Crystal structure and Hirshfeld surface analysis of the hydro­chloride salt of 8-{4-[(6-phenyl­pyridin-3-yl)meth­yl]piperazin-1-yl}-3,4-di­hydro­quinolin-2(1H)-one

The amine 8-{4-[(6-phenyl­pyridin-3-yl)meth­yl]piperazin-1-yl}-3,4-di­hydro­quinolin-2(1H)-one was crystallized as the hydro­chloride salt 4-(2-oxo-1,2,3,4-tetra­hydro­quinolin-8-yl)-1-[(6-phenyl­pyridin-3-yl)meth­yl]piperazin-1-ium chloride. Its structure is compared to that of the salt 4-(2-oxo-1,2,3,4-tetra­hydro­quinolin-8-yl)-1-{[6-(4-fluoro­phen­yl)pyridin-3-yl]meth­yl}piperazin-1-ium chloride monohydrate, a fluorinated analogue.

Key indicators

• Single-crystal X-ray study
• T = 173 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.033
• wR factor = 0.071
• Data-to-parameter ratio = 14.4

checkCIF/PLATON results

No syntax errors found



Datablock: I


Alert level C
PLAT906_ALERT_3_C Large K Value in the Analysis of Variance ......      4.607 Check
PLAT911_ALERT_3_C Missing FCF Refl Between Thmin & STh/L=    0.600          3 Report

Alert level G
PLAT802_ALERT_4_G CIF Input Record(s) with more than 80 Characters         19 Info
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600          6 Note
PLAT933_ALERT_2_G Number of OMIT Records in Embedded .res File ...          3 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          4 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
   4 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
   2 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

---

Computing details

Data collection: X-AREA (Stoe & Cie, 2009); cell refinement: X-AREA (Stoe & Cie, 2009); data reduction: X-RED32 (Stoe & Cie, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015); molecular graphics: Mercury (Macrae et al., 2020); software used to prepare material for publication: SHELXL2018/3 (Sheldrick, 2015), PLATON (Spek, 2020) and publCIF (Westrip, 2010).

4-(2-Oxo-1,2,3,4-tetrahydroquinolin-8-yl)-1-[(6-phenylpyridin-3-yl)methyl]piperazin-1-ium chloride

Crystal data

C25H27N4O^+·Cl^−	Z = 2
Mr = 434.95	F(000) = 460
Triclinic, P1	Dx = 1.312 Mg m^−3
a = 8.4791 (8) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.4091 (10) Å	Cell parameters from 9997 reflections
c = 13.6862 (14) Å	θ = 1.5–26.1°
α = 90.138 (8)°	µ = 0.20 mm^−1
β = 94.833 (8)°	T = 173 K
γ = 113.745 (7)°	Rod, colourless
V = 1100.88 (19) Å^3	0.45 × 0.33 × 0.18 mm

Data collection

Stoe IPDS 2 diffractometer	4156 independent reflections
Radiation source: fine-focus sealed tube	2912 reflections with I > 2σ(I)
Plane graphite monochromator	Rint = 0.077
φ + ω scans	θmax = 25.6°, θmin = 1.5°
Absorption correction: multi-scan (MULABS; Spek, 2020)	h = −10→9
Tmin = 0.379, Tmax = 1.000	k = −12→12
13410 measured reflections	l = −16→16

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.033	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.071	w = 1/[σ^2(Fo^2) + (0.0262P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.83	(Δ/σ)max = 0.001
4156 reflections	Δρmax = 0.22 e Å^−3
289 parameters	Δρmin = −0.22 e Å^−3
0 restraints	Extinction correction: (SHELXL-2018/3; Sheldrick, 2015), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0061 (11)

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
O1	−0.17052 (13)	0.47203 (11)	−0.07307 (8)	0.0288 (3)
N1	0.07882 (16)	0.49233 (13)	−0.13301 (10)	0.0234 (3)
H1N	0.122 (2)	0.5073 (18)	−0.0734 (13)	0.034 (5)*
N2	0.44879 (14)	0.63611 (12)	−0.11540 (9)	0.0220 (3)
N3	0.68062 (15)	0.82122 (13)	0.04180 (9)	0.0217 (3)
H3N	0.746 (2)	0.906 (2)	0.0090 (13)	0.052 (5)*
N4	0.94060 (18)	1.20937 (14)	0.25205 (11)	0.0399 (4)
C1	−0.09235 (18)	0.46487 (15)	−0.14318 (11)	0.0236 (3)
C2	−0.1799 (2)	0.42765 (18)	−0.24529 (12)	0.0329 (4)
H2A	−0.160759	0.514512	−0.280987	0.040*
H2B	−0.306002	0.375119	−0.242625	0.040*
C3	−0.1077 (2)	0.33797 (19)	−0.29954 (13)	0.0392 (4)
H3A	−0.135909	0.247286	−0.267359	0.047*
H3B	−0.160866	0.318222	−0.368136	0.047*
C4	0.0858 (2)	0.41520 (16)	−0.29844 (12)	0.0302 (4)
C5	0.1751 (2)	0.41199 (19)	−0.37763 (13)	0.0392 (4)
H5	0.114179	0.360241	−0.436140	0.047*
C6	0.3535 (2)	0.48412 (19)	−0.37196 (13)	0.0392 (4)
H6	0.414790	0.480812	−0.426264	0.047*
C7	0.4424 (2)	0.56092 (17)	−0.28716 (12)	0.0310 (4)
H7	0.564389	0.610806	−0.284514	0.037*
C8	0.35719 (18)	0.56693 (15)	−0.20549 (11)	0.0230 (3)
C9	0.17520 (18)	0.49231 (15)	−0.21240 (11)	0.0228 (3)
C10	0.63546 (18)	0.67238 (16)	−0.10867 (11)	0.0266 (4)
H10A	0.692624	0.755875	−0.147562	0.032*
H10B	0.656720	0.593449	−0.136332	0.032*
C11	0.71077 (19)	0.70267 (16)	−0.00407 (11)	0.0256 (4)
H11A	0.836721	0.727272	−0.001024	0.031*
H11B	0.657845	0.617257	0.033766	0.031*
C12	0.49249 (17)	0.79433 (16)	0.02658 (11)	0.0238 (3)
H12A	0.476973	0.878517	0.049257	0.029*
H12B	0.425884	0.715170	0.066760	0.029*
C13	0.42172 (18)	0.75986 (15)	−0.08004 (11)	0.0232 (3)
H13A	0.296647	0.739395	−0.086798	0.028*
H13B	0.481455	0.841377	−0.120110	0.028*
C14	0.74694 (19)	0.83801 (16)	0.14807 (11)	0.0271 (4)
H14A	0.863559	0.836905	0.153532	0.033*
H14B	0.670376	0.755999	0.182549	0.033*
C15	0.75825 (19)	0.96984 (16)	0.19971 (11)	0.0259 (4)
C16	0.6286 (2)	0.97397 (16)	0.25369 (11)	0.0276 (4)
H16	0.521948	0.894116	0.253316	0.033*
C17	0.6549 (2)	1.09519 (16)	0.30836 (11)	0.0289 (4)
C18	0.8145 (2)	1.20792 (17)	0.30499 (12)	0.0354 (4)
H18	0.835305	1.290278	0.343377	0.042*
C19	0.9109 (2)	1.09080 (17)	0.20072 (13)	0.0351 (4)
H19	0.998875	1.089041	0.162807	0.042*
C20	0.5209 (2)	1.10509 (17)	0.36734 (12)	0.0326 (4)
C21	0.3467 (2)	1.04802 (18)	0.33182 (13)	0.0366 (4)
H21	0.312714	1.001744	0.268836	0.044*
C22	0.2225 (3)	1.0581 (2)	0.38747 (14)	0.0480 (5)
H22	0.103978	1.017354	0.362924	0.058*
C23	0.2710 (3)	1.1276 (2)	0.47900 (15)	0.0557 (6)
H23	0.186196	1.135071	0.517087	0.067*
C24	0.4438 (3)	1.1856 (2)	0.51400 (14)	0.0515 (5)
H24	0.477753	1.233593	0.576400	0.062*
C25	0.5676 (3)	1.17463 (19)	0.45928 (13)	0.0436 (5)
H25	0.685829	1.214852	0.484499	0.052*
Cl1	0.16918 (5)	0.91117 (4)	0.07387 (3)	0.02965 (12)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0214 (5)	0.0315 (6)	0.0325 (6)	0.0094 (5)	0.0034 (5)	0.0009 (5)
N1	0.0193 (6)	0.0251 (7)	0.0233 (8)	0.0067 (5)	0.0005 (6)	−0.0016 (6)
N2	0.0166 (6)	0.0211 (7)	0.0291 (7)	0.0082 (5)	0.0028 (5)	−0.0021 (5)
N3	0.0168 (6)	0.0190 (6)	0.0284 (7)	0.0063 (5)	0.0026 (5)	0.0015 (5)
N4	0.0338 (8)	0.0276 (8)	0.0486 (9)	0.0042 (6)	−0.0047 (7)	−0.0027 (7)
C1	0.0190 (7)	0.0168 (7)	0.0326 (9)	0.0045 (6)	0.0034 (7)	0.0017 (6)
C2	0.0223 (8)	0.0363 (10)	0.0332 (9)	0.0056 (7)	−0.0024 (7)	−0.0034 (8)
C3	0.0324 (9)	0.0379 (10)	0.0365 (10)	0.0046 (8)	−0.0038 (8)	−0.0151 (8)
C4	0.0314 (9)	0.0255 (9)	0.0318 (9)	0.0100 (7)	0.0002 (7)	−0.0055 (7)
C5	0.0440 (10)	0.0421 (11)	0.0304 (10)	0.0168 (8)	0.0004 (8)	−0.0131 (8)
C6	0.0448 (11)	0.0452 (11)	0.0306 (10)	0.0196 (9)	0.0129 (8)	−0.0062 (8)
C7	0.0277 (8)	0.0314 (9)	0.0346 (9)	0.0120 (7)	0.0074 (7)	−0.0004 (7)
C8	0.0253 (8)	0.0197 (8)	0.0259 (8)	0.0109 (6)	0.0035 (7)	0.0009 (6)
C9	0.0253 (8)	0.0182 (7)	0.0255 (8)	0.0089 (6)	0.0037 (7)	−0.0004 (6)
C10	0.0182 (7)	0.0260 (8)	0.0366 (9)	0.0093 (6)	0.0059 (7)	−0.0005 (7)
C11	0.0184 (7)	0.0223 (8)	0.0383 (10)	0.0105 (6)	0.0021 (7)	−0.0009 (7)
C12	0.0152 (7)	0.0248 (8)	0.0313 (9)	0.0079 (6)	0.0029 (6)	−0.0023 (6)
C13	0.0183 (7)	0.0217 (8)	0.0302 (9)	0.0091 (6)	0.0007 (6)	−0.0018 (6)
C14	0.0217 (8)	0.0273 (9)	0.0311 (9)	0.0092 (6)	−0.0006 (7)	0.0032 (7)
C15	0.0261 (8)	0.0246 (8)	0.0242 (8)	0.0085 (6)	−0.0037 (7)	0.0011 (6)
C16	0.0281 (8)	0.0232 (8)	0.0267 (9)	0.0063 (6)	−0.0019 (7)	0.0001 (7)
C17	0.0379 (9)	0.0271 (9)	0.0216 (9)	0.0144 (7)	−0.0041 (7)	−0.0001 (7)
C18	0.0448 (10)	0.0227 (9)	0.0325 (10)	0.0099 (7)	−0.0103 (8)	−0.0043 (7)
C19	0.0278 (9)	0.0305 (10)	0.0404 (10)	0.0057 (7)	−0.0010 (8)	−0.0003 (8)
C20	0.0492 (11)	0.0253 (9)	0.0252 (9)	0.0179 (8)	−0.0002 (8)	0.0013 (7)
C21	0.0497 (11)	0.0336 (10)	0.0296 (9)	0.0197 (8)	0.0049 (8)	0.0003 (7)
C22	0.0534 (12)	0.0526 (12)	0.0471 (12)	0.0299 (10)	0.0099 (10)	0.0062 (10)
C23	0.0860 (17)	0.0597 (14)	0.0428 (13)	0.0481 (13)	0.0242 (12)	0.0077 (10)
C24	0.0872 (17)	0.0492 (12)	0.0286 (11)	0.0380 (12)	0.0067 (11)	−0.0037 (9)
C25	0.0672 (13)	0.0374 (10)	0.0294 (10)	0.0259 (9)	−0.0023 (9)	−0.0025 (8)
Cl1	0.02283 (19)	0.0261 (2)	0.0381 (2)	0.00758 (15)	0.00489 (17)	0.00481 (17)

Geometric parameters (Å, º)

O1—C1	1.2298 (17)	C10—H10B	0.9900
N1—C1	1.3562 (19)	C11—H11A	0.9900
N1—C9	1.4136 (19)	C11—H11B	0.9900
N1—H1N	0.852 (17)	C12—C13	1.515 (2)
N2—C8	1.4233 (19)	C12—H12A	0.9900
N2—C10	1.4665 (18)	C12—H12B	0.9900
N2—C13	1.4832 (19)	C13—H13A	0.9900
N3—C14	1.4981 (19)	C13—H13B	0.9900
N3—C12	1.5002 (17)	C14—C15	1.507 (2)
N3—C11	1.5031 (19)	C14—H14A	0.9900
N3—H3N	0.967 (18)	C14—H14B	0.9900
N4—C18	1.336 (2)	C15—C16	1.390 (2)
N4—C19	1.340 (2)	C15—C19	1.395 (2)
C1—C2	1.498 (2)	C16—C17	1.394 (2)
C2—C3	1.527 (2)	C16—H16	0.9500
C2—H2A	0.9900	C17—C18	1.394 (2)
C2—H2B	0.9900	C17—C20	1.484 (2)
C3—C4	1.507 (2)	C18—H18	0.9500
C3—H3A	0.9900	C19—H19	0.9500
C3—H3B	0.9900	C20—C25	1.395 (2)
C4—C5	1.381 (2)	C20—C21	1.393 (2)
C4—C9	1.400 (2)	C21—C22	1.387 (2)
C5—C6	1.387 (2)	C21—H21	0.9500
C5—H5	0.9500	C22—C23	1.389 (3)
C6—C7	1.384 (2)	C22—H22	0.9500
C6—H6	0.9500	C23—C24	1.382 (3)
C7—C8	1.395 (2)	C23—H23	0.9500
C7—H7	0.9500	C24—C25	1.380 (3)
C8—C9	1.415 (2)	C24—H24	0.9500
C10—C11	1.496 (2)	C25—H25	0.9500
C10—H10A	0.9900
C1—N1—C9	123.74 (14)	C10—C11—H11B	109.3
C1—N1—H1N	112.8 (11)	N3—C11—H11B	109.3
C9—N1—H1N	123.5 (11)	H11A—C11—H11B	107.9
C8—N2—C10	114.51 (12)	N3—C12—C13	112.12 (12)
C8—N2—C13	118.19 (12)	N3—C12—H12A	109.2
C10—N2—C13	108.27 (11)	C13—C12—H12A	109.2
C14—N3—C12	112.69 (12)	N3—C12—H12B	109.2
C14—N3—C11	108.66 (12)	C13—C12—H12B	109.2
C12—N3—C11	110.14 (11)	H12A—C12—H12B	107.9
C14—N3—H3N	109.2 (11)	N2—C13—C12	109.53 (12)
C12—N3—H3N	108.5 (11)	N2—C13—H13A	109.8
C11—N3—H3N	107.6 (11)	C12—C13—H13A	109.8
C18—N4—C19	116.51 (14)	N2—C13—H13B	109.8
O1—C1—N1	122.03 (14)	C12—C13—H13B	109.8
O1—C1—C2	121.99 (13)	H13A—C13—H13B	108.2
N1—C1—C2	115.97 (14)	N3—C14—C15	115.00 (13)
C1—C2—C3	110.04 (14)	N3—C14—H14A	108.5
C1—C2—H2A	109.7	C15—C14—H14A	108.5
C3—C2—H2A	109.7	N3—C14—H14B	108.5
C1—C2—H2B	109.7	C15—C14—H14B	108.5
C3—C2—H2B	109.7	H14A—C14—H14B	107.5
H2A—C2—H2B	108.2	C16—C15—C19	117.83 (15)
C4—C3—C2	109.40 (13)	C16—C15—C14	122.94 (13)
C4—C3—H3A	109.8	C19—C15—C14	119.00 (15)
C2—C3—H3A	109.8	C15—C16—C17	120.04 (14)
C4—C3—H3B	109.8	C15—C16—H16	120.0
C2—C3—H3B	109.8	C17—C16—H16	120.0
H3A—C3—H3B	108.2	C18—C17—C16	116.57 (15)
C5—C4—C9	119.99 (15)	C18—C17—C20	121.22 (15)
C5—C4—C3	122.79 (15)	C16—C17—C20	122.21 (14)
C9—C4—C3	117.22 (14)	N4—C18—C17	125.19 (16)
C4—C5—C6	120.19 (16)	N4—C18—H18	117.4
C4—C5—H5	119.9	C17—C18—H18	117.4
C6—C5—H5	119.9	N4—C19—C15	123.81 (17)
C7—C6—C5	119.99 (15)	N4—C19—H19	118.1
C7—C6—H6	120.0	C15—C19—H19	118.1
C5—C6—H6	120.0	C25—C20—C21	118.47 (17)
C6—C7—C8	121.68 (14)	C25—C20—C17	120.38 (17)
C6—C7—H7	119.2	C21—C20—C17	121.13 (15)
C8—C7—H7	119.2	C22—C21—C20	120.67 (18)
C7—C8—N2	121.99 (13)	C22—C21—H21	119.7
C7—C8—C9	117.59 (14)	C20—C21—H21	119.7
N2—C8—C9	120.26 (13)	C21—C22—C23	120.2 (2)
C4—C9—N1	118.14 (13)	C21—C22—H22	119.9
C4—C9—C8	120.56 (14)	C23—C22—H22	119.9
N1—C9—C8	121.30 (13)	C24—C23—C22	119.25 (19)
N2—C10—C11	110.45 (12)	C24—C23—H23	120.4
N2—C10—H10A	109.6	C22—C23—H23	120.4
C11—C10—H10A	109.6	C25—C24—C23	120.72 (19)
N2—C10—H10B	109.6	C25—C24—H24	119.6
C11—C10—H10B	109.6	C23—C24—H24	119.6
H10A—C10—H10B	108.1	C24—C25—C20	120.67 (19)
C10—C11—N3	111.72 (13)	C24—C25—H25	119.7
C10—C11—H11A	109.3	C20—C25—H25	119.7
N3—C11—H11A	109.3
C9—N1—C1—O1	−176.62 (13)	C14—N3—C12—C13	−172.97 (12)
C9—N1—C1—C2	2.4 (2)	C11—N3—C12—C13	−51.46 (16)
O1—C1—C2—C3	−143.54 (15)	C8—N2—C13—C12	165.68 (11)
N1—C1—C2—C3	37.46 (18)	C10—N2—C13—C12	−62.04 (14)
C1—C2—C3—C4	−56.18 (18)	N3—C12—C13—N2	57.34 (15)
C2—C3—C4—C5	−141.79 (17)	C12—N3—C14—C15	−69.10 (16)
C2—C3—C4—C9	38.3 (2)	C11—N3—C14—C15	168.56 (12)
C9—C4—C5—C6	0.5 (3)	N3—C14—C15—C16	95.52 (17)
C3—C4—C5—C6	−179.36 (17)	N3—C14—C15—C19	−90.00 (17)
C4—C5—C6—C7	−0.7 (3)	C19—C15—C16—C17	−1.5 (2)
C5—C6—C7—C8	0.8 (3)	C14—C15—C16—C17	173.04 (14)
C6—C7—C8—N2	174.79 (15)	C15—C16—C17—C18	0.1 (2)
C6—C7—C8—C9	−0.5 (2)	C15—C16—C17—C20	−179.93 (14)
C10—N2—C8—C7	−12.7 (2)	C19—N4—C18—C17	−1.9 (3)
C13—N2—C8—C7	116.78 (16)	C16—C17—C18—N4	1.7 (2)
C10—N2—C8—C9	162.54 (13)	C20—C17—C18—N4	−178.24 (15)
C13—N2—C8—C9	−68.01 (17)	C18—N4—C19—C15	0.4 (3)
C5—C4—C9—N1	−179.77 (15)	C16—C15—C19—N4	1.3 (3)
C3—C4—C9—N1	0.1 (2)	C14—C15—C19—N4	−173.47 (16)
C5—C4—C9—C8	−0.3 (2)	C18—C17—C20—C25	−39.3 (2)
C3—C4—C9—C8	179.60 (15)	C16—C17—C20—C25	140.79 (17)
C1—N1—C9—C4	−23.1 (2)	C18—C17—C20—C21	139.46 (17)
C1—N1—C9—C8	157.43 (14)	C16—C17—C20—C21	−40.5 (2)
C7—C8—C9—C4	0.3 (2)	C25—C20—C21—C22	−1.1 (2)
N2—C8—C9—C4	−175.13 (14)	C17—C20—C21—C22	−179.88 (15)
C7—C8—C9—N1	179.77 (14)	C20—C21—C22—C23	1.1 (3)
N2—C8—C9—N1	4.4 (2)	C21—C22—C23—C24	−0.4 (3)
C8—N2—C10—C11	−162.59 (12)	C22—C23—C24—C25	−0.3 (3)
C13—N2—C10—C11	63.20 (15)	C23—C24—C25—C20	0.2 (3)
N2—C10—C11—N3	−58.73 (16)	C21—C20—C25—C24	0.5 (3)
C14—N3—C11—C10	175.64 (11)	C17—C20—C25—C24	179.25 (15)
C12—N3—C11—C10	51.76 (15)

Hydrogen-bond geometry (Å, º)

Cg is the centroid of the C4–C9 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1^i	0.85 (2)	2.01 (2)	2.844 (2)	168 (2)
N3—H3N···Cl1^ii	0.97 (2)	2.12 (2)	3.065 (1)	167 (2)
C10—H10B···O1^iii	0.99	2.40	3.151 (2)	132
C11—H11A···Cl1^iii	0.99	2.80	3.668 (2)	147
C12—H12A···Cl1	0.99	2.81	3.520 (2)	129
C12—H12B···O1^i	0.99	2.26	3.123 (2)	144
C13—H13A···N1	0.99	2.53	3.138 (2)	120
C14—H14A···Cl1^iii	0.99	2.71	3.585 (2)	147
C21—H21···Cl1	0.95	2.83	3.757 (2)	165
C18—H18···Cg^ii	0.95	2.83	3.487 (2)	127

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