N-(9,9-Dipropyl-9H-fluoren-2-yl)-7-(piperidin-1-yl)-2,1,3-benzothia­diazol-4-amine

Bolisetty, M.N.K.P.; Thomas, K.R.J.; Ng, S.W.; Tiekink, E.R.T.

doi:10.1107/S1600536812008239

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 68| Part 3| March 2012| Pages o911-o912

doi:10.1107/S1600536812008239

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N-(9,9-Dipropyl-9H-fluoren-2-yl)-7-(piperidin-1-yl)-2,1,3-benzothiadiazol-4-amine

M. N. K. Prasad Bolisetty,^a K. R. Justin Thomas,^a ‡ Seik Weng Ng ^b,^c and Edward R. T. Tiekink ^b ^*

^aOrganic Materials Laboratory, Department of Chemistry, Indian Institute of Technology Roorkee, Roorkee 247 667, India, ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia, and ^cChemistry Department, Faculty of, Science, King Abdulaziz University, PO Box 80203 Jeddah, Saudi Arabia
^*Correspondence e-mail: edward.tiekink@gmail.com

(Received 23 February 2012; accepted 23 February 2012; online 29 February 2012)

In the title compound, C₃₀H₃₄N₄S, each of the benzothiadiazole and fluorene fused ring systems is almost planar (r.m.s. deviations = 0.010 and 0.013 Å, respectively) and they are inclined to each other with a dihedral angle of 61.69 (3)°; the S atom is directed away from the rest of the molecule. Each of the benzothiadiazole ring N atoms forms a significant intramolecular contact, i.e. N—H⋯N or C—H⋯N. In the crystal, linear supramolecular chains along the c axis are generated by C—H⋯N interactions involving the tertiary amine N atom.

Related literature

For the application of benzo[c][1,2,5]thiadiazole-based polymers and small molecules in organic light-emitting diodes and bulk heterojunction solar cells, see: Beaujuge et al. (2012 ); Horie et al. (2012 ); Thomas et al. (2004 , 2008 ). For related structures, see: Sakurai et al. (2005 ); Chen et al. (2010 ); Tao et al. (2011 ).

Experimental

Crystal data

C₃₀H₃₄N₄S
M_r = 482.67
Monoclinic, P 2₁ /n
a = 9.6111 (1) Å
b = 21.9632 (2) Å
c = 12.6954 (1) Å
β = 103.936 (1)°
V = 2601.00 (4) Å³
Z = 4
Cu Kα radiation
μ = 1.29 mm⁻¹
T = 100 K
0.35 × 0.20 × 0.05 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ) T_min = 0.302, T_max = 1.000
14383 measured reflections
5430 independent reflections
4961 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.106
S = 1.03
5430 reflections
317 parameters
H-atom parameters constrained
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.37 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4⋯N2	0.88	2.55	2.8567 (17)	101
C5—H5B⋯N1	0.99	2.60	3.212 (2)	120
C20—H20⋯N3ⁱ	0.95	2.55	3.4577 (16)	161
Symmetry code: (i) x, y, z+1.

Data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and DIAMOND (Brandenburg, 2006 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812008239/hg5183sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812008239/hg5183Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812008239/hg5183Isup3.cml

checkCIF report

Comment top

Benzo[c][1,2,5]thiadiazole-based polymers (Beaujuge et al., 2012; Horie et al., 2012) and small molecules (Thomas et al., 2004; Thomas et al., 2008) have been explored as functional materials for applications in organic light-emitting diodes and bulk heterojunction solar cells. A new diarylamine, N-(9,9-dipropyl-9H-fluoren-2-yl)-7-(piperidin-1-yl)benzo[c][1,2,5]thiadiazol-4-amine (I), featuring benzo[c][1,2,5]thiadiazole and fluorene units has been synthesized as a building block for the development of organic dyes suitable for use as sensitizers in dye-sensitized solar cells. Herein, the crystal and molecular structure of (I) is described. Related structures are known (Sakurai et al., 2005; Chen et al., 2010; Tao et al., 2011).

In (I), Fig. 1, each of the benzothiadiazole (r.m.s. deviation = 0.010 Å) and fluorene (0.013 Å) fused ring systems are planar and these are inclined at 61.69 (3)° so that the S atom is directed away from the rest of the molecule. Each of the n-propyl groups connected at the C22 atom adopt open conformations with the C22—C25—C26—C27 and C22–C28—C29—C30 torsion angles being -179.98 (10) and 179.50 (11)°, respectively. Each of the ring N atoms forms a significant intramolecular contact, N1 with C5—H and N2 with N4—H, Table 1. The most notable intermolecular contact is of the type C—H···N involving the tertiary amine-N atom, Table 1. These lead to the formation of linear supramolecular chains along the c axis.

Related literature top

For the application of benzo[c][1,2,5]thiadiazole-based polymers and small molecules in organic light-emitting diodes and bulk heterojunction solar cells, see: Beaujuge et al. (2012); Horie et al. (2012); Thomas et al. (2004, 2008). For related structures, see: Sakurai et al. (2005); Chen et al. (2010); Tao et al. (2011).

Experimental top

A mixture of 9,9-dipropyl-9H-fluoren-2-amine (0.66 g, 2.5 mmol), 4-bromo-7-(piperidin-1-yl)benzo[c][1,2,5]thiadiazole (0.75 g, 2.5 mmol), Pd(dba)₂ (dba = (1E,4E)-1,5-diphenylpenta-1,4-dien-3-one; 0.03 mmol), dppf (1,1'-bis(diphenylphosphino)ferrocene; 0.03 mmol), t-BuONa (0.38 g, 3 mmol) and toluene (15 ml) was taken in a Schlenk tube and heated at 353 K with stirring for 48 h. After completion of the reaction, the volatiles were evaporated to leave a pink residue. The residue was purified by column chromatography on silica gel by using a dichloromethane/hexanes mixture (1:2) as eluent. Yield 1.1 g (91%). M.pt. 393–395 K. Crystals were grown from its solution in a dichloromethane/hexanes mixture.

¹H NMR (CDCl₃, 500.13 MHz) δ p.p.m.: 0.65–0.70 (m, 10 H), 1.65–1.70 (m, 2 H), 1.86–1.95 (m, 8 H), 3.3 (t, J = 5.5 Hz, 4 H), 6.78 (d, J = 8.5 Hz, 1 H), 6.92 (s, 1 H), 7.17 (d, J = 8 Hz, 1 H), 7.23–7.25 (m, 3 H), 7.30–7.33 (m, 2 H), 7.63 (t, J = 8.5 Hz, 2 H). ¹³C NMR (CDCl₃, 125.77 MHz) δ p.p.m.: 14.6, 17.3, 24.6, 26.2, 43.0, 52.5, 55.3, 107.4, 113.5, 114.6, 117.5, 119.0, 120.5, 122.8, 126.2, 126.8, 130.0, 135.3, 138.0, 140.9, 141.1,150.0, 150.2, 150.8, 152.4.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO (Agilent, 2010); data reduction: CrysAlis PRO (Agilent, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular structure of (I) showing the atom-labelling scheme and displacement ellipsoids at the 50% probability level.
	Fig. 2. A view of the linear supramolecular chain along the c axis in (I). The C—H···N interactions are shown as orange dashed lines.

N-(9,9-Dipropyl-9H-fluoren-2-yl)-7-(piperidin-1-yl)- 2,1,3-benzothiadiazol-4-amine top

Crystal data top

C₃₀H₃₄N₄S	F(000) = 1032
M_r = 482.67	D_x = 1.233 Mg m⁻³
Monoclinic, P2₁/n	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: -P 2yn	Cell parameters from 8442 reflections
a = 9.6111 (1) Å	θ = 3.6–76.4°
b = 21.9632 (2) Å	µ = 1.29 mm⁻¹
c = 12.6954 (1) Å	T = 100 K
β = 103.936 (1)°	Block, brown
V = 2601.00 (4) Å³	0.35 × 0.20 × 0.05 mm
Z = 4

Data collection top

Agilent SuperNova Dual diffractometer with an Atlas detector	5430 independent reflections
Radiation source: SuperNova (Cu) X-ray Source	4961 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.023
Detector resolution: 10.4041 pixels mm^-1	θ_max = 76.6°, θ_min = 4.0°
ω scan	h = −12→12
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	k = −27→18
T_min = 0.302, T_max = 1.000	l = −14→15
14383 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.038	H-atom parameters constrained
wR(F²) = 0.106	w = 1/[σ²(F_o²) + (0.0594P)² + 0.8093P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
5430 reflections	Δρ_max = 0.38 e Å⁻³
317 parameters	Δρ_min = −0.37 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00114 (17)

Crystal data top

C₃₀H₃₄N₄S	V = 2601.00 (4) Å³
M_r = 482.67	Z = 4
Monoclinic, P2₁/n	Cu Kα radiation
a = 9.6111 (1) Å	µ = 1.29 mm⁻¹
b = 21.9632 (2) Å	T = 100 K
c = 12.6954 (1) Å	0.35 × 0.20 × 0.05 mm
β = 103.936 (1)°

Data collection top

Agilent SuperNova Dual diffractometer with an Atlas detector	5430 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	4961 reflections with I > 2σ(I)
T_min = 0.302, T_max = 1.000	R_int = 0.023
14383 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.106	H-atom parameters constrained
S = 1.03	Δρ_max = 0.38 e Å⁻³
5430 reflections	Δρ_min = −0.37 e Å⁻³
317 parameters

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.

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) top

	x	y	z	U_iso*/U_eq
S1	0.17524 (4)	0.516536 (18)	0.29347 (3)	0.03740 (12)
N1	0.32500 (14)	0.48122 (5)	0.30043 (9)	0.0300 (3)
N2	0.12335 (14)	0.48521 (6)	0.39313 (9)	0.0337 (3)
N3	0.56133 (11)	0.39374 (5)	0.35759 (8)	0.0218 (2)
N4	0.10144 (13)	0.40732 (6)	0.56862 (9)	0.0314 (3)
H4	0.0231	0.4244	0.5295	0.038*
C1	0.63792 (15)	0.33572 (6)	0.36929 (10)	0.0259 (3)
H1A	0.5693	0.3018	0.3666	0.031*
H1B	0.7085	0.3343	0.4403	0.031*
C2	0.71468 (16)	0.32872 (7)	0.27814 (11)	0.0337 (3)
H2A	0.7681	0.2898	0.2871	0.040*
H2B	0.6431	0.3276	0.2075	0.040*
C3	0.81786 (18)	0.38097 (8)	0.27843 (16)	0.0464 (4)
H3A	0.8604	0.3774	0.2150	0.056*
H3B	0.8965	0.3792	0.3450	0.056*
C4	0.73966 (18)	0.44147 (8)	0.27394 (16)	0.0452 (4)
H4A	0.6711	0.4458	0.2024	0.054*
H4B	0.8098	0.4752	0.2821	0.054*
C5	0.65895 (15)	0.44563 (6)	0.36334 (13)	0.0329 (3)
H5A	0.7283	0.4461	0.4350	0.039*
H5B	0.6035	0.4840	0.3555	0.039*
C6	0.34160 (15)	0.44213 (6)	0.38424 (10)	0.0240 (3)
C7	0.45773 (14)	0.39993 (5)	0.41925 (9)	0.0216 (2)
C8	0.45092 (14)	0.36470 (6)	0.50703 (10)	0.0239 (3)
H8	0.5275	0.3373	0.5344	0.029*
C9	0.33591 (15)	0.36683 (6)	0.55952 (10)	0.0254 (3)
H9	0.3385	0.3406	0.6195	0.031*
C10	0.22113 (14)	0.40543 (6)	0.52650 (10)	0.0256 (3)
C11	0.22551 (15)	0.44449 (6)	0.43700 (10)	0.0259 (3)
C12	0.09800 (14)	0.38303 (6)	0.67210 (10)	0.0249 (3)
C13	−0.01831 (14)	0.34774 (6)	0.68202 (10)	0.0266 (3)
H13	−0.0910	0.3381	0.6191	0.032*
C14	−0.02985 (13)	0.32626 (6)	0.78291 (10)	0.0237 (3)
H14	−0.1099	0.3024	0.7892	0.028*
C15	0.07814 (13)	0.34037 (5)	0.87438 (10)	0.0193 (2)
C16	0.09581 (12)	0.32574 (5)	0.98970 (10)	0.0184 (2)
C17	0.00960 (13)	0.29269 (5)	1.04300 (11)	0.0233 (3)
H17	−0.0776	0.2749	1.0036	0.028*
C18	0.05390 (14)	0.28621 (6)	1.15523 (11)	0.0263 (3)
H18	−0.0035	0.2636	1.1926	0.032*
C19	0.18115 (14)	0.31241 (6)	1.21333 (10)	0.0246 (3)
H19	0.2095	0.3076	1.2899	0.030*
C20	0.26771 (13)	0.34567 (5)	1.16012 (10)	0.0209 (2)
H20	0.3546	0.3636	1.1997	0.025*
C21	0.22408 (12)	0.35202 (5)	1.04844 (9)	0.0173 (2)
C22	0.29987 (12)	0.38581 (5)	0.97382 (9)	0.0169 (2)
C23	0.19643 (12)	0.37525 (5)	0.86392 (9)	0.0185 (2)
C24	0.20788 (13)	0.39649 (6)	0.76383 (10)	0.0225 (2)
H24	0.2887	0.4198	0.7573	0.027*
C25	0.31877 (12)	0.45412 (5)	1.00244 (9)	0.0190 (2)
H25A	0.3827	0.4579	1.0760	0.023*
H25B	0.3676	0.4737	0.9510	0.023*
C26	0.18116 (13)	0.48892 (5)	0.99994 (10)	0.0221 (2)
H26A	0.1318	0.4701	1.0518	0.026*
H26B	0.1167	0.4859	0.9264	0.026*
C27	0.20981 (15)	0.55594 (6)	1.02916 (12)	0.0281 (3)
H27A	0.1187	0.5768	1.0257	0.042*
H27B	0.2581	0.5748	0.9777	0.042*
H27C	0.2710	0.5592	1.1028	0.042*
C28	0.44887 (12)	0.35842 (5)	0.97719 (9)	0.0200 (2)
H28A	0.4883	0.3788	0.9212	0.024*
H28B	0.5134	0.3678	1.0487	0.024*
C29	0.45097 (15)	0.29009 (6)	0.95892 (13)	0.0325 (3)
H29A	0.4132	0.2692	1.0154	0.039*
H29B	0.3866	0.2803	0.8875	0.039*
C30	0.59965 (16)	0.26589 (7)	0.96215 (12)	0.0354 (3)
H30A	0.5946	0.2219	0.9492	0.053*
H30B	0.6632	0.2742	1.0335	0.053*
H30C	0.6372	0.2859	0.9058	0.053*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0515 (2)	0.0408 (2)	0.02084 (18)	0.02678 (16)	0.01052 (15)	0.01025 (13)
N1	0.0437 (7)	0.0260 (6)	0.0198 (5)	0.0138 (5)	0.0064 (5)	0.0039 (4)
N2	0.0431 (7)	0.0410 (7)	0.0160 (5)	0.0213 (6)	0.0053 (5)	0.0044 (5)
N3	0.0262 (5)	0.0178 (5)	0.0204 (5)	0.0018 (4)	0.0034 (4)	0.0002 (4)
N4	0.0323 (6)	0.0459 (7)	0.0150 (5)	0.0160 (5)	0.0039 (4)	0.0050 (5)
C1	0.0323 (7)	0.0230 (6)	0.0215 (6)	0.0071 (5)	0.0045 (5)	0.0025 (5)
C2	0.0393 (8)	0.0370 (8)	0.0259 (6)	0.0193 (6)	0.0101 (6)	0.0082 (6)
C3	0.0343 (8)	0.0523 (10)	0.0577 (10)	0.0167 (7)	0.0210 (7)	0.0232 (8)
C4	0.0334 (8)	0.0388 (8)	0.0674 (11)	0.0045 (6)	0.0203 (8)	0.0206 (8)
C5	0.0298 (7)	0.0234 (6)	0.0419 (8)	−0.0027 (5)	0.0018 (6)	0.0014 (6)
C6	0.0351 (7)	0.0203 (6)	0.0152 (5)	0.0060 (5)	0.0030 (5)	−0.0016 (4)
C7	0.0287 (6)	0.0177 (5)	0.0164 (5)	0.0031 (5)	0.0017 (5)	−0.0027 (4)
C8	0.0295 (6)	0.0209 (6)	0.0191 (6)	0.0064 (5)	0.0020 (5)	0.0006 (4)
C9	0.0338 (7)	0.0249 (6)	0.0169 (5)	0.0068 (5)	0.0048 (5)	0.0025 (5)
C10	0.0319 (7)	0.0295 (6)	0.0140 (5)	0.0076 (5)	0.0030 (5)	−0.0022 (5)
C11	0.0336 (7)	0.0276 (6)	0.0142 (5)	0.0103 (5)	0.0012 (5)	−0.0019 (5)
C12	0.0279 (6)	0.0302 (6)	0.0159 (6)	0.0100 (5)	0.0036 (5)	0.0000 (5)
C13	0.0251 (6)	0.0282 (6)	0.0213 (6)	0.0058 (5)	−0.0043 (5)	−0.0059 (5)
C14	0.0205 (6)	0.0211 (6)	0.0266 (6)	0.0010 (5)	−0.0002 (5)	−0.0039 (5)
C15	0.0191 (5)	0.0165 (5)	0.0218 (6)	0.0023 (4)	0.0038 (4)	−0.0016 (4)
C16	0.0179 (5)	0.0146 (5)	0.0229 (6)	0.0015 (4)	0.0052 (4)	−0.0008 (4)
C17	0.0198 (6)	0.0177 (5)	0.0331 (7)	−0.0016 (4)	0.0079 (5)	0.0010 (5)
C18	0.0280 (6)	0.0217 (6)	0.0336 (7)	−0.0005 (5)	0.0161 (5)	0.0058 (5)
C19	0.0297 (6)	0.0248 (6)	0.0216 (6)	0.0018 (5)	0.0105 (5)	0.0047 (5)
C20	0.0223 (6)	0.0216 (6)	0.0192 (6)	−0.0003 (4)	0.0058 (4)	0.0005 (4)
C21	0.0183 (5)	0.0156 (5)	0.0192 (5)	0.0008 (4)	0.0068 (4)	0.0001 (4)
C22	0.0170 (5)	0.0195 (5)	0.0143 (5)	−0.0011 (4)	0.0043 (4)	0.0006 (4)
C23	0.0178 (5)	0.0195 (5)	0.0173 (5)	0.0022 (4)	0.0028 (4)	−0.0015 (4)
C24	0.0229 (6)	0.0267 (6)	0.0183 (6)	0.0031 (5)	0.0054 (5)	0.0003 (5)
C25	0.0185 (5)	0.0198 (5)	0.0189 (5)	−0.0026 (4)	0.0048 (4)	0.0004 (4)
C26	0.0208 (6)	0.0191 (6)	0.0266 (6)	−0.0013 (4)	0.0064 (5)	0.0003 (4)
C27	0.0285 (7)	0.0197 (6)	0.0383 (7)	−0.0012 (5)	0.0124 (5)	0.0001 (5)
C28	0.0168 (5)	0.0254 (6)	0.0177 (5)	−0.0007 (4)	0.0041 (4)	−0.0008 (4)
C29	0.0248 (7)	0.0278 (7)	0.0446 (8)	0.0025 (5)	0.0079 (6)	−0.0072 (6)
C30	0.0330 (7)	0.0407 (8)	0.0333 (7)	0.0122 (6)	0.0097 (6)	−0.0062 (6)

Geometric parameters (Å, º) top

S1—N1	1.6186 (12)	C14—H14	0.9500
S1—N2	1.6208 (13)	C15—C23	1.4035 (17)
N1—C6	1.3464 (16)	C15—C16	1.4683 (16)
N2—C11	1.3455 (16)	C16—C17	1.3934 (17)
N3—C7	1.4136 (16)	C16—C21	1.4023 (16)
N3—C1	1.4611 (15)	C17—C18	1.3926 (19)
N3—C5	1.4668 (17)	C17—H17	0.9500
N4—C10	1.3811 (18)	C18—C19	1.3916 (19)
N4—C12	1.4258 (16)	C18—H18	0.9500
N4—H4	0.8800	C19—C20	1.3974 (17)
C1—C2	1.5225 (18)	C19—H19	0.9500
C1—H1A	0.9900	C20—C21	1.3854 (16)
C1—H1B	0.9900	C20—H20	0.9500
C2—C3	1.516 (2)	C21—C22	1.5202 (15)
C2—H2A	0.9900	C22—C23	1.5235 (15)
C2—H2B	0.9900	C22—C28	1.5443 (16)
C3—C4	1.521 (2)	C22—C25	1.5441 (15)
C3—H3A	0.9900	C23—C24	1.3826 (17)
C3—H3B	0.9900	C24—H24	0.9500
C4—C5	1.524 (2)	C25—C26	1.5212 (16)
C4—H4A	0.9900	C25—H25A	0.9900
C4—H4B	0.9900	C25—H25B	0.9900
C5—H5A	0.9900	C26—C27	1.5269 (17)
C5—H5B	0.9900	C26—H26A	0.9900
C6—C11	1.4339 (19)	C26—H26B	0.9900
C6—C7	1.4365 (17)	C27—H27A	0.9800
C7—C8	1.3710 (17)	C27—H27B	0.9800
C8—C9	1.4223 (19)	C27—H27C	0.9800
C8—H8	0.9500	C28—C29	1.5195 (18)
C9—C10	1.3742 (18)	C28—H28A	0.9900
C9—H9	0.9500	C28—H28B	0.9900
C10—C11	1.4326 (18)	C29—C30	1.5159 (18)
C12—C13	1.391 (2)	C29—H29A	0.9900
C12—C24	1.4023 (17)	C29—H29B	0.9900
C13—C14	1.3943 (19)	C30—H30A	0.9800
C13—H13	0.9500	C30—H30B	0.9800
C14—C15	1.3933 (16)	C30—H30C	0.9800

N1—S1—N2	101.00 (6)	C23—C15—C16	108.18 (10)
C6—N1—S1	106.45 (10)	C17—C16—C21	120.38 (11)
C11—N2—S1	105.91 (10)	C17—C16—C15	131.21 (11)
C7—N3—C1	115.62 (10)	C21—C16—C15	108.41 (10)
C7—N3—C5	115.16 (10)	C18—C17—C16	118.62 (11)
C1—N3—C5	111.84 (11)	C18—C17—H17	120.7
C10—N4—C12	123.49 (11)	C16—C17—H17	120.7
C10—N4—H4	118.3	C19—C18—C17	120.88 (11)
C12—N4—H4	118.3	C19—C18—H18	119.6
N3—C1—C2	109.59 (10)	C17—C18—H18	119.6
N3—C1—H1A	109.8	C18—C19—C20	120.63 (12)
C2—C1—H1A	109.8	C18—C19—H19	119.7
N3—C1—H1B	109.8	C20—C19—H19	119.7
C2—C1—H1B	109.8	C21—C20—C19	118.60 (11)
H1A—C1—H1B	108.2	C21—C20—H20	120.7
C3—C2—C1	110.98 (13)	C19—C20—H20	120.7
C3—C2—H2A	109.4	C20—C21—C16	120.89 (11)
C1—C2—H2A	109.4	C20—C21—C22	127.92 (11)
C3—C2—H2B	109.4	C16—C21—C22	111.19 (10)
C1—C2—H2B	109.4	C21—C22—C23	101.04 (9)
H2A—C2—H2B	108.0	C21—C22—C28	111.89 (9)
C2—C3—C4	110.13 (13)	C23—C22—C28	111.24 (9)
C2—C3—H3A	109.6	C21—C22—C25	112.00 (9)
C4—C3—H3A	109.6	C23—C22—C25	112.17 (9)
C2—C3—H3B	109.6	C28—C22—C25	108.43 (9)
C4—C3—H3B	109.6	C24—C23—C15	121.11 (11)
H3A—C3—H3B	108.1	C24—C23—C22	127.70 (11)
C3—C4—C5	111.10 (13)	C15—C23—C22	111.17 (10)
C3—C4—H4A	109.4	C23—C24—C12	118.77 (12)
C5—C4—H4A	109.4	C23—C24—H24	120.6
C3—C4—H4B	109.4	C12—C24—H24	120.6
C5—C4—H4B	109.4	C26—C25—C22	115.52 (9)
H4A—C4—H4B	108.0	C26—C25—H25A	108.4
N3—C5—C4	110.52 (12)	C22—C25—H25A	108.4
N3—C5—H5A	109.5	C26—C25—H25B	108.4
C4—C5—H5A	109.5	C22—C25—H25B	108.4
N3—C5—H5B	109.5	H25A—C25—H25B	107.5
C4—C5—H5B	109.5	C25—C26—C27	111.98 (10)
H5A—C5—H5B	108.1	C25—C26—H26A	109.2
N1—C6—C11	112.87 (11)	C27—C26—H26A	109.2
N1—C6—C7	126.25 (12)	C25—C26—H26B	109.2
C11—C6—C7	120.85 (11)	C27—C26—H26B	109.2
C8—C7—N3	125.01 (11)	H26A—C26—H26B	107.9
C8—C7—C6	115.47 (12)	C26—C27—H27A	109.5
N3—C7—C6	119.28 (11)	C26—C27—H27B	109.5
C7—C8—C9	123.84 (12)	H27A—C27—H27B	109.5
C7—C8—H8	118.1	C26—C27—H27C	109.5
C9—C8—H8	118.1	H27A—C27—H27C	109.5
C10—C9—C8	122.32 (12)	H27B—C27—H27C	109.5
C10—C9—H9	118.8	C29—C28—C22	115.26 (10)
C8—C9—H9	118.8	C29—C28—H28A	108.5
C9—C10—N4	125.65 (12)	C22—C28—H28A	108.5
C9—C10—C11	115.89 (12)	C29—C28—H28B	108.5
N4—C10—C11	118.38 (12)	C22—C28—H28B	108.5
N2—C11—C10	124.64 (13)	H28A—C28—H28B	107.5
N2—C11—C6	113.77 (12)	C30—C29—C28	112.90 (12)
C10—C11—C6	121.58 (11)	C30—C29—H29A	109.0
C13—C12—C24	120.22 (12)	C28—C29—H29A	109.0
C13—C12—N4	119.31 (12)	C30—C29—H29B	109.0
C24—C12—N4	120.42 (13)	C28—C29—H29B	109.0
C12—C13—C14	121.01 (11)	H29A—C29—H29B	107.8
C12—C13—H13	119.5	C29—C30—H30A	109.5
C14—C13—H13	119.5	C29—C30—H30B	109.5
C15—C14—C13	118.84 (12)	H30A—C30—H30B	109.5
C15—C14—H14	120.6	C29—C30—H30C	109.5
C13—C14—H14	120.6	H30A—C30—H30C	109.5
C14—C15—C23	120.02 (11)	H30B—C30—H30C	109.5
C14—C15—C16	131.79 (11)

N2—S1—N1—C6	−0.18 (11)	C14—C15—C16—C17	0.5 (2)
N1—S1—N2—C11	0.05 (11)	C23—C15—C16—C17	179.88 (12)
C7—N3—C1—C2	164.99 (11)	C14—C15—C16—C21	−179.12 (12)
C5—N3—C1—C2	−60.58 (14)	C23—C15—C16—C21	0.29 (13)
N3—C1—C2—C3	57.96 (15)	C21—C16—C17—C18	−0.27 (17)
C1—C2—C3—C4	−54.55 (18)	C15—C16—C17—C18	−179.82 (12)
C2—C3—C4—C5	53.0 (2)	C16—C17—C18—C19	0.35 (18)
C7—N3—C5—C4	−165.85 (11)	C17—C18—C19—C20	−0.24 (19)
C1—N3—C5—C4	59.49 (14)	C18—C19—C20—C21	0.04 (18)
C3—C4—C5—N3	−55.19 (18)	C19—C20—C21—C16	0.05 (17)
S1—N1—C6—C11	0.25 (14)	C19—C20—C21—C22	−179.99 (11)
S1—N1—C6—C7	178.26 (10)	C17—C16—C21—C20	0.07 (17)
C1—N3—C7—C8	18.27 (17)	C15—C16—C21—C20	179.71 (10)
C5—N3—C7—C8	−114.65 (14)	C17—C16—C21—C22	−179.90 (10)
C1—N3—C7—C6	−155.84 (11)	C15—C16—C21—C22	−0.26 (13)
C5—N3—C7—C6	71.24 (14)	C20—C21—C22—C23	−179.84 (11)
N1—C6—C7—C8	−179.99 (12)	C16—C21—C22—C23	0.13 (12)
C11—C6—C7—C8	−2.13 (17)	C20—C21—C22—C28	61.72 (15)
N1—C6—C7—N3	−5.34 (19)	C16—C21—C22—C28	−118.31 (11)
C11—C6—C7—N3	172.53 (11)	C20—C21—C22—C25	−60.27 (15)
N3—C7—C8—C9	−172.02 (12)	C16—C21—C22—C25	119.70 (10)
C6—C7—C8—C9	2.29 (18)	C14—C15—C23—C24	0.43 (17)
C7—C8—C9—C10	−0.6 (2)	C16—C15—C23—C24	−179.06 (10)
C8—C9—C10—N4	175.53 (13)	C14—C15—C23—C22	179.29 (10)
C8—C9—C10—C11	−1.22 (19)	C16—C15—C23—C22	−0.20 (13)
C12—N4—C10—C9	19.6 (2)	C21—C22—C23—C24	178.82 (11)
C12—N4—C10—C11	−163.75 (13)	C28—C22—C23—C24	−62.27 (15)
S1—N2—C11—C10	−178.62 (11)	C25—C22—C23—C24	59.37 (15)
S1—N2—C11—C6	0.09 (15)	C21—C22—C23—C15	0.05 (12)
C9—C10—C11—N2	179.92 (13)	C28—C22—C23—C15	118.96 (11)
N4—C10—C11—N2	2.9 (2)	C25—C22—C23—C15	−119.39 (11)
C9—C10—C11—C6	1.30 (19)	C15—C23—C24—C12	0.54 (18)
N4—C10—C11—C6	−175.70 (12)	C22—C23—C24—C12	−178.11 (11)
N1—C6—C11—N2	−0.24 (17)	C13—C12—C24—C23	−1.47 (18)
C7—C6—C11—N2	−178.37 (11)	N4—C12—C24—C23	176.02 (11)
N1—C6—C11—C10	178.52 (12)	C21—C22—C25—C26	−57.65 (13)
C7—C6—C11—C10	0.39 (19)	C23—C22—C25—C26	55.16 (13)
C10—N4—C12—C13	−134.62 (14)	C28—C22—C25—C26	178.40 (10)
C10—N4—C12—C24	47.87 (19)	C22—C25—C26—C27	−179.98 (10)
C24—C12—C13—C14	1.44 (19)	C21—C22—C28—C29	51.69 (14)
N4—C12—C13—C14	−176.07 (12)	C23—C22—C28—C29	−60.50 (14)
C12—C13—C14—C15	−0.45 (18)	C25—C22—C28—C29	175.71 (10)
C13—C14—C15—C23	−0.48 (17)	C22—C28—C29—C30	179.50 (11)
C13—C14—C15—C16	178.88 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4···N2	0.88	2.55	2.8567 (17)	101
C5—H5B···N1	0.99	2.60	3.212 (2)	120
C20—H20···N3ⁱ	0.95	2.55	3.4577 (16)	161

Symmetry code: (i) x, y, z+1.

Experimental details

Crystal data
Chemical formula	C₃₀H₃₄N₄S
M_r	482.67
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	9.6111 (1), 21.9632 (2), 12.6954 (1)
β (°)	103.936 (1)
V (Å³)	2601.00 (4)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	1.29
Crystal size (mm)	0.35 × 0.20 × 0.05

Data collection
Diffractometer	Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2010)
T_min, T_max	0.302, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	14383, 5430, 4961
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.631

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.106, 1.03
No. of reflections	5430
No. of parameters	317
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.37

Computer programs: CrysAlis PRO (Agilent, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4···N2	0.88	2.55	2.8567 (17)	101
C5—H5B···N1	0.99	2.60	3.212 (2)	120
C20—H20···N3ⁱ	0.95	2.55	3.4577 (16)	161

Symmetry code: (i) x, y, z+1.

Footnotes

‡Additional correspondence author, e-mail: krjt8fcy@iitr.ernet.in.

Acknowledgements

KRJT is thankful to Department of Science and Technology, New Delhi, India, for financial support (Ref. No. DST/TSG/ME/2010/27). We also thank the Ministry of Higher Education (Malaysia) for funding structural studies through the High-Impact Research scheme (UM.C/HIR/MOHE/SC/12).

References

Agilent (2010). CrysAlis PRO. Agilent Technologies, Yarnton, Oxfordshire, England. Google Scholar
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Volume 68| Part 3| March 2012| Pages o911-o912

doi:10.1107/S1600536812008239

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

N-(9,9-Di­propyl-9H-fluoren-2-yl)-7-(piperidin-1-yl)-2,1,3-benzo­thia­diazol-4-amine

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Experimental

Crystal data

Data collection

Refinement

Supporting information

Footnotes

Acknowledgements

References

organic compounds

N-(9,9-Dipropyl-9H-fluoren-2-yl)-7-(piperidin-1-yl)-2,1,3-benzothiadiazol-4-amine