{2,2′-[(Benzyl­aza­nedi­yl)dimethylene]diphenolato}(methano­lato)boron

Geng, Y.; Wu, W.

doi:10.1107/S1600536811016990

{2,2′-[(Benzylazanediyl)dimethylene]diphenolato}(methanolato)boron

The title compound, C₂₂H₂₂BNO₃, was unintentionally obtained from salicylaldehyde benzylamine and sodium borohydride. The B—O bond lengths lie in the range 1.425 (2)–1.463 (2) Å, and B—N = 1.641 (2) Å. In the crystal, weak intermolecular C—H

O hydrogen bonds link the molecules into chains in the [010] direction.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536811016990/cv5081sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536811016990/cv5081Isup2.hkl Contains datablock I

checkCIF report

Key indicators

Single-crystal X-ray study
T = 273 K
Mean (C-C) = 0.003 Å
R factor = 0.058
wR factor = 0.161
Data-to-parameter ratio = 18.5

checkCIF/PLATON results

No syntax errors found



Alert level C
RINTA01_ALERT_3_C  The value of Rint is greater than 0.12
            Rint given   0.154
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.97
PLAT125_ALERT_4_C No '_symmetry_space_group_name_Hall' Given .....          ?
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          6
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600        147

Alert level G
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        273 K
PLAT200_ALERT_1_G Check the Reported   _diffrn_ambient_temperature        273 K
PLAT793_ALERT_4_G The Model has Chirality at N2      (Verify) ....          S

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   5 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   3 ALERT level G = General information/check it is not something unexpected

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

The title compound, (I), has been unintentionally obtained during the attempts to synthesize the metal complexes with phenolamine derivatives.

In (I), all bond lengths and angles are normal and comparable with those observed in 2,2',2''-nitrilotriphenyl borate(III) (Muller & Burgi, 1987). The B1—N2 bond of 1.642 (2) Å indicates strong contact due to the electric charge action. Weak intermolecular C—H···O hydrogen bonds (Table 1) link the molecules into chains in [010].

Related literature top

For the crystal structure of a related compound, see: Muller & Burgi (1987).

Experimental top

The salicylaldehyde (4.4 ml, 0.04 mol) was disolved in 25 ml anhydrous methanol, then benzylamine 4.4 ml(0. 04 mol) disolved in 15 ml anhydrous methnol was added to the former by drops.After reacted under ultrasonography for 40 min, sodium borohydride (1.5 g, 0.04 mol) were added in batch. After reacted under ultrasonography for another 20 min, 1, 4-dibromo-butane(2.4 ml, 0.02 mol) were added, After stirring of 24 h at room temperature. The precipitate was filtered off and dried. The single-crystal suitable for X-ray diffraction analysis was obtained by recrystallization from methanol.

The yield is 75% and elemental analysis: calc. for C₂₂H₂₂BNO₃: C 73.55, H 6.17, N 3.90; found: C 72.81, H 6.49, N 3.53. The elemental analyses were performed with PERKIN ELMER MODEL 2400 SERIES II.

Structure description top

The title compound, (I), has been unintentionally obtained during the attempts to synthesize the metal complexes with phenolamine derivatives.

For the crystal structure of a related compound, see: Muller & Burgi (1987).

Computing details top

Data collection: SMART (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of title compound showing the atomic numbering and 30% probability displacement ellipsoids. H-atoms omitted for clarity.

{2,2'-[(Benzylazanediyl)dimethylene]diphenolato}(methanolato)boron top

Crystal data top

C₂₂H₂₂BNO₃	F(000) = 760
M_r = 359.22	D_x = 1.267 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 12.5041 (14) Å	Cell parameters from 2910 reflections
b = 10.6029 (12) Å	θ = 2.4–23.2°
c = 17.1420 (14) Å	µ = 0.08 mm⁻¹
β = 124.054 (5)°	T = 273 K
V = 1882.9 (3) Å³	Block, colourless
Z = 4	0.31 × 0.26 × 0.22 mm

Data collection top

Bruker SMART APEX diffractometer	4540 independent reflections
Radiation source: fine-focus sealed tube	2558 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.154
φ and ω scans	θ_max = 28.4°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −16→16
T_min = 0.975, T_max = 0.982	k = −13→14
11689 measured reflections	l = −19→22

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)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.161	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.04P)²] where P = (F_o² + 2F_c²)/3
4540 reflections	(Δ/σ)_max = 0.003
245 parameters	Δρ_max = 0.23 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₂₂H₂₂BNO₃	V = 1882.9 (3) Å³
M_r = 359.22	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.5041 (14) Å	µ = 0.08 mm⁻¹
b = 10.6029 (12) Å	T = 273 K
c = 17.1420 (14) Å	0.31 × 0.26 × 0.22 mm
β = 124.054 (5)°

Data collection top

Bruker SMART APEX diffractometer	4540 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	2558 reflections with I > 2σ(I)
T_min = 0.975, T_max = 0.982	R_int = 0.154
11689 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.058	0 restraints
wR(F²) = 0.161	H-atom parameters constrained
S = 1.01	Δρ_max = 0.23 e Å⁻³
4540 reflections	Δρ_min = −0.24 e Å⁻³
245 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
B1	0.2232 (2)	0.32181 (19)	0.40625 (14)	0.0467 (5)
N2	0.20528 (12)	0.47562 (12)	0.39796 (8)	0.0405 (3)
O3	0.11650 (13)	0.26732 (11)	0.40506 (9)	0.0542 (3)
O4	0.34523 (13)	0.29948 (12)	0.49191 (9)	0.0613 (4)
O5	0.21491 (12)	0.28152 (10)	0.32141 (8)	0.0498 (3)
C6	0.31610 (16)	0.53161 (17)	0.39892 (12)	0.0487 (4)
H6A	0.3922	0.5319	0.4630	0.058*
H6B	0.2959	0.6184	0.3776	0.058*
C7	0.34535 (16)	0.45969 (17)	0.33689 (12)	0.0473 (4)
C8	0.29429 (17)	0.34032 (18)	0.30145 (12)	0.0488 (4)
C9	0.3203 (2)	0.27914 (19)	0.24196 (14)	0.0623 (5)
H9	0.2839	0.2008	0.2167	0.075*
C10	0.4007 (2)	0.3356 (2)	0.22079 (16)	0.0734 (6)
H10	0.4182	0.2947	0.1811	0.088*
C11	0.4551 (2)	0.4515 (2)	0.25773 (15)	0.0704 (6)
H11	0.5105	0.4880	0.2442	0.085*
C12	0.42708 (19)	0.51334 (19)	0.31478 (14)	0.0574 (5)
H12	0.4632	0.5922	0.3390	0.069*
C13	0.20248 (18)	0.52595 (15)	0.47992 (11)	0.0475 (4)
H13A	0.1326	0.4849	0.4792	0.057*
H13B	0.2825	0.5025	0.5382	0.057*
C14	0.18550 (18)	0.66690 (17)	0.48009 (11)	0.0481 (4)
C15	0.2926 (2)	0.74533 (18)	0.52878 (14)	0.0606 (5)
H15	0.3750	0.7106	0.5607	0.073*
C16	0.2782 (3)	0.8744 (2)	0.53036 (17)	0.0793 (7)
H16	0.3508	0.9256	0.5632	0.095*
C17	0.1563 (3)	0.9279 (2)	0.48346 (17)	0.0815 (7)
H17	0.1467	1.0148	0.4836	0.098*
C18	0.0494 (3)	0.8508 (2)	0.43666 (15)	0.0761 (7)
H18	−0.0328	0.8858	0.4059	0.091*
C19	0.0638 (2)	0.7210 (2)	0.43516 (14)	0.0626 (6)
H19	−0.0090	0.6698	0.4037	0.075*
C20	0.08093 (15)	0.50238 (15)	0.30599 (11)	0.0416 (4)
H20A	0.0898	0.4816	0.2548	0.050*
H20B	0.0613	0.5916	0.3019	0.050*
C21	−0.02795 (16)	0.42715 (15)	0.29604 (11)	0.0429 (4)
C22	−0.15376 (18)	0.47161 (18)	0.23826 (13)	0.0558 (5)
H22	−0.1697	0.5459	0.2046	0.067*
C23	−0.2553 (2)	0.4070 (2)	0.23014 (16)	0.0703 (6)
H23	−0.3390	0.4377	0.1913	0.084*
C24	−0.2323 (2)	0.2971 (2)	0.27968 (17)	0.0719 (7)
H24	−0.3006	0.2543	0.2750	0.086*
C25	−0.1073 (2)	0.24931 (18)	0.33692 (15)	0.0598 (5)
H25	−0.0925	0.1742	0.3696	0.072*
C26	−0.00545 (18)	0.31408 (16)	0.34496 (12)	0.0457 (4)
C27	0.4118 (2)	0.18849 (19)	0.50173 (16)	0.0716 (6)
H27A	0.3651	0.1176	0.5031	0.107*
H27B	0.4961	0.1915	0.5593	0.107*
H27C	0.4199	0.1800	0.4495	0.107*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
B1	0.0461 (12)	0.0474 (11)	0.0464 (11)	0.0016 (9)	0.0258 (10)	0.0020 (8)
N2	0.0369 (8)	0.0476 (8)	0.0388 (7)	−0.0015 (6)	0.0222 (7)	0.0012 (6)
O3	0.0582 (8)	0.0479 (7)	0.0628 (8)	−0.0006 (6)	0.0378 (7)	0.0096 (6)
O4	0.0543 (8)	0.0651 (8)	0.0502 (8)	0.0158 (7)	0.0206 (7)	0.0049 (6)
O5	0.0488 (7)	0.0512 (7)	0.0520 (7)	−0.0032 (6)	0.0299 (7)	−0.0048 (5)
C6	0.0384 (9)	0.0544 (10)	0.0531 (10)	−0.0058 (8)	0.0255 (9)	−0.0022 (8)
C7	0.0369 (9)	0.0574 (11)	0.0482 (10)	0.0032 (8)	0.0242 (8)	0.0059 (8)
C8	0.0426 (10)	0.0573 (11)	0.0467 (10)	0.0070 (9)	0.0250 (9)	0.0051 (8)
C9	0.0661 (13)	0.0670 (13)	0.0611 (13)	0.0116 (11)	0.0401 (12)	0.0007 (10)
C10	0.0798 (16)	0.0905 (16)	0.0720 (14)	0.0220 (14)	0.0561 (14)	0.0102 (12)
C11	0.0619 (13)	0.0920 (16)	0.0760 (14)	0.0161 (13)	0.0500 (12)	0.0216 (13)
C12	0.0461 (10)	0.0665 (12)	0.0632 (12)	0.0048 (10)	0.0328 (10)	0.0104 (10)
C13	0.0478 (10)	0.0552 (10)	0.0413 (9)	−0.0022 (8)	0.0260 (8)	−0.0008 (7)
C14	0.0531 (11)	0.0531 (10)	0.0394 (9)	0.0005 (9)	0.0267 (9)	−0.0028 (8)
C15	0.0637 (13)	0.0605 (12)	0.0525 (12)	−0.0071 (11)	0.0293 (11)	−0.0051 (9)
C16	0.1020 (19)	0.0619 (14)	0.0735 (15)	−0.0152 (14)	0.0489 (15)	−0.0104 (11)
C17	0.122 (2)	0.0552 (12)	0.0719 (15)	0.0098 (16)	0.0575 (16)	0.0010 (11)
C18	0.0910 (17)	0.0770 (15)	0.0596 (13)	0.0318 (15)	0.0417 (13)	0.0044 (11)
C19	0.0575 (12)	0.0742 (14)	0.0526 (12)	0.0079 (11)	0.0287 (11)	−0.0077 (10)
C20	0.0381 (9)	0.0464 (9)	0.0410 (9)	0.0011 (7)	0.0226 (8)	0.0029 (7)
C21	0.0409 (9)	0.0472 (9)	0.0427 (9)	−0.0056 (8)	0.0247 (8)	−0.0069 (7)
C22	0.0429 (10)	0.0646 (12)	0.0541 (11)	−0.0019 (9)	0.0236 (9)	−0.0065 (9)
C23	0.0416 (11)	0.0870 (16)	0.0757 (14)	−0.0103 (11)	0.0288 (11)	−0.0199 (12)
C24	0.0570 (14)	0.0882 (17)	0.0850 (16)	−0.0296 (12)	0.0487 (13)	−0.0329 (13)
C25	0.0733 (14)	0.0550 (11)	0.0709 (14)	−0.0205 (11)	0.0524 (13)	−0.0153 (9)
C26	0.0474 (10)	0.0471 (10)	0.0495 (10)	−0.0072 (8)	0.0314 (9)	−0.0081 (8)
C27	0.0639 (14)	0.0677 (13)	0.0718 (14)	0.0189 (11)	0.0309 (13)	0.0179 (10)

Geometric parameters (Å, º) top

B1—O4	1.425 (2)	C14—C15	1.389 (3)
B1—O3	1.443 (2)	C15—C16	1.382 (3)
B1—O5	1.463 (2)	C15—H15	0.9300
B1—N2	1.641 (2)	C16—C17	1.385 (3)
N2—C20	1.4962 (19)	C16—H16	0.9300
N2—C6	1.499 (2)	C17—C18	1.377 (3)
N2—C13	1.521 (2)	C17—H17	0.9300
O3—C26	1.369 (2)	C18—C19	1.390 (3)
O4—C27	1.396 (2)	C18—H18	0.9300
O5—C8	1.368 (2)	C19—H19	0.9300
C6—C7	1.510 (2)	C20—C21	1.503 (2)
C6—H6A	0.9700	C20—H20A	0.9700
C6—H6B	0.9700	C20—H20B	0.9700
C7—C12	1.395 (2)	C21—C22	1.390 (3)
C7—C8	1.394 (3)	C21—C26	1.398 (2)
C8—C9	1.392 (3)	C22—C23	1.379 (3)
C9—C10	1.381 (3)	C22—H22	0.9300
C9—H9	0.9300	C23—C24	1.374 (3)
C10—C11	1.376 (3)	C23—H23	0.9300
C10—H10	0.9300	C24—C25	1.394 (3)
C11—C12	1.375 (3)	C24—H24	0.9300
C11—H11	0.9300	C25—C26	1.385 (3)
C12—H12	0.9300	C25—H25	0.9300
C13—C14	1.510 (2)	C27—H27A	0.9600
C13—H13A	0.9700	C27—H27B	0.9600
C13—H13B	0.9700	C27—H27C	0.9600
C14—C19	1.388 (3)

O4—B1—O3	113.34 (15)	C15—C14—C13	120.28 (17)
O4—B1—O5	114.47 (16)	C16—C15—C14	120.7 (2)
O3—B1—O5	108.60 (15)	C16—C15—H15	119.6
O4—B1—N2	105.64 (14)	C14—C15—H15	119.6
O3—B1—N2	108.45 (14)	C15—C16—C17	120.5 (2)
O5—B1—N2	105.89 (13)	C15—C16—H16	119.7
C20—N2—C6	110.19 (12)	C17—C16—H16	119.7
C20—N2—C13	111.03 (13)	C18—C17—C16	119.2 (2)
C6—N2—C13	110.50 (13)	C18—C17—H17	120.4
C20—N2—B1	106.88 (12)	C16—C17—H17	120.4
C6—N2—B1	108.19 (13)	C17—C18—C19	120.3 (2)
C13—N2—B1	109.94 (12)	C17—C18—H18	119.8
C26—O3—B1	119.80 (13)	C19—C18—H18	119.8
C27—O4—B1	119.10 (15)	C14—C19—C18	120.8 (2)
C8—O5—B1	117.29 (14)	C14—C19—H19	119.6
N2—C6—C7	112.28 (14)	C18—C19—H19	119.6
N2—C6—H6A	109.1	N2—C20—C21	111.08 (12)
C7—C6—H6A	109.1	N2—C20—H20A	109.4
N2—C6—H6B	109.1	C21—C20—H20A	109.4
C7—C6—H6B	109.1	N2—C20—H20B	109.4
H6A—C6—H6B	107.9	C21—C20—H20B	109.4
C12—C7—C8	118.56 (17)	H20A—C20—H20B	108.0
C12—C7—C6	119.24 (17)	C22—C21—C26	119.04 (17)
C8—C7—C6	122.19 (16)	C22—C21—C20	119.51 (15)
O5—C8—C9	118.10 (17)	C26—C21—C20	121.44 (15)
O5—C8—C7	121.60 (15)	C23—C22—C21	120.91 (19)
C9—C8—C7	120.28 (18)	C23—C22—H22	119.5
C10—C9—C8	119.6 (2)	C21—C22—H22	119.5
C10—C9—H9	120.2	C24—C23—C22	119.8 (2)
C8—C9—H9	120.2	C24—C23—H23	120.1
C11—C10—C9	120.7 (2)	C22—C23—H23	120.1
C11—C10—H10	119.6	C23—C24—C25	120.5 (2)
C9—C10—H10	119.6	C23—C24—H24	119.7
C12—C11—C10	119.7 (2)	C25—C24—H24	119.7
C12—C11—H11	120.1	C26—C25—C24	119.70 (19)
C10—C11—H11	120.1	C26—C25—H25	120.2
C11—C12—C7	121.0 (2)	C24—C25—H25	120.2
C11—C12—H12	119.5	O3—C26—C25	118.06 (16)
C7—C12—H12	119.5	O3—C26—C21	121.82 (16)
C14—C13—N2	115.15 (13)	C25—C26—C21	120.04 (18)
C14—C13—H13A	108.5	O4—C27—H27A	109.5
N2—C13—H13A	108.5	O4—C27—H27B	109.5
C14—C13—H13B	108.5	H27A—C27—H27B	109.5
N2—C13—H13B	108.5	O4—C27—H27C	109.5
H13A—C13—H13B	107.5	H27A—C27—H27C	109.5
C19—C14—C15	118.36 (17)	H27B—C27—H27C	109.5
C19—C14—C13	121.31 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C22—H22···O5ⁱ	0.93	2.54	3.399 (2)	153

Symmetry code: (i) −x, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₂₂H₂₂BNO₃
M_r	359.22
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	273
a, b, c (Å)	12.5041 (14), 10.6029 (12), 17.1420 (14)
β (°)	124.054 (5)
V (Å³)	1882.9 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.31 × 0.26 × 0.22

Data collection
Diffractometer	Bruker SMART APEX
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.975, 0.982
No. of measured, independent and observed [I > 2σ(I)] reflections	11689, 4540, 2558
R_int	0.154
(sin θ/λ)_max (Å⁻¹)	0.668

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.058, 0.161, 1.01
No. of reflections	4540
No. of parameters	245
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.24

Computer programs: SMART (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008).