Crystal structure of 3,14-diethyl-2,13-di­aza-6,17-diazo­niatri­cyclo­[16.4.0.0^7,12]docosane dinitrate dihydrate from synchrotron X-ray data

In the title salt, C₂₂H₄₆N₄²⁺·2NO₃⁻·2H₂O, the dication lies about an inversion center. In the crystal, N—H...O, O—H...O and N—H...N hydrogen bonds connect the anions, cations and water mol­ecules, forming a three-dimensional network.

Key indicators

• Single-crystal synchrotron study
• T = 220 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.062
• wR factor = 0.211
• Data-to-parameter ratio = 22.0

checkCIF/PLATON results

No syntax errors found



Alert level C
DIFMX02_ALERT_1_C  The maximum difference density is > 0.1*ZMAX*0.75
            The relevant atom site should be identified.
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full value Low .      0.976 Why?
PLAT097_ALERT_2_C Large Reported Max.  (Positive) Residual Density       0.73 eA-3
PLAT244_ALERT_4_C Low    'Solvent' Ueq as Compared to Neighbors of         N3 Check
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....        2.3 Note
PLAT906_ALERT_3_C Large K Value in the Analysis of Variance ......      2.246 Check
PLAT911_ALERT_3_C Missing FCF Refl Between Thmin & STh/L=    0.600         60 Report
PLAT918_ALERT_3_C Reflection(s) with I(obs) much Smaller I(calc) .          1 Check
PLAT975_ALERT_2_C Check Calcd Resid. Dens.  0.93A   From N1              0.64 eA-3
PLAT976_ALERT_2_C Check Calcd Resid. Dens.  1.05A   From N2             -0.54 eA-3
PLAT977_ALERT_2_C Check Negative Difference Density on H2AN             -0.43 eA-3

Alert level G
ABSMU01_ALERT_1_G  Calculation of _exptl_absorpt_correction_mu
                not performed for this radiation type.
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite          5 Note
PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms ..............          3 Report
PLAT013_ALERT_1_G N.O.K.   _shelx_hkl_checksum Found in CIF ......     Please Check
PLAT042_ALERT_1_G Calc. and Reported MoietyFormula Strings  Differ     Please Check
PLAT072_ALERT_2_G SHELXL First  Parameter in WGHT  Unusually Large       0.13 Report
PLAT092_ALERT_4_G Check: Wavelength Given is not Cu,Ga,Mo,Ag,In Ka    0.61000 Ang.
PLAT172_ALERT_4_G The CIF-Embedded .res File Contains DFIX Records          2 Report
PLAT173_ALERT_4_G The CIF-Embedded .res File Contains DANG Records          1 Report
PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels ..........          2 Note
PLAT793_ALERT_4_G Model has Chirality at C1          (Centro SPGR)          S Verify
PLAT793_ALERT_4_G Model has Chirality at C6          (Centro SPGR)          S Verify
PLAT793_ALERT_4_G Model has Chirality at C9          (Centro SPGR)          R Verify
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............          4 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         50 Note
PLAT951_ALERT_5_G Calculated (ThMax) and CIF-Reported Kmax Differ           2 Units
PLAT957_ALERT_1_G Calculated (ThMax) and Actual (FCF) Kmax Differ           2 Units
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          7 Info

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
  11 ALERT level C = Check. Ensure it is not caused by an omission or oversight
  18 ALERT level G = General information/check it is not something unexpected

   5 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   8 ALERT type 2 Indicator that the structure model may be wrong or deficient
   5 ALERT type 3 Indicator that the structure quality may be low
   9 ALERT type 4 Improvement, methodology, query or suggestion
   2 ALERT type 5 Informative message, check

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Computing details

Data collection: PAL BL2D-SMDC Program (Shin et al., 2016); cell refinement: HKL3000sm (Otwinowski & Minor, 1997); data reduction: HKL3000sm (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXT2018 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: DIAMOND 4 (Putz & Brandenburg, 2014); software used to prepare material for publication: publCIF (Westrip, 2010).

3,14-Diethyl-2,13-diaza-6,17-diazoniatricyclo[16.4.0.0^7,12]docosane dinitrate dihydrate

Crystal data

C22H46N4^2+·2NO3^−·2H2O	F(000) = 576
Mr = 526.68	Dx = 1.254 Mg m^−3
Monoclinic, P21/c	Synchrotron radiation, λ = 0.610 Å
a = 8.6420 (17) Å	Cell parameters from 46866 reflections
b = 16.687 (3) Å	θ = 0.4–33.7°
c = 9.7340 (19) Å	µ = 0.07 mm^−1
β = 96.46 (3)°	T = 220 K
V = 1394.8 (5) Å^3	Block, colorless
Z = 2	0.13 × 0.09 × 0.05 mm

Data collection

Rayonix MX225HS CCD area detector diffractometer	2968 reflections with I > 2σ(I)
Radiation source: PLSII 2D bending magnet	Rint = 0.027
ω scan	θmax = 25.0°, θmin = 2.0°
Absorption correction: empirical (using intensity measurements) (HKL3000sm SCALEPACK; Otwinowski & Minor, 1997)	h = −11→11
Tmin = 0.919, Tmax = 1.000	k = −21→21
14284 measured reflections	l = −13→13
3736 independent reflections

Refinement

Refinement on F^2	4 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.062	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.211	w = 1/[σ^2(Fo^2) + (0.1295P)^2 + 0.2454P] where P = (Fo^2 + 2Fc^2)/3
S = 1.10	(Δ/σ)max < 0.001
3736 reflections	Δρmax = 0.73 e Å^−3
170 parameters	Δρmin = −0.56 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	Uiso*/Ueq
N1	0.51219 (14)	0.59626 (8)	0.36407 (11)	0.0308 (3)
H1N	0.473300	0.634200	0.422800	0.037*
N2	0.28123 (13)	0.47313 (7)	0.42499 (11)	0.0278 (3)
H2AN	0.385711	0.476834	0.431710	0.033*
H2BN	0.246719	0.513235	0.475356	0.033*
C1	0.76020 (15)	0.60393 (9)	0.51374 (13)	0.0286 (3)
H1	0.716885	0.647557	0.566781	0.034*
C2	0.93544 (17)	0.61843 (10)	0.51640 (16)	0.0365 (3)
H2A	0.983763	0.617356	0.612413	0.044*
H2B	0.981148	0.575002	0.466503	0.044*
C3	0.97155 (18)	0.69835 (10)	0.45121 (17)	0.0386 (4)
H3A	0.936038	0.742285	0.506664	0.046*
H3B	1.084368	0.703693	0.450342	0.046*
C4	0.89135 (18)	0.70410 (10)	0.30389 (15)	0.0373 (3)
H4A	0.935358	0.663904	0.245983	0.045*
H4B	0.910323	0.757161	0.266013	0.045*
C5	0.71640 (17)	0.69051 (9)	0.30041 (15)	0.0342 (3)
H5A	0.667680	0.692382	0.204553	0.041*
H5B	0.670830	0.733224	0.352056	0.041*
C6	0.68403 (16)	0.60924 (9)	0.36398 (13)	0.0296 (3)
H6	0.726833	0.566354	0.308993	0.035*
C7	0.42136 (18)	0.59147 (10)	0.22379 (14)	0.0353 (3)
H7A	0.467359	0.550519	0.168718	0.042*
H7B	0.427202	0.643030	0.176434	0.042*
C8	0.25211 (17)	0.57083 (9)	0.23440 (14)	0.0337 (3)
H8A	0.192762	0.580870	0.144215	0.040*
H8B	0.212715	0.607652	0.300777	0.040*
C9	0.21823 (17)	0.48504 (9)	0.27811 (13)	0.0314 (3)
H9	0.103745	0.478672	0.271539	0.038*
C10	0.2802 (3)	0.42191 (11)	0.18588 (16)	0.0471 (4)
H10A	0.393272	0.428242	0.189202	0.056*
H10B	0.259978	0.368749	0.222744	0.056*
C11	0.2090 (4)	0.42595 (16)	0.0363 (2)	0.0792 (8)
H11A	0.096417	0.427628	0.032597	0.119*
H11B	0.239639	0.378996	−0.012820	0.119*
H11C	0.245453	0.473817	−0.006600	0.119*
N3	0.2912 (2)	0.63006 (12)	0.76865 (18)	0.0581 (5)
O1	0.3086 (2)	0.58294 (10)	0.6746 (2)	0.0812 (6)
O2	0.2872 (2)	0.70307 (10)	0.74420 (17)	0.0696 (5)
O3	0.2875 (5)	0.6094 (2)	0.8868 (3)	0.1636 (16)
O4	0.42576 (16)	0.72874 (9)	0.50503 (14)	0.0501 (3)
H1O	0.373 (3)	0.7221 (16)	0.5829 (17)	0.075*
H2O	0.366 (3)	0.7605 (14)	0.439 (2)	0.075*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0327 (6)	0.0418 (7)	0.0171 (5)	−0.0017 (5)	−0.0003 (4)	0.0035 (4)
N2	0.0303 (6)	0.0363 (6)	0.0163 (5)	−0.0001 (4)	−0.0003 (4)	0.0006 (4)
C1	0.0300 (6)	0.0370 (7)	0.0185 (6)	−0.0006 (5)	0.0012 (5)	0.0007 (5)
C2	0.0303 (7)	0.0486 (9)	0.0302 (7)	−0.0013 (6)	0.0012 (5)	0.0050 (6)
C3	0.0361 (7)	0.0496 (9)	0.0305 (7)	−0.0078 (6)	0.0055 (6)	0.0016 (6)
C4	0.0380 (7)	0.0482 (9)	0.0269 (7)	−0.0029 (6)	0.0090 (6)	0.0038 (6)
C5	0.0368 (7)	0.0423 (8)	0.0240 (6)	−0.0006 (5)	0.0048 (5)	0.0065 (5)
C6	0.0317 (6)	0.0389 (7)	0.0180 (6)	0.0007 (5)	0.0024 (5)	0.0015 (5)
C7	0.0393 (8)	0.0476 (8)	0.0176 (6)	−0.0062 (6)	−0.0027 (5)	0.0057 (5)
C8	0.0344 (7)	0.0437 (8)	0.0213 (6)	0.0024 (5)	−0.0040 (5)	0.0046 (5)
C9	0.0329 (7)	0.0430 (8)	0.0172 (6)	−0.0033 (5)	−0.0013 (5)	0.0010 (5)
C10	0.0721 (12)	0.0461 (10)	0.0240 (7)	−0.0041 (8)	0.0097 (7)	−0.0044 (6)
C11	0.141 (3)	0.0743 (15)	0.0214 (8)	−0.0135 (15)	0.0046 (11)	−0.0093 (9)
N3	0.0674 (11)	0.0633 (11)	0.0418 (9)	−0.0045 (8)	−0.0025 (8)	0.0016 (7)
O1	0.1056 (14)	0.0553 (10)	0.0739 (12)	0.0074 (8)	−0.0284 (10)	−0.0228 (8)
O2	0.1060 (14)	0.0545 (9)	0.0509 (9)	0.0048 (8)	0.0204 (9)	−0.0098 (6)
O3	0.285 (5)	0.140 (3)	0.0760 (18)	0.010 (3)	0.063 (2)	0.0501 (17)
O4	0.0555 (8)	0.0574 (8)	0.0384 (7)	0.0082 (6)	0.0088 (6)	−0.0009 (5)

Geometric parameters (Å, º)

N1—C7	1.4987 (17)	C5—H5B	0.9800
N1—C6	1.5009 (18)	C6—H6	0.9900
N1—H1N	0.94	C7—C8	1.517 (2)
N2—C1^i	1.4784 (18)	C7—H7A	0.9800
N2—C9	1.4850 (16)	C7—H7B	0.9800
N2—H2AN	0.9000	C8—C9	1.531 (2)
N2—H2BN	0.9000	C8—H8A	0.9800
C1—C2	1.5309 (19)	C8—H8B	0.9800
C1—C6	1.5330 (18)	C9—C10	1.520 (2)
C1—H1	0.9900	C9—H9	0.9900
C2—C3	1.524 (2)	C10—C11	1.517 (3)
C2—H2A	0.9800	C10—H10A	0.9800
C2—H2B	0.9800	C10—H10B	0.9800
C3—C4	1.524 (2)	C11—H11A	0.9700
C3—H3A	0.9800	C11—H11B	0.9700
C3—H3B	0.9800	C11—H11C	0.9700
C4—C5	1.525 (2)	N3—O3	1.204 (3)
C4—H4A	0.9800	N3—O1	1.229 (3)
C4—H4B	0.9800	N3—O2	1.241 (2)
C5—C6	1.529 (2)	O4—H1O	0.937 (10)
C5—H5A	0.9800	O4—H2O	0.941 (9)
C7—N1—C6	115.09 (11)	N1—C6—C1	108.07 (11)
C7—N1—H1N	114	C5—C6—C1	110.95 (12)
C6—N1—H1N	109	N1—C6—H6	109.0
C1^i—N2—C9	115.19 (10)	C5—C6—H6	109.0
C1^i—N2—H2AN	108.5	C1—C6—H6	109.0
C9—N2—H2AN	108.5	N1—C7—C8	111.11 (11)
C1^i—N2—H2BN	108.5	N1—C7—H7A	109.4
C9—N2—H2BN	108.5	C8—C7—H7A	109.4
H2AN—N2—H2BN	107.5	N1—C7—H7B	109.4
N2^i—C1—C2	114.50 (12)	C8—C7—H7B	109.4
N2^i—C1—C6	109.65 (11)	H7A—C7—H7B	108.0
C2—C1—C6	108.97 (11)	C7—C8—C9	116.55 (12)
N2^i—C1—H1	107.8	C7—C8—H8A	108.2
C2—C1—H1	107.8	C9—C8—H8A	108.2
C6—C1—H1	107.8	C7—C8—H8B	108.2
C3—C2—C1	112.32 (12)	C9—C8—H8B	108.2
C3—C2—H2A	109.1	H8A—C8—H8B	107.3
C1—C2—H2A	109.1	N2—C9—C10	111.14 (12)
C3—C2—H2B	109.1	N2—C9—C8	109.38 (11)
C1—C2—H2B	109.1	C10—C9—C8	113.13 (13)
H2A—C2—H2B	107.9	N2—C9—H9	107.7
C4—C3—C2	110.74 (13)	C10—C9—H9	107.7
C4—C3—H3A	109.5	C8—C9—H9	107.7
C2—C3—H3A	109.5	C11—C10—C9	113.86 (17)
C4—C3—H3B	109.5	C11—C10—H10A	108.8
C2—C3—H3B	109.5	C9—C10—H10A	108.8
H3A—C3—H3B	108.1	C11—C10—H10B	108.8
C3—C4—C5	110.87 (12)	C9—C10—H10B	108.8
C3—C4—H4A	109.5	H10A—C10—H10B	107.7
C5—C4—H4A	109.5	C10—C11—H11A	109.5
C3—C4—H4B	109.5	C10—C11—H11B	109.5
C5—C4—H4B	109.5	H11A—C11—H11B	109.5
H4A—C4—H4B	108.1	C10—C11—H11C	109.5
C4—C5—C6	110.41 (12)	H11A—C11—H11C	109.5
C4—C5—H5A	109.6	H11B—C11—H11C	109.5
C6—C5—H5A	109.6	O3—N3—O1	123.1 (3)
C4—C5—H5B	109.6	O3—N3—O2	117.4 (2)
C6—C5—H5B	109.6	O1—N3—O2	119.23 (19)
H5A—C5—H5B	108.1	H1O—O4—H2O	109.8 (18)
N1—C6—C5	110.75 (11)
N2^i—C1—C2—C3	179.62 (12)	N2^i—C1—C6—C5	176.50 (11)
C6—C1—C2—C3	56.43 (16)	C2—C1—C6—C5	−57.46 (15)
C1—C2—C3—C4	−55.92 (17)	C6—N1—C7—C8	174.85 (12)
C2—C3—C4—C5	55.43 (18)	N1—C7—C8—C9	−71.31 (16)
C3—C4—C5—C6	−57.05 (17)	C1^i—N2—C9—C10	−61.66 (16)
C7—N1—C6—C5	64.03 (15)	C1^i—N2—C9—C8	172.72 (11)
C7—N1—C6—C1	−174.25 (12)	C7—C8—C9—N2	68.87 (16)
C4—C5—C6—N1	178.64 (11)	C7—C8—C9—C10	−55.60 (17)
C4—C5—C6—C1	58.63 (16)	N2—C9—C10—C11	174.71 (16)
N2^i—C1—C6—N1	54.91 (14)	C8—C9—C10—C11	−61.8 (2)
C2—C1—C6—N1	−179.05 (12)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2AN···N1	0.90	2.40	2.9703 (18)	121
N2—H2AN···N1^i	0.90	2.41	2.8141 (17)	107
N1—H1N···O4	0.94	1.84	2.7493 (19)	163
N2—H2AN···N1	0.90	2.40	2.9703 (18)	121
N2—H2BN···O1	0.90	2.27	3.031 (2)	142
O4—H1O···O1	0.94 (1)	2.57 (2)	3.169 (3)	122 (2)
O4—H1O···O2	0.94 (1)	1.84 (1)	2.768 (2)	174 (2)
O4—H2O···O2^ii	0.94 (1)	2.04 (1)	2.914 (2)	155 (2)
O4—H2O···O3^ii	0.94 (1)	2.31 (2)	3.120 (4)	144 (2)

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, −y+3/2, z−1/2.