1,4,7-Tris(p-toluene­sulfonyl)-1,4,7-tri­aza­cyclo­nonane

The X-ray crystal structure of the title compound, C₂₇H₃₃N₃O₆S₃, a key intermediate in the synthesis of 1,4,7-tri­aza­cyclo­nonane and its functionalized derivatives, is presented. Two of the p-tosyl groups are coplanar with the macrocyclic ring, with the third pointing away from it.

Key indicators

• Single-crystal X-ray study
• T = 150 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.041
• wR factor = 0.133
• Data-to-parameter ratio = 18.0

checkCIF/PLATON results

No syntax errors found



Alert level C
DIFMN02_ALERT_2_C  The minimum difference density is < -0.1*ZMAX*0.75
            _refine_diff_density_min given =     -1.272
            Test value =     -1.200
DIFMN03_ALERT_1_C  The minimum difference density is < -0.1*ZMAX*0.75
            The relevant atom site should be identified.
RINTA01_ALERT_3_C  The value of Rint is greater than 0.10
            Rint given   0.127
PLAT020_ALERT_3_C The value of Rint is greater than 0.10 .........       0.13
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.99
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT098_ALERT_2_C Minimum (Negative) Residual Density ............      -1.27 e/A   3
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?

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

   2 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
   1 ALERT type 4 Improvement, methodology, query or suggestion

---

Computing details

Data collection: COLLECT (Nonius, 1999); cell refinement: DENZO-SMN (Otwinowski & Minor, 1996); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: X-SEED (Barbour, 1999); software used to prepare material for publication: local program.

1,4,7-tris(p-toluenesulfonyl)-1,4,7-triazacyclononane

Crystal data

C27H33N3O6S3	Z = 2
Mr = 591.74	F(000) = 624
Triclinic, P1	Dx = 1.399 Mg m^−3
a = 10.3019 (2) Å	Mo Kα radiation, λ = 0.71070 Å
b = 12.3216 (2) Å	Cell parameters from 29674 reflections
c = 12.6131 (2) Å	θ = 2.8–27.5°
α = 101.5528 (8)°	µ = 0.31 mm^−1
β = 113.5558 (8)°	T = 150 K
γ = 96.3429 (6)°	Prism, colourless
V = 1405.22 (4) Å^3	0.23 × 0.17 × 0.11 mm

Data collection

Nonius KappaCCD area-detector diffractometer	6402 independent reflections
Radiation source: fine-focus sealed tube	5459 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.127
area–detector scans	θmax = 27.5°, θmin = 2.8°
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	h = −13→13
Tmin = 0.932, Tmax = 0.967	k = −15→15
29674 measured reflections	l = −16→16

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)] = 0.041	H-atom parameters constrained
wR(F^2) = 0.134	w = 1/[σ^2(Fo^2) + (0.0762P)^2 + 0.4075P] where P = (Fo^2 + 2Fc^2)/3
S = 1.09	(Δ/σ)max = 0.001
6402 reflections	Δρmax = 0.95 e Å^−3
356 parameters	Δρmin = −1.27 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.047 (7)

Special details

Experimental. Detector set at 30 mm from sample with different 2theta offsets 1 degree phi exposures for chi=0 degree settings 1 degree omega exposures for chi=90 degree settings

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. All non-hydrogen atoms were refined with anisotropic displacement parameters. All hydrogen atoms were placed in calculated positions and refined using a riding model. The fixed distances were: C—H(aryl) 0.95 Å, C—H(methyl) 0.98 Å, and C—H(ethylene bridge) 0.99 Å. For all H atoms, U_iso(H) values were set to 1.2U_eq(C)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
S1	0.48822 (4)	0.33243 (3)	0.22081 (4)	0.02576 (14)
S4	0.83908 (4)	−0.00535 (3)	0.23646 (3)	0.02527 (14)
S7	0.33381 (5)	−0.14779 (4)	0.16906 (4)	0.03064 (15)
O11	0.63193 (14)	0.37106 (10)	0.23413 (12)	0.0324 (3)
O12	0.45738 (14)	0.35860 (11)	0.32327 (11)	0.0318 (3)
O41	0.82573 (14)	−0.04532 (11)	0.11719 (11)	0.0322 (3)
O42	0.84549 (13)	−0.08322 (10)	0.30824 (11)	0.0310 (3)
O71	0.43276 (17)	−0.21330 (12)	0.15010 (14)	0.0431 (4)
O72	0.21284 (15)	−0.13421 (11)	0.06850 (11)	0.0378 (3)
N1	0.45143 (15)	0.19480 (11)	0.17298 (12)	0.0253 (3)
N4	0.70007 (15)	0.05222 (12)	0.22742 (12)	0.0248 (3)
N7	0.42815 (16)	−0.01995 (12)	0.24801 (13)	0.0289 (3)
C2	0.51233 (18)	0.13933 (15)	0.09309 (15)	0.0271 (3)
H2A	0.4995	0.1799	0.0305	0.032*
H2B	0.4554	0.0608	0.0521	0.032*
C3	0.67133 (18)	0.13517 (14)	0.15477 (15)	0.0263 (3)
H3A	0.7074	0.1159	0.0929	0.032*
H3B	0.7266	0.2115	0.2076	0.032*
C5	0.68379 (19)	0.08199 (15)	0.34071 (14)	0.0276 (4)
H5A	0.6531	0.1554	0.3489	0.033*
H5B	0.7787	0.0911	0.4095	0.033*
C6	0.5734 (2)	−0.00796 (16)	0.34421 (16)	0.0327 (4)
H6A	0.6036	−0.0815	0.3355	0.039*
H6B	0.5701	0.0128	0.4230	0.039*
C8	0.3470 (2)	0.06908 (15)	0.26399 (16)	0.0290 (4)
H8A	0.4034	0.1231	0.3442	0.035*
H8B	0.2538	0.0337	0.2606	0.035*
C9	0.31693 (18)	0.13343 (15)	0.16844 (16)	0.0279 (4)
H9A	0.2607	0.0793	0.0882	0.034*
H9B	0.2572	0.1883	0.1797	0.034*
C11	0.37034 (19)	0.39008 (14)	0.11166 (15)	0.0281 (4)
C12	0.3769 (2)	0.38062 (17)	0.00178 (18)	0.0376 (4)
H12	0.4386	0.3374	−0.0183	0.045*
C13	0.2811 (2)	0.45412 (15)	0.14099 (17)	0.0324 (4)
H13	0.2767	0.4604	0.2157	0.039*
C14	0.2916 (2)	0.43552 (18)	−0.07774 (18)	0.0397 (4)
H14	0.2941	0.4279	−0.1533	0.048*
C15	0.1983 (2)	0.50902 (16)	0.06064 (18)	0.0354 (4)
H15	0.1371	0.5528	0.0810	0.042*
C16	0.2031 (2)	0.50115 (16)	−0.04922 (18)	0.0348 (4)
C17	0.1151 (2)	0.56421 (19)	−0.1339 (2)	0.0437 (5)
H17A	0.0154	0.5203	−0.1802	0.065*
H17B	0.1579	0.5750	−0.1888	0.065*
H17C	0.1149	0.6382	−0.0876	0.065*
C41	0.99340 (18)	0.10614 (15)	0.31701 (15)	0.0269 (3)
C42	1.07821 (19)	0.11897 (15)	0.43807 (16)	0.0305 (4)
H42	1.0601	0.0631	0.4754	0.037*
C43	1.02154 (19)	0.18701 (16)	0.26112 (16)	0.0307 (4)
H43	0.9654	0.1773	0.1778	0.037*
C44	1.18978 (19)	0.21384 (16)	0.50442 (16)	0.0319 (4)
H44	1.2483	0.2218	0.5870	0.038*
C45	1.1325 (2)	0.28142 (16)	0.32901 (17)	0.0327 (4)
H45	1.1516	0.3367	0.2914	0.039*
C46	1.21725 (19)	0.29733 (15)	0.45199 (17)	0.0300 (4)
C47	1.3314 (2)	0.40341 (16)	0.52600 (19)	0.0383 (4)
H47A	1.2861	0.4637	0.5500	0.057*
H47B	1.3791	0.4270	0.4785	0.057*
H47C	1.4032	0.3887	0.5978	0.057*
C71	0.26464 (19)	−0.20670 (14)	0.25741 (15)	0.0278 (4)
C72	0.12291 (19)	−0.20614 (15)	0.24088 (16)	0.0314 (4)
H72	0.0630	−0.1721	0.1835	0.038*
C73	0.3529 (2)	−0.25481 (16)	0.34303 (17)	0.0321 (4)
H73	0.4502	−0.2538	0.3552	0.039*
C74	0.0699 (2)	−0.25599 (16)	0.30935 (17)	0.0335 (4)
H74	−0.0269	−0.2556	0.2983	0.040*
C75	0.2988 (2)	−0.30423 (16)	0.41064 (17)	0.0327 (4)
H75	0.3596	−0.3369	0.4690	0.039*
C76	0.1562 (2)	−0.30655 (15)	0.39405 (16)	0.0311 (4)
C77	0.0959 (2)	−0.36358 (18)	0.46476 (19)	0.0403 (5)
H77A	0.0457	−0.4417	0.4180	0.060*
H77B	0.0275	−0.3220	0.4817	0.060*
H77C	0.1753	−0.3641	0.5405	0.060*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0274 (2)	0.0236 (2)	0.0255 (2)	0.00539 (16)	0.01088 (17)	0.00628 (16)
S4	0.0251 (2)	0.0251 (2)	0.0242 (2)	0.00684 (16)	0.00851 (17)	0.00730 (16)
S7	0.0398 (3)	0.0256 (2)	0.0320 (2)	0.00597 (18)	0.0208 (2)	0.00858 (17)
O11	0.0291 (6)	0.0276 (6)	0.0374 (7)	0.0029 (5)	0.0132 (5)	0.0063 (5)
O12	0.0385 (7)	0.0303 (6)	0.0265 (6)	0.0074 (5)	0.0151 (5)	0.0055 (5)
O41	0.0347 (7)	0.0362 (7)	0.0262 (6)	0.0138 (5)	0.0128 (5)	0.0066 (5)
O42	0.0329 (7)	0.0258 (6)	0.0322 (6)	0.0062 (5)	0.0099 (5)	0.0125 (5)
O71	0.0596 (9)	0.0314 (7)	0.0581 (9)	0.0144 (6)	0.0434 (8)	0.0133 (6)
O72	0.0476 (8)	0.0349 (7)	0.0270 (6)	0.0013 (6)	0.0135 (6)	0.0096 (5)
N1	0.0262 (7)	0.0225 (7)	0.0286 (7)	0.0061 (5)	0.0128 (6)	0.0071 (5)
N4	0.0253 (7)	0.0269 (7)	0.0225 (6)	0.0066 (5)	0.0098 (5)	0.0078 (5)
N7	0.0306 (7)	0.0252 (7)	0.0344 (8)	0.0061 (6)	0.0162 (6)	0.0105 (6)
C2	0.0286 (8)	0.0288 (8)	0.0238 (8)	0.0092 (7)	0.0107 (7)	0.0067 (6)
C3	0.0277 (8)	0.0266 (8)	0.0267 (8)	0.0070 (6)	0.0124 (7)	0.0095 (6)
C5	0.0287 (8)	0.0323 (9)	0.0210 (7)	0.0059 (7)	0.0100 (7)	0.0072 (6)
C6	0.0330 (9)	0.0387 (10)	0.0309 (9)	0.0087 (8)	0.0148 (8)	0.0162 (8)
C8	0.0318 (9)	0.0271 (8)	0.0317 (8)	0.0054 (7)	0.0177 (7)	0.0077 (7)
C9	0.0258 (8)	0.0267 (8)	0.0318 (8)	0.0066 (6)	0.0127 (7)	0.0076 (7)
C11	0.0295 (9)	0.0247 (8)	0.0299 (8)	0.0051 (7)	0.0121 (7)	0.0094 (7)
C12	0.0464 (11)	0.0397 (10)	0.0361 (10)	0.0188 (9)	0.0219 (9)	0.0157 (8)
C13	0.0355 (9)	0.0295 (9)	0.0366 (9)	0.0085 (7)	0.0185 (8)	0.0109 (7)
C14	0.0452 (11)	0.0442 (11)	0.0345 (10)	0.0143 (9)	0.0175 (9)	0.0175 (9)
C15	0.0349 (10)	0.0308 (9)	0.0447 (10)	0.0104 (8)	0.0185 (8)	0.0141 (8)
C16	0.0313 (9)	0.0296 (9)	0.0403 (10)	0.0036 (7)	0.0105 (8)	0.0152 (8)
C17	0.0405 (11)	0.0422 (11)	0.0503 (12)	0.0126 (9)	0.0151 (9)	0.0244 (10)
C41	0.0236 (8)	0.0292 (8)	0.0290 (8)	0.0078 (6)	0.0113 (7)	0.0093 (7)
C42	0.0291 (9)	0.0309 (9)	0.0303 (8)	0.0046 (7)	0.0101 (7)	0.0126 (7)
C43	0.0276 (9)	0.0370 (9)	0.0317 (9)	0.0090 (7)	0.0137 (7)	0.0153 (7)
C44	0.0274 (8)	0.0342 (9)	0.0305 (9)	0.0054 (7)	0.0093 (7)	0.0089 (7)
C45	0.0321 (9)	0.0321 (9)	0.0406 (10)	0.0083 (7)	0.0188 (8)	0.0164 (8)
C46	0.0267 (8)	0.0275 (8)	0.0391 (9)	0.0077 (7)	0.0173 (7)	0.0083 (7)
C47	0.0348 (10)	0.0296 (9)	0.0486 (11)	0.0036 (8)	0.0188 (9)	0.0066 (8)
C71	0.0322 (9)	0.0235 (8)	0.0298 (8)	0.0047 (7)	0.0157 (7)	0.0074 (6)
C72	0.0303 (9)	0.0286 (9)	0.0352 (9)	0.0067 (7)	0.0121 (7)	0.0127 (7)
C73	0.0303 (9)	0.0323 (9)	0.0387 (10)	0.0097 (7)	0.0167 (8)	0.0144 (8)
C74	0.0303 (9)	0.0320 (9)	0.0429 (10)	0.0080 (7)	0.0183 (8)	0.0142 (8)
C75	0.0351 (9)	0.0318 (9)	0.0344 (9)	0.0102 (7)	0.0146 (8)	0.0146 (7)
C76	0.0371 (10)	0.0242 (8)	0.0353 (9)	0.0057 (7)	0.0190 (8)	0.0083 (7)
C77	0.0459 (11)	0.0391 (10)	0.0479 (11)	0.0103 (9)	0.0281 (10)	0.0197 (9)

Geometric parameters (Å, º)

S1—O12	1.4349 (13)	C13—H13	0.9500
S1—O11	1.4353 (13)	C14—C16	1.387 (3)
S1—N1	1.6277 (14)	C14—H14	0.9500
S1—C11	1.7664 (17)	C15—C16	1.391 (3)
S4—O41	1.4310 (12)	C15—H15	0.9500
S4—O42	1.4350 (12)	C16—C17	1.510 (3)
S4—N4	1.6411 (14)	C17—H17A	0.9800
S4—C41	1.7647 (18)	C17—H17B	0.9800
S7—O71	1.4309 (14)	C17—H17C	0.9800
S7—O72	1.4342 (14)	C41—C42	1.388 (2)
S7—N7	1.6364 (15)	C41—C43	1.398 (2)
S7—C71	1.7667 (17)	C42—C44	1.389 (3)
N1—C9	1.477 (2)	C42—H42	0.9500
N1—C2	1.483 (2)	C43—C45	1.385 (3)
N4—C3	1.482 (2)	C43—H43	0.9500
N4—C5	1.483 (2)	C44—C46	1.391 (3)
N7—C6	1.470 (2)	C44—H44	0.9500
N7—C8	1.481 (2)	C45—C46	1.402 (3)
C2—C3	1.519 (2)	C45—H45	0.9500
C2—H2A	0.9900	C46—C47	1.502 (3)
C2—H2B	0.9900	C47—H47A	0.9800
C3—H3A	0.9900	C47—H47B	0.9800
C3—H3B	0.9900	C47—H47C	0.9800
C5—C6	1.518 (2)	C71—C73	1.391 (2)
C5—H5A	0.9900	C71—C72	1.391 (3)
C5—H5B	0.9900	C72—C74	1.392 (3)
C6—H6A	0.9900	C72—H72	0.9500
C6—H6B	0.9900	C73—C75	1.386 (3)
C8—C9	1.522 (2)	C73—H73	0.9500
C8—H8A	0.9900	C74—C76	1.396 (3)
C8—H8B	0.9900	C74—H74	0.9500
C9—H9A	0.9900	C75—C76	1.395 (3)
C9—H9B	0.9900	C75—H75	0.9500
C11—C13	1.386 (2)	C76—C77	1.508 (3)
C11—C12	1.397 (3)	C77—H77A	0.9800
C12—C14	1.390 (3)	C77—H77B	0.9800
C12—H12	0.9500	C77—H77C	0.9800
C13—C15	1.387 (3)
O12—S1—O11	119.47 (8)	C11—C12—H12	120.5
O12—S1—N1	106.29 (7)	C11—C13—C15	119.63 (17)
O11—S1—N1	106.81 (7)	C11—C13—H13	120.2
O12—S1—C11	106.94 (8)	C15—C13—H13	120.2
O11—S1—C11	106.96 (8)	C16—C14—C12	121.51 (18)
N1—S1—C11	110.24 (8)	C16—C14—H14	119.2
O41—S4—O42	119.77 (8)	C12—C14—H14	119.2
O41—S4—N4	107.68 (7)	C13—C15—C16	121.20 (18)
O42—S4—N4	106.39 (7)	C13—C15—H15	119.4
O41—S4—C41	108.25 (8)	C16—C15—H15	119.4
O42—S4—C41	108.20 (8)	C14—C16—C15	118.39 (17)
N4—S4—C41	105.71 (8)	C14—C16—C17	121.29 (18)
O71—S7—O72	120.17 (9)	C15—C16—C17	120.31 (18)
O71—S7—N7	107.04 (8)	C16—C17—H17A	109.5
O72—S7—N7	106.24 (8)	C16—C17—H17B	109.5
O71—S7—C71	107.63 (8)	H17A—C17—H17B	109.5
O72—S7—C71	107.49 (8)	C16—C17—H17C	109.5
N7—S7—C71	107.73 (8)	H17A—C17—H17C	109.5
C9—N1—C2	118.66 (13)	H17B—C17—H17C	109.5
C9—N1—S1	117.15 (11)	C42—C41—C43	120.33 (16)
C2—N1—S1	119.59 (11)	C42—C41—S4	119.88 (13)
C3—N4—C5	116.22 (13)	C43—C41—S4	119.53 (13)
C3—N4—S4	115.67 (11)	C41—C42—C44	119.74 (16)
C5—N4—S4	114.89 (10)	C41—C42—H42	120.1
C6—N7—C8	117.34 (14)	C44—C42—H42	120.1
C6—N7—S7	118.29 (12)	C45—C43—C41	119.05 (16)
C8—N7—S7	117.42 (12)	C45—C43—H43	120.5
N1—C2—C3	115.41 (13)	C41—C43—H43	120.5
N1—C2—H2A	108.4	C42—C44—C46	121.13 (17)
C3—C2—H2A	108.4	C42—C44—H44	119.4
N1—C2—H2B	108.4	C46—C44—H44	119.4
C3—C2—H2B	108.4	C43—C45—C46	121.53 (16)
H2A—C2—H2B	107.5	C43—C45—H45	119.2
N4—C3—C2	113.94 (14)	C46—C45—H45	119.2
N4—C3—H3A	108.8	C44—C46—C45	118.19 (17)
C2—C3—H3A	108.8	C44—C46—C47	120.86 (17)
N4—C3—H3B	108.8	C45—C46—C47	120.92 (16)
C2—C3—H3B	108.8	C46—C47—H47A	109.5
H3A—C3—H3B	107.7	C46—C47—H47B	109.5
N4—C5—C6	111.89 (14)	H47A—C47—H47B	109.5
N4—C5—H5A	109.2	C46—C47—H47C	109.5
C6—C5—H5A	109.2	H47A—C47—H47C	109.5
N4—C5—H5B	109.2	H47B—C47—H47C	109.5
C6—C5—H5B	109.2	C73—C71—C72	120.20 (16)
H5A—C5—H5B	107.9	C73—C71—S7	119.34 (13)
N7—C6—C5	111.47 (14)	C72—C71—S7	120.45 (13)
N7—C6—H6A	109.3	C71—C72—C74	119.27 (16)
C5—C6—H6A	109.3	C71—C72—H72	120.4
N7—C6—H6B	109.3	C74—C72—H72	120.4
C5—C6—H6B	109.3	C75—C73—C71	119.99 (17)
H6A—C6—H6B	108.0	C75—C73—H73	120.0
N7—C8—C9	112.19 (14)	C71—C73—H73	120.0
N7—C8—H8A	109.2	C72—C74—C76	121.20 (17)
C9—C8—H8A	109.2	C72—C74—H74	119.4
N7—C8—H8B	109.2	C76—C74—H74	119.4
C9—C8—H8B	109.2	C73—C75—C76	120.81 (17)
H8A—C8—H8B	107.9	C73—C75—H75	119.6
N1—C9—C8	112.33 (14)	C76—C75—H75	119.6
N1—C9—H9A	109.1	C75—C76—C74	118.51 (16)
C8—C9—H9A	109.1	C75—C76—C77	120.84 (17)
N1—C9—H9B	109.1	C74—C76—C77	120.65 (17)
C8—C9—H9B	109.1	C76—C77—H77A	109.5
H9A—C9—H9B	107.9	C76—C77—H77B	109.5
C13—C11—C12	120.28 (16)	H77A—C77—H77B	109.5
C13—C11—S1	118.94 (14)	C76—C77—H77C	109.5
C12—C11—S1	120.50 (14)	H77A—C77—H77C	109.5
C14—C12—C11	118.97 (18)	H77B—C77—H77C	109.5
C14—C12—H12	120.5