Synthesis, structure characterization, photoluminescence properties and TD–DFT calculations for two new borates

Due to their rich structural chemistry and wide variety of applications, borate materials have provided a rich area of research. In a continuation of this research, diethylammonium bis­(2-oxidobenzoato-κ²O¹,O²)borate, C₄H₁₂N⁺·BO₄(C₇H₄O)₂⁻, (1), and propyl­ammonium bis­(2-oxidobenzoato-κ²O¹,O²)borate, C₃H₁₀N⁺·BO₄(C₇H₄O)₂⁻, (2), have been synthesized by the reaction of boric acid with salicylic acid under ambient conditions. In both structures, the B atom exhibits a slightly distorted tetra­hedral environment formed by the bidentate coordination of two salicylate anions via the O atoms of the central carboxyl­ate and oxide groups. In the crystals of salts (1) and (2), mixed cation–anion layers lying parallel to the (101) plane are formed through N—H...O, C—H...O and C—H...π/N—H...O hydrogen-bonding inter­actions, resulting, in each case, in a two-dimensional supra­molecular architecture in the solid state. The photoluminescence properties of the salts were studied using the as-synthesized samples and reveal that salts (1) and (2) both display a strong blue-light emission, with maxima at 489 and 491 nm, respectively. In DFT/TD–DFT (time-dependent density functional theory) studies, the blue emission appears to be derived from an intramolecular charge transfer (ICT) excited state. In addition, IR and UV–Vis spectroscopies were used to investigate the title salts.

Computing details

For both structures, data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SIR2002 (Burla et al., 2003); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012), Mercury (Macrae et al., 2008) and POVRay (Persistence of Vision, 2004).

Diethylammonium bis(2-oxidobenzoato-κ²O¹,O²)borate (1)

Crystal data

C4H12N^+·C14H8BO6^−	Z = 2
Mr = 357.16	F(000) = 376
Triclinic, P1	Dx = 1.290 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.050 (5) Å	Cell parameters from 13321 reflections
b = 10.006 (5) Å	θ = 2.8–26.1°
c = 11.082 (5) Å	µ = 0.10 mm^−1
α = 69.207 (5)°	T = 293 K
β = 79.497 (5)°	Prism, colourless
γ = 82.267 (5)°	0.2 × 0.15 × 0.08 mm
V = 919.8 (8) Å^3

Data collection

Bruker APEXII CCD diffractometer	2284 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.039
Graphite monochromator	θmax = 26.1°, θmin = 2.8°
φ and ω scans	h = −11→10
13321 measured reflections	k = −12→12
3606 independent reflections	l = −13→13

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.043	H-atom parameters constrained
wR(F^2) = 0.109	w = 1/[σ^2(Fo^2) + (0.0458P)^2 + 0.1985P] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max < 0.001
3606 reflections	Δρmax = 0.19 e Å^−3
274 parameters	Δρmin = −0.19 e Å^−3
0 restraints

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1	0.83098 (16)	0.87636 (14)	0.66089 (11)	0.0421 (5)
O2	0.72121 (14)	0.73657 (13)	0.56181 (12)	0.0360 (4)
O3	0.72312 (14)	0.99002 (13)	0.46970 (11)	0.0364 (4)
O4	0.95483 (14)	0.83694 (13)	0.46664 (11)	0.0346 (4)
O5	0.62009 (15)	0.53441 (13)	0.67911 (12)	0.0398 (5)
O6	1.08247 (15)	0.82111 (15)	0.28245 (13)	0.0433 (5)
C1	0.7364 (2)	0.6487 (2)	0.78710 (18)	0.0377 (7)
C2	0.8033 (2)	0.7708 (2)	0.77583 (18)	0.0375 (7)
C3A	0.8301 (11)	0.7962 (12)	0.8873 (10)	0.0390 (18)	0.67 (2)
C4A	0.7914 (10)	0.6917 (7)	1.0076 (6)	0.0517 (18)	0.67 (2)
C5A	0.7236 (13)	0.5703 (7)	1.0212 (7)	0.063 (2)	0.67 (2)
C6A	0.6926 (12)	0.5499 (9)	0.9109 (9)	0.046 (2)	0.67 (2)
C7	0.68974 (19)	0.63418 (18)	0.67348 (17)	0.0282 (6)
C8	0.84761 (19)	0.95780 (18)	0.27212 (16)	0.0269 (6)
C9	0.7320 (2)	1.02006 (18)	0.34000 (17)	0.0294 (6)
C10	0.6242 (2)	1.1175 (2)	0.27304 (19)	0.0389 (7)
C11	0.6333 (2)	1.1505 (2)	0.1409 (2)	0.0442 (7)
C12	0.7473 (2)	1.0871 (2)	0.07208 (19)	0.0425 (7)
C13	0.8527 (2)	0.9911 (2)	0.13810 (17)	0.0360 (7)
C14	0.9697 (2)	0.86598 (19)	0.33957 (17)	0.0314 (6)
B1	0.8077 (3)	0.8624 (2)	0.5416 (2)	0.0331 (7)
C5B	0.810 (4)	0.533 (3)	1.0020 (17)	0.101 (8)	0.33 (2)
C3B	0.873 (4)	0.762 (3)	0.878 (3)	0.086 (8)	0.33 (2)
C4B	0.874 (4)	0.655 (3)	0.9903 (17)	0.105 (9)	0.33 (2)
C6B	0.756 (3)	0.526 (3)	0.901 (2)	0.069 (6)	0.33 (2)
N1	0.69787 (16)	0.32588 (16)	0.56209 (14)	0.0325 (5)
C15	0.8622 (3)	0.4782 (2)	0.3760 (2)	0.0494 (8)
C16	0.7489 (2)	0.3670 (2)	0.41928 (18)	0.0416 (7)
C17	0.5678 (2)	0.2349 (2)	0.61138 (19)	0.0407 (7)
C18	0.5242 (3)	0.1990 (2)	0.7550 (2)	0.0533 (8)
H3A	0.87170	0.87910	0.88050	0.0460*	0.67 (2)
H11	0.56180	1.21640	0.09670	0.0530*
H12	0.75200	1.10950	−0.01740	0.0510*
H13	0.92880	0.94740	0.09290	0.0430*
H4A	0.81210	0.70400	1.08210	0.0620*	0.67 (2)
H5A	0.69890	0.50290	1.10340	0.0760*	0.67 (2)
H6A	0.64280	0.47080	0.91930	0.0550*	0.67 (2)
H10	0.54640	1.15990	0.31790	0.0470*
H3B	0.92570	0.84040	0.86780	0.1020*	0.33 (2)
H4B	0.91600	0.66200	1.05830	0.1270*	0.33 (2)
H5B	0.80550	0.45550	1.07980	0.1200*	0.33 (2)
H6B	0.72860	0.43810	0.90510	0.0830*	0.33 (2)
HA	0.67250	0.40630	0.58230	0.0390*
HB	0.77570	0.27850	0.60410	0.0390*
H15A	0.89670	0.50090	0.28420	0.0740*
H15B	0.94630	0.44130	0.42320	0.0740*
H15C	0.81600	0.56320	0.39280	0.0740*
H16A	0.66290	0.40500	0.37300	0.0500*
H16B	0.79400	0.28290	0.39830	0.0500*
H17A	0.59420	0.14720	0.59130	0.0490*
H17B	0.48270	0.28540	0.56760	0.0490*
H18A	0.50380	0.28580	0.77550	0.0800*
H18B	0.60510	0.14140	0.79880	0.0800*
H18C	0.43550	0.14660	0.78310	0.0800*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0652 (10)	0.0394 (8)	0.0244 (7)	−0.0279 (7)	−0.0028 (6)	−0.0073 (6)
O2	0.0463 (8)	0.0359 (8)	0.0289 (7)	−0.0151 (6)	−0.0051 (6)	−0.0108 (6)
O3	0.0451 (8)	0.0348 (7)	0.0290 (7)	−0.0009 (6)	−0.0013 (6)	−0.0133 (6)
O4	0.0342 (8)	0.0383 (7)	0.0278 (7)	−0.0039 (6)	−0.0066 (6)	−0.0055 (6)
O5	0.0474 (9)	0.0308 (7)	0.0462 (8)	−0.0121 (6)	−0.0032 (6)	−0.0178 (6)
O6	0.0307 (8)	0.0550 (9)	0.0414 (8)	0.0058 (7)	−0.0024 (6)	−0.0175 (7)
C1	0.0497 (13)	0.0309 (11)	0.0322 (11)	−0.0121 (9)	−0.0084 (9)	−0.0060 (9)
C2	0.0480 (12)	0.0370 (11)	0.0263 (11)	−0.0144 (9)	−0.0061 (9)	−0.0050 (9)
C3A	0.058 (3)	0.037 (4)	0.026 (2)	−0.013 (2)	−0.0087 (18)	−0.011 (2)
C4A	0.078 (4)	0.055 (3)	0.026 (2)	−0.025 (3)	−0.014 (3)	−0.0083 (18)
C5A	0.108 (6)	0.049 (3)	0.028 (2)	−0.031 (3)	−0.012 (3)	0.0030 (19)
C6A	0.068 (5)	0.034 (3)	0.037 (2)	−0.022 (3)	−0.014 (3)	−0.0023 (19)
C7	0.0270 (10)	0.0246 (10)	0.0345 (11)	−0.0006 (8)	−0.0012 (8)	−0.0138 (8)
C8	0.0261 (10)	0.0284 (10)	0.0239 (9)	−0.0072 (8)	−0.0008 (7)	−0.0056 (8)
C9	0.0348 (11)	0.0239 (9)	0.0279 (10)	−0.0082 (8)	−0.0027 (8)	−0.0057 (8)
C10	0.0379 (12)	0.0299 (11)	0.0459 (13)	0.0012 (9)	−0.0060 (9)	−0.0108 (9)
C11	0.0447 (13)	0.0337 (11)	0.0481 (13)	−0.0028 (10)	−0.0185 (10)	−0.0008 (10)
C12	0.0439 (13)	0.0491 (13)	0.0285 (11)	−0.0126 (10)	−0.0079 (9)	−0.0014 (10)
C13	0.0323 (11)	0.0448 (12)	0.0282 (11)	−0.0107 (9)	0.0012 (8)	−0.0089 (9)
C14	0.0304 (11)	0.0320 (10)	0.0306 (11)	−0.0063 (8)	−0.0029 (8)	−0.0087 (8)
B1	0.0423 (14)	0.0327 (12)	0.0250 (11)	−0.0109 (10)	−0.0033 (10)	−0.0084 (9)
C5B	0.16 (2)	0.093 (12)	0.042 (8)	−0.071 (14)	−0.043 (10)	0.024 (7)
C3B	0.16 (2)	0.055 (13)	0.050 (9)	−0.063 (13)	−0.027 (13)	−0.002 (7)
C4B	0.14 (2)	0.127 (15)	0.049 (8)	−0.087 (15)	−0.041 (10)	0.011 (8)
C6B	0.080 (13)	0.053 (8)	0.061 (8)	−0.029 (9)	−0.026 (9)	0.014 (6)
N1	0.0316 (9)	0.0321 (9)	0.0383 (9)	−0.0004 (7)	−0.0095 (7)	−0.0160 (7)
C15	0.0558 (14)	0.0435 (13)	0.0418 (12)	−0.0055 (11)	−0.0025 (10)	−0.0076 (10)
C16	0.0458 (13)	0.0475 (12)	0.0348 (11)	0.0000 (10)	−0.0124 (9)	−0.0159 (9)
C17	0.0355 (12)	0.0409 (12)	0.0536 (13)	−0.0077 (9)	−0.0087 (10)	−0.0228 (10)
C18	0.0539 (15)	0.0540 (14)	0.0562 (15)	−0.0247 (11)	0.0010 (11)	−0.0208 (11)

Geometric parameters (Å, º)

C2—O1	1.342 (2)	C10—C9	1.396 (3)
B1—O1	1.433 (3)	C11—C10	1.371 (3)
C7—O2	1.309 (2)	C12—C11	1.389 (3)
B1—O2	1.500 (3)	C13—C12	1.370 (3)
C9—O3	1.349 (2)	H3A—C3A	0.9300
B1—O3	1.445 (3)	H3B—C3B	0.9300
C14—O4	1.318 (2)	H4A—C4A	0.9300
B1—O4	1.478 (3)	H4B—C4B	0.9300
C7—O5	1.228 (2)	H5A—C5A	0.9300
C14—O6	1.219 (2)	H5B—C5B	0.9300
C16—N1	1.487 (2)	H6A—C6A	0.9300
C17—N1	1.488 (3)	H6B—C6B	0.9300
HB—N1	0.9000	H10—C10	0.9300
HA—N1	0.9000	H11—C11	0.9300
C6B—C1	1.43 (2)	H12—C12	0.9300
C7—C1	1.458 (3)	H13—C13	0.9300
C2—C1	1.392 (3)	C16—C15	1.506 (3)
C6A—C1	1.400 (10)	C18—C17	1.490 (3)
C3B—C2	1.37 (3)	H15A—C15	0.9600
C3A—C2	1.414 (11)	H15B—C15	0.9600
C4A—C3A	1.390 (13)	H15C—C15	0.9600
C4B—C3B	1.32 (4)	H16A—C16	0.9700
C5A—C4A	1.383 (12)	H16B—C16	0.9700
C5B—C4B	1.38 (5)	H17A—C17	0.9700
C6A—C5A	1.390 (13)	H17B—C17	0.9700
C6B—C5B	1.33 (4)	H18A—C18	0.9600
C13—C8	1.395 (3)	H18B—C18	0.9600
C9—C8	1.385 (3)	H18C—C18	0.9600
C14—C8	1.471 (3)
C2—O1—B1	121.52 (16)	C5A—C4A—H4A	119.00
C7—O2—B1	124.92 (15)	C5B—C4B—H4B	122.00
C9—O3—B1	117.58 (15)	C3B—C4B—H4B	122.00
C14—O4—B1	120.97 (15)	C4A—C5A—H5A	120.00
C16—N1—C17	114.80 (15)	C6A—C5A—H5A	120.00
C17—N1—HB	109.00	C4B—C5B—H5B	120.00
C16—N1—HB	109.00	C6B—C5B—H5B	120.00
C17—N1—HA	109.00	C5A—C6A—H6A	120.00
C16—N1—HA	109.00	C1—C6A—H6A	120.00
HA—N1—HB	107.00	C5B—C6B—H6B	118.00
C6A—C1—C7	119.2 (4)	C1—C6B—H6B	119.00
C2—C1—C6A	119.7 (4)	C9—C10—H10	120.00
C2—C1—C6B	116.3 (12)	C11—C10—H10	120.00
C2—C1—C7	120.38 (17)	C10—C11—H11	119.00
C6B—C1—C7	120.9 (12)	C12—C11—H11	119.00
C1—C2—C3B	116.1 (13)	C13—C12—H12	121.00
C1—C2—C3A	121.2 (5)	C11—C12—H12	121.00
O1—C2—C1	121.75 (17)	C12—C13—H13	119.00
O1—C2—C3A	116.7 (5)	C8—C13—H13	119.00
O1—C2—C3B	120.2 (14)	N1—C16—C15	110.53 (16)
C2—C3A—C4A	117.0 (9)	N1—C17—C18	111.18 (17)
C2—C3B—C4B	127 (3)	C16—C15—H15A	109.00
C3A—C4A—C5A	122.8 (8)	C16—C15—H15B	109.00
C3B—C4B—C5B	117 (3)	H15A—C15—H15C	109.00
C4A—C5A—C6A	119.4 (7)	H15B—C15—H15C	109.00
C4B—C5B—C6B	119 (2)	C16—C15—H15C	110.00
C1—C6A—C5A	119.8 (8)	H15A—C15—H15B	109.00
C1—C6B—C5B	123 (3)	N1—C16—H16A	110.00
O2—C7—O5	119.77 (16)	C15—C16—H16B	110.00
O2—C7—C1	116.84 (16)	N1—C16—H16B	110.00
O5—C7—C1	123.36 (17)	C15—C16—H16A	110.00
C13—C8—C14	120.50 (16)	H16A—C16—H16B	108.00
C9—C8—C13	119.47 (17)	N1—C17—H17B	109.00
C9—C8—C14	119.88 (15)	C18—C17—H17A	109.00
O3—C9—C8	121.12 (16)	N1—C17—H17A	109.00
O3—C9—C10	119.27 (17)	H17A—C17—H17B	108.00
C8—C9—C10	119.60 (16)	C18—C17—H17B	109.00
C9—C10—C11	119.81 (18)	C17—C18—H18A	109.00
C10—C11—C12	121.13 (18)	H18B—C18—H18C	109.00
C11—C12—C13	118.95 (18)	H18A—C18—H18C	109.00
C8—C13—C12	121.02 (18)	H18A—C18—H18B	110.00
O4—C14—C8	116.77 (16)	C17—C18—H18B	109.00
O4—C14—O6	120.34 (17)	C17—C18—H18C	109.00
O6—C14—C8	122.85 (16)	O1—B1—O4	109.52 (19)
C2—C3A—H3A	122.00	O2—B1—O3	107.50 (18)
C4A—C3A—H3A	121.00	O2—B1—O4	105.24 (15)
C2—C3B—H3B	116.00	O3—B1—O4	112.28 (15)
C4B—C3B—H3B	116.00	O1—B1—O3	108.88 (16)
C3A—C4A—H4A	119.00	O1—B1—O2	113.45 (16)
B1—O1—C2—C1	−6.6 (3)	C2—C1—C7—O2	3.5 (3)
B1—O1—C2—C3A	−179.9 (5)	C2—C1—C7—O5	−174.32 (18)
C2—O1—B1—O2	12.2 (3)	C6A—C1—C2—C3A	1.0 (8)
C2—O1—B1—O3	131.84 (18)	C6A—C1—C7—O5	−4.1 (6)
C2—O1—B1—O4	−105.0 (2)	C6A—C1—C2—O1	−172.1 (5)
B1—O2—C7—O5	−178.83 (18)	C6A—C1—C7—O2	173.7 (5)
B1—O2—C7—C1	3.2 (3)	C1—C2—C3A—C4A	2.1 (11)
C7—O2—B1—O1	−10.8 (3)	O1—C2—C3A—C4A	175.5 (7)
C7—O2—B1—O3	−131.24 (17)	C2—C3A—C4A—C5A	−2.8 (14)
C7—O2—B1—O4	108.90 (18)	C3A—C4A—C5A—C6A	0.3 (15)
B1—O3—C9—C8	−18.1 (3)	C4A—C5A—C6A—C1	2.9 (15)
B1—O3—C9—C10	163.06 (19)	C14—C8—C9—O3	−4.8 (3)
C9—O3—B1—O1	158.45 (16)	C14—C8—C9—C10	174.07 (18)
C9—O3—B1—O2	−78.3 (2)	C9—C8—C13—C12	1.6 (3)
C9—O3—B1—O4	37.0 (2)	C14—C8—C13—C12	−173.79 (18)
B1—O4—C14—O6	−166.55 (18)	C9—C8—C14—O4	6.1 (3)
B1—O4—C14—C8	15.6 (3)	C9—C8—C14—O6	−171.75 (19)
C14—O4—B1—O1	−157.80 (16)	C13—C8—C14—O4	−178.51 (17)
C14—O4—B1—O2	79.9 (2)	C13—C8—C14—O6	3.7 (3)
C14—O4—B1—O3	−36.7 (2)	C13—C8—C9—C10	−1.4 (3)
C16—N1—C17—C18	−179.94 (17)	C13—C8—C9—O3	179.76 (17)
C17—N1—C16—C15	170.41 (17)	C8—C9—C10—C11	0.2 (3)
C7—C1—C2—O1	−2.0 (3)	O3—C9—C10—C11	179.04 (18)
C7—C1—C2—C3A	171.1 (5)	C9—C10—C11—C12	0.9 (3)
C2—C1—C6A—C5A	−3.5 (11)	C10—C11—C12—C13	−0.6 (3)
C7—C1—C6A—C5A	−173.8 (7)	C11—C12—C13—C8	−0.6 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—HA···O5	0.90	1.91	2.779 (3)	162
N1—HB···O6^i	0.90	1.89	2.783 (3)	171
C17—H17A···O3^ii	0.97	2.47	3.383 (3)	157
C18—H18C···Cg1^iii	0.96	2.68	3.573 (3)	155 (1)

Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) x, y−1, z; (iii) −x+1, −y+1, −z+1.

Propylammonium bis(2-oxidobenzoato-κ²O¹,O²)borate (2)

Crystal data

C3H10N^+·C14H8BO6^−	F(000) = 720
Mr = 343.13	Dx = 1.361 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 13759 reflections
a = 11.529 (5) Å	θ = 3.0–25.0°
b = 8.885 (5) Å	µ = 0.10 mm^−1
c = 17.216 (5) Å	T = 293 K
β = 108.308 (5)°	Prism, colorless
V = 1674.3 (13) Å^3	0.25 × 0.15 × 0.08 mm
Z = 4

Data collection

Bruker APEXII CCD diffractometer	2395 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.021
Graphite monochromator	θmax = 25.0°, θmin = 3.0°
φ and ω scans	h = −13→13
13759 measured reflections	k = −9→10
2937 independent reflections	l = −20→20

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.050	H-atom parameters constrained
wR(F^2) = 0.154	w = 1/[Σ^2(FO^2) + (0.0934P)^2 + 0.2978P] where P = (FO^2 + 2FC^2)/3
S = 1.09	(Δ/σ)max < 0.001
2937 reflections	Δρmax = 0.23 e Å^−3
226 parameters	Δρmin = −0.25 e Å^−3
0 restraints

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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 (Ų)

	x	y	z	Uiso*/Ueq
O1	0.73685 (11)	0.37010 (14)	0.31029 (7)	0.0493 (4)
O2	0.62630 (9)	0.50406 (13)	0.18544 (7)	0.0442 (4)
O3	0.52299 (10)	0.37165 (14)	0.26389 (6)	0.0445 (4)
O4	0.63604 (10)	0.23584 (13)	0.18857 (7)	0.0455 (4)
O5	0.71769 (12)	0.66275 (16)	0.12628 (8)	0.0592 (4)
O6	0.54284 (13)	0.08825 (14)	0.08470 (7)	0.0560 (4)
C1	0.84223 (14)	0.52620 (19)	0.24101 (10)	0.0433 (5)
C2	0.84163 (14)	0.43206 (19)	0.30517 (10)	0.0437 (5)
C3	0.95041 (17)	0.4028 (2)	0.36734 (12)	0.0589 (6)
C4	1.05781 (17)	0.4655 (3)	0.36401 (15)	0.0689 (7)
C5	1.05973 (18)	0.5586 (3)	0.30045 (15)	0.0697 (8)
C6	0.95227 (17)	0.5898 (2)	0.23930 (14)	0.0584 (7)
C7	0.72606 (15)	0.56923 (19)	0.17959 (10)	0.0424 (5)
C8	0.41897 (14)	0.24106 (18)	0.14018 (9)	0.0411 (5)
C9	0.41691 (14)	0.33136 (19)	0.20576 (9)	0.0396 (5)
C10	0.30679 (16)	0.3794 (2)	0.21366 (11)	0.0512 (6)
C11	0.19952 (17)	0.3388 (3)	0.15534 (13)	0.0646 (7)
C12	0.20020 (18)	0.2509 (3)	0.08903 (14)	0.0699 (8)
C13	0.30898 (17)	0.2018 (2)	0.08171 (11)	0.0568 (6)
C14	0.53601 (16)	0.18277 (18)	0.13487 (9)	0.0426 (5)
B1	0.63163 (16)	0.3710 (2)	0.23856 (11)	0.0411 (6)
N1	0.52463 (13)	0.22527 (16)	−0.07278 (8)	0.0473 (5)
C15	0.8480 (2)	0.3759 (3)	0.02313 (19)	0.0926 (10)
C16	0.74249 (17)	0.2653 (3)	−0.00065 (13)	0.0635 (7)
C17	0.62215 (17)	0.3379 (2)	−0.04290 (13)	0.0592 (6)
H3	0.95040	0.34100	0.41090	0.0710*
H4	1.13030	0.44470	0.40530	0.0830*
H5	1.13300	0.60020	0.29880	0.0840*
H6	0.95300	0.65350	0.19660	0.0700*
H10	0.30550	0.43840	0.25800	0.0610*
H11	0.12540	0.37070	0.16050	0.0780*
H12	0.12700	0.22530	0.04960	0.0840*
H13	0.30940	0.14200	0.03750	0.0680*
HA	0.45430	0.27170	−0.09760	0.0710*
HB	0.51750	0.17200	−0.03080	0.0710*
HC	0.54320	0.16400	−0.10810	0.0710*
H15A	0.92250	0.32310	0.04990	0.1390*
H15B	0.83370	0.45010	0.05960	0.1390*
H15C	0.85460	0.42460	−0.02510	0.1390*
H16A	0.75860	0.18940	−0.03650	0.0760*
H16B	0.73770	0.21490	0.04820	0.0760*
H17A	0.60110	0.40550	−0.00520	0.0710*
H17B	0.62880	0.39700	−0.08870	0.0710*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0425 (7)	0.0611 (8)	0.0382 (7)	−0.0072 (5)	0.0038 (5)	0.0059 (5)
O2	0.0360 (6)	0.0472 (7)	0.0447 (6)	−0.0026 (5)	0.0061 (5)	0.0055 (5)
O3	0.0387 (6)	0.0585 (8)	0.0351 (6)	−0.0095 (5)	0.0101 (5)	−0.0075 (5)
O4	0.0435 (6)	0.0468 (7)	0.0451 (6)	−0.0006 (5)	0.0123 (5)	−0.0044 (5)
O5	0.0544 (7)	0.0614 (8)	0.0615 (8)	0.0012 (6)	0.0176 (6)	0.0200 (7)
O6	0.0823 (9)	0.0451 (7)	0.0448 (7)	−0.0064 (6)	0.0261 (6)	−0.0085 (6)
C1	0.0367 (8)	0.0431 (9)	0.0487 (9)	−0.0003 (7)	0.0113 (7)	−0.0042 (7)
C2	0.0377 (8)	0.0450 (9)	0.0435 (9)	−0.0011 (7)	0.0056 (7)	−0.0064 (7)
C3	0.0471 (10)	0.0659 (12)	0.0512 (10)	0.0014 (9)	−0.0023 (8)	−0.0006 (9)
C4	0.0405 (10)	0.0749 (14)	0.0755 (14)	0.0011 (9)	−0.0046 (9)	−0.0076 (12)
C5	0.0385 (10)	0.0739 (14)	0.0930 (16)	−0.0090 (9)	0.0153 (10)	−0.0144 (13)
C6	0.0471 (10)	0.0563 (11)	0.0737 (13)	−0.0036 (8)	0.0217 (9)	−0.0008 (9)
C7	0.0444 (9)	0.0403 (9)	0.0432 (9)	−0.0001 (7)	0.0148 (7)	−0.0010 (7)
C8	0.0461 (9)	0.0401 (9)	0.0337 (8)	−0.0078 (7)	0.0076 (7)	0.0040 (7)
C9	0.0400 (8)	0.0424 (9)	0.0338 (8)	−0.0086 (6)	0.0079 (6)	0.0031 (6)
C10	0.0456 (9)	0.0579 (11)	0.0508 (10)	−0.0048 (8)	0.0160 (8)	0.0000 (8)
C11	0.0409 (10)	0.0785 (14)	0.0702 (13)	−0.0036 (9)	0.0113 (9)	0.0069 (11)
C12	0.0475 (11)	0.0844 (16)	0.0627 (12)	−0.0137 (10)	−0.0044 (9)	−0.0018 (11)
C13	0.0553 (11)	0.0615 (12)	0.0436 (10)	−0.0119 (9)	0.0011 (8)	−0.0057 (8)
C14	0.0577 (10)	0.0370 (9)	0.0328 (8)	−0.0050 (7)	0.0140 (7)	0.0049 (7)
B1	0.0374 (9)	0.0478 (11)	0.0355 (9)	−0.0031 (7)	0.0079 (7)	−0.0003 (8)
N1	0.0507 (8)	0.0474 (8)	0.0401 (8)	0.0023 (6)	0.0089 (6)	0.0040 (6)
C15	0.0544 (13)	0.110 (2)	0.105 (2)	−0.0073 (13)	0.0129 (13)	−0.0192 (17)
C16	0.0550 (11)	0.0779 (14)	0.0564 (11)	0.0065 (10)	0.0158 (9)	0.0041 (10)
C17	0.0563 (11)	0.0485 (10)	0.0645 (12)	−0.0004 (8)	0.0071 (9)	0.0049 (9)

Geometric parameters (Å, º)

C2—O1	1.355 (2)	C9—C8	1.391 (2)
B1—O1	1.434 (2)	C10—C9	1.386 (3)
C7—O2	1.320 (2)	C11—C10	1.374 (3)
B1—O2	1.484 (2)	C12—C11	1.385 (3)
C9—O3	1.363 (2)	C13—C12	1.371 (3)
B1—O3	1.450 (2)	H3—C3	0.9300
C14—O4	1.318 (2)	H4—C4	0.9300
B1—O4	1.488 (2)	H5—C5	0.9300
C7—O5	1.219 (2)	H6—C6	0.9300
C14—O6	1.225 (2)	H10—C10	0.9300
C17—N1	1.472 (3)	H11—C11	0.9300
HB—N1	0.8900	H12—C12	0.9300
HC—N1	0.8900	H13—C13	0.9300
HA—N1	0.8900	C16—C15	1.517 (4)
C6—C1	1.398 (3)	C17—C16	1.495 (3)
C7—C1	1.473 (3)	H15A—C15	0.9600
C2—C1	1.387 (2)	H15B—C15	0.9600
C3—C2	1.394 (3)	H15C—C15	0.9600
C4—C3	1.375 (3)	H16A—C16	0.9700
C5—C4	1.377 (4)	H16B—C16	0.9700
C6—C5	1.379 (3)	H17A—C17	0.9700
C13—C8	1.393 (3)	H17B—C17	0.9700
C14—C8	1.475 (3)
C2—O1—B1	118.16 (13)	C3—C4—H4	119.00
C7—O2—B1	121.89 (13)	C5—C4—H4	119.00
C9—O3—B1	116.04 (12)	C4—C5—H5	120.00
C14—O4—B1	120.88 (14)	C6—C5—H5	120.00
HA—N1—HB	110.00	C5—C6—H6	120.00
HA—N1—HC	109.00	C1—C6—H6	120.00
HB—N1—HC	109.00	C11—C10—H10	120.00
C17—N1—HC	109.00	C9—C10—H10	120.00
C17—N1—HA	109.00	C12—C11—H11	120.00
C17—N1—HB	109.00	C10—C11—H11	120.00
C6—C1—C7	120.45 (16)	C11—C12—H12	120.00
C2—C1—C6	119.48 (16)	C13—C12—H12	120.00
C2—C1—C7	119.83 (15)	C8—C13—H13	120.00
O1—C2—C1	121.61 (15)	C12—C13—H13	120.00
C1—C2—C3	119.71 (16)	C15—C16—C17	113.3 (2)
O1—C2—C3	118.66 (15)	N1—C17—C16	111.52 (16)
C2—C3—C4	119.81 (18)	C16—C15—H15C	109.00
C3—C4—C5	121.1 (2)	H15A—C15—H15B	109.00
C4—C5—C6	119.5 (2)	H15B—C15—H15C	109.00
C1—C6—C5	120.44 (19)	C16—C15—H15A	109.00
O2—C7—C1	116.70 (14)	H15A—C15—H15C	109.00
O2—C7—O5	119.46 (16)	C16—C15—H15B	109.00
O5—C7—C1	123.82 (17)	C15—C16—H16A	109.00
C9—C8—C14	120.13 (14)	C17—C16—H16A	109.00
C9—C8—C13	119.14 (16)	C17—C16—H16B	109.00
C13—C8—C14	120.67 (15)	H16A—C16—H16B	108.00
C8—C9—C10	120.46 (15)	C15—C16—H16B	109.00
O3—C9—C8	120.49 (15)	N1—C17—H17B	109.00
O3—C9—C10	119.05 (14)	C16—C17—H17A	109.00
C9—C10—C11	119.30 (17)	N1—C17—H17A	109.00
C10—C11—C12	120.9 (2)	H17A—C17—H17B	108.00
C11—C12—C13	119.8 (2)	C16—C17—H17B	109.00
C8—C13—C12	120.36 (18)	O1—B1—O3	108.55 (13)
O4—C14—C8	116.55 (14)	O1—B1—O4	108.69 (14)
O6—C14—C8	123.18 (16)	O2—B1—O4	106.79 (13)
O4—C14—O6	120.27 (17)	O3—B1—O4	111.53 (14)
C4—C3—H3	120.00	O2—B1—O3	108.04 (13)
C2—C3—H3	120.00	O1—B1—O2	113.28 (14)
B1—O1—C2—C1	15.9 (2)	C2—C1—C7—O2	−5.6 (2)
B1—O1—C2—C3	−165.78 (16)	C2—C1—C7—O5	172.42 (17)
C2—O1—B1—O2	−32.2 (2)	C6—C1—C7—O2	180.00 (17)
C2—O1—B1—O3	−152.24 (14)	C6—C1—C7—O5	−1.9 (3)
C2—O1—B1—O4	86.29 (17)	O1—C2—C3—C4	−179.37 (18)
B1—O2—C7—O5	168.78 (15)	C1—C2—C3—C4	−1.0 (3)
B1—O2—C7—C1	−13.1 (2)	C2—C3—C4—C5	0.7 (3)
C7—O2—B1—O1	31.8 (2)	C3—C4—C5—C6	0.2 (4)
C7—O2—B1—O3	152.13 (14)	C4—C5—C6—C1	−0.8 (3)
C7—O2—B1—O4	−87.78 (17)	C13—C8—C9—O3	−179.97 (16)
B1—O3—C9—C8	24.3 (2)	C13—C8—C9—C10	1.2 (2)
B1—O3—C9—C10	−156.82 (15)	C14—C8—C9—O3	2.6 (2)
C9—O3—B1—O1	−162.62 (13)	C14—C8—C9—C10	−176.27 (15)
C9—O3—B1—O2	74.17 (17)	C9—C8—C13—C12	−0.4 (3)
C9—O3—B1—O4	−42.91 (18)	C14—C8—C13—C12	177.06 (18)
B1—O4—C14—O6	167.70 (15)	C9—C8—C14—O4	−8.3 (2)
B1—O4—C14—C8	−13.4 (2)	C9—C8—C14—O6	170.60 (16)
C14—O4—B1—O1	158.21 (14)	C13—C8—C14—O4	174.32 (15)
C14—O4—B1—O2	−79.25 (17)	C13—C8—C14—O6	−6.8 (2)
C14—O4—B1—O3	38.58 (19)	O3—C9—C10—C11	−179.84 (18)
C6—C1—C2—O1	178.71 (16)	C8—C9—C10—C11	−1.0 (3)
C6—C1—C2—C3	0.4 (3)	C9—C10—C11—C12	0.0 (3)
C7—C1—C2—O1	4.3 (2)	C10—C11—C12—C13	0.9 (4)
C7—C1—C2—C3	−174.01 (16)	C11—C12—C13—C8	−0.6 (3)
C2—C1—C6—C5	0.5 (3)	C15—C16—C17—N1	173.86 (18)
C7—C1—C6—C5	174.88 (19)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—HA···O2^i	0.8900	2.5000	3.233 (3)	140.00
N1—HA···O5^i	0.8900	1.9700	2.833 (3)	161.00
N1—HB···O6	0.8900	2.0600	2.919 (2)	163.00
N1—HC···O3^ii	0.8900	2.1700	2.935 (2)	144.00

Symmetry codes: (i) −x+1, −y+1, −z; (ii) x, −y+1/2, z−1/2.