(S)-(-)-1,1'-Bi-2-naphthol dimethyl­formamide sesquisolvate

In the crystal structure of the title compound, C₂₀H₁₄O₂·1.5C₃H₇N O, one of the hydroxyl groups forms a hydrogen bond to the dimethyl­formamide (DMF) mol­ecule that lies on a general position and the other a hydrogen bond to the DMF mol­ecule that lies on a twofold rotation axis. The naphthyl residues are aligned at 75.8 (1)° with respect to each other.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.007 Å
• Disorder in solvent or counterion
• R factor = 0.076
• wR factor = 0.193
• Data-to-parameter ratio = 8.1

checkCIF/PLATON results

No syntax errors found



Datablock: I


Alert level C
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............       0.50 Ratio
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for         N2
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for         N1
PLAT302_ALERT_4_C Anion/Solvent Disorder .........................      23.00 Perc.
PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          7
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          2
              C3 H7 N O
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          3
              C3 H7 N O

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           25.00
           From the CIF: _reflns_number_total               2335
           Count of symmetry unique reflns         2336
           Completeness (_total/calc)             99.96%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured         0
           Fraction of Friedel pairs measured     0.000
           Are heavy atom types Z>Si present         no

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   9 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   3 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
   1 ALERT type 3 Indicator that the structure quality may be low
   6 ALERT type 4 Improvement, methodology, query or suggestion

---

S1. Comment

The preceeding study (Yuan et al., 2005) reports the structure of racemic 1,1'-bi-2-naphthol DMF sesquisolvate. In the title optically active S-analogue, (I) (Fig. 1), the two aromatic moieties enclose a dihedral angle of 75.8 (1)°. One of the hydroxy groups forms a hydrogen bond to the ordered DMF (which lies on a general position) and the other one to the disordered DMF (which lies on a twofold rotation axis) (Table 1).

The hydrogen bonding is similar to that found in the racemic solvate (Yuan et al., 2005). However, the packing is somewhat more efficient, as noted from the density (1.235 Mg m⁻³) compared with that of the racemic solvate (1.222 Mg m⁻³). The angle between the two aromatic systems is similar to that found in the anhydrous compound, which crystallizes in space group P32 (Toda et al., 1997). The structure of the anhydrous R-(+)-enantiomer has also been reported (Mori et al., 1993).

S2. Experimental

S-(-)-1,1'-Bi-2-naphthol (0.29 g, 1 mmol) was dissovled in a mixed-solvent system of water (5 ml) and dimethylformamide (5 ml). This solution was added to an ethanol solution (10 ml) of 2-aminopyrimidine (0.19 g, 2 mmol). Evaporation of the solvent over several weeks gave colourless block-shaped crystals of (I).

S3. Refinement

One DMF molecule is disordered over a twofold rotation axis. A number of restraints were imposed on this molecule, as follows: C24—O4 = 1.25 (1), C24—N2 = 1.35 (1), N2—C25 = N2—C26 = 1.45 (1), O4···C25 = 2.71 (1), C24···C25 = C24···C26 = 2.43 (2) and C25···C26 = 2.51 (2) Å. The displacement parameters of these atoms were restrained to an approximate isotropic behaviour; furthermore, these atoms were restrained to lie in a common plane. H atoms were generated geometrically (O—H = 0.82, C—H_aromatic = 0.93 and C—H_methyl = 0.96 Å), and were included in the refinement in the riding-model approximation, with U_iso(H) = 1.2U_eq(C,O), or 1.5U_eq(C) for methyl groups. As there are no heavy atoms in the structure, Friedel pairs were merged.

Computing details

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.

Figures

Fig. 1. A plot of (I), with displacement ellipsoids drawn at the 30% probability level. H atoms are shown as spheres of arbitrary radii.

S-(-)-1,1'-Bi-2-naphthol dimethylformamide sesquisolvate

Crystal data

C20H14O2·1.5C3H7NO	Dx = 1.235 Mg m^−3
Mr = 395.96	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P43212	Cell parameters from 4002 reflections
Hall symbol: P 4nw 2abw	θ = 2.3–23.0°
a = 8.8430 (5) Å	µ = 0.08 mm^−1
c = 54.486 (3) Å	T = 295 K
V = 4260.7 (3) Å^3	Block, colourless
Z = 8	0.36 × 0.20 × 0.19 mm
F(000) = 1680

Data collection

Bruker APEX CCD area-detector diffractometer	2240 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.046
Graphite monochromator	θmax = 25.0°, θmin = 2.3°
ω and ϕ scans	h = −10→9
22486 measured reflections	k = −10→10
2335 independent reflections	l = −64→64

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)] = 0.076	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.193	H-atom parameters constrained
S = 1.37	w = 1/[σ^2(Fo^2) + (0.0793P)^2 + 1.8739P] where P = (Fo^2 + 2Fc^2)/3
2335 reflections	(Δ/σ)max = 0.001
287 parameters	Δρmax = 0.18 e Å^−3
40 restraints	Δρmin = −0.25 e Å^−3

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1	0.9689 (4)	0.8528 (5)	−0.0938 (1)	0.064 (1)
O2	0.9407 (4)	0.9637 (4)	−0.0363 (1)	0.051 (1)
O3	1.1137 (5)	0.9680 (6)	−0.1328 (1)	0.079 (1)
O4	1.1125 (5)	1.1125 (5)	0.0000	0.078 (2)
N1	1.3244 (6)	0.9178 (6)	−0.1546 (1)	0.069 (1)
N2	1.2937 (5)	1.2937 (5)	0.0000	0.071 (2)
C1	0.7438 (5)	0.8479 (4)	−0.0711 (1)	0.035 (1)
C2	0.8228 (5)	0.8976 (5)	−0.0913 (1)	0.043 (1)
C3	0.7550 (6)	0.9930 (6)	−0.1088 (1)	0.054 (1)
C4	0.6083 (6)	1.0344 (6)	−0.1063 (1)	0.055 (1)
C5	0.5202 (5)	0.9829 (5)	−0.0866 (1)	0.046 (1)
C6	0.5896 (5)	0.8906 (5)	−0.0685 (1)	0.038 (1)
C7	0.5004 (5)	0.8420 (6)	−0.0484 (1)	0.048 (1)
C8	0.3513 (6)	0.8813 (8)	−0.0467 (1)	0.069 (2)
C9	0.2833 (6)	0.9703 (8)	−0.0650 (1)	0.075 (2)
C10	0.3649 (6)	1.0209 (7)	−0.0839 (1)	0.066 (2)
C11	0.8179 (5)	0.7504 (5)	−0.0523 (1)	0.035 (1)
C12	0.9144 (4)	0.8115 (5)	−0.0355 (1)	0.037 (1)
C13	0.9830 (5)	0.7211 (6)	−0.0172 (1)	0.046 (1)
C14	0.9540 (5)	0.5709 (6)	−0.0162 (1)	0.047 (1)
C15	0.8551 (5)	0.5010 (5)	−0.0330 (1)	0.044 (1)
C16	0.7850 (5)	0.5921 (5)	−0.0513 (1)	0.038 (1)
C17	0.6843 (5)	0.5206 (5)	−0.0679 (1)	0.045 (1)
C18	0.6548 (7)	0.3690 (6)	−0.0664 (1)	0.061 (1)
C19	0.7262 (7)	0.2801 (6)	−0.0487 (1)	0.066 (2)
C20	0.8220 (6)	0.3446 (6)	−0.0324 (1)	0.057 (1)
C21	1.2277 (7)	0.8935 (7)	−0.1369 (1)	0.066 (2)
C22	1.304 (1)	1.0453 (9)	−0.1711 (1)	0.105 (3)
C23	1.4567 (8)	0.823 (1)	−0.1577 (2)	0.110 (3)
C24	1.1980 (8)	1.2008 (8)	0.0115 (1)	0.068 (3)	0.50
C25	1.298 (2)	1.291 (2)	−0.0269 (1)	0.119 (5)	0.50
C26	1.394 (1)	1.396 (1)	0.0125 (2)	0.153 (8)	0.50
H1	1.0072	0.8968	−0.1055	0.096*
H2	1.0054	0.9860	−0.0261	0.076*
H3	0.8110	1.0277	−0.1221	0.065*
H4	0.5651	1.0982	−0.1179	0.066*
H7	0.5438	0.7826	−0.0362	0.058*
H8	0.2944	0.8487	−0.0334	0.082*
H9	0.1811	0.9941	−0.0639	0.091*
H10	0.3191	1.0825	−0.0956	0.079*
H13	1.0482	0.7648	−0.0059	0.055*
H14	1.0006	0.5126	−0.0042	0.056*
H17	0.6374	0.5778	−0.0800	0.054*
H18	0.5865	0.3250	−0.0772	0.073*
H19	0.7082	0.1765	−0.0482	0.080*
H20	0.8672	0.2844	−0.0205	0.069*
H21	1.2472	0.8125	−0.1265	0.079*
H22a	1.2036	1.0851	−0.1693	0.158*
H22b	1.3186	1.0125	−0.1877	0.158*
H22c	1.3764	1.1226	−0.1672	0.158*
H23a	1.4632	0.7528	−0.1442	0.165*
H23b	1.5458	0.8845	−0.1580	0.165*
H23c	1.4485	0.7674	−0.1728	0.165*
H24	1.1946	1.2015	0.0286	0.081*	0.50
H25a	1.1984	1.2681	−0.0331	0.179*	0.50
H25b	1.3674	1.2146	−0.0323	0.179*	0.50
H25c	1.3293	1.3877	−0.0330	0.179*	0.50
H26a	1.3493	1.4277	0.0277	0.230*	0.50
H26b	1.4119	1.4833	0.0023	0.230*	0.50
H26c	1.4885	1.3464	0.0157	0.230*	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.043 (2)	0.094 (3)	0.056 (2)	0.006 (2)	0.017 (2)	0.017 (2)
O2	0.048 (2)	0.045 (2)	0.060 (2)	−0.007 (2)	−0.012 (2)	−0.004 (2)
O3	0.061 (3)	0.114 (4)	0.063 (2)	−0.008 (3)	0.019 (2)	0.009 (2)
O4	0.075 (2)	0.075 (2)	0.086 (4)	−0.013 (3)	−0.013 (2)	0.013 (2)
N1	0.062 (3)	0.083 (3)	0.062 (2)	−0.026 (3)	0.022 (2)	−0.016 (3)
N2	0.064 (3)	0.064 (3)	0.085 (4)	−0.006 (3)	0.003 (3)	−0.003 (3)
C1	0.035 (2)	0.031 (2)	0.038 (2)	−0.004 (2)	−0.003 (2)	−0.005 (2)
C2	0.041 (2)	0.046 (3)	0.040 (2)	−0.001 (2)	0.001 (2)	0.001 (2)
C3	0.062 (3)	0.060 (3)	0.041 (2)	−0.012 (3)	0.001 (2)	0.010 (2)
C4	0.068 (3)	0.051 (3)	0.047 (2)	0.006 (3)	−0.021 (2)	0.009 (2)
C5	0.049 (3)	0.040 (2)	0.048 (2)	0.008 (2)	−0.011 (2)	−0.010 (2)
C6	0.037 (2)	0.033 (2)	0.042 (2)	−0.001 (2)	−0.007 (2)	−0.01 (3)
C7	0.044 (3)	0.051 (3)	0.050 (2)	0.002 (2)	0.004 (2)	−0.008 (2)
C8	0.045 (3)	0.090 (4)	0.070 (3)	0.006 (3)	0.012 (3)	−0.013 (3)
C9	0.037 (3)	0.107 (5)	0.083 (4)	0.014 (3)	0.002 (3)	−0.027 (4)
C10	0.057 (3)	0.070 (4)	0.072 (3)	0.019 (3)	−0.023 (3)	−0.020 (3)
C11	0.030 (2)	0.039 (2)	0.037 (2)	0.007 (2)	0.010 (2)	−0.001 (2)
C12	0.026 (2)	0.045 (3)	0.039 (2)	0.003 (2)	0.008 (2)	−0.004 (2)
C13	0.037 (2)	0.060 (3)	0.041 (2)	0.002 (2)	−0.004 (2)	−0.002 (2)
C14	0.044 (3)	0.059 (3)	0.038 (2)	0.016 (2)	−0.004 (2)	0.012 (2)
C15	0.041 (3)	0.043 (3)	0.047 (2)	0.004 (2)	0.011 (2)	0.010 (2)
C16	0.038 (2)	0.038 (2)	0.038 (2)	0.004 (2)	0.010 (2)	−0.002 (2)
C17	0.040 (2)	0.044 (3)	0.051 (2)	0.003 (2)	0.002 (2)	−0.002 (2)
C18	0.063 (3)	0.040 (3)	0.078 (3)	−0.002 (2)	−0.003 (3)	−0.012 (3)
C19	0.075 (4)	0.034 (3)	0.090 (4)	−0.005 (3)	0.006 (3)	0.001 (3)
C20	0.061 (3)	0.047 (3)	0.064 (3)	0.016 (3)	0.008 (3)	0.013 (2)
C21	0.069 (4)	0.077 (4)	0.051 (3)	−0.024 (3)	0.003 (3)	0.000 (3)
C22	0.121 (7)	0.110 (6)	0.084 (4)	−0.039 (5)	0.027 (4)	0.020 (4)
C23	0.077 (5)	0.126 (7)	0.126 (6)	−0.018 (5)	0.036 (5)	−0.048 (5)
C24	0.066 (6)	0.075 (6)	0.062 (5)	0.006 (5)	−0.002 (5)	0.002 (5)
C25	0.124 (9)	0.128 (10)	0.105 (8)	−0.015 (8)	0.013 (8)	0.013 (8)
C26	0.15 (1)	0.15 (1)	0.16 (1)	−0.029 (9)	−0.014 (9)	−0.017 (9)

Geometric parameters (Å, º)

O1—C2	1.358 (6)	C18—C19	1.394 (8)
O2—C12	1.366 (5)	C19—C20	1.356 (7)
O3—C21	1.225 (7)	O1—H1	0.82
O4—C24	1.255 (7)	O2—H2	0.82
N1—C21	1.307 (7)	C3—H3	0.93
N1—C23	1.451 (9)	C4—H4	0.93
N1—C22	1.454 (9)	C7—H7	0.93
N2—C24	1.337 (7)	C8—H8	0.93
N2—C26	1.441 (8)	C9—H9	0.93
N2—C25	1.468 (7)	C10—H10	0.93
C1—C2	1.376 (6)	C13—H13	0.93
C1—C6	1.421 (6)	C14—H14	0.93
C1—C11	1.490 (6)	C17—H17	0.93
C2—C3	1.407 (6)	C18—H18	0.93
C3—C4	1.354 (7)	C19—H19	0.93
C4—C5	1.404 (7)	C20—H20	0.93
C5—C6	1.417 (6)	C21—H21	0.93
C5—C10	1.421 (7)	C22—H22a	0.96
C6—C7	1.417 (6)	C22—H22b	0.96
C7—C8	1.367 (7)	C22—H22c	0.96
C8—C9	1.402 (8)	C23—H23a	0.96
C9—C10	1.336 (8)	C23—H23b	0.96
C11—C12	1.364 (6)	C23—H23c	0.96
C11—C16	1.431 (6)	C24—H24	0.93
C12—C13	1.412 (6)	C25—H25a	0.96
C13—C14	1.354 (7)	C25—H25b	0.96
C14—C15	1.407 (6)	C25—H25c	0.96
C15—C20	1.414 (7)	C26—H26a	0.96
C15—C16	1.427 (6)	C26—H26b	0.96
C16—C17	1.416 (6)	C26—H26c	0.96
C17—C18	1.368 (7)
C21—N1—C23	121.1 (6)	C4—C3—H3	119.9
C21—N1—C22	120.2 (6)	C2—C3—H3	119.9
C23—N1—C22	118.6 (6)	C3—C4—H4	119.3
C24—N2—C26	123.8 (6)	C5—C4—H4	119.3
C24—N2—C25	118.3 (6)	C8—C7—H7	119.6
C26—N2—C25	117.9 (6)	C6—C7—H7	119.6
C2—C1—C6	118.7 (4)	C7—C8—H8	119.7
C2—C1—C11	120.8 (4)	C9—C8—H8	119.7
C6—C1—C11	120.5 (4)	C10—C9—H9	119.9
O1—C2—C1	118.1 (4)	C8—C9—H9	119.9
O1—C2—C3	120.8 (4)	C9—C10—H10	119.3
C1—C2—C3	121.1 (4)	C5—C10—H10	119.3
C4—C3—C2	120.2 (4)	C14—C13—H13	119.9
C3—C4—C5	121.3 (4)	C12—C13—H13	119.9
C4—C5—C6	118.5 (4)	C13—C14—H14	119.3
C4—C5—C10	122.5 (5)	C15—C14—H14	119.3
C6—C5—C10	118.9 (5)	C18—C17—H17	119.3
C5—C6—C7	118.0 (4)	C16—C17—H17	119.3
C5—C6—C1	120.0 (4)	C17—C18—H18	119.8
C7—C6—C1	122.0 (4)	C19—C18—H18	119.8
C8—C7—C6	120.8 (5)	C20—C19—H19	120.0
C7—C8—C9	120.6 (5)	C18—C19—H19	120.0
C10—C9—C8	120.2 (5)	C19—C20—H20	119.1
C9—C10—C5	121.4 (5)	C15—C20—H20	119.1
C12—C11—C16	119.4 (4)	O3—C21—H21	117.1
C12—C11—C1	120.5 (4)	N1—C21—H21	117.1
C16—C11—C1	120.1 (4)	N1—C22—H22a	109.5
C11—C12—O2	118.3 (4)	N1—C22—H22b	109.5
C11—C12—C13	121.1 (4)	H22a—C22—H22b	109.5
O2—C12—C13	120.5 (4)	N1—C22—H22c	109.5
C14—C13—C12	120.2 (4)	H22a—C22—H22c	109.5
C13—C14—C15	121.4 (4)	H22b—C22—H22c	109.5
C14—C15—C20	122.9 (4)	N1—C23—H23a	109.5
C14—C15—C16	118.5 (4)	N1—C23—H23b	109.5
C20—C15—C16	118.6 (4)	H23a—C23—H23b	109.5
C17—C16—C15	117.9 (4)	N1—C23—H23c	109.5
C17—C16—C11	122.8 (4)	H23a—C23—H23c	109.5
C15—C16—C11	119.3 (4)	H23b—C23—H23c	109.5
C18—C17—C16	121.3 (5)	O4—C24—H24	119.1
C17—C18—C19	120.5 (5)	N2—C24—H24	119.1
C20—C19—C18	119.9 (5)	N2—C25—H25A	109.5
C19—C20—C15	121.7 (5)	N2—C25—H25B	109.5
O3—C21—N1	125.7 (6)	N2—C25—H25C	109.5
O4—C24—N2	121.9 (7)	N2—C26—H26A	109.5
C2—O1—H1	109.5	N2—C26—H26B	109.5
C12—O2—H2	109.5	N2—C26—H26C	109.5
C6—C1—C2—O1	−178.4 (4)	C16—C11—C12—O2	−178.1 (4)
C11—C1—C2—O1	1.3 (6)	C1—C11—C12—O2	0.2 (6)
C6—C1—C2—C3	2.1 (6)	C16—C11—C12—C13	0.3 (6)
C11—C1—C2—C3	−178.3 (4)	C1—C11—C12—C13	178.7 (4)
O1—C2—C3—C4	178.7 (5)	C11—C12—C13—C14	0.2 (6)
C1—C2—C3—C4	−1.8 (7)	O2—C12—C13—C14	178.7 (4)
C2—C3—C4—C5	−0.6 (8)	C12—C13—C14—C15	−0.5 (7)
C3—C4—C5—C6	2.5 (7)	C13—C14—C15—C20	−179.8 (4)
C3—C4—C5—C10	−178.1 (5)	C13—C14—C15—C16	0.2 (7)
C4—C5—C6—C7	178.7 (4)	C14—C15—C16—C17	−179.3 (4)
C10—C5—C6—C7	−0.7 (6)	C20—C15—C16—C17	0.7 (6)
C4—C5—C6—C1	−2.1 (6)	C14—C15—C16—C11	0.4 (6)
C10—C5—C6—C1	178.5 (4)	C20—C15—C16—C11	−179.6 (4)
C2—C1—C6—C5	−0.1 (6)	C12—C11—C16—C17	179.0 (4)
C11—C1—C6—C5	−179.8 (4)	C1—C11—C16—C17	0.7 (6)
C2—C1—C6—C7	179.0 (4)	C12—C11—C16—C15	−0.6 (6)
C11—C1—C6—C7	−0.6 (6)	C1—C11—C16—C15	−179.0 (4)
C5—C6—C7—C8	1.0 (7)	C15—C16—C17—C18	0.0 (6)
C1—C6—C7—C8	−178.2 (5)	C11—C16—C17—C18	−179.7 (4)
C6—C7—C8—C9	0.2 (8)	C16—C17—C18—C19	−1.4 (8)
C7—C8—C9—C10	−1.7 (9)	C17—C18—C19—C20	2.2 (8)
C8—C9—C10—C5	2.0 (9)	C18—C19—C20—C15	−1.5 (8)
C4—C5—C10—C9	179.8 (5)	C14—C15—C20—C19	−180.0 (5)
C6—C5—C10—C9	−0.8 (8)	C16—C15—C20—C19	0.0 (7)
C2—C1—C11—C12	77.0 (5)	C23—N1—C21—O3	179.6 (6)
C6—C1—C11—C12	−103.4 (4)	C22—N1—C21—O3	2.0 (9)
C2—C1—C11—C16	−104.6 (5)	C26—N2—C24—O4	−179.7 (3)
C6—C1—C11—C16	75.0 (5)	C25—N2—C24—O4	−0.1 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O3	0.82	1.87	2.681 (5)	171
O2—H2···O4	0.82	2.04	2.820 (5)	158