6,7-Dihydro-3H-1,4-diazepino[1,2,3,4-lmn][1,10]phenanthroline-3,9(5H)-dione

Nadeem, S.; Anis, I.; VanDerveer, D.; Shah, M.R.

doi:10.1107/S1600536810024761

organic compounds

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ISSN: 2056-9890

Volume 66| Part 7| July 2010| Page o1853

doi:10.1107/S1600536810024761

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6,7-Dihydro-3H-1,4-diazepino[1,2,3,4-lmn][1,10]phenanthroline-3,9(5H)-dione

Said Nadeem,^a Itrat Anis,^b Donald VanDerveer ^c and Muhammad Raza Shah ^a ^*

^aH.E.J. Research Institute of Chemistry, International Center for Chemical and Biological Sciences, University of Karachi, Karachi 75270, Pakistan, ^bDepartment of Chemistry, University of Karachi, Karachi 75270, Pakistan, and ^cChemistry Department, Clemson University, Clemson, SC 29634-0973, USA
^*Correspondence e-mail: raza_shahm@yahoo.com

(Received 22 June 2010; accepted 24 June 2010; online 30 June 2010)

In the title compound, C₁₅H₁₂N₂O₂, the seven-membered ring bearing the three methylene C atoms displays a puckered conformation, with the methylene C atoms deviating from the plane of the benzene ring by 0.05 (1), 0.98 (1) and 1.04 (1) Å. The phenanthroline unit is not planar; the dihedral angles between this benzene ring and the other pyridyl rings are 9.62 (4) and 9.31 (4)°. The crystal packing is stabilized by π–π interactions between two phenanthroline ring systems, forming a centrosymmetric dimer with a centroid–centroid distance of 3.656 (1) Å.

Related literature

For background to π–π interactions in supramolecular chemistry, see: Sisson et al. (2006 ). For a related structure, see: Nadeem et al. (2009 ).

Experimental

Crystal data

C₁₅H₁₂N₂O₂
M_r = 252.27
Monoclinic, P 2₁ /n
a = 9.1853 (18) Å
b = 13.931 (3) Å
c = 9.4956 (19) Å
β = 111.14 (3)°
V = 1133.3 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 158 K
0.50 × 0.46 × 0.38 mm

Data collection

Rigaku Mercury CCD diffractometer
Absorption correction: multi-scan (REQAB; Jacobson, 1998 ) T_min = 0.952, T_max = 0.963
8367 measured reflections
2309 independent reflections
2115 reflections with I > 2σ(I)
R_int = 0.016

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.111
S = 1.06
2309 reflections
172 parameters
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Data collection: CrystalClear (Rigaku/MSC, 2006 ); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810024761/ng2793sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810024761/ng2793Isup2.hkl

checkCIF report

Comment top

In supramolecular chemistry it is well establish that the self-association of individual molecules can lead to the formation of highly complex and fascinating supramolecular assemblies if π–π interactions contribute to the formation of specific motifs (Sisson et al., 2006). As a part of our ongoing investigation on the nature of π-π (Nadeem et al., 2009) stacking and supramolecular chemistry, the title compound (Figure-1), has been prepared and its crystal structure is reported here. The crystal packing is stabilized by π-π interactions between two phenanthroline ring systems forming a centrosymmetric dimer with a centroid···centroid distance of 3.656 (1) Å. A typical double bond distance 1.236 (2) Å was observed for C1—O1 C8—O2 while a characteristic single bond distances 1.386 (1) Å and 1.393 (1) Å were observed for C1—N1 and C8—N2 respectively.

Related literature top

For background to π–π interactions in supramolecular chemistry, see: Sisson et al. (2006). For a related structure, see: Nadeem et al. (2009).

Experimental top

To an ice-cooled solution of potassium hexacyanoferrate(III) (58.6g) and sodium hydroxide (26.8g) in water (100ml) were added in small portions a solution of 6,7-dihydro-5H-[1,4]diazepino[1,2,3,4-lmn][1,10]phenanthroline-4,8-diium bromide (7.6g) in water (50ml),maintaining the temperature under 278 K for 10 minutes. The resulting mixture was neutralized by a dropwise addition of concentrated hydrochloric acid at 273 K. The residual brown pasty material was extracted three times with chloroform, subjected to column chromatography (DCM:MeOH; 100ml:1ml v/v), evaporated to dryness, recrystallization from methanol afforded 1.5g (30%) of title compound as pale yellow needles.

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2006); cell refinement: CrystalClear (Rigaku/MSC, 2006); data reduction: CrystalClear (Rigaku/MSC, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

Fig. 1. Molecular Structure of (I) with atom labels and 50% probability displacement ellipsoids.

6,7-Dihydro-3H-1,4-diazepino[1,2,3,4-lmn][1,10]phenanthroline- 3,9(5H)-dione top

Crystal data top

C₁₅H₁₂N₂O₂	F(000) = 528
M_r = 252.27	D_x = 1.478 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 9.1853 (18) Å	Cell parameters from 3526 reflections
b = 13.931 (3) Å	θ = 2.7–26.4°
c = 9.4956 (19) Å	µ = 0.10 mm⁻¹
β = 111.14 (3)°	T = 158 K
V = 1133.3 (4) Å³	Chip, yellow
Z = 4	0.50 × 0.46 × 0.38 mm

Data collection top

Rigaku Mercury CCD diffractometer	2309 independent reflections
Radiation source: Sealed Tube	2115 reflections with I > 2σ(I)
Graphite Monochromator monochromator	R_int = 0.016
Detector resolution: 14.6306 pixels mm^-1	θ_max = 26.4°, θ_min = 2.7°
ω scans	h = −11→9
Absorption correction: multi-scan (REQAB; Jacobson, 1998)	k = −17→17
T_min = 0.952, T_max = 0.963	l = −10→11
8367 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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.111	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0632P)² + 0.3698P] where P = (F_o² + 2F_c²)/3
2309 reflections	(Δ/σ)_max < 0.001
172 parameters	Δρ_max = 0.23 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₁₅H₁₂N₂O₂	V = 1133.3 (4) Å³
M_r = 252.27	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.1853 (18) Å	µ = 0.10 mm⁻¹
b = 13.931 (3) Å	T = 158 K
c = 9.4956 (19) Å	0.50 × 0.46 × 0.38 mm
β = 111.14 (3)°

Data collection top

Rigaku Mercury CCD diffractometer	2309 independent reflections
Absorption correction: multi-scan (REQAB; Jacobson, 1998)	2115 reflections with I > 2σ(I)
T_min = 0.952, T_max = 0.963	R_int = 0.016
8367 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.111	H-atom parameters constrained
S = 1.06	Δρ_max = 0.23 e Å⁻³
2309 reflections	Δρ_min = −0.23 e Å⁻³
172 parameters

Special details top

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. 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 > 2sigma(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
N1	1.02892 (11)	0.14451 (7)	0.36246 (11)	0.0183 (2)
N2	0.79115 (11)	0.11065 (7)	0.06165 (11)	0.0186 (2)
O1	1.09796 (11)	0.14573 (7)	0.61843 (10)	0.0313 (2)
O2	0.53670 (10)	0.10333 (7)	−0.09893 (10)	0.0285 (2)
C1	1.13585 (14)	0.13175 (9)	0.50775 (13)	0.0219 (3)
C2	1.29358 (14)	0.10579 (9)	0.52135 (13)	0.0239 (3)
H2	1.3694	0.0911	0.6190	0.029*
C3	1.33514 (14)	0.10204 (9)	0.39944 (14)	0.0234 (3)
H3	1.4423	0.0905	0.4128	0.028*
C3A	1.22264 (13)	0.11496 (8)	0.24970 (13)	0.0193 (3)
C4	1.26651 (14)	0.11749 (8)	0.12166 (14)	0.0228 (3)
H4	1.3735	0.1075	0.1328	0.027*
C5	1.15645 (14)	0.13419 (9)	−0.01825 (13)	0.0223 (3)
H5	1.1879	0.1443	−0.1032	0.027*
C5A	0.99677 (14)	0.13661 (8)	−0.03786 (13)	0.0197 (3)
C6	0.87822 (15)	0.14730 (9)	−0.18533 (13)	0.0238 (3)
H6	0.9079	0.1576	−0.2713	0.029*
C7	0.72644 (15)	0.14297 (9)	−0.20391 (13)	0.0250 (3)
H7	0.6497	0.1561	−0.3018	0.030*
C8	0.67481 (14)	0.11909 (8)	−0.08064 (14)	0.0216 (3)
C8A	0.94915 (13)	0.12578 (8)	0.08617 (13)	0.0171 (3)
C8B	1.06584 (13)	0.12776 (8)	0.23397 (13)	0.0170 (2)
C9	0.74874 (13)	0.06207 (8)	0.17982 (13)	0.0216 (3)
H9A	0.8241	0.0129	0.2259	0.026*
H9B	0.6488	0.0318	0.1341	0.026*
C10	0.74195 (14)	0.13128 (9)	0.30056 (14)	0.0239 (3)
H10A	0.7405	0.0961	0.3869	0.029*
H10B	0.6483	0.1689	0.2625	0.029*
C11	0.88345 (13)	0.19676 (8)	0.34603 (13)	0.0209 (3)
H11A	0.8667	0.2460	0.2712	0.025*
H11B	0.8950	0.2273	0.4401	0.025*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0176 (5)	0.0208 (5)	0.0166 (5)	0.0005 (4)	0.0063 (4)	0.0000 (4)
N2	0.0164 (5)	0.0197 (5)	0.0181 (5)	−0.0012 (4)	0.0044 (4)	0.0005 (4)
O1	0.0303 (5)	0.0472 (6)	0.0171 (4)	0.0023 (4)	0.0094 (4)	0.0011 (4)
O2	0.0179 (4)	0.0298 (5)	0.0316 (5)	−0.0017 (3)	0.0015 (4)	0.0023 (4)
C1	0.0220 (6)	0.0245 (6)	0.0178 (5)	−0.0021 (4)	0.0055 (4)	0.0008 (4)
C2	0.0206 (6)	0.0270 (6)	0.0194 (5)	−0.0007 (5)	0.0016 (4)	0.0024 (4)
C3	0.0165 (5)	0.0260 (6)	0.0250 (6)	0.0013 (4)	0.0040 (5)	0.0009 (5)
C3A	0.0183 (6)	0.0187 (5)	0.0204 (6)	−0.0006 (4)	0.0065 (4)	−0.0011 (4)
C4	0.0201 (6)	0.0238 (6)	0.0267 (6)	−0.0010 (4)	0.0112 (5)	−0.0032 (5)
C5	0.0255 (6)	0.0229 (6)	0.0220 (6)	−0.0029 (5)	0.0130 (5)	−0.0027 (4)
C5A	0.0228 (6)	0.0174 (5)	0.0189 (5)	−0.0016 (4)	0.0077 (5)	−0.0009 (4)
C6	0.0296 (6)	0.0231 (6)	0.0177 (6)	−0.0016 (5)	0.0073 (5)	−0.0001 (4)
C7	0.0264 (6)	0.0248 (6)	0.0180 (5)	0.0000 (5)	0.0011 (5)	0.0005 (4)
C8	0.0202 (6)	0.0172 (5)	0.0231 (6)	−0.0003 (4)	0.0026 (5)	−0.0009 (4)
C8A	0.0174 (5)	0.0151 (5)	0.0189 (6)	−0.0007 (4)	0.0065 (4)	−0.0005 (4)
C8B	0.0177 (6)	0.0157 (5)	0.0176 (5)	−0.0007 (4)	0.0063 (4)	0.0001 (4)
C9	0.0188 (5)	0.0225 (6)	0.0236 (6)	−0.0034 (4)	0.0077 (4)	0.0019 (4)
C10	0.0195 (6)	0.0290 (6)	0.0254 (6)	−0.0010 (5)	0.0107 (5)	0.0003 (5)
C11	0.0190 (5)	0.0226 (6)	0.0216 (5)	0.0019 (4)	0.0081 (4)	−0.0011 (4)

Geometric parameters (Å, º) top

N1—C1	1.3866 (16)	C5—C5A	1.4107 (17)
N1—C8B	1.3987 (15)	C5—H5	0.9600
N1—C11	1.4795 (14)	C5A—C8A	1.4044 (16)
N2—C8	1.3929 (16)	C5A—C6	1.4385 (17)
N2—C8A	1.4005 (15)	C6—C7	1.3420 (18)
N2—C9	1.4779 (14)	C6—H6	0.9600
O1—C1	1.2358 (15)	C7—C8	1.4512 (18)
O2—C8	1.2364 (15)	C7—H7	0.9600
C1—C2	1.4531 (17)	C8A—C8B	1.4264 (17)
C2—C3	1.3443 (17)	C9—C10	1.5165 (17)
C2—H2	0.9600	C9—H9A	0.9600
C3—C3A	1.4361 (17)	C9—H9B	0.9600
C3—H3	0.9600	C10—C11	1.5176 (16)
C3A—C8B	1.4048 (16)	C10—H10A	0.9600
C3A—C4	1.4124 (17)	C10—H10B	0.9600
C4—C5	1.3684 (18)	C11—H11A	0.9600
C4—H4	0.9600	C11—H11B	0.9600

C1—N1—C8B	122.61 (10)	C6—C7—C8	122.03 (11)
C1—N1—C11	117.18 (10)	C6—C7—H7	119.0
C8B—N1—C11	118.94 (9)	C8—C7—H7	119.0
C8—N2—C8A	122.35 (10)	O2—C8—N2	120.71 (11)
C8—N2—C9	117.07 (9)	O2—C8—C7	123.00 (11)
C8A—N2—C9	118.93 (9)	N2—C8—C7	116.25 (11)
O1—C1—N1	120.68 (11)	N2—C8A—C5A	119.61 (10)
O1—C1—C2	122.76 (11)	N2—C8A—C8B	122.17 (10)
N1—C1—C2	116.50 (10)	C5A—C8A—C8B	118.19 (11)
C3—C2—C1	121.12 (11)	N1—C8B—C3A	119.36 (10)
C3—C2—H2	119.4	N1—C8B—C8A	121.94 (10)
C1—C2—H2	119.4	C3A—C8B—C8A	118.68 (11)
C2—C3—C3A	121.42 (11)	N2—C9—C10	112.13 (10)
C2—C3—H3	119.3	N2—C9—H9A	109.2
C3A—C3—H3	119.3	C10—C9—H9A	109.2
C8B—C3A—C4	120.34 (11)	N2—C9—H9B	109.2
C8B—C3A—C3	117.73 (11)	C10—C9—H9B	109.2
C4—C3A—C3	121.91 (11)	H9A—C9—H9B	107.9
C5—C4—C3A	119.98 (11)	C9—C10—C11	109.44 (9)
C5—C4—H4	120.0	C9—C10—H10A	109.8
C3A—C4—H4	120.0	C11—C10—H10A	109.8
C4—C5—C5A	120.08 (11)	C9—C10—H10B	109.8
C4—C5—H5	120.0	C11—C10—H10B	109.8
C5A—C5—H5	120.0	H10A—C10—H10B	108.2
C8A—C5A—C5	120.67 (11)	N1—C11—C10	112.49 (10)
C8A—C5A—C6	118.17 (11)	N1—C11—H11A	109.1
C5—C5A—C6	121.14 (11)	C10—C11—H11A	109.1
C7—C6—C5A	120.61 (11)	N1—C11—H11B	109.1
C7—C6—H6	119.7	C10—C11—H11B	109.1
C5A—C6—H6	119.7	H11A—C11—H11B	107.8

C8B—N1—C1—O1	−178.75 (11)	C8—N2—C8A—C8B	172.78 (10)
C11—N1—C1—O1	14.27 (16)	C9—N2—C8A—C8B	−22.26 (15)
C8B—N1—C1—C2	3.94 (16)	C5—C5A—C8A—N2	−168.25 (11)
C11—N1—C1—C2	−163.05 (10)	C6—C5A—C8A—N2	9.93 (15)
O1—C1—C2—C3	−172.18 (12)	C5—C5A—C8A—C8B	9.86 (16)
N1—C1—C2—C3	5.07 (17)	C6—C5A—C8A—C8B	−171.97 (10)
C1—C2—C3—C3A	−5.67 (19)	C1—N1—C8B—C3A	−12.22 (16)
C2—C3—C3A—C8B	−2.60 (17)	C11—N1—C8B—C3A	154.55 (10)
C2—C3—C3A—C4	175.74 (11)	C1—N1—C8B—C8A	169.50 (10)
C8B—C3A—C4—C5	1.19 (17)	C11—N1—C8B—C8A	−23.73 (15)
C3—C3A—C4—C5	−177.11 (11)	C4—C3A—C8B—N1	−167.08 (10)
C3A—C4—C5—C5A	−8.16 (17)	C3—C3A—C8B—N1	11.29 (16)
C4—C5—C5A—C8A	2.53 (17)	C4—C3A—C8B—C8A	11.25 (16)
C4—C5—C5A—C6	−175.58 (11)	C3—C3A—C8B—C8A	−170.38 (10)
C8A—C5A—C6—C7	−2.72 (17)	N2—C8A—C8B—N1	−20.18 (16)
C5—C5A—C6—C7	175.44 (11)	C5A—C8A—C8B—N1	161.76 (10)
C5A—C6—C7—C8	−5.58 (18)	N2—C8A—C8B—C3A	161.53 (11)
C8A—N2—C8—O2	178.52 (10)	C5A—C8A—C8B—C3A	−16.53 (15)
C9—N2—C8—O2	13.30 (16)	C8—N2—C9—C10	−109.99 (11)
C8A—N2—C8—C7	1.04 (16)	C8A—N2—C9—C10	84.27 (12)
C9—N2—C8—C7	−164.18 (10)	N2—C9—C10—C11	−44.99 (13)
C6—C7—C8—O2	−170.97 (12)	C1—N1—C11—C10	−108.30 (11)
C6—C7—C8—N2	6.44 (17)	C8B—N1—C11—C10	84.22 (12)
C8—N2—C8A—C5A	−9.19 (16)	C9—C10—C11—N1	−42.52 (13)
C9—N2—C8A—C5A	155.77 (10)

Experimental details

Crystal data
Chemical formula	C₁₅H₁₂N₂O₂
M_r	252.27
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	158
a, b, c (Å)	9.1853 (18), 13.931 (3), 9.4956 (19)
β (°)	111.14 (3)
V (Å³)	1133.3 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.50 × 0.46 × 0.38

Data collection
Diffractometer	Rigaku Mercury CCD diffractometer
Absorption correction	Multi-scan (REQAB; Jacobson, 1998)
T_min, T_max	0.952, 0.963
No. of measured, independent and observed [I > 2σ(I)] reflections	8367, 2309, 2115
R_int	0.016
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.111, 1.06
No. of reflections	2309
No. of parameters	172
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.23

Computer programs: CrystalClear (Rigaku/MSC, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Acknowledgements

The authors thank the Pakistan Science Foundation for financial support.

References

Jacobson, R. (1998). REQAB. Molecular Structure Corporation, The Woodlands, Texas, USA. Google Scholar
Nadeem, S., Shah, M. R. & VanDerveer, D. (2009). Acta Cryst. E65, o897. Web of Science CSD CrossRef IUCr Journals Google Scholar
Rigaku/MSC (2006). CrystalClear. Rigaku/MSC, The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sisson, A. L., Shah, M. R., Bhosale, S. & Matile, S. (2006). Chem. Soc. Rev. 35, 1269–1286 Web of Science CrossRef PubMed CAS Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar