1,1′-{(1E,1′E)-[Octane-1,8-diylbis(aza­nylyl­idene)]bis­(methanylyl­idene)}bis­(naphthalen-2-ol) in the zwitterionic form

The title compound, C₃₀H₃₂O₂N₂, is formed from two units of ortho-hy­droxy­naphthaldehyde bridged with 1,8-di­amino­octane. In the solid state, it exists as a double zwitterion. The N atoms are protonated and the C—O⁻ bonds lengths are 1.265 (2) Å, with intra­molecular N—H...O hydrogen bonds forming S(6) ring motifs. The mol­ecule has twofold rotational symmetry, with the twofold axis bis­ecting the central –CH₂—CH₂– bond of the bridging octane chain. In the crystal, mol­ecules are linked by N—H...O hydrogen bonds, forming chains propagating along the [-201] direction. The chains are linked via C—H...O hydrogen bonds, forming a supra­molecular three-dimensional framework structure.

Key indicators

• Single-crystal X-ray study
• T = 173 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.053
• wR factor = 0.146
• Data-to-parameter ratio = 18.4

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          6 Report
PLAT934_ALERT_3_C Number of (Iobs-Icalc)/SigmaW > 10 Outliers ....          1 Check

Alert level G
PLAT005_ALERT_5_G No Embedded Refinement Details found  in the CIF     Please Do !
PLAT066_ALERT_1_G Predicted and Reported Tmin&Tmax Range Identical          ? Check
PLAT333_ALERT_2_G Check Large Av C6-Ring C-C Dist. C1     -C10           1.43 Ang.
PLAT899_ALERT_4_G SHELXL97   is Deprecated and Succeeded by SHELXL       2014 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600          6 Note
PLAT913_ALERT_3_G Missing # of Very Strong Reflections in FCF ....          3 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          9 Note

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   2 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   7 ALERT level G = General information/check it is not something unexpected

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

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Computing details

Data collection: APEX2 (Bruker, 2010); cell refinement: SAINT (Bruker, 2010); data reduction: SAINT (Bruker, 2010; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

1,1'-{(1E,1'E)-[Octane-1,8-diylbis(azanylylidene)]bis(methanylylidene)}bis(naphthalen-2-ol) in the zwitterion form

Crystal data

C30H32N2O2	F(000) = 968
Mr = 452.58	Dx = 1.258 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 6936 reflections
a = 18.0993 (12) Å	θ = 2.3–28.0°
b = 14.2646 (9) Å	µ = 0.08 mm^−1
c = 9.5990 (6) Å	T = 173 K
β = 105.345 (1)°	Prism, yellow
V = 2389.9 (3) Å^3	0.35 × 0.25 × 0.20 mm
Z = 4

Data collection

Bruker APEXII CCD diffractometer	2907 independent reflections
Radiation source: fine-focus sealed tube	2159 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.025
φ and ω scans	θmax = 28.1°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2010)	h = −22→23
Tmin = 0.973, Tmax = 0.985	k = −18→14
20784 measured reflections	l = −12→10

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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.146	H atoms treated by a mixture of independent and constrained refinement
S = 1.13	w = 1/[σ^2(Fo^2) + (0.0442P)^2 + 2.0625P] where P = (Fo^2 + 2Fc^2)/3
2907 reflections	(Δ/σ)max < 0.001
158 parameters	Δρmax = 0.23 e Å^−3
0 restraints	Δρmin = −0.22 e Å^−3

Special details

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.03219 (9)	1.19048 (15)	0.05578 (16)	0.0474 (5)
C2	0.01367 (10)	1.27725 (17)	−0.02317 (18)	0.0576 (6)
H2	−0.0178	1.2756	−0.1196	0.069*
C3	0.03949 (10)	1.35977 (17)	0.0356 (2)	0.0595 (6)
H3	0.0264	1.4148	−0.0214	0.071*
C4	0.08643 (9)	1.36885 (14)	0.18190 (19)	0.0488 (4)
C5	0.10920 (11)	1.45675 (16)	0.2428 (2)	0.0610 (5)
H5	0.0944	1.5117	0.1863	0.073*
C6	0.15275 (11)	1.46479 (16)	0.3835 (3)	0.0628 (6)
H6	0.1677	1.5248	0.4242	0.075*
C7	0.17461 (10)	1.38405 (14)	0.4656 (2)	0.0524 (5)
H7	0.2045	1.3893	0.5628	0.063*
C8	0.15364 (9)	1.29760 (13)	0.40838 (17)	0.0441 (4)
H8	0.1696	1.2436	0.4665	0.053*
C9	0.10847 (8)	1.28615 (13)	0.26391 (16)	0.0401 (4)
C10	0.08336 (8)	1.19633 (13)	0.19953 (15)	0.0397 (4)
C11	0.10777 (8)	1.11267 (13)	0.27413 (16)	0.0413 (4)
H11	0.1414	1.1180	0.3684	0.050*
C12	0.11699 (10)	0.94316 (14)	0.30608 (17)	0.0478 (4)
H12A	0.0730	0.9030	0.3101	0.057*
H12B	0.1446	0.9600	0.4064	0.057*
C13	0.17022 (10)	0.88827 (14)	0.23865 (17)	0.0481 (4)
H13A	0.2175	0.9251	0.2467	0.058*
H13B	0.1452	0.8790	0.1347	0.058*
C14	0.19159 (10)	0.79304 (14)	0.30986 (17)	0.0493 (5)
H14A	0.2201	0.7571	0.2526	0.059*
H14B	0.1439	0.7581	0.3070	0.059*
C15	0.24003 (9)	0.79781 (13)	0.46606 (16)	0.0461 (4)
H15A	0.2880	0.8321	0.4694	0.055*
H15B	0.2118	0.8337	0.5237	0.055*
N1	0.08863 (8)	1.02829 (11)	0.22613 (15)	0.0460 (4)
O1	0.00462 (7)	1.11356 (11)	−0.00035 (12)	0.0605 (4)
H1N	0.0548 (13)	1.0243 (15)	0.135 (2)	0.067 (6)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0272 (7)	0.0888 (14)	0.0267 (7)	0.0027 (8)	0.0080 (6)	−0.0046 (8)
C2	0.0343 (9)	0.1043 (17)	0.0311 (8)	0.0120 (10)	0.0034 (6)	0.0074 (10)
C3	0.0359 (9)	0.0938 (16)	0.0482 (10)	0.0212 (10)	0.0101 (8)	0.0201 (11)
C4	0.0300 (8)	0.0695 (13)	0.0489 (9)	0.0141 (8)	0.0141 (7)	0.0069 (9)
C5	0.0461 (10)	0.0653 (13)	0.0736 (13)	0.0165 (9)	0.0192 (10)	0.0100 (11)
C6	0.0490 (11)	0.0615 (13)	0.0805 (15)	0.0027 (9)	0.0217 (10)	−0.0120 (11)
C7	0.0392 (9)	0.0656 (12)	0.0516 (10)	−0.0006 (8)	0.0108 (8)	−0.0106 (9)
C8	0.0345 (8)	0.0605 (11)	0.0371 (8)	0.0010 (7)	0.0090 (6)	−0.0031 (7)
C9	0.0237 (7)	0.0641 (11)	0.0347 (7)	0.0066 (7)	0.0112 (6)	−0.0004 (7)
C10	0.0242 (7)	0.0693 (11)	0.0264 (7)	0.0028 (7)	0.0081 (5)	−0.0024 (7)
C11	0.0288 (7)	0.0689 (11)	0.0266 (7)	−0.0028 (7)	0.0080 (6)	−0.0065 (7)
C12	0.0483 (10)	0.0646 (12)	0.0320 (8)	−0.0091 (8)	0.0132 (7)	−0.0030 (7)
C13	0.0437 (9)	0.0713 (12)	0.0291 (7)	−0.0052 (8)	0.0092 (7)	0.0001 (8)
C14	0.0439 (9)	0.0703 (13)	0.0301 (8)	−0.0067 (8)	0.0035 (7)	−0.0045 (8)
C15	0.0367 (8)	0.0679 (12)	0.0308 (8)	−0.0134 (8)	0.0036 (6)	−0.0035 (7)
N1	0.0397 (7)	0.0694 (10)	0.0281 (6)	−0.0057 (7)	0.0076 (5)	−0.0049 (7)
O1	0.0425 (7)	0.1048 (12)	0.0307 (6)	−0.0068 (7)	0.0037 (5)	−0.0135 (7)

Geometric parameters (Å, º)

C1—O1	1.265 (2)	C10—C11	1.402 (2)
C1—C2	1.444 (3)	C11—N1	1.303 (2)
C1—C10	1.446 (2)	C11—H11	0.9500
C2—C3	1.335 (3)	C12—N1	1.455 (2)
C2—H2	0.9500	C12—C13	1.513 (2)
C3—C4	1.442 (3)	C12—H12A	0.9900
C3—H3	0.9500	C12—H12B	0.9900
C4—C5	1.399 (3)	C13—C14	1.524 (3)
C4—C9	1.416 (2)	C13—H13A	0.9900
C5—C6	1.377 (3)	C13—H13B	0.9900
C5—H5	0.9500	C14—C15	1.525 (2)
C6—C7	1.392 (3)	C14—H14A	0.9900
C6—H6	0.9500	C14—H14B	0.9900
C7—C8	1.363 (3)	C15—C15^i	1.514 (4)
C7—H7	0.9500	C15—H15A	0.9900
C8—C9	1.421 (2)	C15—H15B	0.9900
C8—H8	0.9500	N1—H1N	0.93 (2)
C9—C10	1.443 (2)
O1—C1—C2	120.62 (15)	N1—C11—C10	126.00 (14)
O1—C1—C10	122.48 (18)	N1—C11—H11	117.0
C2—C1—C10	116.90 (18)	C10—C11—H11	117.0
C3—C2—C1	121.84 (16)	N1—C12—C13	112.44 (13)
C3—C2—H2	119.1	N1—C12—H12A	109.1
C1—C2—H2	119.1	C13—C12—H12A	109.1
C2—C3—C4	122.73 (19)	N1—C12—H12B	109.1
C2—C3—H3	118.6	C13—C12—H12B	109.1
C4—C3—H3	118.6	H12A—C12—H12B	107.8
C5—C4—C9	120.40 (17)	C12—C13—C14	112.59 (14)
C5—C4—C3	121.34 (19)	C12—C13—H13A	109.1
C9—C4—C3	118.25 (19)	C14—C13—H13A	109.1
C6—C5—C4	120.9 (2)	C12—C13—H13B	109.1
C6—C5—H5	119.5	C14—C13—H13B	109.1
C4—C5—H5	119.5	H13A—C13—H13B	107.8
C5—C6—C7	119.3 (2)	C13—C14—C15	114.38 (15)
C5—C6—H6	120.3	C13—C14—H14A	108.7
C7—C6—H6	120.3	C15—C14—H14A	108.7
C8—C7—C6	120.89 (18)	C13—C14—H14B	108.7
C8—C7—H7	119.6	C15—C14—H14B	108.7
C6—C7—H7	119.6	H14A—C14—H14B	107.6
C7—C8—C9	121.64 (17)	C15^i—C15—C14	113.11 (18)
C7—C8—H8	119.2	C15^i—C15—H15A	109.0
C9—C8—H8	119.2	C14—C15—H15A	109.0
C4—C9—C8	116.85 (17)	C15^i—C15—H15B	109.0
C4—C9—C10	119.43 (15)	C14—C15—H15B	109.0
C8—C9—C10	123.70 (16)	H15A—C15—H15B	107.8
C11—C10—C9	121.09 (13)	C11—N1—C12	124.11 (14)
C11—C10—C1	118.29 (16)	C11—N1—H1N	116.0 (13)
C9—C10—C1	120.63 (16)	C12—N1—H1N	119.9 (13)
O1—C1—C2—C3	177.27 (16)	C4—C9—C10—C11	176.09 (13)
C10—C1—C2—C3	−3.0 (2)	C8—C9—C10—C11	−5.2 (2)
C1—C2—C3—C4	−1.0 (3)	C4—C9—C10—C1	−3.9 (2)
C2—C3—C4—C5	−176.55 (17)	C8—C9—C10—C1	174.82 (13)
C2—C3—C4—C9	2.7 (3)	O1—C1—C10—C11	5.2 (2)
C9—C4—C5—C6	−0.6 (3)	C2—C1—C10—C11	−174.52 (14)
C3—C4—C5—C6	178.70 (17)	O1—C1—C10—C9	−174.87 (14)
C4—C5—C6—C7	0.3 (3)	C2—C1—C10—C9	5.5 (2)
C5—C6—C7—C8	0.2 (3)	C9—C10—C11—N1	−179.99 (14)
C6—C7—C8—C9	−0.4 (3)	C1—C10—C11—N1	0.0 (2)
C5—C4—C9—C8	0.3 (2)	N1—C12—C13—C14	−172.37 (14)
C3—C4—C9—C8	−179.00 (14)	C12—C13—C14—C15	−66.4 (2)
C5—C4—C9—C10	179.08 (15)	C13—C14—C15—C15^i	179.72 (17)
C3—C4—C9—C10	−0.2 (2)	C10—C11—N1—C12	178.34 (14)
C7—C8—C9—C4	0.2 (2)	C13—C12—N1—C11	−111.09 (17)
C7—C8—C9—C10	−178.53 (15)

Symmetry code: (i) −x+1/2, −y+3/2, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1	0.93 (2)	1.87 (2)	2.602 (2)	133.6 (18)
N1—H1N···O1^ii	0.93 (2)	2.44 (2)	3.115 (2)	129.6 (17)
C12—H12A···O1^iii	0.99	2.47	3.201 (2)	131

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