2,9-Dichloro-1,10-phenanthroline

Nadeem, S.; Shah, M.R.; Ng, S.W.

doi:10.1107/S1600536809011180

organic compounds

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ISSN: 2056-9890

Volume 65| Part 4| April 2009| Page o922

doi:10.1107/S1600536809011180

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2,9-Dichloro-1,10-phenanthroline

Said Nadeem,^a Muhammad Raza Shah ^a and Seik Weng Ng ^b ^*

^aHEJ Research Institute of Chemistry, International Center for Chemical and Biological Sciences, University of Karachi, Karachi 75270, Pakistan, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 25 March 2009; accepted 26 March 2009; online 31 March 2009)

The title molecule, C₁₂H₆Cl₂N₂, is almost planar (the r.m.s. deviation of C atoms is 0.04 Å). The C—N and C—C distances indicate delocalization of the π-electrons in the aromatic fused-ring system.

Related literature

For the synthesis, see: Yamada et al. (1990 ). The compound is used for the synthesis of other phenanthroline-like heterocycles; see: Hamilton et al. (2004 ); Ohira et al. (2005 ); Zong & Thummel (2004 , 2005 ).

Experimental

Crystal data

C₁₂H₆Cl₂N₂
M_r = 249.09
Orthorhombic, P n a 2₁
a = 19.4035 (3) Å
b = 4.4330 (1) Å
c = 11.7695 (2) Å
V = 1012.36 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.61 mm⁻¹
T = 100 K
0.36 × 0.18 × 0.02 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.811, T_max = 0.988
8646 measured reflections
2315 independent reflections
2248 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.022
wR(F²) = 0.061
S = 1.02
2315 reflections
145 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.16 e Å⁻³
Absolute structure: Flack (1983 ), 1097 Friedel pairs
Flack parameter: −0.01 (4)

Data collection: APEX2 (Bruker, 2008 ); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809011180/tk2404sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809011180/tk2404Isup2.hkl

checkCIF report

Related literature top

For the synthesis, see: Yamada et al. (1990). The compound is used for the synthesis of other phenanthroline-like heterocycles; see: Hamilton et al. (2004); Ohira et al. (2005); Zong & Thummel (2004, 2005).

Experimental top

A mixture of 6,7-dihydro-3H-[1,4]diazepino[1,2,3,4-lmn][1,10]phenanthroline-3,9(5H)-dione (1.7 g, 6.7 mmol) and phosphorus pentachloride (3 g, 14.4 mmol) was reacted in thionyl chloride (20 ml, 170 mmol) for 16 h at room temperature. The thionyl chloride was removed under reduced pressure and the residue was suspended in cold ammonium hydroxide. A light-tan precipitate was formed which was dissolved in hot benzene; crystals were obtained upon recrystallization from benzene (1.1 g 65%)

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2009).

Figures top

Fig. 1. Thermal ellipsoid plot (Barbour, 2001) plot of C₁₂H₆Cl₂N₂ at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

2,9-Dichloro-1,10-phenanthroline top

Crystal data top

C₁₂H₆Cl₂N₂	F(000) = 504
M_r = 249.09	D_x = 1.634 Mg m⁻³
Orthorhombic, Pna2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 5870 reflections
a = 19.4035 (3) Å	θ = 2.7–28.3°
b = 4.4330 (1) Å	µ = 0.61 mm⁻¹
c = 11.7695 (2) Å	T = 100 K
V = 1012.36 (3) Å³	Plate, colourless
Z = 4	0.36 × 0.18 × 0.02 mm

Data collection top

Bruker SMART APEX diffractometer	2315 independent reflections
Radiation source: fine-focus sealed tube	2248 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
ω scans	θ_max = 27.5°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −25→25
T_min = 0.811, T_max = 0.988	k = −5→5
8646 measured reflections	l = −15→15

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)] = 0.022	H-atom parameters constrained
wR(F²) = 0.061	w = 1/[σ²(F_o²) + (0.0436P)² + 0.147P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max = 0.001
2315 reflections	Δρ_max = 0.27 e Å⁻³
145 parameters	Δρ_min = −0.16 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 1097 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.01 (4)

Crystal data top

C₁₂H₆Cl₂N₂	V = 1012.36 (3) Å³
M_r = 249.09	Z = 4
Orthorhombic, Pna2₁	Mo Kα radiation
a = 19.4035 (3) Å	µ = 0.61 mm⁻¹
b = 4.4330 (1) Å	T = 100 K
c = 11.7695 (2) Å	0.36 × 0.18 × 0.02 mm

Data collection top

Bruker SMART APEX diffractometer	2315 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2248 reflections with I > 2σ(I)
T_min = 0.811, T_max = 0.988	R_int = 0.022
8646 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.022	H-atom parameters constrained
wR(F²) = 0.061	Δρ_max = 0.27 e Å⁻³
S = 1.02	Δρ_min = −0.16 e Å⁻³
2315 reflections	Absolute structure: Flack (1983), 1097 Friedel pairs
145 parameters	Absolute structure parameter: −0.01 (4)
1 restraint

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cl1	0.027691 (18)	0.55270 (8)	0.25010 (3)	0.01876 (10)
Cl2	0.35805 (2)	0.89704 (8)	0.45699 (4)	0.02052 (10)
N1	0.11803 (7)	0.4349 (3)	0.40752 (11)	0.0151 (3)
N2	0.24727 (7)	0.5756 (3)	0.48930 (11)	0.0153 (3)
C1	0.05604 (8)	0.3672 (3)	0.37354 (12)	0.0158 (3)
C2	0.01038 (8)	0.1645 (4)	0.42492 (13)	0.0183 (3)
H2	−0.0341	0.1269	0.3945	0.022*
C3	0.03326 (8)	0.0226 (4)	0.52172 (14)	0.0184 (3)
H3	0.0046	−0.1192	0.5595	0.022*
C4	0.09941 (8)	0.0884 (3)	0.56464 (14)	0.0159 (3)
C5	0.14049 (8)	0.2979 (4)	0.50487 (12)	0.0150 (3)
C6	0.12494 (9)	−0.0487 (3)	0.66693 (14)	0.0178 (3)
H6	0.0980	−0.1968	0.7048	0.021*
C7	0.18689 (8)	0.0307 (4)	0.70984 (13)	0.0176 (3)
H7	0.2025	−0.0587	0.7785	0.021*
C8	0.22933 (8)	0.2478 (3)	0.65313 (13)	0.0158 (3)
C9	0.20767 (8)	0.3756 (3)	0.54864 (13)	0.0150 (3)
C10	0.29315 (8)	0.3417 (4)	0.69870 (14)	0.0189 (3)
H10	0.3088	0.2647	0.7695	0.023*
C11	0.33217 (9)	0.5458 (4)	0.63927 (14)	0.0195 (3)
H11	0.3752	0.6152	0.6676	0.023*
C12	0.30611 (7)	0.6483 (3)	0.53484 (13)	0.0164 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.01835 (17)	0.02130 (17)	0.01663 (17)	0.00087 (13)	−0.00441 (14)	−0.00032 (15)
Cl2	0.01900 (17)	0.02184 (16)	0.02072 (17)	−0.00573 (14)	0.00151 (15)	−0.00218 (15)
N1	0.0165 (6)	0.0163 (6)	0.0124 (6)	0.0010 (5)	0.0008 (5)	−0.0019 (5)
N2	0.0154 (6)	0.0158 (6)	0.0146 (6)	0.0001 (5)	0.0000 (5)	−0.0014 (4)
C1	0.0173 (7)	0.0174 (7)	0.0126 (7)	0.0046 (6)	−0.0004 (6)	−0.0028 (5)
C2	0.0154 (7)	0.0197 (7)	0.0199 (8)	0.0007 (6)	−0.0002 (6)	−0.0062 (6)
C3	0.0183 (8)	0.0186 (7)	0.0182 (8)	−0.0024 (6)	0.0051 (6)	−0.0023 (6)
C4	0.0192 (7)	0.0150 (7)	0.0136 (7)	0.0014 (5)	0.0028 (6)	−0.0030 (5)
C5	0.0158 (7)	0.0170 (7)	0.0121 (6)	0.0017 (5)	0.0013 (5)	−0.0018 (6)
C6	0.0220 (8)	0.0167 (7)	0.0146 (7)	0.0000 (6)	0.0060 (7)	0.0008 (6)
C7	0.0231 (8)	0.0177 (7)	0.0122 (6)	0.0047 (6)	0.0017 (6)	0.0004 (6)
C8	0.0181 (7)	0.0161 (7)	0.0132 (7)	0.0036 (6)	0.0001 (6)	−0.0022 (5)
C9	0.0178 (7)	0.0143 (6)	0.0130 (7)	0.0015 (5)	0.0014 (6)	−0.0027 (6)
C10	0.0212 (8)	0.0212 (8)	0.0145 (7)	0.0056 (6)	−0.0033 (6)	−0.0020 (6)
C11	0.0174 (8)	0.0223 (8)	0.0187 (8)	0.0003 (6)	−0.0041 (6)	−0.0052 (6)
C12	0.0156 (7)	0.0170 (7)	0.0166 (7)	−0.0003 (6)	0.0022 (6)	−0.0030 (6)

Geometric parameters (Å, º) top

Cl1—C1	1.758 (2)	C4—C6	1.437 (2)
Cl2—C12	1.752 (2)	C5—C9	1.443 (2)
N1—C1	1.303 (2)	C6—C7	1.350 (2)
N1—C5	1.368 (2)	C6—H6	0.9500
N2—C12	1.302 (2)	C7—C8	1.432 (2)
N2—C9	1.365 (2)	C7—H7	0.9500
C1—C2	1.399 (2)	C8—C10	1.412 (2)
C2—C3	1.375 (2)	C8—C9	1.418 (2)
C2—H2	0.9500	C10—C11	1.372 (2)
C3—C4	1.410 (2)	C10—H10	0.9500
C3—H3	0.9500	C11—C12	1.405 (2)
C4—C5	1.412 (2)	C11—H11	0.9500

C1—N1—C5	116.68 (13)	C4—C6—H6	119.7
C12—N2—C9	116.36 (14)	C6—C7—C8	120.86 (14)
N1—C1—C2	126.86 (14)	C6—C7—H7	119.6
N1—C1—Cl1	115.78 (12)	C8—C7—H7	119.6
C2—C1—Cl1	117.36 (12)	C10—C8—C9	118.15 (14)
C3—C2—C1	116.59 (14)	C10—C8—C7	121.70 (14)
C3—C2—H2	121.7	C9—C8—C7	120.16 (14)
C1—C2—H2	121.7	N2—C9—C8	122.43 (14)
C2—C3—C4	119.74 (15)	N2—C9—C5	118.74 (14)
C2—C3—H3	120.1	C8—C9—C5	118.81 (14)
C4—C3—H3	120.1	C11—C10—C8	118.99 (15)
C3—C4—C5	118.14 (15)	C11—C10—H10	120.5
C3—C4—C6	121.77 (15)	C8—C10—H10	120.5
C5—C4—C6	120.08 (14)	C10—C11—C12	117.45 (15)
N1—C5—C4	121.97 (14)	C10—C11—H11	121.3
N1—C5—C9	118.72 (14)	C12—C11—H11	121.3
C4—C5—C9	119.29 (14)	N2—C12—C11	126.57 (15)
C7—C6—C4	120.66 (15)	N2—C12—Cl2	116.43 (12)
C7—C6—H6	119.7	C11—C12—Cl2	117.00 (12)

C5—N1—C1—C2	−1.3 (2)	C12—N2—C9—C8	−1.2 (2)
C5—N1—C1—Cl1	178.60 (10)	C12—N2—C9—C5	177.09 (13)
N1—C1—C2—C3	0.2 (2)	C10—C8—C9—N2	2.5 (2)
Cl1—C1—C2—C3	−179.66 (12)	C7—C8—C9—N2	−177.70 (13)
C1—C2—C3—C4	0.8 (2)	C10—C8—C9—C5	−175.77 (13)
C2—C3—C4—C5	−0.8 (2)	C7—C8—C9—C5	4.0 (2)
C2—C3—C4—C6	178.52 (14)	N1—C5—C9—N2	−2.1 (2)
C1—N1—C5—C4	1.3 (2)	C4—C5—C9—N2	179.17 (13)
C1—N1—C5—C9	−177.33 (14)	N1—C5—C9—C8	176.22 (13)
C3—C4—C5—N1	−0.4 (2)	C4—C5—C9—C8	−2.5 (2)
C6—C4—C5—N1	−179.63 (14)	C9—C8—C10—C11	−1.5 (2)
C3—C4—C5—C9	178.30 (14)	C7—C8—C10—C11	178.68 (15)
C6—C4—C5—C9	−1.0 (2)	C8—C10—C11—C12	−0.5 (2)
C3—C4—C6—C7	−176.22 (15)	C9—N2—C12—C11	−1.1 (2)
C5—C4—C6—C7	3.0 (2)	C9—N2—C12—Cl2	178.34 (10)
C4—C6—C7—C8	−1.5 (2)	C10—C11—C12—N2	2.0 (2)
C6—C7—C8—C10	177.72 (15)	C10—C11—C12—Cl2	−177.45 (12)
C6—C7—C8—C9	−2.1 (2)

Experimental details

Crystal data
Chemical formula	C₁₂H₆Cl₂N₂
M_r	249.09
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	100
a, b, c (Å)	19.4035 (3), 4.4330 (1), 11.7695 (2)
V (Å³)	1012.36 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.61
Crystal size (mm)	0.36 × 0.18 × 0.02

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.811, 0.988
No. of measured, independent and observed [I > 2σ(I)] reflections	8646, 2315, 2248
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.022, 0.061, 1.02
No. of reflections	2315
No. of parameters	145
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.16
Absolute structure	Flack (1983), 1097 Friedel pairs
Absolute structure parameter	−0.01 (4)

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2009).

Acknowledgements

We thank the Organization for the Prohibition of Chemical Weapons and the University of Malaya for supporting this study.

References

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