A tripyridylthioether macrocycle: (14,17-dithia-22,23,24-triaza­tetra­cyclo­[16.3.1.1^3,7.1^9,13]tetra­cosa-1(22),3,5,7(24),9,11,13(23),18,20-nona­ene-2,8-dione

The title compound, C₁₉H₁₃N₃O₂S₂, is a macrocycle with a `wheelchair' conformation. The `backrest' pyridine ring is tilted by 142.87 (7)° with respect to the `seat' plane, and the two `wheel' pyridine rings are tilted by 70.33 (3)° with respect to one another.

Key indicators

• Single-crystal X-ray study
• T = 110 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.043
• wR factor = 0.108
• Data-to-parameter ratio = 34.9

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?

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

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

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Computing details

Data collection: COLLECT (Nonius, 2000); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK; program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX publication routines (Farrugia, 1999).

14,17-Dithia-22,23,24-triazatetracyclo[16.3.1.13,7.19,13]tetracosa- 1(22),3,5,7(24),9,11,13 (23),18,20-nonaene-2,8-dione

Crystal data

C19H13N3O2S2	F(000) = 784
Mr = 379.44	Dx = 1.433 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 7195 reflections
a = 8.7102 (10) Å	θ = 2.5–36.3°
b = 13.1725 (13) Å	µ = 0.32 mm^−1
c = 15.497 (2) Å	T = 110 K
β = 98.532 (5)°	Plate, colorless
V = 1758.4 (3) Å^3	0.37 × 0.35 × 0.17 mm
Z = 4

Data collection

Nonius KappaCCD (with Oxford Cryostream) diffractometer	6267 reflections with I > 2σ(I)
ω scans	Rint = 0.026
Absorption correction: multi-scan (SCALPACK; Otwinowski & Minor, 1997)	θmax = 36.4°, θmin = 2.8°
Tmin = 0.890, Tmax = 0.947	h = −14→14
35062 measured reflections	k = −21→21
8240 independent reflections	l = −25→25

Refinement

Refinement on F^2	H-atom parameters constrained
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0415P)^2 + 0.7446P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.043	(Δ/σ)max = 0.001
wR(F^2) = 0.108	Δρmax = 0.47 e Å^−3
S = 1.03	Δρmin = −0.42 e Å^−3
8240 reflections	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
236 parameters	Extinction coefficient: 0.0054 (8)
0 restraints

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
S1	0.21648 (3)	0.62831 (2)	0.67641 (2)	0.02468 (7)
S2	0.21641 (3)	0.82946 (3)	0.53572 (2)	0.02601 (7)
O1	0.89183 (10)	0.94448 (7)	0.61725 (6)	0.02800 (18)
O2	0.86296 (12)	0.45176 (8)	0.64058 (7)	0.0376 (2)
N1	0.49854 (11)	0.55833 (7)	0.65806 (6)	0.01900 (16)
N2	0.77167 (10)	0.69644 (7)	0.64052 (6)	0.01817 (16)
N3	0.52520 (10)	0.85003 (7)	0.56563 (6)	0.01743 (15)
C1	0.59496 (13)	0.49126 (8)	0.62823 (7)	0.02020 (19)
C2	0.54483 (16)	0.40508 (8)	0.58044 (8)	0.0259 (2)
H2	0.6168	0.3592	0.5613	0.031*
C3	0.38582 (17)	0.38836 (9)	0.56161 (8)	0.0291 (3)
H3	0.347	0.3301	0.5294	0.035*
C4	0.28454 (15)	0.45740 (9)	0.59017 (8)	0.0261 (2)
H4	0.1754	0.4478	0.5775	0.031*
C5	0.34682 (13)	0.54211 (8)	0.63837 (7)	0.02035 (19)
C6	0.33559 (13)	0.74106 (8)	0.69817 (7)	0.02077 (19)
H6A	0.3558	0.753	0.7619	0.025*
H6B	0.4367	0.7296	0.6779	0.025*
C7	0.25933 (13)	0.83494 (9)	0.65336 (7)	0.02084 (19)
H7A	0.3283	0.8938	0.6695	0.025*
H7B	0.1612	0.8477	0.6766	0.025*
C8	0.39959 (12)	0.85304 (8)	0.50503 (7)	0.01813 (17)
C9	0.40557 (14)	0.87391 (8)	0.41671 (7)	0.02111 (19)
H9	0.3139	0.873	0.375	0.025*
C10	0.54815 (15)	0.89584 (9)	0.39176 (7)	0.0232 (2)
H10	0.5562	0.9092	0.3324	0.028*
C11	0.67969 (14)	0.89800 (8)	0.45505 (7)	0.02151 (19)
H11	0.7784	0.9156	0.4405	0.026*
C12	0.66168 (12)	0.87359 (7)	0.53986 (7)	0.01741 (17)
C13	0.79831 (12)	0.87499 (8)	0.61091 (7)	0.01911 (18)
C14	0.82082 (12)	0.78724 (8)	0.67325 (7)	0.01817 (17)
C15	0.89879 (13)	0.80147 (10)	0.75742 (7)	0.0228 (2)
H15	0.9281	0.8675	0.7783	0.027*
C16	0.93272 (13)	0.71670 (11)	0.81012 (7)	0.0257 (2)
H16	0.9836	0.7237	0.8684	0.031*
C17	0.89082 (13)	0.62143 (10)	0.77591 (7)	0.0231 (2)
H17	0.9171	0.5617	0.8092	0.028*
C18	0.80937 (12)	0.61562 (8)	0.69166 (7)	0.01907 (18)
C19	0.76386 (14)	0.51380 (8)	0.65160 (7)	0.0229 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.01979 (12)	0.02561 (13)	0.02956 (15)	−0.00449 (9)	0.00670 (10)	−0.00096 (10)
S2	0.01742 (12)	0.03852 (16)	0.02081 (13)	−0.00179 (10)	−0.00132 (9)	0.00493 (11)
O1	0.0245 (4)	0.0234 (4)	0.0352 (5)	−0.0076 (3)	0.0016 (3)	−0.0020 (3)
O2	0.0364 (5)	0.0302 (5)	0.0435 (6)	0.0184 (4)	−0.0030 (4)	−0.0040 (4)
N1	0.0229 (4)	0.0171 (4)	0.0170 (4)	−0.0009 (3)	0.0030 (3)	0.0000 (3)
N2	0.0170 (4)	0.0189 (4)	0.0177 (4)	0.0017 (3)	−0.0002 (3)	−0.0005 (3)
N3	0.0187 (4)	0.0174 (4)	0.0159 (4)	0.0003 (3)	0.0018 (3)	−0.0005 (3)
C1	0.0290 (5)	0.0148 (4)	0.0167 (4)	0.0023 (4)	0.0029 (4)	0.0025 (3)
C2	0.0427 (7)	0.0149 (4)	0.0201 (5)	0.0011 (4)	0.0043 (4)	0.0001 (4)
C3	0.0465 (7)	0.0181 (5)	0.0217 (5)	−0.0087 (5)	0.0020 (5)	−0.0023 (4)
C4	0.0326 (6)	0.0234 (5)	0.0214 (5)	−0.0107 (4)	0.0011 (4)	0.0004 (4)
C5	0.0248 (5)	0.0194 (4)	0.0168 (4)	−0.0045 (4)	0.0032 (4)	0.0011 (3)
C6	0.0209 (4)	0.0213 (5)	0.0196 (5)	−0.0012 (4)	0.0013 (4)	0.0002 (4)
C7	0.0190 (4)	0.0238 (5)	0.0202 (5)	0.0027 (4)	0.0045 (4)	0.0002 (4)
C8	0.0197 (4)	0.0169 (4)	0.0172 (4)	0.0007 (3)	0.0006 (3)	−0.0003 (3)
C9	0.0272 (5)	0.0191 (4)	0.0160 (4)	0.0031 (4)	−0.0002 (4)	0.0000 (3)
C10	0.0340 (6)	0.0198 (4)	0.0164 (4)	0.0015 (4)	0.0054 (4)	0.0010 (3)
C11	0.0265 (5)	0.0192 (4)	0.0202 (5)	−0.0011 (4)	0.0079 (4)	−0.0010 (4)
C12	0.0203 (4)	0.0137 (4)	0.0183 (4)	0.0003 (3)	0.0030 (3)	−0.0021 (3)
C13	0.0181 (4)	0.0190 (4)	0.0206 (5)	−0.0005 (3)	0.0042 (3)	−0.0041 (3)
C14	0.0149 (4)	0.0220 (4)	0.0174 (4)	−0.0014 (3)	0.0020 (3)	−0.0023 (3)
C15	0.0174 (4)	0.0321 (5)	0.0186 (5)	−0.0046 (4)	0.0022 (3)	−0.0049 (4)
C16	0.0184 (5)	0.0426 (7)	0.0154 (4)	−0.0011 (4)	0.0003 (3)	−0.0014 (4)
C17	0.0173 (4)	0.0338 (6)	0.0181 (5)	0.0053 (4)	0.0024 (3)	0.0046 (4)
C18	0.0155 (4)	0.0224 (4)	0.0190 (4)	0.0047 (3)	0.0015 (3)	0.0009 (3)
C19	0.0283 (5)	0.0188 (4)	0.0208 (5)	0.0074 (4)	0.0010 (4)	0.0033 (4)

Geometric parameters (Å, º)

C1—C19	1.4918 (17)	C13—C14	1.5005 (16)
C1—C2	1.3899 (16)	C14—C15	1.3910 (15)
C2—C3	1.390 (2)	C15—C16	1.3891 (18)
C2—H2	0.95	C15—H15	0.95
C3—C4	1.3846 (19)	C16—C17	1.3897 (18)
C3—H3	0.95	C16—H16	0.95
C4—C5	1.4060 (16)	C17—C18	1.3926 (15)
C4—H4	0.95	C17—H17	0.95
C6—C7	1.5218 (15)	C18—C19	1.5060 (16)
C6—H6A	0.99	N1—C1	1.3471 (14)
C6—H6B	0.99	N1—C5	1.3288 (14)
C7—H7A	0.99	N2—C14	1.3440 (14)
C7—H7B	0.99	N2—C18	1.3387 (14)
C8—C9	1.4047 (15)	N3—C12	1.3453 (14)
C9—C10	1.3847 (17)	N3—C8	1.3326 (13)
C9—H9	0.95	O1—C13	1.2196 (13)
C10—C11	1.3935 (17)	O2—C19	1.2190 (14)
C10—H10	0.95	S1—C5	1.7676 (12)
C11—C12	1.3845 (15)	S1—C6	1.8144 (11)
C11—H11	0.95	S2—C7	1.8073 (12)
C12—C13	1.4967 (15)	S2—C8	1.7588 (11)
C2—C1—C19	120.83 (10)	C11—C10—H10	120.5
N1—C1—C19	115.38 (9)	C9—C10—H10	120.5
N1—C1—C2	123.78 (11)	C12—C11—C10	117.79 (10)
C1—C2—C3	117.76 (11)	C10—C11—H11	121.1
C1—C2—H2	121.1	C12—C11—H11	121.1
C3—C2—H2	121.1	N3—C12—C11	124.40 (10)
C4—C3—C2	119.41 (11)	C11—C12—C13	120.39 (10)
C2—C3—H3	120.3	N3—C12—C13	115.19 (9)
C4—C3—H3	120.3	O1—C13—C12	121.14 (10)
C3—C4—C5	118.50 (11)	C12—C13—C14	118.55 (9)
C3—C4—H4	120.7	O1—C13—C14	120.29 (10)
C5—C4—H4	120.7	C15—C14—C13	119.93 (10)
N1—C5—C4	122.81 (11)	N2—C14—C13	116.02 (9)
C4—C5—S1	118.08 (9)	N2—C14—C15	123.89 (10)
N1—C5—S1	119.09 (8)	C16—C15—C14	118.34 (11)
C7—C6—H6A	109.1	C14—C15—H15	120.8
S1—C6—H6A	109.1	C16—C15—H15	120.8
C7—C6—H6B	109.1	C15—C16—C17	118.73 (10)
H6A—C6—H6B	107.9	C15—C16—H16	120.6
S1—C6—H6B	109.1	C17—C16—H16	120.6
C7—C6—S1	112.43 (8)	C16—C17—C18	118.41 (11)
C6—C7—H7A	108.3	C16—C17—H17	120.8
S2—C7—H7A	108.3	C18—C17—H17	120.8
C6—C7—H7B	108.3	N2—C18—C17	123.87 (10)
H7A—C7—H7B	107.4	C17—C18—C19	120.12 (10)
S2—C7—H7B	108.3	N2—C18—C19	115.97 (9)
C6—C7—S2	116.02 (8)	O2—C19—C1	121.73 (11)
N3—C8—C9	123.18 (10)	C1—C19—C18	117.85 (9)
C9—C8—S2	117.67 (8)	O2—C19—C18	120.41 (11)
N3—C8—S2	119.15 (8)	C5—N1—C1	117.72 (10)
C10—C9—C8	118.51 (10)	C18—N2—C14	116.61 (9)
C10—C9—H9	120.7	C8—N3—C12	116.95 (9)
C8—C9—H9	120.7	C5—S1—C6	102.12 (5)
C9—C10—C11	119.05 (10)	C8—S2—C7	101.86 (5)
C2—C1—C19—O2	−10.27 (18)	C14—C15—C16—C17	1.53 (16)
C2—C1—C19—C18	171.15 (10)	C15—C16—C17—C18	−3.28 (16)
N1—C1—C19—O2	168.43 (11)	C16—C17—C18—N2	1.55 (17)
N1—C1—C19—C18	−10.15 (14)	C16—C17—C18—C19	179.07 (10)
C19—C1—C2—C3	179.47 (10)	C17—C18—C19—O2	−61.27 (16)
N1—C1—C2—C3	0.88 (17)	C17—C18—C19—C1	117.33 (11)
C1—C2—C3—C4	0.43 (17)	N2—C18—C19—O2	116.43 (13)
C2—C3—C4—C5	−0.65 (17)	N2—C18—C19—C1	−64.97 (14)
C3—C4—C5—N1	−0.41 (17)	C5—N1—C1—C2	−1.90 (16)
C3—C4—C5—S1	−178.71 (9)	C5—N1—C1—C19	179.44 (9)
S1—C6—C7—S2	−60.06 (10)	C1—N1—C5—C4	1.64 (16)
N3—C8—C9—C10	−2.26 (16)	C1—N1—C5—S1	179.93 (8)
S2—C8—C9—C10	177.98 (8)	C18—N2—C14—C15	−3.94 (16)
C8—C9—C10—C11	−1.00 (16)	C18—N2—C14—C13	171.39 (9)
C9—C10—C11—C12	2.73 (16)	C14—N2—C18—C17	2.00 (16)
C10—C11—C12—N3	−1.48 (16)	C14—N2—C18—C19	−175.61 (9)
C10—C11—C12—C13	−179.71 (10)	C8—N3—C12—C11	−1.61 (15)
C11—C12—C13—O1	44.36 (15)	C8—N3—C12—C13	176.70 (9)
C11—C12—C13—C14	−133.96 (10)	C12—N3—C8—C9	3.51 (15)
N3—C12—C13—O1	−134.02 (11)	C12—N3—C8—S2	−176.74 (7)
N3—C12—C13—C14	47.66 (13)	C6—S1—C5—N1	20.89 (10)
C12—C13—C14—N2	31.63 (13)	C6—S1—C5—C4	−160.75 (9)
C12—C13—C14—C15	−152.84 (10)	C5—S1—C6—C7	127.35 (8)
O1—C13—C14—N2	−146.70 (11)	C8—S2—C7—C6	−78.49 (9)
O1—C13—C14—C15	28.83 (15)	C7—S2—C8—N3	12.27 (10)
C13—C14—C15—C16	−172.94 (10)	C7—S2—C8—C9	−167.96 (8)
N2—C14—C15—C16	2.22 (17)