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The title compound [systematic name: 21,24-di­methyl-3,12,21,24-tetra­aza­hexa­cyclo­[9.7.3.32,10.01,10.04,9.013,18]­tetracosa-4,6,8,13(18),14,16-hexaene monohydrate], C22H28N4·H2O, crystallizes in space group P212121 with Z = 4 and exhibits approximate C2 symmetry. Intermolecular hydrogen bonds [O—H...N = 2.872 (3)° and N—H...O = 3.062 (4) Å] form chains along the direction [010].

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680401178X/hg6049sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S160053680401178X/hg6049Isup2.hkl
Contains datablock I

CCDC reference: 242335

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.004 Å
  • R factor = 0.065
  • wR factor = 0.150
  • Data-to-parameter ratio = 8.1

checkCIF/PLATON results

No syntax errors found



Alert level A PLAT029_ALERT_3_A _diffrn_measured_fraction_theta_full Low ....... 0.87
Author Response: The intensities measurements were extended to theta(max)= 74.86 degrees but 302 reflections could not be measured due to scintillator-collimator collision predicted. The total reflections measured was 2444, but 342 were rejected after data reduction and refinement.
 _diffrn_reflns_theta_full               74.86

 As explained above, the measurements during data collection were
 extended to 74.86, with reduction of expected reflections due to
 obscuration near the collimator.


Alert level B PLAT420_ALERT_2_B D-H Without Acceptor O1 - H2W ... ?
Author Response: `see _publ_section_exptl_refinement'
 PROBLEM:  D-H Without Acceptor       N26    -   H26    ...
 RESPONSE:  `see _publ_section_exptl_refinement'
   `see _publ_section_exptl_refinement'


Alert level C REFLT03_ALERT_1_C Reflection count < 95% complete From the CIF: _diffrn_reflns_theta_max 74.86 From the CIF: _diffrn_reflns_theta_full 0.00 From the CIF: _reflns_number_total 2051 TEST2: Reflns within _diffrn_reflns_theta_max Count of symmetry unique reflns 2200 Completeness (_total/calc) 93.23%
Author Response: The line below shows that the theta_full is 74.86 and not zero, as stated.

 PROBLEM:  Please check that the estimate of the number of Friedel pairs is
             correct. If it is not, please give the correct count in the
             _publ_section_exptl_refinement section of the submitted CIF.
 RESPONSE:  `see _publ_section_exptl_refinement'
   `see _publ_section_exptl_refinement'
            Estimate of Friedel pairs measured        51
            Are heavy atom types Z>Si present         no




PLAT022_ALERT_3_C Ratio Unique / Expected Reflections too Low ....       0.93
PLAT420_ALERT_2_C D-H Without Acceptor       N26    -   H26    ...          ?
Author Response: `see _publ_section_exptl_refinement'
 PROBLEM:  D-H Without Acceptor       N26    -   H26    ...
 RESPONSE:  `see _publ_section_exptl_refinement'
   `see _publ_section_exptl_refinement'


Alert level G REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 74.86 From the CIF: _reflns_number_total 2051 Count of symmetry unique reflns 2200 Completeness (_total/calc) 93.23% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 0 Fraction of Friedel pairs measured 0.000 Are heavy atom types Z>Si present no
Author Response: The line below shows that the theta_full is 74.86 and not zero, as stated.

 PROBLEM:  Please check that the estimate of the number of Friedel pairs is
             correct. If it is not, please give the correct count in the
             _publ_section_exptl_refinement section of the submitted CIF.
 RESPONSE:  `see _publ_section_exptl_refinement'
   `see _publ_section_exptl_refinement'
            Estimate of Friedel pairs measured        51
            Are heavy atom types Z>Si present         no





1 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 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 2 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1994); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); 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 (Farrugia, 1999).

21,24-dimethyl-3,12,21,24-tetraazahexacyclo[9.7.3.32,10. O1,10·O4,9·O13,18]tetracosa-4,6,8,13 (18),14,16-hexaene top
Crystal data top
C22H26N4·H2ODx = 1.292 Mg m3
Mr = 364.48Melting point = 245–250 K
Orthorhombic, P212121Cu Kα radiation, λ = 1.54180 Å
Hall symbol: P 2ac 2abCell parameters from 25 reflections
a = 10.419 (6) Åθ = 21.2–40.1°
b = 12.996 (2) ŵ = 0.64 mm1
c = 13.841 (2) ÅT = 293 K
V = 1874.1 (11) Å3Irregular, brown
Z = 40.35 × 0.32 × 0.20 mm
F(000) = 784
Data collection top
Enraf-Nonius CAD-4
diffractometer
θmax = 74.9°, θmin = 4.7°
non–profiled ω/2θ scansh = 013
2102 measured reflectionsk = 016
2051 independent reflectionsl = 117
2018 reflections with I > 2σ(I)2 standard reflections every 120 min
Rint = 0.015 intensity decay: 1%
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.065H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.150 w = 1/[σ2(Fo2) + (0.1114P)2 + 0.1995P]
where P = (Fo2 + 2Fc2)/3
S = 1.16(Δ/σ)max = 0.023
2051 reflectionsΔρmax = 0.47 e Å3
254 parametersΔρmin = 0.38 e Å3
3 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.141 (8)
Special details top

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 (Å2) top
xyzUiso*/Ueq
O10.1865 (3)0.27333 (17)0.7058 (2)0.0745 (7)
C20.2959 (3)0.83674 (19)0.97945 (19)0.0512 (7)
H20.30710.89041.02310.061*
C30.3848 (3)0.8213 (2)0.90715 (19)0.0491 (7)
H30.45520.86500.90230.059*
C40.3701 (2)0.74026 (19)0.84055 (17)0.0401 (6)
C50.2608 (2)0.67757 (17)0.84627 (15)0.0352 (5)
C60.1743 (3)0.69437 (18)0.92086 (16)0.0399 (6)
H60.10320.65140.92620.048*
C70.1900 (3)0.77290 (19)0.98764 (18)0.0467 (6)
H70.13060.78251.03700.056*
C80.1046 (2)0.56883 (17)0.74923 (16)0.0356 (5)
H80.05930.55070.80890.043*
C90.2463 (2)0.58910 (17)0.77474 (15)0.0345 (5)
N100.0949 (2)0.48025 (15)0.68226 (14)0.0403 (5)
C110.0386 (3)0.4539 (2)0.6651 (2)0.0527 (7)
H11A0.08020.44000.72560.079*
H11B0.04310.39390.62470.079*
H11C0.08090.51030.63360.079*
C120.1595 (3)0.5018 (2)0.58953 (16)0.0457 (6)
H12A0.11560.55760.55690.055*
H12B0.15480.44130.54850.055*
C130.2986 (3)0.5307 (2)0.60507 (17)0.0435 (6)
H13A0.33600.55170.54400.052*
H13B0.34550.47100.62810.052*
C140.3122 (2)0.61881 (19)0.67871 (15)0.0375 (5)
C150.4540 (3)0.6369 (2)0.70445 (18)0.0457 (6)
H150.49900.65610.64500.055*
N160.5111 (2)0.5409 (2)0.73995 (18)0.0493 (6)
C170.6504 (3)0.5455 (3)0.7487 (3)0.0672 (9)
H17A0.68670.56880.68880.101*
H17B0.68310.47830.76370.101*
H17C0.67320.59250.79940.101*
C180.4534 (3)0.5067 (2)0.83102 (18)0.0470 (6)
H18A0.47020.55720.88110.056*
H18B0.49180.44200.85070.056*
C190.3102 (3)0.49285 (18)0.81925 (17)0.0415 (6)
H19A0.27210.47910.88190.050*
H19B0.29390.43390.77800.050*
C200.2469 (4)0.8651 (3)0.5349 (2)0.0642 (9)
H200.29080.90980.49410.077*
C210.3103 (3)0.7830 (2)0.57652 (19)0.0528 (7)
H210.39700.77370.56340.063*
C220.2482 (3)0.71381 (19)0.63748 (16)0.0401 (6)
C230.1159 (3)0.72997 (17)0.65511 (17)0.0395 (6)
C240.0536 (3)0.8136 (2)0.61311 (19)0.0502 (7)
H240.03330.82410.62520.060*
C250.1186 (4)0.8810 (2)0.5539 (2)0.0600 (8)
H250.07610.93700.52680.072*
N260.4621 (2)0.72361 (18)0.77089 (17)0.0481 (6)
H260.52580.76540.76650.058*
N270.0479 (2)0.66176 (16)0.71153 (16)0.0417 (5)
H270.026 (3)0.682 (2)0.735 (2)0.050*
H1W0.157 (3)0.3387 (16)0.698 (2)0.050*
H2W0.222 (3)0.256 (2)0.6479 (17)0.050*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0941 (19)0.0512 (11)0.0782 (15)0.0042 (13)0.0149 (16)0.0032 (12)
C20.0715 (19)0.0386 (11)0.0435 (12)0.0027 (13)0.0103 (13)0.0091 (10)
C30.0585 (17)0.0422 (11)0.0465 (13)0.0064 (13)0.0078 (13)0.0029 (11)
C40.0458 (14)0.0402 (11)0.0342 (10)0.0039 (11)0.0024 (10)0.0009 (9)
C50.0433 (13)0.0337 (9)0.0287 (9)0.0006 (10)0.0032 (10)0.0003 (9)
C60.0484 (14)0.0395 (10)0.0318 (10)0.0053 (12)0.0012 (10)0.0008 (9)
C70.0591 (15)0.0466 (12)0.0344 (11)0.0109 (13)0.0009 (12)0.0058 (10)
C80.0385 (12)0.0367 (10)0.0317 (10)0.0007 (10)0.0015 (10)0.0019 (9)
C90.0404 (12)0.0345 (9)0.0285 (9)0.0021 (10)0.0009 (9)0.0015 (8)
N100.0444 (12)0.0387 (9)0.0378 (9)0.0033 (9)0.0041 (9)0.0036 (8)
C110.0480 (14)0.0557 (14)0.0543 (14)0.0089 (14)0.0095 (13)0.0018 (12)
C120.0569 (16)0.0479 (12)0.0323 (10)0.0004 (14)0.0046 (11)0.0092 (10)
C130.0445 (14)0.0543 (13)0.0318 (10)0.0037 (12)0.0019 (10)0.0103 (10)
C140.0396 (12)0.0450 (10)0.0280 (9)0.0010 (11)0.0022 (9)0.0025 (9)
C150.0427 (13)0.0585 (14)0.0358 (11)0.0037 (13)0.0030 (11)0.0038 (12)
N160.0391 (12)0.0620 (13)0.0466 (11)0.0068 (11)0.0024 (10)0.0086 (11)
C170.0397 (15)0.092 (2)0.0700 (19)0.0046 (17)0.0015 (14)0.010 (2)
C180.0482 (14)0.0493 (12)0.0435 (12)0.0081 (13)0.0030 (11)0.0033 (11)
C190.0477 (14)0.0391 (10)0.0377 (11)0.0062 (12)0.0060 (11)0.0025 (10)
C200.086 (2)0.0607 (15)0.0458 (14)0.0172 (18)0.0014 (16)0.0167 (13)
C210.0633 (17)0.0590 (14)0.0362 (12)0.0143 (16)0.0028 (12)0.0038 (11)
C220.0491 (15)0.0421 (11)0.0290 (10)0.0032 (12)0.0018 (10)0.0012 (9)
C230.0489 (14)0.0377 (10)0.0318 (10)0.0021 (11)0.0059 (10)0.0010 (9)
C240.0608 (16)0.0447 (12)0.0451 (12)0.0027 (13)0.0091 (13)0.0016 (11)
C250.084 (2)0.0461 (12)0.0499 (13)0.0031 (15)0.0137 (16)0.0119 (12)
N260.0433 (12)0.0544 (11)0.0466 (11)0.0140 (11)0.0020 (10)0.0074 (10)
N270.0389 (11)0.0426 (9)0.0434 (11)0.0051 (10)0.0024 (10)0.0049 (9)
Geometric parameters (Å, º) top
O1—H1W0.911 (17)C13—H13B0.9700
O1—H2W0.908 (18)C14—C221.515 (3)
C2—C31.378 (4)C14—C151.537 (4)
C2—C71.385 (4)C15—N261.457 (3)
C2—H20.9300C15—N161.467 (4)
C3—C41.408 (3)C15—H150.9800
C3—H30.9300N16—C171.457 (4)
C4—N261.376 (4)N16—C181.466 (4)
C4—C51.403 (4)C17—H17A0.9600
C5—C61.388 (3)C17—H17B0.9600
C5—C91.525 (3)C17—H17C0.9600
C6—C71.387 (3)C18—C191.512 (4)
C6—H60.9300C18—H18A0.9700
C7—H70.9300C18—H18B0.9700
C8—N271.442 (3)C19—H19A0.9700
C8—N101.481 (3)C19—H19B0.9700
C8—C91.541 (3)C20—C251.377 (6)
C8—H80.9800C20—C211.381 (5)
C9—C191.545 (3)C20—H200.9300
C9—C141.545 (3)C21—C221.393 (4)
N10—C111.453 (4)C21—H210.9300
N10—C121.476 (3)C22—C231.415 (4)
C11—H11A0.9600C23—N271.378 (3)
C11—H11B0.9600C23—C241.393 (4)
C11—H11C0.9600C24—C251.378 (4)
C12—C131.513 (4)C24—H240.9300
C12—H12A0.9700C25—H250.9300
C12—H12B0.9700N26—H260.8600
C13—C141.540 (3)N27—H270.88 (4)
C13—H13A0.9700
H1W—O1—H2W105 (2)C22—C14—C9109.39 (19)
C3—C2—C7120.5 (2)C15—C14—C9105.41 (18)
C3—C2—H2119.7C13—C14—C9110.03 (19)
C7—C2—H2119.7N26—C15—N16115.0 (2)
C2—C3—C4120.7 (3)N26—C15—C14108.7 (2)
C2—C3—H3119.6N16—C15—C14109.7 (2)
C4—C3—H3119.6N26—C15—H15107.7
N26—C4—C5120.9 (2)N16—C15—H15107.7
N26—C4—C3120.1 (2)C14—C15—H15107.7
C5—C4—C3119.0 (2)C17—N16—C18110.5 (3)
C6—C5—C4118.6 (2)C17—N16—C15113.4 (3)
C6—C5—C9122.5 (2)C18—N16—C15112.3 (2)
C4—C5—C9118.8 (2)N16—C17—H17A109.5
C7—C6—C5122.4 (3)N16—C17—H17B109.5
C7—C6—H6118.8H17A—C17—H17B109.5
C5—C6—H6118.8N16—C17—H17C109.5
C2—C7—C6118.7 (3)H17A—C17—H17C109.5
C2—C7—H7120.7H17B—C17—H17C109.5
C6—C7—H7120.7N16—C18—C19110.4 (2)
N27—C8—N10113.37 (18)N16—C18—H18A109.6
N27—C8—C9109.41 (19)C19—C18—H18A109.6
N10—C8—C9109.95 (18)N16—C18—H18B109.6
N27—C8—H8108.0C19—C18—H18B109.6
N10—C8—H8108.0H18A—C18—H18B108.1
C9—C8—H8108.0C18—C19—C9111.8 (2)
C5—C9—C8111.85 (19)C18—C19—H19A109.3
C5—C9—C19108.01 (17)C9—C19—H19A109.3
C8—C9—C19111.4 (2)C18—C19—H19B109.3
C5—C9—C14109.04 (18)C9—C19—H19B109.3
C8—C9—C14105.75 (17)H19A—C19—H19B107.9
C19—C9—C14110.74 (19)C25—C20—C21120.0 (3)
C11—N10—C12109.8 (2)C25—C20—H20120.0
C11—N10—C8110.5 (2)C21—C20—H20120.0
C12—N10—C8111.48 (18)C20—C21—C22122.0 (3)
N10—C11—H11A109.5C20—C21—H21119.0
N10—C11—H11B109.5C22—C21—H21119.0
H11A—C11—H11B109.5C21—C22—C23117.4 (3)
N10—C11—H11C109.5C21—C22—C14123.4 (3)
H11A—C11—H11C109.5C23—C22—C14119.0 (2)
H11B—C11—H11C109.5N27—C23—C24119.9 (3)
N10—C12—C13111.09 (19)N27—C23—C22120.2 (2)
N10—C12—H12A109.4C24—C23—C22119.9 (2)
C13—C12—H12A109.4C25—C24—C23121.0 (3)
N10—C12—H12B109.4C25—C24—H24119.5
C13—C12—H12B109.4C23—C24—H24119.5
H12A—C12—H12B108.0C20—C25—C24119.7 (3)
C12—C13—C14111.5 (2)C20—C25—H25120.2
C12—C13—H13A109.3C24—C25—H25120.2
C14—C13—H13A109.3C4—N26—C15121.6 (2)
C12—C13—H13B109.3C4—N26—H26119.2
C14—C13—H13B109.3C15—N26—H26119.2
H13A—C13—H13B108.0C23—N27—C8122.2 (2)
C22—C14—C15112.7 (2)C23—N27—H27118 (2)
C22—C14—C13108.44 (19)C8—N27—H27119 (2)
C15—C14—C13110.8 (2)
C7—C2—C3—C40.3 (4)C22—C14—C15—N2655.8 (3)
C2—C3—C4—N26177.7 (3)C13—C14—C15—N26177.57 (19)
C2—C3—C4—C52.5 (4)C9—C14—C15—N2663.4 (3)
N26—C4—C5—C6176.8 (2)C22—C14—C15—N16177.60 (19)
C3—C4—C5—C63.4 (3)C13—C14—C15—N1655.9 (3)
N26—C4—C5—C91.0 (4)C9—C14—C15—N1663.1 (2)
C3—C4—C5—C9179.2 (2)N26—C15—N16—C1768.1 (3)
C4—C5—C6—C72.2 (4)C14—C15—N16—C17169.0 (3)
C9—C5—C6—C7177.9 (2)N26—C15—N16—C1858.0 (3)
C3—C2—C7—C61.0 (4)C14—C15—N16—C1864.9 (3)
C5—C6—C7—C20.0 (4)C17—N16—C18—C19175.0 (3)
C6—C5—C9—C837.0 (3)C15—N16—C18—C1957.3 (3)
C4—C5—C9—C8147.4 (2)N16—C18—C19—C951.5 (3)
C6—C5—C9—C1986.0 (3)C5—C9—C19—C1865.1 (3)
C4—C5—C9—C1989.6 (2)C8—C9—C19—C18171.67 (19)
C6—C5—C9—C14153.6 (2)C14—C9—C19—C1854.2 (2)
C4—C5—C9—C1430.8 (3)C25—C20—C21—C220.5 (5)
N27—C8—C9—C556.8 (2)C20—C21—C22—C230.5 (4)
N10—C8—C9—C5178.13 (16)C20—C21—C22—C14175.6 (2)
N27—C8—C9—C19177.78 (18)C15—C14—C22—C2136.8 (3)
N10—C8—C9—C1957.1 (2)C13—C14—C22—C2186.3 (3)
N27—C8—C9—C1461.8 (2)C9—C14—C22—C21153.7 (2)
N10—C8—C9—C1463.3 (2)C15—C14—C22—C23148.2 (2)
N27—C8—N10—C1162.8 (3)C13—C14—C22—C2388.7 (3)
C9—C8—N10—C11174.4 (2)C9—C14—C22—C2331.3 (3)
N27—C8—N10—C1259.6 (3)C21—C22—C23—N27177.3 (2)
C9—C8—N10—C1263.2 (2)C14—C22—C23—N272.0 (3)
C11—N10—C12—C13179.4 (2)C21—C22—C23—C240.9 (3)
C8—N10—C12—C1356.5 (3)C14—C22—C23—C24176.2 (2)
N10—C12—C13—C1452.8 (3)N27—C23—C24—C25177.9 (2)
C12—C13—C14—C2263.8 (3)C22—C23—C24—C250.4 (4)
C12—C13—C14—C15172.0 (2)C21—C20—C25—C241.1 (5)
C12—C13—C14—C955.8 (3)C23—C24—C25—C200.7 (4)
C5—C9—C14—C2260.8 (2)C5—C4—N26—C153.9 (4)
C8—C9—C14—C2259.6 (2)C3—C4—N26—C15176.3 (2)
C19—C9—C14—C22179.53 (19)N16—C15—N26—C487.0 (3)
C5—C9—C14—C1560.6 (2)C14—C15—N26—C436.4 (3)
C8—C9—C14—C15178.95 (19)C24—C23—N27—C8174.0 (2)
C19—C9—C14—C1558.1 (2)C22—C23—N27—C84.2 (3)
C5—C9—C14—C13179.8 (2)N10—C8—N27—C2387.7 (3)
C8—C9—C14—C1359.4 (2)C9—C8—N27—C2335.4 (3)
C19—C9—C14—C1361.5 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1W···N100.91 (2)1.96 (2)2.872 (3)179 (3)
N27—H27···O1i0.88 (4)2.21 (4)3.062 (4)165 (3)
Symmetry code: (i) x, y+1/2, z+3/2.
 

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