Crystal water as the mol­ecular glue for obtaining different co-crystal ratios: the case of gallic acid tris-caffeine hexa­hydrate

This co-crystal structure consists of three caffeine mol­ecules and one gallic acid mol­ecule as well as six hydrate water mol­ecules per formula unit. It can be described as being composed of two types of mol­ecular layers connected via hydrogen-bonding inter­actions to solvent water. The two layers stack in an alternate manner between layers consisting solely of caffeine mol­ecules and layers of caffeine and gallic acid mol­ecules.

Key indicators

• Single-crystal X-ray study
• T = 150 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.033
• wR factor = 0.086
• Data-to-parameter ratio = 14.8

checkCIF/PLATON results

No syntax errors found



Datablock: I


Alert level B
PLAT934_ALERT_3_B Number of (Iobs-Icalc)/SigmaW > 10 Outliers ....          2 Check

Alert level C
PLAT480_ALERT_4_C Long H...A H-Bond Reported H30C     ..O12              2.71 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H42      ..O72              2.66 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H10D     ..O10              2.74 Ang.
PLAT910_ALERT_3_C Missing # of FCF Reflection(s) Below Theta(Min).          5 Note
PLAT915_ALERT_3_C No Flack x Check Done: Low Friedel Pair Coverage         84 %

Alert level G
PLAT012_ALERT_1_G No       _shelx_res_checksum Found in CIF ......     Please Check
PLAT042_ALERT_1_G Calc. and Reported MoietyFormula Strings  Differ     Please Check
PLAT063_ALERT_4_G Crystal Size Likely too Large for Beam Size ....       0.66 mm
PLAT066_ALERT_1_G Predicted and Reported Tmin&Tmax Range Identical          ? Check
PLAT380_ALERT_4_G Incorrectly? Oriented X(sp2)-Methyl Moiety .....        C33 Check
PLAT802_ALERT_4_G CIF Input Record(s) with more than 80 Characters          1 Info
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600        346 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          9 Info

   0 ALERT level A = Most likely a serious problem - resolve or explain
   1 ALERT level B = A potentially serious problem, consider carefully
   5 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
   1 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
   7 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

---

Computing details

Data collection: CrysAlis PRO (Rigaku OD, 2015); cell refinement: CrysAlis PRO (Rigaku OD, 2015); data reduction: CrysAlis PRO (Rigaku OD, 2015); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Gallic Acid Tris-Caffeine hexahydrate

Crystal data

C7H6O5·3C8H10N4O2·6H2O	F(000) = 908
Mr = 860.81	Dx = 1.501 Mg m^−3
Monoclinic, Pc	Mo Kα radiation, λ = 0.71073 Å
a = 16.5434 (3) Å	Cell parameters from 27647 reflections
b = 6.79456 (11) Å	θ = 3.0–29.6°
c = 18.1390 (4) Å	µ = 0.12 mm^−1
β = 110.865 (2)°	T = 150 K
V = 1905.21 (7) Å^3	Plate, clear colourless
Z = 2	0.66 × 0.37 × 0.06 mm

Data collection

Rigaku Oxford Diffraction Xcalibur, Atlas, Gemini ultra diffractometer	8931 reflections with I > 2σ(I)
Detector resolution: 10.3968 pixels mm^-1	Rint = 0.029
ω scans	θmax = 29.6°, θmin = 3.0°
Absorption correction: analytical (CrysAlisPro; Rigaku OD, 2015)	h = −21→22
Tmin = 0.946, Tmax = 0.994	k = −9→9
38532 measured reflections	l = −25→24
9519 independent reflections

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.033	w = 1/[σ^2(Fo^2) + (0.051P)^2 + 0.2608P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.086	(Δ/σ)max < 0.001
S = 1.04	Δρmax = 0.24 e Å^−3
9519 reflections	Δρmin = −0.23 e Å^−3
645 parameters	Absolute structure: Flack x determined using 4000 quotients [(I^+)-(I^-)]/[(I^+)+(I^-)] (Parsons et al., 2013)
2 restraints	Absolute structure parameter: −0.1 (2)
Primary atom site location: dual

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
O12	0.64601 (10)	0.3426 (2)	0.43298 (9)	0.0237 (3)
O74	0.39816 (11)	0.9622 (2)	0.29064 (9)	0.0249 (3)
O10	0.53021 (10)	0.3054 (3)	0.63346 (9)	0.0250 (3)
O72	0.66076 (10)	0.8227 (3)	0.48111 (10)	0.0279 (3)
O102	0.71299 (11)	0.3149 (3)	0.74098 (9)	0.0259 (3)
O11	0.66635 (9)	0.2955 (2)	0.58370 (9)	0.0241 (3)
O32	0.19013 (10)	0.3831 (2)	0.67800 (9)	0.0257 (3)
O34	−0.00090 (10)	0.4828 (2)	0.42738 (9)	0.0259 (3)
O54	1.06258 (11)	0.9604 (3)	0.70872 (10)	0.0289 (3)
O1	0.33315 (11)	0.4973 (3)	0.29402 (10)	0.0292 (4)
O100	0.61941 (12)	0.6181 (3)	0.77785 (10)	0.0266 (3)
O105	0.44257 (11)	0.7234 (3)	0.69929 (10)	0.0288 (3)
O52	1.14078 (10)	0.9016 (3)	0.49147 (10)	0.0300 (4)
O2	0.27018 (10)	0.4707 (3)	0.38411 (10)	0.0300 (4)
O104	0.38756 (11)	0.3238 (3)	0.66710 (11)	0.0312 (4)
O101	0.74791 (12)	0.9351 (3)	0.79622 (11)	0.0325 (4)
N27	0.09392 (11)	0.4384 (3)	0.55358 (11)	0.0200 (3)
N41	0.88046 (12)	1.0593 (3)	0.59097 (11)	0.0210 (3)
N23	−0.09763 (11)	0.5534 (3)	0.63666 (10)	0.0203 (3)
N67	0.52922 (11)	0.8905 (3)	0.38714 (11)	0.0201 (3)
N21	−0.13658 (11)	0.5677 (3)	0.50514 (10)	0.0187 (3)
N61	0.32462 (12)	0.9330 (3)	0.42452 (11)	0.0216 (4)
N63	0.41353 (12)	0.8759 (3)	0.54870 (11)	0.0221 (4)
O103	0.86742 (14)	0.4935 (4)	0.77642 (12)	0.0486 (6)
N45	1.00201 (12)	0.9877 (3)	0.46922 (11)	0.0213 (4)
N47	1.10076 (11)	0.9323 (3)	0.59887 (11)	0.0221 (4)
N43	0.85646 (11)	1.0770 (3)	0.46163 (11)	0.0223 (4)
N25	0.05332 (11)	0.4685 (3)	0.66583 (10)	0.0200 (3)
N65	0.54639 (11)	0.8526 (3)	0.52143 (10)	0.0193 (3)
C9	0.49273 (13)	0.4032 (3)	0.39853 (12)	0.0182 (4)
C28	0.01160 (13)	0.4814 (3)	0.49805 (12)	0.0185 (4)
C68	0.43992 (14)	0.9264 (3)	0.36060 (12)	0.0193 (4)
C64	0.45928 (13)	0.8801 (3)	0.49996 (12)	0.0188 (4)
C5	0.43204 (13)	0.3818 (3)	0.50144 (12)	0.0185 (4)
C22	−0.16156 (14)	0.5854 (3)	0.56754 (12)	0.0204 (4)
C4	0.42193 (13)	0.4139 (3)	0.42310 (12)	0.0180 (4)
C26	0.11628 (13)	0.4278 (3)	0.63532 (12)	0.0198 (4)
C3	0.33445 (14)	0.4627 (3)	0.36677 (12)	0.0202 (4)
C42	0.82336 (14)	1.0955 (3)	0.51858 (13)	0.0227 (4)
C62	0.33233 (14)	0.9082 (3)	0.49978 (13)	0.0241 (4)
C6	0.51354 (13)	0.3398 (3)	0.55560 (12)	0.0189 (4)
C29	−0.04957 (13)	0.5192 (3)	0.53528 (12)	0.0181 (4)
C24	−0.02878 (13)	0.5128 (3)	0.61509 (12)	0.0182 (4)
C8	0.57394 (13)	0.3606 (3)	0.45261 (12)	0.0184 (4)
C69	0.40732 (13)	0.9150 (3)	0.42277 (12)	0.0185 (4)
C7	0.58546 (13)	0.3319 (3)	0.53187 (12)	0.0183 (4)
C49	0.95774 (13)	1.0134 (3)	0.58130 (13)	0.0190 (4)
C48	1.04131 (14)	0.9686 (3)	0.63709 (13)	0.0217 (4)
C46	1.08429 (14)	0.9386 (3)	0.51791 (13)	0.0219 (4)
C30	−0.19092 (13)	0.5917 (3)	0.42252 (12)	0.0208 (4)
H30A	−0.195314	0.465826	0.394977	0.031*
H30B	−0.165253	0.690518	0.398138	0.031*
H30C	−0.248743	0.634908	0.418844	0.031*
C44	0.94005 (13)	1.0249 (3)	0.50165 (12)	0.0197 (4)
C66	0.58361 (14)	0.8529 (3)	0.46485 (13)	0.0206 (4)
C71	0.60075 (14)	0.8227 (3)	0.60429 (13)	0.0258 (4)
H71A	0.578830	0.903248	0.637924	0.039*
H71B	0.660364	0.861399	0.612352	0.039*
H71C	0.599411	0.683589	0.618036	0.039*
C31	0.07288 (15)	0.4634 (4)	0.75120 (13)	0.0263 (4)
H31A	0.049780	0.341920	0.765162	0.039*
H31B	0.046261	0.577200	0.766781	0.039*
H31C	0.135692	0.467660	0.778760	0.039*
C51	0.98219 (16)	0.9950 (4)	0.38378 (14)	0.0280 (5)
H51A	1.028745	1.063988	0.372886	0.042*
H51B	0.927512	1.065112	0.358458	0.042*
H51C	0.977081	0.860691	0.362901	0.042*
C50	0.86261 (17)	1.0583 (4)	0.66409 (15)	0.0284 (5)
C33	0.16380 (14)	0.4060 (4)	0.52176 (14)	0.0259 (5)
H33A	0.148733	0.294353	0.485177	0.039*
H33B	0.218050	0.377880	0.565271	0.039*
H33C	0.170850	0.524415	0.493788	0.039*
C53	1.19054 (14)	0.8887 (4)	0.64940 (15)	0.0301 (5)
H53A	1.225454	1.008608	0.656930	0.045*
H53B	1.214230	0.787698	0.624216	0.045*
H53C	1.191737	0.840579	0.700719	0.045*
C73	0.57111 (16)	0.8896 (4)	0.32820 (15)	0.0292 (5)
H73A	0.573261	0.754593	0.309962	0.044*
H73B	0.630055	0.941262	0.351905	0.044*
H73C	0.538002	0.972313	0.283348	0.044*
H5	0.3845 (19)	0.391 (4)	0.5203 (16)	0.022 (6)*
H9	0.4873 (17)	0.424 (4)	0.3426 (16)	0.017 (6)*
H22	−0.220 (2)	0.629 (4)	0.5596 (17)	0.030 (7)*
H1	0.282 (2)	0.521 (5)	0.2629 (19)	0.035 (8)*
H12	0.631 (2)	0.369 (4)	0.3832 (19)	0.031 (7)*
H62	0.284 (2)	0.912 (5)	0.5170 (18)	0.035 (8)*
H10	0.482 (3)	0.308 (6)	0.641 (2)	0.061 (11)*
C70	0.24418 (15)	0.9659 (4)	0.35795 (14)	0.0265 (4)
H70A	0.194877	0.947555	0.375199	0.040*
H70B	0.240186	0.871975	0.315813	0.040*
H70C	0.243510	1.100411	0.338199	0.040*
H42	0.767 (2)	1.131 (4)	0.5092 (18)	0.033 (7)*
H11	0.669 (2)	0.304 (5)	0.630 (2)	0.041 (9)*
H10G	0.392 (2)	0.449 (5)	0.6864 (19)	0.036 (8)*
H10E	0.425 (3)	0.802 (6)	0.728 (3)	0.062 (11)*
H10F	0.436 (2)	0.781 (6)	0.654 (2)	0.053 (10)*
H10A	0.718 (2)	0.192 (6)	0.760 (2)	0.056 (10)*
H10I	0.781 (2)	0.915 (5)	0.850 (2)	0.039 (8)*
H10C	0.568 (3)	0.622 (6)	0.746 (2)	0.055 (11)*
H10D	0.634 (2)	0.518 (5)	0.7604 (19)	0.034 (8)*
H10B	0.763 (2)	0.367 (5)	0.7558 (19)	0.033 (8)*
H10K	0.905 (3)	0.515 (7)	0.816 (3)	0.076 (14)*
H10L	0.881 (3)	0.528 (6)	0.738 (3)	0.072 (13)*
H10H	0.389 (3)	0.243 (7)	0.709 (3)	0.077 (13)*
H10J	0.714 (3)	0.832 (6)	0.788 (2)	0.057 (11)*
H50A	0.868 (2)	0.928 (5)	0.683 (2)	0.044 (9)*
H50B	0.803 (3)	1.094 (6)	0.651 (2)	0.063 (11)*
H50C	0.902 (3)	1.156 (5)	0.701 (2)	0.055 (10)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O12	0.0148 (7)	0.0379 (8)	0.0204 (7)	0.0037 (6)	0.0089 (6)	0.0030 (6)
O74	0.0245 (8)	0.0298 (7)	0.0219 (7)	−0.0003 (6)	0.0102 (6)	0.0024 (6)
O10	0.0172 (7)	0.0413 (9)	0.0174 (7)	0.0025 (6)	0.0073 (6)	0.0042 (6)
O72	0.0165 (7)	0.0332 (8)	0.0358 (9)	0.0021 (6)	0.0117 (6)	−0.0004 (7)
O102	0.0174 (8)	0.0367 (9)	0.0231 (7)	−0.0010 (7)	0.0065 (6)	−0.0007 (7)
O11	0.0138 (7)	0.0391 (9)	0.0191 (7)	0.0056 (6)	0.0055 (6)	0.0018 (6)
O32	0.0144 (7)	0.0329 (8)	0.0264 (8)	0.0030 (6)	0.0030 (6)	−0.0036 (6)
O34	0.0196 (7)	0.0384 (9)	0.0206 (7)	0.0012 (6)	0.0081 (6)	−0.0031 (6)
O54	0.0235 (8)	0.0373 (8)	0.0233 (8)	0.0024 (7)	0.0049 (7)	−0.0005 (7)
O1	0.0149 (7)	0.0485 (10)	0.0214 (7)	0.0049 (7)	0.0031 (6)	0.0077 (7)
O100	0.0244 (9)	0.0339 (9)	0.0214 (8)	0.0019 (7)	0.0081 (7)	−0.0022 (7)
O105	0.0314 (9)	0.0353 (9)	0.0236 (8)	0.0057 (7)	0.0145 (7)	0.0029 (7)
O52	0.0197 (8)	0.0368 (9)	0.0378 (9)	0.0017 (6)	0.0154 (7)	−0.0023 (7)
O2	0.0150 (7)	0.0467 (10)	0.0282 (8)	0.0038 (7)	0.0075 (7)	0.0045 (7)
O104	0.0268 (8)	0.0426 (10)	0.0290 (8)	0.0020 (7)	0.0159 (7)	0.0003 (8)
O101	0.0279 (9)	0.0394 (10)	0.0288 (9)	−0.0025 (8)	0.0085 (7)	0.0033 (7)
N27	0.0135 (8)	0.0242 (8)	0.0233 (9)	0.0001 (6)	0.0078 (7)	−0.0025 (6)
N41	0.0172 (8)	0.0218 (8)	0.0262 (9)	0.0010 (7)	0.0104 (7)	−0.0017 (7)
N23	0.0164 (8)	0.0250 (8)	0.0203 (8)	0.0000 (7)	0.0074 (7)	−0.0001 (7)
N67	0.0185 (9)	0.0222 (8)	0.0236 (8)	0.0005 (7)	0.0122 (7)	0.0006 (7)
N21	0.0128 (8)	0.0232 (8)	0.0200 (8)	0.0001 (6)	0.0058 (7)	−0.0005 (6)
N61	0.0144 (8)	0.0278 (9)	0.0245 (9)	−0.0001 (7)	0.0094 (7)	0.0000 (7)
N63	0.0190 (9)	0.0281 (9)	0.0224 (8)	−0.0001 (7)	0.0111 (7)	0.0008 (7)
O103	0.0296 (10)	0.0955 (18)	0.0216 (9)	−0.0251 (11)	0.0102 (8)	−0.0029 (10)
N45	0.0164 (8)	0.0253 (9)	0.0234 (9)	0.0010 (7)	0.0086 (7)	−0.0011 (7)
N47	0.0121 (8)	0.0251 (8)	0.0270 (9)	0.0005 (7)	0.0046 (7)	−0.0026 (7)
N43	0.0155 (9)	0.0225 (8)	0.0268 (9)	0.0010 (6)	0.0047 (7)	−0.0012 (7)
N25	0.0146 (8)	0.0250 (8)	0.0187 (8)	0.0013 (6)	0.0038 (7)	0.0010 (6)
N65	0.0147 (8)	0.0231 (8)	0.0210 (8)	0.0011 (6)	0.0073 (7)	0.0015 (7)
C9	0.0166 (9)	0.0211 (9)	0.0177 (9)	−0.0003 (7)	0.0073 (8)	0.0000 (7)
C28	0.0156 (9)	0.0194 (9)	0.0208 (9)	−0.0013 (7)	0.0066 (8)	−0.0014 (7)
C68	0.0194 (10)	0.0170 (9)	0.0242 (10)	−0.0007 (7)	0.0110 (8)	−0.0004 (7)
C64	0.0168 (9)	0.0189 (9)	0.0223 (10)	−0.0015 (7)	0.0090 (8)	−0.0010 (7)
C5	0.0139 (9)	0.0215 (9)	0.0217 (10)	−0.0007 (7)	0.0084 (8)	−0.0001 (7)
C22	0.0156 (10)	0.0245 (10)	0.0221 (10)	−0.0005 (8)	0.0078 (8)	−0.0002 (8)
C4	0.0151 (9)	0.0179 (9)	0.0211 (9)	−0.0003 (7)	0.0066 (8)	−0.0006 (7)
C26	0.0152 (9)	0.0204 (9)	0.0227 (10)	−0.0003 (7)	0.0053 (8)	−0.0022 (8)
C3	0.0161 (9)	0.0222 (9)	0.0214 (10)	0.0000 (7)	0.0056 (8)	0.0008 (8)
C42	0.0134 (10)	0.0236 (10)	0.0307 (11)	0.0011 (7)	0.0076 (8)	−0.0013 (8)
C62	0.0176 (10)	0.0329 (11)	0.0252 (10)	0.0001 (8)	0.0118 (8)	0.0008 (8)
C6	0.0187 (9)	0.0199 (9)	0.0190 (9)	−0.0013 (7)	0.0078 (8)	−0.0009 (7)
C29	0.0128 (9)	0.0200 (9)	0.0206 (9)	−0.0006 (7)	0.0050 (7)	0.0001 (7)
C24	0.0146 (9)	0.0180 (9)	0.0218 (10)	0.0000 (7)	0.0063 (8)	0.0003 (7)
C8	0.0158 (9)	0.0196 (9)	0.0222 (10)	−0.0003 (7)	0.0097 (8)	−0.0005 (7)
C69	0.0151 (9)	0.0193 (9)	0.0225 (10)	0.0004 (7)	0.0086 (8)	0.0003 (7)
C7	0.0145 (9)	0.0196 (9)	0.0193 (9)	0.0016 (7)	0.0042 (7)	−0.0001 (7)
C49	0.0132 (9)	0.0206 (9)	0.0238 (10)	0.0003 (7)	0.0072 (8)	−0.0015 (7)
C48	0.0178 (10)	0.0189 (9)	0.0282 (11)	0.0002 (8)	0.0078 (9)	−0.0021 (8)
C46	0.0167 (10)	0.0204 (9)	0.0291 (11)	−0.0007 (7)	0.0089 (8)	−0.0022 (8)
C30	0.0144 (9)	0.0281 (10)	0.0175 (9)	0.0007 (7)	0.0028 (8)	0.0003 (8)
C44	0.0159 (9)	0.0184 (9)	0.0253 (10)	−0.0011 (7)	0.0078 (8)	−0.0025 (8)
C66	0.0187 (9)	0.0181 (9)	0.0271 (10)	0.0000 (7)	0.0107 (8)	−0.0003 (8)
C71	0.0199 (10)	0.0316 (11)	0.0235 (10)	0.0017 (9)	0.0048 (8)	0.0005 (9)
C31	0.0205 (10)	0.0381 (12)	0.0182 (10)	0.0022 (9)	0.0044 (8)	0.0024 (9)
C51	0.0279 (12)	0.0360 (12)	0.0226 (10)	−0.0008 (9)	0.0119 (9)	−0.0024 (9)
C50	0.0280 (12)	0.0328 (12)	0.0312 (12)	0.0035 (10)	0.0190 (10)	−0.0003 (10)
C33	0.0148 (10)	0.0335 (11)	0.0327 (12)	0.0018 (8)	0.0125 (9)	−0.0035 (9)
C53	0.0146 (10)	0.0324 (11)	0.0376 (13)	0.0031 (8)	0.0023 (9)	−0.0039 (10)
C73	0.0266 (12)	0.0373 (12)	0.0315 (12)	0.0016 (9)	0.0198 (10)	0.0014 (10)
C70	0.0175 (10)	0.0350 (11)	0.0255 (10)	0.0019 (9)	0.0056 (8)	0.0018 (9)

Geometric parameters (Å, º)

O12—C8	1.366 (2)	N43—C44	1.360 (3)
O12—H12	0.86 (3)	N25—C26	1.370 (3)
O74—C68	1.234 (3)	N25—C24	1.376 (3)
O10—C6	1.359 (2)	N25—C31	1.465 (3)
O10—H10	0.86 (4)	N65—C64	1.365 (3)
O72—C66	1.221 (3)	N65—C66	1.372 (3)
O102—H10A	0.89 (4)	N65—C71	1.465 (3)
O102—H10B	0.85 (4)	C9—C4	1.396 (3)
O11—C7	1.356 (2)	C9—C8	1.383 (3)
O11—H11	0.83 (4)	C9—H9	1.00 (3)
O32—C26	1.229 (3)	C28—C29	1.426 (3)
O34—C28	1.224 (3)	C68—C69	1.415 (3)
O54—C48	1.221 (3)	C64—C69	1.378 (3)
O1—C3	1.333 (3)	C5—C4	1.388 (3)
O1—H1	0.85 (3)	C5—C6	1.386 (3)
O100—H10C	0.83 (4)	C5—H5	0.97 (3)
O100—H10D	0.82 (4)	C22—H22	0.97 (3)
O105—H10E	0.86 (5)	C4—C3	1.481 (3)
O105—H10F	0.88 (4)	C42—H42	0.92 (3)
O52—C46	1.219 (3)	C62—H62	0.96 (3)
O2—C3	1.213 (3)	C6—C7	1.403 (3)
O104—H10G	0.91 (3)	C29—C24	1.364 (3)
O104—H10H	0.93 (5)	C8—C7	1.395 (3)
O101—H10I	0.94 (4)	C49—C48	1.425 (3)
O101—H10J	0.88 (4)	C49—C44	1.370 (3)
N27—C28	1.406 (3)	C30—H30A	0.9800
N27—C26	1.396 (3)	C30—H30B	0.9800
N27—C33	1.481 (3)	C30—H30C	0.9800
N41—C42	1.339 (3)	C71—H71A	0.9800
N41—C49	1.387 (3)	C71—H71B	0.9800
N41—C50	1.458 (3)	C71—H71C	0.9800
N23—C22	1.339 (3)	C31—H31A	0.9800
N23—C24	1.358 (3)	C31—H31B	0.9800
N67—C68	1.403 (3)	C31—H31C	0.9800
N67—C66	1.399 (3)	C51—H51A	0.9800
N67—C73	1.467 (3)	C51—H51B	0.9800
N21—C22	1.342 (3)	C51—H51C	0.9800
N21—C29	1.385 (3)	C50—H50A	0.94 (3)
N21—C30	1.456 (3)	C50—H50B	0.96 (4)
N61—C62	1.336 (3)	C50—H50C	1.00 (4)
N61—C69	1.385 (3)	C33—H33A	0.9800
N61—C70	1.461 (3)	C33—H33B	0.9800
N63—C64	1.353 (3)	C33—H33C	0.9800
N63—C62	1.338 (3)	C53—H53A	0.9800
O103—H10K	0.78 (5)	C53—H53B	0.9800
O103—H10L	0.84 (5)	C53—H53C	0.9800
N45—C46	1.374 (3)	C73—H73A	0.9800
N45—C44	1.375 (3)	C73—H73B	0.9800
N45—C51	1.466 (3)	C73—H73C	0.9800
N47—C48	1.412 (3)	C70—H70A	0.9800
N47—C46	1.396 (3)	C70—H70B	0.9800
N47—C53	1.471 (3)	C70—H70C	0.9800
N43—C42	1.336 (3)
C8—O12—H12	107 (2)	N23—C24—C29	112.27 (18)
C6—O10—H10	108 (3)	C29—C24—N25	122.19 (18)
H10A—O102—H10B	109 (3)	O12—C8—C9	123.47 (18)
C7—O11—H11	111 (2)	O12—C8—C7	116.40 (18)
C3—O1—H1	111 (2)	C9—C8—C7	120.14 (18)
H10C—O100—H10D	97 (3)	N61—C69—C68	132.3 (2)
H10E—O105—H10F	109 (4)	C64—C69—N61	104.82 (17)
H10G—O104—H10H	105 (3)	C64—C69—C68	122.86 (19)
H10I—O101—H10J	99 (3)	O11—C7—C6	121.96 (18)
C28—N27—C33	116.29 (17)	O11—C7—C8	118.61 (18)
C26—N27—C28	126.45 (17)	C8—C7—C6	119.43 (18)
C26—N27—C33	117.24 (17)	N41—C49—C48	131.5 (2)
C42—N41—C49	106.10 (18)	C44—C49—N41	105.08 (18)
C42—N41—C50	126.3 (2)	C44—C49—C48	123.34 (19)
C49—N41—C50	127.5 (2)	O54—C48—N47	121.84 (19)
C22—N23—C24	103.11 (17)	O54—C48—C49	127.2 (2)
C68—N67—C73	117.64 (18)	N47—C48—C49	110.97 (19)
C66—N67—C68	126.75 (17)	O52—C46—N45	121.3 (2)
C66—N67—C73	115.61 (18)	O52—C46—N47	121.2 (2)
C22—N21—C29	106.10 (17)	N45—C46—N47	117.47 (18)
C22—N21—C30	126.55 (18)	N21—C30—H30A	109.5
C29—N21—C30	127.34 (17)	N21—C30—H30B	109.5
C62—N61—C69	106.06 (18)	N21—C30—H30C	109.5
C62—N61—C70	126.25 (19)	H30A—C30—H30B	109.5
C69—N61—C70	127.66 (18)	H30A—C30—H30C	109.5
C62—N63—C64	103.07 (18)	H30B—C30—H30C	109.5
H10K—O103—H10L	110 (5)	N43—C44—N45	126.21 (19)
C46—N45—C44	119.25 (18)	N43—C44—C49	111.87 (18)
C46—N45—C51	119.00 (18)	C49—C44—N45	121.92 (18)
C44—N45—C51	121.74 (18)	O72—C66—N67	121.06 (19)
C48—N47—C53	117.03 (19)	O72—C66—N65	121.9 (2)
C46—N47—C48	127.02 (18)	N65—C66—N67	117.06 (18)
C46—N47—C53	115.92 (18)	N65—C71—H71A	109.5
C42—N43—C44	103.33 (18)	N65—C71—H71B	109.5
C26—N25—C24	119.03 (17)	N65—C71—H71C	109.5
C26—N25—C31	120.56 (18)	H71A—C71—H71B	109.5
C24—N25—C31	120.40 (17)	H71A—C71—H71C	109.5
C64—N65—C66	119.72 (17)	H71B—C71—H71C	109.5
C64—N65—C71	120.76 (17)	N25—C31—H31A	109.5
C66—N65—C71	119.51 (18)	N25—C31—H31B	109.5
C4—C9—H9	122.5 (15)	N25—C31—H31C	109.5
C8—C9—C4	119.88 (18)	H31A—C31—H31B	109.5
C8—C9—H9	117.6 (15)	H31A—C31—H31C	109.5
O34—C28—N27	120.75 (18)	H31B—C31—H31C	109.5
O34—C28—C29	127.67 (19)	N45—C51—H51A	109.5
N27—C28—C29	111.58 (17)	N45—C51—H51B	109.5
O74—C68—N67	121.51 (19)	N45—C51—H51C	109.5
O74—C68—C69	126.7 (2)	H51A—C51—H51B	109.5
N67—C68—C69	111.75 (18)	H51A—C51—H51C	109.5
N63—C64—N65	126.15 (19)	H51B—C51—H51C	109.5
N63—C64—C69	112.08 (18)	N41—C50—H50A	108 (2)
N65—C64—C69	121.77 (18)	N41—C50—H50B	107 (3)
C4—C5—H5	122.4 (16)	N41—C50—H50C	108 (2)
C6—C5—C4	119.37 (19)	H50A—C50—H50B	107 (3)
C6—C5—H5	118.2 (16)	H50A—C50—H50C	115 (3)
N23—C22—N21	113.42 (19)	H50B—C50—H50C	111 (3)
N23—C22—H22	126.9 (17)	N27—C33—H33A	109.5
N21—C22—H22	119.4 (17)	N27—C33—H33B	109.5
C9—C4—C3	121.08 (18)	N27—C33—H33C	109.5
C5—C4—C9	120.66 (18)	H33A—C33—H33B	109.5
C5—C4—C3	118.26 (18)	H33A—C33—H33C	109.5
O32—C26—N27	120.64 (19)	H33B—C33—H33C	109.5
O32—C26—N25	121.57 (19)	N47—C53—H53A	109.5
N25—C26—N27	117.80 (18)	N47—C53—H53B	109.5
O1—C3—C4	112.93 (18)	N47—C53—H53C	109.5
O2—C3—O1	122.85 (19)	H53A—C53—H53B	109.5
O2—C3—C4	124.22 (19)	H53A—C53—H53C	109.5
N41—C42—H42	123 (2)	H53B—C53—H53C	109.5
N43—C42—N41	113.62 (19)	N67—C73—H73A	109.5
N43—C42—H42	123 (2)	N67—C73—H73B	109.5
N61—C62—N63	113.97 (19)	N67—C73—H73C	109.5
N61—C62—H62	122.8 (19)	H73A—C73—H73B	109.5
N63—C62—H62	123.2 (19)	H73A—C73—H73C	109.5
O10—C6—C5	123.93 (18)	H73B—C73—H73C	109.5
O10—C6—C7	115.58 (18)	N61—C70—H70A	109.5
C5—C6—C7	120.49 (19)	N61—C70—H70B	109.5
N21—C29—C28	131.99 (19)	N61—C70—H70C	109.5
C24—C29—N21	105.09 (17)	H70A—C70—H70B	109.5
C24—C29—C28	122.92 (18)	H70A—C70—H70C	109.5
N23—C24—N25	125.54 (18)	H70B—C70—H70C	109.5

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O32^i	0.85 (3)	1.86 (3)	2.672 (2)	161 (3)
O10—H10···O104	0.86 (4)	1.79 (4)	2.643 (2)	174 (4)
O11—H11···O10	0.83 (3)	2.32 (4)	2.709 (2)	109 (3)
O11—H11···O102	0.83 (4)	1.88 (4)	2.680 (2)	161 (3)
O12—H12···O100^i	0.86 (3)	1.86 (3)	2.702 (2)	166 (3)
O100—H10C···O105	0.83 (4)	2.07 (4)	2.851 (3)	157 (4)
O100—H10D···O10	0.82 (4)	2.74 (3)	3.286 (2)	126 (3)
O100—H10D···O102	0.82 (4)	2.02 (4)	2.798 (3)	158 (3)
O101—H10I···N43^ii	0.94 (4)	1.97 (4)	2.898 (3)	170 (3)
O101—H10J···O100	0.88 (4)	2.09 (4)	2.960 (3)	170 (4)
O102—H10A···O101^iii	0.89 (4)	1.87 (4)	2.754 (3)	169 (4)
O102—H10B···O103	0.85 (4)	1.85 (4)	2.691 (3)	173 (3)
O103—H10K···O34^iv	0.78 (5)	2.06 (5)	2.832 (3)	168 (5)
O103—H10L···N23^v	0.84 (5)	1.99 (5)	2.823 (3)	168 (4)
O104—H10G···O1^vi	0.91 (3)	2.50 (3)	3.011 (2)	116 (2)
O104—H10G···O105	0.91 (3)	2.03 (3)	2.857 (3)	151 (3)
O104—H10H···O74^vi	0.93 (5)	2.00 (5)	2.924 (2)	171 (4)
O105—H10E···O74^ii	0.86 (5)	2.11 (5)	2.952 (2)	169 (4)
O105—H10F···N63	0.88 (4)	1.92 (4)	2.798 (2)	173 (4)
C22—H22···O72^vii	0.97 (3)	2.38 (3)	3.227 (3)	146 (2)
C30—H30C···O12^vii	0.98	2.71	3.247 (3)	115
C31—H31C···O2^vi	0.98	2.40	3.326 (3)	158
C42—H42···O12^viii	0.92 (3)	2.45 (3)	3.254 (3)	146 (3)
C42—H42···O72	0.92 (3)	2.66 (3)	3.136 (3)	113 (2)
C62—H62···O52^vii	0.96 (3)	2.24 (3)	3.119 (3)	151 (3)

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