Bis[N,N'-o-phenyl­enebis­(pyridine-2,6-dicarboxamide)] dimethyl­formamide solvate

In the title macrocyclic compound, 3,10,18,25,31,32-hexa­aza­penta­cyclo­[25.3.1.1^12,16.0^4,9.0^19,24]dotri­conta-1(30),4,6,8,12,14,-16(32),19,21,23,27(31),28-dodecaene-2,11,17,26-tetrone dimethyl­formamide solvate, C₂₆H₁₈N₆O₄·C₃H₇NO, the two pyridine rings are approximately perpendicular to each other, the dihedral angle between them being 82.1 (1)°. The macrocycle possesses mirror symmetry. The dihedral angle between the two benzene rings is 119.6 (1)°.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.003 Å
• Disorder in main residue
• R factor = 0.047
• wR factor = 0.098
• Data-to-parameter ratio = 12.9

checkCIF/PLATON results

No syntax errors found



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
PLAT076_ALERT_1_C Occupancy       0.50 less than 1.0 for Sp.pos  .        C14
PLAT076_ALERT_1_C Occupancy       0.50 less than 1.0 for Sp.pos  .       H14A
PLAT076_ALERT_1_C Occupancy       0.50 less than 1.0 for Sp.pos  .        C15
PLAT076_ALERT_1_C Occupancy       0.50 less than 1.0 for Sp.pos  .       H15A
PLAT076_ALERT_1_C Occupancy       0.50 less than 1.0 for Sp.pos  .        C16
PLAT076_ALERT_1_C Occupancy       0.50 less than 1.0 for Sp.pos  .       H16A
PLAT076_ALERT_1_C Occupancy       0.50 less than 1.0 for Sp.pos  .         N4
PLAT076_ALERT_1_C Occupancy       0.50 less than 1.0 for Sp.pos  .         O3
PLAT076_ALERT_1_C Occupancy       0.50 less than 1.0 for Sp.pos  .       C14'
PLAT076_ALERT_1_C Occupancy       0.50 less than 1.0 for Sp.pos  .       H14C
PLAT076_ALERT_1_C Occupancy       0.50 less than 1.0 for Sp.pos  .       C15'
PLAT076_ALERT_1_C Occupancy       0.50 less than 1.0 for Sp.pos  .       H15C
PLAT076_ALERT_1_C Occupancy       0.50 less than 1.0 for Sp.pos  .       C16'
PLAT076_ALERT_1_C Occupancy       0.50 less than 1.0 for Sp.pos  .       H16B
PLAT076_ALERT_1_C Occupancy       0.50 less than 1.0 for Sp.pos  .        N4'
PLAT076_ALERT_1_C Occupancy       0.50 less than 1.0 for Sp.pos  .        O3'
PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_C Check the Reported _diffrn_ambient_temperature .        293 K
PLAT301_ALERT_3_C Main Residue  Disorder .........................      11.00 Perc.

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

  21 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
   0 ALERT type 4 Improvement, methodology, query or suggestion

---

Computing details

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

3,10,18,25,31,32-hexaazapentacyclo[25.3.1.1^12,16.0^4,9.0^19,24]dotriconta- 1(30),4,6,8,12,14,16 (32),19,21,23,27 (31),28-dodecaene-2,11,17,26-tetrone dimethylformamide solvate

Crystal data

C26H18N6O4·C6H14N2O2	F(000) = 1152
Mr = 551.06	Dx = 1.376 Mg m^−3
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 1146 reflections
a = 18.2331 (17) Å	θ = 2.4–18.7°
b = 15.3467 (14) Å	µ = 0.10 mm^−1
c = 9.5134 (9) Å	T = 293 K
V = 2662.0 (4) Å^3	Block, colourless
Z = 4	0.32 × 0.28 × 0.26 mm

Data collection

Bruker Smart Apex CCD area-detector diffractometer	2725 independent reflections
Radiation source: sealed tube	1708 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.051
φ and ω scans	θmax = 26.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −22→22
Tmin = 0.966, Tmax = 0.972	k = −18→18
13689 measured reflections	l = −6→11

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.098	H-atom parameters constrained
S = 0.96	w = 1/[σ^2(Fo^2) + (0.0411P)^2] where P = (Fo^2 + 2Fc^2)/3
2725 reflections	(Δ/σ)max < 0.001
211 parameters	Δρmax = 0.16 e Å^−3
0 restraints	Δρmin = −0.15 e Å^−3

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.

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

9.3099 (0.0130) x + 11.5698 (0.0080) y - 3.9332 (0.0073) z = 2.4684 (0.0115)

* 0.0109 (0.0012) N1 * -0.0074 (0.0013) C1 * -0.0059 (0.0014) C2 * 0.0154 (0.0015) C3 * -0.0117 (0.0014) C4 * -0.0013 (0.0013) C5

Rms deviation of fitted atoms = 0.0099

- 9.3099 (0.0130) x + 11.5698 (0.0080) y + 3.9332 (0.0073) z = 3.3165 (0.0126)

Angle to previous plane (with approximate e.s.d.) = 82.14 (0.05)

* -0.0109 (0.0012) N1_$2 * 0.0074 (0.0013) C1_$2 * 0.0059 (0.0014) C2_$2 * -0.0154 (0.0015) C3_$2 * 0.0117 (0.0014) C4_$2 * 0.0013 (0.0013) C5_$2

Rms deviation of fitted atoms = 0.0099

- 6.4416 (0.0202) x - 0.0000 (0.0000) y + 8.8999 (0.0041) z = 4.4085 (0.0093)

Angle to previous plane (with approximate e.s.d.) = 55.45 (0.07)

* -0.0043 (0.0008) C11 * 0.0086 (0.0017) C12 * -0.0043 (0.0008) C13 * -0.0043 (0.0008) C11_$2 * 0.0086 (0.0017) C12_$2 * -0.0043 (0.0008) C13_$2

Rms deviation of fitted atoms = 0.0061

18.0114 (0.0038) x - 0.0000 (0.0002) y - 1.4791 (0.0111) z = 8.8612 (0.0176)

Angle to previous plane (with approximate e.s.d.) = 60.37 (0.10)

* 0.0068 (0.0009) C7 * -0.0136 (0.0018) C8 * 0.0068 (0.0009) C9 * 0.0068 (0.0009) C7_$2 * -0.0136 (0.0018) C8_$2 * 0.0068 (0.0009) C9_$2

Rms deviation of fitted atoms = 0.0096

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)
N1	0.54669 (8)	0.08730 (9)	0.92046 (16)	0.0410 (4)
N2	0.58758 (8)	0.15760 (10)	1.16484 (17)	0.0442 (4)
H2	0.5506	0.1720	1.1137	0.053*
N3	0.42769 (8)	0.15908 (10)	0.80243 (16)	0.0445 (4)
H3	0.4470	0.1729	0.8819	0.053*
C1	0.60768 (10)	0.05629 (12)	0.9783 (2)	0.0429 (5)
C2	0.65301 (12)	−0.00290 (13)	0.9111 (3)	0.0604 (6)
H2A	0.6954	−0.0234	0.9545	0.073*
C3	0.63391 (12)	−0.03071 (13)	0.7786 (3)	0.0588 (6)
H3A	0.6642	−0.0689	0.7298	0.071*
C4	0.56992 (11)	−0.00187 (13)	0.7189 (2)	0.0544 (6)
H4	0.5549	−0.0218	0.6311	0.065*
C5	0.52826 (11)	0.05787 (12)	0.7934 (2)	0.0465 (5)
C6	0.63045 (10)	0.09256 (12)	1.1182 (2)	0.0466 (5)
C7	0.59839 (9)	0.20437 (13)	1.2912 (2)	0.0452 (5)
C8	0.60752 (12)	0.15994 (15)	1.4162 (2)	0.0587 (6)
H8	0.6061	0.0994	1.4171	0.070*
C9	0.61879 (12)	0.20520 (15)	1.5396 (2)	0.0631 (6)
H9	0.6264	0.1750	1.6231	0.076*
C10	0.45964 (11)	0.09506 (13)	0.7273 (2)	0.0457 (5)
C11	0.36433 (10)	0.20495 (12)	0.75855 (18)	0.0387 (4)
C12	0.30357 (10)	0.16061 (14)	0.7160 (2)	0.0440 (5)
H12	0.3032	0.1000	0.7177	0.053*
C13	0.24318 (12)	0.20528 (15)	0.6709 (2)	0.0604 (6)
H13	0.2020	0.1750	0.6401	0.073*
O1	0.68464 (8)	0.06567 (10)	1.18065 (17)	0.0684 (5)
O2	0.43698 (7)	0.06891 (8)	0.61431 (14)	0.0521 (4)
C14	0.4081 (3)	0.2500	0.3693 (6)	0.0477 (14)	0.50
H14A	0.4579	0.2500	0.3369	0.072*	0.50
H14B	0.3995	0.3011	0.4252	0.072*	0.50
C15	0.2811 (3)	0.2500	0.2818 (7)	0.0529 (16)	0.50
H15A	0.2491	0.2500	0.2016	0.079*	0.50
H15B	0.2721	0.1989	0.3374	0.079*	0.50
C16	0.3824 (4)	0.2500	0.1172 (8)	0.0506 (14)	0.50
H16A	0.3494	0.2500	0.0427	0.061*	0.50
N4	0.35369 (13)	0.2500	0.2380 (2)	0.0506 (6)	0.50
O3	0.44841 (9)	0.2500	0.08278 (19)	0.0460 (5)	0.50
C14'	0.3146 (3)	0.2500	0.3682 (6)	0.0479 (15)	0.50
H14C	0.3491	0.2500	0.4443	0.072*	0.50
H14D	0.2843	0.3011	0.3740	0.072*	0.50
C15'	0.2957 (3)	0.2500	0.1085 (6)	0.0564 (16)	0.50
H15C	0.3218	0.2500	0.0209	0.085*	0.50
H15D	0.2654	0.1989	0.1140	0.085*	0.50
C16'	0.4189 (4)	0.2500	0.2000 (7)	0.0490 (14)	0.50
H16B	0.4521	0.2500	0.2742	0.059*	0.50
N4'	0.35369 (13)	0.2500	0.2380 (2)	0.0506 (6)	0.50
O3'	0.44841 (9)	0.2500	0.08278 (19)	0.0460 (5)	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0410 (8)	0.0366 (8)	0.0454 (9)	−0.0029 (7)	0.0108 (7)	0.0015 (7)
N2	0.0457 (9)	0.0366 (9)	0.0504 (10)	0.0030 (7)	−0.0068 (7)	−0.0005 (7)
N3	0.0546 (10)	0.0452 (10)	0.0337 (9)	0.0049 (8)	−0.0014 (7)	−0.0064 (7)
C1	0.0411 (10)	0.0306 (10)	0.0572 (13)	0.0005 (8)	0.0090 (9)	0.0047 (8)
C2	0.0558 (13)	0.0372 (11)	0.0883 (18)	0.0113 (9)	0.0059 (13)	0.0003 (12)
C3	0.0569 (13)	0.0385 (12)	0.0812 (17)	0.0147 (10)	0.0257 (12)	−0.0079 (11)
C4	0.0538 (12)	0.0466 (13)	0.0627 (14)	0.0010 (10)	0.0162 (11)	−0.0132 (11)
C5	0.0571 (12)	0.0381 (11)	0.0444 (11)	−0.0019 (9)	0.0138 (9)	−0.0046 (9)
C6	0.0400 (10)	0.0345 (10)	0.0654 (14)	0.0053 (9)	0.0086 (10)	0.0108 (9)
C7	0.0426 (11)	0.0458 (11)	0.0471 (12)	−0.0031 (9)	−0.0033 (9)	0.0012 (9)
C8	0.0632 (14)	0.0553 (14)	0.0575 (14)	−0.0069 (11)	−0.0094 (11)	0.0123 (11)
C9	0.0627 (13)	0.0760 (15)	0.0507 (13)	−0.0037 (11)	−0.0168 (11)	0.0065 (11)
C10	0.0539 (12)	0.0429 (11)	0.0402 (11)	−0.0022 (9)	0.0133 (9)	−0.0062 (9)
C11	0.0462 (10)	0.0417 (10)	0.0280 (9)	−0.0002 (8)	−0.0007 (7)	−0.0012 (7)
C12	0.0419 (10)	0.0502 (12)	0.0399 (11)	−0.0049 (9)	−0.0068 (8)	−0.0019 (9)
C13	0.0606 (13)	0.0659 (14)	0.0549 (14)	−0.0133 (11)	−0.0155 (11)	−0.0043 (11)
O1	0.0560 (9)	0.0647 (11)	0.0846 (12)	0.0209 (8)	−0.0126 (8)	0.0035 (9)
O2	0.0539 (8)	0.0519 (9)	0.0505 (8)	0.0082 (6)	−0.0024 (6)	−0.0324 (7)
C14	0.034 (3)	0.070 (4)	0.039 (3)	0.000	−0.005 (2)	0.000
C15	0.047 (4)	0.064 (4)	0.048 (4)	0.000	0.024 (3)	0.000
C16	0.046 (4)	0.047 (4)	0.058 (4)	0.000	0.007 (3)	0.000
N4	0.0576 (17)	0.0429 (14)	0.0515 (16)	0.000	0.0203 (12)	0.000
O3	0.0418 (11)	0.0556 (12)	0.0406 (11)	0.000	0.0094 (8)	0.000
C14'	0.055 (4)	0.059 (4)	0.030 (3)	0.000	0.024 (3)	0.000
C15'	0.059 (4)	0.060 (4)	0.050 (4)	0.000	−0.023 (3)	0.000
C16'	0.043 (4)	0.048 (4)	0.055 (4)	0.000	0.009 (3)	0.000
N4'	0.0576 (17)	0.0429 (14)	0.0515 (16)	0.000	0.0203 (12)	0.000
O3'	0.0418 (11)	0.0556 (12)	0.0406 (11)	0.000	0.0094 (8)	0.000

Geometric parameters (Å, º)

N1—C1	1.329 (2)	C12—C13	1.366 (3)
N1—C5	1.333 (2)	C12—H12	0.9300
N2—C6	1.343 (2)	C13—C13^i	1.373 (5)
N2—C7	1.414 (2)	C13—H13	0.9300
N2—H2	0.8600	C14—N4	1.595 (6)
N3—C10	1.347 (2)	C14—H14A	0.9600
N3—C11	1.416 (2)	C14—H14B	0.9601
N3—H3	0.8600	C14—H14C	1.2901
C1—C2	1.384 (3)	C14—H16B	1.2097
C1—C6	1.502 (3)	C15—N4	1.387 (6)
C2—C3	1.375 (3)	C15—H15A	0.9600
C2—H2A	0.9300	C15—H15B	0.9600
C3—C4	1.371 (3)	C15—H14D	1.1782
C3—H3A	0.9300	C16—O3	1.247 (6)
C4—C5	1.386 (3)	C16—N4	1.263 (7)
C4—H4	0.9300	C16—H16A	0.9300
C5—C10	1.512 (3)	N4—C16'	1.243 (6)
C6—O1	1.224 (2)	N4—C14'	1.429 (5)
C7—C8	1.380 (3)	N4—C15'	1.624 (6)
C7—C7^i	1.400 (4)	O3—C16'	1.238 (6)
C8—C9	1.380 (3)	C14'—H15B	1.1407
C8—H8	0.9300	C14'—H14C	0.9600
C9—C9^i	1.375 (5)	C14'—H14D	0.9601
C9—H9	0.9300	C15'—H15A	1.2272
C10—O2	1.219 (2)	C15'—H15C	0.9600
C11—C12	1.362 (2)	C15'—H15D	0.9600
C11—C11^i	1.383 (4)	C16'—H16B	0.9300
C1—N1—C5	117.69 (16)	C12—C13—H13	119.9
C6—N2—C7	125.22 (16)	C13^i—C13—H13	119.9
C6—N2—H2	117.4	N4—C14—H14A	109.7
C7—N2—H2	117.4	N4—C14—H14B	109.4
C10—N3—C11	123.97 (16)	H14A—C14—H14B	109.5
C10—N3—H3	118.0	H14A—C14—H14C	165.2
C11—N3—H3	118.0	H14B—C14—H16B	121.5
N1—C1—C2	122.9 (2)	H14C—C14—H16B	165.1
N1—C1—C6	117.74 (16)	N4—C15—H15A	110.0
C2—C1—C6	119.18 (19)	N4—C15—H15B	109.2
C3—C2—C1	118.4 (2)	H15A—C15—H15B	109.5
C3—C2—H2A	120.8	N4—C15—H14D	100.1
C1—C2—H2A	120.8	H15A—C15—H14D	128.4
C4—C3—C2	119.67 (19)	H15B—C15—H14D	98.1
C4—C3—H3A	120.2	O3—C16—N4	129.7 (7)
C2—C3—H3A	120.2	O3—C16—H16A	115.1
C3—C4—C5	117.9 (2)	N4—C16—H16A	115.1
C3—C4—H4	121.0	O3—C16—H15C	125.1
C5—C4—H4	121.0	N4—C16—H15C	105.2
N1—C5—C4	123.35 (19)	C16'—N4—C15	179.5 (5)
N1—C5—C10	117.24 (16)	C16—N4—C15	132.0 (5)
C4—C5—C10	119.37 (18)	C16'—N4—C14'	136.9 (5)
O1—C6—N2	124.1 (2)	C16—N4—C14'	174.6 (5)
O1—C6—C1	121.88 (18)	C16—N4—C14	117.0 (4)
N2—C6—C1	114.03 (17)	C15—N4—C14	111.0 (4)
C8—C7—C7^i	119.61 (13)	C16'—N4—C15'	113.7 (5)
C8—C7—N2	119.88 (18)	C14'—N4—C15'	109.4 (4)
C7^i—C7—N2	120.50 (10)	C14—N4—C15'	177.8 (3)
C9—C8—C7	120.1 (2)	N4—C14'—H15B	96.7
C9—C8—H8	119.9	N4—C14'—H14C	109.0
C7—C8—H8	119.9	H15B—C14'—H14C	129.8
C9^i—C9—C8	120.23 (13)	N4—C14'—H14D	109.7
C9^i—C9—H9	119.9	H15B—C14'—H14D	100.7
C8—C9—H9	119.9	H14C—C14'—H14D	109.5
O2—C10—N3	124.14 (19)	H15A—C15'—H16A	166.3
O2—C10—C5	121.51 (17)	N4—C15'—H15C	109.5
N3—C10—C5	114.34 (17)	H15A—C15'—H15C	166.0
C12—C11—C11^i	119.98 (11)	N4—C15'—H15D	109.4
C12—C11—N3	120.20 (17)	H15C—C15'—H15D	109.5
C11^i—C11—N3	119.81 (10)	O3—C16'—N4	132.7 (7)
C11—C12—C13	119.89 (19)	O3—C16'—H14A	125.6
C11—C12—H12	120.1	N4—C16'—H14A	101.7
C13—C12—H12	120.1	O3—C16'—H16B	113.7
C12—C13—C13^i	120.12 (12)	N4—C16'—H16B	113.7
C5—N1—C1—C2	1.6 (3)	C7^i—C7—C8—C9	−2.0 (3)
C5—N1—C1—C6	177.10 (16)	N2—C7—C8—C9	179.37 (19)
N1—C1—C2—C3	0.0 (3)	C7—C8—C9—C9^i	2.0 (3)
C6—C1—C2—C3	−175.45 (19)	C11—N3—C10—O2	−1.0 (3)
C1—C2—C3—C4	−2.2 (3)	C11—N3—C10—C5	177.99 (16)
C2—C3—C4—C5	2.8 (3)	N1—C5—C10—O2	−176.57 (18)
C1—N1—C5—C4	−1.0 (3)	C4—C5—C10—O2	5.6 (3)
C1—N1—C5—C10	−178.70 (16)	N1—C5—C10—N3	4.4 (2)
C3—C4—C5—N1	−1.2 (3)	C4—C5—C10—N3	−173.37 (18)
C3—C4—C5—C10	176.50 (19)	C10—N3—C11—C12	51.0 (3)
C7—N2—C6—O1	0.1 (3)	C10—N3—C11—C11^i	−128.84 (15)
C7—N2—C6—C1	−178.08 (16)	C11^i—C11—C12—C13	1.2 (2)
N1—C1—C6—O1	177.72 (17)	N3—C11—C12—C13	−178.56 (18)
C2—C1—C6—O1	−6.6 (3)	C11—C12—C13—C13^i	−1.2 (2)
N1—C1—C6—N2	−4.1 (2)	O3—C16—N4—C15	180.0
C2—C1—C6—N2	171.61 (17)	O3—C16—N4—C15'	180.0
C6—N2—C7—C8	−51.6 (3)	C14—N4—C16'—O3	180.0
C6—N2—C7—C7^i	129.79 (15)

Symmetry code: (i) x, −y+1/2, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O3′^ii	0.86	2.23	3.010 (2)	150
N2—H2···O3^ii	0.86	2.23	3.010 (2)	150
N3—H3···O3′^ii	0.86	2.25	3.034 (2)	152
N3—H3···O3^ii	0.86	2.25	3.034 (2)	152

Symmetry code: (ii) x, y, z+1.