4,5-Diaza-9,9′-spiro­bifluorene

In the title compound, C₂₃H₁₄N₂, biphenyl and 2,2′-bipyridine units are perpendicularly cross-linked by a C atom. The dihedral angle between the mean planes of the biphenyl and 2,2′-bipyridine units is 86.31 (4)°. The crystal structure is stabilized by inter­molecular C—H...N inter­actions.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.043
• wR factor = 0.094
• Data-to-parameter ratio = 8.3

checkCIF/PLATON results

No syntax errors found



Alert level C
RINTA01_ALERT_3_C  The value of Rint is greater than 0.10
            Rint given   0.129
PLAT020_ALERT_3_C The value of Rint is greater than 0.10 .........       0.13
PLAT153_ALERT_1_C The su's on the Cell Axes   are Equal (x 100000)        200 Ang.

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           26.00
           From the CIF: _reflns_number_total               1889
           Count of symmetry unique reflns         1892
           Completeness (_total/calc)             99.84%
           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
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C13    = .          R

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

   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
   2 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

Fluorene and its derivatives have an aromatic biphenyl structure. Due to a wide energy gap in the backbones and high luminescence efficiency, they have drawn much attention of the materials chemists and device physicists (Scherf & List, 2002; Li et al., 2004).

Related literature

For related literature on fluorene and its derivatives see: Scherf & List (2002); Li et al. (2004); Wong et al. (2005).

S2. Experimental

The title compound (m.p. 518 K) was prepared according to the published procedure (Wong et al., 2005). Crystals suitable for X-ray diffraction were obtained during an attempt to prepare a metalorganic compound from 2,5-pyrindine dicarboxylic acid, 4,5-diaza-9,9'-spirobifluorene and zinc(II) nitrate hexahydrate by hydrothermal synthesis.

S3. Refinement

Because the quality of the crystal was not good, and no facility was available for single-crystal structure determination at low temperature, the R_int value is quite high.

H atoms were positioned geometrically and allowed to ride on their parent atoms, with C—H distances of 0.93 Å, and with U_iso(H) = 1.2U_eq of the parent atoms. In the absence of significant anomalous scattering effects, Friedel pairs were averaged.

Computing details

Data collection: APEX2 (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The structure of the title compound, showing 30% probability displacement ellipsoids and the atom-numbering schems.
	Fig. 2. The packing diagram shown along the X axis. Hydrogen bods are shown with dashed lines.

4,5-Diaza-9,9'-spirobifluorene

Crystal data

C23H14N2	F(000) = 664
Mr = 318.36	Dx = 1.258 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 1494 reflections
a = 10.951 (2) Å	θ = 2.3–18.2°
b = 11.885 (2) Å	µ = 0.07 mm^−1
c = 12.916 (2) Å	T = 298 K
V = 1681.1 (5) Å^3	Acicular, orange
Z = 4	0.33 × 0.15 × 0.11 mm

Data collection

Bruker APEXII CCD diffractometer	1889 independent reflections
Radiation source: fine-focus sealed tube	1193 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.129
π and ω scans	θmax = 26.0°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −13→13
Tmin = 0.974, Tmax = 0.982	k = −14→13
9237 measured reflections	l = −14→15

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.043	H-atom parameters constrained
wR(F^2) = 0.094	w = 1/[σ^2(Fo^2) + (0.0138P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.00	(Δ/σ)max < 0.001
1889 reflections	Δρmax = 0.14 e Å^−3
227 parameters	Δρmin = −0.15 e Å^−3
0 restraints	Extinction correction: SHELXL97
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0065 (8)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
C19	0.0854 (2)	0.3926 (2)	0.34109 (19)	0.0457 (7)
C13	0.2359 (3)	0.2578 (2)	0.3985 (2)	0.0511 (7)
C18	0.1646 (3)	0.4480 (2)	0.4176 (2)	0.0502 (7)
N1	−0.0086 (2)	0.43886 (19)	0.29213 (18)	0.0584 (7)
C14	0.2477 (3)	0.3696 (2)	0.45536 (19)	0.0497 (7)
C20	0.1250 (2)	0.2819 (2)	0.3303 (2)	0.0439 (7)
C1	0.4017 (3)	0.1281 (2)	0.3718 (2)	0.0512 (7)
N2	0.1586 (3)	0.55576 (18)	0.44783 (18)	0.0655 (7)
C7	0.3194 (3)	0.0803 (2)	0.4506 (2)	0.0503 (7)
C21	0.0614 (3)	0.2127 (2)	0.2634 (2)	0.0568 (8)
H21	0.0843	0.1382	0.2535	0.068*
C23	−0.0681 (3)	0.3685 (3)	0.2293 (2)	0.0693 (9)
H23	−0.1360	0.3964	0.1945	0.083*
C12	0.2240 (3)	0.1545 (2)	0.4675 (2)	0.0507 (7)
C6	0.3520 (2)	0.2299 (2)	0.3381 (2)	0.0484 (7)
C5	0.4091 (3)	0.2924 (2)	0.2624 (2)	0.0615 (8)
H5	0.3762	0.3604	0.2402	0.074*
C11	0.1342 (3)	0.1312 (3)	0.5388 (2)	0.0698 (9)
H11	0.0716	0.1822	0.5516	0.084*
C2	0.5094 (3)	0.0908 (3)	0.3308 (2)	0.0637 (8)
H2	0.5433	0.0235	0.3538	0.076*
C8	0.3257 (3)	−0.0206 (3)	0.5047 (2)	0.0683 (9)
H8	0.3905	−0.0701	0.4950	0.082*
C3	0.5682 (3)	0.1531 (3)	0.2553 (3)	0.0770 (10)
H3	0.6422	0.1286	0.2281	0.092*
C4	0.5160 (3)	0.2522 (3)	0.2204 (2)	0.0753 (10)
H4	0.5539	0.2922	0.1675	0.090*
C22	−0.0367 (3)	0.2578 (3)	0.2120 (2)	0.0670 (9)
H22	−0.0816	0.2141	0.1660	0.080*
C16	0.3234 (3)	0.5119 (4)	0.5654 (3)	0.0847 (11)
H16	0.3755	0.5373	0.6172	0.102*
C15	0.3284 (3)	0.4009 (3)	0.5330 (2)	0.0720 (10)
H15	0.3831	0.3499	0.5619	0.086*
C9	0.2333 (4)	−0.0450 (3)	0.5731 (3)	0.0780 (10)
H9	0.2341	−0.1135	0.6080	0.094*
C17	0.2412 (4)	0.5841 (3)	0.5208 (3)	0.0813 (11)
H17	0.2426	0.6587	0.5426	0.098*
C10	0.1400 (3)	0.0290 (3)	0.5910 (3)	0.0854 (11)
H10	0.0796	0.0108	0.6388	0.103*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C19	0.0524 (18)	0.0429 (15)	0.0418 (15)	−0.0013 (14)	−0.0013 (14)	0.0024 (13)
C13	0.0577 (19)	0.0476 (16)	0.0479 (15)	0.0030 (15)	0.0013 (14)	0.0026 (13)
C18	0.0657 (19)	0.0399 (16)	0.0449 (16)	−0.0034 (15)	0.0033 (15)	−0.0002 (13)
N1	0.0609 (16)	0.0585 (15)	0.0559 (15)	0.0055 (14)	−0.0094 (13)	0.0028 (13)
C14	0.0534 (18)	0.0533 (17)	0.0424 (15)	−0.0057 (15)	0.0029 (15)	0.0000 (14)
C20	0.0503 (17)	0.0414 (15)	0.0401 (15)	−0.0017 (14)	0.0011 (13)	0.0020 (13)
C1	0.0517 (19)	0.0525 (17)	0.0493 (17)	−0.0007 (16)	−0.0028 (14)	−0.0063 (14)
N2	0.092 (2)	0.0435 (15)	0.0608 (16)	−0.0072 (14)	0.0032 (15)	−0.0102 (13)
C7	0.0590 (19)	0.0438 (15)	0.0480 (17)	0.0017 (15)	−0.0049 (14)	0.0020 (14)
C21	0.065 (2)	0.0498 (16)	0.0561 (18)	−0.0119 (17)	0.0016 (17)	−0.0073 (15)
C23	0.059 (2)	0.080 (2)	0.069 (2)	−0.002 (2)	−0.0152 (18)	0.0069 (19)
C12	0.0546 (19)	0.0518 (17)	0.0456 (16)	0.0004 (15)	0.0007 (14)	0.0031 (14)
C6	0.0520 (17)	0.0505 (16)	0.0428 (15)	−0.0006 (15)	−0.0014 (14)	−0.0006 (14)
C5	0.064 (2)	0.0649 (19)	0.0551 (19)	−0.0057 (17)	0.0036 (17)	0.0100 (16)
C11	0.077 (2)	0.071 (2)	0.060 (2)	−0.0001 (18)	0.0120 (18)	0.0108 (18)
C2	0.064 (2)	0.0612 (19)	0.066 (2)	0.0088 (18)	0.0038 (18)	−0.0131 (18)
C8	0.084 (2)	0.0541 (19)	0.067 (2)	0.0031 (19)	−0.011 (2)	0.0070 (17)
C3	0.066 (2)	0.096 (3)	0.069 (2)	0.004 (2)	0.012 (2)	−0.022 (2)
C4	0.077 (3)	0.093 (3)	0.055 (2)	−0.014 (2)	0.0147 (19)	0.003 (2)
C22	0.072 (2)	0.072 (2)	0.057 (2)	−0.0157 (19)	−0.0134 (18)	−0.0079 (17)
C16	0.096 (3)	0.100 (3)	0.058 (2)	−0.021 (3)	−0.012 (2)	−0.022 (2)
C15	0.073 (2)	0.086 (2)	0.056 (2)	−0.009 (2)	−0.0142 (17)	−0.0092 (18)
C9	0.099 (3)	0.061 (2)	0.074 (2)	−0.008 (2)	−0.003 (2)	0.025 (2)
C17	0.104 (3)	0.073 (2)	0.067 (2)	−0.026 (2)	0.007 (2)	−0.027 (2)
C10	0.101 (3)	0.085 (3)	0.069 (2)	−0.010 (2)	0.010 (2)	0.026 (2)

Geometric parameters (Å, º)

C19—N1	1.327 (3)	C12—C11	1.375 (4)
C19—C20	1.393 (3)	C6—C5	1.378 (3)
C19—C18	1.470 (4)	C5—C4	1.376 (4)
C13—C12	1.522 (4)	C5—H5	0.9300
C13—C14	1.523 (4)	C11—C10	1.392 (5)
C13—C20	1.527 (4)	C11—H11	0.9300
C13—C6	1.529 (4)	C2—C3	1.383 (4)
C18—N2	1.340 (3)	C2—H2	0.9300
C18—C14	1.391 (4)	C8—C9	1.375 (4)
N1—C23	1.335 (3)	C8—H8	0.9300
C14—C15	1.388 (4)	C3—C4	1.384 (4)
C20—C21	1.381 (3)	C3—H3	0.9300
C1—C2	1.367 (4)	C4—H4	0.9300
C1—C6	1.395 (4)	C22—H22	0.9300
C1—C7	1.473 (4)	C16—C17	1.370 (5)
N2—C17	1.350 (4)	C16—C15	1.385 (5)
C7—C12	1.385 (4)	C16—H16	0.9300
C7—C8	1.391 (4)	C15—H15	0.9300
C21—C22	1.372 (4)	C9—C10	1.368 (4)
C21—H21	0.9300	C9—H9	0.9300
C23—C22	1.378 (4)	C17—H17	0.9300
C23—H23	0.9300	C10—H10	0.9300
N1—C19—C20	125.8 (3)	C1—C6—C13	110.7 (2)
N1—C19—C18	126.3 (2)	C4—C5—C6	118.5 (3)
C20—C19—C18	107.9 (2)	C4—C5—H5	120.7
C12—C13—C14	115.4 (2)	C6—C5—H5	120.7
C12—C13—C20	114.9 (2)	C12—C11—C10	117.9 (3)
C14—C13—C20	100.5 (2)	C12—C11—H11	121.1
C12—C13—C6	101.2 (2)	C10—C11—H11	121.1
C14—C13—C6	111.4 (2)	C1—C2—C3	120.0 (3)
C20—C13—C6	114.0 (2)	C1—C2—H2	120.0
N2—C18—C14	124.8 (3)	C3—C2—H2	120.0
N2—C18—C19	126.5 (3)	C9—C8—C7	117.9 (3)
C14—C18—C19	108.7 (2)	C9—C8—H8	121.0
C19—N1—C23	114.1 (2)	C7—C8—H8	121.0
C15—C14—C18	119.4 (3)	C2—C3—C4	119.5 (3)
C15—C14—C13	129.5 (3)	C2—C3—H3	120.2
C18—C14—C13	111.1 (2)	C4—C3—H3	120.2
C21—C20—C19	117.9 (3)	C5—C4—C3	121.2 (3)
C21—C20—C13	130.6 (2)	C5—C4—H4	119.4
C19—C20—C13	111.5 (2)	C3—C4—H4	119.4
C2—C1—C6	119.8 (3)	C21—C22—C23	119.3 (3)
C2—C1—C7	132.1 (3)	C21—C22—H22	120.4
C6—C1—C7	108.1 (2)	C23—C22—H22	120.4
C18—N2—C17	114.1 (3)	C17—C16—C15	119.7 (3)
C12—C7—C8	120.5 (3)	C17—C16—H16	120.1
C12—C7—C1	109.0 (2)	C15—C16—H16	120.1
C8—C7—C1	130.5 (3)	C16—C15—C14	116.6 (4)
C22—C21—C20	117.7 (3)	C16—C15—H15	121.7
C22—C21—H21	121.1	C14—C15—H15	121.7
C20—C21—H21	121.1	C10—C9—C8	121.6 (3)
N1—C23—C22	125.1 (3)	C10—C9—H9	119.2
N1—C23—H23	117.4	C8—C9—H9	119.2
C22—C23—H23	117.4	N2—C17—C16	125.3 (3)
C11—C12—C7	121.2 (3)	N2—C17—H17	117.4
C11—C12—C13	128.0 (3)	C16—C17—H17	117.4
C7—C12—C13	110.9 (2)	C9—C10—C11	120.9 (3)
C5—C6—C1	120.8 (3)	C9—C10—H10	119.5
C5—C6—C13	128.5 (3)	C11—C10—H10	119.5
N2—C18—C19—N1	−2.9 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C21—H21···N1^i	0.93	2.58	3.383 (4)	145
C22—H22···N2^i	0.93	2.53	3.436 (4)	164

Symmetry code: (i) −x, y−1/2, −z+1/2.