N-Benzyl-N-[4-(methyl­sulfan­yl)-3-nitro-4H-chromen-2-yl]amine

In the title compound, C₁₇H₁₆N₂O₃S, the pyran ring adopts a flattened envelope conformation. N—H...O hydrogen bonds generate a centrosymmetric R₂²(12) dimer. The dimers translated by a unit cell along the c axis are linked via C—H...S hydrogen bonds to form a C(6) chain.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.045
• wR factor = 0.138
• Data-to-parameter ratio = 18.4

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.97
PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_C Check the Reported _diffrn_ambient_temperature .        293 K
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.62 Ratio
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.16 Ratio
PLAT230_ALERT_2_C Hirshfeld Test Diff for    C15    -   C16     ..       6.36 su

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   6 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion

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S1. Comment

Chromenes (2H-1-benzopyran derivatives) are frequently found in naturally occurring heterocycles, many of which exhibit biological activity (Bowers et al., 1976). They have been widely employed as important intermediates in the synthesis of natural products and medicinal agents (Wang & Finn, 2000). Chromene derivatives can yield a new family of potassium-channel activating drugs (Atwal et al., 1995; Salamon et al., 2002). In view of the above importance, the structural study of the title compound, (I), was undertaken.

The N—O, C—S and Csp²—N bond lengths (Table 1) deviate slightly from the corresponding mean values of 1.218 (13), 1.819 (19) and 1.353 (7) Å, respectively (Allen et al., 1987). The difference in the C—O bond lengths in the pyran ring is an observation common to the chromene moiety. The C5—C6—C7, C6—C5—C10 and C6—C7—C8 angles deviate from 120°, which may be due to the fusion of the benzene ring (C5—C10) with the non-planar pyran ring. The C4—S1—C18 angle of 101.1 (1)° is comparable with that reported for a diazapentacyclo compound (Bhaskaran et al., 2003).

The pyran ring adopts a flattened envelope conformation, with atom C4 deviating from the O1/C2/C3/C5/C6 plane by 0.229 (2) Å. The asymmetry parameter (Nardelli, 1995) ΔC_s(C4) is 0.7 (2)°, and the puckering parameters (Cremer & Pople, 1975) Q, θ and ϕ are 0.175 (1) Å, 80.7 (5)° and 178.8 (5)°, respectively. The small puckering may be attributed to the resonance in the pyran ring. The O—N—C—C torsion angles (Table 1) indicate that the nitro group is twisted slightly away from the chromene moiety (Fig. 1). The dihedral angle between the O1/C2/C3/C5—C10 and C12—C17 planes is 60.63 (6)°.

In the molecular structure, an intramolecular N1—H1···O3 hydrogen bond generates an S(6) ring motif (Bernstein et al., 1995). The crystal packing is stabilized by N—H··· O and C—H···S intermolecular hydrogen bonds (Table 2). The N1—H1···O3ⁱ and N1ⁱ—H1ⁱ···O3 (symmetry code as in Table 2) hydrogen bonds generate a centrosymmetric R₂²(12) dimer centred at (1/2,0,1). The dimers translated by a unit cell along the c axis are linked via C7—H7···S1ⁱⁱ hydrogen bonds to form a C(6) chain (Fig. 2).

S2. Experimental

To a mixture of 2-hydroxybenzaldehyde (27 mmol) and 60% NaH (40 mmol) in dry tetrahydrofuran (THF, 10 ml) N-benzyl-N-[(E)-1-methylsulfanyl)-2-nitro-1-ethenyl]amine (27 mmol) was added under a nitrogen atmosphere. The reaction mixture was stirred thoroughly for about 1 h and then refluxed for 7 h. Unreacted NaH was quenched with a few drops of acetic acid. The reaction mixture was diluted with dichloromethane (35 ml) and washed with water and brine solution. Evaporation of the solvent and column chromatography (Medium?, hexane and ethyl acetate) afforded compound (I) as a pale-yellow solid. Single crystals were grown by slow evaporation of a hexane–ethyl acetate (8:2 v/v) solution.

S3. Refinement

H atoms were positioned geometrically and were treated as riding on their parent C atoms, with N—H = 0.86 Å and C—H = 0.93–0.98 Å, and with U_iso(H) = 1.5U_eq(C) for methyl H atoms or 1.2U_eq(C) for other H atms.

Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PARST (Nardelli, 1995).

Figures

	Fig. 1. The molecular structure of (I), showing 30% probability displacement ellipsoids.
	Fig. 2. The crystal packing of (I). For clarity, H atoms not involved in the hydrogen-bonding interactions have been omitted. Hydrogen bonds are shown as dashed lines.

N-Benzyl-N-[4-(methylsulfanyl)-3-nitro-4H-chromen-2-yl]amine

Crystal data

C17H16N2O3S	F(000) = 688
Mr = 328.38	Dx = 1.346 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9200 reflections
a = 10.6411 (7) Å	θ = 2.0–28.0°
b = 19.6795 (12) Å	µ = 0.22 mm^−1
c = 8.2268 (5) Å	T = 293 K
β = 109.795 (1)°	Block, pale yellow
V = 1620.99 (18) Å^3	0.21 × 0.20 × 0.20 mm
Z = 4

Data collection

CCD area detector diffractometer	3140 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.022
Graphite monochromator	θmax = 28.0°, θmin = 2.0°
ω scans	h = −13→14
18458 measured reflections	k = −25→25
3844 independent reflections	l = −10→10

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.138	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0853P)^2 + 0.1762P] where P = (Fo^2 + 2Fc^2)/3
3844 reflections	(Δ/σ)max = 0.001
209 parameters	Δρmax = 0.31 e Å^−3
0 restraints	Δρmin = −0.14 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
N2	0.25737 (12)	0.02685 (7)	0.75730 (15)	0.0532 (3)
N1	0.35686 (12)	0.04972 (7)	1.12667 (14)	0.0535 (3)
H1	0.4151	0.0402	1.0789	0.064*
C4	0.04354 (13)	0.07722 (7)	0.74250 (16)	0.0467 (3)
H4	0.0032	0.0397	0.6640	0.056*
O2	0.20397 (11)	0.01437 (7)	0.60086 (13)	0.0678 (3)
O3	0.37783 (11)	0.01208 (7)	0.83399 (15)	0.0728 (4)
S1	0.03827 (5)	0.15310 (2)	0.60905 (5)	0.06725 (17)
C3	0.18208 (13)	0.05667 (7)	0.84587 (16)	0.0452 (3)
C2	0.23497 (13)	0.06399 (7)	1.02481 (16)	0.0458 (3)
O1	0.15851 (10)	0.08751 (6)	1.11296 (11)	0.0542 (3)
C6	0.02092 (14)	0.09371 (7)	1.03243 (17)	0.0480 (3)
C5	−0.03877 (14)	0.08794 (7)	0.85670 (18)	0.0474 (3)
C10	−0.17657 (15)	0.09545 (9)	0.7899 (2)	0.0619 (4)
H10	−0.2204	0.0910	0.6716	0.074*
C9	−0.24914 (18)	0.10938 (10)	0.8961 (3)	0.0742 (5)
H9	−0.3412	0.1149	0.8492	0.089*
C8	−0.1857 (2)	0.11521 (9)	1.0713 (3)	0.0735 (5)
H8	−0.2352	0.1249	1.1425	0.088*
C7	−0.04945 (17)	0.10682 (8)	1.1424 (2)	0.0611 (4)
H7	−0.0061	0.1099	1.2611	0.073*
C18	0.0890 (3)	0.21722 (11)	0.7697 (3)	0.1183 (10)
H18A	0.0196	0.2246	0.8179	0.177*
H18B	0.1056	0.2586	0.7188	0.177*
H18C	0.1691	0.2031	0.8593	0.177*
C11	0.40077 (15)	0.04888 (8)	1.31611 (17)	0.0565 (4)
H11A	0.4718	0.0158	1.3594	0.068*
H11B	0.3268	0.0346	1.3518	0.068*
C12	0.44982 (14)	0.11682 (8)	1.39505 (16)	0.0525 (3)
C13	0.56909 (17)	0.14255 (10)	1.3900 (2)	0.0665 (4)
H13	0.6191	0.1170	1.3388	0.080*
C14	0.6156 (2)	0.20484 (12)	1.4587 (2)	0.0834 (6)
H14	0.6957	0.2215	1.4527	0.100*
C15	0.5443 (3)	0.24215 (12)	1.5355 (3)	0.0916 (7)
H15	0.5750	0.2847	1.5806	0.110*
C16	0.4275 (3)	0.21747 (13)	1.5472 (3)	0.0942 (7)
H16	0.3803	0.2429	1.6025	0.113*
C17	0.37892 (19)	0.15447 (11)	1.4765 (2)	0.0742 (5)
H17	0.2993	0.1378	1.4841	0.089*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N2	0.0525 (7)	0.0658 (7)	0.0419 (6)	0.0078 (5)	0.0166 (5)	−0.0038 (5)
N1	0.0469 (6)	0.0737 (8)	0.0361 (5)	0.0047 (5)	0.0090 (5)	−0.0003 (5)
C4	0.0478 (7)	0.0531 (7)	0.0357 (6)	0.0034 (5)	0.0096 (5)	−0.0067 (5)
O2	0.0720 (7)	0.0911 (8)	0.0401 (5)	0.0100 (6)	0.0186 (5)	−0.0155 (5)
O3	0.0527 (6)	0.1100 (10)	0.0556 (6)	0.0225 (6)	0.0181 (5)	−0.0040 (6)
S1	0.0800 (3)	0.0783 (3)	0.0445 (2)	0.0173 (2)	0.0224 (2)	0.01423 (17)
C3	0.0463 (7)	0.0526 (7)	0.0357 (6)	0.0036 (5)	0.0125 (5)	−0.0044 (5)
C2	0.0474 (7)	0.0509 (7)	0.0383 (6)	0.0011 (5)	0.0137 (5)	−0.0024 (5)
O1	0.0529 (6)	0.0727 (7)	0.0362 (5)	0.0040 (5)	0.0141 (4)	−0.0092 (4)
C6	0.0521 (7)	0.0467 (7)	0.0473 (7)	0.0026 (5)	0.0195 (6)	−0.0022 (5)
C5	0.0487 (7)	0.0461 (7)	0.0474 (7)	0.0026 (5)	0.0163 (6)	−0.0017 (5)
C10	0.0502 (8)	0.0662 (9)	0.0659 (9)	0.0054 (7)	0.0150 (7)	0.0034 (7)
C9	0.0534 (9)	0.0779 (11)	0.0961 (14)	0.0118 (8)	0.0318 (9)	0.0089 (10)
C8	0.0776 (12)	0.0687 (10)	0.0941 (14)	0.0110 (9)	0.0551 (11)	0.0030 (9)
C7	0.0745 (10)	0.0607 (9)	0.0585 (9)	0.0058 (7)	0.0361 (8)	−0.0011 (7)
C18	0.202 (3)	0.0594 (11)	0.0967 (17)	−0.0161 (15)	0.0548 (18)	0.0027 (11)
C11	0.0563 (8)	0.0718 (9)	0.0349 (6)	0.0031 (7)	0.0070 (6)	0.0061 (6)
C12	0.0498 (7)	0.0703 (9)	0.0312 (6)	0.0041 (6)	0.0054 (5)	0.0050 (5)
C13	0.0625 (9)	0.0880 (12)	0.0486 (8)	−0.0040 (8)	0.0183 (7)	0.0017 (8)
C14	0.0843 (13)	0.1019 (15)	0.0603 (10)	−0.0276 (11)	0.0197 (9)	−0.0012 (10)
C15	0.1118 (18)	0.0873 (14)	0.0661 (12)	−0.0217 (13)	0.0175 (12)	−0.0149 (10)
C16	0.1037 (17)	0.1037 (16)	0.0743 (13)	0.0117 (13)	0.0289 (12)	−0.0271 (12)
C17	0.0624 (10)	0.1006 (14)	0.0596 (10)	−0.0003 (9)	0.0207 (8)	−0.0162 (9)

Geometric parameters (Å, º)

N2—O2	1.243 (2)	C8—C7	1.378 (3)
N2—O3	1.256 (2)	C8—H8	0.93
N2—C3	1.383 (2)	C7—H7	0.93
N1—C2	1.314 (2)	C18—H18A	0.96
N1—C11	1.468 (2)	C18—H18B	0.96
N1—H1	0.86	C18—H18C	0.96
C4—C3	1.487 (2)	C11—C12	1.501 (2)
C4—C5	1.501 (2)	C11—H11A	0.97
C4—S1	1.843 (1)	C11—H11B	0.97
C4—H4	0.98	C12—C13	1.380 (2)
S1—C18	1.774 (2)	C12—C17	1.382 (2)
C3—C2	1.394 (2)	C13—C14	1.370 (3)
C2—O1	1.342 (2)	C13—H13	0.93
O1—C6	1.393 (2)	C14—C15	1.356 (3)
C6—C5	1.3727 (19)	C14—H14	0.93
C6—C7	1.380 (2)	C15—C16	1.367 (3)
C5—C10	1.389 (2)	C15—H15	0.93
C10—C9	1.375 (3)	C16—C17	1.393 (3)
C10—H10	0.93	C16—H16	0.93
C9—C8	1.374 (3)	C17—H17	0.93
C9—H9	0.93
O2—N2—O3	120.4 (1)	C7—C8—H8	119.7
O2—N2—C3	119.1 (1)	C6—C7—C8	118.1 (2)
O3—N2—C3	120.6 (1)	C6—C7—H7	121.0
C2—N1—C11	124.75 (12)	C8—C7—H7	121.0
C2—N1—H1	117.6	S1—C18—H18A	109.5
C11—N1—H1	117.6	S1—C18—H18B	109.5
C3—C4—C5	110.9 (1)	H18A—C18—H18B	109.5
C3—C4—S1	112.67 (10)	S1—C18—H18C	109.5
C5—C4—S1	110.65 (9)	H18A—C18—H18C	109.5
C3—C4—H4	107.5	H18B—C18—H18C	109.5
C5—C4—H4	107.5	N1—C11—C12	112.85 (12)
S1—C4—H4	107.5	N1—C11—H11A	109.0
C18—S1—C4	101.1 (1)	C12—C11—H11A	109.0
N2—C3—C2	120.10 (12)	N1—C11—H11B	109.0
N2—C3—C4	116.95 (11)	C12—C11—H11B	109.0
C2—C3—C4	122.9 (1)	H11A—C11—H11B	107.8
N1—C2—O1	112.15 (11)	C13—C12—C17	118.5 (2)
N1—C2—C3	127.56 (12)	C13—C12—C11	120.17 (14)
O1—C2—C3	120.3 (1)	C17—C12—C11	121.37 (15)
C2—O1—C6	120.3 (1)	C14—C13—C12	121.5 (2)
C5—C6—C7	123.1 (1)	C14—C13—H13	119.2
C5—C6—O1	122.1 (1)	C12—C13—H13	119.2
C7—C6—O1	114.88 (13)	C15—C14—C13	119.7 (2)
C6—C5—C10	117.3 (1)	C15—C14—H14	120.1
C6—C5—C4	120.73 (12)	C13—C14—H14	120.1
C10—C5—C4	121.96 (13)	C14—C15—C16	120.4 (2)
C9—C10—C5	121.0 (2)	C14—C15—H15	119.8
C9—C10—H10	119.5	C16—C15—H15	119.8
C5—C10—H10	119.5	C15—C16—C17	120.3 (2)
C8—C9—C10	120.07 (16)	C15—C16—H16	119.8
C8—C9—H9	120.0	C17—C16—H16	119.8
C10—C9—H9	120.0	C12—C17—C16	119.54 (19)
C9—C8—C7	120.52 (15)	C12—C17—H17	120.2
C9—C8—H8	119.7	C16—C17—H17	120.2
C3—C4—S1—C18	−70.72 (14)	O1—C6—C5—C4	−2.4 (2)
C5—C4—S1—C18	54.02 (15)	C3—C4—C5—C6	14.6 (2)
O2—N2—C3—C2	172.60 (13)	S1—C4—C5—C6	−111.14 (12)
O3—N2—C3—C2	−6.9 (2)	C3—C4—C5—C10	−168.30 (14)
O2—N2—C3—C4	−5.0 (2)	S1—C4—C5—C10	65.95 (16)
O3—N2—C3—C4	175.48 (13)	C6—C5—C10—C9	1.2 (2)
C5—C4—C3—N2	162.24 (12)	C4—C5—C10—C9	−175.96 (15)
S1—C4—C3—N2	−73.14 (14)	C5—C10—C9—C8	−0.9 (3)
C5—C4—C3—C2	−15.3 (2)	C10—C9—C8—C7	−0.4 (3)
S1—C4—C3—C2	109.29 (13)	C5—C6—C7—C8	−0.8 (2)
C11—N1—C2—O1	9.1 (2)	O1—C6—C7—C8	178.46 (14)
C11—N1—C2—C3	−170.35 (14)	C9—C8—C7—C6	1.2 (3)
N2—C3—C2—N1	5.1 (2)	C2—N1—C11—C12	−89.07 (17)
C4—C3—C2—N1	−177.39 (14)	N1—C11—C12—C13	−70.50 (17)
N2—C3—C2—O1	−174.28 (12)	N1—C11—C12—C17	110.61 (16)
C4—C3—C2—O1	3.2 (2)	C17—C12—C13—C14	−2.0 (2)
N1—C2—O1—C6	−168.35 (12)	C11—C12—C13—C14	179.05 (15)
C3—C2—O1—C6	11.1 (2)	C12—C13—C14—C15	0.8 (3)
C2—O1—C6—C5	−11.7 (2)	C13—C14—C15—C16	1.0 (3)
C2—O1—C6—C7	169.09 (13)	C14—C15—C16—C17	−1.6 (4)
C7—C6—C5—C10	−0.4 (2)	C13—C12—C17—C16	1.5 (3)
O1—C6—C5—C10	−179.58 (13)	C11—C12—C17—C16	−179.61 (17)
C7—C6—C5—C4	176.81 (14)	C15—C16—C17—C12	0.3 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O3	0.86	2.00	2.600 (2)	126
N1—H1···O3^i	0.86	2.31	2.989 (2)	136
C7—H7···S1^ii	0.93	2.87	3.743 (2)	157

Symmetry codes: (i) −x+1, −y, −z+2; (ii) x, y, z+1.