Crystal structures of 1,4-di­aza­bicyclo­[2.2.2]octan-1-ium 4-nitro­benzoate dihydrate and 1,4-di­aza­bicyclo­[2.2.2]octane-1,4-diium bis­(4-nitro­benzoate): the influence of solvent upon the stoichiometry of the formed salt

Solvent-dependent outcomes are noted in co-crystallization experiments between DABCO and 4-nitrobenzoic acid with mono- and diprotonated forms of DABCO are isolated.

Key indicators

Structure: 1

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.039
• wR factor = 0.099
• Data-to-parameter ratio = 14.3

Structure: 2

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.074
• wR factor = 0.229
• Data-to-parameter ratio = 13.9

checkCIF/PLATON results

No syntax errors found



Datablock: 1


Alert level C
PLAT906_ALERT_3_C Large K value in the Analysis of Variance ......      2.382 Check
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          9 Why ?
PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF ....          5 Note

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite          8 Note
PLAT005_ALERT_5_G No _iucr_refine_instructions_details  in the CIF     Please Do !
PLAT042_ALERT_1_G Calc. and Reported MoietyFormula Strings  Differ     Please Check
PLAT790_ALERT_4_G Centre of Gravity not Within Unit Cell: Resd.  #          3 Note
              H2 O
PLAT790_ALERT_4_G Centre of Gravity not Within Unit Cell: Resd.  #          4 Note
              H2 O
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............          7 Note
PLAT910_ALERT_3_G Missing # of FCF Reflections Below Th(Min) .....          1 Why ?
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         11 Note

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

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 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
   3 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check




Datablock: 2


Alert level C
DIFMX01_ALERT_2_C  The maximum difference density is > 0.1*ZMAX*0.75
            _refine_diff_density_max given =      0.601
            Test value =      0.600
DIFMX02_ALERT_1_C  The maximum difference density is > 0.1*ZMAX*0.75
            The relevant atom site should be identified.
PLAT906_ALERT_3_C Large K value in the Analysis of Variance ......      5.811 Check
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          9 Why ?
PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF ....          1 Note
PLAT939_ALERT_3_C Large Value of Not (SHELXL) Weight Optimized S .      10.17
PLAT975_ALERT_2_C Check Calcd Residual Density  1.08A From      O5       0.58 eA-3
PLAT975_ALERT_2_C Check Calcd Residual Density  0.87A From      O2       0.52 eA-3
PLAT975_ALERT_2_C Check Calcd Residual Density  0.88A From      O1       0.52 eA-3
PLAT975_ALERT_2_C Check Calcd Residual Density  0.84A From      O4       0.52 eA-3
PLAT975_ALERT_2_C Check Calcd Residual Density  0.98A From      O7       0.47 eA-3

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite          4 Note
PLAT005_ALERT_5_G No _iucr_refine_instructions_details  in the CIF     Please Do !
PLAT042_ALERT_1_G Calc. and Reported MoietyFormula Strings  Differ     Please Check
PLAT072_ALERT_2_G SHELXL First  Parameter in WGHT Unusually Large.       0.12 Why ?
PLAT154_ALERT_1_G The su's on the Cell Angles are Equal ..........    0.00300 Degree
PLAT790_ALERT_4_G Centre of Gravity not Within Unit Cell: Resd.  #          2 Note
              C7 H4 N O4
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............          2 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600          2 Note

   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
   8 ALERT level G = General information/check it is not something unexpected

   3 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
   2 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

---

Computing details

For both compounds, data collection: CrysAlis PRO (Agilent, 2013); cell refinement: CrysAlis PRO (Agilent, 2013); data reduction: CrysAlis PRO (Agilent, 2013); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

(1) 1,4-Diazabicyclo[2.2.2]octan-1-ium 4-nitrobenzoate dihydrate

Crystal data

C6H13N2^+·C7H4NO4^−·2H2O	F(000) = 672
Mr = 315.33	Dx = 1.399 Mg m^−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: -P 2ybc	Cell parameters from 7046 reflections
a = 6.5982 (1) Å	θ = 3.9–76.3°
b = 6.6074 (1) Å	µ = 0.94 mm^−1
c = 34.4574 (6) Å	T = 100 K
β = 94.809 (1)°	Prism, colourless
V = 1496.95 (4) Å^3	0.30 × 0.30 × 0.20 mm
Z = 4

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector	3072 independent reflections
Radiation source: SuperNova (Cu) X-ray Source	2949 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.015
Detector resolution: 10.4041 pixels mm^-1	θmax = 75.0°, θmin = 5.2°
ω scan	h = −8→8
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013)	k = −8→5
Tmin = 0.888, Tmax = 1.000	l = −43→42
11203 measured reflections

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)] = 0.039	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.099	w = 1/[σ^2(Fo^2) + (0.0467P)^2 + 0.8811P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.001
3072 reflections	Δρmax = 0.40 e Å^−3
215 parameters	Δρmin = −0.30 e Å^−3
7 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0076 (6)

Special details

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
O1	0.63866 (13)	0.34327 (15)	0.59514 (3)	0.0233 (2)
O2	0.94425 (14)	0.33794 (16)	0.62902 (3)	0.0261 (2)
O3	1.11387 (14)	0.20664 (15)	0.42606 (3)	0.0234 (2)
O4	1.40402 (14)	0.17440 (16)	0.45978 (3)	0.0262 (2)
N1	1.21908 (16)	0.20014 (15)	0.45723 (3)	0.0175 (2)
C1	0.82971 (19)	0.32425 (18)	0.59836 (4)	0.0178 (3)
C2	0.93105 (18)	0.28490 (18)	0.56096 (3)	0.0153 (2)
C3	1.13841 (18)	0.24078 (18)	0.56251 (3)	0.0162 (3)
H3	1.2149	0.2318	0.5871	0.019*
C4	1.23420 (18)	0.20989 (18)	0.52871 (4)	0.0163 (2)
H4	1.3751	0.1786	0.5297	0.020*
C5	1.11798 (18)	0.22606 (17)	0.49335 (3)	0.0149 (2)
C6	0.91145 (18)	0.26736 (17)	0.49062 (3)	0.0155 (2)
H6	0.8354	0.2752	0.4660	0.019*
C7	0.81863 (17)	0.29702 (18)	0.52492 (3)	0.0156 (2)
H7	0.6772	0.3258	0.5238	0.019*
N2	0.48292 (15)	0.59677 (17)	0.64400 (3)	0.0178 (2)
H2N	0.535 (2)	0.503 (2)	0.6291 (4)	0.021*
N3	0.33337 (16)	0.86385 (17)	0.68589 (3)	0.0207 (2)
C8	0.31552 (19)	0.7058 (2)	0.62050 (4)	0.0213 (3)
H8A	0.2168	0.6074	0.6082	0.026*
H8B	0.3720	0.7863	0.5997	0.026*
C9	0.2099 (2)	0.8456 (2)	0.64826 (4)	0.0309 (3)
H9A	0.1903	0.9811	0.6363	0.037*
H9B	0.0744	0.7900	0.6527	0.037*
C10	0.64491 (19)	0.7447 (2)	0.65768 (4)	0.0212 (3)
H10A	0.7121	0.7988	0.6352	0.025*
H10B	0.7491	0.6777	0.6756	0.025*
C11	0.5423 (2)	0.9174 (2)	0.67881 (5)	0.0325 (3)
H11A	0.6212	0.9456	0.7039	0.039*
H11B	0.5416	1.0418	0.6628	0.039*
C12	0.39871 (18)	0.49677 (19)	0.67830 (4)	0.0199 (3)
H12A	0.5038	0.4108	0.6923	0.024*
H12B	0.2810	0.4105	0.6695	0.024*
C13	0.3323 (2)	0.6654 (2)	0.70520 (4)	0.0257 (3)
H13A	0.1938	0.6361	0.7127	0.031*
H13B	0.4257	0.6688	0.7292	0.031*
O1W	0.19593 (16)	1.12932 (16)	0.74123 (3)	0.0268 (2)
H1W	0.243 (3)	1.058 (3)	0.7232 (4)	0.040*
H2W	0.151 (3)	1.039 (2)	0.7565 (4)	0.040*
O2W	−0.12706 (15)	1.33213 (17)	0.70557 (3)	0.0289 (2)
H3W	−0.026 (2)	1.268 (3)	0.7167 (5)	0.043*
H4W	−0.117 (3)	1.328 (3)	0.6810 (3)	0.043*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0175 (4)	0.0299 (5)	0.0231 (5)	0.0006 (4)	0.0055 (3)	−0.0078 (4)
O2	0.0235 (5)	0.0391 (6)	0.0158 (4)	0.0014 (4)	0.0025 (4)	−0.0027 (4)
O3	0.0271 (5)	0.0281 (5)	0.0153 (4)	0.0000 (4)	0.0033 (4)	0.0001 (4)
O4	0.0181 (5)	0.0355 (6)	0.0262 (5)	0.0027 (4)	0.0087 (4)	0.0009 (4)
N1	0.0200 (5)	0.0147 (5)	0.0185 (5)	−0.0011 (4)	0.0058 (4)	0.0004 (4)
C1	0.0190 (6)	0.0167 (6)	0.0181 (6)	−0.0009 (5)	0.0042 (5)	−0.0018 (5)
C2	0.0170 (6)	0.0122 (5)	0.0171 (6)	−0.0017 (4)	0.0034 (4)	−0.0006 (4)
C3	0.0165 (6)	0.0154 (6)	0.0165 (6)	−0.0012 (4)	−0.0004 (4)	0.0003 (4)
C4	0.0137 (5)	0.0144 (5)	0.0209 (6)	−0.0006 (4)	0.0026 (4)	0.0007 (4)
C5	0.0178 (6)	0.0116 (5)	0.0159 (6)	−0.0020 (4)	0.0053 (4)	−0.0006 (4)
C6	0.0174 (6)	0.0124 (5)	0.0164 (5)	−0.0022 (4)	−0.0002 (4)	0.0002 (4)
C7	0.0135 (5)	0.0133 (5)	0.0200 (6)	−0.0016 (4)	0.0021 (4)	−0.0005 (4)
N2	0.0148 (5)	0.0219 (5)	0.0171 (5)	0.0002 (4)	0.0033 (4)	−0.0034 (4)
N3	0.0212 (5)	0.0228 (6)	0.0187 (5)	0.0016 (4)	0.0044 (4)	−0.0023 (4)
C8	0.0200 (6)	0.0270 (7)	0.0167 (6)	0.0018 (5)	0.0005 (5)	−0.0011 (5)
C9	0.0331 (7)	0.0375 (8)	0.0217 (7)	0.0148 (6)	−0.0002 (6)	−0.0017 (6)
C10	0.0153 (6)	0.0274 (7)	0.0215 (6)	−0.0047 (5)	0.0041 (5)	−0.0018 (5)
C11	0.0276 (7)	0.0300 (7)	0.0416 (8)	−0.0100 (6)	0.0126 (6)	−0.0138 (7)
C12	0.0174 (6)	0.0207 (6)	0.0219 (6)	−0.0009 (5)	0.0039 (5)	0.0027 (5)
C13	0.0299 (7)	0.0274 (7)	0.0210 (6)	0.0011 (5)	0.0104 (5)	0.0017 (5)
O1W	0.0311 (5)	0.0285 (5)	0.0210 (5)	0.0053 (4)	0.0026 (4)	−0.0024 (4)
O2W	0.0258 (5)	0.0420 (6)	0.0191 (5)	0.0084 (4)	0.0041 (4)	0.0005 (4)

Geometric parameters (Å, º)

O1—C1	1.2625 (15)	N3—C13	1.4706 (17)
O2—C1	1.2495 (16)	N3—C9	1.4773 (17)
O3—N1	1.2298 (14)	C8—C9	1.5381 (18)
O4—N1	1.2279 (14)	C8—H8A	0.9900
N1—C5	1.4704 (15)	C8—H8B	0.9900
C1—C2	1.5231 (16)	C9—H9A	0.9900
C2—C7	1.3943 (17)	C9—H9B	0.9900
C2—C3	1.3956 (16)	C10—C11	1.5408 (19)
C3—C4	1.3857 (17)	C10—H10A	0.9900
C3—H3	0.9500	C10—H10B	0.9900
C4—C5	1.3884 (17)	C11—H11A	0.9900
C4—H4	0.9500	C11—H11B	0.9900
C5—C6	1.3852 (17)	C12—C13	1.5365 (18)
C6—C7	1.3900 (16)	C12—H12A	0.9900
C6—H6	0.9500	C12—H12B	0.9900
C7—H7	0.9500	C13—H13A	0.9900
N2—C10	1.4951 (16)	C13—H13B	0.9900
N2—C8	1.4982 (16)	O1W—H1W	0.861 (9)
N2—C12	1.5007 (15)	O1W—H2W	0.866 (9)
N2—H2N	0.892 (9)	O2W—H3W	0.852 (9)
N3—C11	1.4635 (17)	O2W—H4W	0.856 (9)
O4—N1—O3	123.50 (10)	N2—C8—H8B	110.2
O4—N1—C5	118.32 (10)	C9—C8—H8B	110.2
O3—N1—C5	118.18 (10)	H8A—C8—H8B	108.5
O2—C1—O1	126.58 (11)	N3—C9—C8	110.47 (11)
O2—C1—C2	116.76 (11)	N3—C9—H9A	109.6
O1—C1—C2	116.65 (11)	C8—C9—H9A	109.6
C7—C2—C3	119.51 (11)	N3—C9—H9B	109.6
C7—C2—C1	120.35 (11)	C8—C9—H9B	109.6
C3—C2—C1	120.13 (11)	H9A—C9—H9B	108.1
C4—C3—C2	120.90 (11)	N2—C10—C11	107.60 (10)
C4—C3—H3	119.6	N2—C10—H10A	110.2
C2—C3—H3	119.6	C11—C10—H10A	110.2
C3—C4—C5	117.96 (11)	N2—C10—H10B	110.2
C3—C4—H4	121.0	C11—C10—H10B	110.2
C5—C4—H4	121.0	H10A—C10—H10B	108.5
C6—C5—C4	122.86 (11)	N3—C11—C10	110.91 (11)
C6—C5—N1	118.62 (11)	N3—C11—H11A	109.5
C4—C5—N1	118.52 (10)	C10—C11—H11A	109.5
C5—C6—C7	118.10 (11)	N3—C11—H11B	109.5
C5—C6—H6	120.9	C10—C11—H11B	109.5
C7—C6—H6	120.9	H11A—C11—H11B	108.0
C6—C7—C2	120.66 (11)	N2—C12—C13	107.39 (10)
C6—C7—H7	119.7	N2—C12—H12A	110.2
C2—C7—H7	119.7	C13—C12—H12A	110.2
C10—N2—C8	109.35 (10)	N2—C12—H12B	110.2
C10—N2—C12	109.99 (9)	C13—C12—H12B	110.2
C8—N2—C12	109.42 (9)	H12A—C12—H12B	108.5
C10—N2—H2N	109.7 (10)	N3—C13—C12	111.17 (10)
C8—N2—H2N	109.0 (10)	N3—C13—H13A	109.4
C12—N2—H2N	109.4 (11)	C12—C13—H13A	109.4
C11—N3—C13	109.35 (11)	N3—C13—H13B	109.4
C11—N3—C9	109.36 (11)	C12—C13—H13B	109.4
C13—N3—C9	107.53 (11)	H13A—C13—H13B	108.0
N2—C8—C9	107.72 (10)	H1W—O1W—H2W	103.0 (15)
N2—C8—H8A	110.2	H3W—O2W—H4W	107.8 (16)
C9—C8—H8A	110.2
O2—C1—C2—C7	−170.56 (11)	C1—C2—C7—C6	178.03 (11)
O1—C1—C2—C7	8.23 (17)	C10—N2—C8—C9	−67.76 (13)
O2—C1—C2—C3	8.02 (17)	C12—N2—C8—C9	52.77 (14)
O1—C1—C2—C3	−173.19 (11)	C11—N3—C9—C8	50.98 (16)
C7—C2—C3—C4	0.32 (18)	C13—N3—C9—C8	−67.65 (14)
C1—C2—C3—C4	−178.27 (11)	N2—C8—C9—N3	13.17 (16)
C2—C3—C4—C5	0.59 (18)	C8—N2—C10—C11	53.58 (13)
C3—C4—C5—C6	−1.34 (18)	C12—N2—C10—C11	−66.60 (13)
C3—C4—C5—N1	178.05 (10)	C13—N3—C11—C10	51.74 (15)
O4—N1—C5—C6	176.15 (11)	C9—N3—C11—C10	−65.75 (15)
O3—N1—C5—C6	−3.43 (16)	N2—C10—C11—N3	11.63 (16)
O4—N1—C5—C4	−3.27 (16)	C10—N2—C12—C13	53.46 (13)
O3—N1—C5—C4	177.15 (10)	C8—N2—C12—C13	−66.68 (13)
C4—C5—C6—C7	1.12 (18)	C11—N3—C13—C12	−65.51 (14)
N1—C5—C6—C7	−178.28 (10)	C9—N3—C13—C12	53.13 (14)
C5—C6—C7—C2	−0.14 (17)	N2—C12—C13—N3	11.20 (14)
C3—C2—C7—C6	−0.56 (18)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···O1	0.89 (1)	1.76 (1)	2.6431 (14)	173 (1)
O1W—H1W···N3	0.86 (2)	1.95 (2)	2.7974 (15)	172 (2)
O1W—H2W···O2W^i	0.86 (2)	1.91 (1)	2.7500 (15)	165 (2)
O2W—H3W···O1W	0.85 (2)	1.87 (2)	2.7218 (15)	180 (2)
O2W—H4W···O2^ii	0.86 (1)	1.87 (1)	2.7182 (15)	171 (2)
C10—H10A···O3^iii	0.99	2.49	3.4253 (17)	158
C12—H12A···O2W^iv	0.99	2.49	3.3711 (16)	147
C12—H12B···O2^v	0.99	2.57	3.4818 (16)	153

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

(2) 1,4-Diazabicyclo[2.2.2]octane-1,4-diium bis(4-nitrobenzoate)

Crystal data

C6H14N2^2+·2C7H4NO4^−	Z = 2
Mr = 446.42	F(000) = 468
Triclinic, P1	Dx = 1.486 Mg m^−3
Hall symbol: -P 1	Cu Kα radiation, λ = 1.54184 Å
a = 9.1036 (4) Å	Cell parameters from 10186 reflections
b = 9.5027 (3) Å	θ = 3.8–76.8°
c = 12.0736 (3) Å	µ = 0.99 mm^−1
α = 73.982 (3)°	T = 100 K
β = 83.624 (3)°	Prism, colourless
γ = 88.661 (3)°	0.40 × 0.40 × 0.20 mm
V = 997.68 (6) Å^3

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector	4101 independent reflections
Radiation source: SuperNova (Cu) X-ray Source	3775 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.046
Detector resolution: 10.4041 pixels mm^-1	θmax = 75.0°, θmin = 3.8°
ω scan	h = −11→11
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013)	k = −11→11
Tmin = 0.991, Tmax = 1.000	l = −15→15
17849 measured reflections

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)] = 0.074	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.229	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	w = 1/[σ^2(Fo^2) + (0.1192P)^2 + 1.3867P] where P = (Fo^2 + 2Fc^2)/3
4101 reflections	(Δ/σ)max < 0.001
295 parameters	Δρmax = 0.60 e Å^−3
2 restraints	Δρmin = −0.58 e Å^−3

Special details

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
O1	0.6213 (2)	0.7377 (2)	0.82692 (16)	0.0320 (5)
O2	0.4577 (2)	0.9073 (2)	0.75460 (15)	0.0301 (4)
O3	0.3598 (2)	0.7520 (2)	1.38056 (16)	0.0365 (5)
O4	0.2049 (2)	0.9218 (2)	1.31087 (17)	0.0343 (5)
N1	0.3033 (3)	0.8347 (2)	1.29939 (18)	0.0278 (5)
C1	0.5159 (3)	0.8269 (3)	0.8358 (2)	0.0230 (5)
C2	0.4601 (3)	0.8288 (3)	0.9588 (2)	0.0225 (5)
C3	0.3361 (3)	0.9096 (3)	0.9783 (2)	0.0239 (5)
H3A	0.2873	0.9646	0.9148	0.029*
C4	0.2829 (3)	0.9105 (3)	1.0906 (2)	0.0245 (5)
H4A	0.1976	0.9649	1.1051	0.029*
C5	0.3578 (3)	0.8300 (3)	1.1807 (2)	0.0244 (5)
C6	0.4829 (3)	0.7496 (3)	1.1642 (2)	0.0269 (5)
H6	0.5320	0.6958	1.2280	0.032*
C7	0.5343 (3)	0.7498 (3)	1.0515 (2)	0.0250 (5)
H7	0.6202	0.6961	1.0374	0.030*
O5	0.8758 (2)	0.7357 (2)	0.20757 (15)	0.0345 (5)
O6	1.0354 (2)	0.5601 (2)	0.27470 (17)	0.0385 (5)
O7	1.3135 (2)	0.6129 (2)	−0.29233 (18)	0.0368 (5)
O8	1.1731 (2)	0.7994 (2)	−0.35307 (16)	0.0347 (5)
N2	1.2191 (2)	0.7014 (3)	−0.27572 (19)	0.0287 (5)
C8	0.9814 (3)	0.6492 (3)	0.1953 (2)	0.0256 (5)
C9	1.0424 (3)	0.6604 (3)	0.0705 (2)	0.0233 (5)
C10	1.1613 (3)	0.5752 (3)	0.0471 (2)	0.0253 (5)
H10	1.2030	0.5075	0.1090	0.030*
C11	1.2196 (3)	0.5889 (3)	−0.0670 (2)	0.0264 (5)
H11	1.3010	0.5311	−0.0841	0.032*
C12	1.1562 (3)	0.6885 (3)	−0.1550 (2)	0.0252 (5)
C13	1.0376 (3)	0.7750 (3)	−0.1345 (2)	0.0259 (5)
H13	0.9963	0.8426	−0.1967	0.031*
C14	0.9806 (3)	0.7597 (3)	−0.0201 (2)	0.0255 (5)
H14	0.8989	0.8174	−0.0034	0.031*
N3	0.6982 (2)	0.7378 (2)	0.61824 (18)	0.0254 (5)
H3N	0.665 (3)	0.734 (4)	0.6902 (12)	0.030*
N4	0.7971 (2)	0.7223 (2)	0.41892 (18)	0.0261 (5)
H4N	0.830 (3)	0.728 (4)	0.3454 (12)	0.031*
C15	0.8607 (3)	0.7624 (3)	0.6003 (2)	0.0274 (5)
H15A	0.9072	0.6984	0.6663	0.033*
H15B	0.8832	0.8655	0.5954	0.033*
C16	0.9224 (3)	0.7273 (3)	0.4870 (2)	0.0310 (6)
H16A	0.9946	0.8035	0.4418	0.037*
H16B	0.9733	0.6317	0.5047	0.037*
C17	0.6672 (3)	0.5903 (3)	0.6066 (2)	0.0269 (5)
H17A	0.5616	0.5648	0.6317	0.032*
H17B	0.7276	0.5163	0.6564	0.032*
C18	0.7046 (3)	0.5908 (3)	0.4791 (2)	0.0299 (6)
H18A	0.7592	0.5009	0.4744	0.036*
H18B	0.6127	0.5935	0.4418	0.036*
C19	0.6263 (3)	0.8510 (3)	0.5300 (2)	0.0304 (6)
H19A	0.6328	0.9477	0.5453	0.036*
H19B	0.5206	0.8261	0.5334	0.036*
C20	0.7063 (3)	0.8562 (3)	0.4098 (2)	0.0318 (6)
H20A	0.6330	0.8614	0.3541	0.038*
H20B	0.7704	0.9444	0.3814	0.038*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0368 (10)	0.0397 (11)	0.0185 (9)	0.0127 (8)	−0.0025 (7)	−0.0077 (7)
O2	0.0355 (10)	0.0357 (10)	0.0175 (8)	0.0069 (8)	−0.0028 (7)	−0.0053 (7)
O3	0.0476 (12)	0.0394 (11)	0.0182 (9)	0.0023 (9)	−0.0009 (8)	−0.0022 (8)
O4	0.0375 (11)	0.0371 (10)	0.0264 (9)	0.0021 (8)	0.0072 (8)	−0.0096 (8)
N1	0.0331 (12)	0.0299 (11)	0.0189 (10)	−0.0031 (9)	0.0022 (8)	−0.0060 (8)
C1	0.0243 (11)	0.0254 (12)	0.0183 (11)	−0.0019 (9)	−0.0008 (9)	−0.0047 (9)
C2	0.0255 (12)	0.0223 (11)	0.0190 (11)	−0.0027 (9)	−0.0012 (9)	−0.0045 (9)
C3	0.0255 (12)	0.0255 (12)	0.0198 (11)	−0.0014 (9)	−0.0041 (9)	−0.0041 (9)
C4	0.0249 (12)	0.0250 (12)	0.0229 (12)	−0.0006 (9)	0.0010 (9)	−0.0066 (9)
C5	0.0300 (12)	0.0256 (12)	0.0162 (11)	−0.0037 (10)	0.0026 (9)	−0.0050 (9)
C6	0.0317 (13)	0.0275 (12)	0.0187 (11)	0.0016 (10)	−0.0043 (10)	−0.0013 (9)
C7	0.0257 (12)	0.0250 (12)	0.0222 (12)	0.0019 (9)	0.0003 (9)	−0.0040 (9)
O5	0.0401 (11)	0.0445 (11)	0.0163 (9)	0.0144 (9)	−0.0005 (7)	−0.0062 (8)
O6	0.0454 (12)	0.0458 (12)	0.0193 (9)	0.0158 (9)	−0.0035 (8)	−0.0019 (8)
O7	0.0349 (10)	0.0484 (12)	0.0294 (10)	0.0019 (9)	0.0053 (8)	−0.0180 (9)
O8	0.0352 (10)	0.0478 (12)	0.0194 (9)	−0.0030 (9)	−0.0015 (7)	−0.0068 (8)
N2	0.0256 (11)	0.0382 (12)	0.0230 (11)	−0.0036 (9)	0.0010 (8)	−0.0105 (9)
C8	0.0264 (12)	0.0291 (12)	0.0192 (12)	0.0002 (10)	−0.0015 (9)	−0.0037 (9)
C9	0.0247 (12)	0.0265 (12)	0.0184 (11)	−0.0009 (9)	−0.0018 (9)	−0.0057 (9)
C10	0.0258 (12)	0.0245 (12)	0.0235 (12)	−0.0003 (9)	−0.0039 (10)	−0.0026 (9)
C11	0.0247 (12)	0.0264 (12)	0.0275 (13)	0.0005 (9)	0.0013 (10)	−0.0080 (10)
C12	0.0255 (12)	0.0298 (12)	0.0204 (12)	−0.0048 (10)	0.0015 (9)	−0.0081 (10)
C13	0.0272 (12)	0.0312 (13)	0.0180 (11)	−0.0008 (10)	−0.0035 (9)	−0.0043 (9)
C14	0.0243 (12)	0.0294 (12)	0.0215 (12)	0.0036 (9)	−0.0013 (9)	−0.0056 (10)
N3	0.0270 (11)	0.0308 (11)	0.0176 (10)	0.0066 (9)	−0.0021 (8)	−0.0061 (8)
N4	0.0290 (11)	0.0304 (11)	0.0169 (10)	0.0033 (9)	0.0004 (8)	−0.0045 (8)
C15	0.0289 (13)	0.0309 (13)	0.0228 (12)	0.0008 (10)	−0.0052 (10)	−0.0072 (10)
C16	0.0258 (12)	0.0425 (15)	0.0232 (12)	0.0004 (11)	0.0003 (10)	−0.0075 (11)
C17	0.0280 (12)	0.0312 (13)	0.0188 (12)	−0.0005 (10)	−0.0002 (9)	−0.0033 (9)
C18	0.0365 (14)	0.0306 (13)	0.0217 (12)	−0.0009 (11)	−0.0018 (10)	−0.0062 (10)
C19	0.0341 (14)	0.0339 (14)	0.0214 (12)	0.0121 (11)	−0.0040 (10)	−0.0056 (10)
C20	0.0408 (15)	0.0317 (13)	0.0195 (12)	0.0090 (11)	−0.0038 (10)	−0.0018 (10)

Geometric parameters (Å, º)

O1—C1	1.281 (3)	C12—C13	1.384 (4)
O2—C1	1.228 (3)	C13—C14	1.390 (3)
O3—N1	1.229 (3)	C13—H13	0.9500
O4—N1	1.228 (3)	C14—H14	0.9500
N1—C5	1.475 (3)	N3—C17	1.483 (3)
C1—C2	1.520 (3)	N3—C15	1.485 (3)
C2—C3	1.386 (3)	N3—C19	1.487 (3)
C2—C7	1.398 (3)	N3—H3N	0.879 (10)
C3—C4	1.390 (3)	N4—C20	1.486 (3)
C3—H3A	0.9500	N4—C16	1.487 (3)
C4—C5	1.384 (4)	N4—C18	1.487 (3)
C4—H4A	0.9500	N4—H4N	0.890 (10)
C5—C6	1.383 (4)	C15—C16	1.539 (3)
C6—C7	1.388 (3)	C15—H15A	0.9900
C6—H6	0.9500	C15—H15B	0.9900
C7—H7	0.9500	C16—H16A	0.9900
O5—C8	1.273 (3)	C16—H16B	0.9900
O6—C8	1.231 (3)	C17—C18	1.538 (3)
O7—N2	1.228 (3)	C17—H17A	0.9900
O8—N2	1.226 (3)	C17—H17B	0.9900
N2—C12	1.479 (3)	C18—H18A	0.9900
C8—C9	1.523 (3)	C18—H18B	0.9900
C9—C10	1.387 (3)	C19—C20	1.538 (3)
C9—C14	1.395 (3)	C19—H19A	0.9900
C10—C11	1.393 (4)	C19—H19B	0.9900
C10—H10	0.9500	C20—H20A	0.9900
C11—C12	1.382 (4)	C20—H20B	0.9900
C11—H11	0.9500
O4—N1—O3	124.0 (2)	C17—N3—C15	108.68 (19)
O4—N1—C5	117.9 (2)	C17—N3—C19	109.7 (2)
O3—N1—C5	118.0 (2)	C15—N3—C19	109.7 (2)
O2—C1—O1	125.6 (2)	C17—N3—H3N	105 (2)
O2—C1—C2	119.0 (2)	C15—N3—H3N	110 (2)
O1—C1—C2	115.4 (2)	C19—N3—H3N	114 (2)
C3—C2—C7	120.3 (2)	C20—N4—C16	109.6 (2)
C3—C2—C1	119.7 (2)	C20—N4—C18	109.5 (2)
C7—C2—C1	120.0 (2)	C16—N4—C18	108.9 (2)
C2—C3—C4	120.2 (2)	C20—N4—H4N	103 (2)
C2—C3—H3A	119.9	C16—N4—H4N	111 (2)
C4—C3—H3A	119.9	C18—N4—H4N	115 (2)
C5—C4—C3	118.2 (2)	N3—C15—C16	108.8 (2)
C5—C4—H4A	120.9	N3—C15—H15A	109.9
C3—C4—H4A	120.9	C16—C15—H15A	109.9
C6—C5—C4	123.2 (2)	N3—C15—H15B	109.9
C6—C5—N1	118.9 (2)	C16—C15—H15B	109.9
C4—C5—N1	117.9 (2)	H15A—C15—H15B	108.3
C5—C6—C7	117.9 (2)	N4—C16—C15	108.4 (2)
C5—C6—H6	121.1	N4—C16—H16A	110.0
C7—C6—H6	121.1	C15—C16—H16A	110.0
C6—C7—C2	120.3 (2)	N4—C16—H16B	110.0
C6—C7—H7	119.8	C15—C16—H16B	110.0
C2—C7—H7	119.8	H16A—C16—H16B	108.4
O8—N2—O7	124.1 (2)	N3—C17—C18	109.0 (2)
O8—N2—C12	118.0 (2)	N3—C17—H17A	109.9
O7—N2—C12	118.0 (2)	C18—C17—H17A	109.9
O6—C8—O5	125.5 (2)	N3—C17—H17B	109.9
O6—C8—C9	119.2 (2)	C18—C17—H17B	109.9
O5—C8—C9	115.3 (2)	H17A—C17—H17B	108.3
C10—C9—C14	120.2 (2)	N4—C18—C17	108.3 (2)
C10—C9—C8	120.2 (2)	N4—C18—H18A	110.0
C14—C9—C8	119.6 (2)	C17—C18—H18A	110.0
C9—C10—C11	120.0 (2)	N4—C18—H18B	110.0
C9—C10—H10	120.0	C17—C18—H18B	110.0
C11—C10—H10	120.0	H18A—C18—H18B	108.4
C12—C11—C10	118.5 (2)	N3—C19—C20	108.2 (2)
C12—C11—H11	120.8	N3—C19—H19A	110.1
C10—C11—H11	120.8	C20—C19—H19A	110.1
C11—C12—C13	122.9 (2)	N3—C19—H19B	110.1
C11—C12—N2	117.8 (2)	C20—C19—H19B	110.1
C13—C12—N2	119.3 (2)	H19A—C19—H19B	108.4
C12—C13—C14	117.9 (2)	N4—C20—C19	109.0 (2)
C12—C13—H13	121.1	N4—C20—H20A	109.9
C14—C13—H13	121.1	C19—C20—H20A	109.9
C13—C14—C9	120.5 (2)	N4—C20—H20B	109.9
C13—C14—H14	119.7	C19—C20—H20B	109.9
C9—C14—H14	119.7	H20A—C20—H20B	108.3
O2—C1—C2—C3	6.3 (4)	C10—C11—C12—N2	−179.8 (2)
O1—C1—C2—C3	−173.0 (2)	O8—N2—C12—C11	−172.9 (2)
O2—C1—C2—C7	−173.4 (2)	O7—N2—C12—C11	7.4 (3)
O1—C1—C2—C7	7.3 (3)	O8—N2—C12—C13	7.4 (3)
C7—C2—C3—C4	−1.2 (4)	O7—N2—C12—C13	−172.3 (2)
C1—C2—C3—C4	179.1 (2)	C11—C12—C13—C14	−0.1 (4)
C2—C3—C4—C5	0.5 (4)	N2—C12—C13—C14	179.7 (2)
C3—C4—C5—C6	0.3 (4)	C12—C13—C14—C9	0.2 (4)
C3—C4—C5—N1	178.4 (2)	C10—C9—C14—C13	−0.2 (4)
O4—N1—C5—C6	170.3 (2)	C8—C9—C14—C13	178.0 (2)
O3—N1—C5—C6	−9.1 (4)	C17—N3—C15—C16	50.7 (3)
O4—N1—C5—C4	−7.9 (3)	C19—N3—C15—C16	−69.2 (3)
O3—N1—C5—C4	172.7 (2)	C20—N4—C16—C15	50.2 (3)
C4—C5—C6—C7	−0.3 (4)	C18—N4—C16—C15	−69.6 (3)
N1—C5—C6—C7	−178.4 (2)	N3—C15—C16—N4	15.8 (3)
C5—C6—C7—C2	−0.4 (4)	C15—N3—C17—C18	−69.4 (2)
C3—C2—C7—C6	1.1 (4)	C19—N3—C17—C18	50.5 (3)
C1—C2—C7—C6	−179.2 (2)	C20—N4—C18—C17	−68.8 (3)
O6—C8—C9—C10	−2.6 (4)	C16—N4—C18—C17	51.1 (3)
O5—C8—C9—C10	177.5 (2)	N3—C17—C18—N4	15.8 (3)
O6—C8—C9—C14	179.2 (2)	C17—N3—C19—C20	−68.8 (3)
O5—C8—C9—C14	−0.7 (4)	C15—N3—C19—C20	50.6 (3)
C14—C9—C10—C11	0.1 (4)	C16—N4—C20—C19	−68.9 (3)
C8—C9—C10—C11	−178.1 (2)	C18—N4—C20—C19	50.5 (3)
C9—C10—C11—C12	0.0 (4)	N3—C19—C20—N4	15.6 (3)
C10—C11—C12—C13	0.0 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3N···O1	0.88 (2)	1.66 (2)	2.539 (3)	173 (2)
N4—H4N···O5	0.89 (2)	1.65 (2)	2.542 (3)	175 (3)
C15—H15A···O6^i	0.99	2.42	3.193 (3)	134
C16—H16A···O4^ii	0.99	2.42	3.375 (3)	161
C17—H17A···O7^iii	0.99	2.42	3.338 (3)	153
C17—H17B···O6^i	0.99	2.42	3.313 (3)	149
C20—H20A···O2^iv	0.99	2.41	3.043 (3)	121
C20—H20B···O8^v	0.99	2.42	3.339 (3)	154

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