Crystal structure of 3,6,6-trimethyl-4-oxo-1-(pyridin-2-yl)-4,5,6,7-tetra­hydro-1H-indazol-7-aminium chloride and its monohydrate

In the title compounds 1 and 2, the organic moieties adopt flattened conformations stabilized by an intra­molecular N—H...N hydrogen bonds formed by the protonated amino group and the N atom of the pyridyl substituent. In 1, the organic moieties are linked with two N—H...Cl⁻-type hydrogen bonds, forming a C(4) graph-set. In its monohydrate, 2, the Cl⁻ anion and a water mol­ecule assemble the moieties into infinite bands showing hydrogen-bond patterns with graph sets C(6), (12) and (8). Both crystals display π–π stacked supra­molecular structures running along the b axis.

Key indicators

Structure: 1

• Single-crystal X-ray study
• T = 190 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.043
• wR factor = 0.101
• Data-to-parameter ratio = 17.0

Structure: 2

• Single-crystal X-ray study
• T = 190 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.039
• wR factor = 0.102
• Data-to-parameter ratio = 16.0

checkCIF/PLATON results

No syntax errors found



Datablock: 1


Alert level C
PLAT906_ALERT_3_C Large K Value in the Analysis of Variance ......      2.521 Check
PLAT911_ALERT_3_C Missing FCF Refl Between Thmin & STh/L=    0.600          9 Report

Alert level G
PLAT128_ALERT_4_G Alternate Setting for Input Space Group  P21/c        P21/n Note
PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels ..........          3 Note
PLAT793_ALERT_4_G Model has Chirality at C5          (Centro SPGR)          R Verify
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min).          3 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600          9 Note
PLAT913_ALERT_3_G Missing # of Very Strong Reflections in FCF ....          3 Note
PLAT933_ALERT_2_G Number of OMIT Records in Embedded .res File ...          1 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.         15 Info

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   2 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

   0 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
   4 ALERT type 3 Indicator that the structure quality may be low
   4 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check




Datablock: 2


Alert level C
PLAT480_ALERT_4_C Long H...A H-Bond Reported H12      ..CL1              2.90 Ang.
PLAT906_ALERT_3_C Large K Value in the Analysis of Variance ......      2.468 Check
PLAT910_ALERT_3_C Missing # of FCF Reflection(s) Below Theta(Min).          8 Note
PLAT911_ALERT_3_C Missing FCF Refl Between Thmin & STh/L=    0.600         12 Report

Alert level G
PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels ..........          3 Note
PLAT793_ALERT_4_G Model has Chirality at C5          (Centro SPGR)          R Verify
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         85 Note
PLAT913_ALERT_3_G Missing # of Very Strong Reflections in FCF ....          1 Note
PLAT933_ALERT_2_G Number of OMIT Records in Embedded .res File ...         12 Note
PLAT955_ALERT_1_G Reported (CIF) and Actual (FCF) Lmax Differ by .          1 Units
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          5 Info

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

   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
   4 ALERT type 3 Indicator that the structure quality may be low
   4 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

---

Computing details

For both structures, data collection: COLLECT (Bruker, 2004); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL2017 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: publCIF (Westrip, 2010).

3,6,6-Trimethyl-4-oxo-1-(pyridin-2-yl)-4,5,6,7-tetrahydro-1H-indazol-7-aminium chloride (1)

Crystal data

C15H19N4O^+·Cl^−	F(000) = 648
Mr = 306.79	Dx = 1.328 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 13.5411 (4) Å	Cell parameters from 6801 reflections
b = 7.7421 (2) Å	θ = 1.0–27.5°
c = 19.2457 (5) Å	µ = 0.25 mm^−1
β = 130.493 (2)°	T = 190 K
V = 1534.39 (8) Å^3	Block, colourless
Z = 4	0.38 × 0.32 × 0.15 mm

Data collection

Nonius KappaCCD diffractometer	Rint = 0.027
Radiation source: fine-focus sealed tube	θmax = 27.5°, θmin = 3.0°
CCD scans	h = −17→17
5860 measured reflections	k = −10→9
3486 independent reflections	l = −24→24
2715 reflections with I > 2σ(I)

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.043	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.101	w = 1/[σ^2(Fo^2) + (0.0363P)^2 + 0.7495P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.001
3486 reflections	Δρmax = 0.29 e Å^−3
205 parameters	Δρmin = −0.25 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
Cl1	0.63264 (4)	0.65297 (6)	0.33536 (3)	0.03342 (14)
O1	0.98736 (12)	−0.08281 (19)	0.66919 (8)	0.0361 (3)
N3	0.59725 (12)	0.17416 (17)	0.53425 (8)	0.0187 (3)
N4	0.65309 (13)	0.13670 (18)	0.62325 (9)	0.0219 (3)
C4	0.67526 (15)	0.1258 (2)	0.51633 (10)	0.0193 (3)
N2	0.41873 (13)	0.26763 (19)	0.38981 (9)	0.0230 (3)
C12	0.42625 (16)	0.3337 (2)	0.51532 (11)	0.0232 (4)
H12	0.471148	0.327724	0.577688	0.028*
C11	0.47588 (15)	0.2621 (2)	0.47773 (10)	0.0190 (3)
N1	0.55052 (14)	0.0192 (2)	0.35950 (9)	0.0220 (3)
C13	0.30686 (17)	0.4145 (2)	0.45593 (12)	0.0282 (4)
H13	0.267881	0.460408	0.477604	0.034*
C3	0.78494 (15)	0.0540 (2)	0.59559 (10)	0.0211 (3)
C6	0.78026 (16)	0.1295 (2)	0.44709 (11)	0.0246 (4)
C15	0.30553 (16)	0.3529 (2)	0.33478 (12)	0.0276 (4)
H15	0.265092	0.362741	0.273282	0.033*
C8	0.88681 (16)	−0.0231 (2)	0.59948 (11)	0.0244 (4)
C5	0.65109 (15)	0.1485 (2)	0.42887 (10)	0.0207 (3)
H5	0.616867	0.265008	0.405413	0.025*
C2	0.76718 (16)	0.0664 (2)	0.66070 (11)	0.0224 (4)
C10	0.75046 (18)	0.1108 (3)	0.35558 (12)	0.0325 (4)
H10A	0.830139	0.113448	0.366104	0.049*
H10B	0.695686	0.204248	0.315864	0.049*
H10C	0.706960	0.002985	0.327613	0.049*
C14	0.24569 (17)	0.4268 (2)	0.36430 (13)	0.0297 (4)
H14	0.166419	0.483251	0.323640	0.036*
C7	0.85647 (16)	−0.0288 (2)	0.50865 (11)	0.0253 (4)
H7A	0.806434	−0.132217	0.476113	0.030*
H7B	0.937384	−0.037310	0.520035	0.030*
C1	0.85803 (17)	0.0141 (3)	0.75907 (11)	0.0312 (4)
H1A	0.809647	−0.005846	0.778844	0.047*
H1B	0.920174	0.104542	0.795200	0.047*
H1C	0.902572	−0.089806	0.766326	0.047*
C9	0.86206 (17)	0.2931 (2)	0.49510 (13)	0.0301 (4)
H9A	0.815252	0.391477	0.456570	0.045*
H9B	0.942494	0.281965	0.507027	0.045*
H9C	0.879617	0.308100	0.551734	0.045*
H1N1	0.487 (2)	0.000 (3)	0.3670 (14)	0.046 (6)*
H2N1	0.503 (2)	0.062 (3)	0.2980 (16)	0.054 (7)*
H3N1	0.584 (2)	−0.088 (3)	0.3627 (14)	0.042 (6)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0363 (3)	0.0353 (3)	0.0225 (2)	0.0052 (2)	0.01632 (19)	−0.00482 (19)
O1	0.0235 (7)	0.0442 (8)	0.0281 (6)	0.0113 (6)	0.0113 (6)	0.0038 (6)
N3	0.0190 (7)	0.0211 (7)	0.0168 (6)	0.0005 (6)	0.0119 (5)	0.0004 (6)
N4	0.0244 (7)	0.0234 (7)	0.0184 (6)	−0.0002 (6)	0.0141 (6)	0.0012 (6)
C4	0.0189 (8)	0.0186 (8)	0.0210 (7)	−0.0011 (6)	0.0132 (7)	−0.0020 (7)
N2	0.0207 (7)	0.0263 (7)	0.0216 (7)	0.0011 (6)	0.0136 (6)	0.0027 (6)
C12	0.0272 (9)	0.0200 (8)	0.0268 (8)	0.0003 (7)	0.0195 (7)	0.0005 (7)
C11	0.0189 (8)	0.0157 (8)	0.0232 (8)	−0.0015 (6)	0.0140 (7)	−0.0004 (7)
N1	0.0204 (7)	0.0266 (8)	0.0191 (7)	0.0023 (6)	0.0129 (6)	−0.0013 (6)
C13	0.0299 (9)	0.0235 (9)	0.0400 (10)	0.0021 (8)	0.0267 (8)	−0.0010 (8)
C3	0.0187 (8)	0.0209 (8)	0.0194 (7)	−0.0011 (7)	0.0105 (6)	−0.0019 (7)
C6	0.0218 (8)	0.0297 (9)	0.0264 (8)	0.0031 (7)	0.0176 (7)	0.0007 (8)
C15	0.0230 (8)	0.0299 (9)	0.0252 (8)	0.0022 (8)	0.0136 (7)	0.0063 (8)
C8	0.0203 (8)	0.0213 (8)	0.0254 (8)	−0.0005 (7)	0.0122 (7)	−0.0016 (7)
C5	0.0205 (8)	0.0220 (8)	0.0212 (7)	0.0022 (7)	0.0143 (7)	0.0010 (7)
C2	0.0214 (8)	0.0212 (8)	0.0201 (8)	−0.0022 (7)	0.0114 (7)	−0.0010 (7)
C10	0.0285 (9)	0.0455 (12)	0.0315 (9)	0.0064 (9)	0.0230 (8)	0.0043 (9)
C14	0.0224 (9)	0.0245 (9)	0.0379 (10)	0.0048 (7)	0.0176 (8)	0.0055 (8)
C7	0.0198 (8)	0.0281 (9)	0.0290 (9)	0.0042 (7)	0.0163 (7)	−0.0020 (8)
C1	0.0291 (9)	0.0364 (11)	0.0205 (8)	0.0007 (8)	0.0127 (8)	0.0025 (8)
C9	0.0251 (9)	0.0299 (10)	0.0390 (10)	0.0022 (8)	0.0224 (8)	0.0014 (8)

Geometric parameters (Å, º)

O1—C8	1.223 (2)	C6—C10	1.537 (2)
N3—C4	1.360 (2)	C6—C7	1.544 (2)
N3—N4	1.3811 (18)	C6—C5	1.552 (2)
N3—C11	1.424 (2)	C15—C14	1.380 (3)
N4—C2	1.325 (2)	C15—H15	0.9300
C4—C3	1.378 (2)	C8—C7	1.515 (2)
C4—C5	1.502 (2)	C5—H5	0.9800
N2—C11	1.328 (2)	C2—C1	1.496 (2)
N2—C15	1.341 (2)	C10—H10A	0.9600
C12—C13	1.383 (2)	C10—H10B	0.9600
C12—C11	1.383 (2)	C10—H10C	0.9600
C12—H12	0.9300	C14—H14	0.9300
N1—C5	1.509 (2)	C7—H7A	0.9700
N1—H1N1	0.97 (2)	C7—H7B	0.9700
N1—H2N1	0.97 (2)	C1—H1A	0.9600
N1—H3N1	0.93 (2)	C1—H1B	0.9600
C13—C14	1.381 (3)	C1—H1C	0.9600
C13—H13	0.9300	C9—H9A	0.9600
C3—C2	1.424 (2)	C9—H9B	0.9600
C3—C8	1.459 (2)	C9—H9C	0.9600
C6—C9	1.535 (3)
C4—N3—N4	111.53 (12)	C3—C8—C7	114.43 (14)
C4—N3—C11	129.76 (13)	C4—C5—N1	109.18 (13)
N4—N3—C11	118.61 (12)	C4—C5—C6	110.02 (13)
C2—N4—N3	105.47 (13)	N1—C5—C6	111.99 (13)
N3—C4—C3	106.66 (13)	C4—C5—H5	108.5
N3—C4—C5	127.76 (14)	N1—C5—H5	108.5
C3—C4—C5	125.56 (14)	C6—C5—H5	108.5
C11—N2—C15	116.33 (14)	N4—C2—C3	110.63 (14)
C13—C12—C11	116.96 (15)	N4—C2—C1	120.64 (15)
C13—C12—H12	121.5	C3—C2—C1	128.72 (16)
C11—C12—H12	121.5	C6—C10—H10A	109.5
N2—C11—C12	125.07 (15)	C6—C10—H10B	109.5
N2—C11—N3	114.67 (13)	H10A—C10—H10B	109.5
C12—C11—N3	120.26 (14)	C6—C10—H10C	109.5
C5—N1—H1N1	110.3 (13)	H10A—C10—H10C	109.5
C5—N1—H2N1	110.9 (14)	H10B—C10—H10C	109.5
H1N1—N1—H2N1	106.3 (18)	C15—C14—C13	118.12 (16)
C5—N1—H3N1	114.2 (13)	C15—C14—H14	120.9
H1N1—N1—H3N1	107.5 (19)	C13—C14—H14	120.9
H2N1—N1—H3N1	107.3 (19)	C8—C7—C6	114.06 (14)
C14—C13—C12	119.76 (16)	C8—C7—H7A	108.7
C14—C13—H13	120.1	C6—C7—H7A	108.7
C12—C13—H13	120.1	C8—C7—H7B	108.7
C4—C3—C2	105.68 (14)	C6—C7—H7B	108.7
C4—C3—C8	121.68 (14)	H7A—C7—H7B	107.6
C2—C3—C8	132.55 (15)	C2—C1—H1A	109.5
C9—C6—C10	108.51 (15)	C2—C1—H1B	109.5
C9—C6—C7	109.37 (14)	H1A—C1—H1B	109.5
C10—C6—C7	110.59 (14)	C2—C1—H1C	109.5
C9—C6—C5	108.97 (14)	H1A—C1—H1C	109.5
C10—C6—C5	109.35 (13)	H1B—C1—H1C	109.5
C7—C6—C5	110.02 (14)	C6—C9—H9A	109.5
N2—C15—C14	123.68 (16)	C6—C9—H9B	109.5
N2—C15—H15	118.2	H9A—C9—H9B	109.5
C14—C15—H15	118.2	C6—C9—H9C	109.5
O1—C8—C3	123.57 (16)	H9A—C9—H9C	109.5
O1—C8—C7	121.97 (15)	H9B—C9—H9C	109.5
C4—N3—N4—C2	0.69 (18)	N3—C4—C5—N1	−74.7 (2)
C11—N3—N4—C2	−176.00 (14)	C3—C4—C5—N1	107.05 (18)
N4—N3—C4—C3	0.27 (18)	N3—C4—C5—C6	162.06 (16)
C11—N3—C4—C3	176.49 (15)	C3—C4—C5—C6	−16.2 (2)
N4—N3—C4—C5	−178.26 (15)	C9—C6—C5—C4	−74.59 (17)
C11—N3—C4—C5	−2.0 (3)	C10—C6—C5—C4	166.95 (14)
C15—N2—C11—C12	1.4 (2)	C7—C6—C5—C4	45.31 (18)
C15—N2—C11—N3	−178.55 (14)	C9—C6—C5—N1	163.80 (14)
C13—C12—C11—N2	1.1 (3)	C10—C6—C5—N1	45.35 (19)
C13—C12—C11—N3	−178.92 (15)	C7—C6—C5—N1	−76.29 (16)
C4—N3—C11—N2	14.7 (2)	N3—N4—C2—C3	−1.36 (18)
N4—N3—C11—N2	−169.29 (14)	N3—N4—C2—C1	177.90 (15)
C4—N3—C11—C12	−165.27 (16)	C4—C3—C2—N4	1.55 (19)
N4—N3—C11—C12	10.7 (2)	C8—C3—C2—N4	−174.86 (17)
C11—C12—C13—C14	−2.6 (3)	C4—C3—C2—C1	−177.64 (17)
N3—C4—C3—C2	−1.05 (18)	C8—C3—C2—C1	6.0 (3)
C5—C4—C3—C2	177.52 (15)	N2—C15—C14—C13	1.0 (3)
N3—C4—C3—C8	175.84 (15)	C12—C13—C14—C15	1.7 (3)
C5—C4—C3—C8	−5.6 (3)	O1—C8—C7—C6	−145.62 (17)
C11—N2—C15—C14	−2.5 (3)	C3—C8—C7—C6	36.1 (2)
C4—C3—C8—O1	177.45 (17)	C9—C6—C7—C8	62.12 (18)
C2—C3—C8—O1	−6.6 (3)	C10—C6—C7—C8	−178.44 (14)
C4—C3—C8—C7	−4.4 (2)	C5—C6—C7—C8	−57.54 (19)
C2—C3—C8—C7	171.59 (17)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12···Cl1^i	0.93	2.80	3.4470 (17)	127
C14—H14···O1^ii	0.93	2.44	3.277 (2)	150
C7—H7A···Cl1^iii	0.97	2.71	3.6401 (18)	160
C1—H1B···O1^iv	0.96	2.60	3.503 (2)	156
N1—H1N1···N4^v	0.97 (2)	2.29 (2)	3.218 (2)	161 (2)
N1—H1N1···N2	0.97 (2)	2.42 (2)	2.928 (2)	112 (2)
N1—H2N1···Cl1^vi	0.97 (2)	2.08 (2)	3.034 (2)	168 (2)
N1—H3N1···Cl1^iii	0.93 (2)	2.27 (2)	3.188 (2)	167 (2)

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

3,6,6-Trimethyl-4-oxo-1-(pyridin-2-yl)-4,5,6,7-tetrahydro-1H-indazol-7-aminium chloride monohydrate (2)

Crystal data

C15H19N4O^+·Cl^−·H2O	F(000) = 688
Mr = 324.81	Dx = 1.382 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 10.1855 (2) Å	Cell parameters from 8626 reflections
b = 7.4951 (2) Å	θ = 1.0–27.5°
c = 20.7961 (4) Å	µ = 0.26 mm^−1
β = 100.545 (1)°	T = 190 K
V = 1560.79 (6) Å^3	Block, colourless
Z = 4	0.42 × 0.25 × 0.14 mm

Data collection

Nonius KappaCCD diffractometer	Rint = 0.023
Radiation source: fine-focus sealed tube	θmax = 27.7°, θmin = 3.6°
CCD scans	h = −13→13
5549 measured reflections	k = −9→9
3552 independent reflections	l = −27→26
2874 reflections with I > 2σ(I)

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.039	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.102	w = 1/[σ^2(Fo^2) + (0.0426P)^2 + 0.794P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max < 0.001
3552 reflections	Δρmax = 0.29 e Å^−3
222 parameters	Δρmin = −0.28 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
Cl1	0.06154 (4)	0.62526 (6)	0.39636 (2)	0.02975 (13)
O1	0.45919 (12)	−0.12171 (17)	0.26173 (5)	0.0286 (3)
N2	0.33632 (13)	0.28400 (18)	0.51823 (6)	0.0210 (3)
O1W	−0.00940 (13)	0.25508 (19)	0.46352 (7)	0.0328 (3)
N3	0.48296 (12)	0.17260 (17)	0.45521 (6)	0.0159 (3)
N1	0.18153 (14)	0.01688 (19)	0.43612 (7)	0.0183 (3)
N4	0.61172 (12)	0.13967 (18)	0.44629 (6)	0.0196 (3)
C5	0.24311 (14)	0.1376 (2)	0.39147 (7)	0.0155 (3)
H5	0.223932	0.261303	0.401963	0.019*
C12	0.57141 (16)	0.3394 (2)	0.55440 (8)	0.0219 (3)
H12	0.658465	0.326736	0.547312	0.026*
C11	0.46319 (15)	0.2686 (2)	0.51150 (7)	0.0174 (3)
C4	0.39179 (14)	0.1150 (2)	0.40322 (7)	0.0153 (3)
C6	0.18454 (15)	0.1060 (2)	0.31807 (7)	0.0176 (3)
C10	0.03220 (16)	0.0870 (2)	0.30801 (8)	0.0246 (4)
H10A	0.009876	−0.020414	0.328751	0.037*
H10B	−0.003916	0.081667	0.262056	0.037*
H10C	−0.004705	0.187831	0.326935	0.037*
C9	0.21584 (16)	0.2703 (2)	0.27933 (8)	0.0227 (3)
H9A	0.180810	0.375246	0.296617	0.034*
H9B	0.175456	0.256460	0.234144	0.034*
H9C	0.310786	0.282002	0.283039	0.034*
C3	0.46350 (15)	0.0404 (2)	0.35966 (7)	0.0166 (3)
C8	0.39804 (16)	−0.0515 (2)	0.30028 (7)	0.0192 (3)
C15	0.31230 (18)	0.3783 (2)	0.56960 (8)	0.0270 (4)
H15	0.224058	0.395222	0.574240	0.032*
C7	0.24693 (16)	−0.0608 (2)	0.29224 (7)	0.0213 (3)
H7A	0.223032	−0.164981	0.315275	0.026*
H7B	0.209284	−0.075806	0.246229	0.026*
C14	0.4120 (2)	0.4514 (2)	0.61590 (8)	0.0299 (4)
H14	0.391561	0.513786	0.651450	0.036*
C13	0.54279 (19)	0.4297 (2)	0.60821 (8)	0.0280 (4)
H13	0.611825	0.475897	0.639260	0.034*
C2	0.59994 (15)	0.0631 (2)	0.38810 (7)	0.0196 (3)
C1	0.72083 (17)	0.0203 (3)	0.36008 (9)	0.0295 (4)
H1A	0.799516	0.046429	0.391767	0.044*
H1B	0.720784	0.090854	0.321550	0.044*
H1C	0.720059	−0.104005	0.348878	0.044*
H1W	−0.026 (3)	0.288 (4)	0.4977 (14)	0.063 (9)*
H2W	0.012 (3)	0.362 (4)	0.4440 (13)	0.066 (8)*
H1N1	0.1557 (19)	−0.083 (3)	0.4188 (9)	0.024 (5)*
H2N1	0.244 (2)	−0.009 (3)	0.4766 (11)	0.036 (5)*
H3N1	0.112 (2)	0.080 (3)	0.4513 (11)	0.049 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0343 (2)	0.0261 (2)	0.0301 (2)	−0.00602 (18)	0.00909 (17)	−0.00145 (17)
O1	0.0328 (7)	0.0360 (7)	0.0182 (6)	0.0076 (5)	0.0077 (5)	−0.0040 (5)
N2	0.0237 (7)	0.0214 (7)	0.0185 (6)	0.0011 (6)	0.0053 (5)	−0.0027 (6)
O1W	0.0343 (7)	0.0287 (7)	0.0385 (8)	0.0014 (6)	0.0152 (6)	−0.0051 (6)
N3	0.0144 (6)	0.0174 (6)	0.0156 (6)	−0.0002 (5)	0.0018 (5)	0.0000 (5)
N1	0.0185 (7)	0.0208 (7)	0.0162 (6)	−0.0037 (6)	0.0045 (5)	−0.0014 (6)
N4	0.0140 (6)	0.0226 (7)	0.0222 (7)	0.0005 (5)	0.0036 (5)	0.0019 (6)
C5	0.0155 (7)	0.0168 (7)	0.0143 (7)	−0.0016 (6)	0.0026 (5)	0.0007 (6)
C12	0.0250 (8)	0.0171 (7)	0.0211 (8)	−0.0021 (6)	−0.0029 (6)	0.0022 (6)
C11	0.0226 (8)	0.0141 (7)	0.0147 (7)	−0.0004 (6)	0.0018 (6)	0.0019 (6)
C4	0.0164 (7)	0.0153 (7)	0.0138 (7)	−0.0017 (6)	0.0022 (5)	0.0020 (6)
C6	0.0156 (7)	0.0224 (8)	0.0140 (7)	−0.0015 (6)	0.0003 (5)	0.0008 (6)
C10	0.0177 (8)	0.0332 (9)	0.0216 (8)	−0.0044 (7)	−0.0002 (6)	−0.0003 (7)
C9	0.0221 (8)	0.0251 (9)	0.0193 (7)	−0.0006 (7)	−0.0004 (6)	0.0054 (7)
C3	0.0185 (7)	0.0171 (7)	0.0146 (7)	0.0000 (6)	0.0039 (6)	0.0017 (6)
C8	0.0262 (8)	0.0180 (7)	0.0139 (7)	0.0015 (6)	0.0045 (6)	0.0031 (6)
C15	0.0344 (9)	0.0263 (9)	0.0222 (8)	0.0030 (7)	0.0100 (7)	−0.0024 (7)
C7	0.0244 (8)	0.0229 (8)	0.0163 (7)	−0.0042 (7)	0.0033 (6)	−0.0034 (6)
C14	0.0506 (12)	0.0225 (9)	0.0173 (7)	−0.0006 (8)	0.0079 (7)	−0.0035 (7)
C13	0.0427 (11)	0.0181 (8)	0.0189 (8)	−0.0055 (7)	−0.0061 (7)	−0.0014 (7)
C2	0.0183 (8)	0.0210 (8)	0.0201 (7)	0.0016 (6)	0.0054 (6)	0.0036 (6)
C1	0.0205 (8)	0.0392 (11)	0.0310 (9)	0.0027 (8)	0.0109 (7)	0.0000 (8)

Geometric parameters (Å, º)

O1—C8	1.2207 (19)	C6—C7	1.543 (2)
N2—C11	1.330 (2)	C10—H10A	0.9600
N2—C15	1.340 (2)	C10—H10B	0.9600
O1W—H1W	0.80 (3)	C10—H10C	0.9600
O1W—H2W	0.94 (3)	C9—H9A	0.9600
N3—C4	1.3601 (18)	C9—H9B	0.9600
N3—N4	1.3800 (17)	C9—H9C	0.9600
N3—C11	1.4196 (19)	C3—C2	1.418 (2)
N1—C5	1.5127 (19)	C3—C8	1.464 (2)
N1—H1N1	0.85 (2)	C8—C7	1.519 (2)
N1—H2N1	0.98 (2)	C15—C14	1.378 (3)
N1—H3N1	0.95 (2)	C15—H15	0.9300
N4—C2	1.325 (2)	C7—H7A	0.9700
C5—C4	1.499 (2)	C7—H7B	0.9700
C5—C6	1.5522 (19)	C14—C13	1.380 (3)
C5—H5	0.9800	C14—H14	0.9300
C12—C13	1.384 (2)	C13—H13	0.9300
C12—C11	1.390 (2)	C2—C1	1.491 (2)
C12—H12	0.9300	C1—H1A	0.9600
C4—C3	1.382 (2)	C1—H1B	0.9600
C6—C10	1.534 (2)	C1—H1C	0.9600
C6—C9	1.537 (2)
C11—N2—C15	116.89 (14)	H10B—C10—H10C	109.5
H1W—O1W—H2W	103 (3)	C6—C9—H9A	109.5
C4—N3—N4	111.34 (12)	C6—C9—H9B	109.5
C4—N3—C11	129.57 (13)	H9A—C9—H9B	109.5
N4—N3—C11	118.90 (12)	C6—C9—H9C	109.5
C5—N1—H1N1	113.5 (13)	H9A—C9—H9C	109.5
C5—N1—H2N1	111.4 (12)	H9B—C9—H9C	109.5
H1N1—N1—H2N1	106.9 (18)	C4—C3—C2	105.85 (13)
C5—N1—H3N1	108.9 (15)	C4—C3—C8	122.00 (13)
H1N1—N1—H3N1	112.7 (19)	C2—C3—C8	132.00 (14)
H2N1—N1—H3N1	102.9 (18)	O1—C8—C3	123.26 (15)
C2—N4—N3	105.71 (12)	O1—C8—C7	122.43 (14)
C4—C5—N1	110.64 (12)	C3—C8—C7	114.23 (13)
C4—C5—C6	109.76 (12)	N2—C15—C14	123.21 (17)
N1—C5—C6	112.59 (12)	N2—C15—H15	118.4
C4—C5—H5	107.9	C14—C15—H15	118.4
N1—C5—H5	107.9	C8—C7—C6	113.45 (13)
C6—C5—H5	107.9	C8—C7—H7A	108.9
C13—C12—C11	116.49 (16)	C6—C7—H7A	108.9
C13—C12—H12	121.8	C8—C7—H7B	108.9
C11—C12—H12	121.8	C6—C7—H7B	108.9
N2—C11—C12	124.81 (14)	H7A—C7—H7B	107.7
N2—C11—N3	114.70 (13)	C15—C14—C13	118.40 (16)
C12—C11—N3	120.48 (14)	C15—C14—H14	120.8
N3—C4—C3	106.48 (13)	C13—C14—H14	120.8
N3—C4—C5	128.05 (13)	C14—C13—C12	120.12 (16)
C3—C4—C5	125.34 (13)	C14—C13—H13	119.9
C10—C6—C9	107.73 (13)	C12—C13—H13	119.9
C10—C6—C7	110.38 (13)	N4—C2—C3	110.57 (13)
C9—C6—C7	109.20 (12)	N4—C2—C1	120.48 (14)
C10—C6—C5	110.21 (12)	C3—C2—C1	128.90 (15)
C9—C6—C5	108.27 (12)	C2—C1—H1A	109.5
C7—C6—C5	110.96 (12)	C2—C1—H1B	109.5
C6—C10—H10A	109.5	H1A—C1—H1B	109.5
C6—C10—H10B	109.5	C2—C1—H1C	109.5
H10A—C10—H10B	109.5	H1A—C1—H1C	109.5
C6—C10—H10C	109.5	H1B—C1—H1C	109.5
H10A—C10—H10C	109.5
C4—N3—N4—C2	0.70 (17)	N3—C4—C3—C2	−1.90 (16)
C11—N3—N4—C2	−174.73 (13)	C5—C4—C3—C2	174.12 (14)
C15—N2—C11—C12	1.5 (2)	N3—C4—C3—C8	174.09 (13)
C15—N2—C11—N3	−178.02 (14)	C5—C4—C3—C8	−9.9 (2)
C13—C12—C11—N2	1.0 (2)	C4—C3—C8—O1	−178.45 (15)
C13—C12—C11—N3	−179.50 (14)	C2—C3—C8—O1	−3.6 (3)
C4—N3—C11—N2	9.7 (2)	C4—C3—C8—C7	−1.5 (2)
N4—N3—C11—N2	−175.82 (13)	C2—C3—C8—C7	173.30 (16)
C4—N3—C11—C12	−169.86 (15)	C11—N2—C15—C14	−2.8 (2)
N4—N3—C11—C12	4.6 (2)	O1—C8—C7—C6	−148.01 (15)
N4—N3—C4—C3	0.81 (17)	C3—C8—C7—C6	35.01 (18)
C11—N3—C4—C3	175.62 (14)	C10—C6—C7—C8	179.76 (13)
N4—N3—C4—C5	−175.06 (14)	C9—C6—C7—C8	61.51 (16)
C11—N3—C4—C5	−0.3 (2)	C5—C6—C7—C8	−57.76 (16)
N1—C5—C4—N3	−72.98 (19)	N2—C15—C14—C13	1.5 (3)
C6—C5—C4—N3	162.17 (14)	C15—C14—C13—C12	1.2 (3)
N1—C5—C4—C3	111.88 (16)	C11—C12—C13—C14	−2.3 (2)
C6—C5—C4—C3	−13.0 (2)	N3—N4—C2—C3	−1.93 (17)
C4—C5—C6—C10	167.33 (13)	N3—N4—C2—C1	175.62 (15)
N1—C5—C6—C10	43.61 (17)	C4—C3—C2—N4	2.45 (18)
C4—C5—C6—C9	−75.07 (15)	C8—C3—C2—N4	−172.97 (15)
N1—C5—C6—C9	161.21 (13)	C4—C3—C2—C1	−174.84 (17)
C4—C5—C6—C7	44.75 (16)	C8—C3—C2—C1	9.7 (3)
N1—C5—C6—C7	−78.96 (15)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12···Cl1^i	0.93	2.90	3.7006 (17)	145
C14—H14···O1^ii	0.93	2.41	3.244 (2)	149
O1W—H1W···Cl1^iii	0.80 (3)	2.39 (3)	3.185 (2)	176 (3)
O1W—H2W···Cl1	0.94 (3)	2.31 (3)	3.247 (2)	179 (2)
N1—H1N1···Cl1^iv	0.85 (2)	2.40 (2)	3.228 (2)	165 (2)
N1—H2N1···N4^v	0.98 (2)	2.20 (2)	3.1475 (19)	164 (2)
N1—H3N1···O1W	0.95 (2)	1.85 (3)	2.775 (2)	162 (2)

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