supplementary materials


ez2287 scheme

Acta Cryst. (2013). E69, o1067-o1068    [ doi:10.1107/S1600536813015134 ]

A co-crystal of 1,10-phenanthroline with boric acid: a novel aza-aromatic complex

A. Mirjafari, L. Pham, P. J. Smith, R. E. Sykora and J. H. Davis Jr

Abstract top

The title compound, C12H8N2·2B(OH)3, is best described as a host-guest complex in which the B(OH)3 molecules form a hydrogen-bonded cyclic network of layers parallel to the ab plane into which the 1,10-phenanthroline molecules are bound. An extensive network of hydrogen bonds are responsible for the crystal stability. No [pi]-stacking interactions occur between the 1,10-phenanthroline molecules.

Comment top

The design and synthesis of novel systems of noncovalent hosts involving hydrogen bonds is a vast research area in both molecular and supermolecular chemistry, see Pedireddi et al. (1997). In the field of supermolecular synthesis, recognition between the complementary functional groups is a main factor for the evaluation of influence of noncovalent interaction in the formation of specific architecture, see: Lehn (1990). In recent times, boric acid derivatives have been well considered to be potential co-crystal formers. In fact, the ability of –B(OH)2 functionality to form a variety of hydrogen bonds through different conformations makes it a very suitable moiety for the synthesis of novel molecular complexes, see Lee et al. (2005). The –B(OH)2 moiety is known to have an affinity for pyridyl N-atoms, often forming O—H···N hydrogen bonds, as observed in some crystals of boronic acids with aza compounds,see Talwelkar & Pedireddi (2010).

Non-covalent hosts are generally designed and synthesized by employing appropriate functional groups at required symmetry positions to form a cyclic network through the hydrogen bonds, see Pedireddi (2001). This effect has been observed vividly in simple molecular adduct such as 1,10-phenanthroline and water, see Tian et al. (1995). In this complex, a water molecule interacts with a molecule of 1,10-phenanthroline through O–H···N hydrogen bonds and an unique aza-aromatic complex is formed. In the latter, 1,10-phenanthroline could be considered as a host. Herein, we report the crystal structure of boric acid with 1,10-phenanthroline as an aza-donor compound.

As seen in Figure 1, the phen molecule forms a H-bonded adduct via two B–O–H···N interacts from one of the included B(OH)3 moieties. A strong network of hydrogen bonds among the B(OH)3 units forms a layered structure with alternating B(OH)3 and phen layers that reside in the ab planes (Figure 2). The B(OH)3 layers alone can be described as a cyclic network formed by hydrogen bonding interactions as can be seen in Figure 3. There are not any significant π-stacking interactions between the phen molecules.

Related literature top

For the design and synthesis of novel systems of non-covalent hosts involving hydrogen bonds, see: Pedireddi et al. (1997). In the field of supermolecular synthesis, recognition between the complementary functional groups is a main factor for the evaluation of influence of noncovalent interactions in the formation of specific architecture, see: Lehn (1990). The ability of the –B(OH)2 functionality to form a variety of hydrogen bonds through different conformations makes it a very suitable moiety for the synthesis of novel molecular complexes, see: Lee et al. (2005). It is known to have an affinity for pyridyl N atoms, often forming O—H···N hydrogen bonds, as observed in some crystals of boronic acids with aza compounds (Talwelkar & Pedireddi, 2010). Non-covalent hosts are generally designed and synthesized by employing appropriate functional groups at required symmetry positions to form a cyclic network through the hydrogen bonds, see: Pedireddi (2001). This effect has been observed vividly in simple molecular adducts such as 1,10-phenanthroline and water (Tian et al., 1995).

Experimental top

(CH3)3NBH3 (0.73 g, 10 mmol) and iodine (2.54 g, 5 mmol) were dissolved in toluene (4 ml) and stirred for 30 min. A solution of 1,10-phenanthroline (1.98 g, 10 mmol) in toluene (4 ml) was added, and the mixture refluxed overnight. The solution was cooled to room temperature, during which process orange-brown crystals were formed. The product was recrystallized twice from CH3CN to obtain analytically pure, red-brown crystalline product.

1H NMR (DMSO-d6, 300 MHz): δH 9.22 (dd, J = 2.8, 1.6 Hz, 2H), 8.67 (dd, J = 6.3, 1.6 Hz, 2H), 8.14 (s, 2H), 7.93 (q, J = 4.4 Hz, 2H), 6.62 (br, 2H); 13C NMR (DMSO-d6, 100 MHz): δC 151.67, 146.27, 139.09, 130.58, 128.77, 125.66.

Refinement top

H-atoms were placed in calculated positions and allowed to ride during subsequent refinement, with Uiso(H) = 1.2Ueq(C) and C—H distances of 0.93 Å for the aromatic H atoms and with Uiso(H) = 1.5Ueq(C) and O—H distances of 0.85 Å for hydroxyl H atoms.

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2011); cell refinement: CrysAlis PRO (Oxford Diffraction, 2011); data reduction: CrysAlis PRO (Oxford Diffraction, 2011); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. The molecular structure of I, with the atom-numbering scheme. Displacement ellipsoids for non-hydrogen atoms are drawn at the 50% probability level.
[Figure 2] Fig. 2. A packing diagram of I viewed along the b axis.
[Figure 3] Fig. 3. A representation of the two-dimensional B(OH)3 layers formed via hydrogen bonding in the structure of I.
Boric acid–1,10-phenanthroline (2/1) top
Crystal data top
C12H8N2·2BH3O3Z = 2
Mr = 303.87F(000) = 316
Triclinic, P1Dx = 1.435 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.1390 (13) ÅCell parameters from 3335 reflections
b = 9.6189 (13) Åθ = 3.2–25.3°
c = 10.4756 (15) ŵ = 0.11 mm1
α = 93.767 (11)°T = 295 K
β = 101.546 (14)°Prism, brown
γ = 90.644 (13)°0.35 × 0.16 × 0.09 mm
V = 703.05 (19) Å3
Data collection top
Oxford Diffraction Xcalibur Eos
diffractometer
2580 independent reflections
Radiation source: fine-focus sealed tube1972 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.023
Detector resolution: 16.0514 pixels mm-1θmax = 25.4°, θmin = 3.2°
ω scansh = 88
Absorption correction: multi-scan
[CrysAlis PRO (Oxford Diffraction, 2011) based on Clark & Reid (1995)]
k = 1111
Tmin = 0.956, Tmax = 1.000l = 1212
10473 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.036Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.096H-atom parameters constrained
S = 1.02 w = 1/[σ2(Fo2) + (0.044P)2 + 0.1204P]
where P = (Fo2 + 2Fc2)/3
2580 reflections(Δ/σ)max < 0.001
199 parametersΔρmax = 0.17 e Å3
0 restraintsΔρmin = 0.13 e Å3
Crystal data top
C12H8N2·2BH3O3γ = 90.644 (13)°
Mr = 303.87V = 703.05 (19) Å3
Triclinic, P1Z = 2
a = 7.1390 (13) ÅMo Kα radiation
b = 9.6189 (13) ŵ = 0.11 mm1
c = 10.4756 (15) ÅT = 295 K
α = 93.767 (11)°0.35 × 0.16 × 0.09 mm
β = 101.546 (14)°
Data collection top
Oxford Diffraction Xcalibur Eos
diffractometer
2580 independent reflections
Absorption correction: multi-scan
[CrysAlis PRO (Oxford Diffraction, 2011) based on Clark & Reid (1995)]
1972 reflections with I > 2σ(I)
Tmin = 0.956, Tmax = 1.000Rint = 0.023
10473 measured reflectionsθmax = 25.4°
Refinement top
R[F2 > 2σ(F2)] = 0.036H-atom parameters constrained
wR(F2) = 0.096Δρmax = 0.17 e Å3
S = 1.02Δρmin = 0.13 e Å3
2580 reflectionsAbsolute structure: ?
199 parametersAbsolute structure parameter: ?
0 restraintsRogers parameter: ?
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 > 2σ(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
xyzUiso*/Ueq
B10.0170 (3)0.65229 (18)0.64598 (18)0.0421 (4)
B20.2786 (3)0.00132 (19)0.59856 (18)0.0439 (4)
C10.1542 (2)0.83587 (17)1.04155 (17)0.0488 (4)
H1A0.10580.90010.98160.059*
C20.1999 (3)0.8822 (2)1.17305 (19)0.0573 (5)
H2A0.18150.97431.19990.069*
C30.2718 (3)0.7893 (2)1.26068 (18)0.0574 (5)
H3A0.30140.81681.34930.069*
C40.3018 (2)0.65145 (18)1.21789 (15)0.0464 (4)
C50.2496 (2)0.61314 (16)1.08273 (14)0.0369 (4)
C60.3852 (3)0.5520 (2)1.30610 (17)0.0587 (5)
H6A0.41950.57841.39480.070*
C70.4149 (3)0.4217 (2)1.26368 (18)0.0567 (5)
H70.47140.35931.32310.068*
C80.3612 (2)0.37654 (17)1.12795 (16)0.0434 (4)
C90.2778 (2)0.47095 (15)1.03670 (14)0.0361 (3)
C100.3890 (2)0.23972 (17)1.08186 (18)0.0521 (5)
H100.44510.17551.13960.062*
C110.3337 (2)0.20134 (17)0.95254 (18)0.0513 (4)
H110.34960.11070.92060.062*
C120.2522 (2)0.30118 (16)0.86861 (16)0.0449 (4)
H120.21500.27410.78020.054*
N10.17492 (17)0.70652 (13)0.99611 (12)0.0403 (3)
N20.22495 (17)0.43158 (12)0.90711 (12)0.0385 (3)
O10.07961 (17)0.52138 (11)0.66548 (10)0.0515 (3)
H10.12610.50500.74410.077*
O20.02929 (18)0.75343 (11)0.74334 (11)0.0548 (3)
H20.07960.72680.81800.082*
O30.06394 (19)0.68679 (11)0.52361 (11)0.0583 (4)
H30.06420.62170.46460.087*
O40.31472 (16)0.10158 (11)0.52210 (12)0.0539 (3)
H40.22510.15950.50810.081*
O50.39825 (18)0.11040 (12)0.61562 (12)0.0587 (3)
H50.48810.10680.57340.088*
O60.12843 (18)0.00858 (12)0.65864 (12)0.0584 (3)
H60.11010.07020.68710.088*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
B10.0496 (11)0.0403 (10)0.0372 (10)0.0098 (8)0.0080 (8)0.0079 (8)
B20.0530 (12)0.0390 (10)0.0376 (10)0.0063 (8)0.0042 (9)0.0014 (8)
C10.0501 (10)0.0455 (10)0.0492 (10)0.0076 (7)0.0074 (8)0.0006 (8)
C20.0585 (11)0.0549 (11)0.0557 (11)0.0042 (9)0.0099 (9)0.0129 (9)
C30.0567 (11)0.0713 (13)0.0406 (10)0.0023 (9)0.0063 (8)0.0125 (9)
C40.0398 (9)0.0612 (11)0.0362 (9)0.0027 (8)0.0036 (7)0.0018 (8)
C50.0307 (8)0.0468 (9)0.0328 (8)0.0008 (6)0.0049 (6)0.0055 (7)
C60.0639 (12)0.0747 (13)0.0333 (9)0.0030 (10)0.0013 (8)0.0078 (9)
C70.0568 (11)0.0685 (13)0.0422 (10)0.0011 (9)0.0019 (8)0.0214 (9)
C80.0355 (9)0.0518 (10)0.0430 (9)0.0009 (7)0.0045 (7)0.0144 (7)
C90.0301 (8)0.0432 (9)0.0354 (8)0.0011 (6)0.0056 (6)0.0091 (7)
C100.0482 (10)0.0480 (10)0.0603 (12)0.0058 (8)0.0051 (9)0.0234 (9)
C110.0540 (10)0.0400 (9)0.0611 (12)0.0059 (7)0.0121 (9)0.0102 (8)
C120.0496 (10)0.0401 (9)0.0447 (9)0.0034 (7)0.0080 (8)0.0046 (7)
N10.0409 (7)0.0419 (7)0.0380 (7)0.0046 (6)0.0071 (6)0.0032 (6)
N20.0397 (7)0.0395 (7)0.0362 (7)0.0021 (5)0.0062 (6)0.0064 (6)
O10.0702 (8)0.0450 (6)0.0346 (6)0.0199 (5)0.0025 (5)0.0063 (5)
O20.0850 (9)0.0415 (6)0.0373 (6)0.0096 (6)0.0093 (6)0.0062 (5)
O30.0905 (9)0.0455 (7)0.0360 (6)0.0270 (6)0.0032 (6)0.0077 (5)
O40.0538 (7)0.0472 (7)0.0644 (8)0.0162 (5)0.0151 (6)0.0198 (6)
O50.0678 (8)0.0517 (7)0.0620 (8)0.0202 (6)0.0188 (6)0.0226 (6)
O60.0742 (9)0.0463 (7)0.0606 (8)0.0099 (6)0.0266 (7)0.0060 (6)
Geometric parameters (Å, º) top
B1—O21.351 (2)C6—H6A0.9300
B1—O11.355 (2)C7—C81.433 (2)
B1—O31.361 (2)C7—H70.9300
B2—O61.349 (2)C8—C101.402 (2)
B2—O51.359 (2)C8—C91.411 (2)
B2—O41.367 (2)C9—N21.3612 (19)
C1—N11.323 (2)C10—C111.358 (2)
C1—C21.393 (2)C10—H100.9300
C1—H1A0.9300C11—C121.397 (2)
C2—C31.355 (3)C11—H110.9300
C2—H2A0.9300C12—N21.3207 (19)
C3—C41.404 (2)C12—H120.9300
C3—H3A0.9300O1—H10.8500
C4—C51.413 (2)O2—H20.8501
C4—C61.425 (2)O3—H30.8500
C5—N11.3559 (19)O4—H40.8501
C5—C91.450 (2)O5—H50.8501
C6—C71.336 (3)O6—H60.8501
O2—B1—O1123.27 (15)C6—C7—H7119.5
O2—B1—O3116.79 (14)C8—C7—H7119.5
O1—B1—O3119.94 (15)C10—C8—C9118.24 (15)
O6—B2—O5121.00 (16)C10—C8—C7121.84 (15)
O6—B2—O4119.75 (15)C9—C8—C7119.92 (16)
O5—B2—O4119.23 (17)N2—C9—C8121.47 (14)
N1—C1—C2124.43 (17)N2—C9—C5119.64 (13)
N1—C1—H1A117.8C8—C9—C5118.88 (14)
C2—C1—H1A117.8C11—C10—C8119.70 (15)
C3—C2—C1118.03 (16)C11—C10—H10120.2
C3—C2—H2A121.0C8—C10—H10120.2
C1—C2—H2A121.0C10—C11—C12118.49 (16)
C2—C3—C4120.11 (16)C10—C11—H11120.8
C2—C3—H3A119.9C12—C11—H11120.8
C4—C3—H3A119.9N2—C12—C11124.05 (15)
C3—C4—C5118.01 (16)N2—C12—H12118.0
C3—C4—C6121.94 (16)C11—C12—H12118.0
C5—C4—C6120.05 (16)C1—N1—C5118.04 (13)
N1—C5—C4121.35 (14)C12—N2—C9118.04 (13)
N1—C5—C9119.78 (13)B1—O1—H1115.9
C4—C5—C9118.86 (14)B1—O2—H2113.4
C7—C6—C4121.23 (16)B1—O3—H3114.0
C7—C6—H6A119.4B2—O4—H4113.0
C4—C6—H6A119.4B2—O5—H5113.6
C6—C7—C8121.04 (16)B2—O6—H6108.1
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···N20.851.902.7360 (16)168.9
O2—H2···N10.851.882.7132 (17)167.4
O3—H3···O1i0.851.862.7076 (15)176.8
O4—H4···O3i0.851.892.7286 (16)169.1
O5—H5···O4ii0.851.892.7355 (18)179.0
O6—H6···O2iii0.851.952.7946 (17)171.8
Symmetry codes: (i) x, y+1, z+1; (ii) x+1, y, z+1; (iii) x, y1, z.

Experimental details

Crystal data
Chemical formulaC12H8N2·2BH3O3
Mr303.87
Crystal system, space groupTriclinic, P1
Temperature (K)295
a, b, c (Å)7.1390 (13), 9.6189 (13), 10.4756 (15)
α, β, γ (°)93.767 (11), 101.546 (14), 90.644 (13)
V3)703.05 (19)
Z2
Radiation typeMo Kα
µ (mm1)0.11
Crystal size (mm)0.35 × 0.16 × 0.09
Data collection
DiffractometerOxford Diffraction Xcalibur Eos
diffractometer
Absorption correctionMulti-scan
[CrysAlis PRO (Oxford Diffraction, 2011) based on Clark & Reid (1995)]
Tmin, Tmax0.956, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections
10473, 2580, 1972
Rint0.023
(sin θ/λ)max1)0.602
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.036, 0.096, 1.02
No. of reflections2580
No. of parameters199
No. of restraints0
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.17, 0.13

Computer programs: CrysAlis PRO (Oxford Diffraction, 2011), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and OLEX2 (Dolomanov et al., 2009), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···N20.851.902.7360 (16)168.9
O2—H2···N10.851.882.7132 (17)167.4
O3—H3···O1i0.851.862.7076 (15)176.8
O4—H4···O3i0.851.892.7286 (16)169.1
O5—H5···O4ii0.851.892.7355 (18)179.0
O6—H6···O2iii0.851.952.7946 (17)171.8
Symmetry codes: (i) x, y+1, z+1; (ii) x+1, y, z+1; (iii) x, y1, z.
Acknowledgements top

The authors acknowledge the National Science Foundation for their generous support (NSF-CAREER grant to RES, CHE-0846680).

references
References top

Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887–897.

Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341.

Lee, S. O., Kariuki, B. M. & Harris, K. D. M. (2005). New. J. Chem. 29, 1266–1271.

Lehn, J. M. (1990). Angew. Chem. Int. Ed. 29, 1304-1319.

Oxford Diffraction (2011). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England

Pedireddi, V. R. (2001). Cryst. Growth Des. 1, 383–385

Pedireddi, V. R., Chatterjee, S., Ranganathan, A. & Rao, C. N. R. (1997). J. Am. Chem. Soc. 119, 10867–10868.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Talwelkar, M. & Pedireddi, V. R. (2010). Tetrahedron Lett. 51, 6901–6905.

Tian, Y.-P., Duan, C.-Y., Xu, X.-X. & You, X.-Z. (1995). Acta Cryst. C51, 2309–2312.

Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.