)
N3—N41.3615 (16)C9—H9A0.96 (2)
N3—C61.3506 (18)C9—H9B0.95 (3)
C3—H30.99 (2)C9—H9C0.98 (3)
C3—C41.395 (2)C10—H100.965 (17)
N4—C81.3278 (18)C10—C111.361 (2)
C4—C51.492 (2)C11—H110.941 (18)
N5—N61.3591 (15)C11—C121.401 (2)
N5—C101.3490 (18)C12—C131.488 (2)
C5—H5A1.045 (13)C13—H13A0.98 (3)
C5—H5B1.045 (13)C13—H13B0.92 (3)
C5—H5C1.045 (13)C13—H13C0.95 (3)
N2—N1—C1121.52 (11)H5B—C5—H5E141.1
C2—N1—C1125.94 (12)H5B—C5—H5F56.3
C2—N1—N2112.52 (12)H5C—C5—H5D56.3
N1—C1—H1107.0 (9)H5C—C5—H5E56.3
N1—C1—N3111.06 (11)H5C—C5—H5F141.1
N1—C1—N5111.55 (11)H5D—C5—H5E109.5
N3—C1—H1108.3 (9)H5D—C5—H5F109.5
N3—C1—N5111.27 (11)H5E—C5—H5F109.5
N5—C1—H1107.4 (9)C12—N6—N5104.82 (11)
C4—N2—N1104.33 (12)N3—C6—H6120.6 (10)
N1—C2—H2121.4 (11)N3—C6—C7106.53 (13)
N1—C2—C3106.24 (15)C7—C6—H6132.8 (10)
C3—C2—H2132.4 (11)C6—C7—H7127.0 (11)
N4—N3—C1117.37 (11)C6—C7—C8105.75 (13)
C6—N3—C1130.02 (12)C8—C7—H7127.2 (11)
C6—N3—N4112.10 (11)N4—C8—C7111.04 (13)
C2—C3—H3126.0 (13)N4—C8—C9120.42 (14)
C2—C3—C4106.23 (15)C7—C8—C9128.53 (14)
C4—C3—H3127.8 (13)C8—C9—H9A110.7 (14)
C8—N4—N3104.56 (11)C8—C9—H9B110.7 (15)
N2—C4—C3110.68 (14)C8—C9—H9C109.5 (15)
N2—C4—C5120.61 (16)H9A—C9—H9B113 (2)
C3—C4—C5128.69 (16)H9A—C9—H9C104.5 (19)
N6—N5—C1117.49 (11)H9B—C9—H9C108 (2)
C10—N5—C1130.21 (12)N5—C10—H10120.1 (10)
C10—N5—N6111.75 (11)N5—C10—C11106.96 (13)
C4—C5—H5A109.5C11—C10—H10132.9 (10)
C4—C5—H5B109.5C10—C11—H11127.0 (10)
C4—C5—H5C109.5C10—C11—C12105.53 (13)
C4—C5—H5D109.5C12—C11—H11127.5 (10)
C4—C5—H5E109.5N6—C12—C11110.93 (13)
C4—C5—H5F109.5N6—C12—C13120.15 (14)
H5A—C5—H5B109.5C11—C12—C13128.92 (15)
H5A—C5—H5C109.5C12—C13—H13A112.2 (15)
H5A—C5—H5D141.1C12—C13—H13B110.5 (16)
H5A—C5—H5E56.3C12—C13—H13C108.8 (16)
H5A—C5—H5F56.3H13A—C13—H13B112 (2)
H5B—C5—H5C109.5H13A—C13—H13C107 (2)
H5B—C5—H5D56.3H13B—C13—H13C106 (2)
N1—C1—N3—N4145.25 (12)C2—C3—C4—C5178.91 (17)
N1—C1—N3—C643.68 (19)N3—C1—N5—N6142.82 (11)
N1—C1—N5—N692.55 (13)N3—C1—N5—C1046.46 (19)
N1—C1—N5—C1078.17 (17)N3—N4—C8—C70.73 (16)
N1—N2—C4—C30.18 (17)N3—N4—C8—C9179.43 (15)
N1—N2—C4—C5179.06 (15)N3—C6—C7—C80.29 (18)
N1—C2—C3—C40.05 (19)N4—N3—C6—C70.78 (17)
C1—N1—N2—C4178.37 (12)N5—C1—N3—N489.84 (14)
C1—N1—C2—C3178.37 (14)N5—C1—N3—C681.22 (18)
C1—N3—N4—C8173.56 (12)N5—N6—C12—C110.56 (15)
C1—N3—C6—C7172.22 (14)N5—N6—C12—C13180.00 (14)
C1—N5—N6—C12173.41 (11)N5—C10—C11—C120.69 (16)
C1—N5—C10—C11172.24 (13)N6—N5—C10—C111.10 (16)
N2—N1—C1—N371.12 (16)C6—N3—N4—C80.94 (16)
N2—N1—C1—N553.63 (16)C6—C7—C8—N40.29 (18)
N2—N1—C2—C30.06 (18)C6—C7—C8—C9179.89 (18)
C2—N1—C1—N3107.19 (16)C10—N5—N6—C121.03 (15)
C2—N1—C1—N5128.06 (15)C10—C11—C12—N60.07 (17)
C2—N1—N2—C40.15 (16)C10—C11—C12—C13179.30 (17)
C2—C3—C4—N20.1 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C1—H1···N6i0.96 (2)2.44 (2)3.3796 (19)167 (1)
C6—H6···N20.932 (17)2.529 (16)3.0918 (19)119.2 (13)
Symmetry code: (i) x+2, y+1, z+2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C1—H1···N6i0.956 (16)2.441 (17)3.3796 (19)166.6 (13)
C6—H6···N20.932 (17)2.529 (16)3.0918 (19)119.2 (13)
Symmetry code: (i) x+2, y+1, z+2.
 

Acknowledgements

Financial support from the State University of New York for acquisition and maintenance of the X-ray diffractometer is gratefully acknowledged.

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