Methyl 1-(4-fluoro­benz­yl)-1H-indazole-3-carboxyl­ate

The title compound, C₁₆H₁₃FN₂O₂, was synthesized by nucleophilic substitution of the indazole N—H hydrogen atom of methyl 1H-indazole-3-carboxyl­ate with 1-(bromo­meth­yl)-4-fluoro­benzene. In the crystal, some hydrogen-bond-like inter­actions are observed.

Key indicators

Structure: I

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.001 Å
• R factor = 0.031
• wR factor = 0.078
• Data-to-parameter ratio = 14.2

checkCIF/PLATON results

No syntax errors found



Alert level G
PLAT142_ALERT_4_G s.u. on b - Axis Small or Missing ..............    0.00013 Ang.
PLAT143_ALERT_4_G s.u. on c - Axis Small or Missing ..............    0.00010 Ang.
PLAT480_ALERT_4_G Long H...A H-Bond Reported H6A      ..O15      .       2.67 Ang.
PLAT480_ALERT_4_G Long H...A H-Bond Reported H12      ..O15      .       2.61 Ang.
PLAT480_ALERT_4_G Long H...A H-Bond Reported H13      ..O15      .       2.62 Ang.
PLAT480_ALERT_4_G Long H...A H-Bond Reported H19      ..F11      .       2.73 Ang.
PLAT480_ALERT_4_G Long H...A H-Bond Reported H9       ..F11      .       2.59 Ang.
PLAT802_ALERT_4_G CIF Input Record(s) with more than 80 Characters          2 Info
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600          1 Note
PLAT961_ALERT_5_G Dataset Contains no Negative Intensities .......     Please Check
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.         20 Info

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

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

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Computing details

Methyl 1-(4-fluorobenzyl)-1H-indazole-3-carboxylate

Crystal data

C16H13FN2O2	F(000) = 592
Mr = 284.28	Dx = 1.429 Mg m^−3
Monoclinic, P21/n	Cu Kα radiation, λ = 1.54184 Å
a = 5.04322 (3) Å	Cell parameters from 29913 reflections
b = 18.11509 (13) Å	θ = 3.9–79.9°
c = 14.46487 (10) Å	µ = 0.88 mm^−1
β = 90.4600 (6)°	T = 100 K
V = 1321.45 (2) Å^3	Block, clear light colourless
Z = 4	0.32 × 0.13 × 0.12 mm

Data collection

XtaLAB Synergy, Single source at home/near, HyPix-Arc 100 diffractometer	2732 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Cu) X-ray Source	2666 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.035
Detector resolution: 10.0000 pixels mm^-1	θmax = 75.3°, θmin = 3.9°
ω scans	h = −6→6
Absorption correction: gaussian (CrysAlisPro; Rigaku OD, 2023)	k = −21→22
Tmin = 0.626, Tmax = 1.000	l = −18→18
47493 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.031	w = 1/[σ^2(Fo^2) + (0.0369P)^2 + 0.532P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.078	(Δ/σ)max = 0.001
S = 1.03	Δρmax = 0.30 e Å^−3
2732 reflections	Δρmin = −0.18 e Å^−3
192 parameters	Extinction correction: SHELXL-2018/3 (Sheldrick 2018), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0027 (3)
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.

Refinement. All the H atoms were included using a riding model starting from calculated positions (aromatic C—H = 0.95 Å, methylene C—H = 0.99 Å, and alkyl C—H = 1.00 Å). The U_iso(H) values were fixed at 1.2 times the equivalent U_eq value of the parent C atoms (1.5 times for the methyl group).

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

	x	y	z	Uiso*/Ueq
F11	0.20188 (14)	0.51087 (4)	0.93308 (4)	0.03075 (18)
O16	0.11216 (15)	0.25606 (4)	0.38007 (5)	0.02287 (18)
O15	0.03249 (15)	0.37833 (4)	0.38349 (5)	0.02512 (19)
N1	0.65913 (16)	0.38193 (5)	0.56604 (6)	0.01720 (19)
N2	0.45483 (16)	0.39395 (5)	0.50783 (6)	0.01800 (19)
C5	0.71051 (19)	0.30814 (5)	0.57692 (7)	0.0168 (2)
C4	0.52753 (19)	0.27022 (5)	0.52017 (7)	0.0170 (2)
C3	0.37458 (19)	0.32774 (5)	0.47872 (7)	0.0172 (2)
C7	0.63589 (19)	0.46374 (5)	0.70088 (7)	0.0180 (2)
C6	0.7843 (2)	0.44440 (6)	0.61369 (7)	0.0194 (2)
H6A	0.786848	0.487719	0.571991	0.023*
H6B	0.970040	0.431674	0.629647	0.023*
C12	0.2762 (2)	0.52949 (6)	0.77426 (7)	0.0201 (2)
H12	0.131495	0.562982	0.771153	0.024*
C13	0.4240 (2)	0.51310 (5)	0.69631 (7)	0.0191 (2)
H13	0.380134	0.535846	0.639021	0.023*
C14	0.1556 (2)	0.32536 (6)	0.41015 (7)	0.0185 (2)
C18	0.5330 (2)	0.19243 (6)	0.51774 (7)	0.0200 (2)
H18	0.411852	0.165588	0.480012	0.024*
C21	0.9019 (2)	0.27162 (6)	0.63117 (7)	0.0198 (2)
H21	1.025145	0.297972	0.668632	0.024*
C10	0.3461 (2)	0.49563 (6)	0.85637 (7)	0.0212 (2)
C20	0.9017 (2)	0.19570 (6)	0.62728 (8)	0.0226 (2)
H20	1.028026	0.168985	0.663067	0.027*
C8	0.7006 (2)	0.43131 (6)	0.78554 (7)	0.0219 (2)
H8	0.845925	0.398046	0.789401	0.026*
C19	0.7187 (2)	0.15640 (6)	0.57148 (8)	0.0225 (2)
H19	0.723970	0.103984	0.571045	0.027*
C9	0.5551 (2)	0.44705 (6)	0.86433 (7)	0.0242 (2)
H9	0.598636	0.424934	0.922035	0.029*
C17	−0.0982 (2)	0.24943 (6)	0.31188 (8)	0.0250 (2)
H17A	−0.046710	0.275111	0.255159	0.038*
H17B	−0.260822	0.271534	0.336094	0.038*
H17C	−0.129430	0.197143	0.298222	0.038*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
F11	0.0376 (4)	0.0365 (4)	0.0183 (3)	0.0086 (3)	0.0041 (3)	−0.0015 (3)
O16	0.0232 (4)	0.0211 (4)	0.0241 (4)	0.0026 (3)	−0.0085 (3)	−0.0028 (3)
O15	0.0253 (4)	0.0218 (4)	0.0281 (4)	0.0045 (3)	−0.0065 (3)	0.0027 (3)
N1	0.0187 (4)	0.0158 (4)	0.0171 (4)	0.0004 (3)	−0.0013 (3)	0.0006 (3)
N2	0.0189 (4)	0.0187 (4)	0.0163 (4)	0.0013 (3)	−0.0001 (3)	0.0014 (3)
C5	0.0170 (4)	0.0165 (5)	0.0171 (5)	0.0003 (4)	0.0025 (4)	0.0006 (4)
C4	0.0160 (4)	0.0183 (5)	0.0168 (5)	0.0005 (4)	0.0012 (4)	0.0009 (4)
C3	0.0179 (5)	0.0169 (5)	0.0168 (5)	0.0008 (4)	0.0009 (4)	0.0009 (4)
C7	0.0190 (5)	0.0151 (5)	0.0199 (5)	−0.0037 (4)	−0.0022 (4)	−0.0014 (4)
C6	0.0202 (5)	0.0165 (5)	0.0216 (5)	−0.0027 (4)	−0.0004 (4)	−0.0010 (4)
C12	0.0209 (5)	0.0168 (5)	0.0224 (5)	0.0009 (4)	−0.0028 (4)	−0.0008 (4)
C13	0.0218 (5)	0.0166 (5)	0.0189 (5)	−0.0022 (4)	−0.0039 (4)	0.0018 (4)
C14	0.0184 (5)	0.0197 (5)	0.0172 (5)	0.0009 (4)	0.0011 (4)	0.0013 (4)
C18	0.0195 (5)	0.0174 (5)	0.0230 (5)	−0.0009 (4)	−0.0001 (4)	−0.0004 (4)
C21	0.0180 (5)	0.0216 (5)	0.0199 (5)	0.0007 (4)	−0.0015 (4)	0.0005 (4)
C10	0.0255 (5)	0.0208 (5)	0.0173 (5)	−0.0008 (4)	0.0003 (4)	−0.0034 (4)
C20	0.0202 (5)	0.0221 (5)	0.0255 (5)	0.0043 (4)	−0.0018 (4)	0.0042 (4)
C8	0.0236 (5)	0.0187 (5)	0.0235 (5)	0.0032 (4)	−0.0043 (4)	−0.0007 (4)
C19	0.0227 (5)	0.0162 (5)	0.0287 (5)	0.0019 (4)	0.0007 (4)	0.0019 (4)
C9	0.0315 (6)	0.0231 (5)	0.0179 (5)	0.0023 (4)	−0.0053 (4)	0.0019 (4)
C17	0.0231 (5)	0.0284 (6)	0.0234 (5)	0.0017 (4)	−0.0082 (4)	−0.0035 (4)

Geometric parameters (Å, º)

F11—C10	1.3601 (12)	C12—H12	0.9500
O16—C14	1.3459 (13)	C12—C13	1.3887 (15)
O16—C17	1.4477 (12)	C12—C10	1.3801 (15)
O15—C14	1.2047 (13)	C13—H13	0.9500
N1—N2	1.3432 (12)	C18—H18	0.9500
N1—C5	1.3704 (13)	C18—C19	1.3767 (15)
N1—C6	1.4653 (13)	C21—H21	0.9500
N2—C3	1.3329 (13)	C21—C20	1.3765 (15)
C5—C4	1.4090 (14)	C10—C9	1.3770 (15)
C5—C21	1.4046 (14)	C20—H20	0.9500
C4—C3	1.4259 (13)	C20—C19	1.4135 (15)
C4—C18	1.4098 (14)	C8—H8	0.9500
C3—C14	1.4790 (14)	C8—C9	1.3900 (15)
C7—C6	1.5129 (14)	C19—H19	0.9500
C7—C13	1.3943 (14)	C9—H9	0.9500
C7—C8	1.3946 (14)	C17—H17A	0.9800
C6—H6A	0.9900	C17—H17B	0.9800
C6—H6B	0.9900	C17—H17C	0.9800
C14—O16—C17	114.47 (8)	O15—C14—O16	123.86 (9)
N2—N1—C5	111.93 (8)	O15—C14—C3	124.86 (9)
N2—N1—C6	119.68 (8)	C4—C18—H18	120.9
C5—N1—C6	128.23 (8)	C19—C18—C4	118.24 (9)
C3—N2—N1	106.36 (8)	C19—C18—H18	120.9
N1—C5—C4	106.64 (8)	C5—C21—H21	121.7
N1—C5—C21	130.70 (9)	C20—C21—C5	116.59 (10)
C21—C5—C4	122.66 (9)	C20—C21—H21	121.7
C5—C4—C3	103.78 (8)	F11—C10—C12	118.50 (9)
C5—C4—C18	119.27 (9)	F11—C10—C9	118.41 (9)
C18—C4—C3	136.95 (9)	C9—C10—C12	123.09 (10)
N2—C3—C4	111.28 (9)	C21—C20—H20	119.1
N2—C3—C14	117.47 (9)	C21—C20—C19	121.78 (10)
C4—C3—C14	131.23 (9)	C19—C20—H20	119.1
C13—C7—C6	119.54 (9)	C7—C8—H8	119.6
C13—C7—C8	119.06 (9)	C9—C8—C7	120.80 (10)
C8—C7—C6	121.36 (9)	C9—C8—H8	119.6
N1—C6—C7	110.90 (8)	C18—C19—C20	121.45 (10)
N1—C6—H6A	109.5	C18—C19—H19	119.3
N1—C6—H6B	109.5	C20—C19—H19	119.3
C7—C6—H6A	109.5	C10—C9—C8	118.12 (10)
C7—C6—H6B	109.5	C10—C9—H9	120.9
H6A—C6—H6B	108.0	C8—C9—H9	120.9
C13—C12—H12	121.0	O16—C17—H17A	109.5
C10—C12—H12	121.0	O16—C17—H17B	109.5
C10—C12—C13	117.95 (9)	O16—C17—H17C	109.5
C7—C13—H13	119.5	H17A—C17—H17B	109.5
C12—C13—C7	120.97 (9)	H17A—C17—H17C	109.5
C12—C13—H13	119.5	H17B—C17—H17C	109.5
O16—C14—C3	111.28 (8)

Hydrogen-bond geometry (Å, º)

Cg is the centroid of the C4/C5/C18–C21 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6A···O15^i	0.99	2.67	3.3417 (13)	125
C12—H12···O15^ii	0.95	2.61	3.2190 (12)	123
C13—H13···O15^ii	0.95	2.62	3.2339 (12)	123
C13—H13···N2^i	0.95	2.62	3.4578 (13)	148
C19—H19···F11^iii	0.95	2.73	3.3840 (13)	127
C9—H9···F11^iv	0.95	2.59	3.2577 (12)	127
C17—H17A···Cg^v	0.98	2.95	3.8114 (12)	148

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