A naphthalene-thio­phene-naphthalene diazo­methine triad solvated with dichloro­methane

The highly conjugated title compound, (E)-N-{(5-[(E)-1-naphthyl­imino­meth­yl]-2-thienylmethyl­ene}naphthalen-1-amine dichloro­methane hemisolvate, C₂₆H₁₈N₂S·0.5CH₂Cl₂, exhibits a non-planar yet extended configuration. The naphthyl ring systems are twisted 33.8 (4) and 32.6 (5)° out of the mean plane that passes through the thio­phene ring. The nitro­gen-containing double bonds are ca 0.05 Å shorter than their carbon analogues and both adopt the thermodynamically favourable E configuration.

Key indicators

• Single-crystal X-ray study
• T = 220 K
• Mean [sigma](C-C) = 0.008 Å
• Disorder in solvent or counterion
• R factor = 0.065
• wR factor = 0.166
• Data-to-parameter ratio = 14.2

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT431_ALERT_2_B Short Inter HL..A Contact  Cl1    ..  Cl2     ..       3.02 Ang.

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
PLAT063_ALERT_3_C Crystal Probably too Large for Beam Size .......       0.76 mm
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for        C31
PLAT302_ALERT_4_C Anion/Solvent Disorder .........................      50.00 Perc.
PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          8
PLAT850_ALERT_2_C Check Flack Parameter Exact Value 0.00 and su ..       0.03

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           72.85
           From the CIF: _reflns_number_total               4127
           Count of symmetry unique reflns         2416
           Completeness (_total/calc)            170.82%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1711
           Fraction of Friedel pairs measured     0.708
           Are heavy atom types Z>Si present        yes

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   8 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
   2 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
   3 ALERT type 4 Improvement, methodology, query or suggestion

---

Computing details

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997) and SHELXTL (Bruker, 1997); software used to prepare material for publication: UdMX (local program).

(E)—N-{(5-[(E)-1-naphthyliminomethyl]-2-thienylmethylene}naphthalen-1-amine dichloromethane hemisolvate

Crystal data

C26H18N2S·0.5CH2Cl2	F(000) = 450
Mr = 432.97	Dx = 1.304 Mg m^−3
Monoclinic, P21	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: P 2yb	Cell parameters from 3232 reflections
a = 11.2320 (8) Å	θ = 2.7–72.1°
b = 5.8762 (2) Å	µ = 2.53 mm^−1
c = 16.7657 (9) Å	T = 220 K
β = 94.872 (4)°	Needle, yellow–orange
V = 1102.56 (11) Å^3	0.76 × 0.09 × 0.05 mm
Z = 2

Data collection

Bruker SMART 2K/PLATFORM diffractometer	4127 independent reflections
Radiation source: Sealed Tube	2223 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.030
Detector resolution: 5.5 pixels mm^-1	θmax = 72.9°, θmin = 2.6°
ω scans	h = −13→10
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	k = −7→7
Tmin = 0.417, Tmax = 0.883	l = −20→20
9046 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.065	w = 1/[σ^2(Fo^2) + (0.0811P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.166	(Δ/σ)max < 0.001
S = 0.87	Δρmax = 0.27 e Å^−3
4127 reflections	Δρmin = −0.25 e Å^−3
290 parameters	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
25 restraints	Extinction coefficient: 0.0022 (5)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 1741 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.00 (3)

Special details

Experimental. X-ray crystallographic data for (1) were collected from a single-crystal sample, which was mounted on a loop fiber. Data were collected using a Bruker Platform diffractometer, equipped with a Bruker SMART 2 K Charged-Coupled Device (CCD) Area Detector using the program SMART and normal focus sealed tube source graphite monochromated Cu—Kα radiation. The crystal-to-detector distance was 4.908 cm, and the data collection was carried out in 512 x 512 pixel mode, utilizing 4 x 4 pixel binning. The initial unit-cell parameters were determined by a least-squares fit of the angular setting of strong reflections, collected by a 9.0 degree scan in 30 frames over four different parts of the reciprocal space (120 frames total). One complete sphere of data was collected, to better than 0.8 Å resolution. Upon completion of the data collection, the first 101 frames were recollected in order to improve the decay correction analysis.

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	Occ. (<1)
S1	0.32408 (12)	0.48586 (19)	0.98036 (7)	0.0587 (4)
N1	0.2676 (4)	0.4222 (6)	0.8000 (2)	0.0574 (11)
N2	0.3741 (4)	0.4300 (6)	1.1610 (2)	0.0554 (11)
C1	0.2888 (5)	0.6260 (8)	0.8230 (3)	0.0581 (14)
H1	0.2853	0.7416	0.7841	0.070*
C2	0.3179 (4)	0.6887 (9)	0.9052 (3)	0.0570 (13)
C3	0.3418 (5)	0.8989 (8)	0.9351 (3)	0.0607 (13)
H3	0.3425	1.0301	0.9030	0.073*
C4	0.3655 (5)	0.9022 (8)	1.0185 (3)	0.0604 (14)
H4	0.3829	1.0358	1.0480	0.072*
C5	0.3607 (4)	0.6912 (8)	1.0525 (3)	0.0535 (12)
C6	0.3801 (5)	0.6338 (8)	1.1345 (3)	0.0600 (14)
H6	0.3985	0.7513	1.1715	0.072*
C7	0.2419 (5)	0.3814 (8)	0.7175 (3)	0.0556 (13)
C8	0.2947 (5)	0.4961 (11)	0.6602 (3)	0.0723 (14)
H8	0.3498	0.6118	0.6753	0.087*
C9	0.2692 (5)	0.4467 (11)	0.5792 (3)	0.0776 (17)
H9	0.3054	0.5313	0.5403	0.093*
C10	0.1902 (5)	0.2719 (11)	0.5561 (3)	0.0768 (18)
H10	0.1735	0.2374	0.5016	0.092*
C11	0.1361 (5)	0.1489 (9)	0.6135 (3)	0.0636 (15)
C12	0.0575 (5)	−0.0365 (12)	0.5915 (3)	0.0824 (17)
H12	0.0423	−0.0766	0.5373	0.099*
C13	0.0049 (6)	−0.1547 (12)	0.6485 (4)	0.092 (2)
H13	−0.0473	−0.2752	0.6333	0.110*
C14	0.0269 (5)	−0.1000 (10)	0.7293 (4)	0.0825 (19)
H14	−0.0108	−0.1825	0.7680	0.099*
C15	0.1029 (5)	0.0722 (8)	0.7521 (3)	0.0682 (16)
H15	0.1178	0.1070	0.8068	0.082*
C16	0.1593 (5)	0.1982 (9)	0.6958 (3)	0.0568 (13)
C17	0.4005 (5)	0.3875 (8)	1.2435 (3)	0.0542 (13)
C18	0.4852 (5)	0.5103 (9)	1.2900 (3)	0.0680 (15)
H18	0.5273	0.6280	1.2670	0.082*
C19	0.5085 (5)	0.4597 (11)	1.3717 (3)	0.0778 (17)
H19	0.5653	0.5461	1.4031	0.093*
C20	0.4505 (6)	0.2885 (11)	1.4061 (3)	0.0775 (18)
H20	0.4672	0.2576	1.4609	0.093*
C21	0.3645 (5)	0.1551 (9)	1.3598 (3)	0.0647 (15)
C22	0.3055 (6)	−0.0328 (12)	1.3943 (3)	0.0783 (16)
H22	0.3242	−0.0709	1.4483	0.094*
C23	0.2236 (6)	−0.1546 (10)	1.3495 (4)	0.088 (2)
H23	0.1852	−0.2775	1.3724	0.106*
C24	0.1948 (6)	−0.0996 (10)	1.2686 (4)	0.0799 (18)
H24	0.1362	−0.1842	1.2381	0.096*
C25	0.2512 (5)	0.0760 (9)	1.2336 (3)	0.0668 (16)
H25	0.2321	0.1091	1.1792	0.080*
C26	0.3382 (5)	0.2083 (8)	1.2788 (3)	0.0535 (12)
C31	0.0066 (18)	0.155 (5)	1.0040 (16)	0.120 (6)	0.50
H31A	0.0874	0.1588	1.0311	0.144*	0.50
H31B	−0.0493	0.1723	1.0455	0.144*	0.50
Cl1	−0.0140 (15)	−0.092 (6)	0.9650 (14)	0.435 (10)	0.50
Cl2	−0.0095 (14)	0.399 (7)	0.9407 (10)	0.503 (18)	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0854 (9)	0.0317 (5)	0.0581 (7)	−0.0012 (7)	0.0003 (6)	−0.0008 (7)
N1	0.074 (3)	0.045 (2)	0.054 (2)	0.003 (2)	0.007 (2)	0.0012 (18)
N2	0.072 (3)	0.043 (3)	0.051 (2)	−0.0002 (19)	0.007 (2)	−0.0011 (18)
C1	0.080 (4)	0.040 (3)	0.055 (3)	0.002 (2)	0.007 (3)	0.012 (2)
C2	0.068 (4)	0.049 (3)	0.053 (3)	0.009 (3)	0.001 (2)	−0.001 (2)
C3	0.088 (4)	0.038 (2)	0.057 (3)	−0.003 (3)	0.010 (3)	0.003 (2)
C4	0.080 (4)	0.033 (2)	0.067 (3)	−0.006 (2)	−0.001 (3)	−0.009 (2)
C5	0.066 (3)	0.041 (3)	0.053 (3)	−0.001 (2)	0.000 (2)	−0.004 (2)
C6	0.082 (4)	0.041 (3)	0.057 (3)	0.000 (3)	0.009 (3)	−0.006 (3)
C7	0.073 (4)	0.049 (3)	0.045 (3)	0.013 (3)	0.006 (2)	0.005 (2)
C8	0.100 (4)	0.063 (3)	0.055 (3)	−0.002 (4)	0.014 (3)	0.005 (3)
C9	0.089 (4)	0.084 (5)	0.063 (3)	−0.003 (4)	0.024 (3)	0.005 (3)
C10	0.093 (5)	0.095 (5)	0.042 (3)	0.023 (4)	0.003 (3)	−0.002 (3)
C11	0.074 (4)	0.063 (3)	0.052 (3)	0.013 (3)	−0.001 (3)	−0.006 (3)
C12	0.094 (5)	0.082 (5)	0.067 (4)	0.000 (4)	−0.016 (3)	−0.010 (4)
C13	0.098 (5)	0.074 (4)	0.098 (5)	−0.014 (4)	−0.027 (4)	−0.007 (4)
C14	0.083 (5)	0.070 (4)	0.091 (5)	−0.015 (3)	−0.010 (3)	0.009 (3)
C15	0.081 (4)	0.055 (3)	0.066 (4)	0.003 (3)	−0.006 (3)	0.000 (3)
C16	0.065 (4)	0.047 (3)	0.059 (3)	0.014 (2)	0.005 (3)	0.004 (2)
C17	0.073 (4)	0.046 (3)	0.044 (3)	0.006 (3)	0.004 (2)	−0.005 (2)
C18	0.100 (4)	0.041 (3)	0.060 (3)	0.003 (3)	−0.008 (3)	−0.008 (3)
C19	0.099 (5)	0.073 (4)	0.057 (3)	0.007 (4)	−0.016 (3)	−0.008 (3)
C20	0.096 (5)	0.082 (4)	0.054 (4)	0.024 (4)	0.004 (3)	0.002 (3)
C21	0.082 (4)	0.063 (3)	0.050 (3)	0.021 (3)	0.014 (3)	0.000 (3)
C22	0.115 (5)	0.068 (4)	0.054 (3)	0.015 (4)	0.022 (3)	0.004 (4)
C23	0.119 (6)	0.055 (4)	0.096 (5)	0.004 (4)	0.041 (4)	0.013 (4)
C24	0.094 (5)	0.061 (3)	0.087 (4)	−0.013 (3)	0.019 (4)	−0.013 (3)
C25	0.089 (5)	0.057 (3)	0.055 (3)	0.001 (3)	0.011 (3)	0.000 (3)
C26	0.074 (4)	0.038 (2)	0.049 (3)	0.007 (2)	0.012 (3)	−0.003 (2)
C31	0.074 (8)	0.146 (11)	0.141 (10)	−0.012 (8)	0.019 (7)	−0.008 (9)
Cl1	0.288 (13)	0.55 (3)	0.50 (2)	0.067 (19)	0.204 (15)	0.01 (3)
Cl2	0.283 (12)	0.84 (6)	0.374 (17)	0.03 (2)	−0.014 (13)	−0.10 (3)

Geometric parameters (Å, º)

S1—C2	1.732 (5)	C13—H13	0.94
S1—C5	1.734 (5)	C14—C15	1.358 (7)
N1—C1	1.274 (6)	C14—H14	0.94
N1—C7	1.409 (6)	C15—C16	1.393 (7)
N2—C6	1.281 (6)	C15—H15	0.94
N2—C17	1.413 (6)	C17—C18	1.381 (6)
C1—C2	1.436 (6)	C17—C26	1.421 (7)
C1—H1	0.94	C18—C19	1.404 (6)
C2—C3	1.351 (6)	C18—H18	0.94
C3—C4	1.401 (6)	C19—C20	1.353 (8)
C3—H3	0.94	C19—H19	0.94
C4—C5	1.368 (6)	C20—C21	1.423 (7)
C4—H4	0.94	C20—H20	0.94
C5—C6	1.414 (7)	C21—C26	1.400 (6)
C6—H6	0.94	C21—C22	1.434 (8)
C7—C8	1.351 (6)	C22—C23	1.344 (8)
C7—C16	1.448 (7)	C22—H22	0.94
C8—C9	1.394 (6)	C23—C24	1.406 (7)
C8—H8	0.94	C23—H23	0.94
C9—C10	1.391 (8)	C24—C25	1.368 (7)
C9—H9	0.94	C24—H24	0.94
C10—C11	1.385 (7)	C25—C26	1.417 (7)
C10—H10	0.94	C25—H25	0.94
C11—C16	1.412 (6)	C31—Cl1	1.603 (19)
C11—C12	1.430 (8)	C31—Cl2	1.78 (4)
C12—C13	1.357 (8)	C31—H31a	0.98
C12—H12	0.94	C31—H31b	0.98
C13—C14	1.394 (7)
C2—S1—C5	91.2 (2)	C13—C14—H14	119.9
C1—N1—C7	118.3 (4)	C14—C15—C16	121.1 (6)
C6—N2—C17	119.5 (4)	C14—C15—H15	119.5
N1—C1—C2	123.6 (5)	C16—C15—H15	119.5
N1—C1—H1	118.2	C15—C16—C11	119.7 (5)
C2—C1—H1	118.2	C15—C16—C7	122.9 (5)
C3—C2—C1	127.7 (5)	C11—C16—C7	117.4 (5)
C3—C2—S1	111.4 (4)	C18—C17—N2	122.5 (5)
C1—C2—S1	120.9 (4)	C18—C17—C26	119.4 (5)
C2—C3—C4	113.4 (4)	N2—C17—C26	118.0 (4)
C2—C3—H3	123.3	C17—C18—C19	120.2 (6)
C4—C3—H3	123.3	C17—C18—H18	119.9
C5—C4—C3	113.1 (4)	C19—C18—H18	119.9
C5—C4—H4	123.4	C20—C19—C18	121.1 (6)
C3—C4—H4	123.4	C20—C19—H19	119.5
C4—C5—C6	127.9 (5)	C18—C19—H19	119.5
C4—C5—S1	110.8 (4)	C19—C20—C21	120.4 (5)
C6—C5—S1	121.3 (4)	C19—C20—H20	119.8
N2—C6—C5	123.5 (5)	C21—C20—H20	119.8
N2—C6—H6	118.3	C26—C21—C20	119.0 (5)
C5—C6—H6	118.3	C26—C21—C22	119.7 (5)
C8—C7—N1	123.2 (5)	C20—C21—C22	121.3 (5)
C8—C7—C16	120.2 (5)	C23—C22—C21	120.2 (5)
N1—C7—C16	116.6 (4)	C23—C22—H22	119.9
C7—C8—C9	121.5 (6)	C21—C22—H22	119.9
C7—C8—H8	119.2	C22—C23—C24	120.5 (6)
C9—C8—H8	119.2	C22—C23—H23	119.7
C10—C9—C8	119.9 (6)	C24—C23—H23	119.7
C10—C9—H9	120.1	C25—C24—C23	120.6 (6)
C8—C9—H9	120.1	C25—C24—H24	119.7
C11—C10—C9	120.0 (5)	C23—C24—H24	119.7
C11—C10—H10	120	C24—C25—C26	120.6 (5)
C9—C10—H10	120	C24—C25—H25	119.7
C10—C11—C16	121.1 (5)	C26—C25—H25	119.7
C10—C11—C12	121.1 (5)	C21—C26—C25	118.4 (5)
C16—C11—C12	117.8 (5)	C21—C26—C17	119.9 (5)
C13—C12—C11	120.3 (5)	C25—C26—C17	121.7 (5)
C13—C12—H12	119.8	CL1—C31—CL2	119 (2)
C11—C12—H12	119.8	CL1—C31—H31A	107.6
C12—C13—C14	120.9 (6)	CL2—C31—H31A	107.6
C12—C13—H13	119.5	CL1—C31—H31B	107.6
C14—C13—H13	119.5	CL2—C31—H31B	107.6
C15—C14—C13	120.1 (6)	H31A—C31—H31B	107
C15—C14—H14	119.9
C7—N1—C1—C2	−179.0 (4)	C12—C11—C16—C15	−2.1 (7)
N1—C1—C2—C3	179.9 (6)	C10—C11—C16—C7	−0.2 (7)
N1—C1—C2—S1	−0.9 (8)	C12—C11—C16—C7	178.1 (5)
C5—S1—C2—C3	−0.4 (5)	C8—C7—C16—C15	179.3 (5)
C5—S1—C2—C1	−179.7 (4)	N1—C7—C16—C15	2.6 (7)
C1—C2—C3—C4	179.2 (5)	C8—C7—C16—C11	−0.8 (7)
S1—C2—C3—C4	0.0 (6)	N1—C7—C16—C11	−177.5 (4)
C2—C3—C4—C5	0.6 (7)	C6—N2—C17—C18	−33.6 (7)
C3—C4—C5—C6	179.8 (5)	C6—N2—C17—C26	147.5 (5)
C3—C4—C5—S1	−0.9 (6)	N2—C17—C18—C19	−179.5 (5)
C2—S1—C5—C4	0.7 (4)	C26—C17—C18—C19	−0.7 (8)
C2—S1—C5—C6	−179.9 (4)	C17—C18—C19—C20	1.1 (9)
C17—N2—C6—C5	177.1 (4)	C18—C19—C20—C21	0.2 (9)
C4—C5—C6—N2	−179.7 (6)	C19—C20—C21—C26	−2.0 (8)
S1—C5—C6—N2	1.0 (8)	C19—C20—C21—C22	177.5 (5)
C1—N1—C7—C8	36.1 (7)	C26—C21—C22—C23	−1.3 (8)
C1—N1—C7—C16	−147.3 (5)	C20—C21—C22—C23	179.2 (5)
N1—C7—C8—C9	178.3 (5)	C21—C22—C23—C24	0.0 (9)
C16—C7—C8—C9	1.8 (8)	C22—C23—C24—C25	1.2 (9)
C7—C8—C9—C10	−1.7 (9)	C23—C24—C25—C26	−1.2 (8)
C8—C9—C10—C11	0.6 (8)	C20—C21—C26—C25	−179.2 (5)
C9—C10—C11—C16	0.3 (8)	C22—C21—C26—C25	1.4 (7)
C9—C10—C11—C12	−177.9 (5)	C20—C21—C26—C17	2.4 (7)
C10—C11—C12—C13	−179.7 (6)	C22—C21—C26—C17	−177.1 (5)
C16—C11—C12—C13	2.0 (8)	C24—C25—C26—C21	−0.1 (7)
C11—C12—C13—C14	−0.7 (9)	C24—C25—C26—C17	178.2 (5)
C12—C13—C14—C15	−0.6 (9)	C18—C17—C26—C21	−1.1 (7)
C13—C14—C15—C16	0.5 (8)	N2—C17—C26—C21	177.8 (4)
C14—C15—C16—C11	0.9 (8)	C18—C17—C26—C25	−179.5 (5)
C14—C15—C16—C7	−179.3 (5)	N2—C17—C26—C25	−0.6 (7)
C10—C11—C16—C15	179.6 (5)