Crystal structure of 5,7-diphenyl-4,7-di­hydro­tetra­zolo[1,5-a]pyrimidine

Price, I.K.; Rougeot, C.; Hein, J.E.

doi:10.1107/S2056989015002984

organic compounds

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Volume 71| Part 3| March 2015| Page o192

doi:10.1107/S2056989015002984

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Crystal structure of 5,7-diphenyl-4,7-dihydrotetrazolo[1,5-a]pyrimidine

Ivy K. Price,^a Celine Rougeot ^a and Jason E. Hein ^a ^*

^aChemistry and Chemical Biology, University of California, Merced, 5200 North Lake Road, Merced, CA 95343, USA
^*Correspondence e-mail: jhein2@ucmerced.edu

Edited by A. J. Lough, University of Toronto, Canada (Received 29 December 2014; accepted 11 February 2015; online 21 February 2015)

In the title molecule, C₁₆H₁₃N₅, the plane of the tetrazole ring forms dihedral angles of 16.37 (7) and 76.59 (7)° with the two phenyl rings. The dihedral angle between the phenyl rings is 68.05 (6)°. The pyrimidine ring is in a flattened boat conformation. In the crystal, molecules are linked by pairs of N—H⋯N hydrogen bonds, forming inversion dimers.

Keywords: crystal structure; tetrazolo[1,5-a]pyrimidine; hydrogen bonding.

CCDC reference: 1048926

1. Related literature

For the synthesis, see: Desenko et al. (2001 ); Ghorbani-Vaghei et al. (2013 ).

2. Experimental

2.1. Crystal data

C₁₆H₁₃N₅
M_r = 275.31
Orthorhombic, P b c n
a = 12.6931 (8) Å
b = 10.9284 (6) Å
c = 18.8915 (12) Å
V = 2620.5 (3) Å³
Z = 8
Cu Kα radiation
μ = 0.71 mm⁻¹
T = 100 K
0.28 × 0.22 × 0.15 mm

2.2. Data collection

Bruker D8 APEX Cu diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2012 ) T_min = 0.631, T_max = 0.753
13662 measured reflections
2357 independent reflections
2047 reflections with I > 2σ(I)
R_int = 0.048

2.3. Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.093
S = 1.06
2357 reflections
194 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.13 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯N5ⁱ	0.94 (2)	1.99 (2)	2.908 (2)	165 (1)
Symmetry code: (i) -x+1, -y+2, -z+2.

Data collection: APEX2 (Bruker, 2013 ); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015 ); molecular graphics: OLEX2 (Dolomanov et al., 2009 ); software used to prepare material for publication: OLEX2.

Supporting information

CCDC reference: 1048926

Crystal structure: contains datablock I. DOI: 10.1107/S2056989015002984/lh5746sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989015002984/lh5746Isup2.hkl

Supporting information file. DOI: 10.1107/S2056989015002984/lh5746Isup3.cdx

Supporting information file. DOI: 10.1107/S2056989015002984/lh5746Isup4.cml

checkCIF report

Comment top

The title compound was synthesized via condensation between chalcone and aminotetrazole using a literature procedure to produce a racemic mixture (Desenko et al., 2001; Ghorbani-Vaghei et al., 2013). Successive recrystallization of this compound from a variety of solvents identified multiple crystal isoforms, which appear to be metastable and rearrange to give the crystal structure reported herein.

The molecular structure of the title compound is shown in Fig. 1. The tetrazole ring [N2–N5/C16] forms dihedral angles of 16.37 (7) [C1–C6] and 76.59 (7)° [C10–C15] with the two phenyl rings. The dihedral angle between the phenyl rings is 68.05 (6)°. The pyrimidine ring [N1/N2/C7/C8/C9/C16] is in a flattened boat conformation with N1 and C9 deviating by 0.1222 (10) and 0.2478 (13) Å respectively, from the mean plane of the other four atoms [N2/C7/C8/C16]. In the crystal, pairs of molecules are linked by N—H···N hydrogen bonds to form invesion dimers.

Related literature top

For the synthesis, see: Desenko et al. (2001); Ghorbani-Vaghei et al. (2013).

Experimental top

1H-Tetrazol-5-amine (2.0g, 23.51mmol) and (E)-chalcone (5.39g, 25.9mmol) was added to DMF (3.92ml) in an oven dried vial then stirred overnight at 423K. Then while still heating, the product was diluted with toluene (0.4mL) and stirred for 2 more hours. The solid precipitate was collected via vacuum filtration, rinsed with toluene and placed on high vacuum until dry. 4.34g of white solid was collected. X-ray quality crystals were grown from slow evaporation of a solution of the title compound in dichloromethane.

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: SHELXL2013 (Sheldrick, 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Figures top

	Fig. 1. The molecular structure of the title compound, showing 50% probability displacement ellipsoids.
	Fig. 2. A pair of molecules linked by intermolecular N—H···N hydrogen bonds (dashed lines).

5,7-Diphenyl-4,7-dihydrotetrazolo[1,5-a]pyrimidine top

Crystal data top

C₁₆H₁₃N₅	D_x = 1.396 Mg m⁻³
M_r = 275.31	Cu Kα radiation, λ = 1.54178 Å
Orthorhombic, Pbcn	Cell parameters from 6133 reflections
a = 12.6931 (8) Å	θ = 4.2–68.2°
b = 10.9284 (6) Å	µ = 0.71 mm⁻¹
c = 18.8915 (12) Å	T = 100 K
V = 2620.5 (3) Å³	Block, colorless
Z = 8	0.28 × 0.22 × 0.15 mm
F(000) = 1152

Data collection top

Bruker D8 APEX Cu diffractometer	2357 independent reflections
Radiation source: Micro Focus Rotating Anode, Bruker FR-591	2047 reflections with I > 2σ(I)
Multilayer Mirrors monochromator	R_int = 0.048
Detector resolution: 8.0 pixels mm^-1	θ_max = 68.2°, θ_min = 4.7°
ω and ϕ scans	h = −10→15
Absorption correction: multi-scan (SADABS; Bruker, 2012)	k = −13→11
T_min = 0.631, T_max = 0.753	l = −22→15
13662 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.035	Hydrogen site location: mixed
wR(F²) = 0.093	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0481P)² + 0.7255P] where P = (F_o² + 2F_c²)/3
2357 reflections	(Δ/σ)_max = 0.001
194 parameters	Δρ_max = 0.13 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₁₆H₁₃N₅	V = 2620.5 (3) Å³
M_r = 275.31	Z = 8
Orthorhombic, Pbcn	Cu Kα radiation
a = 12.6931 (8) Å	µ = 0.71 mm⁻¹
b = 10.9284 (6) Å	T = 100 K
c = 18.8915 (12) Å	0.28 × 0.22 × 0.15 mm

Data collection top

Bruker D8 APEX Cu diffractometer	2357 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2012)	2047 reflections with I > 2σ(I)
T_min = 0.631, T_max = 0.753	R_int = 0.048
13662 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.093	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.13 e Å⁻³
2357 reflections	Δρ_min = −0.23 e Å⁻³
194 parameters

Special details top

Experimental. Absortion correction: SADABS-2012/1 (Bruker,2012) was used for absorption correction. wR2(int) was 0.0847 before and 0.0589 after correction. The Ratio of minimum to maximum transmission is 0.8385. The λ/2 correction factor is 0.0015.

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

	x	y	z	U_iso*/U_eq
N5	0.47790 (8)	0.87666 (9)	1.05756 (5)	0.0178 (2)
N4	0.47318 (8)	0.77893 (9)	1.10314 (6)	0.0196 (3)
N3	0.39481 (9)	0.70757 (10)	1.08856 (6)	0.0206 (3)
N2	0.34601 (8)	0.75851 (10)	1.03147 (6)	0.0175 (3)
N1	0.36681 (8)	0.92953 (10)	0.95763 (5)	0.0174 (2)
H1	0.4132 (13)	0.9922 (16)	0.9444 (8)	0.034 (4)*
C16	0.39775 (10)	0.86051 (11)	1.01341 (6)	0.0158 (3)
C9	0.24638 (10)	0.71622 (12)	1.00051 (7)	0.0184 (3)
H9	0.2508	0.6259	0.9925	0.022*
C8	0.23680 (10)	0.77919 (12)	0.93004 (7)	0.0191 (3)
H8	0.1897	0.7452	0.8963	0.023*
C7	0.29038 (10)	0.88019 (11)	0.91166 (6)	0.0170 (3)
C10	0.15611 (10)	0.74218 (12)	1.05162 (7)	0.0188 (3)
C11	0.13730 (11)	0.66105 (12)	1.10670 (7)	0.0222 (3)
H11	0.1786	0.5889	1.1109	0.027*
C12	0.05843 (11)	0.68479 (13)	1.15568 (7)	0.0263 (3)
H12	0.0466	0.6294	1.1936	0.032*
C13	−0.00323 (11)	0.78893 (13)	1.14952 (7)	0.0263 (3)
H13	−0.0579	0.8045	1.1827	0.032*
C14	0.01545 (11)	0.87026 (13)	1.09460 (7)	0.0258 (3)
H14	−0.0264	0.9420	1.0903	0.031*
C15	0.09509 (10)	0.84739 (12)	1.04586 (7)	0.0218 (3)
H15	0.1079	0.9037	1.0086	0.026*
C6	0.27368 (10)	0.94608 (11)	0.84397 (6)	0.0181 (3)
C1	0.18077 (11)	0.92813 (12)	0.80523 (7)	0.0226 (3)
H1A	0.1285	0.8737	0.8227	0.027*
C2	0.16440 (11)	0.98872 (13)	0.74191 (7)	0.0266 (3)
H2	0.1018	0.9741	0.7157	0.032*
C3	0.23888 (11)	1.07083 (13)	0.71640 (7)	0.0255 (3)
H3	0.2267	1.1137	0.6734	0.031*
C4	0.33095 (11)	1.08969 (12)	0.75403 (7)	0.0238 (3)
H4	0.3823	1.1454	0.7367	0.029*
C5	0.34843 (10)	1.02735 (11)	0.81705 (7)	0.0206 (3)
H5	0.4123	1.0403	0.8422	0.025*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N5	0.0175 (5)	0.0196 (5)	0.0163 (5)	0.0002 (4)	−0.0011 (4)	0.0016 (4)
N4	0.0181 (5)	0.0212 (5)	0.0195 (5)	−0.0002 (4)	−0.0005 (4)	0.0035 (5)
N3	0.0184 (5)	0.0232 (5)	0.0203 (6)	−0.0003 (4)	−0.0025 (5)	0.0041 (5)
N2	0.0169 (5)	0.0183 (5)	0.0173 (5)	−0.0012 (4)	−0.0019 (4)	0.0020 (4)
N1	0.0186 (5)	0.0177 (5)	0.0159 (5)	−0.0024 (5)	−0.0029 (4)	0.0010 (4)
C16	0.0155 (6)	0.0160 (6)	0.0159 (6)	0.0006 (5)	0.0008 (5)	−0.0013 (5)
C9	0.0177 (6)	0.0185 (6)	0.0191 (6)	−0.0036 (5)	−0.0016 (5)	−0.0018 (5)
C8	0.0174 (6)	0.0223 (6)	0.0177 (6)	−0.0020 (5)	−0.0017 (5)	−0.0024 (5)
C7	0.0151 (6)	0.0205 (6)	0.0154 (6)	0.0021 (5)	−0.0004 (5)	−0.0036 (5)
C10	0.0182 (6)	0.0214 (6)	0.0168 (6)	−0.0056 (5)	−0.0032 (5)	−0.0023 (5)
C11	0.0233 (7)	0.0219 (6)	0.0213 (7)	−0.0047 (6)	−0.0011 (5)	−0.0003 (6)
C12	0.0286 (7)	0.0301 (7)	0.0203 (7)	−0.0105 (6)	0.0014 (6)	0.0002 (6)
C13	0.0201 (7)	0.0368 (8)	0.0219 (7)	−0.0059 (6)	0.0021 (6)	−0.0082 (6)
C14	0.0216 (7)	0.0313 (7)	0.0244 (7)	0.0018 (6)	−0.0035 (6)	−0.0050 (6)
C15	0.0209 (7)	0.0246 (7)	0.0198 (6)	−0.0014 (6)	−0.0029 (5)	0.0004 (6)
C6	0.0192 (6)	0.0187 (6)	0.0162 (6)	0.0035 (5)	−0.0001 (5)	−0.0029 (5)
C1	0.0199 (7)	0.0252 (7)	0.0226 (7)	0.0008 (6)	−0.0013 (6)	0.0004 (6)
C2	0.0242 (7)	0.0329 (7)	0.0227 (7)	0.0052 (6)	−0.0057 (6)	−0.0013 (6)
C3	0.0318 (8)	0.0266 (7)	0.0181 (6)	0.0079 (6)	−0.0015 (6)	0.0023 (6)
C4	0.0291 (7)	0.0227 (6)	0.0197 (6)	0.0005 (6)	0.0011 (6)	0.0007 (6)
C5	0.0219 (7)	0.0212 (6)	0.0188 (6)	0.0000 (5)	−0.0022 (5)	−0.0017 (6)

Geometric parameters (Å, º) top

N5—N4	1.3732 (15)	C12—H12	0.9500
N5—C16	1.3274 (16)	C12—C13	1.386 (2)
N4—N3	1.2937 (16)	C13—H13	0.9500
N3—N2	1.3627 (15)	C13—C14	1.387 (2)
N2—C16	1.3381 (16)	C14—H14	0.9500
N2—C9	1.4680 (16)	C14—C15	1.3899 (19)
N1—H1	0.937 (18)	C15—H15	0.9500
N1—C16	1.3541 (16)	C6—C1	1.4018 (18)
N1—C7	1.4093 (16)	C6—C5	1.3955 (18)
C9—H9	1.0000	C1—H1A	0.9500
C9—C8	1.5035 (18)	C1—C2	1.3831 (19)
C9—C10	1.5250 (18)	C2—H2	0.9500
C8—H8	0.9500	C2—C3	1.390 (2)
C8—C7	1.3421 (18)	C3—H3	0.9500
C7—C6	1.4829 (17)	C3—C4	1.3832 (19)
C10—C11	1.3877 (19)	C4—H4	0.9500
C10—C15	1.3905 (19)	C4—C5	1.3896 (19)
C11—H11	0.9500	C5—H5	0.9500
C11—C12	1.3879 (19)

C16—N5—N4	104.90 (10)	C11—C12—H12	119.8
N3—N4—N5	111.65 (10)	C13—C12—C11	120.32 (13)
N4—N3—N2	105.77 (10)	C13—C12—H12	119.8
N3—N2—C9	125.34 (10)	C12—C13—H13	120.2
C16—N2—N3	108.61 (10)	C12—C13—C14	119.51 (13)
C16—N2—C9	125.69 (11)	C14—C13—H13	120.2
C16—N1—H1	115.6 (10)	C13—C14—H14	119.8
C16—N1—C7	117.77 (10)	C13—C14—C15	120.31 (13)
C7—N1—H1	123.2 (10)	C15—C14—H14	119.8
N5—C16—N2	109.07 (11)	C10—C15—H15	119.9
N5—C16—N1	129.58 (11)	C14—C15—C10	120.14 (13)
N2—C16—N1	121.35 (11)	C14—C15—H15	119.9
N2—C9—H9	108.8	C1—C6—C7	120.16 (12)
N2—C9—C8	106.17 (10)	C5—C6—C7	121.75 (12)
N2—C9—C10	109.66 (10)	C5—C6—C1	118.09 (12)
C8—C9—H9	108.8	C6—C1—H1A	119.6
C8—C9—C10	114.50 (11)	C2—C1—C6	120.72 (13)
C10—C9—H9	108.8	C2—C1—H1A	119.6
C9—C8—H8	117.8	C1—C2—H2	119.8
C7—C8—C9	124.36 (12)	C1—C2—C3	120.46 (13)
C7—C8—H8	117.8	C3—C2—H2	119.8
N1—C7—C6	116.36 (11)	C2—C3—H3	120.2
C8—C7—N1	120.28 (11)	C4—C3—C2	119.52 (12)
C8—C7—C6	123.37 (12)	C4—C3—H3	120.2
C11—C10—C9	119.02 (12)	C3—C4—H4	119.9
C11—C10—C15	119.41 (12)	C3—C4—C5	120.14 (13)
C15—C10—C9	121.52 (12)	C5—C4—H4	119.9
C10—C11—H11	119.8	C6—C5—H5	119.5
C12—C11—C10	120.30 (13)	C4—C5—C6	121.04 (12)
C12—C11—H11	119.8	C4—C5—H5	119.5

N5—N4—N3—N2	0.30 (13)	C9—C10—C11—C12	177.42 (11)
N4—N5—C16—N2	0.52 (13)	C9—C10—C15—C14	−178.02 (12)
N4—N5—C16—N1	−179.19 (12)	C8—C9—C10—C11	158.67 (11)
N4—N3—N2—C16	0.03 (13)	C8—C9—C10—C15	−23.84 (17)
N4—N3—N2—C9	−173.39 (11)	C8—C7—C6—C1	18.98 (19)
N3—N2—C16—N5	−0.36 (14)	C8—C7—C6—C5	−161.31 (12)
N3—N2—C16—N1	179.38 (11)	C7—N1—C16—N5	168.75 (12)
N3—N2—C9—C8	−167.03 (11)	C7—N1—C16—N2	−10.94 (17)
N3—N2—C9—C10	68.78 (15)	C7—C6—C1—C2	−179.78 (12)
N2—C9—C8—C7	−19.03 (17)	C7—C6—C5—C4	−179.09 (12)
N2—C9—C10—C11	−82.14 (14)	C10—C9—C8—C7	102.10 (14)
N2—C9—C10—C15	95.35 (14)	C10—C11—C12—C13	0.9 (2)
N1—C7—C6—C1	−160.74 (11)	C11—C10—C15—C14	−0.54 (19)
N1—C7—C6—C5	18.97 (17)	C11—C12—C13—C14	−0.9 (2)
C16—N5—N4—N3	−0.52 (13)	C12—C13—C14—C15	0.3 (2)
C16—N2—C9—C8	20.66 (16)	C13—C14—C15—C10	0.5 (2)
C16—N2—C9—C10	−103.54 (14)	C15—C10—C11—C12	−0.12 (19)
C16—N1—C7—C8	12.02 (17)	C6—C1—C2—C3	−1.5 (2)
C16—N1—C7—C6	−168.25 (11)	C1—C6—C5—C4	0.62 (19)
C9—N2—C16—N5	173.03 (11)	C1—C2—C3—C4	1.4 (2)
C9—N2—C16—N1	−7.23 (19)	C2—C3—C4—C5	−0.3 (2)
C9—C8—C7—N1	4.52 (19)	C3—C4—C5—C6	−0.7 (2)
C9—C8—C7—C6	−175.19 (11)	C5—C6—C1—C2	0.50 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N5ⁱ	0.937 (18)	1.992 (18)	2.9075 (15)	165.3 (14)

Symmetry code: (i) −x+1, −y+2, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N5ⁱ	0.937 (18)	1.992 (18)	2.9075 (15)	165.3 (14)

Symmetry code: (i) −x+1, −y+2, −z+2.

Acknowledgements

The authors thank Christopher Daley, A. Rheingold and C. Moore (UCSD) for performing X-ray crystallography. Funding for this work was provided by the University of California, Merced and National Science Foundation (CHE-1300686)

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