N,N′-Bis(3-bromo-2-hy­droxy­benzyl­idene)propane-1,3-di­amine

Wang, X.-Z.

doi:10.1107/S1600536813025403

organic compounds

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Volume 69| Part 10| October 2013| Page o1584

doi:10.1107/S1600536813025403

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N,N′-Bis(3-bromo-2-hydroxybenzylidene)propane-1,3-diamine

Xiao-Zhen Wang ^a ^*

^aCollege of Chemistry, Dalian University of Technology, Dalian 116024, People's Republic of China
^*Correspondence e-mail: xzwang@mail.dlut.edu.cn

(Received 10 September 2013; accepted 13 September 2013; online 25 September 2013)

In the title compound, C₁₇H₁₆Br₂N₂O₂, the dihedral angle between the benzene rings is 57.7 (3)°. The conformation of the central N—C—C—C—N chain is gauche-anti [torsion angles = −64.2 (4) and −167.8 (4)°]. Two intramolecular O—H⋯N hydrogen bonds occur. In the crystal, molecules are linked by pairs of C—H⋯O hydrogen bonds, forming inversion dimers.

CCDC reference: 960930

Related literature

For a related structure, see: Elerman et al. (1998 ).

Experimental

Crystal data

C₁₇H₁₆Br₂N₂O₂
M_r = 440.14
Monoclinic, P 2₁ /c
a = 12.779 (1) Å
b = 10.1894 (8) Å
c = 14.3953 (12) Å
β = 113.744 (2)°
V = 1715.8 (2) Å³
Z = 4
Mo Kα radiation
μ = 4.74 mm⁻¹
T = 298 K
0.23 × 0.22 × 0.22 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ) T_min = 0.409, T_max = 0.422
19018 measured reflections
3728 independent reflections
2669 reflections with I > 2σ(I)
R_int = 0.055

Refinement

R[F² > 2σ(F²)] = 0.054
wR(F²) = 0.141
S = 1.07
3728 reflections
210 parameters
H-atom parameters constrained
Δρ_max = 0.73 e Å⁻³
Δρ_min = −1.01 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1	0.82	1.83	2.567 (4)	148
O2—H2⋯N2	0.82	1.82	2.553 (5)	149
C7—H7⋯O2ⁱ	0.93	2.60	3.490 (5)	161
Symmetry code: (i) -x, -y, -z+1.

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

CCDC reference: 960930

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536813025403/hb7137sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813025403/hb7137Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813025403/hb7137Isup3.cml

checkCIF report

Related literature top

For a related structure, see: Elerman et al. (1998).

Experimental top

3-Bromosalicylaldehyde (1 mmol, 0.20 g) and propane-1,3-diamine (0.5 mmol, 0.037 g) were dissolved and stirred in 50 ml methanol at room temperature. The resulting yellow solution was kept in air for a few days, generating yellow blocks as the solvent slowly evaporated.

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound with ellipsoids drawn at the 30% probability level.

N,N'-Bis(3-bromo-2-hydroxybenzylidene)propane-1,3-diamine top

Crystal data top

C₁₇H₁₆Br₂N₂O₂	F(000) = 872
M_r = 440.14	D_x = 1.704 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 12.779 (1) Å	Cell parameters from 8352 reflections
b = 10.1894 (8) Å	θ = 2.5–27.9°
c = 14.3953 (12) Å	µ = 4.74 mm⁻¹
β = 113.744 (2)°	T = 298 K
V = 1715.8 (2) Å³	Block, yellow
Z = 4	0.23 × 0.22 × 0.22 mm

Data collection top

Bruker SMART CCD diffractometer	3728 independent reflections
Radiation source: fine-focus sealed tube	2669 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.055
ω scans	θ_max = 27.0°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −16→16
T_min = 0.409, T_max = 0.422	k = −13→12
19018 measured reflections	l = −18→18

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)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.141	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0633P)² + 2.4024P] where P = (F_o² + 2F_c²)/3
3728 reflections	(Δ/σ)_max = 0.001
210 parameters	Δρ_max = 0.73 e Å⁻³
0 restraints	Δρ_min = −1.01 e Å⁻³

Crystal data top

C₁₇H₁₆Br₂N₂O₂	V = 1715.8 (2) Å³
M_r = 440.14	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.779 (1) Å	µ = 4.74 mm⁻¹
b = 10.1894 (8) Å	T = 298 K
c = 14.3953 (12) Å	0.23 × 0.22 × 0.22 mm
β = 113.744 (2)°

Data collection top

Bruker SMART CCD diffractometer	3728 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2007)	2669 reflections with I > 2σ(I)
T_min = 0.409, T_max = 0.422	R_int = 0.055
19018 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	0 restraints
wR(F²) = 0.141	H-atom parameters constrained
S = 1.07	Δρ_max = 0.73 e Å⁻³
3728 reflections	Δρ_min = −1.01 e Å⁻³
210 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
Br1	0.30295 (5)	0.46157 (5)	0.10435 (4)	0.0628 (2)
Br2	−0.37545 (5)	0.26857 (7)	0.63883 (5)	0.0760 (2)
N1	0.0868 (3)	0.1060 (3)	0.2505 (2)	0.0387 (8)
N2	−0.0781 (3)	0.2245 (4)	0.4529 (3)	0.0454 (9)
O1	0.1442 (2)	0.2886 (3)	0.1573 (2)	0.0433 (7)
H1	0.1017	0.2399	0.1714	0.065*
O2	−0.2045 (3)	0.1922 (3)	0.5504 (3)	0.0514 (8)
H2	−0.1583	0.1739	0.5261	0.077*
C1	0.2813 (3)	0.1666 (4)	0.2944 (3)	0.0394 (9)
C2	0.2528 (3)	0.2639 (4)	0.2194 (3)	0.0365 (9)
C3	0.3399 (4)	0.3351 (4)	0.2097 (3)	0.0421 (10)
C4	0.4525 (4)	0.3144 (5)	0.2741 (4)	0.0562 (13)
H4	0.5100	0.3641	0.2671	0.067*
C5	0.4797 (4)	0.2202 (6)	0.3486 (4)	0.0644 (15)
H5	0.5556	0.2072	0.3927	0.077*
C6	0.3956 (4)	0.1454 (5)	0.3583 (4)	0.0560 (12)
H6	0.4148	0.0803	0.4076	0.067*
C7	0.1924 (4)	0.0872 (4)	0.3054 (3)	0.0417 (10)
H7	0.2132	0.0209	0.3539	0.050*
C8	0.0013 (4)	0.0262 (4)	0.2677 (4)	0.0472 (11)
H8A	0.0393	−0.0419	0.3168	0.057*
H8B	−0.0477	−0.0159	0.2048	0.057*
C9	−0.0711 (4)	0.1100 (5)	0.3066 (3)	0.0440 (10)
H9A	−0.1066	0.1798	0.2585	0.053*
H9B	−0.1315	0.0563	0.3112	0.053*
C10	−0.0019 (4)	0.1693 (6)	0.4094 (3)	0.0546 (12)
H10A	0.0462	0.1024	0.4544	0.065*
H10B	0.0472	0.2378	0.4026	0.065*
C11	−0.1054 (4)	0.3460 (5)	0.4441 (3)	0.0440 (10)
H11	−0.0739	0.4017	0.4111	0.053*
C12	−0.1838 (3)	0.3993 (4)	0.4838 (3)	0.0372 (9)
C13	−0.2308 (3)	0.3159 (4)	0.5356 (3)	0.0353 (9)
C14	−0.3080 (4)	0.3746 (5)	0.5709 (3)	0.0429 (10)
C15	−0.3355 (4)	0.5048 (5)	0.5559 (4)	0.0594 (13)
H15	−0.3870	0.5400	0.5799	0.071*
C16	−0.2879 (5)	0.5853 (5)	0.5054 (4)	0.0679 (15)
H16	−0.3074	0.6737	0.4953	0.081*
C17	−0.2116 (5)	0.5328 (5)	0.4708 (4)	0.0580 (13)
H17	−0.1779	0.5865	0.4383	0.070*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0638 (4)	0.0634 (4)	0.0714 (4)	−0.0147 (2)	0.0379 (3)	0.0024 (2)
Br2	0.0673 (4)	0.1079 (5)	0.0731 (4)	−0.0240 (3)	0.0495 (3)	−0.0080 (3)
N1	0.0385 (19)	0.043 (2)	0.0394 (18)	0.0032 (16)	0.0210 (16)	−0.0008 (15)
N2	0.0368 (19)	0.061 (3)	0.0401 (19)	0.0046 (17)	0.0171 (16)	−0.0039 (17)
O1	0.0286 (15)	0.0499 (18)	0.0470 (16)	0.0027 (13)	0.0107 (13)	0.0083 (13)
O2	0.068 (2)	0.0393 (17)	0.064 (2)	0.0023 (15)	0.0438 (17)	0.0047 (14)
C1	0.032 (2)	0.047 (2)	0.035 (2)	0.0082 (18)	0.0099 (18)	−0.0050 (18)
C2	0.031 (2)	0.042 (2)	0.037 (2)	0.0031 (17)	0.0148 (18)	−0.0086 (17)
C3	0.040 (2)	0.044 (2)	0.048 (2)	−0.0009 (19)	0.023 (2)	−0.0100 (19)
C4	0.036 (2)	0.067 (3)	0.068 (3)	−0.004 (2)	0.024 (2)	−0.025 (3)
C5	0.028 (2)	0.079 (4)	0.072 (4)	0.009 (2)	0.006 (2)	−0.021 (3)
C6	0.042 (3)	0.063 (3)	0.052 (3)	0.017 (2)	0.006 (2)	−0.005 (2)
C7	0.047 (3)	0.043 (2)	0.037 (2)	0.011 (2)	0.0186 (19)	0.0043 (18)
C8	0.056 (3)	0.045 (3)	0.049 (3)	−0.006 (2)	0.030 (2)	−0.005 (2)
C9	0.036 (2)	0.054 (3)	0.045 (2)	−0.004 (2)	0.0192 (19)	−0.0015 (19)
C10	0.038 (2)	0.085 (4)	0.043 (2)	0.010 (2)	0.018 (2)	−0.008 (2)
C11	0.041 (2)	0.057 (3)	0.038 (2)	−0.006 (2)	0.0207 (19)	0.0004 (19)
C12	0.036 (2)	0.043 (2)	0.0305 (19)	0.0002 (18)	0.0116 (17)	0.0011 (17)
C13	0.033 (2)	0.041 (2)	0.0299 (19)	−0.0037 (17)	0.0106 (17)	−0.0052 (16)
C14	0.037 (2)	0.056 (3)	0.038 (2)	−0.006 (2)	0.0189 (19)	−0.0071 (19)
C15	0.052 (3)	0.069 (3)	0.054 (3)	0.015 (3)	0.020 (2)	−0.013 (2)
C16	0.081 (4)	0.045 (3)	0.078 (4)	0.019 (3)	0.032 (3)	0.004 (3)
C17	0.071 (3)	0.046 (3)	0.058 (3)	0.005 (2)	0.027 (3)	0.013 (2)

Geometric parameters (Å, º) top

Br1—C3	1.899 (5)	C7—H7	0.9300
Br2—C14	1.883 (4)	C8—C9	1.521 (6)
N1—C7	1.274 (5)	C8—H8A	0.9700
N1—C8	1.462 (5)	C8—H8B	0.9700
N2—C11	1.279 (6)	C9—C10	1.511 (6)
N2—C10	1.465 (5)	C9—H9A	0.9700
O1—C2	1.337 (5)	C9—H9B	0.9700
O1—H1	0.8200	C10—H10A	0.9700
O2—C13	1.300 (5)	C10—H10B	0.9700
O2—H2	0.8200	C11—C12	1.443 (6)
C1—C6	1.394 (6)	C11—H11	0.9300
C1—C2	1.402 (6)	C12—C17	1.400 (6)
C1—C7	1.454 (6)	C12—C13	1.415 (6)
C2—C3	1.382 (6)	C13—C14	1.412 (6)
C3—C4	1.378 (6)	C14—C15	1.366 (7)
C4—C5	1.376 (8)	C15—C16	1.388 (8)
C4—H4	0.9300	C15—H15	0.9300
C5—C6	1.369 (8)	C16—C17	1.370 (8)
C5—H5	0.9300	C16—H16	0.9300
C6—H6	0.9300	C17—H17	0.9300

C7—N1—C8	119.2 (4)	C10—C9—H9A	109.1
C11—N2—C10	122.1 (4)	C8—C9—H9A	109.1
C2—O1—H1	109.5	C10—C9—H9B	109.1
C13—O2—H2	109.5	C8—C9—H9B	109.1
C6—C1—C2	119.7 (4)	H9A—C9—H9B	107.8
C6—C1—C7	119.9 (4)	N2—C10—C9	110.2 (4)
C2—C1—C7	120.3 (4)	N2—C10—H10A	109.6
O1—C2—C3	119.7 (4)	C9—C10—H10A	109.6
O1—C2—C1	121.7 (4)	N2—C10—H10B	109.6
C3—C2—C1	118.6 (4)	C9—C10—H10B	109.6
C4—C3—C2	121.2 (4)	H10A—C10—H10B	108.1
C4—C3—Br1	119.8 (4)	N2—C11—C12	122.1 (4)
C2—C3—Br1	119.0 (3)	N2—C11—H11	119.0
C5—C4—C3	119.9 (5)	C12—C11—H11	119.0
C5—C4—H4	120.1	C17—C12—C13	121.0 (4)
C3—C4—H4	120.1	C17—C12—C11	119.5 (4)
C6—C5—C4	120.4 (4)	C13—C12—C11	119.5 (4)
C6—C5—H5	119.8	O2—C13—C14	121.6 (4)
C4—C5—H5	119.8	O2—C13—C12	122.2 (4)
C5—C6—C1	120.2 (5)	C14—C13—C12	116.2 (4)
C5—C6—H6	119.9	C15—C14—C13	121.8 (4)
C1—C6—H6	119.9	C15—C14—Br2	119.8 (4)
N1—C7—C1	121.8 (4)	C13—C14—Br2	118.4 (3)
N1—C7—H7	119.1	C14—C15—C16	121.1 (5)
C1—C7—H7	119.1	C14—C15—H15	119.4
N1—C8—C9	110.9 (3)	C16—C15—H15	119.4
N1—C8—H8A	109.5	C17—C16—C15	119.1 (5)
C9—C8—H8A	109.5	C17—C16—H16	120.5
N1—C8—H8B	109.5	C15—C16—H16	120.5
C9—C8—H8B	109.5	C16—C17—C12	120.7 (5)
H8A—C8—H8B	108.0	C16—C17—H17	119.7
C10—C9—C8	112.5 (4)	C12—C17—H17	119.7

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.82	1.83	2.567 (4)	148
O2—H2···N2	0.82	1.82	2.553 (5)	149
C7—H7···O2ⁱ	0.93	2.60	3.490 (5)	161

Symmetry code: (i) −x, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.82	1.83	2.567 (4)	148
O2—H2···N2	0.82	1.82	2.553 (5)	149
C7—H7···O2ⁱ	0.93	2.60	3.490 (5)	161

Symmetry code: (i) −x, −y, −z+1.

Acknowledgements

The author acknowledges Dalian University of Technology for financial support.

References

Bruker (2007). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Elerman, Y., Elmali, A., Kabak, M. & Svoboda, I. (1998). Acta Cryst. C54, 1701–1703. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar