1,4,8,11-Tetra­kis(carboxy­meth­yl)-5,5,7,12,12,14-hexa­meth­yl-1,4,8,11-tetra­azoniacyclo­tetra­deca­ne tetra­chloride octa­hydrate

The crystal structure of the centrosymmetric title compound, C₂₄H₄₈N₄O₈⁴⁺·4Cl^-·8H₂O, consists of a 14-membered meth­yl-substituted C₁₀N₄ cationic ring which inter­acts with the chloride ions and water molecules of crystallization to give a three-dimensional hydrogen-bonded network structure.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.044
• wR factor = 0.121
• Data-to-parameter ratio = 16.4

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT417_ALERT_2_B Short Inter D-H..H-D       H1O    ..  H1W2    ..       2.06 Ang.
PLAT417_ALERT_2_B Short Inter D-H..H-D       H3O    ..  H2W2    ..       2.09 Ang.
PLAT417_ALERT_2_B Short Inter D-H..H-D       H2W1   ..  H3O     ..       2.03 Ang.

Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       4.00 Ratio
PLAT417_ALERT_2_C Short Inter D-H..H-D       H1W1   ..  H1O     ..       2.11 Ang.
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........          8
PLAT731_ALERT_1_C Bond    Calc     0.85(3), Rep   0.850(10) ......       3.00 su-Rat
              O1W  -H1W1    1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.85(3), Rep   0.850(10) ......       3.00 su-Rat
              O3W  -H3W1    1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.85(3), Rep   0.850(10) ......       3.00 su-Rat
              O3W  -H3W2    1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.84(3), Rep   0.850(10) ......       3.00 su-Rat
              O4W  -H4W2    1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.85(3), Rep   0.850(10) ......       3.00 su-Rat
              O1W  -H1#     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.85(3), Rep   0.850(10) ......       3.00 su-Rat
              O3W  -H5#     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.85(3), Rep   0.850(10) ......       3.00 su-Rat
              O3W  -H6#     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.84(3), Rep   0.850(10) ......       3.00 su-Rat
              O4W  -H8#     1.555   1.555
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          3
              H2 O

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

   9 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 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
   2 ALERT type 4 Improvement, methodology, query or suggestion

---

Computing details

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.

1,4,8,11-Tetrakis(carboxymethyl)-5,5,7,12,12,14-hexamethyl-1,4,8,11- tetraazoniacyclotetradecane tetrachloride octahydrate

Crystal data

C24H48N4O8^4+·4Cl^−·8H2O	Z = 1
Mr = 806.59	F(000) = 432
Triclinic, P1	Dx = 1.386 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.6283 (3) Å	Cell parameters from 8332 reflections
b = 10.6995 (4) Å	θ = 2.4–28.3°
c = 11.0065 (4) Å	µ = 0.38 mm^−1
α = 100.161 (1)°	T = 295 K
β = 94.482 (1)°	Block, colorless
γ = 103.168 (1)°	0.35 × 0.22 × 0.18 mm
V = 966.42 (6) Å^3

Data collection

Bruker APEX area-detector diffractometer	4153 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.017
Graphite monochromator	θmax = 27.5°, θmin = 1.9°
φ and ω scans	h = −11→11
11066 measured reflections	k = −13→13
4351 independent reflections	l = −14→14

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.121	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0657P)^2 + 0.404P] where P = (Fo^2 + 2Fc^2)/3
4351 reflections	(Δ/σ)max = 0.001
265 parameters	Δρmax = 0.37 e Å^−3
12 restraints	Δρmin = −0.34 e Å^−3

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

	x	y	z	Uiso*/Ueq
Cl1	0.11305 (7)	0.11797 (7)	0.82315 (7)	0.0675 (2)
Cl2	0.33315 (5)	0.50102 (5)	0.64405 (4)	0.0424 (1)
O1	0.5550 (2)	0.3697 (1)	0.9693 (2)	0.0536 (4)
O2	0.7493 (2)	0.3050 (1)	0.8721 (1)	0.0421 (3)
O3	0.4001 (2)	0.0255 (1)	0.3313 (1)	0.0443 (3)
O4	0.5725 (2)	0.1578 (1)	0.2403 (1)	0.0439 (3)
O1w	0.4483 (2)	0.1343 (2)	0.9836 (2)	0.0635 (4)
O2w	0.2368 (2)	−0.0511 (1)	1.1178 (1)	0.0438 (3)
O3w	0.3759 (2)	0.2107 (2)	0.6470 (2)	0.0764 (5)
O4w	1.0933 (2)	0.4259 (2)	0.8388 (1)	0.0462 (3)
N1	0.8187 (1)	0.5171 (1)	0.7665 (1)	0.0231 (2)
N2	0.7704 (1)	0.2683 (1)	0.4607 (1)	0.0229 (2)
C1	0.6725 (2)	0.3838 (2)	0.9025 (1)	0.0321 (3)
C2	0.7058 (2)	0.5156 (2)	0.8643 (1)	0.0300 (3)
C3	0.8961 (2)	0.6603 (1)	0.7503 (1)	0.0266 (3)
C4	0.7630 (2)	0.7287 (2)	0.7296 (2)	0.0479 (5)
C5	1.0092 (3)	0.7278 (2)	0.8689 (2)	0.0506 (5)
C6	0.7308 (2)	0.4239 (1)	0.6477 (1)	0.0252 (3)
C7	0.8344 (2)	0.3347 (1)	0.5937 (1)	0.0247 (3)
C8	0.6282 (2)	0.1562 (2)	0.4566 (1)	0.0313 (3)
C9	0.5319 (2)	0.1135 (2)	0.3288 (2)	0.0303 (3)
C10	0.9026 (2)	0.2277 (1)	0.3879 (1)	0.0247 (3)
C11	0.9892 (2)	0.1493 (2)	0.4596 (2)	0.0414 (4)
C12	1.0085 (2)	0.3545 (1)	0.3619 (1)	0.0244 (3)
H1w1	0.438 (6)	0.127 (5)	1.058 (2)	0.15 (2)*
H1w2	0.351 (2)	0.120 (3)	0.952 (3)	0.08 (1)*
H2w1	0.254 (3)	−0.126 (2)	1.098 (3)	0.07 (1)*
H2w2	0.141 (2)	−0.070 (3)	1.134 (2)	0.06 (1)*
H3w1	0.318 (4)	0.165 (3)	0.690 (3)	0.09 (1)*
H3w2	0.344 (4)	0.278 (2)	0.638 (3)	0.10 (1)*
H4w1	1.085 (4)	0.345 (1)	0.833 (3)	0.07 (1)*
H4w2	1.177 (3)	0.447 (3)	0.805 (3)	0.09 (1)*
H1o	0.528 (4)	0.291 (1)	0.979 (3)	0.08 (1)*
H3o	0.351 (3)	0.005 (3)	0.258 (1)	0.07 (1)*
H1n	0.897 (2)	0.488 (2)	0.792 (2)	0.03 (1)*
H2n	0.738 (2)	0.324 (1)	0.424 (2)	0.02 (1)*
H2a	0.6061	0.5317	0.8315	0.036*
H2b	0.7532	0.5843	0.9361	0.036*
H4a	0.6950	0.6837	0.6540	0.072*
H4b	0.8091	0.8176	0.7233	0.072*
H4c	0.7009	0.7281	0.7982	0.072*
H5a	1.0915	0.6819	0.8785	0.076*
H5b	0.9500	0.7275	0.9391	0.076*
H5c	1.0575	0.8166	0.8636	0.076*
H6a	0.7046	0.4739	0.5871	0.030*
H6b	0.6313	0.3709	0.6656	0.030*
H7a	0.9434	0.3861	0.5970	0.030*
H7b	0.8365	0.2687	0.6436	0.030*
H8a	0.5601	0.1822	0.5173	0.038*
H8b	0.6647	0.0829	0.4787	0.038*
H10	0.8516	0.1715	0.3080	0.030*
H11a	0.9138	0.0725	0.4711	0.062*
H11b	1.0374	0.2021	0.5393	0.062*
H11c	1.0710	0.1239	0.4138	0.062*
H12a	1.0841	0.3965	0.4356	0.029*
H12b	0.9405	0.4130	0.3494	0.029*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0564 (3)	0.0710 (4)	0.0753 (4)	0.0090 (3)	0.0248 (3)	0.0167 (3)
Cl2	0.0412 (2)	0.0526 (3)	0.0425 (2)	0.0205 (2)	0.0062 (2)	0.0214 (2)
O1	0.0642 (9)	0.0442 (8)	0.0643 (9)	0.0175 (7)	0.0435 (8)	0.0210 (7)
O2	0.0440 (7)	0.0409 (7)	0.0510 (7)	0.0174 (5)	0.0180 (6)	0.0201 (6)
O3	0.0398 (7)	0.0426 (7)	0.0390 (7)	−0.0112 (5)	−0.0062 (5)	0.0108 (5)
O4	0.0403 (7)	0.0531 (7)	0.0311 (6)	−0.0043 (6)	−0.0026 (5)	0.0127 (5)
O1w	0.073 (1)	0.058 (1)	0.062 (1)	0.003 (1)	0.016 (1)	0.030 (1)
O2w	0.039 (1)	0.035 (1)	0.050 (1)	0.004 (1)	−0.004 (1)	0.002 (1)
O3w	0.065 (1)	0.081 (1)	0.100 (2)	0.031 (1)	0.045 (1)	0.031 (1)
O4w	0.036 (1)	0.058 (1)	0.047 (1)	0.012 (1)	0.0066 (6)	0.016 (1)
N1	0.024 (1)	0.025 (1)	0.021 (1)	0.007 (1)	0.0045 (4)	0.003 (1)
N2	0.026 (1)	0.022 (1)	0.020 (1)	0.004 (1)	0.0024 (4)	0.004 (1)
C1	0.034 (1)	0.035 (1)	0.028 (1)	0.006 (1)	0.0080 (6)	0.008 (1)
C2	0.036 (1)	0.031 (1)	0.026 (1)	0.009 (1)	0.0127 (6)	0.005 (1)
C3	0.031 (1)	0.023 (1)	0.025 (1)	0.005 (1)	0.0076 (5)	0.002 (1)
C4	0.051 (1)	0.037 (1)	0.070 (1)	0.025 (1)	0.0314 (10)	0.019 (1)
C5	0.063 (1)	0.046 (1)	0.026 (1)	−0.013 (1)	0.0026 (8)	−0.002 (1)
C6	0.024 (1)	0.028 (1)	0.022 (1)	0.005 (1)	0.0023 (5)	0.002 (1)
C7	0.028 (1)	0.025 (1)	0.020 (1)	0.006 (1)	0.0013 (5)	0.001 (1)
C8	0.031 (1)	0.031 (1)	0.026 (1)	−0.004 (1)	0.0031 (6)	0.006 (1)
C9	0.030 (1)	0.026 (1)	0.031 (1)	0.003 (1)	−0.0001 (6)	0.003 (1)
C10	0.030 (1)	0.022 (1)	0.023 (1)	0.007 (1)	0.0065 (5)	0.004 (1)
C11	0.053 (1)	0.038 (1)	0.046 (1)	0.026 (1)	0.0158 (8)	0.019 (1)
C12	0.025 (1)	0.023 (1)	0.025 (1)	0.007 (1)	0.0071 (5)	0.003 (1)

Geometric parameters (Å, º)

O1—C1	1.295 (2)	O3w—H3w2	0.85 (1)
O2—C1	1.205 (2)	O4w—H4w1	0.85 (1)
O3—C9	1.306 (2)	O4w—H4w2	0.85 (1)
O4—C9	1.200 (2)	N1—H1n	0.86 (1)
N1—C2	1.506 (2)	N2—H2n	0.86 (1)
N1—C6	1.523 (2)	C2—H2a	0.97
N1—C3	1.573 (2)	C2—H2b	0.97
N2—C8	1.499 (2)	C4—H4a	0.96
N2—C7	1.510 (2)	C4—H4b	0.96
N2—C10	1.543 (2)	C4—H4c	0.96
C1—C2	1.513 (2)	C5—H5a	0.96
C3—C4	1.519 (2)	C5—H5b	0.96
C3—C5	1.525 (2)	C5—H5c	0.96
C3—C12^i	1.542 (2)	C6—H6a	0.97
C6—C7	1.528 (2)	C6—H6b	0.97
C8—C9	1.515 (2)	C7—H7a	0.97
C10—C11	1.520 (2)	C7—H7b	0.97
C10—C12	1.539 (2)	C8—H8a	0.97
C12—C3^i	1.542 (2)	C8—H8b	0.97
O1—H1o	0.85 (1)	C10—H10	0.98
O3—H3o	0.85 (1)	C11—H11a	0.96
O1w—H1w1	0.85 (1)	C11—H11b	0.96
O1w—H1w2	0.85 (1)	C11—H11c	0.96
O2w—H2w1	0.84 (1)	C12—H12a	0.97
O2w—H2w2	0.84 (1)	C12—H12b	0.97
O3w—H3w1	0.85 (1)
C2—N1—C6	108.4 (1)	H2a—C2—H2b	108.2
C2—N1—C3	112.0 (1)	C3—C4—H4a	109.5
C6—N1—C3	114.8 (1)	C3—C4—H4b	109.5
C8—N2—C7	110.4 (1)	H4a—C4—H4b	109.5
C8—N2—C10	112.9 (1)	C3—C4—H4c	109.5
C7—N2—C10	111.8 (1)	H4a—C4—H4c	109.5
O2—C1—O1	126.4 (2)	H4b—C4—H4c	109.5
O2—C1—C2	122.0 (1)	C3—C5—H5a	109.5
O1—C1—C2	111.6 (1)	C3—C5—H5b	109.5
N1—C2—C1	109.7 (1)	H5a—C5—H5b	109.5
C4—C3—C5	112.0 (2)	C3—C5—H5c	109.5
C4—C3—C12^i	112.6 (1)	H5a—C5—H5c	109.5
C5—C3—C12^i	110.4 (1)	H5b—C5—H5c	109.5
C4—C3—N1	108.7 (1)	N1—C6—H6a	109.5
C5—C3—N1	106.8 (1)	C7—C6—H6a	109.5
C12^i—C3—N1	106.0 (1)	N1—C6—H6b	109.5
N1—C6—C7	110.7 (1)	C7—C6—H6b	109.5
N2—C7—C6	111.2 (1)	H6a—C6—H6b	108.1
N2—C8—C9	111.7 (1)	N2—C7—H7a	109.4
O4—C9—O3	126.2 (2)	C6—C7—H7a	109.4
O4—C9—C8	123.5 (1)	N2—C7—H7b	109.4
O3—C9—C8	110.3 (1)	C6—C7—H7b	109.4
C11—C10—C12	115.5 (1)	H7a—C7—H7b	108.0
C11—C10—N2	109.8 (1)	N2—C8—H8a	109.3
C12—C10—N2	106.5 (1)	C9—C8—H8a	109.3
C10—C12—C3^i	116.6 (1)	N2—C8—H8b	109.3
C1—O1—H1o	109 (2)	C9—C8—H8b	109.3
C9—O3—H3o	106 (2)	H8a—C8—H8b	107.9
H1w1—O1w—H1w2	102 (4)	C11—C10—H10	108.3
H2w1—O2w—H2w2	101 (3)	C12—C10—H10	108.3
H3w1—O3w—H3w2	112 (3)	N2—C10—H10	108.3
H4w1—O4w—H4w2	101 (3)	C10—C11—H11a	109.5
C2—N1—H1n	108 (1)	C10—C11—H11b	109.5
C6—N1—H1n	108 (1)	H11a—C11—H11b	109.5
C3—N1—H1n	105 (1)	C10—C11—H11c	109.5
C8—N2—H2n	107 (1)	H11a—C11—H11c	109.5
C7—N2—H2n	108 (1)	H11b—C11—H11c	109.5
C10—N2—H2n	106 (1)	C10—C12—H12a	108.1
N1—C2—H2a	109.7	C3^i—C12—H12a	108.1
C1—C2—H2a	109.7	C10—C12—H12b	108.1
N1—C2—H2b	109.7	C3^i—C12—H12b	108.1
C1—C2—H2b	109.7	H12a—C12—H12b	107.3
C6—N1—C2—C1	68.5 (2)	C10—N2—C7—C6	155.7 (1)
C3—N1—C2—C1	−163.8 (1)	N1—C6—C7—N2	−164.7 (1)
O2—C1—C2—N1	11.4 (2)	C7—N2—C8—C9	163.0 (1)
O1—C1—C2—N1	−168.5 (1)	C10—N2—C8—C9	−71.1 (2)
C2—N1—C3—C4	−52.2 (2)	N2—C8—C9—O4	5.4 (2)
C6—N1—C3—C4	72.0 (2)	N2—C8—C9—O3	−173.3 (1)
C2—N1—C3—C5	68.8 (2)	C8—N2—C10—C11	−73.5 (2)
C6—N1—C3—C5	−166.9 (1)	C7—N2—C10—C11	51.7 (2)
C2—N1—C3—C12^i	−173.5 (1)	C8—N2—C10—C12	160.8 (1)
C6—N1—C3—C12^i	−49.3 (2)	C7—N2—C10—C12	−74.0 (1)
C2—N1—C6—C7	−132.8 (1)	C11—C10—C12—C3^i	81.8 (2)
C3—N1—C6—C7	101.2 (1)	N2—C10—C12—C3^i	−156.0 (1)
C8—N2—C7—C6	−77.8 (1)

Symmetry code: (i) −x+2, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1o···O1w	0.85 (1)	1.67 (1)	2.514 (2)	171 (3)
O3—H3o···O2w^ii	0.85 (1)	1.69 (1)	2.541 (2)	173 (3)
O1w—H1w1···O4^iii	0.85 (1)	2.17 (3)	2.889 (2)	143 (4)
O1w—H1w2···Cl1	0.85 (1)	2.40 (1)	3.221 (2)	163 (3)
O2w—H2w1···O2^iv	0.84 (1)	2.00 (2)	2.767 (2)	152 (3)
O2w—H2w2···Cl1^v	0.84 (1)	2.25 (1)	3.087 (2)	179 (2)
O3w—H3w1···Cl1	0.85 (1)	2.41 (2)	3.198 (2)	156 (3)
O3w—H3w2···Cl2	0.85 (1)	2.40 (1)	3.216 (2)	163 (3)
O4w—H4w1···Cl1^vi	0.85 (1)	2.47 (1)	3.313 (2)	170 (3)
O4w—H4w2···Cl2^vi	0.85 (1)	2.38 (2)	3.172 (2)	157 (3)
N1—H1n···O4w	0.86 (1)	2.02 (1)	2.869 (2)	174 (2)
N2—H2n···Cl2^vii	0.86 (1)	2.32 (1)	3.173 (2)	170 (2)

Symmetry codes: (ii) x, y, z−1; (iii) x, y, z+1; (iv) −x+1, −y, −z+2; (v) −x, −y, −z+2; (vi) x+1, y, z; (vii) −x+1, −y+1, −z+1.