Supra­molecular arrangement and photophysical properties of a dinuclear cyano­phenyl­boronic acid ester

Boronic esters are useful building blocks for crystal engineering and the generation of supra­molecular architectures, including macrocycles, cages and polymers (one-, two- and three-dimensional), with potential utility in diverse fields such as separation, storage and luminescent materials. The novel dinuclear cyano­phenyl­boronic ester described herein, namely 4,4′-(2,4,8,10-tetra­oxa-3,9-dibora­spiro­[5.5]undecane-3,9-di­yl)dibenzo­nitrile, C₁₉H₁₆B₂N₂O₄, was prepared by condensation of 4-cyano­phenyl­boronic acid and penta­erythritol and fully characterized by elemental analysis, IR and NMR (¹H and ¹¹B) spectroscopy, single-crystal X-ray diffraction analysis and TG-DSC (thermogravimetry–differential scanning calorimetry) studies. In addition, the photophysical properties were examined in solution and in the solid state by UV–Vis and fluorescence spectroscopies. Density functional theory (DFT) calculations with ethanol as solvent reproduced reasonably well the HOMO (highest occupied mol­ecular orbital) and LUMO (lowest unoccupied mol­ecular orbital) of the title compound. Hirshfeld surface and fingerprint plot analyses are presented to illustrate the supra­molecular connectivity in the solid state.

Computing details

Data collection: CrysAlis PRO (Agilent, 2014); cell refinement: CrysAlis PRO (Agilent, 2014); data reduction: CrysAlis PRO (Agilent, 2014); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009) and DIAMOND (Brandenburg, 1997); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009) and WinGX (Farrugia, 2012).

4,4'-(2,4,8,10-Tetraoxa-3,9-diboraspiro[5.5]undecane-3,9-diyl)dibenzonitrile

Crystal data

C19H16B2N2O4	F(000) = 744
Mr = 357.96	Dx = 1.351 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 14.2967 (14) Å	Cell parameters from 4270 reflections
b = 11.5113 (9) Å	θ = 3.4–28.9°
c = 11.0913 (9) Å	µ = 0.09 mm^−1
β = 105.465 (10)°	T = 100 K
V = 1759.3 (3) Å^3	Prism, translucent colourless
Z = 4	0.3 × 0.2 × 0.2 mm

Data collection

Agilent SuperNova Dual Source diffractometer with an EosS2 detector	3090 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	2578 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.046
Detector resolution: 8.0769 pixels mm^-1	θmax = 25.0°, θmin = 2.6°
ω scans	h = −16→13
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	k = −13→13
Tmin = 0.774, Tmax = 1.000	l = −13→13
12023 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.067	H-atom parameters constrained
wR(F^2) = 0.144	w = 1/[σ^2(Fo^2) + (0.0175P)^2 + 3.8888P] where P = (Fo^2 + 2Fc^2)/3
S = 1.17	(Δ/σ)max < 0.001
3090 reflections	Δρmax = 0.24 e Å^−3
244 parameters	Δρmin = −0.25 e Å^−3
0 restraints

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O1	0.36175 (16)	0.80679 (19)	0.3824 (2)	0.0272 (5)
O2	0.29169 (17)	0.86853 (19)	0.54550 (19)	0.0291 (5)
O3	0.22597 (16)	0.46461 (19)	0.40200 (19)	0.0266 (5)
O4	0.14720 (16)	0.61144 (19)	0.25664 (18)	0.0246 (5)
N1	0.4527 (2)	1.4595 (3)	0.3386 (3)	0.0364 (7)
N2	−0.0250 (2)	0.0775 (3)	−0.1535 (3)	0.0356 (7)
C1	0.3451 (2)	0.6870 (3)	0.4053 (3)	0.0260 (7)
H1A	0.4021	0.6556	0.4645	0.031*
H1B	0.3351	0.6437	0.3278	0.031*
C2	0.2568 (2)	0.6713 (3)	0.4570 (3)	0.0251 (7)
C3	0.2677 (3)	0.7515 (3)	0.5694 (3)	0.0299 (8)
H3A	0.2074	0.7516	0.5938	0.036*
H3B	0.3181	0.7210	0.6390	0.036*
C4	0.2526 (3)	0.5463 (3)	0.5028 (3)	0.0311 (8)
H4A	0.3157	0.5252	0.5567	0.037*
H4B	0.2060	0.5421	0.5521	0.037*
C5	0.1637 (2)	0.6960 (3)	0.3563 (3)	0.0264 (7)
H5A	0.1094	0.6951	0.3933	0.032*
H5B	0.1673	0.7729	0.3221	0.032*
C6	0.3632 (2)	1.0192 (3)	0.4320 (3)	0.0244 (7)
C7	0.4124 (2)	1.0445 (3)	0.3409 (3)	0.0271 (7)
H7	0.4298	0.9840	0.2957	0.033*
C8	0.4354 (2)	1.1573 (3)	0.3172 (3)	0.0279 (8)
H8	0.4682	1.1722	0.2569	0.033*
C9	0.4093 (2)	1.2486 (3)	0.3841 (3)	0.0262 (7)
C10	0.3619 (2)	1.2252 (3)	0.4771 (3)	0.0262 (7)
H10	0.3453	1.2857	0.5230	0.031*
C11	0.3403 (2)	1.1126 (3)	0.5000 (3)	0.0253 (7)
H11	0.3095	1.0979	0.5624	0.030*
C12	0.1460 (2)	0.4041 (3)	0.1807 (3)	0.0232 (7)
C13	0.1059 (2)	0.4327 (3)	0.0552 (3)	0.0257 (7)
H13	0.1060	0.5099	0.0305	0.031*
C14	0.0661 (2)	0.3489 (3)	−0.0336 (3)	0.0275 (8)
H14	0.0388	0.3699	−0.1166	0.033*
C15	0.0673 (2)	0.2326 (3)	0.0031 (3)	0.0252 (7)
C16	0.1116 (2)	0.2009 (3)	0.1267 (3)	0.0275 (7)
H16	0.1147	0.1233	0.1507	0.033*
C17	0.1509 (2)	0.2868 (3)	0.2131 (3)	0.0261 (7)
H17	0.1814	0.2655	0.2950	0.031*
C18	0.4321 (2)	1.3666 (3)	0.3583 (3)	0.0277 (8)
C19	0.0174 (2)	0.1461 (3)	−0.0853 (3)	0.0276 (7)
B1	0.3384 (3)	0.8912 (4)	0.4552 (3)	0.0261 (8)
B2	0.1751 (3)	0.4993 (3)	0.2851 (3)	0.0237 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0334 (13)	0.0254 (12)	0.0256 (11)	−0.0028 (10)	0.0128 (10)	−0.0021 (10)
O2	0.0457 (14)	0.0244 (13)	0.0210 (11)	−0.0021 (11)	0.0154 (10)	−0.0014 (10)
O3	0.0369 (13)	0.0212 (12)	0.0212 (11)	−0.0030 (10)	0.0068 (10)	−0.0004 (9)
O4	0.0310 (12)	0.0224 (12)	0.0198 (11)	−0.0008 (10)	0.0057 (9)	−0.0013 (9)
N1	0.0455 (19)	0.0331 (19)	0.0368 (17)	0.0012 (15)	0.0216 (15)	0.0046 (14)
N2	0.0455 (19)	0.0316 (17)	0.0311 (16)	−0.0095 (15)	0.0127 (14)	−0.0046 (14)
C1	0.0308 (18)	0.0241 (18)	0.0220 (16)	0.0026 (14)	0.0051 (14)	−0.0038 (13)
C2	0.0337 (18)	0.0240 (18)	0.0176 (15)	−0.0016 (14)	0.0068 (13)	0.0004 (13)
C3	0.048 (2)	0.0254 (18)	0.0174 (15)	−0.0007 (16)	0.0110 (15)	0.0017 (14)
C4	0.050 (2)	0.0276 (19)	0.0155 (15)	−0.0035 (16)	0.0078 (15)	−0.0009 (14)
C5	0.0330 (18)	0.0259 (18)	0.0230 (16)	−0.0019 (14)	0.0122 (14)	−0.0037 (14)
C6	0.0226 (16)	0.0300 (19)	0.0197 (15)	0.0012 (14)	0.0040 (13)	0.0008 (13)
C7	0.0321 (18)	0.0288 (19)	0.0213 (16)	0.0027 (15)	0.0086 (14)	−0.0038 (14)
C8	0.0274 (17)	0.038 (2)	0.0193 (16)	−0.0013 (15)	0.0085 (13)	0.0010 (14)
C9	0.0243 (17)	0.0317 (19)	0.0207 (15)	0.0009 (14)	0.0027 (13)	0.0018 (14)
C10	0.0288 (18)	0.0284 (19)	0.0220 (16)	0.0033 (14)	0.0081 (14)	−0.0024 (14)
C11	0.0259 (17)	0.0308 (19)	0.0202 (15)	0.0011 (14)	0.0078 (13)	0.0008 (14)
C12	0.0240 (16)	0.0242 (18)	0.0234 (16)	−0.0010 (13)	0.0099 (13)	0.0009 (13)
C13	0.0302 (18)	0.0216 (17)	0.0269 (17)	0.0023 (14)	0.0103 (14)	0.0004 (14)
C14	0.0288 (18)	0.035 (2)	0.0202 (16)	0.0024 (15)	0.0086 (13)	−0.0019 (14)
C15	0.0255 (17)	0.0281 (19)	0.0238 (16)	0.0003 (14)	0.0100 (13)	−0.0061 (14)
C16	0.0339 (18)	0.0220 (17)	0.0296 (17)	−0.0010 (15)	0.0136 (15)	−0.0013 (14)
C17	0.0274 (17)	0.0306 (19)	0.0215 (16)	−0.0003 (14)	0.0084 (13)	−0.0001 (14)
C18	0.0287 (18)	0.032 (2)	0.0234 (17)	0.0045 (15)	0.0093 (14)	0.0007 (15)
C19	0.0334 (19)	0.0253 (18)	0.0274 (17)	−0.0002 (15)	0.0135 (15)	−0.0011 (15)
B1	0.0255 (19)	0.035 (2)	0.0162 (17)	0.0021 (17)	0.0030 (14)	−0.0037 (16)
B2	0.0228 (19)	0.027 (2)	0.0232 (18)	−0.0052 (15)	0.0098 (15)	0.0013 (16)

Geometric parameters (Å, º)

B1—O1	1.360 (4)	C5—H5B	0.9700
B1—O2	1.369 (4)	C6—C7	1.406 (4)
B2—O3	1.366 (4)	C6—C11	1.402 (4)
B2—O4	1.364 (4)	C7—H7	0.9300
B1—C6	1.553 (5)	C7—C8	1.382 (5)
B2—C12	1.567 (5)	C8—H8	0.9300
O1—C1	1.433 (4)	C8—C9	1.394 (5)
O2—C3	1.433 (4)	C9—C10	1.403 (4)
O3—C4	1.433 (4)	C9—C18	1.442 (5)
O4—C5	1.445 (4)	C10—H10	0.9300
N1—C18	1.146 (4)	C10—C11	1.372 (5)
N2—C19	1.149 (4)	C11—H11	0.9300
C1—H1A	0.9700	C12—C13	1.396 (4)
C1—H1B	0.9700	C12—C17	1.395 (5)
C1—C2	1.531 (4)	C13—H13	0.9300
C2—C3	1.525 (4)	C13—C14	1.388 (5)
C2—C4	1.533 (5)	C14—H14	0.9300
C2—C5	1.519 (4)	C14—C15	1.399 (5)
C3—H3A	0.9700	C15—C16	1.396 (4)
C3—H3B	0.9700	C15—C19	1.446 (5)
C4—H4A	0.9700	C16—H16	0.9300
C4—H4B	0.9700	C16—C17	1.387 (5)
C5—H5A	0.9700	C17—H17	0.9300
B1—O1—C1	120.2 (3)	C8—C7—H7	119.3
B1—O2—C3	120.1 (3)	C7—C8—H8	120.1
B2—O3—C4	120.9 (3)	C7—C8—C9	119.8 (3)
B2—O4—C5	118.9 (2)	C9—C8—H8	120.1
O1—C1—H1A	109.2	C8—C9—C10	119.8 (3)
O1—C1—H1B	109.2	C8—C9—C18	119.8 (3)
O1—C1—C2	111.9 (3)	C10—C9—C18	120.4 (3)
H1A—C1—H1B	107.9	C9—C10—H10	120.2
C2—C1—H1A	109.2	C11—C10—C9	119.7 (3)
C2—C1—H1B	109.2	C11—C10—H10	120.2
C1—C2—C4	110.1 (3)	C6—C11—H11	119.1
C3—C2—C1	108.7 (3)	C10—C11—C6	121.9 (3)
C3—C2—C4	107.6 (2)	C10—C11—H11	119.1
C5—C2—C1	110.5 (2)	C13—C12—B2	122.0 (3)
C5—C2—C3	111.5 (3)	C17—C12—C13	117.7 (3)
C5—C2—C4	108.4 (3)	C17—C12—B2	120.1 (3)
O2—C3—C2	113.3 (2)	C12—C13—H13	119.1
O2—C3—H3A	108.9	C14—C13—C12	121.7 (3)
O2—C3—H3B	108.9	C14—C13—H13	119.1
C2—C3—H3A	108.9	C13—C14—H14	120.4
C2—C3—H3B	108.9	C13—C14—C15	119.2 (3)
H3A—C3—H3B	107.7	C15—C14—H14	120.4
O3—C4—C2	112.5 (2)	C14—C15—C19	119.8 (3)
O3—C4—H4A	109.1	C16—C15—C14	120.2 (3)
O3—C4—H4B	109.1	C16—C15—C19	119.9 (3)
C2—C4—H4A	109.1	C15—C16—H16	120.5
C2—C4—H4B	109.1	C17—C16—C15	119.1 (3)
H4A—C4—H4B	107.8	C17—C16—H16	120.5
O4—C5—C2	111.6 (3)	C12—C17—H17	119.0
O4—C5—H5A	109.3	C16—C17—C12	121.9 (3)
O4—C5—H5B	109.3	C16—C17—H17	119.0
C2—C5—H5A	109.3	N1—C18—C9	178.3 (4)
C2—C5—H5B	109.3	N2—C19—C15	177.5 (3)
H5A—C5—H5B	108.0	O1—B1—O2	122.9 (3)
C7—C6—B1	119.7 (3)	O1—B1—C6	118.4 (3)
C11—C6—C7	117.5 (3)	O2—B1—C6	118.6 (3)
C11—C6—B1	122.8 (3)	O3—B2—C12	117.8 (3)
C6—C7—H7	119.3	O4—B2—O3	123.0 (3)
C8—C7—C6	121.4 (3)	O4—B2—C12	119.1 (3)
O1—C1—C2—C3	−51.9 (3)	C8—C9—C10—C11	−1.1 (5)
O1—C1—C2—C4	−169.5 (2)	C9—C10—C11—C6	−0.7 (5)
O1—C1—C2—C5	70.7 (3)	C11—C6—C7—C8	−1.4 (5)
C1—O1—B1—O2	−5.4 (5)	C11—C6—B1—O1	178.5 (3)
C1—O1—B1—C6	176.4 (3)	C11—C6—B1—O2	0.3 (5)
C1—C2—C3—O2	49.2 (4)	C12—C13—C14—C15	−1.0 (5)
C1—C2—C4—O3	−71.7 (3)	C13—C12—C17—C16	−4.4 (5)
C1—C2—C5—O4	66.0 (3)	C13—C12—B2—O3	−171.1 (3)
C3—O2—B1—O1	1.9 (5)	C13—C12—B2—O4	10.3 (5)
C3—O2—B1—C6	−179.9 (3)	C13—C14—C15—C16	−2.5 (5)
C3—C2—C4—O3	170.0 (3)	C13—C14—C15—C19	173.7 (3)
C3—C2—C5—O4	−173.0 (2)	C14—C15—C16—C17	2.4 (5)
C4—O3—B2—O4	0.3 (5)	C15—C16—C17—C12	1.1 (5)
C4—O3—B2—C12	−178.2 (3)	C17—C12—C13—C14	4.4 (5)
C4—C2—C3—O2	168.4 (3)	C17—C12—B2—O3	15.2 (4)
C4—C2—C5—O4	−54.8 (3)	C17—C12—B2—O4	−163.4 (3)
C5—O4—B2—O3	−6.0 (4)	C18—C9—C10—C11	179.7 (3)
C5—O4—B2—C12	172.4 (3)	C19—C15—C16—C17	−173.7 (3)
C5—C2—C3—O2	−72.9 (4)	B1—O1—C1—C2	31.6 (4)
C5—C2—C4—O3	49.4 (4)	B1—O2—C3—C2	−25.4 (4)
C6—C7—C8—C9	−0.3 (5)	B1—C6—C7—C8	179.7 (3)
C7—C6—C11—C10	1.8 (5)	B1—C6—C11—C10	−179.3 (3)
C7—C6—B1—O1	−2.6 (5)	B2—O3—C4—C2	−23.4 (4)
C7—C6—B1—O2	179.1 (3)	B2—O4—C5—C2	34.5 (4)
C7—C8—C9—C10	1.6 (5)	B2—C12—C13—C14	−169.5 (3)
C7—C8—C9—C18	−179.2 (3)	B2—C12—C17—C16	169.5 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1B···N1^i	0.97	2.69	3.222 (5)	115
C3—H3A···O4^ii	0.97	2.71	3.417 (5)	130
C3—H3B···O1^ii	0.97	2.62	3.438 (4)	141
C7—H7···N1^iii	0.93	2.54	3.269 (5)	135
C14—H14···O4^iv	0.93	2.71	3.407 (3)	133
C16—H16···N2^v	0.93	2.65	3.477 (5)	149
C1—H1A···C18^vi	0.97	2.66	3.598 (4)	164

Symmetry codes: (i) x, y−1, z; (ii) x, −y+3/2, z+1/2; (iii) −x+1, y−1/2, −z+1/2; (iv) −x, −y+1, −z; (v) −x, −y, −z; (vi) −x+1, −y+2, −z+1.